EP1461154A1 - Verfahren zur auftrennung von reaktionsgemischen und rückführung von quartärsalzen und basen - Google Patents
Verfahren zur auftrennung von reaktionsgemischen und rückführung von quartärsalzen und basenInfo
- Publication number
- EP1461154A1 EP1461154A1 EP02793097A EP02793097A EP1461154A1 EP 1461154 A1 EP1461154 A1 EP 1461154A1 EP 02793097 A EP02793097 A EP 02793097A EP 02793097 A EP02793097 A EP 02793097A EP 1461154 A1 EP1461154 A1 EP 1461154A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- reaction
- spoke
- solvent
- extraction
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000011541 reaction mixture Substances 0.000 title claims abstract description 24
- 150000003839 salts Chemical group 0.000 title claims description 50
- 238000004064 recycling Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims description 46
- 239000002904 solvent Substances 0.000 claims description 39
- 238000000605 extraction Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 32
- 239000002585 base Substances 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- -1 hexafluorophosphate Chemical compound 0.000 claims description 25
- 239000008346 aqueous phase Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 7
- 150000001768 cations Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 238000000066 reactive distillation Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 150000001983 dialkylethers Chemical class 0.000 claims 1
- 150000004816 dichlorobenzenes Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 230000006315 carbonylation Effects 0.000 abstract description 8
- 238000005810 carbonylation reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 21
- 239000001099 ammonium carbonate Substances 0.000 description 21
- 235000012501 ammonium carbonate Nutrition 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000010626 work up procedure Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229940031826 phenolate Drugs 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- VAOBNUXIUILSCN-UHFFFAOYSA-M tetrabutylazanium;phenoxide Chemical compound [O-]C1=CC=CC=C1.CCCC[N+](CCCC)(CCCC)CCCC VAOBNUXIUILSCN-UHFFFAOYSA-M 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002739 cryptand Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical group NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000004707 phenolate Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 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
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 1
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 1
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GZZSODFQERYCTP-UHFFFAOYSA-K [Mn+3].CC(=O)OC([O-])=O.CC(=O)OC([O-])=O.CC(=O)OC([O-])=O Chemical compound [Mn+3].CC(=O)OC([O-])=O.CC(=O)OC([O-])=O.CC(=O)OC([O-])=O GZZSODFQERYCTP-UHFFFAOYSA-K 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZLLNYWQSSYUXJM-UHFFFAOYSA-M tetraphenylphosphanium;phenoxide Chemical compound [O-]C1=CC=CC=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZLLNYWQSSYUXJM-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/06—Purification or separation of guanidine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0214—Aryloxylates, e.g. phenolates
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- 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
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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 application relates to a process for the separation and recycling of catalyst components of a chemical reaction mixture from the oxidative direct carbonylation.
- a noble metal catalyst preferably palladium, and also an inorganic are generally used.
- Cocatalyst e.g. manganese or cobalt salts
- a base e.g. aluminum, aluminum, copper, magnesium, calcium, magnesium, calcium, magnesium, calcium, magnesium, calcium, magnesium, calcium, magnesium, calcium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
- product mixtures are obtained in these reactions which, among other things, contain one or more quaternary salts A, a hydroxyaromatic compound B, reaction products C such as, for. B. water and diaryl carbonates, a base D (generally a salt of a hydroxyaromatic compound that may have been formed by deprotonation of a hydroxyaromatic compound with another base or used directly) and possibly solvents, further catalyst components, auxiliaries, and impurities.
- the task here is to separate one or more products C from quaternary salts and base (A and D) without destroying sensitive products C, and to return A, B and D as quantitatively as possible to the reaction without impurities contained in the reaction mixture.
- EP AI 913 197 discloses the processing of such streams in the absence of D by extraction and precipitation processes. However, this workup does not immediately lead to recyclable products without contamination.
- the invention therefore relates to a process for removing and recovering quaternary salts A of the formula (Q n + ) m (Y m ⁇ ) n and bases D of the formula (W I + ) k [(O) k Ar '] ⁇ , where n, m, k and 1 are integers and Ar 'is an aromatic radical, from reaction mixtures which, in addition to A and D, contain at least hydroxyaromatic compounds B and reaction products C and, optionally, a solvent, characterized in that the following steps are carried out:
- reaction mixture containing A, B, B2 and C and possibly solvent is separated into mixtures which contain bl.) C and possibly B and / or B2, and b2.) A and possibly B and / or B2.
- the separation process according to the invention is carried out at a temperature of -10 to 250 ° C., preferably 10 to 130 ° C., particularly preferably 20 to 90 ° C., and at a pressure of 0.1 to 200 bar, preferably 0.5 to 50 bar. carried out particularly preferably 1 to 10 bar, pressure and temperature being able to vary in the individual steps.
- Substances whose dielectric constants are less than about 20, preferably solvents with dielectric constants less than about 15 are preferably used as the inert organic solvent.
- the solvent preferably has a boiling point between about 40 and about 200 ° C.
- the inert solvent can be present in the reaction in a proportion of about 1 to 99%, preferably about 20 to 98%, particularly preferably about 40 to 95%, in the reaction mixture.
- the reaction mixture can, if appropriate, be concentrated by partially distilling off the solvent.
- Hydrocarbons, halogenated hydrocarbons and aromatic solvents such as chlorobenzene, dichlorobenzene, fluorobenzene, benzene, toluene, anisole, cyclohexane, petroleum ether, methylene chloride or 1,2-dichloroethane, dipolar aprotic solvents such as dimethylacetamide, acetonitrile, N-methylpyrrolidinone, ethers such as dioxane can be used as solvents , Tetrahydrofuran, t-butyl methyl ether and etherified glycols, optionally also mixtures of different solvents can be used. Chlorobenzene is particularly preferably used.
- Ar bears 1 to 4 substituents meaning -Cis-alkyl, C 6 -C 18 aryl, C 7 -C 18 aralkyl, C 1 -C alkoxy, fluorine, chlorine or Bromine.
- substituents meaning -Cis-alkyl, C 6 -C 18 aryl, C 7 -C 18 aralkyl, C 1 -C alkoxy, fluorine, chlorine or Bromine.
- Mono-hydroxy compounds are preferably used, and phenol is particularly preferred.
- the quaternary salts A used in the context of the present invention can be the quaternary cation Q n + typically compounds of the formula (XR r ⁇ n where X is an atom from the group Va or Via, r is an integer between 0 and 4 and R independently of one another is C 6 to C 18 aryl, C 7 to C 18 aralkyl or to C 20 alkyl radicals.
- these are, for example, ammonium, guanidinium, phosphonium or sulfonium salts substituted with organic radicals, if appropriate also mixtures thereof.
- Ammonium, guanidinium and , Phosphonium, sulfonium and sulfoxonium ions which have as organic radicals C 6 - to C 18 aryl, C - to C 18 aralkyl or - to C 18 alkyl radicals.
- the radicals can all be the same or different, and mixtures of several quaternary cations can optionally also be used.
- Two substituent radicals R can be replaced by one ring.
- Y m for example, halides, nitrates, sulfates, hydrogen sulfates, carbonates, hydrogen carbonates, phosphates, hydrogen phosphates, dihydrogen phosphates, tetrafluoroborates, carboxylates (preferably with dbis C 3 alkyl chains such as formates or acetates ), Perchlorate or Hexafluorophosphate can be used. Mixtures of different anions are possible.
- the letter m stands for a natural number between 1 and 3.
- hexaalkylguanidinium halides Preference is given to hexaalkylguanidinium halides, tetraalkylammonium halides and tetraarylphosphonium halides; tetrabutylammonium bromide, tetrabutylammonium chloride, tetraphenylphosphonium bromide and tetrabutylphosphonium bromide are particularly preferred.
- the amount of such a quaternary salt can be, for example, 0.01 to 30% by weight, based on the weight of the reaction mixture. This amount is preferably 0.5 to 15% by weight, particularly preferably 1 to 5% by weight.
- Base D is added in an amount independent of the stoichiometry.
- the ratio of platinum metal, e.g. Palladium to base is preferably chosen so that per mole of platinum metal, e.g. Palladium, 0.1 to 500, preferably 0.3 to 200, particularly preferably 0.9 to 130 equivalents of base can be used.
- Bases which can be used for the process according to the invention are alkali metal hydroxides, alkali metal salts or quaternary salts of weak acids such as alkari tert-butylates or alkali metal salts or quaternary salts of aromatic hydroxy compounds of the formula (W , + ) k [(O) n Ar '] ⁇ in which Ar '(OH) n in Ar' is defined in the same way as Ar and has the meaning given above and k and 1 stand for natural numbers.
- An alkali metal salt or quaternary salt of the aromatic hydroxy compound of the selection defined by B which may possibly also be converted into the organic carbonate, for example tetrabutylammonium or potassium phenolate, is very particularly preferably used.
- the quaternary salts can be ammonium, phosphonium, pyridinium, sulfonium or guanidinium salts which, as organic radicals, are C 6 to C 18 aryl, C 7 to C 18 aralkyl and / or to C 20 Possess alkyl radicals.
- the residues can all be the same or different, and mixtures of several quaternary salts can optionally be used.
- W 1+ therefore stands for alkali or quaternary cations of the type Q n + , preferably for lithium, sodium, potassium, hexaalkylguanidinium, tetraphenylphosphonium, tetrabutylammonium and tetrabutylphosphomium ions, particularly preferably for sodium and tetabutylammonium ions. Even if other bases (e.g.
- deprotonated hydroxyaromatics of type B such as phenolates
- W I + ) k [(O) k Ar '] ⁇ deprotonated hydroxyaromatic
- D is preferably chosen such that the compound B2 produced therefrom in step a) is identical to B.
- the quaternions Q n + and W 1+ are also preferably identical.
- B2 basically belongs to the group of hydroxyaromatics defined under B, ie it is a compound of the formula (Ar ') (OH) k , in which k represents an integer and Ar', which is as defined above, represents an aromatic radical belonging to the same group as Ar.
- reaction products C which, however, are preferably poorly water-soluble. Since the presence of hydroxyaromatic compounds is sometimes necessary for the process according to the invention, the process is most interesting for reaction products in which phenol or other hydroxyaromatic compounds are used as starting material, auxiliary substance, catalyst or other reaction component. The products of such reactions are therefore preferred.
- Examples are etherifications, esterifications, substitution reactions, oxidations and reductions of hydroxyaromatic compounds.
- a particularly interesting example is the direct carbonylation of phenol, in which diphenyl carbonate is produced from carbon monoxide, oxygen and phenol. Oligo- or diaryl carbonates are therefore preferred as product C, and diphenyl carbonate is particularly preferred.
- the reaction mixtures to be separated are characterized by the presence of the solvent or solvents, one or more quaternary salts A, one or more bases D, a hydroxyaromatic compound B and one or more reactants. tion products C. Some of the reaction products C can also be undesired by-products.
- reaction mixtures occur in the direct carbonylation of hydroxyaromatics.
- product mixtures are typically solvents (e.g. chlorobenzene), phenol (B), diphenyl carbonate and by-products (C), a phenolate base D (e.g. tetrabutylammonium phenolate) as well as impurities, by-products, and possibly also other catalyst components such as palladium compounds, compounds of the transition metal cocatalyst , its ligands, organic cocatalysts and other auxiliaries
- step a) the mixture containing A, B, C and D is mixed with an acid (H) q Z, where D reacts to B2 and thereby a quaternary salt of the formula (W + ) s ([CH) q- s Z] s " ) ⁇ , which is referred to as AI below.
- the quaternary ions Q n + and I + are also preferably identical. If these conditions are met together, AI is identical to A.
- the stoichiometry of (H) q Z relative to D is preferably about 0.95 to 3 equivalents.
- (H) q Z instead of (H) q Z, their anhydrides, ie (H) q Z minus HO (such as, for example, acetic anhydride, CO or SO 3 or similar precursor compounds, can also be used. Acids such as CO 2 , which produces H CO 3 in situ, can be easily removed from the reaction mixture (for example by stripping) and can also be used in a substantially higher excess without problems.
- anhydrides ie (H) q Z minus HO
- Acids such as CO 2 , which produces H CO 3 in situ, can be easily removed from the reaction mixture (for example by stripping) and can also be used in a substantially higher excess without problems.
- the acid (H) q Z (q stands for a natural number) can be added, for example, as an aqueous solution, solid, liquid or gas. Addition as an aqueous solution is preferred.
- Examples of (H) q Z which can be metered in as gases are, for example, CO 2 , SO 3 , SO 2 , HC1 or HBr. HBr is preferred.
- gases are added to the reaction mixture under excess pressure in a suitable mixing device, for example a nozzle or bubble chamber.
- (H) q Z which can be added as solids are, for example, dry ice, oxalic acid, glacial acetic acid, potassium hydrogen sulfate, potassium dihydrogen phosphate, phosphoric acid. If the solid does not change directly into another state of aggregation under the conditions mentioned, it is added in as finely powdered a form as possible.
- liquids (H) q Z examples include approximately 100% acids such as hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid. Hydrobromic acid is preferred. With oxidizing acids (H) q Z such as sulfuric or nitric acid, however, the addition in this form is rather unsuitable in most embodiments.
- the liquids are added in a suitable mixing device.
- Examples of aqueous solutions of (H) q Z are sulfuric acid, nitric acid, phosphoric acid, carbonic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, aqueous formic acid, aqueous acetic acid, aqueous oxalic acid, aqueous citric acid.
- Hydrobromic, sulfuric, phosphoric and hydrochloric acids are preferred, and hydrobromic acid is particularly preferred.
- Preferred, particularly preferred or very particularly preferred etc. are embodiments which make use of the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred.
- step a) can be understood as a reactive extraction and can be carried out in suitable apparatus such as mixer-settlers or extraction columns or cascades of one or more of these elements. Execution in a single mixer-settler is preferred.
- the aqueous to organic phase ratio is generally kept in such a way that the loss of A into the aqueous phase is limited, but adequate contact of the reactants is ensured.
- a volume ratio of the aqueous to the organic phase of 0.8 to 0.01, particularly preferably 0.25 to 0.03, very particularly preferably 0.15 to 0.05 is preferred.
- the necessary contact time of the phases is easy to determine for the person skilled in the art, but is, for example, about 2 seconds to 30 minutes.
- the ratio of the equivalents of (H) q Z to D is preferably 0.95 to 3, particularly preferably 1.03 to 2, since an excess of acid or the likewise preferred addition of a further electrolyte causes the losses of A into the aqueous phase minimized.
- the application therefore also relates to a process for the simultaneous neutralization of a base D and removal of one or more metal salts by reactive extraction of an organic solution which contains at least B, C and D with an aqueous acid solution, an aqueous solution containing B2 organic and a metal salt Phase arise.
- the metal salt can be, for example, a metal from groups III A, HI B, IV A, IV B, VB, IB, II B, VI B, VII B, rare earth metals (atomic numbers 58-71) or the iron group of the periodic table of the elements (Mendeleev), optionally also mixtures thereof, act, it being possible for the metal to be used in various oxidation states. (see, for example, US Pat. No. 5,142,086, US Pat. No. 5,231,210, US Pat. No. 5,284,964, EP-A 350 697, EP-A 350 700, US Pat. No. 5,336,803).
- Mn, Cu, Mo, Pb and Ce are particularly preferably used.
- the metals can be used, for example, as halides, oxides, carboxylates of C 2 -C 18 carboxylic acids, diketonates or nitrates and as complex compounds which, for example, carbon monoxide, olefins, aromatic and aliphatic mono- or polyamines, phosphorus compounds, pyridines, bipyridines, terpyridines, Chmolines, isoquinolines, cryptands, ship bases and halides can contain.
- Manganese compounds are very particularly preferably used in the process according to the invention, in particular manganese ( ⁇ ) and manganese (II ⁇ ) salts, especially as acetylacetonate complexes or halides, or halide or mixed complexes, ideally as manganese (I ⁇ ) bromide.
- the concentration of the metal salt is generally in the range from 0.0001 to 20% by weight of the reaction mixture, the concentration range from 0.001 to 5% by weight, particularly preferably 0.005 to 2% by weight, is preferred.
- the metal salt can then be worked up and recovered from the aqueous phase in a suitable manner.
- processes known to the person skilled in the art such as crystallization from concentrated solutions, concentration to dryness, extraction or precipitation, can be used.
- step b the mixture of A, AI, B, B2 and C and possibly solvent-containing reaction mixture is separated into mixtures which bl.) C and possibly B and / or B2, and b2.) A and possibly AI and possibly contain B and / or B2.
- the process according to the invention has the advantage that, after a) has been carried out, there are no longer any basic components which are undesirable secondary reactions, e.g. can lead to the saponification of diaryl carbonates. This makes it possible, e.g. also carry out distillation at elevated temperature without losing C.
- Step b) is preferably carried out by distillation or extraction or combinations and / or cascades of the two, particularly preferably by extraction.
- step b) When step b) is carried out by distillation, the product C is generally distilled off overhead and the A and Al remain in the bottom after optional removal of the solvent by distillation.
- B or B2 accumulate in the sump or distillate or can optionally be obtained by fractional distillation in enriched fractions.
- diphenyl carbonate (C) for example, phenol (B) and possibly B2 are low boilers, diphenyl carbonate is a medium boiler and A remains in the bottom of the reaction and AI, possibly B2 and high-boiling contaminants, which can be separated from A and AI in a further step from the sump or its partial stream.
- the sump contains A and Al in liquid or solid form and can, if appropriate after dilution with B or solvents and / or further work-up steps, be returned to the reaction.
- distillation is preferably carried out with a temperature slightly below its decomposition temperature and the greatest possible vacuum. Temperature-stable quaternary salts should be used for very low volatility products C or another processing method should be used.
- the distillation can be carried out in the apparatus known to the person skilled in the art.
- step b) is the extraction or a sequence of extraction steps.
- the application DE-A 101 64 145 (in particular p. 2-3.) Describes a particularly preferred method for removing and recovering quaternary salts A of the formula (Q n + ) m (Y m " ) n from reaction mixtures, which besides A contain at least one or more hydroxyaromatic compounds B and one or more reaction products C and optionally a solvent, characterized in that at least one of the following steps aa to ae is carried out:
- aa aal) in a mixture containing A, B, C and optionally a solvent, the ratio of the mass fractions CA of A and CB of B in the mixture to about 0.001 -C A ⁇ C B ⁇ 4-C A , preferably about 0 , 01-CA ⁇ C B ⁇ 3-CA, particularly preferably about 0, 1 • CA ⁇ CB 1, 5 -CA set, aa2)
- the mixture is extracted with water or an aqueous solution, giving an aqueous phase containing A and an organic phase containing C, from which C can be isolated,
- step abl The organic phase obtained in step adl) is mixed with B and used in step abl).
- This method can also contain 2, 3 or more of steps aa) to ae) in any suitable combination. Each of these combinations is the subject of this invention.
- step b) is an depletion of C by crystallization of C or adducts or mixed crystals from C and B.
- the crystals can be used to separate C (fraction bl); the mother liquor (b2) containing A and AI and residual amounts of C can be returned to the reaction.
- step b) When carrying out the direct carbonylation process, it makes sense for the hydroxyaromatic compounds B and B2 to be returned to the reaction. If in step b) in fraction bl.) The product C is obtained in a mixture with B or B2, it makes sense to carry out a further separation step for the separation of C and the hydroxyaromatic compounds B / B2. For example, distillation or crystallization of C are possible (see e.g. EP AI 801 053).
- step c) the fraction of the reaction mixture, which consists of A, Al, B and B2, is reacted with a base E, with Al and B2 reacting to D.
- the base can be added in solid or liquid form or as an aqueous solution. Aqueous solutions are preferred.
- Base E contains one or more elements from the alkaline earth metal, alkali metal or ammonium or quaternary salt (Q n + ) hydroxide group. If necessary, the quaternary salt can be polymer-bound, for example in the form of an anion exchanger.
- Suitable bases E are also triallylamines such as tributylamine,
- MP 62 or MP 64 or VP OC 1072 and the hydroxides of groups Ia and Ha des Periodic Table.
- Calcium hydroxide and potassium hydroxide are particularly preferred, and sodium hydroxide is very particularly preferred.
- base E is dosed as a solid, it should be added in the finest powdered form possible.
- suitable (Q n + ) m (Y m " ) n or crown ethers or cryptands as phase transfer catalysts can accelerate the reaction.
- Step c) is preferably carried out by reactive distillation or reactive extraction or combinations of the two, particularly preferably by reactive extraction.
- the reactive distillation can be carried out in the apparatus known to the person skilled in the art. A preferred embodiment for this is described in DE-A 101 64 144 (in particular p. 2-3).
- the application DE-A 101 64 144 relates to a process for the preparation of organic solutions of salts (Q n + ) k [CO) k -Ar '] n from a quaternary cation (Q n + ) and a hydroxyaromatic (Ar' - (OH) k), characterized in that an aqueous solution of a hydroxide M 0+ (OH " ) 0 , with at least one quaternary salt (Q n + ) m (Y m" ) n , Ar '- (OH) k and at least one not completely with Water-miscible solvent is brought into contact, then water is removed by partially distilling the mixture, and finally a precipitated salt is separated off, whereby an organic solution containing low water to water (Q n + ) k [CO) k -Ar '] "is obtained ,
- water-poor to water-free means a water content of up to 2% by weight, preferably up to 0.5% by weight and particularly preferably up to 0.2% by weight.
- Another object of the application DE-A 101 64 144 is a process for working up quaternary salts from the reaction mixture and their recycling in the reactions as organic solutions of mixtures of salts (Q n + ) k [( " O) k -Ar ']" and (Q n + ) m ( ⁇ m ⁇ ) n, characterized in that mixtures consisting among other things of one or more Quaternary salts (Q n + ) m (Y m " ) n in a hydroxyaromatic Ar '- (OH) and optionally one or more organic solvents are reacted as follows:
- step c) is reactive extraction.
- the application DE-A 101 64 142 relates to a process for the preparation of organic solutions of salts (Q n + ) k [CO) k -Ar '] n from a quaternary cation (Q n + ) and a hydroxyaromatic (Ar' - (OH) k ), characterized in that an aqueous solution of a hydroxide M 0+ (OH " ) 0 , at least one quaternary salt (Q n + ) m (Y m" ) n, Ar '- (OH) k and at least one not completely with water miscible solvent are brought into intimate contact and then the aqueous phase of the (Q n + ) k [CO) k -Ar '] n (and optionally Ar' (OH) k and
- the application DE-A 101 64 142 also relates to a process for working up quaternary salts from reaction mixtures and recycling them as organic solutions of mixtures of salts (Q n + ) k [CO) k -Ar '] n and (Q n + ) m (Y m " ) n5 characterized in that mixtures consisting, inter alia, of one or more quaternary salts (Q n + ) m ( Y m ⁇ ) n, a hydroxyaromatic Ar '- (OH) k and optionally one or more organic solvents are reacted as follows :
- the process is described in DE-A 101 64 142 described in detail, so that reference is made to this application for further explanation.
- Steps a), b) and c) of the present invention can each be carried out as single, multiple or continuous separation operations. Continuous processes, e.g. B. Countercurrent extraction are mostly preferred.
- steps a), b) and c) of the method according to the invention e.g. Extraction methods are used, such as those found in KJJ K-OTHMER, Encyclopedia of Chemical Technology, Fourth Edition, Volume 10, 1993, pages 125-181 and in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Volume B3, Unit Operations II, 1988, Chapter 6, Liquid-Liquid Extraction, pages 6-1 to 6-61.
- Extractors from the following classification groups can be used to carry out the method according to the invention, such as Columns without energy input, columns with pulsed liquid or pulsed internals, columns with rotating internals, mixer-settlers, mixing nozzles and sedimentation tanks, as well as centrifugal extractors.
- Spray columns, packed columns and sieve plate columns, which differ in the dispersion of the phases, may be mentioned as examples of columns without energy input.
- Examples of columns with pulsed liquid or pulsed internals are pulsed sieve plate columns, with piston pump, with pulsator according to Misek or Wepuko, columns with oscillating sieve plates according to Prochazka or Karr.
- Examples of columns with rotating internals include its Rotating Disc Contactor (RDC), Asymmetry Rotating Disc Extractor (ARD), Oldshue-Rushton multiple-mixer column, Kuhni extractor, Scheibel column, SHE extractor and Graesser Contactor.
- mixer-settler extractors examples include Davy McKee Mixer-Settler, Lurgi Tower Extractor, IMI, General Mills and Box-Type Mixer-Settler to Denver.
- centrifugal extractors examples include Podbielniak centrifugal extractor and Robatel centrifugal extractor.
- the extractors can be operated as single extractors, parallel extractors or as a cascade of extractors.
- devices of one or different classification groups can be operated simultaneously in one cascade.
- the phases can be guided in a cascade in cocurrent or preferably in countercurrent.
- FIGS. 1 to 6 show embodiments of the method which are intended to illustrate possible variants without restricting the method in any way.
- Step a) the mixture of quaternary salt A, hydroxyaromatic compound B, reaction product C and base D coming from the reactor is extracted in step a) with an aqueous acid solution (H) q Z, wherein D and (H) q Z to B2 and AI to be converted.
- the products remain in the organic phase, which is then subjected to step b).
- Step b) is characterized here in that water for the extraction is circulated, whereby the amount of waste water can be minimized.
- Base E is added to the mixture of A, Al, B and B2 and in a reactive extraction Al and B2 are converted back to D; A, B and D remain in the organic phase and are returned to the reactor after optional further work-up or cleaning steps, for example removal of by-products or drying.
- step a) takes place in the same way.
- the aqueous solution which contains a metal salt from the catalyst system, can be worked up to recover the metal salt.
- D was chosen so that B2 resulting from neutralization is identical to B and AI identical to A.
- the mixture of A, B and C in the organic phase is then optionally diluted with solvent, mixed with water and extracted.
- An aqueous phase consisting of A and a little B is formed, as well as an organic phase containing B and C.
- the mixture of B and C is crystallized in this example.
- the product C remains in the crystals; B collects in the mother liquor with residues of C.
- step c This stream is used to supplement the amount of B for step c), where the aqueous phase is diluted with solvent and E is added and extracted.
- the organic phase then contains A, B and D and is after optional processing or cleaning steps, e.g. Removal of by-products or drying, returned to the reactor.
- Such a circuit of (H) q Z is useful when working with expensive acids.
- a possible variant is, for example, that A is a tetrabutylammonium bromide, D is a tetrabutylylammonium phenolate.
- (H) q Z is hydrobromic acid
- tetrabutylammonium bromide is formed in step a) and bromide (Z q " ) is released in step c) funneled.
- the valuable bromide can be converted back into hydrobromic acid by adding the cheaper sulfuric acid ((H) W Z1) to the aqueous solution and distilling it, giving an aqueous HBr solution, which in turn can be used in step a).
- a variant of this process partially separates Z q ⁇ from water after step c), for example by reverse osmosis or distillation, and thus permits the return of a water stream as feed for step b).
- Fig. 3 shows a variant in which the acid is metered in substance in solid or liquid form (or dissolved in the solvent).
- D was chosen so that B2 resulting from neutralization is identical to B and AI identical to A.
- step b) the mixture of A, B and C is separated by fractional distillation. A remains in the sump, is dissolved in a B backflow and after optional processing or purification steps, e.g. Removal of by-products or drying, returned to the reaction. Part of the distilled B is used for step c), where D is produced in a reactive extraction. D is dissolved in the B reflux and returned to the reactor.
- FIG. 4 shows an example in which D was chosen again so that B2 resulting from neutralization is identical to B and AI is identical to A. It is a variant in which step a) is carried out with a large aqueous / organic phase ratio and exact stoichiometry. If this extraction is carried out in several stages, step b) can also be carried out in this extraction. An organic phase is obtained which contains B and C and is split into the components by distillation, for example, and an aqueous phase from A and B. D is produced therefrom by partial reaction in a reactive extraction (step c) and the mixture of A, B and D and pure B are returned to the reaction.
- the aqueous phase in step c) optionally contains one or more metal salts from catalyst components and can be worked up to regenerate these metals.
- FIG. 5 describes a process in which B2 is identical to B and the acid is added in bulk or in a solvent.
- Step b) is carried out by fractional distillation, step c) by reactive distillation.
- AI and B are converted to E with D and kept in solution with excess B. If aqueous E has been added, a solvent-water azeotrope is distilled off, for example. Due to the deteriorating solubility, Z q " precipitates with the counter ion and can be separated off. The bottoms containing A, B and D are returned to the reaction.
- AI and A, and B2 and B are identical.
- the mixture of A, B, C and D coming from the reactor is extracted again in step a) with an aqueous acid solution (H) q Z, D being converted into B and A.
- step b) the mixture mixed with solvent and water is extracted, an aqueous phase consisting of A and B and an organic phase consisting of solvent (LM), B and C being formed.
- the organic phase is worked up by distillation to obtain solvent, products C and B.
- the B obtained in this way can be used again in the reaction or in the workup.
- the aqueous phase is reacted in step c) -l in an ion exchanger loaded with base E. This creates A and D. Depending on the B content of this stream, B is also still present in the stream at the outlet of the ion exchanger. At very low B concentrations, a base DI can also be formed.
- the ion exchanger is loaded with NaOH and quaternary hydroxide (Dl) is formed in addition to quaternary phenolate (D).
- Dl quaternary hydroxide
- D quaternary phenolate
- the aqueous stream in the outlet of the ion exchanger from A, B, D and possibly Dl is now mixed with solvent and B, step c) -2, ie the possible conversion of Dl into D taking place. It is extracted, the phases are separated, the organic phase containing A, B and D is returned to the reactor after any working up. The aqueous phase can be fed back into the extraction b) and thus circulated.
- solvents (LM) and B in different concentrations are used at various points to carry out the process according to the invention.
- LM solvents
- Various variants of the method are obvious to the person skilled in the art, in which currents of LM and / or B are formed, which can be set in the desired concentration by suitable separation, concentration and mixing operations and can be connected in a suitable manner within an overall process in order to achieve the individual extraction steps to produce the mixtures required.
- Oxidative carboxylations were carried out with the catalytic system consisting of palladium bromide, manganese (III) acetyl carbonate, tetrabutylammonium bromide (TBAD) and tetrabutylammonium phenolate (TBAP) in chlorobenzene.
- the catalytic system consisting of palladium bromide, manganese (III) acetyl carbonate, tetrabutylammonium bromide (TBAD) and tetrabutylammonium phenolate (TBAP) in chlorobenzene.
- Tetrabutylammonium bromide breaks down into tributylamine (TBA) and butyl bromide, which are detected.
- Tetrabutylammonium bromide TBAB, MonochlorbenzoHvfCB, DiphenylcarbonaHDPC).
- Example 2 200 g of the solution used in Example 2 are extracted at 80 ° C. 3 times with 3 portions of the same volume from a total of 600 g of water. The aqueous phases are then combined.
- Table 2 The compositions of the solutions are summarized in Table 2.
- a mixture of 50 g of tetraphenylphosphonium bromide, 60 g of chlorobenzene, 40 g of phenol and 100 g of diphenyl carbonate is distilled through a column filled with Raschig rings 5 cm high. Work is first carried out at a vacuum of 200 mbar until the bottom temperature has risen to about 180 ° C., then the vacuum is reduced to about 20 mbar and the distillation is continued up to a maximum bottom temperature of about 200 ° C. From the compositions of the individual fractions, the total amount of the compounds found in the distillate is added up. 69.1 g remain in the bottom of the reaction. The result is shown in Tab. 3.
- a mixture of 25 g tetraphenylphosphonium bromide, 25 g tetraphenylphosphonium phenolate, 60 g chlorobenzene, 40 g phenol and 100 g diphenyl carbonate is distilled through a column filled with Raschig rings 5 cm high. Work is first carried out at a vacuum of 200 mbar until the bottom temperature has risen to about 180 ° C., then the vacuum is reduced to about 20 mbar and the distillation is continued up to a maximum bottom temperature of about 200 ° C. The total amount of the compounds found in the distillate is added up from the compositions of the individual fractions. 66.7 g remain in the bottom of the reaction. The result is shown in Tab. 3.
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PCT/EP2002/014618 WO2003055603A1 (de) | 2001-12-27 | 2002-12-20 | Verfahren zur auftrennung von reaktionsgemischen und rückführung von quartärsalzen und basen |
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DE19858967C1 (de) * | 1998-12-21 | 2000-07-13 | Bayer Ag | Flüssige Formulierung von Tetrabutylammoniumphenolat |
DE102008049787A1 (de) | 2008-09-30 | 2010-04-01 | Bayer Technology Services Gmbh | Verfahren zur Herstellung von Diphenylcarbonat mit Katalysator umfassend ionische Flüssigkeiten |
CN117049965A (zh) * | 2023-06-28 | 2023-11-14 | 福建德尔科技股份有限公司 | 锂盐添加剂生产过程中溶剂的高效回收复用方法 |
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US3227748A (en) * | 1963-02-25 | 1966-01-04 | Metal Hydrides Inc | Purification of quaternary ammonium compounds |
US3484348A (en) * | 1964-04-27 | 1969-12-16 | Monsanto Co | Quaternary ammonium salt recovery |
IN148600B (ko) | 1976-10-12 | 1981-04-11 | Gen Electric | |
GB1591214A (en) * | 1977-05-23 | 1981-06-17 | Sumitomo Chemical Co | Recovery of a tertiary amine or quaternary ammonium catalyst used in the production of a-substituted benzyl nitriles |
US4349485A (en) | 1979-11-23 | 1982-09-14 | General Electric Company | Catalytic aromatic carbonate process using manganese tetradentate redox co-catalysts |
DE3216383A1 (de) * | 1982-05-03 | 1983-11-03 | Bayer Ag, 5090 Leverkusen | Extraktion von oniumsalzen aus prozesswaessern und abwaessern |
US5231210A (en) | 1992-08-17 | 1993-07-27 | General Electric Company | Method for making aromatic carbonates |
JP3533533B2 (ja) | 1994-04-11 | 2004-05-31 | ダイセル化学工業株式会社 | エアバッグ用ガス発生器の廃棄処理方法 |
SG48449A1 (en) * | 1995-08-21 | 1998-04-17 | Gen Electric | Method of recycling phase transfer catalyst for displacemtn reaction |
US5898079A (en) | 1997-02-13 | 1999-04-27 | General Electric Company | Method for preparing diaryl carbonates employing hexaalkylguanidinium halides |
US5760272A (en) | 1997-03-24 | 1998-06-02 | General Electric Company | Method for preparing diaryl carbonates with improved selectivity |
US5981788A (en) * | 1997-11-03 | 1999-11-09 | General Electric Company | Method for recovering and recycling catalyst constituents |
US6310232B1 (en) | 2000-11-10 | 2001-10-30 | General Electric Company | Method for recycle of bromide-containing catalyst constituents |
-
2001
- 2001-12-27 DE DE10164143A patent/DE10164143A1/de not_active Withdrawn
-
2002
- 2002-12-16 US US10/320,061 patent/US6740781B2/en not_active Expired - Fee Related
- 2002-12-20 KR KR10-2004-7010036A patent/KR20040068982A/ko not_active Application Discontinuation
- 2002-12-20 AU AU2002358778A patent/AU2002358778A1/en not_active Abandoned
- 2002-12-20 JP JP2003556173A patent/JP2005512806A/ja not_active Withdrawn
- 2002-12-20 EP EP02793097A patent/EP1461154A1/de not_active Withdrawn
- 2002-12-20 WO PCT/EP2002/014618 patent/WO2003055603A1/de active Application Filing
- 2002-12-20 CN CNA028282337A patent/CN1620337A/zh active Pending
- 2002-12-26 TW TW091137402A patent/TWI267506B/zh not_active IP Right Cessation
Non-Patent Citations (1)
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See references of WO03055603A1 * |
Also Published As
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TWI267506B (en) | 2006-12-01 |
CN1620337A (zh) | 2005-05-25 |
TW200306303A (en) | 2003-11-16 |
WO2003055603A1 (de) | 2003-07-10 |
AU2002358778A1 (en) | 2003-07-15 |
JP2005512806A (ja) | 2005-05-12 |
US20030153779A1 (en) | 2003-08-14 |
US6740781B2 (en) | 2004-05-25 |
DE10164143A1 (de) | 2003-07-10 |
KR20040068982A (ko) | 2004-08-02 |
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