Integrated hydrogen production and bio-renewable conversion process

Abstract

A biorenewable conversion process for producing fuels from biorenewable feedstocks is combined with a hydrogen production process that includes CO2 capture. The integrated process uses a purge gas stream containing hydrogen from the biorenewable hydrocarbon production process in the hydrogen production process.

Description

[Technical field]

[0001] (Related Applications) This application claims the benefit of U.S. Provisional Application No. 63 / 220,848, entitled "Method of Recovering Hydrogen and CO2 in a Hydrogen Production Unit," filed on July 12, 2021, U.S. Provisional Application No. 63 / 167,343, entitled "Integrated Hydrogen Production and Bio-Renewable Conversion Process," filed on March 29, 2021, and U.S. Provisional Application No. 63 / 167,341, entitled "Method of Recovering Hydrogen and CO2 in a Hydrogen Production Unit," filed on March 29, 2021, each of which is incorporated herein in its entirety. [Background technology]

[0002] Hydrogen is expected to have great growth potential since it is a clean burning fuel. However, hydrogen production has traditionally been a major source of CO2 emissions, and government regulations and societal pressures are increasingly taxing or penalizing CO2 emissions or encouraging CO2 capture. As a result, a great race is expected to lower the cost of hydrogen production while capturing and sequestering the by-product CO2 underground to capture the growing market. Although CO2 can be separated as steam that is fed into common pipelines, the current lack of CO2 pipeline infrastructure in certain parts of the world means that it will likely need to be produced in a liquefied form for easy transportation by truck or ship.

[0003] The desired level of reducing CO2 emissions depends on local economic conditions, with some hydrogen producers prioritizing maximizing hydrogen production with CO2 capture, others prioritizing minimizing CO2 emissions with hydrogen production, and some falling somewhere in between. Another important factor is the reformer technology selected for a given hydrogen production unit. In a steam reforming plant, 50%-60% CO2 capture may be sufficient, while in an autothermal reformer (ATR), gasifier, or partial oxidation (POX) reformer, greater than 90% or even 95% may be expected.

[0004] Most existing hydrogen production processes utilize pressure swing adsorption (PSA) to recover high purity product hydrogen from the shifted syngas. The low pressure tail gas stream from the PSA unit is typically combusted to generate heat or steam for the process. If the stream is not sent to a combustor, a purge is required to prevent the build-up of impurities in the process.

[0005] US Patent No. 8,021,464 describes a process for the combined production of hydrogen and CO2 from a mixture of hydrocarbons that is converted to synthesis gas. The synthesis gas is separated in a PSA unit into a hydrogen-rich stream and a PSA off-gas stream. The PSA off-gas is compressed and dried, followed by several successive steps of condensing and separating the CO2-rich condensate, each step lowering the temperature, which ranges from ambient to -56°C. However, this process results in a purge stream containing significant amounts of CO2 that must be removed from the process. A permeate module can be used to improve separation, but at the cost of increased power requirements.

[0006] US Patent No. 8,241,400 describes a process for recovering hydrogen and CO2 from a mixture of hydrocarbons utilizing a system including a reformer unit, an optional water gas shift reactor, a PSA unit, and a cryogenic purification unit or catalytic oxidation unit. The PSA unit produces three streams: a high pressure hydrogen stream, a low pressure CO2 stream, and a CH4-rich stream that is removed during a CO2 co-purge step. Purified CO2 from a CO2 purification unit in the process is used as a co-purge in the PSA unit. The adsorption step is carried out at a pressure of about 250 psig to about 700 psig. The pressure during the co-purge step ranges from about 300 psig to about 800 psig, and the CO2 co-purge stream is preferably introduced at a higher pressure than the pressure during the adsorption step.

[0007] The use of a second high pressure feed stream (a CO2 co-purge stream) increases the cost and complexity of the process in U.S. Patent No. 8,241,400. The need to have a segmented adsorber (or two separate vessels) and have an isolation valve between the two vessels and the intermediate side draw further increases the cost and complexity of the process.

[0008] As the demand for fuels, such as aviation fuel, increases worldwide, so too does the interest in utilizing sources other than petroleum crude oil to produce fuel. One source is the so-called bio-renewable feedstocks. These bio-renewable feedstocks include, but are not limited to, vegetable oils, such as corn, jatropha, camelina, rapeseed, canola, soybean and algae oils, animal fats, such as tallow, fish oil, and various waste streams, such as yellow and brown grease and sewage sludge. A common feature of these feedstocks is that they are composed of mono-, di- and tri-glycerides, free fatty acids (FFAs). Another class of compounds suitable for these processes are fatty acid alkyl esters (FAAEs), such as fatty acid methyl esters (FAMEs) or fatty acid ethyl esters (FAEEs). These types of compounds generally contain aliphatic carbon chains with about 8 to about 24 carbon atoms. The aliphatic carbon chains in the glycerides, FFAs or FAAEs can be saturated or mono-, di- or polyunsaturated. The majority of the glycerides in the bio-renewable feedstock are triglycerides, but some of the glycerides in the bio-renewable feedstock may be mono- or diglycerides. Mono- and diglycerides may be processed along with triglycerides.

[0009] There are reports that disclose the production of hydrocarbons from bio-based oils. For example, US Patent No. 4,300,009 discloses the use of crystalline aluminosilicate zeolites to convert vegetable oils such as corn oil into hydrocarbons such as gasoline and chemicals such as paraxylene. US Patent No. 4,992,605 discloses the production of diesel boiling range hydrocarbon products by hydrotreating vegetable oils such as canola oil or sunflower oil. Finally, US Patent No. 2004 / 0230085(A1) discloses a process for treating hydrocarbon components of biogenic origin by hydrodeoxygenation followed by isomerization.

[0010] Therefore, there is a need for improved hydrogen production processes with increased hydrogen production and CO2 capture. [Brief description of the drawings]

[0011] [Figure 1] 1 is a general flow scheme of one embodiment of a process for producing bio-renewable fuels. [Diagram 2] FIG. 1 is a diagram of one embodiment of a method for producing a hydrogen stream and a CO2 stream from the effluent stream of a hydrogen production process unit using a PSA system producing at least two product streams of the present invention. [Diagram 3] FIG. 1 is a diagram of one embodiment of a three product PSA unit for use in a PSA system producing at least two product streams of the present invention. [Figure 4] FIG. 2 is a diagram of another embodiment of a method for producing a hydrogen stream and a CO2 stream from the effluent stream of a hydrogen production process unit using a PSA system for producing at least two product streams of the present invention. [Diagram 5] FIG. 2 is a diagram of another embodiment of a method for producing a hydrogen stream and a CO2 stream from the effluent stream of a hydrogen production process unit using a PSA system for producing at least two product streams of the present invention. [Figure 6] FIG. 2 is a diagram of another embodiment of a method for producing a hydrogen stream and a CO2 stream from the effluent stream of a hydrogen production process unit using a PSA system for producing at least two product streams of the present invention. [Figure 7] FIG. 2 is a diagram of another embodiment of a method for producing a hydrogen stream and a CO2 stream from the effluent stream of a hydrogen production process unit using a PSA system for producing at least two product streams of the present invention. [Figure 8] FIG. 1 is a diagram of an embodiment of a CO2 capture system using a dual refrigerant CO2 fractionation process. [Figure 9] FIG. 1 is a diagram of another embodiment of a CO2 capture system using a mixed refrigerant CO2 fractionation process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A biorenewable conversion process for producing fuels from biorenewable feedstocks is combined with a hydrogen production process to produce hydrogen, increasing hydrogen production and allowing for CO2 capture.

[0013] The biorenewable conversion process produces hydrocarbon products, such as diesel, aviation fuel, and naphtha, from the biorenewable feedstock. It also produces a purge gas stream containing hydrogen that is processed in the hydrogen production process. The integrated process provides economic benefits, reduces net CO2 emissions, and in some cases avoids contamination of CO2 liquid products with hydrocarbons.

[0014] The hydrogen-containing purge gas stream from the currently combusted biorenewable conversion process contains hydrogen, CO2, optionally water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide. All or a portion of the hydrogen-containing purge gas stream is sent to one or more process units in the hydrogen production process. The hydrogen-containing purge gas stream can be sent directly or indirectly to the process unit. In an indirect process, it can first be sent to another process unit, including but not limited to a membrane separation unit, before being sent to the process unit.

[0015] The purge gas stream typically comprises at least 50 mol% hydrogen, or at least 55 mol%, or at least 60 mol% hydrogen, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol% hydrogen.

[0016] The purge gas stream may be a slip stream from the overhead from a separator downstream of a reaction zone in a bio-renewable conversion process.

[0017] One option is to combust a purge gas stream containing hydrogen in the furnace of the steam reforming process unit.

[0018] Another option involves the use of a pressure swing adsorption (PSA) system that produces at least two product streams including two PSA units, as described in more detail below. The hydrogen-containing purge gas stream is introduced into the second PSA unit to recover hydrogen in the hydrogen-containing purge gas stream. This increases the overall hydrogen recovery in the integrated process.

[0019] Yet another option is to separate the purge gas stream containing hydrogen into a permeate stream containing hydrogen and carbon dioxide and a residue stream containing at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide in a membrane separation unit. The permeate stream can be sent to a compressor and a CO2 capture system for recovery of hydrogen and carbon dioxide. About 90% of the hydrogen in the membrane feed stream is recovered in the permeate stream, and about 50% of the CO2 in the membrane feed stream is recovered in the permeate stream. Depending on the particular hydrogen production process unit, there are several possible treatments for the residue stream. If the hydrogen production process is a steam reforming process, the residue stream can be burned in a furnace or a heater in the steam reforming process unit. Alternatively, the residue stream can be mixed with a feed stream containing hydrocarbons and sent to the steam reforming process unit as part of the feed stream. If the process unit includes an autothermal reforming unit with optional gas-heated reformer, gasification unit, or partial oxidation unit, the residue stream can be mixed with a feed stream containing hydrocarbons, and the mixed stream can be partially oxidized in the autothermal reforming unit with optional gas-heated reformer, gasification unit, or partial oxidation unit. Another possibility is to send the residue stream to a bio-renewable conversion process to recover at least one of propane and C4+ hydrocarbons from the residue stream. Alternatively, the residue stream can be mixed with a feed stream containing hydrocarbons and sent to a hydrogen production process unit, and the permeate stream can be combusted in a furnace or furnace.

[0020] Yet another option is to send the hydrogen-containing purge gas stream to a CO2 capture system. This option increases hydrogen production, but the hydrocarbons present in the hydrogen-rich purge stream contaminate the CO2 product stream. Although hydrocarbon contamination of the CO2 product stream is often undesirable, there may be situations where it may be acceptable. As part of an integrated process, at least a portion of the hydrocarbon-containing feed stream for the hydrogen production process may be derived from a biorenewable conversion process.

[0021] One aspect of the present invention is a method for producing a hydrogen-rich product and capturing CO2 in an integrated hydrogen production process and bio-renewable conversion process. In one embodiment, the integrated process includes treating a feed stream comprising a hydrocarbon or carbonaceous feedstock in a hydrogen production process unit to produce a synthesis gas mixture comprising hydrogen, carbon dioxide, water, and at least one of methane, carbon monoxide, nitrogen, and argon; separating an effluent stream from a steam reforming process unit into at least a first high pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream in a first pressure swing adsorption (PSA) system producing at least two product streams; compressing the hydrogen-depleted tail gas stream in a compressor to form a compressed tail gas stream; separating the compressed tail gas stream in a CO2 capture system to produce a CO2 product and a second gas stream comprising hydrogen; and hydrogenating, deoxygenating, isomerizing, and selectively hydrocracking the biorenewable feedstock in a reaction zone in the presence of hydrogen under reaction conditions by contacting the biorenewable feedstock with a multifunctional catalyst or set of catalysts having hydrogenation, deoxygenation, isomerization, and selective hydrocracking functions to produce paraffinic hydrocarbons, hydrogen, C providing a reaction effluent comprising O2, water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide; separating the reaction effluent in a separator into at least one hydrocarbon stream comprising paraffinic hydrocarbons and an overhead stream comprising hydrogen, CO2, optionally water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide; separating the hydrocarbon streams in a fractionation zone to produce a hydrocarbon product stream, the hydrocarbon product stream comprising at least one of a diesel stream comprising hydrocarbons having a boiling point in a diesel boiling range, an aviation fuel stream having hydrocarbons having a boiling point in an aviation fuel boiling range, and a naphtha stream having hydrocarbons in a naphtha boiling range; recovering the hydrocarbon product stream; separating the overhead stream from the separator into at least a hydrogen-rich stream comprising hydrogen; and introducing at least a portion of a purge gas stream comprising hydrogen from the hydrogen-rich stream from the biorenewable conversion process to a process unit of the hydrogen production process.

[0022] In some embodiments, the first PSA system producing at least two product streams includes a first PSA unit having two product streams, the first PSA unit separating an effluent stream into a first high-pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream, and separating the compressed tail gas stream includes separating the compressed tail gas stream in a CO2 capture system into a bottoms stream comprising a purified liquid CO2 product and an overhead stream comprising a portion of the hydrogen, a portion of the carbon dioxide, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon; in a second PSA system producing at least two product streams, separating the overhead stream from the CO2 capture system into at least a second high-pressure hydrogen stream enriched in hydrogen and a low-pressure CO2 stream enriched in carbon dioxide; recovering the second high-pressure hydrogen stream; and recycling the low-pressure CO2 stream to the compressor.

[0023] Suitable biorenewable conversion processes for the production of aviation and diesel fuels, reaction conditions, and catalysts are known in the art and include, but are not limited to, U.S. Pat. Nos. 7,999,142, 8,039,682, 8,198,492, 8,742,183, and 8,865,953, each of which is incorporated herein by reference in its entirety.

[0024] Generally, biorenewable conversion processes include a reaction zone for hydrogenating, deoxygenating, isomerizing, and selective hydrocracking the biorenewable feedstock to produce hydrocarbon products with paraffins that have boiling points in the aviation fuel range. The reaction zone can include one or more reaction vessels, each of which can include one or more catalyst beds for the various reactions. Diesel fuel and / or naphtha can also be produced. The hydrocarbon products are useful as aviation fuel or aviation fuel blend components. Simply deoxygenating the biorenewable feedstock in a hydrogen environment in the presence of a hydrotreating catalyst results in straight-chain paraffins with chain lengths similar to, or slightly shorter than, the fatty acid composition of the feedstock. For many feedstocks, this approach results in products with carbon chain lengths suitable for diesel fuel, but not products that meet aviation fuel specifications. Selective hydrocracking reactions reduce the carbon chain length to maximize selectivity to aviation fuel range paraffins while minimizing lower molecular weight products. Isomerization allows aviation fuel specifications such as freezing point to be met.

[0025] The reaction effluent comprises paraffinic hydrocarbons, hydrogen, CO2, water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide. The reaction effluent is separated into a hydrocarbon stream comprising paraffinic hydrocarbons and an overhead stream comprising hydrogen, CO2, optionally water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide. Other streams may also be formed.

[0026] The hydrocarbon stream is then separated to form various hydrocarbon product streams, such as a diesel stream comprising hydrocarbons boiling in the diesel boiling range, an aviation fuel stream having hydrocarbons boiling in the aviation fuel boiling range, and a naphtha stream having hydrocarbons in the naphtha boiling range. The naphtha stream may also contain liquefied petroleum gas (LPG) and / or off-gas. Alternatively, the LPG and / or off-gas may be separate streams. At least a portion of the naphtha stream and / or LPG stream and / or off-gas stream may be sent to a hydrogen production process and used as part of the hydrocarbon feedstock to the hydrogen production process or as fuel for a furnace in the hydrogen production process unit.

[0027] The hydrogen production process produces hydrogen and allows for the capture of CO2 from the effluent stream of a hydrogen production process unit. It uses a PSA system producing at least two product streams to recover pure hydrogen from a tail gas stream from a hydrogen separation unit in the hydrogen production process. The process utilizes a CO2 capture system integrated with the PSA system producing at least two product streams to recover additional hydrogen and high purity liquid CO2.

[0028] In some embodiments, extracting pure hydrogen directly from the overhead stream of a CO2 capture system using a PSA system that produces at least two product streams provides an economic advantage over systems that use a recycle configuration. The additional hydrogen production substantially improves the economics of the process. The use of a PSA system that produces at least two product streams with the overhead stream of a CO2 capture system also avoids the non-permeation losses of CO2 that occur with the use of membrane separation processes. Utilizing a PSA system that produces at least two product streams provides innovation and flexibility, reduces downstream equipment size and availability, and increases captured CO2 (because the impurity-rich purge stream does not contain significant CO2).

[0029] The hydrogen production process unit may include a steam reforming unit with an optional gas heated reformer, an autothermal reforming unit with an optional gas heated reformer, a gasification unit, or a partial oxidation (POX) unit. The hydrogen production process produces an effluent that includes a mixture of hydrogen, carbon dioxide, water, and gases including at least one of methane, carbon monoxide, nitrogen, and argon.

[0030] Hydrocarbon-containing feed streams suitable for hydrogen production processes include, but are not limited to, natural gas, naphtha, liquefied petroleum gas (LPG) for steam reforming, ATR / GHR, and POX processes. POX and gasification processes can use solid feedstocks, including, but not limited to, coal and petroleum coke. Other hydrogen-containing feed streams, such as hydrothermal liquefaction (HTL) (containing hydrocarbons, water, and oxygen-containing molecules), bio-oil and bio-crude (including those derived from HTL), and biogas, can also be used.

[0031] In some embodiments, the first PSA system producing the at least two streams is a hydrogen pressure swing adsorption (PSA) unit. The effluent stream is first sent to a hydrogen PSA unit to separate a hydrogen-enriched high-pressure hydrogen stream and a hydrogen-depleted tail gas stream containing the remaining hydrogen, carbon dioxide, water, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon. The high-pressure hydrogen stream contains about 90% hydrogen in the effluent, which is recovered.

[0032] The hydrogen-depleted tail gas stream is compressed and sent to a CO2 capture system where it is separated into a liquid CO2 product and an overhead stream containing hydrogen, some carbon dioxide, and some of at least one of methane, carbon monoxide, nitrogen, and argon.

[0033] The overhead stream is sent to a second PSA system that produces at least two product streams. The second PSA system with at least two product streams separates the overhead stream into at least two streams: a high-pressure hydrogen stream and a low-pressure CO2 stream. In some embodiments, the high-pressure hydrogen stream is enriched in hydrogen and is substantially free of carbon dioxide, methane, carbon monoxide, nitrogen, and argon. The low-pressure CO2 stream is enriched in carbon dioxide and contains substantially all of the carbon dioxide in the overhead stream. The second high-pressure hydrogen stream is recovered and the low-pressure CO2 stream is recycled to the compressor. In some embodiments, a second gas stream is also formed that contains at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon.

[0034] In other embodiments, the first PSA system producing at least two product streams is a three-product PSA unit, a PSA unit with two product streams, or two PSA units each with two product streams. The first PSA system producing at least two product streams separates the effluent stream into at least two streams: a high-pressure hydrogen-rich stream and a low-pressure CO2-rich stream. In some embodiments, the high-pressure hydrogen stream is enriched in hydrogen and substantially free of carbon dioxide. In some embodiments, the low-pressure CO2 stream is enriched in carbon dioxide and contains substantially all of the carbon dioxide in the effluent stream. The high-pressure hydrogen stream is recovered and the low-pressure CO2 stream is sent to a compressor. The compressed CO2 stream is separated in the CO2 capture system into a liquid CO2 product and an overhead stream containing hydrogen, some carbon dioxide, methane, and some of at least one of carbon monoxide, nitrogen, and argon. The overhead stream is recycled to the first PSA system. In some embodiments, a second gas stream is also formed that includes at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon.

[0035] This process allows for the recovery of about 80 to about 90% of the hydrogen in the tail gas stream from the hydrogen PSA unit, as well as the capture of substantially all (e.g., about 95% to about 100%) of the CO2.

[0036] In some embodiments, the effluent from the hydrogen production process unit that is fed to the hydrogen PSA system is typically in the range of about 20° C. to about 60° C., or about 30° C. to about 50° C., or about 40° C. (or any combination of temperature ranges). The pressure is typically in the range of about 2,000 to about 5,000 kPa.

[0037] The effluent is separated in the hydrogen PSA unit into a high pressure hydrogen stream and a tail gas stream. The high pressure hydrogen stream contains about 80% to about 90% of the hydrogen in the effluent. The high pressure hydrogen stream is typically at a pressure in the range of about 2,000 to about 5,000 kPa. The high pressure hydrogen stream is a high purity stream (e.g., greater than 99%, or greater than 99.9%, or greater than 99.99%, or greater than 99.999%).

[0038] The tail gas stream from the hydrogen PSA unit, which contains about 10% to about 20% of the hydrogen in the effluent stream, carbon dioxide, water, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon, is at a pressure in the range of about 100 to about 200 kPa.

[0039] The tail gas stream is compressed to a pressure in the range of about 3,000 to about 6,000 kPa and sent to a CO2 capture system. The compressed tail gas stream is dried and cooled to a temperature of about -20°C to about -50°C. It is separated into a CO2-rich stream and an overhead stream comprising hydrogen, a portion of the carbon dioxide, and a portion of at least one of methane, carbon monoxide, nitrogen, and argon. In some embodiments, the CO2-rich stream comprises substantially all (e.g., about 95% to about 100%) of the CO2 in the tail gas stream from the hydrogen PSA unit and is substantially free of methane, carbon monoxide, nitrogen, and argon. In some embodiments, the bottoms stream comprises about 95.0 mol% or more of CO2, about 98.0 mol% or more of CO2, or about 98.5 mol% or more of CO2, or about 99.0 mol% or more of CO2, or about 99.5 mol% or more of CO2, or about 99.9 mol% or more of CO2.

[0040] The CO2 capture system may include a distillation column, with a CO2-enriched product stream being recovered from the bottom of the column and lighter components (hydrogen, methane, nitrogen, etc.) being recovered from the top of the column. The CO2 capture system may alternatively or as well include single or multiple successive flash vapor-liquid separation vessels, each providing an additional theoretical stage of mass transfer, with the CO2-enriched product being recovered in a liquid stream and the lighter components (hydrogen, methane, nitrogen, etc.) being recovered in an overhead vapor stream.

[0041] The CO2-rich stream is recovered. The CO2-rich stream may be a liquid stream. Optionally, the liquid stream may be vaporized for use, if desired.

[0042] The overhead stream is sent to a PSA system producing at least two product streams, which may be a three-product PSA unit, a PSA unit having two product streams, or two PSA units each having two product streams, with the product from the first PSA unit being fed to the second PSA unit.

[0043] The 3-product PSA unit includes four or more PSA adsorption vessels. Generally, there are at least six vessels, typically 8-14 vessels. The vessels include one or more adsorbent beds, generally 1-5, typically 2-3 adsorbent beds. The bed fraction of the adsorbent bed is typically 10%-100%. Different layers of adsorbent have different selectivities for the components in the overhead stream, as known to those skilled in the art. Some layers include adsorbents for selectively adsorbing CO2 relative to methane, carbon monoxide, nitrogen, argon, and hydrogen, adsorbents include, but are not limited to, layers of activated alumina, silica gel, and sodium Y zeolite. Other layers include adsorbents for selectively adsorbing CO2, methane, carbon monoxide, nitrogen, and argon relative to hydrogen, adsorbents include, but are not limited to, layers of activated carbon, silica gel, and molecular sieve zeolites (e.g., 5A or sodium X zeolite). Those skilled in the art will understand that other zeolites can be used and will know how to select the appropriate adsorbent.

[0044] The vessel has a first opening at one end and a second opening at the opposite end. For convenience, these ends are referred to as the top and bottom of the vessel. The first opening at the bottom is selectively connected to a high pressure feed gas inlet line and a low pressure tail gas outlet line. The second opening at the top of the vessel is selectively connected to a high pressure product outlet line, a medium pressure vent gas outlet line, and a low pressure purge gas inlet line.

[0045] Feed gas enters at high pressure through a first opening at the bottom of the vessel, where a high pressure cocurrent adsorption and product removal step takes place, and the product leaves the vessel at high pressure through a second opening at the top of the vessel. There is at least one cocurrent depressurization step, then a medium pressure cocurrent depressurization and vent gas removal step. A second stream is removed through an opening at the top of the vessel at a second pressure. There is a countercurrent blowdown step and a countercurrent purge step. Purge gas enters through an opening at the top of the vessel at low pressure. CO2 can be removed at low pressure through an opening at the bottom of the vessel during either or both of the countercurrent blowdown and countercurrent purge steps. The countercurrent purge and tail gas removal steps are followed by at least one countercurrent repressurization step.

[0046] The PSA system producing at least two product streams can include two PSA units in series. The overhead stream from the CO2 capture system is introduced into the first PSA unit, where it is separated into a low-pressure tail gas stream enriched in CO2 and a high-pressure stream containing substantially all of the hydrogen in the overhead stream (e.g., about 85% to about 95%) and a portion of at least one of methane, carbon monoxide, nitrogen, and argon. The high-pressure stream is fed to the second PSA unit, where it is separated into a high-pressure hydrogen stream enriched in hydrogen and a low-pressure stream containing substantially all of the methane, carbon monoxide, nitrogen, and argon (e.g., about 95% to about 100%).

[0047] The PSA system of the present invention producing at least two product streams offers several advantages. The second stream is not removed at high pressure. In a three-product PSA unit, the second stream is removed at an intermediate pressure between the high pressure at which hydrogen is removed and the low pressure at which CO2 is removed, but at a pressure much closer to the low pressure than the high pressure. The intermediate pressure is typically less than about 450 kPa. When the PSA system producing at least two product streams includes two PSA units, the second stream is removed at low pressure, typically less than 250 kPa.

[0048] In addition, no high pressure co-purge stream is used. Furthermore, the vessel is not segmented and the second stream is removed through an opening in the top of the vessel. Thus, no isolation valves and side draw outlets are required between the two adsorbent beds. These factors make the three product PSA unit much less complex and cheaper to build and operate than the PSA and process of U.S. Pat. No. 8,241,400.

[0049] The temperature of the overhead stream entering the second PSA system producing at least two product streams (after cooling recovery and heat exchange) is typically in the range of about 20° C. to about 60° C., or about 30° C. to about 50° C., or about 40° C. (or any combination of temperature ranges).

[0050] The hydrogen concentration in the overhead stream fed to the second PSA system producing at least two product streams is typically in the range of about 20 mol% to about 60 mol%. For example, the hydrogen concentration in the overhead gas of a CO2 distillation column in a CO2 capture system of a steam methane reforming plant tail gas is about 30 mol% to about 50 mol%.

[0051] About 80% to 90% of the hydrogen in the overhead stream is typically recovered in the high pressure hydrogen stream, which is substantially free of CO2, methane, carbon monoxide, nitrogen, and argon. The high pressure hydrogen stream typically contains less than about 1%, or less than about 0.1%, or less than about 0.01% CO2 relative to the overhead stream. The high pressure hydrogen stream typically contains less than about 10%, or less than about 5%, or less than about 2%, or less than about 1%, or less than about 0.1% methane, carbon monoxide, nitrogen, and argon relative to the overhead stream. The high pressure hydrogen stream is typically removed at a high pressure in the range of about 1,000 to about 6,000 kPa, or about 2,000 kPa to about 5,000 kPa, or about 2,500 kPa to about 4,500 kPa.

[0052] The low pressure tail gas stream is typically withdrawn at a low pressure in the range of from about 50 kPa to about 250 kPa, or from about 100 kPa to about 200 kPa.

[0053] The low pressure CO2 stream typically contains substantially all of the CO2 in the overhead stream (e.g., about 95% to 100%). It typically contains about 10% hydrogen (e.g., about 5% to about 15%) and about 40% methane, carbon monoxide, nitrogen, and argon (e.g., about 20% to about 60%) for the overhead stream.

[0054] When the second PSA system producing at least two product streams includes a three-product PSA unit, the second gas stream is withdrawn at an intermediate pressure between the high pressure and the low pressure, the intermediate pressure being much closer to the low pressure than the high pressure, typically within about 400 kPa, or 300 kPa, or 200 kPa of the low pressure. Typically, the intermediate pressure product stream is withdrawn at a pressure in the range of about 150 kPa to about 450 kPa, or about 250 kPa to about 350 kPa. It will be understood that there is some overlap between the intermediate and low pressure ranges, but in certain cases the low pressure will be lower than the intermediate pressure.

[0055] The second stream typically contains about 40% to 80% of the methane, carbon monoxide, nitrogen, and argon in the overhead stream. The second stream typically contains about 10% hydrogen (e.g., about 5% to about 25%) and less than about 5%, or less than about 1%, or less than about 0.1% CO2 by overhead stream.

[0056] All or a portion of the second stream may be recycled to the hydrogen production process unit, the water gas shift process unit, and / or the combustion unit.

[0057] When the second PSA system producing at least two product streams includes two PSA units in series, the overhead stream is introduced into the first PSA unit where it is separated into a low pressure CO2 stream containing substantially all (about 95% to 100%) of the CO2 and a high pressure stream containing substantially all (e.g., greater than 75%, or about 85% to about 95%) of the hydrogen in the overhead stream, and a portion (about 50% to about 90%) of at least one of methane, carbon monoxide, nitrogen, and argon. The low pressure CO2 stream has a low pressure of about 50 kPa to about 250 kPa, or about 100 kPa to about 200 kPa. The high pressure stream has a high pressure in the range of about 1,000 to about 6,000 kPa, or about 2,000 kPa to about 5,000 kPa, or about 2,500 kPa to about 4,500 kPa.

[0058] The first PSA unit includes an adsorbent for selectively adsorbing CO2 relative to methane, carbon monoxide, nitrogen, argon, and hydrogen, including, but not limited to, activated alumina, silica gel, and a bed of sodium Y zeolite. The second PSA unit includes an adsorbent for selectively adsorbing CO2, methane, carbon monoxide, nitrogen, and argon relative to hydrogen, including, but not limited to, activated carbon, silica gel, and a bed of molecular sieve zeolite (e.g., 5A or sodium X zeolite). Those skilled in the art will understand that other zeolites can be used and will know how to select appropriate adsorbents for the first and second PSA units.

[0059] The high pressure stream is fed to a second PSA unit where it is separated into a high pressure hydrogen stream containing substantially all (e.g., about 80% to about 90%) hydrogen and a second gas stream. The second gas stream contains substantially all (e.g., about 95% to about 100%) of at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon. The high pressure hydrogen stream typically has a high pressure in the range of about 1,000 to about 6,000 kPa, or about 2,000 kPa to about 5,000 kPa, or about 2,500 kPa to about 4,500 kPa. In this configuration, the second stream has a pressure in the range of about 50 kPa to about 250 kPa, or about 100 kPa to about 200 kPa.

[0060] When the PSA system producing at least two product streams includes a three product PSA unit having a three product PSA cycle, a high pressure hydrogen stream may be removed during the high pressure cocurrent adsorption step of the three product PSA cycle, a second gas stream may be removed during the cocurrent depressurization step of the three product PSA cycle, and a low pressure CO2 stream may be removed during the countercurrent depressurization and countercurrent purge steps of the three product PSA cycle.

[0061] In some embodiments, when the PSA system producing the at least two product streams is a three product PSA unit having a three product PSA cycle, the three product PSA cycle comprises: a high pressure co-current adsorption and hydrogen removal step; at least one cocurrent depressurization step following the high pressure cocurrent adsorption step and the hydrogen removal step; at least one cocurrent depressurization step followed by a cocurrent depressurization and a second gas removal step; a medium pressure cocurrent depressurization and second gas removal step followed by a countercurrent blowdown step and a CO2 removal step; a countercurrent blowdown step followed by a countercurrent purge and CO2 removal step; at least one countercurrent repressurization step following a countercurrent purging and CO2 removal step; Optionally, at least one countercurrent repressurization step followed by a cocurrent feed repressurization step, or at least one countercurrent repressurization step followed by a countercurrent product repressurization step.

[0062] In some embodiments, the CO2 capture system includes a refrigeration CO2 fractionation process in which refrigeration cooling is provided by at least two refrigeration circuits, one of which utilizes a portion of the liquid CO2 product recovered from the distillation column, or a single closed-loop multi-component mixed refrigeration circuit as described more fully below.

[0063] In some embodiments, the process can include a catalytic oxidation (CATOX) reactor on the second stream to recover heat in the form of high pressure steam from the unconverted carbon monoxide and methane and unrecovered hydrogen from the hydrogen production process. Approximately the same amount of heat or steam is produced as when the second stream is sent to a furnace. However, sending it to a CATOX reactor unit avoids the CO2 emissions produced from burning these components in the furnace and increases the percentage of CO2 captured from the process. The CATOX reactor unit can be approximately isothermal, with catalyst on one side of the heat exchanger and boiling water on the other side. For example, the CATOX reactor unit can have a water / steam (reactor) temperature of about 250°C. The scale of the reactor can be relatively small, for example, 100,000 Nm 3 / hr hydrogen production plant capacity, total gas supply rate (fuel gas + oxygen) of 6,000 Nm 3 / hr.

[0064] In some embodiments, there is a selective bypass configuration that allows the system to operate if there is a problem with the compressor, the CO2 capture system, and / or the PSA system that produces at least two product streams. In some embodiments, the compressor and the CO2 capture system are bypassed and the hydrogen-depleted tail gas stream from the hydrogen PSA unit is sent to a furnace in a steam reforming process unit or elsewhere. In other embodiments, the compressor, the CO2 capture system, and / or the PSA system that produces at least two product streams are bypassed and the tail gas stream from the hydrogen PSA unit is sent to a furnace in a hydrogen production process unit or elsewhere. Suitable furnace burners include, but are not limited to, the burners described in U.S. Patent No. 6,875,008, modified to include an inlet for the tail gas stream, and the burners described in U.S. Patent Application No. 63 / 167,343, entitled "Active And Passive Combustion Stabilization For Burners For Highly and Rapidly Varying Fuel Gas Compositions," filed on the same day as this application, each of which is incorporated herein in its entirety.

[0065] Additional energy recovery can be obtained from the effluent of the WGS unit in this process. The effluent stream from the WGS unit can be heat exchanged with a process stream to form a cooled effluent steam and a preheated process stream. Waste heat can be recovered from the cooled effluent stream to generate steam using a process involving the reversible oligomerization reaction of phosphoric acid. Contact of the waste heat with phosphoric acid results in oligomerization to diphosphoric acid. As a result of the oligomerization, water molecules separate and condense, and the waste heat is cooled. The pressure of the diphosphoric acid stream is increased. The waste heat then evaporates the water absorbed by the diphosphoric acid. This causes de-oligomerization and hydrolysis, resulting in conversion to phosphoric acid and the production of higher value process heat. The pressure of the phosphoric acid stream is then reduced and the cycle is repeated. A waste heat recovery process using reversible oligomerization of phosphoric acid is available from Qpinch, Antwerp, Belgium.

[0066] In some embodiments, the method further comprises passing at least a portion of the naphtha stream to a hydrogen production process, wherein at least a portion of a hydrocarbon-containing feed stream for the hydrogen production process comprises at least a portion of the naphtha stream.

[0067] In some embodiments, the process unit comprises a steam reforming process unit with an optional gas heated reformer, and the purge gas stream comprising hydrogen is combusted in a furnace or furnace in the steam reforming process unit with an optional gas heated reformer.

[0068] In some embodiments, the process unit includes a PSA system that produces at least two product streams, the PSA system that produces at least two product streams includes two PSA units, each having two product streams, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream into a first PSA unit, separating the overhead stream into a low-pressure CO2 stream and a high-pressure third stream comprising greater than 75% hydrogen and at least a first portion of at least one of methane, carbon monoxide, nitrogen, and argon, and feeding the high-pressure third stream to a second PSA unit, and the second high-pressure hydrogen stream and the second gas stream are removed from the second PSA unit, and a purge gas stream comprising hydrogen from the bio-renewable process is introduced into the second PSA unit.

[0069] In some embodiments, the method further comprises separating the purge gas stream comprising hydrogen into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide in a membrane separation unit, the process unit comprising a compressor, and the permeate stream is compressed in the compressor.

[0070] In some embodiments, the method further comprises at least one of: the second process unit comprises a steam reforming process unit having an optional gas heated reformer, further comprising combusting the residue stream in a furnace or furnace in the steam reforming process unit having an optional gas heated reformer; the second process unit comprises a steam reforming process unit having an optional gas heated reformer, further comprising mixing the residue stream with a feed stream comprising hydrocarbons in the steam reforming process unit having an optional gas heated reformer; the process unit comprises an autothermal reforming unit having an optional gas heated reformer, a gasification unit, or a partial oxidation unit, further comprising mixing the residue stream with a feed stream comprising hydrocarbons and partially oxidizing the mixed stream in the autothermal reforming unit having an optional gas heated reformer, a gasification unit, or a partial oxidation unit; and sending the residue stream to a bio-renewable hydrocarbon production process and recovering at least one of propane and C4+ hydrocarbons from the residue stream.

[0071] In some embodiments, the process unit includes a CO2 capture system, and a purge gas stream comprising hydrogen from the bio-renewable conversion process is introduced into the CO2 capture system.

[0072] In some embodiments, the PSA system producing at least two product streams includes a three-product PSA unit, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to the three-product PSA unit having a PSA cycle, removing a second high-pressure hydrogen stream during a high-pressure cocurrent adsorption step in the PSA cycle, removing a second gas stream during a cocurrent depressurization step in the PSA cycle, and removing a low-pressure CO2 stream during at least one of a countercurrent depressurization step and a countercurrent purge step in the PSA cycle.

[0073] In some embodiments, the CO2 capture system includes a refrigeration circuit, one of which utilizes a portion of the liquid CO2 product recovered from a distillation column in the CO2 capture system, or a refrigeration CO2 fractionation process in which refrigeration cooling is provided by at least two refrigeration circuits in a single closed-loop multi-component mixed refrigeration system.

[0074] In some embodiments, the method further includes selectively bypassing the compressor, the CO capture system, and the PSA system that produces at least two product streams, and directing a hydrogen-depleted tail gas stream from the hydrogen PSA unit to a furnace in the steam reforming process unit.

[0075] In some embodiments, the method further includes separating the purge gas stream comprising hydrogen from the biorenewable conversion process in a membrane separation unit into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide, wherein the process unit comprises a hydrogen production process unit, and wherein the residue stream is introduced as part of a feed stream to the hydrogen production process unit, and wherein the process unit comprises a hydrogen production process unit, and wherein the permeate stream is introduced to the furnace.

[0076] Another aspect of the invention is a method of producing a hydrogen-enriched stream and recovering CO2 from a hydrogen production process unit. In one embodiment, the method includes treating a feed stream comprising a hydrocarbon or carbonaceous feedstock in a hydrogen production process unit to produce a synthesis gas mixture comprising hydrogen, carbon dioxide, water, and at least one of methane, carbon monoxide, nitrogen, and argon, and separating an effluent stream from the hydrogen production process unit in a hydrogen pressure swing adsorption (PSA) unit into a first high pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream comprising a portion of the hydrogen, carbon dioxide, water, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon. compressing the hydrogen-depleted tail gas stream in a compressor to form a compressed tail gas stream; separating the compressed tail gas stream in a CO2 capture system to produce a CO2-enriched product stream and a second gas stream comprising at least a portion of at least one of methane, carbon monoxide, nitrogen gas, and argon gas; and introducing at least a portion of a purge gas stream comprising hydrogen from a biorenewable conversion process to make hydrocarbon products from a biorenewable feedstock into one of the process units in the method of producing hydrogen and capturing CO2.

[0077] In some embodiments, separating the compressed tail gas stream includes separating the compressed tail gas stream in a CO2 capture system into a CO2-enriched product stream and an overhead stream comprising a portion of the hydrogen, a portion of the carbon dioxide, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon; separating the overhead stream from the CO2 capture system in a PSA system producing at least two product streams into at least a second high-pressure hydrogen stream enriched in hydrogen and a low-pressure CO2 stream enriched in carbon dioxide; recovering the second high-pressure hydrogen stream; and recycling the low-pressure CO2 stream to the compressor.

[0078] In some embodiments, the process unit comprises a steam reforming process unit with an optional gas heated reformer, and the purge gas stream comprising hydrogen from the bio-renewable conversion process is combusted in a furnace or furnace in the steam reforming process unit with an optional gas heated reformer.

[0079] In some embodiments, the process unit includes a second PSA system producing at least two product streams, the second PSA system including two PSA units having the two product streams, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to the first PSA unit, separating the overhead stream into a low pressure CO2 stream and a third high pressure stream enriched in hydrogen, and providing the third high pressure stream to the second PSA unit, the second high pressure hydrogen stream and the second gas stream are removed from the second PSA unit, and a purge gas stream comprising hydrogen from the biorenewable conversion process is introduced to the second PSA unit.

[0080] In some embodiments, the method further includes separating a purge gas stream comprising hydrogen from the biorenewable conversion process into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide in a membrane separation unit, the process unit including a compressor, and the residue stream being compressed in the compressor.

[0081] In some embodiments, the method further comprises at least one of: the second process unit comprises a steam reforming process unit having an optional gas heated reformer, further comprising combusting the residue stream in a furnace or furnace in the steam reforming process unit having an optional gas heated reformer; the second process unit comprises a steam reforming process unit having an optional gas heated reformer, further comprising mixing the residue stream with a feed stream comprising hydrocarbons in the steam reforming process unit having an optional gas heated reformer; the process unit comprises an autothermal reforming unit having an optional gas heated reformer, a gasification unit, or a partial oxidation unit, further comprising mixing the residue stream with a feed stream comprising hydrocarbons and partially oxidizing the mixed stream in the autothermal reforming unit having an optional gas heated reformer, a gasification unit, or a partial oxidation unit; and sending the residue stream to a bio-renewable conversion process and recovering at least one of propane and C4+ hydrocarbons from the residue stream.

[0082] In some embodiments, the process unit includes a CO2 capture system, and a purge gas stream comprising hydrogen from the bio-renewable conversion process is introduced into the CO2 capture system.

[0083] In some embodiments, at least a portion of the hydrocarbon-containing feed stream for the hydrogen production process comprises an overhead stream from a product fractionation zone in a biorenewable conversion process.

[0084] In some embodiments, the PSA system producing at least two product streams includes a three-product PSA unit, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to the three-product PSA unit having a PSA cycle, removing a second high-pressure hydrogen stream during a high-pressure cocurrent adsorption step in the PSA cycle, removing a second gas stream during a cocurrent depressurization step in the PSA cycle, and removing a low-pressure CO2 stream during at least one of a countercurrent depressurization step and a countercurrent purge step in the PSA cycle.

[0085] In some embodiments, the CO2 capture system includes a refrigeration circuit, one of which utilizes a portion of the liquid CO2 product captured from the CO2 capture system, or a refrigeration CO2 fractionation process in which refrigeration cooling is provided by at least two refrigeration circuits in a single closed-loop multi-component mixed refrigeration system.

[0086] In some embodiments, the method further includes selectively bypassing the compressor, the CO capture system, and the PSA system that produces at least two product streams, and directing a hydrogen-depleted tail gas stream from the hydrogen PSA unit to a furnace in the steam reforming process unit.

[0087] Another aspect of the invention is a method of producing a hydrogen-enriched product and recovering CO2 from a hydrogen production process unit. In one embodiment, the method includes: treating a feed stream containing a hydrocarbon or carbonaceous feedstock in a hydrogen production process unit to produce a synthesis gas mixture containing hydrogen, carbon dioxide, water, and at least one of methane, carbon monoxide, nitrogen, and argon; separating an effluent stream containing synthesis gas from the hydrogen production process unit into a high-purity hydrogen stream, a carbon dioxide-enriched CO2 stream, and optionally a second gas stream containing at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon; recovering the high-purity hydrogen stream; and introducing at least a portion of a purge gas stream containing hydrogen from a biorenewable conversion process for making a hydrocarbon product from a biorenewable feedstock into one of the process units in the method of producing hydrogen and recovering CO2.

[0088] One embodiment of a bio-renewable conversion process is shown in Figure 1. A bio-renewable feedstock 10 enters a reaction zone 12 along with a make-up hydrogen stream 42 and an optional hydrocarbon recycle 46.

[0089] Bio-renewable feedstocks 10 include feedstocks derived from plants or animals and other than those obtained directly from petroleum crude oil. Another term used to describe this class of feedstocks is renewable fats and oils. Renewable feedstocks that can be used in the present invention include any that contain glycerides and free fatty acids (FFA). Examples of these feedstocks include, but are not limited to, canola oil, corn oil, soybean oil, rapeseed oil, tall oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, cottonseed oil, tallow, yellow and brown grease, lard, whale oil, fat in milk, fish oil, algae oil, sewage sludge, cuphea oil, camelina oil, jatropha oil, curcas oil, babassu oil, palm kernel oil, crambe oil, and the like. Bio-renewable is another term used to describe these feedstocks. Typical vegetable oil or animal fat glycerides, FFAs and fatty acid alkyl esters contain aliphatic hydrocarbon chains with about 8 to about 24 carbon atoms in their structure, with the majority of oils containing high concentrations of fatty acids with 16 and 18 carbon atoms. Mixtures or co-feeds of renewable feedstocks and fossil fuel derived hydrocarbons can also be used as feedstocks. Other feedstock components that can be used as co-feed components, especially in combination with the above feedstocks, include used motor oils and industrial lubricants, used paraffin wax, liquids derived from downstream liquefaction steps such as Fischer-Tropsch technology following gasification of coal, biomass or natural gas, liquids derived from thermal or chemical depolymerization of waste plastics such as polypropylene, high density polyethylene, and low density polyethylene, and other synthetic oils produced as by-products from petrochemical and chemical processes. Mixtures of the above feedstocks can also be used as co-feed components. One advantage of using co-feed components is that what has been considered to be waste from fossil fuel based or other processes is converted into a valuable co-feed component to the current process.

[0090] Contacting the non-petroleum feedstock with a multifunctional catalyst or set of catalysts produces a hydrogenated, deoxygenated, selectively cracked, and isomerized reaction zone effluent 14. The reaction zone effluent 14 is introduced into a separator 16. The separator 16 includes a low temperature separator and, optionally, a high temperature separator. In the low temperature separator only, water is removed as a liquid in line 18 (low temperature separator mode). If a high temperature separator is present, water may be removed as a vapor in line 22 (high temperature separator mode). Hydrogen, CO2, optionally water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide are separated and removed in line 22.

[0091] The overhead in line 22 is a hydrogen-rich gas that is combined with the bio-renewable feedstock 10. A small purge gas stream containing hydrogen 44 is removed to control the hydrogen purity of the recycle gas.

[0092] A liquid stream containing paraffins and some lighter hydrocarbons in the jet fuel and diesel fuel range is removed from separator 16 in line 20 and sent to product fractionation zone 30. Product fractionation zone 30 is operated so that product fraction 34 contains hydrocarbons in the boiling range most useful for meeting the desired aviation fuel specifications. Product fraction 34 is collected for use as aviation fuel or as a blending component of aviation fuel.

[0093] Lighter materials such as naphtha and LPG are removed in fractionation zone overhead stream 36. A portion of fractionation zone overhead stream 36 may be sent in line 38 to a hydrogen production process, as described below. If desired, the naphtha and LPG may be further separated into an LPG stream and a naphtha stream (not shown).

[0094] Hydrocarbons having boiling points higher than allowed by aviation fuel specifications are removed in bottoms stream 32. A portion of bottoms stream 32 may be recovered and used as a fuel, such as, for example, low sulfur heating oil fuel, ethylene plant feedstock, feed to a lube oil plant, paraffinic solvent or dielectric oil. Bottoms stream 32 may be acceptable for use as a diesel or diesel blend component. A portion 46 of bottoms stream 32 is recycled to the reaction zone.

[0095] A portion of the hydrocarbon stream can also be cooled as needed and used as a cooled quench liquid between beds in the reaction zone to further control the heat of reaction and provide quench liquid for emergency situations. The recycle stream can be introduced at the inlet of the reaction zone and / or at any subsequent beds or reactors. One advantage of the hydrocarbon recycle is that it controls the temperature rise across the individual beds. However, as mentioned above, the amount of hydrocarbon recycle can be determined based on the desired hydrogen solubility in the reaction zone, minimizing the cracking rate per pass to provide high selectivity to aeronautical range paraffins. Increasing the hydrogen solubility in the reaction mixture allows for better operation at lower pressures, thus reducing costs. Operating at high recycle and maintaining high levels of hydrogen in the liquid phase helps dissipate hot spots on the catalyst surface and reduces the formation of undesirable heavy components that lead to coking and catalyst deactivation.

[0096] The aviation fuel product fraction 34 produced by the present invention is suitable for use as aviation fuel or as a blending component therefor. Depending on the use, various additives can be combined with the resulting fuel composition to meet the specifications required for various particular fuels. In particular, the hydrocarbon product streams produced herein may be produced in accordance with the following standards: ASTM D1655 standard for aviation turbine fuel Defense Stan 91-91 turbine fuel (aviation kerosene type, Jet A-1 NATO codes F-35, F-34, F-37), Aviation Fuel Quality Requirements for Joint Operated Systems (Joint Checklist), a combination of ASTM and Def Stan requirements (GOST 10227), Jet Fuel Specification (Russia), Canadian CAN / CGSB-3.22 aviation turbine fuel, Canadian CAN / CGSB-3.23 aviation turbine fuel, wide cut type, MIL-DTL-83133, kerosene type, JP-8, MW-DTL-5624, JP-4, JP-5, QAV-1 (Brazil), GB6537 DCSEA 134A (France) Especifcao de Querosene de Aviacao No. 3 Jet by Carbureacteur Pour Turbomachines D'Aviation Aviation fuel meets at least one of the following general grade requirements: Jet A, Jet A-1, Jet B, and TS-1 fuels, and may be a blending component for at least one of the following: Jet Fuel (China), kerosene-type aviation turbine fuels of other countries (conforming to the general grade requirements for Jet A, Jet A-1, Jet B, and TS-1 fuels as set forth in the IATA Guidance Material for Aviation Turbine Fuel Specifications), or may be combined with one or more additives to meet at least one of the following: Aviation fuel is generally referred to herein as "jet fuel," and the term "jet fuel" is meant to encompass aviation fuels that meet the above specifications, as well as aviation fuels that are used as blending components of aviation fuels that meet the above specifications. Additives may be added to jet fuel to meet certain specifications. One particular type of jet fuel is JP-8, as defined by military specification ML-DTL-83133, which is a military grade type of highly refined kerosene-based jet propellant prescribed by the U.S. government.The fuel produced from the glycerides or FAA described herein is very similar to isoparaffinic kerosene, also known as synthetic paraffinic kerosene (SPK) or synthetic jet fuel, iPK.

[0097] FIG. 2 shows an embodiment of a hydrogen production process 100 incorporating the three-product PSA unit of the present invention. Natural gas feed 105 and water 110 are sent to the reaction section 112 of the steam reforming process unit 120, and auxiliary fuel gas 114 and air 115 are sent to the steam reforming process unit 120. Instead of natural gas, other feed streams containing hydrocarbons can be used, including but not limited to naphtha and liquefied petroleum gas (LPG). The auxiliary fuel gas is an additional fuel source to provide stability and sufficient heat for the reforming reaction, since the PSA tail gas or vent gas does not provide enough heat to drive the process. Suitable auxiliary fuel gases include, but are not limited to, natural gas and other primarily hydrocarbon-containing fuels, such as refinery fuel gas, petrochemical complex synthetic fuel gas, vaporized naphtha or vaporized liquefied petroleum gas (LPG), or blends of hydrocarbon-containing fuels and hydrogen up to crude or refined hydrogen. Other hydrocarbon-containing feedstreams that can be used in place of natural gas for the steam reforming, ATR / GHR, and POX processes include, but are not limited to, naphtha and liquefied petroleum gas (LPG). POX and gasification processes can use solid feedstocks, including, but not limited to, coal and petroleum coke.

[0098] The steam reforming and water gas shift reactions produce an effluent stream 125 comprising hydrogen, CO, water, and at least one of methane, carbon monoxide, and nitrogen. A flue gas stream 130 and a steam stream 135 also exit the steam reforming process unit 120.

[0099] The effluent stream 125 has a temperature of about 30° C. to about 50° C. (after heat recovery and cooling in the steam reforming process) and a pressure of about 2,000 to about 3,000 kPa. The effluent stream 125 is sent to a hydrogen PSA unit 140 where it is separated into a high purity hydrogen stream 145 enriched in hydrogen and a hydrogen-depleted tail gas stream 150 containing a portion of the hydrogen, CO2, water, and at least a portion of at least one of methane, carbon monoxide, and nitrogen.

[0100] The tail gas stream 150 is sent to a compressor 155 where it is compressed from a pressure in the range of about 110 kPa to about 200 kPa to a pressure in the range of about 3,000 kPa to about 6,000 kPa.

[0101] The compressed tail gas stream 160 is sent to a CO2 capture unit 165 where it is dried to remove water stream 167, cooled to a temperature of about -20°C to about -50°C, and separated into a bottoms stream 170 and an overhead stream 175. The bottoms stream 170 containing liquid CO2 is recovered.

[0102] Overhead stream 175 is sent to a PSA system 180 that produces at least two product streams, including a three-product PSA unit 185, where it is separated into three streams. A high pressure hydrogen stream 190 is recovered. All or a portion of the high pressure hydrogen stream 190 may be sent to the bio-renewable conversion process and combined with the make-up hydrogen stream 42. A low pressure CO2 stream 195 is recycled to the compressor 155.

[0103] A medium pressure vent gas stream 200 containing at least a portion of at least one of methane, carbon monoxide, and nitrogen and a small amount of hydrogen (e.g., less than about 20%, or about 10% to about 20%) is sent as fuel to the steam reforming process unit 120. A purge gas stream containing hydrogen 44 from the bio-renewable conversion process is mixed with the medium pressure vent gas stream 200 and sent to the furnace 118 of the steam reforming process unit 120.

[0104] A bypass line 202 routes the tail gas stream 150 to a furnace in the steam reforming process unit for combustion, allowing the steam reforming process unit to continue operating without CO2 capture in the event of a problem with the compressor 155, the CO2 capture unit 165, or the PSA system 180 that produces the at least two product streams.

[0105] 3 shows a PSA unit 300 including a PSA adsorption vessel 310. The PSA adsorption vessel 310 includes three adsorption beds 315, 320, 325. The PSA adsorption vessel 310 includes a first opening 330 at a first end 335 and a second opening 340 at a second end 345. The first opening 330 is in selective fluid communication with a high pressure feed gas inlet line 350 via a valve 355 and in selective fluid communication with a low pressure tail gas outlet line 360 ​​via a valve 365. The second opening 340 is in selective fluid communication with a high pressure product outlet line 370 via a valve 375, in selective fluid communication with a medium pressure vent gas outlet line 380 via a valve 385, and in selective fluid communication with a low pressure purge gas inlet line 390 via a valve 395.

[0106] During the high pressure cocurrent adsorption and product removal step of the PSA cycle, valves 355 and 375 can be opened and valves 365, 385, and 395 closed to allow high pressure feed gas to enter PSA adsorption vessel 310 and to exit the high pressure hydrogen stream.

[0107] During at least one cocurrent depressurization step, valves 355, 365, 375, 385, and 395 are closed.

[0108] During the medium pressure co-current depressurization and vent removal step, valve 385 is open and valves 355, 365, 375, and 395 are closed.

[0109] During the countercurrent blowdown and tail gas removal steps, valve 365 is open and valves 355, 375, 385, and 395 are closed. The bed is depressurized through valve 365 and a portion of the CO2 is desorbed.

[0110] During the countercurrent purge and tail gas removal step, valves 365 and 395 are open and valves 355, 375 and 385 are closed. Purge gas is introduced and CO2 is removed.

[0111] During the at least one countercurrent repressurization step, valves 355, 365, 375, 385, and 395 are closed.

[0112] 4 illustrates one embodiment of a hydrogen production process 400 incorporating a three product PSA unit of the present invention. Natural gas feed 105 and water 110 are delivered to a reaction section 112 of a steam reforming process unit 120, and supplemental fuel gas 114 and air 115 are delivered to a furnace 118 within the steam reforming process unit 120. As noted above, other feed streams containing hydrocarbons can be used in place of natural gas. The supplemental fuel gas has been described above.

[0113] The steam reforming and water gas shift reactions produce an effluent stream 125 comprising hydrogen, CO, water, and at least one of methane, carbon monoxide, and nitrogen. A flue gas stream 130 and a steam stream 135 also exit the steam reforming process unit 120.

[0114] The effluent stream 125 has a temperature of about 30° C. to about 50° C. (after heat recovery and cooling in the steam reforming process) and a pressure of about 2,000 to about 3,000 kPa. The effluent stream 125 is sent to a hydrogen PSA unit 140 where it is separated into a high purity hydrogen stream 145 enriched in hydrogen and a hydrogen-depleted tail gas stream 150 containing a portion of the hydrogen, CO2, water, and at least a portion of at least one of methane, carbon monoxide, and nitrogen.

[0115] The tail gas stream 150 is sent to a compressor 155 where it is compressed from a pressure in the range of about 110 kPa to about 200 kPa to a pressure in the range of about 3,000 kPa to about 6,000 kPa.

[0116] The compressed tail gas stream 160 is sent to a CO2 capture unit 165 where it is dried to remove water stream 167, cooled to a temperature of about -20°C to about -50°C, and separated into a bottoms stream 170 and an overhead stream 175. The bottoms stream 170 containing liquid CO2 is recovered.

[0117] Overhead stream 175 is sent to a PSA system 180 that produces at least two product streams, including a three-product PSA unit 185, where it is separated into three streams. A high pressure hydrogen stream 190 is recovered. All or a portion of the high pressure hydrogen stream 190 may be sent to the bio-renewable conversion process and combined with the make-up hydrogen stream 42. A low pressure CO2 stream 195 is recycled to the compressor 155.

[0118] A medium pressure vent gas stream 200 containing at least a portion of at least one of methane, carbon monoxide, and nitrogen and a small amount of hydrogen (e.g., less than about 20%, or between about 10% and about 20%) is sent to a steam reforming process unit 120 as fuel.

[0119] The purge gas stream containing hydrogen 44 from the biorenewable conversion process is sent to a membrane separation unit 405 where it is separated into a permeate stream 410 containing hydrogen and CO2 and a residue stream 415 containing at least one of methane, ethane, propane, C4+ hydrocarbons and carbon monoxide. The permeate stream 410 is sent to a compressor 155 and sent to a CO2 capture system 165 and a PSA system 180 that produces at least two product streams to recover the hydrogen and CO2 in the permeate stream 410. In one embodiment, all or a portion of the residue stream 415 is mixed with the medium pressure vent gas stream 200 and sent to the furnace 118 of the steam reforming process unit 120. In another embodiment, all or a portion of the residue stream 415 can be mixed with the natural gas feed 105 and sent to the steam reforming process unit 120. If the hydrogen process unit is an autothermal reforming unit with optional gas-heated reformer, gasification unit, or partial oxidation unit, all or a portion of the residue stream 415 can be mixed with a feed stream containing hydrocarbons and partially oxidized in the autothermal reforming unit, gasification unit, or partial oxidation unit. In yet another embodiment, all or a portion of the residue stream 415 can be returned to the bio-renewable hydrocarbon production process for recovery of propane and / or C4+ hydrocarbons.

[0120] A bypass line 202 routes the tail gas stream 150 to a furnace in the steam reforming process unit for combustion, allowing the steam reforming process unit to continue operating without CO2 capture in the event of a problem with the compressor 155, the CO2 capture unit 165, or the PSA system 180 that produces the at least two product streams.

[0121] 5 illustrates one embodiment of a hydrogen production process 450 incorporating a three product PSA unit of the present invention. Natural gas feed 105 and water 110 are delivered to a reaction section 112 of a steam reforming process unit 120, and supplemental fuel gas 114 and air 115 are delivered to a furnace 118 within the steam reforming process unit 120. As noted above, other feed streams containing hydrocarbons can be used in place of natural gas. The supplemental fuel gas has been described above.

[0122] The steam reforming and water gas shift reactions produce an effluent stream 125 comprising hydrogen, CO, water, and at least one of methane, carbon monoxide, and nitrogen. A flue gas stream 130 and a steam stream 135 also exit the steam reforming process unit 120.

[0123] The effluent stream 125 has a temperature of about 30° C. to about 50° C. (after heat recovery and cooling in the steam reforming process) and a pressure of about 2,000 to about 3,000 kPa. The effluent stream 125 is sent to a hydrogen PSA unit 140 where it is separated into a high purity hydrogen stream 145 enriched in hydrogen and a hydrogen-depleted tail gas stream 150 containing a portion of the hydrogen, CO2, water, and at least a portion of at least one of methane, carbon monoxide, and nitrogen.

[0124] The tail gas stream 150 is sent to a compressor 155 where it is compressed from a pressure in the range of about 110 kPa to about 200 kPa to a pressure in the range of about 3,000 kPa to about 6,000 kPa.

[0125] A purge gas stream containing hydrogen 44 from the bio-renewable conversion process is combined with the compressed tail gas stream 160 .

[0126] The compressed tail gas stream 160 is sent to a CO2 capture unit 165 where it is dried to remove water stream 167, cooled to a temperature of about -20°C to about -50°C, and separated into a bottoms stream 170 and an overhead stream 175. The bottoms stream 170 containing liquid CO2 is recovered.

[0127] Overhead stream 175 is sent to a PSA system 180 that produces at least two product streams, including a three-product PSA unit 185, where it is separated into three streams. A high pressure hydrogen stream 190 is recovered. All or a portion of the high pressure hydrogen stream 190 may be sent to the bio-renewable conversion process and combined with the make-up hydrogen stream 42. A low pressure CO2 stream 195 is recycled to the compressor 155.

[0128] A medium pressure vent gas stream 200 containing at least a portion of at least one of methane, carbon monoxide, and nitrogen and a small amount of hydrogen (e.g., less than about 20%, or between about 10% and about 20%) is sent to a steam reforming process unit 120 as fuel.

[0129] A bypass line 202 routes the tail gas stream 150 to a furnace in the steam reforming process unit for combustion, allowing the steam reforming process unit to continue operating without CO2 capture in the event of a problem with the compressor 155, the CO2 capture unit 165, or the PSA system 180 that produces the at least two product streams.

[0130] 6 illustrates another embodiment of a hydrogen production process 475 of the present invention. Natural gas feed 105 and water 110 are delivered to a reaction section 112 of a steam reforming process unit 120, and a supplemental fuel gas 114 and air 115 are delivered to a furnace 118 within the steam reforming process unit 120. As noted above, other feed streams containing hydrocarbons can be used in place of natural gas. The supplemental fuel gas has been described above.

[0131] The reforming reaction produces an effluent stream 125 comprising hydrogen, CO2, water, and at least one of methane, carbon monoxide, and nitrogen. A flue gas stream 130 and a steam stream 135 also exit the steam reforming process unit 120.

[0132] The effluent stream 125 is sent to a hydrogen PSA unit 140 where it is separated into a high purity hydrogen stream 145 enriched in hydrogen and a hydrogen-depleted tail gas stream 150 containing a portion of the hydrogen, CO2, water, and at least a portion of at least one of methane, carbon monoxide, and nitrogen.

[0133] Tail gas stream 150 is sent to compressor 155. Compressed tail gas stream 160 is sent to a CO2 capture system 165 and separated into a bottoms stream 170 and an overhead stream 175. Bottoms stream 170 comprising liquid CO2 is recovered.

[0134] The overhead stream 175 is sent to a PSA system 180 that produces at least two product streams including two PSA units 205, 210 in series. The overhead stream 175 is separated into a low pressure CO2 stream 195 and a high pressure stream 215 that includes hydrogen and at least one of methane, carbon monoxide, and nitrogen. All or a portion of the high pressure hydrogen stream 190 can be sent to the bio-renewable conversion process and combined with the make-up hydrogen stream 42. The low pressure CO2 stream 195 is recycled to the compressor 155.

[0135] A purge gas stream containing hydrogen 44 from the bio-renewable conversion process is combined with high pressure stream 215 .

[0136] The high pressure stream 215 is sent to the second PSA unit 210 where it is separated into a high pressure hydrogen stream 190 and a low pressure tail gas stream 200. The high pressure hydrogen stream 190 is recovered. The low pressure tail gas stream 200, which contains at least one of methane, carbon monoxide, and nitrogen, is sent to the steam reforming process unit 120 as fuel.

[0137] A bypass line 202 routes the tail gas stream 150 to the furnace 118 within the steam reforming process unit 120 for combustion.

[0138] 7 illustrates one embodiment of a hydrogen production process 500 incorporating a three product PSA unit of the present invention. Natural gas feed 505 and water 510 are delivered to a reaction section 512 of a steam reforming process unit 520, and supplemental fuel gas 514 and air 515 are delivered to a furnace 518 within the steam reforming process unit 520. As noted above, other feed streams containing hydrocarbons can be used in place of natural gas. The supplemental fuel gas has been described above.

[0139] A portion of the fractionation zone overhead stream 36 , which includes naphtha and LPG, may be sent in line 38 as part of the feed to a steam reforming process unit 520 .

[0140] The steam reforming and water gas shift reactions produce an effluent stream 525 comprising hydrogen, CO, water, and at least one of methane, carbon monoxide, and nitrogen. A flue gas stream 530 and a steam stream 535 also exit the steam reforming process unit 520.

[0141] The effluent stream 525 has a temperature of about 30° C. to about 50° C. (after heat recovery and cooling in the steam reforming process) and a pressure of about 2,000 to about 3,000 kPa. The effluent stream 525 is sent to a PSA system 540 producing at least two product streams, including a three-product PSA unit 545, where it is separated into a high purity hydrogen stream 190 enriched in hydrogen and a hydrogen-depleted tail gas stream 550 containing a portion of the hydrogen, CO2, water, and at least a portion of at least one of methane, carbon monoxide, and nitrogen. Alternatively, the PSA system 540 producing at least two product streams may be one PSA unit with two product streams or two PSA units with two product streams, as described above.

[0142] The high purity stream 190 can be sent to a bio-renewable conversion process and used as some or all of the hydrogen in reaction zone 12 .

[0143] The tail gas stream 550 is sent to a compressor 555 where it is compressed from a pressure in the range of about 110 kPa to about 200 kPa to a pressure in the range of about 3,000 kPa to about 6,000 kPa.

[0144] Compressed tail gas stream 565 is sent to a CO2 capture unit 570 where it is dried to remove water stream 567, cooled to a temperature of about -20°C to about -50°C, and separated into a bottoms stream 575 and an overhead stream 580. Bottoms stream 575 containing liquid CO2 is recovered.

[0145] The overhead stream 580 is sent to a PSA system 540 which produces at least two product streams.

[0146] A medium pressure vent gas stream 560 comprising at least a portion of at least one of methane, carbon monoxide, and nitrogen, and hydrogen (e.g., in some embodiments, the hydrogen is less than about 20 mol%, or between about 10 mol% and about 20 mol%, while in other embodiments the hydrogen can be greater than 90 mol%) is sent to the steam reforming process unit 520 as fuel.

[0147] The purge gas stream containing hydrogen 44 from the bio-renewable conversion process is sent to a membrane separation unit 590 where it is separated into a permeate stream 595 containing hydrogen and CO2 and a residue stream 600 containing at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide. The permeate stream 595 is sent to a furnace 518. The residue stream 600 is sent to a steam reforming process unit 520.

[0148] 8 is a process flow diagram illustrating the design of a CO2 capture system for removing carbon dioxide from hydrogen and lighter components from a syngas stream. The process involves the use of a dual refrigerant CO2 fractionation process.

[0149] In this process, inlet gas enters the plant as feed stream 931. Feed stream 931 is typically dehydrated to prevent hydrate (ice) formation under cryogenic conditions. Both solid and liquid desiccants have been used for this purpose.

[0150] Feed stream 931 is split into two streams (streams 939 and 940). Stream 939 is cooled in heat exchanger 911 by heat exchange with cold carbon dioxide vapor (stream 938c) and cold residue gas stream 933a. Stream 940 is cooled in heat exchanger 910 by heat exchange with column reboiler liquid (stream 936) and column side reboiler liquid (stream 935). The cooled streams from heat exchangers 910 and 911 are recombined into stream 931a. Stream 931a is further cooled with a commercial refrigerant 950 (e.g., propane or R-134A) and the resulting stream (cooled stream 931b) is expanded by expansion valve 912 to the operating pressure of fractionator 913 and cooled stream 931c before being fed to fractionator 913 at the top column feed point.

[0151] Overhead vapor stream 932 exits fractionation tower 913 and is cooled and partially condensed in heat exchanger 914. Partially condensed stream 932a enters separator 915 where vapor (cold residue gas stream 933) is separated from condensed liquid stream 934. Condensed liquid stream 934 is pumped by pump 919 to a pressure slightly above the operating pressure of fractionation tower 913, where it is heated and partially vaporized by heat exchange with carbon dioxide refrigerant from the bottom of the fractionation column, before liquid stream 934a enters heat exchanger 916 (described below). Partially vaporized stream 934b is then provided as feed to fractionation tower 913 at a mid-column feed point. A cold compressor (not shown) can be applied to overhead vapor stream 932 if higher pressure and / or lower carbon dioxide content in the feed to the PSA system is desired. If a compressor is used for this flow, pump 919 can be eliminated and the liquid from separator 915 is sent to fractionation tower 913 via a liquid level control valve.

[0152] Fractionation tower 913 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. It also contains a reboiler (e.g., the reboiler and side reboiler described above) that heats and vaporizes a portion of the liquid flowing down the column to provide stripping steam that rises up the column to strip column bottoms liquid product stream 937 of hydrogen and lighter components. The trays and / or packing provide the necessary contact between the upwardly rising stripping steam and the downwardly falling cryogenic liquid so that column bottoms liquid product stream 937 exits the bottom of the tower based on reducing the concentration of hydrogen and lighter components in the bottoms product to create a very pure carbon dioxide product.

[0153] Column bottoms liquid product stream 937 is primarily liquid carbon dioxide. A minor portion (stream 938) is subcooled in heat exchanger 916 by liquid stream 934a from separator 915 as previously described. The subcooled liquid (stream 938a) is expanded to a lower pressure by expansion valve 920 and partially vaporized, further cooling stream 938b before entering heat exchanger 914. Stream 938b acts as a refrigerant in heat exchanger 914 to cool the partially condensed stream 932a as previously described, and the resulting carbon dioxide vapor exits as stream 938c.

[0154] The cold carbon dioxide vapor (Stream 938c) from heat exchanger 914 is heated in heat exchanger 911 by heat exchange with the feed gas as previously described. The warm carbon dioxide vapor (Stream 938d) is then compressed in three stages by compressors 921, 923, and 925 to a pressure higher than that of fractionator 913, and cooled by discharge coolers 922, 924, and 926 after each stage of compression. The compressed carbon dioxide stream (Stream 938j) is then flash expanded through valve 942 and returned to the bottom feed location in fractionator 913. Recycled carbon dioxide (Stream 938k) provides additional heat duty and stripping gas in fractionator 913. The remaining portion of column bottom liquid product stream 937 (Stream 941) is pumped to high pressure by pump 929, so that Stream 941a forms the high pressure carbon dioxide stream, which then flows to a pipeline or for reinjection. In some cases, the carbon dioxide stream needs to be delivered as a lower pressure sub-cooled liquid that can be transported in an insulated shipping vessel. In these cases, the carbon dioxide product (stream 941) is sub-cooled with refrigerant 950 in heat exchanger 917 before being released to storage tank conditions. Thus, pump 929 is eliminated.

[0155] Cold residue gas stream 933 exits separator 915 and undergoes additional cooling in heat exchanger 914. Warm residue gas stream 933a is further heated after heat exchange with the feed gas in heat exchanger 911 as previously described. Warm residue gas stream 933b is then sent to the PSA system for further processing.

[0156] 9 is a process flow diagram showing a process unit design for removing carbon dioxide from hydrogen and lighter components from a syngas stream. In this process, inlet gas enters the plant as feed stream 931. The process involves the use of a mixed refrigerant CO2 fractionation process.

[0157] The feed stream 931 is typically dehydrated to prevent hydrate (ice) formation under cryogenic conditions. Both solid and liquid desiccants have been used for this purpose.

[0158] Feed stream 931 is cooled in heat exchanger 910 by heat exchange with column reboiler liquid (stream 936) and column side reboiler liquid (stream 935). Stream 931a is further cooled in heat exchanger 911 by heat exchange with cold residue gas stream 933 and a flash expanded multicomponent mixed refrigerant stream containing both hydrocarbon and non-hydrocarbon components. The component mixture in the mixed refrigerant stream is designed to provide the most efficient cooling curve in heat exchanger 911 based on the inlet gas feed conditions. The further cooled stream 931b is expanded by expansion valve 912 to the operating pressure of fractionator 913 and sent to fractionator 913 at a mid-column feed point.

[0159] Overhead vapor stream 932 exits fractionation tower 913 and is cooled and partially condensed in heat exchanger 911 with a mixed refrigerant stream. The partially condensed stream 932a enters separator 915 where vapor (cold residue gas stream 933) is separated from condensed liquid stream 934. Condensed liquid stream 934 is pumped by pump 919 to a pressure slightly higher than the operating pressure of fractionation tower 913 and liquid stream 934a is sent to fractionation tower 913 at the top feed point. A cold compressor (not shown) can be applied to overhead vapor stream 932 if higher pressure and / or lower carbon dioxide content in the feed to the PSA system is desired. If a compressor is used for this stream, pump 919 can be removed and the liquid from separator 915 is sent to fractionation tower 913 via a liquid level control valve.

[0160] Fractionation tower 913 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing. It also contains a reboiler (e.g., the reboiler and side reboiler described above) that heats and vaporizes a portion of the liquid flowing down the column to provide stripping steam that rises up the column to strip column bottoms liquid product stream 937 of hydrogen and lighter components. The trays and / or packing provide the necessary contact between the upwardly rising stripping steam and the downwardly falling cryogenic liquid so that column bottoms liquid product stream 937 exits the bottom of the tower based on reducing the concentration of hydrogen and lighter components in the bottoms product to create a very pure carbon dioxide product.

[0161] Column bottom liquid product stream 937 is primarily liquid carbon dioxide. Column bottom liquid product stream 937 is pumped to high pressure by pump 929, resulting in stream 937a forming a high pressure carbon dioxide stream which then flows to a pipeline or for reinjection. In some cases, the carbon dioxide stream needs to be delivered as a lower pressure sub-cooled liquid that can be transported in an insulated shipping vessel. In these cases, the carbon dioxide product in column bottom liquid product stream 937 is sub-cooled with mixed refrigerant 950 in heat exchanger 911 before being released to storage tank conditions. Thus, pump 929 is eliminated.

[0162] Warm residue gas stream 933a exits heat exchanger 911 after exchanging heat with the feed gas as previously described. Warm residue gas stream 933a is then sent to the PSA system for further processing. EXAMPLES

[0163] The following examples are intended to further illustrate the integrated process. These examples are not intended to limit the scope of the claimed invention to the specific details of the examples. The examples are computer simulations of two embodiments of the process, as described below.

[0164] [Table 1]

[0165] The above results show that approximately 90% of the hydrogen and over 50% of the CO2 in hydrogen purge gas stream 44 is recovered in permeate stream 410. The hydrogen is recovered in the overhead PSA system as high pressure hydrogen stream 190, and the CO2 is recovered in the CO2 capture system 165 as bottoms stream 170. Nearly 100% of the propane and n-butane are recovered in residue stream 415 and sent to a bio-renewable process for recovery.

[0166] [Table 2]

[0167] The above streams were fed to a second PSA unit 210. Approximately 90% of the hydrogen in purge stream 44 was recovered in high pressure hydrogen stream 190. Nearly 100% of the other components in purge stream 44 were recovered in low pressure tail gas stream 200. These components were sent to furnace 118 as fuel gas.

[0168] As used herein, the term "stream" may include a variety of hydrocarbon molecules and other substances.

[0169] As used herein, a "stream," "feed," "product," "part," or "portion" can include various hydrocarbon molecules, such as straight and branched chain alkanes, naphthalenes, alkenes, alkadienes, and alkynes, and, optionally, other substances, such as gases, e.g., hydrogen, or impurities, e.g., heavy metals, and sulfur and nitrogen compounds. Each of the above can also include aromatic and non-aromatic hydrocarbons.

[0170] As used herein, the term "overhead stream" can mean a stream collected at or near the top of a vessel, such as a column.

[0171] As used herein, the term "bottoms stream" can mean a stream withdrawn at or near the bottom of a vessel, such as a column.

[0172] As used herein, the term "unit" can refer to an area that includes one or more pieces of equipment and / or one or more subzones. Equipment can include, but is not limited to, one or more reactors or reaction vessels, separation vessels, distillation columns, heaters, exchangers, pipes, pumps, compressors, and controllers. In addition, equipment such as reactors, dryers, or vessels can further include one or more zones or subzones.

[0173] The term "column" refers to one or more distillation columns for separating one or more components of different volatility. Unless otherwise stated, each column includes a condenser at the top of the column to condense and reflux a portion of the overhead stream returning to the top of the column, and a reboiler at the bottom of the column to vaporize and return a portion of the bottom stream to the bottom of the column. The feed to the column may be preheated. The overhead or overhead pressure is the pressure of the overhead vapor at the vapor outlet of the column. The bottom temperature is the liquid bottom outlet temperature. The net overhead line and net bottom line refer to the net lines from the column downstream of any reflux or reboil to the column, unless otherwise indicated. A stripping column may omit the reboiler at the bottom of the column and instead provide the required heat and driving force for the separation from a fluidized inert medium such as steam. A reboiled absorption column may omit the condenser at the top of the column.

[0174] As depicted, the process flow lines in the diagram may be referred to as, for example, lines, pipes, feeds, gases, products, emissions, parts, portions, or streams.

[0175] The term "pass" means that material passes from a conduit or vessel to an object.

[0176] The terms "hydrogen-enriched" and "hydrogen-enriched stream" mean that the hydrogen content / concentration of the product stream is higher than that of the inlet gas stream. For example, in some embodiments, the product stream may contain more than 40 mol%, or more than 50 mol%, or more than 60 mol%, or more than 70 mol%, or more than 80 mol%, or more than 90 mol%, or more than 95 mol%, or more than 98 mol%, or more than 99 mol%, or more than 99.9 mol% hydrogen.

[0177] The terms "CO2-enriched" and "CO2-enriched stream" mean that the CO2 content / concentration of the product stream is higher than the inlet gas stream. For example, in some embodiments, the product stream may contain more than 40 mol%, or more than 50 mol%, or more than 60 mol%, or more than 70 mol%, or more than 80 mol%, or more than 90 mol%, or more than 95 mol%, or more than 98 mol%, or more than 99 mol%, or more than 99.9 mol% CO2.

[0178] As used herein, the term "about" means within 10%, or within 5%, or within 1% of a value.

[0179] Specific Embodiments While the following is described in conjunction with specific embodiments, it will be understood that this description is illustrative and not intended to limit the scope of the foregoing description and the appended claims.

[0180] A first embodiment of the present invention is a method of producing a hydrogen-enriched product and recovering CO2 from a hydrogen production process unit, the method comprising: treating a feed stream comprising a hydrocarbon or carbonaceous feedstock in the hydrogen production process unit to produce a synthesis gas mixture comprising hydrogen, carbon dioxide, water, and at least one of methane, carbon monoxide, nitrogen, and argon; separating an effluent stream from the hydrogen production process unit into at least a first high pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream in a first pressure swing adsorption (PSA) system producing at least two product streams; compressing the hydrogen-depleted tail gas stream in a compressor to form a compressed tail gas stream; separating the compressed tail gas stream in a CO2 capture system to produce a CO2 product and a second gas stream comprising hydrogen; and introducing at least a portion of a purge gas stream comprising hydrogen from a biorenewable conversion process to make a hydrocarbon product from a biorenewable feedstock into a process unit used in the method of producing hydrogen and recovering CO2. An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, wherein the process unit comprises a steam reforming process unit with an optional gas heated reformer, and wherein a purge gas stream comprising hydrogen from the bio-renewable conversion process is combusted in a furnace in the steam reforming process unit with an optional gas heated reformer.An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, wherein the first PSA system producing at least two product streams includes a first PSA unit producing two product streams, the first PSA unit separating the effluent stream into a first high-pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream, and separating the compressed tail gas stream includes separating the compressed tail gas stream in the CO2 capture system into a CO2-enriched product stream and an overhead stream comprising a portion of the hydrogen, a portion of the carbon dioxide, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon, separating the overhead stream from the CO2 capture system in a second PSA system producing at least two product streams into at least a second high-pressure hydrogen stream enriched in hydrogen and a low-pressure CO2 stream enriched in carbon dioxide, recovering the second high-pressure hydrogen stream, and optionally recycling the low-pressure CO2 stream to the compressor. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, up to and including the first embodiment of this paragraph, wherein the process unit includes a second PSA system producing at least two product streams, the second PSA system producing at least two product streams includes two PSA units each producing the two product streams, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to the first PSA unit, separating the overhead stream into a low-pressure CO2 stream and a hydrogen-enriched third high-pressure hydrogen stream, and providing the third high-pressure hydrogen stream to the second PSA unit, and the second high-pressure hydrogen stream and the second gas stream are removed from the second PSA unit, and a purge gas stream comprising hydrogen from the biorenewable conversion process is introduced to the second PSA unit.An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, further comprising separating a purge gas stream comprising hydrogen from the biorenewable conversion process into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide in a membrane separation unit, and the process unit comprises a compressor, and the residue stream is compressed in the compressor. An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, further comprising: the second process unit comprises a steam reforming process unit with an optional gas-heated reformer, further comprising burning the residue stream in a furnace or a furnace in the steam reforming process unit with an optional gas-heated reformer, and further comprising: ... and the process unit further comprises mixing the residue stream with a feed stream comprising a hydrocarbon or carbonaceous feedstock, the process unit further comprises an autothermal reforming unit having an optional gas-heated reformer, gasification unit, or partial oxidation unit, mixing the residue stream with a feed stream comprising a hydrocarbon or carbonaceous feedstock, partially oxidizing the mixed stream in the autothermal reforming unit having an optional gas-heated reformer, gasification unit, or partial oxidation unit, and sending the residue stream to a bio-renewable conversion process and recovering at least one of propane and C4+ hydrocarbons from the residue stream. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to the first embodiment of this paragraph, wherein the process unit comprises a CO2 capture system, and a purge gas stream comprising hydrogen from the bio-renewable conversion process is introduced to the CO2 capture system.An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, wherein at least a portion of the hydrocarbon-containing feed stream for the hydrogen production process comprises at least a portion of a naphtha stream, a liquefied petroleum gas stream, or an off-gas stream from a product fractionation zone of the bio-renewable conversion process, or at least a portion of the fuel stream for the furnace of the hydrogen production process comprises at least a portion of a naphtha stream, a liquefied petroleum gas stream, or an off-gas stream from a product fractionation zone of the bio-renewable conversion process. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, wherein the PSA system producing at least two product streams includes a three product PSA unit, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to a three product PSA unit having a three product PSA cycle, removing a second high pressure hydrogen stream during a high pressure cocurrent adsorption step in the three product PSA cycle, removing a second gas stream during a cocurrent depressurization step in the three product PSA cycle, and removing a low pressure CO2 stream during at least one of a countercurrent depressurization step and a countercurrent purge step in the three product PSA cycle. An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to and including the first embodiment of this paragraph, wherein separating an effluent stream from a hydrogen production process unit in a first PSA system producing at least two product streams into at least a first high pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream comprises separating an effluent stream from a hydrogen production process unit in the first PSA system producing at least two product streams into a first high pressure hydrogen stream enriched in hydrogen, a hydrogen-depleted tail gas stream, and a second gas stream comprising a portion of the hydrogen and at least a portion of at least one of methane, carbon monoxide, and nitrogen, and further comprising at least one of: introducing at least a portion of the first high pressure hydrogen stream enriched in hydrogen to a biorenewable conversion process; and combusting at least a portion of the second gas stream in the hydrogen production process unit.An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to the first embodiment of this paragraph, further comprising separating a purge gas stream comprising hydrogen from a biorenewable conversion process into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide in a membrane separation unit, wherein the process unit comprises a hydrogen production process unit, and wherein the permeate stream is introduced to a furnace, or the residue stream comprises at least a portion of the feed stream, or both.

[0181] A second embodiment of the present invention is a method of producing a hydrogen-rich product and capturing CO2 in an integrated hydrogen production process and bio-renewable conversion process, the integrated process comprising treating a feed stream comprising a hydrocarbon or carbonaceous feedstock in a hydrogen production process unit to produce a synthesis gas mixture comprising hydrogen, carbon dioxide, water, and at least one of methane, carbon monoxide, nitrogen, and argon; and treating an effluent stream from the hydrogen production process unit in a first pressure swing adsorption (PSA) system to produce at least two product streams. into at least a hydrogen-enriched first high pressure hydrogen stream and a hydrogen-depleted tail gas stream, compressing the hydrogen-depleted tail gas stream in a compressor to form a compressed tail gas stream, separating the compressed tail gas stream in a CO2 capture system to produce a CO2 product and a second gas stream comprising hydrogen, and hydrogenating, deoxygenating, isomerizing, and isocratizing the biorenewable feedstock in a reaction zone in the presence of hydrogen under reaction conditions by contacting the biorenewable feedstock with a multifunctional catalyst or set of catalysts having hydrogenation, deoxygenation, isomerization, and selective hydrocracking functions. and selective hydrocracking to provide a reaction effluent comprising paraffinic hydrocarbons, hydrogen, CO2, water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide; separating the reaction effluent in a separator into at least one hydrocarbon stream comprising paraffinic hydrocarbons and an overhead stream comprising hydrogen, CO2, optionally water, and at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide; and separating the hydrocarbon stream in a fractionation zone to produce a hydrocarbon product stream. the hydrocarbon product stream comprises at least one of a diesel stream comprising hydrocarbons having a boiling point in a diesel boiling range, an aviation fuel stream having hydrocarbons having a boiling point in an aviation fuel boiling range, and a naphtha stream having hydrocarbons in a naphtha boiling range; recovering the hydrocarbon product stream; separating an overhead stream from the separator into at least a hydrogen stream comprising hydrogen; and introducing at least a portion of a purge gas stream comprising hydrogen from the hydrogen stream from a biorenewable conversion process to a process unit of a hydrogen production process.An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, further comprising at least a portion of the feed stream comprising hydrocarbons for the hydrogen production process unit comprising at least a portion of a naphtha stream, a liquefied petroleum gas stream, or an off-gas stream from a product fractionation zone of the bio-renewable conversion process, or at least a portion of the fuel stream for the furnace of the hydrogen production process comprising at least a portion of a naphtha stream, a liquefied petroleum gas stream, or an off-gas stream from a product fractionation zone of the bio-renewable conversion process. An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, further comprising at least a portion of the feed stream comprising hydrocarbons for the hydrogen production process unit comprising at least a portion of a naphtha stream, a liquefied petroleum gas stream, or an off-gas stream from a product fractionation zone of the bio-renewable conversion process. An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, further comprising at least a portion of the process unit comprising a steam reforming process unit with an optional gas-heated reformer, and wherein the purge gas stream comprising hydrogen is combusted in a furnace in the steam reforming process unit with an optional gas-heated reformer. An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, wherein the first PSA system producing at least two product streams includes a first PSA unit having two product streams, the first PSA unit separating the effluent stream into a first high-pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream, and separating the compressed tail gas stream includes separating the compressed tail gas stream in the CO2 capture system into a CO2-enriched product stream and an overhead stream comprising a portion of the hydrogen, a portion of the carbon dioxide, and at least a portion of at least one of methane, carbon monoxide, nitrogen, and argon, separating the overhead stream from the CO2 capture system in a second PSA system producing at least two product streams into at least a second high-pressure hydrogen stream enriched in hydrogen and a low-pressure CO2 stream enriched in carbon dioxide, recovering the second high-pressure hydrogen stream, and optionally recycling the low-pressure CO2 stream to the compressor.An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, up to and including the second embodiment of this paragraph, wherein the process unit includes a second PSA system producing at least two product streams, the second PSA system producing at least two product streams includes two PSA units each having two product streams, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to the first PSA unit and separating the overhead stream into a low pressure CO2 stream and a third high pressure hydrogen stream, and providing the third high pressure third stream to the second PSA unit, and the second high pressure hydrogen stream and the second gas stream are removed from the second PSA unit, and a purge gas stream comprising hydrogen from the bio-renewable process is introduced to the second PSA unit. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, further comprising separating the purge gas stream comprising hydrogen into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide in a membrane separation unit, wherein the process unit comprises a compressor, and wherein the permeate stream is compressed in the compressor.An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, up to and including the second embodiment of this paragraph, further comprising: the second process unit comprising a steam reforming process unit with an optional gas heated reformer, further comprising combusting the residue stream in a furnace or furnace in the steam reforming process unit with an optional gas heated reformer; and the second process unit comprising a steam reforming process unit with an optional gas heated reformer, further comprising combusting the residue stream in a furnace or furnace in the steam reforming process unit with an optional gas heated reformer, further comprising combusting the residue stream in a furnace or furnace in the steam reforming process unit with an optional gas heated reformer, and the process unit comprises an autothermal reforming unit having an optional gas-heated reformer, gasification unit, or partial oxidation unit, mixing the residue stream with a feed stream comprising a hydrocarbon or carbonaceous feedstock, further comprising partially oxidizing the mixed stream in the autothermal reforming unit having an optional gas-heated reformer, gasification unit, or partial oxidation unit, and sending the residue stream to a bio-renewable hydrocarbon production process and recovering at least one of propane and C4+ hydrocarbons from the residue stream. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, wherein the process unit comprises a CO2 capture system, and the purge gas stream comprising hydrogen from the bio-renewable conversion process is introduced into the CO2 capture system. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to and including the second embodiment of this paragraph, wherein the PSA system producing at least two product streams includes a three product PSA unit, and separating the overhead stream from the CO2 capture system includes introducing the overhead stream to a three product PSA unit having a three product PSA cycle, removing a second high pressure hydrogen stream during a high pressure cocurrent adsorption step in the three product PSA cycle, removing a second gas stream during a cocurrent depressurization step in the three product PSA cycle, and removing a low pressure CO2 stream during at least one of a countercurrent depressurization step and a countercurrent purge step in the three product PSA cycle.An embodiment of the present invention is any one, any or all of the previous embodiments of this paragraph, including up to and including the second embodiment of this paragraph, wherein separating an effluent stream from a hydrogen production process unit in a first PSA system producing at least two product streams into at least a first high pressure hydrogen stream enriched in hydrogen and a hydrogen-depleted tail gas stream comprises separating an effluent stream from a hydrogen production process unit in the first PSA system producing at least two product streams into a first high pressure hydrogen stream enriched in hydrogen, a hydrogen-depleted tail gas stream, and a second gas stream comprising a portion of the hydrogen and at least a portion of at least one of methane, carbon monoxide, and nitrogen, and further comprising at least one of: introducing at least a portion of the first high pressure hydrogen stream enriched in hydrogen to a biorenewable conversion process; and combusting at least a portion of the second gas stream in the hydrogen production process unit. An embodiment of the present invention is one, any, or all of the previous embodiments of this paragraph, including up to the second embodiment of this paragraph, further comprising separating in a membrane separation unit a purge gas stream comprising hydrogen from a biorenewable conversion process into a permeate stream comprising hydrogen and CO2 and a residue stream comprising at least one of methane, ethane, propane, C4+ hydrocarbons, and carbon monoxide, wherein the process unit comprises a hydrogen production process unit, and wherein the permeate stream is introduced to a furnace in the hydrogen production process unit, or the residue stream comprises at least a portion of the feed stream, or both.

[0182] Without further elaboration, it is believed that, using the preceding description, one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of the present invention without departing from the spirit and scope of the present invention, and can make various changes and modifications to the present invention to adapt it to various uses and conditions. The preceding preferred specific embodiments are therefore to be construed as merely illustrative, and are not limitative of the remainder of the disclosure in any way, but are intended to cover various modifications and equivalent arrangements falling within the scope of the appended claims.

[0183] Above, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight unless otherwise stated.

Claims

1. A hydrogen-rich product is produced and CO is extracted from the hydrogen production process unit. ２ A method for recovering processing a feed stream (105) comprising a hydrocarbon or carbonaceous feedstock in a hydrogen production process unit (120) to produce a synthesis gas mixture comprising hydrogen, carbon dioxide, water, and at least one of methane, carbon monoxide, nitrogen, and argon; separating an effluent stream (125) from said hydrogen production process unit (120) into at least a hydrogen-enriched first high pressure hydrogen stream (145) and a hydrogen-depleted tail gas stream (150) in a first pressure swing adsorption (PSA) system (140) producing at least two product streams; compressing the hydrogen-depleted tail gas stream (150) in a compressor (155) to form a compressed tail gas stream (160); The compressed tail gas stream (160) is ２ In the capture system (165), ２ Producing an enriched product stream (170) and a second gas stream (175) comprising hydrogen; At least a portion of the purge gas stream (44) containing hydrogen from a biorenewable conversion process for making hydrocarbon products from a biorenewable feedstock is converted to a hydrogen-producing purge gas stream (44) by a process for producing hydrogen and reducing CO ２ and introducing said fluorine-containing amine into a process unit for use in said method of recovering said fluorine-containing amine.

2. 2. The method of claim 1, wherein the process unit comprises a steam reforming process unit (120) with an optional gas-heated reformer, and the purge gas stream (44) containing hydrogen from the bio-renewable conversion process is combusted in a furnace within the steam reforming process unit (120) with an optional gas-heated reformer.

3. the first PSA system (140) producing at least two product streams comprises a first PSA unit producing two product streams, the first PSA unit separating the effluent stream (125) into the first high pressure hydrogen stream (145) enriched in hydrogen and the hydrogen-depleted tail gas stream (150); and Separating the compressed tail gas stream (150) The CO ２ The compressed tail gas stream (160) in a recovery system (165) is ２ an enriched product stream (170) and an overhead stream (175) comprising a portion of the hydrogen, a portion of the carbon dioxide, and at least a portion of at least one of the methane, the carbon monoxide, the nitrogen, and the argon; In a second PSA system (180) producing at least two product streams, ２ The overhead stream (175) from the recovery system is separated into at least a second high pressure hydrogen stream (190) enriched in hydrogen and a low pressure CO2 stream (192) enriched in carbon dioxide. ２ and a stream (195). recovering the second high pressure hydrogen stream (190); and Optionally, the low pressure CO ２ and recirculating the stream (195) to the compressor (155).

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