阅读说明：本技术 使用超临界水的转化工艺 (Conversion process using supercritical water ) 是由 崔基玄 于 2019-02-26 设计创作，主要内容包括：一种用于提质重油的方法,该方法包括以下步骤：将重油进料引入部分氧化单元；将水进料引入部分氧化单元；将氧化剂进料引入部分氧化单元,其中氧化剂进料包含氧化剂；在部分氧化单元中,处理重油进料、水进料和氧化剂进料以产生液体氧化产物,其中液体氧化产物包含含氧化合物；将液体氧化产物引入超临界水单元；将水流引入超临界水单元；以及在超临界水单元中,处理液体氧化产物和水流以产生提质产物流,提质产物流包含相对于重油进料而言提质的烃。(A process for upgrading heavy oil, the process comprising the steps of: introducing a heavy oil feed to a partial oxidation unit; introducing a water feed to a partial oxidation unit; introducing an oxidant feed to a partial oxidation unit, wherein the oxidant feed comprises an oxidant; treating a heavy oil feed, a water feed, and an oxidant feed in a partial oxidation unit to produce a liquid oxidation product, wherein the liquid oxidation product comprises oxygenates; introducing the liquid oxidation product into a supercritical water unit; introducing a water stream into the supercritical water unit; and treating the liquid oxidation products and the water stream in a supercritical water unit to produce an upgraded product stream comprising upgraded hydrocarbons relative to the heavy oil feed.)

1. A process for upgrading heavy oil, the process comprising the steps of:

introducing a heavy oil feed to a partial oxidation unit;

introducing a water feed to a partial oxidation unit;

introducing an oxidant feed to a partial oxidation unit, wherein the oxidant feed comprises an oxidant;

treating the heavy oil feed, the water feed, and the oxidant feed in the partial oxidation unit to produce a liquid oxidation product, wherein the liquid oxidation product comprises oxygenates;

introducing the liquid oxidation product into a supercritical water unit;

introducing a water stream into the supercritical water unit; and

in the supercritical water unit, the liquid oxidation products and the water stream are treated to produce an upgraded product stream comprising upgraded hydrocarbons relative to the heavy oil feed.

2. The method of claim 1, further comprising the steps of:

increasing the pressure of the heavy oil feed in a feed pump to produce a pressurized oil feed;

introducing the pressurized oil feed into a feed heater;

in the feed heater, increasing the temperature of the pressurized oil feed to produce a hot oil feed;

mixing the water feed and the oxidant feed in a premixer to produce a mixed oxidant feed;

introducing the mixed oxidant feed into an oxidant pump;

in the oxidant pump, increasing the pressure of the mixed oxidant feed to produce a pressurized oxidant feed;

introducing the pressurized oxidant feed into an oxidant heater;

increasing the temperature of the pressurized oxidant feed to produce a hot oxidant feed;

mixing the hot oil feed and the hot oxidant feed in an oxidation mixer to produce a mixed oxidation feed;

introducing a mixed oxidation feed into an oxidation reactor;

in the oxidation reactor, subjecting the mixed oxidation feed to an oxidation reaction to produce a reactor effluent;

introducing the reactor effluent into an effluent cooler;

in the effluent cooler, reducing the temperature to produce a cooled effluent;

introducing the cooled effluent into an effluent pressure reduction device; and

reducing the pressure of the cooled effluent in the effluent pressure reduction device to produce a reduced pressure effluent;

introducing the reduced pressure effluent to a separator; and

in the separator, the reduced pressure effluent is separated to produce a gaseous oxidation product and the liquid oxidation product, wherein the gaseous oxidation product comprises unreacted oxidant.

3. The method according to claim 1 or 2, further comprising the steps of:

increasing the pressure of the liquid oxidation product in a pump to produce a pressurized stream;

introducing the pressurized stream into a heater;

increasing the temperature of the pressurized stream in the heater to produce a heat stream;

in a water pump, increasing the pressure of the water stream to produce a pressurized water stream;

introducing the pressurized stream of water into a water heater;

in the water heater, increasing the temperature of the pressurized water stream to produce a supercritical water stream;

mixing the hot and supercritical water streams in a mixer to produce a mixed stream;

introducing the mixed stream into a supercritical water reactor;

in the supercritical water reactor, subjecting the hydrocarbons to a set of conversion reactions to produce reactor products;

introducing the reactor product into a product cooler;

reducing the temperature of the reactor product to produce a cooled product;

introducing the cooled product into a pressure reduction device;

in the pressure reducing device, reducing the pressure of the cooled product to produce a reduced pressure stream;

introducing the reduced pressure stream into a gas-liquid separator to produce a gaseous product stream and a liquid stream;

introducing the liquid stream into a water oil separator; and

in the oil water separator, the liquid stream is separated to produce an upgraded product stream and a wastewater stream.

4. The process of any one of claims 1 to 3, wherein the heavy oil feed is selected from the group consisting of: petroleum, coal liquefaction oil, or biological material, and combinations thereof.

5. The method of any one of claims 1 to 4, wherein the oxidizing agent is selected from the group consisting of: air, oxygen, hydrogen peroxide, organic peroxides, and combinations thereof.

6. The process of any one of claims 1 to 5 wherein the molar ratio of oxygen atoms in the oxidant feed to carbon atoms in the heavy oil feed is between 0.0007 and 0.05.

7. The method of any one of claims 1 to 6, wherein the oxygenate is selected from the group consisting of alcohols, ketones, esters, ethers, carboxylic acids, and combinations thereof.

8. The process of claim 2, wherein the temperature of the oxidation reactor is between 150 ℃ and 374 ℃, and wherein the pressure of the oxidation reactor is between 0.5MPa and 35MPa, such that water in the oxidation reactor is present in the liquid phase.

9. The method of claim 2, wherein the liquid hourly space velocity in the oxidation reactor is in a range between 1hr "1 and 10 hr" 1.

10. The method of claim 2, wherein the oxidation reactor comprises an oxidation catalyst, wherein the oxidation catalyst comprises an active ingredient.

11. The method of claim 3, wherein the ratio of the supercritical water flow to the volumetric flow rate of the hot flow is in a range between 1.1:1 and 5: 1.

12. The method of claim 3, wherein the temperature of the supercritical water reactor is in a range between 380 ℃ and 500 ℃.

13. A system for upgrading a heavy oil feed, the system comprising:

a partial oxidation unit configured to treat the heavy oil feed, water feed, and oxidant feed to produce a liquid oxidation product, wherein the oxidant feed comprises an oxidant, wherein the liquid oxidation product comprises an oxygenate;

a supercritical water unit fluidly coupled to the partial oxidation unit, the supercritical water unit configured to process the liquid oxidation products and a water stream to produce an upgraded product stream comprising hydrocarbons upgraded relative to the heavy oil feed.

14. The system of claim 13, further comprising:

a feed pump configured to increase the pressure of the heavy oil feed to produce a pressurized oil feed;

a feed heater fluidly coupled to the feed pump, the feed heater configured to increase the temperature of the pressurized oil feed to produce a hot oil feed;

a premixer configured to mix the water feed and the oxidant feed to produce a mixed oxidant feed;

an oxidant pump fluidly connected to the premixer, the oxidant pump configured to increase the pressure of the mixed oxidant feed to produce a pressurized oxidant feed;

an oxidant heater fluidly coupled to the oxidant pump, the oxidant heater configured to increase a temperature of the pressurized oxidant feed to produce a hot oxidant feed;

an oxidation mixer fluidly coupled to the feed heater and the oxidant heater, the oxidation mixer configured to mix the hot oil feed and the hot oxidant feed to produce a mixed oxidation feed;

an oxidation reactor in fluid communication with the oxidation mixer, the oxidation reactor configured to subject the mixed oxidation feed to an oxidation reaction to produce a reactor effluent;

an effluent cooler in fluid communication with the oxidation reactor, the effluent cooler configured to reduce the temperature of the reactor effluent to produce a cooled effluent;

an effluent pressure reduction device fluidly coupled to the effluent cooler, the effluent pressure reduction device configured to reduce the pressure of the cooled effluent to produce a reduced pressure effluent; and

a separator in fluid communication with the effluent pressure reduction device, the separator configured to separate the reduced pressure effluent to produce a gaseous oxidation product and a liquid oxidation product, wherein the gaseous oxidation product comprises unreacted oxidant.

15. The system of claim 13 or 14, further comprising:

a pump configured to increase the pressure of the liquid oxidation products to produce a pressurized stream;

a heater fluidly coupled to the pump, the heater configured to increase a temperature of the pressurized flow in the heater to produce a heat flow;

a water pump configured to increase a pressure of the water stream to produce a pressurized water stream;

a water heater fluidly coupled to the water pump, the water heater configured to increase a temperature of the pressurized water stream to generate a supercritical water stream;

a mixer fluidly coupled to the heater and the water heater, the mixer configured to mix the hot and supercritical water streams to produce a mixed stream, wherein the mixed stream comprises hydrocarbons;

a supercritical water reactor fluidly coupled to the mixer, the supercritical water reactor configured to subject the hydrocarbon to a set of conversion reactions to produce a reactor product;

a product cooler fluidly coupled to the supercritical water reactor, the product cooler configured to reduce a temperature of the reactor product to produce a cooled product;

a pressure reduction device fluidly coupled to the product cooler, the pressure reduction device configured to reduce a pressure of the cooled product to produce a reduced pressure stream;

a gas-liquid separator fluidly connected to the pressure reduction device, the gas-liquid separator producing a gas product stream and a liquid stream; and

an oil-water separator fluidly coupled to the gas-liquid separator, the oil-water separator configured to separate the liquid stream to produce the upgraded product stream and a wastewater stream.

16. The system of any one of claims 13 to 15, wherein the oxidizing agent is selected from the group consisting of: air, oxygen, hydrogen peroxide, organic peroxides, and combinations thereof.

17. The system of claim 14, wherein the temperature of the oxidation reactor is between 150 ℃ and 374 ℃, and wherein the pressure of the oxidation reactor is between 0.5MPa and 35MPa such that water in the oxidation reactor exists in a liquid phase.

18. The system of claim 14, wherein the liquid hourly space velocity in the oxidation reactor is in a range between 1hr "1 and 10 hr" 1.

19. The system of claim 14, wherein the oxidation reactor comprises an oxidation catalyst, wherein the oxidation catalyst comprises an active ingredient.

20. The system of claim 14, wherein the temperature of the supercritical water reactor is in a range between 380 ℃ and 500 ℃.

Technical Field

The invention discloses a method for upgrading petroleum. Specifically, methods and systems for upgrading petroleum using a pretreatment process are disclosed.

Background

The supercritical water process can upgrade heavy oil through a radical-mediated reaction route, where chemical bonds are broken by thermal energy and the cage effect imposed by supercritical water prevents the formation of coke. However, severe operating conditions, such as high temperatures and long residence times, are required to achieve deep conversion of heavy oils. In conventional hydrocracking, deep conversion may refer to conversion of vacuum residuum between 50% and 90%, but the cost of deep conversion is the sacrifice of large amounts of hydrogen and the shortened life of the catalyst. These harsh conditions can produce significant amounts of gaseous products as well as coke material. The increase in the production of gaseous products results in a loss of liquid yield. In supercritical water processes, deep conversion can be achieved by increasing the temperature and residence time, which can also increase the yield of coke, thereby reducing the process time affected by plugging.

Disclosure of Invention

The invention discloses a method for upgrading petroleum. Specifically, methods and systems for upgrading petroleum using a pretreatment process are disclosed.

In a first aspect, a process for upgrading heavy oil is provided. The method comprises the following steps: introducing a heavy oil feed to a partial oxidation unit; introducing a water feed to a partial oxidation unit; introducing an oxidant feed to a partial oxidation unit, wherein the oxidant feed comprises an oxidant; treating a heavy oil feed, a water feed, and an oxidant feed in a partial oxidation unit to produce a liquid oxidation product, wherein the liquid oxidation product comprises oxygenates; introducing the liquid oxidation product into a supercritical water unit; introducing a water stream into the supercritical water unit; and treating the liquid oxidation products and the water stream in a supercritical water unit to produce an upgraded product stream comprising upgraded hydrocarbons relative to the heavy oil feed.

In certain aspects, the method further comprises the steps of: increasing the pressure of the heavy oil feed in a feed pump to produce a pressurized oil feed; introducing a pressurized oil feed into a feed heater; increasing the temperature of the pressurized oil feed in the feed heater to produce a hot oil feed; mixing, in a premixer, a water feed and an oxidant feed to produce a mixed oxidant feed; introducing a mixed oxidant feed into an oxidant pump; increasing the pressure of the mixed oxidant feed in the oxidant pump to produce a pressurized oxidant feed; introducing a pressurized oxidant feed into an oxidant heater; increasing the temperature of the pressurized oxidant feed to produce a hot oxidant feed; mixing a hot oil feed and a hot oxidant feed in an oxidation mixer to produce a mixed oxidation feed; introducing a mixed oxidation feed into an oxidation reactor; subjecting the mixed oxidation feed to an oxidation reaction in an oxidation reactor to produce a reactor effluent; introducing the reactor effluent into an effluent cooler; in an effluent cooler, reducing the temperature to produce a cooled effluent; introducing the cooled effluent into an effluent pressure reduction device; and reducing the pressure of the cooled effluent in an effluent pressure reduction device to produce a reduced pressure effluent; introducing the reduced pressure effluent into a separator; and separating, in a separator, the reduced pressure effluent to produce a gaseous oxidation product and a liquid oxidation product, wherein the gaseous oxidation product comprises unreacted oxidant.

In certain aspects, the method further comprises the steps of: increasing the pressure of the liquid oxidation product in the pump to produce a pressurized stream; introducing a pressurized stream into a heater; increasing the temperature of the pressurized stream in the heater to produce a heat stream; in a water pump, increasing the pressure of a water stream to produce a pressurized water stream; introducing a pressurized stream of water into a water heater; increasing the temperature of the pressurized water stream in a water heater to produce a supercritical water stream; mixing the hot and supercritical water streams in a mixer to produce a mixed stream; introducing the mixed stream into a supercritical water reactor; in a supercritical water reactor, subjecting hydrocarbons to a set of conversion reactions to produce reactor products; introducing the reactor product into a product cooler; reducing the temperature of the reactor product to produce a cooled product; introducing the cooled product into a pressure reduction device; reducing the pressure of the cooled product in a pressure reduction device to produce a reduced pressure stream; introducing the reduced pressure stream into a gas-liquid separator to produce a gaseous product stream and a liquid stream; introducing the liquid stream into an oil-water separator; and separating the liquid stream in a water oil separator to produce an upgraded product stream and a wastewater stream.

In certain aspects, the heavy oil feed is selected from the group consisting of: petroleum, coal liquefaction oil, or biological material, and combinations thereof. In certain aspects, the oxidizing agent is selected from the group consisting of: air, oxygen, hydrogen peroxide, organic peroxides, and combinations thereof. In certain aspects, the molar ratio of oxygen atoms in the oxidant feed to carbon atoms in the heavy oil feed is between 0.0007 and 0.05. In certain aspects, the oxygenate is selected from the group consisting of alcohols, ketones, esters, ethers, carboxylic acids, and combinations thereof. In certain aspects, the temperature of the oxidation reactor is between 150 ℃ and 374 ℃, and wherein the pressure of the oxidation reactor is between 0.5MPa and 35MPa such that water in the oxidation reactor is present in the liquid phase. In certain aspects, the liquid hourly space velocity is in a range between 1hr-1 and 10 hr-1. In certain aspects, the oxidation reactor comprises an oxidation catalyst, wherein the oxidation catalyst comprises an active ingredient. In certain aspects, the ratio of the supercritical water flow to the volumetric flow rate of the heat flow is in a range between 1.1:1 and 5: 1. In certain aspects, the temperature of the supercritical water reactor is in a range between 380 ℃ and 500 ℃.

In a second aspect, a system for upgrading a heavy oil feed is provided. The system comprises: a partial oxidation unit configured to treat a heavy oil feed, a water feed, and an oxidant feed to produce a liquid oxidation product, wherein the oxidant feed comprises an oxidant, wherein the liquid oxidation product comprises an oxygenate; a supercritical water unit in fluid communication with the partial oxidation unit, the supercritical water unit configured to process the liquid oxidation products and the water stream to produce an upgraded product stream, the upgraded product stream comprising upgraded hydrocarbons relative to the heavy oil feed.

In certain aspects, the system further comprises: a feed pump configured to increase the pressure of the heavy oil feed to produce a pressurized oil feed; a feed heater fluidly coupled to the feed pump, the feed heater configured to increase a temperature of the pressurized oil feed to produce a hot oil feed; a premixer configured to mix a water feed and an oxidant feed to produce a mixed oxidant feed; an oxidant pump fluidly connected to the premixer, the oxidant pump configured to increase a pressure of the mixed oxidant feed to produce a pressurized oxidant feed; an oxidant heater fluidly coupled to the oxidant pump, the oxidant heater configured to increase a temperature of the pressurized oxidant feed to produce a hot oxidant feed; an oxidation mixer fluidly coupled to the feed heater and the oxidant heater, the oxidation mixer configured to mix a hot oil feed and a hot oxidant feed to produce a mixed oxidation feed; an oxidation reactor fluidly coupled to the oxidation mixer, the oxidation reactor configured to subject a mixed oxidation feed to an oxidation reaction to produce a reactor effluent; an effluent cooler in fluid communication with the oxidation reactor, the effluent cooler configured to reduce the temperature of the reactor effluent to produce a cooled effluent; an effluent pressure reduction device fluidly coupled to the reactor cooler, the effluent pressure reduction device configured to reduce the pressure of the cooled effluent to produce a reduced pressure effluent; and a separator in fluid communication with the effluent pressure reduction device, the separator configured to separate the reduced pressure effluent to produce a gaseous oxidation product and a liquid oxidation product, wherein the gaseous oxidation product comprises unreacted oxidant.

In certain aspects, the system further comprises: a pump configured to increase the pressure of the liquid oxidation products to produce a pressurized stream; a heater fluidly coupled to the pump, the heater configured to increase a temperature of the pressurized flow in the heater to generate a heat flow; a water pump configured to increase a pressure of the water stream to produce a pressurized water stream; a water heater fluidly coupled to the water pump, the water heater configured to increase a temperature of the pressurized water stream to generate a supercritical water stream; a mixer fluidly coupled to the heater and the water heater, the mixer configured to mix the hot and supercritical water streams to produce a mixed stream, wherein the mixed stream comprises hydrocarbons; a supercritical water reactor fluidly coupled to the mixer, the supercritical water reactor configured to subject hydrocarbons to a set of conversion reactions to produce a reactor product; a product cooler fluidly coupled to the supercritical water reactor, the product cooler configured to reduce a temperature of a reactor product to produce a cooled product; a pressure reduction device fluidly coupled to the product cooler, the pressure reduction device configured to reduce a pressure of the cooled product to produce a reduced pressure stream; a gas-liquid separator fluidly connected to the pressure reduction device, the gas-liquid separator producing a gas product stream and a liquid stream;

and an oil-water separator fluidly coupled to the gas-liquid separator, the oil-water separator configured to separate the liquid stream to produce an upgraded product stream and a wastewater stream.

Drawings

These and other features, aspects, and advantages that are within the scope of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings. It is to be noted, however, that the appended drawings illustrate only a few embodiments and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

Figure 1 provides a flow diagram of an embodiment of the process of the present invention.

FIG. 2 provides a flow diagram of an embodiment of a partial oxidation unit.

Fig. 3 provides a flow diagram of an embodiment of a supercritical upgrading unit.

In the drawings, like components or features, or both, may have like reference numerals.

Detailed Description

Although the scope of the apparatus and method has been described with several embodiments, it is understood that one of ordinary skill in the relevant art will recognize that many examples, variations, and modifications of the apparatus and method described herein are within the scope and spirit of the embodiments.

Thus, the described embodiments are set forth without any loss of generality to, and without imposing limitations upon, the embodiments. It will be appreciated by a person skilled in the art that the scope of the present invention includes all possible combinations and uses of the specific features described in the specification.

The described methods and systems relate to upgrading heavy oil feedstocks. The described processes and systems involve partial oxidation of a heavy oil feedstock to produce oxygenates, such as alcohols, ethers, esters, and carboxylic acid compounds. Advantageously, the process sequence of the partial oxidation unit followed by the supercritical water unit allows for improved performance of heavy oil upgrading in the supercritical water unit. Advantageously, the partial oxidation unit provides a method of pretreating heavy oil to produce carbon-oxygen bonds that can be broken in a supercritical water unit. Advantageously, removing gas formed in the partial oxidation unit may improve the efficiency of the system by reducing the likelihood of pump damage due to cavitation caused by pumping of gas-containing liquids. The presence of oxygen and other gases in the supercritical water unit increases the amount of gas produced in the supercritical water unit while decreasing the liquid yield, and thus, removing gas upstream of the supercritical water unit increases the liquid yield. Advantageously, removing solid particles after the partial oxidation unit reduces the production of coke in the supercritical water unit. Advantageously, the upgrading process with partial oxidation pretreatment can increase the production of naphtha and gas oil fractions in the upgraded product from the supercritical water unit, which can increase API gravity. Advantageously, the partial oxidation upstream of the thermal cracking in supercritical water increases the overall liquid yield compared to the complete oxidation and enhances the conversion of the heavy fraction as well as the desulfurization, denitrification and demetallization reactions. Advantageously, the use of a partial oxidation unit upstream of the supercritical water unit reduces the amount of heat to be supplied to the supercritical water reactor.

It is known in the art that hydrocarbon reactions in supercritical water upgrade heavy oils and crude oils containing sulfur compounds, producing products with lighter fractions. Supercritical water has unique properties that make it suitable for use as a petroleum reaction medium where reaction objectives may include conversion reactions, desulfurization reactions, denitrification reactions, and demetallization reactions. Supercritical water is water having a temperature equal to or greater than the critical temperature of water and a pressure equal to or greater than the critical pressure of water. The critical temperature of water is 373.946 ℃. The critical pressure of water is 22.06 megapascals (MPa). Advantageously, under supercritical conditions, water acts as both a source of hydrogen and a solvent (diluent) in the conversion, desulfurization and demetallization reactions, and no catalyst is required. Hydrogen from water molecules is transferred to the hydrocarbons by direct transfer or by indirect transfer (such as the water gas shift reaction). In the water gas shift reaction, carbon monoxide and water react to produce carbon dioxide and hydrogen. Hydrogen may be transferred to hydrocarbons in desulfurization reactions, demetallization reactions, denitrification reactions, and combinations thereof. Hydrogen can also reduce the olefin content.

Without being bound by a particular theory, it is understood that the basic reaction mechanism of supercritical water mediated petroleum processes is the same as the radical reaction mechanism. The free radical reaction includes initiation, propagation, and termination steps. For hydrocarbons, such as C in particular₁₀₊Such as heavy molecules, initiation is the most difficult step and conversion in supercritical water may be limited due to the high activation energy required for initiation. Initiating the cleavage of the desired chemical bond. The bond energy of the carbon-carbon bond is about 350kJ/mol, and the bond energy of the carbon-hydrogen bond is about 420 kJ/mol. Due to the chemical bond energy, carbon-carbon bonds and carbon-hydrogen bonds are not easy to break under the condition of no catalyst or free radical initiator and at the supercritical water process temperature of 380-450 ℃. In contrast, the bond energy of the aliphatic carbon-sulfur bond is about 250 kJ/mol. Aliphatic carbon-sulfur bonds (as in thiols, sulfides, and disulfides) have lower bond energies than aromatic carbon-sulfur bonds.

Thermal energy generates free radicals through chemical bond cleavage. Supercritical water produces a "cage effect" by surrounding free radicals. The radicals surrounded by water molecules cannot easily react with each other, and thus the intermolecular reaction contributing to the formation of coke is suppressed. The cage effect inhibits coke formation by limiting the reactions between free radicals. Supercritical water having a low dielectric constant dissolves hydrocarbons and surrounds radicals to prevent a reaction between the radicals, which is a termination reaction causing condensation (dimerization or polymerization). Because the supercritical water cage provides a barrier, hydrocarbon radical transfer in supercritical water is more difficult than in conventional thermal cracking processes such as delayed coking where radicals move freely without such a barrier.

The sulfur compounds liberated from the sulfur-containing molecule can be converted to H₂S, mercaptans and elemental sulphur. Without being bound by a particular theory, it is believed that hydrogen sulfide is similar to water (H) due to its small size and similarity to water₂O) without being "impeded" by supercritical water cages. Hydrogen sulfide can freely pass through the supercritical water cage to grow radicals and distribute hydrogen. Hydrogen sulfide may lose its hydrogen due to its hydrogen abstraction reaction with hydrocarbon radicals. The resulting Hydrogen Sulfur (HS) radicals are able to abstract hydrogen from the hydrocarbon, which will allow more radicals to be formed. Thus, H in radical reactions₂S acts as a transfer agent to transfer radicals and abstract/donate hydrogen.

As previously mentioned, aromatic sulfur compounds are more stable in supercritical water than aliphatic sulfur compounds, which have higher activity. As a result, a feedstock with more aliphatic sulfur will have higher activity at the early stages of thermal cracking in supercritical water. However, the amount of aliphatic sulfur in the heavy oil feedstock is insufficient to increase the conversion of the heavy oil at temperatures limited to 450 ℃ and residence times of less than 10 minutes.

Aliphatic sulfur compounds are commonly found in light naphthas and vacuum residues. In vacuum residua, it is believed that aliphatic carbon-sulfur bonds are present in the asphaltene fraction. In normal crude oil, the content of aliphatic sulfur compounds is less than that of aromatic sulfur compounds.

As used throughout, "external supply of hydrogen" means that hydrogen is added to the feed to the reactor or to the reactor itself. For example, a reactor without external supply of hydrogen means that the feed to the reactor and the reactor are not fed with gaseous hydrogen (H)₂) Or liquid hydrogen, so that there is no hydrogen (as H)₂In the form of) is the feed or a portion of the feed to the reactor.

As used throughout, "external supply of catalyst" refers to the addition of catalyst to the feed to the reactor or the presence of catalyst in the reactor, such as a fixed bed catalyst in the reactor. For example, an externally supplied reactor without catalyst means that no catalyst is added to the feed to the reactor and the reactor does not include a catalyst bed in the reactor.

As used throughout, "external supply of oxidant" refers to adding oxidant to the feed to the reactor or adding oxidant to the reactor as a separate feed. For example, a reactor without external supply of oxidant means that oxidant is not added to the feed to the reactor in the form of a separate oxidant stream, and the reactor does not include a catalyst bed in the reactor.

As used throughout, "atmospheric resid" or "atmospheric resid fraction" refers to a fraction of an oil-containing stream having a T10% of 650 ° f, such that 90% of the volume of hydrocarbons boil above 650 ° f, and includes vacuum resid fractions. Atmospheric resid can refer to the composition of the entire stream (e.g., when the feedstock is from an atmospheric distillation unit) or can refer to a fraction of the stream (e.g., when a full range crude oil is used).

As used throughout, "vacuum residuum" or "vacuum residuum fraction" refers to a fraction of an oil-containing stream having a T10% of 1050 ° f. Vacuum residuum may refer to the composition of the entire stream (e.g., when the feedstock is from a vacuum distillation unit) or may refer to a fraction of the stream (e.g., when a full range crude oil is used).

As used throughout, "asphaltenes" refer to fractions of an oil-containing stream that are insoluble in n-alkanes, particularly n-heptane.

As used throughout, "coke" refers to toluene-insoluble material present in petroleum.

As used throughout, "cracking" refers to the breaking of hydrocarbons into smaller hydrocarbons containing few carbon atoms due to the breaking of carbon-carbon bonds.

As used throughout, "upgrading" refers to one or both of the following: increasing the API gravity, reducing the amount of impurities (such as sulfur, nitrogen, and metals), reducing the amount of asphaltenes, and increasing the amount of distillate in the process outlet stream relative to the process feed stream. One skilled in the art will appreciate that upgrading may be of relative significance such that a stream may be upgraded compared to another stream, but may still contain undesirable components, such as impurities.

As used herein, "conversion reaction" refers to a reaction that can upgrade a hydrocarbon stream, including cracking, isomerization, alkylation, dimerization, aromatization, cyclization, desulfurization, denitrification, deasphalting, and demetallization.

As used herein, "partial oxidation" refers to oxidation reactions in which the amount of oxygen present is limited such that the extent of the oxidation reaction is limited. Although the carbon and heteroatoms present are in an oxidizing environment, unlike a fully oxidizing environment, not all of the carbon is converted to carbon dioxide in the partial oxidation reaction. The degree of oxidation depends on the amount of oxygen present in the oxidation reactor, the temperature, the residence time and the catalyst.

As used herein, "deep conversion" is a qualitative term and refers to a conversion of greater than 50%, or greater than 70%, of the vacuum resid in the absence of an external supply of hydrogen and in the absence of an external supply of catalyst.

As used herein, a "natural gas to synthetic oil process" or a "GTL process" refers to a process that converts natural gas to liquid hydrocarbons such as gasoline and diesel. An example of a GTL process is the fischer-tropsch synthesis reaction. The hydrocarbons produced in the GTL process may yield paraffins.

The following embodiments, provided with reference to the drawings, describe the upgrading process.

Referring to fig. 1, a process flow diagram of an upgrading process is provided. Heavy oil feed 10, water feed 20, and oxidant feed 30 can be introduced to partial oxidation unit 100. Heavy oil feed 10 may be from any hydrocarbon source derived from petroleum, coal liquefaction oil, or biological material. Examples of heavy oil feed 10 include full range crude oil, distilled crude oil, residual oil, topped crude oil, refinery product streams, product streams from steam cracking processes, liquid hydrocarbons from natural gas to synthetic oil (GTL) processes, liquefied coal, liquid products recovered from oil or tar sands, bitumen, oil shale, asphaltenes, and biomass hydrocarbons. The heavy oil feed 10 may comprise an oxygen content of less than 1.5 wt.%, or less than 0.3 wt.%. "full range crude" refers to passivated crude oil that has been treated by a gas oil separation unit after recovery from a production well. "topped crude" may also be referred to as "distilled crude" and refers to crude without light ends and may include an atmospheric or vacuum residuum stream. The "refinery product stream" may include "cracked oils" (e.g., light cycle oils, heavy cycle oils) and streams from a fluid catalytic cracking unit (FCC) (e.g., slurry oils or decant oils), heavy streams from hydrocrackers boiling above 650 ° f, deasphalted oil (DAO) streams from solvent extraction processes, and mixtures of atmospheric resids and hydrocracker bottoms.

The water feed 20 may be demineralized water having a conductivity of less than 1.0 microsiemens per centimeter (μ S/cm), or less than 0.5 μ S/cm, or less than 0.1 μ S/cm. In at least one embodiment, the water feed 20 is demineralized water having an electrical conductivity of less than 0.1 μ S/cm. The sodium content of the water feed 20 may be less than 5 micrograms/liter (μ g/L), or less than 1 μ g/L. The chloride content of the water feed 20 may be less than 5 μ g/L, or less than 1 μ g/L. The silicon content of the water feed 20 may be less than 3 μ g/L.

The oxidant feed 30 may be a stream containing an oxidant. The oxidizing agent may include air, oxygen, hydrogen peroxide, organic peroxides, and combinations thereof. When the oxidizing agent is hydrogen peroxide, an organic peroxide, and combinations thereof, the oxidizing agent feed 30 can include an aqueous fluid. The aqueous fluid may comprise water. The concentration of the oxidant in the oxidant feed 30 can be adjusted and controlled to adjust the molar ratio of oxygen atoms in the oxidant feed 30 to carbon atoms in the heavy oil feed 10. The molar ratio of oxygen atoms in oxidant feed 30 to carbon atoms in heavy oil feed 10 can be in a range between 0.0007 and 0.05, between 0.005 and 0.1, or between 0.01 and 0.04. Advantageously, adjusting the concentration of the oxidant in the oxidant feed 30 to achieve a range of molar ratios of oxygen atoms to carbon atoms can reduce the amount of gaseous products formed in the partial oxidation unit 100. Reducing the amount of gaseous products increases the liquid yield from the partial oxidation unit 100 and the supercritical upgrading unit 200.

Heavy oil feed 10, water feed 20, and oxidant feed 30 can be treated in partial oxidation unit 100 to produce liquid oxidation product 40 and gaseous oxidation product 50. The gaseous oxidation product 50 may be sent for further processing or disposal. In at least one embodiment, the oxidation product 50 may be sent to a flare stack for disposal. The liquid oxidation products 40 may be introduced into the supercritical upgrading unit 200 along with the water stream 60.

The water stream 60 may be demineralized water having a conductivity of less than 1.0 microsiemens per centimeter (μ S/cm), alternatively less than 0.5 μ S/cm, alternatively less than 0.1 μ S/cm. In at least one embodiment, the water feed 20 is demineralized water having an electrical conductivity of less than 0.1 μ S/cm. The sodium content of the water feed 20 may be less than 5 micrograms/liter (μ g/L), or less than 1 μ g/L. The chloride content of the water stream 60 may be less than 5 μ g/L, or less than 1 μ g/L. The silicon content of the water stream 60 may be less than 3 μ g/L. Water stream 60 may be from the same source as water feed 20, or from a different source than water feed 20.

Liquid oxidation products 40 and water stream 60 can be treated in supercritical upgrading unit 200 to produce wastewater stream 70, upgraded product stream 80, and gaseous products 90. Upgraded product stream 80 can comprise upgraded hydrocarbons relative to heavy oil feed 10. The water content in the upgraded product stream 80 can be less than 0.3 wt%.

Wastewater stream 70 can be treated and, after treatment, wastewater stream 70 can be disposed of for recycle as a water feed to the front end of the partial oxidation unit or wastewater stream 70 can be recycled as a water stream to the supercritical water unit. In at least one embodiment, treatment of the wastewater stream 70 can include passing the wastewater stream 70 through a reverse osmosis membrane.

The partial oxidation unit 100 may be described with reference to fig. 2.

Heavy oil feed 10 can be introduced into feed pump 105. The pressure of heavy oil feed 10 can be increased in feed pump 105 to produce pressurized oil feed 110. The feed pump 105 can be any type of pump capable of increasing the pressure of the heavy oil stream. Examples of feed pump 105 may include a metering pump, such as a diaphragm pump. The pressure of pressurized oil feed 100 may be between 0.5MPa and 35MPa, or between 5MPa and 22 MPa. The pressurized oil feed 110 may be introduced into a feed heater 115.

The temperature of the pressurized oil feed 110 can be increased in the feed heater 110 to produce the hot oil feed 120. The feed heater 115 can be any type of heat exchanger capable of increasing the temperature of the heavy oil stream. Examples of feed heater 115 include shell and tube exchangers, tube-in-tube heat exchangers, plate fin heat exchangers. The temperature of the hot oil feed 120 can be between 50 ℃ and 350 ℃, or between 100 ℃ and 150 ℃. The hot oil feed 120 can be introduced to the oxidizing mixer 155.

The water feed 20 and the oxidizer feed 30 can be introduced into a premixer 125 to produce a mixed oxidizer feed 130. The premixer 125 may be selected from a simple mixer, a tank with an impeller, and combinations thereof. The water feed 20 and the oxidant feed 30 can be mixed in a premixer 125 to produce a mixed oxidant feed 130. In embodiments where the oxidant in the oxidant feed 30 is oxygen or air, the oxygen content in the mixed oxidant feed 130 can be controlled by the temperature and pressure in the premixer 125. The residence time in the premixer 125 may be sufficient to decompose the oxidant to produce oxygen. For example, when the oxidizing agent is hydrogen peroxide, the residence time in the premixer 125 may be sufficient for the decomposition of hydrogen peroxide into water and oxygen. The residence time in the premixer 125 may be between 10 seconds and 1 minute. In at least one embodiment, the premixer 125 is capable of removing undissolved gases. In at least one embodiment, undissolved gas may be removed by venting. The undissolved gas may include oxygen or air that is not mixed in the mixed oxidant feed 130. The mixed oxidant feed 130 can be introduced to an oxidant pump 135.

The pressure of the mixed oxidant feed 130 can be increased in the oxidant pump 135 to produce a pressurized oxidant feed 140. The oxidant pump 135 can be any type of pump capable of increasing the pressure of the aqueous fluid. Examples of oxidant pump 135 can include a metering pump, such as a diaphragm pump. The pressure of the pressurized oxidant feed 140 can be between 0.5MPa and 35MPa, or between 5MPa and 22 MPa. Pressurized oxidant feed 140 can be introduced to oxidant heater 145.

The temperature of the pressurized oxidant feed 140 can be increased in the oxidant heater 145 to produce the hot oxidant feed 150. The oxidant heater 145 may be any type of heat exchanger capable of increasing the temperature of the aqueous fluid. Examples of oxidant heater 145 may include shell and tube exchangers, electric heaters, and gas fired heaters. The temperature of the thermal oxidant feed 150 may be between 150 ℃ and 450 ℃, or between 200 ℃ and 360 ℃. The thermal oxidant feed 150 may be introduced to the oxidizing mixer 155. In at least one embodiment, the thermal oxidant feed 150 may be in supercritical conditions such that the water in the thermal oxidant feed 150 is in a supercritical state. In at least one embodiment, the thermal oxidant feed 150 is in subcritical conditions such that the water is in a liquid state. The hot oxidant feed 150 is at operating conditions such that the water in the oxidant feed is a supercritical fluid, or is in a liquid phase and is free of steam.

The oxidizing mixer 155 can combine the thermal oxidant feed 150 and the hot oil feed 120 to produce a mixed oxidizing feed 160. The oxidizing mixer 155 can be any type of mixer capable of mixing the heavy oil stream and the aqueous stream. Examples of the oxidizing mixer 155 may include a line mixer, a stirrer, and an ultrasonic chamber. The volume ratio of water to heavy oil in mixed oxidation feed 160 can be between 1:1 volume/volume (vol/vol) and 10:1vol/vol, or between 1:1vol/vol and 5:1vol/vol under SATP, at Standard Atmospheric Temperature and Pressure (SATP). In at least one embodiment, the volumetric ratio of water to heavy oil in mixed oxidation feed 160 can be maintained such that mixed oxidation feed 160 contains a greater amount of water than oil because maintaining a greater amount of water than oil minimizes the risk of a runaway reaction due to the exothermic conditions of the oxidation reaction in oxidation reactor 165. The water may act as a heat sink in the oxidation reactor 165 to control the temperature. The volume ratio of water to heavy oil in the mixed oxidation feed 160 can be controlled to maintain the overall molar ratio of oxygen to carbon of the liquid oxidation product 40.

Mixed oxidation feed 160 may be introduced into oxidation reactor 165. Oxidation reactor 165 can be any type of continuous type reactor capable of supporting an oxidation reaction. In at least one embodiment, the paraffins and alkyl chains attached to the aromatic core in the heavy oil are susceptible to oxidation reactions. In at least one embodiment, the aromatic hydrocarbon ring and the alicyclic hydrocarbon ring exhibit stability such that they are not susceptible to oxidation reactions. The oxidation reaction may produce oxygenates such that the reactor effluent 170 may comprise oxygenates. Oxygenates may include alcohols, ketones, esters, ethers, carboxylic acids, and mixtures thereof. In at least one embodiment, the maximum number of oxygenates is ketones having a carbonyl group (carbon-oxygen double bond). Oxidation reactions are different from hydration reactions in that hydration reactions require strong acid/base catalysts such as hydrogen sulfide or sodium hydroxide. Furthermore, hydration reactions only form alcohols, whereas oxidation reactions additionally form carboxylic acids and ketones. Examples of the oxidation reactor 165 may include a fixed bed reactor and a CSTR type reactor. The temperature in oxidation reactor 165 can be between 150 ℃ and 374 ℃, or between 250 ℃ and 320 ℃. The pressure in the oxidation reactor 165 may be between 0.5MPa and 35 MPa. The operating conditions in the oxidation reactor 165 may be controlled such that the water in the oxidation reactor 165 may be maintained in a liquid phase.

The oxidation reactor 165 operates under subcritical conditions in which water is present in the liquid phase, so that the oxidation reaction causes partial oxidation of the carbon compounds. Since oxygen diffusivity in supercritical water is high, supercritical water is an effective medium for oxidation reaction. Under supercritical conditions, the oxidation reaction can completely oxidize the carbon compounds to carbon dioxide, resulting in liquid loss. Therefore, the oxidation reaction under the supercritical water condition can reduce the liquid yield as compared with the oxidation reaction under the subcritical condition. In addition, under subcritical conditions, the degree of oxygen incorporation into the heavy oil can be controlled to maintain a desired oxygen concentration in the reactor effluent. Controlling the degree of oxygen incorporation in supercritical water is more difficult due to temperature. Complete oxidation of the carbon compounds does not occur in the oxidation reactor 165. Heterogeneous catalysts are unstable under supercritical water conditions.

Hydrocarbons in the mixed oxidation feed 160 may be upgraded due to the destruction of carbon-carbon bonds by oxidation.

Oxidation reactor 165 is steam free. The residence time of the oxidation reactor 165 may be determined based on the degree of incorporation of oxygen in the liquid product in the reactor effluent. Residence times, measured as Liquid Hourly Space Velocity (LHSV), can be in the range of per hourTime 1 (hr)^-1) And 10hr^-1In the range of (1), or 3hr^-1And 6hr^-1Within the range of (a). In at least one embodiment, the oxidation reactor 165 may operate without an external supply of catalyst. In at least one embodiment, the oxidation reactor 165 can comprise an oxidation catalyst and can be a fixed bed reactor. Oxidation reactor 165 is not a fluidized bed reactor because operating conditions are such that the water remains in the liquid phase, which is not easily fluidized.

The oxidation catalyst may comprise an active ingredient, or an active ingredient in combination with a support. The active ingredients may include transition metal oxides, noble metals, and lanthanide oxides. The transition metal oxide may include iron (Fe), nickel (Ni), zinc (Zn), copper (Cu), zirconium, and combinations thereof. The noble metal may include platinum (Pt), gold (Au), silver (Ag), and combinations thereof. The lanthanide oxide can include lanthanum oxide (La), cerium oxide (Ce), and combinations thereof. The support may comprise silicon dioxide (SiO)₂) Alumina (Al)₂O₃) Zeolites, and combinations thereof.

The reactor effluent 170 may include heavy oil, oxygenates, water, and oxidant. As described above, the total molar ratio of oxygen to carbon in the reactor effluent 170 can be controlled by adjusting the ratio of oxidant to heavy oil in the mixed oxidation reactor feed to the oxidation reactor, the temperature in the oxidation reactor, the residence time in the oxidation reactor, the catalyst in the oxidation reactor, and combinations thereof.

The reactor effluent 170 may be introduced to an effluent cooler 175. The temperature of the reactor effluent 170 can be reduced in an effluent cooler 175 to produce a cooled effluent 180. The effluent cooler 175 may be any type of heat exchanger capable of reducing the temperature of the mixed hydrocarbon and water stream. An example of effluent cooler 175 includes a shell and tube exchanger. The temperature of the cooled effluent 180 may be between 35 ℃ and 150 ℃. The cooled effluent 180 may be introduced to an effluent pressure reduction device 185.

The pressure of the cooled effluent 180 may be reduced in an effluent pressure reduction device 185 to produce a reduced pressure effluent 190. The effluent pressure reduction device 185 may be any type of unit capable of reducing the pressure of the mixed hydrocarbon and water stream. Examples of effluent pressure reduction devices 185 include pressure control valves, backpressure control valves, and capillary elements. The pressure of the reduced pressure effluent 190 may be in a range between ambient pressure and 0.1 MPa. The reduced pressure effluent 190 may be introduced to a separator 195.

The reduced pressure effluent 190 may be separated in separator 195 to produce a liquid oxidation product 40 and a gaseous oxidation product 50. Separator 195 can be any type of unit capable of separating streams in the vapor and liquid phases. Examples of separator 195 include a flash tank and a simple vessel. The separation in separator 195 means that the entire product stream from the reactor effluent is not diverted to the supercritical upgrading unit 200. In at least one embodiment, the purge stream may be introduced to separator 195. The purge stream may comprise an inert gas. Examples of inert gases in the purge stream may include nitrogen, helium, argon, and combinations thereof. Introducing the purge stream into separator 195 may enhance the separation of the gas in the reduced pressure effluent 190 from the liquid in the reduced pressure effluent 190.

In at least one embodiment, the cooled effluent 180 may be introduced to the separator 195 without an intermediate pressure reduction device. A purge stream such as nitrogen may be used in separator 195 to enhance the separation of the gas phase from the liquid phase. In such embodiments, the means for reducing the pressure may be located in the line to withdraw gaseous oxidation product 50 from separator 195.

Gaseous oxidation product 50 comprises gases formed in oxidation reactor 165, unreacted oxidant, water, and combinations thereof. The gas in the gaseous oxidation product 50 can include carbon monoxide, carbon dioxide, light hydrocarbons, and combinations thereof. The light hydrocarbons may include methane, ethane, butane, and combinations thereof. Advantageously, the separation of the reduced pressure effluent 190 into liquid oxidation products and gaseous oxidation products allows unreacted oxidant to be removed as part of the gaseous oxidation products. Removing unreacted oxidant is advantageous because the oxidant in supercritical water can reduce liquid yield and can cause corrosion problems in the supercritical upgrading unit 200.

The liquid oxidation product 40 comprises heavy oil, oxygenates, water, and combinations thereof. In at least one embodiment, the liquid oxidation product 40 is free of oxidizing agent. The liquid oxidation product 40 is free of blown pitch. The oxygenate may comprise an organic oxygenate, wherein the organic oxygenate may be present in an aqueous phase. The total molar ratio of oxygen to carbon in the liquid oxidation product 40 may be in the range between 0.005 and 0.1, or in the range between 0.01 and 0.04.

The supercritical upgrading unit 200 can be described in more detail with reference to fig. 3.

The liquid oxidation product 40 may be passed to a filter unit 202. The filter unit 202 may be any type of filter unit capable of separating solid particles from a fluid stream. The filter unit 202 may include a filter. The solid particles may include metal compounds, coke, and combinations thereof. The metal compound may include alkali, nickel, iron, vanadium, and combinations thereof. The filter unit 202 may separate solid particles having a size greater than 40 microns or greater than 140 microns. The filter unit 202 may separate solid particles formed in the partial oxidation unit 100 from solid particles present in the heavy oil feed 10. Solid particles in the liquid oxidation product 40 may be separated in a filter unit 202 to produce a solid waste 203 and a filtered stream 204. The filtered stream 204 may be sent to a pump 205.

The pressure of filtered stream 204 may be increased in pump 205 to produce pressurized stream 210. Pump 205 may be any type of pump capable of increasing the pressure of filtered stream 204. Examples of pump 205 include a metering pump, such as a diaphragm pump. The pressure of pressurized stream 210 can be greater than the critical pressure of water. Pressurized stream 210 can be introduced to heater 215.

The temperature of the pressurized stream 210 may be increased in the heater 215 to produce a hot stream 220. Heater 215 may be any type of heat exchanger capable of increasing the temperature of pressurized stream 210. Examples of heat exchangers that can be used as oil heater 215 can include electric heaters, fired heaters, and cross exchangers. The temperature of the hot stream 220 may be less than 250 ℃, or less than 150 ℃, or between 10 ℃ and 250 ℃, or between 50 ℃ and 150 ℃. Maintaining the temperature of hot stream 220 below 300 ℃ reduces the formation of coke in hot stream 220 and supercritical water reactor 255.

The water stream 60 may be delivered to a water pump 225. The pressure of the water stream 60 may be increased in the water pump 225 to produce a pressurized water stream 230. The water pump 225 may be any type of pump capable of increasing the pressure of the water stream 60. In at least one embodiment, the water pump 225 is a metering pump, such as a diaphragm pump. The pressure of the pressurized water stream 230 may be greater than the critical pressure of water. A pressurized water stream 230 may be introduced into a water heater 235.

The temperature of pressurized water stream 230 may be increased in water heater 235 to produce supercritical water stream 240. The water heater 235 may be any type of heat exchanger capable of increasing the temperature of the pressurized water stream 230. Examples of the heat exchanger that may be used as the water heater 235 may include an electric heater and a fired heater. The temperature of supercritical water stream 240 can be equal to or greater than the critical temperature of water, or between 374 ℃ and 550 ℃, or between 400 ℃ and 450 ℃.

The hot stream 220 and supercritical water stream 240 may be delivered to a mixer 245. Mixer 245 may be any type of mixing device capable of mixing a petroleum stream and a supercritical water stream. Examples of mixing devices suitable for use as mixer 245 may include static mixers, inline mixers (e.g., tee fittings), and impeller-embedded mixers. The ratio of the volumetric flow rates of hot water stream 220 and supercritical water stream 240 may be determined based on the amount of water in liquid oxidation product 40. The ratio of the volume flow rate of the supercritical water stream 240 to the hot stream 220 may be in a range between 1.1:1 and 5:1 at standard temperature and pressure (SATP). Advantageously, while the volume of water in liquid oxidation product 40 is sufficient for the conversion reaction to occur in supercritical water reactor 255, the generation of supercritical water stream 240 can reduce the heat load in heater 215 while maintaining the operating conditions in supercritical water reactor 225. The hot stream 220 and the supercritical water stream 240 can be mixed to produce a mixed stream 250. The pressure of the mixed stream 250 may be greater than the critical pressure of water. The temperature of the mixed stream 250 may depend on the temperature of the supercritical water stream 240 and the hot stream 220. The mixed stream 250 may be introduced into a supercritical water reactor 255.

The supercritical water reactor 255 may include one or more reactors in series. The supercritical water reactor 255 may be any type of continuous type reactor capable of allowing the conversion reaction to occur. Examples of reactors suitable for use in supercritical water reactor 255 may include tubular reactors, vessel reactors, and combinations thereof. In at least one embodiment, supercritical water reactor 255 comprises a tubular reactor, which advantageously prevents precipitation of reactants or products. The supercritical water reactor 255 may include an upflow reactor, a downflow reactor, and a combination of an upflow reactor and a downflow reactor. In at least one embodiment, supercritical water reactor 255 comprises an upflow reactor, which advantageously prevents channeling of reactants, thereby achieving improved reaction yields. In at least one embodiment, supercritical water reactor 255 has no external supply of hydrogen. The supercritical water reactor 255 has no external supply of catalyst. Operating the supercritical water reactor 255 without an external supply of hydrogen, an external supply of catalyst, and the removal of gases and unreacted oxidant from the gaseous oxidation product 50 may reduce the extent of over-cracking in the supercritical water reactor 255, which may increase the amount of low economic value gas produced. The supercritical water reactor 255 has no external supply of oxidant.

The temperature in the supercritical water reactor 255 may be maintained above the critical temperature of water, or in the range between 380 ℃ and 500 ℃, or in the range between 400 ℃ and 450 ℃. The pressure in the supercritical water reactor 255 can be maintained at a pressure greater than the critical pressure of water, or between 23MPa and 27 MPa. The residence time of the reactants in supercritical water reactor 255 may be between 1 minute and 120 minutes, or between 2 minutes and 10 minutes. The residence time is calculated by assuming that the density of the reactants in the supercritical water reactor 255 is the same as the density of water under the operating conditions of the supercritical water reactor 255.

The reactants in the supercritical water reactor 255 can undergo a conversion reaction to produce a reactor product 260. In at least one embodiment, a deoxygenation reaction, a hydrolysis reaction, a decarboxylation reaction, a dehydration reaction, a conversion reaction, and combinations thereof may occur in the supercritical water reactor 255. Deoxygenation reactions can include reactions that convert carbonyl groups (such as those found in ketones) to carbon monoxide, reactions that convert carboxyl groups to carbon dioxide, and combinations thereof. In the hydrolysis reaction, the ether may be converted into an alcohol, and the ester may be converted into an alcohol and an aldehyde. In the decarboxylation reaction, carboxyl groups may be removed from any oxygen-containing compound that releases carbon dioxide due to the presence of supercritical water. In the dehydration reaction, the alcohol may be converted to an olefin. In at least one embodiment, in a supercritical water reactor, the alcohol formed in the hydrolysis reaction can be converted to an olefin in a dehydration reaction. Advantageously, the carbon-oxygen bonds of the oxygenates can be broken in the supercritical water reactor, which can enhance the conversion reaction. In at least one embodiment, supercritical water reactor 255 is free of oxidation reactions. The reactor product 260 may be introduced to a product cooler 265.

The temperature of the reactor product 260 can be reduced in a product cooler 265 to produce a cooled product 270. The product cooler 265 can be any type of heat exchange device capable of reducing the temperature of the reactor product 260. Examples of product cooler 265 may include a double pipe exchanger and a shell and tube exchanger. The temperature of the cooled product 270 may be between 10 ℃ and 200 ℃, or between ambient temperature and 150 ℃, or between 30 ℃ and 150 ℃. The cooled product 270 may be introduced into a pressure reduction device 275.

The pressure of the cold product 270 can be reduced to produce a reduced pressure stream 280. The pressure relief device 275 may be any type of device capable of reducing the pressure of a fluid stream. Examples of pressure relief device 275 may include pressure relief valves, pressure control valves, and back pressure regulators. The pressure of the reduced pressure stream 280 can be between atmospheric pressure and 0.1 MPa. The reduced pressure stream 280 may be introduced to a gas-liquid separator 285.

Gas-liquid separator 285 may be any type of separation device capable of separating a fluid stream into a gas phase and a liquid phase. The reduced pressure stream 280 can be separated in a gas-liquid separator 285 to produce a liquid stream 290 and a gaseous product stream 90. The liquid stream 290 may be introduced into a water oil separator 295.

The oil water separator 295 may be any type of separation device capable of separating a fluid stream into a hydrocarbon-containing stream and a water stream. The liquid stream 290 can be separated in an oil water separator 295 to produce a wastewater stream 70 and an upgraded product stream 80. Conditions in oil water separator 295 can be adjusted to control the amount of water in upgraded product stream 80.

Additional equipment such as a storage tank may be used for containing the feed to the units. Instruments may be included on the production line to measure various parameters including temperature, pressure and water concentration.