JPS6363537B2 - - Google Patents
Info
- Publication number
- JPS6363537B2 JPS6363537B2 JP56145518A JP14551881A JPS6363537B2 JP S6363537 B2 JPS6363537 B2 JP S6363537B2 JP 56145518 A JP56145518 A JP 56145518A JP 14551881 A JP14551881 A JP 14551881A JP S6363537 B2 JPS6363537 B2 JP S6363537B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphate
- catalyst
- reaction
- oxide
- acid
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000011973 solid acid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- KDCUNMWWJBHRSC-UHFFFAOYSA-K praseodymium(3+);phosphate Chemical compound [Pr+3].[O-]P([O-])([O-])=O KDCUNMWWJBHRSC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 2
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 claims description 2
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- 238000000034 method Methods 0.000 description 31
- 235000021317 phosphate Nutrition 0.000 description 23
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 150000001408 amides Chemical class 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- -1 aliphatic alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000007130 inorganic reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- NTQWADDNQQUGRH-UHFFFAOYSA-N hydrogen sulfate;2-methylprop-2-enoylazanium Chemical compound OS(O)(=O)=O.CC(=C)C(N)=O NTQWADDNQQUGRH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- SXQFCVDSOLSHOQ-UHFFFAOYSA-N lactamide Chemical compound CC(O)C(N)=O SXQFCVDSOLSHOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium 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
本発明は、α，β−不飽和カルボン酸エステル
の製造方法に関するものである。
更に、詳しくは、本発明は、固体酸を触媒とし
て、α−オキシカルボン酸アミドと水および脂肪
族アルコールを反応させてα，β−不飽和カルボ
ン酸エステルを製造する方法に関するものであ
る。
α，β−不飽和カルボン酸エステル、たとえば
メタクリル酸メチルの製造方法として、アセトン
シアンヒドリンに濃硫酸を作用させてメタクリル
アミド硫酸塩とした後、メタノールを用いてエス
テル化する方法がある。この方法は、従来より工
業的に実施されているが、濃硫酸による装置材質
の腐食および価値の低い硫安が多量に副生するこ
とが欠点とされている。
本発明者らは、硫酸を用いないでシアンヒドリ
ンからα，β−不飽和カルボン酸およびそのエス
テルを製造する方法を鋭意研究した結果、既にシ
アンヒドリンの水和反応によつて得られるα−オ
キシカルボン酸アミドと水および／または脂肪族
アルコールを150℃以上の温度において、気相、
液相または気液混合相で、固体酸触媒を用いて反
応させることによつて、α，β−不飽和カルボン
酸およびそのエステルを製造する方法を見い出
し、その発明を出願した（特願昭55−143591号）。
この方法によつて、α−オキシカルボン酸アミ
ドと水および／またはアルコールの混合物を触媒
と接触させて、不都合な分解、重合等の障害もな
く、しかも高収率で、α，β−不飽和カルボン酸
およびそのエステルを製造できる。
また、従来法では、原料中の窒素分は硫安等の
価値の低い副生成物として取り出されていたが、
この方法では、工業的に重要な中間体であるアル
キルアミン類および／またはアンモニアとして取
り出すことができる。
しかしながら、この方法でα，β−不飽和カル
ボン酸エステルを製造する場合、目的とするα，
β−不飽和カルボン酸エステルのほかに、脂肪族
アルコールの脱水反応によるエーテルの副生が起
こる。エーテルの副生量は使用する触媒の種類お
よび反応条件によつて変化し、α，β−不飽和カ
ルボン酸エステルの生成収率の大きな触媒および
反応条件ほどエーテルの副生も多くなる。
エーテルの副生は、単に、α，β−不飽和カル
ボン酸エステルの分離精製工程を煩雑するだけで
なく、副生するエーテルの経済的価値やその需要
によつてはα，β−不飽和カルボン酸エステル製
造方法としての経済性を悪くするという問題があ
つた。
本発明者らは、α−オキシカルボン酸アミドを
原料とするα，β−不飽和カルボン酸エステルの
製造法について、さらにエーテルの副生を極力抑
制ないしは完全に抑制する方法を鋭意検討した結
果、本発明の方法に至つた。
すなわち、本発明の方法は、シアンヒドリンの
水和反応によつて得られるα−オキシカルボン酸
アミドと脂肪族アルコールを、気相、液相または
気液混合相で、固体酸触媒を用いて反応させるこ
とによつてα，β−不飽和カルボン酸エステルを
製造するに際し、先ず、α−オキシカルボン酸ア
ミドを、好ましくは水の存在下で、第１の固体酸
触媒と接触させ、次いで、得られた反応混合物を
脂肪族アルコールと共に第２の固体酸触媒と接触
させることによつて、α，β−不飽和カルボン酸
エステルを製造する方法であり、脂肪族アルコー
ルの脱水反応によるエーテルの副生を実質的に完
全に抑制することができる。
一般に固体酸触媒とは、金属元素およびａ、
ａ、ａの族の非金属元素のリン酸塩、硫酸塩
および酸化物の少なくとも一種を含有する触媒、
固体リン酸触媒、更に特殊な例として、活性炭、
カチオン交換樹脂、α−ホウ素およびニツケル金
属、等である。
さらに詳しくは、固体リン酸触媒とは、リン酸
を公知の担体、たとえば、ケイソウ土に担持させ
適当な熱焼成を施した触媒である。
また、リン酸塩を含有する固体酸触媒とは、元
素周期律表のａ、ｂ、ａ、ｂ、ａ、
ｂ、ランタニド、アクチニド、ａ、ｂ、
ａ、ｂ、ｂ、ｂおよび族元素から選ばれ
た元素、たとえば、Li、Na、Ｋ、Rb、Cs、Be、
Mg、Ca、Sr、Ba、Sc、Ｙ、La、Ce、Pr、Nd、
Sm、Gd、Th、Ｕ、Ti、Zr、Hf、Ｖ、Nb、Ta、
Cr、Mo、Ｗ、Mn、Fe、Co、Ni、Cu、Ag、
Zn、Cd、Ｂ、Al、Ga、In、Tl、Sn、Pb、Sbお
よびBi、等の少なくとも一種の元素のリン酸塩
または２種以上のリン酸塩の混合物、あるいは、
これらのリン酸塩を含有する触媒である。リン酸
塩中におけるこれらの元素（Ｍと表わす）とリン
（Ｐと表わす）の原子比（Ｍ／Ｐ）は、０〜３の
範囲（ここでＭ／Ｐ＝０は固体リン酸と一致す
る）である。これらのリン酸塩の構造について
は、何ら限定されるものではなく、前記の元素と
リンの原子比（Ｍ／Ｐ）が０〜３の範囲を満して
いればよい。
これらのリン酸塩は、公知の任意の方法により
製造することができる。たとえば、一般には、プ
レパラテイブ インオーガニツク リアクシヨン
ズ第２巻、第139〜167頁、1965年〔Preparative
Inorganic Reactions ２、139−167（1965）〕に
記載されている方法、すなわち、金属、金属酸化
物または金属塩とリン酸またはリン酸塩を反応さ
せる方法で製造することができる。また、金属ア
ルコレートとリン酸の反応による製法のように特
殊な方法によつてもよい。
リン酸塩を含有する触媒は、前記のリン酸塩
と、必要によりその他の硫酸塩、金属酸化物と
を、一般に公知の活性炭、シリカ、シリカ・アル
ミナ、アルミナ等の担体を混練法、浸漬法等の公
知の方法によつて製造することができる。そのほ
か、たとえば、リン酸に対して金属酸化物を過剰
に加えて反応させることによつても金属酸化物と
リン酸塩の混合物触媒を製造することができる。
また、硫酸塩を含有する固体酸触媒とは、Li、
Na、Ｋ、Rb、Cs、Be、Mg、Ca、Sr、Ba、Cr、
Mn、Fe、Co、Ni、Cu、Zn、Cd、Al、In、Sn、
およびPbから選ばれた少なくとも一種の元素の
硫酸塩または酸性硫酸塩、あるいはこれらの硫酸
塩または酸性硫酸塩を含有する触媒である。
これらの硫酸塩を含有する固体酸触媒は、前記
の金属硫酸塩または酸性硫酸塩と、必要によりそ
の他の金属酸化物、リン酸塩、担体とを一般に公
知な混練法、浸漬法、等によつて製造することが
できる。
さらに、酸化物を含有する固体酸触媒とは、
Be、Mg、Ｙ、La、Ce、Th、Ｕ、Ti、Zr、Ｖ、
Cr、Mo、Ｗ、Mn、Fe、Co、Ni、Cu、Zn、
Cd、Ｂ、Al、Si、Sb、およびBiから選ばれた少
なくとも一種の元素の酸化物、または２種以上の
元素の混合酸化物である複合酸化物、あるいはこ
れらの酸化物とリン酸塩、硫酸塩または担体等と
の混合物である。担体としては、公知の活性炭、
シリカ、アルミナ、炭化ケイ素どがあげられる。
これらの酸化物または複合酸化物および他の触媒
構成物質を含む触媒は、公知の方法、たとえば、
沈でん法、浸漬法、等の方法で製造することがで
きる。
これらの固体酸触媒の中から、本発明の方法に
おける第１および第２の固体酸触媒は選ばれる。
すなわち、第１の固体酸触媒としては、りん酸ア
ルミニウム、りん酸マグネシウム、りん酸イツト
リウム、りん酸ランタン、りん酸セリウム、りん
酸プラセオジウムまたは酸化マグネシウムと酸化
ケイ素の複合酸化物を少なくとも一種含有する触
媒が使用され、一方、第２の固体酸触媒として
は、りん酸チタン、りん酸ジルコニウム、酸化チ
タンまたは酸化ジルコニウムを少なくとも一種含
有する触媒が使用される。
本発明の方法で使用されるα−オキシカルボン
酸アミドは、一般式（）
（式中、R1およびR2は水素またはアルキル基を
示す。ただし、少なくとも一方はアルキル基であ
る）で表わされる化合物である。このようなα−
オキシカルボン酸としては、たとえば乳酸アミ
ド、α−オキシ酪酸アミド、α−オキシイソ酪酸
アミド、α−オキシ吉草酸アミド、α−オキシイ
ソ吉草酸アミド、α−メチル−α−オキシ酪酸ア
ミドなど、種々のα−オキシカルボン酸アミドが
あげられる。
また、本発明の方法で使用される脂肪族アルコ
ールとしては、メチルアルコール、エチルアルコ
ール、ｎ−プロピルアルコール、ｉ−プロピルア
ルコール、ｉ−ブチルアルコール、エチレングリ
コール、エチレングリコールモノメチルエーテ
ル、プロピレングリコールモノメチルエーテルな
どの種々の脂肪族アルコールおよび置換脂肪族ア
ルコールがあげられ、目的に応じて、これらのア
ルコール類から選択される。
本発明の方法において、反応は反応物質と固体
酸触媒を接触させる方法であれば気相法、液相法
のいずれの方法でも実施することができるが、気
相または気液混合相が好ましく、その方式として
は、固定床方式、流動床方式、等任意の方式で実
施できる。
本発明の方法では、α−オキシカルボン酸アミ
ドは、好ましくは水と共に、第１の固体酸触媒と
接触させ、次いで、得られた反応混合物を分離す
ることなく、脂肪族アルコールと共に第２の固体
酸触媒と接触させてα，β−不飽和カルボン酸エ
ステルを得る。
使用する原料物質の量は特に制限はないが、通
常、α−オキシカルボン酸アミド１モルに対し
て、水が０〜200モル、好ましくは１〜50モルで
あり、反応混合物とともに反応させる脂肪族アル
コールが１〜200モル、好ましくは１〜50モルの
範囲である。反応温度、反応圧力、接触時間等
は、第１と第２の固体酸触媒との接触反応の間で
同一であつても、異つてもよいが、次の範囲内で
あればよい。すなわち、反応温度は150℃〜500℃
で、特に200℃〜450℃が好ましい。反応物質と接
触時間は、触媒、反応温度等の反応条件により広
い範囲で変化させることができるが、通常0.5〜
360秒の範囲で本発明の目的を達することができ
る。反応圧力は、通常、大気圧でよいが、加圧下
でも、減圧下でもよい。また、反応を実施するに
あたつて、反応原料に窒素ガス等の不活性ガスを
同伴させて触媒層と接触させてもよい。更に、必
ずしも必要ではないが、触媒の前処理として、ア
ンモニアまたはアンモニア水を触媒層に供給した
後に反応を開始してもよい。
以下、本発明の方法を具体的に説明するために
実施例を示す。
なお、実施例において用いたリン酸塩を含有す
る触媒の表示式は、必ずしも触媒に含有されるリ
酸塩の構造を示したものではなく、リン酸塩中の
前記金属とリンの原子比（Ｍ／Ｐ）を示すもので
ある。たとえば、反応条件下におけるリン酸塩
が、たとえメタリン酸塩またはピロリン酸塩等の
縮合リン酸塩であつても、触媒の表示式として
は、対応するオルトリン酸塩として示した。
実施例 １
オキシ塩化ジルコニウム（ZrOCl2・8H2O）
36.1ｇ（0.112モル）を水50mlに溶解し、これを
りん酸１ナトリウム塩（NaH2PO4・2H2O）156
ｇ（１モル）を３規定塩酸200mlに溶解し、80℃
に加温した溶液中に撹拌下加えると白色沈殿が生
成する。１時間撹拌を行つた後、白色沈殿をデカ
ンテーシヨン法で十分に水洗し、別、水洗し
た。得られた白色沈殿を120℃で乾燥し、空気中
で400℃で６時間焼成した後、10〜16メツシユの
粒状に成型し、Zr（HPO4）2触媒を調製した。
酸化ランタン（La2O3）21.2ｇ（0.065モル）を
硝酸水溶液に完全に溶解させた後、加熱濃縮して
硝酸ランタンを調製し、これに水を加えて400c.c.
の硝酸ランタン水溶液とした。次に、リン酸水素
ナトリウム（Na2HPO4）20.3ｇ（0.143モル）含
む水溶液100c.c.を加えると白色沈殿が生成する。
これを80℃で１時間撹拌後、白色沈殿をデカンテ
ーシヨン法で十分に水洗し、過によつて分離、
水洗した。得られた白色沈殿を120℃で乾燥し、
空気気流中にて、400℃で６時間焼成した後、10
〜16メツシユの粒状に成型しLaPO4触媒を調製
した。
第１図に示した内径12mmのパイレツクス製反応
管９の後段触媒層６にZr（HPO4）2触媒５c.c.を充
填し、前段触媒層５にLaPO4触媒５c.c.を充填し、
蒸発部４に直径３mmの熔触アルミナボールを充填
した。この反応管を、前段触媒層温度および後段
触媒層温度を夫々独立して調節できる電気炉に固
定し、ドライアイストラツプに浸漬した反応液受
器８と、第１図に示したように連結した。次に、
反応管上部のキヤリヤ−ガスフイード管３より窒
素ガスを40ml／分で触媒層に通じ、触媒層温度を
前段、後段共に275℃とした。原料フイード管Ｂ
２よりメタノールを1.5ｇ／hrの速度で供給し、
次いで原料フイード管Ａ１より47重量％濃度のα
−オキシイソ酪酸アミド水溶液を1.0ｇ／hrの速
度で供給した。原料供給開始後３時間から４時間
の間の反応液をドライアイストラツプ８で捕集
し、ガスクロマトグラフ法で分析を行つたとこ
ろ、原料α−オキシイソ酪酸アミドに対するメタ
クリル酸メチルのモル収率は89.0％であつた。メ
タクリル酸メチル以外の副反応生成物はアセトン
が8.4％（α−オキシイソ酪酸アミドに対するモ
ル収率）含まれているだけでジメチルエーテルは
検出されなかつた。
実施例 ２〜７
触媒および反応温度を表−１に示したように変
えたほかは実施例１と同じ装置および同じ方法で
実験を行つた。用いたりん酸塩触媒は、通常の公
知の方法によつて調製した。すなわち、金属硝酸
塩、金属塩化物または金属酸化物と、85％リン酸
またはリン酸塩を水溶液中で直接反応させた後、
蒸発乾固または、水溶液より生成したリン酸塩を
分離、水洗して得られた固体を120℃で十分に乾
燥した。このように調製されたリン酸塩および市
販のリン酸塩をペレツト状に成型し、250゜〜600
℃で５時間焼成した後、10〜16メツシユの粒状に
破砕して触媒とした。
また、酸化物触媒の内、SiO2−MgOはケイ酸
ソーダ水溶液に塩化マグネシウム水溶液を加え、
得られた沈殿を十分に水洗後、過乾燥し、500
℃で５時間焼成し、10〜16メツシユの粒状に破砕
して触媒とした。また、TiO2はTiCl4を冷水に添
加溶解後加熱加水分解し、得られた沈殿を十分に
水洗後、過乾燥し、500℃で５時間焼成し、10
〜16メツシユの粒状に破砕して触媒とした。さら
に、ZrO2はZrOCl2水溶液にアンモニア水を加え、
得られた沈殿を十分に水洗後、過乾燥し、500
℃で５時間焼成し、10〜16メツシユの粒状に破砕
して触媒とした。
表−１に使用した触媒、反応温度および結果を
示した。
The present invention relates to a method for producing an α,β-unsaturated carboxylic acid ester. More specifically, the present invention relates to a method for producing an α,β-unsaturated carboxylic acid ester by reacting an α-oxycarboxylic acid amide with water and an aliphatic alcohol using a solid acid as a catalyst. As a method for producing α,β-unsaturated carboxylic acid ester, such as methyl methacrylate, there is a method in which acetone cyanohydrin is reacted with concentrated sulfuric acid to form methacrylamide sulfate, and then esterified using methanol. This method has been carried out industrially for some time, but its disadvantages include corrosion of the equipment material by concentrated sulfuric acid and the production of a large amount of low-value ammonium sulfate as a by-product. As a result of intensive research into a method for producing α,β-unsaturated carboxylic acids and their esters from cyanohydrin without using sulfuric acid, the present inventors have already found that α-oxycarboxylic acids obtained by the hydration reaction of cyanohydrin. Amide and water and/or aliphatic alcohol are mixed in a gas phase at a temperature of 150°C or higher.
He discovered a method for producing α,β-unsaturated carboxylic acids and their esters by reacting them in a liquid phase or a gas-liquid mixed phase using a solid acid catalyst, and filed an application for the invention (Japanese patent application filed in 1983). −143591). By this method, a mixture of α-oxycarboxylic acid amide and water and/or alcohol is brought into contact with a catalyst to produce α,β-unsaturated Carboxylic acids and their esters can be produced. In addition, in conventional methods, the nitrogen content in raw materials was extracted as low-value byproducts such as ammonium sulfate.
With this method, alkylamines and/or ammonia, which are industrially important intermediates, can be extracted. However, when producing α,β-unsaturated carboxylic acid ester using this method, the desired α,β-unsaturated carboxylic acid ester
In addition to the β-unsaturated carboxylic acid ester, ether is produced as a by-product due to the dehydration reaction of the aliphatic alcohol. The amount of ether by-produced varies depending on the type of catalyst used and the reaction conditions, and the catalyst and reaction conditions that produce a higher yield of α,β-unsaturated carboxylic acid ester produce more ether by-product. Ether by-products not only complicate the separation and purification process of α,β-unsaturated carboxylic acid esters, but also produce α,β-unsaturated carboxylic acid esters depending on the economic value and demand for the by-product ethers. There was a problem in that the method for producing acid esters was uneconomical. The present inventors have conducted intensive studies on a method for producing α,β-unsaturated carboxylic acid esters using α-oxycarboxylic acid amide as a raw material, and a method for suppressing ether by-products as much as possible or completely. The method of the present invention has been achieved. That is, the method of the present invention involves reacting an α-oxycarboxylic acid amide obtained by a hydration reaction of cyanohydrin with an aliphatic alcohol in a gas phase, a liquid phase, or a gas-liquid mixed phase using a solid acid catalyst. In preparing an α,β-unsaturated carboxylic acid ester by first contacting an α-oxycarboxylic acid amide, preferably in the presence of water, with a first solid acid catalyst, the resulting This is a method for producing an α,β-unsaturated carboxylic acid ester by contacting a reaction mixture with an aliphatic alcohol with a second solid acid catalyst, and the method involves producing an ether as a by-product due to the dehydration reaction of the aliphatic alcohol. can be virtually completely suppressed. In general, solid acid catalysts include metal elements and a,
a, a catalyst containing at least one of phosphates, sulfates and oxides of nonmetallic elements of group a;
Solid phosphoric acid catalysts, more specifically activated carbon,
cation exchange resins, α-boron and nickel metal, etc. More specifically, the solid phosphoric acid catalyst is a catalyst in which phosphoric acid is supported on a known carrier, such as diatomaceous earth, and subjected to appropriate thermal calcination. In addition, solid acid catalysts containing phosphates include a, b, a, b, a,
b, lanthanide, actinide, a, b,
elements selected from a, b, b, b and group elements, such as Li, Na, K, Rb, Cs, Be,
Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd,
Sm, Gd, Th, U, Ti, Zr, Hf, V, Nb, Ta,
Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag,
A phosphate of at least one element such as Zn, Cd, B, Al, Ga, In, Tl, Sn, Pb, Sb and Bi, or a mixture of two or more phosphates,
These are catalysts containing phosphates. The atomic ratio (M/P) of these elements (denoted as M) and phosphorus (denoted as P) in the phosphate ranges from 0 to 3 (where M/P=0 corresponds to solid phosphoric acid). ). The structure of these phosphates is not limited in any way, as long as the atomic ratio (M/P) between the above elements and phosphorus satisfies the range of 0 to 3. These phosphates can be produced by any known method. For example, Preparative Inorganic Reactions Vol. 2, pp. 139-167, 1965.
Inorganic Reactions 2 , 139-167 (1965)], that is, a method in which a metal, a metal oxide, or a metal salt is reacted with phosphoric acid or a phosphate salt. Alternatively, a special method such as a manufacturing method using a reaction between a metal alcoholate and phosphoric acid may be used. Catalysts containing phosphates can be produced by kneading or dipping the above-mentioned phosphates and, if necessary, other sulfates and metal oxides on a generally known carrier such as activated carbon, silica, silica-alumina, or alumina. It can be manufactured by a known method such as. In addition, a mixture catalyst of a metal oxide and a phosphate can also be produced, for example, by adding an excess of a metal oxide to phosphoric acid and causing the reaction to occur. In addition, solid acid catalysts containing sulfates include Li,
Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Cr,
Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, In, Sn,
and a sulfate or acidic sulfate of at least one element selected from Pb, or a catalyst containing these sulfates or acidic sulfates. These sulfate-containing solid acid catalysts are prepared by mixing the metal sulfate or acid sulfate with other metal oxides, phosphates, and carriers as necessary by a generally known kneading method, dipping method, etc. It can be manufactured by Furthermore, a solid acid catalyst containing an oxide is
Be, Mg, Y, La, Ce, Th, U, Ti, Zr, V,
Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn,
An oxide of at least one element selected from Cd, B, Al, Si, Sb, and Bi, or a composite oxide that is a mixed oxide of two or more elements, or a phosphate of these oxides, It is a mixture with a sulfate or a carrier. As a carrier, known activated carbon,
Examples include silica, alumina, and silicon carbide.
Catalysts containing these oxides or composite oxides and other catalyst constituents can be prepared using known methods, such as
It can be manufactured by methods such as precipitation method and dipping method. Among these solid acid catalysts, the first and second solid acid catalysts in the method of the present invention are selected.
That is, the first solid acid catalyst is a catalyst containing at least one of aluminum phosphate, magnesium phosphate, yttrium phosphate, lanthanum phosphate, cerium phosphate, praseodymium phosphate, or a composite oxide of magnesium oxide and silicon oxide. On the other hand, as the second solid acid catalyst, a catalyst containing at least one of titanium phosphate, zirconium phosphate, titanium oxide, or zirconium oxide is used. The α-oxycarboxylic acid amide used in the method of the present invention has the general formula () (In the formula, R 1 and R 2 represent hydrogen or an alkyl group, provided that at least one of them is an alkyl group.) Such α−
Examples of oxycarboxylic acids include various α-carboxylic acids, such as lactic acid amide, α-oxybutyric acid amide, α-oxyisobutyric acid amide, α-oxyvaleric acid amide, α-oxyisovaleric acid amide, α-methyl-α-oxybutyric acid amide, etc. -Oxycarboxylic acid amide. Furthermore, examples of the aliphatic alcohol used in the method of the present invention include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc. various aliphatic alcohols and substituted aliphatic alcohols, and are selected from these alcohols depending on the purpose. In the method of the present invention, the reaction can be carried out by either a gas phase method or a liquid phase method as long as the reactant is brought into contact with a solid acid catalyst, but a gas phase or a gas-liquid mixed phase is preferable. The method can be any arbitrary method such as a fixed bed method or a fluidized bed method. In the process of the invention, the α-oxycarboxylic acid amide is contacted with a first solid acid catalyst, preferably together with water, and then, without separating the resulting reaction mixture, is brought into contact with a second solid acid catalyst together with an aliphatic alcohol. Contact with an acid catalyst yields an α,β-unsaturated carboxylic acid ester. There is no particular restriction on the amount of raw material used, but usually 0 to 200 mol, preferably 1 to 50 mol of water per 1 mol of α-oxycarboxylic acid amide, and aliphatic acid to be reacted together with the reaction mixture. The alcohol ranges from 1 to 200 moles, preferably from 1 to 50 moles. The reaction temperature, reaction pressure, contact time, etc. may be the same or different between the contact reactions with the first and second solid acid catalysts, as long as they are within the following ranges. That is, the reaction temperature is 150℃~500℃
In particular, 200°C to 450°C is preferable. The contact time with the reactant can be varied within a wide range depending on the catalyst, reaction temperature, and other reaction conditions, but is usually 0.5 to
The purpose of the present invention can be achieved within a range of 360 seconds. The reaction pressure may normally be atmospheric pressure, but may also be under increased pressure or reduced pressure. Further, in carrying out the reaction, the reaction raw material may be brought into contact with the catalyst layer while being accompanied by an inert gas such as nitrogen gas. Further, although not necessarily required, the reaction may be started after ammonia or aqueous ammonia is supplied to the catalyst layer as a pretreatment of the catalyst. Examples will be shown below to specifically explain the method of the present invention. Note that the display formula of the phosphate-containing catalyst used in the examples does not necessarily indicate the structure of the phosphate contained in the catalyst, but rather the atomic ratio of the metal to phosphorus in the phosphate ( M/P). For example, even if the phosphate under the reaction conditions is a condensed phosphate such as a metaphosphate or a pyrophosphate, the catalyst is shown as the corresponding orthophosphate. Example 1 Zirconium oxychloride (ZrOCl 2 8H 2 O)
Dissolve 36.1 g (0.112 mol) in 50 ml of water and add it to phosphate monosodium salt (NaH 2 PO 4・2H 2 O) 156
Dissolve g (1 mol) in 200 ml of 3N hydrochloric acid and heat at 80℃.
When added to a heated solution under stirring, a white precipitate is formed. After stirring for 1 hour, the white precipitate was thoroughly washed with water by decantation and then washed with water separately. The obtained white precipitate was dried at 120° C., calcined in air at 400° C. for 6 hours, and then molded into particles of 10 to 16 meshes to prepare a Zr(HPO 4 ) 2 catalyst. After completely dissolving 21.2 g (0.065 mol) of lanthanum oxide (La 2 O 3 ) in an aqueous nitric acid solution, it was heated and concentrated to prepare lanthanum nitrate, and water was added to this to make 400 c.c.
was made into an aqueous solution of lanthanum nitrate. Next, 100 c.c. of an aqueous solution containing 20.3 g (0.143 mol) of sodium hydrogen phosphate (Na 2 HPO 4 ) is added to form a white precipitate.
After stirring this at 80℃ for 1 hour, the white precipitate was thoroughly washed with water by decantation method, separated by filtration,
Washed with water. The obtained white precipitate was dried at 120°C,
After baking at 400℃ for 6 hours in an air stream, 10
The LaPO 4 catalyst was prepared by molding it into granules of ~16 meshes. The rear catalyst layer 6 of the Pyrex reaction tube 9 with an inner diameter of 12 mm shown in FIG. ,
The evaporation section 4 was filled with molten alumina balls having a diameter of 3 mm. This reaction tube was fixed in an electric furnace in which the temperature of the front catalyst layer and the temperature of the rear catalyst layer could be adjusted independently, and connected to the reaction liquid receiver 8 immersed in a dry ice trap as shown in FIG. . next,
Nitrogen gas was passed through the carrier gas feed pipe 3 at the upper part of the reaction tube to the catalyst layer at a rate of 40 ml/min, and the temperature of the catalyst layer was set at 275° C. in both the front and rear stages. Raw material feed pipe B
2, methanol was supplied at a rate of 1.5 g/hr,
Next, α with a concentration of 47% by weight is supplied from the raw material feed pipe A1.
-Aqueous oxyisobutyric acid amide solution was fed at a rate of 1.0 g/hr. When the reaction solution was collected for 3 to 4 hours after the start of raw material supply using dry ice trap 8 and analyzed by gas chromatography, the molar yield of methyl methacrylate based on the raw material α-oxyisobutyric acid amide was 89.0. It was %. The side reaction products other than methyl methacrylate contained only 8.4% acetone (molar yield relative to α-oxyisobutyric acid amide) and no dimethyl ether was detected. Examples 2 to 7 Experiments were conducted using the same equipment and method as in Example 1, except that the catalyst and reaction temperature were changed as shown in Table 1. The phosphate catalyst used was prepared by conventional known methods. That is, after directly reacting metal nitrate, metal chloride or metal oxide with 85% phosphoric acid or phosphate in an aqueous solution,
The solid obtained by evaporation to dryness or separation of the phosphate produced from the aqueous solution and washing with water was thoroughly dried at 120°C. The phosphates thus prepared and commercially available phosphates were molded into pellets and heated at 250° to 600°.
After calcining at ℃ for 5 hours, the catalyst was crushed into particles of 10 to 16 meshes. Among the oxide catalysts, SiO 2 −MgO is prepared by adding a magnesium chloride aqueous solution to a sodium silicate aqueous solution.
The obtained precipitate was thoroughly washed with water, overdried, and
The mixture was calcined at ℃ for 5 hours and crushed into particles of 10 to 16 meshes to form a catalyst. TiO 2 can be obtained by adding TiCl 4 to cold water, dissolving it, heating and hydrolyzing it, washing the resulting precipitate thoroughly with water, over-drying it, baking it at 500°C for 5 hours, and then heating and hydrolyzing it.
It was crushed into particles of ~16 mesh and used as a catalyst. Furthermore, ZrO 2 is obtained by adding ammonia water to ZrOCl 2 aqueous solution.
The obtained precipitate was thoroughly washed with water, overdried, and
The mixture was calcined at ℃ for 5 hours and crushed into particles of 10 to 16 meshes to form a catalyst. Table 1 shows the catalysts used, reaction temperatures, and results.
【表】
＊ ジメチルエーテルはα−オキシイソ酪酸アミ
ドからの生成物ではないが、便宜上ジメ
チルエーテル生成量をα−オキシイソ酪酸アミ
ド供給量に対するモル％で表示した。
比較例 １〜８
単一の触媒層にα−オキシイソ酪酸アミド、水
およびメタノールを一緒にフイードした時のメタ
クリル酸エチルの生成量と副生するジメチルエー
テルの生成量の関係を見るために、実施例１と同
じ装置を用い、前段触媒層には直径３mmの熔触ア
ルミナボールを充填し、後段触媒層には実施例で
用いたと同じ触媒を５c.c.充填し、第１図に示した
原料フイード管Ａ１より47重量％濃度のα−オキ
シイソ酪酸アミド水溶液を1.0ｇ／hr、メタノー
ルを1.5ｇ／hrの速度で一緒に供給した。その他
は実施例１と同様にして、表−２の結果を得た。[Table] *Although dimethyl ether is not a product from α-oxyisobutyric acid amide, for convenience, the amount of dimethyl ether produced is expressed as mol% relative to the amount of α-oxyisobutyric acid amide supplied.
Comparative Examples 1 to 8 In order to see the relationship between the amount of ethyl methacrylate produced and the amount of dimethyl ether produced as a by-product when α-oxyisobutyric acid amide, water and methanol were fed together into a single catalyst layer, Examples were Using the same equipment as in Figure 1, the first stage catalyst layer was filled with molten alumina balls with a diameter of 3 mm, the second stage catalyst bed was filled with 5 c.c. of the same catalyst used in the example, and the raw materials shown in Figure 1 were filled. An α-oxyisobutyric acid amide aqueous solution having a concentration of 47% by weight was fed together at a rate of 1.0 g/hr and methanol at a rate of 1.5 g/hr from feed pipe A1. Other conditions were the same as in Example 1, and the results shown in Table 2 were obtained.
【表】【table】
第１図は、実施例および比較例で使用した反応
装置を示す。
図中、各記号の意味は次の通りである。１：原
料フイード管Ａ、２：原料フイード管Ｂ、３：キ
ヤリヤーガスフイード管、４：蒸発部、５：前段
触媒層、６：後段触媒層、７：反応液受器、８：
ドライアイストラツプ、９：パイレツクス製反応
管。
FIG. 1 shows the reaction apparatus used in Examples and Comparative Examples. In the figure, the meaning of each symbol is as follows. 1: Raw material feed pipe A, 2: Raw material feed pipe B, 3: Carrier gas feed pipe, 4: Evaporation section, 5: First stage catalyst layer, 6: Second stage catalyst layer, 7: Reaction liquid receiver, 8:
Dry ice trap, 9: Pyrex reaction tube.
Claims (1)
示し、ただし少なくとも一方はアルキル基であ
る） で表されるα−オキシカルボン酸アミドを、好ま
しくは水の存在下で、りん酸アルミニウム、りん
酸マグネシウム、りん酸イツトリウム、りん酸ラ
ンタン、りん酸セリウム、りん酸プラセオジウム
または酸化マグネシウムと酸化ケイ素の複合酸化
物を少なくとも一種含有する第１の固体酸触媒と
接触反応させ、次いで、得られた反応混合物を脂
肪族アルコールとともに、りん酸チタン、りん酸
ジルコニウム、酸化チタンまたは酸化ジルコニウ
ムを少なくとも一種含有する第２の固体酸触媒と
接触反応させることを特徴とするα，β−不飽和
カルボン酸エステルの製造方法。[Claims] 1 formula (In the formula, R 1 and R 2 represent hydrogen or an alkyl group, provided that at least one is an alkyl group.) Preferably in the presence of water, aluminum phosphate, Contact reaction is performed with a first solid acid catalyst containing at least one of magnesium phosphate, yttrium phosphate, lanthanum phosphate, cerium phosphate, praseodymium phosphate, or a composite oxide of magnesium oxide and silicon oxide, and then the obtained An α,β-unsaturated carboxylic acid ester characterized by contacting the reaction mixture with an aliphatic alcohol and a second solid acid catalyst containing at least one of titanium phosphate, zirconium phosphate, titanium oxide, or zirconium oxide. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56145518A JPS5849338A (en) | 1981-09-17 | 1981-09-17 | Preparation of alpha, beta-unsaturated carboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56145518A JPS5849338A (en) | 1981-09-17 | 1981-09-17 | Preparation of alpha, beta-unsaturated carboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5849338A JPS5849338A (en) | 1983-03-23 |
| JPS6363537B2 true JPS6363537B2 (en) | 1988-12-07 |
Family
ID=15387079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56145518A Granted JPS5849338A (en) | 1981-09-17 | 1981-09-17 | Preparation of alpha, beta-unsaturated carboxylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5849338A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002371046A (en) * | 2001-06-11 | 2002-12-26 | Showa Denko Kk | Method for producing 2-hydroxycarboxylic amide |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4613684A (en) * | 1983-10-06 | 1986-09-23 | Mitsubishi Gas Chemical Company, Inc. | Process for the preparation of carboxylic acid esters |
| NL8501788A (en) * | 1985-06-21 | 1987-01-16 | Philips Nv | METHOD FOR MANUFACTURING A DRAWING STONE. |
| JP2580706B2 (en) * | 1988-05-16 | 1997-02-12 | 三菱瓦斯化学株式会社 | Method for producing carboxylic acid ester |
| JP2580707B2 (en) * | 1988-05-16 | 1997-02-12 | 三菱瓦斯化学株式会社 | Method for producing carboxylic acid ester |
| JP4810770B2 (en) * | 2001-07-18 | 2011-11-09 | 三菱瓦斯化学株式会社 | Method for producing allyl methacrylate |
| JP4583830B2 (en) * | 2004-07-22 | 2010-11-17 | 三洋化成工業株式会社 | Unsaturated monocarboxylic acid ester and method for producing the same |
| JP4997497B2 (en) * | 2006-04-28 | 2012-08-08 | 国立大学法人長岡技術科学大学 | Catalyst for esterification reaction in water consisting of sulfonated natural rubber copolymer |
| KR102146094B1 (en) | 2016-08-24 | 2020-08-19 | 주식회사 엘지화학 | Catalyst for dehydration of preparing n-substituted maleimides, method of preparing the same, and preparing method of n-substituted maleimides |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161609A (en) * | 1977-09-14 | 1979-07-17 | E. I. Du Pont De Nemours And Company | Synthesis of carboxylic acid esters |
| JPS554310A (en) * | 1978-06-23 | 1980-01-12 | Nippon Kayaku Co Ltd | Preparation of metacrolein and methacrylic acid |
| JPS5536000A (en) * | 1978-09-05 | 1980-03-13 | Halcon International Inc | Catalyst composition for manufacturing metachlorein*its preparation method and metachlorein manufacturing method |
| JPS5545617A (en) * | 1978-09-27 | 1980-03-31 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid from isobutylene and/or t-butanol |
| JPS5555130A (en) * | 1978-10-19 | 1980-04-22 | Asahi Chem Ind Co Ltd | Preparation of methacrolein |
-
1981
- 1981-09-17 JP JP56145518A patent/JPS5849338A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161609A (en) * | 1977-09-14 | 1979-07-17 | E. I. Du Pont De Nemours And Company | Synthesis of carboxylic acid esters |
| JPS554310A (en) * | 1978-06-23 | 1980-01-12 | Nippon Kayaku Co Ltd | Preparation of metacrolein and methacrylic acid |
| JPS5536000A (en) * | 1978-09-05 | 1980-03-13 | Halcon International Inc | Catalyst composition for manufacturing metachlorein*its preparation method and metachlorein manufacturing method |
| JPS5545617A (en) * | 1978-09-27 | 1980-03-31 | Nippon Kayaku Co Ltd | Preparation of methacrylic acid from isobutylene and/or t-butanol |
| JPS5555130A (en) * | 1978-10-19 | 1980-04-22 | Asahi Chem Ind Co Ltd | Preparation of methacrolein |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002371046A (en) * | 2001-06-11 | 2002-12-26 | Showa Denko Kk | Method for producing 2-hydroxycarboxylic amide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5849338A (en) | 1983-03-23 |
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