JPH08141396A - Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalyst - Google Patents
Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalystInfo
- Publication number
- JPH08141396A JPH08141396A JP6316039A JP31603994A JPH08141396A JP H08141396 A JPH08141396 A JP H08141396A JP 6316039 A JP6316039 A JP 6316039A JP 31603994 A JP31603994 A JP 31603994A JP H08141396 A JPH08141396 A JP H08141396A
- Authority
- JP
- Japan
- Prior art keywords
- silica carrier
- catalyst
- hydrogenation catalyst
- acid
- surface area
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 35
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 150000002596 lactones Chemical class 0.000 claims abstract description 5
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 18
- 239000013335 mesoporous material Substances 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 6
- -1 maleic anhydride Chemical class 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052702 rhenium Inorganic materials 0.000 description 6
- 150000003282 rhenium compounds Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- XZQYTGKSBZGQMO-UHFFFAOYSA-I Rhenium(V) chloride Inorganic materials Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VDVYHNAWVGKJMF-UHFFFAOYSA-N azane;ruthenium(3+) Chemical compound N.N.N.N.N.[Ru+3] VDVYHNAWVGKJMF-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- LVGLLYVYRZMJIN-UHFFFAOYSA-N carbon monoxide;rhodium Chemical group [Rh].[Rh].[Rh].[Rh].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] LVGLLYVYRZMJIN-UHFFFAOYSA-N 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
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZIZHEHXAMPQGEK-UHFFFAOYSA-N dirhenium decacarbonyl Chemical group [Re].[Re].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] ZIZHEHXAMPQGEK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions 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
- 150000002504 iridium compounds Chemical class 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 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
- 238000005406 washing Methods 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
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、触媒成分として第VIII
族貴金属及びReを含有する炭素数4のジカルボン酸類
の水素化反応用触媒の改良及び該触媒によるジカルボン
酸類の水素化反応方法に関するものである。詳しくは、
特定のシリカ担体に第VIII族貴金属及びReを担持した
無水マレイン酸の水素化反応用触媒及び該触媒を用いて
無水マレイン酸を水素化しテトラヒドロフランを選択的
に製造する方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to the catalyst component VIII
The present invention relates to improvement of a hydrogenation reaction catalyst for dicarboxylic acids having a carbon number of 4 and containing a group-noble metal and Re, and a method for hydrogenating a dicarboxylic acid using the catalyst. For more information,
The present invention relates to a catalyst for hydrogenation reaction of maleic anhydride in which a Group VIII noble metal and Re are supported on a specific silica carrier, and a method for hydrogenating maleic anhydride using the catalyst to selectively produce tetrahydrofuran.
【0002】[0002]
【従来の技術】従来、マレイン酸、無水マレイン酸、フ
マル酸、コハク酸、無水コハク酸のようなカルボン酸及
び無水カルボン酸類を水素化し、テトラヒドロフラン、
1,4−ブタンジオール、またはγ−ブチロラクトンを
製造するための触媒に関し、多くの提案がなされてい
る。これらの中、周期律表第VIII族の貴金属成分及
びRe成分を担体に担持して調製した触媒を用いる方法
としては、DE2715667号明細書にPd−Re/
SiO2を触媒として1、4ーブタンジオールを製造す
る方法が記載されているが、この場合メタルシリケート
を酢酸処理するという繁雑な操作によって得られたシリ
カが用いられている。2. Description of the Related Art Conventionally, carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, succinic acid and succinic anhydride have been hydrogenated to give tetrahydrofuran,
Many proposals have been made regarding catalysts for producing 1,4-butanediol or γ-butyrolactone. Among these, as a method of using a catalyst prepared by supporting a noble metal component and a Re component of Group VIII of the Periodic Table on a carrier, DE 2715667 describes Pd-Re /
A method for producing 1,4-butanediol using SiO 2 as a catalyst is described, but in this case, silica obtained by a complicated operation of treating a metal silicate with acetic acid is used.
【0003】更に、特開昭51−133212号明細書
には、パラジウム及びレニウムを珪藻土に担持した触媒
を用いて無水マレイン酸を水素化し、主生成物としてブ
タンジオールを生成したことが、又特開昭52−979
01号明細書にはパラジウムとレニウムを耐酸性担体に
担持した触媒の存在下、高温高圧でカルボン酸を水素化
してアルコールを製造することが記載されているが、い
ずれの方法においてもアルコールの選択性は高いもの
の、無水マレイン酸からγ−ブチロラクトン或いはテト
ラヒドロフランの生成は極めて低い割合である。Further, JP-A-51-133212 discloses that maleic anhydride is hydrogenated by using a catalyst in which palladium and rhenium are supported on diatomaceous earth to produce butanediol as a main product. Kaisho 52-979
No. 01 describes that an alcohol is produced by hydrogenating a carboxylic acid at high temperature and high pressure in the presence of a catalyst in which palladium and rhenium are supported on an acid-resistant carrier. However, in any method, alcohol selection is performed. However, the production of γ-butyrolactone or tetrahydrofuran from maleic anhydride is extremely low.
【0004】また、特公表平4−500813号明細書
にはPd−Re−Ag/TiO2を触媒としてγ−ブチ
ロラクトンを製造する方法が、更に米国特許46596
86号明細書にはPdとReにRh,Co、Pt等を加
えて活性炭に担持した触媒を用いてテトラヒドロフラン
を製造する方法が示されている。しかしながら、これら
の反応触媒は、生成するアルコール類、エーテル類への
選択性が比較的高いものの反応活性の点ではまだ十分満
足しうる結果が得られておらず、またいずれも高温高圧
の厳しい条件下で反応を行う必要があった。In Japanese Patent Publication No. 4-500813, a method for producing γ-butyrolactone using Pd-Re-Ag / TiO 2 as a catalyst is further disclosed in US Pat.
No. 86 discloses a method of producing tetrahydrofuran by adding Rh, Co, Pt and the like to Pd and Re and using a catalyst supported on activated carbon. However, although these reaction catalysts have relatively high selectivity to the alcohols and ethers to be produced, they have not yet been sufficiently satisfactory in terms of reaction activity, and neither of them has a severe condition of high temperature and high pressure. It was necessary to carry out the reaction below.
【0005】[0005]
【発明が解決しようとする課題】そこで、カルボン酸類
を触媒の存在下水素化するにあたり、穏和な条件で効率
よく水素化反応を進行させ、かつ目的化合物を選択的に
生成し得る水素化触媒の開発が望まれていた。本発明者
等は、第VIII族貴金属成分及びRe成分を触媒成分
として担持する担体付き水素化触媒の担体の特性につき
鋭意検討した結果、特定の物性値を有するシリカを使用
した場合には、この触媒を用いてジカルボン酸類、特に
無水マレイン酸を比較的穏和な条件で水素化反応に付す
ると、高活性でしかも選択的に所望のテトラヒドロフラ
ン及び/またはγ−ブチロラクトンのような環状化合物
を製造しうるとの新規な知見を得、本発明を達成した。Therefore, when hydrogenating carboxylic acids in the presence of a catalyst, a hydrogenation catalyst capable of efficiently advancing the hydrogenation reaction under mild conditions and selectively producing a target compound is proposed. Development was desired. The inventors of the present invention have made earnest studies on the characteristics of the carrier of the hydrogenation catalyst with a carrier that carries a Group VIII noble metal component and a Re component as catalyst components, and as a result, when silica having specific physical property values was used, When a dicarboxylic acid, particularly maleic anhydride, is subjected to a hydrogenation reaction with a catalyst under relatively mild conditions, a highly active and selective cyclic compound such as tetrahydrofuran and / or γ-butyrolactone can be produced. The present invention has been achieved by obtaining new knowledge that
【0006】[0006]
【課題を解決するための手段】本発明は、改良された第
VIII族貴金属成分及びRe成分を触媒成分として有
する担体付きカルボン酸類の水素化触媒及び該触媒を用
いて、ジカルボン酸類、特に無水マレイン酸を水素化す
る方法を提供するものであり、その要旨は、シリカ担体
上に周期律表第VIII族の貴金属成分及びRe成分が
担持され、該シリカ担体は120m2/g以上のBET
表面積を有し、且つ2.0〜45.0nmの平均細孔径
を有するか、或いは2<D(細孔径)<50nmにシャ
ープな細孔分布を有するメソ多孔体であることよりなる
ジカルボン酸類の水素化触媒及び炭素数4のジカルボン
酸、その酸無水物、そのモノ又はジ低級アルキルエステ
ル若しくはその分子内エステルから選ばれる少なくとも
1種のカルボン酸類を該水素化触媒の存在下、温度13
0〜350℃、水素圧5.0〜20.0MPaで水素化
し対応する所望の水素化物、即ち、ラクトン類及び/又
は環状エーテル類を生成することよりなるカルボン酸類
の水素化方法に存する。The present invention is directed to a hydrogenation catalyst for a carboxylic acid with a carrier having an improved Group VIII noble metal component and Re component as catalyst components, and a dicarboxylic acid, particularly maleic anhydride, using the catalyst. The present invention provides a method for hydrogenating an acid, the gist of which is to carry a noble metal component and a Re component of Group VIII of the periodic table on a silica carrier, the silica carrier having a BET of 120 m 2 / g or more.
A dicarboxylic acid compound having a surface area and an average pore diameter of 2.0 to 45.0 nm, or a mesoporous material having a sharp pore distribution in 2 <D (pore diameter) <50 nm. A hydrogenation catalyst and at least one carboxylic acid selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof, in the presence of the hydrogenation catalyst at a temperature of 13
A method for hydrogenating carboxylic acids comprises hydrogenating at 0 to 350 ° C. and a hydrogen pressure of 5.0 to 20.0 MPa to produce the corresponding desired hydride, that is, lactones and / or cyclic ethers.
【0007】以下、本発明を詳細に説明する。本発明の
水素化触媒の担体は、120m2/g以上のBET表面
積と2.0〜45.0nmの細孔径を有するシリカであ
る。BET表面積は好ましくは120〜1250m2/
g,より好ましくは180〜1250m2/gの範囲で
ある。特に、無水マレイン酸の水素化反応では、一般的
にシリカ担体の表面積を大きくするに従ってテトラヒド
ロフランの生成を増すことになるが、表面積が230m
2/g以上のシリカ担体を用いて無水マレイン酸を水素
化した場合、平均細孔径がほぼ同程度であってもより小
さい表面積のシリカ担体を使用した場合に比べテトラヒ
ドロフランの収率をより一層高めることができるので、
目的に応じ担体を選定して使用すれば良い。Hereinafter, the present invention will be described in detail. The carrier of the hydrogenation catalyst of the present invention is silica having a BET surface area of 120 m 2 / g or more and a pore size of 2.0 to 45.0 nm. BET surface area is preferably 120-1250 m 2 /
g, more preferably 180 to 1250 m 2 / g. In particular, in the hydrogenation reaction of maleic anhydride, the production of tetrahydrofuran generally increases as the surface area of the silica carrier increases, but the surface area of 230 m
When maleic anhydride is hydrogenated using a silica carrier of 2 / g or more, the yield of tetrahydrofuran is further increased as compared with the case where a silica carrier having a smaller surface area is used even if the average pore size is almost the same. Because you can
A carrier may be selected and used according to the purpose.
【0008】また、平均細孔径は、2.0〜45.0n
m、好ましくは2.0〜30.0nmの範囲である。こ
の範囲のシリカを用いると触媒金属成分が高分散に担持
され、有効な反応場を形成することができる。これらの
シリカ担体は、表面積及び平均細孔径の上記要件を満た
す限り、市販品の中から選択使用することが出来る。The average pore diameter is 2.0 to 45.0n.
m, preferably in the range of 2.0 to 30.0 nm. When silica in this range is used, the catalytic metal component is supported in a highly dispersed state and an effective reaction field can be formed. These silica carriers can be selected and used from commercial products as long as they satisfy the above requirements of surface area and average pore size.
【0009】更に、担体として6方構造のメソ多孔体シ
リカを使用することができる。メソ多孔体はマクロポー
ラスとミクロポーラスの中間に位置する多孔体でその細
孔径(D)が2<D(細孔径)<50nmの範囲に存す
るものであり、ゼオライトよりもはるかに大きい細孔を
有している。メソ多孔体の例として、メソ孔領域(2<
D<50nm)にシャープな細孔分布を持つメソ多孔体
FSM−16が知られている(「触媒」Vol.36 No.2
p.131 1994;73rd CATSJ Meeting Abstracts;No.1
B12)。これらは、その製造条件によって多少の違いは
あるが、BET表面積が1000m2/g程度あり、ゼ
オライトよりも大きな細孔を持つため、担体として用い
た場合、細孔内部への金属の担持が可能であり、高分散
の触媒を得ることができる。Further, mesoporous silica having a hexagonal structure can be used as a carrier. The mesoporous material is a porous material located between macroporous and microporous and has a pore diameter (D) in the range of 2 <D (pore diameter) <50 nm, and has pores much larger than zeolite. Have As an example of the mesoporous material, the mesopore region (2 <
A mesoporous material FSM-16 having a sharp pore distribution at D <50 nm is known (“Catalyst” Vol. 36 No. 2).
p.131 1994 ; 73rd CATSJ Meeting Abstracts ; No.1
B12). These have a BET surface area of about 1000 m 2 / g and have pores larger than zeolite, although they may vary depending on the production conditions. Therefore, when used as a carrier, it is possible to support metals inside the pores. Therefore, a highly dispersed catalyst can be obtained.
【0010】この様なメソ多孔体シリカは、例えば上記
(「触媒」Vol.36 No.2 p.131 1994;73rd CATSJ
Meeting Abstracts;No.1B12)に記載されている様な
公知の方法で合成することができる。即ち、層間にNa
イオンを持つ単層のシリケートシート[(Si2O5)2-
=]から構成されている層状化合物であるカネマイト
(NaHSi2O5・3H2O)の層間Naイオンをヘキ
サデシルトリメチルアンモニウム等のアルキルトリメチ
ルアンモニウムでイオン交換させると、アルキルトリメ
チルアンモニウムは層間に侵入し、単層のシリケートシ
ートと安定な複合体が形成される。次いで、これを焼成
してシラノール基の脱水縮合により層間が架橋された三
次元骨格の6方構造のメソ多孔体(FSM−16)を取
得することができる。このシリカ多孔体は、BET表面
積及び細孔容積がそれぞれ1220m2/g,1.0m
l/gであり、3nmを中心とした均一の細孔分布を示
している。又、この方法によりメソ多孔体を製造するに
当たり、アルキルトリメチルアンモニウムのアルキルの
種類を変えることにより孔径を変化させ、所望の多孔体
シリカを調製することが出来るが、通常アルキル基とし
ては、炭素数8〜20程度のものが使用される。Such mesoporous silica is described, for example, in the above (“Catalyst” Vol. 36 No. 2 p. 131 1994; 73rd CATSJ).
It can be synthesized by a known method as described in Meeting Abstracts; No. 1B12). That is, Na between the layers
Single layer silicate sheet with ions [(Si 2 O 5 ) 2-
= ] When the interlayer Na ion of kanemite (NaHSi 2 O 5 · 3H 2 O), which is a layered compound composed of , A single layer silicate sheet and a stable composite are formed. Next, this is calcined to obtain a mesoporous material (FSM-16) having a hexagonal structure with a three-dimensional skeleton whose layers are crosslinked by dehydration condensation of silanol groups. This silica porous material has a BET surface area and a pore volume of 1220 m 2 / g and 1.0 m, respectively.
1 / g, showing a uniform pore distribution centered on 3 nm. Further, in producing a mesoporous material by this method, it is possible to change the pore size by changing the type of alkyl of alkyltrimethylammonium and prepare a desired porous silica. About 8 to 20 are used.
【0011】シリカ担体の形状は限定されず、粉末状、
顆粒状、粒状、更にはペレット、錠剤、桿状等の成形品
であっても良く、触媒を適用する水素化反応方式により
任意に選ばれる。本発明水素化触媒、特に無水マレイン
酸の水素化触媒に於いては、その反応活性を高めるため
にシリカ担体の表面積を大きくすることが有効であり、
表面積の増大は同時にテトラヒドロフランの選択性をも
増やす傾向がある。本発明では、高い反応活性とテトラ
ヒドロフランへの選択性を維持するために触媒担体の表
面積と平均細孔径を特定の範囲に制御するのであり、本
発明触媒を用いれば、高い反応率で無水マレイン酸の水
素化を行うことが出来、その水素化生成物は環状構造が
維持されたテトラヒドロフラン及びその中間体でもある
γ−ブチロラクトンであり、開環反応によるアルコール
類は極めて僅かである。The shape of the silica carrier is not limited and may be powder or
It may be in the form of granules, granules, pellets, tablets, rods, or the like, and is arbitrarily selected depending on the hydrogenation reaction system in which a catalyst is applied. In the hydrogenation catalyst of the present invention, particularly in the hydrogenation catalyst of maleic anhydride, it is effective to increase the surface area of the silica carrier in order to increase its reaction activity.
Increasing the surface area tends to increase the selectivity of tetrahydrofuran at the same time. In the present invention, in order to maintain high reaction activity and selectivity to tetrahydrofuran, the surface area and average pore diameter of the catalyst carrier are controlled within a specific range, and with the catalyst of the present invention, maleic anhydride is used at a high reaction rate. Can be hydrogenated, and its hydrogenated product is tetrahydrofuran in which the cyclic structure is maintained and γ-butyrolactone which is also an intermediate thereof, and the number of alcohols by the ring-opening reaction is extremely small.
【0012】本発明の水素化触媒は、上記のシリカ担体
を用いそれ自体公知の方法により製造することが出来、
例えば次の方法が挙げられ、これらの方法を適宜採用す
れば良い。 1)加熱分解可能なVIII族の貴金属化合物或いはレ
ニウム化合物を含む溶液を、個々に又は同時にシリカに
含浸し、乾燥、還元する方法。 2)VIII族の貴金属化合物をシリカにイオン交換
し、乾燥、還元した後、レニウム化合物溶液を含浸し、
乾燥、還元する方法。 3)VIII族の貴金属化合物及びレニウム化合物をシ
リカと物理的に混合した後、乾燥、還元する方法。The hydrogenation catalyst of the present invention can be produced by a method known per se using the above silica carrier.
For example, the following methods may be mentioned, and these methods may be appropriately adopted. 1) A method of impregnating silica with a solution containing a group VIII noble metal compound or rhenium compound that can be decomposed by heating, and drying and reducing the same. 2) Ion-exchange the noble metal compound of group VIII with silica, dry and reduce it, and then impregnate it with a rhenium compound solution,
How to dry and reduce. 3) A method of physically mixing a noble metal compound of Group VIII and a rhenium compound with silica, followed by drying and reduction.
【0013】本発明水素化触媒に触媒成分として使用さ
れる周期律表第VIII族の貴金属化合物及びレニウム
化合物としては、触媒調製に際し加熱分解可能なもので
あれば特に制限はない。VIII族の貴金属化合物とし
てはパラジウム、ルテニウム、ロジウム、白金及びイリ
ジウムの化合物が挙げられ、これらは単独でも2種類以
上を組み合わせて用いることも出来る。パラジウム化合
物としては、具体的には塩化パラジウム、硝酸パラジウ
ム、硫酸パラジウム等の無機塩、酢酸パラジウム、パラ
ジウムアセチルアセトナート等の有機化合物、テトラア
ンミンパラジウムクロリド等の配位化合物が挙げられ
る。ルテニウム化合物としては、塩化ルテニウム、硝酸
ルテニウムニトロシル等の無機塩、ルテニウムアセチル
アセトナート等の有機化合物、ペンタアンミンルテニウ
ムクロリド、トリルテニウムドデカカルボニル等の配位
化合物が挙げられ、ロジウム化合物としては、塩化ロジ
ウム、硝酸ロジウム、硫酸ロジウム等の無機塩、ロジウ
ムアセチルアセトナート等の有機化合物、テトラロジウ
ムドデカカルボニル等の配位化合物が挙げられる。The noble metal compound and rhenium compound of Group VIII of the periodic table used as a catalyst component in the hydrogenation catalyst of the present invention are not particularly limited as long as they can be decomposed by heat during catalyst preparation. Examples of the Group VIII noble metal compound include compounds of palladium, ruthenium, rhodium, platinum and iridium, and these may be used alone or in combination of two or more kinds. Specific examples of the palladium compound include inorganic salts such as palladium chloride, palladium nitrate and palladium sulfate, organic compounds such as palladium acetate and palladium acetylacetonate, and coordination compounds such as tetraammine palladium chloride. Examples of ruthenium compounds include inorganic salts such as ruthenium chloride and ruthenium nitrosyl nitrate, organic compounds such as ruthenium acetylacetonate, coordination compounds such as pentaammine ruthenium chloride and triruthenium dodecacarbonyl, and examples of rhodium compounds include rhodium chloride. Inorganic salts such as rhodium nitrate and rhodium sulfate, organic compounds such as rhodium acetylacetonate, and coordination compounds such as tetrarhodium dodecacarbonyl.
【0014】また、白金化合物としては、塩化白金酸、
塩化白金酸ナトリウム等の酸及び無機塩、白金アセチル
アセトナート等の有機化合物、テトラアンミンプラチニ
ウムクロリド等の配位化合物が挙げられ、イリジウム化
合物としては、塩化イリジウム、塩化イリジウム酸等の
酸及び無機塩、イリジウムアセチルアセトナート等の有
機化合物、テトライリジウムドデカカルボニル等の配位
化合物が挙げられる。これらの貴金属化合物の中では、
特にパラジウム化合物が好適に用いられる。As the platinum compound, chloroplatinic acid,
Acids such as sodium chloroplatinate and inorganic salts, organic compounds such as platinum acetylacetonate, coordination compounds such as tetraammineplatinium chloride, and the like, examples of iridium compounds include iridium chloride, iridium chloride and other acids and inorganic salts. , Organic compounds such as iridium acetylacetonate, and coordination compounds such as tetriridium dodecacarbonyl. Among these precious metal compounds,
Particularly, a palladium compound is preferably used.
【0015】レニウム化合物としては、七酸化二レニウ
ム、過レニウム酸、過レニウム酸アンモニウム、塩化レ
ニウム等の無機塩や酸類、ジレニウムデカカルボニル等
の配位化合物等が挙げられる。Examples of the rhenium compound include inorganic salts such as dirhenium heptaoxide, perrhenic acid, ammonium perrhenate and rhenium chloride, acids, and coordination compounds such as dirhenium decacarbonyl.
【0016】金属触媒成分の担持量には特に制限はない
が、少ないと十分な触媒効果が達成されず、他方必要以
上に多すぎるのは経済的に不利となる。通常、VIII
族貴金属は、金属として0.1〜20重量%、好ましく
は1〜10重量%であり、レニウムは、0.1〜20重
量%、好ましくは0.1〜10重量%含まれているのが
望ましい。The amount of the metal catalyst component supported is not particularly limited, but if it is small, a sufficient catalytic effect cannot be achieved, while if it is larger than necessary, it is economically disadvantageous. Usually VIII
The group noble metal is 0.1 to 20% by weight, preferably 1 to 10% by weight, and the rhenium is 0.1 to 20% by weight, preferably 0.1 to 10% by weight. desirable.
【0017】本発明の水素化触媒は、好ましくはVII
I族貴金属化合物及びレニウム化合物を、適当な溶媒、
例えば水、メタノール等に溶解して、上記シリカに含浸
させた後還元する。還元は、通常、水素、メタノール、
ホルムアルデヒド等のガス又は還元性蒸気により、10
0〜700℃で気相で行われるが、ヒドラジン等で還元
する場合は液層でも行うことができる。工業的には、水
素ガスが使用されるが、水素は純粋なものでも、窒素、
アルゴン等の不活性ガスで希釈されていても良い。The hydrogenation catalyst of the present invention is preferably VII.
Group I noble metal compound and rhenium compound in a suitable solvent,
For example, it is dissolved in water, methanol or the like, impregnated in the silica and then reduced. The reduction is usually hydrogen, methanol,
10 with gas such as formaldehyde or reducing vapor
It is carried out in a gas phase at 0 to 700 ° C., but when it is reduced with hydrazine or the like, it can also be carried out in a liquid layer. Industrially, hydrogen gas is used, but even if hydrogen is pure, nitrogen,
It may be diluted with an inert gas such as argon.
【0018】本発明の水素化触媒を使用してカルボン酸
類の水素化反応を行うが、水素化反応に供されるカルボ
ン酸類としては、炭素数4のジカルボン酸、その酸無水
物、そのモノ又はジ低級アルキルエステル並びにその分
子内エステルから選ばれる。炭素数4のジカルボン酸及
びその酸無水物としては、具体的には、マレイン酸、フ
マル酸、無水フマル酸、無水マレイン酸が挙げられる
が、これらの中、特にマレイン酸及びその酸無水物が好
ましい。炭素数4のジカルボン酸のモノ又はジ低級アル
キルエステルのエステルを構成するアルコールは特に限
定されず、メタノール、エタノール、プロパノール、ブ
タノール等の炭素数1〜5の低級アルコールが好まし
い。また、分子内エステルはラクトンであり、具体的に
はγ−ブチロラクトンである。本発明の水素化方法で
は、原料の環状構造を開環することなく環状構造の水素
化物を生成し得るので、これらのカルボン酸類の中、ジ
カルボン酸の酸無水物である無水マレイン酸が最も有効
な出発原料である。The hydrogenation reaction of carboxylic acids is carried out using the hydrogenation catalyst of the present invention. The carboxylic acids to be subjected to the hydrogenation reaction include dicarboxylic acids having 4 carbon atoms, their acid anhydrides, their mono or It is selected from di-lower alkyl esters and their intramolecular esters. Specific examples of the dicarboxylic acid having 4 carbon atoms and its acid anhydride include maleic acid, fumaric acid, fumaric anhydride, and maleic anhydride. Among them, maleic acid and its acid anhydride are particularly preferable. preferable. The alcohol constituting the ester of mono- or di-lower alkyl ester of dicarboxylic acid having 4 carbon atoms is not particularly limited, and lower alcohol having 1 to 5 carbon atoms such as methanol, ethanol, propanol and butanol is preferable. The intramolecular ester is a lactone, specifically, γ-butyrolactone. In the hydrogenation method of the present invention, a hydride having a cyclic structure can be produced without ring-opening the cyclic structure of the raw material. Therefore, among these carboxylic acids, maleic anhydride, which is an acid anhydride of dicarboxylic acid, is most effective. It is a good starting material.
【0019】本発明の水素化反応の条件は、原料カルボ
ン酸類の種類及び触媒の活性によっても異なるが、通
常、温度130〜350℃、好ましくは160〜300
℃、水素圧1.00〜30.0MPa、好ましくは5.
0〜20.0MPaの範囲で選定される。水素化反応に
使用される触媒量は、ジカルボン酸等の反応原料100
重量部に対し、0.1〜100重量部であることが望ま
しいが、反応温度また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おいて任意に選択さ
れる。The conditions of the hydrogenation reaction of the present invention vary depending on the kind of the starting carboxylic acid and the activity of the catalyst, but the temperature is usually 130 to 350 ° C., preferably 160 to 300.
C., hydrogen pressure 1.00 to 30.0 MPa, preferably 5.
It is selected in the range of 0 to 20.0 MPa. The amount of catalyst used in the hydrogenation reaction is 100% of the reaction raw material such as dicarboxylic acid.
The amount is preferably 0.1 to 100 parts by weight with respect to parts by weight, but is arbitrarily selected within the range where a practical reaction rate can be obtained according to various conditions such as reaction temperature or reaction pressure.
【0020】水素化反応に使用される水素は、通常工業
的に使用される純度のものであるが、場合により窒素等
の不活性ガスで希釈したものも使用できる。また、使用
量は原料カルボン酸類に対し、一般には化学量論量より
過剰に用いられる。The hydrogen used in the hydrogenation reaction has a purity that is usually used industrially, but hydrogen diluted with an inert gas such as nitrogen may also be used as the case may be. Further, the amount used is generally in excess of the stoichiometric amount with respect to the raw material carboxylic acids.
【0021】反応方式としては液相懸濁床あるいは固定
床のいずれも採用できる。懸濁床の場合、反応終了後の
触媒と反応液との分離は、通常用いられる手法、例えば
デカンテーションや濾過等により容易に行うことができ
る。また、連続法においては、例えば、トリクルベッド
方式等で行われ、原料ジカルボン酸類は溶融又は反応溶
媒の溶液として反応槽に供給される。得られた反応液か
らの目的物の生成分離は、通常工業的に用いられている
方法、例えば蒸留等によって容易に行うことができる。As the reaction system, either a liquid phase suspension bed or a fixed bed can be adopted. In the case of a suspension bed, the separation of the catalyst and the reaction solution after completion of the reaction can be easily performed by a commonly used method such as decantation or filtration. In the continuous method, for example, a trickle bed method or the like is used, and the raw material dicarboxylic acid is melted or supplied to the reaction tank as a solution of a reaction solvent. The target product can be easily separated from the obtained reaction solution by a method generally used in industry, such as distillation.
【0022】水素化反応は、無溶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ものであれば良
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、エチレ
ングリコ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挙げられる。The hydrogenation reaction may be carried out without a solvent,
A solvent may be used if necessary. When using a solvent,
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, dodecanol and ethylene glycol; tetrahydrofuran,
Ethers such as dioxane and tetraethylene glycol dimethyl ether; and hydrocarbons such as hexane, cyclohexane and decalin.
【0023】本発明の水素化反応によって得られる生成
物は、原料ジカルボン酸の種類によって異なるが、主と
してラクトン或いは環状エーテル等であり、僅かのアル
コール類も得られる。本発明水素化方法は、特に無水マ
レイン酸の水素化反応に有効であり、本発明方法によれ
ば、マレイン酸の転化率が高く、しかも高い選択率でテ
トラヒドロフランを生成することが出来、ブタンジオー
ル及びブチルアルコール等のアルコール類の生成は僅か
である。更に、水素化反応触媒として、シリカ担体のB
ET表面積を比較的大きくし、その平均細孔径をより小
さくすれば、主生成物であるテトラヒドロフランと共に
γ−ブチロラクトンをある割合で生成することができ
る。The product obtained by the hydrogenation reaction of the present invention is mainly a lactone or a cyclic ether, although it depends on the kind of the starting dicarboxylic acid, and a small amount of alcohols can be obtained. INDUSTRIAL APPLICABILITY The hydrogenation method of the present invention is particularly effective for the hydrogenation reaction of maleic anhydride. According to the method of the present invention, the conversion rate of maleic acid is high, and tetrahydrofuran can be produced with a high selectivity. The production of alcohols such as and butyl alcohol is slight. Further, as a hydrogenation reaction catalyst, B of a silica carrier is used.
If the ET surface area is made relatively large and the average pore size is made smaller, γ-butyrolactone can be produced in a certain ratio together with the main product, tetrahydrofuran.
【0024】[0024]
【実施例】以下、本発明を実施例により更に具体的に説
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、以下の実施例及
び比較例において、%は重量%を示す。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the following Examples and Comparative Examples,% means% by weight.
【0025】実施例1〜5 触媒の調製 シリカ担体として、富士デヴィソン化学社製;GRAD
E#12(実施例1)、Cariact Q−6(実施
例2)、洞海化学社製;D−150−200A(実施例
3)、D−150−300A(実施例4)を使用した。
またメソ多孔体シリカとしては(「触媒」Vol.36 No.2
p.131 1994;73rd CATSJ Meeting Abstracts;N
o.1B12)に記載されている方法に準じて次ぎのように合
成した。即ち、50gのカネマイトを0.1Mのヘキサデ
シルトリメチルアンモニウムクロライド水溶液1000mlに
分散させ、60〜70℃で3時間加熱した。室温に冷却後、
固形生成物を濾別し、水1000mlに入れpHを8.5に調整
した。固形物を分離後、十分洗浄し、乾燥した後、550
℃で6時間焼成した。これをFSM−16(実施例5)
として使用した。塩化パラジウム33.3mgと七酸化
二レニウム78mgを5N塩酸水溶液0.86mlに溶
解し、この溶液に上記各シリカ1.92gを加えて含浸
させ、次いで回転減圧乾燥機で水を留去した。その後、
真空中、100℃で2時間乾燥させた後、水素雰囲気
下、300℃で2時間還元して1%Pd−3%Re/シ
リカの触媒を得た。Examples 1 to 5 Preparation of Catalyst As a silica carrier, manufactured by Fuji Davisson Chemical Co .; GRAD
E # 12 (Example 1), Cariact Q-6 (Example 2), Dokai Chemical Co., Ltd .; D-150-200A (Example 3), D-150-300A (Example 4) were used.
As for mesoporous silica (“Catalyst” Vol.36 No.2
p.131 1994 ; 73rd CATSJ Meeting Abstracts ; N
O.1B12) was synthesized according to the method described below. That is, 50 g of kanemite was dispersed in 1000 ml of a 0.1 M hexadecyltrimethylammonium chloride aqueous solution and heated at 60 to 70 ° C. for 3 hours. After cooling to room temperature,
The solid product was filtered off and put into 1000 ml of water to adjust the pH to 8.5. After separating the solid, thoroughly washing and drying, 550
It was calcined at ℃ for 6 hours. This is FSM-16 (Example 5)
Used as. 33.3 mg of palladium chloride and 78 mg of dirhenium heptaoxide were dissolved in 0.86 ml of a 5N aqueous hydrochloric acid solution, and 1.92 g of each silica was added to the solution to impregnate it, and then water was distilled off with a rotary vacuum dryer. afterwards,
After drying in vacuum at 100 ° C. for 2 hours, it was reduced in a hydrogen atmosphere at 300 ° C. for 2 hours to obtain a catalyst of 1% Pd-3% Re / silica.
【0026】水素化反応 無水マレイン酸2gを水8gに溶解し、上記方法で調製
した各触媒0.2gを70mlスピナー攪拌オートクレ
ーブに仕込み、室温下9.8MPaの水素を圧入し、2
40℃で2時間反応を行った。反応生成物につきガスク
ロマトグラフィーで分析を行った結果を、担体の物性値
とともに表−1に示す。Hydrogenation reaction 2 g of maleic anhydride was dissolved in 8 g of water, and 0.2 g of each catalyst prepared by the above method was charged into a 70 ml spinner stirring autoclave.
The reaction was carried out at 40 ° C for 2 hours. The results of gas chromatography analysis of the reaction products are shown in Table 1 together with the physical properties of the carrier.
【0027】比較例1〜2 シリカ担体として、富士デヴィソン化学社製;Cari
act−30(比較例1)、Cariact−50(比
較例2)を用い、実施例と同様にして触媒を調製し、水
素化反応を行った。その結果を表−1に示す。Comparative Examples 1-2 Silica carriers manufactured by Fuji Davisson Chemical Co .; Cari
Using act-30 (Comparative Example 1) and Cariact-50 (Comparative Example 2), a catalyst was prepared in the same manner as in Example, and a hydrogenation reaction was carried out. The results are shown in Table-1.
【0028】[0028]
【表1】 [Table 1]
【0029】[0029]
【発明の効果】本発明の周期律表第VIII族の貴金属
成分及びレニウム成分を特定の物性、即ち、120m2
/g以上のBET表面積を有し、且つ2.0〜45.0
nmの平均細孔径を有するか、或いは2<D(細孔径)
<50nmにシャープな細孔分布を有するメソ多孔体か
らなるシリカに担持した固体触媒を用いて炭素数4のジ
カルボン酸類、とくに無水マレイン酸の水素化反応を行
えば、従来法に比べ穏和な条件で高転換率で所望のテト
ラヒドロフランを選択率良く生成することができる。INDUSTRIAL APPLICABILITY The noble metal component and rhenium component of Group VIII of the periodic table of the present invention have specific physical properties, that is, 120 m 2
BET surface area of / g or more and 2.0 to 45.0
have an average pore size of nm, or 2 <D (pore size)
If hydrogenation of dicarboxylic acids having 4 carbon atoms, especially maleic anhydride, is carried out using a solid catalyst supported on silica composed of a mesoporous material having a sharp pore distribution at <50 nm, milder conditions will be obtained than conventional methods. The desired tetrahydrofuran can be produced with high selectivity at high conversion.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 // C07B 61/00 300 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C07B 61/00 300
Claims (10)
貴金属成分及びRe成分が担持され、且つ該シリカ担体
が120m2/g以上のBET表面積及び2.0〜4
5.0nmの平均細孔径を有することを特徴とする炭素
数4のジカルボン酸、その酸無水物、そのモノ又はジ低
級アルキルエステル若しくはその分子内エステルから選
ばれるカルボン酸類の水素化触媒。1. A noble metal component and a Re component of Group VIII of the periodic table are supported on a silica carrier, and the silica carrier has a BET surface area of 120 m 2 / g or more and 2.0-4.
A hydrogenation catalyst for a carboxylic acid selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof, which has an average pore diameter of 5.0 nm.
250m2/gの範囲であることを特徴とする請求項1
記載の水素化触媒。2. The BET surface area of the silica carrier is 120 to 1.
2. The range is 250 m 2 / g.
The hydrogenation catalyst described.
0.0nmの範囲であることを特徴とする請求項1又は
2記載の水素化触媒。3. The silica carrier has an average pore diameter of 2.0 to 3.
The hydrogenation catalyst according to claim 1 or 2, which has a range of 0.0 nm.
貴金属成分及びRe成分が担持され、且つ該シリカ担体
が120m2/g以上のBET表面積及び2.0〜4
5.0nmの平均細孔径を有することを特徴とするマレ
イン酸又はその酸無水物の水素化によるテトラヒドロフ
ラン製造用触媒。4. A noble metal component and a Re component of Group VIII of the Periodic Table are supported on a silica carrier, and the silica carrier has a BET surface area of 120 m 2 / g or more and 2.0-4.
A catalyst for producing tetrahydrofuran by hydrogenating maleic acid or its acid anhydride, which has an average pore diameter of 5.0 nm.
貴金属成分及びRe成分が担持され、該シリカ担体が1
20m2/g以上のBET表面積を有し、且つ2<D
(細孔径)<50nmにシャープな細孔分布を有するメ
ソ多孔体であることを特徴とする炭素数4のジカルボン
酸、その酸無水物、そのモノ又はジ低級アルキルエステ
ル若しくはその分子内エステルから選ばれるカルボン酸
類の水素化触媒。5. A noble metal component and a Re component of Group VIII of the Periodic Table are supported on a silica carrier, and the silica carrier is 1
BET surface area of 20 m 2 / g or more and 2 <D
(Pore diameter) <40 nm, which is a mesoporous material having a sharp pore distribution, and is selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof. Hydrogenation catalyst for carboxylic acids.
250m2/gの範囲であることを特徴とする請求項5
記載の水素化触媒。6. The BET surface area of the silica carrier is 120 to 1.
6. The range is 250 m 2 / g.
The hydrogenation catalyst described.
オンを、アルキルトリメチルアンモニウムでイオン交換
させ、単層のシリケートシートとアルキルトリメチルア
ンモニウムとの安定な複合体を形成させた後、該複合体
を焼成して得られる2<D(細孔径)<50nmにシャ
ープな細孔分布を有するメソ多孔体であることを特徴と
する請求項5又は6記載の水素化触媒。7. A silica carrier exchanges intercalated Na ions of kanemite with alkyltrimethylammonium to form a stable composite of a monolayer silicate sheet and alkyltrimethylammonium, and then calcinates the composite. The hydrogenation catalyst according to claim 5, which is a mesoporous material having a sharp pore distribution in 2 <D (pore diameter) <50 nm obtained by the above.
貴金属成分及びRe成分が担持され、該シリカ担体が1
20m2/g以上のBET表面積を有し、且つ2<D
(細孔径)<50nmにシャープな細孔分布を有するメ
ソ多孔体であることを特徴とするマレイン酸又はその酸
無水物の水素化によるテトラヒドロフラン製造用触媒。8. A noble metal component and a Re component of Group VIII of the Periodic Table are supported on a silica carrier, and the silica carrier is 1
BET surface area of 20 m 2 / g or more and 2 <D
A catalyst for producing tetrahydrofuran by hydrogenation of maleic acid or its acid anhydride, which is a mesoporous material having a sharp pore distribution in (pore diameter) <50 nm.
物、そのモノ又はジ低級アルキルエステル若しくはその
分子内エステルから選ばれる少なくとも1種のカルボン
酸類を請求項1又は5記載の水素化触媒の存在下、温度
130〜350℃、水素圧5.0〜20.0MPaで水
素化し、ラクトン類及び/又は環状エーテル類を生成す
ることを特徴とするカルボン酸類の水素化方法。9. The hydrogenation catalyst according to claim 1, wherein at least one carboxylic acid selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof is used. A method for hydrogenating carboxylic acids, which comprises hydrogenating in the presence of a temperature of 130 to 350 ° C. and a hydrogen pressure of 5.0 to 20.0 MPa to produce lactones and / or cyclic ethers.
を請求項4又は8記載の触媒の存在下、温度130〜3
50℃、水素圧5.0〜20.0MPaで水素化するこ
とを特徴とするテトラヒドロフランの製造方法。10. Maleic acid and / or maleic anhydride in the presence of the catalyst according to claim 4 or 8 at a temperature of 130-3.
A method for producing tetrahydrofuran, which comprises hydrogenating at 50 ° C. and a hydrogen pressure of 5.0 to 20.0 MPa.
Priority Applications (1)
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---|---|---|---|
JP6316039A JPH08141396A (en) | 1994-11-28 | 1994-11-28 | Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6316039A JPH08141396A (en) | 1994-11-28 | 1994-11-28 | Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH08141396A true JPH08141396A (en) | 1996-06-04 |
Family
ID=18072588
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP6316039A Withdrawn JPH08141396A (en) | 1994-11-28 | 1994-11-28 | Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalyst |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002010147A1 (en) * | 2000-07-27 | 2002-02-07 | Sk Corporation | CONTINUOUS PROCESS FOR THE PRODUCTION OF OPTICALLY PURE (S)-β-HYDROXY-η-BUTYROLACTONE |
JP2003516438A (en) * | 1999-12-08 | 2003-05-13 | ダウ グローバル テクノロジーズ インコーポレーテッド | Method for hydrogenating unsaturated polymers |
JP2013017922A (en) * | 2011-07-08 | 2013-01-31 | Daicel Corp | Iridium-rhenium solid catalyst |
-
1994
- 1994-11-28 JP JP6316039A patent/JPH08141396A/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003516438A (en) * | 1999-12-08 | 2003-05-13 | ダウ グローバル テクノロジーズ インコーポレーテッド | Method for hydrogenating unsaturated polymers |
WO2002010147A1 (en) * | 2000-07-27 | 2002-02-07 | Sk Corporation | CONTINUOUS PROCESS FOR THE PRODUCTION OF OPTICALLY PURE (S)-β-HYDROXY-η-BUTYROLACTONE |
JP2013017922A (en) * | 2011-07-08 | 2013-01-31 | Daicel Corp | Iridium-rhenium solid catalyst |
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