CN103313785B - 用于从合成气生产高级醇的碳担载的催化剂 - Google Patents
用于从合成气生产高级醇的碳担载的催化剂 Download PDFInfo
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- CN103313785B CN103313785B CN201180065317.8A CN201180065317A CN103313785B CN 103313785 B CN103313785 B CN 103313785B CN 201180065317 A CN201180065317 A CN 201180065317A CN 103313785 B CN103313785 B CN 103313785B
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- carbon
- nanofiber
- molecular sieve
- olefin polymeric
- mesoporous
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims description 40
- 230000015572 biosynthetic process Effects 0.000 title description 16
- 238000003786 synthesis reaction Methods 0.000 title description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000002121 nanofiber Substances 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 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 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000001093 holography Methods 0.000 abstract description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- 150000001340 alkali metals Chemical class 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 229910052622 kaolinite Inorganic materials 0.000 description 5
- 238000004375 physisorption Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
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- 230000032683 aging Effects 0.000 description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- -1 copper-aluminium-zinc Chemical compound 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
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- 229920000428 triblock copolymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020637 Co-Cu Inorganic materials 0.000 description 1
- 229910017777 Cu—Al—Zn Inorganic materials 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019064 Mg-Si Inorganic materials 0.000 description 1
- 229910019406 Mg—Si Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 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
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-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
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
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Abstract
担载在纳米纤维的中孔碳分子筛上的钼、硫和碱金属离子的催化剂组合物可用于将合成气转化为高级醇。该组合物经由浸渍制备并且可以特别增强对乙醇的选择性。
Description
相关申请的交叉引用
本申请是非临时申请,要求2010年12月06日提交的题为“CARBON-SUPPORTEDCATALYSTSFORPRODUCTIONOFHIGHERALCOHOLSFROMSYNGAS”的美国临时专利申请61/419,940的优先权,其教导通过参考并入本申请,以下如同全文复制。
技术领域
本发明涉及将合成气转化为醇的催化方法。更具体地,本发明涉及担载在纳米尺寸的碳材料上的基于钼的催化剂,其显示出改善的对高级醇的选择性。
背景技术
多种醇,特别是从甲醇到己醇(C1-6OH),是可以由合成气体合成的产物。合成气体也称为“合成气”,是氢气和一氧化碳气体的混合物(H2/CO))。特别认为C1-C6醇是重要的合成燃料和化学品。通常,在本申请限定为“高级醇(即,具有至少两个碳原子(C2+)的醇)”的醇通常用作特别是汽车燃料和燃料共混物。在本申请中,很多这种醇可提供期望的高辛烷值以及期望的氮氧化物(NOx)、臭氧、CO、和芳族蒸气的低排放。此外,高级醇(C2+OH)可以用作商业重要烯烃(经高级醇的脱水反应制备)的可替换原料,特别是当合成气源自生物质或煤时。
不幸地,并非所有的转化法都可提供对特定高级醇的所需选择性。研究者已经确定改变选择性的各种手段和方法。一种容易想到的方法是使用不同的催化剂。已知的制备醇的催化剂组合物包括以下的组合:铜,氧化锌,和氧化铝(Cu/ZnO/Al2O3);硫化钼(MoS2);钴和铜(Co-Cu);铼(Rh);和碳化钼(Mo2C)。它们各自会产生选择性的各种组合。在这些之中,有用的催化剂是,例如,公开于美国专利5,627,295的催化剂,该催化剂基于铜-铝-锌(Cu-Al-Zn)和选自第IIIA、IIIB、IVA、或IVB族的另一种元素。美国专利7,449,425公开了使用下述催化剂,该催化剂包括在镁-铝(Mg-Al)水滑石载体上的贵金属和某些过渡金属。
基于钼的催化剂(例如,MoS2,Mo2C)包括由碱金属离子促进的MoS2,该催化剂已经显示出可改善乙醇选择性。例如,美国专利4,661,525和美国专利4,825,013公开了如下制备C2-C6脂族醇的混合物的方法:使一氧化碳与氢气在掺杂碱金属的MoS2催化剂上反应,该催化剂通过添加第VIIIB族元素(例如,Co,Fe,或Ni)改性。也已经研究了碱金属促进剂(例如钠(Na)、钾(K)、铯(Cs)、或铷(Rb))与钴-钼-硫(Co-Mo-S)混合的组合物在转化合成气方面的性能。美国专利申请2010/007583718描述了将强碱性促进剂例如K、Cs、钡(Ba)、锶(Sr)、钪(Sc)、镧(La)、或铈(Ce)***分层的MoS2中以制备用于转化合成气的碱性催化剂的方法。美国专利4,675,344公开了控制合成气进料中的硫化氢(H2S)浓度以改善相对于甲醇而言对高级醇的选择性。美国专利4,749,724公开了使用担载在活性炭上的掺杂碱金属的MoS2,其Brunauer-Emmett-Teller(BET)比表面积为100至1,500平方米每克(m2/g)。
最近,材料化学领域的研究者已经成功地合成出了新型纳米结构的材料,例如Mg-Si鱼骨状氧化物,MgO纳米片,纳米多孔的磷铝酸盐,纳米管状二氧化钛和二氧化硅,页硅酸镍纳米管,和碳纳米片,纳米纤维,和纳米晶须。最近公开了关于以下的初步尝试:使用碳纳米管、中孔(mesoporous)碳结构、和碳纳米纤维作为将合成气转化为液体燃料的适当载体。在本领域,通常可互换使用术语“纳米多孔”和“中孔”,表示存在纳米尺寸的孔。
尽管有上述努力尝试,但是本领域仍需要将合成气转化为高级醇的方法,该方法可进一步改善对特别是乙醇的选择性。
发明内容
在一种实施方式中,本发明提供催化剂组合物,其包含在纳米纤维的中孔碳分子筛载体上的钼、硫和碱金属离子。
在另一种实施方式中,本发明提供制备催化剂组合物的方法,其包括用钼、硫和碱金属离子浸渍纳米纤维的中孔碳分子筛载体。
在又另一种实施方式中,本发明提供将氢气和一氧化碳气体的混合物转化为至少一种高级醇的方法,其包括在适于形成至少一种高级醇的条件下,使包括至少氢气和一氧化碳气体的气体混合物和催化剂组合物接触,所述催化剂组合物包括担载在纳米纤维的中孔碳分子筛载体上的钼、硫和碱金属离子。
具体实施方式
本发明包括特别用于从合成气合成乙醇和其它高级醇(即,C2+醇)的催化剂组合物,其中合成气在本申请定义为由H2和CO气体两者组成或包括该两者的任何混合物。该催化剂组合物包括碱金属、钼和硫,它们全部都担载在纳米纤维的中孔碳分子筛载体上。在具体的实施方式中,纳米纤维的碳分子筛载体可以具有一些性质,包括例如,在惰性气氛中高的耐化学性和和高的热稳定性。但是,组合物还可以表现出另外的有利特性,例如孔体积为0.8至1.7立方厘米每克(cm3/g);BET表面积为300至1,500平方米每克(m2/g);和平均孔径为3.0至5.0纳米(nm)。
在具体的实施方式中,中孔碳分子筛载体是由有序的纳米线构成的碳纳米纤维,即,具有基本均匀尺寸的基本上实心柱构造的结构。透射电子显微镜(TEM)图像显示,分子筛作为结构化以包含中孔的纳米纤维的集合,即,纳米纤维形成具有中孔内径空间的六边形横截面的柱状物。在本申请使用的术语“纳米纤维”和“纳米纤维的”表示具有纤维形态且平均横截面直径为1至100nm的结构,而术语“中孔”和“中孔的”表示纳米纤维结构中的具有能够容纳分子的平均内径的开口或空腔。在某些实施方式中,开口或空腔的平均内径为2至20nm,但是可以为稍微小于1nm至稍微小于100nm,这取决于纳米纤维的平均横截面直径。因此,纤维和孔都是纳米尺寸的。
这些碳分子筛载体可以使用任何有效的中孔模板制备,该模板可以是,例如,二氧化硅,硅铝酸盐,磷铝酸盐,氧化物,或其组合。在具体的实施方式中,有用的模板包括中孔氧化物,其优选地在排列和孔尺寸方面都表现出均匀性,其中碳源可渗透到该中孔氧化物内和该中孔氧化物上然后热解以形成碳结构。然后移除模板,所得自由竖立的碳结构基本上为中孔氧化物模板的复制阴模。制备过程可以期望地在两步法中进行,其中第一步是制备模板,第二步是使用模板制备碳分子筛载体。可替换地,模板可以购自或得自另一来源,然后用于形成碳分子筛载体。
例如,一种适当的模板是具有平均直径为约7至10nm的良好排序的六边形排列的中孔的二氧化硅。该模板可以通过正硅酸四乙酯(TEOS)在包含氢氯酸(氯化氢,HCl)和结构导向剂(structure-directingagent)例如PLURONICTMP-123的水溶液中水解合成,其中该PLURONICTMP-123是三嵌段共聚物[(聚(乙二醇)-嵌段-聚(丙二醇)-嵌段-聚(乙二醇),具有结构式HO(CH2CH2O)20(CH2CH(CH)O)70(CH2CH2O)20H)],可购自BASFCorporation。所得混合物可以在例如25摄氏度(°C)至40°C、优选为35°C的所需温度下进行搅拌,然后在较高温度例如60°C至180°C老化1至2天。在老化期间,形成包含表面活性剂填充的孔的沉淀物,然后可以将该沉淀物过滤以除去水,然后在空气中在室温干燥。然后可以在烘箱中在500°C至700°C的温度煅烧回收的固体,这样做可将表面活性剂从孔中除去并使开孔二氧化硅分子筛适宜用作模板。
证实煅烧的模板具有所需的中孔特性并因此可以用作本发明使用的碳分子筛载体的有效模板,该证实可以经由粉末X射线衍射(XRD)和氮气(N2)物理吸着(physisorption)获得。XRD在2θ角度为约0.8,1.4,和1.7处显示三个特征反射峰,它们分别标记为(100),(110),和(200)平面。模板粉末的BET表面积优选为300至1,500m2/g,在某些实施方式中为600至1,000m2/g。该产品可以直接用作碳分子筛载体的二氧化硅模板。
制备用于本发明催化剂组合物的碳分子筛载体的第二步骤包括用模板浸渍碳源例如糖类溶液。该模板可以是如上所述的制备的二氧化硅模板,或者可以是任何其他适当的模板。在该步骤中,可以首先制备包括碳源和无机酸的水溶液,其用作在合成条件下使碳单体聚合的催化剂。例如,单糖如葡萄糖、果糖、蔗糖、或其组合可以用作碳源,无机酸可以选自,例如,盐酸(HCl),硫酸(H2SO4),磷酸(H3PO4),硝酸(HNO3),或其组合。在该反应中,然后可以将水溶液添加到模板从而形成淤浆,其中该模板在该实施方式中为干燥形式。在所需的实施方式中,这可以最方便地在20°C至50°C的温度,优选为20°C至30°C的温度进行。环境温度因此通常是最方便的。将碳源添加到二氧化硅模板的中孔,直至孔几乎完全充满。在无机酸的存在下,其中的碳原子开始聚合,最后形成构成碳分子筛载体的结构的有机聚合物。参见,例如,J.Am.Chem.Soc.,122(2000),其通过参考完全并入本申请。
然后可以将淤浆热处理以确保聚合反应的最大化。优选在80°C至120°C的温度进行4至8小时的时间段以完成该最大化,在很多实施方式中在100°C进行约6小时是有效的。在该热处理之后,样品的聚合可以在较高温度(例如140°C至180°C)保持类似的时间长度(即,为4至8小时,优选为8小时)。在该期间,淤浆可能变为深棕色或黑色,表明任何碳源(例如,单糖,其存在于二氧化硅模板的孔中)的完全聚合。
在聚合反应完成之后,可以使淤浆热解以确保大部分非碳物质从模板移除。在很多实施方式中,这可以最有效地在真空下或在惰性气氛中进行。对于该高温分解,所需温度可以为700°C至1,100°C。
在制备碳分子筛载体的最终子步骤中,所得热解的固体可以用能够溶解二氧化硅模板的溶液处理。例如,可以有效地使用氢氟酸(HF)或强碱例如氢氧化钠(NaOH)或氢氧化钾(KOH)的水溶液。溶液溶蚀(即,溶解)来自碳分子筛载体的模板,然后可以将材料干燥以获得其最终形式作为稳定的分子筛载体。因为用于上述实施方式的特定的二氧化硅模板包含排列的类似尺寸的中孔的队列,其中来自碳源的碳聚合,当移除模板时,留下形成碳纳米纤维的碳纳米线的阵列。
可以通过以下方法证实最终产物确实是所需碳分子筛载体,所述方法包括,例如X射线衍射(XRD),TEM,N2物理吸着,和BET分析。使用小角度铜α辐射粉末XRD的表征显示对于2θ角度在约1.0处尖锐的峰,即,d-间距,通常标记为二维六边形结构的(100)平面。N2物理吸着分析中的吸附/解吸等温线通常为类型IV。BET表面积期望地为300至1,500m2/g,更期望为1,100至1,500m2/g;孔容可以为0.8至1.7cm3/g,更期望为0.85至1.2cm3/g;平均孔径可以为3.0至5.0nm,更期望为3.4至4.2nm。TEM显示作为起始二氧化硅模板的复制阴模的碳分子筛载体的有序结构。
一旦已经制备或获得纳米纤维的中孔碳分子筛载体,该载体已经可用于制备本发明催化剂组合物。在这些组合物中,使用钼(Mo)源和碱金属离子源浸渍碳分子筛载体。碱金属离子源可以是选自钠离子(Na+),钾离子(K+),铯离子(Cs2+),及其组合的任何离子。硫(S)也包括在催化剂组合物中,并且可以在那里与Mo结合作为MoS2,但并不必须。因此,S源可以最初与Mo源包含在组合物中,或在另一种实施方式中,呈其未硫化(没有MoS2,只有Mo)形式的催化剂组合物可以在以下时机用作为S源的硫化氢(H2S)处理:在加入Mo和碱金属离子之后,且于在反应中使用催化剂组合物之前或过程中(或两者),所述反应例如但不限于合成气转化为高级醇。期望钼与碱金属离子的摩尔比为3:1至1:3。
为完成浸渍,首先将所选的Mo源(优选为可溶的Mo盐,例如七钼酸铵((NH4)6Mo7O24.4H2O)))放入水溶液中,然后使该溶液在所需温度接触碳分子筛载体。针对大多数目的,Mo在溶液中的浓度为0.40至1.5标准摩尔浓度(M),这取决于催化剂组合物中Mo含量的所需水平。Mo源和碳分子筛载体之间的接触期望地发生在温度40°C至120°C,更期望地发生在60°C至80°C。然后可以将浸渍的碳分子筛载体干燥并加热(优选在100°C至500°C的温度),从而移除水并使Mo源分解,其中钼源将在分子筛的表面上产生二氧化钼(MoO2)和/或三氧化钼(MoO3)域。
在用钼浸渍之前或之后,也将呈离子形式的碱金属放在碳分子筛载体上。在Mo源的情况下,碱金属离子源也期望地为可溶盐,使其能够溶解于水溶液中,使得碱金属阳离子的摩尔浓度在具体的实施方式中为0.40至1.5M。针对该目的,期望碳分子筛载体在100°C至500°C、更期望地为250°C至400°C的温度接触溶液。然后可以将现在用Mo和K两者浸渍的碳分子筛载体干燥并加热,这优选地在300°C至500°C的温度和在惰性气氛(例如N2流)中进行以便于除去水。
包括碱金属离子促进剂的所得催化剂组合物现在可以由通式“[碱金属]/Mo/碳载体”例如“K/Mo/碳载体”描述,并且在具体的实施方式中也可以呈其硫化的(即,含MoS2的)形式。其期望地包括0.1至20wt%的Mo和0.3至15wt%的碱金属。如前所述,其结构和特征可以通过下述方法证实,例如粉末XRD,N2物理吸着,和TEM分析。这些可以通过粉末XRD分析表征,表明存在在2θ角度为26.1、36.9、和53.8时存在强反射(峰),这些是MoO2的特征峰,以及在2θ角度为23.3、27.3、34.4、39.1、46.2、49.2、49.3、52.7、55.1、和58.8时存在弱反射,这对应于包括K2Mo2O7、K2Mo4O6、和K2Mo7O20的钼酸钾,其中钾是所选的碱金属。促进的催化剂K/Mo/碳载体的BET表面积期望地为300至1,500m2/g,在具体的实施方式中为1,100至1,500m2/g。TEM分析显示在碳纳米纤维上分散良好的钼氧化物粒子。钼氧化物(通常为二氧化物)粒子的平均直径为20至60nm。在较低的Mo含量,可能不能见到XRD峰。
本发明的催化剂组合物可以用于从合成气形成高级醇(C2+OH)。特别可以使用具有低H2/CO比率的合成气,并且该合成气可以得自烃原料,例如石油、煤、天然气或生物质。H2与CO的摩尔比期望地为0.1至5摩尔H2每摩尔CO,其中优选的摩尔比为0.5至2。
如果在放置在用于合成气转化的适当的催化剂床之前并未将催化剂组合物硫化,可以将该组合物在放置之后且在用作催化剂之前、或者在使用过程中硫化。这可以优选在反应器中进行,其中在该反应器中形成高级醇,其中可以将催化剂放置在固定床、移动床、或流化床排列中。在一些实施方式中,预硫化可以通过使20vol%H2S/80vol%H2气体流过催化剂之上进行。该预硫化可以有效地在200°C至700°C、期望地为400°C至500°C的温度进行1至3小时的时间段。在一些实施方式中,该温度可以通过以例如5°C/分钟(°C/min)的速率从环境温度升温达到。一旦完成预硫化,可以用惰性气体流处理反应器,直至温度达到用于将合成气转化为高级醇的所需反应温度。在这些条件下,小浓度的H2S也通常包含在合成气流中,例如,为5至200份每百万份(ppm),这有助于保持硫化水平。
在可替换的方法中,硫化作用可以与高级醇生产同时进行,这是通过在合成气流中引入较大比例的H2S进行的。在该情况下,合成气流中包含的H2S的量可以为0.001vol%至0.1vol%,并最后导致原位形成MoS2组分。为确保硫化作用最优化,作为预硫化或在高级醇原位生产工艺中,硫化的组合物的样品可以通过粉末XRD分析。在以下2θ角度处可见宽反射:14.4;32.2;39.3;和58.3;当Mo含量大于或等于10wt%时,表明存在MoS2。在较低的钼含量,通常未观察到XRD反射,但是扩展的X射线吸收精细结构(EXAFS)和X射线光电子光谱(XPS)分析可以用于证实结构和形态并表明在孔中和在碳分子筛载体上存在细微分散的MoS2。在具体的实施方式中,硫化的催化剂的BET表面积可以为300至1,500m2/g,在具体的实施方式中为1,100至1,500m2/g,即,和非硫化的催化剂近似相同的表面积范围。
在某些实施方式中,可以在235°C至360°C的反应温度在本发明催化剂组合物上将合成气转化为高级醇。在具体的实施方式中,压力可以为约1,000磅每平方英寸(psi)至2,500psi(6.89至17.24兆帕(MPa)。气体时空速度(GHSV)可以为4,000至12,000毫升每克每小时(mL/g/h),而H2与CO的摩尔比可以为约1:4至4:1。N2可以用作内标,由该内标可以计算CO转化率。转化率也可以由反应的总碳质量平衡计算。以这种方式确定的CO的转化率可以为5至40摩尔百分比(mol%)。对乙醇和高级醇的选择性(基于碳原子)可以为40至80mol%,其中对乙醇的选择性为30至50mol%,不包括二氧化碳(CO2)。通常,甲醇选择性可能往往低于乙醇选择性。在很多实施方式中,甲烷可以是形成的主要烃,对其的选择性可以为10至30mol%,不包括CO2。
实施例
实施例1
制备中孔碳分子筛载体
二氧化硅分子筛模板由正硅酸四乙酯(TEOS)使用三嵌段共聚物PLURONICTMP-12343合成。将8.79克(g)的PLURONICTMP-12343添加到包含300mL去离子(DI)水和48.24g10标准摩尔浓度(N)HCl的500毫升(mL)烧瓶中。将溶液在35°C搅拌2小时(h),然后缓慢添加17.32g的TEOS。将合成的溶液密封并在35°C及搅拌下老化24h,然后在75°C在烘箱中老化48h。在冷却至室温之后,将沉淀物过滤并用DI水洗涤。将滤饼在空气中在室温干燥过夜,然后在空气中在550°C以2°C每分钟(°C/min)的升温速率煅烧6小时以除去有机试剂。
将5g中孔二氧化硅模板用包含10gDI水、0.72gH2SO4、和6.25g蔗糖(C12H22O11)的溶液浸渍。然后将混合物在100°C在空气中干燥6小时,然后以10°C/min的升温速率加热6h直到160°C。然后,将固体在50毫升每分钟(mL/min)氮气(N2)流中以2°C/min的升温速率在900°C碳化2小时,然后用5wt%HF溶液洗涤至少两次,之后在烘箱中在105°C干燥过夜。干燥的中孔碳分子筛载体的BET表面积为1,390m2/g。
实施例2
制备催化剂组合物A
首先,将包含1.31g七钼酸铵((NH4)6Mo7O24.4H2O)和5.0gDI水的溶液在65°C搅拌2小时。然后,将2.50g实施例1中描述的中孔碳分子筛载体添加到预加热的溶液中。使所得混合物在75°C保持2小时,然后将其在烘箱中在105°C干燥过夜。在0.5英寸(in)直径石英管中在50mL/min的N2流中以5°C/min的升温速率在500°C加热所得黑色粉末2小时。
然后在室温将加热的固体添加到5.0g包含0.514g碳酸钾(K2CO3)的DI水中。将湿润的固体在烘箱中在10°C干燥过夜,然后在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在400°C煅烧该固体1小时。计算MoO3形式的钼含量为约30wt%,K2CO3含量为约15wt%。煅烧的催化剂的BET表面积为317m2/g。XRD表明:在以下(2θ)存在强反射,表示存在MoO2:26.2;和37.4;在以下(2θ,低强度(“弱”))存在反射表示存在K2Mo7O20:23.2;36.7;51.9;64.1;和65.0。
实施例3
制备催化剂组合物B
首先,将包含0.595g七钼酸铵((NH4)6Mo7O24.4H2O)和4.0gDI水的溶液在65°C搅拌2小时。然后将1.95g实施例1中所述中孔碳分子筛载体添加到预加热的溶液中。使所得混合物在75°C保持2小时,然后将其在烘箱中在105°C干燥过夜。在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在500°C加热所得黑色粉末2小时。然后在室温将加热的固体添加到4.0g包含0.23gK2CO3的DI水中。将湿润的固体在烘箱中在10°C干燥过夜,然后在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在400°C煅烧该固体1小时。计算MoO3形式的钼含量为约20wt%,K2CO3含量为约10wt%。煅烧的催化剂的BET表面积为771m2/g。XRD:MoO2(2θ):26.0;37.4;和53.0;K2Mo2O7(2θ,低强度):27.2;28.4;和36.9。
实施例4
制备催化剂组合物C
首先,将包含0.108g七钼酸铵((NH4)6Mo7O24.4H2O)和1.5gDI水的溶液在65°C搅拌2小时。将0.78g实施例1中所述中孔碳分子筛载体添加到预加热的溶液中。使混合物在75°C保持2小时,然后将其在烘箱中在105°C干燥过夜。在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在500°C加热所得黑色粉末2小时。
然后在室温将加热的固体添加到1.5g包含0.043gK2CO3的DI水中。将湿润的固体在烘箱中在105°C干燥过夜,然后在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在400°C煅烧该固体1小时。计算MoO3形式的钼含量为约10wt%,K2CO3含量为约5wt%。煅烧的催化剂的BET表面积为535m2/g。XRD:K2Mo2O7(2θ,低强度):27.6,42.5,和43.7。
实施例5
制备催化剂组合物D
首先,将包含0.55g七钼酸铵((NH4)6Mo7O24.4H2O)和3.5gDI水的溶液在65°C搅拌2小时。将1.80g实施例1中所述中孔碳分子筛载体添加到预加热的溶液中。使混合物在75°C保持2小时,然后将其在烘箱中在105°C干燥过夜。在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在500°C加热所得黑色粉末2小时。
然后在室温将加热的固体添加到3.5g包含0.645gK2CO3的DI水中。将湿润的固体在烘箱中在105°C干燥过夜,然后在0.5英寸直径石英管中在50mL/min的N2流中以5°C/min的升温速率在400°C煅烧该固体1小时。计算MoO3形式的钼含量为约20wt%,K2CO3含量为约30wt%。煅烧的催化剂的BET表面积为446m2/g。XRD:MoO2(2θ):25.7;37.9;53.9;和60.4;K2Mo2O7,K2Mo4O6,K2Mo7O20(2θ):23.3;27.3;34.4;39.1;46.2;49.2;49.3;52.7;55.1;58.8;62.8;和64.5。
实施例6
制备高级醇
反应器由0.25英寸不锈钢(316SS)管与填装量为0.20g的催化剂组合物组成。将来自机筒的预混合的H2、CO、和N2进料气体压缩并调节为表1、2和3中所述的反应压力。进料气体混合物包含摩尔比为1/1的H2和CO且包含约50ppm的H2S,以及用作内标的约10体积%(vol%)的N2。混合的进料气体流动通过170°C的沸石13X分子筛的床以除去铁(Fe)和进料的CO部分中可能存在的任何其它羰基污染物。进料气体然后以各表中所述的GHSV流动通过保持在各自所述反应温度和在1,500磅每平方英尺表压(psig)(10.34MPa)的压力下的固定床反应器以形成产物流出物。
将反应器流出物进料到气相色谱仪分析产物分布,其中所得催化活性(“生产力”)表示为每小时的以毫克计的单独产物的重量除以以克计的催化剂(cat)的重量(mg/gcat/h),如表1-3所示,其中表3说明了改变单一催化剂组合物(催化剂组合物D)的GHSV的影响。“产物选择性”(基于碳摩尔百分比(mol%C),不包括CO2)定义为各产物中的碳原子总数除以所有醇(包括甲醇和高级醇)、非醇氧化产物、和烃中碳原子的总和。烃(“HC”)主要为甲烷(CH4),氧化产物(“Oxy”)是排除所有醇的全部含氧产物。本发明的催化剂组合物显示,在温度为285°C至310°C和GHSV为6,000mL/g/h时,高级醇(C2+OH)的生产力为38.2至115mg/gcat/h。
表1
GHSV=6,000mL/g/h;温度(°C)=285;H2/CO=1;H2S(ppm)=50;催化剂重量=0.20g。
表2
GHSV=6,000mL/g/h;温度(°C)=310;H2/CO=1;H2S(ppm)=50;催化剂重量=0.20g。
表3.催化剂组合物D
温度(°C)=310;H2/CO=1;H2S(ppm)=50;催化剂重量=0.20g。
Claims (9)
1.催化剂组合物,其包含在纳米纤维的中孔碳分子筛载体上的钼、硫和碱金属离子,其中纳米纤维形成具有中孔内径空间的六边形横截面的实心柱状物。
2.权利要求1的催化剂组合物,其中
所述碱金属离子选自下述离子:钠,钾,铯,及其组合,和/或
所述钼和硫组合为硫化钼。
3.权利要求1或2的催化剂组合物,其中X射线粉末衍射分析表明:在角度2θ为26.1;36.9;和53.8处具有强反射,以及在2θ角度为23.3;27.3;34.4;39.1;46.2;49.2;49.3;52.7;55.1;和58.8处具有弱反射。
4.权利要求1或2的催化剂组合物,其中Brunauer-Emmett-Teller分析显示表面积为300至1,000m2/g。
5.权利要求3的催化剂组合物,其中Brunauer-Emmett-Teller分析显示表面积为300至1,000m2/g。
6.制备权利要求1-5任一项的催化剂组合物的方法,包括用钼、硫和碱金属离子浸渍纳米纤维的中孔碳分子筛载体。
7.权利要求6的方法,其中所述纳米纤维的中孔碳分子筛载体如下制备:(a)使中孔二氧化硅模板与碳源在适于将所述碳源吸收进所述中孔二氧化硅模板中并使碳源聚合的条件下接触形成纳米纤维的中孔碳结构;(b)通过使所述纳米纤维的中孔碳结构与酸或碱的水溶液在适于溶解所述中孔二氧化硅模板和获得纳米纤维的中孔碳分子筛载体的条件下接触,移除所述中孔二氧化硅模板;和(c)回收所述纳米纤维的中孔碳分子筛载体。
8.将氢气和一氧化碳气体的混合物转化为至少一种高级醇的方法,其包括在适于形成至少一种高级醇的条件下,使包括至少氢气和一氧化碳气体的气体混合物和权利要求1-4任一项的催化剂组合物接触。
9.权利要求8的方法,其中,在6,000mL/g/h的气体时空速度下,所述催化剂组合物表现出对至少一种高级醇的生产力为38.2至115.7mg/g催化剂/h。
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- 2011-12-01 CN CN201180065317.8A patent/CN103313785B/zh not_active Expired - Fee Related
- 2011-12-01 EP EP11797083.0A patent/EP2648840B1/en not_active Not-in-force
- 2011-12-01 US US13/883,681 patent/US8999876B2/en not_active Expired - Fee Related
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WO2012078436A1 (en) | 2012-06-14 |
EP2648840B1 (en) | 2015-01-21 |
BR112013011150A2 (pt) | 2020-09-01 |
EP2648840A1 (en) | 2013-10-16 |
US8999876B2 (en) | 2015-04-07 |
CN103313785A (zh) | 2013-09-18 |
US20130245137A1 (en) | 2013-09-19 |
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