CN100345808C - 用于氢化羰基化合物的催化剂和方法 - Google Patents
用于氢化羰基化合物的催化剂和方法 Download PDFInfo
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- CN100345808C CN100345808C CNB2004800083047A CN200480008304A CN100345808C CN 100345808 C CN100345808 C CN 100345808C CN B2004800083047 A CNB2004800083047 A CN B2004800083047A CN 200480008304 A CN200480008304 A CN 200480008304A CN 100345808 C CN100345808 C CN 100345808C
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title description 25
- 150000001728 carbonyl compounds Chemical class 0.000 title description 16
- 230000036571 hydration Effects 0.000 title 1
- 238000006703 hydration reaction Methods 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 31
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- 239000011733 molybdenum Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 25
- 239000010937 tungsten Substances 0.000 claims abstract description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- 239000004568 cement Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims description 44
- 238000007254 oxidation reaction Methods 0.000 claims description 44
- 238000000465 moulding Methods 0.000 claims description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
- -1 adipic acid ester Chemical class 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 229960004643 cupric oxide Drugs 0.000 claims description 12
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
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- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
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- 229910052782 aluminium Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229940051250 hexylene glycol Drugs 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 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
- 150000001879 copper Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-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
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 2
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 2
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- 239000004480 active ingredient Substances 0.000 description 2
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- ZURZPPULRFXVLF-UHFFFAOYSA-N 3-hydroxy-2-methylbutanal Chemical compound CC(O)C(C)C=O ZURZPPULRFXVLF-UHFFFAOYSA-N 0.000 description 1
- YJWJGLQYQJGEEP-UHFFFAOYSA-N 3-methylpentanal Chemical compound CCC(C)CC=O YJWJGLQYQJGEEP-UHFFFAOYSA-N 0.000 description 1
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
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- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
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- 239000005642 Oleic acid Substances 0.000 description 1
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- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
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- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
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- 229920006351 engineering plastic Polymers 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- 238000005243 fluidization Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
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- 229960004232 linoleic acid Drugs 0.000 description 1
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- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 239000004711 α-olefin 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种用于氢化具有至少一个羰基的有机化合物的方法,其中所述有机化合物在氢的存在下与成形体接触,所述成形体可在其中包括以下的方法中制备,(i)制备包括氧化铜、氧化铝和至少一种镧、钨、钼、钛或锆的氧化物的氧化材料,(ii)将粉状金属铜、铜片、粉状水泥、石墨或它们的混合物添加到所述氧化材料中,和(iii)将由(ii)产生的混合物加工成形为成形体。
Description
本发明涉及使用催化剂氢化具有至少一个羰基的有机化合物的方法,其特征尤其在于催化剂由氧化铜、氧化铝和至少一种镧、钨、钼、钛或锆的氧化物组成并且在于具有高选择性和同时具有高稳定性的催化剂是通过添加镧、钨、钼、钛或锆的氧化物来制备的。在其制备中可另外添加铜粉、铜片或水泥。本发明还涉及催化剂本身,并在很普遍的意义上涉及镧氧化物在具有高选择性并同时具有高稳定性的催化剂的制备中的应用。
羰基化合物如,例如,羧酸或羧酸酯的催化氢化在基础化学工业的生产程序中占有重要地位。
在工业过程中羰基化合物如,例如羧酸酯的催化氢化几乎只在固定床反应器中进行。除了阮内型催化剂外,所使用的固定床催化剂是尤其是载体上的催化剂,如铜、镍或贵金属催化剂。
例如,US 3,923,694描述了氧化铜/氧化锌/氧化铝型催化剂。这种催化剂的缺点是,它在反应期间的机械稳定性不足并因此相对快地破碎。由于催化剂成形体的破碎,这导致活性的损失和跨反应器的压差的积累。因此必须过早地关闭装置。
DE 198 09418.3描述了在催化剂存在下催化氢化羰基化合物的方法,所述催化剂包括主要含二氧化钛的载体和作为活性组分的铜或铜与至少一种选自锌、铝、铈、贵金属、VIII族金属的金属的混合物,其中铜表面积不超过10m2/g。优选的载体材料是二氧化钛与氧化铝或氧化锆或者氧化铝和氧化锆的混合物。在优选的实施方案中,所述催化剂材料在添加金属铜粉或铜片的情况下来成形。
DE-A 195 05 347非常概括地描述了制备高机械强度的催化剂片的方法,其中金属粉末或金属合金粉末被添加到待制片的材料中。所添加的金属粉末尤其是铝粉或铜粉或铜片。然而,在氧化铜/氧化锌/氧化铝催化剂的情况下添加铝粉时,所形成的成形体的侧向破碎强度比在没有添加铝粉的情况下所制备的成形体的侧向破碎强度差,并且当用作催化剂时该发明的成形体的转化活性比在没有添加铝粉的情况下所制备的催化剂的转化活性低。在那里亦公开了由NiO、ZrO2、MoO3和CuO组成的氢化催化剂,在制备过程中还将Cu粉混合到其中。然而,在该公开中没有作出关于选择性或活性的说明。
DE 256 515描述了从合成气制备醇的方法,该方法利用通过与金属铜粉或铜片一起研磨并造粒获得的基于Cu/Al/Zn的催化剂。所述方法的主要目的是制备C1至C5醇的混合物,以这样的方式来运用该方法,即使得反应器中的上三分之一层含有铜粉或铜片含量较高的催化剂,而下三分之一含有铜粉或铜片含量较低的催化剂。
本发明的目的是提供不具有现有技术的缺点的方法和催化剂并提供用于羰基化合物的催化氢化的方法,以及催化剂,其中所述催化剂具有高的机械稳定性以及高的氢化活性和选择性。
我们已发现,这个目的可通过铜化合物、铝化合物和至少一种镧、钨、钼、钛或锆化合物的同时沉淀和通过随后的干燥、煅烧、制片和通过添加金属铜粉、铜片或粉状水泥或石墨或混合物,形成一种通过添加至少一种镧、钨、钼、钛或锆化合物而导致用作催化剂的成形体的高活性和选择性以及高稳定性的催化剂来实现。
因此,本发明涉及一种用于氢化具有至少一个羰基的有机化合物的方法,其中所述有机化合物在氢的存在下与成形体接触,所述成形体可在这样的方法中制备,即:
(i)制备包括氧化铜、氧化铝和至少一种镧、钨、钼、钛或锆的氧化物的氧化材料,
(ii)可将粉状金属铜、铜片、粉状水泥、石墨或它们的混合物添加到所述氧化材料中,和
(iii)将由(ii)产生的混合物加工成形为成形体。
在镧、钨、钼、钛或锆的氧化物当中,优选氧化镧。
在优选的实施方案中,本发明的成形体用作无载体的、浸渍的、涂覆的和沉淀的催化剂。
在本发明的方法中使用的催化剂特征在于铜活性组分、铝组分和至少一种镧、钨、钼、钛或锆的氧化物的组分优选地用碳酸钠溶液来同时或相继地沉淀,接着进行干燥、煅烧、制片和再次煅烧。
下列沉淀方法是特别适合的:
A)铜盐溶液、铝盐溶液和至少一种镧、钨、钼、钛或锆的盐的溶液,或者含铜、铝和至少一种镧、钨、钼、钛或锆的盐的溶液,平行地或相继地用碳酸钠来沉淀。沉淀的材料随后干燥并,如果合适的话,煅烧。
B)在预制的氧化铝载体上,进行铜盐溶液的沉淀和至少一种镧、钨、钼、钛或锆的盐的溶液的沉淀或者含有铜盐和至少一种镧、钨、钼、钛或锆的盐的溶液的沉淀。在特别优选的实施方案中,后者呈水悬浮液中的粉末形态。然而,该载体材料也可以呈珠、丸、碎片或平片状。
B1)在一个实施方案(I)中,沉淀铜盐溶液和至少一种镧、钨、钼、钛或锆的盐的溶液或者含有铜盐和至少一种镧、钨、钼、钛或锆的盐的溶液,优选用碳酸钙溶液沉淀。氧化铝载体材料的水悬浮液存在于接收容器中。
由A)或B)产生的沉淀以常规方法来过滤,并优选地,洗涤至不含碱,例如,如在DE198 09 418.3中所描述的那样。
来自A)的最终产物和来自B)的那些最终产物都在50-150℃的温度干燥,优选在120℃,并随后,如果合适的话,煅烧,一般在200-600℃,尤其在300-500℃,优选2小时。
可用于A)和/或B)的起始物质基本上是可溶于用于该应用的溶剂的所有Cu(I)和/或Cu(II)盐,如,例如,硝酸盐、碳酸盐、醋酸盐、草酸盐或铵络合物,类似的铝盐和镧、钨、钼、钛或锆的盐。硝酸铜特别优选地用于方法A)和B)。
在本发明的方法中,上述干燥并,若合适的话,煅烧的粉末优选加工成片、圆环、环状片、挤出物、蜂巢或类似的成形体。可用于此的方法是来自现有技术的所有的那些适合的方法。
所述氧化材料的组成一般是这样的,即使得氧化铜的含量在40-90重量%的范围内,镧、钨、钼、钛或锆的氧化物的含量在0-50重量%的范围内,且氧化铝的含量在至多50%的范围内,在每种情形中都基于所有上述氧化成分的全部重量,煅烧之后这三种氧化物共同代表至少80重量%的的氧化材料,其中以上并未将水泥与所述氧化材料一起考虑在内。
在优选的实施方案中,本发明因此涉及如上所述的方法,其中所述氧化材料包括
(a)含量在50≤x≤80、优选55≤x≤75重量%范围内的氧化铜,
(b)含量在15≤y≤35、优选20≤y≤30重量%范围内的氧化铝,和
(c)含量在2≤z≤20、优选3≤z≤15重量%范围内的至少一种镧、钨、钼、钛或锆的氧化物,
在每种情形中均基于煅烧后的所述氧化材料的总重量,其中适用下式:80≤x+y+z≤100,尤其95≤x+y+z≤100。
本发明的方法和本发明的催化剂的特征在于在所述沉淀中添加镧、钨、钼、钛或锆,导致用作催化剂的成形体的高稳定性。
通常,将粉状铜、铜片、粉状水泥或石墨或它们的混合物以在1-40重量%范围内、优选在2-20重量%范围内和特别优选在3-10重量%范围内的量添加到所述氧化材料中,在每种情况下都基于所述氧化材料的总重量。
优选使用的水泥是高氧化铝水泥。所述高氧化铝水泥特别优选基本上由氧化铝和氧化钙组成,并且它特别优选由约75-85重量%的氧化铝和约15-25重量%的氧化钙组成。还有可能使用基于氧化镁/氧化铝、氧化钙/氧化硅和氧化钙/氧化铝/氧化铁的水泥。
所述氧化材料尤其可具有,基于所述氧化材料的总重量,不超过10重量%、优选不超过5重量%的选自元素Re、Fe、Ru、Co、Rh、Ir、Ni、Pd和Pt的至少一种另外的组分。
在本发明方法的进一步优选的实施方案中,在成形为成形体之前除了铜粉、铜片或粉状水泥或它们的混合物之外还将石墨添加到所述氧化材料中。添加的石墨的量优选使得成形为成形体可更好地进行。在优选的实施方案中,添加基于所述氧化材料的总重量的0.5-5重量%的石墨。是否在铜粉、铜片或粉状水泥或它们的混合物之前或之后或同时将石墨添加到氧化材料中在这一点上并不重要。
因此,本发明也涉及如上所述的方法,其中将石墨以在基于所述氧化材料总重量的0.5-5重量%范围内的含量添加到所述氧化材料中或添加到由(ii)形成的混合物中。
在优选的实施方案中,本发明因此也涉及成形体,该成形体包括
氧化材料,该氧化材料包括
(a)含量在50≤x≤80、优选55≤x≤75重量%范围内的氧化铜,
(b)含量在15≤y≤35、优选20≤y≤30重量%范围内的氧化铝,和
(c)含量在2≤z≤20、优选3≤z≤15重量%范围内的至少一种镧、钨、钼、钛或锆的氧化物,
在每种情形中均基于煅烧后的所述氧化材料的总重量,其中适用下式:80≤x+y+z≤100,尤其95≤x+y+z≤100,
基于所述氧化材料的总重量含量在1-40重量%范围内的金属铜粉、铜片或粉状水泥或它们的混合物,和
基于所述氧化材料的总重量含量在0.5-5重量%范围内的石墨,
其中氧化材料、金属铜粉、铜片或粉状水泥或它们的混合物和石墨的总含量占所述成形体的至少95重量%。
在将铜粉、铜片或粉状水泥或它们的混合物和,当适合时,石墨添加到所述氧化材料之后,将成形后获得的成形体,当适合时,煅烧至少一次,时间一般为0.5-10h,优选0.5-2h。在这至少一个煅烧步骤期间的温度一般在200-600℃的范围内,优选在250-500℃的范围内,并特别优选在270-400℃的范围内。
在用粉状水泥成形的情况下,在煅烧之前用水使获得的成形体变得潮湿然后再干燥可以是有利的。
当用作氧化态的催化剂时,在加入氢化溶液之前,用还原气体,例如氢,优选氢/惰性气体混合物,特别优选氢/氮混合物,在100-500℃范围内、优选在150-350℃范围内并特别优选在180-200℃范围内的温度下预还原所述成形体。在这方面优选使用氢含量在1-100体积%范围内、特别优选在1-50体积%范围内的混合物。
在优选的实施方案中,在用作催化剂之前以本身公知的方式通过用还原介质处理来活化本发明的成形体。活化作用预先在还原炉中发生或者在安装在反应器中之后发生。如果催化剂已被预先在还原炉中活化,则将它安装在反应器中并立即在氢压力下装载氢化溶液。
通过本发明的方法制备的成形体的优选的应用领域是具有羰基的有机化合物的固定床氢化。但是,其他实施方案如,例如,在流体中上、下运动中的催化剂材料的流态化反应,也是可能的。氢化可在气相中或在液相中进行。氢化优选在液相中进行,例如在向下流动或向上流动法中。
对于向下流动法,使含待氢化的羰基化合物的液体前体滴流在布置在在氢压力下的反应器中的催化剂床上,在催化剂上形成薄液体膜。相反,对于向上流动法,将氢气通入到液体反应混合物流过的反应器中,氢气以在上升的气泡中的形式通过催化剂床。
在一个实施方案中,将待氢化的溶液直接泵送穿过催化剂床。在本发明方法的另一个实施方案中,在通过反应器后将一部分产物作为产物流连续地取出并,当适合时,通过如上所定义的第二反应器。将另外部分的产物连同新鲜的含有羰基化合物的前体一起再次送到反应器中。在下文中此法被称为循环法。
如果选择向下流动法作为本发明方法的实施方案,那么循环法是优选的。在该循环法中使用主反应器和第二反应器是进一步优选的。
本发明的方法适于将羰基化合物如醛和酮、羧酸、羧酸酯或羧酸酐氢化成相应的醇,脂族和脂环族、饱和和不饱和的羰基化合物是优选的。对于芳族羰基化合物,经由芳香环的氢化可形成不需要的副产物。羰基化合物可以含有其他官能团如羟基或氨基。不饱和的羰基化合物通常被氢化成相应的饱和醇。在本发明中术语“羰基化合物”包括所有具有C=O基的化合物,包括羧酸及其衍生物。当然,也可一起氢化两种或两种以上羰基化合物的混合物。也还有可能待氢化的各个羰基化合物含有一个以上的羰基。
本发明的方法优选用于氢化脂族醛、羟基醛、酮、酸、酯、酐、内酯和糖。
优选的脂族醛是支化的和非支化的、饱和和/或不饱和的脂族C2-C30醛,例如通过羰基合成从具有内双键或末端双键的直链或支化的烯烃可获得的那些。也可氢化也含有30个以上羰基的低聚化合物。
可提述的脂族醛的例子是:
甲醛、丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛(异戊醛)、2,2-二甲基丙醛(新戊醛)、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2,2-二甲基丁醛、3,3-二甲基丁醛、辛醛、癸醛、戊二醛。
除了所述的短链醛外,长链脂族醛,例如通过羰基合成从直链α-烯烃获得的那些,也是特别适合的。
烯醛化产物是特别优选的,例如2-乙基己烯醛、2-甲基戊烯醛、2,4-二乙基辛烯醛或2,4-二甲基庚烯醛。
优选的羟基醛是C3-C12羟基醛,例如可通过脂族和脂环族醛和酮与它们自身或甲醛的醇醛缩合反应可获得的那些。例子是3-羟基丙醛、二羟甲基乙醛、三羟甲基乙醛(季戊四醛)、3-羟基丁醛(丁间醇醛)、3-羟基-2-乙基己醛(2-乙基1,3-己二醇)、3-羟基-2-甲基戊醛(戊间醇醛)、2-羟甲基丙醛、2,2-二羟甲基丙醛、3-羟基-2-甲基丁醛、3-羟基戊醛、2-羟甲基丁醛、2,2-二羟甲基丁醛、羟基新戊醛。羟基新戊醛(HPA)和二羟甲基丁醛(DMB)是特别优选的。
优选的酮是丙酮、丁酮、2-戊酮、3-戊酮、2-己酮、3-己酮、环己酮、异佛尔酮、甲基异丁基酮、异亚丙基丙酮、苯乙酮、苯基丙基甲酮、二苯基甲酮、亚苄基丙酮、二亚苄基丙酮、亚苄基苯乙酮、2,3-丁二酮、2,4-戊二酮、2,5-己二酮和甲基乙烯基酮。
也可转化羧酸及其衍生物,优选具有1-20碳原子的那些。以下是应特别提及的:
羧酸,如甲酸、乙酸、丙酸、丁酸、异丁酸、正戊酸、三甲基乙酸(新戊酸)、己酸、庚酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、丙烯酸、甲基丙烯酸、油酸、反油酸、亚油酸、亚麻酸、环己烷羧酸、苯甲酸、苯乙酸、邻甲基苯甲酸、间甲基苯甲酸、对甲基苯甲酸、邻氯苯甲酸、对氯苯甲酸、邻硝基苯甲酸、对硝基苯甲酸、水杨酸、对羟基苯甲酸、邻氨基苯甲酸、对氨基苯甲酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸;
羧酸酯例如上述羧酸的C1-C10烷基酯,特别是甲酸甲酯,乙酸乙酯,丁酸丁酯,邻苯二甲酸、间苯二甲酸、对苯二甲酸、己二酸、马来酸的二烷基酯,例如这些酸的二甲基酯,(甲基)丙烯酸甲酯,丁内酯,己内酯和聚羧酸酯,例如聚丙烯酸和聚甲基丙烯酸酯和它们的共聚物和聚酯例如聚甲基丙烯酸甲酯,对苯二甲酸酯和其他工程塑料,在这种情况下尤其进行氢解,即将酯转化成相应的酸和醇;
脂肪;
羧酸酐,如上述羧酸的酐,特别是乙酸酐、丙酸酐、苯甲酸酐和马来酸酐;
羧酰胺,如甲酰胺、乙酰胺、丙酰胺、硬脂酰胺、对苯二甲酰胺。
也可以转化羟基羧酸如乳酸、苹果酸、酒石酸和柠檬酸,或氨基酸如甘氨酸、丙氨酸、脯氨酸和精氨酸,和肽。
特别优选氢化的有机化合物是饱和或不饱和的羧酸、羧酸酯、羧酸酐或内酯或者它们中的两种或两种以上的混合物。
因此,本发明也涉及如上所述的方法,其中所述有机化合物是羧酸、羧酸酯、羧酸酐或内酯。
这些化合物的例子尤其是,马来酸、马来酸酐、琥珀酸、琥珀酸酐、己二酸、6-羟基己酸、2-环十二烷基丙酸、上述酸的酯如,例如,甲酯、乙酯、丙酯或丁酯。进一步的例子是γ-丁内酯和己内酯。
在非常特别优选的实施方案中,本发明涉及如上所述的方法,其中,所述有机化合物是己二酸或己二酸酯。
可将待氢化的羰基化合物单独地或作为与氢化产物的混合物送到氢化反应器中,在该情况下这可以以未稀释的形式或在使用附加溶剂的情况下进行。特别适合的附加溶剂是水,醇如甲醇、乙醇和在反应条件下产生的醇。优选的溶剂是水、THF和NMP,而水是特别优选的。
各自均优选作为循环法进行的向上流动法和向下流动法中的氢化,通常在50-350℃范围内、优选在70-300℃的范围内,特别优选在100-270℃的范围内的温度下,在3-350bar范围内、优选在5-330bar的范围内,特别优选在10-300bar的范围内的压力下进行。
在非常特别优选的实施方案中,本发明的催化剂用于制备己二醇和/或己内酯的方法,如DE 196 07 954、DE 196 07 955、DE 196 47 348和DE 196 47 349中所述。
在使用本发明催化剂的本发明方法中获得了高的转化率和选择性。同时,本发明的催化剂显示出高的化学和机械稳定性。
因此本发明在非常普遍的意义上涉及Cu-Al催化剂的应用,在催化剂的制备过程中镧、钨、钼、钛和/或锆的氧化物已被添加到该Cu-Al催化剂中以增加催化剂的机械稳定性以及活性和选择性。
在优选的实施方案中,本发明涉及如上所述的应用,其中所述催化剂包括作为活性组分的铜。
固体催化剂特别是本发明的催化剂的机械稳定性是由在各种状态(氧化、还原、还原并悬浮在水中)的侧向破碎强度参数来描述的。
本申请中的侧向破碎强度是用由Zwick(Ulm)提供的“Z 2.5/T 919”型仪器测定的。对于还原的催化剂和使用过的催化剂都在氮气氛下进行测定,以避免催化剂的再氧化。
在下列实施例中将更详细地描述本发明。
实施例
实施例1:催化剂1的制备
催化剂的制备
将12.41kg浓度为19.34%的硝酸铜溶液、14.78kg浓度为8.12%的硝酸铝溶液和1.06kg浓度为37.58%的六水合硝酸镧溶液的混合物溶解在1.5L水中(溶液1)。溶液2包括60kg浓度为20%的无水Na2CO3。通过分开的管线将溶液1和溶液2送到设置有搅拌器并含10L加热到60℃的水的沉淀容器中。在这期间适当调整溶液1和溶液2的进料速率使pH达到6.2。
在保持pH恒定在6.2和温度在60℃的同时,整个溶液1与碳酸钠发生反应。然后将这样形成的悬浮液搅拌1h,在这期间通过偶尔添加稀硝酸或碳酸钠溶液2使pH升至7.2。过滤该悬浮液并用蒸馏水洗涤直到水性洗涤的硝酸盐含量小于10ppm为止。
滤饼在120℃干燥16h,然后在300℃煅烧2h。将这样获得的催化剂粉末与1重量%的石墨预压制。将所形成的压制物与5重量%的Unicoat铜片混合,然后与2重量%的石墨混合并压成直径3mm、高度3mm的片。最后将片在350℃煅烧2h。
这样制备的催化剂具有化学组成57%CuO/28.5% Al2O3/9.5%La2O3/5%Cu。在氧化态和还原态的侧向破碎强度列于表1中。
实施例2:己二酸二甲酯在催化剂1上的氢化
在充填了200ml催化剂1的立管反应器中在200bar的压力下及在220℃和240℃的反应温度,以0.3kg/(l*h)的空速在具有循环(进料/循环=10/1)的向下流动过程中连续地氢化己二酸二甲酯。该实验持续共7天。GC分析检测来自220℃和240℃的反应器的排出物,酯转化率分别为98-99%和99%,己二醇含量分别为57%和62%。在去除之后,催化剂仍然十分完整,并显示出高的机械稳定性。侧向破碎强度汇总在表1中。实验结果再次汇总在表2中。
实施例3:对比催化剂的制备
对比催化剂的制备与催化剂1类似,但是没有添加硝酸镧溶液,这意味着:与催化剂1类似,用碳酸钠溶液沉淀14.5kg的浓度为19.34%的硝酸铜溶液和14.5kg的浓度为8.12%的硝酸铝溶液(溶液1)。
这样制备的催化剂具有化学组成66.5%CuO/28.5%Al2O3/5%Cu。在氧化态和还原态的侧向破碎强度列于表1中。
实施例4:己二酸二甲酯在对比催化剂上的氢化
在充填了200ml催化剂2的立管反应器中在200bar的压力下及在220℃和240℃的反应温度,以0.3kg/(l*h)的空速在具有循环(进料/循环=10/1)的向下流动过程中连续地氢化己二酸二甲酯。该实验持续共7天。GC分析检测来自220℃和240℃的反应器的排出物,酯转化率在每种情况下均为98%,己二醇含量为55%。在去除之后,催化剂仍然十分完整,并显示出高的机械稳定性。侧向破碎强度汇总在表1中。实验结果再次汇总在表2中。
表1
催化剂 | 侧向破碎强度(氧化状态)/N | 侧向破碎强度(还原状态)/N | 侧向破碎强度(去除之后)/N | 侧向破碎强度(还原状态,悬浮在水中)/N |
催化剂1 | 111 | 62 | 51 | 41 |
对比催化剂 | 70 | 45 | 20 | 26 |
表1中的数据表明,本发明的催化剂1在还原态和去除之后显示出比对比催化剂明显较高的机械稳定性。
下面的表2中的数据表明,本发明的催化剂与对比催化剂相比在220℃和240℃具有明显较高的氢化活性,即较高的己二酸二甲酯转化率,并且也倾向于具有较高的对所要产物的选择性,即目标产物己二醇在排出物中的含量。
表2
催化剂 | 反应温度/℃ | 己二酸二甲酯转化率/% | 排出物中己二醇的含量/% |
催化剂1 | 220240 | 9899 | 5762 |
对比催化剂 | 220240 | 9296 | 4858 |
Claims (11)
1.一种用于氢化具有至少一个羰基的有机化合物的方法,其中所述有机化合物在氢的存在下与成形体接触,所述成形体可在其中包括以下的方法中制备,
(i)制备包括氧化铜、氧化铝和至少一种镧、钨、钼、钛或锆的氧化物的氧化材料,
(ii)将粉状金属铜、铜片、粉状水泥、石墨或它们的混合物添加到所述氧化材料中,和
(iii)将由(ii)产生的混合物加工成形为成形体。
2.如权利要求1所述的方法,其中所述氧化材料包括
(a)含量在50≤x≤80重量%范围内的氧化铜,
(b)含量在15≤y≤35重量%范围内的氧化铝,和
(c)含量在2≤z≤20重量%范围内的至少一种镧、钨、钼、钛或锆的氧化物,
在每种情形中均基于煅烧后的所述氧化材料的总重量,其中适用下式:80≤x+y+z≤100,其中并未将水泥同以上意义的氧化材料一起考虑在内。
3.如权利要求2所述的方法,其中所述氧化材料包括
(a)含量在55≤x≤75重量%范围内的氧化铜,或
(b)含量在20≤y≤30重量%范围内的氧化铝,或
(c)含量在3≤z≤15重量%范围内的至少一种镧、钨、钼、钛或锆的氧化物。
4.如权利要求2所述的方法,其中95≤x+y+z≤100。
5.如权利要求1-4中任一项所述的方法,其中所述添加导致基于所述氧化材料的总重量含量在1-40重量%范围内的粉状金属铜、铜片或粉状水泥或它们的混合物的添加。
6.如权利要求5所述的方法,其中将石墨以基于所述氧化材料的总重量在0.5-5重量%范围内的含量添加到所述氧化材料中或添加到由(ii)产生的混合物中。
7.如权利要求6所述的方法,其中所述有机化合物是羧酸、羧酸酯、羧酸酐或内酯。
8.如权利要求7所述的方法,其中所述有机化合物是己二酸或己二酸酯。
9.一种成形体,其包括
氧化材料,该氧化材料包括
(a)含量在50≤x≤80重量%范围内的氧化铜,
(b)含量在15≤y≤35重量%范围内的氧化铝,和
(c)含量在2≤z≤20重量%范围内的至少一种镧、钨、钼、钛或锆的氧化物,
在每种情形中均基于煅烧后的所述氧化材料的总重量,其中适用下式:80≤x+y+z≤100,
基于所述氧化材料的总重量含量在1-40重量%范围内的金属铜粉、铜片或粉状水泥或它们的混合物,和
基于所述氧化材料的总重量含量在0.5-5重量%范围内的石墨,其中氧化材料、金属铜粉或粉状水泥或它们的混合物和石墨的总含量占所述成形体的至少95重量%。
10.如权利要求9所述的成形体,其中
氧化材料包括
(a)含量在55≤x≤75重量%范围内的氧化铜,或
(b)含量在20≤y≤30重量%范围内的氧化铝,或
(c)含量在3≤z≤15重量%范围内的至少一种镧、钨、钼、钛或锆的氧化物。
11.如权利要求9所述的成形体,其中95≤x+y+z≤100。
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Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004033556A1 (de) * | 2004-07-09 | 2006-02-16 | Basf Ag | Katalysatorformkörper und Verfahren zur Hydrierung von Carbonylverbindungen |
DE102005032726A1 (de) * | 2005-07-13 | 2007-01-18 | Basf Ag | Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen |
DE102005049135A1 (de) * | 2005-10-14 | 2007-04-19 | Basf Ag | Verfahren zur Hydrierung von Carbonylverbindungen |
CN101541721A (zh) * | 2006-11-27 | 2009-09-23 | 巴斯夫欧洲公司 | 制备3-烷氧基丙-1-醇的方法 |
US7964114B2 (en) * | 2007-12-17 | 2011-06-21 | Sud-Chemie Inc. | Iron-based water gas shift catalyst |
EE200800009A (et) * | 2008-02-21 | 2009-10-15 | Nordbiochem OÜ | Katalsaator ja meetod hdrokskarbokslhapete estrite kataltiliseks redutseerimiseks glkoolideks |
DE102008026210B4 (de) | 2008-05-30 | 2012-06-28 | Süd-Chemie AG | Nanokristallines Kupferoxid und Verfahren zu dessen Herstellung |
CN102203054B (zh) | 2008-11-05 | 2014-07-30 | 巴斯夫欧洲公司 | 生产n,n-取代的3-氨基丙-1-醇的方法 |
JP2012517333A (ja) | 2009-02-09 | 2012-08-02 | ビーエーエスエフ ソシエタス・ヨーロピア | モノリス触媒の触媒活性を改善する方法 |
CN102307660A (zh) | 2009-02-09 | 2012-01-04 | 巴斯夫欧洲公司 | 氢化催化剂及其制备和用途 |
CN102307661A (zh) | 2009-02-09 | 2012-01-04 | 巴斯夫欧洲公司 | 氢化催化剂、其生产和应用 |
WO2010115738A1 (de) | 2009-04-07 | 2010-10-14 | Basf Se | Verfahren zur herstellung von 1,6-hexandiol |
EP2559679A3 (de) | 2009-04-08 | 2013-05-22 | Basf Se | Verfahren zur Herstellung von 1,6-Hexandiol durch Hydrierung von Oligo- und Polyestern |
CN102438972B (zh) * | 2009-05-20 | 2015-09-09 | 巴斯夫欧洲公司 | 通过在含铜非均相催化剂上氢化甘油三脂肪酸酯而制备脂肪醇的方法 |
TWI490034B (zh) | 2009-11-17 | 2015-07-01 | Basf Se | 製備具有增強氫化活性之經承載氫化觸媒之方法 |
US8637668B2 (en) | 2010-06-15 | 2014-01-28 | Basf Se | Process for preparing a cyclic tertiary methylamine |
EP2614056B1 (de) | 2010-09-08 | 2014-07-23 | Basf Se | Verfahren zur herstellung von epsilon-caprolacton und 1,6-hexandiol |
US8933223B2 (en) | 2010-10-14 | 2015-01-13 | Basf Se | Process for preparing a cyclic tertiary amine |
WO2013056463A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013056400A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013056459A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
WO2013056461A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
CN104039752B (zh) | 2012-01-11 | 2017-03-08 | 巴斯夫欧洲公司 | 在液相中制备仲胺的方法 |
US8884015B2 (en) | 2012-06-01 | 2014-11-11 | Basf Se | Process for the preparation of a mono-N-alkypiperazine |
EP2855443B1 (de) | 2012-06-01 | 2016-03-30 | Basf Se | Verfahren zur herstellung eines mono-n-alkyl-piperazins |
US8981093B2 (en) | 2012-06-06 | 2015-03-17 | Basf Se | Process for preparing piperazine |
DE102012012510B4 (de) | 2012-06-22 | 2018-12-06 | Clariant International Ltd. | Graphithaltiger Katalysatorformkörper, dessen Herstellverfahren sowie Verwendung |
US20160311739A1 (en) | 2013-12-13 | 2016-10-27 | Basf Se | Method for preparing 1,6-hexanediol |
TW201536734A (zh) * | 2014-03-12 | 2015-10-01 | Basf Se | 甲酸鹽的分解 |
DE102014004391A1 (de) * | 2014-03-26 | 2015-10-15 | Clariant International Ltd. | Verfahren zur Herstellung von Katalysatoren mit erhöhter Festigkeit und verringertem Volumenschwund |
US10343154B2 (en) * | 2014-11-25 | 2019-07-09 | Graver Technologies Llc | High capacity adsorbent for fluoride ion and oxyanions of phosphorous and arsenic and method for making the same |
US11583846B2 (en) | 2014-11-25 | 2023-02-21 | Graver Technologies Llc | High capacity adsorbent for oxyanions and cations and method for making the same |
MY182072A (en) | 2015-03-26 | 2021-01-18 | Basf Corp | Hydrogenolysis catalysts with high acid tolerance |
DE102016225172A1 (de) * | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Tablettierter Katalysator mit erhöhter Stabilität gegenüber Säureeinwirkung |
DE102016225171A1 (de) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Tablettierter Katalysator für die Methanolsynthese mit erhöhter mechanischer Stabilität |
PL3625199T3 (pl) | 2017-05-16 | 2022-02-07 | Basf Se | Sposób hydroformylowania służący do przemysłowego wytwarzania aldehydów i/lub alkoholi |
DE102019131569A1 (de) | 2019-11-22 | 2021-05-27 | Clariant International Ltd | Chromfreier wasser- und saeurestabiler katalysator fuer hydrierungen |
DE102020106964A1 (de) | 2020-03-13 | 2021-09-16 | Clariant International Ltd | Chromfreier hydrierkatalysator mit erhoehter wasser- und saeurestabilitaet |
WO2023057358A1 (en) | 2021-10-07 | 2023-04-13 | Basf Se | Process for the production of bis(pyrrolidino)butane in the liquid phase |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4287099A (en) * | 1979-04-27 | 1981-09-01 | Basf Aktiengesellschaft | Preparation of catalysts for the hydrogenation of acetylene-alcohols |
US5990040A (en) * | 1995-01-11 | 1999-11-23 | United Catalysts Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE256515C (zh) | 1911-07-04 | 1913-02-14 | ||
GB1296212A (zh) * | 1969-03-04 | 1972-11-15 | ||
US4105590A (en) * | 1972-03-25 | 1978-08-08 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Catalysts and the process for their production |
US3870658A (en) * | 1973-03-02 | 1975-03-11 | Corning Glass Works | Copper chromite-alumina catalysts having high-temperature stability |
US4206150A (en) * | 1976-11-04 | 1980-06-03 | Shell Oil Company | Amine process using copper-molybdenum/tungsten catalyst |
CA1163615A (en) * | 1980-03-11 | 1984-03-13 | Atsushi Nishino | Catalyst for purifying exhaust gases and method for manufacturing same |
KR920000149B1 (ko) * | 1983-07-01 | 1992-01-09 | 가부시기가이샤 히다찌세이사꾸쇼 | 내열성촉매 및 그 사용방법 |
DE3403491A1 (de) * | 1984-02-02 | 1985-08-14 | Süd-Chemie AG, 8000 München | Katalysator zur synthese von methanol und hoehere alkohole enthaltenden alkoholgemischen |
US4666879A (en) * | 1985-09-11 | 1987-05-19 | Harshaw/Filtrol Partnership | Extruded copper chromite-alumina hydrogenation catalyst |
US4762817A (en) * | 1986-11-03 | 1988-08-09 | Union Carbide Corporation | Aldehyde hydrogenation catalyst |
US5008235A (en) * | 1989-12-21 | 1991-04-16 | Union Carbide Chemicals And Plastics Technology Corporation | Catalysts of Cu-Al-third metal for hydrogenation |
DE4037731C2 (de) * | 1990-11-27 | 1996-06-05 | Sued Chemie Ag | Kupferoxid und Chromoxid enthaltender Katalysator und seine Verwendung zur Hydrierung von Fettsäuren und -estern |
DE4244273A1 (de) * | 1992-12-28 | 1994-06-30 | Hoechst Ag | Kupferkatalysator |
DE19505347B4 (de) | 1994-03-02 | 2008-10-02 | Basf Se | Verfahren zur Herstellung von Katalysator-Tabletten mit hoher mechanischer Festigkeit |
US5475159A (en) * | 1994-11-07 | 1995-12-12 | Shell Oil Company | Process for the direct hydrogenation of methyl esters |
MY129140A (en) † | 1994-11-07 | 2007-03-30 | Shell Int Research | Process and a catalyst for the direct hydrogenation of carboxylic esters |
DE69513792T2 (de) * | 1995-01-11 | 2000-04-27 | United Catalysts Inc | Aktivierter und stabilisierter Kupferoxid- und Zinkoxidkatalysator und Verfahren zu seiner Herstellung |
DE19607955A1 (de) | 1996-03-01 | 1997-09-04 | Basf Ag | Verfahren zur Herstellung von 1,6-Hexandiol mit einer Reinheit über 99 % |
DE19647348A1 (de) | 1996-11-15 | 1998-05-20 | Basf Ag | Verfahren zur Herstellung von 1,6-Hexandiol mit einer Reinheit über 99 % |
DE19607954A1 (de) | 1996-03-01 | 1997-09-04 | Basf Ag | Verfahren zur Herstellung von 1,6-Hexandiol und Caprolacton |
DE19647349A1 (de) | 1996-11-15 | 1998-05-20 | Basf Ag | Verfahren zur Herstellung von 1,6-Hexandiol und Caprolacton |
AU733025B2 (en) * | 1996-03-21 | 2001-05-03 | Engelhard Corporation | Preparation and use of non-chrome catalysts for Cu/Cr catalyst applications |
DE19809418A1 (de) * | 1998-03-05 | 1999-09-09 | Basf Ag | Verfahren zur Hydrierung von Carbonylverbindungen |
DE19859776B4 (de) * | 1998-12-23 | 2008-06-19 | Basf Se | Verfahren zur Herstellung von Aminen |
DE19942895A1 (de) † | 1999-09-08 | 2001-03-15 | Basf Ag | Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen |
DE10061553A1 (de) † | 2000-12-11 | 2002-06-13 | Basf Ag | Poröser Katalysator für die Hydrierung von Maleinsäureanhydrid zu Tetrahydrofuran |
DE10119719A1 (de) * | 2001-04-21 | 2002-10-24 | Basf Ag | Verfahren zur Hydrierung von Carbonylverbindungen |
DE10133054A1 (de) * | 2001-07-07 | 2003-01-16 | Basf Ag | Verfahren zur selektiven Herstellung von Tetrahydrofuran durch Hydrierung von Maleinsäureanhydrid |
US7176159B1 (en) * | 2001-08-15 | 2007-02-13 | Iowa State University Research Foundation, Inc. | Catalyst and sorbent material for the production of hydrogen |
-
2003
- 2003-03-27 DE DE2003113702 patent/DE10313702A1/de not_active Withdrawn
-
2004
- 2004-02-27 MY MYPI20040679A patent/MY150679A/en unknown
- 2004-03-20 EP EP04722176.7A patent/EP1613576B2/de not_active Expired - Lifetime
- 2004-03-20 JP JP2006504763A patent/JP4664902B2/ja not_active Expired - Lifetime
- 2004-03-20 KR KR1020057018011A patent/KR101067539B1/ko active IP Right Grant
- 2004-03-20 DE DE200450011209 patent/DE502004011209D1/de not_active Expired - Lifetime
- 2004-03-20 BR BRPI0408384-9B1A patent/BRPI0408384B1/pt not_active IP Right Cessation
- 2004-03-20 MX MXPA05009819A patent/MXPA05009819A/es active IP Right Grant
- 2004-03-20 AT AT04722176T patent/ATE469113T1/de active
- 2004-03-20 WO PCT/EP2004/002929 patent/WO2004085356A1/de active Application Filing
- 2004-03-20 ES ES04722176T patent/ES2344349T5/es not_active Expired - Lifetime
- 2004-03-20 CN CNB2004800083047A patent/CN100345808C/zh not_active Expired - Lifetime
- 2004-03-20 US US10/549,140 patent/US7510591B2/en active Active
-
2007
- 2007-11-09 US US11/937,537 patent/US7663003B2/en not_active Expired - Lifetime
-
2009
- 2009-10-29 US US12/608,125 patent/US7884046B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4287099A (en) * | 1979-04-27 | 1981-09-01 | Basf Aktiengesellschaft | Preparation of catalysts for the hydrogenation of acetylene-alcohols |
US5990040A (en) * | 1995-01-11 | 1999-11-23 | United Catalysts Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation |
Also Published As
Publication number | Publication date |
---|---|
MY150679A (en) | 2014-02-28 |
DE10313702A1 (de) | 2004-10-07 |
KR20050116830A (ko) | 2005-12-13 |
US7663003B2 (en) | 2010-02-16 |
EP1613576A1 (de) | 2006-01-11 |
US20080064882A1 (en) | 2008-03-13 |
DE502004011209D1 (de) | 2010-07-08 |
WO2004085356A1 (de) | 2004-10-07 |
KR101067539B1 (ko) | 2011-09-27 |
BRPI0408384A (pt) | 2006-03-21 |
JP4664902B2 (ja) | 2011-04-06 |
ES2344349T3 (es) | 2010-08-25 |
ATE469113T1 (de) | 2010-06-15 |
US7884046B2 (en) | 2011-02-08 |
US20100056364A1 (en) | 2010-03-04 |
EP1613576B1 (de) | 2010-05-26 |
EP1613576B2 (de) | 2013-10-16 |
CN1764621A (zh) | 2006-04-26 |
US20060178539A1 (en) | 2006-08-10 |
BRPI0408384B1 (pt) | 2014-11-11 |
US7510591B2 (en) | 2009-03-31 |
ES2344349T5 (es) | 2014-01-03 |
MXPA05009819A (es) | 2005-12-05 |
JP2006523186A (ja) | 2006-10-12 |
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