# US 7,745,502 B2 · Hydrogen recovery from hydrocarbon synthesis processes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,745,502 B2 - Document ID: US7745502B2 - Status: Granted - Kind: B2 - Application number: 11/637,802 - Filed: 2006-12-13 - Published: 2007-05-31 - Granted: 2010-06-29 - Earliest claimed: 2004-03-08 - Assignees: Chevron U.S.A. Inc. - Inventors: Clifford M. Lowe; Daniel Chinn - Web page: https://patentgrep.com/patent/US7745502B2 ## CPC - C10G 2/30: {from carbon monoxide with hydrogen} - C01B 3/12: by reaction of water vapour with carbon monoxide - C01B 3/501: by diffusion - C01B 3/56: by contacting with solids; Regeneration of used solids - C10K 1/32: with selectively adsorptive solids, e.g. active carbon - C10K 3/04: reducing the carbon monoxide content {, e.g. water-gas shift [WGS]} - C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step - C01B 2203/0405: Purification by membrane separation - C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration - C01B 2203/0475: the impurity being carbon dioxide - C01B 2203/0495: the impurity being water - C01B 2203/146: At least two purification steps in series - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - C10K: PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE ## Abstract The invention relates to a process for producing a hydrogen-rich stream from a hydrogen-depleted stream. More particularly, the invention relates to a hydrocarbon synthesis process, by way of example, a Fischer Tropsch process, from which both hydrocarbons and high purity hydrogen are obtained. The process comprises contacting the hydrogen-depleted stream with a reverse-selective membrane to provide a CO2-enriched permeate and a hydrogen-containing retentate. The high purity hydrogen is produced from the hydrogen-containing retentate. The high purity hydrogen thus obtained may be used in a process selected from the group consisting of upgrading hydrocarbons produced from the hydrocarbon synthesis process, hydrotreating a natural gas stream, recycling to the hydrocarbon synthesis reaction unit, high purity hydrogen production, catalyst rejuvenation, and combinations thereof. ## Claims ### Claim 1 A process for providing a hydrogen-rich stream comprising: a) performing a hydrocarbon synthesis process using syngas; b) isolating a gaseous stream comprising hydrogen from the hydrocarbon synthesis process, wherein the gaseous stream comprising hydrogen comprises less than 35 vol. % hydrogen; c) contacting the gaseous stream comprising hydrogen with a reverse selective membrane selectively permeable to CO2 to provide a CO2-enriched permeate and a hydrogen-containing retentate; d) passing the retentate through a water gas shift reactor to provide a hydrogen-containing stream comprising greater than 40 vol. % hydrogen; and e) passing the hydrogen-containing stream through a pressure swing adsorption unit to provide a hydrogen-rich stream comprising greater than 90 vol. % hydrogen. ### Claim 2 (depends on 1) The process according to claim 1, wherein the hydrocarbon synthesis process is a Fischer-Tropsch process. ### Claim 3 (depends on 1) The process according to claim 1, wherein the process further comprises passing the hydrogen-containing stream through a vapor-liquid separator to remove water. ### Claim 4 (depends on 1) The process according to claim 1, wherein the process further comprises using the hydrogen-rich stream for a process selected from the group consisting of (i) upgrading a hydrocarbon product stream from the hydrocarbon synthesis process; (ii) hydrotreating a natural gas stream; (iii) recycling the hydrogen-rich stream to a hydrocarbon synthesis reaction unit; (iv) hydrogen production for uses outside the hydrocarbon synthesis process; (v) rejuvenating a hydrocarbon synthesis reaction catalyst; and (vi) combinations thereof. ### Claim 5 (depends on 1) The process according to claim 1, wherein the hydrogen-containing retentate is at a pressure of ≧ about 100 psig. ### Claim 6 (depends on 1) The process according to claim 1, wherein the hydrogen-containing retentate is at a pressure of ≧ about 200 psig. ### Claim 7 (depends on 1) The process according to claim 1, wherein the hydrogen-rich stream comprising greater than 99 vol. % hydrogen. ### Claim 8 (depends on 1) The process according to claim 1, wherein the gaseous stream comprises CO2, CO, H2O(g), gaseous C1-C5 hydrocarbons, and less than 35 vol. % H2. ### Claim 9 (depends on 1) The process according to claim 1, wherein the gaseous stream comprising hydrogen is isolated from a source selected from the group consisting of (i) a tail gas from a hydrocarbon synthesis reaction unit; (ii) the syngas prior to performing the hydrocarbon synthesis reaction; (iii) a tail gas from an upgrading process; and (iv) combinations thereof. ### Claim 10 A process for providing a hydrogen-rich stream comprising: a) performing a hydrocarbon synthesis process using syngas; b) isolating a gaseous stream comprising hydrogen from the hydrocarbon synthesis process, wherein the gaseous stream comprising hydrogen comprises less than 35 vol. % hydrogen; c) passing the gaseous stream comprising hydrogen through a water gas shift reactor to provide a hydrogen-containing stream comprising greater than 40 vol. % hydrogen; d) contacting the hydrogen-containing stream with a reverse-selective membrane selectively permeable to CO2 to provide a CO2-enriched permeate and a hydrogen-containing retentate; and e) passing the hydrogen-containing retentate through a pressure swing adsorption unit to provide a hydrogen-rich stream comprising greater than 90 vol. % hydrogen. ### Claim 11 (depends on 10) The process according to claim 10, wherein the hydrocarbon synthesis process is a Fischer-Tropsch process. ### Claim 12 (depends on 10) The process according to claim 10, wherein the process further comprises passing the hydrogen-containing stream through a vapor-liquid separator to remove water. ### Claim 13 (depends on 10) The process according to claim 10, wherein the process further comprises using the hydrogen-rich stream for a process selected from the group consisting of (i) upgrading a hydrocarbon product stream from the hydrocarbon synthesis process; (ii) hydrotreating a natural gas stream; (iii) recycling the hydrogen-rich stream to a hydrocarbon synthesis reaction unit; (iv) hydrogen production for uses outside the hydrocarbon synthesis process; (v) rejuvenating a hydrocarbon synthesis reaction catalyst; and (vi) combinations thereof. ### Claim 14 (depends on 10) The process according to claim 10, wherein the hydrogen-containing retentate is at a pressure of ≧ about 100 psig. ### Claim 15 (depends on 12) The process according to claim 12, wherein the hydrogen-containing retentate is at a pressure of ≧ about 200 psig. ### Claim 16 (depends on 10) The process according to claim 10, wherein the hydrogen-rich stream comprising greater than 99 vol. % hydrogen. ### Claim 17 (depends on 10) The process according to claim 10, wherein the gaseous stream comprises CO2, CO, H2O(g), gaseous C1-C5 hydrocarbons, and less than 35 vol. % H2. ### Claim 18 (depends on 10) The process according to claim 10, wherein the gaseous stream comprising hydrogen is isolated from a source selected from the group consisting of (i) a tail gas from a hydrocarbon synthesis reaction unit; (ii) the syngas prior to performing the hydrocarbon synthesis reaction; (iii) a tail gas from an upgrading process; and (iv) combinations thereof. ### Claim 19 A process for providing a hydrogen-rich stream comprising: a) performing a hydrocarbon synthesis process; b) isolating a hydrogen-depleted stream comprising less than 35 vol. % hydrogen from the hydrocarbon synthesis process; and c) isolating a hydrogen-rich stream comprising greater than 90 vol. % hydrogen from the hydrogen-depleted stream by a process comprising contacting the hydrogen-depleted stream with a reverse-selective membrane selectively permeable to CO2 to provide a hydrogen-containing retentate and a CO2-enriched permeate and passing the hydrogen-containing retentate through a water gas shift reactor and through a pressure swing adsorption unit or performing a water gas shift reaction on the hydrogen-depleted stream to provide a treated stream and contacting the treated stream with a reverse-selective membrane selectively permeable to CO2 to provide a hydrogen-containing retentate and a CO2-enriched permeate and passing the hydrogen-containing retentate through a pressure swing adsorption unit, wherein the hydrogen-depleted stream is contacted with the reverse selective membrane and passed through the water gas shift reactor prior to the pressure swing adsorption unit. ### Claim 20 (depends on 19) The process according to claim 19, wherein the hydrocarbon synthesis process is a Fischer-Tropsch process. ### Claim 21 (depends on 19) The process according to claim 19, wherein the hydrogen-depleted stream is isolated from a source selected from the group consisting of (i) a tail gas from a hydrocarbon synthesis reaction unit; (ii) syngas prior to performing the hydrocarbon synthesis reaction; (iii) a tail gas from an upgrading process; and (iv) combinations thereof. ### Claim 22 (depends on 19) The process according to claim 19, wherein the hydrogen-rich stream comprising greater than 99 vol. % hydrogen. ### Claim 23 A process for providing a hydrogen-rich stream comprising: a) performing a hydrocarbon synthesis process using syngas to provide at least one hydrocarbon stream and a hydrogen-depleted stream comprising less than 40 vol. % hydrogen; b) isolating a hydrogen-containing stream from the hydrogen-depleted stream by a process comprising contacting the hydrogen-depleted stream with a reverse-selective membrane selectively permeable to CO2 to provide a hydrogen-containing retentate and a CO2-enriched permeate and performing a water gas shift reaction on the hydrogen-containing retentate to provide the hydrogen-containing stream, or performing a water gas shift reaction on the hydrogen-depleted stream to provide a treated stream and contacting the treated stream with a reverse-selective membrane selectively permeable to CO2 to provide the hydrogen-containing stream and a CO2-enriched permeate, wherein the hydrogen concentration on a water-free basis of the hydrogen-containing stream is at least 5 vol. % greater than the hydrogen concentration on a water-free basis of the hydrogen-depleted stream; and c) passing the hydrogen-containing stream through a pressure swing adsorption unit to provide a hydrogen-rich stream comprising greater than 90 vol. % hydrogen. ### Claim 24 (depends on 23) The process according to claim 23, wherein the hydrogen-depleted stream is contacted with the reverse-selective membrane prior to performing the water gas shift reaction. ### Claim 25 (depends on 23) The process according to claim 23, wherein the water gas shift reaction is performed on the hydrogen-depleted stream prior to contacting with a reverse-selective membrane. ### Claim 26 (depends on 23) The process according to claim 23, wherein the process for isolating a hydrogen-containing stream from the hydrogen-depleted stream further comprises removing water in a vapor-liquid separator. ### Claim 27 (depends on 23) The process according to claim 23, wherein the hydrogen-depleted stream comprises less than 35 vol. % hydrogen. ### Claim 28 (depends on 23) The process according to claim 23, wherein the hydrogen-depleted stream is isolated from a source selected from the group consisting of (i) a tail gas from a hydrocarbon synthesis reaction; (ii) the syngas prior to performing the hydrocarbon synthesis reaction; (iii) a tail gas from an upgrading process; and (iv) combinations thereof. ### Claim 29 (depends on 23) The process according to claim 23, wherein the process further comprises using the hydrogen-rich stream for a process selected from the group consisting of (i) upgrading a hydrocarbon product stream from the hydrocarbon synthesis process; (ii) hydrotreating a natural gas stream; (iii) recycling the hydrogen-rich stream to a hydrocarbon synthesis reaction unit; (iv) hydrogen production for uses outside the hydrocarbon synthesis process; (v) rejuvenating a hydrocarbon synthesis reaction catalyst; and (vi) combinations thereof. ### Claim 30 (depends on 23) The process according to claim 23, wherein the hydrocarbon synthesis process is a Fischer-Tropsch process. ### Claim 31 (depends on 1) The process according to claim 1, wherein CO2-enriched permeate is burned as fuel. ### Claim 32 (depends on 1) The process according to claim 1, wherein the pressure swing adsorption unit also provides an absorbed gas stream comprising CO, CO2, H2O(g), gaseous hydrocarbons, and residual hydrogen and the process further comprises combining the absorbed gas stream with the CO2-enriched permeate to form a combined gas stream and burning the combined gas stream as fuel.