Production of fuels from hydrogenated esters and fatty acids, low-carbon hydrogen, and carbon dioxide in an integrated HEFA and fuel plant.

Abstract

An integrated facility for producing renewable diesel fuel or sustainable aviation fuel, or both, from carbon dioxide, including carbon dioxide, which is a by-product in the reaction of hydrogenated esters and fatty acids (HEFAs) with hydrogen to produce renewable fuel. HEFAs are hydrogenated to produce liquid fuel products, which may include water, CO and water, or CO2. It is integrated with an e-fuel process, which produces low-carbon hydrogen as required at various stages of the integrated process. Renewable or low-carbon electricity is used to convert water into hydrogen and oxygen within the electrolyzer. Carbon dioxide reacts with at least a portion of the hydrogen to produce a flow containing carbon monoxide, the carbon dioxide conversion rate of this flow being 50% to 100% per pass, preferably 60% to 100%, and more preferably 70% to 100%.

Description

[Technical Field]

[0001] The field of the present invention is a process for producing one or both of synthetic jet fuel and synthetic diesel fuel by integrating ester and fatty acid hydrogenation plants, low-carbon hydrogen production, and e-fuel production processes. [Background technology]

[0002] The rise in atmospheric carbon dioxide concentrations worldwide is linked to climate change. The combustion of fossil fuels in various engines generates carbon dioxide in the atmosphere. Concerns about climate change are driving significant societal changes regarding renewable energy and fuels. This has also led to increased efforts to decarbonize the transport sector in the economy. As a result, the use of electric vehicles powered by renewable energy is increasing to promote decarbonization of the transport sector. However, there are limits to electrifying vehicle fleets. Large vehicles used for heavy transport are expensive and, in some cases, cannot be electrified. Locomotives used for long-haul trucks, ships, and rail transport are currently difficult to electrify, and not only are there switching costs for these vehicles, but developing charging infrastructure would be enormous and could take decades.

[0003] Furthermore, air transport is one of the most carbon-intensive transport sectors, accounting for more than 2% of global carbon dioxide emissions. The consumption of jet fuel, produced from fossil fuels like petroleum, in the aviation sector accounts for a significant portion of carbon dioxide emissions in the transport sector as a whole. However, jet aircraft are not expected to be electrified in the near future. Efficient and economical production of sustainable aviation fuel (SAF) has the potential to significantly reduce carbon dioxide emissions in the aviation sector.

[0004] Jet engines are complex technological devices that have been optimized for operation on petroleum-derived jet fuel for over 70 years. International standards have been established regarding the properties of jet fuel. ASTM DI 655 is the US standard for petroleum-derived jet fuel. Since 2009, separate standards have been developed for non-petroleum-derived jet fuels or jet fuel components. ASTM D7566-21 (Reference 1) is the current standard for aviation turbine fuels, including (non-petroleum-derived) synthetic hydrocarbons.

[0005] A notable trend in decarbonization is the production and use of non-biological renewable fuels (or RFNBOs). RFNBOs are fuels produced from non-biological resources such as electricity, hydrogen, and carbon dioxide. Because these fuels are produced from inexhaustible resources, they are considered renewable. Unlike biofuels produced from crops such as corn, sugarcane, and soybeans, RFNBOs do not compete with food resources. Biofuel production has been criticized for causing food shortages and soaring food prices. On the other hand, RFNBOs do not require farmland or resources, and therefore make them a sustainable alternative to conventional fuels.

[0006] RFNBOs are attracting attention as a promising alternative to fuels produced from conventional fossil fuels and food sources, as they offer a sustainable and environmentally friendly option for meeting energy demands.

[0007] For the past decade, renewable diesel has been produced from hydrotreated esters and fatty acids (HEFAs), which are chemically nearly identical to jet fuel and diesel fuel produced from Fischer-Tropsch (FT) type processes. Fats, oils, and greases from vegetable oils, animal fats, and tallows are fatty acids that can be converted into renewable diesel fuel and jet fuel. HEFAs, also known as hydrotreated vegetable oils (or HVOs), are involved in the conversion of hydrotreated esters and fatty acids (HEFAs) into fuel. This conversion involves the use of various vegetable oils and fats and can be carried out through three different routes. The first is the decarboxylation reaction (DCOX). Using the DCOX reaction, HEFAs are converted into hydrocarbons and carbon dioxide. The second route is the decarboxylation reaction (DCON). Using the DCON reaction, hydrogen is added to HEFAs and converted into hydrocarbons, water, and carbon monoxide. The third route is the hydrodeoxygenation reaction (HDO). Using the HDO reaction, hydrogen is added to HEFAs and converted into hydrocarbons and water. All three of these routes can ultimately be used to produce renewable fuels. In addition to the main products, all three of these routes produce a certain amount of light gas (C1-C4).

[0008] Carbon monoxide is catalytically hydrogenated to produce light gases, liquids, and waxes (from methane to heavy hydrocarbons (C) 100 The method for producing the above (and further extending to oxygenated hydrocarbons) is typically called Fischer-Tropsch (FT) synthesis. ASTM One route for producing non-petroleum synthetic paraffin kerosene (SPK), as permitted by D7566, is the fuel obtained from the Fischer-Tropsch process. Conventional low-temperature (below 250°C) FT processes yield a high weight (or wt%) of FT wax (C) from a catalytic conversion process. 24The above are the main products. These FT waxes are subsequently hydrocracking and / or further processed to produce diesel, naphtha, and other fractions. During this hydrocracking process, light hydrocarbons are also produced. In some embodiments, these light hydrocarbons require additional modification to produce practical products. Commonly used catalysts for FT are cobalt (Co)-based catalysts or iron (Fe)-based catalysts.

[0009] An advanced alternative to the conventional FT process is called direct liquid fuel production (direct LFP), which produces liquid fuel with high selectivity without first generating wax products. This direct LFP process eliminates hydrocracking, a major capital-intensive process. The directly produced liquid fuel has a high proportion of n-paraffins. In this invention, n-alkanes are converted to isoparaffins with low-temperature fluidity that meet the requirements of aviation fuel standards by light hydrogenation isomerization.

[0010] This invention overcomes the problems of the prior art describing the blending of straight-run FT fuels, and also overcomes the problems in blending straight-run FT kerosene into SPK by focusing on the direct production of liquid fuel and light treatment by hydrogenation isomerization.

[0011] e-fuel or electrofuel refers to the production of a synthetic fuel from waste CO2 that would otherwise be emitted into the atmosphere and low-carbon hydrogen produced from renewable electricity conventionally used to produce hydrogen using electrolysis. The above-mentioned FT process or direct LFP process may be used to produce fuel in the e-fuel process.

[0012] The present invention relates to a process in an integrated HEFA and e-fuel plant for producing a synthetic paraffin kerosene (SPK) blend stock used as sustainable aviation fuel (SAF) and / or synthetic diesel from esters and fatty acids, low-carbon hydrogen, and captured CO2. [Overview of the project]

[0013] The document describes an integrated facility for producing renewable diesel fuel or sustainable aviation fuel, or both, from waste-derived carbon dioxide and / or CO2 derived from by-products in the reaction of hydrogenated esters and fatty acids (HEFAs) with hydrogen to produce renewable fuel. HEFAs are hydrogenated to produce liquid fuel products, which may include water, CO and water, or CO2. DCOX, DCON, or DHO, or a combination thereof, may be involved during the HEFA production process. Light gases, ranging from C1 to C4 or higher, are produced.

[0014] The present invention describes an HEFA process integrated with an e-fuel process, the e-fuel process being used to produce low-carbon hydrogen required at various stages of the integrated process and to treat carbon dioxide, carbon monoxide, water and / or light gases produced from the HEFA process.

[0015] In one embodiment, the C1-C4 product gas from the HEFA reactor may be used downstream. In one embodiment, the C1-C4 product gas is sent to a reverse water-gas shift (RWGS) reactor used in an e-fuel plant, where the hydrocarbons are converted to some extent to H2 and CO, which are then used downstream in an LFP or FT process to generate additional hydrocarbon products.

[0016] In another embodiment, the C1-C4 product gas is sent to an electric steam methane reformer (eSMR). The tubes of the eSMR are filled with a nickel-containing reforming catalyst. The tubes are placed in an electric furnace, which is used to heat the tubes and catalyst to reforming conditions exceeding 1400°F. The reaction equilibrium shifts towards the production of H2 and CO from these light gases as the temperature rises.

[0017] In one embodiment, the C1-C4 product gas is sent to an automatic thermal reforming (ATR) unit. The ATR uses oxygen from the electrolytic unit as the raw material flow. The ATR is an automatic thermal reaction in which oxygen burns some of the hydrocarbons to produce fuel. In some embodiments, the ATR is integrated with a pre-reformer, in which case all hydrocarbons are converted to methane and / or CO and H2 before entering the main oxygen-blown reactor system.

[0018] In the e-fuel process, renewable or low-carbon electricity is used to convert water into hydrogen and oxygen within the electrolytic unit. The carbon dioxide reacts with at least some of the hydrogen to produce a flow containing carbon monoxide, the carbon dioxide conversion rate of this flow being 50% to 100% per pass, preferably 60% to 100%, and more preferably 70% to 100%.

[0019] At least a portion of the generated carbon monoxide is reacted with hydrogen in a direct liquid fuel production (LFP) reactor or a conventional FT reactor, thereby producing a liquid product containing n-alkanes with 5 to 24 carbon atoms. In this process, lighter gases than C5 and C5 are produced. 24 Additional products containing light wax / heavy diesel exceeding are generated, but these products are minimized to optimize the efficiency and economics of the integrated facility. C9-C in liquid products 15 The fraction is 40% to 100%, preferably 45% to 100%, and more preferably 50% to 100%. The LFP liquid product is further separated into three liquid streams within the LFP separation unit. The light LFP separation product stream contains C5-C8 n-alkanes, and the medium LFP separation product stream contains C9-C 15 The heavy LFP separation product stream contains n-alkanes, and is C 16 -C 24 It contains n-alkanes.

[0020] At least a portion of the medium-quality LFP separation unit product stream is supplied to a catalytic hydroisomerization unit to produce a hydroisomerization product stream, and the hydroisomerization product stream is supplied to a hydroisomerization separation unit to produce at least two types of hydroisomerization products. The heavy hydroisomerization product contains branched alkanes having 9 to 15 carbon atoms, and the freezing point of the heavy hydroisomerization product stream is -40°C to -60°C. In one embodiment, the freezing point is -48°C to -60°C. In one embodiment, the freezing point is -48°C to -55°C. In some embodiments, the heavy hydroisomerization product is synthetic paraffinic kerosene (SPK) used as a component of jet fuel.

[0021] In some embodiments of the present invention, at least a portion of the light-quality LFP separation unit product stream is supplied to an oligomerization reactor to produce an oligomerization reactor product containing hydrocarbons having 9 to 15 carbon atoms.

[0022] In some embodiments of the present invention, first the entire liquid product stream is isomerized and then distilled. Thereby, the isomerization not only isomerizes the heavy-quality LFP separation product stream but also performs light cracking of the heavy-quality LFP separation product stream.

[0023] In some embodiments of the present invention, the carbon intensity (CI) of the produced SAF is 0 to 30, preferably 0 to 15, and more preferably 0 to 5.

[0024] In some embodiments of the present invention, (1) reduction of the overall carbon intensity of the product, (2) improvement in economy by using the by-product streams (including light gas, CO2, CO, water, and waste heat or steam) from the HEFA plant as feedstocks and inputs to the e-fuel plant, and (3) use of the by-product CO2 so that the fuel produced from the carbon source can be identified as a renewable fuel not of biological origin (RFNBO). To achieve this, the e-fuel plant and the HEFA plant are further integrated.

[0025] According to the integrated process using unit operations of HEFA and e - fuel containing hydrogen from the electrolysis of water, a well - to - wheel carbon intensity lower than that of the fuel produced by the hydrogenation of HEFA alone will be achieved.

Brief Description of Drawings

[0026] [Figure 1] Figure 1 shows an integrated process for the hydrogenation of fatty acids by a decarbonation (DCOX) or decarbonylation (DCON) reaction using low - carbon hydrogen.

[0027] [Figure 2] Figure 2 shows an enlarged view of the hydrogenation reactor unit U1.3 when using the decarbonation (DCOX) reaction scheme.

[0028] [Figure 3] Figure 3 shows an enlarged view of the hydrogenation reactor unit U1.3 when using the decarbonylation (DCON) reaction scheme.

[0029] [Figure 4] Figure 4 shows an integrated process for the hydrogenation of fatty acids by a hydrodeoxygenation (HDO) reaction using low - carbon hydrogen.

[0030] [Figure 5] Figure 5 shows an integrated process that incorporates CO2 from other sources into the overall process to increase fuel production.

Mode for Carrying Out the Invention

[0031] Conventional conversion of biomass feedstocks into hydrotreated esters and fatty acids (HEFAs) usable as renewable diesel or renewable jet fuel can be carried out via three different routes. The first is decarboxylation (DCOX). Using the DCOX reaction, HEFAs are converted into hydrocarbons and carbon dioxide. The second route is decarboxylation (DCON). Using the DCON reaction, hydrogen is added to HEFAs and converted into hydrocarbons, water, and carbon monoxide. The third route is hydrodeoxygenation (HDO). Using the HDO reaction, hydrogen is added to HEFAs and converted into hydrocarbons and water. All three of these routes can be used to ultimately produce renewable fuels. In some embodiments, one, two, or three of these routes or processes are carried out in a single hydrotreatment or hydroisomerization reactor.

[0032] DCOX or DCON reaction scheme [ka]

[0033] Figure 1 shows an integrated process for producing synthetic paraffin kerosene or jet fuel and / or renewable diesel using either the DCOX reaction scheme or the DCON reaction scheme. Flow S1.1 is low-carbon electricity. Low-carbon electricity includes, but is not limited to, wind power, solar power, nuclear power, geothermal power, biomass power or renewable natural gas power, and hydropower. Supply flow S1.2 is water. This is supplied to unit U1.1, which is an electrolytic unit. In the electrolytic unit, water and low-carbon energy are used to produce hydrogen and oxygen. Water is supplied to the electrolytic unit. The electrolytic unit is powered by low-carbon electricity. Hydrogen is produced by the electrolysis of water. [ka]

[0034] The electrolysis device is composed of an anode and a cathode separated by an electrolyte. Different electrolysis devices have slightly different functions. Various designs of electrolysis devices using different electrolysis technologies are used, and such electrolysis technologies include alkaline electrolysis, solid polymer electrolyte membrane (PEM) electrolysis, solid oxide electrolysis, high-temperature electrolysis, etc., and other emerging types of electrolysis. The various electrolytes used include liquid KOH and liquid NaOH, with or without an activating compound. The activating compound is added to the electrolyte to improve the stability of the electrolyte. Most ion activators for hydrogen generation reactions are ethylene diamine-based metal chloride complexes ([M(en)3]Cl x , M 1 / 4 Co, Ni, etc.) and Na2MoO4 or Na2WO4. A variety of different electrode catalysts, including many different combinations of metals and oxides such as Raney-nickel-aluminum, are used on the electrodes, and such electrode catalysts are strengthened by adding cobalt or molybdenum to the alloy.

[0035] The product from the electrolysis device is a stream containing hydrogen, designated as stream S1.3. Since a renewable energy source is used, the electrolysis device produces "green" hydrogen. Depending on the carbon intensity of the energy used within unit U1.1, other low-carbon hydrogen streams are produced. Other forms of hydrogen production that can use renewable or non-renewable energy sources may also be used, and such forms include methane pyrolysis, steam reforming with carbon capture, biomass gasification, renewable natural gas (RNG) reforming, or securing a source of hydrogen from geological resources where purification of the stream is required to produce the hydrogen used in the process.

[0036] In Figure 1, stream S1.4 contains renewable animal and / or vegetable feedstocks, including materials such as seed oil, palm oil, corn oil, soybean oil, distilled corn oil, and other virgin oils, as well as feedstocks such as waste oil, used cooking oil, tallow, and methyl esters.

[0037] Flow S1.4 is pre-treated within Unit U1.2. Unit U1.2 includes several processes used depending on the application and the contaminants contained in the feedstock. These include acid degumming, adsorption, chloride removal, polyethylene removal, and caustic soda treatment or deoxidation treatment.

[0038] The HEFA pretreatment product is shown as flow S1.5 and is then sent to unit U1.3, which is the hydrogenation reactor. Unit U1.3 is where the selected reaction scheme, either DCOX, DCON, or HDO, as shown in Figure 1, takes place. Green hydrogen from flow S1.3 is added to unit U1.3. In unit U1.3, two separate hydrocarbons are produced. First, both the DCOX and DCON reaction schemes produce hydrocarbons, which become flow S1.11. Next, additional reactions take place in unit U1.3, where carbon dioxide from the DCOX reaction is converted to hydrocarbons, or carbon monoxide from the DCON reaction is converted to hydrocarbons. These hydrocarbons become flow S1.6. Flow S1.6 is fed to unit U1.4, which is the separation unit. The product flow S1.7 is the hydrogenation isomerization feed flow for unit U1.5, which is the hydrogenation isomerization reactor. Product flow S1.8 is the hydrogenation isomerization feed flow for unit U1.6, which is the hydrogenation isomerization separation unit. The reforming feed flow, which is product flow S1.9, is supplied to the reforming unit U1.7 to produce product flow S1.10. Units U1.8, U1.9, U1.10, and U1.11 are the same as units U1.4, U1.5, U1.6, and U1.7, where the initial feed flow S1.11 is the hydrocarbon produced from the hydrogenation reactor U1.3.

[0039] In some embodiments, unit U1.3 performs the DCOX reaction as shown in Figure 2. In some embodiments, unit U1.3 performs the DCON reaction as shown in Figure 3. In some embodiments, unit U1.3 performs the HDO reaction as shown in Figure 4. In some embodiments, unit U1.3 can perform the DCOX reaction, the DCON reaction, and the HDO reaction in a single reactor.

[0040] In an embodiment where the DCOX reaction occurs as shown in Figure 2, the hydrogenation feed stream S1.5 is sent to the DCOX reactor, which is unit U2.1, thereby producing two product streams, stream S2.1 and stream S1.11. At least a portion of the hydrogen-containing stream S1.3 is blended with the carbon dioxide-containing stream S2.1 and sent to unit U2.2, which is a reverse water-gas shift (RWGS) reactor used in the e-fuel production process. The carbon dioxide and hydrogen react with carbon monoxide and water in the RWGS reactor, often with an excess of hydrogen added, and the heat of reaction is supplied by the RWGS heater. The catalyst used in the RWGS reactor is the catalyst described in the published patent application US17 / 300,260.

[0041] At least a portion of flow S2.2 (RWGS product flow) contains hydrogen and carbon monoxide and becomes the feed for the liquid fuel production (LFP) reactor or FT reactor. The RWGS product, which contains carbon monoxide and may also have additional hydrogen added, reacts with fuel and chemicals in unit U2.3, which is the liquid fuel production (LFP) reactor or FT reactor, where a catalyst is used to produce long-chain hydrocarbons to be used as fuel and chemicals. The final product is a mixture of water and hydrocarbons, where the majority of the hydrocarbons (e.g., 51 to 99 volume percent) are hydrocarbons with a length of about 5 to about 24 carbon atoms.

[0042] In an embodiment where the DCON reaction occurs as shown in Figure 3, the hydrogenation feedstock stream S1.5 is sent to the DCON reactor, which is unit U3.1, thereby yielding two product streams, stream S3.1 and stream S1.11. At least a portion of the hydrogen-containing stream S1.3 is blended with the carbon monoxide-containing stream S3.1 to become the feedstock for the liquid fuel production (LFP) reactor or FT reactor. This stream, which may also contain additional hydrogen along with the carbon monoxide, reacts with fuels and chemicals in the liquid fuel production (LFP) reactor or FT reactor, where a catalyst is used to produce long-chain hydrocarbons to be used as fuels and chemicals. The final product is a mixture of hydrocarbon products and water, where the majority of the hydrocarbons (e.g., 51 volume percent to about 99 volume percent) are hydrocarbons with lengths up to 24 carbon atoms. In one embodiment, the water produced in the FT is used as feedstock for the electrolytic unit, with or without water treatment to remove hydrocarbons and other impurities.

[0043] The carbon monoxide produced by the DCON reactor is used for various purposes. In one embodiment, the CO-containing stream produced by the DCON reactor is treated as an additional feed to unit U3.2, which is an LFP reactor or FT reactor, with or without additional hydrogen. This increases the total amount of hydrocarbon fuel produced by the LFP or FT system. In another embodiment, the CO is separated and sold to others.

[0044] In another embodiment, CO sold or used in an integrated facility may be used for hydroformylation. Hydroformylation, also known as oxo synthesis or oxo process, is an industrial process that produces aldehydes (R-CH=O) from alkenes (R2C=CR2). Aldehydes are readily converted into many secondary products. The resulting aldehydes are hydrogenated to alcohols, which are then converted into detergents. Hydroformylation is also used in specialty chemicals used in the manufacture of fragrances and pharmaceuticals.

[0045] The process typically involves treating alkenes at temperatures of 40–200°C using carbon monoxide and hydrogen under high pressure (10–100 atmospheres). A transition metal catalyst is required, which dissolves in the reaction medium and is an example of a homogeneous catalyst.

[0046] In some embodiments, the water produced in the LFP reactor is recycled and returned to the electrolytic unit U1.1, with or without treatment. The LFP hydrocarbon product stream S1.6, containing n-alkanes with 5 to 24 carbon atoms, is fed to the separation unit U1.4, where at least three products are produced. "Carbon number" refers to the number of carbon atoms in each alkane. LFP separation refers to any separation process of absorption, adsorption, filtration, or distillation. The preferred separation process is distillation. The LFP separation unit produces at least three products. The light LFP separation product contains n-alkanes with 5 to 8 carbon atoms. The heavy LFP separation product contains n-alkanes with 16 to 24 carbon atoms. The medium LFP separation product contains n-alkanes with 9 to 15 carbon atoms. The medium LFP separation product is within the boiling point range of synthetic paraffinic kerosene or jet fuel. However, the physical properties of LFP separation products in media rich in n-alkanes do not meet the requirements for SPK jet fuel without additional processing.

[0047] In another embodiment of the present invention, the above-described LFP system replaces a conventional FT system in which, in addition to heavy hydrocarbon waxes, lighter liquid products are also produced, but the proportion of the lighter liquid products to the total product vapor is smaller.

[0048] In one embodiment of the present invention, at least a portion of the heavy LFP separation unit product is sold as a premium low-sulfur, high-cetane diesel fuel or diesel fuel blend stock. "At least a portion" means a portion of the whole. Non-limiting examples of "at least a portion" include 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100%.

[0049] Flow S1.16 shows how the circulating water is returned to the electrolytic unit U1.1.

[0050] At least a portion of the intermediate LFP separation product, flow S1.12, is supplied to unit U1.5 or the hydrogenation isomerization unit. Hydrogenation isomerization improves the properties of the feedstock by converting n-alkane hydrocarbons to branched hydrocarbons with the same number of carbon atoms. This reaction improves the low-temperature flow properties of hydrocarbons. Hydrogenation isomerization lowers the pour point, cloud point, cold filter plug point (CFPP), and / or freezing point of the hydrocarbon flow.

[0051] The hydrogen isomerization reactor may be of any suitable design, but it is preferably a cylindrical reactor in which the liquid feedstock is supplied to the top of the reactor. The liquid feedstock, containing the intermediate LFP separation product, is mixed with a hydrogen-containing flow 1.3. The mixed feedstock reacts on a catalyst bed in the reaction vessel. Typically, the reactor is a trickle bed reactor. At least a portion of the n-alkanes react through the catalyst, thereby producing branched alkanes. The reactor comprises one or more catalyst beds. In some embodiments, additional hydrogen feedstock is injected between the various catalyst beds. The molar ratio of hydrogen to liquid hydrocarbon feedstock is 10 to 300, more preferably 15 to 30, and even more preferably 19 to 25. The operating pressure of the hydrogen isomerization reactor is 10 to 100 bar, more preferably 20 to 80 bar, and even more preferably 30 to 40 bar. The weight-time-space velocity (WHSV) is 0.1 to 10 kg (liquid feedstock) / hr·kg (catalyst), more preferably 0.2 to 5 hr -1 And more preferably 0.5 to 2 hours. -1 The reactor operates at temperatures between 200°C and 350°C.

[0052] Hydrogenation isomerization catalysts are solid particles. The catalyst comprises a metal supported on an acidic support. In some embodiments, the catalyst metal is platinum and palladium, which provide hydrogenation and dehydrogenation activity. In some embodiments, the catalyst metal comprises nickel. In some embodiments, the catalyst metal comprises copper. In some embodiments, the catalyst metal comprises binary metals such as Ni-Cu, Ni-Mo, Pt-Fe, and Pt-Be. The acidic support is selected from any suitable support and includes support comprising ZSM-5, ZSM-22, ZSM-23, silica, alumina, SiO2-Al2O3, beta-zeolite, MCM-41, MCM-48, SBA-15, and blends of these support.

[0053] The conversion rate from n-alkanes to branched alkanes in a hydrogenation isomerization reactor is preferably 50-100%, more preferably 80-100%, and it may be necessary to recycle the raw materials to achieve these conversion rates. The reactor temperature, pressure, hydrogen-to-n-alkane ratio, and weight-time-space rate (WHSV) are adjusted to maintain a high conversion rate from n-alkanes to branched alkanes.

[0054] In some embodiments of the present invention, at least a portion of the light LFP separation unit product, which includes a mixture of alkanes and alkenes, is supplied to an oligomerization reactor to produce an oligomerized product. At least a portion of the product stream S1.13 is supplied back to an LFP separation unit (unit U1.4) or other separation vessel or unit operation.

[0055] The light LFP separation unit product is a mixture of n-alkanes and n-alkenes. The alkene / alkane ratio in the stream is controlled by changing the operating conditions in the LFP reactor. The lower the ratio of carbon monoxide in the feedstock and the higher the temperature of the LFP reactor, the more the formation of n-alkenes is promoted than that of n-alkanes. The alkenes react with each other to produce products within the boiling point range of kerosene.

[0056] In one embodiment, CO2 is a byproduct of the HEFA hydrogenation reactor (U1.3) and also a byproduct of the hydrogenation isomerization reactor (U1.5). In some embodiments, the U1.3 and U1.5 product streams contain CO2. The CO2 in the product streams is captured by a CO2 capture system. Any available technology can be used for the capture system, such technologies include amine and solvent-based systems, membranes, CO2 separation, or other methods known in the art.

[0057] Figure 4 shows an integrated process for producing synthetic paraffinic kerosene or jet fuel, and / or renewable diesel, using an HDO reaction scheme. Flow S1.1 is low-carbon electricity. Low-carbon electricity includes, but is not limited to, wind power, solar power, nuclear power, geothermal power, biomass power or renewable natural gas power, and hydropower. Supply flow S1.2 is water. This is supplied to unit U1.1, which is an electrolytic unit. In the electrolytic unit, water and low-carbon or carbon-free electricity are used to produce hydrogen and oxygen. Water is supplied to the electrolytic unit. The electrolytic unit is powered by low-carbon electricity. Hydrogen is produced by the electrolysis of water. [ka]

[0058] The product from the electrolytic device is a hydrogen-containing stream, referred to as stream S1.3. Because renewable energy sources are used, the electrolytic device produces "green" hydrogen. Depending on the carbon intensity of the energy used within unit U1.1, other low-carbon hydrogen streams are generated.

[0059] In Figure 1, flow S1.4 includes renewable animal and / or plant-based raw materials, including seed oils, palm oil, corn oil, soybean oil, distilled corn oil, and other virgin oils, as well as raw materials such as waste oil, used cooking oil, animal fat, and methyl esters.

[0060] Flow S1.4 is pre-treated within Unit U1.2. Unit U1.2 includes several processes used depending on the application and the contaminants contained in the feedstock. These include acid degumming, adsorption, chloride removal, polyethylene removal, and caustic soda treatment or deoxidation treatment.

[0061] The HEFA pretreatment product is shown as flow S1.5 and is then sent to unit U4.1, which is the hydrogenation reactor. Unit U4.1 is where the HDO reaction scheme in Figure 4 takes place. Green hydrogen from flow S1.3 is added to unit U4.1. In unit U4.1, two separate hydrocarbons are produced. Both of the HDO reaction schemes produce hydrocarbons, and these hydrocarbons become flow S1.11.

[0062] The light LFP separation unit product is a mixture of n-alkanes and n-alkenes. The alkene / alkane ratio in the stream is controlled by changing the operating conditions in the LFP reactor. The lower the ratio of carbon monoxide in the feedstock and the higher the temperature of the LFP reactor, the more the formation of n-alkenes is promoted than that of n-alkanes. The alkenes react with each other to produce products within the boiling point range of kerosene.

[0063] In some embodiments, additional CO2 is supplied into the system (see Figure 5). In these embodiments, CO2 (flow S5.2) is added as a supply flow in addition to renewable fats, oils, greases, and animal fats (flow S5.1), low-carbon electricity (flow S5.3), and water (flow S5.4). Carbon dioxide is obtained from multiple sources and / or HEFA processes. Power plants that generate electricity from various carbon resources emit large amounts of carbon dioxide. Industrial manufacturing plants that produce ammonia for fertilizer emit large amounts of carbon dioxide. Ethanol plants that convert corn or wheat into ethanol emit large amounts of carbon dioxide through fermentation. Other industrial fermentation processes also emit large amounts of carbon dioxide. Municipal wastewater treatment systems using aerobic and anaerobic digestion of sludge also emit large amounts of CO2. The utilization or conversion of CO2 described herein typically involves separating and purifying CO2 from gaseous flows in which CO2 is not the main component (e.g., exhaust gases). Typically, alkylamines are used to remove carbon dioxide from gaseous flows. The alkylamines used in this process include monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, aminoethoxyethanol, or combinations thereof. Metal-organic framework (MOF) materials are also used as a means of capturing carbon dioxide from dilute flows by separating it from the flow using chemiadsorption or physiadsorption. Other methods for obtaining high concentrations of carbon dioxide include chemical loop combustion, in which a circulating metal oxide material recovers the carbon dioxide produced during the combustion process. Carbon dioxide is also captured from the atmosphere by a method called direct air capture (DAC). Carbon dioxide capture processes often involve the regeneration of the capture material.

[0064] Alkylamines are regenerated by heating, typically by heating with a low-pressure flow.

[0065] Captured carbon dioxide is converted into useful products such as fuels (e.g., diesel fuel, gasoline blend stock, jet fuel, etc.) and chemicals (e.g., solvents, olefins, alcohols, aromatic compounds, etc.), which replace fuels and chemicals produced from fossil resources such as petroleum and natural gas, thereby reducing total carbon dioxide emissions into the atmosphere. This is what low-carbon, ultra-low-carbon, zero-carbon, or negative-carbon fuels and chemicals mean.

[0066] Carbon dioxide streams resulting from industrial or biological processes, carbon dioxide streams captured from the atmosphere, or carbon dioxide streams available from commercial carbon dioxide pipelines are not pure carbon dioxide. These industrial facilities or pipelines contain 0-2000 ppm by weight of sulfur-containing compounds and 0-10% by volume of hydrocarbons. Purification of carbon dioxide, including the removal of sulfur-containing compounds and hydrocarbons, is essential to avoid problems in downstream treatment. After purification, the purified carbon dioxide is suitable for the production of low-carbon or zero-carbon fuels and chemicals.

[0067] In these embodiments, the added CO2 is added to the RWGS reactor (unit U5.4) to generate additional CO. This is done in addition to the CO2 produced by the hydrogenation process (unit U5.3) when the DCOX reaction scheme is used. Similar to the embodiments described above, when the HDO reaction scheme is used, hydrogen is supplied to the RWGS reactor (unit U5.4), the hydrogenation isomerization reactor (unit U5.7), and the hydrogenation reactor (unit U5.3) via the electrolytic unit (unit U5.2).

[0068] By supplying additional CO2, more CO is generated and supplied to the LFP reactor or conventional FT reactor (unit U5.5) which produces wax in a high proportion. This is done in addition to the CO (flow S5.8) produced by the hydrogenation treatment when using the DCON reaction scheme. This generates even more hydrocarbons (flow S5.12), in addition to the hydrocarbons produced by the hydrogenation treatment. These hydrocarbons are supplied to the separation unit (U5.6), as in the previously described embodiment. As in the previously described embodiment, the product flow S5.13 containing the separated hydrocarbons is supplied to the hydrogen isomerization reactor unit U5.7. This generates flow S5.14, which is supplied to unit U5.8 (hydrogen isomerization separator). As in the previously described embodiment, this generates flow S5.15, which is supplied to the reforming unit U5.9, which generates product flow S5.16. The residual water from U5.5 is recycled as flow S5.11 and returned to the electrolytic unit U5.2.

Claims

1. A method for producing renewable fuels, a. A step of converting the electrolytic device supply material into a first electrolytic device product stream containing low-carbon hydrogen and a second electrolytic device product stream containing oxygen, wherein the electrolytic device supply material contains water. b. A step of pre-treating biomass to obtain hydrogenated esters and fatty acids, wherein the biomass includes at least one of seed oil, palm oil, corn oil, soybean oil, distilled corn oil, other virgin oils, waste oil, used cooking oil, animal fat, and methyl esters. c. A step of supplying the hydrogenated ester and fatty acid into a hydrogenation reactor that produces liquid fuel, wherein a first hydrocarbon stream and a second hydrocarbon stream are generated in the hydrogenation reactor, and the first hydrocarbon stream is C ９ -C １５ The n-alkane is included, the second hydrocarbon stream is included, and the C ９ -C １５ n-alkanes and the alkenes constitute 40 to 99 volume percent of the liquid fuel, and the steps, d. A step of supplying at least a portion of the first hydrocarbon stream and at least a portion of the first electrolytic product stream to at least one catalyst hydrogenation isomerization unit to generate one or more hydrogenation isomerization product streams, and supplying the one or more hydrogenation isomerization product streams to a hydrogenation isomerization separation unit, wherein the hydrogenation isomerization separation unit generates two or more hydrogenation isomerization products. Methods that include...

2. The method according to claim 1, wherein the hydrogenation reactor includes a decarboxylation reactor that produces a hydrocarbon stream and a carbon dioxide stream, and the method further includes the step of supplying the carbon dioxide stream and a portion of the first electrolytic product stream to a reverse water-gas shift reactor to produce a reverse water-gas shift product stream, wherein the reverse water-gas shift product stream contains CO, and the reverse water-gas shift product stream is supplied to an LFP reactor or F-T reactor to produce hydrocarbons.

3. The method according to claim 1, wherein the hydrogenation reactor includes a decarbonylation reactor that produces a hydrocarbon stream and a stream of water and CO, and the method further comprises the step of supplying the stream of water and CO to an LFP reactor or an F-T reactor to produce hydrocarbons.

4. The method according to claim 1, wherein the one or more hydrogenation isomerization product streams satisfy the ASTM standard, and the ASTM standard is ASTM D7566-21.

5. The method according to claim 1, wherein the one or more hydrogenation isomerized product streams satisfy the ASTM standard, and the ASTM standard is ASTM D975.

6. The method according to claim 1, wherein a hydrogenation deoxygenation reaction is carried out in the hydrogenation reactor.

7. The method according to claim 1, wherein a decarboxylation reaction is carried out in the hydrogenation reactor.

8. The method according to claim 1, wherein a decarbonylation reaction is carried out in the hydrogenation reactor.

9. The method according to claim 1, wherein the biomass is selected from the biomass group consisting of seed oil, palm oil, corn oil, soybean oil, distilled corn oil, waste oil, used cooking oil, animal fat, and methyl esters.

10. The method according to claim 1, wherein the pretreatment of the biomass includes acid degumming, adsorption, chloride removal, polyethylene removal, caustic treatment, or deacidification treatment.

11. The method according to claim 1, wherein the catalyst hydrogenation isomerization unit includes a plurality of hydrogenation isomerization reactors, and the plurality of hydrogenation isomerization reactors are cylindrical trickle bed reactors at which a liquid raw material is supplied to the top of the reactor.

12. The aforementioned plurality of hydrogenation isomerization reactors include a catalyst, the catalyst includes a metal supported on an acidic support, the metal is selected from the group of metals consisting of platinum, palladium, nickel, Ni-Cu, Ni-Mo, Pt-Fe, and Pt-Be, and the acidic support is ZSM-5, ZSM-22, ZSM-23, silica, alumina, SiO ２ - Al ２ O ３ The method according to claim 1, wherein the acidic carrier is selected from the group of acidic carriers consisting of beta-zeolite, MCM-41, MCM-48, SBA-15, and a mixture of the acidic carrier.

13. The method according to claim 6, wherein the biomass is selected from the biomass group consisting of seed oil, palm oil, corn oil, soybean oil, distilled corn oil, waste oil, used cooking oil, animal fat and methyl esters, and the pretreatment of the biomass includes acid degumming, adsorption, chloride removal, polyethylene removal, caustic treatment or deacidification treatment.

14. The method according to claim 7, wherein the biomass is selected from a group of biomass consisting of seed oil, palm oil, corn oil, soybean oil, distilled corn oil, waste oil, used cooking oil, animal fat and methyl esters, and the pretreatment of the biomass includes acid degumming, adsorption, chloride removal, polyethylene removal, caustic treatment or deacidification treatment.

15. The method according to claim 8, wherein the biomass is selected from the biomass group consisting of seed oil, palm oil, corn oil, soybean oil, distilled corn oil, waste oil, used cooking oil, animal fat and methyl esters, and the pretreatment of the biomass includes acid degumming, adsorption, chloride removal, polyethylene removal, caustic treatment or deacidification treatment.

16. The catalytic hydrogenation isomerization unit includes a plurality of hydrogenation isomerization reactors, and the plurality of hydrogenation isomerization reactors are cylindrical trickle bed reactors in which a liquid raw material is supplied at the top of the reactors. The plurality of hydrogenation isomerization reactors contain a catalyst, and the catalyst contains a metal supported on an acidic support. The metal is selected from the group of metals consisting of platinum, palladium, nickel, Ni-Cu, Ni-Mo, Pt-Fe, and Pt-Be. The acidic support is selected from the group of acidic supports consisting of ZSM-5, ZSM-22, ZSM-23, silica, alumina, SiO ２ -Al ２ O ３ , beta zeolite, MCM-41, MCM-48, SBA-15, and a mixture of the acidic supports. The method according to claim 13.

17. The catalyst hydrogenation isomerization unit comprises a plurality of hydrogenation isomerization reactors, each of which is a cylindrical trickle bed reactor supplied with a liquid raw material at the top of the reactor, each of which comprises a catalyst, the catalyst comprising a metal supported on an acidic support, the metal being selected from the group of metals consisting of platinum, palladium, nickel, Ni-Cu, Ni-Mo, Pt-Fe, and Pt-Be, and the acidic support being ZSM-5, ZSM-22, ZSM-23, silica, alumina, SiO ２ - Al ２ O ３ The method according to claim 14, wherein the acidic carrier is selected from the group of acidic carriers consisting of beta zeolite, MCM-41, MCM-48, SBA-15, and a mixture of the acidic carrier.

18. The catalyst hydrogenation isomerization unit comprises a plurality of hydrogenation isomerization reactors, each of which is a cylindrical trickle bed reactor supplied with a liquid raw material at the top of the reactor, each of which comprises a catalyst, the catalyst comprising a metal supported on an acidic support, the metal being selected from the group of metals consisting of platinum, palladium, nickel, Ni-Cu, Ni-Mo, Pt-Fe, and Pt-Be, and the acidic support being ZSM-5, ZSM-22, ZSM-23, silica, alumina, SiO ２ - Al ２ O ３ The method according to claim 15, wherein the acidic carrier is selected from the group of acidic carriers comprising beta-zeolite, MCM-41, MCM-48, SBA-15, and a mixture of the acidic carrier.

19. The hydrogenation reactor generates a third hydrocarbon stream, and the third hydrocarbon stream is C １ -C ４ The method according to claim 2, comprising a generated gas.

20. The method according to claim 19, wherein the third hydrocarbon stream is supplied into an electrically heated steam methane reformer.

21. The method according to claim 19, wherein the third hydrocarbon stream is supplied into an automatic heat reformer.

22. The method according to claim 19, wherein the third hydrocarbon stream is recycled to a reverse water-gas shift reactor.

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