US20130244867A1 - Catalyst for producing n-substituted carbamates, and the preparation and application of the same - Google Patents
Catalyst for producing n-substituted carbamates, and the preparation and application of the same Download PDFInfo
- Publication number
- US20130244867A1 US20130244867A1 US13/875,358 US201313875358A US2013244867A1 US 20130244867 A1 US20130244867 A1 US 20130244867A1 US 201313875358 A US201313875358 A US 201313875358A US 2013244867 A1 US2013244867 A1 US 2013244867A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- oxide
- reaction
- aniline
- mpc
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 150000004657 carbamic acid derivatives Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 229910052752 metalloid Inorganic materials 0.000 claims abstract description 13
- 150000002738 metalloids Chemical class 0.000 claims abstract description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 2
- 229910001887 tin oxide Inorganic materials 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 119
- 150000001412 amines Chemical class 0.000 abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000013341 scale-up Methods 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 166
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 120
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 76
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 description 72
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 44
- 238000004817 gas chromatography Methods 0.000 description 23
- 229910021529 ammonia Inorganic materials 0.000 description 22
- -1 butanonc Chemical compound 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- 150000003141 primary amines Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZZHGIUCYKGFIPV-UHFFFAOYSA-M n-butylcarbamate Chemical compound CCCCNC([O-])=O ZZHGIUCYKGFIPV-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical class NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical group NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- UWIPABKYQALXKH-UHFFFAOYSA-F 1-butyl-3-methylimidazol-3-ium fluoro-dioxido-oxo-lambda5-phosphane Chemical compound [O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1 UWIPABKYQALXKH-UHFFFAOYSA-F 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 241000253387 Rhodobiaceae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000006303 iodophenyl group Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 description 1
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 1
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical compound CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
Definitions
- the present invention relates to N-substituted carbamates, and particularly to a catalyst for preparing these N-substituted carbamates.
- This invention also relates to the novel catalyst, to the preparation of the catalyst, and to the use thereof.
- N-substituted carbamates represent a class of important organic intermediates, which can be used for the manufacture of agrochemicals, dyes, pharmaceuticals, ureas, and isocyanates. Furthermore, they can also be applied as protective groups of amides in various organic syntheses.
- N-substituted carbamates have received considerable attention due to their wide applications.
- U.S. Pat. No. 3,763,217 and U.S. Pat. No. 4,268,683 disclose the synthesis of N-substituted carbamates by reacting aromatic amines with organic carbonates in the presence of AlCl 3 , FeCl 3 , UO 2 (NO) 2 , zinc acetate, zinc propionate, or zinc naphthenate as a catalyst, respectively.
- This method has low selectivity for the desired products.
- the catalyst activity is restricted by the aromatic amines.
- the catalyst should not only be capable of preparing the targeted products in high yields, but should also be convenient to separate from the product and recycled.
- One aspect of the present invention is to provide a method for preparing N-substituted carbamates.
- this method comprises reacting a carbamate with an amine in the presence of a catalyst to form an N-substituted carbamate, wherein the catalyst comprises a heteropoly acid as active component and a metal oxide or a metalloid oxide as catalyst support.
- the catalyst comprises an active component and a catalyst support component.
- the active component of the catalyst is a heteropoly acid
- the component of the catalyst support is a metal oxide or a metalloid oxide.
- the third aspect of the present invention is to provide a method for preparing this catalyst.
- the method comprises (1) impregnating a catalyst support into a heteropoly acid solution comprising one or more heteropoly acids to form a catalyst precursor, and (2) calcinating the catalyst precursor to obtain a catalyst, wherein the calcination temperature ranges from 150 to 1000° C.
- N-substituted carbamates can be prepared with high yield by reacting N-unsttbstituted carbamates with amines in the presence of the catalyst provided here.
- the reaction system can be easily scaled up, due to the fact that the reaction conditions are relatively mild, and the activity and selectivity of the catalyst are high, and the reaction time is rather short. Furthermore, the catalyst can be easily separated from the reaction system and recycled.
- Heteropoly acids are commonly regarded as attractive catalytic materials and are applied to a variety of reactions such as, for example, dehydration, cyclization, esterification, and so on.
- HPAs Heteropoly acids
- homogeneous HPAs are difficult to separate and recover from the reaction mixture. Therefore, HPAs can not be conveniently recycled.
- the present invention provides a new catalyst comprising an active component and a catalyst support component, with the active component comprising a h.eteropoly acid, and the catalyst support component comprising a metal oxide or a metalloid oxide. It has been found that in the presence of such catalyst, carbamates react with amines to form N-substituted carbamates in high yield. In addition, the catalyst can be separated from the reaction system and recycled easily. This makes commercial scale-up and application commercially feasible.
- the catalyst support component comprises vanadium pentoxide (V 2 O 5 ). It has been found that there is a synergistic action between V 2 O 5 as the catalyst support component, and Keggin type HPAs as the active component of the catalyst, which further enhance the selectivity and increase the yield of the reaction.
- the active component of the catalyst of the present invention is a Heteropoly acid (HPAs), preferably a Keggin type Heteropoly acids (HPAs). More preferred Keggin type Heteropoly acids include tungstophoric acid (H 3 PW 12 O 40 .nH 2 O), molybdophosphoric acid (H 3 PMo 12 O 4 .nH 2 O), tungstosilicic acid (H 4 SiW 12 O 40 nH 2 O), molybdosilicic acid (H 4 SiMo 12 O 40 .nH 2 O), or their mixtures.
- HPAs Heteropoly acid
- HPAs Keggin type Heteropoly acids
- More preferred Keggin type Heteropoly acids include tungstophoric acid (H 3 PW 12 O 40 .nH 2 O), molybdophosphoric acid (H 3 PMo 12 O 4 .nH 2 O), tungstosilicic acid (H 4 SiW 12 O 40 nH 2 O),
- Keggin type Heteropoly acid be selected from the group consisting of tungstophosphoric acid (H 3 PW 12 O 40 .nH 2 O), molybdophosphoric acid (H 3 PMo 12 O 40 .nH 2 O) and mixtures thereof.
- the catalyst of this invention also requires a catalyst support component.
- This catalyst support component is a metal oxide or a metalloid oxide.
- the metal oxide or metalloid oxide is selected from the group consisting of zirconia, titania, zinc oxide, silica, magnesia, calcium oxide, stannic oxide, barium oxide, cerium oxide, lanthanum oxide, vanadium pentoxide, alumina and mixtures thereof. More preferably, the catalyst support component is selected from the group consisting of vanadium pentoxide, alumina and mixtures thereof Vanadium pentoxide is a most preferred catalyst support component.
- the average diameter of the catalyst support is preferably (but not limited to) 0.1 to 4 mm, more preferably 0.5 to 3 mm, and most preferably 1 to 2 mm.
- the pore volume of the catalyst support is preferably (but not limited to) 0.01 to 10 cm 3 /g, more preferably 0.1 to 1 cm 3 /g, most preferably 0.2 to 0.8 cm 3 /g, and most particularly preferably 0.4 to 0.6 cm 3 /g.
- the BET surface area of the catalyst support is preferably (but not limited to) less than or equal to 300 m 2 /g, more preferably from 1 to 250 m 2 /g, most preferably from 5 to 100 m 2 /g, and most particularly preferably from 10 to 60 m 2 /g.
- the shape of the catalyst can be spherical, cylindrical or irregular.
- the loading of the active component can be preferably (but is not limited to) from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, and most preferably from 4 to 7% by weight, based on 100% by weight of the catalyst support.
- the method for preparing the catalyst comprises the steps of impregnating and cal.cinating, etc.
- the method can additionally include a drying step for the catalyst precursor after the impregnating step and before the calcinating step.
- the temperature of the drying step can be from (but is not limited to) less than or equal to 140° C., and more preferably from 90 to 120° C.
- the time of the drying step can be, but is not limited to, less than or equal to 24 hours, more preferably less than or equal to 15 hours, and most preferably from 5 to 12 hours.
- the atmosphere of the drying step can be selected from (but is not limited to) preferably air, oxygen, nitrogen, etc. More preferably the atmosphere of the drying step is air and/or oxygen, and is most preferably air.
- heteropoly acid In the impregnating step, one heteropoly acid or a mixture of two or more heteropoly acids is dissolved in a solvent to form a heteropoly acid solution.
- the heteropoly acid can be selected from (but is not limited to) preferably tungstophosphoric acid (H 3 PW 12 O 40 .nH 2 O) molybdophosphoric acid (H 3 PMo 12 O 40 .nH 2 O), tungstosilicic acid (H 4 SiW 12 O 40 .nH 2 O), molybdosilicic acid (H 4 SiMo 12 O 40 .nH 2 O), or their mixtures; and most preferably tungstophosphoric acid (H 3 PW 12 O 40 .nH 2 O), molybdophosphoric acid (H 3 PMo 12 O 40 .nH 2 O), or their mixtures.
- the solvent can be selected from, but is not limited to, water, an aqueous solvent, a non-aqueous solvent, or any mixture of the aforementioned solvents.
- Suitable non-aqueous solvent can be selected from, preferably, ethers, alcohols, ketones, nitriles or amides; more preferably, diethyl ether, methanol, ethanol, propanol, butyl alcohol, acetone, butanonc, acetonitrile, dimethyl sulfone, dimethyl sulfoxide or dimethylformamide.
- the pH value of the aqueous solution comprising the precursor of the catalytically active component can be adjusted through the addition of hydrated or non-hydrated acids.
- the hydrated or non-hydrated acids can be selected from, but are not limited to, HCl, HNO 3 , H 2 SO 4 , H 3 PO 4 or CH 3 COOH.
- the catalyst precursor is obtained by impregnating a catalyst support into a solution containing the heteropoly acids.
- the component of the catalyst support is a metal oxide or a metalloid oxide.
- the metal oxide or metalloid oxide acids can be selected from, but is not limited to, preferably zirconia, titania, zinc oxide, silica, magnesia, calcium oxide, stannic oxide, barium oxide, cerium oxide, lanthanum oxide, vanadium pentoxide, alumina, or their mixtures. More preferably, the metal oxide or metalloid oxide acids are selected from vanadium pentoxide, alumina, or their mixtures. Vanadium pentoxide is the most preferred metal oxide or metalloid oxide acid.
- the temperature of the impregnating step Preferably impregnating occurs at room temperature.
- the time of the impregnating step is typically less than or equal to 20 hours, and preferably from 1 to 4 hours.
- the calcination temperature should be high enough to result in the transformation of the catalyst precursor to the catalyst.
- the calcination temperature can be from preferably 200 to 1000° C., more preferably from 300 to 700° C.
- the calcination step can be carried out either in an inert atmosphere or in an oxidizing atmosphere.
- the inert atmosphere can be selected from preferably (hut is not limited to) a nitrogen gas, a noble gas, a non-oxidizing gas, a non-reducing gas or a mixture of two or more of the aforesaid gases.
- Nitrogen is more preferred as the inert gas.
- the oxidizing atmosphere can be selected from preferably (but is not limited to) oxygen gas or an oxygen containing gas, and more preferably is an oxygen containing gas.
- the oxidizing atmosphere is most preferably air. A mixture of air and nitrogen can be applied as well.
- One aspect of the present invention provides a method for preparing N-substituted carbamates which correspond to the general formula:
- This process comprises (1) reacting (a) one or more N-unsubstantiated carbamates (H 2 N—CO—OR), with (b) one or more amines, in the presence of (c) the novel catalyst described herein.
- the reaction equation is:
- N-unsubstituted carbamates H 2 N—CO—OR
- the N-unsubstituted carbamates can be obtained via known synthetic routes such as the reaction between urea and conesponding compound containing a hydroxyl group.
- R can be selected from preferably, but is not limited to,
- the atoms which are different from C (carbon) and H (hydrogen) can preferably be selected from the group consisting of, preferably, N, O, S. P, Si, F, Cl, Br and I.
- the branched or unbranched, substituted or unsubstituted aliphatic group which optionally contains one or more atoms different from C and H can preferably be selected from, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, 2-methoxy-1-ethyl, 2-ethoxy-1-ethyl, 2-hydroxy-1-ethyl, 1-hydroxy-2-propyl, 2-hydroxy-1-propyl, 4-hydroxy-1-butyl, their higher homologues or their isomers, their corresponding halogenated groups.
- the halogenated groups can be selected from preferably, for example, 2,2,2-triflouroethyl and 1,1,1,3,3,3-hexafluoro-2-propyl.
- the branched or unbranched, substituted or unsubstituted cycloaliphatic group which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but is not limited to, cyclopentyl and cyclohexyl.
- the branched or unbranched, substituted or unsubstituted araliphatic group which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but is not limited to, benzyl, 1-phenyl ethyl and 2-phenyl ethyl.
- the substituted or unsubstituted aromatic group wWhich optionally contains one or more atoms different from C and H can preferably be selected from, for example, but is not limited to, phenyl, hydroxyphenyl or its isomers, methoxyphenyl or its isomers, methylphenyl or its isomers, nitrophenyl or its isomers, chlorophenyl or its isomers, fluorophenyl or its isomers, bromophenyl or its isomers, iodophenyl or its isomers.
- Suitable amines to be used in forming the N-substituted carbamates can be selected from, for example, but are not limited to, primary arnines and secondary amines. Primary amines are preferred.
- R is selected from the groups:
- the ⁇ , ⁇ -diaminoalkanes can be selected from preferably, but are not limited to, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane and 1,6 diaminohexane.
- the branched or unhranched, substituted or unsubstituted cycloaliphatic primary amines which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, cyclohexylamine, cyclohexylainines with substituted cycloaliphatic ring, diaminocyclohexane or its isomers, diaminocyclohexanes with substituted cycloaliphatic ring, isophorone diamine, 4,4′-diamino dicyclohexylmethane or its isomers, 2,4′-diamino dicyclohexylmethane or its isomers, 2,2′-diamino dicyclohexylmethane or its isomers.
- the branched or unbranched, substituted or unsubstituted araliphatic primary amines which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, benzylamine, 2-phenylethylamine, 1-phenylethylamine, o-xylylene diamine m-xylylene diamine, p-xylylene diamine.
- the substituted or unsubstituted aromatic primary amines which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, aniline, methoxyaniline or its isomers, toluidine or its isomers, nitroaniline or its isomers, fluoroaniline or its isomers, chloroaniline or its isomers, bromoaniline or its isomers, iodoaniline or its isomers, o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, aromatic ring substituted phenylene diamines, diaminotoluenes or its isomers, diamino diphenylmethane or its isomers or homologues, naphthalene diamines or its isomers.
- the aromatic ring substituted phenylene diamines can preferably be selected from, for example, but are not limited to, tetramethyl phenylene diamine.
- the diaminotoluenes or its isomers can preferably be selected from, for example, but are not limited to, 2,4-diaminotoluene or 2,6-diaminotoluene.
- the isomer of diamino diphenylmethane can preferably be selected from, for example, but is not limited to, 4,4′-diamino diphenylmethane, 2,4′-diamino diphenylmethane and 2,2′-diamino diphenylmethane.
- the isomer of naphthalene diamines can preferably be selected from, for example, but is not limited to, 1,4-naphthaline diamine, 1,5-naphthaline diamine and 1,8-naphthaline diamine.
- the substituted or unsubstituted aromatic primary amines which optionally contains one or more atoms different from C and H can also include a mixture of amines obtained by the condensation reaction of aniline and formaldehyde, and the mixture comprises diamino diphenylmethane or its isomers, polyfunctional amines of the diphenylmethane series or its isomers or their higher homologues,
- the reaction can be run by using a single amine, or a mixture of two or more of the aforementioned amines.
- the amounts of the raw materials can be employed in such way that at least 1 mole of carbamate (H 2 N—CO—OR) is employed for each mole of amino groups coming from the primary amine R′(—NH 2 ) n ; preferably from 1 to 30 moles of carbamate (H 2 N—CO—OR) are employed for each mole of amino groups coming from the primary amine R′(—NH 2 ) n ; more preferably from 1- to 15 moles of carbamate (H 2 N—CO—OR) are employed for each mole of amino groups coming from the primary amine R′(—NH 2 ) n ; and most preferably from 4 to 10 moles of carbamate (H 2 N—CO—OR) are employed for each mole of amino groups coming from the primary amine R′(—NH 2 ) n .
- carbamate H 2 N—CO—OR
- the process can be run either with or without an additional solvent.
- the excess of carbamate (H 2 N—CO—OR) serves as solvent.
- the additional solvent can be a single solvent or a mixture of two or more solvents.
- the additional solvent can preferably be selected from, for example, but is not limited to, aliphatic or aromatic hydrocarbons or their halogenated derivatives, polar solvents, and R—OH solvents.
- the aliphatic or aromatic hydrocarbons or their halogenated derivatives can preferably be selected from, for example, but are not limited to, benzene, toluene, xylene or its isomers, ethylbenzene, chlorobenzene, dichlorobenzene or its isomers.
- the polar solvents can preferably be selected from, for example, but are not limited to, acetone, butanone, dimethylformamide, dimethyl sulfone, dimethyl sulfoxide, 1-octyl-3-methylimidazolium tetrafluoroborate ([C4-mim]BF 4 ), 1-butyl-3-methylimidazolium tetrafluoroborate ([C4-mim]BF 4 ), 1-butyl-3-methyl-imidazolium tetrafluorophosphate ([bmim]BF 4 ) or 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]BF 6 ).
- the R—OH solvents having the same R.
- the carbamates (H 2 N—CO—OR) as reactant not only can facilitate the reaction, but also can depress side-reactions and enhance product selectivity.
- a variety of intermediates and/or byproducts can be formed, e.g. substituted ureas based on the primary amines.
- the byproducts can be converted partially or completely to carbamates by alcoholysis with the hydroxyl component of R—OH.
- the molar ratio between hydroxyl groups originating from the R—OH and amino groups originating from the primary amine can preferably be selected from, for example, but is not limited to, 1 to 100, more preferably 1 to 50, most preferably 1 to 10, and most particularly preferably 2 to 8.
- the amount of catalyst employed is not critical, but shall be sufficient to provide appropriate reaction rates.
- the amount of catalyst applied can preferably be selected from, for example, but is not limited to, 20 parts by weight, more preferably from 0.1 to 15 parts by weight, particularly preferably from 1 to 10 parts by weight, and most preferably from 3 to 8 parts by weight, based on 100 parts by weight of the amine.
- the reaction temperature can preferably be selected from, for example, but is not limited to, greater than or equal to 100° C., more preferably 100 to 300° C., particularly preferably 120 to 220° C., and most preferably 140 to 200° C. If the reaction temperature is too low, the reaction rate might be reduced too much. If the reaction temperature is too high, the risk of unwanted side reaction significantly reducing yield and/or selectivity will increase.
- the reaction time depends on other reaction conditions and can be determined in orienting experiments.
- the reaction time is preferably less than or equal to 24 hours, more preferably less than or equal to 15 hours; further more preferably less than or equal to 10 hours, particularly preferably from 2 to 10 hours, and most preferably from 3 to 8 hours.
- the reaction pressure is the autogenous pressure developing at the chosen reaction temperature.
- the reaction pressure can also be modified by adding a gas inert under the reaction conditions, which can be selected from, but is not limited to, a nitrogen gas, a noble gas, carbon dioxide, or mixtures of the aforesaid gases.
- the reaction pressure can preferably be selected from, for example, but is not limited to, 1 to 50 atm, more preferably 1 to 30 atm, and most preferably 5 to 25 atm.
- the catalyst can he employed in fixed bed, fluidized bed or slurry reactor.
- the reaction can be carried out continuously, semi-continuously or batch-wise.
- the order of the addition of the raw materials and/or of the catalyst to the reactor is not critical, and the best way and/or most advantageous order to add the material and catalyst can be determined in orienting experiments.
- the ammonia formed during the reaction can be removed from the reactor by appropriate means continuously or intermittently to shift the reaction equilibrium to the product side.
- Appropriate reactors can preferably be selected from, for example, but are not limited to, stirred reactors and tubular reactors.
- the tubular reactors can preferably be selected from, for example, but are not limited to, tubular reactors with or without inserts, tubular reactors with or without mixing elements, tubular reactors with or without redispersing elements, tubular reactors with a combination of two or more members of the group including inserts, mixing elements and redispersing elements.
- the starting materials, intermediates, solvents and/or catalysts can be recovered and/or recycled to any appropriate step of the reaction process.
- reaction product can be removed from the reactor.
- the process of work-up and/or product isolation can be achieved by means of any appropriate technique/means/process step.
- the appropriate technique/means/process step can be selected from, but is not limited to, distillation, crystallization, filtration, sedimentation, decantation, centrifugation, extraction, membrane separation, or other means, or a combination of two or more of the aforesaid techniques/means.
- the catalyst can be recovered and/or recycled by means of any appropriate technique/means/process step.
- the appropriate technique/means/process step can preferably be selected from, for example, but is not limited to, distillation, crystallization, filtration, sedimentation, decantation, centrifugation, extraction, membrane separation, or other means or by a combination of two or more of the aforesaid techniques/means.
- the catalyst can be recycled either without any further treatment or after an appropriate reconditioning or treatment step, including, but not limited to, separating the catalyst, washing the catalyst thoroughly with an appropriate solvent, drying, or a combination of two or more of the aforesaid techniques/means. Drying can be performed in virtue of various manners such as, for example, but not limited to, vacuum drying, microwave drying, ultrasonic drying, supercritical fluid drying or a combination of two or more of the aforesaid techniques/means.
- the synthesis reactions were carried out in a stainless steel autoclave with inner volume of 100 cm 3 .
- the starting materials and catalyst were charged into the reactor.
- the air in the autoclave was replaced.
- the reactor was heated to the desired temperature for a defined period of time as indicated in the examples.
- the resultant products were analyzed either by gas chromatography (GC) or by liquid chromatography (LC), depending on the choice of the starting material, the identification of the products was performed by “liquid chromatography-mass spectrometry” (LC-MS). Yields of products were calculated based on the weight of aromatic amine used.
- V 2 O 5 of analytically pure grade was used as a catalyst support. Phase composition of the V 2 O 5 was confirmed by XRD (X-Ray Diffraction). The BET surface area of the V 2 O 5 was about 40 m 2 /g, and the pore volume of the V 2 O 5 was 0.4 cm 3 /g.
- the catalyst was prepared by impregnating V 2 O 5 into a solution containing 5 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the V 2 O 5 .
- the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere. After drying, the catalyst precursor was calcinated at 450° C. for 4 hours.
- the resulting catalyst was named catalyst A.
- V 2 O 5 of analytically pure grade was used as a catalyst support. Phase composition of the V 2 O 5 was confirmed by XRD. The BET surface area of the V 2 O 5 was about 40 m 2 /g, and the pore volume of the V 2 O 5 was 0.4 cm 3 /g.
- the catalyst was prepared by impregnating V 2 O 5 into a solution containing 1 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the V 2 O 5 .
- the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, and then calcinated at 450° C. for 4 hours.
- the resulting catalyst was named catalyst B.
- V 2 O 5 of analytically pure grade was used as a catalyst support. Phase composition of the V 2 O 5 was confirmed by XRD. The BET surface area of the V 2 O 5 was about 40 m 2 /g, and the pore volume of the V 2 O 5 was 0.4 cm 3 /g.
- the catalyst was prepared by impregnating V 2 O 5 into a solution containing 15 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the V 2 O 5
- the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere.
- the dried catalyst precursor was then calcinated at 450° C. for 4 hours.
- the resulting catalyst was named catalyst C.
- V 2 O 5 of analytically pure grade was used as a catalyst support. Phase composition of the V 2 O 5 was confirmed by XRD. The BET surface area of the V 2 O 5 was about 40 m 2 /g, and the pore volume of the V 2 O 5 was 0.4 cm 3 /g.
- the catalyst was prepared by impregnating V 2 O 5 into a solution containing 5 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the V 2 O 5 .
- the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, thereafter, calcined at 250° C. for 4 hours.
- the resulting catalyst was named catalyst D.
- V 2 O 5 of analytically pure grade was used as a catalyst support. Phase composition of the V 2 O 5 was confirmed by XRD. The BET surface area of the V 2 O 5 was about 40 m 2 /g, and the pore volume of the V 2 O 5 was 0.4 cm 3 /g.
- the catalyst was prepared by impregnating V 2 O 5 into a solution containing 5 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the V 2 O 5 .
- the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, and thereafter, calcinated at 650° C. for 4 hours.
- the resulting catalyst was named catalyst E.
- V 2 O 5 of analytically pure grade was used as a catalyst support. Phase composition of the V 2 O 5 was confirmed by XRD. The BET surface area of the V 2 O 5 was about 40 m 2 /g, and the pore volume of the V 2 O 5 was 0.4 cm 3 /g.
- the catalyst was prepared by impregnating V 2 O 5 into a solution containing 5 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the V 2 O 5 .
- the obtained catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, thereafter, calcinated at 450° C. for 2 hours.
- the resulting catalyst was named catalyst F.
- ⁇ -Alumina of analytically pure grade was used as a catalyst support. Phase composition of the ⁇ -Alumina was confirmed by XRD. The BET surface area of the ⁇ -Alumina was about 230 m 2 /g, and the pore volume of the ⁇ -Alumina was 0.65 cm 3 /g.
- the catalyst was prepared by impregnating ⁇ -Alumina into a solution containing 5 wt % H 3 PW 12 O 40 .
- the volume of the impregnation solution corresponded to the volume of the ⁇ -Alumina.
- the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, thereafter, calcinated at 450° C. for 2 hours.
- the resulting catalyst was named catalyst G.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 91.8%, 88.3% and 81.1%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 91.0%, 85.7% and 78.0%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 90.3%, 86.9% and 78.5%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 85.4%, 78.5% and 67.0%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 82.5%, 81.5% and 67.1%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 88.2%, 80.2% and 70.7%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the reaction step as described above was repeated five times. Therefore, after each run the catalyst A was separated from the reaction mixture by filtration, washed with methanol, dried at 120° C. for 12 hours and charged back into the reactor for the next run. After completion of the 5 repeated runs, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 88.5%, 82.7% and 73.2%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 85.7%, 82.4% and 70.6%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 92.3%, 89.1% and 82.2%, respectively.
- the reaction was performed at 140° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 60.1%, 72.4% and 43.5%, respectively.
- the reaction was performed at 180° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 83.8%, 77.3% and 64.8%, respectively.
- the reaction was performed at 160° C. for 2 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 80.6%, 78.5% and 63.3%, respectively.
- the reaction was performed at 160° C. for 6 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 92.5%, 85.4% and 79.0%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 95.3%, 83.6% and 79.7%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 82.4%, 92.4% and 76.1%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 66.5%, 70.8% and 47.1%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 92.6%, 89.1% and 82.5%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-ethyl N-phenyl carbamate (EPC) was analyzed by gas chromatography.
- the aniline conversion, EPC selectivity and EPC yield were 82.6%, 79.3% and 65.5%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-n-butyl N-phenyl carbamate (BPC) was analyzed by gas chromatography.
- the aniline conversion, BPC selectivity and BPC yield were 50.1%, 75.0% and 37.6%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of corresponding biscarbamate was analyzed by gas chromatography.
- the toluene diamine conversion, selectivity and yield of the corresponding biscarbamate were 40.1%, 76.6% and 30.7%, respectively.
- the reaction was performed at 160° C. for 4 hours under autogenous pressure.
- the ammonia formed during the reaction was continuously removed from the reactor.
- the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography.
- the aniline conversion, MPC selectivity and MPC yield were 74.3%, 72.5% and 53.9%, respectively.
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Abstract
The present invention relates to a novel catalyst for producing N-substituted carbamates, the preparation of the catalyst and an improved method for producing N-substituted carbamates from these novel catalysts. The active component of the catalyst is a heteropoly acid and the catalyst support comprises a metal oxide or a metalloid oxide. The catalyst can be used to promote the reaction of carbamate and amine, thereby generating N-substituted carbamates with high yield. In the presence of the catalyst, the reaction conditions are relatively mild, the catalytic activity and selectivity of the reaction are high, and the reaction time is relatively short. Furthermore, the catalyst can be conveniently separated from the reaction system and recycled, therefore, the catalyst can be used to facilitate the further scale-up test and commercial application.
Description
- The present patent application claims the right of priority under 35 U.S.C. §119 (a)-(d) of Chinese Patent Application No. 200910051496.4, filed May 19, 2009.
- The present invention relates to N-substituted carbamates, and particularly to a catalyst for preparing these N-substituted carbamates. This invention also relates to the novel catalyst, to the preparation of the catalyst, and to the use thereof.
- N-substituted carbamates represent a class of important organic intermediates, which can be used for the manufacture of agrochemicals, dyes, pharmaceuticals, ureas, and isocyanates. Furthermore, they can also be applied as protective groups of amides in various organic syntheses.
- The synthesis of N-substituted carbamates has received considerable attention due to their wide applications. For example, U.S. Pat. No. 3,763,217 and U.S. Pat. No. 4,268,683 disclose the synthesis of N-substituted carbamates by reacting aromatic amines with organic carbonates in the presence of AlCl3, FeCl3, UO2(NO)2, zinc acetate, zinc propionate, or zinc naphthenate as a catalyst, respectively. This method has low selectivity for the desired products. Moreover, the catalyst activity is restricted by the aromatic amines. Both DE 2943480 and U.S. Pat. No. 4,381,403 disclose that homogeneous ZnCl2 or tertiary amine can be used as a catalyst in the synthesis of N-substituted carbamates by reacting carbamates and amines. However, these catalysts are difficult to separate and recover from the reaction mixtures. Thus, these catalyst can not be conveniently recycled.
- From the perspective of commercial application, it is necessary to develop a new catalyst for preparing N-substituted carbamates. The catalyst should not only be capable of preparing the targeted products in high yields, but should also be convenient to separate from the product and recycled.
- One aspect of the present invention is to provide a method for preparing N-substituted carbamates. In accordance with the present invention, this method comprises reacting a carbamate with an amine in the presence of a catalyst to form an N-substituted carbamate, wherein the catalyst comprises a heteropoly acid as active component and a metal oxide or a metalloid oxide as catalyst support.
- Another aspect of the present invention is to provide a novel catalyst which is suitable for preparing N-substituted carbamates. In accordance with the present invention, the catalyst comprises an active component and a catalyst support component. The active component of the catalyst is a heteropoly acid, and the component of the catalyst support is a metal oxide or a metalloid oxide.
- The third aspect of the present invention is to provide a method for preparing this catalyst. According to the present invention, the method comprises (1) impregnating a catalyst support into a heteropoly acid solution comprising one or more heteropoly acids to form a catalyst precursor, and (2) calcinating the catalyst precursor to obtain a catalyst, wherein the calcination temperature ranges from 150 to 1000° C.
- In accordance with the present invention, N-substituted carbamates can be prepared with high yield by reacting N-unsttbstituted carbamates with amines in the presence of the catalyst provided here. The reaction system can be easily scaled up, due to the fact that the reaction conditions are relatively mild, and the activity and selectivity of the catalyst are high, and the reaction time is rather short. Furthermore, the catalyst can be easily separated from the reaction system and recycled.
- Heteropoly acids (HPAs) are commonly regarded as attractive catalytic materials and are applied to a variety of reactions such as, for example, dehydration, cyclization, esterification, and so on. However, homogeneous HPAs are difficult to separate and recover from the reaction mixture. Therefore, HPAs can not be conveniently recycled.
- The present invention provides a new catalyst comprising an active component and a catalyst support component, with the active component comprising a h.eteropoly acid, and the catalyst support component comprising a metal oxide or a metalloid oxide. It has been found that in the presence of such catalyst, carbamates react with amines to form N-substituted carbamates in high yield. In addition, the catalyst can be separated from the reaction system and recycled easily. This makes commercial scale-up and application commercially feasible.
- A preferred embodiment of the catalyst is hat the catalyst support component comprises vanadium pentoxide (V2O5). It has been found that there is a synergistic action between V2O5 as the catalyst support component, and Keggin type HPAs as the active component of the catalyst, which further enhance the selectivity and increase the yield of the reaction.
- The active component of the catalyst of the present invention is a Heteropoly acid (HPAs), preferably a Keggin type Heteropoly acids (HPAs). More preferred Keggin type Heteropoly acids include tungstophoric acid (H3PW12O40.nH2O), molybdophosphoric acid (H3PMo12O4.nH2O), tungstosilicic acid (H4SiW12O40nH2O), molybdosilicic acid (H4SiMo12O40.nH2O), or their mixtures. It is most preferred that the Keggin type Heteropoly acid be selected from the group consisting of tungstophosphoric acid (H3PW12O40.nH2O), molybdophosphoric acid (H3PMo12O40.nH2O) and mixtures thereof.
- The catalyst of this invention also requires a catalyst support component. This catalyst support component is a metal oxide or a metalloid oxide. Preferably, the metal oxide or metalloid oxide is selected from the group consisting of zirconia, titania, zinc oxide, silica, magnesia, calcium oxide, stannic oxide, barium oxide, cerium oxide, lanthanum oxide, vanadium pentoxide, alumina and mixtures thereof. More preferably, the catalyst support component is selected from the group consisting of vanadium pentoxide, alumina and mixtures thereof Vanadium pentoxide is a most preferred catalyst support component.
- The average diameter of the catalyst support is preferably (but not limited to) 0.1 to 4 mm, more preferably 0.5 to 3 mm, and most preferably 1 to 2 mm.
- The pore volume of the catalyst support is preferably (but not limited to) 0.01 to 10 cm3/g, more preferably 0.1 to 1 cm3/g, most preferably 0.2 to 0.8 cm3/g, and most particularly preferably 0.4 to 0.6 cm3/g.
- The BET surface area of the catalyst support is preferably (but not limited to) less than or equal to 300 m2/g, more preferably from 1 to 250 m2/g, most preferably from 5 to 100 m2/g, and most particularly preferably from 10 to 60 m2/g.
- There are no special limitations with regard to the shape of the catalyst. For example, the shape of the catalyst can be spherical, cylindrical or irregular. The loading of the active component can be preferably (but is not limited to) from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, and most preferably from 4 to 7% by weight, based on 100% by weight of the catalyst support.
- The method for preparing the catalyst comprises the steps of impregnating and cal.cinating, etc. The method can additionally include a drying step for the catalyst precursor after the impregnating step and before the calcinating step. The temperature of the drying step can be from (but is not limited to) less than or equal to 140° C., and more preferably from 90 to 120° C., The time of the drying step can be, but is not limited to, less than or equal to 24 hours, more preferably less than or equal to 15 hours, and most preferably from 5 to 12 hours. There is no special limitation with regard to the pressure in the drying step, however, drying preferably occurs at 1 atm. The atmosphere of the drying step can be selected from (but is not limited to) preferably air, oxygen, nitrogen, etc. More preferably the atmosphere of the drying step is air and/or oxygen, and is most preferably air.
- In the impregnating step, one heteropoly acid or a mixture of two or more heteropoly acids is dissolved in a solvent to form a heteropoly acid solution. The heteropoly acid can be selected from (but is not limited to) preferably tungstophosphoric acid (H3PW12O40.nH2O) molybdophosphoric acid (H3PMo12O40.nH2O), tungstosilicic acid (H4SiW12O40.nH2O), molybdosilicic acid (H4SiMo12O40.nH2O), or their mixtures; and most preferably tungstophosphoric acid (H3PW12O40.nH2O), molybdophosphoric acid (H3PMo12O40.nH2O), or their mixtures. The solvent can be selected from, but is not limited to, water, an aqueous solvent, a non-aqueous solvent, or any mixture of the aforementioned solvents. Suitable non-aqueous solvent can be selected from, preferably, ethers, alcohols, ketones, nitriles or amides; more preferably, diethyl ether, methanol, ethanol, propanol, butyl alcohol, acetone, butanonc, acetonitrile, dimethyl sulfone, dimethyl sulfoxide or dimethylformamide.
- The pH value of the aqueous solution comprising the precursor of the catalytically active component can be adjusted through the addition of hydrated or non-hydrated acids. The hydrated or non-hydrated acids can be selected from, but are not limited to, HCl, HNO3, H2SO4, H3PO4 or CH3COOH.
- The catalyst precursor is obtained by impregnating a catalyst support into a solution containing the heteropoly acids. The component of the catalyst support is a metal oxide or a metalloid oxide. The metal oxide or metalloid oxide acids can be selected from, but is not limited to, preferably zirconia, titania, zinc oxide, silica, magnesia, calcium oxide, stannic oxide, barium oxide, cerium oxide, lanthanum oxide, vanadium pentoxide, alumina, or their mixtures. More preferably, the metal oxide or metalloid oxide acids are selected from vanadium pentoxide, alumina, or their mixtures. Vanadium pentoxide is the most preferred metal oxide or metalloid oxide acid.
- There is no special limitation with regard to the temperature of the impregnating step. Preferably impregnating occurs at room temperature. The time of the impregnating step is typically less than or equal to 20 hours, and preferably from 1 to 4 hours.
- In the calcination step, the calcination temperature should be high enough to result in the transformation of the catalyst precursor to the catalyst. The calcination temperature can be from preferably 200 to 1000° C., more preferably from 300 to 700° C. There is no special limitations with regard to the calcination time. Preferably the time ranges from 1 to 20 hours, and more preferably from 2 to 10 hours. The calcination step can be carried out either in an inert atmosphere or in an oxidizing atmosphere. The inert atmosphere can be selected from preferably (hut is not limited to) a nitrogen gas, a noble gas, a non-oxidizing gas, a non-reducing gas or a mixture of two or more of the aforesaid gases. Nitrogen is more preferred as the inert gas. The oxidizing atmosphere can be selected from preferably (but is not limited to) oxygen gas or an oxygen containing gas, and more preferably is an oxygen containing gas. The oxidizing atmosphere is most preferably air. A mixture of air and nitrogen can be applied as well.
- One aspect of the present invention provides a method for preparing N-substituted carbamates which correspond to the general formula:
-
R′(NH—CO—OR)n - This process comprises (1) reacting (a) one or more N-unsubstantiated carbamates (H2N—CO—OR), with (b) one or more amines, in the presence of (c) the novel catalyst described herein. The reaction equation is:
-
nH2N—CO—OR+R′NH2)n→R′(NH—CO—OR)n +nNH3 - The N-unsubstituted carbamates (H2N—CO—OR) can be obtained via known synthetic routes such as the reaction between urea and conesponding compound containing a hydroxyl group.
- For the N-unsubstituted carbamates (H2N—CO—OR), R can be selected from preferably, but is not limited to,
-
- a) a branched or unbranched, substituted or unsubstituted aliphatic group, which optionally contains one or more atoms different from C and H;
- b) a branched or unbranched, substituted or unsubstituted cycloaliphatic group, which optionally contains one or more atoms different from C and H;
- c) a branched or unbranched, substituted or unsubstituted araliphatic group, which optionally contains one or more atoms different from C and H; or
- d) a substituted or unsubstituted aromatic group, Which optionally contains one or more atoms different from C and H.
- In accordance with the above description, the atoms which are different from C (carbon) and H (hydrogen) can preferably be selected from the group consisting of, preferably, N, O, S. P, Si, F, Cl, Br and I.
- The branched or unbranched, substituted or unsubstituted aliphatic group which optionally contains one or more atoms different from C and H can preferably be selected from, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, 2-methoxy-1-ethyl, 2-ethoxy-1-ethyl, 2-hydroxy-1-ethyl, 1-hydroxy-2-propyl, 2-hydroxy-1-propyl, 4-hydroxy-1-butyl, their higher homologues or their isomers, their corresponding halogenated groups. The halogenated groups can be selected from preferably, for example, 2,2,2-triflouroethyl and 1,1,1,3,3,3-hexafluoro-2-propyl.
- The branched or unbranched, substituted or unsubstituted cycloaliphatic group which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but is not limited to, cyclopentyl and cyclohexyl.
- The branched or unbranched, substituted or unsubstituted araliphatic group which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but is not limited to, benzyl, 1-phenyl ethyl and 2-phenyl ethyl.
- The substituted or unsubstituted aromatic group wWhich optionally contains one or more atoms different from C and H can preferably be selected from, for example, but is not limited to, phenyl, hydroxyphenyl or its isomers, methoxyphenyl or its isomers, methylphenyl or its isomers, nitrophenyl or its isomers, chlorophenyl or its isomers, fluorophenyl or its isomers, bromophenyl or its isomers, iodophenyl or its isomers.
- Suitable amines to be used in forming the N-substituted carbamates can be selected from, for example, but are not limited to, primary arnines and secondary amines. Primary amines are preferred.
- The primary amines can be characterized by the general formula:
-
R′(NH2)n, - wherein:
-
- n is 1, 2, or any integer more than 2;
- R′ can be selected from the following groups.
- In accordance with the present invention, R is selected from the groups:
- a) a branched or =branched, substituted or unsubstituted aliphatic group which optionally contains one or more atoms different from C and H;
- a branched or unbranched, substituted or unsubstituted cycloaliphatic group which optionally contains one or more atoms different from C and H;
- c) a branched or unbranched, substituted or unsubstituted araliphatic group which optionally contains one or more atoms different from C and H; and
- d) a substituted or unsubstituted aromatic group which optionally contains one or more atoms different from C and H.
- The above described R groups are not intended to be limiting.
- The branched or unbranched, substituted or =substituted aliphatic primary amines which optionally contain one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, methylamine, ethylamine, propylamine or its isomers, butylamine or its isomers, pentylamine or its isomers as well as their higher homologues, ethylene diamine, 1,2-diaminopropane, α,ω-diaminoalkanes or its isomers, substituted α,ω-diaminoalkanes or its isomers. The α,ω-diaminoalkanes can be selected from preferably, but are not limited to, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane and 1,6 diaminohexane.
- The branched or unhranched, substituted or unsubstituted cycloaliphatic primary amines which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, cyclohexylamine, cyclohexylainines with substituted cycloaliphatic ring, diaminocyclohexane or its isomers, diaminocyclohexanes with substituted cycloaliphatic ring, isophorone diamine, 4,4′-diamino dicyclohexylmethane or its isomers, 2,4′-diamino dicyclohexylmethane or its isomers, 2,2′-diamino dicyclohexylmethane or its isomers.
- The branched or unbranched, substituted or unsubstituted araliphatic primary amines which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, benzylamine, 2-phenylethylamine, 1-phenylethylamine, o-xylylene diamine m-xylylene diamine, p-xylylene diamine.
- The substituted or unsubstituted aromatic primary amines which optionally contains one or more atoms different from C and H can preferably be selected from, for example, but are not limited to, aniline, methoxyaniline or its isomers, toluidine or its isomers, nitroaniline or its isomers, fluoroaniline or its isomers, chloroaniline or its isomers, bromoaniline or its isomers, iodoaniline or its isomers, o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, aromatic ring substituted phenylene diamines, diaminotoluenes or its isomers, diamino diphenylmethane or its isomers or homologues, naphthalene diamines or its isomers. The aromatic ring substituted phenylene diamines can preferably be selected from, for example, but are not limited to, tetramethyl phenylene diamine. The diaminotoluenes or its isomers can preferably be selected from, for example, but are not limited to, 2,4-diaminotoluene or 2,6-diaminotoluene. The isomer of diamino diphenylmethane can preferably be selected from, for example, but is not limited to, 4,4′-diamino diphenylmethane, 2,4′-diamino diphenylmethane and 2,2′-diamino diphenylmethane. The isomer of naphthalene diamines can preferably be selected from, for example, but is not limited to, 1,4-naphthaline diamine, 1,5-naphthaline diamine and 1,8-naphthaline diamine.
- The substituted or unsubstituted aromatic primary amines which optionally contains one or more atoms different from C and H can also include a mixture of amines obtained by the condensation reaction of aniline and formaldehyde, and the mixture comprises diamino diphenylmethane or its isomers, polyfunctional amines of the diphenylmethane series or its isomers or their higher homologues,
- In the present invention, the reaction can be run by using a single amine, or a mixture of two or more of the aforementioned amines.
- In the present invention, the amounts of the raw materials can be employed in such way that at least 1 mole of carbamate (H2N—CO—OR) is employed for each mole of amino groups coming from the primary amine R′(—NH2)n; preferably from 1 to 30 moles of carbamate (H2N—CO—OR) are employed for each mole of amino groups coming from the primary amine R′(—NH2)n; more preferably from 1- to 15 moles of carbamate (H2N—CO—OR) are employed for each mole of amino groups coming from the primary amine R′(—NH2)n; and most preferably from 4 to 10 moles of carbamate (H2N—CO—OR) are employed for each mole of amino groups coming from the primary amine R′(—NH2)n.
- In the present invention, the process can be run either with or without an additional solvent. In the latter case, the excess of carbamate (H2N—CO—OR) serves as solvent.
- When the reaction is conducted in the presence of additional solvent, the additional solvent can be a single solvent or a mixture of two or more solvents. The additional solvent can preferably be selected from, for example, but is not limited to, aliphatic or aromatic hydrocarbons or their halogenated derivatives, polar solvents, and R—OH solvents. The aliphatic or aromatic hydrocarbons or their halogenated derivatives can preferably be selected from, for example, but are not limited to, benzene, toluene, xylene or its isomers, ethylbenzene, chlorobenzene, dichlorobenzene or its isomers. The polar solvents can preferably be selected from, for example, but are not limited to, acetone, butanone, dimethylformamide, dimethyl sulfone, dimethyl sulfoxide, 1-octyl-3-methylimidazolium tetrafluoroborate ([C4-mim]BF4), 1-butyl-3-methylimidazolium tetrafluoroborate ([C4-mim]BF4), 1-butyl-3-methyl-imidazolium tetrafluorophosphate ([bmim]BF4) or 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]BF6). The R—OH solvents having the same R. group as in the carbamates (H2N—CO—OR) as reactant not only can facilitate the reaction, but also can depress side-reactions and enhance product selectivity. In the course of the process, a variety of intermediates and/or byproducts can be formed, e.g. substituted ureas based on the primary amines. The byproducts can be converted partially or completely to carbamates by alcoholysis with the hydroxyl component of R—OH. Generally, the molar ratio between hydroxyl groups originating from the R—OH and amino groups originating from the primary amine can preferably be selected from, for example, but is not limited to, 1 to 100, more preferably 1 to 50, most preferably 1 to 10, and most particularly preferably 2 to 8.
- The amount of catalyst employed is not critical, but shall be sufficient to provide appropriate reaction rates. Preferably, the amount of catalyst applied can preferably be selected from, for example, but is not limited to, 20 parts by weight, more preferably from 0.1 to 15 parts by weight, particularly preferably from 1 to 10 parts by weight, and most preferably from 3 to 8 parts by weight, based on 100 parts by weight of the amine.
- The reaction temperature can preferably be selected from, for example, but is not limited to, greater than or equal to 100° C., more preferably 100 to 300° C., particularly preferably 120 to 220° C., and most preferably 140 to 200° C. If the reaction temperature is too low, the reaction rate might be reduced too much. If the reaction temperature is too high, the risk of unwanted side reaction significantly reducing yield and/or selectivity will increase.
- The reaction time depends on other reaction conditions and can be determined in orienting experiments. The reaction time is preferably less than or equal to 24 hours, more preferably less than or equal to 15 hours; further more preferably less than or equal to 10 hours, particularly preferably from 2 to 10 hours, and most preferably from 3 to 8 hours.
- The reaction pressure is the autogenous pressure developing at the chosen reaction temperature. Alternatively, the reaction pressure can also be modified by adding a gas inert under the reaction conditions, which can be selected from, but is not limited to, a nitrogen gas, a noble gas, carbon dioxide, or mixtures of the aforesaid gases. The reaction pressure can preferably be selected from, for example, but is not limited to, 1 to 50 atm, more preferably 1 to 30 atm, and most preferably 5 to 25 atm.
- In the present invention, the catalyst can he employed in fixed bed, fluidized bed or slurry reactor.
- The reaction can be carried out continuously, semi-continuously or batch-wise. The order of the addition of the raw materials and/or of the catalyst to the reactor is not critical, and the best way and/or most advantageous order to add the material and catalyst can be determined in orienting experiments. Furthermore, the ammonia formed during the reaction can be removed from the reactor by appropriate means continuously or intermittently to shift the reaction equilibrium to the product side.
- Appropriate reactors can preferably be selected from, for example, but are not limited to, stirred reactors and tubular reactors. The tubular reactors can preferably be selected from, for example, but are not limited to, tubular reactors with or without inserts, tubular reactors with or without mixing elements, tubular reactors with or without redispersing elements, tubular reactors with a combination of two or more members of the group including inserts, mixing elements and redispersing elements.
- In the reaction process, the starting materials, intermediates, solvents and/or catalysts can be recovered and/or recycled to any appropriate step of the reaction process.
- After the reaction is finished, the reaction product can be removed from the reactor. The process of work-up and/or product isolation can be achieved by means of any appropriate technique/means/process step. The appropriate technique/means/process step can be selected from, but is not limited to, distillation, crystallization, filtration, sedimentation, decantation, centrifugation, extraction, membrane separation, or other means, or a combination of two or more of the aforesaid techniques/means.
- In the process of the reaction or after the reaction is finished, the catalyst can be recovered and/or recycled by means of any appropriate technique/means/process step. The appropriate technique/means/process step can preferably be selected from, for example, but is not limited to, distillation, crystallization, filtration, sedimentation, decantation, centrifugation, extraction, membrane separation, or other means or by a combination of two or more of the aforesaid techniques/means.
- The catalyst can be recycled either without any further treatment or after an appropriate reconditioning or treatment step, including, but not limited to, separating the catalyst, washing the catalyst thoroughly with an appropriate solvent, drying, or a combination of two or more of the aforesaid techniques/means. Drying can be performed in virtue of various manners such as, for example, but not limited to, vacuum drying, microwave drying, ultrasonic drying, supercritical fluid drying or a combination of two or more of the aforesaid techniques/means.
- The synthesis reactions were carried out in a stainless steel autoclave with inner volume of 100 cm3. The starting materials and catalyst were charged into the reactor. By flushing the reactor with N2, the air in the autoclave was replaced. Thereafter, the reactor was heated to the desired temperature for a defined period of time as indicated in the examples. At the end of the reaction, the resultant products were analyzed either by gas chromatography (GC) or by liquid chromatography (LC), depending on the choice of the starting material, the identification of the products was performed by “liquid chromatography-mass spectrometry” (LC-MS). Yields of products were calculated based on the weight of aromatic amine used.
- V2O5 of analytically pure grade was used as a catalyst support. Phase composition of the V2O5 was confirmed by XRD (X-Ray Diffraction). The BET surface area of the V2O5 was about 40 m2/g, and the pore volume of the V2O5 was 0.4 cm3/g.
- The catalyst was prepared by impregnating V2O5 into a solution containing 5 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the V2O5. After being impregnated for 4 hours, the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere. After drying, the catalyst precursor was calcinated at 450° C. for 4 hours. The resulting catalyst was named catalyst A.
- V2O5 of analytically pure grade was used as a catalyst support. Phase composition of the V2O5 was confirmed by XRD. The BET surface area of the V2O5 was about 40 m2/g, and the pore volume of the V2O5 was 0.4 cm3/g.
- The catalyst was prepared by impregnating V2O5 into a solution containing 1 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the V2O5. After being impregnated for 4 hours, the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, and then calcinated at 450° C. for 4 hours. The resulting catalyst was named catalyst B.
- V2O5 of analytically pure grade was used as a catalyst support. Phase composition of the V2O5 was confirmed by XRD. The BET surface area of the V2O5 was about 40 m2/g, and the pore volume of the V2O5 was 0.4 cm3/g.
- The catalyst was prepared by impregnating V2O5 into a solution containing 15 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the V2O5 After being impregnated for 4 hours, the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere. The dried catalyst precursor was then calcinated at 450° C. for 4 hours. The resulting catalyst was named catalyst C.
- V2O5 of analytically pure grade was used as a catalyst support. Phase composition of the V2O5 was confirmed by XRD. The BET surface area of the V2O5 was about 40 m2/g, and the pore volume of the V2O5 was 0.4 cm3/g.
- The catalyst was prepared by impregnating V2O5 into a solution containing 5 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the V2O5. After being impregnated for 4 hours, the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, thereafter, calcined at 250° C. for 4 hours. The resulting catalyst was named catalyst D.
- V2O5 of analytically pure grade was used as a catalyst support. Phase composition of the V2O5 was confirmed by XRD. The BET surface area of the V2O5 was about 40 m2/g, and the pore volume of the V2O5 was 0.4 cm3/g.
- The catalyst was prepared by impregnating V2O5 into a solution containing 5 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the V2O5. After being impregnated for 4 hours, the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, and thereafter, calcinated at 650° C. for 4 hours. The resulting catalyst was named catalyst E.
- V2O5 of analytically pure grade was used as a catalyst support. Phase composition of the V2O5 was confirmed by XRD. The BET surface area of the V2O5 was about 40 m2/g, and the pore volume of the V2O5 was 0.4 cm3/g.
- The catalyst was prepared by impregnating V2O5 into a solution containing 5 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the V2O5. After being impregnated for 4 hours, the obtained catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, thereafter, calcinated at 450° C. for 2 hours. The resulting catalyst was named catalyst F.
- γ-Alumina of analytically pure grade was used as a catalyst support. Phase composition of the γ-Alumina was confirmed by XRD. The BET surface area of the γ-Alumina was about 230 m2/g, and the pore volume of the γ-Alumina was 0.65 cm3/g.
- The catalyst was prepared by impregnating γ-Alumina into a solution containing 5 wt % H3PW12O40. The volume of the impregnation solution corresponded to the volume of the δ-Alumina. After being impregnated for 4 hours, the resultant catalyst precursor was dried at 120° C. for 12 hours in air atmosphere, thereafter, calcinated at 450° C. for 2 hours. The resulting catalyst was named catalyst G.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 91.8%, 88.3% and 81.1%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst B (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 91.0%, 85.7% and 78.0%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst C (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 90.3%, 86.9% and 78.5%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst D (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 85.4%, 78.5% and 67.0%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst E (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 82.5%, 81.5% and 67.1%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst F (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 88.2%, 80.2% and 70.7%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor.
- In order to check the reusability of the catalyst, the reaction step as described above was repeated five times. Therefore, after each run the catalyst A was separated from the reaction mixture by filtration, washed with methanol, dried at 120° C. for 12 hours and charged back into the reactor for the next run. After completion of the 5 repeated runs, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 88.5%, 82.7% and 73.2%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.30 g catalyst A (3.16 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 85.7%, 82.4% and 70.6%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.90 g catalyst A (9.48 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 92.3%, 89.1% and 82.2%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 140° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 60.1%, 72.4% and 43.5%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 180° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 83.8%, 77.3% and 64.8%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 2 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 80.6%, 78.5% and 63.3%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 6 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 92.5%, 85.4% and 79.0%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 3.25 g methanol (molar ratio of aniline., methyl carbamate and methanol was 1:8:1), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 95.3%, 83.6% and 79.7%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 32.50 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:10), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 82.4%, 92.4% and 76.1%, respectively.
- 9.50 g aniline, 15.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:2:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 66.5%, 70.8% and 47.1%, respectively.
- 9.50 g aniline, 75.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:10:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 92.6%, 89.1% and 82.5%, respectively.
- 9.50 g aniline, 71.27 g ethyl carbamate, 23.04 g ethanol (molar ratio of aniline, ethyl carbamate and ethanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-ethyl N-phenyl carbamate (EPC) was analyzed by gas chromatography. The aniline conversion, EPC selectivity and EPC yield were 82.6%, 79.3% and 65.5%, respectively.
- 9.50 g aniline, 93.72 g n-butyl carbamate, 37.06 g n-butanol (molar ratio of aniline, n-butyl carbamate and n-butanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-n-butyl N-phenyl carbamate (BPC) was analyzed by gas chromatography. The aniline conversion, BPC selectivity and BPC yield were 50.1%, 75.0% and 37.6%, respectively.
- 12.22 g 2,4-toluene diamine, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of 2,4-toluene diamine, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst A (6.32 parts by weight, based on 100 parts by weight of aniline were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of corresponding biscarbamate was analyzed by gas chromatography. The toluene diamine conversion, selectivity and yield of the corresponding biscarbamate were 40.1%, 76.6% and 30.7%, respectively.
- 9.50 g aniline, 60.00 g methyl carbamate, 16.25 g methanol (molar ratio of aniline, methyl carbamate and methanol was 1:8:5), and 0.60 g catalyst G (6.32 parts by weight, based on 100 parts by weight of aniline) were charged into the reactor.
- The reaction was performed at 160° C. for 4 hours under autogenous pressure. The ammonia formed during the reaction was continuously removed from the reactor. After the completion of the reaction, the yield of O-methyl N-phenyl carbamate (MPC) was analyzed by gas chromatography. The aniline conversion, MPC selectivity and MPC yield were 74.3%, 72.5% and 53.9%, respectively.
- Although the present invention is illustrated through Examples, it is not limited by these Examples in any way. Without departing from the spirit and scope of this invention, those skilled in the art can make any modifications and alternatives. And the protection of this invention is based on the scope defined by the claims of this application.
Claims (13)
1-12. (canceled)
13. A catalyst for preparing a N-substituted carbamate, wherein the active component of the catalyst comprises a heteropoly acid and the component of the catalyst support comprise a metal oxide or metalloid oxide.
14. The catalyst of claim 13 , wherein the heteropoly acid is a Keggin type heteropoly acid.
15. The catalyst of claim 14 , wherein the heteropoly acid is selected from the group consisting of H3PW12O40.nH2O, H3PMo12O40.nH2O, H4SiW12O40.nH2O and H4SiMo12O40.nH2O.
16. The catalyst of claim 13 , wherein the catalyst support component comprising a metal oxide or a metalloid oxide is selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, silicon oxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide, lanthanum oxide, vanadium pentoxide, aluminium oxide and mixtures thereof.
17. The catalyst of claim 16 , wherein the metal oxide is selected from the group consisting of a vanadium pentoxide, an aluminium oxide and mixtures thereof.
18. The catalyst of claim 13 , wherein the load of the active component of the catalyst is from 0.1 to 20 wt. %, based on 100 wt. % of the catalyst support.
19. A method for preparing the catalyst of claim 13 , comprising
(1) impregnating (i) a catalyst support into (ii) a heteropoly acid solution comprising one or more heteropoly acids to form a catalyst precursor, and
(2) calcinating said catalyst precursor at a temperature of from 150 to 1000° C. to obtain a catalyst.
20. The method of claim 19 , wherein said heteropoly acid is selected from the group consisting of H3PW12O40.nH2O, H3PMo12O40. nH2O, H4SiW12O40.nH2O and H4SiMo12O40.nH2O.
21. The method of claim 19 , wherein said metal oxide or said metalloid oxide is selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, silicon oxide, magnesium oxide, calcium oxide, tin oxide, barium oxide, cerium oxide, lanthanum oxide, vanadium pentoxide, aluminium oxide and mixtures thereof.
22. The method of claim 21 , wherein said metal oxide is selected from the group consisting of a vanadium pentoxide, an aluminium oxide and mixtures thereof.
23. The method of claim 19 , wherein the load of the active component of the catalyst is from 0.1 to 20 wt. %, based on 100 wt. % of the catalyst support.
24. The method of claim 19 , additionally comprising a drying step after (1) said impregnating step and before (2) said calcinating step, wherein the temperature of the drying step is less than or equal to 140° C.
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CN200910051496.4 | 2009-05-19 | ||
CN200910051496.4A CN101891651B (en) | 2009-05-19 | 2009-05-19 | Catalyst used in preparation of N-substituted carbamate and preparation method and application thereof |
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US13/875,358 Abandoned US20130244867A1 (en) | 2009-05-19 | 2013-05-02 | Catalyst for producing n-substituted carbamates, and the preparation and application of the same |
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CN103752341A (en) * | 2014-01-24 | 2014-04-30 | 郑州大学 | Keggin type heteropoly acid-silicon oxide catalyst of mesopore structure and preparation method thereof |
CN104128193A (en) * | 2014-07-29 | 2014-11-05 | 清华大学深圳研究生院 | CeO2 based SCR catalyst and preparation method thereof |
CN104984766A (en) * | 2015-07-29 | 2015-10-21 | 河南师范大学 | B/POMs/TiO2 ternary composite photocatalytic material and preparation method thereof |
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Also Published As
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DE102010019341A1 (en) | 2010-12-09 |
CN101891651A (en) | 2010-11-24 |
US20100298592A1 (en) | 2010-11-25 |
CN101891651B (en) | 2014-03-12 |
US8450516B2 (en) | 2013-05-28 |
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