JP4472108B2 - Carboxylic acid hydrogenation catalyst - Google Patents
Carboxylic acid hydrogenation catalyst Download PDFInfo
- Publication number
- JP4472108B2 JP4472108B2 JP2000130776A JP2000130776A JP4472108B2 JP 4472108 B2 JP4472108 B2 JP 4472108B2 JP 2000130776 A JP2000130776 A JP 2000130776A JP 2000130776 A JP2000130776 A JP 2000130776A JP 4472108 B2 JP4472108 B2 JP 4472108B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- carboxylic acid
- catalyst
- anhydride
- carboxylic
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 92
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 38
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 133
- 239000011148 porous material Substances 0.000 claims description 91
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 74
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 38
- 239000001361 adipic acid Substances 0.000 claims description 37
- 235000011037 adipic acid Nutrition 0.000 claims description 37
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 29
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 claims description 27
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052702 rhenium Inorganic materials 0.000 claims description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 11
- 235000005074 zinc chloride Nutrition 0.000 claims description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000002994 raw material Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000011135 tin Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 11
- -1 organic acid salts Chemical class 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 9
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 8
- 238000010908 decantation Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000001994 activation Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000001384 succinic acid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WGWBFGXCVJZEPW-UHFFFAOYSA-N [Ru].[Sn].[Pt] Chemical compound [Ru].[Sn].[Pt] WGWBFGXCVJZEPW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000004685 tetrahydrates Chemical class 0.000 description 3
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product 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
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
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- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
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- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
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- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 235000007129 Cuminum cyminum Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 241000737052 Naso hexacanthus Species 0.000 description 1
- GSFHPKBAODBIOC-UHFFFAOYSA-K O=[Mo](Cl)(Cl)Cl.N Chemical compound O=[Mo](Cl)(Cl)Cl.N GSFHPKBAODBIOC-UHFFFAOYSA-K 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910008957 Sn—Mo Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- TTXWERZRUCSUED-UHFFFAOYSA-N [Ru].[Sn] Chemical compound [Ru].[Sn] TTXWERZRUCSUED-UHFFFAOYSA-N 0.000 description 1
- JFTLWSJOAPVNBH-UHFFFAOYSA-N [Sn].[Ru].[Mo] Chemical compound [Sn].[Ru].[Mo] JFTLWSJOAPVNBH-UHFFFAOYSA-N 0.000 description 1
- GSRZPYINOSHFHF-UHFFFAOYSA-N [Sn].[Ru].[Re] Chemical compound [Sn].[Ru].[Re] GSRZPYINOSHFHF-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 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
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- RPKLZQLYODPWTM-KBMWBBLPSA-N cholanoic acid Chemical compound C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@@H](CCC(O)=O)C)[C@@]1(C)CC2 RPKLZQLYODPWTM-KBMWBBLPSA-N 0.000 description 1
- 229960002471 cholic acid Drugs 0.000 description 1
- 235000019416 cholic acid Nutrition 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- LQZOFGQYLVDFBA-UHFFFAOYSA-N iron(2+) oxygen(2-) ruthenium(3+) Chemical compound [O-2].[Fe+2].[Ru+3] LQZOFGQYLVDFBA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- TWIRRPLUAGEFNJ-UHFFFAOYSA-L palladium(2+);sulfate;dihydrate Chemical compound O.O.[Pd+2].[O-]S([O-])(=O)=O TWIRRPLUAGEFNJ-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- MDECULARTTWCDW-UHFFFAOYSA-N pent-2-ynedioic acid Chemical class OC(=O)CC#CC(O)=O MDECULARTTWCDW-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 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
Description
【０００１】
【発明の属する技術的分野】
本発明は、カルボン酸類を原料としてエステル化工程を経ることなく、水存在下、水素により直接水添してアルコール類を得るための触媒および該触媒を用いたカルボン酸類からアルコール類を製造する方法に関するものである。
【０００２】
【従来の技術】
アルコール類は、種々の産業分野で広範に使用されている有用な物質である。特にジオール類はポリエステル樹脂、ウレタンフォームやウレタン塗料、接着剤の原料として有用である。このようなジオールの１種として例えば１，４−ブタンジオールの製造法については、コハク酸あるいはマレイン酸を水添して製造する方法が数多く報告されている。最も良く知られている方法として銅系の触媒を用いてコハク酸あるいはマレイン酸のエステルを高温、高圧で水添する方法がある。しかしながら、この方法では、カルボン酸を直接水添することができず、カルボン酸を一旦エステルに転換後水添しなければならず、製造工程が長くなるという問題があった。
【０００３】
一方、コハク酸あるいはマレイン酸を直接水添して１，４−ブタンジオールを製造する方法もいくつか提案されている。その触媒系のみを列記するとルテニウム−鉄酸化物からなる触媒（米国特許第４，８２７，００１号明細書）、ルテニウム−錫をＢＥＴ表面積２０００ｍ2／ｇ以上の多孔質炭素に担持した触媒（特開平５−２４６９１５号公報）、ルテニウム及び錫をチタン及び／又はアルミナで修飾したシリカに担持した触媒（特開平６−１１６１８２号公報）、ルテニウム及び錫、並びにアルカリ金属化合物またはアルカリ土類金属を担体に担持した触媒（特開平６−２３９７７８号公報）、ルテニウムと白金及びロジウムから選ばれた少なくとも１種と錫とを担体に担持した触媒（特開平７−１６５６４４号公報）、ルテニウムと錫を担体に担持してなる触媒を用い、過剰の水素を反応系に流通させ、同伴してくる生成物を系外に除去しながら反応を行う方法（特開平９−１２４９２号公報）、ルテニウム−錫−白金を担体に担持した触媒（特開平９−５９１９０号公報）、炭素数５以下のカルボニル化合物が共存した担持成分を含有する溶液を活性炭に含浸して調製したルテニウム−錫−白金を活性炭に担持した触媒（特開平１０−１５３８８号公報）、ルテニウム−錫−白金をあらかじめ硝酸と接触した活性炭に担持した触媒（特開平１０−７１３３２号公報）が提案されているが、いずれの触媒を用いる方法においても、水添生成物である１．４−ブタンジオール、テトラヒドロフラン、γ−ブチロラクトンの選択率が十分でなく、１，４−ブタンジオールの収率は不満足なものであった。
【０００４】
また特開平７−８２１９０号公報にはパラジウムとレニウム化合物からなる触媒を用い、三級アルコールを溶媒として水素化を行う方法が提案されているが、反応速度が未だ不十分であった。
上述したように従来技術において、活性炭を担体とした触媒を用いる直接水添の例が開示されており、活性炭の比表面積や前処理方法についても幾つかの検討がなされている。
【０００５】
一般的な活性炭の製造方法として賦活過程という原料炭素質の熱分解工程を経るが、その賦活方法として各種の酸化性ガス（水蒸気、二酸化炭素、空気など）を用いるガス賦活法と、脱水性の塩類及び酸（塩化カルシウム、塩化マグネシウム、塩化亜鉛、リン酸、硫酸、苛性ソーダ、苛性カリなどのアルカリ類など）を用いる薬品賦活法が知られている。現在、ガス賦活法が米国をはじめ世界的に広く、かつ最も多く採用されており、活性炭製造の主流を占めており、薬品賦活法は現在、特殊用途向けにのみ製造されている。
【０００６】
このような賦活法の違いにより、活性炭の物性として細孔分布の異なる活性炭が得られる。例えば塩化亜鉛賦活粉末炭は、トランジショナル孔と呼ばれる細孔半径が１０〜１００Åの細孔が発達し、その細孔容積が特異的に大きい。このような活性炭をジカルボン酸の直接水添触媒の担体に用いることは上記の従来の技術には何も述べられていない。
また、米国特許第５，６９８，７４９号明細書にはパラジウム−銀−レニウムをあらかじめ硝酸酸化処理した活性炭に担持した触媒を用いてマレイン酸から１，４−ブタンジオールが比較的高収率で得られることが述べられているが、グルタル酸あるいはアジピン酸の水素化還元反応の成績については何も記載されていない。
【０００７】
特開平１１−６０５２３号公報にはあらかじめ酸処理した活性炭にルテニウム−錫−白金を担持した触媒を用いてアジピン酸から１，６−ヘキサンジオールが高収率で得られることが述べられているが、前記特開平１０−７１３３２号公報において述べたように、この触媒を用いて、コハク酸あるいはマレイン酸から１，４−ブタンジオールを選択的に高収率で得ることは困難である。
【０００８】
【発明が解決しようとする課題】
本発明は、カルボン酸の種類に関係なく、いずれのカルボン酸を原料に用いてもアルコール類を高収率で得ることができる触媒を提供すること、およびその触媒を用いたカルボン酸の直接水添によるアルコール類の製造方法を提供することを目的とする。特にコハク酸、グルタル酸、アジピン酸のいずれを原料に用いてもジオール類を高収率で得ることができる触媒、および直接水添の方法を提供することを目的とする。
【０００９】
【課題を解決するための手段】
上記課題を解決すべく、本発明者らが鋭意検討した結果、塩化亜鉛賦活を行って製造した、トランジショナル孔と呼ばれる細孔半径が１０Å以上１００Å以下の細孔容積が大きな活性炭を担体として使用し、ルテニウムと錫を担持した触媒が、驚くべきことに、原料に用いるカルボン酸の種類に関係なく、いずれのカルボン酸を原料に用いてもアルコール類を高収率で得ることができる触媒であることを見出し、本発明に至ったものである。
【００１０】
すなわち本発明は、
［１］ ルテニウムおよび錫を活性炭に担持してなる触媒であって、該活性炭が塩化亜鉛賦活炭であることを特徴とするカルボン酸水添触媒、
［２］ ルテニウムおよび錫を活性炭に担持してなる触媒であって、該活性炭の細孔半径が１０Å未満の細孔容積が０．０３ｃｍ3／ｇ以上０．８ｃｍ3／ｇ以下、細孔半径が１０Å以上１００Å以下の細孔容積が０．５ｃｍ3／ｇ以上２．０ｃｍ3／ｇ以下であり、全細孔容積が１．２ｃｍ3／ｇ以上３．０ｃｍ3／ｇ以下、比表面積が８００ｍ2／ｇ以上２，０００ｍ2／ｇ未満であることを特徴とするカルボン酸水添触媒、
［３］ ルテニウムおよび錫を活性炭に担持してなる触媒が、ルテニウムおよび錫に加えてレニウム、モリブデン、パラジウム、銀およびニッケルから選ばれる少なくとも一種の金属を担持することを特徴とする［１］又は［２］に記載のカルボン酸水添触媒、
［４］ カルボン酸および／又はカルボン酸無水物を、触媒と水の存在下、水素と反応させてアルコールを製造する方法において、該触媒として［１］、［２］又は［３］記載のカルボン酸水添触媒を用いることを特徴とするアルコールの製造方法、
［５］ カルボン酸が一般式（１）で表されるジカルボン酸から選ばれる少なくとも一種のジカルボン酸であり、カルボン酸無水物が一般式（２）で表される少なくとも一種のジカルボン酸無水物であることを特徴とする［４］のアルコールの製造方法、
【００１１】
【化２】
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数が２〜２０である二価の炭化水素基を表す。）
［６］ カルボン酸がコハク酸、グルタル酸、アジピン酸、シクロヘキサンジカルボン酸、マレイン酸、フマル酸およびテレフタル酸から選ばれる少なくとも一種を含むカルボン酸であり、カルボン酸無水物が無水コハク酸および無水マレイン酸から選ばれる少なくとも一種を含むカルボン酸無水物であることを特徴とする［４］又は［５］のアルコールの製造方法、
［７］ カルボン酸および／又はカルボン酸無水物がコハク酸、グルタル酸およびアジピン酸を含むカルボン酸の混合物であることを特徴とする［６］のアルコールの製造方法、
［８］ カルボン酸および／又はカルボン酸無水物がシクロヘキサノン及び／又はシクロヘキサノールの酸化反応液から回収されたコハク酸、グルタル酸およびアジピン酸を含むカルボン酸の混合物であることを特徴とする[７］のアルコールの製造方法、
［９］ 温度１００℃〜３００℃、水素圧力１ＭＰａ〜２５ＭＰａの条件下でカルボン酸および／又はカルボン酸無水物を水素と反応させることを特徴とする（４）、（５）、（６）、（７）又は（８）に記載のアルコールの製造方法、
である。
【００１３】
以下、本発明を詳細に説明する。
本発明の水添触媒は、特定の製造方法により製造された活性炭にルテニウムおよび錫を担持させたものであり、好ましくはルテニウムおよび錫に加えてレニウム、モリブデン、パラジウム、銀およびニッケルから選ばれる少なくとも１種の金属を担持させて調製したものである。この中でもレニウムとモリブデンがより好ましく、特にレニウムが好ましい。
【００１４】
本発明において用いられる活性炭は、塩化亜鉛賦活炭である。塩化亜鉛賦活炭の製造方法は公知の方法を用いればよく、その詳細は例えば「活性炭読本第２版」（柳井弘編著、石崎信男著、日刊工業新聞社）等に記載されているように出発原料として、のこくず、低灰分の泥炭、麦わら、あし、堅果およびカラなどを使用し、塩化亜鉛の濃厚溶液を含浸させた後に焼成する工程を含む製造方法によって製造された活性炭である。また、この活性炭は、不純物を除去するためにルテニウムおよび錫などの金属を担持する前に熱水等で処理してもよい。
【００１５】
この塩化亜鉛賦活炭は、トランジショナル孔と呼ばれる、細孔半径が１０Å以上１００Å以下の細孔が発達し、その細孔容積が特異的に大きいという特徴を持つ。この塩化亜鉛賦活炭における細孔半径と細孔容積の関係は、窒素ガス吸着法によって細孔容積、ＢＥＴ比表面積を測定した場合に、細孔半径が１０Å未満の細孔容積が０．０３ｃｍ3／ｇ以上０．８ｃｍ3／ｇ以下であり、細孔半径が１０Å以上１００Å以下の細孔容積が０．５ｃｍ3／ｇ以上２．０ｃｍ3／ｇ以下であり、全細孔容積が１．２ｃｍ3／ｇ以上３．０ｃｍ3／ｇ以下であり、比表面積が８００ｍ2／ｇ以上２０００ｍ2／ｇ未満である。さらに好ましくは、細孔半径１０Å未満の細孔容積が０．０４ｃｍ3／ｇ以上０．７ｃｍ3／ｇ以下であり、細孔半径１０Å以上１００Å以下の細孔容積が０．７ｃｍ3／ｇ以上１．８ｃｍ3／ｇ以下であり、全細孔容積が１．４ｃｍ3／ｇ以上２．７ｃｍ3／ｇ以下であり、比表面積が１０００ｍ2／ｇ以上１８００ｍ2／ｇ以下である。
【００１６】
一般的な水蒸気賦活炭の細孔容積は、トラジショナル孔と呼ばれる、細孔半径が１０Å以上１００Å以下の細孔容積が０．０２ｃｍ3／ｇ以上０．４ｃｍ3／ｇ以下であるが、本発明の目的とする、カルボン酸の種類に関係なくアルコール類を高収率で得る触媒とするには、トラジショナル孔の細孔容積が大きい活性炭を担体に用いることが必要である。即ち、細孔半径が１０Å以上１００Å以下の細孔容積が０．５ｃｍ3／ｇ以上２．０ｃｍ3／ｇ以下の活性炭を用いることが必要である。
【００１７】
一方、触媒の担体としてはその構造が維持される強度も必要であることから、担体として用いる活性炭は、上記細孔半径と細孔容積との関係を有することが必要である。即ち、細孔半径が１０Å未満の細孔容積が０．０３ｃｍ3／ｇ以上０．８ｃｍ3／ｇ以下であり、全細孔容積が１．２ｃｍ3／ｇ以上３．０ｃｍ3／ｇ以下であり、比表面積が８００ｍ2／ｇ以上２，０００ｍ2／ｇ未満であることが必要である。
【００１８】
本発明者らが検討した結果では、測定装置によって窒素吸着法による細孔容積、ＢＥＴ比表面積の測定結果に差が生じることがある。本発明者らは、島津マイクロメリテックス ＡＳＡＰ−２４００（（株）島津製作所製）を用いて測定した。細孔容積を計算するためのデータの処理は、ＢＪＨ法を用いた。なお、本装置によるデータ処理結果として細孔半径５Å〜１５００Åのデータが得られるが、一般的に知られているように窒素吸着法によって測定される細孔半径は、約８Å〜５００Å程度であり、本発明で言う細孔半径１０Å未満とは実質上約８Å〜１０Å未満の細孔半径を言うものであり、全細孔容積とは、実質上約８Å〜５００Å程度の細孔半径の細孔容積を言うものである。
【００１９】
このような細孔構造を有する活性炭をジカルボン酸の直接水添の触媒担体に用いることにより特に有効な効果を発揮する原因については明らかではないが、水蒸気賦活炭等のガス賦活炭に比較してトランジショナル孔と呼ばれる細孔半径が１０Å以上１００Å以下の細孔の細孔容量が大きいために、触媒細孔中でのカルボン酸、水素の拡散がスムーズに進み、特にジカルボン酸を原料とする場合には、ジカルボン酸および中間体のヒドロキシカルボン酸の拡散がスムーズに進み、ジカルボン酸からヒドロキシカルボン酸、さらにジオールへの水添が効率よく進むのではないかと推測している。
【００２０】
活性炭にルテニウムと錫を担持する方法、およびルテニウムと錫に加えてレニウム、モリブデン、パラジウム、銀およびニッケルから選ばれる少なくとも一つの金属を担持する方法としては、浸せき法、イオン交換法、含浸法など担持触媒の調製に一般的に用いられている任意の方法を用いることができる。浸せき法によるときは担持する金属成分の原料化合物を水などの溶媒に溶解して金属化合物の溶液を調製し、この溶液に活性炭を浸せきして担体に担持させる。担体に各金属成分を担持させる順序については特に制限はなく、全ての金属を同時に担持しても、各成分を個別に担持してもよい。
【００２１】
触媒調製に用いる金属成分の原料化合物としては、触媒の調製法にもよるが通常は硝酸塩、硫酸塩、塩酸塩などの鉱酸塩、酢酸塩などの有機酸塩、水酸化物、酸化物、有機金属化合物などを用いることができる。その中でも水溶性の原料化合物が好ましい。具体的にはルテニウムの原料化合物としては、塩化ルテニウム、硝酸ルテニウム、ルテニウムアセチルアセトナート、ルテニウムカルボニル等であり、錫の原料化合物としては塩化錫（ＩＩ）、錫酸ナトリウム、酢酸錫（ＩＩ）等であり、レニウムの原料化合物としては、七酸化二レニウム（ＶＩＩ）、過レニウム酸水溶液などであり、モリブデンの原料化合物としては、七モリブデン酸六アンモニウム四水和物、塩化モリブデン（ＩＩ）、五塩化オキソモリブデン（Ｖ）酸アンモニウムなどであり、パラジウムの原料化合物としては、塩化パラジウム（ＩＩ）二水和物、硝酸パラジウム（ＩＩ）、硫酸パラジウム（ＩＩ）二水和物などであり、銀の原料化合物としては、硝酸銀、過塩素酸銀などであり、ニッケルの原料化合物としては、塩化ニッケル（ＩＩ）六水和物、硫酸ニッケル（ＩＩ）、硝酸ニッケル（ＩＩ）六水和物などである。中でも好ましい原料化合物は、塩化ルテニウム、塩化錫、酢酸錫、過レニウム酸水溶液、七モリブデン酸六アンモニウム四水和物、硝酸パラジウム、塩化ニッケル（ＩＩ）六水和物等である。
【００２２】
金属成分を担持した活性炭は乾燥し、次いで所望により焼成した後に還元して触媒とする。乾燥は通常１００℃未満の温度で、減圧下に保持するか、又は窒素、空気などの乾燥気体を流通させて行う。また焼成は通常１００〜６００℃の温度で窒素、空気などを流通させながら行う。還元は液相還元又は気相還元のいずれで行ってもよい。気相還元に用いる還元ガスとしては、水素、ヒドラジン蒸気、ホルマリン、一酸化炭素等を用いることができる。温度としては、１５０℃〜５００℃の温度が好ましい。
【００２３】
上記焼成した触媒を容器に仕込み、所望の温度に昇温した後に還元ガスを充填することにより還元を行うことができる。所望に応じてこの還元操作を繰り返してもよい。また、容器に還元ガスを流通させて還元操作を行ってもよい。液相還元に用いる還元剤としては、上記気相還元に用いる還元剤の他に水素化硼素ナトリウム、水素化リチウムアルミニウム、ジエチル亜鉛等の還元剤を用いることができる。上記、金属成分を担持した活性炭を水および／またはアルコールなどの溶媒中に懸濁させ、室温から２５０℃の温度で常圧から２０ＭＰａの圧力下、上記した還元剤を用いて還元することにより行うことができる。
【００２４】
本発明の触媒において、ルテニウムと錫の担持量は、担体に対してそれぞれ金属として０．５〜５０重量％、好ましくは１〜１０重量％である。ルテニウム、錫の比率は金属として元素比でルテニウム：錫が１：０．１〜１：２が好ましく、さらに好ましくは１：０．２〜１：１．３である。本発明ではルテニウムと錫に加えてレニウム、モリブデン、パラジウム、銀およびニッケルから選ばれる少なくとも一つの金属を担持することが好ましい。この中でもレニウム、モリブデンがより好ましく、特にレニウムが好ましい。レニウム、モリブデン、パラジウム、銀、ニッケルの担持量は、金属として元素比でルテニウムに対して各々０．１〜５が好ましく、さらに好ましくは各々０．２〜２の範囲である。
【００２５】
本発明においてアルコール類の製造に用いられる原料は、カルボン酸および／又はカルボン酸無水物である。具体的にはギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、ヘプタン酸、カプリル酸、ペラルゴン酸等の脂肪族飽和モノカルボン酸類、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、メチルコハク酸、２，２−ジメチルコハク酸、２，３−ジメチルコハク酸、メチルマロン酸、α−メチルグルタル酸、β−メチルグルタル酸、２，２−ジメチルグルタル酸、２，４−ジメチルグルタル酸、３．３−ジメチルグルタル酸、２−エチル−２−メチルコハク酸、２，２，５，５−テトラメチルヘキサン二酸、３−メチルアジピン酸、コハク酸無水物、アジピン酸無水物、ポリアジピン酸無水物等の脂肪族飽和ジカルボン酸類および脂肪族飽和ジカルボン酸無水物類、アクリル酸、クロトン酸、イソクロトン酸、ビニル酢酸、メタクリル酸等の脂肪族不飽和モノカルボン酸類、フマル酸、マレイン酸、無水マレイン酸、メチルマレイン酸、メチルフマル酸、イタコン酸、シトラコン酸、メサコン酸、グルタコン酸、ムスコン酸、２−メチルムスコン酸、アセチレンジカルボン酸、１−プロピン−１，３−ジカルボン酸類等の脂肪族不飽和ジカルボン酸類および脂肪族不飽和ジカルボン酸無水物、メチントリカルボン酸、エチレントリカルボン酸などの脂肪族ポリカルボン酸類、シクロヘキサンカルボン酸、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、３，３−テトラメチレングルタル酸、コラン酸、リトコール酸、コール酸等の脂肪族脂環式モノ及びジカルボン酸類、安息香酸、トルイル酸、ジメチル安息香酸、クミン酸、フタル酸、無水フタル酸、イソフタル酸、テレフタル酸等の芳香族カルボン酸類および芳香族カルボン酸無水物等が挙げられる。
【００２６】
この中でも下記一般式（１）で示されるジカルボン酸および下記一般式（２）で示されるジカルボン酸無水物が好ましく、具体的にはコハク酸、グルタル酸、アジピン酸、シクロヘキサンジカルボン酸、マレイン酸、フマル酸、テレフタル酸等のジカルボン酸、無水コハク酸、無水マレイン酸等の無水物が挙げられる。分子内に窒素、硫黄、リン元素を持たないカルボン酸および／又はカルボン酸無水物が好ましい。
【００２７】
【化３】
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数が２〜２０である二価の炭化水素基を表す。）
なお、不飽和のカルボン酸および不飽和カルボン酸無水物を原料に用いた場合には、本発明の触媒を用いた水添反応によって飽和のアルコール類が得られ、また芳香族カルボン酸および芳香族カルボン酸無水物を原料に用いた場合には、脂環式アルコール類が得られる。
【００２９】
さらに、原料は、複数のカルボン酸の混合物であっても、複数のカルボン酸無水物の混合物であっても、カルボン酸とカルボン酸無水物の混合物であっても何ら問題ない。好ましいジカルボン酸の混合物としては、コハク酸、グルタル酸、アジピン酸を含有する混合物である。
また、シクロヘキサノンおよび／又はシクロヘキサノールを酸化してアジピン酸を製造する際に副生するジカルボン酸類にはコハク酸、グルタル酸、アジピン酸が含まれており、本発明の特に好適な原料である。このジカルボン酸を原料として有用な化合物を得ることができれば、アジピン酸製造に際して発生する廃棄物の量を減らすことができること、またこの副生物はコハク酸、グルタル酸、アジピン酸が含まれていることから１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールという工業的に有用なジオール類をも併産することができ、本発明による触媒の特徴であるカルボン酸原料の種類を問わず、高収率でアルコール類を得ることができるという点を発揮するに最適の原料であることから特に好ましい。
【００３０】
本発明において特に好ましく用いられる、シクロヘキサノンおよび／又はシクロヘキサノールを硝酸酸化してアジピン酸を製造する際に副生するジカルボン酸混合物とは、アジピン酸を晶析分離したろ液である。本発明ではそのろ液をそのまま用いても良いが、触媒の水添活性が減じる時には硝酸酸化触媒の脱触媒、脱硝酸などの工程を経たものを用いることが好ましい。
本発明では上記のルテニウムと錫、好ましくはルテニウムと錫に加えてレニウム、モリブデン、パラジウム、銀、ニッケルから選ばれる少なくとも一つの金属を、前述の活性炭に担持した触媒を用い、水の存在下にカルボン酸および／又はカルボン酸無水物の水添反応を行う。
【００３１】
該水添反応における水の量は、カルボン酸および／又はカルボン酸無水物に対して０．５〜１００重量倍である。さらに好ましくは１〜２０重量倍である。水添反応の温度においてカルボン酸および／又はカルボン酸無水物の全量が溶解する水量が好ましい。水添反応の温度は、１００〜３００℃が好ましく、さらに好ましくは１３０〜２５０℃である。水素圧は１〜２５ＭＰａ、さらに好ましくは５〜２０ＭＰａである。
【００３２】
水添反応は連続、回分のいずれで行ってもよい、また反応型式としては液相懸濁反応、固定床流通反応のいずれも用いることができる。
本発明において、原料にシクロヘキサノンおよび／又はシクロヘキサノールを硝酸酸化してアジピン酸を製造する際に副生するジカルボン酸混合物を用いた場合には水添生成物として１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールの混合物が得られるが、これらのジオールは必要に応じて通常の精製方法、例えば蒸留分離によって精製することができる。
【００３３】
【発明の実施の形態】
以下、本発明を実施例などを用いて更に詳細に説明する。なお、反応成績のうち、原料の転化率は液体クロマトグラフィーの分析値から算出し、ジオール類の収率はガスクロマトグラフィーの分析値から算出した。また、コハク酸、グルタル酸、アジピン酸の混合物はアジピン酸を晶析分離したろ液から脱水、脱硝酸処理して得たものを用いた。組成は液体クロマトグラフィーの分析によりコハク酸２３重量％、グルタル酸６０重量％、アジピン酸１７重量％であった。
【００３４】
【実施例１】
触媒の担体に用いる活性炭は、二村化学工業（株）製の活性炭で、グレード名「太閤ＳＧＰ」を用いた。窒素吸着法によりカルロエルバ社製ソープトマチックを用いて二村化学（株）でこの活性炭の細孔容積、比表面積を測定した結果は、細孔半径１０Å未満の細孔容積が０．０５ｃｍ3／ｇ、細孔半径１０Å以上１００Å以下の細孔容量が０．７５ｃｍ3／ｇ、全細孔容量が１．０８ｃｍ3／ｇ、比表面積は１０５０ｍ2／ｇであった。さらに島津マイクロメリテックス ＡＳＡＰ−２４００を用いて窒素吸着法により同活性炭を測定したところ、細孔半径１０Å未満の細孔容積が０．５２ｃｍ3／ｇ、細孔半径１０Å以上１００Å以下の細孔容量が１．０２ｃｍ3／ｇ、全細孔容量が２．０２ｃｍ3／ｇ、比表面積は、１７８６ｍ2／ｇであった。
【００３５】
＜Ｒｕ−Ｓｎ触媒の調製＞
１００ｍｌのナスフラスコにイオン交換水２．００ｇ、塩化ルテニウム・３水和物０．３９ｇを入れ溶解した。その溶液に塩化錫（ＩＩ価）・２水和物０．２０ｇを加え溶解した。この溶液に上記活性炭３．００ｇを加え、室温で１５時間静置した。エバポレーターを用いて７０℃、２．７ｋＰａで水を留去した後、窒素雰囲気下１５０℃、２時間焼成処理し、ついで水素雰囲気下４５０℃で２時間還元処理した。再び窒素雰囲気にし、室温まで冷却した後に０．１体積％酸素／窒素雰囲気で２時間静置した。上記方法により５．０重量％ルテニウム−３．５重量％錫を活性炭に担持した触媒（担持量は活性炭に対する値である。）を調製した。
【００３６】
＜コハク酸、グルタル酸、アジピン酸混合物の水素還元反応＞
容量３０ｍｌのオートクレーブに、イオン交換水５ｇ、上記コハク酸、グルタル酸、アジピン酸の混合物２．１ｇと上記方法で調製した触媒０．１５ｇを仕込み、室温下窒素でオートクレーブ内の雰囲気を置換した後、水素を２．０ＭＰａ圧入し、１８０℃まで昇温した。１８０℃に達した時点で水素を圧入し１５ＭＰａとした。この圧力で１０時間水添反応を行った。反応終了後、デカンテーションにより触媒を分離し、触媒はイオン交換水で洗浄した。デカンテーションにより分離した反応液と触媒洗浄液を合わせて各ジカルボン酸の転化率とジオールの収率を液体クロマトグラフィーとガスクロマトグラフィーによる分析で求めた。その結果、コハク酸、グルタル酸、アジピン酸の転化率はそれぞれ８７％、８７％、９０％であり、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールの収率は、それぞれ４３％、６９％、５０％であった。
【００３７】
【実施例２】
＜Ｒｕ−Ｓｎ−Ｒｅ触媒の調製＞
１００ｍｌのナスフラスコにイオン交換水２．００ｇ、塩化ルテニウム・３水和物０．３９ｇを入れ溶解した。その溶液に塩化錫（ＩＩ価）・２水和物０．２０ｇを加え溶解した。更に七酸化二レニウム０．２２ｇを加え溶解した。実施例１で用いたのと同じ活性炭３．００ｇを加え、室温で１５時間振とうした。エバポレーターを用いて７０℃、２．７ｋＰａで水を留去した後、窒素ガス雰囲気下１５０℃、２時間焼成処理し、ついで水素雰囲気下４５０℃で２時間還元処理した。再び窒素ガス雰囲気にし、室温まで冷却した後に０．１体積％酸素／窒素雰囲気で２時間静置した。上記方法により５．０重量％ルテニウム−３．５重量％錫−５．６重量％レニウムを活性炭に担持した触媒を調製した。
【００３８】
＜コハク酸、グルタル酸、アジピン酸混合物の水素還元反応＞
触媒として上記で調製したルテニウム−錫−レニウム／活性炭触媒を用いた以外は実施例１と同様にして水添反応を行った。その結果、コハク酸、グルタル酸、アジピン酸の転化率はそれぞれ９３％、９３％、９７％であり、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールの収率は、それぞれ５３％、７８％、６０％であった。
【００３９】
【実施例３】
＜Ｒｕ−Ｓｎ−Ｍｏ触媒の調整＞
実施例２の七酸化二レニウム０．２２ｇに代えて（ＮＨ4）6［Ｍｏ7Ｏ24］・４水和物０．０８ｇを用いた以外は実施例１と同様にして触媒を調製した。これにより５．０重量％ルテニウム−３．５重量％錫−１．５重量％モリブデンを活性炭に担持した触媒を調製した。
【００４０】
＜コハク酸、グルタル酸、アジピン酸混合物の水素還元反応＞
触媒として上記で調製したルテニウム−錫−モリブデン／活性炭触媒を用いた以外は実施例１と同様にして水添反応を行った。その結果、コハク酸、グルタル酸、アジピン酸の転化率はそれぞれ９１％、９２％、９５％であり、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールの収率は、それぞれ５７％、７６％、５８％であった。
【００４１】
【比較例１】
三菱化学製石炭系活性炭ＣＸ−２の細孔容積、比表面積を実施例１と同様に島津マイクロメリテックス ＡＳＡＰ−２４００を用いて窒素吸着法により測定したところ、細孔半径１０Å以下の細孔容積が０．５７ｃｍ3／ｇ、細孔半径１０Å以上１００Å以下の細孔容量が０．４４ｃｍ3／ｇ、全細孔容量が１．０７ｃｍ3／ｇ、比表面積は、１６１５ｍ2／ｇであった。
【００４２】
特開平１０−７１３３２号公報の実施例に従って、ＣＸ−２に３０％硝酸を加え、９５℃で３時間処理した。この活性炭を濾過、水洗、乾燥後、上記と同様の方法により細孔容積、比表面積を測定した。その結果、細孔半径１０Å以下の細孔容積が０．４５ｃｍ3／ｇ、細孔半径１０Å以上１００Å以下の細孔容量が０．３８ｃｍ3／ｇ、全細孔容量が０．８９ｃｍ3／ｇ、比表面積は、１３３２ｍ2／ｇであり、細孔半径１０Å以上１００Å以下の細孔容量が本発明の塩化亜鉛賦活炭とは異なることを確認した。
【００４３】
この活性炭を用いて実施例２と同様にして、５．０重量％ルテニウム−３．５重量％錫−５．６重量％レニウムを活性炭に担持した触媒を調製した。この触媒を用いて実施例１と同様にしてコハク酸、グルタル酸、アジピン酸の混合物の水添反応を行った。その結果コハク酸、グルタル酸、アジピン酸の転化率は、それぞれ７０％、７８％、６４％であり、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールの収率はそれぞれ３７％、５３％、４３％であった。
【００４４】
【比較例２】
比較例１と同様の方法、装置を用いて測定した細孔容積、比表面積が、細孔半径１０Å未満の細孔容積が０．３５ｃｍ3／ｇ、細孔半径１０Å以上１００Å未満の細孔容積が０．２３ｃｍ3／ｇ、全細孔容量が０．６１ｃｍ3／ｇ、比表面積が９３７ｍ2／ｇである活性炭を用いて、実施例１の触媒調製と同様にしてルテニウム−錫／活性炭触媒を調製した。この触媒を用い、実施例１と同様の手順で上記ジカルボン酸混合物の水添反応を行った。その結果コハク酸、グルタル酸、アジピン酸の転化率はそれぞれ６９％、７３％、７２％であり、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールの収率はそれぞれ２１％、４０％、３６％であった。
【００４５】
【実施例４】
容量５０ｍｌのオートクレーブに、イオン交換水５ｇ、コハク酸２．１０ｇと実施例３で調製した触媒０．３０ｇを仕込み、室温下窒素でオートクレーブ内の雰囲気を置換した後、水素を２．０ＭＰａ圧入し、１８０℃まで昇温した。１８０℃に達した時点で水素を圧入し１５ＭＰａとした。この圧力で５時間水添反応を行った。反応終了後、デカンテーションにより触媒を分離し、触媒はイオン交換水で洗浄した。デカンテーションにより分離した反応液と触媒洗浄液を合わせてコハク酸の転化率と１，４−ブタンジオールの収率を液体クロマトグラフィーとガスクロマトグラフィーによる分析で求めた。その結果、コハク酸の転化率は９８％であり、１，４−ブタンジオールの収率は、８０％であった。
【００４６】
【実施例５】
容量３０ｍｌのオートクレーブに、イオン交換水５ｇ、グルタル酸２．１０ｇと実施例３で調製した触媒０．３０ｇを仕込み、室温下窒素でオートクレーブ内の雰囲気を置換した後、水素を２．０ＭＰａ圧入し、２４０℃まで昇温した。２４０℃に達した時点で水素を圧入し９．８ＭＰａとした。この圧力で３．５時間水添反応を行った。反応終了後、デカンテーションにより触媒を分離し、触媒はイオン交換水で洗浄した。デカンテーションにより分離した反応液と触媒洗浄液を合わせてグルタル酸の転化率と１，５−ペンタンジオールの収率を液体クロマトグラフィーとガスクロマトグラフィーによる分析で求めた。その結果、グルタル酸の転化率は１００％であり、１，５−ペンタンジオールの収率は、９９％であった。
【００４７】
【実施例６】
容量３０ｍｌのオートクレーブに、イオン交換水５ｇ、アジピン酸２．１０ｇと実施例３で調製した触媒０．３０ｇを仕込み、室温下窒素でオートクレーブ内の雰囲気を置換した後、水素を２．０ＭＰａ圧入し、２４０℃まで昇温した。２４０℃に達した時点で水素を圧入し９．８ＭＰａとした。この圧力で３．５時間水添反応を行った。反応終了後、デカンテーションにより触媒を分離し、触媒はイオン交換水で洗浄した。デカンテーションにより分離した反応液と触媒洗浄液を合わせてアジピン酸の転化率と１，６−ヘキサンジオールの収率を液体クロマトグラフィーとガスクロマトグラフィーによる分析で求めた。その結果、アジピン酸の転化率は１００％であり、１，６−ヘキサンジオールの収率は、９６％であった。
【００４８】
【発明の効果】
本発明の触媒を用いることにより、カルボン酸の種類に関わらず高い収率でアルコール類を得ることができる。特に、シクロヘキサンおよび／又はシクロヘキサノールを硝酸酸化してアジピン酸を製造する際の副生物であるコハク酸、グルタル酸、アジピン酸を含むジカルボン酸の混合物から１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールを含むジオール混合物を高収率で製造することができ、産業上大いに有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a catalyst for directly hydrogenating with hydrogen in the presence of water to obtain alcohols without using an esterification step from carboxylic acids as a raw material, and a method for producing alcohols from carboxylic acids using the catalyst It is about.
[0002]
[Prior art]
Alcohols are useful substances that are widely used in various industrial fields. In particular, diols are useful as raw materials for polyester resins, urethane foam, urethane paints, and adhesives. As a method for producing, for example, 1,4-butanediol as one kind of such diols, many methods for producing hydrogenated succinic acid or maleic acid have been reported. As the most well-known method, there is a method in which an ester of succinic acid or maleic acid is hydrogenated at a high temperature and a high pressure using a copper catalyst. However, this method has a problem that the carboxylic acid cannot be directly hydrogenated, and the carboxylic acid must be once converted to an ester and then hydrogenated, resulting in a long production process.
[0003]
On the other hand, several methods for producing 1,4-butanediol by directly hydrogenating succinic acid or maleic acid have been proposed. When only the catalyst system is listed, a catalyst comprising ruthenium-iron oxide (US Pat. No. 4,827,001), a catalyst having ruthenium-tin supported on porous carbon having a BET surface area of 2000 m 2 / g or more (special Kaihei No. 5-246915), a catalyst in which ruthenium and tin are supported on silica modified with titanium and / or alumina (Japanese Patent Laid-Open No. 6-116182), ruthenium and tin, and an alkali metal compound or alkaline earth metal Catalyst (Japanese Patent Laid-Open No. 6-239778), a catalyst having at least one selected from ruthenium, platinum and rhodium and tin supported on a carrier (Japanese Patent Laid-Open No. 7-165644), ruthenium and tin Using the catalyst supported on the catalyst, the excess hydrogen is circulated in the reaction system, and the reaction is carried out while removing the entrained products out of the system. And a solution containing a supported component in which a carbonyl compound having 5 or less carbon atoms coexists, a catalyst having ruthenium-tin-platinum supported on a carrier (Japanese Patent Laid-Open No. 9-59190), A catalyst in which ruthenium-tin-platinum prepared by impregnation into activated carbon is supported on activated carbon (Japanese Patent Laid-Open No. 10-15388), a catalyst in which ruthenium-tin-platinum is supported on activated carbon previously contacted with nitric acid (Japanese Patent Laid-Open No. 10-71332) However, in any of the methods using a catalyst, the selectivity for hydrogenated products 1.4-butanediol, tetrahydrofuran, and γ-butyrolactone is not sufficient, and 1,4-butane The yield of diol was unsatisfactory.
[0004]
Japanese Patent Application Laid-Open No. 7-82190 proposes a method of hydrogenation using a catalyst composed of palladium and a rhenium compound and a tertiary alcohol as a solvent, but the reaction rate is still insufficient.
As described above, in the prior art, examples of direct hydrogenation using a catalyst using activated carbon as a carrier have been disclosed, and some studies have been made on the specific surface area and pretreatment method of activated carbon.
[0005]
As a general method for producing activated carbon, it undergoes a raw carbonaceous pyrolysis process called an activation process. As an activation method, a gas activation method using various oxidizing gases (water vapor, carbon dioxide, air, etc.) Chemical activation methods using salts and acids (calcium chloride, magnesium chloride, zinc chloride, phosphoric acid, sulfuric acid, caustic soda, caustic potassium and other alkalis) are known. Currently, the gas activation method is widely and most widely adopted worldwide including the United States, and occupies the mainstream of activated carbon production. The chemical activation method is currently produced only for special applications.
[0006]
Due to such a difference in activation method, activated carbon having different pore distributions as physical properties of the activated carbon can be obtained. For example, zinc chloride activated powder charcoal develops pores having a pore radius of 10 to 100 mm called transitional pores, and the pore volume is specifically large. The use of such activated carbon as a support for a direct hydrogenation catalyst of dicarboxylic acid has nothing to be described in the above prior art.
In addition, US Pat. No. 5,698,749 discloses a relatively high yield of 1,4-butanediol from maleic acid using a catalyst supported on activated carbon that has been previously oxidized with palladium-silver-rhenium by nitric acid oxidation. Although it is stated that it can be obtained, nothing is described about the results of the hydroreduction reaction of glutaric acid or adipic acid.
[0007]
Japanese Patent Application Laid-Open No. 11-60523 describes that 1,6-hexanediol can be obtained from adipic acid in a high yield using a catalyst in which ruthenium-tin-platinum is supported on activated carbon that has been previously acid-treated. As described in JP-A-10-71332, it is difficult to selectively obtain 1,4-butanediol in high yield from succinic acid or maleic acid using this catalyst.
[0008]
[Problems to be solved by the invention]
The present invention provides a catalyst capable of obtaining alcohols in a high yield regardless of the type of carboxylic acid, and direct water of carboxylic acid using the catalyst. An object of the present invention is to provide a method for producing alcohol by addition. In particular, an object of the present invention is to provide a catalyst capable of obtaining a diol in a high yield even when any of succinic acid, glutaric acid, and adipic acid is used as a raw material, and a direct hydrogenation method.
[0009]
[Means for Solving the Problems]
As a result of intensive studies by the present inventors to solve the above-mentioned problems, activated carbon produced by activating zinc chloride and using activated carbon having a large pore volume with a pore radius of 10 to 100 mm and having a large pore volume is used as a carrier. The catalyst supporting ruthenium and tin is surprisingly a catalyst capable of obtaining alcohols in a high yield regardless of the type of carboxylic acid used as a raw material, regardless of the carboxylic acid used as the raw material. The present invention has been found and has been accomplished.
[0010]
That is, the present invention
[1] A catalyst formed by supporting ruthenium and tin on activated carbon, wherein the activated carbon is zinc chloride activated charcoal,
[2] ruthenium and tin to a catalyst comprising supported on activated carbon, the pore radius of the activated carbon pore volume of less than 10 Å 0.03 cm 3 / g or more 0.8 cm 3 / g or less, the pore radius Has a pore volume of 10 cm or more and 100 cm or less and 0.5 cm 3 / g or more and 2.0 cm 3 / g or less, a total pore volume of 1.2 cm 3 / g or more and 3.0 cm 3 / g or less, and a specific surface area. A carboxylic acid hydrogenation catalyst, which is 800 m 2 / g or more and less than 2,000 m 2 / g,
[3] The catalyst obtained by supporting ruthenium and tin on activated carbon supports at least one metal selected from rhenium, molybdenum, palladium, silver and nickel in addition to ruthenium and tin [1] or The carboxylic acid hydrogenation catalyst according to [2],
[4] In the method for producing alcohol by reacting carboxylic acid and / or carboxylic anhydride with hydrogen in the presence of a catalyst and water, the catalyst according to [1], [2] or [3] is used as the catalyst. A method for producing an alcohol, characterized by using an acid hydrogenation catalyst;
[5] The carboxylic acid is at least one dicarboxylic acid selected from dicarboxylic acids represented by the general formula (1), and the carboxylic acid anhydride is at least one dicarboxylic anhydride represented by the general formula (2). [4] the method for producing alcohol according to [4],
[0011]
[Chemical formula 2]
(In the formula, R 1 and R 2 each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)
[6] The carboxylic acid is a carboxylic acid containing at least one selected from succinic acid, glutaric acid, adipic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid and terephthalic acid, and the carboxylic acid anhydride is succinic anhydride and maleic anhydride A method for producing an alcohol according to [4] or [5], which is a carboxylic acid anhydride containing at least one selected from acids;
[7] The method for producing an alcohol according to [6], wherein the carboxylic acid and / or carboxylic anhydride is a mixture of carboxylic acids including succinic acid, glutaric acid and adipic acid,
[8] The carboxylic acid and / or carboxylic anhydride is a mixture of carboxylic acids including succinic acid, glutaric acid and adipic acid recovered from the oxidation reaction liquid of cyclohexanone and / or cyclohexanol [7] A method for producing alcohol,
[9] (4), (5), (6), wherein carboxylic acid and / or carboxylic anhydride is reacted with hydrogen under conditions of a temperature of 100 ° C. to 300 ° C. and a hydrogen pressure of 1 MPa to 25 MPa. (7) or the method for producing an alcohol according to (8),
It is.
[0013]
Hereinafter, the present invention will be described in detail.
The hydrogenation catalyst of the present invention is obtained by supporting ruthenium and tin on activated carbon produced by a specific production method, preferably at least selected from rhenium, molybdenum, palladium, silver and nickel in addition to ruthenium and tin. It is prepared by supporting one kind of metal. Among these, rhenium and molybdenum are more preferable, and rhenium is particularly preferable.
[0014]
The activated carbon used in the present invention is zinc chloride activated charcoal. A known method may be used as a method for producing zinc chloride activated charcoal, and details thereof are described, for example, as described in “Activated carbon reader second edition” (by Hiroshi Yanai, Nobuo Ishizaki, Nikkan Kogyo Shimbun). It is activated carbon produced by a production method including a step of using a sawdust, low ash peat, straw, straw, nuts, and kala as a raw material, and impregnating a concentrated solution of zinc chloride, followed by firing. The activated carbon may be treated with hot water or the like before carrying a metal such as ruthenium and tin in order to remove impurities.
[0015]
This zinc chloride activated charcoal is characterized by the development of pores having a pore radius of 10 to 100 cm, called transitional pores, and the pore volume being specifically large. The relationship between the pore radius and the pore volume in this zinc chloride activated charcoal is 0.03 cm 3 when the pore volume and the BET specific surface area are measured by the nitrogen gas adsorption method. / G or more and 0.8 cm 3 / g or less, a pore volume of 10 to 100 cm and a pore volume of 0.5 cm 3 / g to 2.0 cm 3 / g and a total pore volume of 1. 2 cm 3 / g or more and 3.0 cm 3 / g or less, and the specific surface area is 800 m 2 / g or more and less than 2000 m 2 / g. More preferably, the pore volume of less than the pore radius 10Å is less 0.04 cm 3 / g or more 0.7 cm 3 / g, 100 Å or less of pore volume over a pore radius 10Å is 0.7 cm 3 / g or more It is 1.8 cm 3 / g or less, the total pore volume is 1.4 cm 3 / g or more and 2.7 cm 3 / g or less, and the specific surface area is 1000 m 2 / g or more and 1800 m 2 / g or less.
[0016]
The pore volume of general steam activated charcoal is referred to as a traditional pore, and the pore volume with a pore radius of 10 to 100 cm is 0.02 cm 3 / g to 0.4 cm 3 / g. In order to obtain a catalyst for obtaining an alcohol in a high yield regardless of the type of carboxylic acid, which is the object of the invention, it is necessary to use activated carbon having a large pore volume of the traditional pores as a support. That is, it is necessary to use activated carbon having a pore radius of 10 cm to 100 cm and a pore volume of 0.5 cm 3 / g to 2.0 cm 3 / g.
[0017]
On the other hand, since the strength of maintaining the structure of the catalyst support is also necessary, the activated carbon used as the support needs to have a relationship between the pore radius and the pore volume. That is, the pore volume pore radius is less than 10Å is less 0.03 cm 3 / g or more 0.8 cm 3 / g, total pore volume 1.2 cm 3 / g or more 3.0 cm 3 / g or less And the specific surface area must be 800 m 2 / g or more and less than 2,000 m 2 / g.
[0018]
As a result of investigations by the present inventors, there may be a difference in the measurement results of the pore volume and the BET specific surface area by the nitrogen adsorption method depending on the measuring device. The inventors measured using Shimadzu Micromeritex ASAP-2400 (manufactured by Shimadzu Corporation). The data processing for calculating the pore volume was performed using the BJH method. As a result of data processing by this apparatus, data with a pore radius of 5 mm to 1500 mm is obtained. As is generally known, the pore radius measured by the nitrogen adsorption method is about 8 mm to 500 mm. In the present invention, a pore radius of less than 10 mm means a pore radius of about 8 mm to less than 10 mm, and a total pore volume means a pore having a pore radius of about 8 mm to 500 mm. It is a volume.
[0019]
It is not clear why the activated carbon having such a pore structure exhibits a particularly effective effect by using it as a catalyst for direct hydrogenation of dicarboxylic acid, but compared with gas activated charcoal such as steam activated charcoal. When the pore radius of the pores called transitional pores with a radius of 10 to 100 mm is large, the diffusion of carboxylic acid and hydrogen in the catalyst pores proceeds smoothly, especially when dicarboxylic acid is used as a raw material It is speculated that the diffusion of dicarboxylic acid and intermediate hydroxycarboxylic acid proceeds smoothly, and hydrogenation from dicarboxylic acid to hydroxycarboxylic acid and further to diol proceeds efficiently.
[0020]
As a method of supporting ruthenium and tin on activated carbon, and a method of supporting at least one metal selected from rhenium, molybdenum, palladium, silver and nickel in addition to ruthenium and tin, an immersion method, an ion exchange method, an impregnation method, etc. Any method commonly used for the preparation of supported catalysts can be used. When the immersion method is used, a metal compound raw material compound to be supported is dissolved in a solvent such as water to prepare a metal compound solution, and activated carbon is immersed in this solution and supported on a carrier. There is no particular limitation on the order in which each metal component is supported on the carrier, and all the metals may be supported simultaneously or each component may be individually supported.
[0021]
As a raw material compound of the metal component used for catalyst preparation, although it depends on the preparation method of the catalyst, mineral salts such as nitrates, sulfates and hydrochlorides, organic acid salts such as acetates, hydroxides, oxides, An organometallic compound or the like can be used. Among these, water-soluble raw material compounds are preferable. Specifically, ruthenium raw material compounds are ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium carbonyl, etc., and tin raw material compounds are tin (II) chloride, sodium stannate, tin acetate (II), etc. Examples of rhenium raw material compounds include dirhenium heptoxide (VII) and perrhenic acid aqueous solution, and examples of molybdenum raw material compounds include hexaammonium heptamolybdate tetrahydrate, molybdenum (II) chloride, five Examples thereof include ammonium oxomolybdenum (V) chloride, and palladium source compounds such as palladium (II) chloride dihydrate, palladium (II) nitrate, palladium (II) sulfate dihydrate, and the like. Examples of raw material compounds include silver nitrate and silver perchlorate, and nickel raw material compounds include salts. Nickel (II) hexahydrate, nickel sulfate (II), and the like nickel (II) nitrate hexahydrate. Among these, preferable raw material compounds are ruthenium chloride, tin chloride, tin acetate, aqueous perrhenic acid solution, hexaammonium hexamolybdate tetrahydrate, palladium nitrate, nickel (II) chloride hexahydrate, and the like.
[0022]
The activated carbon carrying the metal component is dried, then calcined as desired, and then reduced to a catalyst. Drying is usually performed at a temperature of less than 100 ° C. under reduced pressure or by passing a dry gas such as nitrogen or air. Firing is usually performed at a temperature of 100 to 600 ° C. while circulating nitrogen, air, or the like. The reduction may be performed by either liquid phase reduction or gas phase reduction. As the reducing gas used for the gas phase reduction, hydrogen, hydrazine vapor, formalin, carbon monoxide, or the like can be used. As temperature, the temperature of 150 to 500 degreeC is preferable.
[0023]
Reduction can be carried out by charging the calcined catalyst into a container and heating the catalyst to a desired temperature and then charging with a reducing gas. This reduction operation may be repeated as desired. Further, the reducing operation may be performed by circulating a reducing gas in the container. As a reducing agent used for liquid phase reduction, a reducing agent such as sodium borohydride, lithium aluminum hydride, diethyl zinc and the like can be used in addition to the reducing agent used for the gas phase reduction. The above-mentioned activated carbon carrying a metal component is suspended in a solvent such as water and / or alcohol, and reduced by using the above reducing agent at a temperature from room temperature to 250 ° C. under a pressure from normal pressure to 20 MPa. be able to.
[0024]
In the catalyst of the present invention, the supported amount of ruthenium and tin is 0.5 to 50% by weight, preferably 1 to 10% by weight, respectively, as a metal with respect to the support. The ratio of ruthenium and tin is preferably from 0.1 to 1: 2 of ruthenium: tin as a metal, more preferably 1: 0.2 to 1: 1.3. In the present invention, it is preferable to support at least one metal selected from rhenium, molybdenum, palladium, silver and nickel in addition to ruthenium and tin. Among these, rhenium and molybdenum are more preferable, and rhenium is particularly preferable. The supported amount of rhenium, molybdenum, palladium, silver, and nickel is preferably 0.1 to 5, and more preferably 0.2 to 2, respectively, relative to ruthenium in terms of element ratio as a metal.
[0025]
In the present invention, the raw material used for the production of alcohols is carboxylic acid and / or carboxylic anhydride. Specifically, aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Pimelic acid, suberic acid, azelaic acid, sebacic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, methyl malonic acid, α-methyl glutaric acid, β-methyl glutaric acid, 2, 2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3.3-dimethylglutaric acid, 2-ethyl-2-methylsuccinic acid, 2,2,5,5-tetramethylhexanedioic acid, 3-methyladipic acid Aliphatic saturated dicarboxylic acids such as succinic anhydride, adipic anhydride, polyadipic anhydride and aliphatic saturated dicarboxylic anhydrides, acrylic Aliphatic unsaturated monocarboxylic acids such as phosphoric acid, crotonic acid, isocrotonic acid, vinyl acetic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, methyl maleic acid, methyl fumaric acid, itaconic acid, citraconic acid, mesaconic acid, Aliphatic unsaturated dicarboxylic acids and aliphatic unsaturated dicarboxylic acid anhydrides such as glutaconic acid, muskonic acid, 2-methylmuskonic acid, acetylenedicarboxylic acid, 1-propyne-1,3-dicarboxylic acids, methine tricarboxylic acid, ethylene tricarboxylic acid Aliphatic polycarboxylic acids such as acids, cyclohexanecarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3,3-tetramethyleneglutaric acid, colanic acid, lithol Aliphatic rings such as acid and cholic acid Mono- and dicarboxylic acids, benzoic acid, toluic acid, dimethylbenzoic acid, cumin acid, phthalic acid, phthalic anhydride, isophthalic acid, aromatic carboxylic acids and aromatic carboxylic acid anhydrides such as terephthalic acid.
[0026]
Among these, dicarboxylic acids represented by the following general formula (1) and dicarboxylic anhydrides represented by the following general formula (2) are preferable, and specifically, succinic acid, glutaric acid, adipic acid, cyclohexanedicarboxylic acid, maleic acid, Examples thereof include dicarboxylic acids such as fumaric acid and terephthalic acid, and anhydrides such as succinic anhydride and maleic anhydride. Carboxylic acid and / or carboxylic acid anhydride having no nitrogen, sulfur or phosphorus element in the molecule is preferred.
[0027]
[Chemical 3]
(In the formula, R 1 and R 2 each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)
When unsaturated carboxylic acid and unsaturated carboxylic acid anhydride are used as raw materials, saturated alcohols can be obtained by hydrogenation reaction using the catalyst of the present invention, and aromatic carboxylic acids and aromatic carboxylic acids can be obtained. When carboxylic anhydride is used as a raw material, alicyclic alcohols are obtained.
[0029]
Further, the raw material may be a mixture of a plurality of carboxylic acids, a mixture of a plurality of carboxylic anhydrides, or a mixture of carboxylic acid and carboxylic anhydride. A preferred mixture of dicarboxylic acids is a mixture containing succinic acid, glutaric acid, and adipic acid.
Moreover, succinic acid, glutaric acid, and adipic acid are included in the dicarboxylic acids produced as a by-product in the production of adipic acid by oxidizing cyclohexanone and / or cyclohexanol, and are particularly suitable raw materials of the present invention. If a useful compound can be obtained using this dicarboxylic acid as a raw material, the amount of waste generated during the production of adipic acid can be reduced, and this by-product should contain succinic acid, glutaric acid, and adipic acid. Industrially useful diols such as 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol can be produced together with the carboxylic acid raw material which is a feature of the catalyst according to the present invention. Regardless of the type, it is particularly preferable because it is an optimal raw material for exhibiting that alcohols can be obtained in high yield.
[0030]
The dicarboxylic acid mixture by-produced when nitric acid is oxidized to cyclohexanone and / or cyclohexanol to produce adipic acid, which is particularly preferably used in the present invention, is a filtrate obtained by crystallizing and separating adipic acid. In the present invention, the filtrate may be used as it is. However, when the hydrogenation activity of the catalyst is reduced, it is preferable to use a filtrate that has undergone steps such as decatalysis of a nitric acid oxidation catalyst and denitrification.
In the present invention, the above-mentioned ruthenium and tin, preferably, in addition to ruthenium and tin, at least one metal selected from rhenium, molybdenum, palladium, silver and nickel is used in the presence of water by using the above-mentioned catalyst supported on activated carbon. Hydrogenation reaction of carboxylic acid and / or carboxylic anhydride is performed.
[0031]
The amount of water in the hydrogenation reaction is 0.5 to 100 times the weight of the carboxylic acid and / or carboxylic anhydride. More preferably, it is 1 to 20 times by weight. The amount of water in which the entire amount of carboxylic acid and / or carboxylic anhydride is dissolved at the temperature of the hydrogenation reaction is preferred. The temperature of the hydrogenation reaction is preferably 100 to 300 ° C, more preferably 130 to 250 ° C. The hydrogen pressure is 1 to 25 MPa, more preferably 5 to 20 MPa.
[0032]
The hydrogenation reaction may be performed either continuously or batchwise. As a reaction type, either a liquid phase suspension reaction or a fixed bed flow reaction can be used.
In the present invention, when a dicarboxylic acid mixture by-produced when nitric acid is oxidized to cyclohexanone and / or cyclohexanol as a raw material to produce adipic acid, 1,4-butanediol, A mixture of 5-pentanediol and 1,6-hexanediol is obtained, and these diols can be purified by an ordinary purification method such as distillation separation, if necessary.
[0033]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples and the like. Of the reaction results, the conversion rate of the raw material was calculated from the analytical value of liquid chromatography, and the yield of diols was calculated from the analytical value of gas chromatography. The mixture of succinic acid, glutaric acid and adipic acid was obtained by dehydrating and denitrating the filtrate obtained by crystallization separation of adipic acid. The composition was 23% by weight of succinic acid, 60% by weight of glutaric acid, and 17% by weight of adipic acid by liquid chromatography analysis.
[0034]
[Example 1]
The activated carbon used for the catalyst carrier was activated carbon manufactured by Futura Chemical Industry Co., Ltd., and the grade name “Dazai SGP” was used. As a result of measuring the pore volume and specific surface area of this activated carbon by Nimura Chemical Co., Ltd. using a Sorptomatic made by Carlo Elba by the nitrogen adsorption method, the pore volume having a pore radius of less than 10 mm was 0.05 cm 3 / g. The pore volume with a pore radius of 10 to 100 cm was 0.75 cm 3 / g, the total pore volume was 1.08 cm 3 / g, and the specific surface area was 1050 m 2 / g. Further, when the activated carbon was measured by a nitrogen adsorption method using Shimadzu Micromeritex ASAP-2400, the pore volume with a pore radius of less than 10 mm was 0.52 cm 3 / g, and the pore volume with a pore radius of 10 to 100 cm. 1.02 cm 3 / g, the total pore volume was 2.02 cm 3 / g, and the specific surface area was 1786 m 2 / g.
[0035]
<Preparation of Ru-Sn catalyst>
In a 100 ml eggplant flask, 2.00 g of ion exchange water and 0.39 g of ruthenium chloride trihydrate were dissolved. To the solution, 0.20 g of tin chloride (II) dihydrate was added and dissolved. To this solution was added 3.00 g of the activated carbon, and the mixture was allowed to stand at room temperature for 15 hours. After distilling off water at 70 ° C. and 2.7 kPa using an evaporator, it was baked at 150 ° C. for 2 hours in a nitrogen atmosphere and then reduced at 450 ° C. for 2 hours in a hydrogen atmosphere. The atmosphere was again nitrogen, cooled to room temperature, and allowed to stand for 2 hours in a 0.1 vol% oxygen / nitrogen atmosphere. By the above method, a catalyst in which 5.0 wt% ruthenium-3.5 wt% tin was supported on activated carbon (the supported amount is a value relative to the activated carbon) was prepared.
[0036]
<Hydrogen reduction reaction of succinic acid, glutaric acid, adipic acid mixture>
After charging 5 g of ion exchange water, 2.1 g of the mixture of succinic acid, glutaric acid and adipic acid and 0.15 g of the catalyst prepared by the above method into an autoclave having a capacity of 30 ml, and substituting the atmosphere in the autoclave with nitrogen at room temperature. Then, hydrogen was injected at 2.0 MPa and the temperature was raised to 180 ° C. When the temperature reached 180 ° C., hydrogen was injected to a pressure of 15 MPa. Hydrogenation reaction was performed at this pressure for 10 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with ion-exchanged water. The reaction liquid and catalyst washing liquid separated by decantation were combined, and the conversion rate of each dicarboxylic acid and the yield of diol were determined by analysis by liquid chromatography and gas chromatography. As a result, the conversion rates of succinic acid, glutaric acid, and adipic acid were 87%, 87%, and 90%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were obtained. Were 43%, 69% and 50%, respectively.
[0037]
[Example 2]
<Preparation of Ru-Sn-Re catalyst>
In a 100 ml eggplant flask, 2.00 g of ion exchange water and 0.39 g of ruthenium chloride trihydrate were dissolved. To the solution, 0.20 g of tin chloride (II) dihydrate was added and dissolved. Further, 0.22 g of dirhenium heptoxide was added and dissolved. 3.00 g of the same activated carbon as used in Example 1 was added and shaken at room temperature for 15 hours. After distilling off water at 70 ° C. and 2.7 kPa using an evaporator, it was baked at 150 ° C. for 2 hours in a nitrogen gas atmosphere, and then reduced at 450 ° C. for 2 hours in a hydrogen atmosphere. The atmosphere was again a nitrogen gas atmosphere, cooled to room temperature, and allowed to stand for 2 hours in a 0.1 vol% oxygen / nitrogen atmosphere. By the above method, a catalyst having 5.0 wt% ruthenium-3.5 wt% tin-5.6 wt% rhenium supported on activated carbon was prepared.
[0038]
<Hydrogen reduction reaction of succinic acid, glutaric acid, adipic acid mixture>
A hydrogenation reaction was performed in the same manner as in Example 1 except that the ruthenium-tin-rhenium / activated carbon catalyst prepared above was used as the catalyst. As a result, the conversion rates of succinic acid, glutaric acid and adipic acid were 93%, 93% and 97%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were as follows. Were 53%, 78% and 60%, respectively.
[0039]
[Example 3]
<Preparation of Ru-Sn-Mo catalyst>
A catalyst was prepared in the same manner as in Example 1 except that 0.08 g of (NH 4 ) 6 [Mo 7 O 24 ] · tetrahydrate was used instead of 0.22 g of dirhenium heptoxide in Example 2. Thus, a catalyst in which 5.0 wt% ruthenium-3.5 wt% tin-1.5 wt% molybdenum was supported on activated carbon was prepared.
[0040]
<Hydrogen reduction reaction of succinic acid, glutaric acid, adipic acid mixture>
A hydrogenation reaction was carried out in the same manner as in Example 1 except that the ruthenium-tin-molybdenum / activated carbon catalyst prepared above was used as the catalyst. As a result, the conversion rates of succinic acid, glutaric acid and adipic acid were 91%, 92% and 95%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were as follows. Were 57%, 76% and 58%, respectively.
[0041]
[Comparative Example 1]
When the pore volume and specific surface area of coal-based activated carbon CX-2 manufactured by Mitsubishi Chemical Corporation were measured by the nitrogen adsorption method using Shimadzu Micromeritex ASAP-2400 in the same manner as in Example 1, the pore volume having a pore radius of 10 mm or less was measured. Of 0.57 cm 3 / g, pore volume of pore radius 10 to 100 mm was 0.44 cm 3 / g, total pore volume was 1.07 cm 3 / g, and specific surface area was 1615 m 2 / g. .
[0042]
According to the example of JP-A-10-71332, 30% nitric acid was added to CX-2 and treated at 95 ° C. for 3 hours. The activated carbon was filtered, washed with water, and dried, and then the pore volume and specific surface area were measured by the same method as described above. As a result, the pore volume with a pore radius of 10 mm or less was 0.45 cm 3 / g, the pore volume with a pore radius of 10 to 100 cm was 0.38 cm 3 / g, and the total pore volume was 0.89 cm 3 / g. The specific surface area was 1332 m 2 / g, and it was confirmed that the pore volume with a pore radius of 10 to 100 kg was different from the zinc chloride activated carbon of the present invention.
[0043]
Using this activated carbon, a catalyst having 5.0 wt% ruthenium-3.5 wt% tin-5.6 wt% rhenium supported on activated carbon was prepared in the same manner as in Example 2. Using this catalyst, a hydrogenation reaction of a mixture of succinic acid, glutaric acid and adipic acid was carried out in the same manner as in Example 1. As a result, the conversion rates of succinic acid, glutaric acid and adipic acid were 70%, 78% and 64%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were as follows. Were 37%, 53%, and 43%, respectively.
[0044]
[Comparative Example 2]
The pore volume and specific surface area measured using the same method and apparatus as in Comparative Example 1 were 0.35 cm 3 / g for a pore volume with a pore radius of less than 10 mm, and a pore volume with a pore radius of 10 to less than 100 mm. There 0.23 cm 3 / g, total pore volume 0.61 cm 3 / g, the specific surface area by using the activated carbon is a 937m 2 / g, ruthenium in the same manner as the catalyst preparation of example 1 - tin / activated carbon catalyst Was prepared. Using this catalyst, the hydrogenation reaction of the dicarboxylic acid mixture was carried out in the same procedure as in Example 1. As a result, the conversion rates of succinic acid, glutaric acid and adipic acid were 69%, 73% and 72%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol were as follows. They were 21%, 40%, and 36%, respectively.
[0045]
[Example 4]
An autoclave with a capacity of 50 ml was charged with 5 g of ion-exchanged water, 2.10 g of succinic acid and 0.30 g of the catalyst prepared in Example 3, and after substituting the atmosphere in the autoclave with nitrogen at room temperature, hydrogen was injected under 2.0 MPa. The temperature was raised to 180 ° C. When the temperature reached 180 ° C., hydrogen was injected to a pressure of 15 MPa. Hydrogenation reaction was performed at this pressure for 5 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with ion-exchanged water. The reaction liquid and catalyst washing liquid separated by decantation were combined, and the conversion of succinic acid and the yield of 1,4-butanediol were determined by analysis by liquid chromatography and gas chromatography. As a result, the conversion of succinic acid was 98%, and the yield of 1,4-butanediol was 80%.
[0046]
[Example 5]
A 30 ml autoclave was charged with 5 g of ion-exchanged water, 2.10 g of glutaric acid and 0.30 g of the catalyst prepared in Example 3, and after substituting the atmosphere in the autoclave with nitrogen at room temperature, hydrogen was injected under 2.0 MPa. The temperature was raised to 240 ° C. When the temperature reached 240 ° C., hydrogen was injected to reach 9.8 MPa. Hydrogenation reaction was performed at this pressure for 3.5 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with ion-exchanged water. The reaction liquid and catalyst washing liquid separated by decantation were combined, and the conversion rate of glutaric acid and the yield of 1,5-pentanediol were determined by analysis by liquid chromatography and gas chromatography. As a result, the conversion rate of glutaric acid was 100%, and the yield of 1,5-pentanediol was 99%.
[0047]
[Example 6]
A 30 ml autoclave was charged with 5 g of ion-exchanged water, 2.10 g of adipic acid and 0.30 g of the catalyst prepared in Example 3, and the atmosphere in the autoclave was replaced with nitrogen at room temperature. The temperature was raised to 240 ° C. When the temperature reached 240 ° C., hydrogen was injected to reach 9.8 MPa. Hydrogenation reaction was performed at this pressure for 3.5 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with ion-exchanged water. The reaction solution separated by decantation and the catalyst washing solution were combined and the conversion of adipic acid and the yield of 1,6-hexanediol were determined by analysis by liquid chromatography and gas chromatography. As a result, the conversion of adipic acid was 100%, and the yield of 1,6-hexanediol was 96%.
[0048]
【The invention's effect】
By using the catalyst of the present invention, alcohols can be obtained in high yield regardless of the type of carboxylic acid. In particular, 1,4-butanediol, 1,5-butanediol is obtained from a mixture of dicarboxylic acids including succinic acid, glutaric acid and adipic acid, which are by-products in the production of adipic acid by nitric acid oxidation of cyclohexane and / or cyclohexanol. A diol mixture containing pentanediol and 1,6-hexanediol can be produced in a high yield, which is very useful industrially.
Claims (9)
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| JP4640748B2 (en) * | 2001-07-12 | 2011-03-02 | 旭化成ケミカルズ株式会社 | Catalyst for direct hydrogenation of carboxylic acid |
| US6706658B2 (en) * | 2001-12-21 | 2004-03-16 | Engelhard Corporation | Catalyst for purification of aromatic acids |
| CN100381411C (en) * | 2002-11-01 | 2008-04-16 | 嘉吉有限公司 | Process for preparation of 1,3-propanediol |
| KR100922998B1 (en) * | 2008-03-06 | 2009-10-22 | 한국화학연구원 | Process for preparing monohydric alcohols from monocarboxylic acids or derivatives thereof |
| US9108895B2 (en) * | 2012-10-26 | 2015-08-18 | Eastman Chemical Company | Promoted ruthenium catalyst for the improved hydrogenation of carboxylic acids to the corresponding alcohols |
| JP6442956B2 (en) * | 2013-09-30 | 2018-12-26 | 三菱ケミカル株式会社 | Method for producing polycarbonate diol |
| CN114644552B (en) * | 2022-04-25 | 2023-04-14 | 中国科学院兰州化学物理研究所 | Method for preparing propionic acid by acrylic acid hydrogenation |
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