JP2549799B2 - Catalyst for producing carbonic acid diester and method for producing carbonic acid diester using the same - Google Patents
Catalyst for producing carbonic acid diester and method for producing carbonic acid diester using the sameInfo
- Publication number
- JP2549799B2 JP2549799B2 JP4171331A JP17133192A JP2549799B2 JP 2549799 B2 JP2549799 B2 JP 2549799B2 JP 4171331 A JP4171331 A JP 4171331A JP 17133192 A JP17133192 A JP 17133192A JP 2549799 B2 JP2549799 B2 JP 2549799B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonic acid
- catalyst
- acid diester
- porous carrier
- producing
- 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 77
- 150000004650 carbonic acid diesters Chemical class 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000010949 copper Substances 0.000 claims description 49
- -1 copper halide Chemical class 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000002903 organophosphorus compounds Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000010574 gas phase reaction Methods 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 229960003280 cupric chloride Drugs 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 150000004699 copper complex Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 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
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
- PIZLBWGMERQCOC-UHFFFAOYSA-N dibenzyl carbonate Chemical compound C=1C=CC=CC=1COC(=O)OCC1=CC=CC=C1 PIZLBWGMERQCOC-UHFFFAOYSA-N 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- YPBHRLSWEVCXBV-UHFFFAOYSA-N dicyclobutyl carbonate Chemical compound C1CCC1OC(=O)OC1CCC1 YPBHRLSWEVCXBV-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- AJHQRWJZHVBYLU-UHFFFAOYSA-N dicyclopentyl carbonate Chemical compound C1CCCC1OC(=O)OC1CCCC1 AJHQRWJZHVBYLU-UHFFFAOYSA-N 0.000 description 1
- IBVLDEJBDWVBQY-UHFFFAOYSA-N dicyclopropyl carbonate Chemical compound C1CC1OC(=O)OC1CC1 IBVLDEJBDWVBQY-UHFFFAOYSA-N 0.000 description 1
- OKQDSOXFNBWWJL-UHFFFAOYSA-N dihexyl carbonate Chemical compound CCCCCCOC(=O)OCCCCCC OKQDSOXFNBWWJL-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【0001】[0001]
【発明の技術分野】本発明は、炭酸ジエステル製造用触
媒およびこれを用いる炭酸ジエステルの製造方法に関
し、さらに詳しくは、アルコールを一酸化炭素および酸
素と反応させて炭酸ジエステルを製造するに際して長期
間に亘り活性を維持しうるような炭酸ジエステル製造用
触媒およびこれを用いた炭酸ジエステルの製造方法に関
する。TECHNICAL FIELD The present invention relates to a catalyst for producing a carbonic acid diester and a method for producing a carbonic acid diester using the catalyst, and more specifically, to reacting an alcohol with carbon monoxide and oxygen to produce a carbonic acid diester for a long period of time. TECHNICAL FIELD The present invention relates to a catalyst for producing a carbonic acid diester capable of maintaining activity for a long time and a method for producing a carbonic acid diester using the same.
【0002】[0002]
【発明の技術的背景】炭酸ジメチルなどの炭酸ジエステ
ルは、ガソリンの増量剤、オクタン価向上剤、有機溶剤
として広く用いられており、また近年イソシアネート
類、ポリカーボネート類および種々の医薬品、農薬など
を製造する際にホスゲンの代替原料として用いられてお
り、その用途がますます拡大されている。BACKGROUND OF THE INVENTION Carbonic acid diesters such as dimethyl carbonate are widely used as extenders for gasoline, octane number improvers and organic solvents, and in recent years produce isocyanates, polycarbonates and various pharmaceuticals, agricultural chemicals and the like. At the same time, it is used as an alternative raw material for phosgene, and its application is expanding more and more.
【0003】この炭酸ジエステルの製造方法としては、
従来アルコール、一酸化炭素および酸素を、ハロゲン化
銅系触媒の存在下に液相で反応させる液相法が知られて
いる。さらにこの液相法を改良するものとして、銅系ま
たはパラジウム系触媒が種々研究されている。The method for producing this carbonic acid diester is as follows:
A liquid phase method is known in which alcohol, carbon monoxide and oxygen are reacted in the liquid phase in the presence of a copper halide catalyst. Further, various copper-based or palladium-based catalysts have been studied to improve the liquid phase method.
【0004】しかしながらこのような液相法は、(1) 反
応中に生成する水によって著しく触媒活性が低下する、
(2) 触媒であるハロゲン化物を溶液状態で使用するため
反応装置材料が腐蝕される、(3) 反応によって得られる
反応混合物から炭酸ジエステルを分離するのに手間がか
かるとともに、反応混合物中に溶解している触媒を分離
するのが困難であるなどの問題点があった。However, in such a liquid phase method, (1) the water generated during the reaction markedly reduces the catalytic activity,
(2) Since the catalyst halide is used in solution, the reactor material is corroded, (3) It takes time to separate the carbonic acid diester from the reaction mixture obtained by the reaction, and it dissolves in the reaction mixture. There is a problem that it is difficult to separate the existing catalyst.
【0005】このような液相法に代わる方法として、炭
酸ジエステルを気相反応によって製造する方法も提案さ
れている。たとえば国際出願公開WO87/07601
号公報には、ハロゲン化銅を活性炭などの多孔質担体に
担持した触媒の存在下に、アルコール、一酸化炭素およ
び酸素を、気相で反応させて炭酸ジエステルを製造する
方法が示されている。また特開平4−89458号公報
には、白金族金属の塩化物と、鉄、銅、ビスマス、コバ
ルト、ニッケル、スズから選ばれる金属の化合物とを多
孔質担体に担持させてなる触媒たとえばPdCl2−BiC
l3/Cの存在下に、一酸化炭素と亜硝酸エステルとを気
相接触反応させることを特徴とする炭酸ジエステルの製
造方法が開示されている。As an alternative to the liquid phase method, a method of producing a carbonic acid diester by a gas phase reaction has been proposed. For example, international application publication WO87 / 07601
The publication discloses a method for producing a carbonic acid diester by reacting alcohol, carbon monoxide and oxygen in a gas phase in the presence of a catalyst in which a copper halide is supported on a porous carrier such as activated carbon. . Further, in JP-A-4-89458, a catalyst formed by supporting a chloride of a platinum group metal and a compound of a metal selected from iron, copper, bismuth, cobalt, nickel and tin on a porous carrier, such as PdCl 2 -BiC
Disclosed is a method for producing a carbonic acid diester, which comprises subjecting carbon monoxide and a nitrite ester to a gas phase catalytic reaction in the presence of l 3 / C.
【0006】しかしこれら公報に開示された触媒は、ア
ルコールの転化率が低かったり、あるいは炭酸ジエステ
ルの選択率が低いなど触媒活性が必ずしも充分ではな
く、このため炭酸ジエステルを製造するための高活性触
媒の出現が望まれていた。However, the catalysts disclosed in these publications do not necessarily have sufficient catalytic activity such as low conversion of alcohol or low selectivity of carbonic acid diester, and therefore, the high activity catalyst for producing carbonic acid diester. Was expected.
【0007】ところで本出願人は、先に国際出願公開W
O90/15791号公報において、フェニル基または
アルキル基を有する第三級有機リン化合物とハロゲン化
銅とを含有する触媒の存在下に、アルコール、一酸化炭
素および酸素を反応させることを特徴とする炭酸ジエス
テルの製造方法を提案した。この公報に開示された触媒
は、触媒成分を好ましくは活性炭などの多孔質担体に担
持させて用いられる。[0007] By the way, the applicant of the present invention has previously published the international application W
O90 / 15791, carbonic acid characterized by reacting alcohol, carbon monoxide and oxygen in the presence of a catalyst containing a copper halide and a tertiary organic phosphorus compound having a phenyl group or an alkyl group. A method for producing diester was proposed. The catalyst disclosed in this publication is preferably used by supporting a catalyst component on a porous carrier such as activated carbon.
【0008】このような炭酸ジエステル製造用触媒は、
アルコール転化率が高く、しかも炭酸ジエステル選択率
も高く高活性を有しているが、長期間に亘って高活性を
維持しうるような炭酸ジエステル製造用触媒の出現が望
まれている。Such a catalyst for producing carbonic acid diester is
Although it has a high alcohol conversion rate and a high carbonic acid diester selectivity and a high activity, the advent of a carbonic acid diester-producing catalyst capable of maintaining a high activity for a long period of time is desired.
【0009】本発明者は、上記のような従来技術に鑑み
て鋭意研究の結果、ハロゲン化銅とアルカリ金属水酸化
物またはアルカリ土類金属水酸化物とを、あるいは、ハ
ロゲン化銅とフェニル基またはアルキル基を有する第三
級有機リン化合物とを、特定の粒径を有する多孔質担体
に担持させて得られる触媒が、炭酸ジエステルを製造す
るに際して長期間に亘って高活性を示すことを見出して
本発明を完成するに至った。As a result of earnest research in view of the above-mentioned prior art, the present inventor has found that copper halide and alkali metal hydroxide or alkaline earth metal hydroxide, or copper halide and phenyl group. Further, it was found that a catalyst obtained by supporting a tertiary organic phosphorus compound having an alkyl group on a porous carrier having a specific particle size shows high activity for a long period of time when producing a carbonic acid diester. As a result, the present invention has been completed.
【0010】[0010]
【発明の目的】本発明は、アルコールを一酸化炭素およ
び酸素と反応させて炭酸ジエステルを製造するに際し
て、長期間に亘り高活性を示すような炭酸ジエステル製
造用触媒およびこれを用いる炭酸ジエステルの製造方法
を提供することを目的としている。An object of the present invention is to provide a catalyst for producing a carbonic acid diester which exhibits high activity for a long period of time when an alcohol is reacted with carbon monoxide and oxygen to produce a carbonic acid diester, and a carbonic acid diester using the same. It is intended to provide a way.
【0011】[0011]
【発明の概要】本発明に係る炭酸ジエステル製造用触媒
は、(i) ハロゲン化銅と(ii)アルカリ金属水酸化物また
はアルカリ土類金属水酸化物とが、あるいは、(i) ハロ
ゲン化銅と(iii) フェニル基またはアルキル基を有する
第三級有機リン化合物とが、粒径が1.0mm以下であ
る多孔質担体に担持されてなることを特徴としている。SUMMARY OF THE INVENTION A catalyst for producing a carbonic acid diester according to the present invention comprises (i) a copper halide and (ii) an alkali metal hydroxide or an alkaline earth metal hydroxide, or (i) a copper halide. And (iii) a tertiary organic phosphorus compound having a phenyl group or an alkyl group is supported on a porous carrier having a particle size of 1.0 mm or less.
【0012】この多孔質担体は、粒径が0.02〜1.
0mmであることが好ましい。本発明に係る炭酸ジエス
テルの製造方法は、上記のような触媒の存在下に、好ま
しくは気相反応条件下で、アルコールを一酸化炭素およ
び酸素と反応させて炭酸ジエステルを製造することを特
徴としている。This porous carrier has a particle size of 0.02-1.
It is preferably 0 mm. The method for producing a carbonic acid diester according to the present invention is characterized by reacting an alcohol with carbon monoxide and oxygen in the presence of a catalyst as described above, preferably under gas phase reaction conditions, to produce a carbonic acid diester. There is.
【0013】[0013]
【発明の具体的説明】まず本発明に係る炭酸ジエステル
製造用触媒について説明する。本発明に係る炭酸ジエス
テル製造用触媒は、アルコールを一酸化炭素および酸素
と反応させて炭酸ジエステルを製造するにためのもので
あり、(i) ハロゲン化銅と、(ii)アルカリ金属水酸化物
またはアルカリ土類金属水酸化物とが、あるいは、(i)
ハロゲン化銅と、(iii) フェニル基またはアルキル基を
有する第三級有機リン化合物とが、特定の粒径を有する
多孔質担体に担持されてなる。DETAILED DESCRIPTION OF THE INVENTION First, the catalyst for producing carbonic acid diester according to the present invention will be explained. The catalyst for producing carbonic acid diester according to the present invention is for reacting alcohol with carbon monoxide and oxygen to produce carbonic acid diester, and (i) copper halide and (ii) alkali metal hydroxide. Or alkaline earth metal hydroxide, or (i)
A copper halide and (iii) a tertiary organic phosphorus compound having a phenyl group or an alkyl group are supported on a porous carrier having a specific particle size.
【0014】このような(i) ハロゲン化銅としては、1
価または2価の銅のハロゲン化物が挙げられ、具体的
に、塩化銅(CuCl、CuCl2)、臭化銅(CuB
r、CuBr2)、沃化銅(CuI、CuI2 )、フッ化
銅が挙げられる。これらは、単独であるいは組み合わせ
て用いられる。これらのうち、ハロゲン化第二銅が好ま
しく、特に塩化第二銅(CuCl2)が好ましい。As such (i) copper halide, 1
Examples of divalent or divalent copper halides include copper chloride (CuCl, CuCl 2 ), copper bromide (CuB).
r, CuBr 2 ), copper iodide (CuI, CuI 2 ), and copper fluoride. These may be used alone or in combination. Of these, cupric halide is preferable, and cupric chloride (CuCl 2 ) is particularly preferable.
【0015】(ii)アルカリ金属水酸化物およびアルカリ
土類金属水酸化物としては、水酸化リチウム、水酸化ナ
トリウム、水酸化カリウムなどのアルカリ金属水酸化
物、水酸化バリウム、水酸化カルシウムなどのアルカリ
土類金属水酸化物が挙げられる。(Ii) Alkali metal hydroxides and alkaline earth metal hydroxides include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Examples thereof include alkaline earth metal hydroxides.
【0016】これらは、単独であるいは組み合わせて用
いられる。また(iii) フェニル基またはアルキル基を有
する第三級有機リン化合物としては、具体的に、トリフ
ェニルホスフィン、亜リン酸トリフェニル、ジメチルフ
ェニルホスフィンなどのアルキルアリールホスフィン、
亜リン酸トリメチル、亜リン酸トリエチルなどの亜リン
酸トリアルキル、リン酸トリメチル、リン酸トリエチル
などのリン酸トリアルキルなどが挙げられる。These may be used alone or in combination. Further, (iii) as the tertiary organic phosphorus compound having a phenyl group or an alkyl group, specifically, an alkylarylphosphine such as triphenylphosphine, triphenylphosphite, or dimethylphenylphosphine,
Examples thereof include trimethyl phosphite and trialkyl phosphite such as triethyl phosphite, and trialkyl phosphite such as trimethyl phosphate and triethyl phosphite.
【0017】本発明で用いられる炭酸ジエステル製造用
触媒は、上記のような(i) ハロゲン化銅と(ii)アルカリ
金属水酸化物およびアルカリ土類金属水酸化物とが、あ
るいは、(ii)ハロゲン化銅と、(iii) フェニル基または
アルキル基を有する第三級有機リン化合物とが、粒径が
1.0mm以下の多孔質担体に担持されてなる。The catalyst for producing carbonic acid diester used in the present invention comprises (i) a copper halide and (ii) an alkali metal hydroxide and an alkaline earth metal hydroxide as described above, or (ii) A copper halide and (iii) a tertiary organic phosphorus compound having a phenyl group or an alkyl group are supported on a porous carrier having a particle size of 1.0 mm or less.
【0018】この多孔質担体は、表面積が10m2/g
以上、好ましくは30〜1000m2/gであることが
望ましい。具体的に、活性炭、酸化チタン、酸化ニオ
ブ、シリカ、酸化ジルコニウム、酸化マグネシウム、ア
ルミナなどが挙げられる。本発明では、多孔質担体とし
て、特に活性炭が好ましく用いられる。This porous carrier has a surface area of 10 m 2 / g
As described above, it is preferably 30 to 1000 m 2 / g. Specific examples include activated carbon, titanium oxide, niobium oxide, silica, zirconium oxide, magnesium oxide and alumina. In the present invention, activated carbon is particularly preferably used as the porous carrier.
【0019】本発明では、このような多孔質担体は、そ
の粒径が1.0mm以下、好ましくは0.02〜1.0
mm、さらに好ましくは0.06〜0.8mmであるこ
とが望ましい。In the present invention, such a porous carrier has a particle size of 1.0 mm or less, preferably 0.02 to 1.0.
mm, and more preferably 0.06 to 0.8 mm.
【0020】本発明に係る炭酸ジエステル製造用触媒
は、(i) ハロゲン化銅と(ii)アルカリ金属水酸化物また
はアルカリ土類金属水酸化物とを、あるいは、(i) ハロ
ゲン化銅と(iii) フェニル基またはアルキル基を有する
第三級有機リン化合物とを、多孔質担体に担持すること
により調製される。The catalyst for producing carbonic acid diester according to the present invention comprises (i) copper halide and (ii) alkali metal hydroxide or alkaline earth metal hydroxide, or (i) copper halide and ( iii) It is prepared by supporting a tertiary organic phosphorus compound having a phenyl group or an alkyl group on a porous carrier.
【0021】触媒の調製に際しては、これら(i) および
(ii)成分を、あるいは(i) および(iii) 成分をそのまま
であるいは適切な溶媒に溶解して溶液状態で多孔質担体
と接触させ担持させる。溶液状態で用いられる場合に
は、たとえば(i) ハロゲン化銅はエタノール、メタノー
ル、水などの溶液として、また(ii)アルカリ金属水酸化
物またはアルカリ土類金属水酸化物は水溶液として、(i
ii) フェニル基またはアルキル基を有する第三級有機リ
ン化合物はアルコールなどの溶液として用いられる。In preparing the catalyst, these (i) and
The component (ii) or the components (i) and (iii) is dissolved as it is or in an appropriate solvent and brought into contact with and carried by the porous carrier in a solution state. When used in a solution state, for example, (i) copper halide as a solution of ethanol, methanol, water, etc., (ii) an alkali metal hydroxide or alkaline earth metal hydroxide as an aqueous solution, (i)
ii) The tertiary organic phosphorus compound having a phenyl group or an alkyl group is used as a solution of alcohol or the like.
【0022】これらの触媒成分を多孔質担体に担持させ
るに際しては、触媒成分として(i)ハロゲン化銅と(ii)
アルカリ金属水酸化物またはアルカリ土類金属水酸化物
とを多孔質担体に担持させる場合には、始めに(i) ハロ
ゲン化銅を担持させ、次いで(ii)アルカリ金属水酸化物
またはアルカリ土類金属水酸化物を担持させてもよく、
また(ii)アルカリ金属金属水酸化物またはアルカリ土類
金属水酸化物を担持させ、次いで(i) ハロゲン化第二銅
を担持させてもよく、あるいはこれら(i) および(ii)成
分を同時に担持させてもよい。さらに予めたとえば溶液
状態で(i) および(ii)成分を混合した後、同時に多孔質
担体に担持させてもよい。When supporting these catalyst components on the porous carrier, (i) copper halide and (ii) are used as catalyst components.
When an alkali metal hydroxide or an alkaline earth metal hydroxide is supported on the porous carrier, first, (i) a copper halide is supported, and then (ii) an alkali metal hydroxide or an alkaline earth metal. You may carry a metal hydroxide,
Further, (ii) an alkali metal hydroxide or an alkaline earth metal hydroxide may be supported, and then (i) a cupric halide may be supported, or these (i) and (ii) components may be simultaneously added. It may be supported. Further, for example, the components (i) and (ii) may be mixed in advance in a solution state and then simultaneously supported on the porous carrier.
【0023】このような調製は、不活性ガス(窒素、ア
ルゴン、ヘリウムなど)の流通下に行なうことが好まし
い。このような多孔質担体への担持は、含浸法、混練
法、共沈法などが適宜採用される。Such preparation is preferably carried out under the flow of an inert gas (nitrogen, argon, helium, etc.). For loading on such a porous carrier, an impregnation method, a kneading method, a coprecipitation method, or the like is appropriately adopted.
【0024】またこのように(i) および(ii)成分を含浸
させて得られる触媒を、水などで洗浄してもよい。さら
に窒素などの不活性ガスで乾燥させてもよい。上記のよ
うな触媒成分を多孔質担体に担持するための含浸法をよ
り具体的に説明すると、たとえば(i) ハロゲン化第二銅
溶液を多孔質担体に含浸させた後、空気雰囲気下あるい
は不活性ガスを流通させながら、80〜100℃で乾燥
させ、次いでこの多孔質担体に(ii)アルカリ金属水酸化
物またはアルカリ土類金属水酸化物の溶液を含浸させた
後、空気雰囲気下あるいは不活性ガスを流通させなが
ら、80〜400℃で熱処理すればよい。The catalyst obtained by impregnating the components (i) and (ii) in this way may be washed with water or the like. Further, it may be dried with an inert gas such as nitrogen. More specifically, the impregnation method for supporting the above-mentioned catalyst component on the porous carrier will be explained. For example, (i) after the cupric halide solution is impregnated into the porous carrier, the impregnation method is carried out in an air atmosphere or under a vacuum. It is dried at 80 to 100 ° C. while circulating an active gas, and then this porous carrier is impregnated with a solution of (ii) an alkali metal hydroxide or an alkaline earth metal hydroxide, and then under an air atmosphere or under an inert atmosphere. The heat treatment may be performed at 80 to 400 ° C. while circulating the active gas.
【0025】このような触媒の調製に際して、(i) およ
び(ii)成分の多孔質担体への担持量は、得られる触媒が
炭酸ジエステルの合成反応において活性を有しうる量で
あればよく特に限定されないが、通常(i) ハロゲン化銅
は、Cu/(ハロゲン化銅+多孔質担体)として、好ま
しくは1.5〜20重量%、さらに好ましくは5〜15
重量%の量で担持される。また(ii)アルカリ金属水酸化
物またはアルカリ土類金属水酸化物は、水酸化物中の水
酸基(OH基)当量換算で、(i) ハロゲン化銅中のCu
原子に対して、モル比((OH基)/Cu)で好ましく
は0.3〜2、さらに好ましくは0.5〜1.5の量で
担持される。In the preparation of such a catalyst, the amount of the components (i) and (ii) loaded on the porous carrier may be any amount so long as the resulting catalyst has activity in the synthesis reaction of carbonic acid diester. Although not limited, usually (i) the copper halide is preferably 1.5 to 20% by weight, more preferably 5 to 15% by weight as Cu / (copper halide + porous carrier).
It is supported in an amount of wt%. Further, (ii) alkali metal hydroxide or alkaline earth metal hydroxide is (i) Cu in copper halide in terms of hydroxyl group (OH group) equivalent in hydroxide.
It is supported in an amount of preferably 0.3 to 2, more preferably 0.5 to 1.5 in terms of molar ratio ((OH group) / Cu) with respect to the atom.
【0026】本発明に係る炭酸ジエステル製造用触媒
は、上記のように(i) ハロゲン化銅と(ii)アルカリ金属
水酸化物またはアルカリ土類金属水酸化物とが多孔質担
体に担持されてなるが、この触媒において、成分(i) と
(ii)とは、複塩および/またはその分解物を形成してい
ると考えられる。たとえば、ハロゲン化第二銅(CuC
l2)とNaOHとが担持された触媒では、CuCl2・
3Cu(OH)2なる複塩さらにこの分解物であるCu2
OCl2なるメタルオキシドハロゲン化物が形成してい
るものと考えられる。As described above, the catalyst for producing carbonic acid diester according to the present invention comprises (i) copper halide and (ii) alkali metal hydroxide or alkaline earth metal hydroxide supported on a porous carrier. In this catalyst, the component (i) and
It is considered that (ii) forms a double salt and / or a decomposition product thereof. For example, cupric halide (CuC
l 2 ) and NaOH supported catalyst, CuCl 2 ·
3Cu (OH) 2 double salt and its decomposed product Cu 2
It is considered that a metal oxide halide of OCl 2 is formed.
【0027】また触媒成分として(i) ハロゲン化銅と(i
ii) フェニル基またはアルキル基を有する第三級有機リ
ン化合物とを多孔質担体に担持させるに際しては、(i)
または(iii) 成分のいずれかをはじめに担持し、次いで
残りの成分を担持させる方法、あるいは、これら(i) お
よび(iii) 成分を同時に担持させてもよい。Further, (i) copper halide and (i
ii) When supporting a tertiary organic phosphorus compound having a phenyl group or an alkyl group on a porous carrier, (i)
Alternatively, either component (iii) may be loaded first, and then the remaining components may be loaded, or these components (i) and (iii) may be loaded simultaneously.
【0028】また(i) と(iii) とから予め銅錯体を合成
し、これを担体に担持させてもよい。このような銅錯体
は、たとえば、下記一般式で表される。 Cu(PPh3 )nX 〔ここでPPh3 はP(C6H5)3 であり、Xはハロゲン
であり、nは1、2または3である。〕具体的には、国
際出願公開WO90/15791号公報に記載された方
法により担持される。Alternatively, a copper complex may be previously synthesized from (i) and (iii) and supported on a carrier. Such a copper complex is represented by the following general formula, for example. Cu (PPh 3) n X [wherein PPh 3 is P (C 6 H 5) 3 , X is halogen, n represents 1, 2 or 3. Specifically, it is supported by the method described in WO90 / 15791.
【0029】このような触媒の調製に際して、(i) およ
び(iii) 成分の多孔質担体への担持量は、(i) ハロゲン
化銅は担体に対してハロゲン化銅中のCu(Cu/多孔
質担体)として好ましくは2〜10重量%の量で、また
(iii) フェニル基またはアルキル基を有する第三級有機
リン化合物は(i) ハロゲン化銅中のCu原子に対して、
モル比で好ましくは0.06〜0.4の量で担持され
る。In the preparation of such a catalyst, the amount of the components (i) and (iii) loaded on the porous carrier is (i) the copper halide is Cu (Cu / porous / porosity) in the copper halide with respect to the carrier. As a solid carrier), preferably in an amount of 2 to 10% by weight, and
(iii) The tertiary organic phosphorus compound having a phenyl group or an alkyl group is (i) with respect to the Cu atom in the copper halide,
The molar ratio is preferably 0.06 to 0.4.
【0030】また予め(i) および(iii) 成分から銅錯体
を合成し、これを多孔質担体に担持させる場合には、触
媒中の銅錯体は担体に対して、銅錯体中のCu換算(C
u/多孔質担体)で好ましくは2〜10重量%の量で担
持される。When a copper complex is previously synthesized from the components (i) and (iii) and is supported on a porous carrier, the copper complex in the catalyst is converted to Cu in the copper complex in the carrier ( C
u / porous carrier), preferably 2 to 10% by weight.
【0031】このような本発明に係る炭酸ジエステル製
造用触媒は、アルコールを一酸化炭素および酸素と反応
させて炭酸ジエステルを製造するに際して、アルコール
の転化率が高く、しかも炭酸ジエステルの選択率も高
く、かつ長期間に亘って高活性を維持することができ
る。The catalyst for producing a carbonic acid diester according to the present invention has a high alcohol conversion rate and a high carbonic acid diester selectivity when a carbonic acid diester is produced by reacting an alcohol with carbon monoxide and oxygen. Moreover, high activity can be maintained over a long period of time.
【0032】次に本発明に係る炭酸ジエステルの製造方
法について説明する。本発明では、炭酸ジエステルの製
造方法は、上記のような炭酸ジエステル製造用触媒の存
在下、気相反応条件下に、アルコールを一酸化炭素およ
び酸素と反応させることによって炭酸ジエステルを製造
している。Next, the method for producing the carbonic acid diester according to the present invention will be described. In the present invention, the method for producing a carbonic acid diester produces a carbonic acid diester by reacting an alcohol with carbon monoxide and oxygen under gas phase reaction conditions in the presence of the catalyst for producing a carbonic acid diester as described above. .
【0033】本発明で用いられる反応原料としてのアル
コールとしては、炭素数1〜6の脂肪族アルコール、脂
環族アルコールおよび芳香族アルコールなどが挙げられ
る。具体的には、メタノール、エタノール、プロピルア
ルコール、ブタノール、ペンタノール、ヘキサノール、
シクロプロパノール、シクロブタノール、シクロペンタ
ノール、シクロヘキサノール、ベンジルアルコールなど
の1価アルコールが例示される。これらは、単独である
いは組み合わせて用いられる。これらのうち、特にメタ
ノール、エタノールなどが好ましい。Examples of the alcohol as a reaction raw material used in the present invention include aliphatic alcohols having 1 to 6 carbon atoms, alicyclic alcohols and aromatic alcohols. Specifically, methanol, ethanol, propyl alcohol, butanol, pentanol, hexanol,
Examples are monohydric alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol and benzyl alcohol. These may be used alone or in combination. Of these, methanol and ethanol are particularly preferable.
【0034】本発明において、上記アルコールとして1
種類のアルコールを用いると対称な炭酸ジエステルが得
られ、異なるアルコールを組み合わせて用いると、対称
または非対称の炭酸ジエステルが得られる。In the present invention, 1 is used as the alcohol.
The use of different alcohols gives symmetrical carbonic diesters, and the use of different alcohols in combination gives symmetrical or asymmetric carbonic diesters.
【0035】上記のような反応系において、一酸化炭素
は、アルコールに対するモル比(CO/アルコール)
で、通常約0.01〜100、好ましくは0.5〜2
0、さらに好ましくは1〜10の量で用いられ、また酸
素は、アルコールに対するモル比(O2 /アルコール)
で、0.01〜2.0、好ましくは0.05〜1.0、
さらに好ましくは0.05〜0.5の量で用いられる。In the above reaction system, carbon monoxide is in a molar ratio to alcohol (CO / alcohol).
And usually about 0.01 to 100, preferably 0.5 to 2
0, more preferably used in an amount of 1 to 10, and oxygen is a molar ratio to alcohol (O 2 / alcohol).
And 0.01 to 2.0, preferably 0.05 to 1.0,
More preferably, it is used in an amount of 0.05 to 0.5.
【0036】また一酸化炭素と酸素とは、通常モル比
(CO/O2)で1〜1000、好ましくは10〜10
0、さらに好ましくは20〜50の量で用いられる。上
記のような反応系に、酸素は純粋な分子状酸素として、
あるいは窒素またはアルゴンなどの不活性ガスで希釈し
て供給される。The carbon monoxide and oxygen are usually in a molar ratio (CO / O 2 ) of 1 to 1000, preferably 10 to 10.
It is used in an amount of 0, more preferably 20 to 50. In the reaction system as described above, oxygen is pure molecular oxygen,
Alternatively, it is diluted with an inert gas such as nitrogen or argon and supplied.
【0037】一酸化炭素は純粋なもの以外に、水素など
の反応に不活性なガスとの混合物であってもよい。たと
えばメタノールの分解反応により得られる一酸化炭素お
よび水素の混合ガスを使用することもできる。The carbon monoxide may be not only pure but also a mixture with a gas inert to the reaction such as hydrogen. For example, a mixed gas of carbon monoxide and hydrogen obtained by a decomposition reaction of methanol can be used.
【0038】また原料アルコールとしてメタノールを使
用する場合には、少なくともその一部を分解反応工程に
導入し、メタノール分解率を適宜調節した分解生成ガス
を使用することもできる。When methanol is used as the raw material alcohol, it is also possible to use a decomposition product gas in which at least a part thereof is introduced into the decomposition reaction step and the decomposition rate of methanol is appropriately adjusted.
【0039】本発明では、上記のような反応を気相反応
条件下に行なうに際しては、具体的に、反応温度は通常
70〜350℃、好ましくは80〜250℃、さらに好
ましくは100〜200℃であり、反応圧力は通常常圧
〜35kg/cm2G、好ましくは2〜20kg/cm2G、さら
に好ましくは5〜15kg/cm2Gであることが望まし
い。In the present invention, when the above reaction is carried out under gas phase reaction conditions, specifically, the reaction temperature is usually 70 to 350 ° C, preferably 80 to 250 ° C, more preferably 100 to 200 ° C. The reaction pressure is usually normal pressure to 35 kg / cm 2 G, preferably 2 to 20 kg / cm 2 G, and more preferably 5 to 15 kg / cm 2 G.
【0040】上記気相反応は、固定床形式、流動床形式
など反応形式を限定されない。本発明で得られる炭酸ジ
エステルとしては、具体的には、ジメチルカーボネー
ト、ジエチルカーボネート、ジプロピルカーボネート、
ジブチルカーボネート、ジペンチルカーボネート、ジヘ
キシルカーボネート、ジシクロプロピルカーボネート、
ジシクロブチルカーボネート、ジシクロペンチルカーボ
ネート、ジシクロヘキシルカーボネート、ジベンジルカ
ーボネート、メチルエチルカーボネート、メチルプロピ
ルカーボネート、エチルプロピルカーボネートなどが挙
げられる。The gas phase reaction is not limited to a fixed bed type, a fluidized bed type, or the like. As the carbonic acid diester obtained in the present invention, specifically, dimethyl carbonate, diethyl carbonate, dipropyl carbonate,
Dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclopropyl carbonate,
Examples thereof include dicyclobutyl carbonate, dicyclopentyl carbonate, dicyclohexyl carbonate, dibenzyl carbonate, methyl ethyl carbonate, methyl propyl carbonate and ethyl propyl carbonate.
【0041】[0041]
【発明の効果】本発明に係る炭酸ジエステル製造用触媒
は、上述のように特定の成分が特定の粒径を有する多孔
質担体に担持されてなり、アルコールを一酸化炭素およ
び酸素と反応させて炭酸ジエステルを製造するに際し
て、長期間に亘り高活性を維持することができる。EFFECT OF THE INVENTION The catalyst for producing carbonic acid diester according to the present invention comprises a specific component supported on a porous carrier having a specific particle size as described above, and an alcohol is reacted with carbon monoxide and oxygen. When producing a carbonic acid diester, high activity can be maintained over a long period of time.
【0042】本発明に係る炭酸ジエステルの製造方法に
よれば、長期間に亘って高収率で炭酸ジエステルを製造
しうる。次に本発明を実施例により具体的に説明する
が、本発明はこれら実施例により限定されるものではな
い。According to the method for producing a carbonic acid diester of the present invention, the carbonic acid diester can be produced in a high yield over a long period of time. Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
【0043】[0043]
(溶液調製) (1) 蒸留水100mlに、塩化第二銅25.0gを加え、
塩化第二銅溶液を調製した。 (2) 蒸留水100mlに、水酸化ナトリウム22.3gを
加え、水酸化ナトリウム水溶液を調製した。(Solution preparation) (1) Add 25.0 g of cupric chloride to 100 ml of distilled water,
A cupric chloride solution was prepared. (2) 22.3 g of sodium hydroxide was added to 100 ml of distilled water to prepare an aqueous sodium hydroxide solution.
【0044】(触媒調製例1)粒径0.7mm〜1.0mm
の活性炭15gに対して上記塩化第二銅溶液を8ml含浸
し、次いで不活性ガス(窒素)を流通させながら100
℃にて3時間乾燥した。冷却後、以上の工程をさらに2
度行なった。次に、塩化第二銅を担持した活性炭に、上
記水酸化ナトリウム水溶液を8ml含浸させ、次いで不活
性ガス(窒素)を流通させながら100℃にて3時間乾
燥した。このようにして、触媒A(Cu担持量13.5
重量%、OH/Cu=1)を調製した。(Catalyst preparation example 1) Particle size 0.7 mm to 1.0 mm
8 g of the above cupric chloride solution was impregnated into 15 g of activated carbon, and then 100% while circulating an inert gas (nitrogen).
It dried at 3 degreeC for 3 hours. After cooling, perform the above two steps
I did it once. Next, activated carbon carrying cupric chloride was impregnated with 8 ml of the above sodium hydroxide aqueous solution, and then dried at 100 ° C. for 3 hours while circulating an inert gas (nitrogen). In this way, catalyst A (Cu loading 13.5
% By weight, OH / Cu = 1) was prepared.
【0045】(触媒調製例2)上記触媒調製例1におい
て粒径0.7mm〜0.75mmの活性炭15gを用いた以
外は、調製例1と同様の方法により触媒Bを調製した。(Catalyst Preparation Example 2) Catalyst B was prepared in the same manner as in Preparation Example 1 except that 15 g of activated carbon having a particle size of 0.7 mm to 0.75 mm was used in Catalyst Preparation Example 1 above.
【0046】(触媒調製例3)上記触媒調製例1におい
て粒径0.3mm〜0.35mmの活性炭15gを用いた以
外は、調製例1と同様の方法により触媒Cを調製した。(Catalyst Preparation Example 3) Catalyst C was prepared in the same manner as in Preparation Example 1 except that 15 g of activated carbon having a particle size of 0.3 mm to 0.35 mm was used in Catalyst Preparation Example 1 above.
【0047】(触媒調製例4)上記触媒調製例1におい
て粒径2.8mm〜4.0mmの活性炭15gを用いた以外
は、調製例1と同様の方法により触媒Dを調製した。(Catalyst Preparation Example 4) Catalyst D was prepared in the same manner as in Preparation Example 1 except that 15 g of activated carbon having a particle size of 2.8 mm to 4.0 mm was used in Catalyst Preparation Example 1 above.
【0048】(触媒調製例5)上記触媒調製例1におい
て粒径1.7mm〜2.4mmの活性炭15gを用いた以外
は、調製例1と同様の方法により触媒Eを調製した。(Catalyst Preparation Example 5) Catalyst E was prepared in the same manner as in Preparation Example 1 except that 15 g of activated carbon having a particle size of 1.7 mm to 2.4 mm was used in Catalyst Preparation Example 1.
【0049】(触媒調製例6)上記触媒調製例1におい
て粒径1.0mm〜1.7mmの活性炭15gを用いた以外
は、調製例1と同様の方法により触媒Fを調製した。(Catalyst Preparation Example 6) A catalyst F was prepared in the same manner as in Preparation Example 1 except that 15 g of activated carbon having a particle size of 1.0 mm to 1.7 mm was used in Catalyst Preparation Example 1.
【0050】[0050]
【実施例1】高圧固定床反応装置を用いて、炭酸ジメチ
ル(DMC)を下記のようにして製造した。すなわち内
径16mmのステンレス製反応管に、触媒Aを7ml充填
し、反応圧力6kg/cm2G、反応温度130℃の条件
下、メタノール5g/時、一酸化炭素57.8ml/分、
酸素3.6ml/分の割合で導入してDMCを製造した。Example 1 Dimethyl carbonate (DMC) was produced as follows using a high pressure fixed bed reactor. That is, 7 ml of a catalyst A was filled in a stainless steel reaction tube having an inner diameter of 16 mm, and the reaction pressure was 6 kg / cm 2 G and the reaction temperature was 130 ° C. under the conditions of methanol 5 g / hour, carbon monoxide 57.8 ml / minute,
DMC was produced by introducing oxygen at a rate of 3.6 ml / min.
【0051】反応開始した後所定時間(3時間、50時
間、100時間)経過後のそれぞれの触媒活性を表1に
示す。表1中、上段にメタノール転化率(%)を、下段
にメタノールのDMCへの選択率(%)を示した。Table 1 shows the respective catalyst activities after a lapse of a predetermined time (3 hours, 50 hours, 100 hours) after the start of the reaction. In Table 1, the upper column shows the methanol conversion rate (%), and the lower column shows the methanol selectivity to DMC (%).
【0052】[0052]
【実施例2】実施例1において、触媒Aに代えて触媒B
を用いた以外は、実施例1と同様にして炭酸ジメチル
(DMC)を製造した。[Example 2] The catalyst B was replaced with the catalyst B in Example 1.
Dimethyl carbonate (DMC) was produced in the same manner as in Example 1 except that was used.
【0053】結果を表1に示す。The results are shown in Table 1.
【0054】[0054]
【実施例3】実施例1において、触媒Aに代えて触媒C
を用いた以外は、実施例1と同様にして炭酸ジメチル
(DMC)を製造した。Example 3 In Example 1, instead of the catalyst A, the catalyst C was used.
Dimethyl carbonate (DMC) was produced in the same manner as in Example 1 except that was used.
【0055】結果を表1に示す。The results are shown in Table 1.
【0056】[0056]
【比較例1〜3】実施例1において、触媒Aに代えてそ
れぞれ触媒D、E、Fを用いた以外は、実施例1と同様
にして炭酸ジメチル(DMC)を製造した。Comparative Examples 1 to 3 Dimethyl carbonate (DMC) was produced in the same manner as in Example 1 except that the catalyst A was replaced by the catalysts D, E and F, respectively.
【0057】結果を表1に示す。Table 1 shows the results.
【0058】[0058]
【表1】 [Table 1]
【0059】なお表1中、Cu含有量=〔Cu重量/
(ハロゲン化銅重量+担体重量)〕×100(%)であ
る。In Table 1, Cu content = [Cu weight /
(Weight of copper halide + weight of carrier)] × 100 (%).
【0060】上記表1から明らかなように、粒径が1.
0mm以下である多孔質担体に担持させた触媒は、触媒
活性が長期間に亘り保持されている。一方粒径が1.0
mmよりも大きい多孔質担体に担持させた触媒は、反応
開始後時間の経過とともに著しく触媒活性が低下した。As is clear from Table 1 above, the particle size is 1.
The catalyst supported on the porous carrier having a diameter of 0 mm or less retains its catalytic activity for a long period of time. On the other hand, the particle size is 1.0
The catalyst supported on the porous carrier having a size larger than mm showed a marked decrease in catalytic activity with the lapse of time after the start of the reaction.
【0061】また各触媒について、表1に示したメタノ
ール転化率(%)の経時変化を図に示す。(表2)The change with time of the methanol conversion rate (%) shown in Table 1 for each catalyst is shown in the figure. (Table 2)
【0062】[0062]
【表2】 [Table 2]
【0063】(触媒調製例7)塩化第二銅とトリフェニ
ルホスフィン〔P(C6H5)3 ;以下PPh3 と略記〕
から得た錯体Cu(PPh3 )Cl 3.751gに、粒
径0.3mm〜0.35mmの活性炭20gとエタノール溶
媒を加えて混合し、乾燥後不活性ガスを流通しながら2
50℃で3時間処理して触媒Gを調製した。(Catalyst Preparation Example 7) Cupric chloride and triphenylphosphine [P (C 6 H 5 ) 3 ; hereinafter abbreviated as PPh 3 ]
To 3.751 g of the complex Cu (PPh 3 ) Cl obtained from the above, 20 g of activated carbon having a particle size of 0.3 mm to 0.35 mm and an ethanol solvent were added and mixed, and after drying, while flowing an inert gas, 2
Catalyst G was prepared by treating at 50 ° C. for 3 hours.
【0064】(触媒調製例8)上記触媒調製例7におい
て粒径1.7mm〜2.4mmの活性炭20gを用いた以外
は、調製例7と同様の方法により触媒Hを調製した。(Catalyst Preparation Example 8) A catalyst H was prepared in the same manner as in Preparation Example 7 except that 20 g of activated carbon having a particle size of 1.7 mm to 2.4 mm was used in Catalyst Preparation Example 7.
【0065】[0065]
【実施例4】実施例1において、触媒Aに代えて触媒G
を用いた以外は、実施例1と同様にして炭酸ジメチル
(DMC)を製造した。[Example 4] The catalyst G was replaced with the catalyst G in Example 1.
Dimethyl carbonate (DMC) was produced in the same manner as in Example 1 except that was used.
【0066】結果を表3に示す。The results are shown in Table 3.
【0067】[0067]
【比較例4】実施例1において、触媒Aに代えてそれぞ
れ触媒Hを用いた以外は、実施例1と同様にして炭酸ジ
メチル(DMC)を製造した。Comparative Example 4 Dimethyl carbonate (DMC) was produced in the same manner as in Example 1 except that the catalyst H was used instead of the catalyst A.
【0068】結果を表3に示す。表3中、上段にメタノ
ール転化率(%)を、下段にメタノールのDMCへの選
択率(%)を示した。The results are shown in Table 3. In Table 3, the upper part shows the methanol conversion rate (%), and the lower part shows the methanol selectivity to DMC (%).
【0069】またCu含有量(重量%)=〔Cu重量/
担体重量〕×100(%)である。Cu content (wt%) = [Cu weight /
Carrier weight] × 100 (%).
【0070】[0070]
【表3】 [Table 3]
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 C07C 68/00 9546−4H C07C 68/00 B 69/96 9546−4H 69/96 Z (72)発明者 山 田 伸 広 愛知県半田市州の崎町2−110 日揮株 式会社 衣浦研究所内 (56)参考文献 特開 平3−190846(JP,A)Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI Technical indication location C07C 68/00 9546-4H C07C 68/00 B 69/96 9546-4H 69/96 Z (72) Inventor Yama Nobuhiro Ta, 2-110, Sakinomachi, Handa, Aichi Prefecture, Kinuura Research Laboratories, JGC Co., Ltd. (56) Reference: JP-A-3-190846 (JP, A)
Claims (6)
酸化物またはアルカリ土類金属水酸化物とが、あるい
は、 (i) ハロゲン化銅と、(iii) フェニル基またはアルキル
基を有する第三級有機リン化合物とが、 粒径が1.0mm以下である多孔質担体に担持されてな
ることを特徴とする、 アルコールを一酸化炭素および酸素と反応させて炭酸ジ
エステルを製造するための炭酸ジエステル製造用触媒。1. (i) copper halide and (ii) alkali metal hydroxide or alkaline earth metal hydroxide, or (i) copper halide and (iii) phenyl group or alkyl group And a tertiary organophosphorus compound having: are supported on a porous carrier having a particle size of 1.0 mm or less, and an alcohol is reacted with carbon monoxide and oxygen to produce a carbonic acid diester. For the production of carbonic acid diesters.
0mmであることを特徴とする請求項1に記載の炭酸ジ
エステル製造用触媒。2. The porous carrier has a particle size of 0.02-1.
It is 0 mm, The catalyst for carbonic acid diester manufacture of Claim 1 characterized by the above-mentioned.
徴とする請求項1または2に記載の炭酸ジエステル製造
用触媒。3. The catalyst for carbonic acid diester production according to claim 1, wherein the porous carrier is activated carbon.
酸化物またはアルカリ土類金属水酸化物とが、あるい
は、 (i) ハロゲン化銅と、(iii) フェニル基またはアルキル
基を有する第三級有機リン化合物とが、 粒径が1.0mm以下である多孔質担体に担持されてな
る触媒の存在下、気相反応条件下に、アルコールを一酸
化炭素および酸素と反応させることを特徴とする炭酸ジ
エステルの製造方法。4. (i) a copper halide and (ii) an alkali metal hydroxide or an alkaline earth metal hydroxide, or (i) a copper halide and (iii) a phenyl group or an alkyl group. With a tertiary organophosphorus compound having the following formula: Alcohol is reacted with carbon monoxide and oxygen under gas phase reaction conditions in the presence of a catalyst supported on a porous carrier having a particle size of 1.0 mm or less. A method for producing a carbonic acid diester, comprising:
0mmであることを特徴とする請求項4に記載の炭酸ジ
エステルの製造方法。5. The particle size of the porous carrier is 0.02-1.
It is 0 mm, The manufacturing method of the carbonic acid diester of Claim 4 characterized by the above-mentioned.
徴とする請求項4または5に記載の炭酸ジエステルの製
造方法。6. The method for producing a carbonic acid diester according to claim 4 or 5, wherein the porous carrier is activated carbon.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4171331A JP2549799B2 (en) | 1992-06-29 | 1992-06-29 | Catalyst for producing carbonic acid diester and method for producing carbonic acid diester using the same |
US07/929,294 US5347031A (en) | 1991-08-19 | 1992-08-13 | Catalysts used for producing carbonic acid esters and methods of producing carbonic acid esters using the same |
CA002076157A CA2076157C (en) | 1991-08-19 | 1992-08-14 | Catalyst used for producing carbonic acid esters and methods of producing carbonic acid esters using the same |
EP92202512A EP0528498B1 (en) | 1991-08-19 | 1992-08-17 | Catalysts used for producing carbonic acid esters and methods of producing carbonic acid esters using the same |
DE69206076T DE69206076T2 (en) | 1991-08-19 | 1992-08-17 | Catalysts for the production of carbonic acid esters and process for the production of carbonic acid esters. |
US08/215,518 US5512528A (en) | 1991-08-19 | 1994-03-22 | Catalysts used for producing carbonic acid esters and methods of producing carbonic acid esters using the same |
US08/433,039 US5650369A (en) | 1991-08-19 | 1995-05-03 | Catalysts used for producing carbonic acid esters and methods of producing carbonic acid esters using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4171331A JP2549799B2 (en) | 1992-06-29 | 1992-06-29 | Catalyst for producing carbonic acid diester and method for producing carbonic acid diester using the same |
Publications (2)
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---|---|
JPH06285375A JPH06285375A (en) | 1994-10-11 |
JP2549799B2 true JP2549799B2 (en) | 1996-10-30 |
Family
ID=15921254
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JPH0813788B2 (en) * | 1988-12-15 | 1996-02-14 | ダイセル化学工業株式会社 | Method for producing carbonate ester |
JP2767146B2 (en) * | 1989-12-21 | 1998-06-18 | 日揮株式会社 | Method for producing carbonate ester |
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