JPH06116182A - Method for hydrogenating organic carboxylic acid and / or organic carboxylic acid ester - Google Patents
Method for hydrogenating organic carboxylic acid and / or organic carboxylic acid esterInfo
- Publication number
- JPH06116182A JPH06116182A JP4271986A JP27198692A JPH06116182A JP H06116182 A JPH06116182 A JP H06116182A JP 4271986 A JP4271986 A JP 4271986A JP 27198692 A JP27198692 A JP 27198692A JP H06116182 A JPH06116182 A JP H06116182A
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- organic carboxylic
- catalyst
- acid ester
- hydrogenating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 24
- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000737 periodic effect Effects 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- -1 fatty acid esters Chemical class 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 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
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-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
- 229910003449 rhenium oxide Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- MAZJFWHKKPFVND-UHFFFAOYSA-N aluminum propan-2-ol propan-2-olate Chemical compound [Al+3].CC(C)O.CC(C)[O-].CC(C)[O-].CC(C)[O-] MAZJFWHKKPFVND-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機カルボン酸及び／
又は有機カルボン酸エステルの水素化方法に係り、特に
金属酸化物で修飾したシリカを担体として用いた担持触
媒の存在下、有機カルボン酸及び／又は有機カルボン酸
エステルの水素化反応を温和な条件で効率よく進行させ
ることができる。有機カルボン酸及び／又は有機カルボ
ン酸エステルの水素化方法に関する。The present invention relates to an organic carboxylic acid and / or
Alternatively, the present invention relates to a method for hydrogenating an organic carboxylic acid ester, particularly in the presence of a supported catalyst using silica modified with a metal oxide as a carrier, under a mild condition for hydrogenation reaction of an organic carboxylic acid and / or an organic carboxylic acid ester. It can proceed efficiently. The present invention relates to a method for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester.
【０００２】[0002]
【従来の技術】従来、有機カルボン酸及び／又は有機カ
ルボン酸エステルを水素化して対応するアルコール類を
製造する方法は数多く知られている。例えば、有機カル
ボン酸からアルコールを得る方法としては、カルボン酸
を予め低級アルコールでエステル化した後、Ａｄｋｉｎ
ｓ触媒（銅クロマイト系触媒）で還元する方法が良く知
られている。しかし、この接触還元方法は、一般に２０
０気圧以上の水素圧下で行われるので、エネルギー的に
も設備的にも不経済な方法である。また、このような銅
系の触媒を使う限り、有機カルボン酸を直接還元するこ
とができず、カルボン酸を一旦カルボン酸エステルに転
換して還元しなければならないという問題もある。2. Description of the Related Art Heretofore, many methods have been known for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester to produce a corresponding alcohol. For example, as a method of obtaining an alcohol from an organic carboxylic acid, the carboxylic acid is esterified with a lower alcohol in advance and then Adkin
The method of reducing with an s catalyst (copper chromite catalyst) is well known. However, this catalytic reduction method generally requires 20
Since it is performed under a hydrogen pressure of 0 atm or more, it is an uneconomical method in terms of energy and equipment. Further, as long as such a copper-based catalyst is used, there is also a problem that the organic carboxylic acid cannot be directly reduced and the carboxylic acid must be once converted into a carboxylic acid ester for reduction.
【０００３】一方、有機カルボン酸を直接還元できる触
媒も知られており、周期律表第VIII族の貴金属とレニウ
ム、錫又はゲルマニウムを組み合わせた触媒が提案され
ている。例えば、米国特許４，１０４，４７８号にはル
テニウム担持活性炭触媒に酸化レニウムを添加すること
により、アルコールの選択性が向上することが記載され
ている。また、米国特許４，６５９，６８６号には、活
性炭に担持したパラジウム−レニウム触媒を用いて、マ
レイン酸水溶液からテトラヒドロフラン又はγ−ブチロ
ラクトンを製造する方法が記載されている。更に、欧州
特許２８２，４０９号には、多孔質担体にルテニウム−
錫を担持した触媒を用いる高級脂肪酸エステルの水素化
反応が記載されている。これらの方法では、アルコール
又はエーテルが比較的高い選択率で得られる。On the other hand, a catalyst capable of directly reducing an organic carboxylic acid is also known, and a catalyst in which a noble metal of Group VIII of the Periodic Table and rhenium, tin or germanium is combined has been proposed. For example, U.S. Pat. No. 4,104,478 describes that the selectivity of alcohol is improved by adding rhenium oxide to a ruthenium-supported activated carbon catalyst. US Pat. No. 4,659,686 describes a method for producing tetrahydrofuran or γ-butyrolactone from an aqueous maleic acid solution using a palladium-rhenium catalyst supported on activated carbon. Further, in EP 282,409, a ruthenium-containing porous carrier is used.
The hydrogenation reaction of higher fatty acid esters using a tin supported catalyst is described. These methods yield alcohols or ethers with relatively high selectivity.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記貴
金属触媒を用いる方法のうち米国特許４，１０４，４７
８号、同４，６５９，６８６号記載の方法では、１５０
気圧以上の水素圧が必要であり、反応活性的に十分満足
し得る結果が得られない。また、欧州特許２８２，４０
９号の方法においても、やはり反応活性的に十分満足し
得る結果が得られない。However, among the methods using the above-mentioned precious metal catalysts, US Pat. No. 4,104,47 is known.
In the method described in No. 8 and No. 4,659,686, 150
A hydrogen pressure higher than atmospheric pressure is required, and the reaction activity cannot be sufficiently satisfactory. In addition, European Patent 282,40
Even in the method of No. 9, the reaction activity is not sufficiently satisfactory.
【０００５】本発明は上記従来の問題点を解決し、高活
性担持触媒の存在下、有機カルボン酸及び／又はカルボ
ン酸エステルの水素化反応を温和な条件で効率良く進行
させることができる有機カルボン酸及び／又はカルボン
酸エステルの水素化方法を提供することを目的とする。The present invention solves the above-mentioned conventional problems and enables the hydrogenation reaction of an organic carboxylic acid and / or a carboxylic acid ester to proceed efficiently under mild conditions in the presence of a highly active supported catalyst. It is an object to provide a method for hydrogenating an acid and / or a carboxylic acid ester.
【０００６】[0006]
【課題を解決するための手段】請求項１の有機カルボン
酸及び／又は有機カルボン酸エステルを、触媒の存在
下、水素と接触させて水素化する方法において、触媒と
して、周期律表第VIII族の貴金属の１種又は２種以上
を、チタニア及び／又はアルミナで修飾したシリカに担
持してなる担持触媒を用いることを特徴とする。A method of hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester according to claim 1 by contacting with hydrogen in the presence of a catalyst, wherein the catalyst is a group VIII of the periodic table. The use of a supported catalyst comprising one or more of the above precious metals supported on silica modified with titania and / or alumina.
【０００７】請求項２の有機カルボン酸及び／又は有機
カルボン酸エステルの水素化方法は、請求項１の方法に
おいて、第VIII族の貴金属がパラジウム及び／又はルテ
ニウムであることを特徴とする。請求項３の有機カルボ
ン酸及び／又は有機カルボン酸エステルの水素化方法
は、請求項１又は２の方法において、触媒として、周期
表第VIII族の貴金属と、錫、レニウム及びゲルマニウム
よりなる群から選ばれる１種又は２種以上の金属成分と
を担体に担持してなる担持触媒を用いることを特徴とす
る。The method for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester according to claim 2 is characterized in that in the method according to claim 1, the noble metal of Group VIII is palladium and / or ruthenium. A method for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester according to claim 3 is the method according to claim 1 or 2, wherein the catalyst is a noble metal of Group VIII of the periodic table and a group consisting of tin, rhenium and germanium. It is characterized by using a supported catalyst in which one or more selected metal components are supported on a carrier.
【０００８】即ち、本発明者らは、従来の貴金属系触媒
よりも更に活性の高いカルボン酸及び／又はカルボン酸
エステル還元用触媒について鋭意検討を重ねた結果、担
体としてチタニア及び／又はアルミナで修飾したシリカ
に貴金属を担持してなる担持触媒を用いることによっ
て、最大限の活性が示されることを見出し本発明を完成
させた。That is, the inventors of the present invention have conducted extensive studies on a catalyst for reducing a carboxylic acid and / or a carboxylic acid ester, which has a higher activity than conventional noble metal catalysts, and as a result, modified it with titania and / or alumina as a carrier. The present invention has been completed by finding that the maximum activity is exhibited by using a supported catalyst obtained by supporting a noble metal on the above silica.
【０００９】以下に本発明を詳細に説明する。本発明で
使用される触媒を構成する周期表第VIII族の貴金属とし
ては、パラジウム（Ｐｄ）、白金（Ｐｔ）、ロジウム
（Ｒｈ）、ルテニウム（Ｒｕ）及びイリジウム（Ｉｒ）
が挙げられる。これらの貴金属は１種を単独或いは２種
以上を組み合わせて用いることができるが、特にパラジ
ウム、ルテニウムが好適に用いられる。該シリカのＢＥ
Ｔ表面積は、通常５０〜１０００ｍ2 ／ｇ、好ましくは
１００〜７００ｍ3 ／ｇである。なお、ＢＥＴ表面積と
は、公知の表面積表示手段であり、窒素吸着量を測定
し、ＢＥＴ式で算した値である。本発明では、これらの
貴金属、更には第２金属成分を担持させる担体として、
チタニア及び／又はアルミナで修飾したシリカを用いる
ことを特徴とする。The present invention will be described in detail below. Examples of the noble metal of Group VIII of the periodic table that constitutes the catalyst used in the present invention include palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and iridium (Ir).
Is mentioned. These noble metals can be used alone or in combination of two or more, and palladium and ruthenium are particularly preferably used. BE of the silica
The T surface area is usually 50 to 1000 m 2 / g, preferably 100 to 700 m 3 / g. The BET surface area is a known surface area display means, and is a value calculated by measuring the nitrogen adsorption amount and using the BET formula. In the present invention, as a carrier for supporting these noble metals and further the second metal component,
It is characterized by using silica modified with titania and / or alumina.
【００１０】また、本発明においては、上記貴金属の他
に、更に、錫、レニウム、ゲルマニウムの１種又は２種
以上の金属成分（以下「第２金属成分」と称する場合が
ある。）を触媒中に、前記貴金属に対して、通常０．１
〜５重量倍量共存させるのが、生成物の選択性向上の面
で好ましい。シリカを修飾する金属酸化物としてはチタ
ニア及び／又はアルミナが用いられる。このような金属
酸化物のシリカ重量に対する担持量としては、通常０．
１〜２０重量％、好ましくは１〜１５重量％である。２
０重量％を越える添加では効果の更なる向上はあまり認
められない。Further, in the present invention, in addition to the above noble metal, one or more metal components of tin, rhenium and germanium (hereinafter sometimes referred to as "second metal component") are used as catalysts. In the above, it is usually 0.1 with respect to the precious metal.
The coexistence of 5 to 5 times by weight is preferable from the viewpoint of improving the selectivity of the product. Titania and / or alumina is used as a metal oxide for modifying silica. The amount of such a metal oxide supported on the weight of silica is usually 0.
It is 1 to 20% by weight, preferably 1 to 15% by weight. Two
When the amount added exceeds 0% by weight, the effect is not further improved.
【００１１】金属酸化物修飾シリカを製造するには、例
えば、チタン及び／又はアルミナの原料化合物をシリカ
に接触させて担持した後、空気中で焼成すれば良い。こ
の場合、使用されるチタン及び／又はアルミナの化合物
としては、アルコキサイドが一般的に使用されるが、硝
酸、硫酸、塩酸等の鉱酸塩、酢酸等の有機酸塩、水酸化
物、酸化物、或いは錯塩を使用できる。In order to produce the metal oxide-modified silica, for example, a raw material compound of titanium and / or alumina may be brought into contact with and loaded on the silica, followed by firing in air. In this case, as the compound of titanium and / or alumina used, alkoxide is generally used, but mineral acid salts such as nitric acid, sulfuric acid and hydrochloric acid, organic acid salts such as acetic acid, hydroxides and oxides. Alternatively, complex salts can be used.
【００１２】チタン及び／又はアルミナの原料化合物を
シリカと接触させる方法としては特に制限はないが、通
常、浸漬法が採用される。即ち、例えば、原料化合物を
溶解可能な溶媒、例えば、アルコールに溶解させて溶液
とし、この溶液にシリカを浸漬して含浸担持させる。担
持後は、乾燥し、焼成する。焼成温度は、通常１５０〜
７００℃、好ましくは３００〜６００℃である。The method of contacting the raw material compound of titanium and / or alumina with silica is not particularly limited, but the dipping method is usually employed. That is, for example, the raw material compound is dissolved in a solvent capable of dissolving it, for example, alcohol to form a solution, and silica is immersed in this solution and impregnated and supported. After loading, it is dried and calcined. The firing temperature is usually 150-
The temperature is 700 ° C, preferably 300 to 600 ° C.
【００１３】本発明に係わる担持触媒を製造するには、
例えば、上記金属酸化物修飾シリカに前記貴金属成分、
更に第２金属成分の原料化合物を接触させて担持させた
後、還元処理して金属を生成させれば良い。この場合使
用される貴金属成分、第２金属成分の化合物としては硝
酸、硫酸、塩酸等の鉱酸塩が一般的に使用されるが、酢
酸等の有機酸塩、水酸化物、酸化物、或いは錯塩を使用
することもできる。To produce the supported catalyst according to the present invention,
For example, the noble metal component in the metal oxide modified silica,
Further, after the raw material compound of the second metal component is brought into contact with and carried, the reduction treatment may be carried out to generate the metal. In this case, as the compound of the noble metal component and the second metal component used, mineral acid salts such as nitric acid, sulfuric acid and hydrochloric acid are generally used, but organic acid salts such as acetic acid, hydroxides, oxides, or Complex salts can also be used.
【００１４】貴金属成分、第２金属成分の原料化合物を
金属酸化物修飾シリカと接触させる方法は特に制限はな
いが、通常、浸漬法が採用される。即ち、例えば、原料
化合物を溶解可能な溶媒、例えば水に溶解させて溶液と
し、この溶液に金属酸化物修飾シリカを浸漬して含浸担
持させる。担持後は、乾燥し、必要に応じて焼成した
後、還元する。還元処理としては、公知の液相還元、気
相還元が用いられ、気相還元の場合、通常１００〜５０
０℃、好ましくは２５０〜３５０℃で行われる。かかる
方法で担持される総金属成分は、担体重量に対する担持
量として、通常０．１〜２０重量％、好ましくは１〜１
５重量％である。The method of contacting the raw material compounds of the noble metal component and the second metal component with the metal oxide-modified silica is not particularly limited, but the dipping method is usually adopted. That is, for example, the raw material compound is dissolved in a solvent capable of dissolving it, for example, water to form a solution, and the metal oxide-modified silica is immersed in this solution and impregnated and supported. After the supporting, it is dried and, if necessary, calcined and then reduced. As the reduction treatment, known liquid-phase reduction or vapor-phase reduction is used, and in the case of vapor-phase reduction, it is usually 100 to 50.
It is carried out at 0 ° C, preferably 250 to 350 ° C. The total metal component supported by such a method is usually 0.1 to 20% by weight, preferably 1 to 1 as a supported amount relative to the weight of the carrier.
It is 5% by weight.
【００１５】本発明では、このようにして得られた貴金
属（及び第２金属成分）担持金属酸化物修飾シリカより
なる触媒を用いる、本発明の有機カルボン酸及び／又は
有機カルボン酸エステルの水素による還元反応は、通
常、温度１３０〜３５０℃、好ましくは１６０〜３００
℃、水素圧１０〜３００ｋｇ／ｃｍ2 、好ましくは５０
〜２００ｋｇ／ｃｍ2 の範囲で行われる。この場合、反
応方式としては液相懸濁反応或いは固定床反応のいずれ
も採用できる。また水素化反応は、無触媒で行っても良
いし、必要に応じて、溶媒を用いても良い。溶媒を用い
る場合、溶媒としては、反応に悪影響を与えない物であ
れば良く、特に制限されないが、具体的には、水；メタ
ノール、エタノール、オクタノール、ドデカノール等の
アルコール類；テトラヒドロフラン、ジオキサン、テト
ラエチレングリコールジメチルエーテル等のエーテル
類；その他、ヘキサン、シクロヘキサン、デカリン等の
炭化水素類が例示される。In the present invention, the catalyst of the thus obtained noble metal (and second metal component) -supporting metal oxide-modified silica is used, and the hydrogen of the organic carboxylic acid and / or organic carboxylic acid ester of the present invention is used. The reduction reaction is usually carried out at a temperature of 130 to 350 ° C., preferably 160 to 300.
C, hydrogen pressure 10-300 kg / cm 2 , preferably 50
It is carried out in the range of up to 200 kg / cm 2 . In this case, either liquid phase suspension reaction or fixed bed reaction can be adopted as the reaction system. The hydrogenation reaction may be carried out without a catalyst, or a solvent may be used if necessary. When a solvent is used, the solvent is not particularly limited as long as it does not adversely affect the reaction, and specifically, water; alcohols such as methanol, ethanol, octanol and dodecanol; tetrahydrofuran, dioxane and tetra Examples thereof include ethers such as ethylene glycol dimethyl ether; and hydrocarbons such as hexane, cyclohexane and decalin.
【００１６】反応に使用される触媒量は、原料の有機カ
ルボン酸及び／又はカルボン酸エステル１００重量部に
対し０．１〜１００重量部であることが望ましいが、反
応温度又は反応圧力等の諸条件に応じ、実用的な反応速
度が得られる範囲内に置いて任意に選択できる。なお、
本発明において水素化される有機カルボン酸（カルボン
酸無水物も含む）及びカルボン酸エステルとしては、上
記発明に係わる触媒を用いて接触還元することができる
ものであれば良く、特に制限はないが、例えば、酢酸、
カプロン酸、カプリル酸、ウンデセン酸、ラウリン酸、
ミリスチン酸、パルミチン酸、ステアリン酸、イソステ
アリン酸、オレイン酸、シュウ酸、マレイン酸、コハク
酸、アジピン酸、セバシン酸、シクロヘキサンカルボン
酸、安息香酸、フタル酸これらのエステル、無水フタル
酸、無水マレイン酸、無水コハク酸等が例示される。カ
ルボン酸エステルを構成するところのアルコール部は、
特に限定されるものではないが、メタノール、エタノー
ル等の低級アルコールよりなるものが好ましい。そし
て、本発明では、特に、炭素数１〜１５の脂肪族モノカ
ルボン酸及びそのエステル或いは、炭素数４〜６のジカ
ルボン酸及びそのエステル、又はその酸無水物が好適に
用いられる。The amount of the catalyst used in the reaction is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the organic carboxylic acid and / or carboxylic acid ester as a raw material, but various factors such as reaction temperature and reaction pressure may be used. Depending on the conditions, it can be arbitrarily selected within a range where a practical reaction rate can be obtained. In addition,
The organic carboxylic acid (including carboxylic acid anhydride) and carboxylic acid ester to be hydrogenated in the present invention are not particularly limited as long as they can be catalytically reduced using the catalyst according to the above invention. , For example, acetic acid,
Caproic acid, caprylic acid, undecenoic acid, lauric acid,
Myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, oxalic acid, maleic acid, succinic acid, adipic acid, sebacic acid, cyclohexanecarboxylic acid, benzoic acid, phthalic acid These esters, phthalic anhydride, maleic anhydride , Succinic anhydride and the like. The alcohol part constituting the carboxylic acid ester is
Although not particularly limited, a lower alcohol such as methanol or ethanol is preferable. And in this invention, especially C1-C15 aliphatic monocarboxylic acid and its ester, C4-C6 dicarboxylic acid and its ester, or its acid anhydride is used suitably.
【００１７】なお、炭素数４のジカルボン酸類を本発明
による水素化反応に供すると、相当するジオールの他
に、ラクトン類或いは環状エーテル等が水素化生成物と
して得られる。例えば、無水マレイン酸及び／又は無水
コハク酸を本発明による水素化反応を行うと、１，４−
ブタンジオール、γ−ブチロラクトン及びテトラヒドロ
フランの３つの水素化生成物が高選択的に得られる。When the dicarboxylic acid having 4 carbon atoms is subjected to the hydrogenation reaction according to the present invention, lactones, cyclic ethers and the like are obtained as hydrogenation products in addition to the corresponding diol. For example, when maleic anhydride and / or succinic anhydride is subjected to the hydrogenation reaction according to the present invention, 1,4-
Three highly hydrogenated products of butanediol, γ-butyrolactone and tetrahydrofuran are obtained with high selectivity.
【００１８】[0018]
【作用】従来、一般に単一の金属酸化物を触媒担体とし
て用いているが、これに対し、本発明においては、触媒
担体として、チタン、アルミナといった金属酸化物で修
飾したシリカを用いる。このような金属酸化物修飾シリ
カを用いることにより、得られる担持触媒の触媒活性は
著しく高められ、従って、接触的水素化反応の収率及び
選択率は大幅に向上する。In the past, a single metal oxide was generally used as a catalyst carrier, but in the present invention, silica modified with a metal oxide such as titanium or alumina is used as the catalyst carrier. By using such a metal oxide-modified silica, the catalytic activity of the obtained supported catalyst is remarkably enhanced, and thus the yield and selectivity of the catalytic hydrogenation reaction are significantly improved.
【００１９】[0019]
【実施例】以下に実施例及び比較例を挙げて、本発明を
より具体的に説明するが、本発明はその要旨を超えない
限り以下の実施例に限定されるものではない、なお、以
下において「％」は「重量％」を示す。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In, "%" means "% by weight".
【００２０】実施例１ チタニウムテトライソプロポキシドをトルエンに溶解
し、ＢＥＴ表面積３９０ｍ2 ／ｇのシリカ（洞海化学
製、Ｄ−１５０−１２０Ａ）を加え、回転減圧乾燥器で
トルエンを除去した後空気雰囲気下、５００℃で３時間
焼成しＳｉＯ2 ・ＴｉＯ2 （１％）を得た。塩化ルテニ
ウム（III ）と塩化スズ（II）を５Ｎ−ＨＣｌ水溶液に
溶解し、担体として上記ＳｉＯ2 ・ＴｉＯ2 を加え、回
転減圧乾燥器で水を除去した後窒素雰囲気下、１５０℃
で２時間焼成し、ついで水素雰囲気下、２００℃で２時
間還元して、５％Ｒｕ−５％Ｓｎ／ＳｉＯ2 ・ＴｉＯ2
触媒を得た。無水マレイン酸０．５ｇを水９．５ｇに溶
解し、上記の方法で調製した触媒０．２ｇと共に７０ｍ
ｌスピンナー撹拌オートクレーブに仕込み、室温下１０
０ｋｇ／ｃｍ2 の水素を圧入し、２００℃で２時間反応
を行った。反応結果を表−１に示す。Example 1 Titanium tetraisopropoxide was dissolved in toluene, silica having a BET surface area of 390 m 2 / g (D-150-120A, manufactured by Dokai Kagaku) was added, and toluene was removed by a rotary vacuum dryer. In an air atmosphere, firing was performed at 500 ° C. for 3 hours to obtain SiO 2 · TiO 2 (1%). Ruthenium (III) chloride and tin (II) chloride are dissolved in a 5N-HCl aqueous solution, the above-mentioned SiO 2 · TiO 2 is added as a carrier, water is removed by a rotary vacuum dryer, and then 150 ° C under a nitrogen atmosphere.
2 hours at 200 ° C. in a hydrogen atmosphere, then 5% Ru-5% Sn / SiO 2 · TiO 2
A catalyst was obtained. 0.5g of maleic anhydride was dissolved in 9.5g of water and 70m together with 0.2g of the catalyst prepared by the above method.
l Spinner stirred autoclave was charged and kept at room temperature for 10
Hydrogen of 0 kg / cm 2 was injected under pressure, and the reaction was carried out at 200 ° C. for 2 hours. The reaction results are shown in Table 1.
【００２１】実施例２ アルミニウムテトライソプロポキシドをエチルアルコー
ルに溶解し、ＢＥＴ表面積３９０ｍ2 ／ｇのシリカ（洞
海化学製、Ｄ−１５０−１２０Ａ）を加え、回転減圧乾
燥器でエチルアルコールを除去した後、空気雰囲気下、
５００℃で３時間焼成しＳｉＯ2 ・Ａｌ2 Ｏ3 （１％）
を得た。実施例１において、担体としてＳｉＯ2 ・Ａｌ
2 Ｏ3 （１％）を使用した以外は、同様にして触媒を調
製し、同様に水素化反応を行った。結果を表−１に示
す。Example 2 Aluminum tetraisopropoxide was dissolved in ethyl alcohol, silica having a BET surface area of 390 m 2 / g (D-150-120A, manufactured by Dokai Kagaku) was added, and the ethyl alcohol was removed by a rotary vacuum dryer. And then in an air atmosphere,
Sintered at 500 ° C for 3 hours, SiO 2 · Al 2 O 3 (1%)
Got In Example 1, as a carrier, SiO 2 .Al
A catalyst was prepared in the same manner except that 2 O 3 (1%) was used, and the hydrogenation reaction was carried out in the same manner. The results are shown in Table-1.
【００２２】比較例１ 実施例１において、担体としてＢＥＴ表面積が３９０ｍ
2 ／ｇの未修飾のシリカ（洞海化学製、Ｄ−１５０−１
２０Ａ）を使用した以外は、同様にして触媒を調製し同
様に水素化反応を行った。結果を表−１に示す。Comparative Example 1 In Example 1, the carrier has a BET surface area of 390 m.
2 / g of unmodified silica (manufactured by Dokai Kagaku, D-150-1)
A catalyst was prepared and a hydrogenation reaction was carried out in the same manner except that 20A) was used. The results are shown in Table-1.
【００２３】比較例２ 実施例１において、担体としてＢＥＴ表面積が５０ｍ2
／ｇのチタニア（触媒学会参照触媒、ＪＲＣ−ＴＩＯ−
４）を使用し、触媒の水素還元温度が３００℃である以
外は同様にして触媒を調製し、同様に水素化反応を行っ
た。結果を表−１に示す。COMPARATIVE EXAMPLE 2 In Example 1, the carrier has a BET surface area of 50 m 2.
/ G of titania (catalyst society reference catalyst, JRC-TIO-
Using 4), a catalyst was prepared in the same manner except that the hydrogen reduction temperature of the catalyst was 300 ° C., and the hydrogenation reaction was performed in the same manner. The results are shown in Table-1.
【００２４】[0024]
【表１】 ＣＭＬ：無水マレイン酸 ＴＨＦ：テトラヒドロフラン ＧＢＬ：γ−ブチロラクトン ＢＤＯ：１，４−ブタンジオール[Table 1] CML: maleic anhydride THF: tetrahydrofuran GBL: γ-butyrolactone BDO: 1,4-butanediol
【００２５】実施例３ チタニウムテトライソプロポキシドをトルエンに溶解
し、ＢＥＴ表面積１８０ｍ2 ／ｇのシリカ（洞海化学
製、Ｄ−１５０−３００Ａ）を加え回転減圧乾燥器でト
ルエンを除去した後、空気雰囲気下５００℃で３時間焼
成しＳｉＯ2 ・ＴｉＯ2 （１％）を得た。Example 3 Titanium tetraisopropoxide was dissolved in toluene, silica having a BET surface area of 180 m 2 / g (D-150-300A, manufactured by Dokai Kagaku) was added, and the toluene was removed by a rotary vacuum drier. It was calcined in an air atmosphere at 500 ° C. for 3 hours to obtain SiO 2 .TiO 2 (1%).
【００２６】塩化ルテニウム（III ）と酸化レニウム
（VII ）を水に溶解し、担体として上記ＳｉＯ2 ・Ｔｉ
Ｏ2 を加え回転減圧乾燥器で水を除去した後、窒素雰囲
気下１５０℃で２時間焼成し、ついで水素雰囲気下３０
０℃で２時間下還元して、１％Ｒｕ−２％Ｒｅ／ＳｉＯ
2 ・ＴｉＯ2 を得た。無水マレイン酸０．５ｇを水９．
５ｇに溶解し、上記の方法て調製した触媒０．２ｇと共
に７０ｍｌスピンナー撹拌オートクレーブに仕込み、室
温下１００ｋｇ／ｃｍ2 の水素を圧入し、２００℃で２
時間反応を行った。反応結果を表−２に示す。Ruthenium (III) chloride and rhenium oxide (VII) are dissolved in water, and the above SiO 2 .Ti is used as a carrier.
After adding O 2 and removing water with a rotary vacuum dryer, baking was performed at 150 ° C. for 2 hours under a nitrogen atmosphere, and then under a hydrogen atmosphere for 30 hours.
Reduced at 0 ° C. for 2 hours to give 1% Ru-2% Re / SiO 2.
2 · TiO 2 was obtained. Maleic anhydride 0.5 g was added to water 9.
It was dissolved in 5 g and charged in a 70 ml spinner stirring autoclave together with 0.2 g of the catalyst prepared by the above method, and 100 kg / cm 2 of hydrogen was introduced under pressure at room temperature and the temperature was adjusted to 2 at 200 ° C.
The reaction was carried out over time. The reaction results are shown in Table-2.
【００２７】比較例３ 実施例３において、担体としてＢＥＴ表面積が１８０ｍ
2 ／ｇの未修飾シリカ（洞海化学製、Ｄ−１５０−３０
０Ａ）を使用した以外は、同様にして触媒を調製し同様
に水素化反応を行った。結果を表−２に示す。実施例３
と比較例３の結果を比較してみると、実施例３の方が比
較例３より原料ＣＭＬの転化率が高く、生成物としてＢ
ＤＯ、ＴＨＦの収率が高い。ＢＤＯ、ＴＨＦは、ＣＭＬ
が初めに水素化されて生成するＧＢＬが、更に水素化さ
れることにより生成するものと推定されるので、実施例
３の触媒の方が比較例３の触媒よりも、水素化触媒とし
てはより高活性で優れていると判断される。Comparative Example 3 In Example 3, the BET surface area of the carrier is 180 m.
2 / g unmodified silica (D-150-30, manufactured by Dokai Kagaku)
A catalyst was prepared and a hydrogenation reaction was carried out in the same manner except that 0A) was used. The results are shown in Table-2. Example 3
When the results of Comparative Example 3 and Comparative Example 3 are compared, Example 3 has a higher conversion rate of the raw material CML than Comparative Example 3, and B as a product
The yield of DO and THF is high. BDO and THF are CML
It is estimated that GBL which is firstly hydrogenated and produced is further hydrogenated, so that the catalyst of Example 3 is more suitable as a hydrogenation catalyst than the catalyst of Comparative Example 3. It is judged to be highly active and excellent.
【００２８】[0028]
【表２】 ＣＭＬ ：無水マレイン酸 ＴＨＦ ：テトラヒドロフラン ＰｒＯＨ：１−プロパノール ＢｕＯＨ：１−ブタノール ＧＢＬ ：γ−ブチロラクトン ＢＤＯ ：１，４−ブタンジオール[Table 2] CML: Maleic anhydride THF: Tetrahydrofuran PrOH: 1-Propanol BuOH: 1-Butanol GBL: γ-butyrolactone BDO: 1,4-butanediol
【００２９】実施例４ 実施例１において反応基質をプロピオン酸に変えた以外
は、同様の触媒を用い、同様に水素化反応を行った。結
果を表−３に示す。Example 4 A hydrogenation reaction was carried out in the same manner as in Example 1 except that the reaction substrate was changed to propionic acid. The results are shown in Table-3.
【００３０】比較例４ 比較例１において反応基質をプロピオン酸に変えた以外
は、同様の触媒を用い、同様に水素化反応を行った。結
果を表−３に示す。Comparative Example 4 A hydrogenation reaction was carried out in the same manner as in Comparative Example 1, except that the reaction substrate was changed to propionic acid. The results are shown in Table-3.
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【発明の効果】以上記述した通り、本発明の有機カルボ
ン酸及び／又はカルボン酸エステルの水素化方法によれ
ば、接触的水素化反応により、高収率かつ高選択率にて
対応するアルコール類を得ることが可能とされる。特
に、無水マレイン酸及び／又は無水コハク酸を本発明の
方法により水素化した場合、１，４−ブタンジオール、
γ−ブチロラクトン及びテトラヒドロフランを高選択的
に併産することが可能である。As described above, according to the method for hydrogenating an organic carboxylic acid and / or a carboxylic acid ester of the present invention, alcohols corresponding to a high yield and a high selectivity can be obtained by a catalytic hydrogenation reaction. Can be obtained. In particular, when maleic anhydride and / or succinic anhydride is hydrogenated by the method of the present invention, 1,4-butanediol,
It is possible to co-produce γ-butyrolactone and tetrahydrofuran with high selectivity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/64 １０４ Ｘ 8017−4Ｇ Ｃ０７Ｂ 35/02 7419−4Ｈ Ｃ０７Ｃ 31/20 Ｂ 8930−4Ｈ Ｃ０７Ｄ 307/08 307/33 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location B01J 23/64 104 X 8017-4G C07B 35/02 7419-4H C07C 31/20 B 8930-4H C07D 307/08 307/33 // C07B 61/00 300
Claims (4)
酸エステルを、触媒の存在下、水素と接触させて水素化
する方法において、触媒として、周期律表第VIII族の貴
金属の１種又は２種以上を、チタニア及び／又はアルミ
ナで修飾したシリカに担持してなる担持触媒を用いるこ
とを特徴とする有機カルボン酸及び／又は有機カルボン
酸エステルの水素化方法。1. A method of hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester by contacting with hydrogen in the presence of a catalyst, wherein one or two noble metals of Group VIII of the periodic table are used as the catalyst. A method for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester, characterized in that a supported catalyst prepared by supporting silica modified with titania and / or alumina is used.
はルテニウムであることを特徴とする請求項１に記載の
有機カルボン酸及び／又は有機カルボン酸エステルの水
素化方法。2. The method for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester according to claim 1, wherein the noble metal of Group VIII is palladium and / or ruthenium.
と、錫、レニウム及びゲルマニウムよりなる群から選ば
れる１種又は２種以上の金属成分とを担体に担持してな
る担持触媒を用いることを特徴とする請求項１又は請求
項２に記載の有機カルボン酸及び／又は有機カルボン酸
エステルの水素化方法。3. A supported catalyst comprising a noble metal of Group VIII of the Periodic Table and one or more metal components selected from the group consisting of tin, rhenium and germanium as a catalyst. The method for hydrogenating an organic carboxylic acid and / or an organic carboxylic acid ester according to claim 1 or 2, wherein
を、周期律表第VIII族の貴金属の１種又は２種以上を、
チタニア及び／又はアルミナで修飾したシリカに担持し
てなる担持触媒の存在下で、水素と接触させて水素化す
ることを特徴とするγ−ブチロラクトン、１，４−ブタ
ンジオール及びテトラヒドロフランの併産方法。4. Maleic anhydride and / or succinic anhydride are added to one or more noble metals of Group VIII of the periodic table,
A method for co-production of γ-butyrolactone, 1,4-butanediol and tetrahydrofuran, which comprises contacting with hydrogen for hydrogenation in the presence of a supported catalyst supported on silica modified with titania and / or alumina. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4271986A JPH06116182A (en) | 1992-10-09 | 1992-10-09 | Method for hydrogenating organic carboxylic acid and / or organic carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4271986A JPH06116182A (en) | 1992-10-09 | 1992-10-09 | Method for hydrogenating organic carboxylic acid and / or organic carboxylic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06116182A true JPH06116182A (en) | 1994-04-26 |
Family
ID=17507560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4271986A Pending JPH06116182A (en) | 1992-10-09 | 1992-10-09 | Method for hydrogenating organic carboxylic acid and / or organic carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06116182A (en) |
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