US20230271172A1 - Catalysts and process for liquid hydrocarbon fuel production - Google Patents
Catalysts and process for liquid hydrocarbon fuel production Download PDFInfo
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- US20230271172A1 US20230271172A1 US18/303,556 US202318303556A US2023271172A1 US 20230271172 A1 US20230271172 A1 US 20230271172A1 US 202318303556 A US202318303556 A US 202318303556A US 2023271172 A1 US2023271172 A1 US 2023271172A1
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- Prior art keywords
- catalyst
- zeolite
- hydrocarbon
- metal
- group
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 67
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 51
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 40
- 239000007788 liquid Substances 0.000 title claims description 30
- 239000000446 fuel Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000010457 zeolite Substances 0.000 claims abstract description 72
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 67
- 239000007789 gas Substances 0.000 claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- 229910052750 molybdenum Inorganic materials 0.000 claims description 36
- 150000001298 alcohols Chemical class 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000012013 faujasite Substances 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 229910052680 mordenite Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000005899 aromatization reaction Methods 0.000 claims 4
- 239000002638 heterogeneous catalyst Substances 0.000 claims 2
- 238000006317 isomerization reaction Methods 0.000 claims 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 2
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims 2
- 229910003449 rhenium oxide Inorganic materials 0.000 claims 2
- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 claims 2
- 229910003182 MoCx Inorganic materials 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 13
- 239000003502 gasoline Substances 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 22
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- 241000894007 species Species 0.000 description 20
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 20
- 239000000306 component Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000012263 liquid product Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
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- 238000009826 distribution Methods 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002006 petroleum coke Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- -1 silica-alumina Chemical compound 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 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 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 238000004927 wastewater treatment sludge Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Classifications
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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- 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- 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
- C10L3/12—Liquefied petroleum gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Definitions
- This invention relates to the field of syngas conversion and more specifically to the field of converting synthesis gas to high quality hydrocarbon mixtures and includes the novel catalysts involved in such conversion.
- the Fischer-Tropsch process involves a catalyzed chemical reaction whereby synthesis gas, which is a mixture of carbon monoxide and hydrogen, is converted into liquid hydrocarbons.
- the most common catalysts generally used in the process are based on iron, cobalt, nickel, and ruthenium.
- the catalysts generally contain, in addition to the active metal, a number of promoters as well as high surface area binders/supporters such as silica, alumina, or zeolites.
- This process which has been in commercial use for many years, produces higher hydrocarbon materials in the form of synthetic petroleum substitutes from coal, natural gas, heavier oil, or solid biomass for use as synthetic lubrication oil or synthetic fuel.
- the process involves multiple competing chemical reactions that subsequently result in both desirable products and undesirable byproducts.
- the present invention discloses a novel process and system in which syngas is converted into high quality gasoline components, aromatic compounds, and lower molecular olefins in one reactor. Moreover, the process utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion. Additionally, the process also utilizes a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst in high pressure hydrogen for conversion.
- the present invention provides for novel catalysts and a novel process and system for utilizing these catalysts for converting low H 2 /CO molar ratio synthesis gas to hydrocarbon mixtures composed of high quality gasoline, low molecular weight gaseous olefins, and/or benzene/naphthalene-derived aromatic compounds.
- the composition of the liquid hydrocarbon phase can be adjusted to show >90% aromatics (e. g., benzene, toluene, and para-xylene) using HZSM-5 as the acid function; whereas, the H-Y-faujasite acid catalyst produces a liquid having a composition of >90% iso-paraffins and cyclo-paraffins.
- the invention is distinct and different from existing prior art and processes in many respects including, but not limited to: the catalysts use molybdenum (Mo) or rhenium (Re) as the main active components for the reaction; the catalysts use a zeolite (HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, H-beta, and the like) as the supporting material; the active phase of the catalysts is composed of carburized/reduced Mo-species (Re) or a non-zeolite, such as silica-alumina, heteropolyacid; the reaction proceeds mainly inside cages of the zeolite support, which effectively inhibits the formation of heavier linear-chain hydrocarbons (>C 7 ); and the catalysts produce alcohols (methanol, ethanol, and propanol) as the primary intermediate products for hydrocarbon formation which results from the dehydration of these alcohols. Moreover, the process of the present invention effectively removes one or more reactors in the process
- This invention demonstrates how a mixture of carbon monoxide and hydrogen (synthesis gas) can be converted into various hydrocarbon products.
- the origin of the synthesis gas may be from biorenewable sources such as biomass, grass, woody biomass, wastewater treatment sludges, industrial and municipal, and any type of lignocelluloses.
- the source of the synthesis gas can be derived from petroleum sources such as natural gas, light hydrocarbons, liquid hydrocarbons, or petroleum coke.
- the synthesis gas can be developed from a host of alternative sources of carbon such as coal, lignite, tar sands, shale oils, coal bed methane, and the hydrocarbon “ices” such as methane hydrate, and mixtures of light gas hydrates.
- FIG. 1 is a graphical illustration of the overall process of the present invention.
- FIG. 2 is a graphical illustration showing the response of selectivity ratio (liquid hydrogens/CO 2 ) versus the composition of the finished catalyst (millimol MO species/millimol framework Al). These data show a non-linear response (parabolic) of this selectivity ratio versus the ratio of Mo/Al (framework). Both parabolas unexpectedly show maximum values when the abscissa values are near unity (1.07 for 573 K data; and 1.002 for 623 K data). One interpretation of these data is that maximum selectivity for liquids is realized when the number of Mo species is in about even ratio of framework Al species of the finished catalyst. These data were obtained under the conditions of low CO conversion ( ⁇ 15%) so that the coke yields were very low ( ⁇ 0.1 wt % carbon/catalyst).
- the present invention discloses a process and system for the conversion of a mixture of carbon monoxide and hydrogen (synthesis gas) into various hydrocarbon products.
- the origin of the synthesis gas may be from biorenewable sources including, but not limited to, biomass, grass, woody biomass, wastewater treatment sludges, industrial and municipal, and any type of lignocelluloses.
- the source of the synthesis gas can be derived from petroleum sources such as natural gas, light hydrocarbons, liquid hydrocarbons, or petroleum coke.
- the synthesis gas can be developed from a host of alternative sources of carbon such as coal, lignite, tar sands, shale oils, coal bed methane, and the hydrocarbon “ices” such as methane hydrate, and mixtures of light gas hydrates.
- the present invention comprises solid catalysts for the selective conversion of a gas mixture containing carbon monoxide and hydrogen as the major components into liquid hydrocarbons.
- One novel element of this technology is the use of a bi-functional catalyst: (1) showing a metal component that converts the CO and H 2 into alcohols; and (2) showing an acid component that converts the alcohols into olefins, alkanes, branched alkanes, cyclic alkanes, and aromatics.
- the metal component is chosen to produce a mixture of higher-molecular-weight alcohols, such as ethanol, propanol, etc. and oxygenates, the chemical equilibrium reactions do not limit the conversion of synthesis gas as has been observed when the intermediate product is only methanol.
- the synthesis gas conversion into higher-molecular-weight alcohols of the present invention was achieved using a transition metal that was active as either the oxide or the sulfide. This last consideration allows the use of the catalyst in feed streams that show sulfur-containing compounds in low concentrations as might be encountered in synthesis gas obtained from gasification of coals and petroleum coke products. Such a sulfur-tolerant catalyst precludes the need for desulfurization of the raw synthesis gas stream.
- metal syngas conversion catalyst component An additional consideration for the choice of the metal syngas conversion catalyst component is the desirability for producing higher molecular weight alcohols. It has been shown that the reaction rate to form gasoline liquids over H-ZSM-5 was 8-10 times higher when the substrate was butanol rather than methanol. Amit C. Gujar, Vamshi Krishna Guda, Michael Nolan, Qiangu Yan, Hossein Toghiani, and Mark G. White, “Reactions of Methanol and Higher Alcohols over H-ZSM-5”, Applied Catalysis, A. General 363 (2009) 115-121. Thus, a metal synthesis gas conversion catalyst that produces higher-molecular-weight-alcohol intermediates is highly desirable over a metal catalyst that makes only methanol as an intermediate.
- An essential part of the novel design of the present invention is the use of metal-containing, acidic solids that show a pore structure which determines the types of hydrocarbon products obtained under reaction conditions. That is, the reaction products obtained over a medium-pore zeolite such as H-ZSM-5 show a high preference for aromatic hydrocarbons (>80%) over alkanes and alkenes.
- a medium-pore zeolite such as H-ZSM-5
- H-ZSM-5 medium-pore zeolite
- H-ZSM-5 medium-pore zeolite
- By increasing the size of the acidic pore structure, such as that found in H-Y zeolite one can realize a catalyst that favors the formation of long, branched-chain and cyclic alkanes and alkenes with less than 10% aromatics.
- Additional metals and non-metals are often added to a catalyst formulation to improve the properties and performance of the catalyst.
- alkali and alkali earths are added in low loadings to the metal to decrease the carbon dioxide forming reactions, such as the water gas shift reaction.
- the catalytic agent to accomplish the conversion of the present invention in a single catalyst bed is comprised of two functions which are inculcated into the catalyst particles: a CO conversion element which reduces the carbon monoxide into organic acids, esters, aldehydes, ketones, ethers, and alcohols; and an oxygenate dehydration/decarboxylation conversion element which reduces this list of oxygenates (organic acids, esters, aldehydes, ketones, ethers, and alcohols) into hydrocarbons, carbon dioxide, and water.
- a CO conversion element which reduces the carbon monoxide into organic acids, esters, aldehydes, ketones, ethers, and alcohols
- an oxygenate dehydration/decarboxylation conversion element which reduces this list of oxygenates (organic acids, esters, aldehydes, ketones, ethers, and alcohols) into hydrocarbons, carbon dioxide, and water.
- the oxygenate dehydration/decarboxylation conversion element may be chosen from a family of high surface area, acidic solids such as the crystalline, alumino-silicates (H + -ZSM-5, Y-faujasite, H-beta, X-faujasite, mordenite, etc.), the mesoporous solids derived from the sol/gel/template process (MCM-41, etc.), or the amorphous silica alumina, and heteropolyacids, etc.
- acidic solid such as the crystalline, alumino-silicates (H + -ZSM-5, Y-faujasite, H-beta, X-faujasite, mordenite, etc.
- MCM-41 sol/gel/template process
- the choice of acidic solid will determine the types of hydrocarbons that will be made by this process.
- the hydrocarbon liquids when the acidic solid is H+ZSM-5, a highly acidic, medium-sized pore ( ⁇ 0.56 nm) zeolite, then the hydrocarbon liquids will be characterized by a composition that is >90 wt % aromatics with the remainder being paraffins/iso-paraffins.
- the acidic solid is Y-faujasite, a large-pore zeolite, ⁇ 0.9 nm, of intermediate acidity, the liquid products are >90 wt % cycloparaffins and iso-paraffins with the remainder being aromatic compounds.
- an acidic solid such as H-beta, no liquid hydrocarbons are produced and the light hydrocarbon gases are characterized by large amounts of ethylene and propylene.
- the metals mentioned above may be deposited onto these high surface area supports using the technique known as incipient wetness technique or also known as the “pore filling” technique.
- the CO conversion element which reduces the carbon monoxide into the oxygenates can be chosen from a list of transition metals to include molybdenum, rhodium, rhenium, and combinations of these metals/metal oxides. Some of these transition metals may be converted to the sulfide state, MoS 2 , to enhance the selectivity to the desired hydrocarbons.
- Other catalyst cluster materials which may be added to promote the desired reactions include at least one metal modifier member of the elements of Groups IA and IIA of the Periodic Table, as referenced by S. R. Radel and M. H. Navidi, in Chemistry, West Publishing Company, New York, 1990, and mixtures of these elements, including but not limited to lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.
- the present invention discloses novel catalysts and a novel process and system utilizing these catalysts for converting low H 2 /CO molar ratio synthesis gas to hydrocarbon mixtures composed of high quality gasoline, low molecular weight gaseous olefins, and/or benzene/naphthalene-derived aromatic compounds.
- the invention uses catalysts comprising molybdenum (Mo) or rhenium (Re) as the main active components for the reaction.
- the catalysts use a zeolite (HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, H-beta, and the like) as the supporting material.
- the active phase of the catalysts is composed of carburized/reduced Mo-species (Re) or a non-zeolite, such as silica-alumina, heteropolyacid, while the reaction proceeds mainly inside cages of the zeolite support, which thereby effectively inhibits the formation of heavier linear-chain hydrocarbons (>C 7 ).
- the catalysts produce alcohols (methanol, ethanol, and propanol) as the primary intermediate products for hydrocarbon formation which results from the dehydration of these alcohols.
- the process of the present invention removes one or more reactors in the process of producing high quality gasoline hydrocarbon products and produces such products from syngas in only one step or reactor.
- Another feature of the present invention is the Mo/framework Al ratio of the zeolite structure.
- the number of Mo species in the zeolite structure is equal or close to equal to the number of Al species left in the zeolite framework after the catalyst has been made.
- an amorphous Al residue that is not catalytically active for the reactions of interest.
- syngas ⁇ alcohols ⁇ aromatics is a series reaction network so that at steady state, the rate of reaction to form alcohols is equal to the rate of alcohol consumption to form aromatics when the number of Mo species equals the number of framework Al species which equals the number of highly acidic protons.
- the material catalyzes two reactions which are in series: synthesis gas to mixtures of alcohols using Mo, and the further conversion of mixed alcohols to a mixture of olefins, aromatics and iso-paraffins using framework Al acid sites.
- the reaction rates of the two classes of reactions dictate that the number of Mo sites be about equal to framework Al acid sites so as to obtain the optimum yields of liquid hydrocarbons.
- the Mo/Al framework ratio is about 0.5 to about 1.5. In other embodiment, it is about 0.6 to about 1.4. In other embodiments, it is about 0.7 to about 1.3. In other embodiments, it is about 0.8 to about 1.2. In other embodiments, it is about 0.9 to about 1.1. In other embodiments, it is about 1.0 to about 1.0. In other embodiments, it is about 1.1 to about 0.9. In other embodiments, it is about 1.2 to about 0.8. In other embodiments, it is about 1.3 to about 0.7. In other embodiments, it is about 1.4 to about 0.6. In other embodiments, it is about 1.5 to about 0.5.
- novel catalysts are suitable for synthesis using lower H 2 /CO molar ratio syngas and comprise carburized/reduced Mo-species (Re), a zeolite, and at least one alkali metal as the promoter, where the metal is selected from elements of Groups IA and IIA of the Periodic Chart and combinations or mixtures thereof.
- these catalysts produce liquid hydrocarbons enriched with lower branched alkanes and alkyl-substituted aromatics.
- the aromatics content of the hydrocarbon liquids can be greatly reduced when the H-ZSM-5 is replaced with H-Y-faujasite to make a liquid product that is mainly iso- and cyclo-paraffins.
- the catalysts and process of the present invention produce mainly branched alkanes and alkyl-substituted aromatics as high quality gasoline components, which differs from traditional Fe- and Co-based Fischer-Tropsch synthesis and catalysts that produce mainly linear-chain hydrocarbons and that requires further processing via additional steps or reactors.
- the process and system of the present invention converts syngas into high quality gasoline components (more than 90% branched/cyclic products) in one reactor.
- the conversion occurs over an alcohol-forming catalyst found in the same matrix as a gasoline-forming catalyst, whereby the alcohol-forming catalyst creates or produces higher alcohols from syngas.
- One embodiment of the present invention is a process whereby syngas is converted into high quality gasoline hydrocarbon components (more than 90% branched/cyclic paraffin products) over a molybdenum-zeolite catalyst in high pressure hydrogen.
- the molybdenum allows the conversion of olefins/lower alcohols (that are initially formed in the catalytic process) into higher alcohols (C 2 , C 3 , C 4 ).
- the zeolite allows the conversion of syngas into hydrocarbons; alcohols into liquid hydrocarbons;
- Another embodiment of the present invention is a process whereby syngas is converted into high quality gasoline hydrocarbon components (more than 90% branched/cyclic paraffinic products) over a rhenium-zeolite catalyst in high pressure hydrogen.
- the metal function can be placed on H-beta to produce a catalyst which converts the synthesis gas mainly to a gas mixture containing low molecular olefins, such as ethylene and propylene.
- FIG. 1 illustrates graphically the overall process of the present invention.
- Solid biomass, coal, and/or heavier oil is gasified to form syngas.
- the syngas is exposed to a zeolite-encaged molybdenum-based or rhenium-based catalyst.
- the product that results is a combination of gas and liquid.
- the liquid products are separated out using a gas-liquid separation unit and comprise the high quality end product.
- the gas products are recycled back for reprocessing.
- the designated Mo loading amount was 5 wt. % or 10 wt. %.
- the samples were finally calcined in air at 773 K for 3 h and pelletized into 0.25-0.5 mm particles for activity tests.
- the synthesis gas conversion to hydrocarbon liquids reaction was performed using a continuous flow, fixed-bed BTRS-Jr Laboratory Reactor Systems from Autoclave Engineers.
- the gas hourly space velocity (GHSV) was 3000 h ⁇ 1 .
- Liquid products were collected using a condenser kept at 271 K and the pressure was 500 psig and 1000 psig, respectively, and the effluent gas from the condenser was analyzed with an on-line gas chromatograph (GC, HP 6980) equipped with thermal conductive detector (TCD) and flame ionization detector (FID).
- GC on-line gas chromatograph
- TCD thermal conductive detector
- FID flame ionization detector
- a packed Molecular Sieve 5A column and a HP-1 capillary column were employed for separation of inorganic gases and light hydrocarbons.
- Liquid products collected from the condenser, were separated into an oil phase and a water phase, and analyzed with GC-mass spectrometer (Agilent) equipped with DB-Wax capillary column for oxygenated compounds and HP-5 ms capillary column for hydrocarbons.
- GC-mass spectrometer Agilent spectrometer
- Six (6) % N 2 was added into the syngas as internal standard for CO conversion calculation.
- Selectivity of lower hydrocarbons was estimated on carbon basis based on FID signal.
- Equations (1) and (2) were calculated according to Equations (1) and (2), respectively, (below) where F.° and F are the flow rates of the syngas and effluent gas after the reaction, respectively; C° i and C i are the concentrations of component i in the syngas and effluent gas, respectively; and n is the carbon number in a product i molecule:
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 573 K
- the pressure was 1000 psi
- the conversion and selectivity results are shown in Table 1.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 623 K
- the pressure was 500 psi
- the conversion and selectivity results are shown in Table 1.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 573 K
- the pressure was 1000 psi
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 623 K
- the pressure was 500 psi
- the conversion and selectivity results are shown in Table 1.
- the liquid product distribution is shown in Table 2.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 573 K
- the pressure was 1000 psi
- the conversion and selectivity results are shown in Table 1.
- the liquid product distribution is shown in Table 2.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 623 K
- the pressure was 500 psi
- the conversion and selectivity results are shown in Table 1.
- the liquid product distribution is shown in Table 2.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 573 K
- the pressure was 1000 psi
- the conversion and selectivity results are shown in Table 1.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 623 K
- the pressure was 500 psi
- the conversion and selectivity results are shown in Table 1.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 573 K
- the pressure was 1000 psi
- the conversion and selectivity results are shown in Table 1.
- the liquid product distribution is shown in Table 2.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 573 K
- the pressure was 1000 psi
- the conversion and selectivity results are shown in Table 1.
- the GHSV was 3,000 h ⁇ 1
- the reaction temperature was 623 K
- the pressure was 500 psi
- the conversion and selectivity results are shown in Table 1.
- This disclosure has for the first time described and fully characterized a novel process and system in which syngas is converted into high quality gasoline components, aromatic compounds, and lower molecular olefins in one reactor.
- the invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion and a novel rhenium-zeolite catalyst in place of 15 the molybdenum-zeolite catalyst in high pressure hydrogen for conversion.
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Abstract
The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.
Description
- This application claims priority to U.S. Ser. No. 17/108,886, filed Dec. 1, 2020, now allowed; which claims priority to U.S. Ser. No. 15/714,238, filed Sep. 25, 2017, now U.S. Pat. No. 10,850,266; which is a continuation-in-part of U.S. Ser. No. 14/533,977, filed Nov. 5, 2014; which is a divisional of U.S. Ser. No. 12/806,340, filed Aug. 10, 2010, now U.S. Pat. No. 8,906,971; which claims benefit of U.S. Provisional Patent Application Ser. No. 61/273,856 filed Aug. 10, 2009. The above applications are incorporated herein by reference.
- This invention was made with government support under Contract No. DE-FG3606G086025 awarded by the U.S. Department of Energy. The government may have certain rights in the invention.
- This invention relates to the field of syngas conversion and more specifically to the field of converting synthesis gas to high quality hydrocarbon mixtures and includes the novel catalysts involved in such conversion.
- The Fischer-Tropsch process involves a catalyzed chemical reaction whereby synthesis gas, which is a mixture of carbon monoxide and hydrogen, is converted into liquid hydrocarbons.
- The most common catalysts generally used in the process are based on iron, cobalt, nickel, and ruthenium. The catalysts generally contain, in addition to the active metal, a number of promoters as well as high surface area binders/supporters such as silica, alumina, or zeolites. This process, which has been in commercial use for many years, produces higher hydrocarbon materials in the form of synthetic petroleum substitutes from coal, natural gas, heavier oil, or solid biomass for use as synthetic lubrication oil or synthetic fuel. The process involves multiple competing chemical reactions that subsequently result in both desirable products and undesirable byproducts.
- Numerous patents exist that involve the Fischer-Tropsch synthesis process and catalysts used in such syntheses. However, the present invention discloses a novel process utilizing novel catalysts to produce high quality liquid hydrocarbons in only one step, thereby eliminating the necessity for typical further processing and effectively eliminating one or more processing steps or reactors and producing high quality hydrocarbon products via only one reactor.
- The present invention discloses a novel process and system in which syngas is converted into high quality gasoline components, aromatic compounds, and lower molecular olefins in one reactor. Moreover, the process utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion. Additionally, the process also utilizes a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst in high pressure hydrogen for conversion.
- The present invention provides for novel catalysts and a novel process and system for utilizing these catalysts for converting low H2/CO molar ratio synthesis gas to hydrocarbon mixtures composed of high quality gasoline, low molecular weight gaseous olefins, and/or benzene/naphthalene-derived aromatic compounds. The composition of the liquid hydrocarbon phase can be adjusted to show >90% aromatics (e. g., benzene, toluene, and para-xylene) using HZSM-5 as the acid function; whereas, the H-Y-faujasite acid catalyst produces a liquid having a composition of >90% iso-paraffins and cyclo-paraffins. The invention is distinct and different from existing prior art and processes in many respects including, but not limited to: the catalysts use molybdenum (Mo) or rhenium (Re) as the main active components for the reaction; the catalysts use a zeolite (HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, H-beta, and the like) as the supporting material; the active phase of the catalysts is composed of carburized/reduced Mo-species (Re) or a non-zeolite, such as silica-alumina, heteropolyacid; the reaction proceeds mainly inside cages of the zeolite support, which effectively inhibits the formation of heavier linear-chain hydrocarbons (>C7); and the catalysts produce alcohols (methanol, ethanol, and propanol) as the primary intermediate products for hydrocarbon formation which results from the dehydration of these alcohols. Moreover, the process of the present invention effectively removes one or more reactors in the process of producing high quality gasoline hydrocarbon products and produces such products from syngas in one step. The zeolite pore size typically ranges from about 0.4 to about 0.7 nm.
- This invention demonstrates how a mixture of carbon monoxide and hydrogen (synthesis gas) can be converted into various hydrocarbon products. The origin of the synthesis gas may be from biorenewable sources such as biomass, grass, woody biomass, wastewater treatment sludges, industrial and municipal, and any type of lignocelluloses. In addition, the source of the synthesis gas can be derived from petroleum sources such as natural gas, light hydrocarbons, liquid hydrocarbons, or petroleum coke. Finally, the synthesis gas can be developed from a host of alternative sources of carbon such as coal, lignite, tar sands, shale oils, coal bed methane, and the hydrocarbon “ices” such as methane hydrate, and mixtures of light gas hydrates.
- With the foregoing and other objects, features, and advantages of the present invention that will become apparent hereinafter, the nature of the invention may be more clearly understood by reference to the following detailed description of the preferred embodiments of the invention and to the appended claims.
- These drawings accompany the detailed description of the invention and are intended to illustrate further the invention and its advantages:
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FIG. 1 is a graphical illustration of the overall process of the present invention. -
FIG. 2 is a graphical illustration showing the response of selectivity ratio (liquid hydrogens/CO2) versus the composition of the finished catalyst (millimol MO species/millimol framework Al). These data show a non-linear response (parabolic) of this selectivity ratio versus the ratio of Mo/Al (framework). Both parabolas unexpectedly show maximum values when the abscissa values are near unity (1.07 for 573 K data; and 1.002 for 623 K data). One interpretation of these data is that maximum selectivity for liquids is realized when the number of Mo species is in about even ratio of framework Al species of the finished catalyst. These data were obtained under the conditions of low CO conversion (˜15%) so that the coke yields were very low (<0.1 wt % carbon/catalyst). - The present invention discloses a process and system for the conversion of a mixture of carbon monoxide and hydrogen (synthesis gas) into various hydrocarbon products. The origin of the synthesis gas may be from biorenewable sources including, but not limited to, biomass, grass, woody biomass, wastewater treatment sludges, industrial and municipal, and any type of lignocelluloses. In addition, the source of the synthesis gas can be derived from petroleum sources such as natural gas, light hydrocarbons, liquid hydrocarbons, or petroleum coke. Finally, the synthesis gas can be developed from a host of alternative sources of carbon such as coal, lignite, tar sands, shale oils, coal bed methane, and the hydrocarbon “ices” such as methane hydrate, and mixtures of light gas hydrates.
- The present invention comprises solid catalysts for the selective conversion of a gas mixture containing carbon monoxide and hydrogen as the major components into liquid hydrocarbons. One novel element of this technology is the use of a bi-functional catalyst: (1) showing a metal component that converts the CO and H2 into alcohols; and (2) showing an acid component that converts the alcohols into olefins, alkanes, branched alkanes, cyclic alkanes, and aromatics. The choice of a catalyst that produces alcohol intermediates circumvents the problems of a broad molecular weight distribution of the products that plagues other synthesis gas conversion catalysts and techniques which employ CO-insertion chemistry as the chain growth mechanism. When the metal component is chosen to produce a mixture of higher-molecular-weight alcohols, such as ethanol, propanol, etc. and oxygenates, the chemical equilibrium reactions do not limit the conversion of synthesis gas as has been observed when the intermediate product is only methanol.
- The synthesis gas conversion into higher-molecular-weight alcohols of the present invention was achieved using a transition metal that was active as either the oxide or the sulfide. This last consideration allows the use of the catalyst in feed streams that show sulfur-containing compounds in low concentrations as might be encountered in synthesis gas obtained from gasification of coals and petroleum coke products. Such a sulfur-tolerant catalyst precludes the need for desulfurization of the raw synthesis gas stream.
- An additional consideration for the choice of the metal syngas conversion catalyst component is the desirability for producing higher molecular weight alcohols. It has been shown that the reaction rate to form gasoline liquids over H-ZSM-5 was 8-10 times higher when the substrate was butanol rather than methanol. Amit C. Gujar, Vamshi Krishna Guda, Michael Nolan, Qiangu Yan, Hossein Toghiani, and Mark G. White, “Reactions of Methanol and Higher Alcohols over H-ZSM-5”, Applied Catalysis, A. General 363 (2009) 115-121. Thus, a metal synthesis gas conversion catalyst that produces higher-molecular-weight-alcohol intermediates is highly desirable over a metal catalyst that makes only methanol as an intermediate.
- An essential part of the novel design of the present invention is the use of metal-containing, acidic solids that show a pore structure which determines the types of hydrocarbon products obtained under reaction conditions. That is, the reaction products obtained over a medium-pore zeolite such as H-ZSM-5 show a high preference for aromatic hydrocarbons (>80%) over alkanes and alkenes. By increasing the size of the acidic pore structure, such as that found in H-Y zeolite, one can realize a catalyst that favors the formation of long, branched-chain and cyclic alkanes and alkenes with less than 10% aromatics. Finally, with the use of zeolite such as H-beta, one obtains hydrocarbon products showing only C1-C3 alkanes and alkenes. This novel concept of the present invention of shape and/or size selectivity can be extended to other porous, acidic solids to develop the desired hydrocarbon products to include distillates such as jet, diesel, and kerosene.
- Additional metals and non-metals are often added to a catalyst formulation to improve the properties and performance of the catalyst. In the case of the alcohol-forming metal component, alkali and alkali earths are added in low loadings to the metal to decrease the carbon dioxide forming reactions, such as the water gas shift reaction. Zhenyu Liu, Xianguo Li, Michael R. Close, Edwin L. Kugler, Jeffrey L. Petersen, and Dady B. Dadyburjor, “Screening of Alkali-Promoted Vapor-Phase-Synthesized Molybdenum Sulfide Catalysts for the Production of Alcohols from Synthesis Gas”, Ind. Eng. Chem. Res., 1997, 36 (8), pp. 3085-3093. Also, changing the metal oxide to the metal sulfide has been shown to decrease the conversion of carbon monoxide to carbon dioxide. Kegong Fang, Debao Li, Minggui Lin, Minglin Xiang, Wei Wei and Yuhan Sun, “A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas”, Catalysis Today, Volume 147, Issue 2, 30 Sep. 2009, pp. 133-138. Accordingly, the metal syngas conversion component will be modified with the addition of alkali and alkaline earth oxides together with sulfiding of the metal to form the metal sulfide.
- The catalytic agent to accomplish the conversion of the present invention in a single catalyst bed is comprised of two functions which are inculcated into the catalyst particles: a CO conversion element which reduces the carbon monoxide into organic acids, esters, aldehydes, ketones, ethers, and alcohols; and an oxygenate dehydration/decarboxylation conversion element which reduces this list of oxygenates (organic acids, esters, aldehydes, ketones, ethers, and alcohols) into hydrocarbons, carbon dioxide, and water.
- The oxygenate dehydration/decarboxylation conversion element may be chosen from a family of high surface area, acidic solids such as the crystalline, alumino-silicates (H+-ZSM-5, Y-faujasite, H-beta, X-faujasite, mordenite, etc.), the mesoporous solids derived from the sol/gel/template process (MCM-41, etc.), or the amorphous silica alumina, and heteropolyacids, etc. The choice of acidic solid will determine the types of hydrocarbons that will be made by this process. For example, when the acidic solid is H+ZSM-5, a highly acidic, medium-sized pore (˜0.56 nm) zeolite, then the hydrocarbon liquids will be characterized by a composition that is >90 wt % aromatics with the remainder being paraffins/iso-paraffins. When the acidic solid is Y-faujasite, a large-pore zeolite, ˜0.9 nm, of intermediate acidity, the liquid products are >90 wt % cycloparaffins and iso-paraffins with the remainder being aromatic compounds. Finally, for an acidic solid such as H-beta, no liquid hydrocarbons are produced and the light hydrocarbon gases are characterized by large amounts of ethylene and propylene. The metals mentioned above may be deposited onto these high surface area supports using the technique known as incipient wetness technique or also known as the “pore filling” technique.
- The CO conversion element which reduces the carbon monoxide into the oxygenates can be chosen from a list of transition metals to include molybdenum, rhodium, rhenium, and combinations of these metals/metal oxides. Some of these transition metals may be converted to the sulfide state, MoS2, to enhance the selectivity to the desired hydrocarbons. Other catalyst cluster materials which may be added to promote the desired reactions include at least one metal modifier member of the elements of Groups IA and IIA of the Periodic Table, as referenced by S. R. Radel and M. H. Navidi, in Chemistry, West Publishing Company, New York, 1990, and mixtures of these elements, including but not limited to lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.
- The present invention discloses novel catalysts and a novel process and system utilizing these catalysts for converting low H2/CO molar ratio synthesis gas to hydrocarbon mixtures composed of high quality gasoline, low molecular weight gaseous olefins, and/or benzene/naphthalene-derived aromatic compounds. The invention uses catalysts comprising molybdenum (Mo) or rhenium (Re) as the main active components for the reaction. The catalysts use a zeolite (HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, H-beta, and the like) as the supporting material. The active phase of the catalysts is composed of carburized/reduced Mo-species (Re) or a non-zeolite, such as silica-alumina, heteropolyacid, while the reaction proceeds mainly inside cages of the zeolite support, which thereby effectively inhibits the formation of heavier linear-chain hydrocarbons (>C7). Finally, the catalysts produce alcohols (methanol, ethanol, and propanol) as the primary intermediate products for hydrocarbon formation which results from the dehydration of these alcohols. The process of the present invention removes one or more reactors in the process of producing high quality gasoline hydrocarbon products and produces such products from syngas in only one step or reactor.
- Another feature of the present invention is the Mo/framework Al ratio of the zeolite structure. In embodiments of the present invention, the number of Mo species in the zeolite structure is equal or close to equal to the number of Al species left in the zeolite framework after the catalyst has been made. Also present in the zeolite is an amorphous Al residue that is not catalytically active for the reactions of interest. When the molybdenum species enters the zeolite during the catalyst preparation, these Mo species displace some of the framework aluminum species on a one-for-one basis. For example, if 10,000 framework aluminum species were present initially in a zeolite, and if 5,000 Mo species were introduced into the zeolite, then 5,000 framework Al species would be displaced from the zeolite to leave (10,000-5,000)=5,000 framework Al species behind in the zeolite. Thus, this assembly of Mo species in the zeolite equals the number of framework Al species left in the framework (i.e., Mo/framework Al=1). Each of these remaining framework Al species are associated with one proton, and each proton is highly acidic and capable of converting alcohols to aromatics. Each of the Mo species in the zeolite is capable of reacting with syngas to make alcohols. And the reaction sequence: syngas→alcohols→aromatics is a series reaction network so that at steady state, the rate of reaction to form alcohols is equal to the rate of alcohol consumption to form aromatics when the number of Mo species equals the number of framework Al species which equals the number of highly acidic protons.
- When the number of Mo species is not equal to the number of Al species (ergo, number of protons), 1 then the rate of alcohol formation does not equal the rate of alcohol consumption and the overall rate of reaction becomes equal to the limiting reaction rate. The present inventors have found that when the value at Mo/framework Al is at about 1, the maximum amount of liquids/aromatics are produced. Thus, in embodiments of the present invention, the material catalyzes two reactions which are in series: synthesis gas to mixtures of alcohols using Mo, and the further conversion of mixed alcohols to a mixture of olefins, aromatics and iso-paraffins using framework Al acid sites. The reaction rates of the two classes of reactions dictate that the number of Mo sites be about equal to framework Al acid sites so as to obtain the optimum yields of liquid hydrocarbons.
- Thus, in embodiments of the present invention, the Mo/Al framework ratio is about 0.5 to about 1.5. In other embodiment, it is about 0.6 to about 1.4. In other embodiments, it is about 0.7 to about 1.3. In other embodiments, it is about 0.8 to about 1.2. In other embodiments, it is about 0.9 to about 1.1. In other embodiments, it is about 1.0 to about 1.0. In other embodiments, it is about 1.1 to about 0.9. In other embodiments, it is about 1.2 to about 0.8. In other embodiments, it is about 1.3 to about 0.7. In other embodiments, it is about 1.4 to about 0.6. In other embodiments, it is about 1.5 to about 0.5.
- The novel catalysts are suitable for synthesis using lower H2/CO molar ratio syngas and comprise carburized/reduced Mo-species (Re), a zeolite, and at least one alkali metal as the promoter, where the metal is selected from elements of Groups IA and IIA of the Periodic Chart and combinations or mixtures thereof. In one formulation or embodiment, these catalysts produce liquid hydrocarbons enriched with lower branched alkanes and alkyl-substituted aromatics. The aromatics content of the hydrocarbon liquids can be greatly reduced when the H-ZSM-5 is replaced with H-Y-faujasite to make a liquid product that is mainly iso- and cyclo-paraffins. The catalysts and process of the present invention produce mainly branched alkanes and alkyl-substituted aromatics as high quality gasoline components, which differs from traditional Fe- and Co-based Fischer-Tropsch synthesis and catalysts that produce mainly linear-chain hydrocarbons and that requires further processing via additional steps or reactors.
- The process and system of the present invention converts syngas into high quality gasoline components (more than 90% branched/cyclic products) in one reactor. The conversion occurs over an alcohol-forming catalyst found in the same matrix as a gasoline-forming catalyst, whereby the alcohol-forming catalyst creates or produces higher alcohols from syngas. One embodiment of the present invention is a process whereby syngas is converted into high quality gasoline hydrocarbon components (more than 90% branched/cyclic paraffin products) over a molybdenum-zeolite catalyst in high pressure hydrogen. The molybdenum allows the conversion of olefins/lower alcohols (that are initially formed in the catalytic process) into higher alcohols (C2, C3, C4). The zeolite allows the conversion of syngas into hydrocarbons; alcohols into liquid hydrocarbons;
- higher alcohols into aromatic liquid hydrocarbons; and long, linear hydrocarbons into branched/cyclic hydrocarbons. Another embodiment of the present invention is a process whereby syngas is converted into high quality gasoline hydrocarbon components (more than 90% branched/cyclic paraffinic products) over a rhenium-zeolite catalyst in high pressure hydrogen. In yet another embodiment, the metal function can be placed on H-beta to produce a catalyst which converts the synthesis gas mainly to a gas mixture containing low molecular olefins, such as ethylene and propylene.
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FIG. 1 illustrates graphically the overall process of the present invention. Solid biomass, coal, and/or heavier oil is gasified to form syngas. The syngas is exposed to a zeolite-encaged molybdenum-based or rhenium-based catalyst. The product that results is a combination of gas and liquid. The liquid products are separated out using a gas-liquid separation unit and comprise the high quality end product. The gas products are recycled back for reprocessing. - The invention is further clarified by the following examples, which are intended to be purely illustrative of the use of the invention. Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention as disclosed herein. All percentages are on a mole percent basis and selectivities are on a carbon atom percent basis, unless noted otherwise.
- Mo/zeolite catalysts were prepared by incipient wetness impregnation of (NH4)6Mo7O24 4H2O (Fisher Scientific) aqueous solution with the ammonium form of either: 1) ZSM-5 (SiO2/Al2O3=23, 50, 80, and 280), 2) zeolite Y (SiO2/Al2O3=80) or zeolite β (SiO2/Al2O3=25) obtained from Zeolyst International. The designated Mo loading amount was 5 wt. % or 10 wt. %. The samples were finally calcined in air at 773 K for 3 h and pelletized into 0.25-0.5 mm particles for activity tests.
- One detailed description of the preparation is as follows. Ninety-five (95) grams of H-ZSM-5 (SiO2/Al2O3=50) were treated with an aqueous solution of 9.5 g of (NH4)6Mo7O24⋅4H2O dissolved in 47.7 grams of distilled water. The amount of water used in this incipient wetness preparation was just sufficient to fill the pores of the H-ZSM-5. The resulting solid was dried at 110° C. for 18 hours before it was calcined for 3 h at 500° C. Other catalysts were prepared using H-ZMS-5 having SiO2/Al2O3=23, 80, and 280 and the protocol listed in this example.
- Ninety-five (95) grams of Y-faujasite (SiO2/Al2O3=80) were treated with an aqueous solution of 9.5 g of (NH4)6Mo7O24⋅4H2O dissolved in 95 grams of distilled water. The amount of water used in this incipient wetness preparation was just sufficient to fill the pores of the Y-faujasite. The resulting solid was dried at 110° C. for 18 hours before it was calcined for 3 h at 500° C.
- Ninety-five (95) grams of H-beta zeolite (SiO2/Al2O3=25) were treated with an aqueous solution of 9.5 g of (NH4)6Mo7O24⋅4H2O dissolved in 75 grams of distilled water. The amount of water used in this incipient wetness preparation was just sufficient to fill the pores of the Y-faujasite. The resulting solid was dried at 110° C. for 18 hours before it was calcined for 3 h at 500° C.
- The synthesis gas conversion to hydrocarbon liquids reaction was performed using a continuous flow, fixed-bed BTRS-Jr Laboratory Reactor Systems from Autoclave Engineers.
- Before the reaction, the catalyst (1.0 g) was pretreated in syngas (H2/CO=1.0) flow at 673 K for 1 h. The gas hourly space velocity (GHSV) was 3000 h−1. Liquid products were collected using a condenser kept at 271 K and the pressure was 500 psig and 1000 psig, respectively, and the effluent gas from the condenser was analyzed with an on-line gas chromatograph (GC, HP 6980) equipped with thermal conductive detector (TCD) and flame ionization detector (FID). A packed Molecular Sieve 5A column and a HP-1 capillary column were employed for separation of inorganic gases and light hydrocarbons. Liquid products, collected from the condenser, were separated into an oil phase and a water phase, and analyzed with GC-mass spectrometer (Agilent) equipped with DB-Wax capillary column for oxygenated compounds and HP-5 ms capillary column for hydrocarbons. Six (6) % N2 was added into the syngas as internal standard for CO conversion calculation. Selectivity of lower hydrocarbons was estimated on carbon basis based on FID signal. The catalyst activity and selectivity were calculated according to Equations (1) and (2), respectively, (below) where F.° and F are the flow rates of the syngas and effluent gas after the reaction, respectively; C°i and Ci are the concentrations of component i in the syngas and effluent gas, respectively; and n is the carbon number in a product i molecule:
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- (1) Conversion of CO (%)=[F°C°co−FCco]/F°C°co=100×[C°co−C°N2(C°co/C°N2)]/C°co
- (2) Selectivity of product I (%)=nFCi/[F°C°co−F°C°co]=100×nC°N2Ci/[CN2C°co−C°N2Cco]
- In the first reaction example (4), the GHSV was 3,000 h−1, the reaction temperature was 573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=23. The conversion and selectivity results are shown in Table 1.
- In example (5), the GHSV was 3,000 h−1, the reaction temperature was 623 K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=23. The conversion and selectivity results are shown in Table 1.
- In example (6), the GHSV was 3,000 h−1, the reaction temperature was 573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=50.
- The conversion and selectivity results are shown in Table 1. The liquid product distribution is shown in Table 2.
- In example (7), the GHSV was 3,000 h−1, the reaction temperature was 623 K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=50. The conversion and selectivity results are shown in Table 1. The liquid product distribution is shown in Table 2.
- In example (8), the GHSV was 3,000 h−1, the reaction temperature was 573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=80. The conversion and selectivity results are shown in Table 1. The liquid product distribution is shown in Table 2.
- In example (9), the GHSV was 3,000 h−1, the reaction temperature was 623 K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=80. The conversion and selectivity results are shown in Table 1. The liquid product distribution is shown in Table 2.
- In example (10), the GHSV was 3,000 h−1, the reaction temperature was 573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=280. The conversion and selectivity results are shown in Table 1.
- In example (11), the GHSV was 3,000 h−1, the reaction temperature was 623 K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/HZSM-5 zeolite showing a SiO2/Al2O3=280. The conversion and selectivity results are shown in Table 1.
- In example (12), the GHSV was 3,000 h−1, the reaction temperature was 573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/H-Y zeolite showing a SiO2/Al2O3=80. The conversion and selectivity results are shown in Table 1. The liquid product distribution is shown in Table 2.
- In example (13), the GHSV was 3,000 h−1, the reaction temperature was 573 K, the pressure was 1000 psi, and the catalyst was the 5 wt % Mo/H-β zeolite showing a SiO2/Al2O3=25. The conversion and selectivity results are shown in Table 1.
- In example (14), the GHSV was 3,000 h−1, the reaction temperature was 623 K, the pressure was 500 psi, and the catalyst was the 5 wt % Mo/H-β zeolite showing a SiO2/Al2O3=25. The conversion and selectivity results are shown in Table 1.
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TABLE 1 Examples Showing Reaction Results Example SiO2/ Temperature, Pressure, Number Catalyst Al2O3 K psi 4 5% Mo/HZSM-5 23 573 1000 5 5% Mo/HZSM-5 23 623 500 6 5% Mo/HZSM-5 50 573 1000 7 5% Mo/HZSM-5 50 623 500 8 5% Mo/HZSM-5 80 573 1000 9 5% Mo/HZSM-5 80 623 500 10 5% Mo/HZSM-5 280 573 1000 11 5% Mo/HZSM-5 280 623 500 12 5% Mo/H-Y 80 573 1000 13 5% Mo/H-ß 25 573 1000 14 5% Mo/H-ß 25 623 500 Example CO Product Selectivity, % Number Conversion % CO2 C1-C3 C4+-Hydrocarbons 4 10.5 58.6 15.5 2.9 5 47.5 54 47.1 — 6 15.2 49.6 24.5 25.8 7 31.8 51.7 35.2 13.0 8 32.4 62.3 26.7 11.0 9 51.2 57.6 41.8 0.6 Example CO Number Conversion % Product Selectivity, % 10 20.6 64.2 25.5 10.3 11 44.6 61.7 36.5 1.8 12 13.9 38.6 30.4 31.0 13 13.5 61.0 39.0 — 14 39.1 61.3 38.7 — -
TABLE 2 Liquid Product Distribution Example Catalyst SiO2/Al2O3 Temperature Pressure, psi 6 5% Mo/HZSM-5 50 573 1000 7 5% Mo/HZSM-5 50 623 500 8 5% Mo/HZSM-5 80 573 1000 9 5% Mo/HZSM-5 80 623 500 12 5% Mo/H-Y 80 573 1000 Product Distribution % Cyclized Linear Linear % Branched & Example Alkanes Alkenes Aromatics Alkanes 6 15 5 30 50 7 12 5 45 38 8 5 0 65 30 9 5 2 80 13 12 35 5 10 50 - This disclosure has for the first time described and fully characterized a novel process and system in which syngas is converted into high quality gasoline components, aromatic compounds, and lower molecular olefins in one reactor. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion and a novel rhenium-zeolite catalyst in place of 15 the molybdenum-zeolite catalyst in high pressure hydrogen for conversion.
- The above detailed description is presented to enable any person skilled in the art to make and use the invention. Specific details have been disclosed to provide a comprehensive understanding of the present invention and are used for explanation of the information provided. These specific details, however, are not required to practice the invention, as is apparent to one skilled in the art. Descriptions of specific applications, analyses, and calculations are meant to serve only as representative examples. Various suitable changes, modifications, combinations, and equivalents to the preferred embodiments may be readily apparent to one skilled in the art and the general principles defined herein may be applicable to other embodiments and applications while still remaining within the spirit and scope of the invention. The claims and specification should not be construed to unduly narrow the complete scope of protection to which the present invention is entitled. It should also be understood that the figures are presented for example purposes only.
- There is no intention for the present invention to be limited to the embodiments shown and the invention is to be accorded the widest possible scope consistent with the principles and features disclosed herein.
Claims (31)
1. A process for the production of hydrocarbon fuel products from synthesis gas comprising a single reactor system and a steam reformer, wherein chemical reactions in the single reactor system occur over an alcohol-forming catalyst found in the same matrix as a gasoline-forming catalyst and wherein the alcohol-forming catalyst produces high quality alcohols from the synthesis gas.
2. The process of claim 1 , wherein the synthesis gas is contacted in a Fischer-Tropsch reaction with the alcohol-forming catalyst in high pressure hydrogen.
3. The process of claim 2 , wherein the catalyst is a zeolite-encaged, molybdenum-based catalyst active for deoxy-aromatization of alcohols and synthesis gas to mixed alcohols, isomerization of alkanes, and aromatization.
4. The process of claim 3 , wherein the catalyst is a cluster comprising a molybdenum oxide represented by MoCxOy encaged in a zeolite and wherein the cluster comprises the active phase.
5. The process of claim 4 , wherein the cluster comprises a molybdenum sulfide.
6. The process of claim 4 , wherein the cluster further comprises at least one metal modifier selected from the group consisting of the elements of Groups 1A and 2A of the Periodic Table and mixtures of the aforementioned elements.
7. The process of claim 3 , wherein the zeolite comprises a support.
8. The process of claim 7 , wherein the zeolite comprises one or more members selected from the group consisting of the zeolite-based heterogeneous catalyst HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, and H-beta zeolites.
9. The process of claim 2 , wherein the catalyst is a zeolite-encaged, rhenium-based catalyst active for deoxy-aromatization of alcohols and synthesis gas to mixed alcohols, isomerization of alkanes, and aromatization.
10. The process of claim 9 , wherein the catalyst is a cluster comprising a rhenium oxide represented by ReCxOy encaged in a zeolite and wherein the cluster comprises the active phase.
11. The process of claim 10 , wherein the cluster comprises a rhenium sulfide.
12. The process of claim 10 , wherein the cluster further comprises at least one metal modifier selected from the group consisting of the elements of Groups 1A and 2A of the Periodic Table and mixtures of the aforementioned elements.
13. The process of claim 9 , wherein the zeolite comprises a support.
14. The process of claim 13 , wherein the zeolite comprises one or more members selected from the group consisting of the zeolite-based heterogeneous catalyst HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, and H-beta zeolites.
15. The process of claim 1 , wherein the hydrocarbon fuel products comprise liquid hydrocarbons and gas hydrocarbons and wherein the products are separated in a separation unit.
16. The process of claim 15 , wherein the liquid hydrocarbons comprise branched alkanes and alkyl-substituted aromatics.
17. The process of claim 15 , wherein the gas hydrocarbons are fed to and processed through the steam reformer and returned to the single reactor system.
18. A catalyst for the production of hydrocarbon fuel products from synthesis gas comprising a molybdenum catalyst encaged in a zeolite support comprising one or more members selected from the group consisting of HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, and H-beta zeolites.
19. The catalyst of claim 18 , further comprising at least one alkali metal as a promoter for minimizing carbon dioxide products in the production of hydrocarbon fuel products, wherein the alkali metal is selected from the group consisting of the elements of Groups 1A and 2A of the Periodic Table and mixtures thereof.
20. The catalyst of claim 18 , wherein the molybdenum catalyst is chosen from the group consisting of molybdenum oxide and molybdenum sulfide.
21. The catalyst of claim 19 , wherein the size and shape of the catalyst encaged in the zeolite support selected determines the types of hydrocarbon fuel products that are produced.
22. A catalyst for the production of hydrocarbon fuel products from synthesis gas comprising a rhenium catalyst encaged in a zeolite support comprising one or more members selected from the group consisting of HZSM-5, Y, Mordenite, MCM-22, MCM-41, H-Y-faujasite, and H-beta zeolites.
23. The catalyst of claim 22 , further comprising at least one alkali metal as a promoter for minimizing carbon dioxide products in the production of hydrocarbon fuel products, wherein the alkali metal is selected from the group consisting of the elements of Groups 1A and 2A of the Periodic Table and mixtures thereof
24. The catalyst of claim 22 , wherein the rhenium catalyst is chosen from the group consisting of rhenium oxide and rhenium sulfide.
25. The catalyst of claim 23 , wherein the size and shape of the catalyst encaged in the zeolite support selected determines the types of hydrocarbon fuel products that are produced.
26. A catalyst system for producing a hydrocarbon liquid having an aromatics content of about 90% or greater, wherein the system comprises a metal on an HZSM-5 zeolite.
27. A catalyst system for producing a hydrocarbon liquid having a cyclo-paraffin and iso-paraffin content of about 90% or greater, wherein the system comprises a metal on an H-Y-faujasite zeolite.
28. A catalyst system for producing an ethylene-rich and propylene-rich hydrocarbon gas and producing no hydrocarbon liquid, wherein the system comprises a metal on an H-beta zeolite.
29. The process of claim 1 , wherein the chemical reactions produce a hydrocarbon liquid having an aromatics content of about 90% or greater and wherein the alcohol-forming catalyst comprises a metal on an HZSM-5 zeolite.
30. The process of claim 1 , wherein the chemical reactions produce a hydrocarbon liquid having a cyclo-paraffin and iso-paraffin content of about 90% or greater and wherein the alcohol-forming catalyst comprises a metal on an H-Y-faujasite zeolite.
31. The process of claim 1 , wherein the chemical reactions produce an ethylene-rich and propylene-rich hydrocarbon gas and produce no hydrocarbon liquid and wherein the alcohol-forming catalyst comprises a metal on an H-beta zeolite.
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