CN1008088B - 通过羧酸加氢制备醇 - Google Patents
通过羧酸加氢制备醇Info
- Publication number
- CN1008088B CN1008088B CN86102452A CN86102452A CN1008088B CN 1008088 B CN1008088 B CN 1008088B CN 86102452 A CN86102452 A CN 86102452A CN 86102452 A CN86102452 A CN 86102452A CN 1008088 B CN1008088 B CN 1008088B
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- CN
- China
- Prior art keywords
- carrier
- catalyzer
- metal
- precious metal
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- 238000005984 hydrogenation reaction Methods 0.000 title description 18
- 150000001735 carboxylic acids Chemical class 0.000 title description 5
- 150000001298 alcohols Chemical class 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 50
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 5
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 claims abstract 2
- 239000003610 charcoal Substances 0.000 claims description 43
- 239000010970 precious metal Substances 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000001149 thermolysis Methods 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003658 tungsten compounds Chemical class 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 229910001947 lithium oxide Inorganic materials 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- -1 carboxylate salt Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 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
- 229910052702 rhenium Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001983 dialkylethers Chemical class 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
- 150000002500 ions Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 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 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000004580 weight loss Effects 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/525—Perovskite
Landscapes
- 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
在多相催化剂的存在下，在较高的温度和压力下，使羧酸与氢接触，可由C2至C12羧酸制取醇和/或羧酸酯。该方法的特征在于催化剂含有第一组分，该组分为钼或钨，和第二组分，该组分为元素周期表第VIII族贵金属，该催化剂可载在载体上，例如大表面积的石曼化碳。
Description
本发明涉及到将羧酸催化加氢制备相应的醇和/或羧酸酯。
在多相催化剂的存在下，将羧酸加氢制备相应的醇的方法是已知的，例如可参考USP-A-4524225，USP-A-4104478，GB-A-1534232，GB-A-1551741，DE-A-3221077和EP-A-147219。
在USP-A-4524225中描述了在100-300℃和100-3000磅/平方英寸〔表压〕下，在分散在载体上的、从Cu、Cr、Ru、Pt、Pd、Re及其混合物中选出的零价金属的存在下，通过将脂肪酸同氢接触将C6-C24脂肪酸加氢。载体可以是α、θ或含钛氧化铝，二氧化钛，或AlPO4或它们的混合物。
USP-A-4104478描述了在170-250℃及20-140大气压下，通过含有（a）一份（重量）的活性Re，和（b）0.25-1.5份的含杂质的从Ru，Rh，Pt和Pd中选出的金属催化剂，将相应的脂肪酸催化加氢制备C4-C24脂肪族醇。
GB-A-1534232描述了在高温、高压下，在水和/或溶剂的存在下，使用在载体上的Pd/Re催化剂，通过将羧酸催化加氢制备醇的方法。催化剂中Pd与Re的重量比为0.01到5∶1。
GB-A-1551741描述了在催化剂的存在下，通过将马来酸加氢一步制备1，4-丁二醇的方法。此催化剂含有（A）Ⅶ族元素，较好的为Mn或Re，或它们的化合物，和（B）Ⅶ族元素，较好的为Ru，Rh，Pd，Os，Ir或Pt，更好的为Pd或Pt或它们的化合物或其混合物。
DE-A-3221077描述了在高温、高压下，使用基于Co的催化剂将乙酸加氢连续制备乙醇的方法。
在本申请所要求的优先权日之后公开的EP-A-147219描述了用Pd/Re/C将马来酸加氢的方法。该
公开文件是以一份要求更早的优先权的申请书为基础的。
我们已经发现了用于C2-C12羧酸加氢的新催化剂。
这样，本发明提供了一种通过将羧酸在高温、高压及多相催化剂的存在下与氢接触从而用C2-C12羧酸制备醇和/或羧酸酯的方法。此多相催化剂的特征在于其组成中第一成份为钼或钨，第二组份为元素周期表中第Ⅷ族的贵金属。
除醇之外，本发明的方法一般还生成作为副产物的相应酯。例如，乙酸的加氢一般也生成乙酸乙酯，丙酸的加氢一般也生成丙酸丙酯。产物中酯的含量取决于催化剂的性质;例如，含钨催化剂一般产生高含量的酯，酯含量还取决于反应条件，例如，在低转化率〔例如单程转化率小于50%〕下操作易于生成酯。如果需要的话，可以通过加入更多的羧酸和/或通过将酸化作用引入催化剂以促进“原地”酯化，可进一步提高产物中酯的含量。因此，有可能制备含大量羧酸酯的产物，特别是通过在低转化率下，例如低于50%，于液相中操作来制备。
适用的C2-C12羧酸可以为饱和的或不饱和的羧酸，较好的为饱和羧酸。一元的和多元羧酸，例如二元羧酸，是可以使用的。适用的一元酸类包括具有通式R-COOH的酸，其中，R为一被取代的或未被取代的脂族基、芳族基、或芳香脂族基，这类酸加氢制备出通式为RCH2OH的醇。适用的酸的实例包括乙酸、丙酸、丁酸、庚酸、琥珀酸、戊二酸、马来酸和富马酸。
氢气可以大规模地从市场上得到，并且在使用前经过〔或不经过〕进一步的提纯。
催化剂含有第一组分为钼或钨，第二组分为Ⅷ族贵金属。为避免混淆，Ⅷ族贵金属是锇、钯、铂、铑、钌和铱。上述金属中，钯、铑和钌是较好的。催化剂最好还包括作为第三组分的载体。适用的载体包括大表面积的石墨化炭，石墨，二氧化硅，氧化铝和二氧化硅/氧化铝，其中的大表面积的石墨化炭和二氧化硅的较好的。
特别适宜的载体是在GB-A-2136704中描述的大表面积的石墨化炭。炭最好为颗粒状，如为丸状。炭颗粒的尺寸取决于在任何给定的反应器中允许的压降（这决定了颗粒尺寸的最小值）和颗粒内的反应物的扩散限度（这决定了颗粒尺寸的最大值）。较好的颗粒尺寸的最小值为0.5毫米，最大值为10毫米，例如不大于5毫米。
炭最好为多孔炭。在较好的颗粒尺寸中，需要多孔的炭以达到较佳的表面积特性。
炭的特性可以由其BET表面积，基面表面积（basalplane areas），和侧表面积（edge surfaucareas）来确定。BET表面积是使用Brunauer Emmett和Teller（J.Am.Chem.Soc.60.309（1938））的方法由吸附氮气测定的表面积。基面表面积是使用Proc.Roy.Soc.A314中473-498页，特别是参照其中的第489页所述的方法，由炭对正-庚烷中的正-三十二烷的吸附热所确定的表面积。侧表面积是使用上面引用的Proc.Roy.Soc.文章，特别是参照其中的第495页所述的方法，由炭对正-庚烷中的正-丁醇的吸附热所确定的表面积。
用于本发明的炭具有至少100平方米/克的BFT表面积是较好的，更好是具有至少200平方米/克，最好是具有至少300平方米/克的BET表面积。BET表面积最好不大于1000平方米/克，不大于750平方米/克是更好的。
BET与基面表面积之比不大于4∶1是较好的，不大于2.5∶1是更好的。使用BET与基面表面积之比不大于1.5∶1的炭是最佳的。
使用基面表面积与侧表面积之比至少为10∶1的炭是较好的，更好的比例为至少100∶1。尽管在实践中两者之比一般不超过200∶1，但不相信存在一个比例上限。
较好的炭载体可以通过将含碳的原料进行热处理来制备。此原料可以是亲油石墨，例如可通过GB1，168，785中公开的方法制备，或可以是炭黑。
然而，亲油石墨含有以薄片状极细颗粒存在的炭，因此不太适宜作催化剂载体。我们倾向于避免使用它们。这种想法同样适用于也含有极细颗粒的炭黑。
较好的材料是从植物性物质中得到的活性炭，如椰子炭，或从泥煤或煤或碳化了的聚合物中得到的活性炭。进行热处理的原料的颗粒尺寸最好不小于上述较好的炭载体的颗粒尺寸。
较好的原料具有下列特性：BET表面至少为100，更好为至少500平方米/克。
制备具有上述特性的炭载体的热处理过程依次包括下列步骤：（1）在900到3300℃温度下于惰性气
氛中加热炭，（2）在300-1200℃温度下将炭氧化，（3）在900-3000℃温度下于惰性气氛中加热。
当使用氧气（例如：空气）作氧化剂时，氧化步骤最好是在300-600℃温度下进行。
在惰性气体中的加热时间不是很严格的。将炭加热到所要求的最高温度所需的时间足以使炭发生所要求的变化。
氧化步骤一定不要在使炭完全燃烧的条件下进行。氧化过程最好是在控制气态氧化剂进料速率的情况下进行，以防止过度氧化。气态氧化剂的例子是水蒸汽，二氧化碳，和含有分子氧的气体如空气。经过氧化过程最好使炭失掉至少10%重量（基于进行氧化的炭重量），失掉至少15%重量更好。
重量减轻最好不要大于进行氧化的炭重量的40%，不大于炭重量的25%是更好的。
氧化剂的进料速度最好控制在使所要求的重量减轻经过至少2小时完成的水平上，经过4小时完成是更好的。
可以用氮气或惰性气体提供所需要的惰性气氛。
较好的二氧化硅载体具有大表面积，一般大于50平方米/克。
较适宜的催化剂中含有0.1-20%（重量），较好的是含有1-10%（重量）的第一组分，含有0.1-20%（重量），较好的是含有1-10%（重量）的第二组分，其余为载体。
还可通过加入一种或多种元素周期表中ⅠA族、ⅡA族或Ⅳ族、最好为ⅠA族金属，将催化剂进一步改良，一种适宜的金属是钾。添加的改良金属的适宜量为催化剂总重量的1-20%。将上述改良金属添加到催化剂中可以产生有利的作用。通过添加金属可以将羧酸加氢过程中发生的碳-碳键氢解限制在较大的或较小的范围内，因此，改进了本方法中对所需要产品的选择性。
可以使用任何常规的制备催化剂的方法制备本催化剂，例如通过浸渍（包括共浸渍和连续浸渍），沉淀（包括共沉淀和连续沉淀），以及通过金属在载体上的气相淀积来制备催化剂。实施这些方法的技术在本领域内是公知的，不需要进一步详细介绍。
制备用于本发明方法中的催化剂的适宜方法包括如下步骤：
（A）用可热分解/还原成贵金属的可溶的贵金属化合物的溶液浸渍载体，随后从中移出溶剂，
（B）加热在载体上的Ⅷ族贵金属，
（C）用可热分解/还原成钼或钨金属和/或氧化物的可溶的钼或钨化合物的溶液浸渍经贵金属浸渍过的载体，随后从中移出溶剂。
上述制备催化剂的方法可以避免在步骤（A）中浸渍在载体上的贵金属在步骤（C）中被浸出任何明显的量。
在本发明的这一方案中，用于步骤（A）和（C）的溶剂可以是任何适宜的溶剂，如水。
在载体上的Ⅷ族贵金属可以适宜地在惰性气体如氮气，或还原气体如氢气，或含氧气体如氧气或空气的存在下加热。在惰性气体存在下的加热可以适宜地在150-350℃高温下进行。在还原气体存在下的加热可以适宜地在100-350℃高温下进行。在含氧气体存在下的加热可以适宜地在100-300℃高温下进行，假如以大表面积的石墨化炭作载体则温度上限为200℃。
最好在步骤（A）与（B）之间加入一个附加步骤。在这一步骤中将经Ⅷ族贵金属浸渍过的载体干燥，适宜的方法是在50-150℃温度范围内将其加热。本领域的技术人员可以意识到，如果需要的话，可以将此步骤并入步骤（B）中。
适宜的可分解/还原成金属和/或氧化物的钼或钨化合物包括金属盐和那些在负离子基团中存在金属的盐，如钼酸铵或钨酸铵。适宜的可分解/还原成贵金属的贵金属化合物包括，例如，贵金属盐如羧酸盐，卤化物和硝酸盐和在负离子基团中含有贵金属的铵盐如四氯钯酸铵。
在制备催化剂的任何时刻都可以将元素周期表中ⅠA族、ⅡA族或ⅣA族金属加入到催化剂的组成中。因此，所以用可溶的金属化合物的溶液浸渍载有贵金属/钼或钨的催化剂。另一方面，可以将可溶的金属化合物加入到共浸渍溶液中或连续浸渍溶液中。
一种较好的催化剂含有载在前述GB-A-2136704中所描述的大表面积的石墨化炭上的钯和钼或钨。
在用于本发明的方法中之前，最好通过在高温下与氢气或氢气/惰性气体（例如氮气）混合气接触使催化剂活化。适宜的接触时间为1-20小时。适宜的温度可以在200-350℃范围之内。另一方面，可以在反应物存在下将催化剂加热至反应温度使其活化。
虽然不能以任何可信的等级来确定在载体上的
催化剂的精确性质，但可以相信Ⅷ族贵金属成分是以金属单质的形式存在的，而钼或钨成分是以金属单质和/或其氧化物的形式存在的。
本发明的方法适宜在100-300℃高温下操作，150-250℃是较好的。适宜的操作压力为小于50巴。
本方法可以间歇地或连续地操作，连续操作是较好的。催化剂可以是固定床，移动床或流化床。连续操作的气体每小时空间速度在50-50，000h-1范围内是适宜的，2，000-30，000h-1是较好的。
本发明的另一方面提供了用于前述方法中的催化剂，此催化剂含有作为第一组分的钼或钨和作为第二组分的元素周期表中Ⅷ族贵金属。
现在让我们通过参照下面的实施例来进一步说明本发明。催化剂的制备
催化剂是根据下面介绍的步骤来制备的。在下述步骤中，“HSAG炭”代表具有大表面积的石墨化炭，其制备方法和特征如下：
所用的载体是用市场上可买到的Degussa所出售的、牌号为BKⅣ的活性炭来制备的。活性炭用下述方法进行热处理。将此炭在大约1小时的时间内，在氩气流中从室温加热到1700℃。当温度达到1700℃时，将此炭在氩气流中冷却至25℃。然后将此炭在马弗炉（maffle furnace）内，在空气中加热到大约520℃，加热时间靠经验掌握，使重量损失为20%（重量）。然后将此炭在氩气中加热到1800℃至1850℃。使此炭在氩气中冷却至室温。然后将所得到的含石墨的炭磨至16～30目（英国标准筛）。
所制得的炭具有下述性质：
BET表面积 710米2/克
基面表面积 389米2/克
侧表面积 2.3米2/克
BET/基面表面积比 1.83
基面表面积/侧面表面积比 169
实施例1
在下述步骤中，额定负载（nominal loading）的定义为：用载体总重量的百分量表示的加在载体上的金属（而不是盐）的重量。
A.向HSAG碳中加入含有硝酸钯和/或钨酸铵的水溶液。用转动式蒸发器除去溶剂，然后在真空烘箱中，在100℃下把催化剂通宵干燥。所选择的
入量使额定负载如下：A1-2.5%Pd;5%W;A2- %W（不含钯）;A3-5%Pd（不含钨）。A2和A3并不是用在本发明方法中的催化剂的例子，它们在这里仅起对比作用。
B.重复上述步骤，其中用钼酸铵代替钨酸铵。选择各组分的加入量，使额定负载如下：B1-2.5%Pd，5.1%Mo;B2-5.1%Mo（不含钯）。B2并不是用在本发明方法中的催化剂的例子，它在此仅起对比作用。
C.向HSAG炭中加入硝酸钯水溶液。用转动式蒸发器把溶剂除去，然后用真空烘箱把所得到的浸渍过的炭在100℃下通宵干燥。然后将此催化剂置入玻璃管中，然后在氢气流下，在6个小时之内从大约30℃加热至280℃。在最终温度上十小时之后，将此催化剂在氢气中冷却，再用氮净化几个小时。选择硝酸钯的用量，使额定负载为2.5%（重量）。
D.把步骤C中得到的催化剂与钨酸铵水溶液混合，同样用转动式蒸发器除去溶剂，用直空烘箱把催化剂在100℃下通宵干燥。选择钨酸铵的用量，使额定负载为10%（重量）。
E.应用步骤D，所不同的是用钼酸铵代替了钨酸铵。钼的额定负载为10%。
F.向HSAG炭中加入含三氯化铑和钨酸铵的水溶液。接着按上面的步骤A操作，以得到含有（额定值）5%铑和5%钨的催化剂。
催化剂试验
当压力在1-11巴（表压）范围之内做蒸气相实验时，把2.5毫升催化剂载在内径为6-7毫米的耐腐蚀不锈钢管中，然后把组装好的管置入筒状炉中。然后在两小时之内，在280℃或300℃下使催化剂活化，再维持最终温度1小时。活化之后，使催化剂在氢中冷却到所需的反应温度，然后使羧酸蒸气和氢气的混合物通过催化剂。用反压调节器（back-presure regulator）把压力调节在所需的值上。此蒸气/氢气混合物是在蒸发区中形成的。液态醋酸和氢气是分别经计量加入到此区域内的。离开反应器的蒸气和气体产物直接取样，并用气-液色谱（glc）分析。
温度是用插在催化剂床上的热电偶测出的。
典型的产物混合物含有相应的醇和酯（后者是醇与未反应的酸发生酯化而形成的）。同时还有微量相应的二烷基醚、醛、和副产品甲烷和乙烷。一般来讲，当用炭或二氧化硅做催化剂的载体时，尤其当转化率高和/或在蒸气相中，主产物是醇。
为举例之目的，转化率和选择性是分别用氢化了的羧酸的比例和未转化成副产物烷的氢化了的羧酸的比例来计算的。这样，选择性表示了催化剂促进氢化而不带来烷化的能力。在所用的实施例中（除非另有说明）只形成了微量的（≤2%）二烷基醚和醛。
定义：
WHSV＝每小时重量空间速度＝每小时每公斤催化剂通入液体的公斤数。
LHSV＝每小时液体空间速度＝每小时每升催化剂通入的液体的升数。
生产能力＝每小时每公斤催化剂转化的酸的公斤数。
实施例2-8
在10.3巴（表压）下测试了实施例1中A和B的催化剂在醋酸加氢中的活性。WHSV大约为1.1（LHSV＝0.35），醋酸与氢气的摩尔比约为1∶11，表1给出了结果。
结果表明催化剂A2、A3和B2的性能较差，而它们并不在本发明的范围内。同时它还说明钨催化剂既促进醚化也促进酯化，这可由产物中生成高含量的醚和低的醇∶醚比例判断出来。
实施例9和10
将由实施例1中步骤D和E制得的催化剂分别用于在液相中庚酸的加氢上。反应在容量大约为80毫升的高压釜内进行。在两种情况下，将20克正庚酸和0.5克催化剂加入到反应器中，用氢气冲洗容器并加压，然后在230℃下加热12小时，然后将容器冷却，收取产物并用气-液色谱进行分析，发现产品中含有正庚酸正庚酯。显然，产物正庚醇在釜内与未反应的酸发生了酯化反应。
表2给出了结果。
实施例11和12
这里研究了实施例1中步骤F的催化剂在醋酸蒸气相加氢中的作用。实验细节与例2-8的相同。表3给出了结果。
表1
实施例 催化剂 T/℃ 转化率 选择性（%） 摩尔比
（%） 醇+酯 醚 醇：酯
2 A1 189 16.5 84.3 13.0 0.06
3 A2 203 0.3 - - -
4 A3 200 0.6 - - -
5 B1 189 10.6 86.6 0.8 2.3
6 B2 188 0.17 - - -
7 A1 248 44.6 73.1 13.9 0.21
8 B1 249 58.0 82.7 3.5 2.4
表2
实施例 催化剂 正庚酸正庚酯浓度（重量%）
9 D 11.9
10 E 13.2
表3
实施例 T/℃ 转化率 对醇+酯的选择性 对烷的选择性
（%）
9 182 25 58 41.5
10 204 43.5 50.5 49.5
Claims (16)
1、在多相催化剂的存在下，在100-300℃温度和小于50巴压力下通过使羧酸与氢接触，由C2至C12羧酸制取醇和/或羧酸酯的方法，其特征在于所用催化剂含有第一组分，该第一组分为钼或钨，和第二组分，该第二组分为元素周期表上第Ⅷ族贵金属。
2、根据权利要求1的方法，其中第二组分为钯或铑或钌。
3、根据权利要求1或2的方法，其中催化剂含有第三组分载体。
4、根据权利要求3的方法，其中载体为大表面积的石墨化炭。
5、根据权利要求3的方法，其中载体为二氧化硅。
6、根据前面所述的任一权利要求的方法，其中通过加入一种或多种元素周期表上的ⅠA族、ⅡA族、或ⅣA族金属使催化剂得到改良。
7、根据权利要求6的方法，其中改良金属为钾。
8、用于权利要求1的方法中的催化剂的制备方法，该方法包括下述步骤：
（A）用可溶性的贵金属化合物溶液浸渍载体，该贵金属化合物可热分解/还原为此金属，然后除去溶剂。
（B）把载体上的Ⅷ族贵金属加热，
（C）用可溶性的钼或钨化合物溶液浸渍已被贵金属浸渍了的载体，该化合物可热分解/还原为此金属和/或氧化物，然后除去溶剂。
9、根据权利要求8的方法，其中载体上的Ⅷ族贵金属在惰性气体存在下被高温加热到150至350℃。
10、根据权利要求8的方法，其中载体上的Ⅷ族贵金属在还原性气体存在下被高温加热到100至350℃。
11、根据权利要求8的方法，其中载体上的Ⅷ族贵金属在含氧气体存在下被高温加热到100至300℃，当载体是大表面积的石墨化碳时，温度上限为200℃。
12、根据前面所述的任一权利要求的方法，其中催化剂在应用到权利要求1中的方法中之前，通过在200至350℃较高温度下与氢接触1至20小时而活化。
13、根据权利要求1至11中所述的任一方法，其中催化剂是在反应物的存在下被加热到反应温度而活化的。
14、根据权利要求1至6中所述的任一方法，其中所述的温度在150至250℃之间。
15、根据权利要求1至6和10所述的任一方法，其中羧酸以蒸气的形式与氢接触。
16、根据权利要求1的方法，该方法为在低转化率下于液相中操作，所得产物主要含有羧酸酯。
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| CN86102420A Expired CN1006788B (zh) | 1985-04-13 | 1986-04-12 | 羧酸氢化生产醇的方法 |
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| US (5) | US4777303A (zh) |
| EP (2) | EP0198681B1 (zh) |
| JP (2) | JPH0825931B2 (zh) |
| CN (2) | CN1006788B (zh) |
| AT (2) | ATE61327T1 (zh) |
| AU (2) | AU592980B2 (zh) |
| CA (2) | CA1264727A (zh) |
| DE (2) | DE3677809D1 (zh) |
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- 1986-04-11 DE DE8686302692T patent/DE3677809D1/de not_active Expired - Lifetime
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102781895A (zh) * | 2010-08-06 | 2012-11-14 | 国际人造丝公司 | 纯化乙醇的方法 |
| CN102781895B (zh) * | 2010-08-06 | 2015-11-25 | 国际人造丝公司 | 纯化乙醇的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0198681A2 (en) | 1986-10-22 |
| GB8509530D0 (en) | 1985-05-15 |
| AU592981B2 (en) | 1990-02-01 |
| JPS61275237A (ja) | 1986-12-05 |
| EP0198682B1 (en) | 1991-03-06 |
| NZ215766A (en) | 1988-11-29 |
| JPH0825931B2 (ja) | 1996-03-13 |
| US4826795A (en) | 1989-05-02 |
| CN86102452A (zh) | 1986-12-03 |
| EP0198682A3 (en) | 1988-06-08 |
| DE3689050D1 (de) | 1993-10-28 |
| US5061671A (en) | 1991-10-29 |
| AU5601386A (en) | 1986-10-16 |
| ATE61327T1 (de) | 1991-03-15 |
| CA1264727A (en) | 1990-01-23 |
| EP0198682A2 (en) | 1986-10-22 |
| JPS61275234A (ja) | 1986-12-05 |
| CN1006788B (zh) | 1990-02-14 |
| CA1262719A (en) | 1989-11-07 |
| EP0198681B1 (en) | 1993-09-22 |
| NZ215765A (en) | 1988-11-29 |
| US4804791A (en) | 1989-02-14 |
| CN86102420A (zh) | 1986-10-08 |
| ATE94861T1 (de) | 1993-10-15 |
| AU5601286A (en) | 1986-10-16 |
| US4990655A (en) | 1991-02-05 |
| AU592980B2 (en) | 1990-02-01 |
| US4777303A (en) | 1988-10-11 |
| DE3689050T2 (de) | 1994-01-13 |
| EP0198681A3 (en) | 1988-05-04 |
| DE3677809D1 (de) | 1991-04-11 |
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