JPH02300156A - Method for recovering catalyst - Google Patents
Method for recovering catalystInfo
- Publication number
- JPH02300156A JPH02300156A JP1118361A JP11836189A JPH02300156A JP H02300156 A JPH02300156 A JP H02300156A JP 1118361 A JP1118361 A JP 1118361A JP 11836189 A JP11836189 A JP 11836189A JP H02300156 A JPH02300156 A JP H02300156A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- reaction
- catalyst
- platinum group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- -1 platinum group metal compound Chemical class 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 239000002198 insoluble material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 3
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 abstract 2
- 150000005309 metal halides Chemical class 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 31
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- 235000019441 ethanol Nutrition 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002828 nitro derivatives Chemical class 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XNKFCDGEFCOQOM-UHFFFAOYSA-N 1,2-dinitronaphthalene Chemical compound C1=CC=CC2=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C21 XNKFCDGEFCOQOM-UHFFFAOYSA-N 0.000 description 2
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 description 2
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical class C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 description 2
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical group CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101100037762 Caenorhabditis elegans rnh-2 gene Proteins 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 2
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- HEZQRPHEDDAJTF-UHFFFAOYSA-N chloro(phenyl)methanol Chemical compound OC(Cl)C1=CC=CC=C1 HEZQRPHEDDAJTF-UHFFFAOYSA-N 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002390 heteroarenes Chemical class 0.000 description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- QHFKWIKCUHNXAU-UHFFFAOYSA-N (4-nitrophenyl) carbamate Chemical compound NC(=O)OC1=CC=C([N+]([O-])=O)C=C1 QHFKWIKCUHNXAU-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- OWJVEZJJRYZWNI-UHFFFAOYSA-N 1,1-dinitrocyclohexane Chemical compound [O-][N+](=O)C1([N+]([O-])=O)CCCCC1 OWJVEZJJRYZWNI-UHFFFAOYSA-N 0.000 description 1
- LKKHEZBRRGJBGH-UHFFFAOYSA-N 1,1-dinitroethane Chemical compound [O-][N+](=O)C(C)[N+]([O-])=O LKKHEZBRRGJBGH-UHFFFAOYSA-N 0.000 description 1
- HLUAPIYZVLAARK-UHFFFAOYSA-N 1,1-dinitrohexane Chemical compound CCCCCC([N+]([O-])=O)[N+]([O-])=O HLUAPIYZVLAARK-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
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- BDLNCFCZHNKBGI-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)benzene Chemical group C1=CC([N+](=O)[O-])=CC=C1C1=CC=C([N+]([O-])=O)C=C1 BDLNCFCZHNKBGI-UHFFFAOYSA-N 0.000 description 1
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- JBDYKGMNMDIHFL-UHFFFAOYSA-N 1-nitroanthracene Chemical class C1=CC=C2C=C3C([N+](=O)[O-])=CC=CC3=CC2=C1 JBDYKGMNMDIHFL-UHFFFAOYSA-N 0.000 description 1
- NALZTFARIYUCBY-UHFFFAOYSA-N 1-nitrobutane Chemical compound CCCC[N+]([O-])=O NALZTFARIYUCBY-UHFFFAOYSA-N 0.000 description 1
- KLGHUFNKRIWCDQ-UHFFFAOYSA-N 1-nitrooctane Chemical compound CCCCCCCC[N+]([O-])=O KLGHUFNKRIWCDQ-UHFFFAOYSA-N 0.000 description 1
- XUKJDTCEYYOATE-UHFFFAOYSA-N 10h-phenothiazin-1-amine Chemical class S1C2=CC=CC=C2NC2=C1C=CC=C2N XUKJDTCEYYOATE-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical class C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical class NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 150000005006 2-aminopyrimidines Chemical class 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- FEJLPMVSVDSKHJ-UHFFFAOYSA-N 3-methyl-1-nitrobutane Chemical compound CC(C)CC[N+]([O-])=O FEJLPMVSVDSKHJ-UHFFFAOYSA-N 0.000 description 1
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 1
- MWWNNNAOGWPTQY-UHFFFAOYSA-N 3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MWWNNNAOGWPTQY-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- CYZXADZRNSLZKI-UHFFFAOYSA-N 4-[1-(4-aminophenoxy)ethoxy]aniline Chemical compound C=1C=C(N)C=CC=1OC(C)OC1=CC=C(N)C=C1 CYZXADZRNSLZKI-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- JCQPONUUPNAEGZ-UHFFFAOYSA-N 4-aminobenzoyl chloride Chemical compound NC1=CC=C(C(Cl)=O)C=C1 JCQPONUUPNAEGZ-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QNDFYLBDUWCFJO-UHFFFAOYSA-N 4-fluorobenzene-1,3-diamine Chemical compound NC1=CC=C(F)C(N)=C1 QNDFYLBDUWCFJO-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- NOYDQGFVFOQSAJ-UHFFFAOYSA-N 5-nitropyrimidine Chemical compound [O-][N+](=O)C1=CN=CN=C1 NOYDQGFVFOQSAJ-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical class C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 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
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000005182 dinitrobenzenes Chemical class 0.000 description 1
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PHWSCBWNPZDYRI-UHFFFAOYSA-N ethyl 4-nitrobenzoate Chemical compound CCOC(=O)C1=CC=C([N+]([O-])=O)C=C1 PHWSCBWNPZDYRI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- OSILBMSORKFRTB-UHFFFAOYSA-N isoquinolin-1-amine Chemical class C1=CC=C2C(N)=NC=CC2=C1 OSILBMSORKFRTB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- PWXJULSLLONQHY-UHFFFAOYSA-N phenylcarbamic acid Chemical compound OC(=O)NC1=CC=CC=C1 PWXJULSLLONQHY-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は触媒回収方法に関し、特にアミノ基を有する化
合物、ニトロ基を有する化合物、一酸化炭素（Ｃｏ）お
よび有機含水酸基化合物からカルバミン酸エステル類を
製造する際に、反応液から触媒として用いられる高価な
白金族化合物を回収する方法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for recovering a catalyst, and in particular, the present invention relates to a method for recovering a catalyst, and in particular, the recovery of carbamic acid ester from a compound having an amino group, a compound having a nitro group, carbon monoxide (Co), and an organic hydrous acid group compound. The present invention relates to a method for recovering expensive platinum group compounds used as catalysts from reaction solutions in the production of compounds.
カルバミン酸エステルは、農薬またはイソシアナートの
前駆体として重要である。イソシアナートは軟硬質フオ
ーム、塗料、防水剤、接着剤、弾性繊維等のウレタン製
品の原料として広く用いられている。特にジフェニルメ
タンジイソシアナー）（ＭＤＩ）は断熱材、自動車用耐
衝撃軽量化材料としての新用途開発も盛んで、その需要
は大幅な伸びを見せている。Carbamate esters are important as precursors for pesticides or isocyanates. Isocyanates are widely used as raw materials for urethane products such as soft and hard foams, paints, waterproofing agents, adhesives, and elastic fibers. In particular, demand for diphenylmethane diisocyaner (MDI) is rapidly increasing, with active development of new applications as insulation materials and impact-resistant and lightweight materials for automobiles.
カルバミン酸エステルは従来アミンとホスゲンとの反応
で合成されるイソシアナート（反応式１）とアルコール
から合成されている（反応式２）。Carbamate esters have conventionally been synthesized from alcohols and isocyanates (reaction formula 1), which are synthesized by the reaction of amines and phosgene (reaction formula 2).
ＲＮＨ２＋Ｃ０Ｃｊｔ２
→ＲＮＣＯ＋２ＨＣｆ （１）
ＲＮＣＯ＋Ｒ’ ０Ｈ−ＲＮＨＣＯＯＲ’ （２）ホ
スゲンは猛毒であり、電力を多く必要とする塩素を用い
るので、プロセスの簡略化と省エネルギー化を図るため
、ホスゲンを用いないカルバミン酸エステルの製造法が
検討されてきた。RNH2+C0Cjt2 →RNCO+2HCf (1) RNCO+R'0H-RNHCOOR' (2) Since phosgene is highly poisonous and uses chlorine, which requires a lot of electricity, in order to simplify the process and save energy, we developed a carbamate ester that does not use phosgene. Manufacturing methods have been investigated.
このうち、例えばニトロベンゼンとＣＯとアルコールか
ら１段でカルバミン酸エステルを合成する方法（反応式
３）では、エステル１モル当り３モルのＣＯが消費され
る。Among these, for example, in the method of synthesizing carbamate ester in one step from nitrobenzene, CO, and alcohol (reaction formula 3), 3 moles of CO are consumed per 1 mole of ester.
Ｃｓ Ｈ＆１ＮＯ２＋３ＣＯ＋ＲＯＨ
→ Ｃ５ＨきＮＨＣＯＯＲ＋２ＣＯ２（３）このＣＯの
１／３はカルバミン酸基形成に利用されるが、残りの２
７３は無用の不活性Ｃ０２として消費され、さらにＣＯ
２の発熱生成において大量の熱が放出されるため、高価
な反応熱除熱装置が必要となり、また反応圧力も８０〜
２００ ｋｇ／ｄと高く、さらに助触媒の使用は液をス
ラリー化し、ハンドリングを困難にしたり、製品純度の
低下を招いたりする原因となっており、実用化に至って
いない（特公昭５２−４３８２２号、特開昭５１−９８
２４０号、特開昭５４−１４５６０１号）。一方、最近
アミンとＣＯとアルコールと０２からＰｄ黒と■−を触
媒としてカルバミン酸エステルを直接合成する方法が試
みられている（反応式４、Ｓ、Ｆｕｋｕｏｋａ ｅｔ
ａｌ、。Cs H & 1NO2 + 3CO + ROH → C5H NHCOOR + 2CO2 (3) 1/3 of this CO is used for carbamate group formation, but the remaining 2
73 is consumed as useless inert CO2, and further CO
Since a large amount of heat is released during the exothermic generation in step 2, an expensive reaction heat removal device is required, and the reaction pressure is also 80~80℃.
It is as high as 200 kg/d, and the use of a cocatalyst turns the liquid into a slurry, making handling difficult and reducing product purity, so it has not been put to practical use (Japanese Patent Publication No. 43822/1983). , Japanese Patent Publication No. 51-98
No. 240, JP-A-54-145601). On the other hand, a method of directly synthesizing carbamate ester from amine, CO, alcohol, and 02 using Pd black and ■- as a catalyst has recently been attempted (reaction formula 4, S, Fukuoka et al.
al.
Ｃｈｅｍ、Ｃｏｍｍｕ、１９８４．３９９）。Chem, Commu, 1984.399).
ＲＮＨ２＋Ｃ○＋Ｒ’ＯＨ＋１／２０２” ＲＮＨＣ
ＯＯＲ’ ＋８２０ （４）この方法は、生成する
エステル１モルに対し、わずか１モルのＣＯＬか必要と
せず、さらに反応式（３）のニトロ化合物を原料とする
場合のようにＣｏ２を副生せず、ＣＯをすべて有効に利
用できる。また反応によって１モルの水しか副生せず、
反応による発熱も少ない。しかしながら、Ｃｏ圧は８０
ｋｇ／ｃ＋ａと高（，１７０℃、２時間でアニリン転化
率は９５％と低いのが難点である。RNH2+C○+R'OH+1/202" RNHC
OOR' +820 (4) This method requires only 1 mole of COL per mole of ester to be produced, and furthermore, it does not produce Co2 as a by-product as in the case of using the nitro compound of reaction formula (3) as a raw material. Therefore, all CO can be used effectively. Also, only 1 mole of water is produced as a by-product during the reaction,
There is also little heat generated by the reaction. However, the Co pressure was 80
The drawback is that the aniline conversion rate is as low as 95% in 2 hours at 170°C.
また同上の原料から、ｐａｃ１２とＦｅ０Ｃ１のような
助触媒を用いた場合でも、反応温度１５０℃、反応時間
２ｈ、Ｃｏ圧１００ｂａｒと高く、アニリン転化率７７
％、エステル選択率９０％である（特開昭５５−１２０
５５１号）。さらに、有機ニトロ化合物を酸化剤として
、第１級アミン、ＣＯ１アルコールから、カルバミン酸
エステルを合成する方法が提案されている（特開昭５５
−１２０５５１号）。例えば、アニリン、ニトロベンゼ
ン、ＣＯ、アルコールから反応式（５）にしたがってＮ
−フェニルカルバミン酸エチルを合成する場合、
２Ｃ６Ｈ＠ ＮＨ２＋ ＮＯ２＋３ＧＯ＋３ＲＯＨ→
３Ｃｓ ＨＩＩＮＨＣＯＯＲ＋２Ｈ２０（５）最高の収
率を得るためには、ニトロ基１モルに対し、２モルのア
ミノ基を供給することが好ましい。ニトロ化合物中のニ
トロ基が当量より少ない場合は、アミンの転化率が低く
なるため、ニトロ化合物を過剰にすることが好ましい。Furthermore, even when using the same raw materials as pac12 and co-catalysts such as Fe0C1, the reaction temperature was 150°C, the reaction time was 2h, the Co pressure was as high as 100bar, and the aniline conversion rate was 77.
%, ester selectivity is 90% (Japanese Unexamined Patent Publication No. 120-1208)
No. 551). Furthermore, a method has been proposed for synthesizing carbamate esters from primary amines and CO1 alcohols using organic nitro compounds as oxidizing agents (Japanese Patent Laid-Open No. 55
-120551). For example, from aniline, nitrobenzene, CO, and alcohol, N
-When synthesizing ethyl phenylcarbamate, 2C6H@NH2+ NO2+3GO+3ROH→
3Cs HIINHCOOR+2H20 (5) In order to obtain the highest yield, it is preferred to supply 2 moles of amino groups per mole of nitro groups. If the number of nitro groups in the nitro compound is less than the equivalent amount, the conversion rate of the amine will be low, so it is preferable to use an excess of the nitro compound.
しかしながら、反応式（５）の場合にはＣＯの一部は反
応式（６）に示すようにＣＯ２として消費されて不利で
ある。However, in the case of reaction formula (5), a part of CO is consumed as CO2 as shown in reaction formula (6), which is disadvantageous.
ＣＢＨ性ＮＯ２＋３ＣＯ＋ＲＯＨ
→Ｃｓ Ｈ＊ ＮＨＣＯＯＲ＋２ＣＯ２（６）また、ニ
トロベンゼン、アニリンとＣＯからまずジフェニールウ
レアを合成し、次にアルコール分解してＮ−フェニルカ
ルバミン酸エステルを合成する方法（反応式７．８）が
ある。この方法では助触媒を用いずＲｕ３ （Ｃｏ）
１２クラスタ触媒（特開昭６２−５９２５２号）を用い
るもので反応液のスラリー化の問題がない。しかし、反
応に長時間を要すること、少量の水素ガスにより活性が
著しく低下し水素含有Ｃｏガスを使用できない等の問題
がある。CBH NO2+3CO+ROH →Cs H* NHCOOR+2CO2 (6) Also, a method in which diphenylurea is first synthesized from nitrobenzene, aniline, and CO, and then N-phenylcarbamate is synthesized by alcoholysis (reaction formula 7.8) There is. In this method, Ru3 (Co) is
This method uses a 12-cluster catalyst (Japanese Patent Application Laid-Open No. 62-59252), so there is no problem of slurrying the reaction solution. However, there are problems such as the reaction takes a long time and the activity is significantly reduced by a small amount of hydrogen gas, making it impossible to use hydrogen-containing Co gas.
Ｃ６Ｈ！ｌ ＮＨ２＋Ｃ６Ｈ性ＮＯ２＋３ＣＯ→ Ｃ６
Ｈｉ＋ ＮＨＣＯＨＮＣｓ Ｈ！！＋２ＣＯ２（７）
Ｃｅ Ｈ！ｌ ＮＨＣＯＨＮＣ６Ｈ！Ｊ ＋ＲＯＨ→
Ｃ５ＨジＮＨＣＯＯＲ
＋ Ｃ６Ｈ！ＩＮＨ２（８）
〔発明が解決しようとする課題〕
近年、ホスゲンを使用しない製造法として、芳香族ニト
ロ化合物を原料とし、触媒の存在下、有機含水酸基化合
物および一酸化炭素と高温高圧下で反応させる方法が種
々提案されているが、課題も多くその工業化は困難であ
る。C6H! l NH2+C6H NO2+3CO→ C6
Hi+ NHCOHNCs H! ! +2CO2(7) Ce H! l NHCOHNC6H! J+ROH→
C5H diNHCOOR + C6H! INH2 (8) [Problem to be solved by the invention] In recent years, as a production method that does not use phosgene, aromatic nitro compounds are used as raw materials and reacted with organic hydrous acid group compounds and carbon monoxide in the presence of a catalyst at high temperature and high pressure. Various methods have been proposed, but there are many problems and their industrialization is difficult.
特に本発明で扱っているパラジウムなどの資金属系触媒
反応では、ルイス酸および第３級アミンの使用に伴い液
に難溶な化合物を多量に形成し、反応液が濃厚なスラリ
ー状となってしまう。これによって、液の取扱い、貴金
属系触媒の回収、さらに生成ウレタンの分離、精製が困
難となる。In particular, in metal-based catalytic reactions such as palladium, which is the subject of this invention, the use of Lewis acids and tertiary amines results in the formation of large amounts of compounds that are poorly soluble in the liquid, resulting in the reaction liquid becoming a thick slurry. Put it away. This makes handling of the liquid, recovery of the precious metal catalyst, and separation and purification of the produced urethane difficult.
一方、本発明者らは特開昭５７−１２００５５号記載の
方法にしたがって、アニリン、ニトロベンゼン、エタノ
ールおよび水素を１０％含有したＣＯを用いて触媒とし
て５％Ｐｄ／Ｃを用いて反応を試みたところカルバミン
酸エステルはほとんど生成しなかった。さらに、触媒と
して２価のＰｄを用いるほかは、上記と同様の実験を行
ったところカルバミン酸エステルがかなり生成した。On the other hand, the present inventors attempted a reaction using aniline, nitrobenzene, ethanol, and CO containing 10% hydrogen, using 5% Pd/C as a catalyst, according to the method described in JP-A-57-120055. However, almost no carbamate ester was produced. Furthermore, when an experiment similar to the above was conducted except that divalent Pd was used as a catalyst, a considerable amount of carbamate ester was produced.
しかしながら、この高価なＰｄを主触媒に用いる方法で
は、このＰｄの僅かな損失でもコストに影響するために
、その高効率な回収が必要となってくる。However, in the method of using this expensive Pd as the main catalyst, even a small loss of Pd affects the cost, so it is necessary to recover it with high efficiency.
そこで、触媒（Ｐｄ）回収および分離法について鋭意検
討したところ、反応液中にアルカリを添加することによ
りＰｄ化合物を高効率で回収できることを見出し、本発
明を完成するに至った。Therefore, as a result of intensive study on catalyst (Pd) recovery and separation methods, it was discovered that Pd compounds can be recovered with high efficiency by adding an alkali to the reaction solution, and the present invention was completed.
本発明は、アミノ基を有する化合物、ニトロ基を有する
化合物、一酸化炭素、有機含水酸基化合物を非金属ハロ
ゲン化物存在下で、触媒として周期律第■族の白金族に
属する遷移金属化合物および担体を用い、水または水と
酸素を追加的に添加してカルバミン酸エステル類を合成
するに際し、反応液中に溶出して（る白金族に属する化
合物を、アルカリ金属またはアルカリ土類金属の水酸化
物、炭酸塩、炭酸水素塩または酸化物を０．０００１〜
１ｗｔ％添加することにより白金族化合物を不溶物とし
て回収することを特徴とする触媒回収方法である。The present invention uses a compound having an amino group, a compound having a nitro group, carbon monoxide, an organic hydrous acid group compound in the presence of a nonmetal halide, and a transition metal compound belonging to the platinum group of Group Ⅰ of the periodic table as a catalyst and a carrier. When synthesizing carbamate esters by additionally adding water or water and oxygen using substance, carbonate, hydrogen carbonate or oxide from 0.0001 to
This catalyst recovery method is characterized in that platinum group compounds are recovered as insoluble substances by adding 1 wt%.
上記目的は反応後の液にアルカリを添加することにより
白金族化合物を含有する不溶物として分離することによ
り達成される。The above object is achieved by adding an alkali to the reaction solution to separate the platinum group compound as an insoluble material.
カルバミン酸エステルの合成後の反応液中にアルカリを
添加することにより、白金族としてＰｄを例にとると、
反応液中のＰｄ化合物は次式のようにＰｄ （ＯＨ）２
を主成分とする不溶物となる。Taking Pd as an example of a platinum group metal, by adding an alkali to the reaction solution after synthesis of carbamate ester,
The Pd compound in the reaction solution is Pd (OH)2 as shown in the following formula.
It becomes an insoluble substance whose main component is
ＰｄＣｌ２ ＋２ＮａＯＨ
−Ｐｄ （ＯＨ） ２ ＋２ＮａＣｆｆｉこの不溶物を
反応液中から分離することによりＰｄ化合物を回収する
ことができる。PdCl2 +2NaOH -Pd (OH)2 +2NaCffi By separating this insoluble matter from the reaction solution, the Pd compound can be recovered.
〔実施例〕
本発明で使用されるアルカリは、アルカリ金属またはア
ルカリ土類金属の水酸化物、炭酸塩、炭酸水素塩、酸化
物、およびアンモニアとその炭酸塩であって、例えば水
酸化リチウム、水酸化ナトリウム、水酸化カリウム、水
酸化マグネシウム、水酸化カルシウム、炭酸リチウム、
炭酸ナトリウム、炭酸カリウム、炭酸マグネシウム、炭
酸カルシウム、酸化リチウム、酸化ナトリウム、酸化マ
グネシウム、酸化カルシウム、アンモニア、炭酸アンモ
ニウム等が挙げられる。これらは単独または２種以上混
合して使用することができる。[Example] The alkalis used in the present invention include hydroxides, carbonates, hydrogen carbonates, and oxides of alkali metals or alkaline earth metals, and ammonia and its carbonates, such as lithium hydroxide, Sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbonate,
Examples include sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, lithium oxide, sodium oxide, magnesium oxide, calcium oxide, ammonia, and ammonium carbonate. These can be used alone or in combination of two or more.
カルバミン酸エステルの合成触媒として用いられる白金
族の遷移金属は、Ｐｄ、Ｒｈ、Ｒｕの単体またはその化
合物であり、それらは１種またはそれ以上混合してもよ
い。化合物としてはハロゲン化物、チオシアン化物、シ
アン化物、イソシアン化物、硫酸塩、硝酸塩、酢酸塩、
酸化物などがあげられる。担体として、炭酸カルシウム
、ケイ酸アルミニウム、ケイ酸マグネシウム、硫酸バリ
ウム、シリカ、アルミナ、シリカアルミナ、アルミナア
スベスト、ベントナイト、けいそう土、フラー土、有機
イオン交換体、無機イオン交換体、モレキュラーシーブ
などに担持させて用いてもよい。さらにこれらはＰｄ、
Ｒｈ、Ｒｕとは別に反応器に仕込んでもよい。The transition metal of the platinum group used as a synthesis catalyst for carbamate ester is Pd, Rh, Ru, or a compound thereof, and one or more of them may be mixed. Compounds include halides, thiocyanides, cyanides, isocyanides, sulfates, nitrates, acetates,
Examples include oxides. As a carrier, calcium carbonate, aluminum silicate, magnesium silicate, barium sulfate, silica, alumina, silica alumina, alumina asbestos, bentonite, diatomaceous earth, Fuller's earth, organic ion exchanger, inorganic ion exchanger, molecular sieve, etc. It may be supported and used. Furthermore, these are Pd,
It may be charged into the reactor separately from Rh and Ru.
白金族化合物の量はその種類、反応条件によって変化す
るがニトロ化合物に対して金属単体として重量比で１〜
ｌＸｌ０−”、好ましくは５×１〇−１〜ｌＸｌ０−４
の範囲で用いられる。また担体の使用量は、金属単体に
対して重量比で５〜１０００倍程度、好ましくは１０〜
５００倍程度である。The amount of the platinum group compound varies depending on its type and reaction conditions, but the weight ratio of the metal itself to the nitro compound is 1 to 1.
lXl0-”, preferably 5×10-1 to lXl0-4
Used within the range of The amount of carrier to be used is about 5 to 1000 times, preferably 10 to 1000 times the weight of the metal itself.
It is about 500 times larger.
助触媒として用いる非金属ハロゲン化物としては塩化水
素、臭化水素、ヨウ化水素等のハロゲン化水素、塩化ア
ンモニウム、臭化アンモニウム、ヨウ化アンモニウム等
のハロゲン化アンモニウム、塩化チオニル等のイオウの
酸ハロゲン化物、三塩化ホスホリル等のすキシハロゲン
化リン、塩化ベンジル、ヨウ化ベンジル等のハロゲン化
ベンジル化合物、ヨウ化メチル等のハロゲン化アルキル
が用いられるが塩化水素が特に好ましい。助触媒として
用いる非金属ハロゲン化物の量は、白金族金属単体１グ
ラム原子に対してハロゲン原子が２〜１ｓｏｏグラム原
子、好ましくは１０〜５００グラム原子程度である。Examples of nonmetal halides used as promoters include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; ammonium halides such as ammonium chloride, ammonium bromide, and ammonium iodide; and sulfur acid halides such as thionyl chloride. Phosphorus chloride, sulfuric acid halides such as phosphoryl trichloride, benzyl halides such as benzyl chloride and benzyl iodide, and alkyl halides such as methyl iodide are used, but hydrogen chloride is particularly preferred. The amount of the nonmetal halide used as a cocatalyst is about 2 to 1 so grams of halogen atoms, preferably about 10 to 500 grams of halogen atoms per gram of platinum group metal alone.
本発明の方法で原料として用いるアミンとしては、芳香
族モノアミン類、ポリアミン類または脂肪族モノアミン
類、ポリアミン類、アミノ酸としては芳香族アミノ酸、
脂肪族アミノ酸のいずれでもよい。例えば、アニリン、
トルイジン類、キシリジン類、ベンジルアミン類、フェ
ニレンジアミン類、トリレンジアミン類、アミノフェノ
ール類、ナフチルアミン類、オキシナフチルアミン類、
ナフチレンジアミン類、アミノアントラセン類、アミノ
ビフェニル類、ビス（アミノフェニル）アルカン類、ビ
ス（アミノフェニル）エーテル類、ヒス（アミノフェニ
ル）チオエーテル類、ビス（アミノフェニル）スルホン
類、アミノジフェノキシアルカン類、アミノフェノチア
ジン類、２−アミノピリミジン類、アミノイソキノリン
類、アミノインドール類のようなヘテロ芳香族化合物な
どがあげられる。具体的な化合物としては、アニリン、
０−ｌｍ−またはＰ−）ルイジン、２．３−１２゜４−
１２，５−１２，６−１または３．４−キシリジン、ｏ
−５ｍ−またはｐ−フェニレンジアミン、２，３−１２
，４−５２，５−１２，６−または３，４−ジアミノト
リレン、ベンジルアミン、キシレンアミン、α−または
β−ナフチルアミン、アミノ安息香酸、アミノアントラ
キノン、０−ｌｍ−またはｐ−アミノフェノール、ｌ、
２−２１゜３−１１．４−１１．５−１１．６−１１．
７−１１．８−１２，３−１２，６−または２．７−ナ
フチレンジアミン、１−アンドラミン、ｏ−ｌｍ−また
はｐ−アミノビフェニル、１−オキシ−２−ナフチルア
ミン、１−オキシ−５−ナフチルアミン、１−オキシ−
７−ナフチルアミン、１−オキシ−８−ナフチルアミン
、２−オキシ−１−ナフチルアミン、３−オキシ−１−
ナフチルアミン、４−オキシ−１−ナフチルアミン、５
−オキシ−１−ナフチルアミン、６−オキシ−１−ナフ
チルアミン、７−オキシ−１−ナフチルアミン、８−オ
キシ−１−ナフチルアミン、２．２’−１２゜３１−１
２．４’−１３，３’−２３，４′−または４，４′−
ジアミノビフェニル、２．２”−１２，４”−１３，３
’−１３，４ｆ−または４゜４′−ジアミノジフェニル
メタン、ビス（４−アミノフェニル）エーテル、４．４
’−ジアミノスルホン、ビス（４−アミノフェノキシ）
エタン、０−１ｍ−１ｐ−クロロアニリン、４−クロル
−１，３−フェニレンジアミン、ｐ−ブロモアニリン、
４−フルオロ−１，３−フェニレンジアミン、ｏ−１ｍ
−１ｐ−アミノフェニレンウレタン、〇−１ｍ−１ｐ−
アニリジン、２，４−ジアミノフェネトール、ｏ−１ｍ
−１ｐ−アミノベンズアルデヒド、ｐ−アミノベンゾイ
ルクロライドなどがあげられ、またこれらの芳香族アミ
ン化合物の異性体、同族体または混合物も使用できる。The amines used as raw materials in the method of the present invention include aromatic monoamines, polyamines or aliphatic monoamines, polyamines, and the amino acids include aromatic amino acids,
Any aliphatic amino acid may be used. For example, aniline,
Toluidines, xylidines, benzylamines, phenylenediamines, tolylenediamines, aminophenols, naphthylamines, oxynaphthylamines,
Naphthylene diamines, aminoanthracenes, aminobiphenyls, bis(aminophenyl)alkanes, bis(aminophenyl)ethers, his(aminophenyl)thioethers, bis(aminophenyl)sulfones, aminodiphenoxyalkanes , aminophenothiazines, 2-aminopyrimidines, aminoisoquinolines, and heteroaromatic compounds such as aminoindoles. Specific compounds include aniline,
0-lm- or P-) luidine, 2.3-12°4-
12,5-12,6-1 or 3,4-xylidine, o
-5m- or p-phenylenediamine, 2,3-12
, 4-52, 5-12,6- or 3,4-diaminotrilene, benzylamine, xyleneamine, α- or β-naphthylamine, aminobenzoic acid, aminoanthraquinone, 0-lm- or p-aminophenol, l,
2-21°3-11.4-11.5-11.6-11.
7-11.8-12,3-12,6- or 2.7-naphthylenediamine, 1-andramine, o-lm- or p-aminobiphenyl, 1-oxy-2-naphthylamine, 1-oxy- 5-naphthylamine, 1-oxy-
7-naphthylamine, 1-oxy-8-naphthylamine, 2-oxy-1-naphthylamine, 3-oxy-1-
naphthylamine, 4-oxy-1-naphthylamine, 5
-oxy-1-naphthylamine, 6-oxy-1-naphthylamine, 7-oxy-1-naphthylamine, 8-oxy-1-naphthylamine, 2.2'-12゜31-1
2.4'-13,3'-23,4'- or 4,4'-
Diaminobiphenyl, 2.2"-12,4"-13,3
'-13,4f- or 4°4'-diaminodiphenylmethane, bis(4-aminophenyl)ether, 4.4
'-Diaminosulfone, bis(4-aminophenoxy)
Ethane, 0-1m-1p-chloroaniline, 4-chloro-1,3-phenylenediamine, p-bromoaniline,
4-Fluoro-1,3-phenylenediamine, o-1m
-1p-aminophenylene urethane, 〇-1m-1p-
Aniridine, 2,4-diaminophenethole, o-1m
Examples include -1p-aminobenzaldehyde and p-aminobenzoyl chloride, and isomers, homologs, or mixtures of these aromatic amine compounds can also be used.
脂肪族アミンとしては、メチルアミン、エチルアミン、
アミルアミン等の第一アミン、ジメチルアミン、ジエチ
ルアミン等の第二アミン、シクロペンチルアミン、シク
ロヘキシルアミン等の脂環式アミン、エチレンジアミン
、トリメチレンジアミン、４．４−ジアミノジシクロヘ
キシルメタン、ヘキサメチレンジアミン等のジアミン、
１，２゜３−トリアミノプロパン等のトリアミンがあげ
られる。アミンは単独または２種以上混合して使用する
ことができる。有機含水酸基化合物としては、第一、第
二または第三級水酸基を含む一価アルコールまたは多価
アルコールが含まれる。具体的にはメチルアルコール、
エチルアルコール、ｎ−および１ｓｏ−ブチルアルコー
ル、ｎ−１ｉｓｏ−およびｔ−ブチルアルコール、ｎ−
またはｉｓ。Examples of aliphatic amines include methylamine, ethylamine,
Primary amines such as amylamine, secondary amines such as dimethylamine and diethylamine, alicyclic amines such as cyclopentylamine and cyclohexylamine, diamines such as ethylenediamine, trimethylenediamine, 4,4-diaminodicyclohexylmethane, and hexamethylenediamine;
Examples include triamines such as 1,2°3-triaminopropane. The amines can be used alone or in combination of two or more. The organic hydrous acid group compound includes a monohydric alcohol or a polyhydric alcohol containing a primary, secondary or tertiary hydroxyl group. Specifically, methyl alcohol,
Ethyl alcohol, n- and 1so-butyl alcohol, n-1iso- and t-butyl alcohol, n-
Or is.
−アミルアルコール、ヘキシルアルコール、ラウリルア
ルコール、セチルアルコール等の脂肪族−価アルコール
、シクロペンタノール、シクロヘキシルアルコール等の
脂環式−価アルコール、ベンジルアルコール、クロルベ
ンジルアルコールおよびメトキシベンジルアルコール等
の芳香族−価アルコール、エチレングリコール、ジエチ
レングリコール、プロピレングリコール、ジプロピレン
グリコール等の二価アルコール、グリセロール、ヘキサ
ントリオール等の三価アルコールがあげられる。- Aliphatic alcohols such as amyl alcohol, hexyl alcohol, lauryl alcohol, cetyl alcohol, alicyclic alcohols such as cyclopentanol and cyclohexyl alcohol, aromatic alcohols such as benzyl alcohol, chlorobenzyl alcohol and methoxybenzyl alcohol - Examples include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, and trihydric alcohols such as glycerol and hexanetriol.
本発明の方法で原料の有機ニトロ化合物は、芳香族モノ
ニトロ化合物、ポリニトロ化合物、脂肪族モノニトロ化
合物またはポリニトロ化合物のいずれでもよい。例えば
、芳香族ニトロ化合物の中には、ニトロベンゼン類、ジ
ニトロベンゼン類、ジニトロトルエン類、ニトロナフタ
レン類、ニトロアンスラセン類、ニトロビフェニル類、
ビスにトロフェニル）アルカン類、ビスにトロフェニル
）エーテル類、ビスにトロフェニル）チオエーテル類、
ビスにトロフェニル）スルホン類、ニトロジフェノキシ
アルカン類、ニトロフェノチアジン類あるいは５−二ト
ロピリミジンのようなヘテロ芳香族化合物などがあげら
れる。具体的な化合物としては、ニトロベンゼン、０−
ｌｍ−またはｐ−二トロトルエン、Ｏ−ニトロ−ｐ−キ
シレン、１−ニトロナフタレン、ｍまたはｐ−ジニトロ
ベンゼン、２，４−または２．６−シニトロトルエン、
ジニトロナフタレン、４．４’−ジニトロビフェニル、
４．４’−ジニトロベンジル、ビス（４−ニトロフェニ
ル）エーテル、ビス（２゜４−ジニトロフェニル）エー
テル、ビス（４−ニトロフェニル）チオエーテル、ビス
（４−ニトロフェニル）スルホン、ビス（４−ニトロフ
ェノキシ）エタン、α、α１−ジニトローｐ−キシレン
、α、α１−ジニトローｍ−キシレン、２，４．６−ト
リニトロトルエン、ｏ−ｌｍ−またはｐ−クロロニトロ
ベンゼン、１−クロロ−２，４−’；ニトロヘンゼン、
１−７’ロモー４−二トロベンゼン、１−フルオロ−２
，４−ジニトロベンゼン、０−ｌｍ−またはｐ−ニトロ
フェニルカルバミン酸エステル、ｏ−ｌｍ−またはｐ−
ニトロアニソール、２、 ４−ジニトロフェニルール、
ｍ−ニトロベンズアルデヒド、ｐ−ニトロベンゾクロラ
イド、エチル−ｐ−ニトロベンゾエート、ｍ−二トロベ
ンゼンスルホニルクロリド、ｐ−ニトロｉ水フタール酸
、３，３１−ジメチルまたは４．４１−ジニトロビフェ
ニル、１，５−ジニトロナフタレンなどがあげられる。The organic nitro compound used as a raw material in the method of the present invention may be an aromatic mononitro compound, a polynitro compound, an aliphatic mononitro compound, or a polynitro compound. For example, aromatic nitro compounds include nitrobenzenes, dinitrobenzenes, dinitrotoluenes, nitronaphthalenes, nitroanthracenes, nitrobiphenyls,
Bis-trophenyl) alkanes, bis-trophenyl) ethers, bis-trophenyl) thioethers,
Examples include heteroaromatic compounds such as bis(trophenyl) sulfones, nitrodiphenoxyalkanes, nitrophenothiazines, and 5-nitropyrimidine. Specific compounds include nitrobenzene, 0-
lm- or p-nitrotoluene, O-nitro-p-xylene, 1-nitronaphthalene, m- or p-dinitrobenzene, 2,4- or 2,6-cynitrotoluene,
dinitronaphthalene, 4,4'-dinitrobiphenyl,
4.4'-Dinitrobenzyl, bis(4-nitrophenyl) ether, bis(2°4-dinitrophenyl) ether, bis(4-nitrophenyl)thioether, bis(4-nitrophenyl)sulfone, bis(4- nitrophenoxy)ethane, α,α1-dinitro p-xylene, α,α1-dinitro m-xylene, 2,4,6-trinitrotoluene, o-lm- or p-chloronitrobenzene, 1-chloro-2,4- '; Nitrohenzene,
1-7'lomo-4-nitrobenzene, 1-fluoro-2
, 4-dinitrobenzene, o-lm- or p-nitrophenylcarbamate, o-lm- or p-
Nitroanisole, 2,4-dinitrophenylur,
m-nitrobenzaldehyde, p-nitrobenzochloride, ethyl-p-nitrobenzoate, m-nitrobenzenesulfonyl chloride, p-nitrohydrophthalic acid, 3,31-dimethyl or 4,41-dinitrobiphenyl, 1,5 - Examples include dinitronaphthalene.
また、脂肪族ニトロ化合物としては、ニトロメタン、ニ
トロブタン、２．２’−ジメチルニトロブタン１、ニト
ロシクロペンクン、３−メチルニトロブタン、ニトロオ
クタン、３−ニトロプロペン−１、フェニルニトロメタ
ン、ｐ−ブロモフェニルニトロメタン、ｐ−メトキシフ
ェニルニトロメタン、ジニトロエタン、ジニトロヘキサ
ン、ジニトロシクロヘキサン、ジーにトロヘキシル）メ
タンが挙げられる。さらに、これらの化合物の異性体、
混合物、同族体も使用できる。In addition, as aliphatic nitro compounds, nitromethane, nitrobutane, 2,2'-dimethylnitrobutane-1, nitrocyclopenkune, 3-methylnitrobutane, nitrooctane, 3-nitropropene-1, phenylnitromethane, p-bromo Examples include phenylnitromethane, p-methoxyphenylnitromethane, dinitroethane, dinitrohexane, dinitrocyclohexane, and di(trohexyl)methane. Additionally, isomers of these compounds,
Mixtures and congeners can also be used.
有機含水酸基化合物としては、第一、第二または第三級
水酸基を含むｍ個アルコールまたは多価アルコールが含
まれる。具体的にはメチルアルコール、エチルアルコー
ル、ｎ−およヒｔ ｓ ｏ −７”チルアルコール、ｎ
−１ｉｓｏ−およびｔ−ブチルアルコール、ｎ−または
１ｓｏ−アミルアルコール、ヘキシルアルコール、ラウ
リルアルコール、セチルアルコール等の脂肪族−価アル
コール、シクロペンタノール、シクロヘキシルアルコー
ル等の脂環式−価アルコール、ベンジルアルコール、ク
ロルベンジルアルコールおよびメトキシベンジルアルコ
ール等の芳香族−価アルコール、エチレングリコール、
ジエチレングリコール、プロピレングリコール、ジプロ
ピレングリコール等の二価アルコール、グリセロール、
ヘキサントリオール等の三価アルコールがあげられる。Examples of the organic hydrated acid group compound include m-alcohols or polyhydric alcohols containing primary, secondary, or tertiary hydroxyl groups. Specifically, methyl alcohol, ethyl alcohol, n- and human tso-7” methyl alcohol, n
Aliphatic alcohols such as -1iso- and t-butyl alcohol, n- or 1so-amyl alcohol, hexyl alcohol, lauryl alcohol, cetyl alcohol, cycloaliphatic alcohols such as cyclopentanol, cyclohexyl alcohol, benzyl alcohol , aromatic-hydric alcohols such as chlorobenzyl alcohol and methoxybenzyl alcohol, ethylene glycol,
Dihydric alcohols such as diethylene glycol, propylene glycol, dipropylene glycol, glycerol,
Examples include trihydric alcohols such as hexanetriol.
本発明の方法は、溶媒を存在させずに行うこともできる
が、溶媒を用いてもよい。溶媒としては、ベンゼン、ト
ルエン、キシレンのような芳香族炭化水素、アセトニト
リル、プロピオニトリル、ベンゾニトリルのようなニト
リル類、ｈｍｐ ａのような有機リン化合物、スルホラ
ン、ジメチルスルホランのようなスルホラン系溶媒、モ
ノクロルベンゼン、ジクロルベンゼンのようなハロゲン
化芳香族炭化水素、ヘプタン、メチルシクロヘキサン、
ケトン類、エステル類、ＴＨＦ、１，４−ジオキサン、
プロピレンカーボネート、Ｎ−メチルピロリドン、１．
２−ジメトキシエタンなどから選ばれた少なくとも１種
の溶媒、またはこれらの混合物を用いることができる。The method of the invention can be carried out without the presence of a solvent, but a solvent may also be used. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, nitriles such as acetonitrile, propionitrile, and benzonitrile, organic phosphorus compounds such as HMP A, and sulfolane solvents such as sulfolane and dimethylsulfolane. , halogenated aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene, heptane, methylcyclohexane,
Ketones, esters, THF, 1,4-dioxane,
Propylene carbonate, N-methylpyrrolidone, 1.
At least one solvent selected from 2-dimethoxyethane and the like or a mixture thereof can be used.
ＣＯおよび水素は単体ガスとしてまたは混合ガスの形と
して使用される。これらのガスとしてはナフサ等の熱分
解ガス、石炭ガス化からのガス各種製鉄所の副生ガスが
利用できる。CO and hydrogen are used as single gases or in the form of a gas mixture. As these gases, pyrolysis gas such as naphtha, gas from coal gasification, and various by-product gases from steel plants can be used.
ハロゲン化水素水溶液の水は、あまり過剰に存在すると
反応速度を小さくして好ましくなく、その濃度は５００
ｐｐｍ以上５０００ｐｐｍ以下であることが好ましい。If the water in the hydrogen halide aqueous solution is present in too much excess, it will reduce the reaction rate, which is undesirable;
It is preferably at least 5000 ppm.
合成反応圧力は、ＣＯの分圧として１〜５０ｋｇ／ｃｄ
、好ましくは５〜３０ｋｇ／−である。The synthesis reaction pressure is 1 to 50 kg/cd as partial pressure of CO.
, preferably 5 to 30 kg/-.
合成反応温度は６０〜２３０℃、特に１５０〜２１０℃
が好ましい。The synthesis reaction temperature is 60-230℃, especially 150-210℃
is preferred.
合成反応時間は、用いる該アミノ基およびニトロ基化合
物の種類、他の反応条件によって異なるが、一般に５分
〜６時間の範囲で行われる。The synthesis reaction time varies depending on the type of the amino group and nitro group compound used and other reaction conditions, but is generally carried out in a range of 5 minutes to 6 hours.
合成反応終了後、アルカリを添加するが、添加するアル
カリの量は反応液の種類、性状等によって変化するが、
例えば水酸化ナトリウム等の場合は反応液に対して０．
０００１〜１ｗｔ％、好ましくは０．００１〜０．１
ｗ ｔ％である。温度は合成温度〜室温であり、処理時
間としては１０分〜２時間である。これらの条件下で反
応液中にＰｄおよび／またはＰｄ化合物の不溶物が生じ
る。ここで、濾過、遠心分離等の一般の分離操作により
Ｐｄおよび／またはＰｄ化合物を回収することができる
。After the synthesis reaction is complete, an alkali is added, but the amount of alkali added varies depending on the type and properties of the reaction solution.
For example, in the case of sodium hydroxide, etc., 0.0% of the reaction solution is used.
0001-1wt%, preferably 0.001-0.1
wt%. The temperature is from the synthesis temperature to room temperature, and the treatment time is from 10 minutes to 2 hours. Under these conditions, insoluble Pd and/or Pd compounds are generated in the reaction solution. Here, Pd and/or Pd compounds can be recovered by common separation operations such as filtration and centrifugation.
Ｐｄおよび／またはＰｄ化合物を回収後、反応液から蒸
留または他の適当な分離法により、カルバミン酸エステ
ルを分離する。After recovering Pd and/or the Pd compound, the carbamate ester is separated from the reaction solution by distillation or other suitable separation method.
本発明は、下記の実施例によって、さらに詳細に説明さ
れるが、下記の例で制限されるものではない。The invention will be explained in more detail by the following examples without being restricted thereto.
実施例１
アルミナ１ｇにＰｄ（ＮＯ３）２水溶液を含浸し、１１
０℃、２ｈ乾燥後、さらに５００℃、２ｈ乾燥し担体付
き触媒を調製した。触媒はＰｄＯであり、Ｐｄ単位で３
．４４重量％であった。Example 1 1 g of alumina was impregnated with Pd(NO3)2 aqueous solution,
After drying at 0°C for 2 hours, it was further dried at 500°C for 2 hours to prepare a supported catalyst. The catalyst is PdO, with 3 Pd units
．． It was 44% by weight.
内容積１００ｍβのテフロン加工したステンレス製オー
トクレーブに上記触媒６１．９■（０，０２０モル）、
アニリン０．９３１ｇ（０，０１０モル）、ニトロベン
ゼン１．２３ ｇ （０，０１０モル）、エタノール４
．６１ ｇ （０，１０モル）、トルエン１０．６ｇ
（０，１１モル）および３５％塩酸水溶液０．０３６ｇ
（ＨＣ１＝０．３４ミリモル、Ｈ２０＝０．０３４ミリ
モル）を仕込み、系内の空気をパージせずに室温で１０
０％ＣＯガスを２８ｋｇ／ａｄまで導入し反応温度１９
０℃で３時間反応させた。反応終了後、室温まで冷却し
系内を大気圧に戻し反応生成物をガスクロマトグラフィ
ーおよび液体クロマトグラフィーで分析したところ、Ｎ
−フェニルカルバミン酸エステル（以下、ＮＰＵと省略
する）が２．９７ ｇ生成しくＮＰＵ収率９０％）、ア
ニリンが０，０９３ ｇ （０，００１モル）、ニトロ
ベンゼンが０．１２３ｇ（０，００１モル）未反応のま
まであった。反応復液中に溶出したＰｄをＩＣＰ（高周
波発光プラズマ）法により分析した。この結果液中のＰ
ｄは１５ｐｐｍ存在していることが確認された。The above catalyst 61.9μ (0,020 mol) was placed in a Teflon-treated stainless steel autoclave with an internal volume of 100 mβ.
Aniline 0.931 g (0,010 mol), nitrobenzene 1.23 g (0,010 mol), ethanol 4
．． 61 g (0.10 mol), toluene 10.6 g
(0.11 mol) and 35% aqueous hydrochloric acid solution 0.036 g
(HC1 = 0.34 mmol, H20 = 0.034 mmol) was charged, and 10
0% CO gas was introduced up to 28 kg/ad and the reaction temperature was 19
The reaction was carried out at 0°C for 3 hours. After the reaction was completed, the system was cooled to room temperature and returned to atmospheric pressure, and the reaction product was analyzed by gas chromatography and liquid chromatography.
-2.97 g of phenylcarbamate ester (hereinafter abbreviated as NPU) was produced (NPU yield 90%), 0,093 g (0,001 mol) of aniline, and 0.123 g (0,001 mol) of nitrobenzene. ) remained unreacted. Pd eluted into the reaction condensate was analyzed by ICP (high frequency luminescent plasma) method. As a result, P in the liquid
It was confirmed that d was present at 15 ppm.
反応終了後の液に水酸化ナトリウムを、０．０１３６ｇ
（０，３４ミリモル）含んだ水酸化ナトリウム水溶液を
添加して、１０分間攪拌した。その後、濾過により、膣
液中より固形物を分離した。固形物分離後の液中のＰｄ
を分析したところ検出限界以下（＜０．００１ｐｐｍ）
であった。Add 0.0136g of sodium hydroxide to the solution after the reaction is completed.
An aqueous sodium hydroxide solution containing (0.34 mmol) was added and stirred for 10 minutes. Thereafter, solid matter was separated from the vaginal fluid by filtration. Pd in the liquid after solids separation
When analyzed, it was below the detection limit (<0.001ppm)
Met.
実施例２
実施例１において、ＨＣ１濃度を０．６８ミリモルとし
、他は同じ条件下で反応させ、反応終了後、液中の溶出
したＰｄを分析したところ２５ｐｐｍであった０反応終
了後の液に水酸化ナトリウムを、０．０２７ ｇ （０
，６８ミリモル）を含んだ水酸化ナトリウム水溶液を添
加して、１０分間攪拌した。Example 2 In Example 1, the HC1 concentration was set to 0.68 mmol, and the reaction was performed under the same conditions. After the reaction was completed, the Pd eluted in the solution was analyzed and found to be 25 ppm. Add sodium hydroxide to 0.027 g (0
, 68 mmol) was added and stirred for 10 minutes.
その後、濾過により、膣液中より固形物を分離した。固
形物分離後の液中のＰｄを分析したところ検出限界以下
（＜０．００１ ｐｐｍ）であった。Thereafter, solid matter was separated from the vaginal fluid by filtration. Analysis of Pd in the liquid after solid matter separation revealed that it was below the detection limit (<0.001 ppm).
なお、本実施例１．２において水酸化ナトリウム水溶液
を添加後、液は有機相と水相に分離し水相中にＰｄを含
む不溶物が存在していた。この水相中の不溶物を濾過操
作により固形物を回収した。In Example 1.2, after adding the sodium hydroxide aqueous solution, the liquid was separated into an organic phase and an aqueous phase, and insoluble matter containing Pd was present in the aqueous phase. Insoluble matter in this aqueous phase was filtered to recover solid matter.
濾過後の水相中にはＮａ塩（ＮａＣ／等）が含まれてい
た。The aqueous phase after filtration contained Na salts (NaC/etc.).
以下、本発明を系統図に基づき説明する。Hereinafter, the present invention will be explained based on a system diagram.
第１図は、本発明におけるカルバミン酸エステル製造の
系統図である。ＣＯを含有するガスＡは合成塔１に加圧
後供給される。また、原料のアニリンＪ１ニトロベンゼ
ンＢ１エタノールＣも合成塔１へ供給される。合成塔１
では塔内に白金族触媒／担体が充填されており、反応温
度、反応圧力、反応時間を所定値で操作される。反応液
は触媒との接触を十分に行うためポンプにより合成塔１
内を循環することもできる。未反応のＣｏガスは副生成
ガスのＣ０２Ｅを除去後再び合成塔１に循環される。こ
とで、水、エタノール、溶媒等が塔頂よす、アニリン、
ニトロベンゼン、Ｎ−フェニルカルバミン酸エチルは塔
底より抜き出される。塔底からの抜き出し液は転化基２
１に導かれる。そして、水素を含有するガスＤを加圧後
供給される。FIG. 1 is a systematic diagram of carbamate ester production in the present invention. Gas A containing CO is supplied to the synthesis tower 1 after being pressurized. In addition, the raw materials aniline J1 nitrobenzene B1 ethanol C are also supplied to the synthesis column 1. Synthesis tower 1
In this method, a platinum group catalyst/support is packed in a column, and the reaction temperature, reaction pressure, and reaction time are controlled at predetermined values. The reaction solution is pumped into synthesis column 1 to ensure sufficient contact with the catalyst.
It can also be circulated within. The unreacted Co gas is recycled to the synthesis column 1 again after removing CO2E as a by-product gas. This means that water, ethanol, solvents, etc. are at the top of the tower, aniline,
Nitrobenzene and ethyl N-phenylcarbamate are extracted from the bottom of the column. The liquid extracted from the bottom of the tower contains the conversion group 2
I am guided by 1. Gas D containing hydrogen is then supplied after being pressurized.
反応後の液はＮａＯＨ添加槽６に導かれる。ここで、Ｎ
ａＯＨ水溶液を添加し、液を攪拌し、回収槽７に導かれ
る。回収槽７では有機相と水相に分離され、水相は固形
物回収槽８に導かれる。ここで、水相中の固形物が回収
される。固形物中には白金族金属Ｐｄおよび／または白
金族金属の水酸化物Ｐｄ （ＯＨ）２が含有されている
。The liquid after the reaction is led to the NaOH addition tank 6. Here, N
An aOH aqueous solution is added, the liquid is stirred, and then led to the recovery tank 7. In the recovery tank 7 , the solids are separated into an organic phase and an aqueous phase, and the aqueous phase is led to the solids recovery tank 8 . Here, the solids in the aqueous phase are recovered. The solid substance contains platinum group metal Pd and/or platinum group metal hydroxide Pd (OH)2.
回収槽７での有機相は低沸蒸留塔２に導かれる。The organic phase in the recovery tank 7 is led to the low-boiling distillation column 2.
低沸蒸留塔２の蒸留操作温度は１００〜１２０℃で行わ
れ、低沸蒸留塔２の塔底からの抜き出し液は蒸留塔４に
導かれ、蒸留操作温度１８０〜２００℃で塔底よりＮ−
フェニルカルバミン酸エチルｌを回収する。低沸蒸留塔
２の塔頂からの液は副生成物の水Ｇを除去後再び合成塔
１に循環される。The distillation operation temperature of the low-boiling distillation column 2 is carried out at 100 to 120°C, and the liquid extracted from the bottom of the low-boiling distillation column 2 is led to the distillation column 4, where N is distilled from the bottom of the column at a distillation operating temperature of 180 to 200°C. −
Collect l of ethyl phenylcarbamate. The liquid from the top of the low-boiling distillation column 2 is recycled to the synthesis column 1 again after removing the by-product water G.
蒸留塔４の塔頂からの回収液も再び合成塔１に循環され
る。The recovered liquid from the top of the distillation column 4 is also circulated to the synthesis column 1 again.
本発明によれば、反応液中にアルカリを添加するという
簡便な操作で効率よく白金族金属および／または白金族
金属化合物を回収することができる。According to the present invention, a platinum group metal and/or a platinum group metal compound can be efficiently recovered by a simple operation of adding an alkali to a reaction solution.
第１図は、本発明におけるカルバミン酸エステル製造方
法を示す系統図である。FIG. 1 is a system diagram showing the method for producing a carbamate ester according to the present invention.
Claims (1)
物、一酸化炭素、有機含水酸基化合物を非金属ハロゲン
化物存在下で、触媒として周期律第VIII族の白金族に属
する遷移金属化合物および担体を用い、水または水と酸
素を追加的に添加してカルバミン酸エステル類を合成す
るに際し、反応液中に溶出してくる白金族に属する化合
物を、アルカリ金属またはアルカリ土類金属の水酸化物
、炭酸塩、炭酸水素塩または酸化物を０．０００１〜１
ｗｔ％添加することにより白金族化合物を不溶物として
回収することを特徴とする触媒回収方法。(1) A compound having an amino group, a compound having a nitro group, carbon monoxide, an organic hydrous acid group compound in the presence of a nonmetal halide, and a transition metal compound belonging to the platinum group of Group VIII of the Periodic Table as a catalyst and a carrier. When synthesizing carbamate esters by additionally adding water or water and oxygen, the compound belonging to the platinum group eluted into the reaction solution is treated with an alkali metal or alkaline earth metal hydroxide, Carbonate, hydrogen carbonate or oxide from 0.0001 to 1
A method for recovering a catalyst, comprising recovering a platinum group compound as an insoluble substance by adding wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1118361A JPH02300156A (en) | 1989-05-11 | 1989-05-11 | Method for recovering catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1118361A JPH02300156A (en) | 1989-05-11 | 1989-05-11 | Method for recovering catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02300156A true JPH02300156A (en) | 1990-12-12 |
Family
ID=14734804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1118361A Pending JPH02300156A (en) | 1989-05-11 | 1989-05-11 | Method for recovering catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02300156A (en) |
-
1989
- 1989-05-11 JP JP1118361A patent/JPH02300156A/en active Pending
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