CN104870091A - 用于生产丁醇的涂覆的水滑石催化剂和方法 - Google Patents
用于生产丁醇的涂覆的水滑石催化剂和方法 Download PDFInfo
- Publication number
- CN104870091A CN104870091A CN201380066305.6A CN201380066305A CN104870091A CN 104870091 A CN104870091 A CN 104870091A CN 201380066305 A CN201380066305 A CN 201380066305A CN 104870091 A CN104870091 A CN 104870091A
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- China
- Prior art keywords
- hydrotalcite
- metal
- magnesium
- copper
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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 title claims abstract description 168
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 164
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 164
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims description 43
- 230000008569 process Effects 0.000 title description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 231
- 229910052751 metal Inorganic materials 0.000 claims abstract description 103
- 239000002184 metal Substances 0.000 claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 78
- 239000011777 magnesium Substances 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 57
- 239000011248 coating agent Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 229910052749 magnesium Inorganic materials 0.000 claims description 49
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 46
- 229910052763 palladium Inorganic materials 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 30
- 239000004411 aluminium Substances 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 239000011135 tin Substances 0.000 claims description 28
- 229910052718 tin Inorganic materials 0.000 claims description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052732 germanium Inorganic materials 0.000 claims description 25
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 20
- 229910052733 gallium Inorganic materials 0.000 claims description 20
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 150000002739 metals Chemical class 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 13
- 239000011133 lead Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 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 7
- 229910052730 francium Inorganic materials 0.000 claims description 7
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 43
- -1 butanol Chemical class 0.000 abstract description 11
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 18
- 239000006187 pill Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 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
- 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
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 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
- 239000012876 carrier material Substances 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 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
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IQULGZQMMPRBLA-UHFFFAOYSA-N 2-carboxyethylgermanium Chemical compound OC(=O)CC[Ge] IQULGZQMMPRBLA-UHFFFAOYSA-N 0.000 description 2
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-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
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229940093626 germanium sesquioxide Drugs 0.000 description 2
- 238000010438 heat treatment Methods 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
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- ZATZOOLBPDMARD-UHFFFAOYSA-N magnesium;hydrate Chemical compound O.[Mg] ZATZOOLBPDMARD-UHFFFAOYSA-N 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Chemical class 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
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Abstract
公开了将乙醇转化成更高级的醇(例如丁醇)的催化剂组合物。催化剂组合物包含金属涂覆的水滑石及其制备方法。
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13/719,857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。
水滑石也已经作为用于由乙醇制备丁醇的催化剂被研究。例如,J.I.Di Cosimo等人公开了将MgyAlOx催化剂用于醇反应,包括乙醇。Journal of Catalysis(1998),178,499-510;Journal of Catalysis(2000),190,261-275;和Journal of Catalysis(2003)215,220-233。美国专利号7,705,192和7,700,810公开了将部分或完全热分解的水滑石用于将乙醇转化成丁醇。美国专利号7,700,812公开了将乙二胺四乙酸的阴离子并入水滑石,用于将乙醇分别转化成异丁醇和丁醇。美国专利号7,700,811公开了用于将乙醇转化成丁醇的水滑石/金属碳酸盐组合。
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。
上述文献以引用方式并入本文。
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,本发明涉及用于生产催化剂组合物的方法,所述催化剂组合物用于将醇转化成更高级的醇。该方法包括以下步骤:用一种或多种金属前体涂覆水滑石以形成含有金属的水滑石,并且煅烧含有金属的水滑石以形成催化剂组合物。在优选实施方案中,一种或多种金属前体包括选自以下的一种或多种金属:镁、铝、镓、锗、锡、铅、铜和其它过渡金属。也可以使用次级金属的次级金属前体。适合的次级金属包括锂、钠、钾、铷、铯、钫、镁、钙、锶或钡。
在第二实施方案中,本发明涉及用于将醇转化成根据如下方法生产的更高级的醇的催化剂组合物,所述方法包括以下步骤:用一种或多种金属前体涂覆水滑石以形成含有金属的水滑石,并且煅烧含有金属的水滑石以形成催化剂组合物。在优选实施方案中,催化剂具有下式:HT-M,其中HT=Mg6Al2CO3(OH)16·4(H2O),并且其中M是选自以下的一种或多种金属:镁、铝、镓、锗、锡、铅、铜和其它过渡金属。
在第三实施方案中,本发明涉及用于生产更高级的醇的方法。该方法包括以下步骤:在反应器中的催化剂组合物之上进料包含乙醇的气态物流以形成更高级的醇,其中催化剂组合物包含用一种或多种金属涂覆的水滑石,其中一种或多种金属选自镁、铝、镓、锗、锡、铅、铜和其它过渡金属。
在第四实施方案中,本发明涉及用于将醇转化成更高级的醇的组合物,所述催化剂具有下式:HT-Ma-M’b-M”c-Ad,其中HT为Mg6Al2CO3(OH)16·4(H2O);M为锗、锡、钯或镁;M’为镁、铝或铜;M”为铝或铜,条件是M、M’和M”不相同;A为锂、钠、钾、铷、铯或钫;a为0.001-1,b为0-2,c为0-2,并且d为0-2。在一个实施方案中该式可以包含HT上的锂/钯。
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并且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,本发明的这些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,发明人发现用一种或多种金属涂覆的水滑石(HT)的催化剂体系有益地导致乙醇转化率和/或丁醇的丁醇选择性的改进。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
在一个实施方案中,本发明涉及金属涂覆的水滑石(HT)。金属涂覆的HT包含选自以下的一种或多种金属(M):镁、铝、镓、锗、锡、铅、铜和其它过渡金属。适合的过渡金属包括但不限于,铁、镍、钯和钴。金属可以作为金属性金属或金属氧化物存在。一种或多种金属优选选自镁、铝、镓、锗、锡、铅、钯和铜。
在一些实施方案中,金属的组合可以包含镁,以及铜、钯和铝中的至少一者。例如,金属组合可以包括镁/铜,镁/钯和镁/铝/铜。金属涂覆的水滑石可以进一步包含选自锂、钠、钾、铷、铯、钫、镁、钙、锶和钡的一种或多种次级金属。特别地,锂和过渡金属的金属组合是优选的,例如锂/钯。
如本申请中使用的“水滑石”(HT)通常是指可商购的水滑石,例如碱式碳酸镁铝,具有化学式:Mg6Al2CO3(OH)16·4H2O。合成碱式碳酸镁铝可以获自Sigma-Aldrich。当然,具有相似化学式的合成或天然水滑石也可以用于制备催化剂组合物。
在一个实施方案中,催化剂包含含有金属的水滑石(HT)。例如,催化剂包含70wt.%-99.9wt.%的水滑石和0.1wt.%-30wt.%的金属,例如,包含75wt.%-95wt.%的水滑石和5wt.%-25wt.%的金属,或包含80wt.%-90wt.%的水滑石和10wt.%-20wt.%的金属。金属的wt.%包括所有金属,包括次级金属(如果存在的话)。
在一个实施方案中,水滑石用选自以下的一种或多种金属(M)涂覆:镁、铝、锗、锡、铅、钯和铜。涂覆可以形成多层金属-涂覆的水滑石,并且这样,金属的一个或多个层可以涂覆在水滑石上。在一个实施方案中,金属的一个或多个层是不同的金属并且可以单独地涂覆在水滑石上。次级金属(如果存在的话)也可以单独地涂覆在水滑石上。在其它实施方案中,不同的金属可以在涂覆之前混合在一起并且一起涂覆在水滑石上。
本申请中使用的“涂覆”、“涂覆的”或“涂层”通常是指在分布在水滑石的表面上的一种或多种金属。表面上的该分布形成金属-涂覆的水滑石复合物(complex)。
金属-涂覆的水滑石复合物可以由下式表示:HT-M。催化剂可以包含水滑石和选自镁、铝、镓、锗、锡、铅、铜和其它过渡金属的金属。金属负载量取决于金属而不同。在一个实施方案中,催化剂可以包含水滑石和镓、锗或锡,并且HT-M组合物的金属负载量可以为0.1wt%-20wt.%,例如,0.5wt.%-18wt.%,或1wt.%-15wt.%。在另一个实施方案中,催化剂可以包含水滑石和钯并且HT-M组合物包含0.1wt%-10wt.%的钯,例如,0.5wt.%-8wt.%,或1wt.%-7wt.%。
在另一个实施方案中,催化剂包含具有选自镁、铝、镓、锗、锡、铅、铜和其它过渡金属的两种金属(M和M’)的水滑石(HT)。两种金属涂覆的水滑石复合物可以由下式表示:HT-M-M’。催化剂也可以包含次级金属(A)并且该式可以由下式表示:HT-M-A。次级金属(A)可以选自锂、钠、钾、铷、铯、钫、镁、钙、锶和钡。在一个示例性实施方案中,催化剂可以包含水滑石、镁和铜,并且HT-M-M’组合物包含0.1wt.%-10wt.%的镁(例如,0.5wt.%-8wt.%,或1wt.%-7wt.%)和0.1wt.%-10wt.%的铜(例如,0.5wt.%-8wt.%,或1wt.%-7wt.%)。在另一个实施方案中,催化剂可以包含水滑石、镁和钯并且HT-M-M’组合物包含0.1wt.%-10wt.%的镁(例如,0.5wt.%-8wt.%,或1wt.%-7wt.%)和0.1wt.%-10wt.%的钯(例如,0.5wt.%-8wt.%,或1wt.%-7wt.%)。在又一个实施方案中,催化剂可以包含钯-锂和水滑石,并且HT-M-A组合物包含0.01wt.%-20wt.%的钯(例如,0.05wt.%-18wt.%,或0.1wt.%-16wt.%)和0.1wt.%-20wt.%的锂(例如,0.5wt.%-18wt.%,或1wt.%-16wt.%)。具有两种金属的催化剂组合物也可以包含60wt.%-99.89wt.%的水滑石,例如,64wt.%-99.45wt.%或68wt.%-98.9wt.%。
在一个实施方案中,催化剂可以包含具有三种金属或更多种金属的水滑石,条件是金属中的至少一种选自镁、铝、镓、锗、锡、铅、铜和其它过渡金属。具有三种金属或更多种复合物的水滑石可以由下式表示:HT-M-M’-M”。催化剂也可以包含次级金属(A)并且该式可以由下式表示:HT-M-M’-A或HT-M-M’-M”-A。在一个实施方案中,催化剂可以包含水滑石、镁、铝和铜。在一个实施方案中,HT-M-M’--M”组合物包含0.1wt.%-10wt.%的镁,例如,0.5wt.%-8wt.%,或1wt.%-7wt.%;0.1wt.%-10wt.%的铝,例如,0.5wt.%-8wt.%,或1wt.%-7wt.%;和0.1wt.%-10wt.%的铜,例如,0.5wt.%-8wt.%,或1wt.%-7wt.%。
在一个实施方案中,催化剂对应于式:
HT-Ma-M’b-M”c-Ad
其中a、b、c和d是催化剂中水滑石、第一金属(M)、第二金属(M’)和第三金属(M”)分别的相对摩尔量(相对于1)。次级金属(A)选自锂、钠、钾、铷、铯、钫、镁、钙、锶和钡。在一个实施方案中,a为0.001-1,并且b、c和d各自独立地为0-2。现在已经发现,相比于其它水滑石催化剂,金属-涂覆的水滑石催化剂令人惊奇地实现了出人意料地高的乙醇转化率。使用金属-涂覆的水滑石催化剂组合物可以实现至少28%,例如,至少30%,或至少40%的乙醇转化率。令人惊奇和出人意料的是,乙醇转化率的这样的提高伴随着改进的对丁醇的选择性而实现,例如,至少30%,例如,至少40%,或至少50%的对丁醇的选择性。不希望受限于理论,要求金属包含特定的功能性质,以用于Guerbet反应。相比于金属-水滑石催化剂的均匀共沉淀(其中金属分布在水滑石内),作为涂覆水滑石表面的结果,催化剂组合物的涂覆金属可以驱使Guerbet反应有利于乙醇转化率和对丁醇的选择性两者。
如上所述,通过在酸的存在下的乙醇脱水,反应混合物中产生了二乙基醚(DEE)和乙烯。令人惊奇和出人意料的是,现在已经发现镁催化剂抑制了DEE和乙烯的形成。例如,对DEE的选择性小于10%,并且乙烯选择性小于5%。在一个实施方案中,令人惊奇和出人意料的是,还发现了钯催化剂也可以抑制DEE的形成。具体地,发明人发现通过抑制DEE和乙烯的形成,催化剂组合物增强了丁醇选择性。
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。就本发明的目的,载体材料为水滑石。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。
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
与先前公开的其中金属均匀混合以形成水滑石的水滑石-金属复合物不同,用于制备本发明的催化剂的方法涉及将一种或多种金属涂覆在水滑石表面上。本发明的催化剂可以通过以下方法合成。
在第一方面,研磨金属前体(例如金属氧化物)和水滑石并且混合在一起直至混合物显得均匀并且显得为固体,通常约五分钟。混合物可以使用本领域技术人员公知的方法(例如,经由研钵和研杵或碾磨机)来研磨和混合。在另一个实施方案中,金属氧化物和水滑石可以在混合之前压碎。煅烧均匀固体混合物。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。对于过渡金属,煅烧温度可以更低,例如300℃。
在力下压制经经煅烧组合物一段时间以形成丸粒。例如,组合物可以以至少10,000N,例如,至少15,000N,至少20,000N,或至少25,000N压制。就范围而言,组合物可以以10,000N-500,000N,例如,15,000N-400,000N,或20,000N-200,000N压制。在一个实施方案中,在力下压制经煅烧组合物至少5分钟,例如,至少20分钟,至少40分钟,或至少60分钟。在另一个实施方案中,经煅烧组合物可以在增加的压力曲线下压制。例如,经煅烧组合物可以在特定压力下压制预定的时间段并且压力可以逐渐增加持续另一预定的时间段。例如,经煅烧组合物可以在100,000N下压制1分钟,并且然后压力可以以每分钟另外100,000N增加直到它达到预定的压力。
然后稍微将丸粒压碎至适合的粒度。
在第二方面,金属前体,例如金属硝酸盐,可以添加至草酸铵的溶液并且可以加热混合物直至溶液澄清。然后,一定量的丙酮和/或水可以添加至澄清溶液。所得溶液可以逐滴添加至水滑石。金属-涂覆的水滑石可以使用与先前方面的方法相似的温度曲线干燥和煅烧。
在另一个实施方案中,可以通过将第二或第三金属层添加至金属-涂覆的水滑石制备多层化的金属-涂覆的水滑石。例如,金属-涂覆的水滑石可以在煅烧之后冷却并且第二金属硝酸盐或金属氧化物可以涂覆在其上。二次涂覆的水滑石可以在添加第三金属层之前干燥和煅烧。
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。金属前体也可以用于次级金属。金属前体可以选自金属氧化物、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)、金属乙酰丙酮酸盐,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氧化锗、丁醇锗、乙醇酸锗、氯化锗、乙酸锗、氢氧化锗、甲醇锗、氮化锗和双(2-羧乙基三氧化二锗);氧化锡(II)、草酸锡、乙酸锡、氯化锡和硝酸锡;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;六水合硝酸镁、硝酸镁、水合硝酸镁、氯化镁、水合氯化镁、六水合氯化镁、四水合乙酸镁、二水合乙酰丙酮酸镁、五水合碱式碳酸镁、高氯酸镁、六水合高氯酸镁、硫酸镁、七水硫酸镁和单水合硫酸镁;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;硝酸锂、乙酸锂、脱水乙酸锂和磷酸锂;硝酸钾、乙酸钾、硫酸钾和亚硫酸钾;硝酸铯、氯化铯、氢氧化铯、碳酸铯、碳酸铯、草酸铯、高氯酸铯、丙酸铯和甲酸铯;烷氧化铝、硝酸铝、氢氧化铝、氧化铝、乙酸铝、硫酸铝、氯化铝和溴化铝。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氧化锗、双(2-羧乙基三氧化二锗)、氧化锡(II)、草酸锡、水合硝酸钯、水合硝酸镁、水合硝酸铜、水合硝酸铝和硝酸锂。
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。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,使用水滑石和第一金属前体,和任选第二金属前体和第三金属前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。优选地,催化剂为金属-涂覆的水滑石。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-涂覆的水滑石之上进行。在一个实施方案中,粗产物物流是气相反应的产物。
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28%,例如,至少30%,至少40%,或至少60%。
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。优选地,对丁醇的选择性为至少30%,例如,至少40%,或至少60%。在一些实施方案中,对C4+醇(例如,正丁醇、异丁醇、2-丁醇、叔丁醇、1-己醇、2-乙基丁醇或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%。
本发明的优选实施方案展示出对不希望的产物(例如DEE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250℃,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℃。反应器中的停留时间可以为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可以为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
通过压制粉末以形成催化剂的制备
实施例1-锡涂覆的水滑石(Sn-HT)
将0.355g的SnO和10g的水滑石经由研钵和研杵混合在一起(3wt.%的Sn)持续大约5分钟直至黑色和白色粉末看上去是均匀的。然后使用以下温度程序煅烧固体混合物:以60℃开始,以5℃/min升温至600℃,保持在600℃下5小时,随后冷却至室温。锡涂覆的水滑石粉末然后以180,000N压制1小时以形成丸粒,随后将以上丸粒稍微压碎至0.85mm和1.18mm的粒度用于进一步使用。
实施例2–锗涂覆的水滑石(Ge-HT)
将0.45g的GeO2和10g的水滑石经由研钵和研杵混合在一起(3wt.%的Ge)持续大约5分钟直至黑色和白色粉末看上去是均匀的。然后使用以下温度程序煅烧固体混合物:以60℃开始,以5℃/min升温至600℃,保持在600℃下5小时,随后冷却至室温。锗涂覆的水滑石粉末然后以180,000N压制1小时以形成丸粒,随后将以上丸粒稍微压碎至0.85mm和1.18mm的粒度用于进一步使用。
通过浸渍、干燥和煅烧的制备
实施例3-锡涂覆的水滑石(Sn-HT)
将0.56g的草酸铵溶解于10g的蒸馏H2O,随后添加0.54g的草酸锡至溶液。所得的混合物然后在60℃下加热,直到溶液变得澄清,并且然后将1g的丙酮添加至澄清溶液。使用旋转干燥器通过逐步始润将所得的澄清溶液浸渍至10g的水滑石。将获得的样品在烘箱中在120℃下干燥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600℃,保持在600℃下5小时,随后冷却至室温。
实施例4–锗涂覆的水滑石(Ge-HT)
将0.36g的双(2-羧基乙基三氧化二锗(IV)添加至25g的蒸馏水并且在约65℃加热直至溶液澄清,随后添加1g的丙酮。使用旋转干燥器通过逐步始润将所得的澄清溶液浸渍至5g的水滑石。在实施例3中描述的条件下干燥和煅烧获得的样品。
实施例5–钯涂覆的水滑石(Pd-HT)
水滑石粉末在180,000N下压制1小时以形成丸粒。丸粒然后稍微压碎至0.85mm和1.18mm的粒度。量出5g的稍微压碎的水滑石丸粒并且放置在圆底反应器中。将0.39g的Pd(NO3)2·2H2O溶解于5g的水和5g的丙酮的混合物中。使用旋转干燥器通过逐步始润将所得的溶液浸渍至5g的水滑石。在实施例3中描述的条件下干燥和煅烧获得的样品。
实施例6–镓涂覆的水滑石(Ga-HT)
量出如实施例5中制备的10g的稍微压碎的水滑石丸粒并且放置在圆底反应器中。将1.13g的Ga(NO3)3溶解于10g的水。使用旋转干燥器通过逐步始润将所得的溶液浸渍至10g的水滑石。在实施例3中描述的条件下干燥和煅烧获得的样品。
实施例7–铜-镁涂覆的水滑石(Cu-Mg-HT)
量出如实施例5中制备的10g的稍微压碎的水滑石丸粒并且放置在圆底反应器中。涂至水滑石的镁的第一层涂层通过以下制备:将0.45g的Mg(NO3)2·2H2O溶解于5g的水和5g的丙酮的混合物中。使用旋转干燥器通过逐步始润将所得的溶液浸渍至5g的水滑石。在实施例3中描述的条件下干燥和煅烧获得的样品。铜的第二层涂覆以与第一层相同的方式制备,即,通过将0.545g的Cu(NO3)2·2H2O(摩尔比:Cu/Mg=1:1)溶解于5g的水和5g的丙酮的混合物中制备。使用旋转干燥器通过逐步始润将所得的溶液浸渍至以上的镁涂覆的水滑石。将获得的样品在烘箱中在120℃下干燥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300℃,保持在300℃下5小时,随后冷却至室温。
实施例8–3wt.%的钯锂水滑石
使用序列浸渍方法合成具有内层上的锂和外层上的钯的催化剂。量出如实施例5中制备的10g的所制备的水滑石丸粒并且放置在圆底反应器中。通过以下制备水滑石上的锂层:将0.24g的硝酸锂溶解于5g的水和5g的丙酮中,随后使用旋转干燥器通过逐步始润浸渍至水滑石。然后在与实施例3中所描述的条件下干燥和煅烧锂涂覆的水滑石。通过以下制备钯层:将0.773g的硝酸钯(II)水合物溶解于5g的水和5g的丙酮中,随后使用旋转干燥器通过逐步始润浸渍至锂涂覆的水滑石。在与以上相似的条件下干燥和煅烧钯-锂涂覆的水滑石。
实施例9–钯-镁涂覆的水滑石(Pd-Mg-HT)
量出如实施例5中制备的10g的稍微压碎的水滑石丸粒并且放置在圆底反应器中。涂至水滑石的镁的第一层涂层通过以下制备:将0.270g的Mg(NO3)2·2H2O溶解于5g的水和5g的丙酮的混合物中。使用旋转干燥器通过逐步始润将所得的溶液浸渍至5g的水滑石。在实施例3中描述的条件下干燥和煅烧获得的样品。钯的第二层以与第一层相同的方式制备,即,通过将0.39g的Pd(NO3)2·2H2O(摩尔比:Pd/Mg=1:1)溶解于5g的水和5g的丙酮的混合物中。使用旋转干燥器通过逐步始润将所得的溶液浸渍至以上的镁涂覆的水滑石。将获得的样品在烘箱中在120℃下干燥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300℃,保持在300℃下5小时,随后冷却至室温。
实施例10–铜-镁/铝涂覆的水滑石(Cu-Mg/Al-HT)
量出如实施例5中制备的10g的稍微压碎的水滑石丸粒并且放置在圆底反应器中。通过以下制备涂至水滑石的镁/铝的第一层:将0.45g的Mg(NO3)2·2H2O和0.305g的Al(NO3)3·9H2O(Mg/Al摩尔比=3:1)溶解于5g的水和5g的丙酮中。在反应器中使用旋转干燥器通过逐步始润将所得的溶液缓慢进至5g的水滑石。在实施例3中描述的条件下干燥和煅烧获得的样品。铜的第二层以与第一层相同的方式制备,即,通过将0.545g的Cu(NO3)2·2H2O(摩尔比:Cu/Mg=1:1)溶解于5g的H2O和5g的丙酮中。在反应器中使用旋转干燥器通过逐步始润将所得的溶液缓慢添加至以上的Mg/Al涂覆的HT。在相似的条件下干燥和煅烧所获得的样品。
实施例11
评估以上制备的催化剂。还在相同的测试条件评估不具有任何金属涂覆的水滑石并且用作对照。将固定床气体流动催化反应器用作反应器。将3ml的以上制备的催化剂填充于直径为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-涂覆的水滑石和作为对照的水滑石而言的乙醇转化率、丁醇产物选择性、丁醇收率和C4+醇选择性显示在表1-9中。
使用方法1制备实施例1锡涂覆的水滑石并且使用方法2制备实施例3锡涂覆的水滑石。如在表1中显示的,在相同测试条件下,两种锡涂覆的水滑石都比未涂覆的水滑石具有更好的乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。使用浸渍方法制备的锡涂覆的水滑石令人惊奇地提供了比使用混合方法制备的锡涂覆的水滑石更好的乙醇转化率和稍微更好的收率和C4+醇选择性。
如在表2中显示的,在相同测试条件下,钯-锂涂覆的水滑石具有比不含金属的水滑石更好的乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。此外,金属涂覆的水滑石催化剂将DEE选择性显著地降低至零。使用金属涂覆的水滑石,对丁醇的选择性大于乙烯选择性。
如在表2中显示的,在相同测试条件下,在乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性上,金属涂覆的水滑石性能优于未涂覆的水滑石。
如在表4中显示的,在相同测试条件下,金属涂覆的水滑石具有与未涂覆的水滑石相似的乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。实施例2、3和4中更高的对丁醇的选择性也可以降低在回收丁醇时的纯化要求。
如在表5中显示的,在不同的压力下测试样品未涂覆的HT和钯涂覆的水滑石。似乎压力的增加在未涂覆的水滑石中没有影响。相比之下,压力增加将钯水滑石的乙醇转化率从28%增加至54%并且将收率从20%增加至34%。此外,当在相同测试条件下比较未涂覆的水滑石和钯涂覆的水滑石时,钯涂覆的水滑石具有比未涂覆的水滑石更高的乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。
表6表明了压力和温度对钯涂覆的水滑石的影响。在各温度和压力下测试钯涂覆的水滑石的样品。在250℃下,随着压力从0kPa增加至3,400kPa,乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性全部都随着压力的增加而增加。令人惊奇和出人意料的是,在290℃下,尽管乙醇转化率和收率增加,但是丁醇选择性降低并且C4+醇选择性保持稳定。在325℃下,压力的增加似乎也增加了乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。
如在表7中显示的,就未涂覆的水滑石而言的反应在290℃下进行并且就镓涂覆的水滑石而言的反应在270℃下进行。甚至在更低的温度下,镓涂覆的水滑石具有比未涂覆的水滑石更高的乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。
如在表8中显示的,在相同测试条件下,钯-镁涂覆的水滑石具有比未涂覆的水滑石更好的乙醇转化率和更高的丁醇选择性、丁醇收率和C4+醇选择性。
因此,在每种测试条件下,金属-涂覆的水滑石催化剂具有与未涂覆的水滑石相似的或比未涂覆的水滑石更好的乙醇转化率、丁醇选择性、丁醇收率和C4+醇选择性。认为将(一种或多种)金属涂覆在水滑石上为催化剂组合物提供了另外的功能性并且有益地将反应驱使向更高的选择性和转化率。
对比实施例
美国专利号7,700,811公开了水滑石/金属碳酸盐组合物。根据7,700,811的实施例1,通过组合硝酸铝、硝酸镁和硝酸铜制备催化剂组合物。因此,与要求保护的催化剂不同,7,700,811的催化剂包含均匀分布的铜、铝和镁。表7提供了7,700,811的铜-镁-铝催化剂(对比实施例A)与本发明的水滑石-镁/铝-铜催化剂(实施例10)之间的比较。
如在表9中显示的,在乙醇转化率、丁醇选择性和收率方面,根据本发明的催化剂性能优于7,700,811中公开的催化剂。认为相比于其中金属分布在水滑石内的金属-水滑石催化剂的均匀共沉淀,将金属涂覆在水滑石表面上有益地驱使Guerbet反应有利于乙醇转化率和对丁醇的选择性。
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 (15)
1.用于生产催化剂组合物的方法,所述催化剂组合物用于将醇转化成更高级的醇,该方法包括:
用一种或多种金属前体涂覆水滑石,优选在水滑石表面上,以形成含有金属的水滑石,其中所述一种或多种金属前体包含选自以下的一种或多种金属:镁、铝、镓、锗、锡、铅、铜和其它过渡金属,所述一种或多种金属优选选自镁、铝、镓、锗、锡、钯和铜;和
煅烧所述含有金属的水滑石以形成催化剂组合物。
2.根据权利要求1的方法,其进一步包括用一种或多种次级金属前体涂覆水滑石,其中所述一种或多种次级金属前体包含选自锂、钠、钾、铷、铯、钫、镁、钙、锶和钡的金属。
3.根据权利要求1的方法,其中所述一种或多种金属前体选自金属氧化物、金属硝酸盐、金属乙酸盐、金属草酸盐和金属乙酰丙酮酸盐。
4.根据权利要求1的方法,其中涂覆步骤包括混合和研磨所述一种或多种金属前体与所述水滑石,以形成含有金属的水滑石。
5.根据权利要求4的方法,其进一步包括以下步骤:在压力下,优选在10,000N-500,000N的压力下,压制所述含有金属的水滑石,以形成催化剂。
6.根据权利要求1的方法,其中涂覆步骤包括用所述一种或多种金属前体浸渍水滑石。
7.根据权利要求1的方法,其中煅烧步骤在10℃-150℃的第一温度和300℃-900℃的第二温度下进行。
8.催化剂组合物,所述催化剂组合物用于将醇转化成根据权利要求1的方法生产的更高级的醇。
9.权利要求8的催化剂组合物,其中所述催化剂包含70wt.%-99.9wt.%的水滑石和0.1wt.%-30wt.%的金属。
10.权利要求8的催化剂组合物,其中所述催化剂具有下式:
HT-M,
其中HT为Mg6Al2CO3(OH)16·4(H2O),和
其中M为选自以下的一种或多种金属:镁、铝、镓、锗、锡、铅、铜和其它过渡金属,优选选自镓,锗、锡、钯、镁/铜、镁/钯和镁/铝/铜。
11.用于生产更高级的醇的方法,所述方法包括以下步骤:
在反应器中的催化剂组合物之上进料包含乙醇的气态物流以形成丁醇,其中所述催化剂组合物包含用一种或多种金属涂覆的水滑石,其中所述一种或多种金属选自镁、铝、镓、锗、锡、铅、铜和其它过渡金属,优选选自镁、铝、镓、锗、锡、钯和铜。
12.根据权利要求11的方法,其中乙醇转化率为至少28%和/或丁醇选择性为至少30%。
13.根据权利要求11的方法,其中所述催化剂包含70wt.%-99.9wt.%的水滑石和0.01wt.%-30wt.%的金属。
14.根据权利要求11的方法,其中所述催化剂具有下式:
HT-M,其中M选自镓、锗、锡、钯、镁/铜、镁/钯和镁/铝/铜。
15.用于将醇转化成更高级的醇的催化剂组合物,其中所述催化剂具有下式:
HT-Ma-M’b-M”c-Ad,
其中HT为Mg6Al2CO3(OH)16·4(H2O);
M为镓、锗、锡、钯或镁;
M’为镁、铝或铜;和
M”为铝或铜,条件是M、M’和M”不相同;
A为锂、钠、钾、铷、铯或钫;
a为0.001-1,
b为0-2,
c为0-2;和
d为0-2,
优选其中M、M’、M”、A或其组合涂覆在HT上。
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PCT/US2013/076034 WO2014100131A1 (en) | 2012-12-19 | 2013-12-18 | Coated hydrotalcite catalysts and processes for producing butanol |
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CN107983328A (zh) * | 2017-12-07 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | 一种醇醇缩合反应的催化剂及其制备方法和应用 |
CN109093529A (zh) * | 2018-07-23 | 2018-12-28 | 湖州星星研磨有限公司 | 一种超轻切削抛磨块及其制备方法 |
CN109529897A (zh) * | 2018-12-04 | 2019-03-29 | 西南化工研究设计院有限公司 | 一种生产正丁醇的钯镓双金属催化剂及其制备方法及应用 |
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WO2017031439A1 (en) * | 2015-08-19 | 2017-02-23 | Greenyug, Llc | Composition of catalysts for converion of ethanol to n-butanol and higher alcohols |
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