CN104884159A - 用于生产丁醇的催化剂和方法 - Google Patents
用于生产丁醇的催化剂和方法 Download PDFInfo
- Publication number
- CN104884159A CN104884159A CN201380066333.8A CN201380066333A CN104884159A CN 104884159 A CN104884159 A CN 104884159A CN 201380066333 A CN201380066333 A CN 201380066333A CN 104884159 A CN104884159 A CN 104884159A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- palladium
- copper
- cobalt
- butanols
- Prior art date
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- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims description 29
- 230000008569 process Effects 0.000 title description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 188
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011135 tin Substances 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 13
- 239000000969 carrier Substances 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 71
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 66
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 20
- 235000013495 cobalt Nutrition 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 239000002243 precursor Substances 0.000 description 15
- 238000007598 dipping method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000000543 intermediate Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 7
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- -1 trifluoroacetate) Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 3
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000006187 pill Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Chemical class 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000010452 phosphate Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- BYSUYBCCLCSGPR-UHFFFAOYSA-N 1h-pyrazol-5-yloxyboronic acid Chemical compound OB(O)OC1=CC=NN1 BYSUYBCCLCSGPR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BCKARVLFIJPHQU-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole-4-carboxylic acid ethyl ester Chemical compound CCOC(=O)C=1C(C)=NNC=1C BCKARVLFIJPHQU-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 150000003973 alkyl amines Chemical class 0.000 description 1
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- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- NWTVGQNUHYHLHX-UHFFFAOYSA-N butan-1-ol;prop-1-ene Chemical class CC=C.CCCCO NWTVGQNUHYHLHX-UHFFFAOYSA-N 0.000 description 1
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- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 229940011182 cobalt acetate Drugs 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
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- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
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- 239000013527 degreasing agent Substances 0.000 description 1
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- 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
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
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- 150000003053 piperidines Chemical class 0.000 description 1
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- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 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
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
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- 239000003981 vehicle Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
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Classifications
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- 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
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/42—Platinum
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- 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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Abstract
在一个实施方案中,本发明涉及用于将乙醇转化成更高级的醇,例如丁醇的催化剂组合物。催化剂组合物包含一种或多种金属和一种或多种载体。一种或多种金属选自钴、镍、钯、铂、锌、铁、锡和铜。一种或多种载体选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO,及其混合物,其中催化剂基本上不含碱金属和碱土金属。
Description
优先权要求
本申请要求2012年12月19日提交的美国申请号13/719,886的优先权。该申请的全部内容以引用方式并入本文。
本发明领域
本发明大体上涉及由乙醇制备更高分子量醇的方法,并且特别涉及将乙醇催化转化成丁醇。
本发明背景技术
已经就用于生产丁醇的经济上有活力的方法进行了研究。与乙醇相似,丁醇可以是对油的依赖的可能的解决方案,因为这两者都可以用作内燃机中的燃料。事实上,归因于更长的烃链和非极性特征,丁醇可以是比乙醇更好的燃料选项,因为丁醇比乙醇更类似于汽油。此外,丁醇可以用于生产药物、聚合物、硝棉塑料、除草剂酯和黄原酸丁酯。丁醇也可以作为溶剂用于提取精油或作为香水中的成分;作为抗生素、激素和维生素生产中的提取剂;作为溶剂用于漆料、涂料、天然树脂、树胶、合成树脂、生物碱和樟脑。丁醇的其它应用包括作为纺织品中的溶胀剂;作为突破(break)流体、清洁配制剂、脱脂剂和驱虫剂的组分;和作为矿石浮选剂和木材处理系统的组分。
工业上,通常在铑系均相催化剂的存在下由石油化学原料丙烯生产丁醇。在该工艺过程中,将丙烯加氢甲酰基化成丁醛,并且然后将丁醛加氢成产物丁醇。然而,归因于波动的天然气和原油价格,使用该方法生产丁醇的成本也变得更不可预测和显著。
已知,丁醇可以通过在碱性催化剂上在高温下使用Guerbet反应由乙醇缩合来制备。经由Guerbet反应将乙醇转化成丁醇的反应机理包括四步骤的序列,如反应路线1中所示。在第一步骤中,乙醇氧化成中间体乙醛并且两个中间体乙醛经历羟醛缩合反应以形成巴豆醛,其经由加氢还原成丁醇。参见,例如,J.Logsdon in Kirk-othmerEncyclopedia of Chemical Technology,John Wiley and Sons,Inc.,NewYork,2001;J.Mol.Catal.A:Chem.,2004,212,p.65;和J.Org.Chem.,2006,71,p.8306。
已经研究了各种催化剂来改进乙醇至丁醇的转化率和选择性。例如,M.N.Dvornikoff and M.W.Farrar,J.of Organic Chemistry(1957),11,540-542公开了使用MgO-K2CO3-CuCrO2催化剂体系来促进乙醇缩合成更高级的醇,包括丁醇。美国专利号5,300,695公开了这样的方法,其中将L-类型沸石催化剂,例如钾L-类型沸石,用于与具有X个碳原子的醇反应,以生产具有更高分子量的醇。
WO2006059729中公开了使用羟基磷灰石Ca10(PO4)6(OH)2、磷酸三钙Ca3(PO4)2、磷酸一氢钙CaHPO4·(0-2)H2O、二磷酸钙Ca2P2O7、磷酸八钙Ca8H2(PO4)6·5H2O、磷酸四钙Ca4(PO4)2O,或无定形的磷酸钙Ca3(PO4)2·nH2O,来将乙醇转化成更高分子量的醇。
Carlini等人,Journal of Molecular Catalysis A:Chemical(2005),232,13-20公开了双功能非均匀水滑石,用于将甲醇和正丙醇转化成异丁醇。
还研究了用于由甲醇或乙醇制备更高分子量的醇的其它催化剂体系。例如,US4,551,444讨论了使用各种金属的多组分催化剂体系的用途;US5,095,156和US5,159,125讨论了氧化镁的影响;US4,011,273讨论了不可溶的铅催化剂的用途;US7,807,857关注的是第II族金属的盐;并且US4,533,775讨论了包含金属乙炔化物、氢化物、醇盐和促进剂的催化剂体系。
上述文献以引用方式并入本文。
尽管如此,依然需要用于由乙醇制备丁醇的改进的催化剂,尤其是具有对丁醇的改进的活性和选择性的那些。
发明内容
在第一实施方案中,本发明涉及用于将醇转化成更高级的醇的催化剂。催化剂包含一种或多种金属和一种或多种载体。优选地,一种或多种金属选自钴、镍、钯、铂、铁、锌、锡和铜。优选地,一种或多种载体选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物。
在第二实施方案中,本发明涉及用于将醇转化成更高级的醇的催化剂。催化剂包含一种或多种载体和一种或多种载体上的一个或多个金属层。优选地,一种或多种载体选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物。优选地,一种或多种载体上的金属层包含选自钴、镍、钯、铂、铁、锌、锡和铜的一种或多种金属。
在第三实施方案中,本发明涉及用于生产丁醇的方法。该方法包括以下步骤:在反应器中的催化剂之上进料包含乙醇的气态物流以形成丁醇,其中催化剂包含一种或多种金属和一种或多种载体。优选地,一种或多种金属选自钴、镍、钯、铂、铁、锌、锡和铜。优选地,一种或多种载体选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物。
具体实施方式
介绍
本发明大体上涉及用于由具有两个或更少个碳的醇合成直链多碳醇(其作为化学工业原材料和燃料组合物或其混合物是有用的)的方法。
使用最常规的方法生产多碳醇(例如丁醇)受到了经济和环境约束的限制。最为人知的方法之一是Guerbet反应。具体地,乙醇可以用作原料来生产丁醇。然而,反应的中间体可以形成竞争副产物,例如二乙基醚、乙烯、1-己醇、2-乙基丁醇和/或2-乙基己醇。这些中间体可能导致丁醇产物中的杂质。例如,二乙基醚和乙烯可能由于在酸性催化剂的存在下的乙醇的脱水而形成。1-己醇也可以经由将乙醛加成至丁醛(巴豆醛中间体)形成。丁醛也可以与其它中间体反应以形成2-乙基丁醇和2-乙基己醇。多碳醇和杂质的粗制混合物会增加回收丁醇所需要的纯化。
催化剂(例如多催化剂体系、羟基磷灰石和磷酸盐衍生物)已经用于优化对丁醇的收率和选择性。此外,还研究了用于Guerbet反应的工艺条件来优化对丁醇的收率和选择性。
Guerbet反应通过多种中间体将两摩尔的乙醇转化成一摩尔的丁醇。反应包括首先氧化乙醇以形成乙醛,将乙醛缩合成3-羟基-丁醛,将3-羟基-丁醛脱水至巴豆醛,并且将巴豆醛还原成丁醇。
现在已经发现某些催化剂有效地氧化乙醇以形成中间体乙醛(其形成巴豆醛),并且将巴豆醛还原成丁醇。优选地,本发明的催化剂充当氧化乙醇并且促进羟醛缩合的基底,并且还充当用于巴豆醛的加氢位点以形成丁醇。令人惊奇和出人意料的是,发明人发现涂覆在载体上的至少一种碱金属和金属的催化剂体系有益地导致乙醇转化率和/或丁醇选择性的改善。此外,新型催化剂体系有益地降低了对DEE和乙烯的选择性。就本申请的目的,直链多碳醇是优选的,并且因此,丁醇是指正丁醇,除非另有说明。
催化剂组合物
在另一个实施方案中,本发明涉及包含载体上的选自钴、镍、钯、铂、铁、锌、锡和铜的金属的催化剂。更优选地,金属选自钯、铜、锡和钴。金属可以涂覆在载体上。在一个实施方案中,催化剂包含0.01wt.%-20wt.%,例如,0.05wt.%-18wt.%,或0.1wt.%-16wt.%的量的金属。载体可以包括上述那些,优选的是,Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物。优选地,在该实施方案中,催化剂不包含碱金属和/或碱土金属。因此,催化剂可以基本上不含碱金属和/或碱土金属。
在一个实施方案中,载体可以为Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物。优选载体为Al2O3、ZrO2或ZnO。适合的载体可以具有至少500m2/g,例如,至少200m2/g或至少50m2/g的表面积。
氧化铝载体可以包括γ-氧化铝(γ-Al2O3)、η-氧化铝(η-Al2O3)、κ氧化铝(κ-Al2O3)、θ-氧化铝(θ-Al2O3)或其它氧化铝相,其在用于催化剂煅烧和将醇(例如乙醇)转化成其它醇(例如丁醇)的温度下是稳定的。除非另有说明,就本发明的目的,γ-氧化铝是优选的。
如本申请中使用的沸石通常是指微孔硅铝酸盐矿物。适合的沸石的实例包括但不限于硅铝磷酸盐(SAPO-34)、斜发沸石、ZSM-5、X-沸石、Y-沸石。
载体的量可以取决于金属负载量而改变并且通常包含催化剂的余量。在一个实施方案中,催化剂包含80wt.%-99.99wt.%,例如,82wt.%-99.95wt.%,或84wt.%-99.9wt.%的量的载体。
在一个实施方案中,催化剂可以包含铜和γ-Al2O3。催化剂组合物可以包含0.1wt.%-20wt.%的铜,例如,0.5wt.%-18wt.%,或1wt.%-16wt.%。催化剂组合物包含80wt.%-99.9wt.%的γ-Al2O3,例如,82wt.%-99.5wt.%或84wt.%-99wt.%。
在另一个实施方案中,催化剂可以包含钴和θ-Al2O3。催化剂组合物可以包含0.1wt.%-20wt.%的钴,例如,0.5wt.%-18wt.%,或1wt.%-16wt.%。催化剂组合物包含80wt.%-99.9wt.%的θ-Al2O3,例如,82wt.%-99.5wt.%或84wt.%-99wt.%。
在又一个实施方案中,催化剂可以包含铜和ZrO2。催化剂组合物可以包含0.1wt.%-20wt.%的铜,例如,0.5wt.%-18wt.%,或1wt.%-16wt.%。催化剂组合物包含80wt.%-99.9wt.%的ZrO2,例如,82wt.%-99.5wt.%或84wt.%-99wt.%。
在一个实施方案中,催化剂可以包含由包含一种金属的一个金属层涂覆的载体。金属选自钴、镍、钯、铂、锌、铁、锡和铜。在优选实施方案中,金属选自钴、镍、钯、铂、锡和铜。
在一个实施方案中,催化剂包含载体、金属层。金属层可以涂覆在载体上。在一个实施方案中,金属层为选自钴、镍、钯、铂、铁、锌、锡和铜的金属。金属层可以通过浸渍方法施涂在载体上。
现在已经发现,相比于不含金属的催化剂,金属-涂覆的载体催化剂令人惊奇地实现了出人意料地高的丁醇选择性和收率。此外,丁醇选择性和收率的增加伴随着对副产物(例如二乙基醚(DEE)和乙烯)的选择性的降低。如上所述,反应混合物中DEE和乙烯通过乙醇在酸的存在下脱水而产生。在一个实施方案中,令人惊奇和出人意料的是,现在已经发现催化剂抑制了DEE和乙烯的形成。例如,使用该催化剂组合物可以实现至少20%,例如,至少30%,或至少40%的丁醇选择性。令人惊奇和出人意料的是,丁醇选择性的该增加伴随副产物选择性的降低。例如,对DEE的选择性小于15wt.%,例如,小于10wt.%,或小于5wt.%。此外,乙烯选择性小于10wt.%,例如,小于5wt.%,或小于1wt.%。在一个实施方案中,二乙基醚和乙烯选择性可以小于丁醇选择性。因此,催化剂有利于形成丁醇。不希望受限于理论,认为作为用至少一种金属涂覆载体表面的结果,相比于不含金属的载体催化剂,催化剂组合物可以驱使Guerbet反应有利于丁醇选择性,同时抑制DEE和乙烯的产生。
在一个实施方案中,令人惊奇和出人意料的是,还发现了金属-涂覆的催化剂还可以抑制DEE的形成。在一个实施方案中,令人惊奇和出人意料的是,已经发现铜γ-Al2O3、铜θ-Al2O3和铜ZrO2催化剂抑制了DEE和乙烯的形成。具体地,发明人发现通过抑制DEE和乙烯的形成,催化剂组合物提高了丁醇的选择性。
在将乙醇转化成丁醇时水是副产物。因为水比乙醇更有极性,据信水可以在催化剂的极性表面上与乙醇竞争。发明人已经发现催化剂的表面极性可以通过将有机金属前体引入至载体的表面来改性,以最小化水/乙醇竞争。有机金属前体可以包括吡啶、氢氧化铵四甲基氢氧化铵、四丁基氢氧化铵、甲基胺、咪唑和其它适合的载体改性剂。有机金属前体可以为这样的载体改性剂,其可以调节载体材料的化学或物理性质,例如载体材料的酸度或碱度。如此,催化剂表面上乙醇的量和停留时间可以增加并且由此促进碳-碳毛细管缩合。
在其它实施方案中,除载体之外,催化剂可以进一步包含载体改性剂。在一个实施方案中,改性载体是指包括载体材料和载体改性剂的载体,所述载体改性剂,例如,可以调节载体材料的化学或物理性质,例如载体材料的酸度或碱度。
催化剂可以进一步包含其它添加剂,其实例可以包括:用于提高可模塑性的模制助剂;用于提高催化剂强度的强化物(reinforcement);用于在催化剂中形成适当的孔的成孔剂或孔改性试剂,和粘合剂。这些其它添加剂的实例包括草酸、柠檬酸、聚丙烯酸、己二酸、硬脂酸、石墨、淀粉、纤维素、二氧化硅、氧化铝、玻璃纤维、碳化硅和氮化硅。优选地,这些添加剂对催化性能(例如,转化率和/或活性)不具有有害的影响。这些各种添加剂可以以这样的量添加,所述量使得催化剂的物理强度不易劣化到使得实际地将催化剂用作工业催化剂变得不可能的程度。
在一些实施方案中催化剂组合物包含孔改性试剂,例如草酸。孔改性试剂的优选类型是热稳定的并且在低于300℃,例如,低于250℃的温度下具有显著蒸气压。在一个实施方案中,在150℃-250℃,例如,150℃-200℃的温度下,孔改性试剂的蒸气压为至少0.1kPa,例如,至少0.5kPa。
孔改性试剂具有相对高熔点,例如,大于60℃,例如,大于75℃,以在将催化剂压缩成块状物、片剂或丸粒的过程中防止熔化。优选地,孔改性试剂包含相对纯的物质而不是混合物。如此,在形成块状物或片剂的过程中,较低熔点的组分不将在压缩下液化。例如,在孔改性试剂为脂肪酸时,脂肪酸混合物的较低熔点的组分可以通过压制作为液体除去。如果该现象在块状物或片剂压缩过程中发生,液体的流动可能扰乱孔结构并且随着催化剂组合物上孔直径的变化而产生不希望的孔体积分布。在其它实施方案中,孔改性试剂在低于其熔点的温度下具有显著的蒸气压,使得其可以通过升华至载气中除去。
催化剂制备
使用浸渍方法合成具有金属涂覆载体的催化剂。在力下压制载体持续预定的时间以形成丸粒。例如,载体可以以180,000N的力压制。丸粒稍微压碎至希望的粒度。量出一定量的丸粒形式的载体并且放置在圆底反应器中。第一金属通过如下制备:将金属前体(例如金属硝酸盐)溶解于一定量的水和/或丙酮中以形成第一金属前体溶液,其使用旋转干燥器通过逐步始润而浸渍至载体上。第一金属涂覆的载体在烘箱中在希望的温度下干燥一段时间并且随后煅烧。。
初始温度可以为10℃-150℃,例如,30℃-120℃,或50℃-90℃。升温速率可以为1℃-5℃/分钟。最终温度可以取决于催化剂组成而变化并且通常为300℃-900℃,例如,450℃-800℃,或500℃-700℃。保持时间为1小时-10小时,例如,2小时-8小时,或4小时-6小时。取决于使用的金属,其它温度曲线可以是适合的。混合物的煅烧可以在希望的温度下在惰性气氛、空气或含氧气体中进行。蒸汽、烃或其它气体或蒸气可以在煅烧步骤过程中或在煅烧后添加到气氛中以对物理和化学表面性质以及组织性质产生希望的效果,例如增加大孔隙率。
作为实例,温度曲线可以以60℃开始,以5℃/分钟的速率增加直到温度达到600℃,并且保持在600℃下5小时,并且冷却至室温。对于第VIII族金属,煅烧温度可以更低,例如300℃。
在一个实施方案中,可以将任何适合的金属前体用于制备催化剂组合物。适合的金属前体的非限制实例包括:金属氧化物、金属氢氧化物(包括水合氧化物)、无机和有机酸的金属盐,例如,硝酸盐、亚硝酸盐、硫酸盐、卤化物(例如,氟化物、氯化物、溴化物和碘化物)、碳酸盐、磷酸盐、叠氮化物、硼酸盐(包括氟硼酸盐、吡唑基硼酸盐等)、磺酸盐、羧酸盐(例如,甲酸盐、乙酸盐、丙酸盐、草酸盐和柠檬酸盐)、取代羧酸盐(包括卤代羧酸盐(例如,三氟乙酸盐)、羟基羧酸盐、氨基羧酸盐等)和其中金属为阴离子的部分的盐和酸(例如,六氯铂酸盐、四氯合金酸盐、钨酸盐和相应的酸)。
用于本发明的方法的适合的金属前体的另外的非限制性实例包括金属的醇盐、金属的配合物化合物(例如,配合物盐)。例如,β-二酮(例如,乙酰丙酮酸盐)、与胺的复合物、N-杂环化合物(如吡咯、氮丙啶、吲哚、哌啶、吗啉、吡啶、咪唑、哌嗪、三唑及其取代的衍生物)、氨基醇(例如、乙醇胺等等)、氨基酸(例如,甘氨酸等)、酰胺(例如,甲酰胺、乙酰胺等),和腈(例如,乙腈等)。优选的金属前体的非限制性实例包括硝酸盐和氧化物。
用于本发明的方法的具体金属前体的非限制性实例包括溴化钯、氯化钯、碘化钯、硝酸钯、水合硝酸钯、四胺硝酸钯、氧化钯、水合氧化钯和硫酸钯;氧化铜、氢氧化铜、硝酸铜、硫酸铜、氯化铜、甲酸铜、乙酸铜、新癸酸铜、乙基己酸铜、甲基丙烯酸铜、三氟乙酸铜、乙酰乙酸铜和六氟乙酰丙酮酸铜;和乙酸钴、氢氧化钴、碳酸钴、硝酸钴、2,4-戊二酮酸钴、甲酸钴、氧化钴、氯化钴、钴醇盐、高氯酸钴和羧酸钴。可以如此使用以上化合物或任选地以溶剂化物等等的形式,例如,作为水合物的形式使用。可以用于本发明的具体金属前体的实例包括水合硝酸钯、水合硝酸铜和硝酸钴。
本发明还构思了使用相同金属的不同的化合物(例如,不同的盐)的混合物和/或使用不同的金属和/或混合的金属前体(例如,混合的盐和/或混合的氧化物)的化合物的混合物。条件是不同的金属中没有一个包含碱金属或碱土金属。因此,如本文所用的术语“金属前体”包括单一的金属前体和两种或更多种金属前体的任何混合物。在优选实施方案中,使用至少一种金属和载体制备催化剂组合物。
丁醇的生产
可以采用适合的反应和/或分离路线使用催化剂以形成包含丁醇的粗产物物流。例如,在一些实施方案中,通过使低分子量醇(例如,乙醇)与催化剂接触以形成粗制的更高级醇产物物流(即,具有丁醇的物流)而形成粗产物物流。催化剂也可以为载体上的金属。在优选实施方案中,粗产物物流为乙醇的缩合反应的反应产物,所述反应在金属-涂覆的载体之上进行。在一个实施方案中,粗产物物流是气相反应的产物。
进料物流可以为包含乙醇的气态物流。优选地,气态物流包含大于5vol.%的乙醇,例如,大于10vol.%或大于20vol.%。进料物流也可以包含其它分子,例如吡啶、NH3和烷基胺。惰性气体可以处于气态物流中并且因此,可以包括氮、氦、氩和甲烷。优选地,没有氢随着气态物流引入,并且因此,气态物流基本上不含氢。不希望受限于理论,中间体反应所需要的氢可以原位产生。
在一些实施方案中,缩合反应可以实现有利的乙醇转化率和有利的对丁醇的选择性和生产率。就本发明的目的,术语“转化率”是指进料中转化成除了乙醇之外的化合物的乙醇的量。转化率表示为基于进料中的乙醇的百分比。乙醇转化率可以为至少20%,例如,至少30%,至少40%,或至少50%。
在涉及丁醇的形成时,选择性表示为希望的(一种或多种)产物中的碳量与总产物中的碳量的比例。该比例可以乘以100以得到选择性。优选地,对丁醇的选择性为至少20%,例如,至少30%,或至少40%。在一些实施方案中,对C4+醇(例如,丁醇、异丁醇、2-丁醇、叔丁醇、1-己醇、2-乙基丁醇和2-乙基己醇)的催化剂选择性为至少30%,例如,至少50%,至少60%,或至少80%。
该方法的优选实施方案展示出对不希望的产物(例如二乙基醚和乙烯)的低选择性。对这些不希望的产物的选择性优选小于20%,例如,小于5%或小于1%。更优选地,这些不希望的产物不可检测。
乙醇可以作为液体物流或蒸气物流进料至反应器。优选地,乙醇作为蒸气物流进料。反应器可以是任何适合的反应器或反应器组合。优选地,反应器包含固定床反应器或一系列固定床反应器。在一个实施方案中,反应器为气体流动催化反应器或一系列气体流动催化反应器。当然,可以采用其它反应器例如连续搅拌釜反应器或流化床反应器。在一个实施方案中,蒸气乙醇物流基本上不含氢,例如,小于1wt.%,小于0.1wt.%,或小于0.01wt.%的氢。
缩合反应可以在至少200℃,例如,至少300℃,或至少350℃的温度下进行。就范围而言,反应温度可以为200℃-500℃,例如,250℃-400℃,或250℃-350℃。反应时间可以为0.01-100小时,例如,1-80小时,或5-80小时。没有特别限定反应压力,并且反应通常在大气压力附近进行。在一个实施方案中,反应可以在0.1kPa-9,000kPa,例如,20kPa-5,000kPa,或90-3500kPa的压力下进行。乙醇转化率可以取决于反应温度和/或压力变化。
在一个实施方案中,反应以大于600小时-1,例如,大于1000小时-1或大于2000小时-1的气时空速(“GHSV”)进行。GHSV为600小时-1-10000小时-1,例如,1000小时-1-8000小时-1或1500小时-1-7500小时-1。
惰性或反应性气体可以为供应至反应物物流。惰性气体的实例包括但不限于,氮、氦、氩和甲烷。反应性气体或蒸气的实例包括但不限于,氧、碳氧化物、硫氧化物和烷基卤化物。在一些实施方案中,当将反应性气体(例如氧)添加至反应器时,这些气体可以按阶段以希望的水平添加遍布催化剂床,并且与其它进料组分一起在反应器开始处进料。这些另外的组分的添加可以改善反应效率。
在一个实施方案中,将未反应的组分(例如乙醇)以及剩余的惰性或反应性气体在从希望的产物中分离之后循环至反应器。
实施例
实施例1-3wt.%的铜γ-氧化铝
使用浸渍方法合成催化剂。将γ-氧化铝压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的γ-氧化铝放置在圆底反应器中。将1.09g的水合硝酸铜溶解于5g的水中,随后使用旋转干燥器通过逐步始润而浸渍至以上γ-氧化铝。将铜-涂覆的γ-氧化铝在烘箱中在120℃干燥5小时,随后使用以下温度程序煅烧:以60℃开始,以2℃/min升温至350℃,保持在350℃下持续5小时,随后冷却至室温。
实施例2-3wt.%的钴θ-氧化铝
使用浸渍方法合成催化剂。将θ-氧化铝压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的θ-氧化铝放置在圆底反应器中。将1.53g的水合硝酸钴溶解于5g的水中,随后使用旋转干燥器通过逐步始润而浸渍至以上θ-氧化铝。将钴-涂覆的θ-氧化铝在烘箱中在120℃干燥5小时,随后使用以下温度程序煅烧:以60℃开始,以2℃/min升温至500℃,保持在500℃下持续5小时,随后冷却至室温。
实施例3-3wt.%的铜氧化锆
使用浸渍方法合成催化剂。将氧化锆压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的氧化锆放置在圆底反应器中。将1.09g的水合硝酸铜溶解于5g的水中,使用旋转干燥器通过逐步始润而随后浸渍至以上氧化锆。在实施例1中的条件下干燥并且煅烧铜-涂覆的氧化锆。
实施例4-3wt.%的钯氧化锆
使用浸渍方法合成催化剂。将10g的以上压碎的氧化锆(0.85mm和1.18mm)放置在圆底反应器中。将0.3g的水合硝酸钯溶解于5g的水中,随后使用旋转干燥器通过逐步始润而浸渍至以上氧化锆。在实施例1中的条件下干燥并且煅烧钯-涂覆的氧化锆。
实施例5-3wt.%的铂氧化锆
使用浸渍方法合成催化剂。将10g的以上压碎的氧化锆(0.85mm和1.18mm)放置在圆底反应器中。将0.3g的硝酸四氨合铂(II)溶解于5g的水中,随后使用旋转干燥器通过逐步始润而浸渍至以上氧化锆。在实施例1中的条件下干燥并且煅烧铂-涂覆的氧化锆。
实施例6-3wt.%的锡氧化锆
使用浸渍方法合成催化剂。将10g的以上压碎的氧化锆(0.85mm和1.18mm)放置在圆底反应器中。将0.3g的草酸锡溶解于5g的水中,随后使用旋转干燥器通过逐步始润而浸渍至以上氧化锆。在实施例1中的条件下干燥并且煅烧锡-涂覆的氧化锆。
实施例7-3wt.%的钯铂锡氧化锆
使用浸渍方法合成催化剂。将10g的以上压碎的氧化锆(0.85mm和1.18mm)放置在圆底反应器中。将0.56g的草酸锡和0.54g的草酸铵溶解于10ml的水。将0.3g的水合硝酸钯、硝酸四氨合铂(II)添加至草酸锡溶液,随后使用旋转干燥器通过逐步始润而浸渍至以上氧化锆。在实施例1中的条件下干燥并且煅烧金属-涂覆的氧化锆。
实施例8
制备并且评估以上催化剂。在相同测试条件下评估没有任何金属涂覆的氧化锆、γ-氧化铝、θ-氧化铝,以充当对照。将固定床气体流动催化反应器用作反应器。将3ml的催化剂填充在直径为0.95cm的不锈钢管反应器中。在预处理时,氢还原在载气气氛下(10%的H2/N2基;流速:125ml/min)在400℃下进行1小时。在预处理之后,测试在250℃和325℃的温度下和1kPa和5,100kPa的压力下进行,氮流速为125sccm并且乙醇流速为0.2ml/min。反应持续时间为5~80小时。
就催化剂金属-涂覆的γ-氧化铝和作为参照的θ-氧化铝而言的乙醇转化率、丁醇产物选择性、丁醇收率和C4+醇选择性显示在以下表1-3中。
如表1中所示,γ-氧化铝具有61%的乙醇转化率,但是具有0%的丁醇选择性、丁醇收率、C4+醇选择性。DEE选择性为96%的DEE。通过用铜涂覆γ-氧化铝,丁醇选择性、丁醇收率和C4+醇选择性显著增加,同时抑制了DEE和乙烯选择性。
如表2中所示,θ-氧化铝具有94%的乙醇转化率,但是具有0%的丁醇选择性、丁醇收率、C4+醇选择性。DEE选择性为72%。通过用钴涂覆θ-氧化铝,丁醇选择性、丁醇收率和C4+醇选择性显著增加,同时抑制了DEE和乙烯选择性。
如表3中所示,铜涂覆的氧化锆、钯涂覆的氧化锆、铂涂覆的氧化锆、锡涂覆的氧化锆和钯/铂/锡涂覆的氧化锆具有比不含金属的氧化锆更好的乙醇转化率、丁醇选择性、丁醇收率、C4+醇选择性和更低的DEE和乙烯选择性。具体地,铜涂覆的氧化锆具有79%的高乙醇转化率和各自1%的低DEE和乙烯选择性。相似地,钯涂覆的氧化锆具有78%的高乙醇转化率和分别为4%和1%的低DEE和乙烯选择性。此外,钯涂覆的氧化锆具有73%的高C4+醇选择性。此外,铂涂覆的氧化锆具有61%的乙醇转化率、0%的DEE选择性和6%的乙烯选择性。相似地,钯/铂/锡涂覆的锆具有58%的乙醇转化率、42%的丁醇选择性、25%的丁醇收率、60%的C4+醇选择性和6%的低DEE选择性和5%的低乙烯选择性。因此,用一种或多种金属涂覆的氧化锆显著增加了乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性,同时抑制了DEE和乙烯选择性。
实施例9-NH3改性的γ-氧化铝上的3wt.%的钯催化剂
使用浸渍方法合成催化剂。将γ-氧化铝压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的γ-氧化铝放置在圆底反应器中。将0.832g的乙酸钯(II)溶解于20ml的丙酮随后在搅拌下逐滴添加氢氧化铵直到将pH调节至12.5并且获得澄清溶液。使用旋转干燥器通过逐步始润而将钯溶液浸渍至γ-氧化铝以获得3wt.%的钯涂覆的γ-氧化铝。钯-涂覆的γ-氧化铝在烘箱中在120℃干燥5小时,随后使用以下温度程序煅烧:以60℃开始,以2℃/min升温至350℃,保持在350℃下持续5小时,随后冷却至室温。
实施例10-NH3改性的γ-氧化铝上的3wt.%的钴催化剂
使用浸渍方法合成催化剂。将γ-氧化铝压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的γ-氧化铝放置在圆底反应器中。将1.53g的水合硝酸钴溶解于5g的水中,随后在搅拌下逐滴添加氢氧化铵直到将pH调节至12.5并且获得澄清溶液。使用旋转干燥器通过逐步始润而将钴溶液浸渍至γ-氧化铝以获得3wt.%的钴涂覆的γ-氧化铝。钴涂覆的γ-氧化铝在烘箱中在120℃干燥5小时,随后使用以下温度程序煅烧:以60℃开始,以2℃/min升温至350℃,保持在350℃下持续5小时,随后冷却至室温。
对比实施例A–γ-氧化铝上的3wt.%的钯催化剂
使用浸渍方法合成催化剂。将γ-氧化铝压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的γ-氧化铝放置在圆底反应器中。将0.832g的乙酸钯(II)溶解于20ml的丙酮,随后使用旋转干燥器通过逐步始润而浸渍至γ-氧化铝。钯-涂覆的γ-氧化铝在烘箱中在120℃干燥5小时,随后使用以下温度程序煅烧:以60℃开始,以2℃/min升温至350℃,保持在350℃下持续5小时,随后冷却至室温。
对比实施例B-γ-氧化铝上的3wt.%的钴催化剂
使用浸渍方法合成催化剂。将γ-氧化铝压碎至0.85mm和1.18mm的粒度。将10g的以上压碎的γ-氧化铝放置在圆底反应器中。将1.53g的水合硝酸钴溶解于20ml的丙酮,随后使用旋转干燥器通过逐步始润而浸渍至γ-氧化铝。钴-涂覆的γ-氧化铝在烘箱中在120℃干燥5小时,随后使用以下温度程序煅烧:以60℃开始,以2℃/min升温至350℃,保持在350℃下持续5小时,随后冷却至室温。
实施例11
表4对比了两组催化剂。实施例9是钯涂覆的NH3改性的γ-氧化铝催化剂和实施例10是钴涂覆的NH3改性的γ-氧化铝催化剂。如表4中所示,相比于钯涂覆的未改性γ-氧化铝催化剂,实施例9具有相似乙醇转化率。然而,相比于钯涂覆的未改性γ-氧化铝催化剂,实施例9具有高得多的丁醇选择性、丁醇收率、C4+醇选择性。此外,实施例9显著地将DEE选择性从51%降低至8%并且将乙烯选择性从22%降低至0%。
相比于钯涂覆的未改性γ-氧化铝催化剂,实施例10也具有更好的丁醇选择性、丁醇收率和C4+醇选择性。实施例10也显著地将DEE选择性从60%降低至8%并且将乙烯选择性从5%降低至1%。
尽管已经详细描述了本发明,本发明的精神和范围内的修改将对本领域技术人员显而易见。应该理解本发明的方面和以上所述的和/或所附的权利要求中的各种实施方案和各种特征的部分可以整体或部分地组合或互换。在各种实施方案的上述说明中,那些涉及另一个实施方案的实施方案可以恰当地与其它实施方案组合,如本领域技术人员将要理解的。此外,本领域技术人员将要理解上述的说明仅是示例的方式,并且不意图限制本发明。
Claims (14)
1.用于将醇转化成更高级的醇的催化剂,所述催化剂包含:
一种或多种金属,优选以0.01wt.%-20wt.%的量存在,其选自钴、镍、钯、铂、铁、锌、锡和铜;和
载体,优选以80wt.%-99.99wt.%的量存在,其选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物,其中所述催化剂基本上不含碱金属和碱土金属。
2.权利要求1的催化剂,其中所述催化剂选自钯、铜和钴。
3.权利要求1的催化剂,其进一步包含载体改性剂,所述载体改性剂选自吡啶、四甲基氢氧化铵、四丁基氢氧化铵、氢氧化铵、甲基胺、咪唑和其它适合的载体改性剂。
4.用于将醇转化成更高级的醇的催化剂,所述催化剂包含:
一种或多种载体,优选以80wt.%-99.99wt.%的量存在,其选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物;
一种或多种载体上的一个或多个金属层,优选以0.01wt.%-20wt.%的量存在,其包含选自钴、镍、钯、铂、铁、锌、锡和铜的一种或多种金属。
5.权利要求4的催化剂,其中所述催化剂选自钯、铜和钴。
6.用于生产丁醇的方法,所述方法包括以下步骤:
在反应器中的催化剂之上进料包含乙醇的气态物流以形成丁醇,其中所述催化剂包含
一种或多种金属,其选自钴、镍、钯、铂、铁、锌、锡,和铜;和
一种或多种载体,其选自Al2O3、ZrO2、MgO、TiO2、沸石、ZnO及其混合物。
7.根据权利要求6的方法,其中所述反应器在200℃-500℃的温度和/或100kPa-20,000kPa的压力下操作。
8.根据权利要求6的方法,其中乙醇转化率为至少20%。
9.根据权利要求6的方法,其中丁醇选择性为至少20%。
10.根据权利要求6的方法,其中乙烯选择性小于10%。
11.根据权利要求6的方法,其中二乙基醚选择性小于15%。
12.根据权利要求6的方法,其中所述一种或多种金属以0.01wt.%-20wt.%的量存在,并且所述一种或多种载体以80wt.%-99.99wt.%的量存在。
13.根据权利要求6的方法,其中所述气态物流基本上不含氢。
14.根据权利要求6的方法,其中所述催化剂基本上不含碱金属和碱土金属。
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WO2014100133A1 (en) | 2014-06-26 |
US8962897B2 (en) | 2015-02-24 |
US20140171696A1 (en) | 2014-06-19 |
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