System and method for ethylene to liquids

文档序号：1595057 发布日期：2020-01-07 浏览：31次中文

阅读说明：本技术 乙烯成液体的系统和方法 (System and method for ethylene to liquids ) 是由格雷格·尼斯理查德·布莱克彼得·西泽帕克卡洛斯·法兹埃里克·弗里尔哈特姆·哈拉兹于 2015-01-07 设计创作，主要内容包括：本申请涉及一种乙烯成液体的系统和方法。本发明提供了由甲烷生产高级烃组合物例如液体烃组合物的集成系统,其使用甲烷氧化偶合系统将甲烷转化为乙烯,然后将乙烯转化为可选择的高级烃产物。本发明提供了将甲烷处理成这些高级烃产物的集成系统和方法。(The present application relates to a system and method for ethylene to liquids. The present invention provides an integrated system for producing higher hydrocarbon compositions, such as liquid hydrocarbon compositions, from methane using a methane oxidative coupling system to convert methane to ethylene and then ethylene to an alternative higher hydrocarbon product. The present invention provides an integrated system and process for processing methane into these higher hydrocarbon products.)

1. A method of producing a plurality of hydrocarbon products, the method comprising:

(a) introducing methane and an oxidant source into an Oxidative Coupling of Methane (OCM) reactor system capable of converting methane to ethylene at a C of at least 50% at a reactor inlet temperature of between 400 ℃ and 600 ℃ and a reactor pressure of between 15psig and 150psig under conditions to convert methane to ethylene₂₊Selectively converting methane to ethylene;

(b) converting methane to a product gas comprising ethylene;

(c) introducing separate portions of the product gas into at least a first integrated ethylene conversion reaction system and a second integrated ethylene conversion reaction system, each integrated ethylene conversion reaction system configured for converting ethylene to a different higher hydrocarbon product; and

(d) ethylene is converted to different higher hydrocarbon products.

2. The process of claim 1, wherein the first and second integrated ethylene conversion reaction systems are selected from the group consisting of selective and full-range ethylene conversion systems.

3. The process of any one of claims 1 and 2, further comprising introducing a portion of the product gas into a third integrated ethylene conversion system.

4. The method of claim 3, further comprising introducing a portion of the product gas into a fourth integrated ethylene conversion system.

5. The process of any of claims 1-4, wherein the at least first and second integrated ethylene conversion reaction systems are selected from the group consisting of Linear Alpha Olefin (LAO) systems, dimerization, metathesis, disproportionation, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, and hydrocarbon polymer systems.

6. The process of any one of claims 1-5, wherein the first and second integrated ethylene conversion reaction systems are selected from the group consisting of LAO systems that produce one or more of 1-butene, 1-hexene, 1-octene, and 1-decene.

7. The method of claim 6, wherein at least one of the LAO systems is configured for performing selective LAO procedures.

8. The method of claim 6, wherein the first integrated ethylene conversion reaction system or second integrated ethylene conversion reaction system comprises a reactor configured for production at C₃To C₃₀A full range ethylene oligomerization system for a range of higher hydrocarbons.

9. The method of any of claims 1-8, wherein the OCM reactor system comprises a nanowire OCM catalyst material.

10. The process of any one of claims 1-9, wherein the product gas comprises less than 5 mol% ethylene.

Background

The modern petrochemical industry uses cracking and fractionation techniques extensively to produce and separate various desired compounds from crude oil. Cracking and fractionation operations are energy intensive and produce considerable amounts of greenhouse gases.

The gradual depletion of worldwide oil reserves and the corresponding rise in oil prices can place great pressure on refiners to minimize losses and improve efficiency in producing products from existing feedstocks, and also to find viable alternative feedstocks that can provide affordable hydrocarbon intermediates and liquid fuels to downstream consumers.

Methane, due to its wide availability and relatively low cost compared to crude oil, can provide an attractive alternative feedstock for the production of hydrocarbon intermediates and liquid fuels. Worldwide methane reserves are available at current consumption rates for hundreds of years, and new production promotion technologies may make previously unattractive methane reserves commercially viable.

Ethylene is an important commodity chemical intermediate. It can be used to produce polyethylene plastics, polyvinyl chloride, ethylene oxide, ethylene chloride, ethylbenzene, alpha olefins, linear alcohols, vinyl acetate and fuel blending stocks such as but not limited to aromatics, alkanes and alkenes. The demand for ethylene and ethylene-based derivatives continues to increase with the economic growth in developed and developing countries. Currently, ethylene is produced by the cracking of ethane derived from crude oil distillates known as naphtha or from the relatively minor ethane component of natural gas. Ethylene production is primarily limited to mass production as commodity chemicals in relatively large steam cracking plants, or in other petrochemical plants that also process the large quantities of other hydrocarbon by-products generated during the crude oil cracking process. For ethylene derived from ethane in natural gas or crude oil, the production of ethylene from methane, which is richer in natural gas and significantly cheaper, provides an attractive alternative.

Disclosure of Invention

A need is recognized herein for an efficient and commercially viable system and process for converting ethylene to higher molecular weight hydrocarbons, including gasoline, diesel fuel, jet fuel, and aromatic chemicals. In some cases, the higher molecular weight hydrocarbons may be produced from methane in an integrated process that converts methane to ethylene and converts ethylene to higher molecular weight compounds. Oxidative coupling of methane ("OCM") is a reaction in which methane can form one or more hydrocarbon compounds (also referred to herein as "C") with two or more carbon atoms₂₊Compound), for example, an olefin such as ethylene.

In an OCM process, methane can be oxidized to produce a product containing C₂₊Product of a compound, the C₂₊Compounds include alkanes (e.g., ethane, propane, butane, pentane, etc.) and alkenes (e.g., ethylene)Propylene, etc.). Such alkane (also referred to herein as "paraffin") products may not be suitable for use in downstream processes. Unsaturated chemical compounds such as olefins (or alkenes) may be more suitable for use in downstream processes. Such compounds can be polymerized to produce polymeric materials that are useful for use in a variety of commercial environments.

Oligomerization processes can be used to further convert ethylene to longer chain hydrocarbons that can be used as polymer components for plastics, vinyl compounds (vinyls), and other high value polymeric products. In addition, these oligomerization processes can be used to convert ethylene to other longer hydrocarbons such as C₆、C₇、C₈And longer hydrocarbons useful for fuels such as gasoline, diesel, jet fuel, and blended feedstocks of these fuels, as well as other high value specialty chemicals.

One aspect of the present disclosure provides an Oxidative Coupling of Methane (OCM) system comprising: (a) OCM subsystem(s) which (i) employ a catalyst comprising methane (CH)₄) And a feed stream comprising an oxidant, and (ii) generating a product stream comprising C from the methane and the oxidant₂₊Compound and non-C₂₊A product stream of impurities; (b) at least one separation subsystem downstream of and fluidly coupled to the OCM subsystem, wherein the separation subsystem comprises a first heat exchanger, a de-methanizer unit downstream of the first heat exchanger, and a second heat exchanger downstream of the demethanizer unit, wherein (i) the first heat exchanger cools a product stream, (ii) the demethanizer unit receives the product stream from the first heat exchanger and generates a product stream comprising non-C₂₊(ii) an overhead stream of at least a portion of the impurities, and (iii) cooling at least a portion of the overhead stream in a second heat exchanger and subsequently directing to a first heat exchanger to cool the product stream; and (C) an olefin to liquids subsystem downstream of the OCM subsystem, wherein the olefin to liquids subsystem is configured to be operated by a liquid-containing gas stream contained in C₂₊One or more olefins in the compound produce higher hydrocarbons.

In some embodiments of aspects provided herein, the oxidizing agent is O₂. In aspects provided hereinIn some embodiments, the O is₂Is supplied by air. In some embodiments of aspects provided herein, the OCM subsystem comprises at least one OCM reactor. In some embodiments of aspects provided herein, the OCM subsystem comprises at least one post-bed cracking unit (post-bed cracking unit) downstream of the at least one OCM reactor, the post-bed cracking unit configured to convert at least a portion of alkanes in the product stream to alkenes. In some embodiments of aspects provided herein, the system further comprises a non-OCM process upstream of the OCM subsystem. In some embodiments of aspects provided herein, the non-OCM process is a natural gas liquefaction process. In some embodiments of aspects provided herein, the post-bed cracking unit is configured to receive an additional stream comprising propane separately from the product stream. In some embodiments of aspects provided herein, the non-C is₂₊The impurities include nitrogen (N)₂) Oxygen (O)₂) Water (H)₂O), argon (Ar), carbon monoxide (CO), carbon dioxide (CO)₂) Hydrogen (H)₂) And methane (CH)₄) One or more of (a). In some embodiments of aspects provided herein, the higher hydrocarbon is a higher molecular weight hydrocarbon.

In some embodiments of aspects provided herein, methane generated in the methanation subsystem is reacted with a catalyst to form a catalystIs recycled to the OCM subsystem. In some embodiments of aspects provided herein, the oxidizing agent is O₂. In some embodiments of aspects provided herein, the O is₂Is supplied by air. In some embodiments of aspects provided herein, the OCM subsystem comprises at least one OCM reactor. In some embodiments of aspects provided herein, the OCM subsystem comprises at least one post-bed cracking unit downstream of the at least one OCM reactor, the post-bed cracking unit configured to convert at least a portion of alkanes in the product stream to alkenes. In some embodiments of aspects provided herein, the system further comprises a non-OCM process upstream of the OCM subsystem. In some embodiments of aspects provided herein, the non-OCM process is a natural gas liquefaction process. In some embodiments of aspects provided herein, the post-bed cracking unit is configured to receive an additional stream comprising propane separately from the product stream. In some embodiments of aspects provided herein, the higher hydrocarbons comprise aromatic hydrocarbons. In some embodiments of aspects provided herein, the non-C is₂₊The impurities include nitrogen (N)₂) Oxygen (O)₂) Water (H)₂O), argon (Ar), carbon monoxide (CO), carbon dioxide (CO)₂) Hydrogen (H)₂) And methane (CH)₄) One or more of (a). In some embodiments of aspects provided herein, the methanation subsystem comprises at least one methanation reactor.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, the method comprising: (a) introducing methane and an oxidant source into an Oxidative Coupling of Methane (OCM) reactor system capable of operating at least about 50% C at a reactor inlet temperature of about 450 ℃ to 600 ℃ and a reactor pressure of about 15psig to 125psig under conditions to convert methane to ethylene₂₊Selectively converting methane to ethylene; (b) converting methane to a product gas comprising ethylene; (c) introducing separate portions of the product gas into at least first and second integrated ethylene conversion reaction systems, each integrated ethylene conversion reaction system configured for the introduction of ethyleneThe conversion of alkenes to different higher hydrocarbon products; and (d) converting ethylene to a different higher hydrocarbon product.

In some embodiments of aspects provided herein, the first and second integrated ethylene conversion systems are selected from selective and full range (full range) ethylene conversion systems. In some embodiments of aspects provided herein, the process further comprises introducing a portion of the product gas into a third integrated ethylene conversion system. In some embodiments of aspects provided herein, the process further comprises introducing a portion of the product gas into a fourth integrated ethylene conversion system. In some embodiments of aspects provided herein, the at least first and second integrated ethylene conversion systems are selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, and hydrocarbon polymer systems. In some embodiments of aspects provided herein, the first and second ethylene conversion systems are selected from LAO systems that produce one or more of 1-butene, 1-hexene, 1-octene, and 1-decene. In some embodiments of aspects provided herein, at least one of the LAO systems is configured to perform a selective LAO procedure. In some embodiments of aspects provided herein, the first or second integrated ethylene conversion system comprises a reactor configured for production at C₃To C₃₀A full range ethylene oligomerization system for a range of higher hydrocarbons. In some embodiments of aspects provided herein, the OCM reactor system comprises a nanowire OCM catalyst material. In some embodiments of aspects provided herein, the product gas comprises less than 5 mol% ethylene. In some embodiments of aspects provided herein, the product gas comprises less than 3 mol% ethylene. In some embodiments of aspects provided herein, the product gas further comprises at least one additive selected from CO, and mixtures thereof₂、CO、H₂、H₂O、C₂H₆、CH₄And C₃₊One or more gases of hydrocarbons. Some implementations of aspects provided hereinIn embodiments, the process further comprises enriching the product gas for ethylene prior to introducing the separate portions of the product gas into the at least first and second integrated ethylene conversion reaction systems. In some embodiments of aspects provided herein, the method further comprises introducing vent gas from the first or second integrated ethylene conversion reaction systems into the OCM reactor system.

One aspect of the present disclosure provides a method of producing a plurality of liquid hydrocarbon products, the method comprising: (a) catalytically converting methane to a product gas comprising ethylene; and (b) treating separate portions of the product gas with at least two discrete catalytic reaction systems selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, and hydrocarbon polymer systems.

One aspect of the present disclosure provides a processing system, comprising: (a) an Oxidative Coupling of Methane (OCM) reactor system comprising an OCM catalyst, the OCM reactor system fluidly connected at an input to a source of methane and a source of oxidant, wherein the OCM reactor system (i) employs methane and oxidant as inputs, and (ii) produces a product comprising C from the methane and oxidant₂₊A product stream of compounds; (b) at least a first catalytic ethylene conversion reactor system and a second catalytic ethylene conversion reactor system downstream of the OCM reactor system, the first catalytic ethylene reactor system configured to convert ethylene to a first higher hydrocarbon and the second catalytic ethylene reactor system configured to convert ethylene to a second higher hydrocarbon different from the first higher hydrocarbon; and (c) a selective coupling unit between the OCM reactor system and the first and second catalytic ethylene reactor systems, the selective coupling unit configured to selectively direct at least a portion of the product gas to each of the first and second catalytic ethylene reactor systems.

In some embodiments of aspects provided herein, the first and second ethylene conversion systems are selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, ethylene copolymerization systems, and hydrocarbon polymer systems. In some embodiments of aspects provided herein, the OCM catalyst comprises a nanowire catalyst. In some embodiments of aspects provided herein, the system further comprises an ethylene recovery system between the OCM reactor system and the first and second catalytic ethylene conversion reactor systems, the ethylene recovery system configured to enrich the product gas for ethylene.

One aspect of the present disclosure provides a chemical production system, comprising: an OCM subsystem comprising an OCM reactor, wherein the OCM reactor (i) employs a reactor system comprising methane (CH)₄) And a feed stream comprising an oxidant as inputs, and (ii) generating C from the methane and the oxidant₂₊Compound and non-C₂₊Impurities; and an ethylene-to-liquids (ETL) subsystem downstream of the OCM subsystem, the ETL subsystem comprising an ETL reactor, wherein the ETL reactor converts C into C₂₊At least a portion of the compound is converted to comprise C₃₊Product stream of compounds, C₃₊The compound is produced at a per pass conversion of at least about 40%.

In some embodiments of aspects provided herein, the methane is from a non-OCM process. In some embodiments of aspects provided herein, the ETL reactor is operated at a pressure of about 4 to 50 bar. In some embodiments of aspects provided herein, the single pass conversion without recycle is at least about 40%.

One aspect of the present disclosure provides a method of producing hydrocarbons, comprising: (a) will comprise methane (CH)₄) And a feed stream comprising an oxidant is directed to the OCM reactor; (b) in the OCM reactor, generating a product comprising C from the methane and the oxidant₂₊Compound and non-C₂₊An OCM product stream of impurities; (c) adding the C₂₊At least a portion of the compounds are directed to the ethylene liquid downstream of the OCM subsystemAn ETL subsystem, wherein the ETL subsystem has a function of converting C in the OCM product stream₂₊At least a portion of the compound is converted to comprise C₃₊An ETL reactor of an ETL product stream of compounds; and (d) recycling less than 25% of the ethylene in the product stream to the ETL subsystem.

In some embodiments of aspects provided herein, the OCM and ETL subsystems produce C with a single pass conversion efficiency of at least about 40%₃₊A compound is provided. In some embodiments of aspects provided herein, the single pass conversion efficiency without recycle is at least about 40%. In some embodiments of aspects provided herein, the methane is from a non-OCM process. In some embodiments of aspects provided herein, the ETL reactor is operated at a pressure of about 10 to 50 bar.

One aspect of the present disclosure provides a method for generating a catalyst, comprising: (a) providing a catalyst substrate having a first set of pores, wherein the substrate comprises an active component that promotes the conversion of an olefin to a first set of hydrocarbons, at least some of which are liquid at room temperature and atmospheric pressure; (b) introducing a second set of pores into the substrate, the second set of pores having an average diameter of at least about 10 nanometers as measured by BET isotherms; and (c) providing one or more dopants on one or more surfaces of the substrate, wherein the one or more dopants promote conversion of the olefin to a second group of hydrocarbons, at least some of which are liquid at room temperature and atmospheric pressure, wherein the second group of hydrocarbons has a different product distribution than the first group of hydrocarbons.

In some embodiments of aspects provided herein, the first set of pores has an average diameter of at least about 4 to 10 angstroms. In some embodiments of aspects provided herein, the substrate comprises a zeolite. In some embodiments of aspects provided herein, (b) is after (c). In some embodiments of aspects provided herein, (b) and (c) are performed simultaneously. In some embodiments of aspects provided herein, the substrate has about 100m²G to 1000m²Surface area in g. In some embodiments of aspects provided herein, (c) is) Including providing a dopant selected from the group consisting of Ga, Zn, Al, In, Ni, Mg, B, and Ag. In some embodiments of aspects provided herein, the catalyst substrate is H-Al-ZSM-5, H-Ga-ZSM-5, H-Fe-ZSM-5, H-B-ZSM-5, or any combination thereof. In some embodiments of aspects provided herein, the second set of hydrocarbons has a narrower product distribution than the first set of hydrocarbons.

One aspect of the present disclosure provides a system for producing hydrocarbons, comprising: an ethylene-to-liquids (ETL) unit comprising one or more ETL reactors, wherein a separate ETL reactor receives ethylene from a non-ETL process and generates a product stream comprising higher hydrocarbons through an oligomerization process, wherein at least some of the higher hydrocarbons are liquid at room temperature and atmospheric pressure; and at least one separation unit downstream of and fluidly coupled to the ETL unit, wherein the separation unit separates the product stream into separate streams each comprising a subset of the higher hydrocarbons.

In some embodiments of aspects provided herein, the ETL reactor comprises a catalyst having an active material and one or more dopants on the surface of the active material. In some embodiments of aspects provided herein, the system further comprises an Oxidative Coupling of Methane (OCM) unit upstream of the ETL unit, wherein the OCM unit comprises one or more OCM reactors, each OCM reactor (i) employing a catalyst comprising methane (CH)₄) And a feed stream comprising an oxidant as inputs, (ii) generating C from the methane and the oxidant₂₊Compound and non-C₂₊(ii) impurities, and (iii) adding C₂₊At least a subset of the compounds of ethylene is directed to the ETL unit.

One aspect of the present disclosure provides a catalyst for converting ethylene to liquid hydrocarbon fuel, the catalyst comprising: (a) a ZSM-5 substrate; (b) a binder material; and (c) a dopant material; wherein the catalyst has a cycle life of at least about 1 week when contacted with up to about 100 parts per million (ppm) of acetylene, and wherein the catalyst has a replacement life of at least about 1 year when contacted with up to about 100ppm of acetylene.

One aspect of the present disclosure provides a catalyst for hydrogenating acetylene in an Oxidative Coupling of Methane (OCM) and ethylene-to-liquid (ETL) process, the catalyst comprising at least one elemental metal, wherein the catalyst is capable of reducing the concentration of acetylene to less than about 100 parts per million (ppm) in the OCM effluent prior to the OCM effluent flowing to the ETL process.

In some embodiments of aspects provided herein, the catalyst is capable of reducing the concentration of acetylene to less than about 10ppm in the OCM effluent. In some embodiments of aspects provided herein, the catalyst is capable of reducing the concentration of acetylene to less than about 1ppm in the OCM effluent. In some embodiments of aspects provided herein, the at least one elemental metal comprises palladium. In some embodiments of aspects provided herein, the at least one elemental metal is part of a metal oxide. In some embodiments of aspects provided herein, the catalyst is capable of providing an OCM effluent comprising at least about 0.5% carbon monoxide. In some embodiments of aspects provided herein, the catalyst is capable of providing an OCM effluent comprising at least about 1% carbon monoxide. In some embodiments of aspects provided herein, the catalyst is capable of providing an OCM effluent comprising at least about 3% carbon monoxide. In some embodiments of aspects provided herein, the catalyst has a lifetime of at least about 1 year. In some embodiments of aspects provided herein, the catalyst is capable of providing an OCM effluent comprising at least about 0.1% acetylene. In some embodiments of aspects provided herein, the catalyst is capable of providing an OCM effluent comprising at least about 0.3% acetylene. In some embodiments of aspects provided herein, the catalyst is capable of providing an OCM effluent comprising at least about 0.5% acetylene. In some embodiments of aspects provided herein, the ETL process converts ethylene in the OCM effluent to higher hydrocarbons. In some embodiments of aspects provided herein, the at least one metal comprises a plurality of metals.

One aspect of the present disclosure provides a method for oxidative coupling of methane (OC)M) and Ethylene To Liquids (ETL) process carbon monoxide (CO) and/or carbon dioxide (CO)₂) Conversion to methane (CH)₄) Wherein the catalyst comprises at least one elemental metal, and wherein the catalyst converts CO and/or CO₂Conversion to CH₄A selectivity to methane formation that is at least about 10 times the selectivity of the catalyst to coke formation in the ETL effluent.

In some embodiments of aspects provided herein, the selectivity of the catalyst for methane formation is at least about 100 times the selectivity of the catalyst for coke formation. In some embodiments of aspects provided herein, the selectivity of the catalyst for methane formation is at least about 1000 times the selectivity of the catalyst for coke formation. In some embodiments of aspects provided herein, the selectivity of the catalyst for methane formation is at least about 10000 times the selectivity of the catalyst for coke formation. In some embodiments of aspects provided herein, the ETL effluent comprises at least about 3% olefins and/or acetylenic compounds. In some embodiments of aspects provided herein, the ETL effluent comprises at least about 5% olefins and/or acetylenic compounds. In some embodiments of aspects provided herein, the ETL effluent comprises at least about 10% olefins and/or acetylenic compounds. In some embodiments of aspects provided herein, the at least one elemental metal comprises nickel. In some embodiments of aspects provided herein, the at least one elemental metal is part of a metal oxide.

One aspect of the present disclosure provides a method for preventing coke formation on a methanation catalyst during Oxidative Coupling of Methane (OCM) and Ethylene To Liquid (ETL), the method comprising: (a) providing a composition comprising carbon monoxide (CO) and/or carbon dioxide (CO)₂) The ETL effluent of (2); and (b) methanation with the ETL effluent using a methanation catalyst, wherein: (i) adding hydrogen and/or water to the ETL effluent prior to (b); (ii) hydrogenating olefins and/or acetylenes in the ETL effluent prior to (b); and/or (iii) venting olefin and/or acetylene from the ETL prior to (b)Separated and/or condensed in the substance.

In some embodiments of aspects provided herein, the (iii) is performed using absorption or adsorption. In some embodiments of aspects provided herein, the methanation reaction forms at least about 1000 times as much methane as coke. In some embodiments of aspects provided herein, the methanation reaction forms at least about 10000 times as much methane as coke. In some embodiments of aspects provided herein, the methanation reaction forms at least about 100000 times as much methane as coke. In some embodiments of aspects provided herein, the method further comprises any two of (i), (ii), and (iii). In some embodiments of aspects provided herein, the method further comprises all of (i), (ii), and (iii). In some embodiments of aspects provided herein, C is removed from the ETL effluent prior to methanation using a methanation catalyst₅₊A compound is provided. In some embodiments of aspects provided herein, C is removed from the ETL effluent prior to methanation using a methanation catalyst₄₊A compound is provided. In some embodiments of aspects provided herein, C is removed from the ETL effluent prior to methanation using a methanation catalyst₃₊A compound is provided.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) in an Oxidative Coupling of Methane (OCM) reactor, methane and an oxidant are reacted in an OCM process to generate heat and a hydrocarbon compound (C) comprising two or more carbon atoms₂₊Compound) comprising ethylene; (b) directing the OCM product stream from the OCM reactor to a post-bed cracking (PBC) unit downstream of the OCM reactor; (c) subjecting the OCM product stream to thermal cracking in the PBC unit under conditions suitable for cracking ethane to ethylene, wherein the thermal cracking is carried out at least in part with heat from (a), thereby producing a product stream comprising ethylene and hydrogen (H)₂) PBC product stream of (a), ethylene and hydrogen (H)₂) Relative to ethylene and H in the OCM product stream₂A corresponding increase in concentration of; (d) directing a PBC product stream from a PBC unit to a PBC reactorAn ethylene-to-liquid (ETL) reactor downstream of the PBC unit, wherein said ETL reactor converts ethylene in the PBC product stream to higher hydrocarbons.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: ethylene and hydrogen (H)₂) Directing into an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to convert hydrocarbon compounds (C) having two or more carbon atoms₂₊Compounds) to higher hydrocarbons, including ethylene; and in the ETL reactor, in H₂Converting said ethylene to higher hydrocarbons in the presence of H₂The conversion results in less coke formation than when the conversion is carried out.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: mixing ethylene and water (H)₂O) into an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to introduce hydrocarbon compounds (C) having two or more carbon atoms₂₊Compounds) to higher hydrocarbons, including ethylene; and in an ethylene-to-liquids (ETL) reactor, in H₂Converting said ethylene to higher hydrocarbons in the presence of O, and in the absence of H₂The conversion results in less coke formation than when the conversion is carried out in the case of O.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) introducing a feed stream comprising ethylene and ethane into an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to introduce hydrocarbon compounds (C) having two or more carbon atoms₂₊Compound) to higher hydrocarbons and wherein the molar ratio of ethylene to ethane in the feed stream is at least about 3:1, and (b) in the ETL reactor, converting the ethylene to higher hydrocarbons.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: directing ethylene to an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to direct hydrocarbon compounds (C) having two or more carbon atoms₂₊Compound) to higherA hydrocarbon; in the ETL reactor, converting said ethylene to said higher hydrocarbons; and separating the higher hydrocarbons into at least two product streams, at least one of the at least two product streams being characterized by five or more characteristics selected from the group consisting of: (a) no more than 1.30 vol% benzene; (b) not more than 50 vol% aromatic hydrocarbons; (c) no more than 25 vol% olefins; (d) a Motor Octane Number (MON) of at least 82; (e) a total octane number of at least 87; (f) reid Vapor Pressure (RVP) of not more than 15 psi; (g) 10% of boiling point is not higher than 70 ℃; (h) 50% of the boiling point is not higher than 121 ℃; (i) 90% of the boiling point is not higher than 190 ℃; (j) a Final Boiling Point (FBP) of not higher than 221 ℃; and (k) an oxidation induction time of at least 240 minutes.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: directing ethylene into an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to direct hydrocarbon compounds (C) having two or more carbon atoms₂₊Compounds) to higher hydrocarbons, including ethylene; and in the ETL reactor, converting ethylene to higher hydrocarbon products in an ETL product stream comprising less than 60% water.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) directing ethylene into an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor comprises an ETL catalyst configured to convert hydrocarbon compounds (C) having two or more carbon atoms₂₊Compounds) to higher hydrocarbons, including ethylene; (b) in the ETL reactor, converting said ethylene to higher hydrocarbons to provide an ETL product stream comprising said higher hydrocarbons and forming coke on said ETL catalyst; (c) contacting the ETL catalyst with an oxidant to regenerate the ETL catalyst by burning coke on the ETL catalyst; and (d) repeating (b) - (c) for at least 20 cycles, wherein the composition of the ETL product stream from the first cycle differs by no more than 0.1% from the composition of the ETL product stream from the second ten cycles.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) introducing a feed stream comprising hydrocarbons into a Fluid Catalytic Cracking (FCC) reactor comprising an FCC catalyst, wherein the FCC catalyst is configured to crack the hydrocarbons into lower molecular weight hydrocarbons; (b) in the FCC reactor, (i) cracking the hydrocarbons to lower molecular weight hydrocarbons, and (ii) forming coke on the FCC catalyst; (c) transferring at least a portion of the FCC catalyst to a regeneration unit and introducing an oxidant stream into the regeneration unit; (d) in the regeneration unit, combusting coke on the FCC catalyst in the presence of said oxidant stream, thereby regenerating the FCC catalyst and producing a flue gas stream comprising carbon monoxide and/or carbon dioxide; (e) directing the flue gas stream into a heat exchanger to transfer heat from the flue gas stream to a first stream comprising ethane or propane; and (f) subjecting the first stream to thermal cracking under conditions (i) to crack the ethane to ethylene and/or (ii) to crack the propane to propylene, wherein the thermal cracking is at least partially carried out with heat from (e).

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) in a first Oxidative Coupling of Methane (OCM) reactor, methane and a first oxidant are reacted in an OCM process to produce a hydrocarbon compound (C) comprising unreacted methane and having two or more carbon atoms₂₊Compound) comprising ethylene; (b) introducing the first OCM product stream to a reactor configured to introduce C₂₊An ethylene-to-liquids (ETL) reactor for the conversion of compounds to higher hydrocarbons; (c) converting at least a portion of the ethylene in the first OCM product stream to higher hydrocarbons in an ETL reactor to provide an ETL product stream comprising the higher hydrocarbons and the unreacted methane; (d) introducing a second oxidant stream and at least a portion of the ETL product stream into a second OCM reactor; and (e) reacting said unreacted methane and said second oxidant in another OCM process in said second OCM reactor to produce a stream comprising C₂₊A second OCM product stream of compounds, C₂₊The compound comprises ethylene.

In some embodiments of aspects provided herein, the method further comprises removing at least a portion of the higher hydrocarbons from the ETL product stream prior to the introducing of (e).

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) directing a feed stream comprising ethylene to an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to direct hydrocarbon compounds (C) having two or more carbon atoms₂₊Compound) to higher hydrocarbons; (b) converting the ethylene to an ETL product stream comprising the higher hydrocarbons; (c) directing the ETL product stream to a separation system and separating the ETL product stream in the separation system into a higher hydrocarbon stream and a lower olefin stream comprising propylene and butenes; (d) introducing the lower olefin stream into an oligomerization reactor, wherein the oligomerization reactor comprises feeding C₂₊Oligomerization catalysts for the oligomerization of compounds to higher hydrocarbons; and (e) oligomerizing propylene and butene in the lower olefin stream in the oligomerization reactor to produce an oligomerization product stream comprising oligomerization products of propylene and butene.

In some embodiments of aspects provided herein, the oligomerization product stream comprises olefins having a carbon number of 6 to 16. In some embodiments of aspects provided herein, the temperature within the oligomerization reactor during oligomerization is about 50 ℃ to 200 ℃. In some embodiments of aspects provided herein, the oligomerization catalyst comprises a solid acid catalyst. In some embodiments of aspects provided herein, the oligomerization reactor is in a form selected from a slurry bed reactor, a fixed bed reactor, a tubular isothermal reactor, a moving bed reactor, and a fluidized bed reactor.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) in an Oxidative Coupling of Methane (OCM) reactor, methane and an oxidant are reacted in an OCM process to produce a hydrocarbon compound (C) comprising unreacted methane and having two or more carbon atoms₂₊Compounds) including ethylene, ethane, and propane; (b) introducing the OCM product stream into an ethylene-to-liquids (ETL) reactor, wherein the ETL reactor is configured to introduce unreacted methane and at least a portion of the C₂₊Conversion of a CompoundIs an aromatic hydrocarbon and wherein the ETL reactor comprises an ETL catalyst doped with one or more dopants selected from molybdenum (Mo), gallium (Ga), and tungsten (W); and (C) in the ETL reactor, passing unreacted methane and said at least a portion of C₂₊The compounds are converted to an aromatic product stream comprising aromatic hydrocarbons.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) hydrogen (H)₂) And directing a low octane stream comprising n-hexane to an isomerization reactor configured to isomerize n-hexane to isohexane, wherein the low octane stream is characterized by an octane no greater than 62; and (b) reacting said H₂And the n-hexane to produce an isomerization product stream comprising isohexane, wherein the isomerization product stream is characterized by an octane number of at least 73.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) in a Natural Gas Liquids (NGL) system, hydrocarbon compounds (C) comprising four or more carbon atoms are produced from natural gas₄₊Compound) comprising a hydrocarbon compound comprising butane; (b) introducing the first NGL product stream to a reactor configured to subject the C to₄₊An isomerization reactor for isomerizing compounds; and (C) in the isomerization reactor, passing the C₄₊At least a portion of the compound isomerizes to form an isomerized product, thereby producing an isomerate (isomerate) stream comprising the isomerized product.

One aspect of the present disclosure provides a method of producing a plurality of hydrocarbon products, comprising: (a) in an Oxidative Coupling of Methane (OCM) reactor, methane and an oxidant are reacted in an OCM process to produce a hydrocarbon compound (C) comprising unreacted methane and containing two or more carbon atoms₂₊Compound) comprising ethylene; (b) introducing said OCM product stream into an ethylene-to-liquids (ETL) reactor that reacts ethylene in the OCM product stream to produce an ETL product stream of higher hydrocarbons and unreacted methane; and (c) introducing the ETL product stream into at least one separation unit,the separation unit separates the ETL product stream into a gas stream comprising the unreacted methane and at least one product stream comprising hydrocarbon compounds having at least 3, 4, or 5 carbon atoms.

In some embodiments of aspects provided herein, the methane is provided at least in part by a natural gas pipeline, and wherein the method further comprises outputting the gas stream to a natural gas pipeline. In some embodiments of aspects provided herein, the methane is provided at least in part by a cryogenic separation system, and wherein the method further comprises directing the gas stream to a recompressor unit. In some embodiments of aspects provided herein, the methane is provided at least in part by a cryogenic separation system, and wherein the method further comprises compressing the gas stream in a compressor to produce a compressed stream, and directing the compressed stream to a cryogenic separation unit. In some embodiments of aspects provided herein, the methane is provided at least in part by a cryogenic separation unit, and the method further comprises: compressing the gas stream in a compressor to produce a compressed stream; directing the compressed stream to a cryogenic separation unit; in the cryogenic separation unit, along C from the gas stream₂₊Product stream removal of any C₂₊A compound; and optionally directing the gas stream to a recompressor unit.

One aspect of the present disclosure provides a method of producing a hydrocarbon compound (C) comprising two carbon atoms₂Compound), hydrocarbon compound having three carbon atoms (C)₃Compound), hydrocarbon compound having four carbon atoms (C)₄Compound) and hydrocarbon compound (C) having five or more carbon atoms₅₊Compound), the process comprising: (a) introducing a natural gas stream comprising methane into a gas treatment system and removing at least one of mercury, water, and acid gases from the natural gas stream in the gas treatment system; (b) directing a natural gas stream from a gas processing system into a Natural Gas Liquids (NGL) extraction system that produces a first stream comprising methane, and comprising C from the natural gas stream₂Compound, C₃Compound, C₄Compounds and C₅₊A second stream of compounds; (c) directing a first portion of the first stream to a liquefaction unit and, in the liquefaction unit, producing liquid natural gas from the first portion of the first stream; (d) directing the second stream into an NGL fractionation system that separates the second stream into at least (i) a product stream comprising C₂Compounds and C₃C of the Compound₂-C₃Stream, (ii) containing C₄C of the Compound₄(ii) a stream, and (iii) contains C₅₊C of the Compound₅₊A stream; (e) second part of the first stream, C₂-C₃The streams and oxidant are directed to an Oxidative Coupling of Methane (OCM) system that converts methane in a second portion of the first stream during OCM to produce an OCM product stream comprising ethylene; (f) directing said OCM product stream into an ethylene-to-liquids (ETL) reactor that converts ethylene in said OCM product stream to higher hydrocarbons, thereby forming a product stream comprising C₂Compound, C₃Compound, C₄Compounds and C₅₊An ETL product stream of compounds; and (g) directing the ETL product stream into the NGL extraction system.

In some embodiments of aspects provided herein, the method further comprises, prior to the directing of (b), directing the natural gas stream from the gas treatment system into a pre-cooling system, and removing a first fuel gas stream comprising methane from the natural gas stream in the pre-cooling system. In some embodiments of aspects provided herein, the process further comprises directing the liquid natural gas stream into a denitrification unit, and in the denitrification unit, removing a stream comprising nitrogen from the liquid natural gas stream.

One aspect of the present disclosure provides a method of producing a hydrocarbon compound (C) comprising two carbon atoms₂Compound), hydrocarbon compound having three carbon atoms (C)₃Compound), hydrocarbon compound having four carbon atoms (C)₄Compound) and hydrocarbon compound (C) having five or more carbon atoms₅₊Compound), the process comprising: (a) introducing a first natural gas stream comprising methane into a gas treatment system that removes at least one of mercury, water, and acid gases from the first natural gas stream; (b) introducing a second natural gas stream comprising methane into a gas conditioning system that removes at least one sulfur compound from the second natural gas stream; (c) directing a first portion of a first natural gas stream from the gas treatment system and a second natural gas stream from the gas conditioning systemTo a Natural Gas Liquids (NGL) extraction system that produces from a first portion of the first natural gas stream and the second natural gas stream (i) a first stream comprising methane, (ii) a first stream comprising C₂(ii) a second stream of compounds, and (iii) comprising C₂Compound, C₃Compound, C₄Compounds and C₅₊A third stream of compounds, wherein a portion of the first stream is removed as a pipeline gas product stream; (d) directing the third stream into an NGL fractionation system that separates the third stream into at least (i) a C-containing stream₂C of the Compound₂Stream, (ii) containing C₃Compounds and C₄C of the Compound₃-C₄(ii) a stream, and (iii) contains C₅₊C of the Compound₅₊A stream; (e) combining a second portion of the second natural gas stream from the gas conditioning system, a second stream from the NGL extraction system, C from an NGL fractionation system₂Directing the streams and an oxidant into an Oxidative Coupling of Methane (OCM) reactor that converts methane in at least some of the streams during OCM to produce an OCM product stream comprising ethylene; (f) directing said OCM product stream into an ethylene-to-liquids (ETL) reactor that converts ethylene in said OCM product stream to comprise C₂Compound, C₃Compound, C₄Compounds and C₅₊An ETL product stream of compounds; and (g) directing the ETL product stream into the NGL extraction system.

In some embodiments of aspects provided herein, the method further comprises passing the C from the heat exchanger₂The flow is directed to the ETL reactor.

One aspect of the present disclosure provides a method of producing a hydrocarbon compound (C) comprising two carbon atoms₂Compound), hydrocarbon compound having three carbon atoms (C)₃Compound), hydrocarbon compound having four carbon atoms (C)₄Compound) and hydrocarbon compound (C) having five or more carbon atoms₅₊Compound), the process comprising: (a) directing a first stream comprising ethylene from a refinery gas facility into a demethanizer that removes a first methane stream comprising methane from the first stream, wherein the first stream undergoes desulfurization prior to being directed to the demethanizer; (b) directing the first methane stream, a second methane stream comprising methane, and an oxidant into an Oxidative Coupling of Methane (OCM) system that converts methane therein during an OCM process to produce an OCM product stream comprising ethylene; (c) directing said first stream and said OCM product stream into an ethylene-to-liquids (ETL) reactor that converts ethylene in said OCM product stream to comprise C₂Compound, C₃Compound, C₄Compounds and C₅₊An ETL product stream of compounds; (d) directing said ETL product stream to a separation system that separates at least the ETL product stream into a stream comprising C₂Compounds and C₃C of the Compound₂-C₃A stream of the stream; and (e) using a heat exchangerFrom said C₂-C₃Heat of the stream is transferred to a second stream comprising ethane and/or propane; and (f) subjecting the second stream to thermal cracking under conditions to crack the ethane to ethylene and/or the propane to propylene, wherein the thermal cracking is at least partially carried out with heat from (e).

In some embodiments of aspects provided herein, the method further comprises passing the C from the heat exchanger₂-C₃At least a portion of the stream is directed to an OCM reactor system. In some embodiments of aspects provided herein, the method further comprises passing the C from the heat exchanger₂-C₃At least a portion of the stream is directed to the ETL reactor.

One aspect of the present disclosure provides a method of producing a hydrocarbon compound (C) comprising two or more carbon atoms₂₊Compound), the process comprising: (a) directing methane and an oxidant to an Oxidative Coupling of Methane (OCM) reactor upstream of a post-bed cracking (PBC) unit, wherein the OCM reactor is configured to facilitate an OCM reaction using the methane and the oxidant to produce C comprising ethylene and one or more alkanes₂₊A compound, and wherein the PBC unit is configured to convert the one or more alkanes, including ethane, to one or more alkenes, including ethylene; (b) reacting, in the OCM reactor, the methane and the oxidant in an OCM reaction to generate an OCM product stream and heat, wherein the OCM product stream comprises ethylene and one or more alkanes; (c) directing the OCM product stream to a PBC unit; (d) subjecting the OCM product stream to thermal cracking in said PBC unit under conditions to crack ethane to ethylene, wherein said thermal cracking is carried out at least in part with heat from (c), thereby producing a PBC product stream comprising ethylene; (e) directing the PBC product stream to a separation module and, in the separation module, separating ethane from the PBC product stream to produce an ethane stream; and (f) directing the ethane stream to the PBC unit.

Additional aspects and advantages of the present disclosure will become apparent to those skilled in the art from the following detailed description, which shows and describes only illustrative embodiments of the disclosure. As will be realized, the disclosure is capable of other and different embodiments and its several details are capable of modifications in various obvious respects, all without departing from the disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.

Is incorporated by reference

All publications, patents and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference.

Drawings

The novel features believed characteristic of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings or figures (also referred to herein as "fig.), (fig.):

FIG. 1 shows an Oxidative Coupling of Methane (OCM) reactor system;

FIG. 2 schematically illustrates a differentially cooled tubular reactor system;

FIG. 3 schematically illustrates a reactor system having two or more tubular reactors;

FIG. 4A schematically illustrates an alternative method for varying the reactor volume in order to vary the residence time of the reactants in the catalyst bed;

FIG. 4B schematically illustrates an exemplary fluidized bed reactor;

FIG. 4C schematically illustrates exemplary moving bed, fluidized bed, and slurry bed reactors;

FIG. 5 is an example of the manner in which product distribution may vary over time for an ETL catalyst;

FIG. 6 schematically illustrates an ethylene-to-liquids (ETL) reactor system in which a process inlet and a recycle stream are combined to form a reactor inlet process stream;

FIG. 7A shows the results as C when a single pass reactor is used₂H₄Liquid phase hydrocarbon yield as a function of conversion;

fig. 7B shows the use of recycled material: fresh material ratio of 5:1 as C₂H₄Liquid phase hydrocarbon yield as a function of conversion;

FIG. 8 is a graph showing increasing C with increasing recycle reaction conditions₅₊Graph of yield (liquid condensed at about 0 ℃);

FIG. 9 shows an example of a Pressure Swing Adsorption (PSA) unit;

FIG. 10 schematically illustrates an integrated OCM system with an integrated separation system;

FIG. 11 shows an example of NGL extraction in a Liquefied Natural Gas (LNG) facility;

FIG. 12 shows an integrated OCM-ETL system for LNG production;

FIG. 13 shows the system of FIG. 12 modified for use with a dilute C1 (methane) fuel gas stream;

FIG. 14 shows an exemplary OCM-ETL system comprising an OCM and ETL subsystem, and a separation subsystem downstream of the ETL subsystem;

FIG. 15 shows an OCM-ETL system comprising an OCM and ETL subsystem, and a cryogenic cooling tank downstream of the ETL subsystem;

FIG. 16 shows another OCM-ETL as an alternative configuration to the system shown in FIG. 14;

FIG. 17 shows an example of OCM-ETL midstream integration;

FIG. 18 shows an example of OCM-ETL midstream integration;

FIG. 19 shows an OCM-ETL system with different skimmer (skimmer) and recirculation configurations.

FIG. 20 shows an example of ETL integration in a refinery;

FIG. 21 shows another example of ETL integration in a refinery;

FIG. 22 shows another example of ETL integration in a refinery;

FIG. 23A schematically illustrates a Natural Gas Liquids (NGL) system; FIG. 23B schematically illustrates the NGL process of FIG. 23A retrofitted with an OCM and ethylene to liquids system;

FIG. 24 schematically illustrates an integrated Oxidative Coupling of Methane (OCM) to olefins into liquids process in an NGL system using air in an OCM process;

FIG. 25 schematically illustrates oxygen (O) in a process employing OCM₂) Integration of OCM-ETL with existing NGL systems;

FIG. 26 schematically illustrates a methanation system;

FIG. 27 shows an example of a methanation system for OCM and ETL;

FIG. 28 illustrates a separation system that may be used with the systems and methods of the present disclosure;

FIG. 29 illustrates another separation system that may be used with the systems and methods of the present disclosure;

FIG. 30 illustrates another separation system that may be used with the systems and methods of the present disclosure;

FIG. 31 illustrates another separation system that may be used with the systems and methods of the present disclosure;

FIG. 32 shows an example of an ethane skimmer embodiment of OCM and ETL; and is

FIG. 33 shows a computer system programmed or otherwise configured to modulate OCM responses;

FIG. 34 schematically illustrates a process flow for converting ethylene to higher liquid hydrocarbons for use in, for example, fuels and fuel blendstocks;

FIG. 35 shows a graph of exemplary product composition over time on stream;

FIGS. 36A-36E show graphs of ETL products with different feedstocks. FIG. 36A shows a diagram of an ETL product with ethylene feedstock; FIG. 36B shows a diagram of ETL product with propylene feed;

FIG. 36C shows a diagram of ETL product with butene feedstock; FIG. 36D shows a diagram of an ETL product with a 50:50 ethylene/propylene feedstock; and figure 36E shows a diagram of an ETL product with a 50:50 ethylene/butene feedstock;

FIG. 37 shows a plot of product composition versus peak catalyst bed temperature;

figure 38 shows a diagram of the ETL product separated into a gasoline fraction and a jet fuel fraction;

FIG. 39 shows a graph of crush strength for various catalyst formulations;

FIG. 40 shows a graph comparing catalyst aging under industrial and accelerated conditions; and is

Figure 41 shows a graph comparing product composition as a function of catalyst regeneration cycle.

Detailed Description

While various embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood in an open, inclusive sense, i.e. to mean "including but not limited to". Further, the headings provided herein are for convenience only and do not interpret the scope or meaning of the claimed invention.

Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Also, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.

The term "OCM process" as used herein generally refers to a process that employs or substantially employs an Oxidative Coupling of Methane (OCM) reaction. The OCM reaction may include oxidation of methane to higher hydrocarbons (e.g., higher molecular weight hydrocarbons or higher chain hydrocarbons) and water, and involves an exothermic reaction. In an OCM reaction, methane may be partially oxidized to one or more C' s₂₊Compounds such as ethylene, propylene, butylene, and the like. In one example, the OCM reaction is 2CH₄+O₂+O₂H₄+2H₂And O. OCM reaction can produce C₂₊A compound is provided. The OCM reaction may be promoted by a catalyst such as a heterogeneous catalyst. Additional byproducts of the OCM reaction may include CO, CO₂、H₂And hydrocarbons such as ethane, propane, propylene, butane, butene, and the like.

The term "non-OCM process" as used herein generally refers to a process that does not employ or substantially does not employ an oxidative coupling reaction of methane. Examples of processes that may be non-OCM processes include non-OCM hydrocarbon processes such as those employed in hydrocarbon processing in refineries, natural gas liquids separation processes, steam cracking of ethane, steam cracking of naphtha, Fischer-Tropsch processes, and the like.

The term "ethylene-to-liquid" (ETL) as used herein generally refers to any device, system, process (or process) that can convert an olefin (e.g., ethylene) into a higher molecular weight hydrocarbon that can be in a liquid state.

The term "non-ETL process" as used herein generally refers to a process that does not employ, or does not substantially employ, the conversion of olefins to higher molecular weight hydrocarbons by oligomerization. Examples of processes that may be non-ETL processes include processes employed in hydrocarbon processing in refineries, natural gas liquids separation processes, steam cracking of ethane, steam cracking of naphtha, Fischer-Tropsch processes, and the like.

The term "C" as used herein₂₊"and" C₂₊Compound "generally refers to a compound containing two or more carbon atomsSubstances, e.g. C₂、C₃And the like. C₂₊Compounds include, but are not limited to, alkanes, alkenes, alkynes, and aromatics containing two or more carbon atoms. In some cases, C₂₊Compounds include aldehydes, ketones, esters and carboxylic acids. C₂₊Examples of compounds include ethane, ethylene, acetylene, propane, propylene, butane, butene, and the like.

The term "non-C" as used herein₂₊Impurities "generally means excluding C₂₊A substance of a compound. non-C that may be found in certain OCM reaction product streams₂₊Examples of impurities include nitrogen (N)₂) Oxygen (O)₂) Water (H)₂O), argon (Ar), hydrogen (H)₂) Carbon monoxide (CO) and carbon dioxide (CO)₂) And methane (CH)₄)。

The term "weight hourly space velocity" (WHSV), as used herein, generally refers to the mass flow rate of olefin in the feed divided by the mass of catalyst, which may have units of the inverse of time (e.g., hr)^-1)。

The term "slate" as used herein generally refers to a distribution, such as a product distribution.

The term "oligomerization" as used herein generally refers to a reaction that combines hydrocarbons to form longer chain hydrocarbons.

The term "greenfield" as used herein generally refers to an investment in manufacturing, office, industrial, or other physical business related structures or groups of structures in an area where no previous facilities exist or have existed.

The term "brown zone (brown field)" as used herein generally refers to an investment in a site previously used for commercial purposes such as a steel mill or oil refinery but subsequently expanded or upgraded to obtain revenue.

The term "catalyst" as used herein generally refers to a substance that alters the rate of a chemical reaction. The catalyst may increase the rate of a chemical reaction (i.e., a "positive catalyst") or decrease the rate of a reaction (i.e., a "negative catalyst"). The catalyst may be a heterogeneous catalyst. The catalyst may participate in the reaction in a cyclic manner such that the catalyst is cyclically regenerated. "catalyzed" generally means having the characteristics of a catalyst.

The term "nanowire" as used herein generally refers to a nanowire structure having at least one nanoscale diameter (e.g., about 1 to 100 nanometers) and an aspect ratio greater than 10: 1. The "aspect ratio" of a nanowire is the ratio of the actual length (L) of the nanowire to the diameter (D) of the nanowire. The aspect ratio is expressed as L: D.

The term "polycrystalline nanowire" as used herein generally refers to a nanowire having a plurality of crystalline domains. Polycrystalline nanowires generally have a different morphology (e.g., curved versus straight) than corresponding "single crystal" nanowires.

The term "effective length" of a nanowire as used herein generally refers to the shortest distance between two distal ends of a nanowire, as measured by Transmission Electron Microscopy (TEM) in bright field mode at 5 kilo electron volts (keV). "average effective length" refers to the average of the effective lengths of individual nanowires within a plurality of nanowires.

The term "actual length" of a nanowire as used herein generally refers to the distance between two distal ends of the nanowire when traced through the backbone of the nanowire, as measured by TEM in bright field mode at 5 keV. "average actual length" refers to an average of the actual lengths of individual nanowires within a plurality of nanowires.

The "diameter" of the nanowire can be measured on an axis perpendicular to the actual length of the nanowire (i.e., perpendicular to the nanowire backbone). The diameter of the nanowire will vary from narrow to wide, as measured at different points along the nanowire backbone. As used herein, the diameter of the nanowire is the most common (i.e., mode) diameter.

The "ratio of effective length to actual length" may be determined by dividing the effective length by the actual length. As described in more detail herein, nanowires having a "curved morphology" can have a ratio of effective length to actual length that is less than 1. A straight nanowire will have a ratio of the effective length to the actual length equal to 1.

The term "inorganic" as used herein generally refers to a substance comprising a metallic or semi-metallic element. In some instancesIn the embodiment, the inorganic substance refers to a substance containing a metal element. The inorganic compound may contain one or more metals in elemental form, or more typically consists of a metal ion (M)ⁿ⁺Wherein n is 1,2, 3, 4, 5, 6 or 7) and an anion (X)^m-And m is 1,2, 3 or 4), the anion balancing and neutralizing the positive charge of the metal ion by electrostatic interaction. Non-limiting examples of inorganic compounds include oxides, hydroxides, halides, nitrates, sulfates, carbonates, phosphates, acetates, oxalates of metallic elements, and combinations thereof. Other non-limiting examples of inorganic compounds include Li₂CO₃、Li₂PO₄、LiOH、Li₂O、LiCl、LiBr、LiI、Li₂C₂O₄、Li₂SO₄、Na₂CO₃、Na₂PO₄、NaOH、Na₂O、NaCl、NaBr、NaI、Na₂C₂O₄、Na₂SO₄、K₂CO₃、K₂PO₄、KOH、K₂O、KCl、KBr、KI、K₂C₂O₄、K₂SO₄、Cs₂CO₃、CsPO₄、CsOH、Cs₂O、CsCl、CsBr、CsI、CsC₂O₄、CsSO₄、Be(OH)₂、BeCO₃、BePO₄、BeO、BeCl₂、BeBr₂、BeI₂、BeC₂O₄、BeSO₄、Mg(OH)₂、MgCO₃、MgPO₄、MgO、MgCl₂、MgBr₂、MgI₂、MgC₂O₄、MgSO₄、Ca(OH)₂、CaO、CaCO₃、CaPO₄、CaCl₂、CaBr₂、CaI₂、Ca(OH)₂、CaC₂O₄、CaSO₄、Y₂O₃、Y₂(CO₃)₃、Y₂(PO₄)₃、Y(OH)₃、YCl₃、YBr₃、YI₃、Y₂(C₂O4)₃、Y₂(SO4)₃、Zr(OH)₄、Zr(CO₃)₂、Zr(PO₄)₂、ZrO(OH)₂、ZrO2、ZrCl₄、ZrBr₄、ZrI₄、Zr(C₂O₄)₂、Zr(SO₄)₂、Ti(OH)₄、TiO(OH)₂、Ti(CO₃)₂、Ti(PO₄)₂、TiO2、TiCl₄、TiBr₄、TiI₄、Ti(C₂O₄)₂、Ti(SO₄)₂、BaO、Ba(OH)₂、BaCO₃、BaPO₄、BaCl₂、BaBr₂、BaI₂、BaC₂O₄、BaSO₄、La(OH)₃、La₂(CO₃)₃、La₂(PO₄)₃、La₂O₃、LaCl₃、LaBr₃、LaI₃、La₂(C₂O₄)₃、La₂(SO₄)₃、Ce(OH)₄、Ce(CO₃)₂、Ce(PO₄)₂、CeO₂、Ce₂O₃、CeCl₄、CeBr₄、CeI₄、Ce(C₂O₄)₂、Ce(SO₄)₂、ThO₂、Th(CO₃)₂、Th(PO₄)₂、ThCl₄、ThBr₄、ThI₄、Th(OH)₄、Th(C₂O₄)₂、Th(SO₄)₂、Sr(OH)₂、SrCO₃、SrPO₄、SrO、SrCl₂、SrBr₂、SrI₂、SrC₂O₄、SrSO₄、Sm₂O₃、Sm₂(CO₃)₃、Sm₂(PO₄)₃、SmCl₃、SmBr₃、SmI₃、Sm(OH)₃、Sm₂(CO3)₃、Sm₂(C₂O₃)₃、Sm₂(SO₄)₃、LiCa₂Bi₃O₄Cl₆、Na₂WO₄、K/SrCoO₃、K/Na/SrCoO₃、Li/SrCoO₃、SrCoO₃Molybdenum oxide, molybdenum hydroxide, molybdenum carbonate, molybdenum phosphate, molybdenum chloride, molybdenum bromide, molybdenum iodide, molybdenum oxalate, molybdenum sulfate, manganese oxide, manganese chloride, manganese bromide, manganese iodide, manganese hydroxide, manganese oxalate, manganese sulfate, manganese tungstate, vanadium oxide, vanadium carbonate, vanadium phosphate, vanadium chloride, vanadium bromide, vanadium iodide, vanadium hydroxide, vanadium oxalate, vanadium sulfate, tungsten oxide, tungsten carbonate, tungsten phosphate, tungsten chloride, tungsten hydroxide, tungsten oxalate, tungsten sulfate, neodymium oxide, neodymium sulfate, neodymium oxide, neodymium carbonate, neodymium hydroxide, neodymium carbonate, neodymium phosphate, tungsten iodide, tungsten hydroxide, tungsten oxalate, tungsten sulfate, neodymium oxide, neodymium carbonate, neodymium phosphate, neodymium chloride, neodymium bromide, neodymium iodide, neodymium hydroxide, neodymium oxide, neodymium carbonate, neodymium phosphate, neodymium oxide, neodymium hydroxide, neodymium oxide, molybdenum oxide, Neodymium oxalate, neodymium sulfate, europium oxide, europium carbonate, europium phosphate, europium chloride, europium bromide, europium iodide, europium hydroxide, europium oxalate, europium sulfate, rhenium oxide, rhenium carbonate, rhenium phosphate, rhenium chloride, rhenium bromide, rhenium iodide, rhenium hydroxide, rhenium oxalate, rhenium sulfate, chromium oxide, chromium carbonate, chromium phosphate, chromium chloride, chromium bromide, chromium iodide, chromium hydroxide, chromium oxalate, chromium sulfate, potassium molybdenum oxide, and the like.

The term "salt" as used herein generally refers to a compound comprising a cation and an anion. Salts generally consist of a cation and a counter ion. Under appropriate conditions, the solution may also contain, for example, a template, a metal ion (M)ⁿ⁺) And an anion (X)^m-) Binding to template to induce M_mX_nNucleation and growth of nanowires on the template. Thus, an "anionic precursor" is a compound comprising an anion and a cationic counterion, which renders the anion (X) in solution^m-) Disassociates from the cationic counter ion. The metal salts andspecific examples of the anion precursor.

The term "oxide" as used herein generally refers to a metal or semiconductor compound that includes oxygen. Examples of oxides include, but are not limited to, oxides of metals (M)_xO_y) Oxyhalides of metals (M)_xO_yX_z) Metal hydroxyhalides (M)_xOH_yX_z) Metal oxynitrate (M)_xO_y(NO₃)_z) Metal phosphate (M)_x(PO₄)_y) Metal oxycarbonate (M)_xO_y(CO₃)_z) Metal carbonate (M)_x(CO₃)_z) Metal sulfate (M)_x(SO₄)_z) Metal oxysulfate (M)_xO_y(SO₄)_z) Metal phosphate (M)_x(PO₄)_z) Metal acetate (M)_x(CH₃CO₂)_z) Oxalate of metal (M)_x(C₂O₄)_z) Metal oxyhydroxide (M)_xO_y(OH)_z) Metal hydroxide (M)_x(OH)_z) Hydrated metal oxide (M)_xO_y)^.(H₂O)_zEtc., wherein X, at each occurrence, is independently fluorine, chlorine, bromine, or iodine, and X, y, and z are independently a number from 1 to 100.

The term "mixed oxide" or "mixed metal oxide" as used herein generally refers to a compound comprising two or more metals and oxygen (i.e., M1)_xM2_yO_zWherein M1 and M2 are the same or different metal elements, O is oxygen, and x, y, and z are numbers from 1 to 100). The mixed oxide may contain metallic elements in various oxidation states and may contain more than one type of metallic element. For example, mixed oxides of manganese and magnesium include oxidized forms of magnesium and manganese. Each individual manganese and magnesium atom may or may not have the same oxidation state. Mixed oxides containing 2, 3, 4, 5, 6 or more metal elements may be represented in a similar manner. Mixed oxides also include oxyhydroxides (e.g., M)_xO_yOH_zWherein M is a metal element, O is oxygen, x, y and z are numbers of 1 to 100, and OH is a hydroxyl group). The mixed oxide may be represented herein as M1-M2, wherein M1 and M2 are each independently a metal element.

The term "crystalline domain" as used herein generally refers to a continuous region over which a substance is crystalline.

The term "single-crystal" or "single-crystal" as used herein generally refers to a substance (e.g., a nanowire) having a single crystalline domain.

The term "dopant" or "dopant" as used herein generally refers to a substance (e.g., an impurity) added to or incorporated into a catalyst to alter (e.g., optimize) catalytic performance (e.g., increase or decrease catalytic activity). Doped catalysts may increase or decrease the selectivity, conversion, and/or yield of a reaction catalyzed by the catalyst as compared to undoped catalysts.

The term "OCM catalyst" as used herein generally refers to a catalyst capable of catalyzing an OCM reaction.

"group 1" elements include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and Francium (FR).

The "group 2" elements include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).

The "group 3" element includes scandium (Sc) and yttrium (Y).

The "group 4" elements include titanium (Ti), zirconium (Zr), hafnium (Hf), and (Rf).

The "group 5" elements include vanadium (V), niobium (Nb), tantalum (Ta) and

(Db)。

the "group 6" elements include chromium (Cr), molybdenum (Mo), tungsten (W) and(seaborgium)(Sg)。

"group 7" elementElements include manganese (Mn), Technetium (TC), rhenium (Re) and

(bohrium)(Bh)。

the "group 8" elements include iron (Fe), ruthenium (Ru), osmium (Os) and

(Hs)。

the "group 9" element includes cobalt (Co), rhodium (Rh), iridium (Ir) and(Mt)。

the "group 10" elements include nickel (Ni), palladium (Pd), platinum (Pt) and darmistadium (Ds).

The "group 11" elements include copper (Cu), silver (Ag), gold (Au), and sunglasses (Rg).

The "group 12" elements include zinc (Zn), cadmium (Cd), mercury (Hg), and copernicium (Cn).

"lanthanides" include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

"actinides" include actinium (Ac), thorium (Th), protactinium (Pa), uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium (Cm), berkelium (Bk), californium (Cf), einsteinium (Es), fermium (Fm), mendelevium (Md), nobelium (No), and lawrencium (Lr).

"rare earth" elements include group 3, lanthanides, and actinides.

The "metallic element" or "metal" is any element selected from groups 1 to 12, lanthanides, actinides, aluminum (Al), gallium (Ga), indium (In), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi) other than hydrogen. The metal element includes a metal element in its elemental form and a metal element in an oxidized or reduced state, for example, when the metal element is combined with other elements in the form of a compound containing the metal element. For example, the metal element may be in the form of a hydrate, a salt, an oxide, various polymorphs, and the like thereof.

The term "semimetal element" As used herein generally refers to an element selected from boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), antimony (Te), and polonium (Po).

The term "non-metallic element" as used herein generally refers to an element selected from the group consisting of carbon (C), nitrogen (N), oxygen (O), fluorine (F), phosphorus (P), sulfur (S), chlorine (Cl), selenium (Se), bromine (Br), iodine (I), and astatine (At).

The term "higher hydrocarbons" as used herein generally refers to higher molecular weight and/or longer chain hydrocarbons. The higher hydrocarbons may have a higher molecular weight and/or carbon content that is higher or greater relative to the starting material in a given process (e.g., OCM or ETL). The higher hydrocarbons may be higher molecular weight and/or longer chain hydrocarbon products produced during OCM or ETL. For example, in an OCM process, ethylene is a higher hydrocarbon product relative to methane. As another example, in an ETL process, C₃₊The hydrocarbon is a higher hydrocarbon relative to ethylene. As another example, in an ETL process, C₅₊The hydrocarbon is a higher hydrocarbon relative to ethylene. In some cases, the higher hydrocarbons are higher molecular weight hydrocarbons.

The present disclosure relates generally to processes and systems for use in the production of hydrocarbon compositions. These processes and systems may be characterized in that they obtain the hydrocarbon composition from ethylene derived from methane, e.g., originally present in natural gas. The disclosed processes and systems are generally further characterized by integrating a process for converting methane to ethylene with one or more processes or systems for converting ethylene to one or more higher hydrocarbon products, which in some embodiments include a liquid hydrocarbon composition. By converting the methane present in natural gas into a liquid substance, one of the key obstacles faced in the exploitation of the vast reserves of natural gas in the world, namely transport, can be eliminated. In particular, the exploitation of natural gas resources traditionally requires a large and expensive pipeline infrastructure for transporting the gas from a source to its final destination. By converting the gas into a liquid substance, more conventional transportation systems such as trucks, rail cars, tankers, etc. become available.

In some embodiments, the processes and systems provided herein include multiple (i.e., two or more) ethylene conversion process pathways integrated into the overall process or system to produce multiple different higher hydrocarbon compositions from a single source of raw methane. Further advantages are obtained by: integration of these multiple conversion processes or systems in a convertible or alternative architecture is provided whereby a portion or all of the ethylene-containing product of the methane to ethylene conversion system is selectively directed to one or more different process pathways, such as two, three, four, five or more different process pathways, to produce as many different products as possible. This overall process flow is schematically illustrated in fig. 1. As shown, a methane oxidative coupling ("OCM") reactor system 100 is schematically illustrated, which includes an OCM reactor train 102 coupled to an OCM product gas separation train (train)104, such as a cryogenic separation system. An ethylene-rich effluent from the separation train 104 is shown (as indicated by arrow 106) routed to a plurality of different ethylene conversion reactor systems and processes 110, e.g., ethylene conversion systems 110a-110e, each of which produces a different hydrocarbon product, e.g., products 120a-120 e.

As noted, in some embodiments, the fluid connection between the OCM reactor system 100 and each of the different ethylene conversion systems 110a-110e may be a controllable and selective connection, e.g., the output of the OCM reactor system may be distributed to the valve and control systems of one, two, three, four, five or more different ethylene conversion systems. The valves and piping used to accomplish this can take a variety of different forms, including valves at each pipe junction, multi-way valves, multi-valve manifold assemblies, and the like.

Ethylene-to-liquids (ETL) system

The ethylene-to-liquids (ETL) systems and methods of the present disclosure can be used to form a variety of products, including hydrocarbon products. The products and product distribution can be tailored to suit a given application, such as products used as fuels (e.g., jet fuel or automotive fuels such as diesel or gasoline).

The present disclosure provides a reactor for converting olefins to higher molecular weight hydrocarbons that may be liquid. Such a reactor may be an ETL reactor, which may be used to convert ethylene and/or other olefins to higher molecular weight hydrocarbons.

The ETL system (or subsystem) may include one or more reactors. The ETL system can include at least 1,2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 ETL reactors, which can be parallel, series, or a combination of parallel and series configurations.

The ETL reactor can be in the form of a tube, a packed bed, a moving bed, or a fluidized bed. The ETL reactor may comprise a single tube or multiple tubes, such as tubes in a shell. The multi-tubular reactor can be used for highly exothermic conversions, such as the conversion of ethylene to other hydrocarbons. Such a design may allow for efficient management of heat flux and control of reactor and catalyst bed temperatures.

The ETL reactor may be an isothermal or adiabatic reactor. The ETL reactor can have one or more of the following: 1) a plurality of cooling zones and arrangements within the reactor shell, wherein the temperature within each cooling zone can be independently set and controlled; 2) a plurality of residence times of the reactants as they pass through the tubular reactor from the inlet to the outlet of each tube; and 3) a multiple pass design, wherein the reactants can be passed several times within the reactor shell from the inlet to the outlet of the reactor.

The multi-tubular reactor of the present disclosure can be used to convert ethylene to liquid hydrocarbons in a variety of ways. In some cases, the disclosed multi-tubular ETL reactor may result in a smaller reactor and gas compressor compared to an adiabatic ETL design. The ETL hydrocarbon reaction is exothermic, so the reaction heat control (management) may be important for reaction control and improved product selectivity. In adiabatic ETL reactor designs, there is an upper limit on the concentration of ethylene flowing through the reactor due to the exotherm and subsequent temperature rise inside the reactor. To control the heat of reaction, adiabatic reactors can use large amounts of diluent gas to moderate the temperature rise in the reactor bed. In some cases, multiple reactors with inter-reactor cooling and limited inter-reactor conversion (i.e., about 20%, about 30%, about 40%, about 50%, about 60%, or about 70% conversion in one reactor), cooling the product effluent, and converting the remaining feedstock in one or more subsequent reactors may be used to control the heat of reaction. The use of dilution gas can result in a larger catalyst bed, reactor, and gas compressor. The multi-tubular reactor described herein can allow for significantly greater ethylene concentrations while controlling the reactor bed temperature, since heat can be removed at the reactor walls. Thus, for a target production rate, smaller catalyst beds, reactors, and gas compressors may be used.

In addition to smaller ETL reactors, the disclosed multi-tubular ETL reactor may also result in smaller downstream liquid-gas product separation equipment because less dilution gas is needed to cool the reactor.

The multi-tubular ETL reactor of the present disclosure may result in more favorable process conditions for higher carbon number hydrocarbon liquids than an adiabatic ETL design. The disclosed multi-tubular design can allow for more highly concentrated ethylene feed to the reactor while maintaining good reactor temperature control relative to adiabatic reactors that can dilute the ethylene feed to control the reaction temperature. Since reactant concentration is an important process parameter for producing higher hydrocarbon oligomers, higher ethylene concentrations in the reactor can promote the formation of higher hydrocarbon liquids such as jet and/or diesel fuel. In some cases, olefin liquids of a particular carbon number range and type may also be recycled to the reactor bed to further generate higher carbon number liquids (e.g., jet fuel/diesel).

The multi-tubular reactor can have multiple temperature zones and provide multiple residence times. This may allow a wide range of process flexibility to target a particular product slate. As an example, the reactor may have multiple temperature zones and/or residence times. One use of this design may be in the production of jet and/or diesel fuel from ethylene. Oligomerization of ethylene may require relatively high reaction temperatures. The temperatures required to react ethylene, start the oligomerization process, may be incompatible with the jet or diesel products due to the rapid cracking and/or disproportionation of these jet/diesel products at elevated temperatures. Multiple reactor temperature zones may allow a separate and higher temperature zone to initiate ethylene oligomerization while having another lower temperature zone to promote further oligomerization to jet/diesel fuel while preventing cracking and disproportionation side reactions.

The use of multiple temperature zones may require different residence times within the reactor bed. In the jet fuel/diesel example, the residence time for the ethylene reaction may be different from the residence time of the lower temperature finishing (refining) step that forms the jet fuel/diesel. To maximize the yield of jet fuel/diesel liquid, a higher ethylene oligomerization reaction bed temperature but a shorter residence time may be required than in the jet fuel/diesel production step, while the jet fuel/diesel production step may require a lower temperature but a longer residence time. In an adiabatic ETL reactor, a multiple temperature process can occur over multiple reactor beds with different temperatures associated with each reactor. The multiple temperature zone process disclosed herein can avoid the need for multiple reactors, as in the case of adiabatic ETL, because multiple temperature zones can be achieved in a single reactor and thus reduce capital expenditure for reactor deployment.

Catalyst aging can be an important design constraint in ETL reaction engineering. The ETL catalyst can deactivate over time until the catalyst bed is no longer able to maintain high ethylene conversion. Slower catalyst deactivation rates may be required because more ethylene may be converted per catalyst bed before the catalyst bed may need to be taken off-line and regenerated. Typically, catalysts are deactivated by "coke," a deposit of carbonaceous material, which results in a reduction in catalyst performance when coke accumulates. The rate of "coke" accumulation can be attributed to a number of different parameters. In ETL adiabatic reactors, the formation of catalyst bed "hot spots" can play an important role in causing coking of the catalyst. The "hot spots" favor the formation of aromatics, which are coke-forming precursors. "hot spots" are the result of temperature non-uniformities within the catalyst bed caused by inadequate heat transfer. Localized "hot spots" increase the rate of catalyst coking/deactivation. The disclosed multi-tube design may reduce localized "hot spots" due to the better heat transfer characteristics of the multi-tube design relative to an adiabatic design. It is expected that a reduction in catalyst "hot spots" can slow catalyst deactivation.

The product makeup of ETL is a result of many factors. One important factor is the catalyst bed temperature. For example, for some catalysts, higher catalyst bed temperatures may shift product slate away to aromatic products. In large adiabatic reactors, controlling the formation of "hot spots" is challenging, and inhomogeneities in the catalyst bed temperature distribution lead to a wider product distribution. The proposed multi-tubular design can significantly reduce catalyst bed temperature inhomogeneity/"hot spots" due to better heat transfer characteristics relative to adiabatic designs. Thus, a narrower product distribution can be more easily achieved than with adiabatic reactor designs. Although the multi-tubular design provides excellent catalyst bed temperature uniformity, catalyst bed temperature uniformity can be further enhanced by injecting a "trim gas (trimgas)" and/or a "trim liquid".

The heat capacity of the "trim gas" can be used to fine tune the catalyst bed to the target temperature. The trim gas composition may be an inert/high heat capacity gas, such as: ethane, propane, butane and other high heat capacity hydrocarbons.

In some cases, liquid hydrocarbons may be injected into the ETL reactor to further condition and cool the reactor bed using the heat of vaporization in order to reach the desired temperature. In addition, both of them (gas and liquid) can also be used as "conditioning" agents in this design of the ETL.

It may be desirable to regenerate the ETL catalyst from a low ethylene conversion (e.g., 20% or less) state to a high ethylene conversion, e.g., greater than 20%, 30%, 40%, 50%, 60%, or 70%. Regeneration may occur by heating the catalyst bed to an appropriate temperature while introducing a portion of the dilution air. The oxygen in the air can be used to remove the coke by combustion and thus restore the activity of the catalyst. Too much oxygen can cause uncontrolled combustion, a highly exothermic process, and the resulting rise in catalyst bed temperature can cause irreversible catalyst damage. Thus, the amount of air allowed during regeneration of the adiabatic reactor is limited and monitored.

The catalyst regeneration time of an adiabatic reactor may be determined primarily by the amount of oxygen allowable in the reactor. The better heat transfer characteristics of the disclosed multitubular reactor may allow for greater oxygen concentrations during catalyst regeneration to accelerate catalyst regeneration while ensuring that the catalyst bed temperature does not reach the point of irreversible catalyst deactivation.

The present disclosure also provides a reactor system for performing an ethylene conversion process. Multiple ethylene conversion processes may involve exothermic catalytic reactions, wherein the processes generate large amounts of heat. Also, for many of these catalytic systems, the regeneration process of the catalyst material involves an exothermic reaction as well. Likewise, reactor systems for use in these processes can generally be configured to efficiently manage the excess heat energy produced by the reaction, so as to control the reactor bed temperature to most effectively control the reaction, prevent deleterious reactions, and prevent catalyst or reactor damage or destruction.

Tubular reactor configurations that can exhibit high wall surface area per unit catalyst bed volume can be useful for reactions where thermal control is desired or otherwise required, as they can allow greater heat transfer out of the reactor. A reactor system comprising a plurality of parallel tube reactors may be used in performing the ethylene conversion process described herein. In particular, an array of parallel tubular reactors each containing a catalyst suitable for one or more ethylene conversion reaction processes may be spaced apart therebetween to allow for a cooling medium to be present therebetween. Such a cooling medium may include any cooling medium suitable for a given process. For example, the cooling medium may be air, water or other aqueous coolant formulation, steam, oil (upstream of the reaction feed or for very high temperature reactor systems), molten salt coolant.

In some cases, a reactor system is provided that includes a plurality of tubular reactors divided into one, two, three, four, or more distinct discrete cooling zones, where each zone is isolated to contain its own, separately controlled cooling medium. The temperature of each of the different cooling zones may be independently regulated by its respective cooling medium and associated temperature control system, such as a thermally coupled heat exchanger or the like. Such differential temperature control in different reactors may be used to differentially control different catalytic reactions or reactions with catalysts of different ages. As such, it allows real-time control of the reaction progress in each reactor in order to maintain a more uniform temperature distribution throughout the reactors and thus synchronize catalyst life, regeneration cycles, and regeneration cycles.

A differentially cooled tubular reactor system is schematically illustrated in fig. 2. As shown, the overall reactor system 200 includes a plurality of discrete tubular reactors 202, 204, 206, and 208 contained within a larger reactor shell 210. Within each tubular reactor a catalyst bed is positioned to carry out a given catalytic reaction. The catalyst bed in each tubular reactor may be the same, or it may be different from the catalyst in the other tubular reactors, e.g. optimized for catalyzing different reactions or for catalyzing the same reaction under different conditions. As shown, the plurality of tubular reactors 202, 206, 208, and 210 share a common manifold 212 to deliver reactants to the reactors. However, each individual tubular reactor or subgroup of tubular reactors may alternatively comprise a single reactant delivery conduit or manifold to deliver reactants to that tubular reactor or subgroup of reactors, while separate delivery conduits or manifolds are provided to deliver the same or different reactants to other tubular reactors or subgroups of tubular reactors.

Alternatively or in addition, the reactor system used in conjunction with the olefin (e.g., ethylene) conversion process described herein can provide variability in the residence time of the reactants within the catalytic portion of the reactor. The residence time within the reactor can be varied by varying any of a number of different application parameters (e.g., increasing or decreasing flow rate, pressure, catalyst bed length, etc.). However, by varying the volume of the different reactor tubes or reactor tube sections ("catalyst bed length") within a single reactor unit, a single reactor system with variable residence time, despite sharing a single reactor inlet, may be provided. Due to the differences in volume between reactor tubes or reactor tube sections into which reactants are introduced at a given flow rate, the residence time of those reactants within those reactor tubes or reactor tube sections of those different volumes may be different.

The change in reactor volume can be achieved by a variety of methods. For example, the different volumes may be provided by including two or more different reactor tubes that introduce reactants at a given flow rate, wherein the two or more reactor tubes each have a different volume, for example by providing different diameters. It will be appreciated that the residence time of the gas introduced at the same flow rate into two or more different reactors having different volumes may be different. In particular, the residence time may be longer in larger volume reactors and shorter in smaller volume reactors. The larger volumes in the two different reactors can be provided by providing each reactor with a different diameter. Likewise, the length of the reactor catalyst bed can be varied to vary the volume of the catalytic portion.

Alternatively or in addition, the volume of the individual reactor tubes may be varied by varying their diameter along the length of the reactor to effectively vary the volume of different sections of the reactor. In addition, in wider reactor sections, the residence time of the gases introduced into the reactor tube may be longer in wider reactor sections than in narrower reactor sections.

Different volumes may also be provided by routing different inlet reactant streams to different numbers of similarly sized reactor conduits or tubes. In particular, reactants, such as gases, may be introduced into a single reactor tube at a given flow rate to produce a particular residence time within the reactor. In contrast, reactants introduced at the same flow rate into two or more parallel reactor tubes may have much longer residence times within those reactors.

The above-described method for varying residence time within a reactor catalyst bed is described with reference to fig. 3-4. Fig. 3 schematically illustrates a reactor system 300 in which two or more tubular reactors 302 and 304 are disposed, each having its own catalyst bed 306 and 308, respectively, disposed therein. The two reactors are connected to the same inlet manifold so that the flow rate of reactants introduced into each of the reactors 302 and 304 is the same. Because reactor 304 has a larger volume (shown as a wider diameter), reactants may remain within catalyst bed 308 for a longer period of time. In particular, as shown, reactor 304 has a larger diameter, resulting in a slower linear velocity of the reactant through catalyst bed 308 than the linear velocity of the reactant through catalyst bed 306. As described above, the residence time within the catalyst bed of reactor 304 can be similarly increased by providing a longer reactor. However, such longer reactor beds may need to have a similar back pressure (back pressure) as the shorter reactor to ensure that the reactants are introduced at the same flow rate as the shorter reactor.

Figure 4 schematically illustrates an alternative method for varying the reactor volume in order to vary the residence time of the reactants in the catalyst bed. As shown, individual reactor units, such as reactor tubes 400, may be configured to provide different residence times within different portions of the reactor tubes by varying the diameter of the reactor between reactor sections 404, 406, and 408. In particular, by providing larger diameters for the reactor tubes in sections 404 and 406, respectively, the residence time of the reactants through these sections can be increased as the linear velocity of the reactants through these sections decreases.

The residence time of the reactants within the reactor system can be controlled by varying the diameter of the ETL reactor along the path of the fluid flow. In some cases, a reactor system may include a plurality of different reactor tubes, wherein each reactor tube includes a catalyst bed disposed therein. Different residence times may be employed in catalyzing different catalytic reactions or catalyzing the same reaction under different conditions. In particular, it may be desirable to vary the residence time of a given set of reactants over a single catalyst system in order to more fully catalyze a reaction, catalyze a different or additional reaction, and the like. Likewise, different reactors within the system may be provided with different catalyst systems that may benefit from different residence times of the reactants within the catalyst beds to catalyze reactions that are the same or different from one another.

Alternatively or in addition, the residence time of the reactants within the catalyst bed may be configured to optimize thermal control within the overall reactor system. In particular, residence times can be longer at regions in the reactor system where removal of excess heat is less critical or more easily controlled (e.g., because the overall reaction has not yet begun to produce excess heat). Conversely, in other regions of the reactor, for example, where removal of excess heat is difficult due to a rapidly exothermic reaction, the reactor section may be maintained for only a short period of time with the reactants by providing a narrower reactor diameter. It will be appreciated that thermal management is made easier by the presence of the reactants and the shorter period of time during which the reaction takes place to generate heat. Likewise, the reduced volume of the tubular reactor within the reactor housing also provides a greater volume of cooling medium for more efficient removal of thermal energy.

The systems and methods of the present disclosure may employ a fixed bed reactor. The fixed bed reactor may be an adiabatic reactor. A fixed bed adiabatic ETL reactor can provide a simple reactor design. An active external cooling mechanism of the reactor may not be necessary. To control reactor temperature, a total dilution (profile dilution) of the reactive olefins or other feedstocks (e.g., ethylene, propylene, butenes, pentenes, etc.) may be necessary. The diluent gas may be any material that is non-reactive or non-toxic to the ETL catalyst but preferably has a high heat capacity to slow the temperature rise within the catalyst bed. Examples of the diluent gas include nitrogen (N)₂) Argon, methane, ethane, propane and helium. The reactive portion of the feedstock may be diluted directly or indirectly in the reactor by recycling the process gas to dilute the feedstock to an acceptable concentration. The temperature profile can also be controlled by an internal reactor heat exchanger that can actively control the heat within the catalyst bed. Catalyst bed temperature control can also be achieved by limiting feedstock conversion within the catalyst bed. In this case, in order to achieve complete conversion of the raw materials, the fixation is carried outThe bed adiabatic reactor is placed in series with a heat exchanger between the reactors to slow the temperature rise of the reactor followed by the reactor. Partial conversion occurs in each reactor with interstage cooling to achieve the desired conversion and selectivity of the ETL process.

Because the ETL catalyst can deactivate over time through coke deposition, the fixed bed reactor can be taken off-line and regenerated through, for example, oxidative or non-oxidative processes, as described elsewhere herein. Once regenerated to full activity, the ETL reactor can be returned on-line to process more feedstock.

The systems and methods of the present disclosure may use an ETL continuous catalyst regeneration reactor. Continuous Catalyst Regeneration Reactors (CCRR) may be attractive for processes where the catalyst deactivates over time and requires a trip for regeneration. By regenerating the catalyst in a continuous manner, the process will require less catalyst, fewer reactors, and less operations to regenerate the catalyst. There are two types of CCRR reactor deployments: (1) a moving bed reactor and (2) a fluidized bed reactor. In the moving bed CCRR design, a bed of particulate catalyst is moved along the length of the reactor and removed and regenerated in a separate vessel. Once the catalyst is regenerated, the catalyst particles are placed back into the ETL conversion reactor to process more feedstock. The on-line/regeneration process may be continuous and a constant flow of active catalyst may be maintained in the ETL reactor. In a fluidized bed ETL reactor, ETL catalyst particles are "fluidized" by a combination of ETL process gas velocity and catalyst particle weight. During fluidization of the bed, the bed expands, swirls and agitates during operation of the reactor. Advantages of ETL fluidized bed reactors are excellent mixing of the process gases within the reactor, uniform temperature within the reactor, and the ability to continuously regenerate coked ETL catalyst.

Other reactor designs, such as Moving Bed (MBR), fluidized bed, and slurry bed reactors, may also be employed. An exemplary fluidized bed reactor 410 is shown in fig. 4B. The gas inlet stream 411 enters at the bottom of the reactor and the gas outlet stream 412 exits from the top of the reactor. Solid particles (e.g., catalyst) enter 413 on one side and exit 414 on the other side. Within the fluidized bed, the gas bubbles 415 may encounter the solid particles 416. The reactor may comprise a distributor 417 for distributing the gas flow. Fig. 4C shows a further schematic of an exemplary reactor configuration of a co-current moving bed reactor (420), a counter-current moving bed reactor (430), a fluidized bed reactor (440), and a slurry bed reactor (450). Moving bed and fluidized bed reactors have separate gas inlet (421, 431, 434), gas outlet (422, 432, 442), catalyst inlet (423, 433, 443) and catalyst outlet (424, 434, 444) configurations. The slurry bed reactor has a combined gas/catalyst inlet 451 and gas/catalyst outlet 452.

The ETL catalyst can be regenerated with methane or natural gas. The regeneration stream may contain oxygen (O)₂) Or other oxidizing agents. The concentration of oxygen in the regeneration stream may be below the Limiting Oxygen Concentration (LOC), such that the mixture is not flammable. In some embodiments, O in the regeneration stream₂Is less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%. In some cases, O in the regeneration stream₂Is 0% to about 3%. One advantage of regenerating the ETL catalyst with methane or natural gas is that after flowing through the ETL catalyst for regeneration, the stream can be used in the OCM and/or ETL process (e.g., the stream can be combusted to provide energy). Regenerating an ETL catalyst using methane and/or natural gas may not introduce any new components into the process that effect catalyst regeneration, which may result in efficient use of materials. In some cases, the use of methane and/or natural gas makes the economics of the process insensitive or less dependent on the time period that the ETL catalyst can be operated between regeneration cycles.

Catalyst for converting olefins to liquids

The present invention also provides catalysts and catalyst compositions for use in ethylene conversion processes according to the processes described herein. In some embodiments, the present disclosure provides modified zeolite catalysts and catalyst compositions for conducting a plurality of desired ethylene conversion reaction processes. In some cases, impregnated or ion-exchanged zeolite catalysts are provided that can be used to convert ethylene to higher hydrocarbons, such as gasoline or gasoline blendstocks, diesel and/or jet fuel, and a variety of different aromatics. For example, when an ethylene conversion process is used to convert the OCM product gas to gasoline or gasoline feedstock products or aromatics mixtures, a modified ZSM catalyst, such as a Ga, Zn, Al or mixtures thereof modified ZSM-5 catalyst may be employed. In some cases, Ga, Zn and/or Al modified ZSM-5 catalysts are preferred for the conversion of ethylene to gasoline or gasoline feedstock. Modified catalyst substrates other than ZSM-5 may also be used with the present invention, including, for example, zeolite Y, ferrierite (ferrierite), mordenite (mordenite), and additional catalyst substrates described herein.

In some cases, a ZSM catalyst such as ZSM-5 is modified with Co, Fe, Ce or mixtures thereof and used in an ethylene conversion process using a dilute ethylene stream comprising carbon monoxide and hydrogen components (see, e.g., Choudhary et al, Microporous and MeOporous Materials 2001, 253-. In particular, these catalysts may be capable of reacting ethylene with H₂And CO components are CO-oligomerized to higher hydrocarbons and can be used as a blend of gasoline, diesel or jet fuels or blendstocks thereof. In such embodiments, dilute or non-dilute ethylene concentrations and CO/H are included₂The mixed stream of gas may be passed over the catalyst under conditions that cause co-oligomerization of the two sets of feed components. The use of ZSM catalysts to convert synthesis gas to higher hydrocarbons may be described, for example, in Li et al, Energy and Fuels2008,22: 1897-.

The present disclosure provides a variety of catalysts for converting olefins to liquids. Such catalysts may include active materials on a solid support. The active material may be configured to catalyze the ETL process to convert olefins to higher molecular weight hydrocarbons.

The ETL reactor of the present disclosure can contain multiple types of ETL catalysts. In some cases, such catalysts are zeolite and/or amorphous catalysts. Examples of zeolite catalysts include ZSM-5, zeolite Y, zeolite beta and mordenite. Examples of amorphous catalysts include solid phosphoric acid and amorphous aluminum silicate. Such catalysts may be doped, for example with metal and/or semiconductor dopants. Examples of dopants include, but are not limited to, Ni, Pd, Pt, Zn, B, Al, Ga, In, Be, Mg, Ca, and Sr. Such dopants may be located at the surface of the catalyst, in the pore structure of the catalyst, and/or in the bulk region (bulk region) of such catalysts.

The catalyst may be doped with a substance selected to achieve a given or predetermined product distribution. For example, Mg or Ca doped catalysts can provide selectivity to olefins for gasoline. As another example, a Zn or Ga doped catalyst (e.g., Zn doped ZSM-5 or Ga doped ZSM-5) may provide selectivity to aromatics. As another example, a Ni-doped catalyst (e.g., Ni-doped zeolite Y) can provide selectivity to diesel or jet fuel.

The catalyst may be located on a solid support. The solid support may be formed of an insulating material such as TiOx or AlOx, or a ceramic material, where 'x' is a number greater than zero.

The catalysts of the present disclosure may have different cycle lives (e.g., average time period between catalyst regeneration cycles). In some cases, the ETL catalyst may have a lifetime of at least about 50 hours, 100 hours, 110 hours, 120 hours, 130 hours, 140 hours, 150 hours, 160 hours, 170 hours, 180 hours, 190 hours, 200 hours, 210 hours, 220 hours, 230 hours, 240 hours, 250 hours, 300 hours, 350 hours, or 400 hours. With such cycle life, olefin conversion efficiencies of less than about 90%, 85%, 80%, 75%, 70%, 65%, or 60% may be observed.

As described elsewhere herein, the catalysts of the present disclosure can be regenerated by a variety of regeneration procedures. Such a procedure may extend the overall life of the catalyst (e.g., the length of time before the catalyst is treated). Examples of catalyst regeneration Processes are provided in Lubo Zhou, "BP-UOP cycle Processes," Handbook of Petroleum Refining Processes, The McGraw-Hill companies (2004), pages 2.29-2.38, which are incorporated herein by reference in their entirety.

In some embodiments, the ETL catalyst may consist of a substrate (first active component) and a dopant (second active component). Dopants may be introduced into the substrate by suitable methods and procedures, such as vapor or liquid phase deposition. The dopant may be selected from a variety of elements, including metallic, non-metallic, or amphoteric elements in elemental, ionic, or compound form. Several representative doping elements are Ga, Zn, Al, In, Ni, Mg, B and Ag. Such dopants may be provided by a dopant source. For example, the silver may be provided by AgCl or sputtering. The choice of dopant species may depend on the target product properties, such as product distribution. For example, Ga favors the production of aromatics-rich liquids, while Mg favors the production of aromatics-lean liquids.

The substrate may be selected from crystalline zeolitic materials such as ZSM-5, ZSM-11, ZSM-22, zeolite Y, zeolite beta, mordenite, zeolite L, ferrierite, MCM-41, SAPO-34, SAPO-11, TS-1, SBA 15, or amorphous porous materials such as Amorphous Silicoaluminophosphates (ASA) and solid phosphoric acid catalysts. The cation of these materials may be NH₄ ⁺、H⁺Or otherwise. The surface area of these materials may be in the range of 1m²G to 10000m²/g、10m²G to 5000m²In g or 100m²G to 1000m²In the range of/g. The substrate may be used directly for synthesis or subjected to some chemical treatment, such as desilication (de-Si) or dealumination (de-Al), to further modify the functionality of these materials.

The substrate may be used directly for synthesis or subjected to chemical treatments such as desilication (de-Si) or dealumination (de-Al) to obtain derivatives of the substrate. Such treatment may improve catalyst life performance by forming larger pore volumes, such as pores having diameters greater than or equal to about 1 nanometer (nm), 2nm, 3nm, 4, nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, or 100 nm. In some cases, mesopores having a diameter of about 1nm to 100nm or 2nm to 50nm are formed. In some examples, silica or alumina or a combination of silica and alumina may be etched from the substrate to form larger pore structures in the base catalyst that may enhance diffusion of reactants and products into the catalyst material. In addition to porosity, pore diameter and volume can also be determined by adsorption or desorption isotherms (e.g., Brunauer-Emmett-teller (bet) isotherms), such as the method using Barrett-Joyner-halenda (bjh). See Barrett E.P. et al, "the determination of pore volumes and area distributions in pore substations.I. Compounds from Nitrogen isomers," J.Am.chem.Soc.1951.V.73. P.373-380. Such methods can be used to calculate material porosity and mesopore volume, in some cases 3-7 times their volume of the original material. In general, any change in catalyst structure, composition and morphology can be measured by techniques such as BET, SEM and TEM.

There are a variety of methods for catalyst doping. In one example, the doping component may be added to the substrates and their derivatives by impregnation, in some cases using Incipient Wetness Impregnation (IWI), ion exchange or framework displacement in the zeolite synthesis operation. In some cases, IWI may comprise i) mixing a salt solution of the doping component with the substrate, wherein the amount of salt is calculated based on the doping level, ii) drying the mixture in an oven, and iii) calcining the product at a temperature and for a time period, typically 550-650 ℃, for 6-10 hr. Ion exchange catalyst synthesis may comprise i) mixing a salt solution with the substrate, the salt solution may contain at least 1.5, 2, 3, 4, 5, 6,7, 8, 9 or 10 fold excess of the doping component, ii) heating the mixture at a temperature of, for example, about 50 ℃ to 100 ℃, 60 ℃ to 90 ℃, or 70 ℃ to 80 ℃ for a period of at least about 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours to perform a first ion exchange, iii) separating a first ion exchange mother liquor, iv) adding a fresh salt solution and repeating ii) and iii) to perform a second ion exchange, v) washing the wet solids with deionized water to remove or reduce the concentration of soluble components, vi) drying the crude product, such as air drying or drying in an oven, and vii) calcining the crude product at a temperature of about 450 ℃ to 800 ℃, 500 ℃ to 750 ℃, or 550 ℃ to 650 ℃ for a period of time of about 1 hour to 24 hours, 4 hours to 12 hours, or 6 hours to 10 hours.

In some cases, prior to use, a powder catalyst prepared according to the methods of the present disclosure may need to be shaped prior to preparation in a predetermined shape (or form factor). In some examples, the shape may be selected from cylindrical extrudates, rings, trilobes (trilobes), and granules. The size of the shape may depend on the reactor size. For example, for a 1 "-2" Internal Diameter (ID) reactor, 1.7mm to 3.0mm extrudates or other shapes of the same size may be used. Larger shapes can be used on different industrial scales (e.g. 5mm shapes). The ETL reactor Inner Diameter (ID) can be any diameter, including the range of 2 inches to 10 feet, 1 foot to 6 feet, and 3 feet to 4 feet. In commercial reactors, the diameter of the catalyst (e.g., extrudate) may be greater than about 3mm, greater than about 4mm, greater than about 5mm, greater than about 7mm, greater than about 10mm, greater than about 15mm, or greater than about 20 mm. A bonding material (binder) may be used to form the catalyst and improve the catalyst particle strength. Various solid materials inert to olefins (e.g., ethylene) such as Boehmite (Boehmite), alumina, silicates, Bentonite (Bentonite), or kaolin may be used as binders.

A wide range of catalysts can be used: the ratio of the binder is, for example, about 95:5 to 30:70, or 90:10 to 50: 50. In some cases, a ratio of 80:20 was used for lab scale and pilot reactor catalyst synthesis. For shaped catalysts, the crush strength may be in the range of about 1N/mm to 60N/mm, 5N/mm to 30N/mm, or 7N/mm to 15N/mm.

Catalysts prepared according to the methods of the present disclosure can be tested for the production of various hydrocarbon products, such as gasoline and/or aromatics. In some cases, such catalysts were tested for both gasoline and aromatic hydrocarbon production.

In one example, the short term test conditions for gasoline production are 300 ℃, atmospheric pressure, WHSV 0.65hr^-1，N ₂50% and C₂H₄50%, run for two hours. In another example, the short term test conditions for aromatic hydrocarbon production are 450 ℃, atmospheric pressure, WHSV of 1.31hr^-1，N ₂50% and C₂H₄50%, run for two hours. In addition to the two hour short term test to obtain initial catalytic activity data, for some selected catalysts, long term tests (life tests) were also performed to obtain data on catalyst life, catalyst capacity, and average product composition over life runs.

In one example, the result of the initial catalytic activity test under gasoline production conditions is C₂H₄Conversion greater than about 99%, C₅₊C molar selectivity greater than about 65% (e.g., 65% -70%), and C₅₊The C molar yield is greater than about 65% (e.g., 65% -70%). Catalyst life performance in one cycle operation under gasoline conditions may be at least about 189 hours, decreasing to 80% at conversion; catalyst capacity of about 182g-C per g catalyst conversion₂H₄In which C is₅₊+C_3＝C_4＝Is greater than about 70%. With recirculation, C_3＝And C_4＝Can be considered as a liquid product.

In another example, the result of the initial catalytic activity under aromatic hydrocarbon production conditions is C₂H₄Conversion greater than about 99%, C₅ ⁺C molar selectivity greater than about 75% (e.g., 75% -80%), C₅₊C molar yield greater than about 75% (e.g., 75-80%), and C₅₊The aromatic hydrocarbons in (a) is greater than about 90%. The catalyst life performance in one cycle operation under aromatic production conditions may be at least about 228 hours, reduced to 82% at conversion, and a catalyst capacity of 143g-C per g catalyst conversion₂H₄Wherein average C₅₊The yield was about 72%, and the aromatic yield was about 62%.

The ETL catalyst can have a porosity selected to optimize catalyst performance, including selectivity, lifetime, and product output. The ETL catalyst can have a porosity from about 4 angstroms to about 1 micron, from 0.01nm to 500nm, from 0.1nm to 100nm, or from 1nm to 10nm, as measured according to pore symmetry (e.g., nitrogen porosimetry). The ETL catalyst can contain a substrate with a set of pores having an average pore size (e.g., diameter) of about 4 angstroms to 100nm, or 4 angstroms to 10 angstroms.

Any number of forms of catalytic material may also be employed. In this regard, the physical form of the catalytic materials may contribute to their performance in various catalytic reactions. In particular, for a catalytic reactor, the performance of a number of operating parameters that affect its performance may be significantly affected by the form in which the catalyst is disposed within the reactor. The catalyst may be provided in the form of discrete particles (e.g., pellets, extrudates, or other shaped aggregated particles), or the catalyst may be provided in the form of one or more monoliths (e.g., blocks, honeycombs, foils, lattices, etc.). These operating parameters include, for example, heat transfer, flow rate and pressure drop through the reactor bed, catalyst accessibility, catalyst life, aggregate strength, performance and manageability.

In some cases, it is also desirable that the catalyst form used will have a crush strength that meets the operating parameters of the reactor system. In particular, the catalyst particle crush strength should generally support the pressure applied to the particles by operating conditions such as air inlet pressure and the weight of the catalyst bed. Generally, it is desirable for the catalyst particles to have a particle size of greater than about 1N/mm²And preferably greater than about 10N/mm²E.g. greater than 1N/mm²And preferably greater than 10N/mm²The crush strength of (a). It will be appreciated that by using a more compact, e.g. having a lower surface: the volume ratio of the catalyst form can increase the crush strength. However, performance may be adversely affected in such a form. Thus, the form providing the above-mentioned crush strength, pressure drop, etc., within the desired activity range is selected. The crush strength is also affected by the use of binders and the method of preparation (e.g., extrusion or pelletization).

For example, in some embodiments, the catalytic material is in the form of an extrudate or particulate. The extrudate can be prepared by passing a semi-solid composition comprising the catalytic material through a suitable orifice or using molding or other suitable techniques. The granulate may be prepared by compressing a solid composition comprising the catalytic material under pressure in the die of a tablet press. Other forms of catalyst include catalysts supported or impregnated on a support material or structure. In general, any support material or structure may be used to support the active catalyst. The support material or structure may be inert or catalytically active in the reaction of interest. For example, the catalyst may be supported or impregnated on a monolithic support. In some particular embodiments, the active catalyst is actually supported on the walls of the reactor itself, which may be used to minimize the oxygen concentration at the inner wall, or to facilitate heat exchange by generating the heat of reaction only at the reactor walls (e.g., a loop reactor in this case, and higher space velocity).

The stability of a catalytic material is defined as the length of time that the catalytic material will maintain its catalytic performance without a significant decrease in performance (e.g., a decrease in hydrocarbon or soot combustion activity of > 20%, > 15%, > 10%, > 5%, or greater than 1%) occurring. In some embodiments, the catalytic material has a stability of >1hr, >5hr, >10hr, >20hr, >50hr, >80hr, >90hr, >100hr, >150hr, >200hr, >250hr, >300hr, >350hr, >400hr, >450hr, >500hr, >550hr, >600hr, >650hr, >700hr, >750hr, >800hr, >850hr, >900hr, >950hr, >1,000hr, >2,000hr, >3,000hr, >4,000hr, >5,000hr, >6,000hr, >7,000hr, >8,000hr, >9,000hr, >10,000hr, >11,000hr, >12,000hr, >13,000, >14,000, >15,000hr, >16,000hr, >18,000hr, >19,000hr, >3,000hr, >4,000hr, >3,000hr, >4,000 hr.

Poisoning of catalyst

The catalysts of the present disclosure may be poisoned in catalyzing the formation of a given product. For example, ETL catalysts can be poisoned when higher molecular weight hydrocarbons are produced from olefins (e.g., ethylene). The present disclosure provides various methods for avoiding such poisons.

The alkynes may be oligomerized over an ETL catalyst such as a zeolite or acid catalyst. During oligomerization of alkynes, alkynes can be rapidly converted to polycyclic aromatic hydrocarbon molecules, precursors to coke, which can deactivate the catalyst. Selectivity to coke for acetylene can deactivate the ETL catalyst at a faster rate than olefins and may require the catalyst to be taken off-line for regeneration. Any molecule containing an alkyne functional group can deactivate the ETL catalyst at a faster rate than an olefin group. An example is acetylene, an alkyne produced in small amounts in an OCM process.

One method for eliminating an alkyne from a feedstock for an ETL catalyst is to convert the alkyne into other species that may not poison the ETL catalyst. For example, an alkyne can be selectively hydrogenated to produce an alkene using a variety of transition metal catalysts without hydrogenating the alkene to an alkane. Examples of such catalysts are catalysts comprising Pd, Fe, Co, Ni, Zn and Cu. Such catalyst may be introduced into one or more reactors upstream of the ETL catalyst.

The diolefins may be oligomerized over an ETL catalyst such as a zeolite or acid catalyst. However, during diene oligomerization, the dienes can be rapidly converted to polydiene molecules, precursors to coke, which can deactivate the ETL catalyst. Selectivity to coke for diolefins can deactivate the ETL catalyst quickly and may require catalyst to be taken off-line for regeneration. Any molecule containing a diene functional group can rapidly deactivate the ETL catalyst. An example is butadiene, a diolefin that is produced in small quantities during OCM.

One way for the ETL catalyst to eliminate diolefins from the feedstock is to convert the diolefins to other materials that may not poison the ETL catalyst. For example, dienes can be selectively hydrogenated to form olefins using a variety of transition metal catalysts without hydrogenating the olefins to alkanes. Examples of such catalysts are catalysts comprising Pd, Fe, Co, Ni, Zn and Cu.

The base may react to neutralize the acid functionality that catalyzes the ETL reaction. If sufficient base reacts with the ETL catalyst, the catalyst may no longer be active for oligomerization and may need to be regenerated. Bases include nitrogen-containing compounds, especially ammonia, amines, pyridine, pyrrole and other organic nitrogen-containing compounds. Metal hydroxide compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and group IIA metal hydroxides, and group IA and group IIA metal carbonates, can deactivate the catalyst.

The base may be removed from the feed to the ETL reactor by, for example, contacting the feed stream with water. This can remove or reduce the concentration of bases such as amines, carbonates and hydroxides.

The sulfur-containing compound can deactivate the ETL catalyst, especially when the catalyst is doped with a transition metal compound. Sulfur can bind irreversibly to the catalyst or metal dopant to deactivate the catalyst for oligomerization reactions. Organosulfur compounds such as mercaptans, disulfides, thioethers, thiophenes, and other mercaptan compounds can be detrimental to the ETL catalyst.

Sulfur-containing compounds may be removed from the feed to the ETL reactor by gas scrubbing, such as amine gas scrubbing. The amine may be reacted with a sulfur compound (e.g., H)₂S) to remove such compounds from the gas stream. Other ways of removing the sulfur compounds are by molecular sieve or hydrotreating. Examples of methods for removing sulfur-containing compounds from gas streams are provided in Nielsen, Richard B, et al, "Treat LPGs with amines," Hydrocarbon Process 79(1997):49-59, which is incorporated herein by reference in its entirety.

The effect that certain non-ethylene gases may have on ETL catalysts is summarized in table 1.

Table 1: effect of non-ethylene gases on ETL catalyst

Catalyst regeneration

During the life cycle of a catalyst (e.g., an ETL catalyst), carbonaceous material (e.g., petroleum coke) can deposit and accumulate on the catalyst. Over time, such carbonaceous materials can reduce the activity of the catalyst and may even render the catalyst incapable of converting feedstock into products. The catalyst may need to be replaced or regenerated. There are various methods for regenerating the ETL catalyst, such as oxidative regeneration and non-oxidative regeneration.

In oxidative regeneration, an oxidant (e.g., O) may be introduced at elevated temperatures₂) Is directed over the ETL catalyst to remove or reduce the concentration of carbonaceous material deposited on or over the catalyst. This may occur by burning carbonaceous material. In some cases, an inert gas (e.g., He, Ar, or N) may be used before subjecting the catalyst to the oxidizing agent₂) The catalyst is purged to remove any volatile or residual hydrocarbon products on the surface of the catalyst. The catalyst may then be exposed to an oxidizing agent. In some cases, the oxidant is O, which may be provided by air₂。

In an exemplary oxidative regeneration process, process conditions and the amount of air (or oxygen) can be predetermined to limit or control the amount of heat and water generated during the combustion process for coke removal. Can be mixed with O₂The amount of (c) is limited to a concentration of no more than 50%, 40%, 30%, 20%, 10%, or 5%. Can use N₂Or diluting air with another gas inert to combustion to dilute the concentration to less than or equal to about 50%, 40%, 30%, 20%, 10%, or 5%. The process conditions can be selected to maintain a temperature increase of the ETL catalyst of less than or equal to about 700 ℃, 650 ℃, 600 ℃, 550 ℃, or 500 ℃ during regeneration. This can help prevent catalyst damage during regeneration. The oxidative regeneration reactor inlet temperature may be in the range of about 100 ℃ to 800 ℃, 150 ℃ to 700 ℃, or 200 ℃ to 600 ℃. The inlet gas temperature may be raised from a low temperature to a high temperature to safely control the regeneration process. During oxidative regeneration, the process gas pressure may be in the range of about 1 bar (bar) (gauge) or "barg") to 100 bar, 1 bar to 80 bar, or 1 bar to 50 bar.

In non-oxidative regeneration, hydrogen (H) may be used₂) And/or hydrocarbons regenerate the catalyst bed to improve the catalyst activity of the ETL catalyst. Can be at a temperature of about 100 ℃ to 800 ℃, 150 ℃ to 600 ℃, or 200 ℃ to 500 ℃Hydrogen or a hydrocarbon gas is directed onto the catalyst bed. This may assist in removing or reducing the concentration of carbonaceous material from the catalyst.

Other methods exist for reducing the concentration of catalyst poisons. Acetylene can be a poison at low levels. It may be desirable to remove acetylene and in some cases methylacetylene, butadiene, propadiene and benzene to certain allowable levels. One method of reducing the acetylene concentration is to direct the acetylene to a hydrogenation reactor that hydrogenates the acetylene and butadiene to a mixture of ethylene and ethane and butane and/or butenes.

The acetylene may be hydrogenated, for example, prior to contact with the ETL catalyst. The acetylene hydrogenation reaction can be over a palladium-based catalyst, such as a catalyst used to convert acetylene to ethylene with conventional steam cracking (e.g., PRICAT)^TMSeries, including PD 301/1, PD 308/4, PD 308/6, PD 508/1, PD 408/5, PD 408/7, and PD 608/1 types, commercially available as tablets or spheres supported on alumina). The palladium-based catalyst may comprise one or more metals, including palladium. In some cases, the acetylene hydrogenation catalyst is a doped or modified form of a commercially available catalyst.

However, in some cases, application of an acetylene hydrogenation catalyst to an OCM process that has been developed or optimized for another process (e.g., a steam cracking separation and purification process) can lead to operational problems and/or non-optimized performance. For example, in steam cracking, the acetylene conversion reactor may be located at the front end (before cryogenic separation) or back end (after cryogenic separation) of the process. In steam cracking, these differences in the front end and back end of the run are generally related to the hydrogen to acetylene ratio, ethylene to acetylene ratio, and the ratio of olefins other than ethylene (e.g., butadiene) to acetylene present. All of these factors can affect the selectivity of the catalyst for the formation of ethylene from acetylene, the life and regeneration of the catalyst, green oil formation, the specific process conditions of the reactor, and the additional hydrogen required for the reaction. These factors also differ between steam cracking and OCM and/or ETL processes, and thus, an acetylene hydrogenation catalyst designed for use in an OCM process is provided herein.

In OCM and/or ETL implementations, the chemical components entering the acetylene reactor may be different from steam cracking. For example, the OCM effluent may comprise carbon monoxide and hydrogen. Carbon monoxide may be undesirable because it can compete with acetylene for active sites on the hydrogenation catalyst and result in lower catalyst activity (i.e., by occupying those active sites). Hydrogen may be desirable because it is required for the hydrogenation reaction, however hydrogen is present in the OCM effluent in a certain proportion and adjusting that proportion may be difficult. Thus, the catalysts described herein provide a desired acetylene outlet concentration in the OCM effluent gas, a desired selectivity of acetylene to ethylene, a desired acetylene conversion, a desired lifetime, and a desired activity. As used herein, "OCM effluent gas" generally refers to an effluent taken directly from an OCM reactor or first subjected to any number of other unit operations, such as changing temperature, pressure, or separating the OCM reactor effluent. The OCM exhaust gas may contain CO, H₂And butadiene.

In some embodiments, the catalyst reduces the acetylene concentration to less than about 100 parts per million (ppm), less than about 80ppm, less than about 60ppm, less than about 40ppm, less than about 20ppm, less than about 10ppm, less than about 5ppm, less than about 3ppm, less than about 2ppm, less than about 1ppm, less than about 0.5ppm, less than about 0.3ppm, less than about 0.1ppm, or less than about 0.05 ppm.

The concentration of acetylene can be achieved in the presence of carbon monoxide (CO). In some embodiments, the feed stream to the acetylene hydrogenation reactor contains at least about 10%, at least about 9%, at least about 8%, at least about 7%, at least about 6%, at least about 5%, at least about 4%, at least about 3%, at least about 2%, or at least about 1% carbon monoxide.

When used in an OCM and/or ETL process, the acetylene hydrogenation catalyst can have a lifetime of at least about 6 months, at least about 1 year, at least about 2 years, at least about 3 years, at least about 4 years, at least about 5 years, at least about 6 years, at least about 7 years, at least about 8 years, at least about 9 years, or at least about 10 years.

Another option may be to use a guard bed in front of the ETL reactor (or a reactor train containing multiple ETL reactors). The guard bed may enable the ETL reactor to preferentially coke acetylene. Guard beds can coke relatively quickly and may need to be placed in a lead-lag (lead-lag) configuration so that one bed can be regenerated while another bed is running. The guard bed may contain catalyst and in some cases spent ETL catalyst for preferential coking. The guard bed inlet temperature may be lower than the inlet temperature of the ETL and the space velocity may be higher.

In one example, two guard beds are placed upstream of four or five parallel ETL reactor beds. The two guard beds are designed in a lead-lag configuration. The guard bed has an inlet temperature about 40 ℃, about 60 ℃, about 80 ℃, or about 100 ℃ lower than the inlet of the ETL reactor and a space velocity that is at least about 5 times, at least about 10 times, at least about 20 times, or at least about 50 times the space velocity of the ETL reactor. The ETL reactor was run on a schedule with regeneration and decoking every three weeks for each parallel reactor. But the guard bed was regenerated and decoked every 36 hours.

Catalyst activator

Activators may be used to extend the life of the catalyst. An activator may be used with the catalyst of the present disclosure, such as an ETL catalyst. With the activators of the present disclosure, the life of the catalyst can be extended by at least about 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 100 hours, 110 hours, 120 hours, 130 hours, 140 hours, 150 hours, 160 hours, 170 hours, 180 hours, 190 hours, 200 hours, 210 hours, 220 hours, 230 hours, 240 hours, 250 hours, 300 hours, 350 hours, or 400 hours. The activators of the present disclosure can be used to extend the life of the catalyst by a factor of at least about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4, 5, 6,7, 8, 9, or 10 relative to the absence of the activator. The activator can be a molecule included in the process flow that contacts the catalyst and/or a molecule or element (e.g., a dopant) included in the catalyst itself. For example, Ga-doped ZSM-5 has an extended lifetime (cycle life and/or replacement life) relative to undoped ZSM-5 (e.g., because doped catalysts have lower selectivity for coke formation).

For example, adding water can extend the ETL catalyst life by inhibiting coke formation. Coke formation can be inhibited with water by reacting the water with the coke to form carbon monoxide and hydrogen. One of the attractive features of the OCM-ETL process is that the addition of water can be optimized to have the greatest benefit for reducing coke formation in the reactor. The water may be provided at a concentration of at least about 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%, 25%, or 30%. In some cases, the concentration of water in the feed to the ETL reactor is from 0% to 30%, or from 1% to 25%.

The addition of hydrogen to the feed stream to the ETL reactor can extend the ETL catalyst life. Hydrogen (H) can be introduced₂) Directed over the ETL reactor and the ETL catalyst, which can reduce the concentration of carbonaceous material (e.g., coke) that may be present on the catalyst and prevent the deposition of carbonaceous material by hydrocracking reactions, e.g., by breaking down larger molecules that may eventually convert to coke and reduce the activity of the catalyst.

ETL Process and operating conditions

The present disclosure provides methods for operating an ETL reactor to achieve a given or predetermined product distribution or selectivity. The process conditions may be applied in a single or multiple ETL reactors in series and/or in parallel.

The hydrocarbon stream entering or exiting the ETL reactor can contain various other non-hydrocarbon materials. In some cases, the hydrocarbon stream may include one or more elements filtered from an OCM catalyst (e.g., La, Nd, Sr, W) or an ETL catalyst (e.g., Ga dopant).

Reactor conditions may be selected to provide a given selectivity and product distribution. In some cases, for catalyst selectivity to aromatics, the ETL reactor can be operated at a temperature greater than or equal to about 300 ℃, 350 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, or 500 ℃ and a pressure greater than or equal to about 250 pounds Per Square Inch (PSI) (absolute), 200PSI, 250PSI, 300PSI, 350PSI, or 400 PSI. For catalyst selectivity for jet or diesel fuel, the ETL reactor can be operated at a temperature greater than or equal to about 100 ℃, 150 ℃,200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, or 300 ℃ and a pressure greater than or equal to about 350PSI, 400PSI, 450PSI, or 500 PSI. For catalyst selectivity to gasoline, the ETL reactor can be operated at a temperature greater than or equal to about 200 ℃, 250 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, or 400 ℃ and a pressure greater than or equal to about 250PSI, 300PSI, 350PSI, or 400 PSI.

In some cases, the operating conditions of the ETL process are substantially determined by one or more of the following parameters: the process temperature range, the weight hourly space velocity (mass flow rate of reactants per mass of solid catalyst), the partial pressure of reactants at the reactor inlet, the concentration of reactants at the reactor inlet, and the recycle ratio and recycle split (split). The reactant may be a (lower) olefin, for example, an olefin having a carbon number in the range of C2-C7, C2-C6, or C2-C5.

The temperature used in the gasoline process may be about 150 to 600 ℃, 220 to 520 ℃, or 270 to 450 ℃. Lower temperatures can result in insufficient conversion, while higher temperatures can result in excessive coking and cracking of the products. In one example, the WHSV may be about 0.5hr^-1To 3hr^-1The partial pressure may be about 0.5 bar (absolute) to 3 bar and the concentration at the reactor inlet may be about 2% to 30%. Higher concentrations can produce temperature excursions that are difficult to control, while lower temperatures can make it difficult to obtain sufficiently high partial pressures and separation of the products. When recycling a portion of the effluent, the process can achieve longer catalyst life and higher average yield. The recycle may depend on the recycle ratio (e.g., volume of recycle gas/volume of make-up feed) and the post-reactor vapor-liquid separation that determines the composition of the recycle stream. There may be several degrees of freedom for the recycle separation, but in some cases the composition of the recycle stream may be important, with post-reactor separation (i.e., the typical carbon number/boiling point range of recycle versus fromCarbon number/boiling point range removed in the product and/or secondary process stream).

To obtain longer average chain lengths and avoid cracking extended chains such as those found in jet fuels and distillates, ETL can be carried out at reactor operating temperatures of about 150 ℃ to 500 ℃, 180 ℃ to 400 ℃, or 200 ℃ to 350 ℃. Slower kinetics may suggest about 0.1hr^-1Lower minimum WHSV. High partial pressures may favor longer chain lengths, so the upper limit for jet fuel/distillate may be higher than gasoline, in some cases up to about 30 bar (absolute), 20 bar, 15 bar, or 10 bar.

More consistent aromatic hydrocarbon production can be obtained at high temperature ranges, such as temperatures up to about 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, or 500 ℃. In adiabatic or even pseudo-isothermal reactors, the ethylene/olefin feed can be fed with an inert gas (e.g., N₂Ar, methane, ethane, propane, butane or He). The inert gas may be used to slow the temperature rise in the reactor bed and maintain and stabilize the contact time. The olefin concentration at the reactor inlet may be less than about 50%, 40%, 30%, 20%, or 10%. In some cases, the higher the molar heat capacity of the diluent, the higher the inlet concentration of olefin needed to obtain the same temperature rise.

The following is a list of suitable compounds that may be found in significant amounts during the process. These compounds are listed in order of increasing heat capacity: nitrogen, carbon dioxide, methane, ethane, propane, n-butane, isobutane.

In some cases, a continuous process for producing a mixture of hydrocarbons from (lower) olefins by oligomerization includes feeding an olefinic compound to a reaction zone of an ETL reactor. The reactor zone may contain a heterogeneous catalyst. One or more inert gases may be co-fed to the reactor inlet and constitute from about 50% (volume%) to 99%, 60% to 98%, or 70% to 98% of the feedstock. The mixture may comprise at least one of the following compounds: nitrogen, carbon dioxide, methane, ethane, propane, n-butane, isobutane. Temperature of the process (e.g., ETL reactor)May be about 150 ℃ to 600 ℃, 180 ℃ to 550 ℃, or 200 ℃ to 500 ℃. The partial pressure of the olefin in the feed may be about 0.1 bar (absolute) to 30 bar, 0.1 bar to 15 bar, or 0.2 bar to 10 bar. The total pressure may be from about 1 bar (absolute) to 100 bar, 5 bar to 50 bar, or 10 bar to 50 bar. The weight hourly space velocity may be about 0.05hr^-1To 20hr^-1、0.1hr^-1To 10hr^-1Or 0.1hr^-1To 5hr^-1。

The effluent or product stream from the ETL reactor can be characterized by a low water content. For example, the ETL product stream can comprise less than 60 wt%, 56 wt%, 55 wt%, 50 wt%, 45 wt%, 40 wt%, 39 wt%, 35 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, 5 wt%, 3 wt%, or 1 wt% water.

In some cases, at least a portion of the reactor effluent is recycled to the reactor inlet. Alternatively, at most a portion of the reactor effluent is recycled to the reactor inlet. The volumetric recycle ratio (i.e., the flow rate of the recycle gas stream divided by the flow rate of the make-up gas stream (i.e., fresh feed)) may be about 0.1 to 30, 0.3 to 20, or 0.5 to 10.

A continuous process for producing a mixture of hydrocarbons for use as gasoline may include feeding an olefinic compound to a reaction zone of an ETL reactor. The ETL reactor may contain a catalyst selected for the production of gasoline, as described elsewhere herein. The process temperature may be about 200 ℃ to 600 ℃, 250 ℃ to 500 ℃, or 300 ℃ to 450 ℃. The partial pressure of the olefin in the feed may be about 0.1 bar (absolute) to 10 bar, 0.3 bar to 5 bar, or 0.5 bar to 3 bar. The total pressure may be from about 1 bar (absolute) to 100 bar, 5 bar to 50 bar, or 10 bar to 50 bar. The weight hourly space velocity may be about 0.1hr^-1To 20hr^-1、0.3hr^-1To 10hr^-1Or 0.5hr^-1To 3hr^-1。

For products in the distillate range (e.g., C)₁₀₊Molecules, which in some cases may not include gasoline), the catalyst composition may be selected as described elsewhere herein. The process temperature may be about 100 ℃ to 600 ℃, 150 ℃ to 500 ℃, or 200 ℃ to 375 ℃. The partial pressure of the olefin in the feed may beAnd is about 0.5 bar (absolute) to 30 bar, 1 bar to 20 bar, or 1.5 bar to 10 bar. The total pressure may be from about 1 bar (absolute) to 100 bar, 5 bar to 50 bar, or 10 bar to 50 bar. The weight hourly space velocity may be about 0.05hr^-1To 20hr^-1、0.1hr^-1To 10hr^-1Or 0.1hr^-1To 1hr^-1。

For products comprising a hydrocarbon mixture consisting essentially of aromatic hydrocarbons, the catalyst composition may be selected as described elsewhere herein. The process temperature may be about 200 ℃ to 800 ℃, 300 ℃ to 600 ℃, or 400 ℃ to 500 ℃. The partial pressure of the olefin in the feed may be about 0.1 bar (absolute) to 10 bar, 0.3 bar to 5 bar, or 0.5 bar to 3 bar. The total pressure may be from about 1 bar (absolute) to 100 bar, 5 bar to 50 bar, or 10 bar to 50 bar. The weight hourly space velocity may be about 0.05hr^-1To 20hr^-1、0.1hr^-1To 10hr^-1Or 0.2hr^-1To 1hr^-1。

The ETL process can produce a variety of long-chain hydrocarbons, including normal and iso-paraffins, naphthenes (napthene), aromatics, and olefins, which may not be present in the feed to the ETL reactor. The catalyst may deactivate due to the deposition of carbonaceous deposits ("coke") on the catalyst surface. As deactivation progresses, the conversion of the process changes until a point is reached at which the catalyst can be regenerated.

In some cases, the product distribution may contain a large fraction of aromatics and short-chain alkanes early in the reaction cycle. The latter feature may be an increase in the fraction of olefins. All stages may be characterized by varying amounts of isoparaffins, normal paraffins, naphthenes, aromatics, and olefins, including olefins other than the feed olefins. The separation of the products can take advantage of the change in selectivity over time. For example, the aromatic-rich effluent characteristic of the early part of the reaction cycle can be easily separated from the effluent of the catalyst bed later in the reaction cycle. This can result in high selectivity of the individual products. Figure 5 gives an example of how the product distribution may change over time, which is for a Ga-ZSM-5 catalyst.

The ETL process can generate a variety of byproducts, such as carbonaceous byproducts (e.g., coke) and hydrogen. The selectivity to coke may be on the order of at least about 1%, 2%, 3%, 4%, or 5% as the ETL process progresses. The production of hydrogen may vary over time and the amount of hydrogen produced may be related to the production of aromatics.

In some cases, the time-averaged product of the process may produce a liquid having a composition that meets the specifications of a reformulated oxygen blended gasoline blendstock (RBOB). In some cases, the RBOB has an octane number of at least about 93 using the (RON + MON)/2 process, has less than about 1.3 vol% benzene as measured by ASTM D3606, has less than about 50 vol% aromatics as measured by ASTM D5769, has less than about 25 vol% olefins as measured by ASTM D1319 and/or D6550, has less than 80ppm (wt) sulfur as measured by ASTM D2622, or any combination thereof. Such liquids may be employed as a fuel or other combustion environment. The liquid may be characterized in part by the content of aromatic hydrocarbons. In some cases, the liquid has an aromatic content of 10% to 80%, 20% to 70%, or 30% to 60%, and an olefin content of 1% to 60%, 5% to 40%, or 10% to 30%. Gasoline may comprise about 60% to 95%, 70% to 90%, or 80-90% of such liquids, the remainder of which in some cases are alcohols such as ethanol.

In some cases, a mixture of hydrocarbons is produced from lower olefin compounds (e.g., ethylene) using an ETL process. The mixture may be a liquid at room temperature and atmospheric pressure. The process can be used to form a mixture of hydrocarbons having a hydrocarbon content that can be adapted for various uses. For example, a mixture of blended feedstocks or aromatic compounds, typically characterized as gasoline or distillate (e.g., kerosene, diesel), may contribute at least 30%, 40%, 50%, 60%, or 70% (by weight) of the final fuel product.

The product selectivity of the ETL process can vary over time. With this change in selectivity, the product may contain a changing hydrocarbon distribution. A separation unit may be used to produce a product distribution that may be tailored for a given end use, such as gasoline.

The products of the ETL process of the present disclosure can include other elements or compounds that can be leached from the reactor or catalyst of the system (e.g., OCM and/or ETL reactor). Examples of OCM catalysts and elements comprising catalysts that can be leached into the product can be found in U.S. patent application serial No. 13/689,611 or U.S. provisional patent application 61/988,063, each of which is incorporated herein by reference in its entirety. Such elements may include transition metals and lanthanides. Examples include, but are not limited to, Mg, La, Nd, Sr, W, Ga, Al, Ni, Co, Ga, Zn, In, B, Ag, Pd, Pt, Be, Ca, and Sr. The concentration of such elements or compounds may be at least about 0.01 parts per billion (ppb), 0.05ppb, 0.1ppb, 0.2ppb, 0.3ppb, 0.4ppb, 0.5ppb, 0.6ppb, 0.7ppb, 0.8ppb, 0.9ppb, 1ppb, 5ppb, 10ppb, 50ppb, 100ppb, 500ppb, 1 part per million (ppm), 5ppm, 10ppm, or 50ppm as measured by Inductively Coupled Plasma Mass Spectrometry (ICPMS).

The composition of the ETL product from the system can be consistent over several cycles of catalyst use and regeneration. The reactor system may be used and regenerated for at least about 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 cycles. After a plurality of regeneration cycles, the composition of the ETL product stream differs from the composition of the first recycle ETL product stream by no more than about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

ETL Process design

The present disclosure provides various methods for designing an ETL process. At C₂H₄Can form a series of hydrocarbons, including C₂H₆And CH₄And H₂. Shorter chain hydrocarbons (e.g., C1-C4) and hydrogen in the product stream can be separated from C₅₊The liquid fraction is separated. Fractions of the process stream containing these lighter molecular weight products may be combined with incoming C₂H₄The feed streams are combined or recycled as shown in fig. 6. In this figure, product stream 605 may be separated by, for example, condenser/phase separator 606. From condensationThe gas stream 608 from the separator/separator may be partially recovered 609 and partially recycled 610 back to the reactor 604 for further contact with the catalyst. The OCM reactor effluent 601, which may be treated and/or compressed, is then routed to a treatment unit 602, which may consist of a water removal unit or any other purification unit. The treated ETL feed 603 is reacted in the ETL reactor 604 to produce a pure liquid product 607 from the condenser and phase separator unit. The condenser and phase separator unit also sends recycle 608 back to the ETL reactor inlet.

Recycling can have a number of benefits, such as: 1) the shorter chain hydrocarbon products further react to form higher molecular weight products, 2) extend catalyst life, and 3) dilute C₂H₄The feed stream is fed to control the reactant concentration and the reactor process conditions for adiabatic temperature rise.

In the same C₂H₄At WHSV, conversion of the reactor inlet stream with recycle can have a higher yield of liquid production (C) than conversion of the reactor inlet stream without recycle product₅₊) Especially C condensable at a temperature of about 0 deg.C₅₊(see fig. 7 and 8). The use of recycle can also extend catalyst life, such as C converted by run time and per gram of catalyst₂H₄As measured in grams. The recycle ratio and the liquid (g) condensed at about 0 ℃ are shown in Table 2.

FIG. 7A shows the use of a single pass reactor, C₂H₄Liquid phase mass balance of conversion. FIG. 7B shows a reactor with 5:1 recycle, C₂H₄Liquid phase mass balance of conversion. The reactor was operated at a pressure of about 30 bar for about 0.7h^-1And a Weight Hourly Space Velocity (WHSV) of about 350 ℃. The amount of each hydrocarbon produced ranges from 0% to 100% for different ethylene conversions, where paraffin 700, isoparaffin 705, olefin 710, cycloparaffin 715, aromatic 720, and C are shown₁₂₊ Compound 725. FIG. 8 is a graph showing increasing C as recirculation increases₅₊Graph of yield (liquid condensed at about 0 ℃). The reaction conditions include WHSV of 0.27h^-1(ii) a Reaction ofInlet C of the device₂H₄ mol％＝2；T _peakbed315 ℃ is set; total pressure 300psi (gauge);

table 2: reactor conditions characterized by the product stream data shown in FIG. 8, including recycle ratio, Process inlet C₂H₄mol% reactor inlet C₂H₄mol% and per gram of C₂H₄Grams of liquid condensed from the feed.

In some cases, the inlet feed stream diluted with the recycle product stream allows for a smaller adiabatic temperature rise in the reactor and reduced C entering the reactor₂H₄And (4) concentration. A lower adiabatic temperature rise and thus the resulting peak reactor temperature can change the composition of the effluent product stream. For example, higher reactor peak temperatures can increase the yield and selectivity of aromatic products.

Different amounts of ethylene in the ETL product stream can be recycled. In some cases, at least about 5%, 10%, 15%, 20%, 25%, 30%, 25%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% of the ethylene in the ETL product stream is recycled. In some cases, up to about 5%, 10%, 15%, 20%, 25%, 30%, 25%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% of the ethylene in the ETL product stream is recycled.

The ETL process can be characterized as a single pass conversion or at least 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.9%, or 99.99% C₂₊Compound to C₃₊Per pass conversion of the compound.

ETL Process feed

The feed to the ETL reactor can affect the product distribution leaving the ETL reactor. The product distribution may be related to the concentration of olefins, such as ethylene, propylene, butenes, and pentenes, entering the ETL reactor. Feedstock concentration can affect ETL catalyst efficiency. Feedstocks having olefin concentrations greater than or equal to about 5%, 10%, 15%, 20%, 25%, 30%, or 40% may be effective for producing higher molecular weight hydrocarbons. In some cases, the optimal olefin concentration may be less than about 80%, 85%, 75%, 70%, or 60%. The ETL feedstock can be characterized based on the molar ratio of ethylene to ethane of the feedstock, which can be at least about 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, or 8: 1.

Others C₂₊Compound and non-C₂₊Impurities (e.g. CO, CO)₂、H₂O and H₂) May affect ETL selectivity and/or product distribution. For example, since acetylene can be a deactivating agent and a coking promoter, the presence of acetylene and/or diolefins in the feed to the ETL reactor can significantly affect ETL selectivity and/or product distribution.

Separation of ETL

In the ETL scheme, the separation of the ETL process of the present disclosure can be done in three locations: before, within and downstream of the ETL reactor. In each of these three positions, a different separation technique may be employed.

To treat the ETL reactor feed, conventional gas separation equipment may be used. These separations can include pressure swing adsorption, temperature swing adsorption, and membrane-based separations. The reactor feed can also be increased by utilizing cryogenic separation equipment found in conventional mid-stream gas facilities.

To change the composition within the reactor, different types of catalysts may be mixed together or layered within the catalyst bed or reactor vessel. Different types of zeolite catalysts (e.g., ZSM-5 and SAPO 34 mixed at 60%/40% or mixed at 50%/50%) can produce different hydrocarbon distributions at the reactor vessel outlet. Also within the vessel, there may be a combination of multiple beds with suitable built-in quenching devices to affect the final product composition.

To separate the reactor outlet mixture, a combination of flash separation, hydrogenation, isomerization and distillation may be used. Flash separation will remove most of the light ends of the liquid hydrocarbon product. This can affect product properties such as Reid vapor pressure. Hydrogenation, isomerization, and distillation, much like conventional refining processes, can then be used to produce alternative products.

ETL separation can be performed upstream of the ETL reactor. Membranes used in conjunction with the ETL process can be used on the process feedstock to enrich the components before directing the feedstock to the ETL reactor. Ethylene may be an enrichable component. Other components of the feedstock such as H may also be enriched₂And/or CO₂. In some cases, CO may be rejected.

For example, CO in the feedstock may be a catalyst poison. The CO may be removed prior to directing the feedstock to the ETL reactor. Hydrogen can be a beneficial species present in the feed as it can reduce the coking rate, thereby extending the run time between decoking cycles.

In some cases, a membrane separation unit upstream of the ETL reactor may be employed. The membrane unit may remove at least about 20%, 30%, 40%, 50%, or 60% of one component, or increase the amount of ethylene from at least about 1%, 2%, 3%, 4%, or 5% to at least about 10%, 15%, 20%, 30%, or 40%.

As another example, ethylene may be enriched using a membrane having a certain chemical affinity for ethylene. For oxygen separation membranes, cobalt may be used within the membrane to chemically pass oxygen through the membrane. Chemically modified membranes can be used to achieve such separations.

Another technique that may be employed for upstream separation is Pressure Swing Adsorption (PSA). Pressure swing adsorption can be used to remove substantially all of a particular poison or to enrich nearly pure ethylene. In some cases, a PSA may be used instead of or in addition to a film. The PSA unit may comprise at least 2, 3, 4, 5, 6,7, 8, 9, or 10 vessels containing adsorbent. For example, the adsorbent may be a combination of zeolites, molecular sieves, or activated carbon. Each container may be contained within a container in commonMixed or layered one or more adsorbents. One example of a PSA unit is shown in fig. 9. The system shown in fig. 9 is an activated carbon-based system 900 for separating oxygen from nitrogen. The system includes a carbon molecular sieve 901 that receives a gas stream 902 to be treated. A portion of the gas stream may be released as exhaust 903. The treated gas 904 may include generated nitrogen. The activated carbon system may include carbon particles 905, and the carbon particles 905 may be reacted with N₂Molecule 906 and O₂Molecule 907 interacts. The carbon particles can have a size of, for example, about 1 to about 20 microns, with a pore size of about 0.4 nanometers to about 25 nanometers.

The PSA unit may be operated at ETL reactor pressure (e.g., 5-50 bar) and blown down to atmospheric pressure. Activated carbon, 3A, 4A, 5A molecular sieves and zeolites may be used in these beds. The vessel can be operated so that the desired gas (e.g., ethylene) is passed through the bed at high pressure and so that the undesired gas (e.g., CO)₂Or methane) is blown out of the bed at low pressure.

As an example, the particular choice of adsorbent may determine the substance that passes under high pressure or that is expelled under low pressure. In some cases, PSA may use layered adsorbents, for example, to achieve separation of methane and nitrogen. This stratification within the bed makes methane a blown gas, rather than nitrogen.

PSA technology may also be used in other cases. Multiple beds may be used in series to further enrich the desired process gas. PSA units having at least 2, 3, 4, 5, 6,7, 8, 9, 10, 20, or 30 vessels can be employed. PSA can operate at high frequencies, which can further facilitate better separation.

Another separation technique that may be used with ETL is Temperature Swing Adsorption (TSA). In TSA, separation is achieved using temperature variation. The hydrocarbon mixture may be separated using TSA after the ETL reactor. TSA may assist in removing the heavy fraction from the light fraction as the gas mixture approaches a phase change.

The present disclosure also provides a separation (product enhancement) process in a reactor. For example, reactive separations can be used to achieve some separation goals within the catalyst bed or within the reactor vessel itself. In reactive separation, a first molecule may react to form a larger or smaller molecule that can be separated from a given stream.

In some cases, the vapor phase ethylene may be condensed to a liquid via reaction. Within the catalyst bed, this increase can take two forms: the product may be added to bring it to a given specification, or may be added to remove downstream equipment. As an example of bringing the product to a given specification, the hydrogenation catalysts may be co-mixed or layered within the bed, or as a second bed within the reactor vessel. The catalyst can utilize available hydrogen to reduce the olefin content of the final product. Since alternative gasolines (and many other products) may have olefin specifications that prevent cementation, this in situ separation can remove a significant amount of the olefin content from the resulting liquid to bring it to a given specification.

A co-mixed bed with multiple types of different zeolites can affect the overall product composition. For example, the low aromatics production catalyst may be added to a typical ETL catalyst in an 80%/20% mix. The resulting product stream can be low in aromatics and can bring out-of-specification products to a given specification.

As an alternative, a downstream (in a vessel) isomerization bed may be used to remove unwanted isomers such as durene. Any suitable hydrocarbon compound of carbon number, such as hydrocarbon compounds having four or more carbon atoms (C)₄₊Compound) is isomerized. A reactor in bed process may be employed if downstream equipment is required to isomerize components such as durene or to remove components such as high boiling components.

In some cases, the mixture of zeolites added via the process may also provide the desired separation. Such mixtures can be used to provide an increase in product.

The present disclosure also provides a separation process downstream of the ETL reactor. The downstream separation equipment of the ETL process may be similar to that employed in a refinery. In some cases, downstream unit operations may include flash separation, isomerization, hydrogenation, and distillation, which may help bring the final product to a given specification.

The isomerization unit can convert the undesired isodurene into a more volatile form. The hydrogenation unit can reduce the amount of olefins/aromatics in the final product. Distillation can separate materials according to boiling point. These units can be readily used to produce products having the desired product distribution.

The isomerization unit can be used to boost the octane number of the hydrocarbon product composition. For example, n-hexane can be isomerized to isohexane. N-pentane (62 octane) may be isomerized to 2-methyl-butane (93 octane). Hexane (25 octane) can be isomerized to 2-methyl-pentane (73 octane).

The alkylation and dimerization unit can upgrade lighter fractions such as butane to more valuable high octane products. If the ETL reactor produces a larger amount of butenes than butanes, dimerization can be used to convert the butenes to isooctenes/isooctanes.

The catalytic reforming unit may upgrade the light naphtha fraction to reformate. The unit functions by combining molecules and generating hydrogen. The hydrogen produced in the unit can be used in downstream units if placed in the appropriate location.

Depending on the size and scale of the ETL reactor, the hydrocarbon product output from the ETL reactor can be further refined using vacuum distillation. If such products are valuable, such as lubricants, oils and waxes, an additional step of vacuum distilling these products may be advantageous. In some cases, the amount of heavies produced in the ETL reactor is less than 20%, 15%, 10%, 5%, or 1%, but the value produced by these products can be significant.

Another method for separating hydrocarbons is cryogenic separation. Such separation may be used to capture C from the ETL reactor effluent product stream₄And C₅₊A compound is provided. In some cases, the cryogenic separation unit may include a cold box that may not use conventional cryogenic temperatures and may not require the conventional unit operations of a demethanizer and deethanizer. Such cryogenic separation units may not produce high purity methane, ethane, or propane products. However, it is not limited toIt may produce a mixed (in some cases mainly methane) stream with impurities ethane, propane, other light hydrocarbons and inert gases that may be acceptable for use in other environments, such as reinjection of pipeline gas, as a residual gas, or as a feedstock for a syngas plant that meets fuel requirements for a power plant or for the production of methanol or ammonia.

In some examples, the cryogenic separation unit can be operated at a temperature of about-100 ℃ to-20 ℃, -90 ℃ to-40 ℃, or-80 ℃ to-50 ℃. Such temperatures may be obtained by a process using turboexpansion of high pressure pipeline natural gas or turboexpansion of medium to high methane content feed gases, which may be a typical feature of the OCM reactor inlet requirements, where additional cooling may be achieved using conventional process plant refrigeration cycles, including propane refrigeration or other mixed refrigerants.

In some cases, depending on the end purpose and the use of unreacted and unrecoverable lighter hydrocarbons and other components, the pressure reduction power can be largely recovered by coupling a turboexpander and a residue gas compressor.

In one example of an OCM-ETL system, the gas is expanded and/or additional refrigeration cools it and feeds it to a cryogenic cooling box unit where it exchanges heat with multiple downstream product streams. The gas may then be fed to the OCM reaction and heat recovery section. The pressure may be increased by a plurality of process gas compressors, followed by heating the ETL and then heating the ETL reaction section. Recovery of the non-refrigerated liquid may be achieved using air and cooling water equipment before the product gas enters the cryogenic cooling tank unit where it is cooled, depressurized for cooling effect, and additional condensed liquid removed via a liquid-liquid separator. The separated liquid may be re-entered into the cryogenic cooling tank unit where it is heat exchanged prior to being fed to the depropanizer unit which is fed from the final C₄₊The impurity propane and other light compounds are removed from the product. The separated gas from the liquid-liquid separator is also re-introduced into the low temperature cooling tank unit where it is heat exchanged before being mixed with the depropanizer overhead product gas andand then fed to a residue gas compressor according to the final residue gas usage. Depropanizer reflux condensing is also provided by passing the gas stream through the cryogenic cooling box unit.

In some cases, a debutanizer column may be installed with the bottoms from the depropanizer column as feed. The use of which can provide the final C₄₊RVP control of the product. In some cases, RVP control can be avoided and other purification or chemical transformations can be employed.

ETL reactor feed

The olefin to liquid (e.g., ETL) process of the present disclosure can be carried out using a feedstock comprising one or more olefins, such as pure ethylene or dilute ethylene. Ethylene may be mixed with non-hydrocarbon molecules or other hydrocarbons including olefins, paraffins, naphthenes and aromatics. When a feedstock containing these materials is directed over a bed of an ETL catalyst, such as a zeolite catalyst, at a temperature of at least about 150 ℃,200 ℃, 250 ℃, or 300 ℃, the reactants can oligomerize to form a combination of olefins and longer chain isomers of paraffins, naphthenes, and aromatics. The product composition may include carbon numbers having 1 to 19 (i.e., C)₁–C₁₉) The hydrocarbon of (1).

The concentration of ethylene (or other olefin) may be varied by adjusting the partial pressure of ethylene (or other olefin) at a constant total pressure by dilution with an inert gas such as nitrogen or methane, or by adding an inert gas to increase the total pressure while keeping the partial pressure of ethylene constant. Concentration variations caused by changes in total pressure may not result in significant changes to the process unless the system is operated in adiabatic mode, where temperature spikes introduce additional variability.

In isothermal reactor operation, increasing the liquid content and decreasing the olefin can be promoted by adjusting the concentration change of the ethylene partial pressure in favor of the paraffin and aromatic hydrocarbons. The changes observed in product make-up and liquid formation may depend on the temperature regime and the class of molecules formed under that regime (i.e., isoparaffins and aromatics at temperatures below or above about 400 ℃, respectively). For example, increasing the concentration of ethylene from 5% to 15% at a constant total pressure of 1 bar and a WHSV of 1g ethylene/g catalyst/hour may result in a change of 15% to 45% liquid at 300 ℃.

As the temperature increases, the starting liquid percentage increases, but the net change as the concentration increases decreases. For example, increasing the concentration of ethylene from 5% to 15% at a constant total pressure of 1 bar at 390 ℃ may result in a change of 45% to 65% liquid. The composition of the product may also change as the ethylene concentration increases. This trend is consistent with temperature: as the concentration increases, the olefin content decreases, favoring the paraffin isomers, naphthenes, and aromatics. As the temperature is increased to at least about 300 ℃, 350 ℃, 400 ℃ or 450 ℃ and the product composition is predominantly aromatic, the change in ethylene partial pressure may not change the product composition, but may cause a reduction in the liquid content.

In adiabatic operation, the concentration of ethylene can cause changes in the liquid and product make-up, which are related to changes in the temperature zone throughout the reactor bed. In this mode, the rate of heat transfer from the differential volume units of the reactor bed is a function of the heat capacity of the catalyst and the gas molecules in the stream, especially the inerts. Thus, reducing the concentration of ethylene helps to increase the heat rejection and temperature per volume unit. Generally, as the ethylene concentration increases, the temperature of the bed can rise and the aromatics and pure liquids content can also increase at the expense of paraffins, isoparaffins, olefins, and naphthenes. When the temperature reaches at least about 300 ℃, 350 ℃, 400 ℃ or 450 ℃, the net amount of liquid may decrease as cracking of liquid molecules becomes more and more common.

In some cases, the addition of other hydrocarbons from recycle, refining or mid-stream operations in combination with the ethylene feed may have a positive effect on the formation of liquids. The ETL process is an oligomerization reaction, in which the alkylation forms longer chain hydrocarbons. Thus, except for C₂Incorporating, in addition to ethylene, a catalyst having C₃₊Hydrocarbons of olefin chain length will promote liquid formation. The addition of longer chain hydrocarbons to the feed can produce oligomerization products that are the sum of the two molecules, as long as the reaction conditions or the inherent properties of the catalyst itself prevent cracking (beta-scission) of the hydrocarbons. That isThat is, by minimizing the number of molecular units at reactor start-up (C)₂+C₂+C₂+C₂＝C₈Relative to C₂+C₆＝C₈) The barrier to longer chain molecules is reduced.

The gas molecules that may be co-fed with ethylene may come from recycle streams, natural gas liquids, mid-stream operations, or contain ethane, propylene, propane, butene isomers and butane isomers, as well as other C' s₄₊Olefin refinery effluent. By introducing propene, isobutene and trans-2-butene (with similar expectations for the other butene isomers), the overall product composition can be more or less unchanged. At a constant volumetric flow rate of hydrocarbon material, longer chain hydrocarbons may replace shorter chain hydrocarbons (e.g., propylene instead of ethylene) may result in the formation of a higher content of liquid.

For example, a 50:50 mixture of propylene or isobutylene and ethylene at T300 ℃, 0.15 bar hydrocarbon partial pressure, 1 bar total pressure, increased liquid yield by 10% to 20% compared to pure ethylene feed (the increase in liquid may be due to liquid (C)₅₊) An increase in isoparaffins). When the temperature is 390 ℃ or higher and the aromatic hydrocarbon molecules are the main product species, the influence of the hydrocarbon length has less effect on the liquid formation. In any event, we have found that the presence of propylene or isobutylene in the feed promotes the formation of liquid (aromatics) to an extent (a few percent) greater than using a separate pure feed.

Additional paraffins (e.g., ethane, propane, and butane) can affect the ETL reaction and product distribution. The introduction of normal paraffins may result in an increase in the isoparaffin content due to isomerization of the molecules over the acidic zeolite catalyst. As the temperature and dehydrogenation rates increase, the effect of the introduced paraffins may reflect the phenomena observed with the addition of olefins. Due to the nature of the oligomerization process, C₅₊The co-feeding of hydrocarbons with ethylene may also improve the liquid conversion performance of the ETL process.

Oxidative Coupling of Methane (OCM) process

In the OCM process, methane (CH)₄) In catalysis with oxidizing agentsOn-bed reaction to form C₂₊A compound is provided. For example, methane may be reacted with oxygen over a suitable catalyst to produce ethylene, e.g., 2CH₄+O₂→C₂H₄+2H₂O (see, e.g., Zhang, Q., Journal of Natural Gas chem.,12:81,2003; Olah, G. "Hydrocarbon Chemistry", 2 nd edition, John Wiley&Sons (2003)). The reaction is exothermic (Δ H ═ 67kcal/mol) and has been shown to be generally at very high temperatures (c: (c) (a))>700 deg.C). Experimental evidence suggests that radical chemistry is involved. (Lunsford, J.chem.Soc., chem.Comm., 1991; H.Lunsford, Angew.chem., int.Ed.Engl.,34:970,1995). In the reaction, methane (CH)₄) Is activated at the catalyst surface to form methyl radicals, which are subsequently coupled in the gas phase to form ethane (C)₂H₆) Then dehydrogenated to ethylene (C)₂H₄). Several catalysts have been shown to be active for OCM, including various forms of iron oxide, V, on various supports₂O₅、MoO₃、Co₃O₄、Pt-Rh、Li/ZrO₂、Ag-Au、Au/Co₃O₄、Co/Mn、CeO₂、MgO、La₂O₃、Mn₃O₄、Na₂WO₄MnO, ZnO, and combinations thereof. Multiple doping elements have also proven useful in combination with the above catalysts.

Since the OCM reaction was first reported thirty years ago, it has attracted strong scientific and commercial interest, but fundamental limitations of the conventional methods of C-H bond activation appear to limit the yield of this attractive reaction under practical operating conditions. In particular, many publications from industrial and academic laboratories consistently demonstrate the characteristic behavior of high selectivity at low conversion of methane or low selectivity at high conversion (j.a. labinger, cat.lett.,1:371,1988). Without the OCM catalyst being able to exceed 20-25% of the combined C, subject to this conversion/selectivity threshold₂Yields (i.e., ethane and ethylene), and more importantly, all of these reported yields are at very high temperatures: (>Run at 800 ℃). Have described the temperature at which it is substantially more feasibleCatalysts and processes are used to perform the production of OCM in ethylene from methane under pressure and catalyst activity. These are described in U.S. patent publication nos. 2012/0041246, 2013/0023079, and 2013/165728, and U.S. patent application nos. 13/936,783 and 13/936,870 (both filed on 7/8/2013), the entire disclosure of each being incorporated herein by reference in its entirety for all purposes.

The OCM reactor may contain a catalyst that facilitates the OCM process. The catalyst may include a compound including at least one of an alkali metal, an alkaline earth metal, a transition metal, and a rare earth metal. The catalyst may be in the form of a honeycomb, a packed bed or a fluidized bed. In some embodiments, at least a portion of the OCM catalyst in at least a portion of the OCM reactor may include one or more OCM catalysts and/or nanostructure-based OCM catalyst compositions, forms, and formulations described in, for example, U.S. patent publication nos. 2012/0041246, 2013/0023709, 2013/0158322, 2013/0165728 and pending U.S. application nos. 13/901,309 (filed 5/23/2013) and 14/212,435 (filed 3/14/2014), each of which is incorporated herein by reference in its entirety. By using one or more nanostructure-based OCM catalysts in an OCM reactor that convert methane to the desired C₂₊The selectivity in the compound may be about 10% or greater; about 20% or greater; about 30% or greater; about 40% or greater; about 50% or greater; about 60% or greater; about 65% or greater; about 70% or greater; about 75% or greater; about 80% or greater; or about 90% or greater.

The size, shape, configuration, and/or selection of the OCM reactor may be set based on the need to dissipate the heat generated by the OCM reaction. In some embodiments, multiple tubular fixed bed reactors may be arranged in parallel to facilitate heat rejection. At least a portion of the heat generated within the OCM reactor may be recovered, for example, the heat may be used to generate high temperature and/or high pressure steam. When co-located with a process requiring heat input, at least a portion of the heat generated within the OCM reactor may be transferred to the co-located process using, for example, a heat transfer fluid. When there is no other use for the heat generated within the OCM reactor, the heat can be released to the environment using, for example, a cooling tower or similar evaporative cooling device. In some embodiments, an adiabatic fixed bed reactor system may be used, and the subsequent heat may be directly utilized to convert or crack alkanes to alkenes. In some embodiments, a fluidized bed reactor system may be used. OCM reactor systems useful in the context of the present invention may include those described, for example, in U.S. patent application No. 13/900,898 (filed on 2013, 5/23) which is incorporated herein by reference in its entirety for all purposes.

The methane feedstock for the OCM reactor can be provided from various sources, such as non-OCM processes. In one example, the methane is provided by natural gas, such as methane generated in a Natural Gas Liquids (NGL) system.

The methane may be combined with a recycle stream from a downstream separation unit prior to or during introduction into the OCM reactor. In an OCM reactor, methane may be catalytically reacted with an oxidant to produce C₂₊A compound is provided. The oxidant may be oxygen (O)₂) The oxygen may be provided by air or enriched air. Oxygen may be extracted from air, for example, in a cryogenic air separation unit.

In order to carry out the OCM reaction with the preferred catalytic system, it is generally necessary to bring the methane and oxygen containing gas to a suitable reaction temperature (e.g., typically in excess of 450 ℃ for the preferred catalytic OCM process) prior to introduction to the catalyst in order to allow initiation of the OCM reaction. Once the reaction is initiated or "started up," the heat of reaction is generally sufficient to maintain the reactor temperature at a suitable level. Furthermore, the processes may be operated at pressures above atmospheric pressure, such as in the range of about 1 to 30 bar (absolute).

In some cases, the oxidant and/or methane is preconditioned prior to or during the OCM process. The reactant gases can be preconditioned in a safe and efficient manner prior to their introduction into the catalytic reactor or reactor bed. Such preconditioning may include (i) mixing reactant streams, such as a methane-containing stream and an oxidant (e.g., oxygen) stream, in or before directing the streams to the OCM reactor, (ii) heating or pre-heating the methane-containing stream and/or the oxidant stream using, for example, heat from the OCM reactor, or (iii) a combination of mixing and pre-heating. Such preconditioning can be minimized if the auto-ignition of methane and oxidant is not eliminated. Systems and methods for preconditioning reactant gases are described, for example, in U.S. patent application serial No. 14/553,795 filed on 25/11/2014, which is incorporated herein by reference in its entirety.

A large group of competing reactions can occur simultaneously or substantially simultaneously with the OCM reaction, which includes complete combustion of both methane and other partial oxidation products. The OCM process may produce C₂₊Compound and non-C₂₊Impurities. C₂₊The compounds may include a variety of hydrocarbons, such as hydrocarbons having saturated or unsaturated carbon-carbon bonds. Saturated hydrocarbons may include alkanes such as ethane, propane, butane, pentane, and hexane. Unsaturated hydrocarbons may be more suitable for use in downstream non-OCM processes such as the preparation of polymeric materials (e.g., polyethylene). Thus, it may be preferred to combine C₂₊At least a portion, all, or substantially all of the alkanes in the compounds are converted to compounds having unsaturated moieties, such as alkenes, alkynes, alkoxides, ketones, including aromatic variants thereof.

Once formed, C₂₊The compound may undergo further processing to produce a desired or other predetermined chemical. In some cases, the C₂₊The alkane component of a compound undergoes cracking in the OCM reactor or a reactor downstream of the OCM reactor to produce other compounds such as olefins (or alkenes). See, for example, U.S. patent application serial No. 14/553,795, filed on 25/11/2014, which is incorporated herein by reference in its entirety.

In some cases, OCM systems produce ethylene, which may undergo further processing with the aid of a conversion process (or system) to produce different hydrocarbons. Such processes may be Ethylene To Liquid (ETL) or ethylene, propylene, butene gas to a portion of the liquid. The ETL process includes OCM olefin gas, ethylene, propylene, butylene, or other OCM gas products that produce liquids. The OCM-ETL process flow includes one or more OCM reactors, separation units, and one or more conversion processes for producing higher molecular weight hydrocarbons. The conversion process can be integrated in a switchable or alternative manner, wherein at least a portion or all of the ethylene-containing product can be selectively directed to 1,2, 3, 4, 5, 6,7, 8, 9, 10 or more different process paths to produce as many different hydrocarbon products as possible. An exemplary OCM and ETL (collectively referred to herein as "OCM-ETL") process is schematically illustrated in fig. 1, which shows an OCM reactor system 100 including an OCM reactor train 102 coupled to an OCM product gas separation train 104. The OCM product gas separation train 104 may include various separation unit operations ("units") such as distillation units and/or cryogenic separation units. The ethylene-rich effluent from the separation train 104, as indicated by arrow 106, is routed to a plurality of different ethylene conversion reactor systems and processes 110, e.g., ethylene conversion systems 110a-110e, each of which produces a different hydrocarbon product, e.g., products 120a-120 e. The products 120a-120e can include, for example, hydrocarbons having three to twelve carbon atoms per molecule (C3-C12 hydrocarbons). Such hydrocarbons may be suitable for use as fuels for various machines, such as automobiles.

The fluid connection between the OCM reactor system 100 and each of the different ethylene conversion systems 110a-110e may be controllable and selective, for example, with the aid of valve and control systems that can distribute the output of the OCM reactor system 100 to 1,2, 3, 4, 5, 6,7, 8, 9, 10 or more different ethylene conversion systems. Conversion systems 110a-110e may be ETL or gas-to-liquid (GTL) reactors. The valves and piping used to accomplish this can take a variety of different forms, including valves at each pipe junction, multi-way valves, multi-valve manifold assemblies, and the like. Additional details of the OCM-ETL process of fig. 1 are provided, for example, in U.S. patent application No. 14/099,614 filed on 12/6/2013, which is incorporated herein by reference in its entirety.

As noted, the present disclosure includes methods for producing various higher hydrocarbons (i.e., C) from ethylene₃₊) And in particular to processes and systems for liquid hydrocarbon compositions. In thatIn some aspects, the ethylene itself is derived from methane in a methane-containing feedstock, such as natural gas. The production of ethylene from methane can be accomplished through a variety of different catalytic pathways, for example, in some embodiments, the processes and systems of the present disclosure convert methane to ethylene by OCM in an OCM reactor system. In some embodiments, the ethylene produced in the OCM reactor system is charged to one or more ethylene conversion reactor systems where the ethylene may be converted to higher hydrocarbons, such as a different higher hydrocarbon in each ethylene conversion reactor system.

OCM reactions, processes and systems can be operated within an economical and reasonable process window. In some cases, the catalysts, processes, and reactor systems are capable of conducting OCM reactions at commercially attractive temperatures, pressures, selectivities, and yields. See, for example, U.S. patent application nos. 13/115,082, 13/479,767, 13/689,611, 13/739,954, 13/900,898, 13/901,319, 13/936,783, and 14/212,435, the entire disclosures of which are incorporated herein by reference in their entirety for all purposes.

As used herein, an OCM process or system typically employs one or more reactor vessels containing a suitable OCM catalyst material, typically together with other system components. A variety of OCM catalysts have been described previously. See, for example, U.S. patent nos. 5,712,217, 6,403,523, and 6,576,803, the entire disclosures of which are incorporated herein by reference in their entireties for all purposes. Catalysts have been developed that have conversion and selectivity to achieve economical methane conversion under practical operating conditions. These are described, for example, in published U.S. patent application No. 2012-0041246, as well as in patent application No. 13/479,767 filed on day 5-24 of 2012 and in patent application No. 13/689,611 filed on day 11-29 of 2012, the entire disclosure of each of which is incorporated herein by reference in its entirety for all purposes.

Accordingly, in some embodiments, the present disclosure provides a method of producing a hydrocarbon product, the method comprising: (a) introducing methane and an oxidant source into an OCM reactor system capable of converting methane toAt least 50% C under ethylene conditions at a reactor inlet temperature of about 450 ℃ to 600 ℃ and a reactor pressure of about 15psig to 125psig₂₊Selectively converting methane to ethylene; (b) converting methane to a product gas comprising ethylene; (c) introducing at least a portion of the product gas into an integrated ethylene conversion reaction system configured to convert ethylene to higher hydrocarbon products; and (d) converting ethylene to higher hydrocarbon products.

In some embodiments, the method is used to produce a plurality of hydrocarbon products. Accordingly, in some embodiments, the present invention provides a method of producing a plurality of hydrocarbon products, the method comprising: (a) introducing methane and an oxidant source into an OCM reactor system capable of converting methane to ethylene at a C of at least 50% at a reactor inlet temperature of about 450 ℃ to 600 ℃ and a reactor pressure of about 15psig to 125psig₂₊Selectively converting methane to ethylene; (b) converting methane to a product gas comprising ethylene; (c) introducing separate portions of the product gas into at least first and second integrated ethylene conversion reaction systems, each integrated ethylene conversion reaction system configured for converting ethylene to a different higher hydrocarbon product; and (d) converting ethylene to a different higher hydrocarbon product. In some embodiments, the integrated ethylene conversion system is selected from a selective and a full-range ethylene conversion system.

In some embodiments, the process further comprises introducing a portion of the product gas into at least a third integrated ethylene conversion system. Some embodiments further comprise introducing a portion of the product gas into at least the first, second, third, and fourth integrated ethylene conversion systems.

In any of the processes described herein, the integrated ethylene conversion system can be selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic systems, and hydrocarbon polymer systems.

In some embodiments, the integrated ethylene conversion system may be selected from LAO systems that produce one or more of 1-butene, 1-hexene, 1-octene, and 1-decene. For example, in certain embodiments, at least one of the LAO systems is configured to perform a selective LAO procedure.

In some embodiments, at least one integrated ethylene conversion system comprises a reactor configured for production at C₄To C₃₀A full range ethylene oligomerization system for a range of higher hydrocarbons.

In some embodiments, the OCM reactor system includes a nanowire OCM catalyst material. In some embodiments, the product gas comprises less than 5 mol% ethylene. For example, in certain embodiments, the product gas comprises less than 3 mol% ethylene. In some embodiments, the product gas may further comprise a gas selected from CO₂、CO、H₂、H₂O、C₂H₆、CH₄And C₃₊One or more gases of hydrocarbons.

In some embodiments, the process further comprises enriching the product gas for ethylene prior to introducing the separate portions of the product gas into the at least first and second integrated ethylene conversion reaction systems.

In some embodiments, the method further comprises introducing vent gas from the first or second integrated ethylene conversion reaction system into the OCM reactor system. For example, in some of these embodiments, the process further comprises converting methane present in the vent gas to ethylene and charging the ethylene to one or more of the integrated ethylene conversion systems.

In various embodiments, the present disclosure relates to a method of producing a plurality of hydrocarbon products, the method comprising: (a) introducing methane and an oxidant source into an OCM reactor system capable of converting methane to ethylene at a C of at least 50% at a reactor inlet temperature of about 450 ℃ to 600 ℃ and a reactor pressure of about 15psig to 125psig₂₊Selectively converting methane to ethylene; (b) ethylene recovery from OCM reactor system(ii) a And (c) introducing separate portions of the ethylene recovered from the OCM reactor system into at least two integrated but discrete and distinct catalytic ethylene conversion reaction systems to convert the ethylene to at least two different higher hydrocarbon products.

In some embodiments, the at least two ethylene conversion systems are selected from selective and full-range ethylene conversion systems. In some embodiments, the at least two ethylene conversion systems comprise at least three ethylene conversion systems. For example, in some embodiments, the at least two ethylene conversion systems comprise at least four ethylene conversion systems.

In further embodiments, the at least two ethylene conversion systems are selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, and hydrocarbon polymer systems.

In some cases, the at least two ethylene conversion systems are selected from LAO systems that produce one or more of 1-butene, 1-hexene, 1-octene, and 1-decene. For example, in some embodiments, at least one of the at least two LAO processes comprises a selective LAO process, and in other exemplary embodiments, at least one of the at least two ethylene conversion systems comprises a process for producing at C₄To C₃₀A full range ethylene oligomerization system for a range of higher hydrocarbons. In some cases, the OCM reactor system includes a nanowire OCM catalyst material.

In some embodiments, the present disclosure provides a method of producing a plurality of liquid hydrocarbon products, the method comprising: (a) converting methane to a product gas comprising ethylene using a catalytic reactor process; and (b) contacting separate portions of the product gas with at least two discrete catalytic reaction systems selected from the group consisting of: linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, and hydrocarbon polymer systems.

In some cases, a method of producing a plurality of liquid hydrocarbon products is provided. The method comprises the following steps: (a) converting methane to ethylene using a catalytic reactor process; (b) recovering ethylene from the catalytic reactor process; and (c) contacting separate portions of the ethylene recovered from the OCM reactor system with at least two discrete catalytic reaction systems selected from the group consisting of: linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, and hydrocarbon polymer systems.

Some embodiments of the present disclosure relate to a process for producing C from methane₂₊A system for processing hydrocarbon products. For example, in some embodiments, the present invention provides a processing system comprising: (a) an OCM reactor system comprising an OCM catalyst, the OCM reactor system fluidly connected at an input to a source of methane and a source of oxidant; (b) an integrated ethylene conversion reactor system configured to convert ethylene to higher hydrocarbons; and (c) a selective coupling device between the OCM reactor system and the ethylene reactor system configured to selectively direct a portion or all of the product gas to the ethylene conversion reactor system.

In some cases, the present disclosure provides a processing system comprising: (a) an OCM reactor system comprising an OCM catalyst, the OCM reactor system fluidly connected at an input to a source of methane and a source of oxidant; (b) at least first and second catalytic ethylene conversion reactor systems, the first catalytic ethylene reactor system configured to convert ethylene to a first higher hydrocarbon and the second catalytic ethylene reactor system configured to convert ethylene to a second higher hydrocarbon different from the first higher hydrocarbon; and (c) a selective coupling device between the OCM reactor system and the first and second catalytic ethylene reactor systems, the selective coupling device configured to selectively direct a portion or all of the product gas to each of the first and second catalytic ethylene reactor systems.

In some embodiments, the ethylene conversion system is selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, ethylene copolymerization systems, and hydrocarbon polymer systems.

In some cases, the OCM catalyst comprises a nanowire catalyst. In some embodiments, the system further comprises an ethylene recovery system fluidly coupled between the OCM reactor system and the at least first and second catalytic ethylene conversion reactor systems, the ethylene recovery system configured to enrich the product gas for ethylene.

In some cases, the present disclosure relates to a processing system comprising: (a) an OCM reactor system comprising an OCM catalyst, the OCM reactor system fluidly connected at an input to a source of methane and a source of oxidant; (b) an ethylene recovery system fluidly coupled to the OCM reactor system at an outlet for recovering ethylene from the OCM product gas; (c) at least first and second catalytic ethylene conversion reactor systems, the first catalytic ethylene reactor system configured to convert ethylene to a first higher hydrocarbon composition and the second catalytic ethylene reactor system configured to convert ethylene to a second higher hydrocarbon composition different from the first higher hydrocarbon composition; and (d) a selective coupling device between the outlet of the ethylene recovery system and the first and second catalytic ethylene reactor systems to selectively direct a portion or all of the ethylene recovered from the OCM product gas to each of the first and second catalytic ethylene reactor systems.

In some cases, two or more of the at least two ethylene conversion systems are selected from the group consisting of Linear Alpha Olefin (LAO) systems, linear olefin systems, branched olefin systems, saturated linear hydrocarbon systems, branched hydrocarbon systems, saturated cyclic hydrocarbon systems, olefinic cyclic hydrocarbon systems, aromatic hydrocarbon systems, oxygenated hydrocarbon systems, halogenated hydrocarbon systems, alkylated aromatic hydrocarbon systems, ethylene copolymerization systems, and hydrocarbon polymer systems. In other embodiments, the OCM catalyst comprises a nanowire catalyst.

In some embodiments, the catalyst system used in any of the foregoing OCM reactions comprises a nanowire catalyst. Such nanowire catalysts may include substantially straight nanowires or nanowires having a tortuous, twisted or curved morphology. The actual length of the nanowire catalyst may vary. For example, in some embodiments, the nanowires have an actual length of 100nm to 100 μm. In other embodiments, the nanowires have a physical length of 100nm to 10 μm. In other embodiments, the nanowires have an actual length of 200nm to 10 μm. In other embodiments, the nanowires have an actual length of 500nm to 5 μm. In other embodiments, the actual length is greater than 5 μm. In other embodiments, the nanowires have an actual length of 800nm to 1000 nm. In other further embodiments, the nanowires have an actual length of 900 nm. The actual length of the nanowires can be determined by TEM in bright field mode, e.g. at 5keV, as described below.

The diameter of the nanowire may be different at different points along the nanowire backbone. However, nanowires include a mode diameter (i.e., the most frequently occurring diameter). As used herein, the diameter of a nanowire refers to the mode diameter. In some embodiments, the nanowires have a diameter of 1nm to 10 μ ι η, 1nm to 1 μ ι η, 1nm to 500nm, 1nm to 100nm, 7nm to 50nm, 7nm to 25nm, or 7nm to 15 nm. In other embodiments, the diameter is greater than 500 nm. The diameter of the nanowires can be determined by TEM in bright field mode, e.g. at 5keV, as described below.

The nanowire catalysts may have different aspect ratios. In some embodiments, the nanowires have an aspect ratio greater than 10: 1. In other embodiments, the nanowires have an aspect ratio greater than 20: 1. In other embodiments, the nanowires have an aspect ratio of greater than 50: 1. In other embodiments, the nanowires have an aspect ratio greater than 100: 1.

In some embodiments, the nanowires comprise a solid core, while in other embodiments, the nanowires comprise a hollow core. In general, the morphology of the nanowires (including length, diameter and other parameters) can be determined by Transmission Electron Microscopy (TEM). Transmission Electron Microscopy (TEM) is a technique in which an electron beam is transmitted through an ultra-thin sample so that it interacts with the sample as it passes through. An image is formed by the interaction of the electrons transmitted through the sample. The image is magnified and focused on an imaging device such as a fluorescent screen, on a layer of photographic film, or detected by a sensor such as a CCD camera.

In some embodiments, the nanowire catalyst comprises one or more crystalline domains, e.g., single crystal or polycrystalline, respectively. In some other embodiments, the nanowires have an average domain of less than 100nm, less than 50nm, less than 30nm, less than 20nm, less than 10nm, less than 5nm, or less than 2 nm. The crystal structure, composition and phase, including domain size of the nanowires, can be determined by XRD.

Typically, the nanowire catalytic material comprises a plurality of nanowires. In certain embodiments, the plurality of nanowires form a network of nanowires randomly distributed and interconnected to varying degrees, which is present as a porous matrix.

The total surface area per gram of nanowire or plurality of nanowires can affect catalytic performance. Pore size distribution can also affect nanowire catalytic performance. The surface area and pore size distribution of the nanowire or nanowires can be determined by BET (Brunauer, Emmett, Teller) measurements. The BET technique utilizes nitrogen adsorption at different temperatures and partial pressures to determine the surface area and pore size of the catalyst. BET techniques for determining surface area and pore size distribution are currently available. In some embodiments, the nanowires have 0.0001 to 3000m²0.0001 to 2000 m/g²0.0001 to 1000 m/g²0.0001 to 500 m/g²0.0001 to 100 m/g²0.0001 to 50 m/g²0.0001 to 20 m/g²0.0001 to 10 m/g²(ii)/g, or 0.0001 to 5m²Surface area in g. In some embodiments, the nanowires have a diameter of 0.001 to 3000m²0.001 to 2000 m/g²0.001 to 1000 m/g²0.001 to 500 m/g²0.001 to 100 m/g²0.001 to 50 m/g²0.001 to 20 m/g²0.001 to 10 m/g²In the range of 0.001 to 5 m/g²Surface area in g. In some other embodiments, the nanowires have 2000 to 3000m²G, 1000 to 2000m²500 to 1000 m/g ²100 to 500 m/g ²10 to 100 m/g²G, 5 to 50m²G, 2 to 20m²(ii) g or 0.0001 to 10m²Surface area in g. In other embodiments, the nanowires have a diameter of greater than about 2000m²A ratio of the total of the carbon atoms to the carbon atoms of greater than about 1000m²A ratio of the total of the carbon atoms to the carbon atoms of greater than about 500m²A ratio of the total of the carbon atoms to the carbon atoms of greater than about 100m²A ratio of the total of the components of the composition to the total of the components of the composition greater than about 50m²A ratio of the total of the components of the composition to the total of the components of the composition greater than about 20m²A ratio of the total of the carbon atoms to the carbon atoms of greater than about 10m²A ratio of the total of the carbon atoms to the carbon atoms of greater than about 5m²A ratio of the total of the carbon atoms to the carbon atoms of greater than about 1m²A/g of greater than about 0.0001m²Surface area in g.

The nanowire catalysts and catalyst compositions used in conjunction with the processes and systems of some embodiments of the present invention may have any number of compositions and/or morphologies. These nanowire catalysts may be inorganic and polycrystalline or monocrystalline. In some other embodiments, the nanowires are inorganic and polycrystalline. In certain examples, the nanowire catalyst comprises one or more elements from any of groups 1 through 7, lanthanides, actinides, or combinations thereof. Thus, in certain aspects, the catalyst comprises inorganic catalytic polycrystalline nanowires having an effective length to actual length ratio of less than 1, and an aspect ratio of greater than 10 as measured by TEM in bright field mode at 5keV, wherein the nanowires comprise one or more elements from any one of groups 1-7, lanthanides, actinides, or combinations thereof.

In other cases, the nanowire catalyst comprises one or more metal elements from any of groups 1-7, lanthanides, actinides, or combinations thereof, e.g., the nanowire can be monometallic, bimetallic, trimetallic, etc. (i.e., comprise one, two, three, etc. metal elements), wherein the metal elements can be present in the nanowire in elemental or oxidized form or in a compound comprising the metal elements. The metallic element or the compound containing the metallic element may be in the form of an oxide, hydroxide, oxyhydroxide, salt, hydrous oxide, carbonate, oxycarbonate, sulfate, phosphate, acetate, oxalate, or the like. The metallic element or the compound containing the metallic element may also be in the form of any one of a number of different polymorphs or crystal structures.

In some examples, the metal oxide may be hygroscopic and may change form upon exposure to air, may absorb carbon dioxide, may undergo incomplete calcination, or any combination of the above. Thus, although the nanowires are generally referred to as metal oxides, in some embodiments, the nanowires further comprise hydrated oxides, oxyhydroxides, hydroxides, oxycarbonates (or oxide carbonates), carbonates, or combinations thereof.

In some cases, the nanowires comprise one or more metal elements from group 1, group 2, group 3, group 4, group 5, group 6, group 7, lanthanide, and/or actinide elements, or combinations of these, as well as oxides of these metals. In other cases, the nanowires comprise hydroxides, sulfates, carbonates, oxide carbonates, acetates, oxalates, phosphates (including hydrogen and dihydrogen phosphates), oxycarbonates, oxyhalides, hydroxyhalides, oxyhydroxides, oxysulfates, mixed oxides, or combinations thereof of one or more metallic elements from any of groups 1-7, lanthanides, actinides, or combinations thereof. Examples of such nanowire materials include, but are not limited to, nanowires comprising, for example: li₂CO₃、LiOH、Li₂O、Li₂C₂O₄、Li₂SO₄、Na₂CO₃、NaOH、Na₂O、Na₂C₂O₄、Na₂SO₄、K₂CO₃、KOH、K₂O、K₂C₂O₄、K₂SO₄、Cs₂CO₃、CsOH、Cs₂O、CsC₂O₄、CsSO₄、Be(OH)₂、BeCO₃、BeO、BeC₂O₄、BeSO₄、Mg(OH)₂、MgCO₃、MgO、MgC₂O₄、MgSO₄、Ca(OH)₂、CaO、CaCO₃、CaC₂O₄、CaSO₄、Y₂O₃、Y₂(CO₃)₃、Y(OH)₃、Y₂(C₂O4)₃、Y₂(SO₄)₃、Zr(OH)₄、ZrO(OH)₂、ZrO2、Zr(C₂O₄)₂、Zr(SO₄)₂、Ti(OH)₄、TiO(OH)₂、TiO₂、Ti(C₂O₄)₂、Ti(SO₄)₂,BaO、Ba(OH)₂、BaCO₃、BaC₂O₄、BaSO₄、La(OH)₃、La₂O₃、La₂(C₂O₄)₃、La₂(SO₄)₃、La₂(CO₃)₃、Ce(OH)₄、CeO₂、Ce₂O₃、Ce(C₂O₄)₂、Ce(SO₄)₂、Ce(CO₃)₂、ThO₂、Th(OH)₄、Th(C₂O₄)₂、Th(SO₄)₂、Th(CO₃)₂、Sr(OH)₂、SrCO₃、SrO、SrC₂O₄、SrSO₄、Sm₂O₃、Sm(OH)₃、Sm₂(CO₃)₃、Sm₂(C₂O₄)₃、Sm₂(SO₄)₃、LiCa₂Bi₃O₄Cl₆、NaMnO₄、Na₂WO₄、NaMn/WO₄、CoWO₄、CuWO₄、K/SrCoO₃、K/Na/SrCoO₃、Na/SrCoO₃、Li/SrCoO₃、SrCoO₃、Mg₆MnO₈、LiMn₂O₄、Li/Mg₆MnO₈、Na₁₀Mn/W₅O₁₇、Mg₃Mn₃B₂O₁₀、Mg₃(BO₃)₂Oxides, hydroxides, oxalates, sulfates of molybdenum, Mn, of molybdenum₂O₃、Mn₃O₄Examples of the material include, but are not limited to, manganese oxide, manganese hydroxide, manganese oxalate, manganese sulfate, manganese tungstate, manganese carbonate, vanadium oxide, vanadium hydroxide, vanadium oxalate, vanadium sulfate, tungsten oxide, tungsten hydroxide, tungsten oxalate, tungsten sulfate, neodymium oxide, neodymium hydroxide, neodymium carbonate, neodymium oxalate, neodymium sulfate, europium oxide, europium hydroxide, europium carbonate, europium oxalate, europium sulfate, praseodymium oxide, praseodymium hydroxide, praseodymium carbonate, praseodymium oxalate, praseodymium sulfate, rhenium oxide, rhenium hydroxide, rhenium oxalate, chromium oxide, chromium hydroxide, chromium oxalate, chromium sulfate, potassium molybdenum oxide/silicon oxide, or combinations thereof.

Other examples of these nanowire materials include, but are not limited to, nanowires comprising, for example: li₂O、Na₂O、K₂O、Cs₂O、BeO、MgO、CaO、ZrO(OH)₂、ZrO₂、TiO₂、TiO(OH)₂、BaO、Y₂O₃、La₂O₃、CeO₂、Ce₂O₃、ThO₂、SrO、Sm₂O₃、Nd₂O₃、Eu₂O₃、Pr₂O₃、LiCa₂Bi₃O₄C_l6、NaMnO₄、Na₂WO₄、Na/Mn/WO₄、Na/MnWO₄、Mn/WO₄、K/SrCoO₃、K/Na/SrCoO₃、K/SrCoO₃、Na/SrCoO₃、Li/SrCoO₃、SrCoO₃、Mg₆MnO₈、Na/B/Mg₆MnO₈、Li/B/Mg₆MnO₈、Zr₂Mo₂O₈Molybdenum oxide, Mn₂O₃、Mn₃O₄An oxide of manganese, an oxide of vanadium, an oxide of tungsten, an oxide of neodymium, an oxide of rhenium, an oxide of chromium, or a combination thereof. A variety of different nanowire compositions have been described, for example, in published U.S. patent application No. 2012-0041246 and U.S. patent application No. 13/689,611 filed on 11/29 of 2012 (the entire disclosures of these patent applications are incorporated herein in their entireties for all purposes) and are contemplated for use with the present invention.

The products produced by these catalytic reactions typically include CO, CO₂，H₂O，C₂₊Hydrocarbons such as ethylene, ethane and larger alkanes and alkenes such as propane and propylene. In some embodiments, the OCM reactor system is operated to convert methane to the desired higher hydrocarbon products (ethane, ethylene, propane, propylene, butane, pentane, etc.), collectively referred to as C, in high yield₂₊A compound is provided. In particular, it is usual to use in methane conversion, C₂₊Selectivity and C₂₊The progress of the OCM reaction is discussed in terms of yield. As used herein, methane conversion generally refers to the percentage or fraction of methane introduced into the reaction that is converted to products other than methane. C₂₊Selectivity generally refers to the percentage of total non-methane carbon-containing products of the OCM reaction that are the desired C₂₊Products such as ethane, ethylene, propane, propylene, and the like. Although described primarily as C₂₊Selectivity, but it is understood that selectivity may be described in terms of the desired product, for example, only C2 or only any one of C2 and C3. Finally, C₂₊Yield generally refers to incorporation of C₂₊The amount of carbon in the product is a percentage of the amount of carbon introduced into the reactor as methane. This can generally be calculated by dividing the product of conversion and selectivity by the number of carbon atoms in the desired product. C₂₊Yields are generally included in the identified C₂₊Different C in the component₂₊The sum of the yields of the components, for example, ethane yield + ethylene yield + propane yield + propylene yield, etc.

Exemplary OCM processes and systems typically provide at least 10% methane conversion per pass process (C) in a single integrated reactor system (e.g., a single isothermal reactor system or an integrated multi-stage adiabatic reactor system)₂₊The selectivity is at least 50% while the reactor inlet temperature is 400 to 600 ℃ and the reactor inlet pressure is about 15psig to about 150 psig. Thus, the catalysts employed in these reactor systems are capable of providing the conversion and selectivity at the reactor conditions of temperature and pressure. In the context of some OCM catalyst and system embodiments, it should be understood that the reactor inlet or feed temperature generally corresponds substantially to the minimum "start-up" or reaction start-up temperature of the catalyst or system. Again, the feed gas, when introduced into the reactor, is contacted with the catalyst at a temperature capable of initiating the OCM reaction. Because the OCM reaction is exothermic, once start-up is achieved, the heat of reaction can be expected to maintain the reaction at the appropriate catalytic temperature, and even generate excess heat.

In some aspects, when performing an OCM reaction, the OCM reactor and reactor system are operated at the above-described temperatures at pressures of from about 15psig to about 125psig while providing the conversions and selectivities described herein, and in even more embodiments, at pressures of less than 100psig, e.g., from about 15psig to about 100 psig.

Examples of particularly useful catalyst materials are described, for example, in published U.S. patent application No. 2012-0041246, and in patent application No. 13/479,767 filed on day 24, 5, 2012 and 13/689,611 filed on day 29, 11, 2012, which are incorporated herein by reference in their entirety for all purposes. In some embodiments, the catalyst comprises, for example, a bulk (bulk) catalyst material having a relatively undefined morphology, or in certain embodiments, the catalyst material comprises, at least in part, a catalytic material comprising nanowires. The catalyst used according to the invention may be employed in any form, under all the ranges of reaction conditions mentioned above or within any narrower range of said conditions. Similarly, the catalyst material may be provided in a range of different larger scale forms and formulations, for example, as a mixture of materials having different catalytic activities, a mixture of catalyst and relatively inert or diluent materials, combined in an extrudate, pellet or monolith form, and the like. A series of exemplary catalyst forms and formulations are described, for example, in U.S. patent application No. 13/901,319 and U.S. provisional patent application No. 62/051,779, the entire disclosures of which are incorporated herein by reference in their entirety for all purposes.

The reactor vessel used to carry out the OCM reaction in the OCM reactor system of the present invention may comprise one or more discrete reactor vessels, each containing an OCM catalyst material, fluidly coupled to a source of methane and a source of oxidant, as further described elsewhere herein. A feed gas comprising methane (e.g., natural gas) is contacted with a catalyst material within the reactor under conditions suitable to initiate and carry out the reaction to catalyze the conversion of methane to ethylene and other products.

For example, in some embodiments, the OCM reactor system comprises one or more staged reactor vessels operating under isothermal or adiabatic conditions for conducting an OCM reaction. For adiabatic reactor systems, the reactor system may comprise one, two, three, four, five or more staged reactor vessels arranged in series, the staged reactor vessels being fluidly connected such that the effluent or "product gas" of one reactor is at least partially directed to the inlet of a subsequent reactor. Such staged reactors in series achieve higher yields of the overall process by allowing for the catalytic conversion of previously unreacted methane. These adiabatic reactors are generally characterized by the absence of an integrated thermal control system for keeping the entire reactor free of temperature gradients or with small temperature gradients. Without the integrated temperature control system, the exothermic nature of the OCM reaction results in a temperature gradient between the reactors that indicates the progress of the reaction, where the inlet temperature may range from about 450 ℃ to about 600 ℃, while the outlet temperature ranges from about 700 ℃ to about 900 ℃. Typically, such a temperature gradient may range from about 100 ℃ to about 450 ℃. By staging the adiabatic reactor, with an interstage cooling system, more complete catalytic reactions can be stepped through without producing extreme temperatures, e.g., in excess of 900 ℃.

In operation of certain embodiments, a feed gas comprising methane is introduced into the inlet side of a reactor vessel (e.g., the first reactor in a staged reactor system). As described above, in this reactor methane is converted to C ₂₊Hydrocarbons, and other products. At least a portion of the product gas stream is then cooled to a suitable temperature and introduced into a subsequent reactor stage for continuous catalytic reaction. In particular, the effluent from a prior reactor, which in some cases may contain unreacted methane, may provide at least a portion of the methane source for a subsequent reactor. An oxidant source and a methane source separate from unreacted methane from the first reactor stage are also typically coupled to the inlet of each of the subsequent reactors.

In some aspects, the reactor system comprises one or more "isothermal" reactors that maintain a relatively low temperature gradient throughout the total reactor bed (e.g., between the inlet and outlet gases or product gas) and maintain a flat (flat) or insignificant temperature gradient between the reactor inlet and outlet by incorporating integrated temperature control elements such as cooling systems that contact the heat exchange surfaces of the reactor to remove excess heat. Typically, such reactors employ molten salt or other cooling systems operating at temperatures below 593 ℃. Like the adiabatic system, the isothermal reactor system may comprise one, two, three, or more reactors, which may be configured in a series or parallel orientation. Reactor systems for carrying out these catalytic reactions are also described in U.S. patent application No. 13/900,898, the entire disclosure of which is hereby incorporated by reference in its entirety for all purposes.

The OCM reactor system used in certain embodiments of the present invention also typically includes a thermal control system configured to maintain a desired thermal or temperature profile throughout the overall reactor system or individual reactor vessels. In the case of adiabatic reactor systems, it will be appreciated that the thermal control system includes, for example, heat exchangers disposed upstream, downstream, or between the reactors in series within the overall system in order to maintain a desired temperature profile in one or more of the reactors. In the case of a reactor (such as an OCM) in which an exothermic reaction is conducted, such a thermal control system also optionally includes a control system for adjusting the flow of reactants, such as a methane-containing feed gas and an oxidant, into the reactor vessel in response to temperature information feedback in order to adjust the reaction to achieve a reactor thermal profile within a desired temperature range. These systems are also described in U.S. patent application No. 13/900,898, previously incorporated by reference herein.

For isothermal reactors, such thermal control systems include the above, as well as integrated heat exchange assemblies, such as integrated heat exchangers built into the reactor, such as tube/shell reactors/heat exchangers, wherein a void space surrounding the reactor vessel or a void space through which one or more reactor vessels or tubes pass is provided. The heat exchange medium then removes heat from the individual reactor tubes through the gap. The heat exchange medium is then routed to an external heat exchanger, thereby cooling the medium prior to recycling to the reactor.

Following the OCM process, ethylene may optionally be recovered from the OCM product gas using an ethylene recovery process that separates the ethylene present in the product gas from other components (e.g., residues, i.e., unreacted methane, ethane, and higher hydrocarbons such as propane, butane, pentane, etc.). Alternatively, the OCM product is used in subsequent reactions without further purification or isolation of ethylene, as described below. In various other embodiments, the OCM product gas is enriched for ethylene prior to use in subsequent reactions. In this regard, "enrichment" includes, but is not limited to, operations that increase the total mol% of ethylene in the product gas.

In accordance with the present disclosure, ethylene derived from methane, for example, using an OCM process and system, will be further processed into higher hydrocarbon compositions, particularly liquid hydrocarbon compositions. For ease of discussion, when referring to the inclusion of an OCM process and system in the overall process flow from methane to higher hydrocarbon compositions, reference to an OCM process and system is also arbitraryOptionally including purifying ethylene from the OCM product gas (e.g., recycling of the product gas through the OCM reactor system), separating methane and higher hydrocarbons (e.g., NGL and other C's) from the OCM product gas₂₊Compounds) and the like. For example, examples of such intermediate processes include use in different hydrocarbons and other components (e.g., CO that may be present in the OCM product gas₂Water, nitrogen, residual methane, ethane, propane, and other higher hydrocarbon compounds) from ethylene, Temperature Swing Adsorption (TSA), Pressure Swing Adsorption (PSA), and membrane separation. Examples of such systems are described, for example, in U.S. patent application nos. 13/739,954, 13/936,783, and 13/936,870, the entire disclosures of which are hereby incorporated by reference in their entirety for all purposes.

FIG. 10 diagrammatically illustrates an exemplary OCM system having one or more integrated split system components. Specifically, shown in FIG. 10 is an exemplary process flow diagram illustrating a process for methane-based C in the product gas from one or more OCM reactors 1002₂Process 1000 of preparation, and including providing a C-rich₂A first separator 1006 for effluent 1052 and methane/nitrogen-rich effluent 1074. In the embodiment shown in fig. 10, OCM product gas from OCM reactor 1002 is compressed by compressor 1026. The temperature of the compressed OCM product gas 1050 is reduced using one or more heat exchangers 1010. The temperature of compressed OCM product gas 1050 can be reduced by using an externally provided cooling medium, introducing or exchanging heat with a cold process stream, or a combination of the methods. Reducing the temperature of the OCM product gas 1050 will generally condense at least a portion of the higher boiling components of the compressed OCM product gas 1050, including the C present in the compressed OCM product gas 1050₂And at least a portion of the heavier hydrocarbon components.

At least a portion of the condensed high boiling components may be separated from compressed OCM product gas 1050 using one or more liquid gas separators, such as knockout 1012, to provide OCM product gas condensate 1054 and compressed OCM product gas 1056. OCM product gas condensate 1054 is directed to first separator 1006, and at least a portion 1058 of compressed OCM product gas 1056 may be introduced to one or more turboexpanders 1014. Isentropic expansion of compressed OCM product gas 1058 within turboexpander 1014 may produce axial work used to drive one or more compressors or other devices in separation unit 1004. Isentropic expansion of compressed OCM product gas 1058 within the turboexpander reduces the temperature of compressed OCM product gas 1060 exiting the turboexpander or turboexpanders. Compressed OCM product gas 1060 from the one or more turboexpanders 1014 is introduced to first separator 1006.

First separator 1006 may be adapted to facilitate C₂And heavier hydrocarbon components from a gas stream comprising methane and nitrogen. For example, cryogenic distillation at relatively high temperatures may be used to promote C₂And separation of heavier hydrocarbon components from the methane and nitrogen components of the gas stream. Will be rich in C₂Is withdrawn from the first separator 1006 and a gas mixture 1074 containing mixed nitrogen and methane is also withdrawn from the first separator 1054. The nitrogen content of the nitrogen/methane containing gas mixture 1074 withdrawn from the first separator 1006 may be about 95 mol% or less; about 85 mol% or less; about 75 mol% or less; about 55 mol% or less; about 30 mol% or less. The balance of the nitrogen/methane gas mixture 1054 comprises primarily methane, along with minor amounts of hydrogen, carbon monoxide, and inert gases such as argon. The nitrogen/methane rich gas 1074 is then further cooled using a heat exchanger 1022, and the cooled nitrogen/methane containing gas 1076 is then introduced into a second separator 1008, described in more detail below.

In at least some embodiments, methane is reacted with C based thereon₂And heavier hydrocarbon components, the first separator functioning as a "demethanizer". Exemplary first separator 1006 includes a vertical distillation column operating at a sub-ambient temperature and a super-ambient pressure. In particular, the operating temperature and pressure within first separator 1006 may be determined to improve C enrichment₂Desired C in the effluent 1052₂And (4) recovering the hydrocarbon. In exemplary embodiments, the first separator 1006 may have a diameter from about-260 DEG F (-162 ℃) to about-180 DEG F (-118 ℃); about-250 ° F (-157 ℃) to about-190 ° F (-123 ℃); about-240 ° F (-151 ℃) to about-200 ° F (-129 ℃); or even from about-235 ° F (-148 ℃) to about-210 ° F (-134 ℃) and from about-150 ° F (-101 ℃) to about-50 ° F (-46 ℃); about-135 ° F (-93 ℃) to about-60 ° F (-51 ℃); from about-115 ° F (-82 ℃) to about-70 ° F (-57 ℃); or a bottom run temperature of about-100 deg.F (-73 deg.C) to about-80 deg.F (-62 deg.C). In exemplary aspects, the first separator 1006 can be at from about 30psig (205kPa) to about 130psig (900 kPa); about 40psig (275kPa) to about 115psig (790 kPa); about 50psig (345kPa) to about 95psig (655 kPa); or from about 60psig (415kPa) to about 80psig (550 kPa).

At least a portion of the C-rich stream from first separator 1006 may be elevated in one or more heat exchangers 1016, again using an externally provided heat exchange medium, introducing or in thermal contact with a hotter process stream, or a combination of these, or other heating systems₂The temperature of the effluent 1052. The one or more heat exchanger devices 1016 may include any type of heat exchange device or system, including, but not limited to, one or more flat plates and frames, shell and tube, or similar heat exchange systems. After exiting the one or more heat exchangers 1016, the heated C-rich₂The temperature of the effluent 1052 may be 50 ° F (10 ℃) or less; 25 ℃ F (-4 ℃ C.) or less; about 0 ° F (-18 ℃) or less; about-25 ° F (-32 ℃) or less; or about-50 deg.F (-46 deg.C) or less. Further, the pressure may be about 130psig (900kPa) or less; about 115psig (790kPa) or less; about 100psig (690kPa) or less; or about 80psig (550kPa) or less.

In some embodiments, one or more heat exchangers 1018 may be used to cool a portion 1062 of OCM product gas 1056 removed from knockout 1012 and not introduced into one or more turboexpanders 1014. As mentioned above, the heat exchanger may comprise any type of heat exchanger suitable for operation. One or more refrigerants, one or more relatively cold process streams, or a combination of these may be used to reduce the temperature of a portion 1062 of OCM product gas 1056. The cooled portion 1064 of the OCM product gas 1056 containing the mixture of nitrogen and methane is introduced into the second separator 1008.

Second separator 1008 may include any system, device, or combination of systems and devices suitable for separating methane from nitrogen. For example, cryogenic distillation at relatively low temperatures may be used to facilitate the separation of liquid methane from gaseous nitrogen within second separator 1008. Exemplary second separator 1008 may include another vertical distillation column that operates at a temperature significantly below ambient temperature and above ambient pressure, and also typically below the temperature at which the cryogenic distillation column operates as, for example, the first separator as described above. For example, the second separator 1008 can have a temperature range from about-340 ° F (-210 ℃) to about-240 ° F (-151 ℃); from about-330 ° F (-201 ℃) to about-250 ° F (-157 ℃); about-320 ° F (-196 ℃) to about-260 ° F (-162 ℃); about-310 ° F (-190 ℃) to about-270 ° F (-168 ℃); or a top operating temperature of about 300 DEG F (-184 ℃) to about-280 DEG F (-173 ℃); and from about-280 ° F (-173 ℃) to about-170 ° F (112 ℃); about-270 ℃ F (-168 ℃) to about-180 ℃ F (-118 ℃); about-260 ° F (-162 ℃) to about-190 ° F (-123 ℃); about-250 ° F (-159 ℃) to about-200 ° F (-129 ℃); or a bottom operating temperature of about-240 deg.F (-151 deg.C) to about-210 deg.F (-134 deg.C). In exemplary embodiments, the second separator 1008 will typically be at about 85psig (585kPa) or less; about 70psig (480kPa) or less; about 55psig (380kPa) or less; or about 40psig (275kPa) or less.

One or more heat exchangers 1020, as described above, may be used to raise the temperature of at least a portion of the methane-rich effluent 1066 from the second separator 1008. After exiting the one or more heat exchangers 1020, in exemplary embodiments, the methane-rich effluent 1066 may have a temperature of about 125 ° F (52 ℃) or less; about 100 ° F (38 ℃) or less; or about 90F (32 c) or less and the pressure of the effluent 1066 can be about 150psig (1035kPa) or less; about 100psig (690kPa) or less, or about 50psig (345kPa) or less. In one embodiment, such as illustrated in fig. 10, at least a portion of methane-rich effluent 1066 may be recycled back into feed gas 1068 for OCM reactor 1002, feed gas/oxygen mixture 1070, compressed oxygen-containing gas 1072 (from compressor 1028), or directly into one or more OCM reactors 1002.

One or more heat exchangers 1024 as described above can be used to raise the temperature of at least a portion of the nitrogen-rich effluent 1068 from the second separator 1008 so that the temperature can be raised to about 125 ° F (52 ℃) or less; 100 ℃ F. (38 ℃ C.) or less; or about 90F (32 ℃ C.) or less at a pressure of about 150psig (1035kPa) or less; about 100psig (690kPa) or less; or about 50psig (345kPa or less.

It is to be appreciated that while one or more of the heat exchangers 1010, 1016, 1018, 1020, 1022, and 1024 are shown as separate heat exchange devices when integrating an overall system, such heat exchangers can be integrated into one or more integrated systems, wherein process streams of different temperatures can be provided in thermal contact within the heat exchange devices or systems, e.g., as heat exchange media with one another. In particular, a cooled process stream that is desired to be heated can be passed through a portion of the heat exchanger opposite a heated process stream that is desired to be cooled, such that heat from the heated stream heats the cooler stream and thus cools itself.

Then, the processes are allowed to proceed (e.g., rich in C)₂In the effluent 1052) is subjected to additional processing to obtain the desired high hydrocarbon composition. For ease of discussion, the processes and systems for converting ethylene to higher hydrocarbons are generally referred to as ethylene conversion processes and systems. Many exemplary processes for ethylene conversion are described in more detail herein.

Integration of ETL with Hydrocarbon Processes

The conversion of methane to ethylene and the conversion of ethylene to higher hydrocarbon compositions can be performed in an integrated process. In some cases, the conversion of ethylene to higher hydrocarbons is carried out without the conversion of methane to ethylene. As used herein, an integrated process refers to two or more processes or systems that are fluidically integrated or coupled together. Thus, the process for the conversion of methane to ethylene may be fluidly coupled with one or more processes for the conversion of ethylene to one or more higher hydrocarbon compounds. Fluid integration or fluid coupling generally refers to a permanent fluid connection or fluid coupling between two systems within an overall system or facility. Such permanent fluid communication generally refers to an interconnected network of pipes coupling one system with another. Such interconnecting piping may also contain other elements between two systems, such as control elements, e.g., heat exchangers, pumps, valves, compressors, turboexpanders, sensors, and other fluid or gas transmission and/or storage systems, e.g., piping, manifolds, storage vessels, etc., but which are typically completely enclosed systems, as opposed to two systems where materials are transported from one to another by any non-integrated component, such as rail car or truck transport, or systems that are not co-located in the same facility or in closely adjacent facilities. As used herein, a fluid connection and/or fluid coupling includes a complete fluid coupling, for example, where all of the effluent from a given point, e.g., a reactor outlet, is directed to the inlet of another unit in fluid connection with the reactor. Such a fluid connection or coupling also includes a partial connection, for example, where only a portion of the effluent from a given first cell is routed into the fluidly connected second cell. Further, while described with respect to fluid connections, it will be understood that such connections include connections for transporting either or both of a liquid and/or a gas.

In some cases, the methane to ethylene conversion process is integrated not only with a single ethylene conversion process, but with multiple (i.e., two or more) different ethylene conversion processes or systems. In particular, a plurality of different ethylene conversion processes may be employed to convert ethylene produced from a single methane feed stream into a plurality of different products. For example, in some embodiments, a single OCM reactor system is fluidly coupled to one, two, three, four, five, or more different catalytic or other reactor systems for further converting the ethylene-containing product of the OCM reactor system (also referred to herein as "ethylene product") into a plurality of different higher hydrocarbon compositions.

In some aspects, the ethylene product is selectively directed, in whole or in part, to any one or more of a plurality of ethylene conversion processes or systems integrated with the OCM reactor system. For example, at a given time, all of the ethylene product produced by an OCM reactor system may be routed through a single process. Alternatively, a portion of the ethylene product may be routed through a first ethylene conversion process or system, while some or all of the remaining ethylene product is routed through one, two, three, four, or more different ethylene conversion systems.

Although described in terms of directing ethylene streams to single or multiple different ethylene conversion processes, in some aspects those ethylene streams may be relatively dilute ethylene streams containing, for example, other components in addition to ethylene, such as other products of the OCM reaction, unreacted feed gas, or other byproducts. Typically, such other components may include other reaction products, unreacted feed gas, or other reactor effluents from an ethylene production process (e.g., OCM), such as methane, ethane, propane, propylene, CO₂、O₂、N₂、H₂And/or water. The use of dilute ethylene streams, particularly dilute ethylene streams containing other hydrocarbon components, can be particularly advantageous in ethylene conversion processes. In particular, because these ethylene conversion processes may utilize more dilute and less pure streams, the incoming ethylene stream may not need to undergo as severe a separation process as may be required by other processes intended to produce higher purity ethylene (e.g., separation processes based on cryogenic separation systems, lean oil separators, TSA, and PSA). These separation processes typically have relatively high capital costs, the scale of which depends at least in part on the volume of the incoming gas. Thus, the separation process for a highly diluted ethylene stream may have significant capital and operating costs associated therewith. By providing less stringent separation requirements for these ethylene streams, capital costs can be greatly reduced. Furthermore, because the ethylene conversion process used in connection with the present invention typically results in the production of the desired liquid hydrocarbons, the separation of the gas co-product or unreacted feed gas is much simpler.

In addition to reducing capital and operating costs, the use of ethylene streams containing other hydrocarbon components may also increase the product slate from the ethylene conversion process through which those ethylene streams are routed. In particular, higher hydrocarbonsC₃、C₄、C₅The presence of such in the ethylene stream entering the ethylene conversion process can improve the overall efficiency of those processes by providing enriched raw materials, and also affect the overall carbon efficiency of the OCM and ethylene conversion processes by ensuring that a greater portion of the carbon input is converted to higher hydrocarbon products.

Although the ethylene stream routed to the ethylene conversion process of the present invention may vary in the range of trace concentrations of ethylene to substantially pure or pure ethylene (e.g., near 100% ethylene), the dilute ethylene stream described herein may generally be characterized as having, among other components, varying from about 1% to about 50% ethylene, preferably from about 5% to about 25% ethylene, and in further preferred aspects, from 10% to about 25% ethylene. In other embodiments, the ethylene feed gas comprises less than about 5% ethylene, for example, less than about 4%, less than about 3%, less than about 2%, or even less than about 1% ethylene. In some embodiments, the dilute ethylene product gas employed in the ethylene conversion process further comprises one or more gases produced during the OCM reaction or unreacted during the OCM process. For example, in some embodiments, the product gas comprises ethylene in any of the above concentrations, and is selected from CO₂、CO、H₂、H₂O、C₂H₆、CH₄And C₃₊One or more gases of hydrocarbons. In some embodiments, such dilute ethylene feed gases, optionally comprising one or more of the above gases, are advantageous for use in reactions comprising the conversion of ethylene to higher olefins and/or saturated hydrocarbons (e.g., the conversion of ethylene to liquid fuels such as gasoline diesel or jet fuel with higher efficiencies than previously available (e.g., from methane)).

By feeding one or more ethylene conversion processes with a dilute ethylene stream, the need for ethylene separation or purification, e.g., entering the OCM reaction process as a product of the process, can be eliminated. The elimination of additional costly process steps is particularly useful when the ethylene conversion process is used to produce low-margin products such as gasoline, diesel or jet fuel or blended feedstocks for such fuels. In particular, OCM may be used when the desired product is a low value productThe feed gas is passed directly to one or more ethylene conversion processes that produce a hydrocarbon mixture that can be used as a feedstock for gasoline, diesel fuel, or jet fuel, or blends thereof. Such direct transfer can be carried out without any intermediate purification step such as any process for removing the above-mentioned impurities. Alternatively, it may include a separation step for some or all of the non-hydrocarbon impurities (e.g., N)₂、CO₂、CO、H₂Etc.) are used. Direct transfer avoids any fractionation of hydrocarbons, including C₁、C₂、C₃、C₄The removal of any of the compounds, or for example it may include some fractionation to improve carbon efficiency. For example, the fractionation so included may include separation of methane and/or ethane from the OCM effluent gas for recycle back to the OCM process. In addition to the above, other components such as CO₂、H₂O and H₂The presence in the feed stream can also be expected to improve catalyst life in the ethylene conversion process by reducing deactivation, thereby requiring fewer catalyst regeneration cycles.

Conversely, when it is desired to produce more selective pure compounds such as aromatics, pretreatment of the feed gas may be required to remove many impurities other than ethylene.

Other components of these dilute ethylene streams may include co-products of ethylene production processes, such as OCM reactions, e.g., other C₂₊Compounds such as ethane, propane, propylene, butane, pentane and larger hydrocarbons, and other products such as CO, CO₂、H₂、H₂O、N₂And the like.

A variety of different ethylene conversion processes can be employed in various aspects of the present invention to produce higher hydrocarbon materials for use in, for example, chemical manufacturing, polymer production, fuel production, and various other products. In particular, ethylene produced using an OCM process can be oligomerized and/or reacted through a variety of different processes and reactor systems for producing Linear Alpha Olefins (LAOs), olefinic linear and/or branched hydrocarbons, saturated and/or olefinic cyclic hydrocarbons, aromatic hydrocarbons, oxygenated hydrocarbons, halogenated hydrocarbons, alkylated aromatic hydrocarbons and/or hydrocarbon polymers.

In some cases, an ETL subsystem configured to perform an ethylene conversion process (e.g., oligomerization reaction) may be located between two OCM subsystems. The first OCM subsystem produces a first OCM effluent comprising ethylene and other olefins (e.g., propylene). The first OCM effluent may be fed to an ETL subsystem, where olefins (e.g., ethylene, propylene) are oligomerized and converted to higher hydrocarbon products. These higher hydrocarbon oligomerization products can be recovered from the ETL effluent. The ETL effluent can be fed to a second OCM subsystem, where unreacted methane can be converted to ethylene and other olefins (e.g., propylene) in the second OCM process. C₂And C₃Reduction of the content of compound in the second OCM feed stream (due to C)₂And C₃Consumption of compound during ETL or oligomerization) can lead to a reduction in OCM side reactions and C in the second OCM subsystem₂The selectivity is increased. The effluent from the second OCM subsystem may be processed in a variety of ways, including by separation in a separation system (e.g., a 3-way cryogenic separation system). Separation systems can be used to recover methane, olefin products (e.g., ethylene, propylene), and gases such as N that can be recycled to the first or second OCM system₂CO and H₂。

The ETL process can result in products such as C₃And C₄Products, including olefins. These lower olefins can be oligomerized into high value products rather than being burned off or used for fuel value. Can be combined with C₃Olefin, C₄Olefins or combinations thereof are recovered from the ETL product stream as a lower olefin fraction. The lower olefin fraction may be reacted in a separate oligomerization reactor to produce higher molecular weight olefins, such as at C₆To C₁₆Those within the range. The molecular weight range of the oligomerisation product can be adjusted by appropriate selection of the catalyst and the process parameters. This approach provides the benefit of increasing the yield of higher molecular weight products, including non-aromatic and mostly olefinic products. This oligomerization process may result in less or no coke formation or other deactivation mechanisms. The oligomerization process can be operated at a temperature of at least about 50 ℃. The oligomerization process can be up to aboutRun at a temperature of 200 ℃. The oligomerization process can be operated at a temperature of about 50 ℃ to about 200 ℃. Oligomerization catalysts useful for this process include strong Lewis acid catalysts, AlCl₃Aqueous solutions, solid super acids, and other solid acid catalysts capable of oligomerizing C3 and C4 olefins. The C4 olefin in the process can also be used in the alkylation process to produce isooctane. Reactor configurations useful for the process include slurry beds, fixed bed, tubular/isothermal, moving bed, and fluidized bed reactors, including those disclosed herein (e.g., fig. 4).

The OCM process, ETL process, and combinations thereof (e.g., OCM-ETL) can result in methane (e.g., unreacted methane), ethane, and C₃₊A non-olefinic hydrocarbon compound. These compounds (e.g., methane, ethane, propane, and combinations thereof) can be converted to aromatic hydrocarbons. For example, excess methane and ethane from the OCM process may be converted to aromatics by using a catalyst suitable for ETL, such as those discussed in this disclosure. Such catalysts may be doped with compounds including, but not limited to, molybdenum (Mo), gallium (Ga), tungsten (W), and combinations thereof. These conversions to aromatic products may occur in the ETL reactor as described, and may also involve the conversion of ethylene to aromatic products.

Integration of ETL and/or OCM-ETL with hydrocarbon processes

The present disclosure provides a method for integrating an ETL subsystem (or module) with an OCM subsystem. Such integration may advantageously enable the formation of products that may be suitable for various uses, such as, for example, fuels. Such integration may result in C from the OCM reactor₂₊The ethylene in the product stream can be converted to higher molecular weight hydrocarbons.

The OCM, ETL, and OCM-ETL methods and systems of the present disclosure may be used in the environment of green (greenfield) and brown (brown field) zones. For example, in a brown zone investment initiative, the OCM-ETL system may be installed in an old oil refinery. As another example, in green zone investment initiatives, the OCM-ETL system may be installed in a new lot with natural gas access. Brown and green zone initiatives for OCM can be used to achieve world-scale ethylene production.

The present disclosure may be used to form ethylene for various uses such as Liquefied Natural Gas (LNG) integration. As is made possible by cooling from vapor to liquid, Liquefied Natural Gas (LNG) can be used to simplify the transportation of natural gas with a reduction in its volume of at least about 100x, 200x, 300x, 400x, 500x, or 600 x. An LNG facility may include several main process zones, gas treatment zones, in which acid gases, water and mercury of the natural gas are removed; an NGL extraction zone; an NGL fractionation zone; and LNG liquefaction and storage areas. C from crude natural gas₄₊The product is typically recovered in a fractionation zone.

Significant capital reduction and improved hybrid C can be achieved by integrating OCM/ETL process trains into traditional LNG facilities₄And C₅₊Yield. The OCM-ETL process can be added to the LNG facility such that it utilizes a portion of the main gas stream that has been passed through gas treatment and NGL extraction. The additional feed to the column-bed reactor section of the OCM may include ethane and propane, both fed from the high purity stream produced in the NGL fractionation zone. The additional C blend produced can be recovered by using the available capacity in the NGL fractionation process zone₄And C₅₊And (3) obtaining the product. The C is₄And C₅₊The product may be referred to as "SBOB" and may be any composition that is similar to RBOB but does not meet one or more ASTM standards.

Alternatively, the process may utilize the above-described gas streams (main gas stream from the fractionation zone, ethane and propane) in addition to the dilute methane-containing stream produced by the nitrogen rejection unit in the LNG liquefaction zone. The LNG plant may use this stream as a low BTU fuel gas for internal energy generation. The product gas from the OCM-ETL process zone can be fed back to the pre-cooling section of NGL extraction, thereby enabling proper C extraction₃₊The components and generate low BTU fuel gas. Blended C can be recovered by using the available capacity in the NGL fraction process zone₄And C₅₊(SBOB) product.

In one example, the OCM-ETL process zone may include an OCM reaction and heat recovery zone, process gas compression, ETL guard bed, and reaction section. The flow generated in the OCM heat recovery zone can be efficiently used in the refrigeration compressor zone to reduce external power usage.

The OCM-ETL system may be integrated with the LNG facility. To meet LNG specifications, any Heavy Hydrocarbons (HHCs) (e.g., butanes, pentanes, and higher molecular weight) in the natural gas stream may be removed. However, in the case of natural gas drying, it may be difficult to remove the HHC. Thus, LNG plants may require some HHC removal process. In one example, the liquid from the ETL system can be extracted in a pre-cooling process section of the LNG plant, which requires little additional investment. This may eliminate any other NGL recovery systems that may be required in a standalone OCM/ETL facility. Furthermore, a large amount of flow can be generated in the OCM/ETL system, which can be effectively used as axial work for the refrigerant compressor. Figure 11 shows an example of NGL extraction in an LNG facility. The front end NGL extraction unit 1100 may use natural gas 1105 and separate out Natural Gas Liquids (NGL) 1110. The remaining methane 1115 may be compressed 1120 and cooled 1125 to provide Liquefied Natural Gas (LNG) 1130.

FIG. 12 shows an integrated OCM-ETL system for use in LNG production. The system includes a gas treatment unit, a downstream NGL extraction unit, a liquefaction unit, and an OCM/ETL subsystem that produces olefins such as ethylene. The direction of fluid flow is shown by the arrows. The system of FIG. 12 may provide increased C₅₊And mixing C₄And (4) yield. The system of FIG. 12 is an example of a typical gas processing plant 1200 with OCM-ETL integration. The system contains a gas treatment unit 1202 that utilizes an incoming natural gas feed stream 1201. The gas treatment unit may comprise one or more of an acid gas removal unit, a dehydration unit, a mercury removal unit, a sulfur removal unit, or other treatment unit. In some cases, the acid gas removal unit is an amine unit, a Pressure Swing Adsorption (PSA) unit, or another CO unit₂And removing the system. In some cases, the dehydration unit may be a glycol-based water removal unit, a Pressure Swing Adsorption (PSA) unit, and may include a series of separators. The mercury removal unit may include a molecular sieve or activated carbon based system. The gas processing unit may also include a Nitrogen Removal Unit (NRU). NRU may employ cryogenic processes or processes based on absorption or adsorption. The treated natural gas feed 1203 is fed to an NGL extraction unit 1204, which feeds an NGL stream1205 are separated from the condensate stream containing the heavier hydrocarbons 1210. The heavier hydrocarbon may be C₄₊A hydrocarbon. The NGL extraction units may comprise adsorption process units, cooling units (e.g., cooling by Joule Thompson expansion, methanol or glycol refrigeration, or turbo-expanders), or lean oil absorption units. A portion of stream 1205 is fed as stream 1208 to OCM-ETL reactor system 1207, where the methane contained in stream 1208 is converted to heavier liquid hydrocarbons via OCM and subsequent ETL conversion in reactor 1207. Liquid hydrocarbons are fed back to the NGL extraction units along stream 1209 to recover unconverted methane and separate the heavier condensate and pass it along stream 1210 to the NGL ETL fractionation unit 1211. The NGL ETL fractionation unit may comprise a series of fractionation tower units, including but not limited to depropanizer and debutanizer, to produce a mixed C₄Product 1214, C₅₊Product 1215. Liquefaction unit 1206 produces LNG product 1213. In this case, the advantage of integrating the OCM-ETL reactor system with existing natural gas processing facilities is envisioned to generate more valuable mixed C₄And C₅₊And (3) obtaining the product. In addition, C from the fractionation unit 1211₂And C₃The lighter hydrocarbons may be recycled to the post-bed cracking (PBC) section of the OCM reactor.

As shown in FIG. 13, the system of FIG. 12 can be modified to work with diluted C₁(methane) fuel gas streams are used together. The system 1300 of FIG. 13 includes a system for extracting C upstream of an NGL extraction unit₃₊ A pre-cooling system 1320 for the compound, and a nitrogen rejection unit 1316 downstream of the liquefaction unit. In addition to the system of fig. 12, the system in fig. 13 recycles stream 1319 to the OCM-ETL reactor system to make more use of the methane contained in the natural gas feed. Stream 1319 may contain high levels of methane and inert gases such as nitrogen. The fuel gas stream 1321 is purged from the pre-cooling section to avoid accumulation of inert gas in the system. The nitrogen rejection unit may include a cryogenic based, absorption based or adsorption based system.

Fig. 14 shows an exemplary OCM-ETL system comprising OCM and ETL subsystems, and a separation subsystem downstream of the ETL subsystem, where 1418 is a condensate water separator (knock out), 1421 is a process gas compressor,1423 is guard beds for removing impurities such as acetylene and butadiene, 1415 and 1430 are heat recovery, 1437 is a secondary gas compressor, and 1439 is a cryogenic separator. The system in fig. 14 takes in a treated natural gas feed stream 1410 and oxygen 1411 from an Air Separation Unit (ASU) or pipeline and reacts them in an OCM reactor 1413 to generate an olefin rich stream 1414, which olefin rich stream 1414 is then sent to an ETL reactor 1425 for conversion to higher hydrocarbons. The system shows various subsystems of the heat recovery system as a compressor, utilizing the high heat of reaction, to generate a stream and run the compressor on the generated stream. The system may contain any CO and CO for production₂Methanation reactor 1427 which converts back to methane, thus increasing the methane content of the sales gas. Separation subsystem 1403 may include cryogenic separator 1439 for generating lighter methane-rich components. Debutanizer 1442 separates heavy hydrocarbon condensate into C₄And C₅₊And (3) obtaining the product.

FIG. 15 shows an OCM-ETL system comprising OCM 1906 and ETL 1907 subsystems, and a cryogenic cooling box 1504 downstream of the ETL subsystems. The OCM-ETL system comprises a separation unit for separating C from ETL product leaving the ETL subsystem ₃1521 and C ₄1524 multiple separation units of components. The depropanizer 1521 produces C-rich that is recycled back to the sales gas export 1509_2-And (4) streaming. C can also be recycled via recycle stream 1522₂Recycle is added to the OCM-ETL reactor subsystem. Debutanizer to produce C₄Products 1525 and C₅₊Product 1526. Refrigeration for the cryogenic cooling tank may be provided by natural gas expansion 1502 from at least about 500PSI, 600PSI, 700PSI, 800PSI, 900PSI, 1000PSI, 1500PSI, or 2000 PSI. The system may also have a methanation reactor (not shown) to further increase the methane concentration of the sales gas product. FIG. 15 illustrates a method for different flows in a thermally integrated unit. The system may have an external refrigeration system for providing the low temperature requirements of the unit.

FIG. 16 shows another OCM-ETL that is an alternative configuration to the system shown in FIG. 14. This system allows for recycling of multiple streams to the OCM reactor to improve overall conversion. A methane-rich stream 1648 from the cryogenic separation unit 1437 and a stream fromC-rich of deethanizer 1619₂ Stream 1412 is recycled to sales gas compressor 1617 and OCM reactor 1413, respectively. The incoming natural gas feed 1610 is treated in a processing unit 1611 (to remove one or more of sulfur, mercury, water, or other components) and then sent to a cryogenic unit 1613 to separate the heavier NGL liquids 1614 that will be fed to the deethanizer 1619. Deethanizer 1619 will mix lighter LNG product 1620 with heavier C₂₊The stream 1412 separates. After the low temperature unit, the feed of OCM is withdrawn. In the system of FIGS. 14 and 15, the separation subsystem generates C₄And C₅₊And (3) obtaining the product.

It may be noted that the systems of fig. 14, 15, and 16 may be integrated with existing gas processing facilities that may utilize one or more existing subsystems. This utilization may result from the fact that the existing subsystem is no longer used or has extra capacity available to allow integration.

The OCM-ETL system of the present disclosure can be integrated and incorporated into the conventional NGL extraction and NGL fractionation sections of a midstream gas facility. Deployment of OCM-ETL can take advantage of existing facilities to generate additional liquid streams when NGL in the gas stream is reduced (or the gas is dry). Implementation of OCM-ETL may allow for the generation of in-spec "pipeline gas". The products from the facility may be suitable for use as (or in compliance with specification or "spec") pipeline gas, gasoline products, Hydrocarbon (HC) streams with high aromatic content and mixed C₄And (3) obtaining the product.

The facility integrating OCM-ETL can reduce the ethane and propane product quantities to reduce pipeline (sales gas) specifications and liquid handling limitations. Utilities and off-site facilities can be effectively utilized. For example, the steam generated in the process may offset other shaft power requirements. The capacity of an OCM-ETL facility can vary and can be selected to best match a particular need.

FIGS. 17-18 show an example of OCM-ETL midstream integration. Natural gas 1701 from upstream may be fed to a gas treatment system 1702, and the treated natural gas may be fed to an NGL extraction unit 1704. In FIG. 17, C from the NGL extraction unit 1704 can be separated₂And C₃Product 1705 is directed to OCM-ETL System 1707 to generateAn olefin (e.g., ethylene) and a liquid 1709 from the olefin. Any excess or extracted methane may be directed for use as the pipeline gas 1713. C from the NGL extraction unit can be separated₄₊Hydrocarbons 1710 are directed to the NGL product fractionation unit for separation into mixed C in separation system 1711₄1714 and C₅₊1715, with lower hydrocarbons 1712 recycled to OCM-ETL system 1707. In the system 1800 of fig. 18, methane from other natural gas sources 1816 is directed to a gas conditioning unit 1817 (e.g., to remove sulfur compounds) and then to an OCM-ETL system 1707. Excess methane 1808 may be used as pipeline gas 1713, as additional feed 1806 to the OCM-ETL system, or both.

The oxygen feed to the OCM unit in the OCM-ETL system can be provided from air using, for example, an air separation unit (e.g., a cryogenic air separation unit), or from an oxygen source such as pipeline oxygen.

The OCM-ETL system provided herein can be integrated into a pipeline NG source, or as part of a new gas processing facility installation that can provide an NG source. The NG may be provided from an NG pipeline and/or a non-OCM process.

In some cases, the gas that has been depleted of recoverable hydrocarbon liquids may be recompressed to a pressure of about 700PSI to 1500PSI, or 800PSI to 1300PSI, or 900PSI to 1200PSI, and returned to the line from which the gas was originally skimmed (skimmed). Alternatively or in addition, the gas depleted in recoverable hydrocarbon liquids may be recompressed and transported downstream of the cryogenic gas processing facility as required. Alternatively or in addition, the gas depleted of recoverable hydrocarbon liquids may be sent to a power plant instead of being compressed. Alternatively or in addition, the gas depleted in recoverable hydrocarbon liquids may be recompressed and transported to an ammonia plant as needed for use as a synthesis gas mixed feedstock. Alternatively or in addition, the gas depleted of recoverable hydrocarbon liquids may be recompressed and sent to a methanol plant as needed for use as a synthesis gas feedstock blend.

FIG. 19 shows an OCM-ETL system with different skimmer and recirculation configurations, including a stand-alone skimmer (top left), a tote skimmer (bottom left), a stand-alone recirculation (top right), and a tote recirculation (bottom right). In the skimmer configuration, operation is a single pass process (feed forward movement) in which all of the feed stream exits the system as product or effluent without recirculation. In the recycle configuration, some or all of the NG feed stream is exposed to the OCM catalyst multiple times (feed moving backwards). Such a configuration may be employed in a standalone setting (where all or substantially all of the unit operations are for OCM/ETL purposes) or a hosted setting (where unit operations of existing non-OCM systems at least partially support OCM-ETL systems). The configuration of fig. 19 may be used with NG feeds of at least about 10 million cubic feet per day (mmcfd), 20mmcfd, 30mmcfd, 40mmcfd, 50mmcfd, 100mmcfd, 200mmcfd, 300mmcfd, 400mmcfd, 500mmcfd, or 1000 mmcfd.

In some cases, various separation strengths may be used for additional liquid product recovery, depending on economic considerations. In one example, the process gas remaining after the primary liquid recovery section is not further processed but returned. In another example, the process gas remaining after primary liquid recovery is fed to a cryogenic separator (LTS) unit, where additional hydrocarbon liquid, such as C₄₊Is recovered. The effluent gas from the LTS is then returned for recycle as described elsewhere herein.

In some cases, the process gas remaining after primary liquid recovery may be fed to a cold box based cryogenic unit, where additional hydrocarbon liquids such as C₄₊Is recovered. The cold box based cryogenic unit may not employ cryogenic temperatures and may not require the conventional unit operations of a demethanizer and deethanizer. The effluent gas from the cell may then be returned as described elsewhere herein. In some cases, a debutanizer column may be installed to provide the final C₄₊Product and additional C₄RVP control of flows.

There are some situations where it may be desirable to burn off gas from a midstream gas collection and/or gas processing facility. In some cases, gas from the midstream system may be burned due to operational limitations, product gas fluctuations that may result in gas collection and limited capacity of the processing facility, feed gas conditions that may prevent the gas from being processed to meet gas specifications, and/or process gas conditions that may not allow co-processing in the gas facility.

The ETL system of the present disclosure can be integrated in a variety of existing systems, such as petroleum refineries and/or petrochemical complexes. Such integration may or may not be with an OCM system.

Petroleum refineries and/or petrochemical plants may produce significant quantities of purge and other waste gas streams that may be burned at fuel value for power generation due to the inability to further process or recover the hydrocarbons. These waste gas streams may contain mixtures of inert gases with hydrocarbons such as olefinic materials. The ETL process can be integrated into a refinery or petrochemical complex such that it consumes one or several of these olefin streams and chemically converts them into higher value oligomers, such as mixed C4 and C₅₊And (3) mixing. Many of these ETL feedstocks can be produced within a refinery.

Several examples of off-gas streams having suitable olefins include, but are not limited to, an absorber overhead gas stream containing intermediate levels of ethylene and propylene produced in the lights recovery process zone, or a deethanizer overhead stream containing similar olefins. The streams may be reacted separately or mixed as desired to meet the ETL reactor inlet gas requirements.

The ETL process may include feedstock gas treatment, process gas compression, ETL reaction, and heat recovery sections and units. If existing unit operations and capacity are available, the ETL reactor effluent can be returned to the refinery separation unit. If such capacity is unavailable, a small ETL separation subsystem may be provided to recover effluent C using a series of process-intensive separation methods₄And C₅₊Product stream: cooling water or freeze condensate recovery, sponge oil systems, and shallow-grade (shallow-grade) cryogenic units for the deepest recovery. Additional processing units may be added for further chemical recovery benefits, including membrane separation for recovering hydrogen from the ETL reactor effluent after hydrocarbon recovery.

Fig. 20-22 show various examples of ETL integration in a refinery. Such systems can employ existing fractionation systems of a refinery to achieve product separation.

Referring to FIG. 20, gas from cracking or other unit 2001 generates C in refinery gas facility 2002₃And C₄Product 2004, which is directed to ETL system 2005, which generates higher molecular weight hydrocarbons 2006, which are directed to product separation system 2007. Product separation system 2007 may employ existing separation systems of a refinery. The direction of fluid flow and separation system can be selected to achieve a given product distribution, such as C_2-Fuel gas 2008, C₃Products 2009 and C₄₊Flow 2010. The products 2013 from the fractionation unit 2011 can be processed to produce gasoline blending components 2017, and heavier products 2012 can be sent to a refinery aromatic separation unit 2016. There are ample integration/mixing opportunities in a typical refinery complex.

The system of fig. 20 can include a heat exchange ethane cracker (HXEC)2119 as shown in fig. 21. The HXEC can use heat from flue gas 2118 to crack ethane to ethylene. The HXEC may thermally crack the ethane with one or more waste heat streams (e.g., during the FCC regeneration stage) to generate an additional olefin-rich stream that is the feed to the ETL reactor. In some cases, this concept can be used to crack propane feeds to produce an olefin rich stream. For example, the removal of coke from the catalyst by combustion can generate hot flue gas, in some cases by using an integrated boiler. The flue gas can reach temperatures of 1600F (about 870 c), 1800F (about 980 c), or higher. Heat may be transferred to a stream comprising ethane, propane, or a combination thereof, for example, in a heat exchanger. This heat can be used to crack ethane to ethylene or propane to propylene. These olefin products can be used in other processes such as ETL.

As shown in FIG. 22, an OCM-ETL system can be used to retrofit a refinery gas facility 2202 that receives gas 2201 from a cracking or other unit. OCM reactor 2212 contains a post-bed cracking (PBC) unit. OCM reactor 2212 receives methane via natural gas feed 2211 and produces product stream 2213, which is directed to C₁A separator 2207 which separates methane (C)₁)2208 from the product streamIs removed to produce C₂₊Compound 2214. This methane may be recycled to OCM reactor 2210 or directed for use as refinery fuel 2209. C directed to ETL reactor 2215₂₊ Compound 2214 is used to produce higher molecular weight hydrocarbons 2216 that are directed to refinery gas facilities 2202. C from refinery gas facilities₃₊Compound 2204 is directed to production fractionation system 2217 for separation. The system of fig. 22 may include a HXEC 2223 coupled to the ETL reactor 2215. The HXEC can convert ethane 2222 to ethylene 2224, which can then be directed to ETL reactor 2215. In some cases, HXEC is excluded.

Integration of the ETL system into a refinery or petrochemical facility may include a cracker and in some cases is done without an OCM. This may allow, for example, polymer grade ethylene to be converted to gasoline.

With respect to the above disclosure regarding the systems described in fig. 17, 18, 19, 20, 21, and 22, it should be noted that these descriptions are illustrative and not limited to the concepts and configurations presented. One or more of the following may additionally be integrated into systems such as those described: methanation reactors, ethane skimmers, and various heat integration configurations and optimizations based on refinery configuration, product demand, and economics. The ETL reactor system, including the OCM-ETL reactor system, can be a general purpose system with a wide range of configurations for achieving economic value from refinery flue gas, exhaust gas, and other natural gas feeds.

Integration of Ethylene To Liquids (ETL) with natural gas processing

One aspect of the present disclosure provides systems and methods for olefin to liquid. The olefin-to-liquid process may be integrated in a non-OCM process such as a Natural Gas Liquids (NGL) system. The olefin to liquid process may be an Ethylene To Liquid (ETL) process. As described elsewhere herein, the ETL process can be part of an OCM system that can be derived from methane and an oxidant (e.g., O)₂) To produce olefins (e.g., ethylene). The olefins may be used as a feedstock to one or more ETL reactors for converting the olefins to higher molecular weight hydrocarbons, which may be in liquid form.

Natural gas processing is typically a complex industrial process for producing pipeline quality dry natural gas by separating impurities and various non-methane hydrocarbons as well as fluids to clean crude natural gas. Most of the extracted natural gas may contain low molecular weight hydrocarbon compounds to varying degrees. Examples of such compounds include methane (CH)₄) Ethane (C)₂H₆) Propane (C)₃H₈) And butane (C)₄H₁₀). When brought to the surface and processed into a purified, finished by-product, all of these are collectively referred to as NGLs.

Natural gas processing facilities can remove common contaminants such as water, carbon dioxide (CO)₂) And hydrogen sulfide (H)₂S) purifying the crude natural gas from (a) the underground gas field and/or (b) the gas at the wellhead associated with the natural gas. Some of the material that contaminates natural gas is of economic value and is therefore further processed or sold. A fully operational facility can provide pipeline quality dry natural gas that can be used as fuel by residential, commercial, and industrial consumers.

In some embodiments, existing NGL processing and/or fractionation systems can be integrated with OCM and ETL processes to produce various hydrocarbons (which can be liquids), such as alkanes, alkenes, alkynes, alkoxides, aldehydes, ketones, acids (e.g., carboxylic acids), aromatics, alkanes, isoparaffins, higher alkenes, oligomers, or polymers. In some examples, such hydrocarbons include Liquefied Petroleum Gas (LPG), oxygen blended reformed gasoline blendstocks (RBOB), and/or gasoline (e.g., natural gasoline or premium gasoline), and/or other hydrocarbon blendstocks (e.g., condensates or diluents) that are typically fed to a refinery or blending terminal. LPG may contain propane and butane and may be used as a fuel in heating appliances and vehicles.

ETLs can be used to generate hydrocarbons for various end uses, such as gasoline for machinery (e.g., automobiles and aircraft). For example, the product of the ETL process of the present disclosure can be used as a gasoline or jet fuel blendstock. In some examples, ETL can be used to produce benzene, toluene, ethylbenzene, and xylenes (BTEX).

The ETL-gasoline process may have a heat of reaction from about 80KJ/mol to 100 KJ/mol. The adiabatic ETL reactor can have an inlet temperature of at least about 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃,350 ℃, 360 ℃, 370 ℃,380 ℃, 390 ℃,400 ℃ or 500 ℃. In the reactor, the temperature may be raised by at least about 50 ℃ to 150 ℃,60 ℃ to 120 ℃, or 75 ℃ to 100 ℃, and the process pressure may be increased by at least about 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 20 bar, 30 bar, 40 bar, or 50 bar (absolute).

In some cases, the primary product exiting the ETL reactor is an olefin, such as pentene, hexene, or heptene. However, other secondary products are possible, such as aromatics and paraffins. In one example, the ETL product has a liquid distribution that is selective for C5-C10 hydrocarbons with relatively low levels of benzene and durene. This product can be used as gasoline. In another example, the ETL product has a liquid distribution selective for BTEX.

In some examples, a crude Natural Gas (NG) feedstock may be directed to an OCM-ETL system to generate C for the production of higher molecular weight hydrocarbons (such as the hydrocarbon products described in the context of FIG. 1)₂₊A compound is provided. Such hydrocarbon products can be further processed for various end uses. For example, the hydrocarbon product may comprise a component of gasoline, and may be combined with ethanol for use as an automotive fuel.

The OCM-ETL system of the present disclosure can be integrated with NGL systems to produce NGLs and premium gasoline, as well as NGLs associated with a natural gas feed or any other hydrocarbon gas feedstock. In some examples, NGL processing and/or fractionation or midstream gas facilities or systems may be integrated with OCM reactor systems, ETL reactor systems, separation units, compression units, methanation units, and/or other processing units such as those described in U.S. patent application No. 14/099,614 filed on 12/6/2013, which is hereby incorporated by reference in its entirety.

The OCM-ETL system of the present disclosure may advantageously enable existing NGL processing systems to be retrofitted for producing various hydrocarbons in an efficient and economical manner as compared to other systems currently available. In some examples, existing NGL processing and/or fractionation facilities are integrated with the OCM-ETL systems provided herein, in addition to other systems that may be needed for further processing. Integration of OCM-ETL with NGL processing can include recycle separation steam (RSV), Gas Subcooling Process (GSP) processes, or modification of any gas processing technology. The OCM-ETL facility may contain other systems that may be needed for further processing. Existing NGL systems can be retrofitted with the OCM-ETL systems provided herein and configured, for example, to achieve a given product distribution and/or yield. Such integration may take into account excess or full capacity of existing NGL processing facilities to reduce capital investment and operating expenses for the retrofit. The OCM-ETL system can be designed to accommodate any excess capacity of the NGL processing facility, or to accommodate an NGL facility operating as an OCM/ETL facility at maximum capacity. The feed (or input) to the OCM-ETL can be a quantity of fresh natural gas, residue gas, or sales gas (sales gas and pipeline gas refer to the same natural gas meaning pipeline specifications) that meets the OCM inlet gas specifications and excess capacity of the NGL facility. A necessary amount of oxidant (e.g., air or oxygen) may be used in the OCM reactor of the OCM-ETL system.

In some examples, the amount of NGL product from an OCM-ETL system of the present disclosure is at least about 0.3, 0.5, 0.1, 1, 1.5, 2, 3,4, 5,6, 7,8, 9, or 10 gallons per 1000 Standard Cubic Feet (SCF) of inlet gas of inlet natural gas. In some cases, the amount of NGL product from an OCM-ETL system of the present disclosure is at least about 0.3, at least about 0.5, at least about 0.1, at least about 1, at least about 1.5, at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9, or at least about 10 gallons per 1000 Standard Cubic Feet (SCF) of inlet gas of inlet natural gas. In some cases, the amount of NGL product from an OCM-ETL system of the present disclosure is at most about 0.3, at most about 0.5, at most about 0.1, at most about 1, at most about 1.5, at most about 2, at most about 3, at most about 4, at most about 5, at most about 6, at most about 7, at most about 8, at most about 9, or at most about 10 gallons per 1000 Standard Cubic Feet (SCF) of inlet gas of inlet natural gas. In some cases, the amount of NGL product from the OCM-ETL system of the present disclosure is in the range of 0.8 gallons to 1.5 gallons per 1000 Standard Cubic Feet (SCF) of inlet gas of inlet natural gas.

Fig. 23A shows the NGL process. The NGL system comprises a raw natural gas feedstream 2301, an NGL system 2302, and a product stream 2303. In addition to other chemicals (e.g., H)₂O、CO₂And H₂S), the raw natural gas feedstream 2301 also comprises methane (CH)₄). The NGL system 2302 can include various processing equipment for refining the feed stream 2301 to produce a product stream 2303, where the product stream includes one or more hydrocarbon products, such as methane, ethane, propane, and/or butane. Such processing equipment may include a separation unit, such as a distillation column. In some examples, product stream 2303 comprises methane at a higher concentration (or purity) than feed stream 2301. Product stream 2303 can be directed to a natural gas pipeline to distribute natural gas to end users.

In fig. 23B, the NGL process of fig. 23A has been retrofitted with the OCM-ETL system of the present disclosure. Fig. 23B shows a feed stream 2301 directed to an NGL system 2304. NGL system 2304 may include at least a portion or all of the equipment of NGL system 2302 described in the context of fig. 23A. In one example, NGL system 2304 is NGL system 2302. NGL system 2304 produces product stream 2303 and additional product stream 2305. Additional product stream 2305 is directed to OCM-ETL system 2306. OCM-ETL System 2306 Generation may include C₂₊Product stream 2307 of compounds. In some examples, the product stream comprises C₃-C₁₂A hydrocarbon.

Although FIG. 23B illustrates an NGL process retrofitted with an OCM-ETL system, other non-OCM processes may be retrofitted with an OCM-ETL system. For example, the OCM-ETL system may be integrated in a refinery and the products from the crude oil refining may be directed to the OCM-ETL system for further processing.

FIG. 24 shows a system 2400 that includes an existing gas plant 2401 that has been retrofitted with an OCM-ETL system 2402. The OCM-ETL system 2402 can be used with ethylene or other olefins. Crude Natural Gas (NG) feed 2403 is directed to a process unit 2404 comprising, an NGL extraction unit2405. Compression unit 2406 and fractionation unit 2407 in an existing gas plant 2401. The NGL extraction unit 2405 can be a demethanization unit, optionally combined with a recycle split steam (RSV) modification or a separate unit. Treatment unit 2404 mixes water and CO₂Is removed from NG feed 2403 and the natural gas is directed to NGL extraction unit 2405. In some cases, the processing unit removes sulfur from the NG feed. NGL extraction unit 2405 extracts methane, ethane, CO₂And N₂Remove from NG feed 2403 and stream 2408 methane, ethane, CO₂And N₂To the compression unit 2406. At least a portion of the methane from fluid stream 2408 is directed along stream 2409 to OCM reactor 2410 of OCM-ETL system 2402. Compression unit 2406 compresses the methane in fluid stream 2408 and directs the compressed methane to natural gas pipeline 2411 for distribution of the methane to end users.

With continued reference to fig. 24, compounds from the NGL extraction unit 2405 can be directed to a fractionation unit 2407, which can be a distillation column. Fractionating unit 2407 separates C₂₊The compounds being divided to contain different C₂₊Streams of compounds, e.g. C₂Flows 2412 and C ₃ 2423、C₄And C₅And (4) streaming. Can be combined with C₂Flows 2412 and/or C₃Stream 2423 is directed to a post-bed cracking (PBC) unit 2413 of OCM-ETL system 2402. In some cases, C may be₃、C₄And/or C₄₊The compound is directed to the PBC unit. An example of post-bed cracking is described in U.S. patent application serial No. 14/553,795, filed on 25/11/2014, which is incorporated herein by reference in its entirety.

In OCM-ETL system 2402, methane and air 2414 from stream 2409 are directed to OCM reactor 2410. As discussed elsewhere herein, OCM reactor 2410 produces a product comprising C during OCM₂₊OCM product stream of compounds. C in product stream₂₊Alkanes (e.g. ethane) and C₂C in stream 2412₂Alkanes may be cracked to C in a post-bed cracking (PBC) unit 2413 (which may be a downstream component of OCM reactor 2410)₂₊An olefin (e.g., ethylene). The product stream is then directed to remove water from the streamCondenser 2415 removed in the product stream. The product stream is then directed to a compression unit 2416 and then to a Pressure Swing Adsorption (PSA) unit 2417. The PSA will be N₂、CO、CO₂、H₂O、H₂And some methane with C in the product stream₂₊The compound is isolated and the C is₂₊The compounds are directed to one or more ETL reactors 2418 of the OCM-ETL system 2402. May comprise nitrogen (and in some cases CH)₄、CO₂、H₂O、H₂And/or CO) stream 2424 is fed into the fuel gas stream for power generation, combustion, use as a thermal oxidizer. C directed to ETL reactor 2418₂₊The compound may comprise ethane, ethylene, propane, propylene, and methane, CO₂、H₂、N₂And water. ETL reactor 2418 produces higher molecular weight hydrocarbons, such as C₄-C₁₂(e.g., C)₄₊Or C₅₊) A compound (e.g., propane, butene, pentane, hexane, etc.). The product stream from the ETL reactor 2418 is directed to another compression unit 2419 and then to a vapor-liquid separator (or knockout) 2420 that directs the liquid (e.g., C)₅₊Compound) is separated from the vapor (e.g., methane) of the product stream and provided to contain C₅₊Product stream 2421 of compounds. The remaining compounds, including steam (e.g., methane), are recycled along recycle stream 2422 to feed stream 2403. Methane directed along flow 2422 may be directed to OCM reactor 2410 for further C₂₊And (4) generating a product.

The OCM-ETL 2402 system may comprise one or more OCM reactors 2410. For example, OCM reactor 2410 may be an OCM reactor train comprising a plurality of OCM reactors. In addition, or alternatively, the OCM-ETL system 2402 can include one or more ETL reactors 2418. For example, the ETL reactor 2418 can be a plurality of ETL reactors in parallel, where each ETL reactor is configured to generate a given hydrocarbon (see, e.g., fig. 1). In some cases, C may be₃And/or C₄Compounds are withdrawn from the fractionator and fed to a region further downstream of the post-bed cracking (PBC) reactor for olefin production.

Compression units 2406, 2416, and 2419 may each be a multi-stage gas compression unit. Each stage of such a multi-stage gas compression unit may be followed by cooling and liquid hydrocarbon and water removal.

OCM-ETL system 2402 may operate with other oxidants, such as previously separated O₂E.g. O from pipelines or as a product of an Air Separation Unit (ASU)₂. In the alternative configuration of FIG. 25, O₂Feed stream 414 is directed to OCM reactor 2410. For example, separation of air into fractions containing O may be used₂And N₂A separate gas stream cryogenic gas separation unit (not shown) to produce O₂Feed stream 2514. The system of FIG. 25 further comprises passing CO, CO from the vapor-liquid separator₂And H₂A methanation system 2523 (see below) to methane, where the methane may be recycled along stream 2422.

In this figure, the direction of fluid flow between the cells is indicated by the arrows. Fluid can be directed from one unit to another with the aid of valves and fluid flow systems. As described elsewhere herein, in some examples, a fluid flow system may include a compressor and/or a pump and a control system for regulating fluid flow.

Methanation system

Oxidative Coupling of Methane (OCM) is a process that can convert natural gas (or methane) into ethylene and other longer hydrocarbon molecules via the reaction of methane with oxygen. In view of the operating conditions of OCM, side reactions may include reforming and combustion, which may result in significant amounts of H being present in the exhaust stream₂CO and CO₂. Typical H in the effluent stream₂The content may range from about 5% to about 15%, from about 1% to about 15%, from about 5% to about 10%, or from about 1% to about 5% (by mole). CO and CO₂May each be in the range of about 1% to about 5%, about 1% to about 3%, or about 3% to about 5% (by moles). In some cases, the ethylene and all other longer hydrocarbon molecules contained in the effluent stream are separated and purified to yield the final product of the process. This may leave a gas mixture containing unconverted methane, hydrogen, CO and CO₂And a plurality ofAn effluent stream of other compounds, including small amounts of the product itself depending on its recovery.

In some cases, this effluent stream needs to be recycled to the OCM reactor. However, if CO and H₂Recycled with methane to the OCM reactor, they can be reacted with oxygen to produce CO₂And H₂O, have various negative consequences for the process including, but not limited to: (a) increased natural gas feed consumption (e.g., because a larger portion thereof can lead to CO)₂Formation rather than product formation); (b) OCM single pass methane conversion is reduced (e.g., because a portion of the allowable adiabatic temperature rise may be driven by H)₂And CO combustion reaction rather than OCM reaction); and increased oxygen consumption (e.g., because some oxygen feed may be with CO and H)₂React instead of with methane).

In some cases, the effluent stream is exported to a natural gas pipeline (i.e., to be sold as a sales gas to a natural gas infrastructure). Given that the specifications of natural gas pipelines may be fixed (in place), it may be desirable to reduce H in the effluent₂CO and CO₂To meet pipeline requirements.

In some embodiments, the effluent stream may also be used as H, which may require lower concentrations₂CO and CO₂As a feedstock for certain processes.

Thus, it may be desirable to reduce H in an OCM effluent stream upstream or downstream of final product separation and recovery₂CO and CO₂The concentration of (c). This may be done using a methanation system and/or by separating H from the vent stream₂And CO (e.g., using cryogenic separation or adsorption processes). The present disclosure also includes the use of CO₂Removal processes, such as chemical or physical adsorption or absorption or membranes, separate CO from the effluent stream₂. However, these separation processes may require a large capital investment and may be capable of consuming a significant amount of energy, in some cases making OCM-based processes economically less attractive.

Methods for reducing CO, CO in a methane stream are described herein₂And H₂Concentration ofSystems and methods of (1). The process involves reacting these compounds to form methane in a reaction known as methanation.

Can be via CO₂Removal units, e.g. amine based systems, caustic systems or any other physical or chemical adsorption or absorption units, to separate CO₂And/or sulfur-containing compounds (e.g., H)₂S). CO and H can be separated in a cryogenic separator₂Separated together with methane. If CO and H₂Recycled to the OCM reactor with methane, they can be recycled with oxygen (e.g., pure O)₂Or O in air₂) React to produce CO₂And H₂O, have various negative consequences for the process including, but not limited to: (i) increased natural gas feed consumption and C₂₊The product generation is reduced; (ii) reduced OCM single pass methane conversion; and (iii) increased oxygen consumption. In view of the presence of CO and H in the methane-containing stream₂Has the potential negative effects of reducing CO and H₂May be preferred. Furthermore, by reacting CO with H₂Conversion back to methane can increase the carbon efficiency of the process by recycling the methane to the OCM reactor or natural gas pipeline.

One aspect of the present disclosure provides a methanation system that may be used to reduce CO, CO in a given stream, such as an OCM product stream₂And H₂And improve carbon efficiency. This may advantageously recycle CO, CO in any stream that may ultimately be recycled to the OCM reactor₂And H₂Is minimized. The methanation system may be used with any system of the present disclosure, such as OCM-ETL system 302 described above.

In methanation systems, via CO +3H₂→CH₄+H₂O, CO and H₂The reaction produces methane. In the methanation system, via CO₂+4H₂→CH₄+2H₂O，CO₂Can be reacted with H₂The reaction produces methane. Such processes are exothermic and generate heat that can be used as a heat output to other process units, such as heating the OCM reactor of the PBC reactor, or preheating reactants, such as methane and/or methane, prior to the OCM reactionOxidizing agents (e.g. O)₂)。

In some cases, to limit the exotherm per unit of reactant stream, one can treat the reaction mixture containing CO, CO₂、H₂And a suitable carrier gas. The carrier gas may comprise an inert gas, e.g., N₂He or Ar, or an alkane (e.g., methane, ethane, propane, and/or butane). The carrier gas may increase the heat capacity and significantly reduce the adiabatic temperature rise caused by the methanation reaction.

In some examples, methane and higher carbon content alkanes (e.g., ethane, propane, and butane) and nitrogen may be used as carrier gases in the methanation process. These molecules may be present in an OCM process, for example, in the presence of C₂₊OCM product stream of compounds. Downstream separation units, such as cryogenic separation units, can be configured to produce a product containing CO and H₂A stream of any (or none) of these compounds in combination. This stream may then be directed to a methanation system.

The methanation system may include one or more methanation reactors and a heat exchanger. CO, CO₂And H₂May be added to the one or more methanation reactors along various streams. CO can be compressed using a compressor₂The pressure of the stream is increased to a methanation operating pressure, which may be about 2 bar (absolute) to 60 bar, or 3 bar to 30 bar. CO may be added to the inlet of the system₂So as to produce and consume all of the available H stoichiometrically₂The required amount is compared with the excess of CO₂. This was done to recycle H to OCM₂At a minimum, this may not be preferred.

In view of the exothermicity of the methanation reaction, the methanation system may include various methanation reactors for performing methanation. In some cases, the methanation reactor is an adiabatic reactor, such as an adiabatic fixed bed reactor. According to, for example, CO in the feed stream to the methanation system₂And H₂The adiabatic reactor may be one or more stages. If multiple stages are used, the effluent may be passed through a heat exchanger (e.g., the stage effluent may be directed against the feed stream or any other cooler stream available in the facility, such as boiler feedwaterCooling) or interstage cooling via cold bead (cold shots) (i.e., dividing the feed stream into multiple streams, with one stream directed to the first stage and each other feed stream mixed with each stage effluent for cooling purposes). Alternatively, or in addition, the methanation reactor may be an isothermal reactor. In such cases, the heat of reaction can be removed from the isothermal reactor by, for example, generating steam, which can result in higher concentrations of CO, CO₂And H₂Can be used with the isothermal reactor. In addition to adiabatic and isothermal reactors, other types of reactors may be used for methanation.

FIG. 26 illustrates an exemplary methanation system 2600. System 2600 includes a first reactor 2601, a second reactor 2602, and a heat exchanger 2603. The first reactor 2601 and the second reactor 2602 can be adiabatic reactors. In use, comprises methane, CO and H₂Recycle stream 2604 (e.g., from a cryogenic separation unit) is directed to heat exchanger 2603. In one example, recycle stream 2604 comprises about 65% to 90% (by moles) methane, about 5% to 15% H ₂1% to 5% CO, about 0% to 0.5% ethylene, and the balance inert gas (e.g., N)₂Ar and He). Recycle stream 2604 may have a temperature of about 20 ℃ to 30 ℃, and a pressure of about 2 bar to 60 bar (absolute) or 3 bar to 30 bar. Recycle stream 2604 can be generated by a separation unit downstream of the OCM reactor, such as a cryogenic separation unit.

In heat exchanger 2603, the temperature of recycle stream 2604 is raised to about 100 ℃ to 400 ℃, or about 200 ℃ to 300 ℃. Heated recycle stream 2604 is then directed to first reactor 2601. In the first reactor 2601, CO and H in the recycle stream 2604₂The reaction produces methane. The reaction can be run until all of the H is consumed₂And/or to a near equilibrium temperature of about 0 to 30 ℃ or 0 to 15 ℃. The methanation reaction in the first reactor 2601 may result in an adiabatic temperature rise of about 20 ℃ to 300 ℃ or 50 ℃ to 150 ℃.

Next, the products from the first reactor, including methane and unreacted CO and/or H₂Can be directed to heat along the first product streamExchangers 2603 in which they are cooled to a temperature of about 100 ℃ to 400 ℃ or 200 ℃ to 300 ℃. In heat exchanger 2603, heat from first product stream 2603 is removed and directed to recycle stream 2604, after which recycle stream 2604 is directed to first reactor 2601.

Next, a portion of the heated first product stream is mixed with CO₂The streams 2605 mix to produce a mixed stream that is directed to the second reactor 2602. CO production by a separation unit, such as a cryogenic separation unit, downstream of the OCM reactor₂Flow 2605. The separation unit may be the same separation unit that generates recycle stream 2604. In some cases, the processes described herein improve carbon efficiency compared to processes that do not use methanation. For example, CO and/or CO₂The amount of (a) can be reduced by at least about 5%, at least about 10%, at least about 20%, at least about 50%, at least about 75%, or at least about 80%.

In the second reactor 2602, CO and CO₂And H₂Reacts to produce a second product stream 2606 comprising methane. The reaction in the second reactor 2602 can proceed until substantially all of the H is consumed₂And/or to a near equilibrium temperature of about 0 to 30 ℃ or 0 to 15 ℃. Can select CO and CO in the mixed flow₂And H₂Such that second product stream 2606 is substantially depleted of CO and H₂. In some cases, second product stream 2606 is fed back into the natural gas feed to the natural gas to liquids facility.

The first reactor 2601 and the second reactor 2602 may be two catalytic stages in the same reactor vessel, or may be arranged in two separate vessels. The first reactor 2601 and the second reactor 2602 can each comprise a catalyst, such as a catalyst comprising one or more of ruthenium, cobalt, nickel, and iron. The first reactor 2601 and the second reactor 2602 can be fluidized bed or packed bed reactors. Further, although system 2600 comprises two reactors 2601 and 2602, system 2600 can comprise any number of reactors in series and/or parallel, such as at least 1,2, 3,4, 5,6, 7,8, 9, 10, 20, 30, 40, or 50 reactors.

Although showing CO₂Stream 2605Is directed to the second reactor 2602 instead of the first reactor 2601, but in an alternative configuration, at least a portion or the entire CO₂Stream 2605 may be directed to a first reactor 2601. Can select CO and CO₂And H₂Such that the methanation product stream is substantially depleted in CO and H₂。

The methane generated in system 2600 can be used for various purposes. In one example, at least a portion of the methane can be recycled to the OCM reactor (e.g., as part of an OCM-ETL system) to generate C₂₊A compound, including an olefin (e.g., ethylene). Alternatively, or in addition, at least a portion of the methane may be directed to a non-OCM process, such as a natural gas stream of a natural gas facility (see, e.g., fig. 3 and 4). Alternatively, or in addition, at least a portion of the methane may be directed to an end user, for example, along a natural gas pipeline.

The methanation reaction may be over a nickel-based catalyst such as for producing SNG (substitute natural gas or synthetic natural gas) from synthesis gas or for purifying a gas containing CO and CO₂For example, to remove CO and CO present in the make-up feed to an ammonia synthesis unit₂) Is carried out on the catalyst of (1). Examples of such catalysts include KATALCO^TMSeries (including 11-4, 11-4R, 11-4M and 11-4MR types) comprising nickel supported on a refractory oxide; HTC series with nickel supported on alumina (including NI500RP 1.2.2); and type 146 with ruthenium supported on alumina. Other methanation catalysts include the PK-7R and METH-134 types. The methanation catalyst may be a tableted or an extrudate. Such catalysts may be, for example, cylindrical, spherical, or ring structures in shape, or partial in shape and/or combinations thereof. In some cases, the ring structure is advantageous because it has a reduced pressure drop across the reactor bed relative to cylindrical and spherical commercial forms. In some cases, the methanation catalyst is a doped or modified form of a commercially available catalyst.

In some cases, merely applying a methanation catalyst to an OCM and/or ETL process that has been developed or optimized for another process (e.g., SNG production or gas purification) may result in operational problems and/or non-optimal performance, including carbon formation (coking) on the methanation catalyst. Coking can lead to deactivation of the catalyst and ultimately to a loss of conversion through the methanation reactor, thus rendering the methanation process ineffective, severely limiting the performance of the overall OCM and/or ETL based process, and possibly preventing the final product from reaching the desired specifications.

Existing and/or commercially available methanation catalysts may produce selectivities and/or conversions at given process conditions (e.g., gas-hourly space velocity, molar composition, temperature, pressure) that may be undesirable for OCM and/or ETL practice. For example, an ammonia plant may have about 100ppm to 1% CO with a molar excess of H₂(e.g., 2,5, 10, 50, 100 or more fold excess) to drive equilibrium toward complete methanation. The methanation system in the ammonia plant has a small temperature difference (e.g., 20 to 30 ℃) between the inlet and the outlet of the adiabatic methanation reactor, and may be sized for catalyst life. In some cases, SNG production does not have very large H₂Molar excess. Methanation in the SNG process may have an inlet to outlet temperature difference of greater than 100 ℃ and may be carried out in multiple stages. Also, the purpose of methanation may be different for OCM and/or ETL. Ammonia and SNG processes are typically methanated primarily to eliminate CO and/or CO₂(albeit H)₂May also be eliminated or significantly reduced in concentration), while methanation in the OCM and/or ETL process is primarily to eliminate H₂(albeit CO and/or CO)₂May also be eliminated or significantly reduced in concentration).

Methanation catalysts and/or catalytic processes that may prevent or reduce carbon formation or other operational failures in methanation reactors are described herein. The catalyst and/or catalytic process may be achieved by any combination of: (a) removing chemicals from the methanation inlet feed that may contribute to coke formation; (b) introducing a chemical to the methanation feed that eliminates or reduces the rate of coke formation; and (c) using a methanation catalyst as described herein that reduces or eliminates coke formation and/or is designed to operate at process conditions (e.g., gas-hourly space velocity, molar composition, temperature, pressure) of the OCM and/or ETL effluent or OCM and/or ETL process stream.

In some cases, separation or reactive processes are employed to remove or reduce the concentration of species present in the OCM and/or ETL effluent stream that can lead to carbon formation in the methanation reactor. Typical operating conditions for a methanation reactor may be a pressure of about 3 to about 50 bar and a temperature of about 150 to about 400 ℃. Any hydrocarbon material containing carbon-carbon double or triple bonds is reactive enough to form carbon deposits (i.e., coke). Examples of these materials are acetylene, all olefins and aromatic compounds. Removal or significant reduction of these species can be achieved via various methods including, but not limited to: (a) hydrogenation over a suitable catalyst prior to the methanation reactor (i.e. these react with hydrogen present in the effluent stream itself to produce alkanes); (b) condensation and separation of these substances from methane prior to the methanation reactor; (c) absorption or adsorption of these substances; (d) by using a suitable membrane; or (d) any combination thereof.

In embodiments of the present disclosure, a new species that eliminates or reduces the rate of carbon formation is introduced into the methanation inlet stream. Molecular species that create a reducing atmosphere can be used to counteract the oxidation reaction and can thereby reduce the carbon formation rate. Hydrogen and water are examples of these specific compounds and may be added to the OCM and/or ETL effluent stream prior to methanation to increase its concentration in the methanation reactor.

One aspect of the present disclosure provides a methanation catalyst for an OCM and/or ETL process. Coke formation is typically the product of a surface-driven reaction. Thus, methanation catalysts for OCM and/or ETL alter the local electronic environment around the active sites of the catalyst. This can be achieved by changing the elemental composition (e.g., via doping after impregnation, or creating a new mixed metal of nickel and another transition metal), morphology, and structure (e.g., via synthesizing the metal in a non-bulk form factor). Examples of such syntheses include: nanowires of the same material, nanoparticles coated on a support, and vapor deposition of the active material on the support material. Other modifications to the surface may result from: post-synthesis processing steps such as surface etching, oxidation and reduction of metals to create different surface reconstructions, calcination steps under different atmospheres (e.g., oxidizing or reducing atmospheres), heating to obtain different crystalline phases, and inducing defect formation. The end result of the modification of the methanation catalyst is specifically designed to minimize carbon (coke) formation while still being effective for carrying out the methanation reaction.

The methanation process and/or methanation catalyst is operated with the OCM and/or ETL product gas directly or after one or more heat exchangers or separation operations. For example, the methanation feed stream may have the following composition on a molar basis: about 65% to about 90% CH₄(ii) a About 5% to about 15% H₂(ii) a About 1% to about 5% (by mole) CO; about 0% to about 0.5% C₂H₄(ii) a And about 0% to about 0.1% C₂H₂. As described herein, the ETL effluent can contain C₂₊Compounds including propane, propylene, butane, butylene and C₅₊A compound is provided. These C₂₊The compound may be present in the stream entering the methanation reactor in any concentration. The balance of the feed stream may be an inert gas such as N₂Ar and He. The methanation feed stream typically has a temperature near ambient temperature and a pressure in the range of about 3 to about 50 bar.

In some cases, all of the C present in the entire ETL product stream, and/or the ETL effluent, is removed₂₊The compounds, and/or any or all of the olefins present in the ETL effluent, are fed to the methanation reactor (i.e., the methanation feed). In some cases, the temperature of the ETL effluent is not reduced or significantly reduced prior to being fed into the methanation reactor such that all or a majority (at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99%) of the C₂₊The compounds and/or olefins remain in the methanation feed. In some cases, the temperature of the ETL effluent is reduced prior to feeding to the methanator to separate some C from the stream₂₊A compound and/or an olefin. The temperature may be reduced to a temperature low enough to remove a substantial portion (at least about 70%, at least about 80%, at least about 90%, toAbout 95% less, or at least about 99%) C₅₊A compound (e.g., about 40 ℃) that removes a majority (at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99%) of the C₄₊A compound (e.g., about 10 ℃), or a majority (at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99%) of the C is removed₃₊Compounds (e.g., about-40 ℃ C.).

The methanation reaction may produce water and/or contain water in the methanation effluent. In some cases, it may be desirable to remove this water prior to recycling the methanation effluent to the OCM reactor. This can be achieved by reducing the temperature of the methanation effluent or performing any separation procedure to remove water. In some embodiments, at least about 70%, at least about 80%, at least about 70%, at least about 90%, at least about 95%, or at least about 99% of the water is removed from the methanation effluent prior to the OCM reactor. Removing water may increase the life and/or performance of the OCM catalyst.

In some cases, the ETL process may be designed to use a methanation catalyst that is not optimized for the ETL process. The OCM or OCM-ETL process can be designed to produce gasoline or distillate or aromatics (or any combination thereof) from natural gas. In this case, the effluent of the OCM reactor is fed to an ETL reactor where all short olefins (e.g., ethylene and propylene) are converted to longer chain hydrocarbons over a suitable oligomerization catalyst. An example of such a catalyst is zeolite ZSM-5. Will contain unconverted methane, unconverted olefin, CO₂、H₂The product streams of water, inerts and total oligomerization products (paraffins, isoparaffins, olefins and aromatics) are fed to the methanation module. The concentration of oligomerization product in the methanation feed stream may vary depending on the type and extent of separation performed prior to the methanation step. The methanation feed stream typically has a temperature near or below ambient temperature and a pressure in the range of from 3 to 50 bar.

Referring to fig. 27, a methanation system may be designed to use a catalyst that is not necessarily optimized for OCM and/or ETL process streams. Methanation feed stream 2700 is first sent to a first heat exchangerThe exchanger 2705, in which its temperature is raised to the inlet temperature of the methanation reactor, typically 150 to 300 ℃. Steam 2710 is injected directly downstream of the heat exchanger to increase the water concentration in the methanation feed stream. The heated stream is then fed to a first adiabatic reactor 2715 in which ethylene, acetylene, and any other hydrocarbons exhibiting multiple carbon-carbon bonds are passed through H present in the stream itself₂Is hydrogenated.

The effluent from 2715 is then fed to a second reactor 2720, where CO and CO are fed₂And H₂The reaction is carried out until the desired route to equilibrium is achieved, typically from 0 to 15 ℃. From CO and CO₂The adiabatic temperature rise resulting from methanation may depend on the composition of the feed stream and is typically in the range of 50-150 ℃.

The effluent from the second reactor 2720 is then sent to a first heat exchanger 2705 and a second heat exchanger 2725 where it is cooled to a temperature below which water condenses. This stream is then fed to a phase separator 2730 where condensed water and a portion of the longer hydrocarbons are separated from the vapor.

Depending on its concentration, the vapor stream from phase separator 2725 is sent to a final product purification and recovery section, or injected into a natural gas pipeline. Alternatively, the vapor stream 2735 from phase separator 2730 may be further methanated in a second methanation reactor to further reduce CO, CO₂And H₂Concentration (not shown).

The liquid stream from phase separator 2740 is reinjected into the methanation feed stream alongside the steam. Alternatively, the liquid stream may be first vaporized and then re-injected, or it may be sent to a water treatment system (not shown) for water recovery and purification.

Reactors 2715, 2720 (and the third reactor, if present), or any combination thereof, can be physically located in the same vessel, or can be arranged in separate, separate vessels.

In the processes, systems, and methods of the present disclosure, a Fischer-Tropsch (F-T) reactor may be used in place of a methanation reactor, for example, in a methane recycle stream. CO andH₂CO and H as found in methane recycle streams₂And can be converted in a fischer-tropsch reaction to a variety of paraffinic linear hydrocarbons, including methane. High levels of straight chain hydrocarbons, such as ethane, can improve the efficiency and economics of the OCM process. For example, the effluent from the OCM reactor may be directed through a cooling/compression system and other processes prior to removing the recycle stream in the demethanizer. The recycle stream may comprise CH₄CO and H₂And may be directed to an F-T reactor. The F-T reactor can produce CH for recycling to the OCM reactor₄And C₂₊An alkane. A range of catalysts may be employed, including any suitable F-T catalyst. Reactor designs, including those discussed in the present disclosure, may be employed. The F-T reactor operating conditions, including temperature and pressure, can be optimized. The process can reduce H compared to methanation reactor₂And (4) consumption.

Hydrocarbon separation

In natural gas processing facilities, methane can be separated from ethane and higher carbon content hydrocarbons (conventionally referred to as natural gas liquids or NGLs) to produce a methane-rich stream that can meet pipeline and sales gas specifications. Such separation can be carried out using cryogenic separation, for example with the aid of one or more cryogenic units.

The crude natural gas fed to the gas processing facility can have a molar composition of 70% to 95% methane and 4% to 20% NGL, with the balance being inert gases (e.g., CO)₂And N₂). The ratio of methane to ethane can be in the range of 5-25: 1. In view of the relatively large amounts of methane present in the streams fed to the cryogenic portion of the gas processing facility, at least some or substantially all of the cooling duty required for separation is provided by the multiple compression and expansion steps performed on the feed stream and the methane product stream. The cooling load may not be supplied by the external refrigeration unit or a limited portion thereof may be supplied by the external refrigeration unit.

There are a variety of methods for separating higher carbon content alkanes (e.g., ethane) from natural gas, such as recycle separation steam (RSV) and Gas Subcooling Process (GSP) processes, which can maximize ethane recovery (e.g., recovery)>95％) While providing most or all of the cooling load via internal compression and expansion of the methane itself. However, application of such processes when separating olefins (e.g., ethylene) from an OCM product stream comprising methane can result in limited recovery of the olefin product (e.g., provide less than 95% recovery), at least in part due to (i) the different vapor pressures of the olefin and alkane, and/or (ii) the presence of significant amounts of H in the OCM product stream₂This can change the boiling curve, particularly the Joule-Thomson coefficient of the methane stream that needs to be compressed and expanded to provide the cooling duty. The hydrogen gas may exhibit a negative or relatively low Joule-Thomson coefficient, which may result in a temperature increase or a relatively low temperature decrease as the hydrogen-rich gas stream expands.

In some embodiments, the design of the cryogenic separation system of an OCM-based facility may be characterized by different combinations of compression/expansion steps for internal refrigeration and (in some cases) external refrigeration. The present disclosure provides a separation system comprising one or more cryogenic separation units and one or more demethanizer units. Such systems can be used to remove contaminants from gases containing alkanes, alkenes, and other gases (e.g., H₂) For example, in the OCM product stream (e.g., to provide greater than 95% recovery) (see fig. 24 and 25 and associated text).

In such a separation system, the cooling load may be provided by a combination of: expansion of the OCM effluent (feed stream to the lower temperature section) when the OCM effluent pressure is higher than the demethanizer; expansion of at least a portion or all of the methane-rich stream at the top of the demethanizer; compression and expansion of a portion of the methane-rich stream at the top of the demethanizer; and/or an external propane, propylene, or ethylene refrigeration unit.

28-33 illustrate various separation systems as may be employed by the various systems and methods of the present disclosure. Such a system may be used with the OCM-ETL system described herein, such as with the vapor-liquid separator 320 described above in the context of fig. 3 and 4.

FIG. 28 shows a section comprising a first heat exchanger 2801, a second heat exchanger 2802, a demethanizer 2803, and a third heat exchanger 2804From the system 2800. The direction of fluid flow is shown in the figure. Demethanizer 2803 can be a distillation unit or multiple distillation units (e.g., in series). In such a case, the demethanizer may include a reboiler and a condenser, each of which may be a heat exchanger. OCM exhaust stream 2805 is directed to first heat exchanger 2801 at a pressure of about 10 to 100 bar (absolute) or 20 to 40 bar. OCM effluent stream 2805 can comprise methane and C₂₊Compounds, and may be provided in an OCM product stream from an OCM reactor (not shown). OCM exhaust stream 2805 is then directed from first heat exchanger 2801 to second heat exchanger 2802. In first and second heat exchangers 2801 and 2802, OCM effluent stream 2805 is cooled in heat transfer with demethanizer top stream 2806, demethanizer reboiler stream 2807, demethanizer bottom product stream 2808, and refrigeration stream 2809 having a heat exchange fluid comprising propane or an equivalent cooling medium such as, but not limited to, propylene or a mixture of propane and propylene.

The cooled OCM effluent 2805 can be directed to a demethanizer 2803 where light components such as CH₄、H₂And CO is separated from heavier components such as ethane, ethylene, propane, propylene, and any other less volatile components present in OCM effluent stream 2805. The light components are directed out of the demethanizer along a top stream 2806. The heavier components are directed out of the demethanizer along bottoms stream 2808. The demethanizer can be designed such that at least about 60%, 70%, 80%, 90%, or 95% of the ethylene in OCM effluent stream 2805 is directed to bottom product stream 2808.

The demethanizer overhead stream 2806 may contain at least 60%, 65%, or 70% methane. The top stream 2806 may be expanded (e.g., in a turbo-expander or similar machine, or flashed via a vacuum line or similar device) to reduce the temperature of the top stream 2806 before the top stream 2806 is directed to the second heat exchanger 2802 and then to the first heat exchanger 2801. The overhead stream 2806 can be cooled in a third heat exchanger 2804, which can be cooled with a reflux stream and a hydrocarbon-containing cooling fluid, such as ethylene.

The overhead stream 2806, which may include methane, may be recycled to the OCM reactionAnd/or for other uses, such as natural gas pipelines. In some examples, may contain C₂₊A bottoms product stream of compounds (e.g., ethylene) can be directed to the ETL system.

Fig. 29 illustrates another separation system 2900 that may be employed when used with the systems and methods of the present disclosure. The direction of fluid flow is shown in the figure. System 2900 includes a first heat exchanger 2901, a demethanizer 2902, and a second heat exchanger 2903. Demethanizer 2902 may be a distillation unit or a plurality of distillation units (e.g., in series). OCM exhaust stream 2904 is directed to first heat exchanger 2901. OCM effluent stream 2904 may include methane and C₂₊Compounds, and may be provided in an OCM product stream from an OCM reactor (not shown). OCM effluent stream 2904 may be provided at a pressure of about 10 bar (absolute) to 100 bar or 40 bar to 70 bar. OCM effluent stream 2904 may be cooled in heat transfer relationship with demethanizer overhead streams 2905 and 2906, demethanizer reboiler stream 2907, and a refrigeration stream having a cooling fluid comprising, for example, propane or an equivalent cooling medium (such as, but not limited to, propylene or a mixture of propane and propylene) from second heat exchanger 2903. In some cases, the demethanizer overhead streams 2905 and 2906 are combined into an output stream 2912 before or after passing through the first heat exchanger 2901.

After cooling in first heat exchanger 2901, OCM effluent stream 2904 may be expanded in a turboexpander or similar device, or flashed via a vacuum line or similar device, to a pressure of at least about 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, or 10 bar. The cooled OCM effluent stream 2904 may then be directed to a demethanizer 2902 where light components (e.g., CH) may be directed₄、H₂And CO) from heavier components (e.g., ethane, ethylene, propane, propylene, and any other less volatile components present in OCM effluent stream 2904). The light components are directed to overhead stream 2909, while the heavier components (e.g., C)₂₊) Is directed along bottom stream 2910. A portion of the top stream 2909 is directed to the second heat exchanger 2903, then to the first heat exchanger 2901 along stream 2906. The remainder of the overhead stream 2909 is pressurized in a compressor and directed to a second heat exchangeAnd a machine 2903. The remainder of the overhead stream 2909 is then directed to a phase separation unit 2911 (e.g., a distillation unit or vapor-liquid separator). The liquid from the phase separation unit 2911 is directed to a second heat exchanger 2903 and then returned to the demethanizer 2902. The vapor from phase separation unit 2911 is expanded (e.g., in a turboexpander or similar device) and directed to second heat exchanger 2903, and then directed along stream 2905 to the first heat exchanger. Demethanizer 2902 can be designed such that at least about 60%, 70%, 80%, 90%, or 95% of the ethylene in OCM effluent stream 2904 is directed to bottom product stream 2910.

Fig. 30 illustrates another separation system 3000 that may be employed in use with the systems and methods of the present disclosure. The direction of fluid flow is shown in the figure. System 3000 includes a first heat exchanger 3001, a demethanizer 3002, a second heat exchanger 3003, and a third heat exchanger 3004. System 3000 may not require external refrigeration. Demethanizer 3002 can be a distillation unit or multiple distillation units (e.g., in series). OCM exhaust stream 3005 is directed to first heat exchanger 3001 at a pressure of about 10 bar (absolute) to 100 bar or 40 bar to 70 bar. In first heat exchanger 3001, OCM effluent stream 3005 can be cooled in heat transfer with demethanizer top streams 3006 and 3007, demethanizer reboiler stream 3008, and demethanizer bottom product stream 3009. In some cases, demethanizer overhead streams 3006 and 3007 are combined into common stream 3015 before or after passing through first heat exchanger 3001. OCM exhaust stream 3005 may then be expanded, for example in a turboexpander or similar machine, to a pressure of at least about 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, or 10 bar, or flashed via a vacuum line or similar device. The cooled OCM effluent stream 3005 is then directed to a demethanizer 3002 where the light components (e.g., CH)₄、H₂And CO) from heavier components (e.g., ethane, ethylene, propane, propylene, and any other less volatile components present in OCM effluent stream 3005). The light components are directed to top stream 3010, while the heavier components are directed along bottom product stream 3009. Demethanizer 3002 can be designed such that at least about 60%, 70%, 80%, 90%, or 95% of the b in OCM effluent stream 3005 is presentThe alkenes are directed to a bottom product stream 3009.

The demethanizer overhead stream 3010, which may contain at least 50%, 60%, or 70% methane, may be split into two streams. First stream 3011 is compressed in compressor 3012 and cooled in second heat exchanger 3003 and phase separated in phase separation unit 3013 (e.g., a vapor-liquid separator or distillation column). The steam from the phase separation unit 3013 is expanded (e.g., in a turboexpander or similar device) to provide a portion of the cooling load required in the heat exchangers 3001, 3003, and 3004. The liquid from phase separation unit 3013 is subcooled in third heat exchanger 3004 and recycled to demethanizer 3002. The second stream 3014 from the overhead stream 3010 can be expanded (e.g., in a turbo-expander or similar device) to reduce its temperature and provide additional cooling to the heat exchangers 3001, 3003, and 3004.

Fig. 31 illustrates another separation system 3100 that may be employed in connection with the systems and methods of the present disclosure. The direction of fluid flow is shown in the figure. System 3100 includes a first heat exchanger 3101, a demethanizer 3102, and a second heat exchanger 3103. OCM effluent stream 3104 is directed to first heat exchanger 3101 at a pressure of about 2 bar (absolute) to 100 bar or 3 bar to 10 bar. First heat exchanger 3101 may be interfaced with propane refrigeration unit 3115 and/or ethylene refrigeration unit 3116. In first heat exchanger 3101, OCM effluent stream 3104 can be cooled while in heat transfer with demethanizer overhead streams 3105 and 3106, the demethanizer reboiler stream, the demethanizer pumparound stream, and external refrigeration at each stage (e.g., using a cooling fluid comprising ethylene and propylene). In some cases, demethanizer top streams 3105 and 3106 are combined into a single stream 3114 before or after it is cooled. The cooled OCM effluent stream 3104 is then directed to demethanizer 3102, where light components (e.g., CH)₄、H₂And CO) from heavier components (e.g., ethane, ethylene, propane, propylene, and any other less volatile components present in OCM effluent stream 3104). The light components are directed to top stream 3107 and the heavier components are directed along bottom product stream 3108. Demethanizer 3102 can be designed such that at least OCM effluent stream 3104 isAbout 60%, 70%, 80%, 90%, or 95% of the ethylene is directed to bottom product stream 3108.

The demethanizer overhead stream, which may contain at least about 50%, 60%, or 70% methane, may be split into two streams. First stream 3113 may be compressed in compressor 3109, cooled in second heat exchanger 3103, and phase separated in phase separation unit 3110 (e.g., a distillation column or vapor-liquid separator). The steam from phase separation unit 3110 may be expanded (e.g., in a turboexpander or similar device) to provide a portion of the cooling load required by heat exchangers 3101 and 3103. The liquid from phase separation unit 3110 can be subcooled and flashed (e.g., via vacuum tube or similar device), and the resulting two-phase stream separated in additional phase separation unit 3111. The liquid from the additional phase separation unit 3111 is recycled to demethanizer 3102 and the vapor from the additional phase separation unit is mixed with the expanded vapor from phase separation unit 3110 before being directed to second exchanger 3103.

The second stream 3112 from the top stream 3107 may be expanded (e.g., in a turbo-expander or similar device) to reduce its temperature and provide additional cooling to the heat exchangers 3101 and 3103. Any additional cooling that may be required by second heat exchanger 3103 may be provided by an external refrigeration system that may employ a cooling fluid comprising ethylene or an equivalent cooling medium.

In some cases, recycle split steam (RSV) splitting may be performed in combination with demethanization.

In some cases, methane undergoes an OCM and/or ETL process to produce a liquid fuel or aromatic (e.g., higher hydrocarbon liquid) and contains molecules that have undergone methanation. In some embodiments, the compound has been subjected to a Recycle Separation Vapor (RSV) separation process. In some cases, alkanes (e.g., ethane, propane, butane) are cracked in a post-bed cracker.

The systems described above and elsewhere herein are not limited to ethylene and may be configured to operate with other olefins such as propylene, butenes, pentenes, or other alkanes. While the various systems and methods herein have been described in the context of ethylene to liquids, it is to be understood that other olefins may be used. For example, the OCM reactor may produce an OCM effluent stream comprising propylene and/or one or more butenes, which may be used to provide one or more streams comprising higher molecular weight hydrocarbons.

The system of the present disclosure may be adapted to generate liquids at less than or equal to about 25 ten thousand tons per year (KTA) ("small scale"), or at greater than about 250KTA ("world scale"). In some examples, a world-scale OCM-ETL system generates at least about 1000, 1100, 1200, 1300, 1400, 1500, or 1600KTA of liquid.

Ethane skimmer

The systems and methods described herein can process natural gas into a gas suitable for sale (i.e., "sales gas" that meets the specifications required for transport via pipeline). In some cases, the systems and methods of the present disclosure can convert methane and/or ethane (e.g., from natural gas) into sales gas as well as products, such as LPG, gasoline, distillate fuels, and/or aromatic chemicals. Such systems or methods are referred to as "ethane skimmers".

Ethane may be fed directly to a post-bed cracker (PBC), which may be part of an OCM reactor downstream of the OCM catalyst, where the heat generated in the OCM reaction may be used to crack the ethane to ethylene. Alternatively, the PBS may be a separate unit from the OCM reactor, and in some cases in thermal communication with the OCM reactor. The ethane feed stream to the OCM reactor can include (a) ethane recycled from the OCM reactor effluent stream to the OCM reactor, which can be separated in at least one downstream separation module and recycled to the OCM reactor; (b) ethane present in other feed streams (e.g., natural gas), which may be separated in at least one separation module and recycled to the OCM reactor; and (c) any additional (i.e., fresh) ethane feed.

The maximum amount of ethane that can be converted in the PBC may be limited by the flow rate of the material exiting the OCM catalyst and/or its temperature. It may be advantageous to utilize a high proportion of the maximum amount of PBC. In some cases, the amount of ethane converted to ethylene is about 50%, about 60%, about 70%, about 80%, about 85%, about 90%, about 95%, or about 99% of the maximum amount of ethane that can be converted to ethylene in PBC. In some cases, the amount of ethane converted to ethylene is at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99% of the maximum amount of ethane that can be converted to ethylene in PBC.

Achieving a high proportion of maximum PBC capacity can be achieved by adding natural gas to the system, which may have an ethane concentration that depends on many factors, including the topography and type of the gas well and age. The treatment and separation modules of the processes described herein can be used to purify or fractionate ETL effluent, and can additionally be used for treatment (e.g., removal of water and CO)₂) And purifying the natural gas added to the system with the ETL effluent, such as by adding C₂₊The compounds are separated from methane and ethane is separated from ethylene. In some cases, the ethane contained in the natural gas feed may be recycled to the OCM reactor (e.g., PBC zone) as pure ethane, and the system may be insensitive to the purity and composition of the natural gas, making crude natural a suitable input to the system.

The maximum PBC capacity may depend on the ratio of methane to ethane in the input to the OCM reactor (including the PBC portion in some cases). In some cases, PBC capacity is saturated when the molar ratio of methane to ethane is about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, or about 15. In some cases, PBC capacity is saturated when the methane to ethane molar ratio is at least about 1, at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9, at least about 10, at least about 11, at least about 12, at least about 13, at least about 14, or at least about 15. In some cases, PBC capacity is saturated when the molar ratio of methane to ethane is at most about 5, at most about 6, at most about 7, at most about 8, at most about 9, at most about 10, at most about 11, at most about 12, at most about 13, at most about 14, or at most about 15. In some cases, PBC productivity is saturated when the molar ratio of methane to ethane is about 7 to 10 parts methane to 1 part ethane.

The natural gas (feed gas or sales gas) may have an ethane concentration of less than about 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, or 1 mol%. In some cases, the natural gas has a methane to ethane ratio of greater than about 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, or 40: 1. More natural gas feed than may be required to produce the desired or predetermined amount of ethylene or other products may be injected into the system using the ethane skimmer embodiments described herein. Excess methane may be withdrawn from the stream downstream of the methanation unit and sold as a sales gas (which may lack appreciable amounts of ethane, but may still meet pipeline specifications and/or may be directed to a power plant for power generation). Additional ethane in the natural gas feed may be used to saturate PBC production. Any excess of ethane may be removed from C₂Which is withdrawn in the splitter and output as pure ethane. The ethane skimmer embodiments described herein can result in additional product streams (i.e., sales gas, natural gas liquids, gasoline, diesel or jet fuel, and/or aromatic chemicals) from the system. In such a case, both natural gas processing and C can be achieved using this process₂₊Production of chemicals or fuels.

The ethane skimmer embodiment can be readily understood by reference to fig. 32. Natural gas 3200 may be fed to desulfurization unit 3202 and then to gas compressor 3204. Oxygen may be provided from an air separation unit 3206 powered by a gas turbine and a combined cycle 3208 powered by combustion of a portion of the natural gas and/or methane. Oxygen and methane 3210 produced by the process may be injected into OCM reactor 3212 with PBC portion 3214. The OCM effluent may be fed to a process gas compressor 3204 and then to an ETL module 3216. The product of the ETL module can be dried in a dryer 3218. The separation module can include a demethanizer 3220, a deethanizer 3222, and a debutanizer 3224. The demethanizer can remove C₁Compounds with C₂₊The compound is separated and C is₁Compounds (e.g., methane, carbon monoxide, and carbon dioxide) are directed to methanator 3226. C₁The compound stream may have any amount of C₂₊A compound (e.g., about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, or about 3.5%). The methanator may convert the carbon monoxide and/or carbon dioxide to methane (e.g., using hydrogen generated in the process). The methane may be divided into any number of streams that may be directed to OCM reactor 3212, gas turbine 3208, and/or pipeline 3228 or other means for transporting the methane product to market (i.e., sales gas). Ethane 3230 from the separation module may be directed to the PBC. The system can generate C₃₊Products, e.g. liquefied petroleum gas (LPG; with C)₃And C₄Molecule) 3232, and C₅₊Product 3234, such as gasoline, diesel fuel, jet fuel, and/or aromatic chemicals.

In summary, during an ethane skimmer process as shown in fig. 32, at least some or most of the natural gas feed 3200 (e.g.,>70％、>80％、>85％、>90％、>95% or>99%) methane is terminated in methane recycle 3210, at least some or a majority (e.g.,>70％、>80％、>85％、>90％、>95% or>99%) of the ethane ends up in ethane recycle stream 3230, at least some or most of the natural gas feed (e.g.,>70％、>80％、>85％、>90％、>95% or>99%) propane ends up in C₃₊Product streams 3232 and 3234. In some cases, ethane (not shown in figure 32) is added until PBC cracking capacity is at or near saturation (e.g.,>70％、>80％、>85％、>90％、>95% or>99%) of the points. Excess ethane (e.g., beyond that required to saturate PBC) may end up in the ethane product stream (not shown). The ethane skimmer embodiment does not require a separate (i.e., fresh) ethane stream to saturate or nearly saturate the PBC capacity of the system.

Additional products and Processes

In addition to the ethylene conversion process described herein, ethylene may also be producedComponents produced in the process other than ethylene (e.g., contained in the OCM off-gas) are directed to, and thus fluidly coupled to, additional conversion processes. Specifically, the OCM reaction process produces several additional products in addition to ethylene, including, for example, hydrogen (H)₂) And carbon monoxide (CO). In some cases, H is made up of OCM reaction products₂And the CO component undergoes additional processing to produce other products and intermediates, for example, dimethyl ether (DME) methanol and hydrocarbons. These components can be used in a variety of different end products, including liquid fuels, lubricants, and propellants. In some embodiments, the OCM reaction effluent is treated with H₂And the CO component is separated from other OCM products. Then H can be reacted₂And CO, to produce a variety of different products, such as methanol, dimethyl ether, hydrocarbons, lubricants, waxes, and fuels or fuel blendstocks. In one example, let H₂And the CO component is subjected to a catalytic process to produce DME via a methanol intermediate. This catalytic process is described in detail, for example, in U.S. patent No. 4,481,305, the entire disclosure of which is hereby incorporated by reference in its entirety for all purposes.

As described herein, the ethylene conversion process employed in the integrated processes and systems of the present invention can produce olefin products for a variety of different end products or applications. For example, a portion or all of the ethylene produced by the OCM process may be routed through one or more catalytic processes or systems to oligomerize the ethylene into LAOs of different carbon numbers. These compounds are particularly useful in chemical manufacturing, for example, the production of amines, amine oxides, carbonyl alcohols, alkylated aromatic hydrocarbon epoxides, tanning oils, synthetic lubricants, lubricant additives, alpha-olefin sulfonates, mercaptans, organoalkylaluminum compounds, hydrogenated oligomers, and synthetic fatty acids. Alternatively or additionally, ethylene may be oligomerized by the LAO process to produce C₄-C₂₀LAOs are used as liquid blending stocks for gasoline, diesel or jet fuel. These LAOs can also be hydrogenated to linear alkanes for fuel blending stocks for gasoline, jet and diesel fuels.

For producing product ranges (examples)E.g. C₄-C₃₀LAO) is generally referred to herein as a "full-scale process" or a "narrow-scale process" because it produces a range of chemicals in a single process, for example, LAOs of different chain lengths, such as 1-butene, 1-hexene, 1-octene, 1-decene, and the like. The product from the full or narrow range process may be distilled or fractionated into, for example, C for use as a feedstock for a chemical process₄-C₁₀LAO, C used as jet fuel blending stock, diesel fuel blending stock and chemical stock₁₀-C₂₀And LAO. In contrast, processes that produce a single chemical species (e.g., a single chain length of LAO, such as 1-butene, 1-hexene, 1-octene, 1-decene, etc.) in high yield are often referred to as selective processes.

A wide variety of LAO processes can be used to produce a full and narrow range of products from ethylene, for example,

processes (see, for example, published international patent application No. WO 2009/074203, european patent No. EP 1749806B1, and U.S. patent No. 8,269,055, the entire disclosures of which are incorporated herein by reference in their entirety for all purposes), the Shell Higher Olefin Process (SHOP), the Alphabutol process, the Alphahexol process, the AlphaSelect process, the Alpha-Octol process, the Linear-1 process, the Linear process, the Ethyl process, the Gulftene process, and the Phillips 1-hexene process.

Briefly, the α -Sablin process employs a two-component catalyst system of zirconium salt and an aluminum alkyl co-catalyst for homogeneous, liquid phase oligomerization of ethylene to a narrow range of LAOs. The catalytic cycle includes a chain extension step by insertion of ethylene at the coordination site, and displacement of the coordinated hydrocarbon from the organometallic complex. The ratio of zirconium to aluminum can be used to adjust between chain growth and displacement, thereby adjusting the product spectrum to be closer to lighter or heavier LAOs. For example, with a high Zr to Al ratio, the product spectrum can be shifted to C4-C8 LAO above 80%, while a lower Zr to Al ratio will shift the product spectrum to heavier LAO. The reaction is typically carried out in a bubble column reactor at a temperature of about 60 ℃ to 100 ℃ and a pressure of about 20 bar to 30 bar, with a solvent such as toluene and catalyst being fed into the liquid phase. The liquid LAO is then sent to a separation train to deactivate the catalyst, separate the solvent, and optionally perform any other desired product separations.

Alternatively, all or a portion of these olefin products may be hydrogenated, followed by distillation to convert the olefins to the corresponding alkanes for use as alkane blendstocks for fuel products, which are then again subjected to distillation or other separation processes to produce the desired products.

In various embodiments, a wide variety of other ethylene conversion processes may be integrated in the back end of the OCM process described above, depending on the desired product or products of the overall process and system. For example, in an alternative or additional aspect, an integrated ethylene conversion process for producing LAO may include a SHOP system, i.e., one that may be used to produce C₆-C₁₆Full range ethylene conversion process for a range of LAOs. Briefly, the SHOP system employs a nickel-phosphine complex catalyst to oligomerize ethylene at a temperature of about 80 ℃ to about 120 ℃ and a pressure of about 70 bar to about 140 bar.

A variety of other full-range ethylene conversion processes may be employed, including, but not limited to, the AlphaSelect process, the Alpha-Octol process, the Linear-1 process, the Linear process, the Synthol process, the Ethyl process, the Gulftene process, the Phillips 1-hexene process, and the like. These processes are well described in the literature and are reported, for example, in Nexant/Chemsys PERP report, Alpha Olefins,2004, month 1, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.

As an alternative or in addition to the full-range and/or narrow-range ethylene conversion processes, the ethylene conversion processes that may be integrated into the overall system of the present invention include processes for selectively producing high purity single compound LAO compositions. As used herein, a process that is highly selective for the production of a single chemical is generally referred to as a selective or "targeted" process because it is directed to producing a single chemical with high selectivity. In the case of LAO production, such a targeted process will typically produce a single LAO species, e.g., 1-butene, 1-hexene, 1-octene, etc., with a selectivity to the single LAO species of over 50%, in some cases over 60%, over 75%, and even over 90%.

Examples of such targeted processes for the conversion of ethylene to LAO include, for example, the Alphahexol process from IFP, the Alphabutol process or the Phillips 1-hexene process for the oligomerization of ethylene to high purity 1-hexene, as well as a variety of other processes that may be integrated with the overall OCM reactor system.

For example, the Alphahexol process is carried out using the phenolate ligand process. In particular, ethylene trimerization can be carried out at 120 ℃ and 50 bar ethylene pressure using a catalyst system involving a chromium precursor, a phenoxy aluminum compound or alkaline earth metal phenate, and a trialkylaluminum activator (see, e.g., U.S. Pat. No. 6,031,145 and european patent No. EP1110930, the entire disclosures of which are incorporated herein by reference in their entirety for all purposes). Similarly, the Phillips 1-hexene process employs chromium (III) alkanoates such as chromium tris (2-ethylhexanoate), pyrroles such as 2, 5-dimethylpyrrole and Et3Al to produce 1-hexene with high selectivity, e.g., over 93%. See, for example, european patent No. EP0608447 and U.S. patent No. 5,856,257, the entire disclosures of which are incorporated herein by reference in their entireties for all purposes. Various other ethylene trimerization processes can be similarly integrated into the back end of the OCM system described herein. These include, for example, the british petroleum PNP trimerization system (see, for example, published international patent application No. WO 2002/04119, and Carter et al, chem. commun.2002,858) and the Sasol PNP trimerization system (see, for example, published international patent application No. WO2004/056479, discussed in more detail), the entire disclosures of which are incorporated herein by reference for all purposes.

The Alphabutol process employs a proprietary liquid phase soluble ti (iv)/AlEt3 catalyst system in the dimerization of ethylene to 1-butene at relatively high purity and is licensed through Axens (Rueil-malman, France). Ethylene is fed to a continuous liquid phase dimerization reactor. The system surrounding the pump removes the exothermic heat of reaction from the reactor. The reactor was operated at 50-60 ℃ and 300-. The catalyst is removed from the product effluent and ultimately fed to a 1-butene purification column where comonomer grade 1-butene is produced.

An additional selective ethylene conversion process involves the catalytic tetramerization of ethylene to 1-octene. For example, one exemplary tetramerization process employs a liquid phase catalytic system using cr (iii) precursors such as or, and bis (phosphine) amine ligands and Methylalumoxane (MAO) activators at temperatures of about 40 ℃ to 80 ℃ and ethylene pressures of 20 bar to 100 bar to produce 1-octene with high selectivity. See, for example, published International patent application No. WO2004/056479, and Bollmann, et al, "Ethylene polymerization: A New Route to product 1-olefin ExceptionAlly High selection" J.Am.chem.Soc.,2004,126(45), pp 14712-14713, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.

In addition to the LAO process described herein, the ethylene produced from the integrated OCM reactor system can be used to prepare olefinic non-LAO straight chain and branched olefinic hydrocarbons by the same or different integrated processes and systems. For example, the ethylene product from the OCM reactor system may be subjected to an integrated reactor system configured to perform a SHOP process, Alphabutol process, Alphahexol process, AlphaSelect process, Alpha-Octol process, Linear-1 process, Linear process, Ethyl process, Gulftene process, and/or Phillips 1-hexene process to yield a resultant LAO product. The output of these systems and processes can then be subjected to an olefin isomerization step to produce linear olefins, branched olefins, and the like, in addition to LAOs. In addition, olefinic non-LAO linear and branched olefinic hydrocarbons can be prepared by oligomerization of ethylene over heterogeneous catalysts such as zeolites, amorphous silica/alumina, solid phosphoric acid catalysts, and doped versions of the foregoing catalysts.

Other oligomerization processes have been described in the art, including the olefin oligomerization process set forth in published U.S. patent application No. 2012/0197053 (incorporated by reference herein in its entirety for all purposes), which describes a process for producing liquid fuel components from olefinic materials.

Although many of the processes are described with some specificity, this description is by way of example and not of limitation. In particular, it is contemplated that a full range of ethylene oligomerization and/or conversion processes can be readily integrated onto the back end of the OCM reactor system for conversion of methane to ethylene products and subsequently to a variety of different higher hydrocarbon products. As previously noted, certain embodiments of the ethylene conversion processes integrated into the overall system of the present invention are those that produce liquid hydrocarbon products. Other embodiments of the ethylene conversion process integrated into the overall system include processes that are particularly suitable for use with dilute ethylene feedstocks that optionally contain other components, such as higher hydrocarbons, unreacted OCM raw materials (methane and/or other natural gas components), and/or by-products of the OCM reaction. Examples of such other components are provided herein.

Additionally or alternatively, the ethylene product produced from the OCM reactor system may be routed through one or more catalytic or other systems and processes to produce a non-olefinic hydrocarbon product. For example, saturated straight and branched chain hydrocarbon products can be produced from the ethylene product of an OCM reactor system by hydrogenation of the products of the above-described olefin processes, such as the SHOP process, Alphabutol process, Alphahexol process, AlphaSelect process, Alpha-Octol process, Linear-1 process, Linear process, Ethyl process, Gulfene process, and/or Phillips 1-hexene process.

Other catalytic ethylene conversion systems that may be employed include reacting ethylene over heterogeneous catalysts such as zeolites, amorphous silica/alumina, solid phosphoric acid catalysts, and/or doped versions of these catalysts to produce mixtures of hydrocarbons such as saturated straight and/or branched chain hydrocarbons, saturated olefinic cyclic hydrocarbons, and/or aromatic hydrocarbons. By varying the catalyst and/or process conditions, the selectivity of the process to a particular component can be enhanced. For example, ethylene purified from the OCM effluent or an unpurified OCM effluent containing ethylene may be passed over a zeolite catalyst such as ZSM-5, or SiO at a temperature above 350 ℃ at an ethylene partial pressure (undoped, or in some embodiments doped with Zn and/or Ga, or some combination thereof) of from 0.01 bar to 100 bar₂/Al₂O₃Amorphous silica/alumina material in a ratio of 23 to 280 to obtain a high liquid hydrocarbon yield (80 +%) andhigh selectivity of aromatic hydrocarbon (benzene, toluene, xylene (BTX) selectivity in liquid hydrocarbon fraction)>90%). Ethylene purified from the OCM effluent or unpurified OCM effluent containing ethylene may be passed over a zeolite catalyst such as ZSM-5, or SiO at a temperature above 200 ℃ at an ethylene partial pressure (undoped, or having dopants including, but not limited to, for example, Ni, Mg, Mn, Ca, and Co, or some combination of these) of from 0.01 bar to 100 bar₂/Al₂O₃Amorphous silica/alumina materials in a ratio of 23 to 280 to obtain high liquid hydrocarbon yield (80 +%) and high gasoline selectivity (gasoline selectivity in the liquid hydrocarbon fraction)>90%). The ethylene purified from the OCM effluent or the unpurified OCM effluent containing ethylene may be passed over a zeolite catalyst such as ZSM-5, or SiO at an ethylene partial pressure of from 0.01 bar to 100 bar, at a temperature above 200 deg.C₂/Al₂O₃Amorphous silica/alumina materials in a ratio of 23 to 280 to obtain high liquid hydrocarbon yields (80 +%) and high distillate selectivity (gasoline selectivity in the liquid hydrocarbon fraction)>90％)。

In some embodiments, to achieve high jet/diesel fuel yields, a system of two oligomerization reactors is used in series. The first oligomerization reactor uses ethylene and oligomerizes it to C over a modified ZSM-5 catalyst, e.g., Mg, Ca or Sr doped ZSM-5 catalyst₃-C₆An olefin. The C is₃-C₆The olefins may be the final product of the process or alternatively may be placed in a second oligomerization reactor for coupling into a jet/diesel fuel range liquid.

In addition, some embodiments of the ethylene conversion process also include processes for producing oxygenated hydrocarbons, such as alcohols and/or epoxides. For example, the ethylene product can be routed through an integrated system comprising a heterogeneous catalyst system (e.g., a solid phosphoric acid catalyst in the presence of water) to convert ethylene to ethanol. This process has been conventionally used to produce 200 proof of strength (proof) ethanol in the process used by LyondellBasell. In other embodiments, longer chain olefins and/or LAOs derived from OCM ethylene by oligomerization can be similarly converted to alkyl alcohols using this same process. See, for example, U.S. patent nos. 2,486,980; 3,459,678, respectively; 4,012,452, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes. In an alternative embodiment, ethylene is subjected to a steam oxidation reaction to produce ethylene oxide with high selectivity (80 +%) over a silver-based catalyst at 200-. Ethylene oxide is an important precursor for the synthesis of ethylene glycol, polyethylene glycol, ethylene carbonate, ethanolamine and halohydrins. See, for example, Chemsystems perreport Ethylene Oxide/Ethylene Glycol 2005, which is incorporated herein by reference.

In other aspects, the ethylene product produced from an OCM reactor system can be routed to a reactor system that reacts ethylene with various halogen sources (acids, gases, and others) to produce halogenated hydrocarbons that can be used, for example, as monomers in the production of halogenated polymers such as polyvinyl chloride (PVC). For example, in an Ethylene Dichloride (EDC) process available from thyssen krupp Uhde, ethylene may be reacted with chlorine to produce EDC, an important precursor of Vinyl Chloride Monomer (VCM) for the production of polyvinyl chloride (PVC). The process may also be a modified EDC process to react ethylene with hydrochloric acid (HCl) to produce EDC via oxychlorination.

In other exemplary ethylene conversion processes, the ethylene product of the OCM reactor system may be converted to alkylated aromatics, which are also useful as chemical and dye feedstocks. For example, in the Lummus CD-TechEB process and Badger EB process, benzene can be reacted with OCM ethylene in the presence of a catalyst to produce ethylbenzene. See, for example, U.S. Pat. No. 4,107,224, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes. Ethylbenzene may be added to gasoline as a high octane gasoline blendstock, or may be dehydrogenated to produce styrene, a precursor to polystyrene.

In addition to the above-described liquids and other hydrocarbons, in certain aspects, one or more integrated ethylene conversion processes are used to convert the ethylene product from the OCM reactor system into one or more hydrocarbon polymers or polymer precursors. For example, in some embodiments, the ethylene product from an integrated OCM reactor system is routed through an integrated innoven process system available through Technologies, inc. where ethylene is polymerized in a slurry or gas phase system in the presence of a catalyst to produce long hydrocarbon chains or polyethylene. The process and system can be used to produce high density polyethylene or branched low density polyethylene, etc. by varying the process conditions and catalyst. The innoven G and innoven S processes are described, for example, on "inoos technologies. See also, Nexant/Chemsys HDPE Report, PERP 09/10-3,2011, 1 month, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.

Alternatively, ethylene from the OCM can be introduced at high pressure in the presence of a free radical initiator such as O₂Or a peroxide in an autoclave or tubular reactor to initiate the polymerization reaction for the preparation of Low Density Polyethylene (LDPE). See, e.g., "Advanced Polyethylene Technologies" Adv Polym Sci (2004)169:13-27, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes. Alternatively, ethylene from the OCM can be introduced in the presence of a chromia-based catalyst, a Ziegler-Natta catalyst or a single site (metallocene-based or non-metallocene-based) catalyst at low pressure to produce HDPE, MDPE, LLDPE, mLLDPE or bimodal polyethylene. The reactor configuration for the synthesis of HDPE, LLDPE, MDPE and bimodal polyethylene may be a slurry process, wherein ethylene is polymerised to form solid polymer particles suspended in a hydrocarbon diluent; a solution process, wherein dissolved ethylene polymerizes to form a polymer dissolved in a solvent; and/or gas phase processes in which ethylene is polymerized to form a solid polymer in a fluidized bed of polymer particles. Ethylene from the OCM can be copolymerized with different monomers to produce random and block copolymers. Comonomers used in the copolymerization of ethylene include, but are not limited to: at least one olefin comonomer having from three to fifteen carbons per molecule (examples are propylene and LAO, such as 1-butene, 1-hexene, 1-octene), oxygenated comonomers, such as: carbon oxide, vinyl acetate, methyl acrylate; vinyl alcohol; an allyl ether; cyclic monomers such as norbornene and its derivatives; aromatic olefins, such as: styrene and its derivatives. These ethylenes orLAO copolymerization processes (e.g., wherein ethylene is copolymerized with different monomers) are generally referred to herein as copolymerization processes or systems.

Further exemplary ethylene conversion processes that may be integrated with the OCM reactor system include processes and systems for performing olefin metathesis reactions (also known as disproportionation reactions) in the production of propylene. Olefin metathesis is a reversible reaction between ethylene and butene in which the double bond is broken and subsequently reformed to form propylene. "Propylene Production via metadata, Technology Economics Program" by Intratec, ISBN 978-0-615-. A propylene yield of about 90 wt% was achieved. This option can also be used when there is no butene feed. In this case, part of the ethylene from the OCM reaction is fed to the ethylene dimerization unit which converts ethylene to butene.

As described herein, for example, as shown in fig. 1, one, two, three, four, or more different ethylene conversion processes integrated into the overall system of the present invention are provided. It should be understood that these ethylene conversion systems will include fluid communication with the OCM system described herein, and may be within the same facility or within an adjacent facility. Further, these fluid communications may be selective. In particular, in certain embodiments, the interconnection between an OCM system component and an ethylene conversion system component is capable of selectively directing all of the ethylene product from the OCM system to any one ethylene conversion system at a given time, and subsequently directing all of the ethylene product to a second, different ethylene conversion system component at a different time. Alternatively, such selective fluid communication can also simultaneously direct a portion of the ethylene product to two or more different ethylene conversion systems fluidly connected to the OCM system.

These fluid communications will typically include interconnected piping and manifolds with associated valves, pumps, thermal controls, etc. for selectively directing the ethylene product of the OCM system to the appropriate ethylene conversion system component or components.

In one example, ethylene produced by the methods described herein (e.g., by OCM) can be converted to 1-butene or 2-butene. In some cases, 1-butene but no significant 2-butene, or 2-butene but no significant 1-butene, can be formed using the ETL processes and systems provided herein. Processes for producing 1-butene from ethylene are disclosed in U.S. patent No. 2,943,125, U.S. patent No. 3,686,350, U.S. patent No. 4,101,600, U.S. patent No. 8,624,042, and U.S. patent No. 5,792,895, each of which is incorporated herein by reference in its entirety.

Alternatively or additionally, ethylene produced by the methods described herein (e.g., by OCM) can be converted to 1-hexene. Processes for converting ethylene to 1-hexene are described in U.S. patent No. 6,380,451, U.S. patent No. 7,157,612, U.S. patent No. 5,057,638, U.S. patent No. 8,658,750, and U.S. patent No. 5,811,618, each of which is incorporated herein by reference in its entirety. Alternatively or additionally, ethylene produced by the processes described herein (e.g., by OCM) can be converted to 1-octene. Processes for converting ethylene to 1-octene are described in U.S. patent No. 5,292,979, U.S. patent No. 5,811,619, U.S. patent No. 5,817,905, and U.S. patent No. 6,103,654, each of which is incorporated herein by reference in its entirety.

In some cases, ethylene produced by the processes described herein (e.g., by OCM) can be converted to C4 to C18 and higher alpha olefins (1-butene, 1-hexene, 1-octene, 1-decene, and higher). The oligomerization of ethylene to Linear Alpha Olefins (LAO) may be carried out in a bubble column reactor, wherein the solvent and dissolved catalyst components are fed to the liquid phase. For converting ethylene to C₄-C₁₈And higher alpha-olefins are described in canadian patent application No. CA 2,765,769, german patent No. DE4338414, german patent No. DE 4338416, U.S. patent No. 3,862,257, U.S. patent No. 4,966,874, and U.S. patent No. 5,449,850, each of which is incorporated herein by reference in its entirety.

Alternatively or additionally, ethylene produced by the methods described herein (e.g., by OCM) can be converted to C₄To C₁₀Alpha-olefins (1-butene, 1-hexene, 1-octene and 1-octene)-decene). For converting ethylene to C₄To C₁₀Processes for alpha-olefins are described in U.S. patent No. 3,660,519, U.S. patent No. 3,584,071, european patent No. EP0,722,922, U.S. patent No. 4,314,090, U.S. patent No. 5,345,023, and U.S. patent No. 6,221,986, each of which is incorporated herein by reference in its entirety.

In another example, ethylene produced by the methods described herein (e.g., by OCM) can be converted to propylene. For example, n-butenes may be reacted with ethylene in a fixed bed reactor process using a heterogeneous catalyst system. Processes for converting ethylene to propylene are described in U.S. patent No. 6,683,019, U.S. patent No. 7,214,841, U.S. patent No. 8,153,851, and U.S. patent No. 8,258,358, each of which is incorporated herein by reference in its entirety.

Alternatively or additionally, ethylene produced by the processes described herein (e.g., by OCM) can be converted to Ethylene Dichloride (EDC). For example, ethylene may be reacted with chlorine in the liquid phase in the presence of a catalyst system. Processes for converting ethylene to EDC are described in german patent No. DE 1905517, german patent No. DE 2540257, german patent No. DE 4039960 a16, U.S. patent No. 7,579,509, U.S. patent No. 7,671,244 and U.S. patent No. 6,841,708, each of which is incorporated herein by reference in its entirety.

Ethylene produced by the methods described herein (e.g., by OCM) can be converted to High Density Polyethylene (HDPE) or other types of polyethylene. For example, ethylene or a mixture of ethylene and one or more alpha olefins may be reacted in the gas phase in the presence of a catalyst system. Processes for converting ethylene to HDPE are described in U.S. patent No. 5,473,027, U.S. patent No. 6,891,001, and U.S. patent No. 4,882,400, each of which is incorporated herein by reference in its entirety.

Ethylene produced by the methods described herein (e.g., by OCM) can be converted to ethanol. For example, a mixture of ethylene and water is reacted in a reactor over a heterogeneous catalyst (e.g., a solid phosphoric acid catalyst) to form ethanol by direct hydration of ethylene. Processes for converting ethylene to ethanol are described in U.S. patent No. 2,486,980, U.S. patent No. 2,579,601, U.S. patent No. 2,673,221, and U.S. patent No. 3,686,334, each of which is incorporated herein by reference in its entirety.

Acetylene can be selectively hydrogenated to ethylene without hydrogenating the ethylene while the acetylene is present in a mixture containing ethylene and other components. For example, a feed containing acetylene and ethylene is reacted over a heterogeneous catalyst in the presence of hydrogen in a fixed bed reactor system. Processes for the selective hydrogenation of acetylene are described in U.S. Pat. No. 3,128,317, U.S. Pat. No. 4,126,645, U.S. Pat. No. 4,367,353, U.S. Pat. No. 4,329,530, U.S. Pat. No. 4,440,956, U.S. Pat. No. 5,414,170, U.S. Pat. No. 6,509,292, and Xu, Link et al, "maximum ethylene glycol and diene selective hydrogenation reaction efficiency," Petroleum technology catalyst 18.3(2013):39-42, each of which is incorporated herein by reference in its entirety.

Acetylene and dienes such as butadiene can be selectively hydrogenated while present in a mixture containing ethylene and other components without hydrogenating the ethylene present. For example, a feed containing acetylene and diene is reacted over a heterogeneous catalyst in the presence of hydrogen in a fixed bed reactor system. Processes for the selective hydrogenation of acetylene and dienes are described in U.S. patent No. 3,900,526, U.S. patent No. 5,679,241, U.S. patent No. 6,759,562, U.S. patent No. 5,877,363, U.S. patent No. 7,838,710, and U.S. patent No. 8,227,650, each of which is incorporated herein by reference in its entirety.

Olefin to liquid reactorControl system

The present disclosure provides a computer control system that may be used to regulate or otherwise control the methods and systems provided herein. The control system of the present disclosure can be programmed to control process parameters to, for example, achieve a given product profile, such as a higher concentration of olefins compared to alkanes in the product stream exiting the OCM and/or ETL reactor.

Fig. 33 illustrates a computer system 3301 programmed or otherwise configured to adjust the OCM and/or ETL reactions, such as adjusting fluid properties (e.g., temperature, pressure, and flow rate of the flow), mixing, heat exchange, and OCM and/or ETL reactions. For example, the computer system 3301 may adjust a fluid flow ("flow") flow rate, a flow temperature, a flow pressure, an OCM and/or ETL reactor temperature, an OCM and/or ETL reactor pressure, an amount of recycled product, and an amount of a first flow (e.g., a methane flow) mixed with a second flow (e.g., an air flow).

Computer system 3301 includes a central processing unit (CPU, also referred to herein as a "processor" and "computer processor") 3305, which may be a single or multi-core processor, or multiple processors for parallel processing. Computer system 3301 also includes a memory or memory location 3310 (e.g., random access memory, read only memory, flash memory), an electronic storage unit 3315 (e.g., hard disk), a communication interface 3320 (e.g., a network adapter) for communicating with one or more other systems, and peripheral devices 3325 such as cache, other memory, data storage, and/or an electronic display adapter. The memory 3310, storage unit 3315, interface 3320, and peripheral devices 3325 communicate with the CPU 3305 through a communication bus (solid lines), such as a motherboard. The storage unit 3315 may be a data storage unit (or data store) for storing data.

CPU 3305 may execute a series of machine-readable instructions, which may be embodied in a program or software. The instructions may be stored in a memory location, such as the memory 3310. Examples of operations performed by the CPU 3305 may include fetch, decode, execute, and write-back.

The storage unit 3315 may store files such as drivers, libraries, and saved programs. The storage unit 3315 may store programs and recorded sessions generated by the user, and outputs related to the programs. The storage unit 3315 may store user data, such as user preferences and user programs. In some cases, the computer system 3301 can include one or more additional data storage units that are external to the computer system 3301, such as located on a remote server that communicates with the computer system 3301 over an intranet or the internet.

Computer system 3301 may be in communication with an OCM and/or ETL system 3330 that includes an OCM and/or ETL reactor and a plurality of process elements. Such process elements may include sensors, flow regulators (e.g., valves), and pumping systems configured to direct fluids.

The methods as described herein may be implemented by way of machine (e.g., computer processor) executable code stored on an electronic storage location of the computer system 3301 (e.g., on the memory 3310 or electronic storage unit 3315). The machine-executable or machine-readable code may be provided in the form of software. In use, the code may be executed by the processor 3305. In some cases, the code may be retrieved from the memory unit 3315 and stored on the memory 3310 ready for access by the processor 3305. In some cases, the electronic storage unit 3315 may be eliminated, and the machine-executable instructions stored on the memory 3310.

The code may be pre-compiled and configured for use with a machine having a processor adapted to execute the code, or may be compiled at run-time. The code may be provided in a programming language that may be selected to enable the code to be executed in a pre-compiled or originally compiled manner.

Aspects of the systems and methods provided herein, such as computer system 3301, may be embodied in programming. Various aspects of the technology may be considered as an "article of manufacture" or "article of manufacture" typically in the form of machine (or processor) executable code and/or associated data carried on or embodied in some type of machine-readable medium. The machine executable code may be stored on an electronic storage unit such as a memory (e.g., read only memory, random access memory, flash memory) or a hard disk. A "storage" type medium may include any or all of a computer's tangible memory, processors, etc., or its associated modules, such as various semiconductor memories, tape drives, disk drives, etc., that may provide non-transitory storage for software programming at any time. Some or all of the software may sometimes communicate over the internet or various other telecommunications networks. For example, such communication may cause software to be loaded from one computer or processor into another, e.g., from a management server or host into the computer platform of an application server. Thus, another type of media which may carry software elements includes optical, electrical, and electromagnetic waves through wired and optical land line networks and over various air links, as used through physical interfaces between local devices. The physical elements carrying such waves, such as wired or wireless links, optical links, etc., may also be considered as media carrying software. As used herein, unless limited to a non-transitory, tangible "storage" medium, terms such as a computer or machine "readable medium" refer to any medium that participates in providing instructions to a processor for execution.

Thus, a machine-readable medium, such as computer executable code, may take many forms, including but not limited to tangible storage media, carrier wave media, or physical transmission media. Non-volatile storage media include, for example, optical or magnetic disks, any storage device in any computer, etc., such as may be used to implement the databases and the like shown in the figures. Volatile storage media includes dynamic memory, such as the main memory of such a computer platform. Tangible transmission media include coaxial cables; copper wire and fiber optics, including the wires that comprise a bus within a computer system. Carrier-wave transmission media can take the form of electrical or electromagnetic signals, or acoustic or light waves, such as those generated during Radio Frequency (RF) and Infrared (IR) data communications. Thus, common forms of computer-readable media include, for example: a floppy disk, a flexible disk, hard disk, magnetic tape, any other magnetic medium, a CD-ROM, DVD or DVD-ROM, any other optical medium, punch cards, paper tape, any other physical storage medium with patterns of holes, a RAM, a ROM, a PROM, and EPROM, a FLASH-EPROM, any other memory chip or cartridge, a carrier wave transporting data or instructions, cables or links transporting such a carrier wave, or any other medium from which a computer can read programming code and/or data. Many of these forms of computer-readable media may be involved in carrying one or more sequences of one or more instructions to a processor for execution.

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System and method for ethylene to liquids

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