CA2718536C - Sour shift process for the removal of carbon monoxide from a gas stream - Google Patents
Sour shift process for the removal of carbon monoxide from a gas stream Download PDFInfo
- Publication number
- CA2718536C CA2718536C CA2718536A CA2718536A CA2718536C CA 2718536 C CA2718536 C CA 2718536C CA 2718536 A CA2718536 A CA 2718536A CA 2718536 A CA2718536 A CA 2718536A CA 2718536 C CA2718536 C CA 2718536C
- Authority
- CA
- Canada
- Prior art keywords
- gas stream
- methane
- hydrogen
- carbon monoxide
- gasification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 129
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 266
- 239000007789 gas Substances 0.000 claims abstract description 245
- 238000002309 gasification Methods 0.000 claims abstract description 85
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 85
- 239000001257 hydrogen Substances 0.000 claims abstract description 85
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 102
- 239000003054 catalyst Substances 0.000 claims description 57
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 51
- 239000001569 carbon dioxide Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000006227 byproduct Substances 0.000 claims description 14
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 239000000567 combustion gas Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 24
- 239000003245 coal Substances 0.000 description 21
- 239000002006 petroleum coke Substances 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 239000003209 petroleum derivative Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000003027 oil sand Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- -1 e.g. Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ARAVOODWJJJNBY-IRXDYDNUSA-N 5-chloro-thiophene-2-carboxylic acid ((3s,4s)-1-{[2-fluoro-4-(2-oxo-2h-pyridin-1-yl)-phenylcarbamoyl]-methyl}-4-hydroxy-pyrrolidin-3-yl)-amide Chemical compound C([C@@H]([C@H](C1)NC(=O)C=2SC(Cl)=CC=2)O)N1CC(=O)NC(C(=C1)F)=CC=C1N1C=CC=CC1=O ARAVOODWJJJNBY-IRXDYDNUSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011335 coal coke Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical class C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000003476 subbituminous coal Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/482—Gasifiers with stationary fluidised bed
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
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Abstract
Processes for the catalytic conversion of a carbonaceous composition into a gas stream comprising methane are provided, where a sour shift reaction is used to remove carbon monoxide gas stream produced by the gasification process. The in-corporation of the sour shift reaction provides an efficient and cost-effective means of eliminating carbon monoxide from the gas stream. In addition, the sour shift reaction also generates additional hydrogen, thus increasing the amount of hydrogen produced from the gasification process.
Description
SOUR SHIFT PROCESS FOR THE REMOVAL OF CARBON MONOXIDE
FROM A GAS STREAM
Field of the Invention [0001] The present invention relates to processes for converting a carbonaceous feedstock into a plurality of gaseous products contained in a gas stream, and for separating hydrogen and methane from the gas stream. Further, the invention relates to processes for removing carbon monoxide from a gas stream by contacting the carbon monoxide-containing gas stream with an aqueous medium under conditions suitable for conversion of the carbon monoxide to carbon dioxide.
Background of the Invention
FROM A GAS STREAM
Field of the Invention [0001] The present invention relates to processes for converting a carbonaceous feedstock into a plurality of gaseous products contained in a gas stream, and for separating hydrogen and methane from the gas stream. Further, the invention relates to processes for removing carbon monoxide from a gas stream by contacting the carbon monoxide-containing gas stream with an aqueous medium under conditions suitable for conversion of the carbon monoxide to carbon dioxide.
Background of the Invention
[0002] In view of numerous factors such as higher energy prices and environmental concerns, the production of value-added gaseous products from lower-fuel-value carbonaceous feedstocks, such as biomass, coal and petroleum coke, is receiving renewed attention. The catalytic gasification of such materials to produce methane and other value-added gases is disclosed, for example, in US3828474, US3998607, US4057512, US4092125, US4094650, US4204843, US4468231, US4500323, US4541841, US4551155, US4558027, US4606105, US4617027, US4609456, US5017282, US5055181, US6187465, US6790430, US6894183, US6955695, US2003/0167961A1, US2006/0265953A1, US2007/000177A1, US2007/083072A1, US2007/0277437A1 and GB1599932.
[0003] Reaction of lower-fuel-value carbonaceous feedstocks under conditions described in the above references typically yields a crude product gas and a char. The crude product gas typically comprises an amount of particles, which are removed from the gas stream to produce a gas effluent. This gas effluent typically contains a mixture of gases, including, but not limited to, methane, carbon dioxide, hydrogen, carbon monoxide, hydrogen sulfide, ammonia, unreacted steam, entrained fines, and other contaminants such as COS.
Through processes known in the art, the gas effluent can be treated to remove carbon dioxide, hydrogen sulfide, steam, entrained fines, COS, and other contaminants, yielding a cleaned gas stream comprising methane, carbon monoxide, and hydrogen.
Through processes known in the art, the gas effluent can be treated to remove carbon dioxide, hydrogen sulfide, steam, entrained fines, COS, and other contaminants, yielding a cleaned gas stream comprising methane, carbon monoxide, and hydrogen.
[0004] For some applications, it may be desirable to recover a gas stream that is enriched in either methane or hydrogen gas. In some situations, it may even be desirable to recover a gas stream that almost entirely comprises methane or hydrogen. In such situations, the cleaned gas stream must undergo additional processing to remove carbon monoxide. This additional processing can complicate the recovery of methane and/or hydrogen, especially if there is no need to recover a gas stream comprising appreciable quantities of carbon monoxide. Thus, there is a need for processes which can obviate the need to treat a cleaned gas stream to remove carbon monoxide.
Summary of the Invention
Summary of the Invention
[0005] In a first aspect, the present invention provides a process for converting a carbonaceous feedstock into a plurality of gaseous products contained in a gas stream, the gas stream comprising hydrogen, methane and other gaseous products, and for separating hydrogen and methane from the other gaseous products in the gas stream, the process comprising the steps of: (a) supplying a carbonaceous feedstock to a gasification reactor; (b) reacting the carbonaceous feedstock in the gasification reactor in the presence of steam, carbon monoxide, hydrogen and a gasification catalyst and under suitable temperature and pressure to form a first gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous by-products; (c) contacting the first gas stream with an aqueous medium to convert at least 80 mol % of the carbon monoxide in the first gas stream to carbon dioxide and generate hydrogen, thereby forming a carbon monoxide-depleted gas stream comprising methane, hydrogen, carbon dioxide, and the one or more additional gaseous by-products; (d) removing carbon dioxide and the one or more additional gaseous by-products from the carbon monoxide-depleted gas stream to form a second gas stream comprising at least 90 mol % methane and hydrogen; and (e) at least partially separating the hydrogen in the second gas stream and the methane in the second gas stream from each other to form at least a hydrogen-enriched gas stream and a first methane-enriched gas stream.
[0006] In a second aspect, the present invention provides a process for converting a carbonaceous feedstock into a plurality of gaseous products contained in a gas stream, the gas stream comprising hydrogen, methane and other gaseous products, and for separating hydrogen and methane from the other gaseous products in the gas stream, the process comprising the steps of: (a) supplying a first carbonaceous feedstock to a reactor; (b) at least partially combusting the first carbonaceous feedstock in the reactor in the presence of oxygen and under suitable temperature and pressure to generate (i) heat energy, and (ii) a combustion gas stream comprising hydrogen, carbon monoxide, and carbon dioxide; (c) using the heat energy from the combustion of the first carbonaceous feedstock to generate steam; (d) introducing at least a portion of the steam, at least a portion of the combustion gas stream, a second carbonaceous feedstock, and a gasification catalyst to a gasification reactor; (e) reacting the second carbonaceous feedstock in the gasification reactor in the presence of steam, carbon monoxide and hydrogen and the gasification catalyst, and under suitable temperature and pressure to form a first gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous by-products; (f) contacting the first gas stream with an aqueous medium to convert at least 80 mol % of the carbon monoxide in the first gas stream to carbon dioxide and generate hydrogen, thereby forming a carbon monoxide-depleted gas stream comprising methane, hydrogen, carbon dioxide, and the one or more additional gaseous by-products; (g) removing carbon dioxide and the one or more gaseous by-products from the carbon monoxide-depleted gas stream to form a second gas stream comprising at least 90 mol % methane and hydrogen; and (h) at least partially separating the hydrogen in the second gas stream and the methane in the second gas stream from each other to form at least a hydrogen-enriched gas stream and a first methane-enriched gas stream.
Brief Description of the Drawings
Brief Description of the Drawings
[0007] Figure 1 depicts a block diagram that illustrates a continuous process for gasification of a carbonaceous feedstock, where the process includes the conversion of carbon monoxide to carbon dioxide using a sour shift procedure.
Detailed Description
Detailed Description
[0008] The present invention provides processes for removing carbon monoxide before achieving a cleaned gas stream and for increasing the potential yield of hydrogen gas.
By contacting the crude gas stream with an aqueous medium, e.g., water, under suitable conditions, the carbon monoxide substantially converts to carbon dioxide and hydrogen gas.
This process is alternatively referred to as a "sour gas shift." By depleting the gas stream of carbon monoxide through an inexpensive and efficient sour gas shift step, carbon monoxide need not be separated from methane and hydrogen in the cleaned gas stream.
Furthermore, because the sour gas shift leads to the generation of hydrogen gas, the processes or the invention can serve as an inexpensive and efficient way of increasing yield of hydrogen from a gasification process. Although the processes of the invention can be employed in a variety of gasification processes, the processes of the invention are particularly useful in situations where it is desirable to recover a substantially pure stream of hydrogen gas rather than a syngas that comprises hydrogen and carbon monoxide.
By contacting the crude gas stream with an aqueous medium, e.g., water, under suitable conditions, the carbon monoxide substantially converts to carbon dioxide and hydrogen gas.
This process is alternatively referred to as a "sour gas shift." By depleting the gas stream of carbon monoxide through an inexpensive and efficient sour gas shift step, carbon monoxide need not be separated from methane and hydrogen in the cleaned gas stream.
Furthermore, because the sour gas shift leads to the generation of hydrogen gas, the processes or the invention can serve as an inexpensive and efficient way of increasing yield of hydrogen from a gasification process. Although the processes of the invention can be employed in a variety of gasification processes, the processes of the invention are particularly useful in situations where it is desirable to recover a substantially pure stream of hydrogen gas rather than a syngas that comprises hydrogen and carbon monoxide.
[0009] The present invention can be practiced, for example, using any of the developments to catalytic gasification technology disclosed in commonly owned US2007/0000177A1, US2007/0083072A1, US2007/0277437A1, US2009/0048476A1, 1JS2009/0090055A1 and US2009/0090056A1.
100101 Moreover, the present invention can be practiced in conjunction with the subject matter of the following US Patent Publications: US2009/0165383A1, IJS2009/0166588A1, US2009/01665379A1, US2009/0170968A1, US2009/0165380A1, 1JS2009/0165381A1, US2009/0165361A 1 , US2009/0165382A1, US2009/0169449A1, US2009/0169448A1, US2009/0165376A1 and US2009/0165384A1.
[0011] Further, the present invention can be practiced in conjunction with the subject matter of the following US Patent Publications: US2009/0217582A1, US2009/0217584A1, US2009/0217585A1, US2009/0260287A1, US2009/0220406A1, US2009/0217590A1, US2009/0217586A1, US2009/0217588A1, US2009/0218424A1, US2009/0217589A1, US2009/0217575A1, US2009/0229182A1, and US2009/0217587A1.
[0012] The present invention can also be practiced in conjunction with the subject matter of US Patent Publication No. U52009/0259080A1.
100141 Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
[0015] Except where expressly noted, trademarks are shown in upper case.
[0016] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
[0017] Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
[0018] When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present invention be limited to the specific values recited when defining a range.
[0019] When the term "about" is used in describing a value or an end-point of a range, the invention should be understood to include the specific value or end-point referred to.
[0020] As used herein, the terms "comprises," "comprising," "includes,"
"including,"
"has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following:
A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[0021] The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
[0022] The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting.
Gasification Methods [0023] The methods of the present invention are particularly useful in integrated gasification processes for converting carbonaceous feedstocks, such as petroleum coke, liquid petroleum residue, asphaltenes, biomass and/or coal to combustible gases, such as methane.
[0024] The gasification reactors for such processes are typically operated at moderately high pressures and temperature, requiring introduction of a carbonaceous material (i.e., a feedstock) to the reaction zone of the gasification reactor while maintaining the required temperature, pressure, and flow rate of the feedstock. Those skilled in the art are familiar with feed systems for providing feedstocks to high pressure and/or temperature environments, including, star feeders, screw feeders, rotary pistons, and lock-hoppers. It should be understood that the feed system can include two or more pressure-balanced elements, such as lock hoppers, which would be used alternately.
[0025] The catalyzed feedstock is provided to the catalytic gasifier from a feedstock preparation operation, and generally comprises a particulate composition of a crushed carbonaceous material and a gasification catalyst, as discussed below. In some instances, the catalyzed feedstock can be prepared at pressures conditions above the operating pressure of catalytic gasifier. Hence, the catalyzed feedstock can be directly passed into the catalytic gasifier without further pressurization.
[0026] Any of several catalytic gasifiers can be utilized. Suitable gasifiers include counter-current fixed bed, co-current fixed bed, fluidized bed, entrained flow, and moving bed reactors. A catalytic gasifier for gasifying liquid feeds, such as liquid petroleum residues, is disclosed in previously mentioned US6955695.
[0027] The pressure in the catalytic gasifier typically can be from about 10 to about 100 atm (from about 150 to about 1500 psig). The gasification reactor temperature can be maintained around at least about 450 C, or at least about 600 C, or at least about 900 C, or at least about 750 C, or about 600 C to about 700 C; and at pressures of at least about 50 psig, or at least about 200 psig, or at least about 400 psig, to about 1000 psig, or to about 700 psig, or to about 600 psig.
[0028] The gas utilized in the catalytic gasifier for pressurization and reactions of the particulate composition comprises steam, and optionally, oxygen or air, and is supplied, as necessary, to the reactor according to methods known to those skilled in the art.
[0029] For example, steam can be supplied to the catalytic gasifier from any of the steam boilers known to those skilled in the art can supply steam to the reactor.
Such boilers can be powered, for example, through the use of any carbonaceous material such as powdered coal, biomass etc., and including but not limited to rejected carbonaceous materials from the particulate composition preparation operation (e.g., fines, supra). Steam can also be supplied from a second gasification reactor coupled to a combustion turbine where the exhaust from the reactor is thermally exchanged to a water source and produce steam.
Alternatively, the steam may be provided to the gasification reactor as described previously mentioned U.S. Patent Publiction Nos. 2009/0165376A1, US2009/0217584A1 and US2009/0217585A1.
[0030] Recycled steam from other process operations can also be used for supplementing steam to the catalytic gasifier. For example in the preparation of the catalyzed feedstock, when slurried particulate composition are dried with a fluid bed slurry drier, as discussed below, then the steam generated can be fed to the catalytic gasification reactor.
[0031] The small amount of heat input that may be required for the catalytic gasifier can be provided by superheating a gas mixture of steam and recycle gas feeding the gasification reactor by any method known to one skilled in the art. In one method, compressed recycle gas of CO and H2 can be mixed with steam and the resulting steam/recycle gas mixture can be further superheated by heat exchange with the catalytic gasifier effluent followed by superheating in a recycle gas furnace.
[0032] A methane reformer can be optionally included in the process to supplement the recycle CO and H2 stream and the exhaust from the slurry gasifier to ensure that enough recycle gas is supplied to the reactor so that the net heat of reaction is as close to neutral as possible (only slightly exothermic or endothermic), in other words, that the catalytic gasifier is run under substantially thermally neutral conditions. In such instances, methane can be supplied for the reformer from the methane product, as described below.
[0033] Reaction of the catalyzed feedstock in the catalytic gasifier, under the described conditions, provides a crude product gas and a char from the catalytic gasification reactor.
[0034] The char produced in the catalytic gasifier processes is typically removed from the catalytic gasifier for sampling, purging, and/or catalyst recovery in a continuous or batch-wise manner. Methods for removing char are well known to those skilled in the art.
One such method taught by EP-A-0102828, for example, can be employed. The char can be periodically withdrawn from the catalytic gasification reactor through a lock hopper system, although other methods are known to those skilled in the art.
[0035] Often, the char from the catalytic gasifier is directed to a catalyst recovery and recycle process. Processes have been developed to recover alkali metal from the solid purge in order to reduce raw material costs and to minimize environmental impact of a catalytic gasification process. For example, the char can be quenched with recycle gas and water and directed to a catalyst recycling operation for extraction and reuse of the alkali metal catalyst. Particularly useful recovery and recycling processes are described in US4459138, as well as previously mentioned US4057512, US2007/0277437A1, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/0169448A1.
' 76909-428 Further process details are disclosed therein.
[0036] Upon completion of catalyst recovery, both the char, substantially free of the gasification catalysts and the recovered catalyst (as a solution or solid) can be directed to the feedstock preparation operation comprising a catalyzed feedstock preparation process and a slurry feedstock preparation process.
Carbonaceous Feedstock [0037] The term "carbonaceous feedstock" as used herein includes a carbon source, typically coal, petroleum coke, asphaltene and/or liquid petroleum residue, but may broadly include any source of carbon suitable for gasification, including biomass.
[0038] The term "petroleum coke" as used herein includes both (i) the solid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues - "resid petcoke") and (ii) the solid thermal decomposition product of processing tar sands (bituminous sands or oil sands - "tar sands petcoke"). Such carbonization products include, for example, green, calcined, needle and fluidized bed petroleum coke.
[0039] Resid petcoke can be derived from a crude oil, for example, by coking processes used for upgrading heavy-gravity residual crude oil, which petroleum coke contains ash as a minor component, typically about 1.0 wt% or less, and more typically about 0.5 wt% of less, based on the weight of the coke. Typically, the ash in such lower-ash cokes predominantly apprises metals such as nickel and vanadium.
[0040] Tar sands petcoke can be derived from an oil sand, for example, by coking processes used for upgrading oil sand. Tar sands petcoke contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the tar sands petcoke. Typically, the ash in such higher-ash cokes predominantly comprises materials such as compounds of silicon and/or aluminum.
[0041] The petroleum coke can comprise at least. about 70 wt% carbon, at least about 80 wt% carbon, or at least about 90 wt% carbon, based on the total weight of the petroleum coke. Typically, the petroleum coke comprises less than about 20 wt% percent inorganic compounds, based on the weight of the petroleum coke.
9=
[0042] The term "asphaltene" as used herein is an aromatic carbonaceous solid at room temperature, and can be derived, from example, from the processing of crude oil and crude oil tar sands.
[0043] The term "liquid petroleum residue" as used herein includes both (i) the liquid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues ¨ "resid liquid petroleum residue") and (ii) the liquid thermal decomposition product of processing tar sands (bituminous sands or oil sands ¨
"tar sands liquid petroleum residue"). The liquid petroleum residue is substantially non-solid at room temperature; for example, it can take the form of a thick fluid or a sludge.
[0044] Resid liquid petroleum residue can also be derived from a crude oil, for example, by processes used for upgrading heavy-gravity crude oil distillation residue.
Such liquid petroleum residue contains ash as a minor component, typically about 1.0 wt%
or less, and more typically about 0.5 wt% of less, based on the weight of the residue.
Typically, the ash in such lower-ash residues predominantly comprises metals such as nickel and vanadium.
[0045] Tar sands liquid petroleum residue can be derived from an oil sand, for example, by processes used for upgrading oil sand. Tar sands liquid petroleum residue contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the residue. Typically, the ash in such higher-ash residues predominantly comprises materials such as compounds of silicon and/or aluminum.
[0046] The term "coal" as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof. In certain embodiments, the coal has a carbon content of less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% by weight, based on the total coal weight. In other embodiments, the coal has a carbon content ranging up to about 85%, or up to about 80%, or up to about 75% by weight, based on total coal weight. Examples of useful coals include, but are not limited to, Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon, and Powder River Basin (PRB) coals. Anthracite, bituminous coal, sub-bituminous coal, and lignite coal may contain about 10 wt%, from about 5 to about 7 wt%, from about 4 to about 8 wt %, and from about 9 to about 11 wt%, ash by total weight of the coal on a dry basis, respectively. However, the ash content of any particular coal source will depend on the rank and source of the coal, as is familiar to those skilled in the art. See, e.g., Coal Data: A
Reference, Energy Information Administration, Office of Coal, Nuclear, Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), February 1995.
[0047] The term "ash" as used herein includes inorganic compounds that occur within the carbon source. The ash typically includes compounds of silicon, aluminum, calcium, iron, vanadium, sulfur, and the like. Such compounds include inorganic oxides, such as silica, alumina, ferric oxide, etc., but may also include a variety of minerals containing one or more of silicon, aluminum, calcium, iron, and vanadium. The term "ash" may be used to refer to such compounds present in the carbon source prior to gasification, and may also be used to refer to such compounds present in the char after gasification.
Catalyst-Loaded Carbonaceous Feedstock [0048] The carbonaceous composition is generally loaded with an amount of an alkali metal compound to promote the steam gasification to methane. Typically, the quantity of the alkali metal compound in the composition is sufficient to provide a ratio of alkali metal atoms to carbon atoms ranging from about 0.01, or from about 0.02, or from about 0.03, or from about 0.04, to about 0.06, to about 0.07, or to about 0.08, or to about 0.1. Further, the alkali metal is typically loaded onto a carbon source to achieve an alkali metal content of from about 3 to about 10 times more than the combined ash content of the carbonaceous material (e.g., coal and/or petroleum coke), on a mass basis.
[0049] Alkali metal compounds suitable for use as a gasification catalyst include compounds selected from the group consisting of alkali metal carbonates, bicarbonates, formates, oxalates, amides, hydroxides, acetates, halides, nitrates, sulfides, and polysulfides.
For example, the catalyst can comprise one or more of Na2CO3, K2CO3, Rb2CO3, Li2CO3, Cs2CO3, NaOH, KOH, RbOH, or Cs0H, and particularly, potassium carbonate and/or potassium hydroxide.
[0050] Any methods known to those skilled in the art can be used to associate one or more gasification catalysts with the carbonaceous composition. Such methods include, but are not limited to, admixing with a solid catalyst source and impregnating the catalyst onto the carbonaceous solid. Several impregnation methods known to those skilled in the art can be employed to incorporate the gasification catalysts. These methods include, but are not limited to, incipient wetness impregnation, evaporative impregnation, vacuum impregnation, dip impregnation, and combinations of these methods.
Gasification catalysts can be impregnated into the carbonaceous solids by slurrying with a solution (e.g., aqueous) of the catalyst.
[0051] That portion of the particulate carbonaceous feedstock of a particle size suitable for use in the gasifying reactor can then be further processed, for example, to impregnate one or more catalysts and/or co-catalysts by methods known in the art, for example, as disclosed in previously mentioned US4069304, US4092125, US4468231, US4551155 and US5435940; and previously mentioned US Patent Publication Nos.
US2009/0090055A1, US2009/0090056A1, US2009/0166588A1, US2009/0165379A1, US2009/0165380A1, US2009/0165384A1, US2009/0165379A1 and US2009/0170968A1.
[0052] One particular method suitable for combining the coal particulate with a gasification catalyst to provide a catalyzed carbonaceous feedstock where the catalyst has been associated with the coal particulate via ion exchange is described in previously mentioned US2009/0048476A1. The catalyst loading by ion exchange mechanism is maximized (based on adsorption isotherms specifically developed for the coal), and the additional catalyst retained on wet including those inside the pores is controlled so that the total catalyst target value is obtained in a controlled manner. Such loading provides a catalyzed coal particulate as a wet cake. The catalyst loaded and dewatered wet coal cake typically contains, for example, about 50% moisture. The total amount of catalyst loaded is controlled by controlling the concentration of catalyst components in the solution, as well as the contact time, temperature and method, as can be readily determined by those of ordinary skill in the relevant art based on the characteristics of the starting coal.
[0053] The catalyzed feedstock can be stored for future use or transferred to a feed operation for introduction into the gasification reactor. The catalyzed feedstock can be conveyed to storage or feed operations according to any methods known to those skilled in the art, for example, a screw conveyer or pneumatic transport.
Steam Generation [0054] The steam supplied to the gasification reactor can originate from a variety of sources, including commercial gasification reactors, oxy-fuel combustors, and boilers. The gasification or combustion reaction of a carbonaceous feedstock generates large amounts of heat energy. Advantageously, this heat energy can be used to contact any type of heat exchanger which is also in contact with a water source, thereby generating steam. For example, any of the boilers known to those skilled in the art can supply steam to the reactor.
While any water source can be used to generate steam, the water commonly used in known boiler systems is purified and deionized (about 0.3-1.0 microsiemens/cm) so that corrosive processes are slowed. Such boilers can be powered, for example, through the combustion of any carbonaceous material, including pulverized/powdered coal, biomass, and rejected carbonaceous materials from the feedstock preparation operation (e.g., fines, supra). The thermal energy from the burning the carbonaceous material heats the water in the boiler, which eventually converts into steam (at about 700 F and 3,200 psi). The steam is routed from the boiler into heated tubes, which are typically located in the furnace at or near the exit conduit carrying the combustion gases. The steam can be routed via heated conduits to the gasification reactor, it can be used to dry a carbonaceous feedstock, or it can be prepared and routed to a steam turbine for generation of electricity. In order to avoid excessive cooling of the steam during transport, the heated conduits for carrying steam can also be superheated (e.g., via contact with a heat exchanger) prior to delivery of the steam to its endpoint. Suitable methods of steam generation are described in previously mentioned US
Patent Publication Nos. US2009/0217584A1 and US2009/0217585A1.
[0055] Steam can also be supplied from a second gasification reactor coupled with a combustion turbine, the exhaust of which contacts a heat exchanger in contact with a water source, which can include a boiler system as described above, to produce steam.
[0056] Recycled steam from other process operations can also be used for supplying steam to the reactor. For example, when a slurried carbonaceous feedstock is dried with a fluid bed slurry drier, as discussed herein, the steam generated through vaporization can be fed to the gasification reactor. Similarly, steam can be generated directly from a slurry gasifier which produces steam and synthesis gas from an aqueous carbonaceous feed slurry, such as described in previously mentioned US Patent Publication No.
US2009/0165376A1.
At least a portion of the steam can also be used to drive a steam turbine that generates electricity.
Treatment of Crude Product Gas [0057] Crude product gas effluent leaving the catalytic gasifier can pass through a portion of the reactor which serves as a disengagement zone where particles too heavy to be entrained by the gas leaving the reactor (i.e., fines) are returned to the fluidized bed. The disengagement zone can include one or more internal cyclone separators or similar devices for removing fines and particulates from the gas. The gas effluent passing through the disengagement zone and leaving the catalytic gasifier generally contains CH4, CO2, H2 and CO, HS, NH3, unreacted steam, entrained fines, and other contaminants such as COS.
[0058] The gas stream from which the fines have been removed can then be passed through a heat exchanger to cool the gas and the recovered heat can be used to preheat recycle gas and generate high pressure steam. Residual entrained fines can also be removed by any suitable means such as external cyclone separators, optionally followed by Venturi scrubbers. The recovered fines can be processed to recover alkali metal catalyst then passed to the slurry feedstock preparation process or returned to the catalytic gasification reactor, or directly recycled back to feedstock preparation as described in previously mentioned US
Patent Publication No. US2009/0217589A1.
[0059] The gas stream from which the fines have been removed is fed to a gas purification operation optionally comprising COS hydrolysis reactors for COS
removal (sour process) and further cooled in a heat exchanger to recover residual heat. Methods for COS hydrolysis are known to those skilled in the art, for example, see US4100256.
[0060] The gas stream is then subjected to a water-gas shift reaction in the presence of steam to convert the CO to CO2 and to increase the fraction of H2. This sour shift process is described in detail, for example, in US7074373. The process involves adding water, or using water contained in the gas, and reacting the resulting water-gas mixture adiabatically over a steam reforming catalyst. Typical steam reforming catalysts include one or more Group VIII metals on a heat-resistant support.
[0061] The invention provides a process in which a gas stream is contacted with an aqueous medium (e.g., water) under conditions suitable to convert a substantial portion of the carbon dioxide in the gas stream to carbon dioxide, and simultaneously generate hydrogen gas. In some embodiments, at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol%, or at least about 99 mol% of the carbon monoxide in the gas stream is converted to carbon dioxide.
[0062] Methods and reactors for performing the sour gas shift reaction on a CO-containing gas stream are well known to those of skill in the art. Suitable reaction conditions and suitable reactors can vary depending on the amount of CO that must be depleted from the gas stream. In some embodiments, the sour gas shift can be performed in a single stage within a temperature range from about 100 C, or from about 150 C, or from about 200 C, to about 250 C, or to about 300 C, or to about 350 C. In these embodiments, the shift reaction can be catalyzed by any suitable catalyst known to those of skill in the art.
Such catalysts include, but are not limited to, Fe203-based catalysts, such as Fe203-Cr203 catalysts, and other transition metal-based and transition metal oxide-based catalysts. In other embodiments, the sour gas shift can be performed in multiple stages. In one particular embodiment, the sour gas shift is performed in two stages. This two-stage process uses a high-temperature sequence followed by a low-temperature sequence. The gas temperature for the high-temperature shift reaction ranges from about 350 C to about 1050 C. Typical high-temperature catalysts include, but are not limited to, iron oxide optionally combined with lesser amounts of chromium oxide. The gas temperature for the low-temperature shift ranges from about 150 C to about 300 C, or from about 200 C to about 250 C.
Low-temperature shift catalysts include, but are not limited to, copper oxides that may be supported on zinc oxide or alumina.
[0063] Steam shifting is often carried out with heat exchangers and steam generators to permit the efficient use of heat energy. Shift reactors employing these features are well known to those of skill in the art. An example of a suitable shift reactor is illustrated in previously mentioned US7074373, although other designs known to those of skill in the art are also effective.
[0064] Following the sour gas shift procedure, the gas stream generally contains CH4, CO2, H2, H2S, NH3, and steam. This CO-depleted gas stream can be further treated in a water scrubber for recovery of ammonia, yielding a CO-depleted scrubbed gas that comprises at least 112S, CO2, Hz, and CH4.
[0065] Scrubber water and sour process condensate can be processed to strip and recover H2S, CO2 and NH3; such processes are well known to those skilled in the art.
NH3 can typically be recovered as an aqueous solution (e.g., 20 wt%).
[0066] A subsequent acid gas removal process can be used to remove H2S and CO2 from the scrubbed gas stream by a physical absorption method involving solvent treatment of the gas to give a cleaned gas stream. Such processes involve contacting the scrubbed gas with a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like. One method can involve the use of SELEXOL
(UOP
LLC, Des Plaines, IL USA) or RECTISOL (Lurgi AG, Frankfurt am Main, Germany) solvent having two trains; each train consisting of an H2S absorber and a CO2 absorber.
The spent solvent containing H2S, CO2 and other contaminants can be regenerated by any method known to those skilled in the art, including contacting the spent solvent with steam or other stripping gas to remove the contaminants or by passing the spent solvent through stripper columns. Recovered acid gases can be sent for sulfur recovery processing; for example, any recovered H2S from the acid gas removal and sour water stripping can be converted to elemental sulfur by any method known to those skilled in the art, including the Claus process. Sulfur can be recovered as a molten liquid. Stripped water can be directed for recycled use in preparation of the catalyzed feedstock. One method for removing acid gases from the scrubbed gas stream is described in previously mentioned US
Patent Publication No. US2009/0220406A1.
[0067] Advantageously, CO2 generated in the process, whether in the steam generation or catalytic gasification or both, can be recovered for subsequent use or sequestration, enabling a greatly decreased carbon footprint (as compared to direct combustion of the feedstock) as a result. Processes for reducing a carbon footprint are described in previously mentioned US Patent Publication Nos. US2009/0217584A1 and US2009/0217585A1.
[0068] The resulting cleaned gas stream exiting the gas purification operation contains mostly CH4 and H2 and, typically, small amounts of CO2 and H20.
[0069] In accordance with the present invention, this cleaned gas stream can be further processed to provide at least a partial separation of methane and hydrogen.
Various methods for effecting this separation are known to those of skill in the art.
Such methods include cryogenic separation and membrane-based separation. In addition, the separation can be effected through the methods involving the formation of methane hydrates, as illustrated in previously mentioned US Patent Publication No.
US2009/0260287A1. In some embodiments, combinations of the separation procedures can be used.
Reference can also be had to previously mentioned US Patent Publication No.
US2009/0259080A1.
[0070] The separation step yields a methane-enriched gas stream and a hydrogen-enriched gas stream. The methane-enriched gas stream at least comprises methane. In some embodiments, the methane-enriched gas stream should have a heating value of at least 950 btu/scf (dry basis). For example, in some embodiments, the methane-enriched gas stream comprises at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol% methane. In some embodiments, however, the methane-enriched gas stream at least comprises both methane and carbon monoxide, and optionally a minor amount of hydrogen (generally about 4 mol% or less). In some such embodiments, the methane-enriched gas comprises at least about 1000 ppm carbon monoxide. In other embodiments, the methane-enriched gas stream is substantially free of carbon monoxide, having, for example, less than about 1000 ppm carbon monoxide. In some embodiments, the hydrogen-enriched gas stream substantially comprises hydrogen.
[0071] In embodiments where the methane-enriched gas stream comprises 1000 ppm or more carbon monoxide and where the heating value of the methane-enriched gas stream is less than 950 btu/scf (dry basis), the methane in the methane-enriched gas stream and the carbon monoxide in the methane-enriched gas stream can be at least partially separated from each other. Various methods for effecting separation of methane and carbon monoxide are known to those of skill in the art. Such methods include, but are not limited to, cryogenic separation and membrane-based separation. This partial separation of methane and carbon monoxide yields at least a second methane-enriched gas stream and a carbon monoxide-enriched gas stream. The methane-enriched gas stream comprises at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol% methane.
Moreover, in typical embodiments, the methane-enriched gas stream has a heating value of at least 950 btu/scf (dry basis). The carbon monoxide-enriched gas stream comprises at least about 50 mol%, or at least about 65 mol%, or at least about 80 mol% carbon monoxide.
[0072] In some embodiments, the methane-enriched gas stream, if it contains appreciable amounts of CO, can be further enriched in methane by performing trim methanation to reduce the CO content. One may carry out trim methanation using any suitable method and apparatus known to those of skill in the art, including, for example, the method and apparatus disclosed in U54235044.
[0073] In embodiments where the separation yields a methane-enriched gas stream that substantially comprises methane, the methane stream can be recovered and used as a high-quality energy source. For example, the methane can be compressed and introduced into the existing natural gas pipeline system. Or, a portion of the methane product can also be used as plant fuel for a gas turbine.
[0074] In embodiments where the separation yields a hydrogen-enriched gas stream that substantially comprises hydrogen, the hydrogen stream can be recovered and used as an energy source and/or as a reactant. For example, the hydrogen can be used as an energy source for hydrogen-based fuel cells or for a subsequent catalytic gasification process. In another example, hydrogen can be used as a fuel for a steam generation process, such as described in previously mentioned US Patent Publication Nos. US2009/0217584A1 and US2009/0217585A1.
[0075] In some embodiments of the invention, the hydrogen is recycled back to the catalytic gasifier, directly and/or via another unit operation such as discussed below.
Continuous Gasification Process Employing Sour Shift [0076] As described above, the invention provides for a continuous catalytic gasification process wherein the use of the sour shift process to convert CO and H20 to CO2 and HZ.
1. Introduction of a carbonaceous feedstock to a gasification reactor [0077] The processes of the invention require the supplying of a carbonaceous feedstock and a gas feed (comprising steam, carbon monoxide and hydrogen) to a gasification reactor.
[0078] Suitable gasification reactors and carbonaceous feedstocks are described above.
In typical embodiments, the carbonaceous feedstock is provided in particulate form, although this need not be the case in all embodiments. In typical embodiments, the carbonaceous feedstock is loaded with, or at least mixed with, a suitable gasification catalyst. Suitable catalysts are described above. Typical processes at least include potassium carbonate and/or potassium hydroxide.
[0079] In some embodiments, steam may also be introduced into the gasification reactor in the same step as the introduction of the carbonaceous feedstock. The steam can be generated by any suitable method for the generation of steam known to those of skill in the art. Suitable methods of steam generation are described above.
[0080] In some embodiments, a stream of feed gases (in addition to the steam) can also be introduced into the gasification reactor within the same step as the introduction of the carbonaceous feedstock. This feed gas stream at least comprises hydrogen and carbon monoxide, but can also include carbon dioxide and water vapor. The feed gas stream can be generated in a variety of ways.
[0081] In some embodiments, the feed gas stream comprises the product of reforming methane in a methane reformer. In a particular embodiment, the input gases for the methane reformation are a portion of the methane product of catalytic gasification of a carbonaceous feedstock. The methane reacts in the methane reformer to generate a gas stream that at least comprises carbon monoxide and hydrogen gas. This gas stream comprising CO and H2 can serve as a recycle gas stream (combined with the hydrogen-enriched gas stream) that is introduced (i.e., recycled) into the gasification reactor as the product gas stream.
[0082] In some embodiments, the feed gas stream is the product of a combustion reaction. In a particular embodiment, the combustion reaction occurs in a reactor (e.g., an oxy-blown gasifier or a combustion reactor). A carbonaceous feedstock is supplied to the reactor in the presence of oxygen. The carbonaceous feedstock may or may not be in particulate form, and can have the same or different composition that the carbonaceous feedstock used for the catalytic gasification. The combustion process typically yields a resulting gas stream that at least comprises CO, H2 and CO2, and H20 if the combustion process is used to generate steam. The combustion gas stream, in combination with the hydrogen enriched gas stream, can serve as a gas stream that is introduced into the gasification reactor as the feed gas stream.
[0083] In embodiments where the feed gas stream is the product of a combustion reaction, the heat energy from the combustion reaction can be used as a heat source for the steam generation process, described above.
2. Catalytic gasification of carbonaceous feedstock [0084] A carbonaceous feedstock is reacted in a gasification reactor in the presence of the feed gas stream (including steam) and a gasification catalyst under suitable temperature and pressure to form a gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous products. Catalytic gasification, including suitable reactors and reaction conditions, is described above.
3. Sour shift treatment of product gas stream [0085] Catalytic gasification of the carbonaceous feedstock generates a gas stream that typically comprises CH4, CO2, H2, CO, H2S, NH3, unreacted steam, entrained fines, and other contaminants such as COS. As discussed above, this gas stream typically undergoes initial processing to remove the entrained fines and hydrolyze any COS, although some embodiments may omit one or both of these initial processing steps. When the crude gas stream undergoes such processing, the resulting gas stream at least comprises CH4, CO2, H2, CO, H2S, NH3, and steam.
[0086] A water gas shift reaction, or "sour gas shift," is used to convert carbon monoxide and water to carbon dioxide and hydrogen. The invention provides a process in which a gas stream is contacted with an aqueous medium (e.g., water or steam) under conditions suitable to convert a substantial portion of the carbon monoxide in the gas stream to carbon dioxide, and simultaneously generate hydrogen gas. In some embodiments, at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol%, or at least about 99 mol%, or substantially all of the carbon monoxide in the gas stream is converted to carbon dioxide.
[0087] The sour gas shift yields a carbon monoxide-depleted gas stream that at least comprises CH4, CO2, H25 and additional gases, such as, for example, H2S, NH3, and steam.
In some embodiments, the CO-depleted gas stream will comprise less than about 1000 ppm CO, or less than about 500 ppm CO, or less than about 250 ppm CO, or less than about 100 ppm CO, based on the amount of methane in the CO-depleted gas stream.
[0088] Methods and reactors for performing the sour gas shift reaction on a CO-containing gas stream are well known to those of skill in the art. Suitable reaction conditions and suitable reactors can vary depending on the amount of CO that must be depleted from the gas stream, and are discussed above.
4. Removal of CO2 and other gaseous by-products [0089] Following CO depletion, carbon dioxide and other gaseous by-products (e.g., hydrogen sulfide, ammonia, etc.) can be removed from the gas stream. Suitable methods for removal of these gases from the gas stream are described above. The resulting gas stream at least comprises hydrogen and methane. In typical embodiments, the resulting gas stream comprises at least about 90 mol%, or at least about 95 mol%, or at least about 99 mol%, methane and/or hydrogen. The relative proportions of methane and hydrogen can vary depending on a variety of factors, including the gasification conditions and the amount of CO depleted from the gas stream.
5. Separation of hydrogen and methane [0090] It is generally desirable to separate, at least partially, the methane and the hydrogen to yield a methane-enriched gas stream and a hydrogen-enriched gas stream. The desired degree of separation can vary depending on the proposed use of the methane-enriched and hydrogen-enriched gas streams. For some uses, for example, it can be desirable to have appreciable quantities of both gases present, although the gas stream may be enriched in one gas or the other. For other applications, however, it is desirable to have enriched gas streams that substantially comprise only a single gas (either methane or hydrogen).
[0091] Suitable methods for separation of methane and hydrogen are discussed above.
[0092] The separation step yields a methane-enriched gas stream and a hydrogen-enriched gas stream, as discussed above.
[0093] In some embodiments, the hydrogen-enriched gas stream and/or the methane-enriched gas stream can be recovered following separation. In such embodiments, the invention includes any suitable means of gas recovery known to those of skill in the art.
The recovery method and apparatus can vary depending on factors such as the means used to effect separation and the desired use of the enriched gas stream following separation. For example, in embodiments where the methane-enriched gas stream substantially comprises methane (e.g., is at least about 99% methane), the methane-enriched gas stream can be recovered by pressurizing the gas in a suitable pressurizing apparatus and introducing the pressurized methane into a network of natural gas pipelines.
[0094] Further process details can be had by reference to the previously incorporated patents and publications.
Pipeline Quality Natural Gas [0095] The invention provides processes that, in certain embodiments, can generate pipeline-quality natural gas from the catalytic gasification of a carbonaceous feedstock. A
"pipeline-quality natural gas" typically refers to a natural gas that is (1) within 5% of the heating value of pure methane (whose heating value is 1010 btu/ft3 under standard atmospheric conditions), and (2) free of water and toxic or corrosive contaminants. In some embodiments of the invention, the methane-enriched gas stream described in the above processes satisfies such requirements.
[0096] Pipeline-quality natural gas can contain gases other than methane, as long as the resulting gas mixture has a heating value that is within 5% of 1010 btu/ft3 and is neither toxic nor corrosive. Therefore, a methane-enriched gas stream can comprise gases whose heating value is less than that of methane and still qualify as a pipeline-quality natural gas, as long as the other gases' presence does not lower the gas stream's heating value below 950 btu/scf (dry basis). Therefore, a methane-enriched gas stream can comprise up to about 4 mol% hydrogen and still serve as a pipeline-quality natural gas. Carbon monoxide has a higher heating value than hydrogen. Thus, pipeline-quality natural gas could contain even higher percentages of CO without degrading the heating value of the gas stream. A
methane-enriched gas stream that is suitable for use as pipeline-quality natural gas preferably has less than about 1000 ppm CO.
Examples [0097] The following examples illustrate one or more particular embodiments of the invention. These examples are merely embodiments of the claimed invention, and are not intended to be limiting in any manner.
Example 1 ¨ Continuous process with sour shift various separation options [0098] Figure 1 illustrates one embodiment of a continuous process encompassed by the present invention. A quantity of feedstock can be prepared by wet grinding it into a fine particulate using a wet grinder. After grinding, the feedstock particulate should have a particle size ranging from about 45 [tm to about 2500 um. A portion of the feedstock particulate can be removed from the grinder and introduced to a catalyst loading unit (e.g., one or more slurry tanks), where gasification catalyst can be loaded onto the feedstock particulate. The loaded catalyst typically will comprise a mixture of catalyst recovered from a previous gasification process and raw make-up catalyst. After calatyst is loaded onto the feedstock particulate, the catalyst-loaded feedstock can be introduced into a gasification reactor (21). Another portion of the feedstock particulate can be removed from the grinder, blended with wet char recovered from a previous gasification process, and introduced into an oxy-blown gasifier (7).
[0099] The oxy-blown gasifier (7) combusts the feedstock/char fuel in the presence of oxygen, and the resulting thermal energy is used to generate steam that is introduced into the gasification reactor (21). Optionally, steam from the hydrolysis reactor and from the scrubbing unit can be introduced into the oxy-blown gasifier (7).
[00100] The gasification reactor (21) converts the catalyzed feedstock into a plurality of gaseous products comprising at least CH4, CO2, H25 CO, H2S5 NH3, steam, and COS. The COS can be removed through a hydrolysis process prior to or after heat recovery. Then the gas stream can be depleted of CO by substantially converting the CO to CO2 in a gas-water shift process carried out in a shift reactor (22). Then, ammonia can be removed by scrubbing the gas in a multi-unit scrubber apparatus (shown as part of a single gas purification unit (23)). Then, CO2 and H2S can be substantially removed from the gas stream in an acid gas removal process involving the exposure of the gas stream to a solvent in a solvent treatment vessel (shown as part of a single gas purification unit (23)). At this point, the gas stream should substantially comprise methane and hydrogen.
[00101] Methane and hydrogen gases can be substantially separated from each other by several available processes. In a first option, the gas mixture can be introduced to a membrane separator (24), which effects separation of the gases into a gas stream that substantially comprises methane and another gas stream that substantially comprises hydrogen. In a second option, the gas mixture can be introduced to a methane hydrate separator (25), which effects separation of the gases into a gas stream that substantially comprises methane and another gas stream that substantially comprises hydrogen. In a third option, the gas mixture can be introduced to a cryogenic separator (26), which effects separation of the gases into a gas stream that substantially comprises methane and another gas stream that substantially comprises hydrogen. In a fourth option, the methane-enriched gas stream can be introduced into a trim methanation reactor, such as described above.
Each of these separation methods is described in greater detail above and in the incorporated references.
[00102] The methane gas stream (15) can be recovered and used for pipeline grade natural gas. The hydrogen gas stream can have at least several uses, but is typically recycled back to the gasifier (21).
100101 Moreover, the present invention can be practiced in conjunction with the subject matter of the following US Patent Publications: US2009/0165383A1, IJS2009/0166588A1, US2009/01665379A1, US2009/0170968A1, US2009/0165380A1, 1JS2009/0165381A1, US2009/0165361A 1 , US2009/0165382A1, US2009/0169449A1, US2009/0169448A1, US2009/0165376A1 and US2009/0165384A1.
[0011] Further, the present invention can be practiced in conjunction with the subject matter of the following US Patent Publications: US2009/0217582A1, US2009/0217584A1, US2009/0217585A1, US2009/0260287A1, US2009/0220406A1, US2009/0217590A1, US2009/0217586A1, US2009/0217588A1, US2009/0218424A1, US2009/0217589A1, US2009/0217575A1, US2009/0229182A1, and US2009/0217587A1.
[0012] The present invention can also be practiced in conjunction with the subject matter of US Patent Publication No. U52009/0259080A1.
100141 Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
[0015] Except where expressly noted, trademarks are shown in upper case.
[0016] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
[0017] Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.
[0018] When an amount, concentration, or other value or parameter is given as a range, or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper and lower range limits, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present invention be limited to the specific values recited when defining a range.
[0019] When the term "about" is used in describing a value or an end-point of a range, the invention should be understood to include the specific value or end-point referred to.
[0020] As used herein, the terms "comprises," "comprising," "includes,"
"including,"
"has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following:
A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[0021] The use of "a" or "an" to describe the various elements and components herein is merely for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
[0022] The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting.
Gasification Methods [0023] The methods of the present invention are particularly useful in integrated gasification processes for converting carbonaceous feedstocks, such as petroleum coke, liquid petroleum residue, asphaltenes, biomass and/or coal to combustible gases, such as methane.
[0024] The gasification reactors for such processes are typically operated at moderately high pressures and temperature, requiring introduction of a carbonaceous material (i.e., a feedstock) to the reaction zone of the gasification reactor while maintaining the required temperature, pressure, and flow rate of the feedstock. Those skilled in the art are familiar with feed systems for providing feedstocks to high pressure and/or temperature environments, including, star feeders, screw feeders, rotary pistons, and lock-hoppers. It should be understood that the feed system can include two or more pressure-balanced elements, such as lock hoppers, which would be used alternately.
[0025] The catalyzed feedstock is provided to the catalytic gasifier from a feedstock preparation operation, and generally comprises a particulate composition of a crushed carbonaceous material and a gasification catalyst, as discussed below. In some instances, the catalyzed feedstock can be prepared at pressures conditions above the operating pressure of catalytic gasifier. Hence, the catalyzed feedstock can be directly passed into the catalytic gasifier without further pressurization.
[0026] Any of several catalytic gasifiers can be utilized. Suitable gasifiers include counter-current fixed bed, co-current fixed bed, fluidized bed, entrained flow, and moving bed reactors. A catalytic gasifier for gasifying liquid feeds, such as liquid petroleum residues, is disclosed in previously mentioned US6955695.
[0027] The pressure in the catalytic gasifier typically can be from about 10 to about 100 atm (from about 150 to about 1500 psig). The gasification reactor temperature can be maintained around at least about 450 C, or at least about 600 C, or at least about 900 C, or at least about 750 C, or about 600 C to about 700 C; and at pressures of at least about 50 psig, or at least about 200 psig, or at least about 400 psig, to about 1000 psig, or to about 700 psig, or to about 600 psig.
[0028] The gas utilized in the catalytic gasifier for pressurization and reactions of the particulate composition comprises steam, and optionally, oxygen or air, and is supplied, as necessary, to the reactor according to methods known to those skilled in the art.
[0029] For example, steam can be supplied to the catalytic gasifier from any of the steam boilers known to those skilled in the art can supply steam to the reactor.
Such boilers can be powered, for example, through the use of any carbonaceous material such as powdered coal, biomass etc., and including but not limited to rejected carbonaceous materials from the particulate composition preparation operation (e.g., fines, supra). Steam can also be supplied from a second gasification reactor coupled to a combustion turbine where the exhaust from the reactor is thermally exchanged to a water source and produce steam.
Alternatively, the steam may be provided to the gasification reactor as described previously mentioned U.S. Patent Publiction Nos. 2009/0165376A1, US2009/0217584A1 and US2009/0217585A1.
[0030] Recycled steam from other process operations can also be used for supplementing steam to the catalytic gasifier. For example in the preparation of the catalyzed feedstock, when slurried particulate composition are dried with a fluid bed slurry drier, as discussed below, then the steam generated can be fed to the catalytic gasification reactor.
[0031] The small amount of heat input that may be required for the catalytic gasifier can be provided by superheating a gas mixture of steam and recycle gas feeding the gasification reactor by any method known to one skilled in the art. In one method, compressed recycle gas of CO and H2 can be mixed with steam and the resulting steam/recycle gas mixture can be further superheated by heat exchange with the catalytic gasifier effluent followed by superheating in a recycle gas furnace.
[0032] A methane reformer can be optionally included in the process to supplement the recycle CO and H2 stream and the exhaust from the slurry gasifier to ensure that enough recycle gas is supplied to the reactor so that the net heat of reaction is as close to neutral as possible (only slightly exothermic or endothermic), in other words, that the catalytic gasifier is run under substantially thermally neutral conditions. In such instances, methane can be supplied for the reformer from the methane product, as described below.
[0033] Reaction of the catalyzed feedstock in the catalytic gasifier, under the described conditions, provides a crude product gas and a char from the catalytic gasification reactor.
[0034] The char produced in the catalytic gasifier processes is typically removed from the catalytic gasifier for sampling, purging, and/or catalyst recovery in a continuous or batch-wise manner. Methods for removing char are well known to those skilled in the art.
One such method taught by EP-A-0102828, for example, can be employed. The char can be periodically withdrawn from the catalytic gasification reactor through a lock hopper system, although other methods are known to those skilled in the art.
[0035] Often, the char from the catalytic gasifier is directed to a catalyst recovery and recycle process. Processes have been developed to recover alkali metal from the solid purge in order to reduce raw material costs and to minimize environmental impact of a catalytic gasification process. For example, the char can be quenched with recycle gas and water and directed to a catalyst recycling operation for extraction and reuse of the alkali metal catalyst. Particularly useful recovery and recycling processes are described in US4459138, as well as previously mentioned US4057512, US2007/0277437A1, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/0169448A1.
' 76909-428 Further process details are disclosed therein.
[0036] Upon completion of catalyst recovery, both the char, substantially free of the gasification catalysts and the recovered catalyst (as a solution or solid) can be directed to the feedstock preparation operation comprising a catalyzed feedstock preparation process and a slurry feedstock preparation process.
Carbonaceous Feedstock [0037] The term "carbonaceous feedstock" as used herein includes a carbon source, typically coal, petroleum coke, asphaltene and/or liquid petroleum residue, but may broadly include any source of carbon suitable for gasification, including biomass.
[0038] The term "petroleum coke" as used herein includes both (i) the solid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues - "resid petcoke") and (ii) the solid thermal decomposition product of processing tar sands (bituminous sands or oil sands - "tar sands petcoke"). Such carbonization products include, for example, green, calcined, needle and fluidized bed petroleum coke.
[0039] Resid petcoke can be derived from a crude oil, for example, by coking processes used for upgrading heavy-gravity residual crude oil, which petroleum coke contains ash as a minor component, typically about 1.0 wt% or less, and more typically about 0.5 wt% of less, based on the weight of the coke. Typically, the ash in such lower-ash cokes predominantly apprises metals such as nickel and vanadium.
[0040] Tar sands petcoke can be derived from an oil sand, for example, by coking processes used for upgrading oil sand. Tar sands petcoke contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the tar sands petcoke. Typically, the ash in such higher-ash cokes predominantly comprises materials such as compounds of silicon and/or aluminum.
[0041] The petroleum coke can comprise at least. about 70 wt% carbon, at least about 80 wt% carbon, or at least about 90 wt% carbon, based on the total weight of the petroleum coke. Typically, the petroleum coke comprises less than about 20 wt% percent inorganic compounds, based on the weight of the petroleum coke.
9=
[0042] The term "asphaltene" as used herein is an aromatic carbonaceous solid at room temperature, and can be derived, from example, from the processing of crude oil and crude oil tar sands.
[0043] The term "liquid petroleum residue" as used herein includes both (i) the liquid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues ¨ "resid liquid petroleum residue") and (ii) the liquid thermal decomposition product of processing tar sands (bituminous sands or oil sands ¨
"tar sands liquid petroleum residue"). The liquid petroleum residue is substantially non-solid at room temperature; for example, it can take the form of a thick fluid or a sludge.
[0044] Resid liquid petroleum residue can also be derived from a crude oil, for example, by processes used for upgrading heavy-gravity crude oil distillation residue.
Such liquid petroleum residue contains ash as a minor component, typically about 1.0 wt%
or less, and more typically about 0.5 wt% of less, based on the weight of the residue.
Typically, the ash in such lower-ash residues predominantly comprises metals such as nickel and vanadium.
[0045] Tar sands liquid petroleum residue can be derived from an oil sand, for example, by processes used for upgrading oil sand. Tar sands liquid petroleum residue contains ash as a minor component, typically in the range of about 2 wt% to about 12 wt%, and more typically in the range of about 4 wt% to about 12 wt%, based on the overall weight of the residue. Typically, the ash in such higher-ash residues predominantly comprises materials such as compounds of silicon and/or aluminum.
[0046] The term "coal" as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof. In certain embodiments, the coal has a carbon content of less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% by weight, based on the total coal weight. In other embodiments, the coal has a carbon content ranging up to about 85%, or up to about 80%, or up to about 75% by weight, based on total coal weight. Examples of useful coals include, but are not limited to, Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon, and Powder River Basin (PRB) coals. Anthracite, bituminous coal, sub-bituminous coal, and lignite coal may contain about 10 wt%, from about 5 to about 7 wt%, from about 4 to about 8 wt %, and from about 9 to about 11 wt%, ash by total weight of the coal on a dry basis, respectively. However, the ash content of any particular coal source will depend on the rank and source of the coal, as is familiar to those skilled in the art. See, e.g., Coal Data: A
Reference, Energy Information Administration, Office of Coal, Nuclear, Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), February 1995.
[0047] The term "ash" as used herein includes inorganic compounds that occur within the carbon source. The ash typically includes compounds of silicon, aluminum, calcium, iron, vanadium, sulfur, and the like. Such compounds include inorganic oxides, such as silica, alumina, ferric oxide, etc., but may also include a variety of minerals containing one or more of silicon, aluminum, calcium, iron, and vanadium. The term "ash" may be used to refer to such compounds present in the carbon source prior to gasification, and may also be used to refer to such compounds present in the char after gasification.
Catalyst-Loaded Carbonaceous Feedstock [0048] The carbonaceous composition is generally loaded with an amount of an alkali metal compound to promote the steam gasification to methane. Typically, the quantity of the alkali metal compound in the composition is sufficient to provide a ratio of alkali metal atoms to carbon atoms ranging from about 0.01, or from about 0.02, or from about 0.03, or from about 0.04, to about 0.06, to about 0.07, or to about 0.08, or to about 0.1. Further, the alkali metal is typically loaded onto a carbon source to achieve an alkali metal content of from about 3 to about 10 times more than the combined ash content of the carbonaceous material (e.g., coal and/or petroleum coke), on a mass basis.
[0049] Alkali metal compounds suitable for use as a gasification catalyst include compounds selected from the group consisting of alkali metal carbonates, bicarbonates, formates, oxalates, amides, hydroxides, acetates, halides, nitrates, sulfides, and polysulfides.
For example, the catalyst can comprise one or more of Na2CO3, K2CO3, Rb2CO3, Li2CO3, Cs2CO3, NaOH, KOH, RbOH, or Cs0H, and particularly, potassium carbonate and/or potassium hydroxide.
[0050] Any methods known to those skilled in the art can be used to associate one or more gasification catalysts with the carbonaceous composition. Such methods include, but are not limited to, admixing with a solid catalyst source and impregnating the catalyst onto the carbonaceous solid. Several impregnation methods known to those skilled in the art can be employed to incorporate the gasification catalysts. These methods include, but are not limited to, incipient wetness impregnation, evaporative impregnation, vacuum impregnation, dip impregnation, and combinations of these methods.
Gasification catalysts can be impregnated into the carbonaceous solids by slurrying with a solution (e.g., aqueous) of the catalyst.
[0051] That portion of the particulate carbonaceous feedstock of a particle size suitable for use in the gasifying reactor can then be further processed, for example, to impregnate one or more catalysts and/or co-catalysts by methods known in the art, for example, as disclosed in previously mentioned US4069304, US4092125, US4468231, US4551155 and US5435940; and previously mentioned US Patent Publication Nos.
US2009/0090055A1, US2009/0090056A1, US2009/0166588A1, US2009/0165379A1, US2009/0165380A1, US2009/0165384A1, US2009/0165379A1 and US2009/0170968A1.
[0052] One particular method suitable for combining the coal particulate with a gasification catalyst to provide a catalyzed carbonaceous feedstock where the catalyst has been associated with the coal particulate via ion exchange is described in previously mentioned US2009/0048476A1. The catalyst loading by ion exchange mechanism is maximized (based on adsorption isotherms specifically developed for the coal), and the additional catalyst retained on wet including those inside the pores is controlled so that the total catalyst target value is obtained in a controlled manner. Such loading provides a catalyzed coal particulate as a wet cake. The catalyst loaded and dewatered wet coal cake typically contains, for example, about 50% moisture. The total amount of catalyst loaded is controlled by controlling the concentration of catalyst components in the solution, as well as the contact time, temperature and method, as can be readily determined by those of ordinary skill in the relevant art based on the characteristics of the starting coal.
[0053] The catalyzed feedstock can be stored for future use or transferred to a feed operation for introduction into the gasification reactor. The catalyzed feedstock can be conveyed to storage or feed operations according to any methods known to those skilled in the art, for example, a screw conveyer or pneumatic transport.
Steam Generation [0054] The steam supplied to the gasification reactor can originate from a variety of sources, including commercial gasification reactors, oxy-fuel combustors, and boilers. The gasification or combustion reaction of a carbonaceous feedstock generates large amounts of heat energy. Advantageously, this heat energy can be used to contact any type of heat exchanger which is also in contact with a water source, thereby generating steam. For example, any of the boilers known to those skilled in the art can supply steam to the reactor.
While any water source can be used to generate steam, the water commonly used in known boiler systems is purified and deionized (about 0.3-1.0 microsiemens/cm) so that corrosive processes are slowed. Such boilers can be powered, for example, through the combustion of any carbonaceous material, including pulverized/powdered coal, biomass, and rejected carbonaceous materials from the feedstock preparation operation (e.g., fines, supra). The thermal energy from the burning the carbonaceous material heats the water in the boiler, which eventually converts into steam (at about 700 F and 3,200 psi). The steam is routed from the boiler into heated tubes, which are typically located in the furnace at or near the exit conduit carrying the combustion gases. The steam can be routed via heated conduits to the gasification reactor, it can be used to dry a carbonaceous feedstock, or it can be prepared and routed to a steam turbine for generation of electricity. In order to avoid excessive cooling of the steam during transport, the heated conduits for carrying steam can also be superheated (e.g., via contact with a heat exchanger) prior to delivery of the steam to its endpoint. Suitable methods of steam generation are described in previously mentioned US
Patent Publication Nos. US2009/0217584A1 and US2009/0217585A1.
[0055] Steam can also be supplied from a second gasification reactor coupled with a combustion turbine, the exhaust of which contacts a heat exchanger in contact with a water source, which can include a boiler system as described above, to produce steam.
[0056] Recycled steam from other process operations can also be used for supplying steam to the reactor. For example, when a slurried carbonaceous feedstock is dried with a fluid bed slurry drier, as discussed herein, the steam generated through vaporization can be fed to the gasification reactor. Similarly, steam can be generated directly from a slurry gasifier which produces steam and synthesis gas from an aqueous carbonaceous feed slurry, such as described in previously mentioned US Patent Publication No.
US2009/0165376A1.
At least a portion of the steam can also be used to drive a steam turbine that generates electricity.
Treatment of Crude Product Gas [0057] Crude product gas effluent leaving the catalytic gasifier can pass through a portion of the reactor which serves as a disengagement zone where particles too heavy to be entrained by the gas leaving the reactor (i.e., fines) are returned to the fluidized bed. The disengagement zone can include one or more internal cyclone separators or similar devices for removing fines and particulates from the gas. The gas effluent passing through the disengagement zone and leaving the catalytic gasifier generally contains CH4, CO2, H2 and CO, HS, NH3, unreacted steam, entrained fines, and other contaminants such as COS.
[0058] The gas stream from which the fines have been removed can then be passed through a heat exchanger to cool the gas and the recovered heat can be used to preheat recycle gas and generate high pressure steam. Residual entrained fines can also be removed by any suitable means such as external cyclone separators, optionally followed by Venturi scrubbers. The recovered fines can be processed to recover alkali metal catalyst then passed to the slurry feedstock preparation process or returned to the catalytic gasification reactor, or directly recycled back to feedstock preparation as described in previously mentioned US
Patent Publication No. US2009/0217589A1.
[0059] The gas stream from which the fines have been removed is fed to a gas purification operation optionally comprising COS hydrolysis reactors for COS
removal (sour process) and further cooled in a heat exchanger to recover residual heat. Methods for COS hydrolysis are known to those skilled in the art, for example, see US4100256.
[0060] The gas stream is then subjected to a water-gas shift reaction in the presence of steam to convert the CO to CO2 and to increase the fraction of H2. This sour shift process is described in detail, for example, in US7074373. The process involves adding water, or using water contained in the gas, and reacting the resulting water-gas mixture adiabatically over a steam reforming catalyst. Typical steam reforming catalysts include one or more Group VIII metals on a heat-resistant support.
[0061] The invention provides a process in which a gas stream is contacted with an aqueous medium (e.g., water) under conditions suitable to convert a substantial portion of the carbon dioxide in the gas stream to carbon dioxide, and simultaneously generate hydrogen gas. In some embodiments, at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol%, or at least about 99 mol% of the carbon monoxide in the gas stream is converted to carbon dioxide.
[0062] Methods and reactors for performing the sour gas shift reaction on a CO-containing gas stream are well known to those of skill in the art. Suitable reaction conditions and suitable reactors can vary depending on the amount of CO that must be depleted from the gas stream. In some embodiments, the sour gas shift can be performed in a single stage within a temperature range from about 100 C, or from about 150 C, or from about 200 C, to about 250 C, or to about 300 C, or to about 350 C. In these embodiments, the shift reaction can be catalyzed by any suitable catalyst known to those of skill in the art.
Such catalysts include, but are not limited to, Fe203-based catalysts, such as Fe203-Cr203 catalysts, and other transition metal-based and transition metal oxide-based catalysts. In other embodiments, the sour gas shift can be performed in multiple stages. In one particular embodiment, the sour gas shift is performed in two stages. This two-stage process uses a high-temperature sequence followed by a low-temperature sequence. The gas temperature for the high-temperature shift reaction ranges from about 350 C to about 1050 C. Typical high-temperature catalysts include, but are not limited to, iron oxide optionally combined with lesser amounts of chromium oxide. The gas temperature for the low-temperature shift ranges from about 150 C to about 300 C, or from about 200 C to about 250 C.
Low-temperature shift catalysts include, but are not limited to, copper oxides that may be supported on zinc oxide or alumina.
[0063] Steam shifting is often carried out with heat exchangers and steam generators to permit the efficient use of heat energy. Shift reactors employing these features are well known to those of skill in the art. An example of a suitable shift reactor is illustrated in previously mentioned US7074373, although other designs known to those of skill in the art are also effective.
[0064] Following the sour gas shift procedure, the gas stream generally contains CH4, CO2, H2, H2S, NH3, and steam. This CO-depleted gas stream can be further treated in a water scrubber for recovery of ammonia, yielding a CO-depleted scrubbed gas that comprises at least 112S, CO2, Hz, and CH4.
[0065] Scrubber water and sour process condensate can be processed to strip and recover H2S, CO2 and NH3; such processes are well known to those skilled in the art.
NH3 can typically be recovered as an aqueous solution (e.g., 20 wt%).
[0066] A subsequent acid gas removal process can be used to remove H2S and CO2 from the scrubbed gas stream by a physical absorption method involving solvent treatment of the gas to give a cleaned gas stream. Such processes involve contacting the scrubbed gas with a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like. One method can involve the use of SELEXOL
(UOP
LLC, Des Plaines, IL USA) or RECTISOL (Lurgi AG, Frankfurt am Main, Germany) solvent having two trains; each train consisting of an H2S absorber and a CO2 absorber.
The spent solvent containing H2S, CO2 and other contaminants can be regenerated by any method known to those skilled in the art, including contacting the spent solvent with steam or other stripping gas to remove the contaminants or by passing the spent solvent through stripper columns. Recovered acid gases can be sent for sulfur recovery processing; for example, any recovered H2S from the acid gas removal and sour water stripping can be converted to elemental sulfur by any method known to those skilled in the art, including the Claus process. Sulfur can be recovered as a molten liquid. Stripped water can be directed for recycled use in preparation of the catalyzed feedstock. One method for removing acid gases from the scrubbed gas stream is described in previously mentioned US
Patent Publication No. US2009/0220406A1.
[0067] Advantageously, CO2 generated in the process, whether in the steam generation or catalytic gasification or both, can be recovered for subsequent use or sequestration, enabling a greatly decreased carbon footprint (as compared to direct combustion of the feedstock) as a result. Processes for reducing a carbon footprint are described in previously mentioned US Patent Publication Nos. US2009/0217584A1 and US2009/0217585A1.
[0068] The resulting cleaned gas stream exiting the gas purification operation contains mostly CH4 and H2 and, typically, small amounts of CO2 and H20.
[0069] In accordance with the present invention, this cleaned gas stream can be further processed to provide at least a partial separation of methane and hydrogen.
Various methods for effecting this separation are known to those of skill in the art.
Such methods include cryogenic separation and membrane-based separation. In addition, the separation can be effected through the methods involving the formation of methane hydrates, as illustrated in previously mentioned US Patent Publication No.
US2009/0260287A1. In some embodiments, combinations of the separation procedures can be used.
Reference can also be had to previously mentioned US Patent Publication No.
US2009/0259080A1.
[0070] The separation step yields a methane-enriched gas stream and a hydrogen-enriched gas stream. The methane-enriched gas stream at least comprises methane. In some embodiments, the methane-enriched gas stream should have a heating value of at least 950 btu/scf (dry basis). For example, in some embodiments, the methane-enriched gas stream comprises at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol% methane. In some embodiments, however, the methane-enriched gas stream at least comprises both methane and carbon monoxide, and optionally a minor amount of hydrogen (generally about 4 mol% or less). In some such embodiments, the methane-enriched gas comprises at least about 1000 ppm carbon monoxide. In other embodiments, the methane-enriched gas stream is substantially free of carbon monoxide, having, for example, less than about 1000 ppm carbon monoxide. In some embodiments, the hydrogen-enriched gas stream substantially comprises hydrogen.
[0071] In embodiments where the methane-enriched gas stream comprises 1000 ppm or more carbon monoxide and where the heating value of the methane-enriched gas stream is less than 950 btu/scf (dry basis), the methane in the methane-enriched gas stream and the carbon monoxide in the methane-enriched gas stream can be at least partially separated from each other. Various methods for effecting separation of methane and carbon monoxide are known to those of skill in the art. Such methods include, but are not limited to, cryogenic separation and membrane-based separation. This partial separation of methane and carbon monoxide yields at least a second methane-enriched gas stream and a carbon monoxide-enriched gas stream. The methane-enriched gas stream comprises at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol% methane.
Moreover, in typical embodiments, the methane-enriched gas stream has a heating value of at least 950 btu/scf (dry basis). The carbon monoxide-enriched gas stream comprises at least about 50 mol%, or at least about 65 mol%, or at least about 80 mol% carbon monoxide.
[0072] In some embodiments, the methane-enriched gas stream, if it contains appreciable amounts of CO, can be further enriched in methane by performing trim methanation to reduce the CO content. One may carry out trim methanation using any suitable method and apparatus known to those of skill in the art, including, for example, the method and apparatus disclosed in U54235044.
[0073] In embodiments where the separation yields a methane-enriched gas stream that substantially comprises methane, the methane stream can be recovered and used as a high-quality energy source. For example, the methane can be compressed and introduced into the existing natural gas pipeline system. Or, a portion of the methane product can also be used as plant fuel for a gas turbine.
[0074] In embodiments where the separation yields a hydrogen-enriched gas stream that substantially comprises hydrogen, the hydrogen stream can be recovered and used as an energy source and/or as a reactant. For example, the hydrogen can be used as an energy source for hydrogen-based fuel cells or for a subsequent catalytic gasification process. In another example, hydrogen can be used as a fuel for a steam generation process, such as described in previously mentioned US Patent Publication Nos. US2009/0217584A1 and US2009/0217585A1.
[0075] In some embodiments of the invention, the hydrogen is recycled back to the catalytic gasifier, directly and/or via another unit operation such as discussed below.
Continuous Gasification Process Employing Sour Shift [0076] As described above, the invention provides for a continuous catalytic gasification process wherein the use of the sour shift process to convert CO and H20 to CO2 and HZ.
1. Introduction of a carbonaceous feedstock to a gasification reactor [0077] The processes of the invention require the supplying of a carbonaceous feedstock and a gas feed (comprising steam, carbon monoxide and hydrogen) to a gasification reactor.
[0078] Suitable gasification reactors and carbonaceous feedstocks are described above.
In typical embodiments, the carbonaceous feedstock is provided in particulate form, although this need not be the case in all embodiments. In typical embodiments, the carbonaceous feedstock is loaded with, or at least mixed with, a suitable gasification catalyst. Suitable catalysts are described above. Typical processes at least include potassium carbonate and/or potassium hydroxide.
[0079] In some embodiments, steam may also be introduced into the gasification reactor in the same step as the introduction of the carbonaceous feedstock. The steam can be generated by any suitable method for the generation of steam known to those of skill in the art. Suitable methods of steam generation are described above.
[0080] In some embodiments, a stream of feed gases (in addition to the steam) can also be introduced into the gasification reactor within the same step as the introduction of the carbonaceous feedstock. This feed gas stream at least comprises hydrogen and carbon monoxide, but can also include carbon dioxide and water vapor. The feed gas stream can be generated in a variety of ways.
[0081] In some embodiments, the feed gas stream comprises the product of reforming methane in a methane reformer. In a particular embodiment, the input gases for the methane reformation are a portion of the methane product of catalytic gasification of a carbonaceous feedstock. The methane reacts in the methane reformer to generate a gas stream that at least comprises carbon monoxide and hydrogen gas. This gas stream comprising CO and H2 can serve as a recycle gas stream (combined with the hydrogen-enriched gas stream) that is introduced (i.e., recycled) into the gasification reactor as the product gas stream.
[0082] In some embodiments, the feed gas stream is the product of a combustion reaction. In a particular embodiment, the combustion reaction occurs in a reactor (e.g., an oxy-blown gasifier or a combustion reactor). A carbonaceous feedstock is supplied to the reactor in the presence of oxygen. The carbonaceous feedstock may or may not be in particulate form, and can have the same or different composition that the carbonaceous feedstock used for the catalytic gasification. The combustion process typically yields a resulting gas stream that at least comprises CO, H2 and CO2, and H20 if the combustion process is used to generate steam. The combustion gas stream, in combination with the hydrogen enriched gas stream, can serve as a gas stream that is introduced into the gasification reactor as the feed gas stream.
[0083] In embodiments where the feed gas stream is the product of a combustion reaction, the heat energy from the combustion reaction can be used as a heat source for the steam generation process, described above.
2. Catalytic gasification of carbonaceous feedstock [0084] A carbonaceous feedstock is reacted in a gasification reactor in the presence of the feed gas stream (including steam) and a gasification catalyst under suitable temperature and pressure to form a gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous products. Catalytic gasification, including suitable reactors and reaction conditions, is described above.
3. Sour shift treatment of product gas stream [0085] Catalytic gasification of the carbonaceous feedstock generates a gas stream that typically comprises CH4, CO2, H2, CO, H2S, NH3, unreacted steam, entrained fines, and other contaminants such as COS. As discussed above, this gas stream typically undergoes initial processing to remove the entrained fines and hydrolyze any COS, although some embodiments may omit one or both of these initial processing steps. When the crude gas stream undergoes such processing, the resulting gas stream at least comprises CH4, CO2, H2, CO, H2S, NH3, and steam.
[0086] A water gas shift reaction, or "sour gas shift," is used to convert carbon monoxide and water to carbon dioxide and hydrogen. The invention provides a process in which a gas stream is contacted with an aqueous medium (e.g., water or steam) under conditions suitable to convert a substantial portion of the carbon monoxide in the gas stream to carbon dioxide, and simultaneously generate hydrogen gas. In some embodiments, at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol%, or at least about 99 mol%, or substantially all of the carbon monoxide in the gas stream is converted to carbon dioxide.
[0087] The sour gas shift yields a carbon monoxide-depleted gas stream that at least comprises CH4, CO2, H25 and additional gases, such as, for example, H2S, NH3, and steam.
In some embodiments, the CO-depleted gas stream will comprise less than about 1000 ppm CO, or less than about 500 ppm CO, or less than about 250 ppm CO, or less than about 100 ppm CO, based on the amount of methane in the CO-depleted gas stream.
[0088] Methods and reactors for performing the sour gas shift reaction on a CO-containing gas stream are well known to those of skill in the art. Suitable reaction conditions and suitable reactors can vary depending on the amount of CO that must be depleted from the gas stream, and are discussed above.
4. Removal of CO2 and other gaseous by-products [0089] Following CO depletion, carbon dioxide and other gaseous by-products (e.g., hydrogen sulfide, ammonia, etc.) can be removed from the gas stream. Suitable methods for removal of these gases from the gas stream are described above. The resulting gas stream at least comprises hydrogen and methane. In typical embodiments, the resulting gas stream comprises at least about 90 mol%, or at least about 95 mol%, or at least about 99 mol%, methane and/or hydrogen. The relative proportions of methane and hydrogen can vary depending on a variety of factors, including the gasification conditions and the amount of CO depleted from the gas stream.
5. Separation of hydrogen and methane [0090] It is generally desirable to separate, at least partially, the methane and the hydrogen to yield a methane-enriched gas stream and a hydrogen-enriched gas stream. The desired degree of separation can vary depending on the proposed use of the methane-enriched and hydrogen-enriched gas streams. For some uses, for example, it can be desirable to have appreciable quantities of both gases present, although the gas stream may be enriched in one gas or the other. For other applications, however, it is desirable to have enriched gas streams that substantially comprise only a single gas (either methane or hydrogen).
[0091] Suitable methods for separation of methane and hydrogen are discussed above.
[0092] The separation step yields a methane-enriched gas stream and a hydrogen-enriched gas stream, as discussed above.
[0093] In some embodiments, the hydrogen-enriched gas stream and/or the methane-enriched gas stream can be recovered following separation. In such embodiments, the invention includes any suitable means of gas recovery known to those of skill in the art.
The recovery method and apparatus can vary depending on factors such as the means used to effect separation and the desired use of the enriched gas stream following separation. For example, in embodiments where the methane-enriched gas stream substantially comprises methane (e.g., is at least about 99% methane), the methane-enriched gas stream can be recovered by pressurizing the gas in a suitable pressurizing apparatus and introducing the pressurized methane into a network of natural gas pipelines.
[0094] Further process details can be had by reference to the previously incorporated patents and publications.
Pipeline Quality Natural Gas [0095] The invention provides processes that, in certain embodiments, can generate pipeline-quality natural gas from the catalytic gasification of a carbonaceous feedstock. A
"pipeline-quality natural gas" typically refers to a natural gas that is (1) within 5% of the heating value of pure methane (whose heating value is 1010 btu/ft3 under standard atmospheric conditions), and (2) free of water and toxic or corrosive contaminants. In some embodiments of the invention, the methane-enriched gas stream described in the above processes satisfies such requirements.
[0096] Pipeline-quality natural gas can contain gases other than methane, as long as the resulting gas mixture has a heating value that is within 5% of 1010 btu/ft3 and is neither toxic nor corrosive. Therefore, a methane-enriched gas stream can comprise gases whose heating value is less than that of methane and still qualify as a pipeline-quality natural gas, as long as the other gases' presence does not lower the gas stream's heating value below 950 btu/scf (dry basis). Therefore, a methane-enriched gas stream can comprise up to about 4 mol% hydrogen and still serve as a pipeline-quality natural gas. Carbon monoxide has a higher heating value than hydrogen. Thus, pipeline-quality natural gas could contain even higher percentages of CO without degrading the heating value of the gas stream. A
methane-enriched gas stream that is suitable for use as pipeline-quality natural gas preferably has less than about 1000 ppm CO.
Examples [0097] The following examples illustrate one or more particular embodiments of the invention. These examples are merely embodiments of the claimed invention, and are not intended to be limiting in any manner.
Example 1 ¨ Continuous process with sour shift various separation options [0098] Figure 1 illustrates one embodiment of a continuous process encompassed by the present invention. A quantity of feedstock can be prepared by wet grinding it into a fine particulate using a wet grinder. After grinding, the feedstock particulate should have a particle size ranging from about 45 [tm to about 2500 um. A portion of the feedstock particulate can be removed from the grinder and introduced to a catalyst loading unit (e.g., one or more slurry tanks), where gasification catalyst can be loaded onto the feedstock particulate. The loaded catalyst typically will comprise a mixture of catalyst recovered from a previous gasification process and raw make-up catalyst. After calatyst is loaded onto the feedstock particulate, the catalyst-loaded feedstock can be introduced into a gasification reactor (21). Another portion of the feedstock particulate can be removed from the grinder, blended with wet char recovered from a previous gasification process, and introduced into an oxy-blown gasifier (7).
[0099] The oxy-blown gasifier (7) combusts the feedstock/char fuel in the presence of oxygen, and the resulting thermal energy is used to generate steam that is introduced into the gasification reactor (21). Optionally, steam from the hydrolysis reactor and from the scrubbing unit can be introduced into the oxy-blown gasifier (7).
[00100] The gasification reactor (21) converts the catalyzed feedstock into a plurality of gaseous products comprising at least CH4, CO2, H25 CO, H2S5 NH3, steam, and COS. The COS can be removed through a hydrolysis process prior to or after heat recovery. Then the gas stream can be depleted of CO by substantially converting the CO to CO2 in a gas-water shift process carried out in a shift reactor (22). Then, ammonia can be removed by scrubbing the gas in a multi-unit scrubber apparatus (shown as part of a single gas purification unit (23)). Then, CO2 and H2S can be substantially removed from the gas stream in an acid gas removal process involving the exposure of the gas stream to a solvent in a solvent treatment vessel (shown as part of a single gas purification unit (23)). At this point, the gas stream should substantially comprise methane and hydrogen.
[00101] Methane and hydrogen gases can be substantially separated from each other by several available processes. In a first option, the gas mixture can be introduced to a membrane separator (24), which effects separation of the gases into a gas stream that substantially comprises methane and another gas stream that substantially comprises hydrogen. In a second option, the gas mixture can be introduced to a methane hydrate separator (25), which effects separation of the gases into a gas stream that substantially comprises methane and another gas stream that substantially comprises hydrogen. In a third option, the gas mixture can be introduced to a cryogenic separator (26), which effects separation of the gases into a gas stream that substantially comprises methane and another gas stream that substantially comprises hydrogen. In a fourth option, the methane-enriched gas stream can be introduced into a trim methanation reactor, such as described above.
Each of these separation methods is described in greater detail above and in the incorporated references.
[00102] The methane gas stream (15) can be recovered and used for pipeline grade natural gas. The hydrogen gas stream can have at least several uses, but is typically recycled back to the gasifier (21).
Claims (10)
1. A process for converting a carbonaceous feedstock into a plurality of gaseous products contained in a gas stream, the gas stream comprising hydrogen, methane and other gaseous products, and for separating hydrogen and methane from the other gaseous products in the gas stream, wherein the process comprises the steps of:
(a) supplying a carbonaceous feedstock to a gasification reactor;
(b) reacting the carbonaceous feedstock in the gasification reactor in the presence of steam, carbon monoxide, hydrogen and a gasification catalyst and under suitable temperature and pressure to form a first gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous byproducts;
(c) contacting the first gas stream with an aqueous medium to convert at least 80 mol % of the carbon monoxide in the first gas stream to carbon dioxide and to generate hydrogen, thereby forming a carbon monoxide-depleted gas stream comprising methane, hydrogen, carbon dioxide, and the one or more additional gaseous by-products;
and (d) removing carbon dioxide and the one or more additional gaseous by-products from the carbon monoxide-depleted gas stream to form a second gas stream comprising at least 90 mol % methane and hydrogen; and (e) at least partially separating the hydrogen in the second gas stream and the methane in the second gas stream from each other to form at least a hydrogen-enriched gas stream and a first methane-enriched gas stream.
(a) supplying a carbonaceous feedstock to a gasification reactor;
(b) reacting the carbonaceous feedstock in the gasification reactor in the presence of steam, carbon monoxide, hydrogen and a gasification catalyst and under suitable temperature and pressure to form a first gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous byproducts;
(c) contacting the first gas stream with an aqueous medium to convert at least 80 mol % of the carbon monoxide in the first gas stream to carbon dioxide and to generate hydrogen, thereby forming a carbon monoxide-depleted gas stream comprising methane, hydrogen, carbon dioxide, and the one or more additional gaseous by-products;
and (d) removing carbon dioxide and the one or more additional gaseous by-products from the carbon monoxide-depleted gas stream to form a second gas stream comprising at least 90 mol % methane and hydrogen; and (e) at least partially separating the hydrogen in the second gas stream and the methane in the second gas stream from each other to form at least a hydrogen-enriched gas stream and a first methane-enriched gas stream.
2. The process of claim 1, wherein a char is formed in step (b), and the char is removed from the gasification reactor and sent to a catalyst recovery and recycle process.
3. The process of claim 2, wherein the gasification catalyst comprises gasification catalyst recycled from the catalyst recovery and recycle process.
4. A process for converting a carbonaceous feedstock into a plurality of gaseous products contained in a gas stream, the gas stream comprising hydrogen, methane and other gaseous products, and for separating hydrogen and methane from the other gaseous products in the gas stream, wherein the process comprises the steps of:
(a) supplying a first carbonaceous feedstock to a reactor;
(b) at least partially combusting the first carbonaceous feedstock in the reactor in the presence of oxygen and under suitable temperature and pressure so as to generate (i) heat energy and (ii) a combustion gas stream comprising hydrogen, carbon monoxide, and carbon dioxide;
(c) using the heat energy from the combustion of the first carbonaceous feedstock to generate steam;
(d) introducing at least a portion of the steam, at least a portion of the combustion gas stream, a second carbonaceous feedstock, and a gasification catalyst to a gasification reactor;
(e) reacting the second carbonaceous feedstock in the gasification reactor in the presence of steam, carbon monoxide, hydrogen and the gasification catalyst, and under suitable temperature and pressure to form a first gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous by-products;
(f) contacting the first gas stream with an aqueous medium to convert at least 80 mol % of the carbon monoxide in the first gas stream into carbon dioxide and generate hydrogen, thereby forming a carbon monoxide-depleted gas stream comprising methane, hydrogen, carbon dioxide, and the one or more additional gaseous by-products;
(g) removing carbon dioxide and the one or more gaseous by-products from the carbon monoxide-depleted gas stream to form a second gas stream comprising at least 90 mol % methane and hydrogen; and (h) at least partially separating the hydrogen in the second gas stream and the methane in the second gas stream from each other to form at least a hydrogen-enriched gas stream and a first methane-enriched gas stream.
(a) supplying a first carbonaceous feedstock to a reactor;
(b) at least partially combusting the first carbonaceous feedstock in the reactor in the presence of oxygen and under suitable temperature and pressure so as to generate (i) heat energy and (ii) a combustion gas stream comprising hydrogen, carbon monoxide, and carbon dioxide;
(c) using the heat energy from the combustion of the first carbonaceous feedstock to generate steam;
(d) introducing at least a portion of the steam, at least a portion of the combustion gas stream, a second carbonaceous feedstock, and a gasification catalyst to a gasification reactor;
(e) reacting the second carbonaceous feedstock in the gasification reactor in the presence of steam, carbon monoxide, hydrogen and the gasification catalyst, and under suitable temperature and pressure to form a first gas stream comprising methane, hydrogen, carbon monoxide, carbon dioxide, and one or more additional gaseous by-products;
(f) contacting the first gas stream with an aqueous medium to convert at least 80 mol % of the carbon monoxide in the first gas stream into carbon dioxide and generate hydrogen, thereby forming a carbon monoxide-depleted gas stream comprising methane, hydrogen, carbon dioxide, and the one or more additional gaseous by-products;
(g) removing carbon dioxide and the one or more gaseous by-products from the carbon monoxide-depleted gas stream to form a second gas stream comprising at least 90 mol % methane and hydrogen; and (h) at least partially separating the hydrogen in the second gas stream and the methane in the second gas stream from each other to form at least a hydrogen-enriched gas stream and a first methane-enriched gas stream.
5. The process of claim 4, wherein a char is formed in step (e), and the char is removed from the gasification reactor and sent to a catalyst recovery and recycle process.
6. The process of claim 5, wherein the gasification catalyst comprises gasification catalyst recycled from the catalyst recovery and recycle process.
7. The process of any one of claims 4 to 6, wherein the first carbonaceous feedstock is in the form of an aqueous slurry.
8. The process of any one of claims 4 to 7, wherein, in step (c), the steam is generated within the reactor.
9. The process of any one of claims 4 to 6, wherein, in step (c), the heat energy is transferred to a heat exchanger which generates the steam upon contact with water.
10. The process of any one of claims 1 to 9, wherein the first methane-enriched gas stream comprises methane, optionally carbon monoxide, and up to about 4 mol%
hydrogen;
and wherein, if the heating value of the first methane-enriched gas stream is less than 950 btu/scf (dry basis), and if the first-methane-enriched gas stream comprises 1000 ppm or more of carbon monoxide: (1) at least partially separating carbon monoxide from the first methane-enriched gas stream to form (i) a carbon-monoxide-enriched gas stream and (ii) a second methane-enriched gas stream having a heating value of at least 950 btu/scf (dry basis); or (2) at least partially methanating the carbon monoxide in the first methane-enriched gas stream to form a second methane-enriched gas stream.
hydrogen;
and wherein, if the heating value of the first methane-enriched gas stream is less than 950 btu/scf (dry basis), and if the first-methane-enriched gas stream comprises 1000 ppm or more of carbon monoxide: (1) at least partially separating carbon monoxide from the first methane-enriched gas stream to form (i) a carbon-monoxide-enriched gas stream and (ii) a second methane-enriched gas stream having a heating value of at least 950 btu/scf (dry basis); or (2) at least partially methanating the carbon monoxide in the first methane-enriched gas stream to form a second methane-enriched gas stream.
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KR20100122109A (en) | 2010-11-19 |
CA2718536A1 (en) | 2009-10-08 |
US8192716B2 (en) | 2012-06-05 |
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US20090246120A1 (en) | 2009-10-01 |
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