Method for maximizing production of ethylene or propylene
阅读说明:本技术 一种乙烯或丙烯最大化的生产方法 (Method for maximizing production of ethylene or propylene ) 是由 辛本恩 叶宗君 于 2020-08-12 设计创作,主要内容包括:本发明公开了一种乙烯或丙烯最大化的生产方法,其主要步骤:以原油及其馏份油,城市混合废塑料等为原料经预处理后进入催化裂解反应器,反应后的高温油气经两段式预洗塔降温除杂及相关分离后,得到轻、重两种馏份油;重馏份油进行加氢反应操作;轻馏份油分离处理,其烯烃进行重组操作,其烷烃进蒸汽裂解装置富产乙烯,其芳烃组份分离后作为副产品;上述加氢和重组反应的产物,及蒸汽裂解的馏份油循环至催化裂解反应器。本发明的生产方法,其乙烯加丙烯收率为原料的45~75m%,芳烃收率为原料的15~30m%;特别的,以城市混合废塑料为原料时,其生产乙烯或丙烯由常规聚合工艺重新生产出新塑料,实现废塑料的化学循环利用。(The invention discloses a method for producing ethylene or propylene in a maximized mode, which mainly comprises the following steps: crude oil and distillate oil thereof, urban mixed waste plastic and the like are used as raw materials, pretreated and then enter a catalytic cracking reactor, and high-temperature oil gas after reaction is subjected to temperature reduction, impurity removal and relevant separation in a two-section pre-washing tower to obtain light distillate oil and heavy distillate oil; carrying out hydrogenation reaction operation on the heavy distillate oil; separating light fraction oil, recombining olefin, feeding alkane into steam cracking device to produce ethylene, and separating aromatic hydrocarbon component to obtain byproduct; the products of the above hydrogenation and recombination reactions, and the distillate oil from steam cracking are recycled to the catalytic cracking reactor. According to the production method, the yield of ethylene and propylene is 45-75 m% of the raw material, and the yield of aromatic hydrocarbon is 15-30 m% of the raw material; particularly, when urban mixed waste plastics are used as raw materials, ethylene or propylene produced by the urban mixed waste plastics is regenerated into new plastics by a conventional polymerization process, so that the chemical recycling of the waste plastics is realized.)
1. A process for maximizing the production of ethylene or propylene, characterized in that it comprises the following steps:
s1: pretreating raw materials, mixing the pretreated raw materials with superheated steam in a mixer, uniformly mixing the mixture, then feeding the mixture into a catalytic cracking reactor, converting the raw materials into high-temperature oil gas and waste residues under the action of a catalyst, and cooling and removing impurities from the high-temperature oil gas by a two-section pre-washing tower to obtain light distillate oil, heavy distillate oil, gas products and other products; the two-section pre-washing tower comprises a preheating section and a de-superheating section;
s2: carrying out hydrogenation reaction operation on the heavy distillate oil in the step S1; the olefin component in the light distillate oil is recombined, and the BTX component is separated to be used as one of the products; the alkane component enters a steam cracking device;
s3: recycling the products of hydrogenation and recombination reactions obtained in the step S2 and steam cracking distillate oil to the catalytic cracking reactor of the step S1, and carrying out selective catalytic cracking reaction again in the catalytic cracking reactor; the mass ratio of the total product output in circulation to the fresh raw material is 10-60: 100, respectively;
s4: sending the gas product in the step S1 to a steam cracking device, and intensively separating methane, ethane, ethylene, propane, propylene and the like, wherein the ethylene and the propylene are used as products; ethane, propane and other alkanes are returned to the steam cracking device;
the raw materials are finally converted into products such as methane, ethylene, propylene, BTX and the like through the operations, wherein the yield of ethylene and propylene is 45-75 m% of the raw materials, the yield of aromatic hydrocarbon BTX is 15-30 m% of the raw materials, and the rest most of the raw materials are methane.
2. The method for maximizing the production of ethylene or propylene as claimed in claim 1, wherein the pretreatment operation comprises the steps of, when the raw material is urban mixed waste plastic: firstly, carrying out at least one operation treatment of shredding and iron removal processes on urban mixed waste plastics; secondly, conveying the waste plastics into a hot melting kettle, melting the waste plastics in the hot melting kettle into liquefied substances by adopting superheated steam, and collecting the liquefied substances at the bottom of the hot melting kettle; the operation conditions for melting the waste plastics into liquefied materials by heating are as follows: the temperature is 150-250 ℃; the pressure is 0.01-0.5 MPa; and finally, the waste plastic liquefied substance is sent to a two-section type prewashing tower to be preheated by using high-temperature oil gas as a heat source, and the preheated waste plastic liquefied substance is used as a raw material to be mixed with superheated steam and then enters a catalytic cracking reactor.
3. The method for maximizing ethylene or propylene as claimed in claim 2, wherein the temperature of the waste plastic liquefact is raised plate by plate after passing through the preheating section and the de-superheating section, the temperature is raised to 250 to 320 ℃ when reaching the bottom of the tower, part of the preheated waste plastic liquefact passes through the mixer and then enters the catalytic cracking reactor for catalytic cracking operation, and part of the waste plastic liquefact is recycled to the hot melting kettle.
4. The method for maximizing the production of ethylene or propylene as claimed in claim 1, wherein the pretreatment operation comprises at least one of the process steps of electro-desalting, atmospheric fractionation and butane deasphalting when the raw oil is crude oil, wherein the crude oil after atmospheric fractionation is subjected to a topping oil to produce ethylene rich in the steam cracking unit, a normal first line and a normal second line can produce aviation kerosene by using a fixed bed hydrocracking process, and the rest of the normal bottom oil is completely fed into the catalytic cracking reactor.
5. The method for maximizing the production of ethylene or propylene as claimed in claim 4, wherein a butane deasphalting process is selected before the bottom oil enters the catalytic cracking reactor to upgrade the bottom oil so as to remove more impurities such as heavy metals, asphaltenes, colloids and the like in the crude oil; the butane deasphalting operation temperature is 100-200 ℃, and the pressure is 2.0-6.0 MPa.
6. The method for maximizing the production of ethylene or propylene according to claim 1, wherein the pretreated raw material is selected from any one of the raw materials of claims 2 to 5, or a mixture of any two or more of the raw materials.
7. The process for the maximum production of ethylene or propylene according to claim 1, wherein said superheated steam is also selected from other superheated inert media.
8. The method for maximizing the production of ethylene or propylene according to claim 1, wherein the temperature of the top of the two-stage pre-scrubber is 100 to 200 ℃, and the pressure is 0.05 to 0.30 MPa; the temperature of a tower kettle is 250-320 ℃, in a de-superheating section, high-temperature oil gas is cooled from a superheated state to a saturated state, meanwhile, dust carried by the oil gas is washed, heavy distillate oil is obtained in the tower kettle, the oil gas at the top of the tower is cooled through heat exchange and then enters a three-phase separator, light distillate oil is discharged from the bottom of the tower, and products such as non-condensable gas are ejected from the tank.
9. The method for maximizing the production of ethylene or propylene according to claim 1, wherein in the step S1, the operating conditions of the catalytic cracking reactor are: the reaction temperature is 300-600 ℃, the reaction pressure is 0.05-0.5 MPa, the weight ratio of the catalyst to the oil is 6-12, and the airspeed is 0.1-30 h-1(ii) a The catalyst in the catalytic cracking reactor is a molecular sieve catalyst, and the molecular sieve catalyst refers to one or modification of molecular sieves such as ZSM5, ZSM35, BETA, USY and the like; the catalytic cracking reactor can be one of a fixed fluidized bed or a circulating fluidized bed or a combination of the fixed fluidized bed and the circulating fluidized bed.
10. The process for the maximum production of ethylene or propylene according to claim 1, wherein in step S2, the reforming operation is carried out in a polymerization reactor under the operating conditions: the reaction temperature is 40-200 ℃, and the reaction pressure is 0.5-6.0MPa and airspeed of 0.1-6 h-1。
Technical Field
The invention belongs to the technical field of ethylene or propylene production, and particularly relates to a production method for maximizing ethylene or propylene. The invention also belongs to the technical field of solid waste treatment and utilization, and particularly relates to a method for chemically recycling waste plastics in household garbage and industrial garbage.
Background
The conventional raw materials of the ethylene production by steam cracking are always limited to naphtha, and because the naphtha resource is limited and part of naphtha is required to enter a reforming device to produce aromatic hydrocarbons, the limitation of the raw materials always restricts the production capacity of the ethylene; how to expand the steam cracking feedstock in large quantities is one of the key issues in addressing ethylene production.
Plastics are widely used in various industries, for example: in textile industry, household appliance industry, building industry, automobile industry, agriculture and the like, waste plastics are increasing with the increasing consumption of plastic products. At present, the waste plastics in China mainly comprise plastic films, plastic wires, woven products, foamed plastics, plastic packing cases and containers, daily plastic products, plastic bags, agricultural mulching films and the like.
The biggest problem with plastic recycling, as compared to metal recycling, is the difficulty in automated sorting by machine, with the process involving a lot of manpower. The recycling rate of the plastic is generally low, which causes huge resource waste, and the garbage generated by using a large amount of plastic products can cause serious environmental pollution if being treated by methods such as burying, burning and the like.
In view of the above, it is desirable to provide a method for maximizing the production of ethylene or propylene from waste plastics or other oils.
Disclosure of Invention
Disclosed herein is a method for maximizing the production of ethylene or propylene, the method comprising the steps of:
s1: pretreating raw materials, mixing the pretreated raw materials with superheated steam in a mixer, uniformly mixing the mixture, then feeding the mixture into a catalytic cracking reactor, converting the raw materials into high-temperature oil gas and waste residues under the action of a catalyst, and cooling and removing impurities from the high-temperature oil gas by a two-section pre-washing tower to obtain light distillate oil, heavy distillate oil, gas products and other products; the two-section pre-washing tower comprises a preheating section and a de-superheating section;
s2: carrying out hydrogenation reaction operation on the heavy distillate oil in the step S1; the olefin component in the light distillate oil is recombined, and the BTX component is separated to be used as one of the products; the alkane component enters a steam cracking device;
s3: recycling the products of hydrogenation and recombination reactions obtained in the step S2 and steam cracking distillate oil to the catalytic cracking reactor of the step S1, and carrying out selective catalytic cracking reaction again in the catalytic cracking reactor; the mass ratio of the total product output in circulation to the fresh raw material is 10-60: 100, respectively;
s4: sending the gas product in the step S1 to a steam cracking device, and intensively separating methane, ethane, ethylene, propane, propylene and the like, wherein the ethylene and the propylene are used as products; ethane, propane, butane and other alkanes are returned to the steam cracking device;
the raw materials are finally converted into products such as methane, ethylene, propylene, BTX and the like through the operations, wherein the yield of ethylene and propylene is 45-75 m% of the raw materials, the yield of aromatic hydrocarbon BTX is 15-30 m% of the raw materials, and the balance is methane.
The catalytic cracking reaction is characterized in that the products are optional; if the product is the maximum ethylene production, the main products of the catalytic cracking reaction are firstly propane and butane, the yield of the main products is about more than 60m percent of the raw material, and the propane and the butane are subjected to steam cracking to produce ethylene, namely the maximum ethylene production is obtained; if the product is maximized propylene, the main product of the catalytic cracking reaction is propylene, the yield of the propylene is about more than 40 m% of the raw material, and the yield of the de-steamed cracked propane and butane is about 10-20 m% of the raw material. Therefore, the catalytic cracking process is mainly responsible for converting raw materials such as plastic oil (or waste plastic liquefaction), bottom oil and the like into propylene and BTX or propane and BTX; the steam cracking process is mainly responsible for converting the topped oil and alkanes such as propane, butane and the like generated by catalytic cracking into ethylene; in addition, liquid phase products such as pyrolysis gasoline and the like generated by steam cracking are returned to the catalytic cracking reactor for recycling.
These and other features, advantages, and objects of the present disclosure will be further understood and appreciated by those skilled in the art by reference to the following specification, claims, and appended drawings.
Drawings
FIG. 1 is a process flow diagram showing the steps of pretreatment, hot melting and catalytic cracking of urban mixed waste plastics as raw materials;
FIG. 2 shows a process flow diagram of the pretreatment and catalytic cracking steps for crude oil;
FIG. 3 is a flow chart showing a process for producing ethylene and/or propylene by steam cracking of alkane in the intermediate product of the reaction;
FIG. 4 is a process flow diagram showing the operation of reforming olefins in a light distillate;
FIG. 5 is a flow chart showing a process for hydrogenation of heavy distillate oil;
FIG. 6 is a schematic diagram of the two-stage pre-washing column of FIG. 1;
wherein, the hot melting kettle 1, the two-section pre-washing
Detailed Description
In this document, relational terms such as first, second, third, 1#, 2#, 3#, and the like may be used solely to distinguish one feed, product, apparatus, or unit operation from another feed, product, apparatus, or unit operation without necessarily requiring or implying any actual such relationship or order between such feeds, products, apparatus, or unit operations. The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a device that comprises a list of steps does not include only those elements but may include other elements not expressly listed.
As used herein, the term "and/or," when used in a list of two or more items, means that any one of the listed items can be used alone, or any combination of the two or more listed items can be separate. For example, if a starting material or product is described as comprising components a and/or B, the starting material or product may comprise one of a or B alone, or a and B in combination.
Referring now to fig. 1, in the method for maximizing the production of ethylene or propylene of at least one embodiment, in the process for maximizing the production of ethylene or propylene, municipal mixed waste plastics are used as raw materials. The main components of the urban mixed waste plastics are Polyethylene (PE), polypropylene (PP), Polystyrene (PS), polystyrene foam (PSF), polyvinyl chloride (PVC) and the like, and because the plastics are products of petrochemical industry, the plastics are macromolecular hydrocarbon compounds in terms of chemical structure and contained components, and can be converted into raw materials ethylene or propylene products for producing most plastics again through the breaking degradation and separation operation of carbon-hydrogen bonds of the macromolecular compounds. Before performing maximum production of ethylene or propylene from the waste plastics, the waste plastics are first subjected to a pretreatment operation including at least one of shredding, iron removal process. The shredding operation adopts a shredding device 101, waste plastic raw materials are conveyed to the shredding device 101, different shredders or crushers or a combination mode of the two are needed according to the characteristics of different plastic raw materials, so that waste plastic fragments with moderate sizes and uniform distribution of fragments, such as films, packaging bags and other soft plastics, can be obtained, and the waste plastic fragments are shredded by the shredding device; for example, the hard plastics such as the outer shell of the electric appliance are crushed by a crusher. The iron removal operation is mainly magnetic removal of iron-containing impurities by the pipeline de-ironing separator 102 to reduce the influence of the iron-containing impurities on the subsequent waste plastic degradation reaction. It will be appreciated that the iron-containing impurities in the raw municipal mixed waste plastic are low, or have been subjected to an iron removal treatment, the iron removal step can be omitted. The waste plastics after being shredded and/or deironing operation can be directly conveyed to a hot melting kettle 1 through a conveying machine for hot melting treatment.
Next, the waste plastics transferred to the hot melt pot 1 are melted into a liquefied material (plastic oil) by superheated steam and collected at the bottom of the hot melt pot 1. The operation conditions for melting the waste plastics into liquefied materials by heating are as follows: the temperature is 200-300 ℃; the pressure is 0.01 to 0.5 MPa. The hot melted waste plastics are converted into plastic oil and conveyed to the top of a two-stage pre-washing
In at least one embodiment, a filter element is arranged in the middle section of the hot melt kettle 1, and an inert heating medium inlet, an inert heating medium outlet, a liquid outlet and a solid outlet are further arranged on the tank body of the hot melt kettle 1. The inert heating medium inlet and the inert heating medium outlet are respectively arranged at the bottom and the top of the hot melting kettle 1 and are used for introducing and discharging superheated steam, and the discharged steam and part of low molecular gas products thereof are conveyed to the
The plastic oil mixed by the
High-temperature oil gas discharged from the catalytic cracking reactor 4 is subjected to temperature reduction and impurity removal by a two-section pre-washing
Turning now to fig. 2, in at least one embodiment of the ethylene or propylene maximized production process, crude oil is used as a feedstock during the ethylene or propylene maximized production process. Crude oil is first subjected to a pretreatment operation before it is subjected to maximum production of ethylene or propylene. When the raw material is crude oil, the pretreatment operation comprises at least one operation of the process steps of electric desalting, atmospheric fractionation, butane deasphalting and the like, wherein the crude oil is subjected to atmospheric fractionation through an
The modified bottom oil is conveyed to the
And (3) conveying the high-temperature oil gas into a two-
In at least one embodiment of the process for maximizing the production of ethylene or propylene, the feedstock is a mixture of a municipal mixed plastic, crude oil. The components in the mixture are respectively pretreated according to the pretreatment method of the raw materials, then are uniformly mixed in the
Turning now to fig. 3, the non-condensable gaseous products and/or topped oil are conveyed to a downstream steam cracking unit 16 for steam cracking of the paraffins; the reaction conditions of the steam cracking are as follows: the reaction temperature is 700-1000 ℃, the reaction pressure is 0.01-1.0 MPa, and the residence time is 0.01-0.6 s. Cracking products including methane, ethane, ethylene, propane, propylene and the like are obtained at the top of the steam cracking device 16, steam cracking distillate oil is obtained at the bottom, and the steam cracking distillate oil is circularly returned to the catalytic cracking reactor 4 for carrying out selective catalytic cracking reaction again.
The cleavage product is first conveyed to the decarbonation2Tower 17 for removing C2Operating; removing C2Cooling the tower top product of the tower 17 by a # 1 tower top cooler 172, then entering a # 1 two-phase separator 170 for cooling and separating, returning part of the separated product to the top of the C2 removing tower 17 by a # 1 reflux pump 171, and pumping part of the product to be conveyed to the demethanizer 18; the bottoms crude propylene fraction is fed to a propylene column 20 for propylene separation operations. Cooling the product at the top of the demethanizer 18 by a # 2 top cooler 182, then feeding the product into a # 2 two-phase separator 180 for cooling and separation, returning part of the separated product to the top of the demethanizer 18 by a # 2 reflux pump 181, and extracting part of the product to obtain methane gas; the bottoms crude ethylene fraction is fed to ethylene column 19 via # 3 transfer pump 183 for ethylene separation. Cooling the top product of the ethylene tower 19 by a No. 3 top cooler 192, then feeding the cooled product into a No. 3 two-phase separator 190 for cooling and separation, returning part of the separated product to the top of the ethylene tower 19 by a No. 3 reflux pump 191, and extracting part of the product to obtain ethylene gas; the bottom product of the ethylene tower 19 is ethane, and the ethane is conveyed to the steam cracking device 16 for steam cracking to produce ethylene. Cooling the top product of the propylene tower 20 by a No. 4 top cooler 212, then feeding the cooled product into a No. 4 two-phase separator 210 for cooling and separation, returning part of the separated product to the top of the propylene tower 20 by a No. 4 reflux pump 211, and extracting part of the product to obtain propylene gas; the bottom product of the propylene tower 20 is propane, and the propane is conveyed to the steam cracking device 16 for steam cracking to produce ethylene.
Turning now to FIG. 4, the light distillate oil undergoes a reforming reaction of olefins in a
Turning to fig. 5, the heavy fraction oil is preheated by a # 1
Reaction conditions of No. 2 hydrogenation reactor 9: the reaction temperature is 300-550 ℃, the reaction pressure is 10.0-30.0 Mpa, and the airspeed is 0.1-3 h-1;
Operating pressure of the
the operating pressure of the
the operating conditions of the hydrogenated-
In at least one embodiment, the superheated steam has a temperature of 450 to 550 ℃ and a pressure of 0.2 to 0.5 MPa. The superheated steam may also be selected from other superheated inert media, such as nitrogen.
The steam cracking distillate oil, the recombinant product and the hydrogenation reaction product are circularly returned to the catalytic cracking reactor 4 for carrying out the selective catalytic cracking reaction again, and the mass ratio of the total product output in circulation to the fresh raw material feed is 10-60: 100.
in at least one embodiment, the greatest feature of the catalytic cracking reaction described above is that its products are selectable; if the product is the maximum ethylene production, the main products of the catalytic cracking reaction are firstly propane and butane, the yield of the main products is about more than 60m percent of the raw material, and the propane and the butane are subjected to steam cracking to produce ethylene, namely the maximum ethylene production is obtained; if the product is maximized propylene, the main product of the catalytic cracking reaction is propylene, the yield of the propylene is about more than 40 m% of the raw material, and the yield of the de-steamed cracked propane and butane is about 10-20 m% of the raw material. It can be seen that the catalytic cracking process is responsible for converting plastic oil (or called waste plastic liquefaction), bottom oil, etc. into propylene and BTX, or propane and BTX; the steam cracking process is responsible for converting the topped oil and the alkanes such as propane, butane and the like generated by catalytic cracking into ethylene; liquid phase products such as pyrolysis gasoline and the like generated by steam pyrolysis are returned to the catalytic pyrolysis reactor 4 for recycling.
The raw materials are finally converted into products such as methane, ethylene, propylene, BTX and the like through the operations, wherein the yield of ethylene and propylene is 45-75 m% of the raw materials, the yield of aromatic hydrocarbon BTX is 15-30 m% of the raw materials, and the balance is methane.
Turning again to fig. 1 and 2, after a period of catalytic cracking reaction, the catalyst in the catalytic cracking reactor 4 is deactivated by carbon deposition, at which time the catalyst is regenerated; it mainly comprises the following steps; the catalyst leaves the catalytic cracking reactor 4 through a catalyst unloading line and is collected in a
The regenerated catalyst can be reused; the catalyst can be circulated for many times, and the regenerated heat source can adopt a superheated medium, such as steam, nitrogen and the like; a certain amount of air is introduced into the superheated medium during regeneration; when the catalytic cracking reactor 4 adopts a fluidized bed as a reactor, the catalyst is continuously circulated between the reactor and the regenerator 5, and air is directly introduced into the regenerator 5.
In at least one specific example, as shown in tables 1 and 2, the process operating conditions and product distribution for maximizing the production of propylene or ethylene for different feed compositions are listed.
TABLE 1
TABLE 2
Therefore, the yield of the chemical products is obviously higher than that of the conventional oil refining process combination in use, the yield of the ethylene and the propylene is 45-75 m% of the raw material, and the ethylene and the propylene can be recycled as the raw material for preparing plastics in industry; in addition, aromatic hydrocarbon BTX is byproduct in the whole process, the yield of the aromatic hydrocarbon is 15-30 m% of the raw material, and the yield of byproduct methane and coke is low.
The method for producing ethylene or propylene in a maximized mode can not only take crude oil as a raw material for catalytic cracking reaction, but also maximize the production of high-value ethylene, propylene and BTX raw materials; and the urban mixed waste plastics can be used as raw materials, and after the waste plastics are correspondingly pretreated, high-value ethylene, propylene and BTX raw materials can be maximally produced, so that the economic benefit and the social benefit are remarkable.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
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