CN1043697A - 羧酸和酐氢化制备脂 - Google Patents
羧酸和酐氢化制备脂 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 18
- -1 acid anhydride ester Chemical class 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 22
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 17
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000010970 precious metal Substances 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
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- 239000002184 metal Substances 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000009466 transformation Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 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 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 33
- 239000003054 catalyst Substances 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
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- 239000000377 silicon dioxide Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
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- 229910052697 platinum Inorganic materials 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- 229910003449 rhenium oxide Inorganic materials 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000007518 monoprotic acids Chemical class 0.000 description 4
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 4
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- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
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- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001030 gas--liquid chromatography Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
由羧酸或其酐通过在高温下在作为催化剂的组合物存在下使该酸或酐与氢反应在选择性大于50%下制备羧酸酯,而得到的相应醇的选择性小于10%,该组合物含有至少含第VIII族中的一种贵金属的组分(i)和/或至少含钼、钨和铼中的一种的组分(ii)以及含第VIb族中的一种元素的氧化物的组分(iii)。本方法特别适于将乙酸氢化为乙酸乙酯。
Description
本发明涉及羧酸和其酐的氢化制备相应的酯。
用羧酸的氢化制备醇是早已知道的。现有技术的代表有专利文献US4,446,073、4,398,039、4,104,478、3,985,814和4,524,255;DE-A-2,605,107、GB-A-1534232和GB-A-1551741。
美国专利4,446,073公开了用含有组合于固体载体上的低价氧化态镉和钌及任选的一种铂族金属的催化剂使不饱和羧酸还原成酯或醇。
英国专利4,393,039公开了在蒸汽和含有钌和钴与镍中至少一种以及镉、锌、铜、铁、铑、钯、锇、铱和铂中任选一种的混合氧化物的催化剂存在下羧酸汽相氢化成相应的醇。催化剂可被支承在惰性载体,比如铝酸盐、硅酸盐、钛酸盐、氧化锆及其混合物上。在无蒸汽时也可制得羧酸酯。
美国专利4,104,478公开了在含有铼和钌、铑、钯或铂的催化剂上用氢化使脂肪酸转化为相应的脂肪醇。
美国专利3,985,814公开了使用铂催化剂靠氢化使-CO2H基团转化成-CH2OH基团的方法。
美国专利4,524,225公开了使用支承在α-氧化铝、θ-氧化铝、钛酸盐化氧化铝、二氧化钛或磷酸铝上的铜、铬、钌、铂、钯和铼的催化剂组合物使脂肪酸氢化。
DE-A-2,605,107公开了用钌/铼组合物催化使羧酸氢化为醇。
GB-A-1534232公开了一种制备具有五个或更多个碳原子醇的方法,即在水和/或其它溶剂和一种含有钯和铼以及一种耐酸载体,例如二氧化硅、氧化铝或活性炭的催化剂存在下使相应的羧酸或其内酯或其酐催化氢化。
GB-A-1551741公开了一种制备丁二醇(1,4)的方法,即在一种含有一种门捷列夫周期表第ⅦA族元素或其一种化合物和钌、铑、钯、锇、铱、或铂或其一种化合物或这些元素和化合物的混合物的催化剂存在下氢化马来酐、马来酸或其混合物。
最近的专利文献包括我们的EP-A-0198681,它涉及靠与氢和一种含有(ⅰ)周期表第Ⅷ族一种贵金属和(ⅱ)铼,任选地支承在高表面积的石墨化的炭、石墨、二氧化硅、氧化铝或二氧化硅/氧化铝上的催化剂在汽相接触由乙酸制备乙醇或由丙酸制备丙醇;EP-A-0198682涉及靠与氢和一种含有(ⅰ)钼或钨和(ⅱ)周期表第Ⅷ族一种贵金属,任选地支承在一种高表面积的石墨化的炭、石墨、二氧化硅和氧化铝或二氧化硅/氧化铝上的多相催化剂接触由C2至C12羧酸制备醇和/或羧酸酯;EP-A-0201795涉及在一种还原性活化的固态含铜催化剂(并另外加入镁,镧系金属或锕系金属中的至少一种)存在下使羧酸氢化制备醇,以及EP-A-0285420,它涉及在含有一种(ⅰ)至少一种周期表第Ⅷ族贵金属和(ⅱ)至少一种能够与贵金属(比如银)合金化的金属的合金的组合物催化剂存在下,该催化剂任选地支承在高表面积的石墨化的炭、石墨、活性炭、二氧化硅、氧化铝或二氧化硅/氧化铝上,由羧酸或其酐靠与氢反应制备相应的醇和/或羧酸酯。
现在我们意外地发现,通过对催化剂和反应条件进行审慎的选择,C2至C12羧酸及其酐可优先被氢化成其相应羧酸酯而不是相应醇。
从而,本发明提供了一种从C2至C12羧酸或其酐制备相应羧酸酯的选择性大于50%而得到相应醇的选择性小于10%的方法,该方法包括在高温下在含有至少一种元素周期表第Ⅷ族贵金属的组分(ⅰ)和/或含钼、钨和铼中至少一种的组分(ⅱ),以及含元素周期表第Ⅳb族一种元素的氧化物的组分(ⅲ)的组合物催化剂存在下在使酸或酐向氢化产物的转化维持在低于同达到上述选择性一致的值的反应条件下使该酸或酐与氢反应。
本说明书中所指的元素周期表指的是化学物理手册(Handbook of Chemistry and Physics)第63版中的元素周期表。
我们认为(尽管这种看法不能够解释为在任何情况下都正确)本发明含第Ⅳb族催化剂与碳和二氧化硅支承的催化剂,比如EP-A-0198681中的作用有很大不同,后者的催化剂生成作为第一形成产物的醇,而作为第二形成产物的酯是由醇与未反应的羧酸或酐反应产生的。在这种情况下酯与醇的比例受到酯化反应的热力学平衡的限制,尤其是在乙酸氢化成的乙酸乙酯与乙醇之比为大约1.9∶1的情况下。相比而言,本发明的催化剂被认为形成酯作为第一形成产物,而其后酯氢化成醇。不论该理论是否正确,仍然可看到,通过限制酸的转化醇的形成可保持在非常低的程度或完全消失。因此,可能由乙酸制备比如乙酸乙酯(选择性大于90%),而伴生乙醇的选择性为5%或更小,有时为零。本发明的方法能够制备无醇酯,从而使醇一般很难从酯中的分离得以避免。而且,从羧酸中选择性的生成酯本身就是一个希望达到的目的,因为它避免了对在制备酯的常规酯化方法中与酸反应的醇的需求。
除了催化剂之外,影响酯形成选择性的主要参数是转化率,低于该转化率可获得对酯所要求的选择性,该转化率取决于所使用的催化剂以及欲氢化的羧酸的性能。典型地,比如对乙酸氢化,必须把酸转化率限制在小于90%。通过限制获得对酯的高选择的酸转率,回收未转化酸和减少分离问题是可能的。
本发明的方法既适用于C2至C12羧酸又适用于其酐。羧酸或其酐可以是饱和的或者是不饱和的。可以使用一元、二元或多元羧酸和其酐衍生物。合适的一元酸包括具有通式R-COOH的酸,式中R为取代的或未取代的脂族基或芳族基,这种酸被氢化成通式为RCOOR的酯。合适的基团R可以是C1至C12,尤其是C1至C5烷基。合适的一元酸的例子包括乙酸、丙酸、丁酸和庚酸。最佳一元酸包括可由之得到乙酸乙酯的乙酸和可由之得到丙酸丙酯的丙酸。
另外可使用二元酸、多元酸及其酐。合适的二元酸可以是饱和的也可以是不饱和的。合适的二元酸的例子包括戊二酸、戊二酐己二酸、己二酐、丁二酸、丁二酐、马来酸和马来酐。最佳的是C4二元酸和其酐。还可使用酸、酐和酸/酐的混合物。
氢大量市售,依其存在的杂质使用时可进一步提纯或不提纯。希望的提纯可以除去一氧化碳。
作为催化剂使用的组合物含有含周期表第Ⅷ族中至少一种贵金属的组分(ⅰ)和/或含钼、钨和铼中的至少一种的组分(ⅱ)以及含元素周期表第Ⅳb族元素的一种氧化物的组分(ⅲ)。至少对本说明书的目的而言,周期表第Ⅷ族贵金属至少是钯、铂、铑、钌、锇和铱。上述贵金属中,至少钯、铑和钌中的一种是较佳的,而至少钯和钌之一是更佳的。
组分(ⅱ)可以是金属、金属氧化物或其混合物。最佳组分(ⅱ)包括铼。
对本说明书的目的而言,元素周期表第Ⅳb族元素至少是钛、锆和铪。在催化剂中第Ⅳb族元素以其氧化物的形式存在。最佳氧化物是二氧化钛。二氧化钛可以以锐钛矿型二氧化钛和金红石型二氧化钛形式存在。有迹象表明优选的是锐钛矿型二氧化钛或主要含锐钛矿型二氧化钛的锐钛矿型和金红石型二氧化钛的混合物。
催化剂可以以组分(ⅰ)和/或组分(ⅱ)支承在组分(ⅲ)上的形式使用或以组分(ⅰ)和/或组分(ⅱ)和支承在惰性载体上的组分(ⅲ)的形式使用。合适的惰性载体包括高表面积石墨化的炭(HSAGs)、石墨、活性炭、二氧化硅、氧化铝和二氧化硅/氧化铝。
催化剂可结合一种或多种其它组分。这样,可以结合一种或多种选自元素周期表第ⅠA族或ⅡA族的金属。合适的金属是钾。
合适的催化剂含0.1~20%(重量),最佳1~10%(重量)的组分(ⅰ)和/或0.1~20%(重量),最佳1~10%(重量)的组分(ⅱ)。
合适的催化剂的例子包括钯/二氧化钛、铼/二氧化钛、钯/铼/二氧化钛和钌/二氧化钛。
本发明方法中使用的催化剂可用浸渍适当地制备。制备该催化剂的一种方法包括用组分(ⅰ)和/或组分(ⅱ)的可溶的可热分解的化合物的水溶液或非水溶液浸渍组分(ⅲ),其后将可热分解的化合物热分解成金属和/或金属氧化物。对该方法的详细叙述,读者可参阅我们的EP-A-0198681和本说明书所附的实施例。
在本发明方法中催化剂使用前最好活化,即在高温下与氢(也可任意地含一种惰性气体,比如氮)接触合适时间,例如1至24小时。活化可由催化剂制造者完成或在该方法进行之前直接由该方法操作人员完成或两种方法均可。
本方法制备酯可在液相或汽相中进行。它可分批地或连续地进行。连续操作是最佳的,回收未转化羧酸或酐是希望的选择。催化剂可以以固定床、活动床或流化床的形式使用。
合适的高温范围为50-300℃,尽管在一定程度上取决于羧酸反应物的性能、使用的催化剂和操作方式。对一元酸而言,高温范围一般为100-300℃,最佳为150-250℃。使用不饱和二元酸,高温范围一般为50-350℃,最佳是150-300℃。压力范围一般在1-300巴,尽管这也取决于上述因素。对于一元酸压力适当地低于50巴,对于不饱和二元酸压力范围一般在10-150巴。
依照下述实施例对本发明作进一步说明。
在实施例中采用了许多需进一步定义的术语。如下所示。
名义填充量定义为加到载体上金属(不是金属化合物)的重量(以载体重量百分数表示)。
WHSV是Weight Hourly Space Velocity的缩写,定义为每小时每千克催化剂的液体给料的千克数。
LHSV是Liquid Hourly Space Velocity的缩写,定义为每小时每升催化剂的液体给料的升数。
转化率定义为羧酸转化成产物的比例。
选择性定义为转化成特定产物的反应酸比例。
(Ⅰ)催化剂制备
催化剂A
把含有溶解的亚硝酰硝酸钌的水溶液加入到高表面积二氧化钛中并把混合物放置一夜。在旋转式蒸发器上把水除去,把浸渍的二氧化钛在烘箱内在110℃干燥一夜。选择各种组分的量以得到2%的Ru名义填充量。
催化剂B
按照用于催化剂A的制备步骤。然后把所得的组合物转移到玻璃试管中并在氢气流中加热,使用的条件如下:从室温至500℃时间5小时,然后在500℃保持2小时随后冷却至室温。然后把气流换成氮气时间几小时。
催化剂C
除了钌名义填充量为1%之外,按照用于催化剂B的步骤。该催化剂的X-射线衍射分析表明它主要地含锐钛矿型二氧化钛而没有金红石型二氧化钛痕迹。用BET方法测得的表面积为108米2/克。用X-射线萤光法(XRF)测得的钌含量为1.5%Ru。
催化剂D
把硝酸钯的水溶液加到锐钛矿型二氧化钛粉末(由Tioxide提供)样品中,用BET方法测得该粉末的表面积为200米2/米。在旋转式蒸发器上把水除去,并把组合场在真空烘箱中在100℃干燥一夜。把组合物制成丸并把丸粉碎,过筛颗粒度为0.5毫米-1毫米。选择各种组分的量以得到2.5%的钯名义填充量(用X-射线萤光法(XRF)测量为2.0%)。
催化剂E
除了使用BET表面积为50米2/克(用XRF法为Pd2.1%)的金红石型二氧化钛(由Tioxide提供)代替锐钛矿型二氧化钛外,按照催化剂D使用的步骤。
催化剂F
除了使用氧化铼Re2O7而不使用硝酸钯之外,按照催化剂D使用的步骤。选择各种组分的量以得到5%的铼名义填充量(用XRF测量为8%)。
催化剂G
除了使用氧化铼Re2O7而不使用硝酸钯之外,按照用于催化剂E的步骤。选择各种组分的量以得到5%的铼名义填充量(用XRF测量为8%)
催化剂H
按照用于催化剂D的步骤,把所得组合物在氮气流中加热,使用的条件如下:用6小时把温度升高到300℃,在300℃保持10小时,然后冷却到室温。把组合物加到氧化铼水溶液中,并用旋转式蒸发器除去水。象催化剂D的描述,把该催化剂干燥、制成丸、粉碎并过筛。选择各种组分的量以得到名义填充量2.5%Pd、5%Re(用XRF法为2.4%Pd、3.5%Re)。
催化剂I
把乙酸钯的乙酸乙酯溶液加到锐钛矿型二氧化钛(0.5-1.0毫米小丸)(由Degussa)样品中,用BET方法测得二氧化钛表面积为57米2/克。在旋转式蒸发器上除去乙酸乙酯,并把组合物在真空烘箱中于100℃干燥一夜。把所得组合物在氮气流中加热,使用的条件如下:用6小时把温度升高到300℃,在300℃保持10小时,然后冷却至室温
把所得组合物加到氧化铼的乙酸乙酯溶液中,并用旋转式蒸发器除去乙酸乙酯。把催化剂在真空烘箱中干燥一夜。选择各种组分的量以得到名义填充量2.5%Pd、5%Re。
催化剂J
除了使用BET表面积为178米2/克锐钛矿型二氧化钛(0.5-1.00毫米小丸)(由Norton提供)之外,按照催化剂Ⅰ的步骤。(Ⅱ)催化剂试验
方法
把2-2.5毫升催化剂装入内径6-7毫米的耐蚀不锈钢管内,将反应器管装入水平管式炉内。然后在大气压力下在氢气流中把催化剂加热使之活化。活化后,把催化剂在氢气中冷却到希望的反应温度。然后让乙酸蒸气和氢气的混合物通过催化剂,用反压调节阀把压力调节到要求值。蒸汽/氢气混合物在蒸发区生成,分别测量乙酸液体和氢气。从离开反应器的产物蒸汽和气体中取样,并用气-液色谱法(GLC)分析。把热电偶插入催化剂床中测量温度。
主要产物为乙酸乙酯,带有一些乙醇(在高转化率下)和乙烷与甲烷付产物。
实施例1-3
在氢气中用2小时加热到280℃,然后在280℃保持2小时实现催化剂活化。
在230℃、10巴、LHSV为1和氢与乙酸摩尔比为10∶1下,经过催化剂A(实施例1)、B(实施例2)和C(实施例3)使乙酸氢化。
结果列于表1。
实施例4至8
在氢气中用2小时加热到300℃,然后在300℃保持2小时实现催化剂活性。
在氢:乙酸摩尔比为10∶1、压力为10巴和表2所示温度下,经过催化剂D(实施例4)、E(实施例5)、F(实施例6)、G(实施例7)和H(实施例8)使乙酸氢化。
结果列于表2。
*其它=甲烷、乙烷、乙醛和丙酮
实施例9
在氢气中用2小时加热到300℃,然后在300℃保持2小时实现催化剂活化。
在氢∶乙酸摩尔比为10∶1、压力为10巴和表3所示温度下经过催化剂J(实施例9)使乙酸氢化。
结果列于表3中。
*其它=甲烷、乙烷、乙醛和丙酮。
实现催化剂活化
在乙酸LHSV=1.34、压力为10巴、温度为228℃和表4所示氢∶乙酸摩尔比下,经过催化剂H使乙酸氢化。
结果列于表4中。这些结果表明在较低酸转化率之下对乙酸乙酯的选择性增加。
*其它=甲烷、乙烷、乙醛和丙酮
实施例12
在氢气中用2小时加热到300℃,然后在300℃保持2小时实现催化剂活化。
在乙酸LHSV=1.34,压力为10巴,表5所示温度和氢∶乙酸摩尔比下经过催化剂Ⅰ使乙酸氢化。
结果列于表5中。
*其它=甲烷、乙烷、乙醛和丙酮。
对比试验A
在催化剂D、F和H中使用的锐钛矿型二氧化钛经实施例4至8的方法活化后试验乙酸的氢化。
结果列于表2中。结果表明二氧化钛本身对乙酸氢化成乙酸乙酯的活性几乎可以忽略。
这不是本发明的实施例而仅仅用于对比。
Claims (13)
1、一种由C2至C12羧酸或其酐以大于50%选择性制备相应羧酸酯,而产生相应醇的选择性小于10%的方法,该方法包括在高温下在作为催化剂的组合物存在下使酸或酐与氢反应,该组合物含有至少含元素周期表第VIII族中一种贵金属的组分(i)和/或含钼、钨和铼中至少一种的组分(ii)和含元素周期表第IVb族中一种元素的氧化物的组分(iii),在反应条件下酸或酐的氢化产物的转化率保持在达到上述选择性相一致的值之下。
2、权利要求1的方法,其中组分(ⅲ)包括二氧化钛。
3、权利要求2的方法,其中二氧化钛主要含锐钛矿型二氧化钛。
4、上述任一权利要求中的方法,其中催化剂含0.1%-20%的组分(ⅰ)。
5、上述任一权利要求中的方法,其中组分(ⅰ)至少含钯、铑和钌中的一种。
6、权利要求5的方法,其中组分(ⅰ)至少含钯和钌中的一种。
7、上述任一权利要求中的方法,其中催化剂含0.1%-20%的组分(ⅱ)。
8、上述任一权利要求中的方法,其中组分(ⅱ)含铼。
9、上述任一权利要求中的方法,其中催化剂另外至少含元素周期表第ⅠA族或第ⅡA族的一种金属。
10、上述任一权利要求中的方法,其中催化剂由在非水溶液中浸渍制备的。
11、上述任一权利要求中的方法,其中羧酸包括乙酸、丙酸、丁酸或庚酸。
12、上述任一权利要求中的方法,其中催化剂使用前由在高温下与氢接触来活化。
13、权利要求1的方法中使用的催化剂,含有至少含元素周期表第Ⅷ族中的一种贵金属的组分(ⅰ)和/或至少含钼、钨和铼中的一种的组分(ⅱ)以及含元素周期表第Ⅳb族中的一种元素的氧化物。
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CN1326610C (zh) * | 2002-04-12 | 2007-07-18 | 松下电工株式会社 | 根据水煤气转化反应除去富含氢的气体内的一氧化碳用的催化剂、使用该催化剂的处理装置及其方法 |
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GB8707595D0 (en) * | 1987-03-31 | 1987-05-07 | British Petroleum Co Plc | Chemical process |
GB8917157D0 (en) * | 1989-07-27 | 1989-09-13 | Bp Chem Int Ltd | Chemical process |
-
1988
- 1988-12-07 GB GB888828616A patent/GB8828616D0/en active Pending
-
1989
- 1989-12-01 EP EP19890312549 patent/EP0372847A3/en not_active Withdrawn
- 1989-12-06 JP JP1315502A patent/JPH02202848A/ja active Pending
- 1989-12-06 NO NO89894888A patent/NO894888L/no unknown
- 1989-12-06 AU AU45963/89A patent/AU614682B2/en not_active Ceased
- 1989-12-06 CA CA002004753A patent/CA2004753A1/en not_active Abandoned
- 1989-12-07 ZA ZA899376A patent/ZA899376B/xx unknown
- 1989-12-07 NZ NZ231676A patent/NZ231676A/en unknown
- 1989-12-07 BR BR898906331A patent/BR8906331A/pt unknown
- 1989-12-07 CN CN89109779A patent/CN1043697A/zh active Pending
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CN1326610C (zh) * | 2002-04-12 | 2007-07-18 | 松下电工株式会社 | 根据水煤气转化反应除去富含氢的气体内的一氧化碳用的催化剂、使用该催化剂的处理装置及其方法 |
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CN102271804B (zh) * | 2009-10-26 | 2014-04-02 | 国际人造丝公司 | 由乙酸制备乙酸乙酯的方法 |
CN102421730A (zh) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | 产生用于生产酯和联产乙醇的酯进料流的方法 |
Also Published As
Publication number | Publication date |
---|---|
AU614682B2 (en) | 1991-09-05 |
EP0372847A3 (en) | 1991-03-27 |
EP0372847A2 (en) | 1990-06-13 |
JPH02202848A (ja) | 1990-08-10 |
BR8906331A (pt) | 1990-08-21 |
CA2004753A1 (en) | 1990-06-07 |
ZA899376B (en) | 1991-08-28 |
NZ231676A (en) | 1991-04-26 |
AU4596389A (en) | 1990-06-14 |
NO894888D0 (no) | 1989-12-06 |
NO894888L (no) | 1990-06-08 |
GB8828616D0 (en) | 1989-01-11 |
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