CN105263618B - Solid catalyst and used the solid catalyst isocyanate compound manufacture method - Google Patents
Solid catalyst and used the solid catalyst isocyanate compound manufacture method Download PDFInfo
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- CN105263618B CN105263618B CN201480029670.4A CN201480029670A CN105263618B CN 105263618 B CN105263618 B CN 105263618B CN 201480029670 A CN201480029670 A CN 201480029670A CN 105263618 B CN105263618 B CN 105263618B
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- Prior art keywords
- solid catalyst
- compound
- silica
- catalyst
- manufacture method
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- 238000000034 method Methods 0.000 title claims abstract description 167
- -1 isocyanate compound Chemical class 0.000 title claims abstract description 139
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 132
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 108
- 239000012948 isocyanate Substances 0.000 title claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 197
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 55
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000011148 porous material Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 27
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052753 mercury Inorganic materials 0.000 claims description 20
- 230000035515 penetration Effects 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical group 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 150000003388 sodium compounds Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 31
- 230000008569 process Effects 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 19
- 239000000741 silica gel Substances 0.000 description 18
- 229910002027 silica gel Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 13
- 125000006630 butoxycarbonylamino group Chemical group 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 238000007210 heterogeneous catalysis Methods 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000004452 microanalysis Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000006627 ethoxycarbonylamino group Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 125000004436 sodium atom Chemical group 0.000 description 4
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
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- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- IESROWBDLANHBQ-UHFFFAOYSA-N dimethylcarbamic acid;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound CN(C)C(O)=O.CC1=CC(=O)CC(C)(C)C1 IESROWBDLANHBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 150000002513 isocyanates Chemical class 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- OXNAJPQXTZANJL-UHFFFAOYSA-N methyl n-hexylcarbamate Chemical compound CCCCCCNC(=O)OC OXNAJPQXTZANJL-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
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- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 1
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical class CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- UMSGIWAAMHRVQI-UHFFFAOYSA-N 1-ethyl-4-(4-ethylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(CC)C=C1 UMSGIWAAMHRVQI-UHFFFAOYSA-N 0.000 description 1
- KBRSJPHSCOAFDR-UHFFFAOYSA-N 3-chloro-6-methyl-5,5-dioxo-11h-benzo[c][2,1]benzothiazepin-11-ol Chemical compound O=S1(=O)N(C)C2=CC=CC=C2C(O)C2=CC=C(Cl)C=C21 KBRSJPHSCOAFDR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
- PILVIBLEOYWKLP-UHFFFAOYSA-N diethylcarbamic acid;toluene Chemical class CC1=CC=CC=C1.CCN(CC)C(O)=O PILVIBLEOYWKLP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- KXABTIOYSXLRSL-UHFFFAOYSA-N dodecyl(methyl)carbamic acid Chemical class CCCCCCCCCCCCN(C)C(O)=O KXABTIOYSXLRSL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LQHZJYFIRFRDKF-UHFFFAOYSA-N gold magnesium Chemical compound [Mg].[Au] LQHZJYFIRFRDKF-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- JFOZKMSJYSPYLN-QHCPKHFHSA-N lifitegrast Chemical compound CS(=O)(=O)C1=CC=CC(C[C@H](NC(=O)C=2C(=C3CCN(CC3=CC=2Cl)C(=O)C=2C=C3OC=CC3=CC=2)Cl)C(O)=O)=C1 JFOZKMSJYSPYLN-QHCPKHFHSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- ONDKZBMQUACRQG-UHFFFAOYSA-N methyl n-[1,6-bis(methoxycarbonylamino)hexan-3-yl]carbamate Chemical class COC(=O)NCCCC(NC(=O)OC)CCNC(=O)OC ONDKZBMQUACRQG-UHFFFAOYSA-N 0.000 description 1
- VLPBGAPTYGNIII-UHFFFAOYSA-N methyl n-[4-[4-(methoxycarbonylamino)phenyl]phenyl]carbamate Chemical group C1=CC(NC(=O)OC)=CC=C1C1=CC=C(NC(=O)OC)C=C1 VLPBGAPTYGNIII-UHFFFAOYSA-N 0.000 description 1
- ZWZIHLRSOOMEKT-UHFFFAOYSA-N methyl n-benzylcarbamate Chemical compound COC(=O)NCC1=CC=CC=C1 ZWZIHLRSOOMEKT-UHFFFAOYSA-N 0.000 description 1
- GSJBUZRBVXHKIU-UHFFFAOYSA-N methyl n-dodecylcarbamate Chemical compound CCCCCCCCCCCCNC(=O)OC GSJBUZRBVXHKIU-UHFFFAOYSA-N 0.000 description 1
- RRQZQNFQNFVZCU-UHFFFAOYSA-N methyl n-nonylcarbamate Chemical class CCCCCCCCCNC(=O)OC RRQZQNFQNFVZCU-UHFFFAOYSA-N 0.000 description 1
- VBJIQWCGMYVMKK-UHFFFAOYSA-N methyl n-pentylcarbamate Chemical class CCCCCNC(=O)OC VBJIQWCGMYVMKK-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 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
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 1
- VXMFUQFJHWRHDL-UHFFFAOYSA-N phenyl n-dodecylcarbamate Chemical class CCCCCCCCCCCCNC(=O)OC1=CC=CC=C1 VXMFUQFJHWRHDL-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The problem of the present invention is, repeatability provides well can manufacture isocyanate compound with high selectivity and in high yield and with the easy catalyst of separation of product etc..The present invention relates to containing the solid catalyst that is at least one kind of metallic compound and silica and meeting 2 following conditions simultaneously in alkali metal compound and alkali earth metallic compound, the manufacture method of isocyanate compound for utilizing carbamate compounds to manufacture isocyanate compound in the presence of the catalyst is further related to:(1) it is 0.5~20 using the metallic atom of x-ray photoelectron analytical equipment measure, described metallic compound and the atomic ratio (M/Si) of the silicon atom in the silica.(2) it is 0.01m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure2/ g~50m2/g。
Description
Technical field
The present invention relates to a kind of at least one kind of metal containing in alkali metal compound and alkali earth metallic compound
The solid catalyst of compound and silica.Moreover, it relates to manufactured in the presence of described solid catalyst
The method of isocyanate compound.
Background technology
Isocyanate compound is that the manufacture raw material such as carbamate or medical agricultural chemicals is widely used
Useful compound.In the past, isocyanate compound was industrially to be manufactured by the reaction of amine and phosgene (referring for example to special
Sharp document 1).
As the manufacture method of the isocyanate compound without using phosgene, for example, it is known have make three haloacetyl amines
Compound carries out the side of haloform in the presence of the haloid of alkali metal or the catalyst such as haloid of alkaline-earth metal
Method (referring for example to patent document 2).
In addition, the manufacture method as the isocyanate compound without using phosgene, it is also known that have amino for example
The method of formic acid ester compound thermal decomposition (referring for example to patent document 3).
As the method for manufacturing isocyanate compound by the carbamate compounds using homogeneous catalyst, such as
Proposed method (example carbamate compounds decomposed in the liquid phase and with organotin catalysts and solid acid catalyst
As with reference to patent document 4).
Thermal decomposition of these the known tin catalysts for carbamate compounds shows suitable reaction achievement.
And on the other hand, it was also proposed that cross and carbamate compounds are thermally decomposed using heterogeneous catalysis and manufacture isocyanide
The method of ester compound.
It is known to have following method:As described heterogeneous catalysis, calcium oxide, magnesia, barium monoxide, magnesium gold are used
Category etc., toluene diethylamino formic acid esters is thermally decomposed to manufacture isocyanate compound as carbamate compounds
(referring for example to patent document 3);As heterogeneous catalysis, using sodium carbonate, calcium carbonate etc., by N- (isopropenyl-α, α-
Dimethyl benzyl) carbamic acid such as carbamic acid isopropyl ester, N- (vinyl-alpha, alpha-dimethylbenzyl) carbamic acid isopropyl ester
Ester compounds are thermally decomposed to manufacture isocyanate compound (for example, referring to patent document 5 and patent document 6).
On the other hand, as using heterogeneous catalysis, without using solvent, make carbamate under gas phase condition with urging
Agent contacts, and is thermally decomposed to manufacture the method for isocyanate compound, such as known has following method etc.:As catalysis
Agent, using at least one kind of in the IB races in periodic table or the transition metal of VIII, lanthanide and actinides
The oxidate sintered body of element above or the oxidate sintered body containing alkali metal and/or alkaline-earth metal element, come
Manufacture isocyanate compound (referring for example to patent document 7 and patent document 8).
In addition, it further developed and be loaded with being selected from alkali metal compound and alkaline-earth metal on silica supports
The isocyanate compound catalyst for producing of at least one kind of metallic compound in compound (referring for example to patent document 9).
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 11-310566 publications
Patent document 2:International Publication No. 2011/049023
Patent document 3:Japanese Unexamined Patent Application 54-88201 publications
Patent document 4:Japanese Unexamined Patent Publication 2004-262892 publications
Patent document 5:Japanese Unexamined Patent Publication 2003-012632 publications
Patent document 6:Japanese Unexamined Patent Publication 2004-018507 publications
Patent document 7:Japanese Unexamined Patent Publication 5-186414 publications
Patent document 8:Japanese Unexamined Patent Publication 5-186415 publications
Patent document 9:International Publication No. 2012/111750
The content of the invention
Invent problem to be solved
However, phosgene used in the manufacture method of foregoing patent document 1 is severe toxicity, it is secondary in large quantities to generate hydrogen chloride,
The manufacture method of patent document 2 secondary can generate the halide such as chloroform, and the manufacture method of patent document 3 is needed in harsh temperature strip
Thermally decomposed under part, therefore easily cause side reaction, the manufacture method of patent document 4 is due to tin catalyst equably to dissolve
State exist, therefore poisonous organotin catalysts being mixed into product can be caused cumbersome with catalyst reclaimer operation
Change, the activity of reaction in carbamate compounds and the choosing of isocyanate compound in the manufacture method of patent document 5~8
The aspect of selecting property is not abundant enough, from these from the aspect of, it cannot be said that be adapted for the manufacture method actually manufactured.
It is as described above in order to solve the problems, such as, as shown in described in patent document 9, develop and be selected from supported on carriers
The isocyanate compound catalyst for producing of at least one kind of metallic compound in alkali metal compound and alkali earth metallic compound
Agent, but in order to realize the manufacture method for being more suitable for actually manufacturing, it is desirable to propose repeatability or selective higher catalyst.
For the present invention in view of the situation of foregoing conventional art, its problem are, repeatability provides well can be high
Selectivity and in high yield manufacture isocyanate compound and the catalyst easily separated with product.In addition it is of the invention
Problem also resides in, there is provided has used the manufacture method of the isocyanate compound of such a catalyst.
For solving the method for problem
For this problem, the parameter of the catalyst impacted so far to selectivity, yield is unclear.Using
In the manufacture of the isocyanate compound of the catalyst of patent document 9, be carried on carrier selected from alkali metal compound and
At least one kind of metallic compound in alkali earth metallic compound plays a role as alkali, sloughs the nitrogen of carbamate compounds
On hydrogen atom, carry out decomposition reaction.
Thus it is expected that by increasing the content of foregoing metallic compound or increasing the specific surface area of catalyst
Deng and increase metal and the frequency of exposure of matrix, yield or selectivity can improve.
If however, the research such as the present inventor as a result, the content or catalyst of increase metallic compound
Specific surface area, then selectivity or yield can reduce.
The present inventor etc. are studied in further detail, are as a result found, are present in catalyst by control
The metallic atom on surface and the specific surface area of the atomic ratio of silicon atom and catalyst, can solve the problem, so as to complete
The present invention.
It has further been found that can by the ratio surface of the atomic ratio of the metallic atom of catalyst surface and silicon atom, catalyst
Product controls in scope described later, catalyst preparation condition, and excellent catalysis can be provided well with repeatability by completing
The manufacture method of the solid catalyst of agent.
Additionally, it is observed that when manufacturing isocyanate compound by carbamate compounds, by using containing metal
The catalyst of compound and silica, the new of isocyanate compound can be manufactured with high selectivity and in high yield
Industrialization production method, so as to complete the present invention.
The present invention is as follows.
The present invention 1 is related to a kind of solid catalyst, and it contains in alkali metal compound and alkali earth metallic compound
At least one kind of metallic compound and silica, while meet 2 following conditions.
(1) metallic atom in the metallic compound of x-ray photoelectron analytical equipment measure and the dioxy are utilized
The ratio of number of the atom of silicon atom in SiClx (hereinafter sometimes referred to as atomic ratio, is expressed as M/Si.) it is 0.5~20.
(2) it is 0.01m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure2/ g~50m2/g。
The present invention 2 is related to the solid catalyst described in the present invention 1, wherein, while meet 2 following conditions.
(3) M/Si is 0.8~10.
(4) it is 0.1m using the surface area of the solid catalyst of nitrogen adsorption methods measure2/ g~10m2/g。
The present invention 3 is related to the solid catalyst described in the present invention 1 or 2, wherein, the alkali metal compound closes for sodium
Thing or cesium compound.
The present invention 4 is related to the solid catalyst that the present invention any one of 1~3 records, wherein, the alkaline-earth metal chemical combination
Thing is magnesium compound or calcium compound.
The present invention 5 is related to the solid catalyst that the present invention any one of 1~4 records, wherein, the silica is porous
Silica.
The present invention 6 is related to the solid catalyst that the present invention any one of 1~5 records, wherein, the silica is amorphous
Matter silica.
The present invention 7 is related to the solid catalyst that the present invention any one of 1~6 records, wherein, the utilization of the silica
The intermediate value pore diameter of mercury penetration method measure is 0.1 μm~10 μm.
The present invention 8 be related to the present invention any one of 1~7 record solid catalyst, wherein, by make 700 DEG C~
1200 DEG C are burnt till silica obtained by 1~20 hour and adsorb the metallic compound, then burn till 1 at 300 DEG C~1200 DEG C
~40 hours and prepare.
The present invention 9 be related to the present invention any one of 1~7 record solid catalyst, wherein, by make 800 DEG C~
1100 DEG C are burnt till silica obtained by 1~10 hour and adsorb the metallic compound, then burn till 1 at 500 DEG C~1000 DEG C
~20 hours and prepare.
The present invention 10 is related to a kind of manufacture method of isocyanate compound, and it is recorded in the present invention any one of 1~9
In the presence of solid catalyst, isocyanate compound is manufactured using carbamate compounds.
The present invention 11 is related to the manufacture method described in the present invention 10, wherein, the carbamate compounds are following
The compound of formula (1) expression is stated,
[changing 1]
In formula, R1And R2Both can be the same or different, represent can have substituent alkyl, n represent 1~4 it is whole
Number.
The isocyanate compound is the compound represented with following formulas (2),
[changing 2]
In formula, n, R1With it is foregoing synonymous.
The present invention 12 is related to the manufacture method described in the present invention 11, wherein, the n in the formula (1) and (2) is 2.
The present invention 13 is related to the manufacture method that the present invention any one of 10~12 records, wherein, utilize the carbamic acid
Reaction temperature when ester compounds manufacture the isocyanate compound is 300 DEG C~500 DEG C.
The present invention 14 is related to the manufacture method that the present invention any one of 10~13 records, wherein, utilize the carbamic acid
Reaction pressure during the ester compounds manufacture isocyanate compound is absolute pressure 0.1kPa~101.33kPa.
The present invention 15 is related to the manufacture method that the present invention any one of 10~14 records, wherein, carried out in the form of gas phase
The reaction during isocyanate compound is manufactured using the carbamate compounds.
The present invention 16 is related to the manufacture method that the present invention any one of 10~14 records, wherein, carried out in the form of liquid phase
The reaction during isocyanate compound is manufactured using the carbamate compounds.
The present invention 17 is related to the solid catalyst of the record of the present invention any one of 1~9 in isocyanate compound is manufactured
Application.
Invention effect
According to the solid catalyst of the present invention, in the solid catalyst containing defined metallic compound and silica
The metallic compound metallic atom and the silica in silicon atom atomic ratio (M/Si) and the solid
Catalyst using nitrogen adsorption methods measure specific surface area this two simultaneously meet foregoing condition when, can with high selectivity,
Isocyanate compound is manufactured in high yield.
According to the present invention it is possible to repeatability manufactures such a solid catalyst well, it may, furthermore, provide having used this
The manufacture method of the isocyanate compound of kind solid catalyst.
Brief description of the drawings
Fig. 1 is the schematic diagram of the reaction unit of the gas phase fixed bed mode used in embodiment.
Fig. 2 be by the atomic ratio Ca/Si ratios of the specific surface area of the solid catalyst of embodiment, calcium atom and silicon atom and
The yield of diisocyanate cpd concentrates figure in the graph (comparative example 1 is not shown).It should be noted that in Fig. 2,
" S.A. " represents the specific surface area (m of the solid catalyst using nitrogen adsorption methods measure2/ g), " Ca/Si " represents solid catalysis
The atomic ratio of calcium atom and silicon atom on agent surface, " BII yields (BII Yield) " represent the receipts of diisocyanate cpd
Rate (%).
Embodiment
Hereinafter, the present invention is described in detail.3 following contents are illustrated.
(A) composition of solid catalyst
(B) preparation method of solid catalyst
(C) manufacture method of isocyanate compound
[composition of (A) solid catalyst]
The solid catalyst of the present invention is containing at least one kind of in alkali metal compound and alkali earth metallic compound
Metallic compound and silica, manufacture suitable for isocyanate compound catalyst.The solid catalyst of the present invention
It can use with other catalyst combinations, therefore in the solid catalyst of the present invention, also include relative to described containing gold
Category compound and silica solid catalyst and be physically mixed with containing with described metallic compound and silica
The catalyst of the solid catalyst of different inorganic compounds.
In the solid catalyst of the present invention, in the metallic atom and silica in the metallic compound on its surface
The atomic ratio (M/Si) of silicon atom is 0.5~20,0.7~10 is more preferably from the viewpoint of selectivity or yield, further
Preferably 0.8~10, particularly preferably 1~6.By like this by the metallic compound (metal compound on the surface of catalyst
Thing is considered as the material for mainly helping catalyst reaction) in metallic atom and silica in silicon atom atomicity
Ratio be set to certain scope, it is possible to realize excellent selectivity and yield.
It should be noted that in this specification, the atomic ratio (M/Si) on the surface of foregoing solid catalyst is penetrated using X
The value of Photoelectron analytical equipment (ESCA) measure.
In addition, the specific surface area using nitrogen adsorption methods measure of the solid catalyst of the present invention is 0.01m2/ g~50m2/
G, 0.1m is more preferably from the viewpoint of selectivity or yield2/ g~10m2/ g, more preferably 0.1m2/ g~5m2/ g,
Particularly preferably 0.2m2/ g~3m2/g。
Pore is there are in silica, and the pore is generally divided into this 3 kinds of micropore, mesopore, macropore.Micropore is diameter
Pore less than 2nm, mesopore are a diameter of 2nm~50nm pores, macropore be diameter more than 50nm pore (referring for example to
Carbon, 2008,850-857.).
Micropore, mesopore are believed to provide catalyst substantial amounts of reflecting point, but on the other hand in the part consumingly
Association reaction matrix, it may will not also depart from even if reaction end product at this or non-targeted reaction is carried out.Examined in the present invention
Consider, such as silica is handled by using defined method described later, be one by the specific surface area control of solid catalyst
Fixed scope and reduce these micropores, mesopore, so as to overcome described drawback.
It should be noted that in the solid catalyst of the present invention, in addition to silica, such as activity can also be used
Charcoal;The metal oxides such as aluminum oxide, sial, zirconium oxide, titanium oxide;The composition metals such as titanium silicon, titanium zirconium, zirconium silicon, hydrotalcite aoxidize
Thing;The clay minerals such as kaolin, montmorillonite, bentonite, chlorite, illite;The metal silicates such as zeolite;Silica is molten
The metal oxide precursors such as glue, alumina sol, containing them and in alkali metal compound and alkali earth metallic compound
The solid catalyst of at least one kind of metallic compound can also realize excellent selectivity, yield.
It is preferably metal oxide and metal composite oxide, more preferably aluminum oxide and sial among them.
As the silica used in the present invention, amorphous silica is preferably enumerated.As the noncrystalline titanium dioxide
Silicon, any one for synthesizing amorphous silica manufactured using dry process or damp process can be used.In addition, noncrystalline two
Silica for example can directly provide the commercially available product containing moisture firing process before (2) with catalyst preparation process described later
Or (3) absorption process.In addition it is also possible to suitably use silica gel.
In addition, porous silica can also be used as silica.As its example, Fuji can be enumerated
Silysia Chemical company systems CARiACT Q10, CARiACT Q50, CARiACT Q100, CARiACT Q300 etc..It is more
Hole silica can also in order to applied in device and sieve after use.
The particle diameter of the silica used in the present invention is not particularly limited, usually 0.5mm~10mm.
In addition, the intermediate value pore diameter using mercury penetration method measure of the silica is usually 8nm~300 μm,
Preferably 10nm~50 μm, more preferably 50nm~20 μm, more preferably 0.1 μm~10 μm.It should be noted that dioxy
The pore diameter of SiClx can utilize any one method of nitrogen adsorption methods and mercury penetration method measure.
In addition, the pore volume and specific surface area of foregoing porous silica can utilize nitrogen adsorption methods and mercury pressure
Enter any one method measure of method.But for pore volume and specific surface area, it is in the pore diameter of porous silica
During 0.4nm~200nm, nitrogen adsorption methods can be utilized to determine, when pore diameter is 3.6nm~400 μm, mercury can be utilized
Plunging determines.When pore diameter is 3.6nm~200nm, any one of nitrogen adsorption methods and mercury penetration method can be utilized
Kind method measure.
From the aspect of reactivity and selectivity, the pore determined using mercury penetration method of the porous silica
Volume is preferably 0.01mL/g~2mL/g, more preferably 0.1mL/g~1.5mL/g, more preferably 0.3mL/g~1mL/
g.In addition, the specific surface area determined using the mercury penetration method of porous silica is preferably 0.01m2/ g~100m2/ g, it is more excellent
Elect 0.1m as2/ g~80m2/ g, more preferably 0.3m2/ g~50m2/g。
Meanwhile the pore volume of the porous silica determined using nitrogen adsorption methods is preferably 0.0001mL/g~1mL/
G, more preferably 0.0002mL/g~0.8mL/g, more preferably 0.0004mL/g~0.5mL/g.In addition, porous silica
The specific surface area using nitrogen adsorption methods measure of silicon is preferably 0.01m2/ g~1000m2/ g, more preferably 0.01m2/ g~
100m2/ g, more preferably 0.01m2/ g~50m2/ g, particularly preferably 0.1m2/ g~10m2/g。
Silica described above in the present invention, both can be used alone any a kind, can also be applied in combination 2 kinds
More than.
The present invention solid catalyst in, using in alkali metal compound and alkali earth metallic compound at least
1 kind of metallic compound.As the alkali metal in the metallic compound, such as lithium, sodium, potassium, rubidium and caesium can be enumerated.In addition, make
For the alkaline-earth metal in the metallic compound, such as beryllium, magnesium, calcium, strontium, barium etc. can be enumerated.Among them, it is preferably
Sodium, caesium, magnesium, calcium (that is, are preferably sodium compound and cesium compound as alkali metal compound, as alkali earth metallic compound
Preferably magnesium compound and calcium compound), more preferably calcium.
As long as in addition, the metallic compound alkali metal or alkaline-earth metal, compound with defined element, just
It is not particularly limited, as the metallic compound, such as answering for metal oxide, metal oxide and silica can be enumerated
Close oxide etc..
In addition, in the preparation of the solid catalyst of invention described below, silica is set to adsorb alkali metal first
Compound or alkali earth metallic compound, are then burnt till.The metallic compound used during as the absorption process, such as can
To enumerate:The inorganic acid salt of the alkali metal such as nitrate, carbonate, bicarbonate, silicate or alkaline-earth metal;Fluoride, chlorine
The halide of the alkali metal such as compound or alkaline-earth metal;The hydroxide of alkali metal or alkaline-earth metal;And acetate, oxalates
Deng alkali metal or the acylate of alkaline-earth metal.In addition, alkali metal compound and alkali earth metallic compound can also be water
Compound.
In the solid catalyst of the present invention, relative to the overall quality of solid catalyst, metallic compound described above
Content it is total be scaled each metallic atom and preferably 0.01 mass %~50 mass %, more preferably 0.05 mass %~
The mass % of 30 mass %, more preferably 0.1 mass %~20.It should be noted that the metal compound in solid catalyst
The content of thing measure such as can use fluorescent X-ray elemental microanalysis method (XRF) or ICP-AES methods.
In addition, the particle diameter of the solid catalyst of the present invention is usually 1mm~10mm, preferably 1mm~5mm.
[preparation method of (B) solid catalyst]
Below, the manufacture method of the solid catalyst of the present invention is illustrated.The solid catalyst of the present invention for example may be used
To prepare as follows:Make to be selected from alkali metal compound and alkaline earth in 700 DEG C~1200 DEG C silica for burning till 1~20 hour absorption
At least one kind of metallic compound in metal compound, by this adsorbed metallic compound burn till silica 300 DEG C~
1200 DEG C are burnt till 1~40 hour to prepare.More specifically, such as according to step as follows prepare.
(1) synthesis procedure;Synthetic silica.
(2) firing process before;The silica of gained is burnt till, reduces micropore and mesopore.
(3) absorption process;Using method of impregnation etc., make silica adsorbing metal compound.
(4) drying process;The solid of gained is dried as needed.
(5) firing process;Dried solid is burnt till as needed.
Among this 5 processes, explanation is proceeded by from the process of important (2) and (5).
(2) firing process before
Before the silica adsorbing metal compound used when making the solid catalyst of the preparation present invention, for reduction
Foregoing micropore and the purpose of mesopore need to carry out burning till processing.
The described temperature for burning till processing needs the high temperature for 700 DEG C~1200 DEG C, is examined from the viewpoint of selectivity and yield
Consider more preferably 800 DEG C~1100 DEG C, more preferably 900 DEG C~1000 DEG C.
It may be considered because of by being set to the scope, it is possible to reduce the micropore and mesopore of silica, it will be passed through
The solid catalyst of the invention that each operation afterwards obtains is foregoing using the specific surface area control of nitrogen adsorption methods measure
Scope.As a result, matrix easily suitably departs from from the solid catalyst of the present invention after the reaction, so as to reduce the anti-of target
Reaction beyond answering.It should be noted that in the stage of the synthesis procedure (1) before the preceding firing process (2), silica
Specific surface area be in defined scope, even if not implementing this process (2) then, by the process by (3) described later~(5),
Sometimes the scope of the specific surface area of solid catalyst specified in the present invention can also be realized.Thus, in the solid catalysis of the present invention
In the manufacture method of agent, this process (2) can also be omitted sometimes.It should be noted that for can also omit process (2),
The approximate range of the specific surface area of the silica in the stage of process (1), those skilled in the art can be by implementing this area
The experiment for the resonable degree that technical staff is expected and easily grasp.
In addition, to silica burn till the time of processing in the present invention before silica adsorbing metal compound is made
It it is 1~20 hour, more preferably 1~10 hour within the scope of foregoing temperature., can be by the present invention's by being set to the scope
Solid catalyst is foregoing scope using the specific surface area control of nitrogen adsorption methods measure.
It should be noted that from the viewpoint of uniform burn till, the titanium dioxide preferably to being used in preceding firing process (2)
Silicon sieves etc., is burnt till after being unified for 1mm~10mm by its particle diameter, be more preferably unified for 1mm~5mm.
(5) firing process
After being burnt till before being carried out in process (2) to silica, make silica adsorbing metal in process described later (3)
Compound, it is necessary to be burnt till again after the solid of gained is dried as desired by process (4).Firing condition can basis
Species, form, the content or dry of the inorganic compounds such as metallic compound, silica (foregoing silica, activated carbon etc.)
Dry state etc. suitably adjusts.
Firing temperature is preferably 300 DEG C~1200 DEG C, more preferably 500 DEG C~1000 DEG C, more preferably 500 DEG C~
800℃.By burning till in this range, can by the metallic atom in the metallic compound of the solid catalyst surface of gained with
Silicon atom in silica atomic ratio M/Si control be foregoing scope, obtain required catalyst activity (reaction speed,
Raising of reaction yield and selectivity etc.).
In addition, as long as firing time is sufficiently carried out the time burnt till, just it is not particularly limited, but preferably 1 is small
When~40 hours, more preferably 1 hour~20 hours.By burning till in this range, it is possible to by solid catalyst surface
The atomic ratio M/Si controls of the silicon atom in metallic atom and silica in metallic compound are foregoing scope, obtain institute
The catalyst activity (raising of reaction speed, reaction yield and selectivity etc.) needed.
Below, the process of (1), (3) and (4) in the preparation to the solid catalyst of the present invention illustrates.
(1) synthesis procedure
Silica can be synthesized according to known method, can also use commercially available product as described above in addition,
One of the synthetic method of silica is illustrated herein.By mixing positive silicon with the mixed solvent of polyethylene glycol relative to water
Sour tetra-ethyl ester and nitric acid, dried after stirring and cleaning, so as to synthetic silica.
The amount of water used herein is preferably 0.1mL~3mL relative to tetraethyl orthosilicate 1mL, and more preferably 0.5mL~
2mL.In addition, used polyethylene glycol is preferably 0.01mL~0.2mL relative to tetraethyl orthosilicate 1mL, more preferably
0.02mL~0.1mL.By being set to the scope, it is possible to while good stirring is maintained, prevent the solidification of reaction solution.
Used nitric acid for example concentration be 60% when, relative to tetraethyl orthosilicate 1mL be preferably 0.01mL~
0.1mL, more preferably 0.02mL~0.08mL.
Drying time after silica gel synthesis is preferably 5 hours~100 hours, more preferably 10 hours~80 hours.In addition,
Drying temperature is preferably 90 DEG C~150 DEG C, more preferably 100 DEG C~120 DEG C.By being set to the scope, so as to foregoing
Time in the solvent in silica gel is reduced to the amount for not interfering with subsequent processing.
In addition, after the drying, in order to remove the remnant of the material used in the synthesis of the silica such as polyethylene glycol,
It can be burnt till in 600 DEG C or so of temperature.
(3) absorption process
After synthesizing silica by process (1), burnt till before being carried out using above-mentioned process (2) to silica.This
Afterwards, metallic compound is made to be infiltrated in silica.Used metallic compound is as it was previously stated, be alkali metal or alkaline-earth metal
Inorganic acid salt etc..
After described infiltration, solid (original text is utilized:The universe is consolidated) and filtering, solid or filtering, it is possible to obtain in dioxy
The solid of metallic compound has been adsorbed in SiClx.As the method for solid filtering, in general method can be used.
In addition, as metallic compound is made in the method for silica, can be using logical in the preparation of solid catalyst
Normal method, such as pore filling (pore filling) method, the solid method of evaporation, Equilibrium Adsorption Method, first wet impregnation can be applied
(Incipient wetness) method etc..
(4) drying process
The solid obtained in described absorption process generally for the purpose of solvent used in removing, is preferably done
It is dry.Drying temperature during the solid catalyst manufacture of the present invention is preferably 50 DEG C~150 DEG C, more preferably 80 DEG C~120 DEG C.It is dry
The dry time is preferably 6 hours~36 hours, more preferably 12 hours~24 hours., can be by solid by being set to the scope
Solvent be reduced to the amount for not interfering with subsequent processing.
By the way that so obtained solid is burnt till in the firing process (5) of described above, it is possible to obtain this hair
Bright solid catalyst.It should be noted that think when the middle inorganic acid salt using alkali metal of absorption process (3),
The inorganic acid salt etc. is oxidized because burning till, and is changed into metal oxide or the composite oxides with silica.
If carry out the manufacture of solid catalyst by regulation process described above, based on rated condition, so that it may
Manufactured well with repeatability can ground as described later high selectivity and generate in high yield isocyanate compound etc., it is excellent
Different solid catalyst.
[manufacture method of (C) isocyanate compound]
The solid catalyst of present invention mentioned above can use as the catalyst of various reactions, especially as profit
With carbamate compounds come to manufacture the catalyst of the reaction of isocyanate compound be useful.The isocyanates of the present invention
The manufacture method (hereinafter also referred to as " manufacture method of the invention ") of compound is by the solid catalyst in the present invention
In the presence of, make carbamate compounds react and implement.The manufacture method of the present invention is implemented preferably by pyrolysis.
As carbamate compounds used in the manufacture method of the present invention, it is adapted to use with following formulas (1) table
That shows has at least one amino-formate bond (- NHCO in intramolecular2-) compound.
[changing 3]
In the formula (1), R1Represent there can be the alkyl of substituent.
As the alkyl, for example, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2- ethylhexyls,
The alkyl of the carbon numbers such as nonyl, decyl, dodecyl, octadecyl 1~20;
The alkenyl of the carbon numbers such as acrylic, cyclobutenyl, pentenyl 2~20;
The alkylidene radical of the carbon numbers 1~20 such as methene base, ethidine, propylidene base, butane, pentylidene base, oneself fork base;
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, cyclooctyl, methylcyclohexylmethyl, diformazan basic ring
Hexyl, isophorone base, norborny, decahydronaphthalene naphthyl, adamantyl, 4,4 '-di-2-ethylhexylphosphine oxide (hexamethylene) base, 2,4 '-Asia
The cycloalkyl of the carbon numbers 3~20 such as double (hexamethylene) bases of methyl;
The ring alkylidene radical of the carbon numbers such as Isosorbide-5-Nitrae-cyclohexylidene base 3~20;
Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl, 4,4 '-methylene diphenylene
Deng aryl comprising 1~3 aromatic ring etc..It should be noted that these groups include various isomers.
In the formula (1), R2Represent there can also be the alkyl of substituent.
As the alkyl, for example, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2- ethylhexyls,
The alkyl of the carbon numbers such as nonyl, decyl, dodecyl, octadecyl 1~20;
The alkenyl of the carbon numbers such as acrylic, cyclobutenyl, pentenyl 2~20;
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, cyclooctyl, Dimethylcyclohexyl, isophorone
The cycloalkyl of the carbon numbers 3~20 such as base, norborny, decahydronaphthalene naphthyl, adamantyl;
Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl etc. include 1~3 aromatic ring
Aryl etc..It should be noted that these groups include various isomers.
The R of the formula (1)1And R2In, as the substituent that can have in the alkyl of substituent, such as can be with
Enumerate hydroxyl, halogen atom, cyano group, amino, alkyl amino, carboxyl, alkoxy, aryloxy group, alkylthio group, arylthio, (methyl)
Acryloxy etc..
In the formula (1), n is 1~4 integer, and this is according to R1Corresponding bonding valence mumber and the value determined, such as
In R1In the case of group (such as cyclohexyl) for 1 valency, n 1, in R1For the situation of the group (such as cyclohexylidene) of divalent
Under, n 2.In addition, as R1The example of alkyl can enumerate alkyl, such as in n be 2 (R1For divalent) in the case of, the hydrocarbon
Base is the group (alkylidene) of the divalent corresponding to alkyl.It is the group (chain of similarly corresponding trivalent in the case where n is 3
The base of alkane three).The other groups enumerated for the example as alkyl are also identical.
In addition, from as the various manufacture raw materials of isocyanate compound obtained using manufacture method of the invention etc.
From the viewpoint of serviceability, n is preferably 2.
Carbamate compounds used are preferably described above to be represented with formula (1) in the manufacture method of the present invention
Compound, as its example, such as fatty family carbamate compounds, alicyclic ring family urethane can be enumerated
Compound, fragrant family carbamate compounds etc..
Fatty family carbamate compounds used are, for example, following carbamic acid in the manufacture method of the present invention
Ester compounds:In the formula (1), R1Be can have substituent, the alkyl of carbon number 1~20, carbon number 2~
20 alkenyl or the alkylidene radical of carbon number 1~20, R2It is can have substituent, carbon number 1~20, preferably carbon former
The alkyl or phenyl of subnumber 1~6.As fatty family carbamate compounds used in the manufacture method of the present invention, example
It can such as enumerate:Methylhexyl carbamate, Methyl Octyl carbamate, methyl dodecylamino formic acid esters, methyl ten
Eight alkyl carbamates, Isosorbide-5-Nitrae-bis- (methyloxycarbonylaminos) butane, Isosorbide-5-Nitrae-bis- (ethoxycarbonylamino group) butane, Isosorbide-5-Nitrae-bis-
Double (methyloxycarbonylamino) pentanes of (butoxycarbonylamino group) butane, 1,5-, 1,6- double (methyloxycarbonylamino) hexane, 1,
Double (ethoxycarbonylamino group) hexanes of 6-, double (butoxycarbonylamino group) hexanes of 1,6-, 1,8- double (methyloxycarbonylaminos) are pungent
Double (butoxycarbonylamino group) octanes of alkane, 1,8-, double (the phenoxycarbonylamino) -4- (phenoxycarbonylamino methyl) of 1,8- are pungent
Double (methyloxycarbonylamino) nonanes of alkane, 1,9-, double (butoxycarbonylamino group) nonanes of 1,9-, double (the methoxycarbonyl ammonia of 1,10-
Base)-decane, double (the butoxycarbonylamino group)-dodecanes of 1,12-, 1,12- double (methyloxycarbonylamino)-dodecane, 1,12-
Double (phenoxycarbonylamino)-dodecanes, 1,3,6- tri- (methyloxycarbonylamino) hexanes, 1,3,6- tri- (phenyloxycarbonyl ammonia
Base) hexane etc..
Alicyclic ring family carbamate compounds used are, for example, following carbamic acid in the manufacture method of the present invention
Ester compounds:In the formula (1), R1It is can have substituent, the cycloalkyl of carbon number 3~20, R2It is to have
Alkyl or phenyl of substituted base, carbon number 1~6.As alicyclic ring family amino used in the manufacture method of the present invention
Formic acid ester compound, such as can enumerate:1,3- or Isosorbide-5-Nitrae-bis- (methyloxycarbonylaminos) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (second
Epoxide carbonyl amino) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (butoxycarbonylamino groups) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (methoxyl group carbonyls
Base amino methyl) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (ethoxycarbonylamino group methyl) hexamethylene, 1,3- or Isosorbide-5-Nitrae-bis- (butoxy
Carbonylamino-methyl) hexamethylene, 2,4 '-or 4,4 '-bis- (methyloxycarbonylamino) dicyclohexyl methyl hydrides, 2,4 '-or 4,4 '-it is bis-
(ethoxycarbonylamino group) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis- (butoxycarbonylamino group) dicyclohexyl methyl hydrides, 2,4 '-
Or 4,4 '-bis- (phenoxycarbonylamino) dicyclohexyl methyl hydrides, 2,5- double (methyloxycarbonylamino methyl) two rings [2,2,1] heptan
Double (Butyloxycarbonylaminomethyl) two ring [2,2, the 1] heptane of alkane, 2,5-, double (methyloxycarbonylamino methyl) two rings of 2,6-
[2,2,1] heptane, 2,6- couples of (Butyloxycarbonylaminomethyl) two ring [2,2,1] heptane, 1- (methyloxycarbonylamino) -3,3,
5- trimethyls -5- (methyloxycarbonylamino methyl)-hexamethylene, 1- (butoxycarbonylamino group) -3,3,5- trimethyl -5- (fourths
Epoxide carbonyl amino methyl)-hexamethylene, trimethyl -1- (the methoxycarbonyl ammonia of 3- (methyloxycarbonylamino methyl) -3,5,5-
Base) hexamethylene, 4,4 '-bis- (methyloxycarbonylamino) -2,2 '-dicyclohexyl propane, 4,4 '-bis- (butoxycarbonylamino groups) -
2,2 '-dicyclohexyl propane etc..
Fragrant family carbamate compounds used are following urethanes in the manufacture method of the present invention
Compound:R1It is can have substituent, the aryl for including aromatic ring of carbon number 6~18, R2It is can have substituent
, the alkyl or phenyl of carbon number 1~6.As fragrant family urethane used in the manufacture method of the present invention
Compound, such as can enumerate:1,3- or Isosorbide-5-Nitrae-bis- (methyloxycarbonylamino methyl) benzene, 1,3- or Isosorbide-5-Nitrae-bis- (ethoxy carbonyls
Amino methyl) benzene, 1,3- or Isosorbide-5-Nitrae-bis- (Butyloxycarbonylaminomethyls) benzene, 1,3- or Isosorbide-5-Nitrae-bis- (methyloxycarbonylaminos)
Benzene, 1,3- or Isosorbide-5-Nitrae-bis- (butoxycarbonylamino groups) benzene, 2,2 '-bis- (4- propoxy carbonylaminos phenyl) propane, 2,4 '-or 4,
4 '-bis- (methyloxycarbonylamino) diphenyl methanes, 2,4 '-bis- (ethoxycarbonylamino group) diphenyl methanes, 2,4 '-bis- (fourths
Epoxide carbonyl amino) diphenyl methane, 4,4 '-bis- (phenoxycarbonylamino) diphenyl methanes, 1,5- or the double (methoxyl groups of 2,6-
Carbonylamino) naphthalene, double (butoxycarbonylamino group) naphthalenes of 1,5- or 2,6-, 4,4 '-bis- (methyloxycarbonylamino) biphenyl, 4,4 '-
Double (methyloxycarbonylamino) toluene of double (butoxycarbonylamino group) biphenyl, 2,4- or 2,6-, 2,4- or double (the ethyoxyl carbonyls of 2,6-
Base amino) toluene, 2,4- or double (butoxycarbonylamino group) toluene of 2,6- etc..
In the manufacture method of the present invention, such as utilize the carbamate compounds described above represented with formula (1)
To manufacture corresponding isocyanate compound, but the isocyanate compound is preferably the compound represented with following formulas (2).
[changing 4]
In formula, R1And n and the formula (1) R1And n is synonymous.In addition, in the case where n is more than 2, in foregoing change
Beyond compound, obtained sometimes as intermediate by 1, there occurs isocyanation esterification for (n-1) individual carbamate groups
Compound.For example, using isophorone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- front threes
Base -5- (methyloxycarbonylamino methyl)-hexamethylene) in the case of, it is shown below, beyond diisocyanate body, can also
Obtain 2 kinds of monoisocyanates bodies.
[changing 5]
The solid catalyst of the present invention is by by metallic atom/silicon of the metallic compound of catalyst surface and silica
The atom ratio of atom is set to defined scope and turns into the suitable catalyst of reactivity, by that nitrogen adsorption methods will be utilized to determine
The specific surface area of catalyst be set to certain scope, reaction product is moderately easily separated from.
Therefore, in the reaction of solid catalyst of the present invention has been used, the carbamate of carbamate compounds
The major part of key is transformed to NCO, can suppress the generation of the intermediate of above-mentioned shown monoisocyanates etc.
In addition it is also possible to suppress the generation of the chlorinated isocyanurates body that is generated when catalyst activity is too high etc..Thus, if made
With the solid catalyst of the present invention, it is possible to high selectivity and manufacture isocyanate compound in high yield.
In the manufacture method of the present invention, isocyanate compound is by making carbamic acid in the presence of the catalyst
Ester compounds react and manufactured.It is preferred that in the presence of the catalyst, make the carbamate compounds of the formula (1) anti-
Answer, manufacture the isocyanate compound of the formula (2).
Reaction form now is not particularly limited, and can be any one in gas phase reaction, liquid phase reactor, but excellent
Select gas phase reaction.In addition, reactive mode can use the solid catalysts such as fixed bed mode, fluid bed process, suspension bed mode
Reaction mode used.Particularly preferably use fixed bed mode.
The head tank that the gas phase fixed bed mode that preferably uses for example can be as shown in Figure 1 in the manufacture method of the present invention
(1), the thermal source (tubular electric furnace etc.) of matrix supply pump (2), the tubular reactor (3) filled with catalyst, heating response device
(4), product heat exchanger (6), the chilled product of recovery isocyanate compound receiver (7), for condensed alcohol (by
Carbamate compounds manufacture isocyanate compound when generate) heat exchanger (8), the receiver (9) for obtaining alcohol,
The vacuum pipeline being connected with vavuum pump (17) is formed, but is not limited to this.It should be noted that for carrying in Fig. 1
The composition of other symbols, illustrate in the embodiment that will be described below.
Relative to the feed speed 1mL/h of the matrix in gas phase fixed bed mode, solid catalyst of the invention preferably with
0.01mL~10mL, more preferably used with 0.02mL~5mL amount.
, then can be with inactive gas such as nitrogen if the state that matrix has been gasified in gas phase fixed bed mode
And reacted, it can also be reacted without using inactive gas, can also be carried out under normal or reduced pressure.
In the manufacture method of the present invention, in the case where using solid catalyst in a manner of suspension bed, these catalyst phases
For the mass parts of carbamate compounds 100 for example preferably with the scope of the mass parts of 0.1 mass parts~100, more preferably with 0.5
The scope of the mass parts of mass parts~50 uses.
In the manufacture method of the present invention, the reactions of carbamate compounds for example can also be by by urethane
Compound and solid catalyst are heated and implemented together with torpescence solvent.The manufacture method of the present invention is preferably by making this anti-in addition
The reaction distillation mode that isocyanate compound, the alcoholic compound of middle generation are separated to outside system is answered to implement.Need what is illustrated
It is in manufacture method of the invention, to be not necessarily required to together heat torpescence solvent and carbamate compounds, can also
It is allowed to react in a manner of without solvent.
In the manufacture method of the present invention, as long as the torpescence solvent is relative to carbamate compounds and generation
Isocyanate compound is torpescence, is just not particularly limited, but in order to efficiently implement to react, it is however preferred to have higher than ammonia
The solvent of the boiling point of carbamate compound.As such a solvent, such as can enumerate:Dioctyl phthalate, adjacent benzene two
The esters such as formic acid didecyl, phthalic acid two (dodecyl) ester, or, such as dibenzyl toluene, triphenyl methane, phenyl
Fragrant family hydrocarbon or the fatty family hydrocarbon such as naphthalene, biphenyl, terphenyl, diethyl biphenyl, triethyl group biphenyl, 1,3,5- triisopropylbenzenes
Deng.These solvents can be used alone or and with two or more.Its usage amount can according to reaction unit, form and suitably adjust
It is whole.
In the manufacture method of the present invention, torpescence solvent for example preferably uses 0.1 relative to carbamate compounds 1mL
~150mL, more preferably using 1~50mL.By being set to the scope, can be prevented anti-while good stirring is maintained
Answer the solidification of liquid.
It is excellent relative to the feed speed 1mL/h of carbamate compounds, solid catalyst in the manufacture method of the present invention
Select with 0.01mL~10mL, more preferably with 0.02mL~5mL amount use.By being set to the scope, it is possible to industrially to close
Suitable reaction speed obtains isocyanate compound.
In the manufacture method of the present invention, the reaction temperature of carbamate compounds is, for example, 80 DEG C~600 DEG C, is preferably
200 DEG C~500 DEG C, more preferably 300 DEG C~500 DEG C.By being set to the scope, reaction (the particularly heat of practicality can be obtained
Decompose) speed, the undesirable side reaction such as the polymerization of isocyanate compound can be suppressed.
In the manufacture method of the present invention, reaction pressure is preferably capable the isocyanide of generation relative to above-mentioned reaction temperature
Ester compound and the pressure of alcoholic compound gasification, in terms of slave unit and using from the aspect of income, in practical preferably definitely
Pressure is 0.1kPa~101.33kPa, and more preferably absolute pressure is 0.5kPa~30kPa.
In the present invention, when reacting carbamate compounds with batch (-type), foregoing solid catalyst is relative to ammonia
The mass parts of carbamate compound 100, preferably with the scope of the mass parts of 0.1 mass parts~100, more preferably with 0.5 mass parts~
The scope of 50 mass parts uses.
In addition, though be not necessarily required to together heat torpescence solvent and carbamate compounds, and can also be with
Mode without solvent is allowed to react, but in the case of using torpescence solvent, its usage amount is relative to urethane
Compound 1g is usually 1~30mL, preferably 1~10mL.
For reaction pressure, temperature as previously described.
Reaction time can suitably be adjusted according to catalytic amount, temperature, the concentration of matrix and pressure etc., and usually 0.5
~10 hours, preferably 1~5 hour.
, then can be with nitrogen if the state that isocyanate compound has been gasified in the manufacture method of the present invention
Reacted, can also be reacted Deng inactive gas without using inactive gas, can also be under normal or reduced pressure
Carry out.
The isocyanate compound obtained using the manufacture method of the present invention can utilize such as mistake by reacted solution
The operation of the in general such as filter, concentration, extraction, distillation, distillation, recrystallization, column chromatography is separated, purified.As different by obtained by
Cyanate esters further purify repeatedly, and the isocyanate compound of high-purity can be made.
In addition, after the reaction of carbamate compounds terminates, can be by residual liquid filtering, the centrifugation point of reaction solution
Solid catalyst is easily reclaimed from separation method known to grade, the solid catalyst of recovery directly or can also be utilized
Solvent clean, burn till etc. known to method activate again after reuse.
Embodiment
Below, enumerate embodiment and the present invention is specifically described, but the scope of the present invention is not limited by them
It is fixed.
[(the Ca/SiO of Production Example 12The preparation of catalyst)]
Water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g are existed
Mix, stir in polyethylene can, homogeneous solution is made.Tetraethyl orthosilicate (TEOS) 120mL, 60% nitric acid are added thereto
The aqueous solution (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL, closed container and to be stirred vigorously 1 under room temperature (20 DEG C~30 DEG C) small
When.
Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 60 are dried at about 110 DEG C
Hour, at about 600 DEG C burn till within 2 hours in atmosphere, at about 1000 DEG C burn till within 3 hours.
Burned material is crushed in mortar, the size for being sieved into particle is 1mm~2mm scope, obtains porous and amorphous
The silica gel 25g of matter.Utilize mercury penetration method (measure device:The full-automatic broad pore distribution measure device of Quanta Chrome Co. systems
Pore Master 60-GT) measure the silica gel intermediate value pore diameter be 7.5 μm.
On the other hand, calcium nitrate tetrahydrate 0.196g (0.83mmol) and ion exchange water 2.6g are mixed in flask and stirred
Mix and obtain calcium nitrate aqueous solution.It will be added using the silica gel 2.0g (33mmol) of the operation preparation in the calcium nitrate aqueous solution
(Ca/Si ratio=0.025) afterwards, stand 1 hour.
Dried again at about 110 DEG C 12 hours, about 500 DEG C burn till and obtain catalyst (Ca/ within 5 hours in atmosphere
SiO2)2.1g.Determined using fluorescent X-ray elemental microanalysis method (XRF), as a result, the catalyst (Ca/SiO of gained2) in, phase
It is overall for solid catalyst, be scaled calcium atom and containing 1.8 mass % calcium compound.That is, solid catalyst is overall
The atomic ratio of calcium atom and silicon atom (Ca/Si) is 0.027.
In addition, it is 0.3m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure2/ g, utilize X ray photoelectricity
The atomic ratio (Ca/Si) of calcium atom and silicon atom that analytical equipment determines, in solid catalyst surface is 5.8.
[(the various Ca/SiO of Production Example 2~112The preparation of catalyst)]
In addition to it will be changed shown in various conditions such as following table 1, table 2, operate and prepare identically with Production Example 1
Go out various Ca/SiO2Solid catalyst.
[table 1]
[table 2]
In table 1, so-called silica gel intermediate value pore diameter is as follows using the value of mercury penetration method measure, condition determination.
As the measure device based on mercury penetration method, the full-automatic broad pore distribution of Quanta Chrome Co. systems has been used
Determine device Pore Master 60-GT.In addition, the condition determination as mercury penetration method, boosts from about 7kPa at room temperature
It is measured while to 414Mpa.It should be noted that 480dyn/cm has been used as the value of the surface tension of mercury,
140 ° have been used as the value of contact angle.
In table 2, so-called catalyst totality Ca/Si ratios refer to the atomic ratio of calcium atom and silicon atom in solid catalyst,
It is the value calculated according to the quality of mixed silica gel and calcium nitrate.It should be noted that the solid after solid catalyst preparation
The overall Ca/Si ratios of catalyst can utilize the measure such as fluorescent X-ray elemental microanalysis method (XRF).
In table 2, (the work in foregoing catalyst preparation after so-called solid catalyst specific surface area represents absorption calcium and burnt till
Sequence (5)) solid catalyst specific surface area, be using nitrogen adsorption methods measure value.Condition determination is as follows.
This measure is to be carried out using BET formulas powder specific-surface area detection measure device using physisorphtion (nitrogen adsorption method).This
In invention, " Japanese Baeyer (strain) is made, BELSORP-miniII ", and adsorbed gas uses nitrogen, carried out BET multipoint mode methods for use
Measure.Specifically, powder sample is subjected to heat de-airing at a temperature of 150 DEG C under vacuo, is then cooled to liquid nitrogen temperature
Spend and make nitrogen adsorption, determine absorption/desorption isotherm, the specific surface area of sample is calculated according to the absorption/desorption isotherm.
In table 2, atomic ratios of the so-called surface C a/Si than representing calcium atom and silicon atom in solid catalyst surface, it is
The value analyzed using x-ray photoelectron analytical equipment.Condition determination is as follows.
(x-ray photoelectron optical spectroscopy (ESCA) condition determination)
Device name:PHI company systems Quantum2000
X-ray source:Monochromatization Al-K α, power output 15kV-20W (X-ray generating surface accumulates 100 μm of φ)
Charged neutralization:Electron gun (20 μ A), ion gun (30V) are used in combination
Beam splitting system:The narrow spectrum (full element) of pulse energy 187.85eV@wide ranges, 46.95eV@
Mensuration region:Point irradiation (340 μm of φ of irradiated area <)
Exit angle (takes り to go out angles):45 ° (relative to surfaces)
[(formula (1) R of embodiment 11=1,3,3- trimethyl -1- methylene cyclohexylidenes, R2=methyl, n=2;Based on different Buddhist
That ketone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl) -
Hexamethylene) thermal decomposition IPDI manufacture)]
[changing 6]
As shown in figure 1, using diameter 10mm, long 42cm glass tube (3) as reactor so that the portion filled with catalyst
Point (hereinafter referred to as " mode that catalyst layer ") is about 360 DEG C from outside set electric furnace (4).Reactor lower part is set to branch into two
The pipeline of series, respectively via the receiver (room temperature) (7) for obtaining isocyanate compound and (13), for cooled product
Product heat exchanger (6) and (12), for obtain methanol receiver (with cold ethanol cool down) (9) and (15) (before it
Have respectively for condensing the heat exchanger of methanol (8) and (14)), the pipeline of two sides is connected with vavuum pump (17), by vacuum tube
Line links.The switching of two pipelines is the pipeline (pipeline of the opposing party by only opening valve (5 and 10 and 11 and 16) side
Close) and carry out.
As catalyst, the Ca/SiO that will be prepared in Production Example 12Solid catalyst (1.1~2.2mm of particle diameter) 2mL is filled
Into above-mentioned glass tube (3) (glass tube (3) is formed using gasification layer (3a) and catalyst layer (3b)), vavuum pump is started
(17) absolute pressure 1.33kPa, is depressurized to, opens valve (5), valve (10), valve (11), valve (16) is closed, uses electric furnace
(4) temperature of catalyst layer is heated to about 360 DEG C.Will be in about 150 DEG C of molten isophorone dimethylamino first of heating
Acid esters (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl)-hexamethylene) uses syringe pump
(2) supplied with 4mL/h to glass tube (3).
Pass through 30 minutes confirming that the chilled product containing isocyanate compound starts to have been reclaimed by receiver (7)
Afterwards, valve (5), valve (10) are closed, valve (11), valve (16) is opened, contained isocyanates by chilled with 30 minutes
The product of compound is recovered in receiver (13), by Methanol Recovery to receiver (15).To what is reclaimed by receiver (13)
The chilled product containing isocyanate compound is analyzed with liquid chromatogram, to being condensed and recycled to receiver (15)
Methanol is analyzed with gas-chromatography, calculates diamino acid ester conversion rate, the yield of diisocyanate, the receipts of monoisocyanates
Rate.
As a result, as product, IPDI is obtained with yield 94% (selection rate 94%), with yield
2% obtains monoisocyanates body.
[embodiment 2~6, comparative example 1~5 (have used various Ca/SiO2, based on isophorone dimethyl carbamic acid
The thermal decomposition of ester (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl)-hexamethylene) it is different
The manufacture of isophorone diisocyanate)]
In addition to it will be changed shown in various conditions such as following table 3, operate and synthesize different same as Example 1ly
Isophorone diisocyanate.
[table 3]
From table 1, table 2, table 3, extract out the overall Ca/Si of catalyst than, the specific surface area of solid catalyst, solid catalysis
Ca/Si ratios, conversion ratio, the yield on agent surface, by the data recordation summarized in table 4.In addition, the table 4 is subject to pictorialization,
The result of gained is shown in Fig. 2 and (does not show comparative example 1).
[table 4]
According to table 4 and Fig. 2, the atomic ratio Ca/Si of calcium atom and silicon atom on solid catalyst surface is met is 0.5
~20, the specific surface area of solid catalyst is 0.01m2/ g~50m2(embodiment 1~6), two isocyanides during the condition of/g these two aspects
The yield of ester compound is more than 85%, and the conversion ratio of diurethane compound is 100%.On the other hand, in solid
Catalyst is unsatisfactory for during some foregoing condition (comparative example 1~5), and yield, conversion ratio reduce.
[(the Na/SiO of Production Example 122The preparation of catalyst)]
By water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20,000) 9.6g
Mix, stir in polyethylene can, homogeneous solution is made.Tetraethyl orthosilicate (TEOS) 120mL, 60% nitre are added thereto
Aqueous acid (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL, closed container are simultaneously stirred vigorously 1 under room temperature (20 DEG C~30 DEG C)
Hour.
Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 60 are dried at about 110 DEG C
Hour, at about 600 DEG C burn till within 2 hours in atmosphere, at about 1000 DEG C burn till within 3 hours.
Burned material is crushed in mortar, the size for being sieved into particle is 2mm~4mm scope, is obtained porous and non-
The silica gel 55g of crystalloid.Utilize mercury penetration method (measure device:The full-automatic broad pore distribution measure dress of Quanta Chrome Co. systems
Put Pore Master 60-GT) measure the silica gel intermediate value pore diameter be 7.5 μm.
On the other hand, sodium nitrate 0.106g (1.25mmol) and ion exchange water 3.7g are mixed in flask and obtained
To sodium nitrate aqueous solution.After silica gel 3.0g (49.9mmol) using the operation preparation is added in the sodium nitrate aqueous solution
(Na/Si ratio=0.025), stand 1 hour.
Dried 12 hours at about 110 DEG C again, in atmosphere after about 500 DEG C are burnt till 8 hours, in atmosphere at about 700 DEG C
Burn till and obtain solid catalyst (Na/SiO within 8 hours2)3.03g.Determined using fluorescent X-ray elemental microanalysis method (XRF),
As a result, solid catalyst (the Na/SiO of gained2) in, it is overall relative to solid catalyst, it is scaled sodium atom and contains
0.84 mass % sodium compound.That is, the atomic ratio (Na/Si) of the overall sodium atom of solid catalyst and silicon atom is 0.022.
In addition, it is 0.51m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure2/ g, analyzed and filled using x-ray photoelectron
Atomic ratio (Na/Si) that put measure, sodium atom on catalyst surface and silicon atom is 0.5.
[(formula (1) R of embodiment 71=1,3,3- trimethyl -1- methylene cyclohexylidenes, R2=methyl, n=2;Based on different Buddhist
That ketone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl) -
Hexamethylene) thermal decomposition IPDI manufacture)]
[changing 7]
Except the temperature of catalyst layer is set into 365 DEG C, urged as catalyst using the solid obtained in Production Example 12
Agent (Na/SiO2:1.1~2.2mm of particle diameter) beyond 3mL, operate same as Example 1ly and produce the isocyanide of isophorone two
Acid esters.
The yield of IPDI is 83% (selection rate 84%), and the yield of monoisocyanates is 17%.
[(the Mg/SiO of Production Example 132The preparation of catalyst)]
Water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g are existed
Mix, stir in polyethylene can, homogeneous solution is made.Tetraethyl orthosilicate (TEOS) 120mL, 60% nitric acid are added thereto
The aqueous solution (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL, closed container and to be stirred vigorously 1 under room temperature (20 DEG C~30 DEG C) small
When.
Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 60 are dried at about 110 DEG C
Hour, carry out burning till for 2 hours in atmosphere at about 600 DEG C, at about 1000 DEG C burn till within 3 hours.
Burned material is crushed in mortar, the size for being sieved into particle is 2mm~4mm scope, is obtained porous and non-
The silica gel 55g of crystalloid.Utilize mercury penetration method (measure device:The full-automatic broad pore distribution measure dress of Quanta Chrome Co. systems
Put Pore Master 60-GT) measure the silica gel intermediate value pore diameter be 7.5 μm.
On the other hand, magnesium nitrate hexahydrate 0.320g (1.25mmol) and ion exchange water 3.5g are mixed in flask and stirred
Mix and obtain magnesium nitrate aqueous solution.It is water-soluble that silica gel 3.0g (49.9mmol) using the operation preparation is added to the magnesium nitrate
After in liquid (Mg/Si ratio=0.025), 1 hour is stood.
Dried again at about 110 DEG C 12 hours, carry out 8 hours burning till at about 500 DEG C in atmosphere and obtain solid catalyst
(Mg/SiO2)3.03g.Determined using fluorescent X-ray elemental microanalysis method (XRF), as a result, the solid catalyst (Mg/ of gained
SiO2) in, it is overall relative to solid catalyst, be scaled magnesium and containing 1.50 mass % magnesium compound.That is, solid catalyst
Overall magnesium atom and the atomic ratio (Mg/Si) of silicon atom are 0.038.In addition, the solid catalysis determined using nitrogen adsorption methods
The specific surface area of agent is 0.58m2/ g, magnesium atom determined using x-ray photoelectron analytical equipment, in solid catalyst surface
Atomic ratio (Mg/Si) with silicon atom is 1.9.
[(formula (1) R of embodiment 81=1,3,3- trimethyl -1- methylene cyclohexylidenes, R2=methyl, n=2;Based on different Buddhist
That ketone dimethylcarbamate (1- (methyloxycarbonylamino) -3,3,5- trimethyl -5- (methyloxycarbonylamino methyl) -
Hexamethylene) thermal decomposition IPDI manufacture)]
[changing 8]
Except the temperature of catalyst layer is set into 365 DEG C, urged as catalyst using the solid obtained in Production Example 13
Agent (Mg/SiO2:1.1~2.2mm of particle diameter) beyond 3mL, operate same as Example 1ly and produce the isocyanide of isophorone two
Acid esters.
The yield of IPDI is 85% (selection rate 85%), and the yield of monoisocyanates is 12%.
It can be seen from embodiment 7 and 8 more than, the sodium atom or magnesium atom and silicon on solid catalyst surface is met are former
The atomic ratio M/Si of son is 0.5~20, the specific surface area of solid catalyst is 0.01m2/ g~50m2The condition of/g these two aspects
When, the yield of diisocyanate cpd is more than 83%.
[(the Ca/SiO of Production Example 142The preparation of catalyst)]
By water 60g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 3.6g poly-
Mix, stir in ethene container, homogeneous solution is made.It is water-soluble that tetraethyl orthosilicate (TEOS) 60mL, 60% nitric acid are added thereto
Liquid (Wako Pure Chemical Industries, Ltd.'s system) 4.2mL, closed container are simultaneously stirred vigorously 1 hour under room temperature (20 DEG C~30 DEG C).
Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 12 are dried at about 110 DEG C
Hour, at about 600 DEG C burn till within 2 hours in atmosphere, at about 1000 DEG C burn till within 3 hours.
A part for burned material is crushed in mortar, the size for being sieved into particle is 1mm~2mm scope, is obtained more
Hole and amorphous silica gel 8.0g.Utilize mercury penetration method (measure device:The full-automatic pore of Quanta Chrome Co. systems
Distribution measurement device Pore Master 60-GT) measure, the intermediate value pore diameter of the silica gel be 6.1 μm.
On the other hand, calcium nitrate tetrahydrate 0.393g (1.7mmol) and ion exchange water 2.2g are mixed in flask and stirred
Mix and obtain calcium nitrate aqueous solution.It will be added using the silica gel 2.0g (33mmol) of the operation preparation in the calcium nitrate aqueous solution
(Ca/Si ratio=0.05) afterwards, stand 1 hour.
Dried again at about 110 DEG C 12 hours, carry out 3 hours burning till at about 500 DEG C in atmosphere and obtain solid catalyst
(Ca/SiO2)2.3g.Specific surface area using the solid catalyst of nitrogen adsorption methods measure is 0.8m2/ g, utilize X ray photoelectricity
The atomic ratio (Ca/Si) of calcium atom and silicon atom that analytical equipment determines, in solid catalyst surface is 1.1.
[(formula (1) R of embodiment 91=hexamethylene -1,3- glycol dimethylene, R2=methyl, n=2;By the double (first of 1,3-
Epoxide carbonyl amino methyl) hexamethylene thermal decomposition double (isocyanatomethyl) hexamethylenes of 1,3- manufacture)]
[changing 9]
Except the temperature of catalyst layer is set into 365 DEG C, the solid obtained in Production Example 14 has been used as catalyst
Catalyst (Ca/SiO2:1~2mm of particle diameter) 3mL, as carbamate compounds 1 is used, double (the methoxycarbonyl ammonia of 3-
Ylmethyl) beyond hexamethylene, operate same as Example 1ly and produce 1, double (isocyanatomethyl) hexamethylenes of 3-.
The yield of 1,3- double (isocyanatomethyl) hexamethylenes is 95% (selection rate 95%), the yield of monoisocyanates
For 1%.
[(the Ca/SiO of Production Example 152The preparation of catalyst)]
By water 120g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g poly-
Mix, stir in ethene container, homogeneous solution is made.It is water-soluble that tetraethyl orthosilicate (TEOS) 120mL, 60% nitric acid are added thereto
Liquid (Wako Pure Chemical Industries, Ltd.'s system) 8.5mL, closed container are simultaneously stirred vigorously 1 hour under room temperature (20 DEG C~30 DEG C).
Then 12 hours are stood at about 50 DEG C, takes out the gel of generation, after being cleaned with purified water, 12 are dried at about 110 DEG C
Hour, carry out burning till for 2 hours in atmosphere at about 600 DEG C, at about 1000 DEG C burn till within 3 hours.
A part for burned material is crushed in mortar, the size for being sieved into particle is 1mm~2mm scope, is obtained more
Hole and amorphous silica gel 9g.Utilize mercury penetration method (measure device:The full-automatic broad pore distribution of Quanta Chrome Co. systems
Determine device Pore Master 60-GT) measure, the intermediate value pore diameter of the silica gel be 1.0 μm.
On the other hand, calcium nitrate tetrahydrate 0.008g (0.03mmol) and ion exchange water 2.5g are mixed in flask and stirred
Mix and obtain calcium nitrate aqueous solution.It will be added using the silica gel 2.0g (33mmol) of the operation preparation in the calcium nitrate aqueous solution
(Ca/Si ratio=0.001) afterwards, stand 1 hour.
Dried again at about 110 DEG C 12 hours, carry out 3 hours burning till at about 500 DEG C in atmosphere and obtain solid catalyst
(Ca/SiO2)2.0g.Specific surface area using the solid catalyst of nitrogen adsorption methods measure is 1.7m2/ g, utilize X ray photoelectricity
The atomic ratio (Ca/Si) of calcium atom and silicon atom that analytical equipment determines, in solid catalyst surface is 0.75.
[(formula (1) R of embodiment 101=2,4- tolyl, R2=methyl, n=2;It is double (methyloxycarbonylamino) based on 2,4-
The Toluene-2,4-diisocyanate of the thermal decomposition of toluene, the manufacture of 4- diisocyanate)]
[changing 10]
Except the temperature of catalyst layer is set into 375 DEG C, the solid obtained in Production Example 15 has been used as catalyst
Catalyst (Ca/SiO2:1~2mm of particle diameter) 3mL, as carbamate compounds 2 are used, double (the methoxycarbonyl ammonia of 4-
Base) beyond toluene, operate same as Example 1ly and produce Toluene-2,4-diisocyanate, 4- diisocyanate.
Toluene-2,4-diisocyanate, the yield of 4- diisocyanate is 95% (selection rate 95%), and the yield of monoisocyanates is 3%.
Industrial applicability
Using the present invention, can provide can high selectivity and manufacture in high yield isocyanate compound and with production
Thing is segregative, for example may be used as the solid catalyst of the heterogeneous catalysis of isocyanate compound manufacture.
According to the present invention it is possible to repeatability manufactures such a solid catalyst well, it is furthermore possible to also provide having used such a
The manufacture method of the isocyanate compound of solid catalyst.
The explanation of symbol
1 head tank
2 matrix supply pumps
3 are filled with the tubular reactor of catalyst
3a gasification layers (Filled with Quartz)
3b catalyst layers
The thermal source (tubular electric furnace) of 4 heating response devices
5 valves
6 product heat exchangers
The receiver of the isocyanate compound of the 7 chilled products of recovery
8 are used for the heat exchanger of condensed alcohol
9 receiver for obtaining alcohol
10 valves
11 valves
12 product heat exchangers
The receiver of the isocyanate compound of the 13 chilled products of recovery
14 are used for the heat exchanger of condensed alcohol
15 receiver for obtaining alcohol
16 valves
17 vavuum pumps
Claims (20)
1. a kind of solid catalyst, it contains at least one kind of metal in alkali metal compound and alkali earth metallic compound
Compound and silica, it meets 2 following conditions simultaneously:
(1) using in surface, the described metallic compound of x-ray photoelectron analytical equipment measure, described solid catalyst
Alkali metal atom and/or alkaline-earth metal atom and the silica in the atomic ratio M/Si of silicon atom be 0.8~10;
(2) it is 0.1m using the specific surface area of the solid catalyst of nitrogen adsorption methods measure2/ g~10m2/g。
2. solid catalyst according to claim 1, wherein,
The metallic compound for contributing to catalyst reaction is at least 1 in alkali metal compound and alkali earth metallic compound
Kind metallic compound.
3. solid catalyst according to claim 1, wherein,
The alkali metal compound is sodium compound or cesium compound.
4. solid catalyst according to claim 1, wherein,
The alkali earth metallic compound is magnesium compound or calcium compound.
5. solid catalyst according to claim 1, wherein,
The silica is porous silica.
6. solid catalyst according to claim 5, wherein,
The pore volume using mercury penetration method measure of the porous silica is 0.01mL/g~2mL/g, utilizes nitrogen
The pore volume of determination of adsorption method is 0.0002mL/g~0.8mL/g, the specific surface area determined using mercury penetration method is
0.1m2/ g~80m2/ g, the specific surface area determined using nitrogen adsorption methods are 0.01m2/ g~50m2/g。
7. solid catalyst according to claim 1, wherein,
The silica is amorphous silica.
8. solid catalyst according to claim 1, wherein,
The intermediate value pore diameter using mercury penetration method measure of the silica is 0.1 μm~10 μm.
9. solid catalyst according to claim 1, wherein,
Relative to the overall quality of solid catalyst, the total of the content of the metallic compound is scaled each metallic atom and is
The mass % of 0.05 mass %~30.
10. solid catalyst according to claim 1, wherein,
The particle diameter of solid catalyst is 1mm~5mm.
11. solid catalyst according to claim 1, its two by making to burn till 1~20 hour at 700 DEG C~1200 DEG C
Silica adsorbs the metallic compound, then burns till 1~40 hour at 300 DEG C~1200 DEG C and prepares.
12. solid catalyst according to claim 1, its two by making to burn till 1~10 hour at 800 DEG C~1100 DEG C
Silica adsorbs the metallic compound, then burns till 1~20 hour at 500 DEG C~1000 DEG C and prepares.
13. a kind of manufacture method of isocyanate compound, in the presence of the solid catalyst described in claim 1, utilize
Carbamate compounds manufacture isocyanate compound.
14. manufacture method according to claim 13, wherein,
The carbamate compounds are the compounds represented with following formulas (1),
In formula, R1And R2Both it can be the same or different, and represented can there is the alkyl of substituent, n represents 1~4 integer;
The isocyanate compound is the compound represented with following formulas (2),
In formula, n, R1With it is foregoing synonymous.
15. manufacture method according to claim 14, wherein,
N in the formula (1) and (2) is 2.
16. the manufacture method according to any one of claim 13~15, wherein,
The reaction temperature when isocyanate compound is manufactured using the carbamate compounds is 300 DEG C~500 DEG C.
17. the manufacture method according to any one of claim 13~15, wherein,
The reaction pressure when isocyanate compound is manufactured using the carbamate compounds is absolute pressure
0.1kPa~101.33kPa.
18. the manufacture method according to any one of claim 13~15, wherein,
Carry out manufacturing the reaction during isocyanate compound in the form of gas phase using the carbamate compounds.
19. the manufacture method according to any one of claim 13~15, wherein,
Carry out manufacturing the reaction during isocyanate compound in the form of liquid phase using the carbamate compounds.
20. application of the solid catalyst in isocyanate compound is manufactured described in claim 1.
Applications Claiming Priority (3)
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JP2013110316 | 2013-05-24 | ||
JP2013-110316 | 2013-05-24 | ||
PCT/JP2014/063619 WO2014189120A1 (en) | 2013-05-24 | 2014-05-22 | Solid catalyst, and method for producing isocyanate compound using said solid catalyst |
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CN105263618B true CN105263618B (en) | 2018-02-16 |
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JP (1) | JP6372484B2 (en) |
CN (1) | CN105263618B (en) |
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---|---|---|---|---|
US4788329A (en) * | 1986-11-03 | 1988-11-29 | American Cyanamid Company | Preparation of cyclohexyl mono- and diurethanes and isocyanates derived therefrom by addition of methylcarbamate to limonene, process and compositions |
JPH08804B2 (en) * | 1992-01-10 | 1996-01-10 | 株式会社日本触媒 | Method for producing isocyanates |
JPH07119190B2 (en) * | 1992-01-10 | 1995-12-20 | 株式会社日本触媒 | Method for producing isocyanates |
JP5211316B2 (en) * | 2006-07-28 | 2013-06-12 | 群馬県 | Catalyst for the production of propylene from ethylene |
WO2012111750A1 (en) * | 2011-02-17 | 2012-08-23 | 宇部興産株式会社 | Catalyst for isocyanate compound production and method for producing isocyanate compound using same |
JP6060902B2 (en) * | 2011-07-13 | 2017-01-18 | 宇部興産株式会社 | Method for producing isocyanate compound |
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JPWO2014189120A1 (en) | 2017-02-23 |
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