CN105263618A - Solid catalyst, and method for producing isocyanate compound using said solid catalyst - Google Patents
Solid catalyst, and method for producing isocyanate compound using said solid catalyst Download PDFInfo
- Publication number
- CN105263618A CN105263618A CN201480029670.4A CN201480029670A CN105263618A CN 105263618 A CN105263618 A CN 105263618A CN 201480029670 A CN201480029670 A CN 201480029670A CN 105263618 A CN105263618 A CN 105263618A
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- Prior art keywords
- solid catalyst
- compound
- silica
- manufacture
- catalyst
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- 239000011949 solid catalyst Substances 0.000 title claims abstract description 136
- -1 isocyanate compound Chemical class 0.000 title claims abstract description 135
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 115
- 239000012948 isocyanate Substances 0.000 title claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 181
- 238000000034 method Methods 0.000 claims abstract description 152
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 77
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 16
- 229910000765 intermetallic Inorganic materials 0.000 claims description 57
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 29
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052753 mercury Inorganic materials 0.000 claims description 18
- 230000035515 penetration Effects 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 7
- 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 4
- 239000003054 catalyst Substances 0.000 abstract description 72
- 229910052784 alkaline earth metal Chemical class 0.000 abstract description 10
- 150000002736 metal compounds Chemical class 0.000 abstract description 7
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical group 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- 238000005979 thermal decomposition reaction Methods 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 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 11
- 206010013786 Dry skin Diseases 0.000 description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 125000000217 alkyl group Chemical class 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- 150000001342 alkaline earth metals Chemical class 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000006630 butoxycarbonylamino group Chemical group 0.000 description 6
- 238000004140 cleaning 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
- 239000000499 gel Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium 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
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 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
- 238000004452 microanalysis Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 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
- 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 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
- 0 CC(C)(C1)*C(C)(CNC(O)OC)CC1NC(*)=* Chemical compound CC(C)(C1)*C(C)(CNC(O)OC)CC1NC(*)=* 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000001273 butane 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
- 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
- 150000002148 esters Chemical class 0.000 description 3
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BAMOLHXSXMKLAA-UHFFFAOYSA-N methyl n-[3-[(methoxycarbonylamino)methyl]-3,5,5-trimethylcyclohexyl]carbamate Chemical compound COC(=O)NCC1(C)CC(NC(=O)OC)CC(C)(C)C1 BAMOLHXSXMKLAA-UHFFFAOYSA-N 0.000 description 3
- ZWZIHLRSOOMEKT-UHFFFAOYSA-N methyl n-benzylcarbamate Chemical compound COC(=O)NCC1=CC=CC=C1 ZWZIHLRSOOMEKT-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 125000004436 sodium atom Chemical group 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate 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
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 125000006627 ethoxycarbonylamino group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 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 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 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
- 238000012423 maintenance Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- RDZZSLRUHLWLAV-UHFFFAOYSA-N methyl n-(cyclohexylmethyl)carbamate Chemical compound COC(=O)NCC1CCCCC1 RDZZSLRUHLWLAV-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
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 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
- 239000000725 suspension Substances 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 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
- 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
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-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
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 239000002253 acid Substances 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 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
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 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
- 230000006837 decompression Effects 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
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[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 PWZFXELTLAQOKC-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 group CC1=CC=CC=C1.CCN(CC)C(O)=O PILVIBLEOYWKLP-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 238000004821 distillation Methods 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
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005179 haloacetyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004677 hydrates Chemical class 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
- 229910052900 illite 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
- 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 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 compound 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
- IZPAJCSXPWFEPU-UHFFFAOYSA-N methyl n-naphthalen-1-ylcarbamate Chemical compound C1=CC=C2C(NC(=O)OC)=CC=CC2=C1 IZPAJCSXPWFEPU-UHFFFAOYSA-N 0.000 description 1
- RRQZQNFQNFVZCU-UHFFFAOYSA-N methyl n-nonylcarbamate Chemical compound CCCCCCCCCNC(=O)OC RRQZQNFQNFVZCU-UHFFFAOYSA-N 0.000 description 1
- QXOUFQKDZIMOMU-UHFFFAOYSA-N methyl n-octylcarbamate Chemical compound CCCCCCCCNC(=O)OC QXOUFQKDZIMOMU-UHFFFAOYSA-N 0.000 description 1
- VBJIQWCGMYVMKK-UHFFFAOYSA-N methyl n-pentylcarbamate Chemical compound 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
- 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
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 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
- VOQWIAQVTYSSPY-UHFFFAOYSA-N phenyl n-[1,6-bis(phenoxycarbonylamino)hexan-3-yl]carbamate Chemical compound C=1C=CC=CC=1OC(=O)NCCCC(NC(=O)OC=1C=CC=CC=1)CCNC(=O)OC1=CC=CC=C1 VOQWIAQVTYSSPY-UHFFFAOYSA-N 0.000 description 1
- RWIJOAWRPFEYNZ-UHFFFAOYSA-N phenyl n-[4-[(phenoxycarbonylamino)methyl]octyl]carbamate Chemical compound C=1C=CC=CC=1OC(=O)NCC(CCCC)CCCNC(=O)OC1=CC=CC=C1 RWIJOAWRPFEYNZ-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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 230000009257 reactivity 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
- 238000012216 screening Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007873 sieving Methods 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
- 239000000243 solution Substances 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 239000010457 zeolite Substances 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The purpose of the present invention is to provide, with a high degree of reproducibility, a catalyst which can be used to produce isocyanate compounds with a high degree of selectivity and at high yield, and which can be easily separated from resultant products. The present invention is: a solid catalyst which contains silica and at least one metal compound selected from a group consisting of alkali metal compounds and alkali earth metal compounds, said catalyst simultaneously satisfying the following two conditions; and a method for producing an isocyanate compound from a carbamate compound in the presence of said catalyst. (1) the atomic ratio (M/Si) between silicon atoms in the silica and metals atoms in the metal compound as measured by X-ray photoelectron spectroscope falls within the range 0.5-20. (2) The specific surface area of the solid catalyst measured by the nitrogen gas adsorption method is from 0.01m2/g to 50m2/g.
Description
Technical field
The present invention relates to the solid catalyst of a kind of metallic compound of at least a kind containing being selected from alkali metal compound and alkali earth metallic compound and silica.In addition, the present invention relates to the method manufacturing isocyanate compound under the existence of described solid catalyst.
Background technology
Isocyanate compound is such as the useful compound that the manufacture raw material of carbamate or medical agricultural chemicals etc. uses widely.In the past, isocyanate compound was industrially manufactured (such as with reference to patent document 1) by the reaction of amine and phosgene.
As the manufacture method of isocyanate compound not using phosgene, such as, under there will be a known the existence of the catalyst such as the haloid making three haloacetyl aminated compounds at alkali-metal haloid or alkaline-earth metal, carry out the method (such as with reference to patent document 2) of haloform.
In addition, as the manufacture method of isocyanate compound not using phosgene, also there will be a known such as by the method (such as with reference to patent document 3) of carbamate compounds thermal decomposition.
Manufactured the method for isocyanate compound as use homogeneous catalyst by this carbamate compounds, such as, proposed in the liquid phase and the method (such as with reference to patent document 4) of carbamate compounds being decomposed with organotin catalysts and solid acid catalyst.
These tin catalysts known demonstrate suitable reaction achievement for the thermal decomposition of carbamate compounds.
And on the other hand, also proposed to use heterogeneous catalysis carbamate compounds thermal decomposition to be manufactured the method for isocyanate compound.
There will be a known following method: as described heterogeneous catalysis, use calcium oxide, magnesia, barium monoxide, magnesium metal etc., as carbamate compounds, the thermal decomposition of toluene diethylamino formic acid esters is manufactured isocyanate compound (such as with reference to patent document 3); As heterogeneous catalysis, use sodium carbonate, calcium carbonate etc., by N-(isopropenyl-α, α-dimethylbenzyl) carbamic acid isopropyl ester, a N-(vinyl-α, α-dimethylbenzyl) the carbamate compounds thermal decomposition such as carbamic acid isopropyl ester manufactures isocyanate compound (for example, referring to patent document 5 and patent document 6).
On the other hand, as use heterogeneous catalysis, do not use solvent, make carbamate under gas phase condition with catalyst exposure, carry out thermal decomposition to manufacture the method for isocyanate compound, such as there will be a known following method etc.: as catalyst, use the transition metal of IB race or the VIII be selected from periodic table, the oxidate sintered body of the element of more than at least a kind in lanthanide and actinides, or contain the oxidate sintered body of alkali metal and/or alkaline-earth metal element, manufacture isocyanate compound (such as with reference to patent document 7 and patent document 8).
In addition, further developed the isocyanate compound catalyst for producing (such as with reference to patent document 9) that load on silica supports has at least a kind of metallic compound be selected from alkali metal compound and alkali earth metallic compound.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-310566 publication
Patent document 2: No. 2011/049023rd, International Publication
Patent document 3: Japanese Laid-Open Patent Publication 54-88201 publication
Patent document 4: Japanese Unexamined Patent Publication 2004-262892 publication
Patent document 5: Japanese Unexamined Patent Publication 2003-012632 publication
Patent document 6: Japanese Unexamined Patent Publication 2004-018507 publication
Patent document 7: Japanese Unexamined Patent Publication 5-186414 publication
Patent document 8: Japanese Unexamined Patent Publication 5-186415 publication
Patent document 9: No. 2012/111750th, International Publication
Summary of the invention
Invent problem to be solved
But, the phosgene that the manufacture method of aforesaid patent document 1 uses is severe toxicity, secondary generation hydrogen chloride in large quantities, the manufacture method of patent document 2 secondaryly can generate the halide such as chloroform, the manufacture method of patent document 3 needs to carry out thermal decomposition under harsh temperature conditions, therefore easily side reaction is caused, the manufacture method of patent document 4 exists with the state of dissolving equably due to tin catalyst, therefore poisonous organotin catalysts can be caused to loaded down with trivial detailsization with catalyst recovery operation that be mixed in product, in the manufacture method of patent document 5 ~ 8 the activity of the reaction of carbamate compounds and isocyanate compound optionally in abundant not, from the viewpoint of these, not talkative is the manufacture method being suitable for actual manufacture.
In order to solve problem as above, as shown in record in patent document 9, develop the isocyanate compound catalyst for producing having at least a kind of metallic compound be selected from alkali metal compound and alkali earth metallic compound at supported on carriers, but in order to realize the manufacture method being more suitable for actual manufacture, require to propose repeatability or selective higher catalyst.
The present invention is in view of the situation of foregoing conventional art, and its problem is, repeatability provides well can high selectivity and manufacture isocyanate compound and easily and the catalyst of product separation with high yield.In addition problem of the present invention is also, provides the manufacture method of the isocyanate compound employing this kind of catalyst.
For solving the method for problem
For this problem, up to now the parameter of the catalyst that selective, yield impact be it be unclear that.Employ patent document 9 catalyst isocyanate compound manufacture in, the at least a kind of metallic compound be selected from alkali metal compound and alkali earth metallic compound be carried on carrier plays a role as alkali, hydrogen atom on the nitrogen of deaminate formic acid ester compound, carries out decomposition reaction.
Thus can predict, by increasing the content of aforesaid metallic compound or increasing the specific area etc. of catalyst and increase the frequency of exposure of metal and matrix, yield or selectively to improve.
But, if the research such as the present inventor as a result, increase the content of metallic compound or the specific area of catalyst, then selective or yield can reduce.
The present inventor etc. are studied in further detail, found that, by controlling the specific area being present in the metallic atom of catalyst surface and the atomic ratio of silicon atom and catalyst, can solve described problem, thus completing the present invention.
Also find in addition the metallic atom of catalyst surface and the atomic ratio of silicon atom, the specific area of catalyst to be controlled preparation condition in scope described later, catalyst, completed and repeatability can provide the manufacture method of the solid catalyst of excellent catalyst well.
Find when manufacturing isocyanate compound by carbamate compounds in addition, by using the described catalyst containing metallic compound and silica, can high selectivity and manufacture the new industrialization production method of isocyanate compound with high yield, thus complete the present invention.
The present invention is as follows.
The present invention 1 relates to a kind of solid catalyst, and it contains and is selected from least a kind of metallic compound in alkali metal compound and alkali earth metallic compound and silica, meets 2 following conditions simultaneously.
(1) metallic atom in the described metallic compound utilizing x-ray photoelectron analytical equipment to measure (hereinafter sometimes referred to as atomic ratio, is expressed as M/Si with the ratio of the quantity of the atom of the silicon atom in described silica.) be 0.5 ~ 20.
(2) specific area of the described solid catalyst utilizing nitrogen adsorption methods to measure is 0.01m
2/ g ~ 50m
2/ g.
The present invention 2 relates to the solid catalyst recorded in the present invention 1, wherein, meets 2 following conditions simultaneously.
(3) M/Si is 0.8 ~ 10.
(4) surface area of the described solid catalyst utilizing nitrogen adsorption methods to measure is 0.1m
2/ g ~ 10m
2/ g.
The present invention 3 relates to the solid catalyst recorded in the present invention 1 or 2, and wherein, described alkali metal compound is sodium compound or cesium compound.
The present invention 4 relates to the solid catalyst recorded any one of the present invention 1 ~ 3, and wherein, described alkali earth metallic compound is magnesium compound or calcium compound.
The present invention 5 relates to the solid catalyst recorded any one of the present invention 1 ~ 4, and wherein, described silica is porous silica.
The present invention 6 relates to the solid catalyst recorded any one of the present invention 1 ~ 5, and wherein, described silica is amorphous silica.
The present invention 7 relates to the solid catalyst recorded any one of the present invention 1 ~ 6, and wherein, the intermediate value pore diameter utilizing mercury penetration method to measure of described silica is 0.1 μm ~ 10 μm.
The present invention 8 relates to the solid catalyst recorded any one of the present invention 1 ~ 7, wherein, by making to burn till 1 ~ 20 hour and the silica that obtains adsorbs described metallic compound at 700 DEG C ~ 1200 DEG C, then burning till 1 ~ 40 hour at 300 DEG C ~ 1200 DEG C and prepares.
The present invention 9 relates to the solid catalyst recorded any one of the present invention 1 ~ 7, wherein, by making to burn till 1 ~ 10 hour and the silica that obtains adsorbs described metallic compound at 800 DEG C ~ 1100 DEG C, then burning till 1 ~ 20 hour at 500 DEG C ~ 1000 DEG C and prepares.
The present invention 10 relates to a kind of manufacture method of isocyanate compound, and it utilizes carbamate compounds to manufacture isocyanate compound under the existence of the solid catalyst recorded any one of the present invention 1 ~ 9.
The present invention 11 relates to the manufacture method recorded in the present invention 10, and wherein, described carbamate compounds is the compound represented with following general formula (1),
[changing 1]
In formula, R
1and R
2both can be the same or different, expression can have substituent alkyl, and n represents the integer of 1 ~ 4.
Described isocyanate compound is the compound represented with following general formula (2),
[changing 2]
In formula, n, R
1with aforementioned synonym.
The present invention 12 relates to the manufacture method recorded in the present invention 11, and wherein, the n in described general formula (1) and (2) is 2.
The present invention 13 relates to the manufacture method recorded any one of the present invention 10 ~ 12, and wherein, reaction temperature when utilizing described carbamate compounds to manufacture described isocyanate compound is 300 DEG C ~ 500 DEG C.
The present invention 14 relates to the manufacture method recorded any one of the present invention 10 ~ 13, and wherein, reaction pressure when utilizing described carbamate compounds to manufacture described isocyanate compound is absolute pressure 0.1kPa ~ 101.33kPa.
The present invention 15 relates to the manufacture method recorded any one of the present invention 10 ~ 14, wherein, and reaction when carrying out utilizing described carbamate compounds to manufacture described isocyanate compound with the form of gas phase.
The present invention 16 relates to the manufacture method recorded any one of the present invention 10 ~ 14, wherein, and reaction when carrying out utilizing described carbamate compounds to manufacture described isocyanate compound with the form of liquid phase.
The present invention 17 relates to the solid catalyst recorded any one of the present invention 1 ~ 9 and is manufacturing the application in isocyanate compound.
Invention effect
According to solid catalyst of the present invention, when the metallic atom of described metallic compound in the solid catalyst of the metallic compound containing regulation and silica and the atomic ratio (M/Si) of silicon atom in described silica and the specific area utilizing nitrogen adsorption methods to measure these two of described solid catalyst meet aforesaid condition simultaneously, can high selectivity, manufacture isocyanate compound with high yield.
According to the present invention, repeatability can manufacture this kind of solid catalyst well, in addition, the manufacture method of the isocyanate compound employing this kind of solid catalyst can also be provided.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the reaction unit of the gas phase fixed bed mode used in embodiment.
The specific area of the solid catalyst of embodiment, calcium atom are concentrated figure in the graph (comparative example 1 does not show) with the atomic ratio Ca/Si ratio of silicon atom and the yield of diisocyanate cpd by Fig. 2.It should be noted that, in Fig. 2, " S.A. " represents the specific area (m of the solid catalyst utilizing nitrogen adsorption methods to measure
2/ g), " Ca/Si " represents the atomic ratio of calcium atom in solid catalyst surface and silicon atom, and " BII productive rate (BIIYield) " represents the yield (%) of diisocyanate cpd.
Detailed description of the invention
Below, the present invention is described in detail.Following 3 contents are described.
(A) formation of solid catalyst
(B) preparation method of solid catalyst
(C) manufacture method of isocyanate compound
[formation of (A) solid catalyst]
Solid catalyst of the present invention be containing at least a kind of metallic compound be selected from alkali metal compound and alkali earth metallic compound and silica, the catalyst of the manufacture that is applicable to isocyanate compound.Solid catalyst of the present invention can use with other catalyst combination, therefore, in solid catalyst of the present invention, the catalyst being physically mixed with the solid catalyst containing the inorganic compound different with silica from described metallic compound relative to described solid catalyst containing metallic compound and silica is also comprised.
In solid catalyst of the present invention, the atomic ratio (M/Si) of the metallic atom in the described metallic compound on its surface and the silicon atom in silica is 0.5 ~ 20,0.7 ~ 10 is more preferably from the viewpoint of selective or yield, more preferably 0.8 ~ 10, be particularly preferably 1 ~ 6.By like this ratio of the atomicity of the metallic atom in the metallic compound (this metallic compound is considered to mainly contain the material helping catalyst reaction) on the surface of catalyst and the silicon atom in silica being set to certain scope, excellent selective and yield just can be realized.
It should be noted that, in this description, the atomic ratio (M/Si) on the surface of aforesaid solid catalyst is the value utilizing x-ray photoelectron analytical equipment (ESCA) to measure.
In addition, the specific area utilizing nitrogen adsorption methods to measure of solid catalyst of the present invention is 0.01m
2/ g ~ 50m
2/ g, is more preferably 0.1m from the viewpoint of selective or yield
2/ g ~ 10m
2/ g, more preferably 0.1m
2/ g ~ 5m
2/ g, is particularly preferably 0.2m
2/ g ~ 3m
2/ g.
Have pore in silica, this pore is divided into micropore, mesopore, macropore these 3 kinds haply.Micropore is the pore that diameter is less than 2nm, and the pore of mesopore to be diameter be 2nm ~ 50nm, macropore is the pore (such as with reference to Carbon, 2008,850-857.) that diameter is greater than 50nm.
Micropore, mesopore are considered to provide a large amount of reflecting points to catalyst, but on the other hand in this part association reaction matrix consumingly, even if may also can not carry out from this disengaging or non-targeted reaction by reaction end product.Consider in the present invention, such as, by utilizing the method for regulation described later to process silica, the specific area of solid catalyst is controlled as certain scope and reduce these micropores, mesopore, thus overcomes described drawback.
It should be noted that, in solid catalyst of the present invention, except silica, such as, can also use active carbon; The metal oxides such as aluminium oxide, sial, zirconia, titanium oxide; The composite metal oxides such as titanium silicon, titanium zirconium, zirconium silicon, hydrotalcite; The clay minerals such as kaolin, montmorillonite, bentonite, chlorite, illite; The metal silicates such as zeolite; The metal oxide precursor such as silicon dioxide gel, alumina sol, also can realize excellent selective, yield containing them and the solid catalyst being selected from least a kind of metallic compound in alkali metal compound and alkali earth metallic compound.
Be preferably metal oxide and composite metal oxide in the middle of them, be more preferably aluminium oxide and sial.
As the silica used in the present invention, preferably enumerate amorphous silica.As this amorphous silica, any one of the synthesis amorphous silica utilizing dry process or damp process to manufacture can be used.In addition, the commercially available product containing moisture such as can directly provide and (2) front firing process of catalyst preparing operation described later or (3) absorption process by amorphous silica.In addition, also silica gel can be used aptly.
In addition, also porous silica can be used as silica.As its example, FujiSilysiaChemical Inc. CARiACTQ10, CARiACTQ50, CARiACTQ100, CARiACTQ300 etc. can be enumerated.Porous silica also can use after screening to be applied in device.
The particle diameter of the silica used in the present invention is not particularly limited, and is generally 0.5mm ~ 10mm.
In addition, the intermediate value pore diameter utilizing mercury penetration method to measure of described silica is generally 8nm ~ 300 μm, is preferably 10nm ~ 50 μm, is more preferably 50nm ~ 20 μm, more preferably 0.1 μm ~ 10 μm.It should be noted that, the pore diameter of silica can utilize any one method of nitrogen adsorption methods and mercury penetration method to measure.
In addition, the pore volume of aforesaid porous silica and specific area can utilize any one method of nitrogen adsorption methods and mercury penetration method to measure.But, for pore volume and specific area, when the pore diameter of porous silica is 0.4nm ~ 200nm, nitrogen adsorption methods can be utilized to measure, when pore diameter is 3.6nm ~ 400 μm, mercury penetration method can be utilized to measure.When pore diameter is 3.6nm ~ 200nm, any one method of nitrogen adsorption methods and mercury penetration method can be utilized to measure.
From the viewpoint of reactivity and optionally, the pore volume utilizing mercury penetration method to measure of this porous silica is preferably 0.01mL/g ~ 2mL/g, is more preferably 0.1mL/g ~ 1.5mL/g, more preferably 0.3mL/g ~ 1mL/g.In addition, the specific area utilizing the mercury penetration method of porous silica to measure is preferably 0.01m
2/ g ~ 100m
2/ g, is more preferably 0.1m
2/ g ~ 80m
2/ g, more preferably 0.3m
2/ g ~ 50m
2/ g.
Meanwhile, the pore volume of the porous silica utilizing nitrogen adsorption methods to measure is preferably 0.0001mL/g ~ 1mL/g, is more preferably 0.0002mL/g ~ 0.8mL/g, more preferably 0.0004mL/g ~ 0.5mL/g.In addition, the specific area utilizing nitrogen adsorption methods to measure of porous silica is preferably 0.01m
2/ g ~ 1000m
2/ g, is more preferably 0.01m
2/ g ~ 100m
2/ g, more preferably 0.01m
2/ g ~ 50m
2/ g, is particularly preferably 0.1m
2/ g ~ 10m
2/ g.
Silica described above in the present invention, both can be used alone any a kind, also can combinationally use two or more.
In solid catalyst of the present invention, use at least a kind of metallic compound be selected from alkali metal compound and alkali earth metallic compound.As the alkali metal in this metallic compound, such as, can enumerate lithium, sodium, potassium, rubidium and caesium.In addition, as the alkaline-earth metal in described metallic compound, such as, can enumerate beryllium, magnesium, calcium, strontium, barium etc.In the middle of them, be preferably sodium, caesium, magnesium, calcium (that is, be preferably sodium compound and cesium compound as alkali metal compound, be preferably magnesium compound and calcium compound as alkali earth metallic compound), be more preferably calcium.
In addition, as long as described metallic compound alkali metal or alkaline-earth metal, with the compound of the element of regulation, just be not particularly limited, as this metallic compound, such as, can enumerate the composite oxides etc. of metal oxide, metal oxide and silica.
In addition, when the preparation of the solid catalyst of the present invention of following explanation, first make silica adsorb alkali metal compound or alkali earth metallic compound, then burn till.As the metallic compound used during this absorption process, such as, can enumerate: the inorganic acid salt of the alkali metal such as nitrate, carbonate, bicarbonate, silicate or alkaline-earth metal; The halide of the alkali metal such as fluoride, chloride or alkaline-earth metal; The hydroxide of alkali metal or alkaline-earth metal; And the acylate of the alkali metal such as acetate, oxalates or alkaline-earth metal.In addition, alkali metal compound and alkali earth metallic compound also can be hydrates.
In solid catalyst of the present invention, the quality overall relative to solid catalyst, the total of the content of metallic compound described above is scaled each metallic atom and is preferably 0.01 quality % ~ 50 quality %, be more preferably 0.05 quality % ~ 30 quality %, more preferably 0.1 quality % ~ 20 quality %.It should be noted that, the content of the metallic compound in solid catalyst such as can use the mensuration such as fluorescent X-ray elemental microanalysis method (XRF) or ICP-AES method.
In addition, the particle diameter of solid catalyst of the present invention is generally 1mm ~ 10mm, is preferably 1mm ~ 5mm.
[preparation method of (B) solid catalyst]
Below, the manufacture method of solid catalyst of the present invention is described.Solid catalyst of the present invention such as can be prepared as follows: make the silica burnt till 1 ~ 20 hour at 700 DEG C ~ 1200 DEG C adsorb at least a kind of metallic compound be selected from alkali metal compound and alkali earth metallic compound, the silica that burns till this having been adsorbed metallic compound burns till 1 ~ 40 hour to prepare at 300 DEG C ~ 1200 DEG C.More specifically, such as prepare according to step as follows.
(1) synthesis procedure; Synthetic silica.
(2) front firing process; The silica of gained is burnt till, reduces micropore and mesopore.
(3) absorption process; Utilize method of impregnation etc., make silica adsorbing metal compound.
(4) drying process; As required by the solid drying of gained.
(5) firing process; As required dried solid is burnt till.
In the middle of these 5 operations, be described from the operation of important (2) and (5).
(2) front firing process
Before the silica adsorbing metal compound used when making preparation solid catalyst of the present invention, need to carry out burning till process for the object reducing aforesaid micropore and mesopore.
The described temperature of burning till process needs to be the high temperature of 700 DEG C ~ 1200 DEG C, is more preferably 800 DEG C ~ 1100 DEG C, more preferably 900 DEG C ~ 1000 DEG C from the viewpoint of selective and yield.
Can think because by being set to this scope, micropore and the mesopore of silica just can be reduced, the specific area utilizing nitrogen adsorption methods to measure of the solid catalyst of the present invention obtained through each operation is thereafter controlled as aforesaid scope.Consequently, matrix easily departs from from solid catalyst of the present invention after the reaction aptly, thus the reaction beyond the reaction of minimizing target.It should be noted that, in the stage of the synthesis procedure (1) before this front firing process (2), the specific area of silica is in the scope of regulation, even if then do not implement this operation (2), by the operation through (3) described later ~ (5), the scope of the specific area of the solid catalyst specified in the present invention sometimes also can be realized.Thus, in the manufacture method of solid catalyst of the present invention, sometimes this operation (2) also can be omitted.It should be noted that, for also can omit operation (2), the approximate range of the specific area of the silica in stage of operation (1), those skilled in the art easily can grasp by implementing the test of the resonable degree that those skilled in the art expect.
In addition, the time of silica being burnt till to process in the present invention before making silica adsorbing metal compound is 1 ~ 20 hour in aforesaid temperature range, is more preferably 1 ~ 10 hour.By being set to this scope, the specific area utilizing nitrogen adsorption methods to measure of solid catalyst of the present invention can be controlled as aforesaid scope.
It should be noted that, from the viewpoint of burning till uniformly, preferably sieving etc. the silica used in front firing process (2), is that 1mm ~ 10mm, more preferably unification are burnt till for after 1mm ~ 5mm by the unification of its particle diameter.
(5) firing process
After burning till before silica being carried out in operation (2), in operation described later (3), make silica adsorbing metal compound, by the solid of gained as required by after operation (4) drying, need to burn till again.Firing condition suitably can adjust according to kind, form, content or the drying regime etc. of the inorganic compound such as metallic compound, silica (aforesaid silica, active carbon etc.).
Firing temperature is preferably 300 DEG C ~ 1200 DEG C, is more preferably 500 DEG C ~ 1000 DEG C, more preferably 500 DEG C ~ 800 DEG C.By burning till in this range, can the atomic ratio M/Si of the metallic atom in the metallic compound of the solid catalyst surface of gained and the silicon atom in silica be controlled as aforesaid scope, catalyst activity needed for acquisition (reaction speed, reaction yield and optionally improve).
In addition, as long as firing time carries out the time of burning till fully, be just not particularly limited, but be preferably 1 hour ~ 40 hours, be more preferably 1 hour ~ 20 hours.By burning till in this range, just can the atomic ratio M/Si of the metallic atom in the metallic compound of solid catalyst surface and the silicon atom in silica be controlled as aforesaid scope, catalyst activity needed for acquisition (reaction speed, reaction yield and optionally improve).
Below, the operation of (1), (3) and (4) in the preparation of solid catalyst of the present invention is described.
(1) synthesis procedure
Silica can synthesize according to known method, also can use commercially available product as mentioned above in addition, is described an example of the synthetic method of silica herein.By relative to the mixed solvent mixing tetraethyl orthosilicate of water and polyethylene glycol and nitric acid, dry after stirring and cleaning, thus can synthetic silica.
The amount of water used herein is preferably 0.1mL ~ 3mL relative to tetraethyl orthosilicate 1mL, is more preferably 0.5mL ~ 2mL.In addition, the polyethylene glycol used is preferably 0.01mL ~ 0.2mL relative to tetraethyl orthosilicate 1mL, is more preferably 0.02mL ~ 0.1mL.By being set to this scope, just while the stirring that maintenance is good, the solidification of reactant liquor can be prevented.
The nitric acid used such as when concentration is 60%, is preferably 0.01mL ~ 0.1mL relative to tetraethyl orthosilicate 1mL, is more preferably 0.02mL ~ 0.08mL.
Drying time after silica gel synthesis is preferably 5 hours ~ 100 hours, is more preferably 10 hours ~ 80 hours.In addition, baking temperature is preferably 90 DEG C ~ 150 DEG C, is more preferably 100 DEG C ~ 120 DEG C.By being set to this scope, thus within the aforesaid time, the solvent in silica gel can be reduced to the amount that can not affect 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, also can burn till the temperature of about 600 DEG C.
(3) absorption process
After synthesizing silica by operation (1), burn till before utilizing above-mentioned operation (2) to carry out silica.After this, metallic compound is made to be infiltrated in silica.The metallic compound used as previously mentioned, is the inorganic acid salt etc. of alkali metal or alkaline-earth metal.
After described infiltration, utilize solid (original text: the universe is solid) and filtration, solid or filtration, just can have been adsorbed the solid of metallic compound on silica.As method that is solid, that filter, general method can be adopted.
In addition, as the method making metallic compound in silica, the usual way in the preparation of solid catalyst can be used, such as, can apply pore filling (porefilling) method, evaporate solid method, Equilibrium Adsorption Method, just wet impregnation (Incipientwetness) method etc.
(4) drying process
The solid obtained in described absorption process for the object removing the solvent used, preferably carries out drying usually.Baking temperature when solid catalyst of the present invention manufactures is preferably 50 DEG C ~ 150 DEG C, is more preferably 80 DEG C ~ 120 DEG C.Be preferably 6 hours ~ 36 hours drying time, be more preferably 12 hours ~ 24 hours.By being set to this scope, the solvent in solid can be reduced to the amount that can not affect subsequent processing.
By being burnt till in the firing process (5) of above-mentioned explanation by the solid so obtained, just solid catalyst of the present invention can be obtained.It should be noted that, thinking that use the situations such as alkali-metal inorganic acid salt in absorption process (3) under, this inorganic acid salt etc. are oxidized because burning till, and become metal oxide or the composite oxides with silica.
If through described above, carry out solid catalyst based on the regulation operation of rated condition manufacture, just can repeatability manufacture well can high selectivity and generate isocyanate compound etc. with high yield, excellent solid catalyst as described later.
[manufacture method of (C) isocyanate compound]
Solid catalyst of the present invention described above can use as the catalyst of various reaction, particularly as utilizing carbamate compounds to be useful to manufacture the catalyst of the reaction of isocyanate compound.The manufacture method (hereinafter also referred to as " manufacture method of the present invention ") of isocyanate compound of the present invention be by under the existence of solid catalyst of the present invention, make carbamate compounds react and implement.Manufacture method of the present invention preferably utilizes pyrolysis to implement.
As carbamate compounds used in manufacture method of the present invention, what applicable use represented with following general formula (1) has at least 1 amino-formate bond (-NHCO in molecule
2-) compound.
[changing 3]
In described general formula (1), R
1expression can have substituent alkyl.
As this alkyl, such as, can enumerate the alkyl of the carbon numbers 1 ~ 20 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl;
The thiazolinyl of the carbon numbers 2 ~ 20 such as acrylic, cyclobutenyl, pentenyl;
The alkylidene radical of the carbon numbers 1 ~ 20 such as methene base, ethidine, propylidene base, fourth fork base, pentylidene base, oneself fork base;
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, ring octyl group, methylcyclohexylmethyl, Dimethylcyclohexyl, isophorone base, norborny, decahydronaphthalene naphthyl, adamantyl, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexane) base, 2, the cycloalkyl of the carbon numbers 3 ~ 20 such as 4 '-di-2-ethylhexylphosphine oxide (cyclohexane) base;
The ring alkylidene radical of the carbon numbers 3 ~ 20 such as Isosorbide-5-Nitrae-cyclohexylidene base;
Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl, 4,4 '-methylene diphenylene etc. comprise the aryl etc. of 1 ~ 3 aromatic ring.It should be noted that, these groups comprise various isomers.
In described general formula (1), R
2represent also can have substituent alkyl.
As this alkyl, such as, can enumerate the alkyl of the carbon numbers 1 ~ 20 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl;
The alkenyl of the carbon numbers 2 ~ 20 such as acrylic, cyclobutenyl, pentenyl;
The cycloalkyl of the carbon numbers 3 ~ 20 such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclohexyl, ring octyl group, Dimethylcyclohexyl, isophorone base, norborny, decahydronaphthalene naphthyl, adamantyl;
Phenyl, tolyl, xylyl, naphthyl, xenyl, anthryl, trimethylphenyl etc. comprise the aryl etc. of 1 ~ 3 aromatic ring.It should be noted that, these groups comprise various isomers.
The R of described general formula (1)
1and R
2in, as the described substituting group that can have in substituent alkyl, such as, can enumerate hydroxyl, halogen atom, cyano group, amino, alkyl amino, carboxyl, alkoxyl, aryloxy group, alkylthio group, arylthio, (methyl) acryloxy etc.
In described general formula (1), n is the integer of 1 ~ 4, and this is according to R
1corresponding one-tenth bond valence number and the value determined, such as, at R
1when being group (such as the cyclohexyl) of 1 valency, n is 1, at R
1when group (such as cyclohexylidene) for divalent, n is 2.In addition, as R
1the example of alkyl can enumerate alkyl, be such as 2 (R at n
1for divalent) when, described alkyl is the group (alkylidene) of the divalent corresponding to alkyl.When n is 3, it is the group (alkane three base) of 3 similarly corresponding valencys.Other groups enumerated for the example as alkyl are also identical.
In addition, from the viewpoint of the serviceability of the various manufacture raw materials as the isocyanate compound utilizing manufacture method of the present invention to obtain etc., n is preferably 2.
Carbamate compounds used in manufacture method of the present invention is preferably the compound represented with general formula (1) described above, as its example, such as, can enumerate aliphatic urethane compound, alicyclic urethane compound, aromatic series urethane compound etc.
Aliphatic urethane compound used in manufacture method of the present invention is such as following carbamate compounds: in described general formula (1), R
1can have substituent, the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20 or carbon number 1 ~ 20 alkylidene radical, R
2alkyl or the phenyl can with substituent, carbon number 1 ~ 20, preferably carbon number 1 ~ 6.As aliphatic urethane compound used in manufacture method of the present invention, such as, can enumerate: methylhexyl carbamate, Methyl Octyl carbamate, methyl dodecylamino formic acid esters, methyl octadecyl carbamate, Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino) butane, Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group) butane, Isosorbide-5-Nitrae-bis-(butoxycarbonylamino group) butane, two (methyloxycarbonylamino) pentane of 1,5-, two (methyloxycarbonylamino) hexane of 1,6-, two (ethoxycarbonylamino group) hexane of 1,6-, two (butoxycarbonylamino group) hexane of 1,6-, two (methyloxycarbonylamino) octane of 1,8-, two (butoxycarbonylamino group) octane of 1,8-, two (phenoxycarbonylamino)-4-(phenoxycarbonylamino methyl) octane of 1,8-, two (methyloxycarbonylamino) nonane of 1,9-, two (butoxycarbonylamino group) nonane of 1,9-, two (the methyloxycarbonylamino)-decane of 1,10-, two (the butoxycarbonylamino group)-dodecane of 1,12-, two (the methyloxycarbonylamino)-dodecane of 1,12-, two (the phenoxycarbonylamino)-dodecane of 1,12-, 1,3,6-tri-(methyloxycarbonylamino) hexane, 1,3,6-tri-(phenoxycarbonylamino) hexane etc.
Alicyclic urethane compound used in manufacture method of the present invention is such as following carbamate compounds: in described general formula (1), R
1can have cycloalkyl that is substituent, carbon number 3 ~ 20, R
2alkyl or the phenyl can with substituent, carbon number 1 ~ 6.As alicyclic urethane compound used in manufacture method of the present invention, such as, can enumerate: 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(butoxycarbonylamino group) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino methyl) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group methyl) cyclohexane, 1,3-or Isosorbide-5-Nitrae-bis-(Butyloxycarbonylaminomethyl) cyclohexane, 2,4 '-or 4,4 '-bis-(methyloxycarbonylamino) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis-(ethoxycarbonylamino group) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis-(butoxycarbonylamino group) dicyclohexyl methyl hydride, 2,4 '-or 4,4 '-bis-(phenoxycarbonylamino) dicyclohexyl methyl hydride, two (methyloxycarbonylamino methyl) two rings [2,2, the 1] heptane of 2,5-, 2,5-two (Butyloxycarbonylaminomethyl) two ring [2,2,1] heptane, two (methyloxycarbonylamino methyl) two rings [2,2, the 1] heptane of 2,6-, 2,6-two (Butyloxycarbonylaminomethyl) two ring [2,2,1] heptane, 1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane, 1-(butoxycarbonylamino group)-3,3,5-trimethyl-5-(Butyloxycarbonylaminomethyl)-cyclohexane, 3-(methyloxycarbonylamino methyl)-3,5,5-trimethyl-1-(methyloxycarbonylamino) cyclohexane, 4,4 '-bis-(methyloxycarbonylamino)-2,2 '-dicyclohexyl propane, 4,4 '-bis-(butoxycarbonylamino group)-2,2 '-dicyclohexyl propane etc.
Aromatic series urethane compound used in manufacture method of the present invention is following carbamate compounds: R
1can have the aryl comprising aromatic ring that is substituent, carbon number 6 ~ 18, R
2alkyl or the phenyl can with substituent, carbon number 1 ~ 6.As aromatic series urethane compound used in manufacture method of the present invention, such as, can enumerate: 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino methyl) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(ethoxycarbonylamino group methyl) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(Butyloxycarbonylaminomethyl) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(methyloxycarbonylamino) benzene, 1,3-or Isosorbide-5-Nitrae-bis-(butoxycarbonylamino group) benzene, 2,2 '-bis-(4-propoxy carbonylamino phenyl) propane, 2,4 '-or 4,4 '-bis-(methyloxycarbonylamino) diphenyl methane, 2,4 '-bis-(ethoxycarbonylamino group) diphenyl methane, 2,4 '-bis-(butoxycarbonylamino group) diphenyl methane, 4,4 '-bis-(phenoxycarbonylamino) diphenyl methane, two (methyloxycarbonylamino) naphthalene of 1,5-or 2,6-, two (butoxycarbonylamino group) naphthalene of 1,5-or 2,6-, 4,4 '-bis-(methyloxycarbonylamino) biphenyl, 4,4 '-bis-(butoxycarbonylamino group) biphenyl, two (methyloxycarbonylamino) toluene of 2,4-or 2,6-, two (ethoxycarbonylamino group) toluene of 2,4-or 2,6-, two (butoxycarbonylamino group) toluene of 2,4-or 2,6-etc.
In manufacture method of the present invention, the carbamate compounds represented with general formula (1) described above is such as utilized to manufacture corresponding isocyanate compound, but the compound that this isocyanate compound preferably represents with following general formula (2).
[changing 4]
In formula, R
1and the R of n and described general formula (1)
1and n synonym.In addition, when n is more than 2, beyond aforesaid compound, sometimes obtain as intermediate by 1, (n-1) individual carbamate groups there occurs the compound of isocyanation esterification.Such as, employing isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) when, be shown below, beyond vulcabond body, also can obtain 2 kinds of monoisocyanates bodies.
[changing 5]
Solid catalyst of the present invention is set to the scope of regulation by the atom ratio of the metallic atom/silicon atom by the metallic compound of catalyst surface and silica and becomes reactive suitable catalyst, by the specific area of the catalyst utilizing nitrogen adsorption methods to measure is set to certain scope, product moderately easily departs from.
Therefore, in the reaction employing solid catalyst of the present invention, the major part of the amino-formate bond of carbamate compounds is transformed to NCO, can suppress the generation of the intermediate of above-mentioned shown monoisocyanates and so on.In addition, the generation of the chlorinated isocyanurates body that generates under catalyst activity crosses high situation etc. can also be suppressed.Thus, if use solid catalyst of the present invention, just can high selectivity and manufacture isocyanate compound with high yield.
In manufacture method of the present invention, isocyanate compound manufactures by making carbamate compounds react under the existence of described catalyst.Preferably under the existence of described catalyst, the carbamate compounds of described general formula (1) is reacted, manufactures the isocyanate compound of described general formula (2).
Reaction form is now not particularly limited, and can be any one in gas-phase reaction, liquid phase reactor, but preferred gas-phase reaction.In addition, reactive mode can use the solid catalysts such as fixed bed mode, fluid bed process, suspension bed mode to react mode used.Particularly preferably use fixed bed mode.
The gas phase fixed bed mode preferably adopted in manufacture method of the present invention such as can head tank (1) as shown in Figure 1, matrix supply pump (2), be filled with the tubular reactor (3) of catalyst, thermal source (tubular electric furnace etc.) (4) of reactor heating, product heat exchanger (6), reclaim the receiver (7) of the isocyanate compound of chilled product, for the heat exchanger (8) of condensed alcohol (generating when manufacturing isocyanate compound by carbamate compounds), for obtaining the receiver (9) of alcohol, the vacuum pipeline be connected with vavuum pump (17) is formed, but be not limited thereto.It should be noted that, for the formation with other symbols in Fig. 1, 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 present invention is preferably with 0.01mL ~ 10mL, more preferably use with the amount of 0.02mL ~ 5mL.
In gas phase fixed bed mode, if the state that matrix has been vaporized, then can react with inactive gas such as nitrogen, react with also can not using inactive gas, can also carry out under normal or reduced pressure.
In manufacture method of the present invention, when using solid catalyst in suspension bed mode, these catalyst are such as preferred with the scope of 0.1 mass parts ~ 100 mass parts, more preferably use with the scope of 0.5 mass parts ~ 50 mass parts relative to carbamate compounds 100 mass parts.
In manufacture method of the present invention, the reaction of carbamate compounds such as also can by heating carbamate compounds and solid catalyst and implement together with torpescence solvent.The reaction distillation mode that manufacture method of the present invention preferably utilizes the isocyanate compound, the alcoholic compound that make to generate in this reaction to be separated to outside system is in addition implemented.It should be noted that, in manufacture method of the present invention, not necessarily need torpescence solvent to heat together with carbamate compounds, also can to make it reaction without the mode of solvent.
In manufacture method of the present invention, as long as described torpescence solvent is torpescence relative to the isocyanate compound of carbamate compounds and generation, just be not particularly limited, but in order to implement reaction efficiently, preferably there is the solvent of the boiling point higher than carbamate compounds.As this kind of solvent, such as can enumerate: the ester classes such as dioctyl phthalate, didecyl phthalate, phthalic acid two (dodecyl) ester, or, such as dibenzyl toluene, triphenyl methane, phenylnaphthalene, biphenyl, terphenyl, diethyl biphenyl, triethyl group biphenyl, 1, the fragrant family hydrocarbon such as 3,5-triisopropylbenzene or fatty family hydrocarbon etc.These solvents can be used alone or and with two or more.Its use amount can according to reaction unit, form and suitably adjusting.
In manufacture method of the present invention, torpescence solvent such as preferably uses 0.1 ~ 150mL relative to carbamate compounds 1mL, more preferably uses 1 ~ 50mL.By being set to this scope, while the stirring that maintenance is good, the solidification of reactant liquor can be prevented.
In manufacture method of the present invention, relative to the feed speed 1mL/h of carbamate compounds, solid catalyst is preferably with 0.01mL ~ 10mL, more preferably use with the amount of 0.02mL ~ 5mL.By being set to this scope, just isocyanate compound can be obtained with industrial suitable reaction speed.
In manufacture method of the present invention, the reaction temperature of carbamate compounds is such as 80 DEG C ~ 600 DEG C, is preferably 200 DEG C ~ 500 DEG C, is more preferably 300 DEG C ~ 500 DEG C.By being set to this scope, practical reaction (particularly thermal decomposition) speed can be obtained, the not preferred side reactions such as the polymerization of isocyanate compound can be suppressed.
In manufacture method of the present invention, the pressure that the isocyanate compound generated and alcoholic compound preferably can gasify relative to above-mentioned reaction temperature by reaction pressure, consider from equipment aspect and use income aspect, preferably absolute pressure is 0.1kPa ~ 101.33kPa in practical, and more preferably absolute pressure is 0.5kPa ~ 30kPa.
In the present invention, when making carbamate compounds react with batch (-type), aforesaid solid catalyst relative to carbamate compounds 100 mass parts, preferably with the scope of 0.1 mass parts ~ 100 mass parts, more preferably use with the scope of 0.5 mass parts ~ 50 mass parts.
In addition, although not necessarily need torpescence solvent to heat together with carbamate compounds, and also can with make it without the mode of solvent reaction, but when use torpescence solvent, its use amount is generally 1 ~ 30mL relative to carbamate compounds 1g, is preferably 1 ~ 10mL.
For reaction pressure, temperature as previously mentioned.
Reaction time suitably can regulate according to the concentration of catalytic amount, temperature, matrix and pressure etc., is generally 0.5 ~ 10 hour, is preferably 1 ~ 5 hour.
In manufacture method of the present invention, if the state that isocyanate compound has been vaporized, then can react with inactive gas such as nitrogen, react with also can not using inactive gas, can also carry out under normal or reduced pressure.
The isocyanate compound utilizing manufacture method of the present invention to obtain can be utilized by reacted solution such as filter, concentrate, extract, distill, distil, be recrystallized, the general operation such as column chromatography carries out being separated, purifying.By repeatedly being purified further by the isocyanate compound of gained, highly purified isocyanate compound can be made.
In addition, after the reaction of carbamate compounds terminates, can be filtered by the residual liquid of reactant liquor, the known separation method such as centrifugation easily reclaims solid catalyst, also can by the solid catalyst of recovery directly or utilize solvent to clean, the known method such as to burn till and again re-use after activate.
Embodiment
Below, enumerate embodiment and the present invention is specifically described, but scope of the present invention does not limit by them.
[Production Example 1 (Ca/SiO
2the preparation of catalyst)]
Water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g are mixed, stir in polyethylene can, makes homogeneous solution.Add tetraethyl orthosilicate (TEOS) 120mL, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL wherein, closed container and under room temperature (20 DEG C ~ 30 DEG C) vigorous stirring 1 hour.
Then leave standstill 12 hours at about 50 DEG C, take out the gel generated, after purified water cleaning, about 110 DEG C of dryings 60 hours, carry out burning till for 2 hours at about 600 DEG C in atmosphere, carry out burning till for 3 hours at about 1000 DEG C.
Burned material pulverized in mortar, the size being sieved into particle is the scope of 1mm ~ 2mm, obtains porous and amorphous silica gel 25g.The intermediate value pore diameter of this silica gel utilizing mercury penetration method (determinator: QuantaChromeCo. system full-automatic pore distribution measurement device PoreMaster60-GT) to measure is 7.5 μm.
On the other hand, by calcium nitrate tetrahydrate 0.196g (0.83mmol) and ion exchange water 2.6g mix and blend and obtain calcium nitrate aqueous solution in flask.By utilizing the silica gel 2.0g (33mmol) of described operation preparation to add (Ca/Si is than=0.025) after in this calcium nitrate aqueous solution, leave standstill 1 hour.
Again about 110 DEG C of dryings 12 hours, about 500 DEG C are carried out burning till and obtaining catalyst (Ca/SiO for 5 hours in atmosphere
2) 2.1g.Fluorescent X-ray elemental microanalysis method (XRF) is utilized to measure, consequently, the catalyst (Ca/SiO of gained
2) in, overall relative to solid catalyst, be scaled calcium atom and calcium compound containing 1.8 quality %.That is, the atomic ratio (Ca/Si) of the calcium atom that solid catalyst is overall and silicon atom is 0.027.
In addition, the specific area of the solid catalyst utilizing nitrogen adsorption methods to measure is 0.3m
2/ g, the atomic ratio (Ca/Si) utilizing that x-ray photoelectron analytical equipment measures, in solid catalyst surface calcium atom and silicon atom is 5.8.
[Production Example 2 ~ 11 (various Ca/SiO
2the preparation of catalyst)]
Except various condition is changed as shown in following table 1, table 2, operate identically with Production Example 1 and prepare various Ca/SiO
2solid catalyst.
[table 1]
[table 2]
In table 1, so-called silica gel intermediate value pore diameter is the value utilizing mercury penetration method to measure, and condition determination is as follows.
As the determinator based on mercury penetration method, employ QuantaChromeCo. system full-automatic pore distribution measurement device PoreMaster60-GT.In addition, as the condition determination of mercury penetration method, at room temperature measure while about 7kPa boosts to 414Mpa.It should be noted that, as mercury capillary value and employ 480dyn/cm, as contact angle value and employ 140 °.
In table 2, the overall Ca/Si of so-called catalyst, than the atomic ratio of the calcium atom referred in solid catalyst and silicon atom, is the value calculated according to the quality of mixed silica gel and calcium nitrate.It should be noted that, the overall Ca/Si ratio of solid catalyst after solid catalyst preparation can utilize the mensuration such as fluorescent X-ray elemental microanalysis method (XRF).
In table 2, so-called solid catalyst specific area represents absorption calcium and burns till the specific area of the solid catalyst of rear (operation (5) in aforesaid catalyst preparing), is the value utilizing nitrogen adsorption methods to measure.Condition determination is as follows.
This mensuration uses BET formula powder specific-surface area detection determinator to utilize physisorphtion (nitrogen adsorption method) to carry out.In the present invention, use " Japanese Baeyer (strain) system, BELSORP-miniII ", adsorbed gas uses nitrogen, has carried out BET multipoint mode method and has measured.Specifically, powder sample is carried out heat de-airing under vacuo at the temperature of 150 DEG C, is then cooled to liquid nitrogen temperature and makes nitrogen adsorption, measure absorption/desorption isotherm, calculate the specific area of sample according to this absorption/desorption isotherm.
In table 2, the calcium atom in so-called surface C a/Si ratio expression solid catalyst surface and the atomic ratio of silicon atom are the values utilizing x-ray photoelectron analytical equipment to analyze.Condition determination is as follows.
(x-ray photoelectron optical spectroscopy (ESCA) condition determination)
Device name: PHI Inc. Quantum2000
X-ray source: monochromatization Al-K α, power output 15kV-20W (X-ray generating surface amasss 100 μm of φ)
Charged neutralization: electron gun (20 μ A), ion gun (30V) using
Beam splitting system: the narrow spectrum of pulse energy 187.85eV@wide range, 46.95eV@(full element)
Measure region: point irradiates (irradiated area < 340 μm of φ)
Effusion angle (get り and go out angle): 45 ° (relative to surface)
[embodiment 1 (formula (1) R
1=1,3,3-trimethyl-1-methylene cyclohexylidene, R
2=methyl, n=2; Manufacture based on the IPDI of the thermal decomposition of isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane))]
[changing 6]
As shown in Figure 1, using the glass tube (3) of diameter 10mm, long 42cm as reactor, to make the part being filled with catalyst (hereinafter referred to as " catalyst layer ") is about the mode of 360 DEG C from outer setting electric furnace (4).Reactor lower part is made to branch into two serial pipelines, respectively via receiver (room temperature) (7) and (13) for obtaining isocyanate compound, for the product heat exchanger (6) of cooled product and (12), for obtaining receiver (cooling with cold ethanol) (9) and (15) (having the heat exchanger (8) for condensation methyl alcohol and (14) before it respectively) of methyl alcohol, the pipeline of two sides is connected with vavuum pump (17), vacuum pipeline is linked.Article two, the switching of pipeline is pipeline by only opening valve (5 and 10 and 11 and 16) side (pipeline of the opposing party is closed) and carries out.
As catalyst, by the Ca/SiO of preparation in Production Example 1
2solid catalyst (particle diameter 1.1 ~ 2.2mm) 2mL is filled into (glass tube (3) utilizes gasification layer (3a) and catalyst layer (3b) to form) in above-mentioned glass tube (3), start vavuum pump (17), decompression is to absolute pressure 1.33kPa, open valve (5), valve (10), valve-off (11), valve (16), with electric furnace (4) by the heating temperatures of catalyst layer to about 360 DEG C.Will at the about 150 DEG C of molten isophorone dimethylcarbamate of heating (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) supply to glass tube (3) with 4mL/h with syringe pump (2).
Confirming that the chilled product containing isocyanate compound starts received device (7) and reclaimed after 30 minutes, valve-off (5), valve (10), open valve (11), valve (16), with 30 minutes, the chilled product containing isocyanate compound is recovered in receiver (13), by Methanol Recovery in receiver (15).The chilled product liquid chromatogram containing isocyanate compound reclaimed by receiver (13) is analyzed, the methyl alcohol gas-chromatography being condensed and recycled to receiver (15) is analyzed, calculates diamino acid ester conversion rate, the yield of vulcabond, the yield of monoisocyanates.
Consequently, as product, obtain IPDI with yield 94% (selection rate 94%), obtain monoisocyanates body with yield 2%.
[embodiment 2 ~ 6, comparative example 1 ~ 5 (employ various Ca/SiO
2, based on isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane) the manufacture of IPDI of thermal decomposition)]
Except various condition is changed as Suo Shi following table 3, operate identically with embodiment 1 and synthesize IPDI.
[table 3]
From table 1, table 2, table 3, extract overall Ca/Si ratio, the specific area of solid catalyst, the Ca/Si ratio of solid catalyst surface, conversion ratio, the yield of catalyst out, by the data recordation that summarizes in table 4.In addition, by this table 4 pictorialization in addition, 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 the calcium atom met in solid catalyst surface and silicon atom be 0.5 ~ 20, the specific area of solid catalyst is 0.01m
2/ g ~ 50m
2during the condition of/g these two aspects (embodiment 1 ~ 6), the yield of diisocyanate cpd is more than 85%, and the conversion ratio of diurethane compound is 100%.On the other hand, when solid catalyst does not meet certain condition aforesaid (comparative example 1 ~ 5), yield, conversion ratio reduce.
[Production Example 12 (Na/SiO
2the preparation of catalyst)]
Water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20,000) 9.6g are mixed, stir in polyethylene can, makes homogeneous solution.Add tetraethyl orthosilicate (TEOS) 120mL, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL wherein, closed container and under room temperature (20 DEG C ~ 30 DEG C) vigorous stirring 1 hour.
Then leave standstill 12 hours at about 50 DEG C, take out the gel generated, after purified water cleaning, about 110 DEG C of dryings 60 hours, carry out burning till for 2 hours at about 600 DEG C in atmosphere, carry out burning till for 3 hours at about 1000 DEG C.
Burned material pulverized in mortar, the size being sieved into particle is the scope of 2mm ~ 4mm, obtains porous and amorphous silica gel 55g.The intermediate value pore diameter of this silica gel utilizing mercury penetration method (determinator: QuantaChromeCo. system full-automatic pore distribution measurement device PoreMaster60-GT) to measure is 7.5 μm.
On the other hand, by sodium nitrate 0.106g (1.25mmol) and ion exchange water 3.7g mix and blend and obtain sodium nitrate aqueous solution in flask.By utilizing the silica gel 3.0g (49.9mmol) of described operation preparation to add (Na/Si is than=0.025) after in this sodium nitrate aqueous solution, leave standstill 1 hour.
Again about 110 DEG C of dryings 12 hours, after burning till 8 hours at about 500 DEG C in atmosphere, carry out burning till for 8 hours at about 700 DEG C and obtain solid catalyst (Na/SiO in atmosphere
2) 3.03g.Fluorescent X-ray elemental microanalysis method (XRF) is utilized to measure, consequently, the solid catalyst (Na/SiO of gained
2) in, overall relative to solid catalyst, be scaled sodium atom and sodium compound containing 0.84 quality %.That is, the atomic ratio (Na/Si) of the sodium atom that solid catalyst is overall and silicon atom is 0.022.In addition, the specific area of the solid catalyst utilizing nitrogen adsorption methods to measure is 0.51m
2/ g, the atomic ratio (Na/Si) utilizing that x-ray photoelectron analytical equipment measures, on catalyst surface sodium atom and silicon atom is 0.5.
[embodiment 7 (formula (1) R
1=1,3,3-trimethyl-1-methylene cyclohexylidene, R
2=methyl, n=2; Manufacture based on the IPDI of the thermal decomposition of isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane))]
[changing 7]
Except the temperature of catalyst layer being set to 365 DEG C, using the solid catalyst (Na/SiO obtained in Production Example 12 as catalyst
2: particle diameter 1.1 ~ 2.2mm) beyond 3mL, operate identically with embodiment 1 and produce IPDI.
The yield of IPDI is 83% (selection rate 84%), and the yield of monoisocyanates is 17%.
[Production Example 13 (Mg/SiO
2the preparation of catalyst)]
Water 144.0g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g are mixed, stir in polyethylene can, makes homogeneous solution.Add tetraethyl orthosilicate (TEOS) 120mL, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 8.4mL wherein, closed container and under room temperature (20 DEG C ~ 30 DEG C) vigorous stirring 1 hour.
Then leave standstill 12 hours at about 50 DEG C, take out the gel generated, after purified water cleaning, about 110 DEG C of dryings 60 hours, carry out within 2 hours, burning till, carrying out burning till for 3 hours at about 1000 DEG C at about 600 DEG C in atmosphere.
Burned material pulverized in mortar, the size being sieved into particle is the scope of 2mm ~ 4mm, obtains porous and amorphous silica gel 55g.The intermediate value pore diameter of this silica gel utilizing mercury penetration method (determinator: QuantaChromeCo. system full-automatic pore distribution measurement device PoreMaster60-GT) to measure is 7.5 μm.
On the other hand, by magnesium nitrate hexahydrate 0.320g (1.25mmol) and ion exchange water 3.5g mix and blend and obtain magnesium nitrate aqueous solution in flask.By utilizing the silica gel 3.0g (49.9mmol) of described operation preparation to join (Mg/Si is than=0.025) after in this magnesium nitrate aqueous solution, leave standstill 1 hour.
Again about 110 DEG C of dryings 12 hours, carry out burning till for 8 hours at about 500 DEG C and obtain solid catalyst (Mg/SiO in atmosphere
2) 3.03g.Fluorescent X-ray elemental microanalysis method (XRF) is utilized to measure, consequently, the solid catalyst (Mg/SiO of gained
2) in, overall relative to solid catalyst, be scaled magnesium and magnesium compound containing 1.50 quality %.That is, the atomic ratio (Mg/Si) of the magnesium atom that solid catalyst is overall and silicon atom is 0.038.In addition, the specific area of the solid catalyst utilizing nitrogen adsorption methods to measure is 0.58m
2/ g, the atomic ratio (Mg/Si) utilizing that x-ray photoelectron analytical equipment measures, in solid catalyst surface magnesium atom and silicon atom is 1.9.
[embodiment 8 (formula (1) R
1=1,3,3-trimethyl-1-methylene cyclohexylidene, R
2=methyl, n=2; Manufacture based on the IPDI of the thermal decomposition of isophorone dimethylcarbamate (1-(methyloxycarbonylamino)-3,3,5-trimethyl-5-(methyloxycarbonylamino methyl)-cyclohexane))]
[changing 8]
Except the temperature of catalyst layer being set to 365 DEG C, using the solid catalyst (Mg/SiO obtained in Production Example 13 as catalyst
2: particle diameter 1.1 ~ 2.2mm) beyond 3mL, operate identically with embodiment 1 and produce IPDI.
The yield of IPDI is 85% (selection rate 85%), and the yield of monoisocyanates is 12%.
According to above embodiment 7 and 8, the atomic ratio M/Si of the sodium atom met in solid catalyst surface or magnesium atom and silicon atom be 0.5 ~ 20, the specific area of solid catalyst is 0.01m
2/ g ~ 50m
2during the condition of/g these two aspects, the yield of diisocyanate cpd is more than 83%.
[Production Example 14 (Ca/SiO
2the preparation of catalyst)]
Water 60g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 3.6g are mixed, stir in polyethylene can, makes homogeneous solution.Add tetraethyl orthosilicate (TEOS) 60mL, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 4.2mL wherein, closed container and under room temperature (20 DEG C ~ 30 DEG C) vigorous stirring 1 hour.
Then leave standstill 12 hours at about 50 DEG C, take out the gel generated, after purified water cleaning, about 110 DEG C of dryings 12 hours, carry out burning till for 2 hours at about 600 DEG C in atmosphere, carry out burning till for 3 hours at about 1000 DEG C.
A part for burned material pulverized in mortar, the size being sieved into particle is the scope of 1mm ~ 2mm, obtains porous and amorphous silica gel 8.0g.Intermediate value pore diameter that mercury penetration method (determinator: QuantaChromeCo. system full-automatic pore distribution measurement device PoreMaster60-GT) measures, this silica gel is utilized to be 6.1 μm.
On the other hand, by calcium nitrate tetrahydrate 0.393g (1.7mmol) and ion exchange water 2.2g mix and blend and obtain calcium nitrate aqueous solution in flask.By utilizing the silica gel 2.0g (33mmol) of described operation preparation to add (Ca/Si is than=0.05) after in this calcium nitrate aqueous solution, leave standstill 1 hour.
Again about 110 DEG C of dryings 12 hours, carry out burning till for 3 hours at about 500 DEG C and obtain solid catalyst (Ca/SiO in atmosphere
2) 2.3g.The specific area of the solid catalyst utilizing nitrogen adsorption methods to measure is 0.8m
2/ g, the atomic ratio (Ca/Si) utilizing that x-ray photoelectron analytical equipment measures, in solid catalyst surface calcium atom and silicon atom is 1.1.
[embodiment 9 (formula (1) R
1=cyclohexane-1,3-glycol dimethylene, R
2=methyl, n=2; Manufacture by 1,3-two (isocyanatomethyl) cyclohexane of the thermal decomposition of two (methyloxycarbonylamino methyl) cyclohexane of 1,3-)]
[changing 9]
Except the temperature of catalyst layer being set to 365 DEG C, employing the solid catalyst (Ca/SiO obtained in Production Example 14 as catalyst
2: particle diameter 1 ~ 2mm) 3mL, employ 1 as carbamate compounds, beyond two (methyloxycarbonylamino methyl) cyclohexane of 3-, operate identically with embodiment 1 and produce 1, two (isocyanatomethyl) cyclohexane of 3-.
The yield of two (isocyanatomethyl) cyclohexane of 1,3-is 95% (selection rate 95%), and the yield of monoisocyanates is 1%.
[Production Example 15 (Ca/SiO
2the preparation of catalyst)]
Water 120g, polyethylene glycol (PEG, Wako Pure Chemical Industries, Ltd.'s system, mean molecule quantity 20000) 9.6g are mixed, stir in polyethylene can, makes homogeneous solution.Add tetraethyl orthosilicate (TEOS) 120mL, 60% aqueous solution of nitric acid (Wako Pure Chemical Industries, Ltd.'s system) 8.5mL wherein, closed container and under room temperature (20 DEG C ~ 30 DEG C) vigorous stirring 1 hour.
Then leave standstill 12 hours at about 50 DEG C, take out the gel generated, after purified water cleaning, about 110 DEG C of dryings 12 hours, carry out within 2 hours, burning till, carrying out burning till for 3 hours at about 1000 DEG C at about 600 DEG C in atmosphere.
A part for burned material pulverized in mortar, the size being sieved into particle is the scope of 1mm ~ 2mm, obtains porous and amorphous silica gel 9g.Intermediate value pore diameter that mercury penetration method (determinator: QuantaChromeCo. system full-automatic pore distribution measurement device PoreMaster60-GT) measures, this silica gel is utilized to be 1.0 μm.
On the other hand, by calcium nitrate tetrahydrate 0.008g (0.03mmol) and ion exchange water 2.5g mix and blend and obtain calcium nitrate aqueous solution in flask.By utilizing the silica gel 2.0g (33mmol) of described operation preparation to add (Ca/Si is than=0.001) after in this calcium nitrate aqueous solution, leave standstill 1 hour.
Again about 110 DEG C of dryings 12 hours, carry out burning till for 3 hours at about 500 DEG C and obtain solid catalyst (Ca/SiO in atmosphere
2) 2.0g.The specific area of the solid catalyst utilizing nitrogen adsorption methods to measure is 1.7m
2/ g, the atomic ratio (Ca/Si) utilizing that x-ray photoelectron analytical equipment measures, in solid catalyst surface calcium atom and silicon atom is 0.75.
[embodiment 10 (formula (1) R
1=2,4-tolyl, R
2=methyl, n=2; Based on the Toluene-2,4-diisocyanate of the thermal decomposition of two (methyloxycarbonylamino) toluene of 2,4-, the manufacture of 4-vulcabond)]
[changing 10]
Except the temperature of catalyst layer being set to 375 DEG C, employing the solid catalyst (Ca/SiO obtained in Production Example 15 as catalyst
2: particle diameter 1 ~ 2mm) 3mL, to employ as carbamate compounds beyond two (methyloxycarbonylamino) toluene of 2,4-, operate identically with embodiment 1 and produce Toluene-2,4-diisocyanate, 4-vulcabond.
Toluene-2,4-diisocyanate, the yield of 4-vulcabond is 95% (selection rate 95%), and the yield of monoisocyanates is 3%.
Utilizability in industry
Utilize the present invention, can provide can high selectivity and manufacture isocyanate compound with high yield and the solid catalyst of heterogeneous catalysis that is segregative with product, that such as can be used as isocyanate compound manufacture.
According to the present invention, repeatability can manufacture this kind of solid catalyst well, in addition, the manufacture method of the isocyanate compound employing this kind of solid catalyst can be provided.
The explanation of symbol
1 head tank
2 matrix supply pumps
3 tubular reactors being filled with catalyst
3a gasification layer (Filled with Quartz)
3b catalyst layer
The thermal source (tubular electric furnace) of 4 reactor heatings
5 valves
6 product heat exchanger
The receiver of the isocyanate compound of the chilled product of 7 recovery
8 for the heat exchanger of condensed alcohol
9 for obtaining the receiver of alcohol
10 valves
11 valves
12 product heat exchanger
The receiver of the isocyanate compound of the chilled product of 13 recovery
14 for the heat exchanger of condensed alcohol
15 for obtaining the receiver of alcohol
16 valves
17 vavuum pumps
Claims (17)
1. a solid catalyst, it contains and is selected from least a kind of metallic compound in alkali metal compound and alkali earth metallic compound and silica, and it meets 2 following conditions simultaneously:
(1) the atomic ratio M/Si of the metallic atom in the described metallic compound utilizing x-ray photoelectron analytical equipment to measure and the silicon atom in described silica is 0.5 ~ 20;
(2) specific area of the described solid catalyst utilizing nitrogen adsorption methods to measure is 0.01m
2/ g ~ 50m
2/ g.
2. solid catalyst according to claim 1, it meets 2 following conditions simultaneously:
(3) M/Si is 0.8 ~ 10;
(4) specific area of the described solid catalyst utilizing nitrogen adsorption methods to measure is 0.1m
2/ g ~ 10m
2/ g.
3. solid catalyst according to claim 1 and 2, wherein,
Described alkali metal compound is sodium compound or cesium compound.
4. the solid catalyst according to any one of claims 1 to 3, wherein,
Described alkali earth metallic compound is magnesium compound or calcium compound.
5. the solid catalyst according to any one of Claims 1 to 4, wherein,
Described silica is porous silica.
6. the solid catalyst according to any one of Claims 1 to 5, wherein,
Described silica is amorphous silica.
7. the solid catalyst according to any one of claim 1 ~ 6, wherein,
The intermediate value pore diameter utilizing mercury penetration method to measure of described silica is 0.1 μm ~ 10 μm.
8. the solid catalyst according to any one of claim 1 ~ 7, it adsorbs described metallic compound by making the silica burnt till 1 ~ 20 hour at 700 DEG C ~ 1200 DEG C, then burns till 1 ~ 40 hour at 300 DEG C ~ 1200 DEG C and prepares.
9. the solid catalyst according to any one of claim 1 ~ 7, it adsorbs described metallic compound by making the silica burnt till 1 ~ 10 hour at 800 DEG C ~ 1100 DEG C, then burns till 1 ~ 20 hour at 500 DEG C ~ 1000 DEG C and prepares.
10. a manufacture method for isocyanate compound, under the existence of the solid catalyst according to any one of claim 1 ~ 9, utilizes carbamate compounds to manufacture isocyanate compound.
11. manufacture methods according to claim 10, wherein,
Described carbamate compounds is the compound represented with following general formula (1),
In formula, R
1and R
2both can be the same or different, expression can have substituent alkyl, and n represents the integer of 1 ~ 4;
Described isocyanate compound is the compound represented with following general formula (2),
In formula, n, R
1with aforementioned synonym.
12. manufacture methods according to claim 11, wherein,
N in described general formula (1) and (2) is 2.
13. manufacture methods according to any one of claim 10 ~ 12, wherein,
Reaction temperature when utilizing described carbamate compounds to manufacture described isocyanate compound is 300 DEG C ~ 500 DEG C.
14. manufacture methods according to any one of claim 10 ~ 13, wherein,
Reaction pressure when utilizing described carbamate compounds to manufacture described isocyanate compound is absolute pressure 0.1kPa ~ 101.33kPa.
15. manufacture methods according to any one of claim 10 ~ 14, wherein,
Reaction when carrying out utilizing described carbamate compounds to manufacture described isocyanate compound with the form of gas phase.
16. manufacture methods according to any one of claim 10 ~ 14, wherein,
Reaction when carrying out utilizing described carbamate compounds to manufacture described isocyanate compound with the form of liquid phase.
Solid catalyst according to any one of 17. claims 1 ~ 9 is manufacturing the application in isocyanate compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-110316 | 2013-05-24 | ||
| JP2013110316 | 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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| Publication Number | Publication Date |
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| CN105263618A true CN105263618A (en) | 2016-01-20 |
| CN105263618B CN105263618B (en) | 2018-02-16 |
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| CN201480029670.4A Expired - Fee Related CN105263618B (en) | 2013-05-24 | 2014-05-22 | Solid catalyst and used the solid catalyst isocyanate compound manufacture method |
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| Country | Link |
|---|---|
| JP (1) | JP6372484B2 (en) |
| CN (1) | CN105263618B (en) |
| WO (1) | WO2014189120A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008029949A (en) * | 2006-07-28 | 2008-02-14 | Gunma Prefecture | Catalyst for selective carbon chain-extension reaction, method for manufacturing the catalyst and method for producing hydrocarbons by using the same |
| 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 |
| WO2013008891A1 (en) * | 2011-07-13 | 2013-01-17 | 宇部興産株式会社 | Method for producing isocyanate compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH07119190B2 (en) * | 1992-01-10 | 1995-12-20 | 株式会社日本触媒 | Method for producing isocyanates |
| JPH08804B2 (en) * | 1992-01-10 | 1996-01-10 | 株式会社日本触媒 | Method for producing isocyanates |
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2014
- 2014-05-22 CN CN201480029670.4A patent/CN105263618B/en not_active Expired - Fee Related
- 2014-05-22 JP JP2015518293A patent/JP6372484B2/en not_active Expired - Fee Related
- 2014-05-22 WO PCT/JP2014/063619 patent/WO2014189120A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008029949A (en) * | 2006-07-28 | 2008-02-14 | Gunma Prefecture | Catalyst for selective carbon chain-extension reaction, method for manufacturing the catalyst and method for producing hydrocarbons by using the same |
| 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 |
| WO2013008891A1 (en) * | 2011-07-13 | 2013-01-17 | 宇部興産株式会社 | Method for producing isocyanate compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6372484B2 (en) | 2018-08-15 |
| JPWO2014189120A1 (en) | 2017-02-23 |
| WO2014189120A1 (en) | 2014-11-27 |
| CN105263618B (en) | 2018-02-16 |
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