CN1974509B - Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative - Google Patents
Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative Download PDFInfo
- Publication number
- CN1974509B CN1974509B CN2006101531408A CN200610153140A CN1974509B CN 1974509 B CN1974509 B CN 1974509B CN 2006101531408 A CN2006101531408 A CN 2006101531408A CN 200610153140 A CN200610153140 A CN 200610153140A CN 1974509 B CN1974509 B CN 1974509B
- Authority
- CN
- China
- Prior art keywords
- quaternary phosphine
- iodate
- water
- iodide
- liquid
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims description 92
- 125000002947 alkylene group Chemical group 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- 230000001172 regenerating effect Effects 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 301
- 238000006243 chemical reaction Methods 0.000 claims abstract description 171
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 139
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 41
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 571
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 284
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 179
- 239000007788 liquid Substances 0.000 claims description 84
- 230000031709 bromination Effects 0.000 claims description 79
- 238000005893 bromination reaction Methods 0.000 claims description 79
- -1 alkylene carbonates Chemical class 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 36
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 35
- 235000011089 carbon dioxide Nutrition 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 101
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 27
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 8
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical group [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 abstract description 5
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical group ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 95
- 239000000243 solution Substances 0.000 description 77
- 239000003960 organic solvent Substances 0.000 description 38
- 239000002244 precipitate Substances 0.000 description 37
- 235000014121 butter Nutrition 0.000 description 36
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 36
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000011084 recovery Methods 0.000 description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 20
- 229910052801 chlorine Inorganic materials 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 238000005660 chlorination reaction Methods 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 235000007715 potassium iodide Nutrition 0.000 description 12
- 229960004839 potassium iodide Drugs 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 235000015320 potassium carbonate Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000006200 vaporizer Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- 229910001505 inorganic iodide Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- DUBASSMOXQNSEZ-UHFFFAOYSA-N 2-methyloxirane;propane-1,2-diol Chemical compound CC1CO1.CC(O)CO DUBASSMOXQNSEZ-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- KDPMIBMNNGCWTF-UHFFFAOYSA-N C(CCC)O.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical class C(CCC)O.CC1(CC(C(=O)O)=CC=C1)C(=O)O KDPMIBMNNGCWTF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- TVSRMSLHNQZQBM-UHFFFAOYSA-M [I-].[PH4+].C(CCC)[P+](C)(CCCC)CCCC.[I-] Chemical compound [I-].[PH4+].C(CCC)[P+](C)(CCCC)CCCC.[I-] TVSRMSLHNQZQBM-UHFFFAOYSA-M 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- JOZHCQBYRBGYAJ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 JOZHCQBYRBGYAJ-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- ZWRUINPWMLAQRD-UHFFFAOYSA-N n-Nonyl alcohol Natural products CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for producing an ethylene glycol or ethylene carbonate wherein ethylene oxide is reacted with water or carbon dioxide in the presence of carbon dioxide by the use of a quaternary phosphonium iodide or bromide catalyst, characterized in that the quaternary phosphonium iodide or bromide catalyst is recovered efficiently from the reaction system and is circulated for use, and in that quaternary phosphonium chloride formed in the reaction system is converted efficiently to quaternary phosphonium iodide or bromide, and the resultant iodide or bromide is recovered and circulated to the reaction system for use.
Description
Technical field
The application is to be on February 9th, 2004 applying date, and application number is 2004800033584, is entitled as dividing an application of " method and the catalyst regeneration process that is used to produce alkylene derivative of producing alkylene derivative " application.
The present invention relates to produce the method for alkylene derivative such as aklylene glycol or alkylene carbonates.The present invention be more particularly directed to produce the method for aklylene glycol such as ethylene glycol, this method comprise with alkylene oxide such as oxyethane and water in the presence of carbonic acid gas by bromination and/or iodate quaternary phosphine catalyst reaction; Or relating to the method for producing ethylene carbonate or its analogue, this method comprises alkylene oxide and carbon dioxide reaction.The method that the invention particularly relates to from reaction system efficient recovery bromination and/or iodate quaternary phosphine catalyzer and its recirculation is used.
In the present invention, aklylene glycol is meant aklylene glycol such as ethylene glycol or the propylene glycol with about 2 to 10 carbon atoms, and alkylene carbonates is meant the alkylene carbonates with about 2 to 10 carbon atoms, as ethylene carbonate or Texacar PC.
Background technology
Ethylene glycol is by oxyethane and the scale operation of water direct reaction.Yet, in the method, during being suppressed at hydrolysis, form byproduct such as glycol ether or triglycol, need to use with respect to the excessive a lot of water of the stoichiometry of oxyethane.Correspondingly, must remove so big excessive water, therefore exist for the problem that pure ethylene glycol needs big energy that obtains by the aqueous glycol solution that distillation forms.
As a method of head it off, proposed wherein oxyethane and water react the method for producing ethylene glycol in the presence of carbonic acid gas.This reaction is for two-step reaction, wherein by oxyethane with carbon dioxide reaction formation ethylene carbonate with the ethylene carbonate hydrolysis.In this two step reaction, in reaction system, there is water, reaction can be carried out in identical reactor like this, but in order to finish the reaction of second step, can another reactor be set to back one step.When the hydrolysis ethylene carbonate, do not form glycol ether or triglycol basically, so hydrolysis can carry out in the presence of the excessive water of slight stoichiometry as byproduct, can significantly reduce like this from the aqueous glycol solution that forms except that anhydrating required cost.Simultaneously, will form carbonic acid gas by hydrolysis by the ethylene carbonate that oxyethane and carbon dioxide reaction form, this carbonic acid gas is capable of circulation to be re-used.
In addition, in the method, can also be by reducing the water yield in the initial substance, producing ethylene carbonate by reducing the formation that temperature as reaction conditions suppresses ethylene glycol.
Therefore, various catalyst types by ethylene oxide production ethylene glycol and/or ethylene carbonate have been proposed.A kind of preferred catalyzer is a You Ji phosphonium salt, preferred especially iodate or bromination quaternary phosphine (JP-B-55-47617).In addition, as promotor, alkaline carbonate can be used in combination (JP-A-12-128814) with You Ji phosphonium salt.
For by the oxyethane of oxidation of ethylene production,, reaction system is supplied with hydrochloric ether such as ethyl chloride as selective modulator (JP-A-2-104579) in the case for improving the selectivity of oxidizing reaction as raw material.
As mentioned above, by oxyethane and water or carbonic acid gas in the presence of carbonic acid gas, react the method for producing ethylene glycol or ethylene carbonate since no above-mentioned byproduct industrial be favourable, but when continuous production, have the problem of reaction efficiency reduction.
The inventor has studied the reason that causes this reaction efficiency to reduce, has found that reason is that iodate or bromination quaternary phosphine are converted into the muriate with low catalytic activity in reaction system.In fact, move about 1 year by reactor, about 20% iodate or bromination quaternary phosphine are converted into the Lvization quaternary phosphine in the discovery reaction system.
Think that the reason that iodate or bromination quaternary phosphine are converted into the Lvization quaternary phosphine is that the muriate as impurity contained in the oxyethane raw material is introduced in the reaction system.In other words, as mentioned above, in the method for producing oxyethane, hydrochloric ether is added in the reaction system to improve the selectivity of reaction as selective modulator, even and contained chlorine also is retained in the product of ethylene oxide as muriate after by purification system in this hydrochloric ether, so this muriate is blended into and produces in ethylene glycol or the ethylene carbonate step.Think to be included in the product oxyethane that iodate or bromination quaternary phosphine will be converted into the Lvization quaternary phosphine, although the details of these reaction mechanisms is not clear by introducing muriate.。
Therefore, in the method for producing ethylene glycol or ethylene carbonate, must from reaction system, separate and remove low activity Lvization quaternary phosphine, so that only keep high reactivity iodate or bromination quaternary phosphine from catalyzer.Yet, determine still up to now that reaction efficiency reduces in time by being converted into muriate in time to cause.In addition, as yet not in reaction system from as the method for separating the Lvization quaternary phosphine the iodate of catalyzer or the bromination quaternary phosphine, or the method that the Lvization quaternary phosphine is converted into iodate or bromination quaternary phosphine is studied.
Summary of the invention
An object of the present invention is to solve above-mentioned general issues and provide and produce alkylene derivative such as aklylene glycol such as ethylene glycol, or the method for alkylene carbonates such as ethylene carbonate, this method comprise with alkylene oxide such as oxyethane and water or carbonic acid gas in the presence of carbonic acid gas by iodate and/or bromination quaternary phosphine catalyst reaction, wherein the Lvization quaternary phosphine that forms in the reaction system is effectively removed, maybe this Lvization quaternary phosphine is converted into iodate and/or bromination quaternary phosphine, then it is recirculated in the reaction system and re-uses, so the catalytic activity in the reaction system is remained on high level, and the reaction that is used to form alkylene derivative can be carried out effectively constantly for a long time.
The invention provides as follows:
(1) a kind of method of producing alkylene derivative, it comprises alkylene oxide and the water reactions steps by iodate or bromination quaternary phosphine catalyst reaction formation aklylene glycol in the presence of carbonic acid gas, it is characterized in that from removing this aklylene glycol partial reaction solution and/or the catalyst solution at least, so that the mol ratio of aklylene glycol and catalyzer becomes 20 times at the most, then mix to reclaim catalyzer with water.
(2), it is characterized in that the mol ratio of aklylene glycol and catalyzer is 2 times at the most according to the method for top (1).
(3) according to the method for (1) or (2), it is characterized in that mixing the service temperature that reclaims catalyzer with water is 30 ℃ at the most.
(4) according to any one method of top (1) to (3), it is characterized in that the blended water yield is at least 0.1 times, by the catalyst weight that reclaims.
(5) according to any one method of top (1) to (4), it is characterized in that mixing water after, carry out solid-liquid and separate, with this catalyzer with solids constituent from after be recirculated in the reactions steps.
(6) according to the method for top (5), wherein will separate isolating liquid and use as the water cycle of washing catalyst by solid-liquid.
(7) according to any one method of top (1) to (6), it is characterized in that alkylene oxide is an oxyethane.
(8) a kind of method of regenerated catalyst, it is characterized in that the mixture that will comprise Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine mixes with iodide and/or bromide so that the Lvization quaternary phosphine is converted into iodate and/or bromination quaternary phosphine, it is separated out in water, and described mixture obtains the reactions steps as catalyst reaction formation aklylene glycol by iodate and/or bromination quaternary phosphine in the presence of carbonic acid gas from the alkylene oxide and the water of chloride compound as impurity.
(9) a kind of method of regenerated catalyst, it is characterized in that the mixture that will comprise Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine mixes with iodide and/or bromide so that the Lvization quaternary phosphine is converted into iodate and/or bromination quaternary phosphine, separate out in water, described mixture obtains the reactions steps as catalyst reaction formation alkylene carbonates by iodate and/or bromination quaternary phosphine from alkylene oxide and carbonic acid gas.
(10) according to the method for top (8) or (9), it is characterized in that comprising the reaction soln of mixture for from top reactions steps, drawing off of chlorine quaternary phosphine and iodate and/or bromination quaternary phosphine, or from this reaction soln distilled water and/or to the resistates of small part after as the alkylene derivative of desired product.
(11) according to the method for top (8) or (9), it is characterized in that comprising the mixture of Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine, for by the reaction soln that from top reactions steps, draws off or from this reaction soln distilled water and/or mix with water to the resistates of small part after as the alkylene derivative of desired product, above-mentioned catalyzer is separated out as solid, and separate behind this catalyzer of separating out and the aqueous solution that obtains.
(12), it is characterized in that reclaiming the iodate and/or the bromination quaternary phosphine of separating out and be recirculated in the top reactions steps according to any one method of top (8) to (11).
(13) a kind of method of regenerated catalyst, it is characterized in that iodide and/or bromide adding are comprised in the mixture of Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine, so that in organic solvent, separate out as butter derived from the chlorine of Lvization quaternary phosphine, reclaim iodate and/or bromination quaternary phosphine thus, described mixture obtains the reactions steps as catalyst reaction by iodate and/or bromination quaternary phosphine in the presence of carbonic acid gas as the alkylene oxide and the water of impurity from containing the chlorating compound.
(14) a kind of method of regenerated catalyst, it is characterized in that iodide and/or bromide adding are comprised in the mixture of Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine, so that in organic solvent, separate out as butter from the chlorine of Lvization quaternary phosphine, reclaim iodate and/or bromination quaternary phosphine thus, described mixture obtains the reactions steps as catalyst reaction formation alkylene carbonates by iodate and/or bromination quaternary phosphine from alkylene oxide and carbonic acid gas.
(15) according to the method for top (13) or 14, the mixture that it is characterized in that comprising Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine is any in following (a) to (c):
(a) a kind of by water being added in the reaction soln from top reactions steps, draw off so that catalyzer is separated out and separating catalyst after with the liquid or solid of aqueous solution dehydration acquisition,
(b) a kind of by water being added in the resistates so that catalyzer is separated out as solid and the liquid or solid that after the catalyzer that separation is separated out aqueous solution dehydration obtained, described resistates is a dephlegmate and/or obtain to the alkylene derivative of small part as desired product from the reaction soln that reactions steps draws off
(c) a kind ofly will be dissolved in the liquid that obtains in the organic solvent by the liquid or solid that dehydration at (a) or (b) obtains.
(16) according to the method for top (13) or 14, the mixture that it is characterized in that comprising Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine be following (d) and (e) in any:
(d) liquid that obtains by the reaction soln that draws off with organic solvent diluting autoreaction step,
(e) from the reaction soln that reactions steps draws off, steam and dewater and/or to the resistates of small part after as the alkylene derivative of desired product, or by this resistates being dissolved in the liquid that obtains in the organic solvent.
(17) according to any one method of top (13) to (16), it is characterized in that the iodate and/or the bromination quaternary phosphine that reclaim are recirculated in the top reactions steps.
(18) a kind of method of producing alkylene derivative, comprise the step that the alkylene oxygen and carbon dioxide is formed alkylene carbonates by iodate and/or bromination quaternary phosphine as catalyst reaction, it is characterized in that iodide and/or bromide are added in the mixture that comprises Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine of autoreaction step acquisition, so that the Lvization quaternary phosphine is converted into iodate and/or bromination quaternary phosphine, in water, separate out, and reclaim and be recirculated in the reactions steps.
(19) a kind of method of producing alkylene derivative, comprise the step that the alkylene oxygen and carbon dioxide is formed alkylene carbonates by iodate and/or bromination quaternary phosphine as catalyst reaction, it is characterized in that iodide and/or bromide are added in the mixture that comprises Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine of autoreaction step acquisition, so that in organic solvent, separate out, reclaim iodate and/or bromination quaternary phosphine thus and be recirculated in the reactions steps as butter from the chlorine of Lvization quaternary phosphine.
In the present invention, when the reaction soln of the catalyzer that contains high density and/or catalyst solution mix with water, iodide or bromide will be separated out, and the muriate from catalyzer will keep with the form that is dissolved in the liquid simultaneously.That is, each iodide, bromide and muriate very easily are dissolved in aklylene glycol or the alkylene carbonates, but iodide or bromide have low solubility in water, and muriate is very easily soluble in water.Carry out the solid-liquid separation by the iodate or the bromination quaternary phosphine of will separate out, but separate easily and recovery catalyzer.
In the present invention, catalyzer for example can be separated out by following.
The reaction soln that 1. will contain catalyzer and/or catalyst solution mixes with water, then cooling.
2. from the reaction soln that contains catalyzer and/or catalyst solution, remove, then mix with water to the small part aklylene glycol.
In the case, needn't require cooling.Yet,, preferably cool off for reducing the solubleness of catalyzer.
The iodate of so reclaiming or bromination quaternary phosphine can be recirculated in the reactions steps and re-use.
On the other hand, in by the separating liquid behind iodate of solid-liquid Separation and Recovery or the bromination quaternary phosphine, contain the chlorination quaternary phosphine as villaumite.This Lvization quaternary phosphine for example is converted into iodate or bromination quaternary phosphine by ion-exchange, reclaims then or be recirculated in the reactions steps and re-use with solution state.
In addition, in the present invention, generate in the mixture that comprises Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine of reactions steps acquisition of aklylene glycol or alkylene carbonate by iodate and/or bromination quaternary phosphine catalyst reaction in the presence of carbonic acid gas by iodide and/or bromide being added, the Lvization quaternary phosphine in this mixture can be converted into iodide and/or bromide by alkylene oxide and water or carbonic acid gas.Like this, iodate and/or bromination quaternary phosphine that iodate that has existed and/or bromination quaternary phosphine and logical superchlorination quaternary phosphine and iodide and/or bromide reaction form can be separated out in water, and as recycling precipitate.
Below, wherein can be described as " mixture to be processed " sometimes for the mixture that comprises Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine that the Lvization quaternary phosphine is converted into iodate and/or bromination quaternary phosphine adding iodide and/or bromide.In addition, below will be from reactor effusive liquid or the liquid that from reactor, draws off can be described as " reaction soln " sometimes, and will wherein from reaction soln, divide dried up and aklylene glycol or alkylene carbonates come the liquid of catalyst concentration can abbreviate " catalyst solution " as sometimes by distillation.
The present invention can be directly applied for the reaction solution that contains catalyzer that draws off from the reactions steps of aklylene glycol or alkylene carbonates as mixture to be processed.Yet, as other method, separate out in the resistates of the present invention applicable to catalyst solution by water being added liquid form or solid form and the recovery part catalyzer after solution, the catalyst solution of described liquid form or the resistates of solid form are to remove in the reaction soln as (below, will separate out the reclaimer operation of part catalyzer in the resistates of this catalyst solution or solid form and be sometimes referred to as " the pre-recovery " by adding entry) that obtain behind some or all aklylene glycols of solvent or the alkylene carbonates by distillation.By this pre-recovery, can improve the concentration of Lvization quaternary phosphine in mixture to be processed, and can improve the transformation efficiency and the rate of recovery to iodate and/or bromination quaternary phosphine.
In other words, iodate and/or bromination quaternary phosphine have the solubleness lower than the Lvization quaternary phosphine in water.Therefore, by so adding entry, a large amount of iodate and/or bromination quaternary phosphine will be separated out, and a large amount of Lvization quaternary phosphines are with soluble in water, by this pre-recycling, can improve the concentration of Lvization quaternary phosphine in mixture to be processed, and can improve the transformation efficiency and the rate of recovery to iodate and/or bromination quaternary phosphine.
In addition, as other method, when carrying out above-mentioned pre-recycling, the available aqueous solution with dissolved iodide and/or bromide replaces adding the water in the residue of catalyst solution or solid state, can improve the rate of recovery of iodate and/or bromination quaternary phosphine thus.
In the method, when iodide and/or bromide added in the Lvization quaternary phosphine soluble in water, the Lvization quaternary phosphine was separated out precipitation with iodide and/or bromide form, and in this solution, kept dissolving corresponding to the muriate of the compound that adds.Correspondingly, the precipitation of separating out is carried out solid-liquid separate, but separate easily Lvization quaternary phosphine like this, and with iodate and/or the recovery of bromination quaternary phosphine form.
But the reactions steps that iodate of reclaiming like this and/or the recirculation of bromination quaternary phosphine are used for preparing aklylene glycol or alkylene carbonates.
In addition, according to the present invention, by iodide and/or bromide are added the mixture that comprises Lvization quaternary phosphine and iodate and/or bromination quaternary phosphine that is obtained by this reactions steps and top recycling step, make from the chlorine of Lvization quaternary phosphine and separate out in organic solvent, can reclaim iodate and/or bromination quaternary phosphine with the butter form.
In other words, in the presence of carbonic acid gas, in the mixture that comprises chlorine quaternary phosphine and iodate and/or bromination quaternary phosphine by the reactions steps acquisition of iodate and/or bromination quaternary phosphine catalyst reaction, can make the chlorine quaternary phosphine in this compound be converted into iodate and/or bromination quaternary phosphine by iodide and/or bromide being added by alkylene oxide and water or carbonic acid gas.On the other hand, separate out out with the butter that in organic solvent, has low solubility and separate this precipitate, can reclaim the iodate and/or the bromination quaternary phosphine that are dissolved in the organic solvent by making from the chlorine of Lvization quaternary phosphine.
Make chlorine in organic solvent, can be described as " operation of separating out butter " sometimes with this below with the operation that the butter form is separated out from the Lvization quaternary phosphine.In addition, can be called " mixture to be processed " with wherein adding the mixture that comprises chlorine quaternary phosphine and iodate and/or bromination quaternary phosphine that iodide and/or bromide make the chlorine of chlorine quaternary phosphine separate out with the butter form sometimes.
The Lvization quaternary phosphine is being converted into iodide or bromide, is making from muriatic chlorine and in organic solvent, separate out and, comprise the iodate and/or the bromination quaternary phosphine that are dissolved in organic solvent the liquid of this butter after separating with the butter form.Therefore, remove organic solvent, the iodate of recyclable solid form and/or bromination quaternary phosphine in this isolating liquid by evaporation.If need, the iodate of this recovery and/or the washing of bromination quaternary phosphine used water, it can in statu quo or be dissolved in the reactions steps that the recirculation afterwards of suitable solvent is used for preparing aklylene glycol or alkylene carbonates then.
Embodiment
Describe the practical ways of the method for production aklylene glycol of the present invention below in detail.
The present invention is primarily aimed at and wherein implements to be described by the situation of iodate quaternary phosphine catalyzer by the reaction of ethylene oxide production ethylene glycol, but and does not mean that the present invention is so limited.For example the present invention also be fit to produce various aklylene glycols, as by the production of propylene oxide propylene glycol.
In addition, the present invention is fit to equally wherein the bromination quaternary phosphine as the situation of catalyzer, or wherein iodate quaternary phosphine and the combination of bromination quaternary phosphine as the situation of catalyzer.
In addition, as mentioned above, the present invention's method same with the method for producing this aklylene glycol changes reaction conditions to the growing amount of low reaction temperatures with inhibition aklylene glycol such as ethylene glycol, the reaction that also goes for producing alkylene carbonates such as ethylene carbonate.In addition, the present invention is also applicable to wherein alkylene carbonates or aklylene glycol all are the reaction of desired product.
In addition, also exemplify a kind of method below, in the method, iodide are added in the mixture to be processed, so that the Lvization quaternary phosphine is converted into the iodate quaternary phosphine and reclaims.Except iodide, can add bromide so that the Lvization quaternary phosphine is converted into the bromination quaternary phosphine and reclaims, or adding iodide capable of being combined and bromide so that the Lvization quaternary phosphine be converted into iodate quaternary phosphine and bromination quaternary phosphine and reclaim.
In addition, can exemplify a kind of method below, wherein inorganic iodide be added mixture to be processed and make the Lvization quaternary phosphine be converted into the iodate quaternary phosphine, meanwhile separate out with the butter form derived from the chlorine of Lvization quaternary phosphine.Except iodide, bromide can be added so that the Lvization quaternary phosphine is converted into the bromination quaternary phosphine, meanwhile separate out with the butter form from the chlorine of Lvization quaternary phosphine, or adding iodide capable of being combined and bromide meanwhile spread out and separate out with the butter form from the chlorine of Lvization quaternary phosphine so that the Lvization quaternary phosphine is converted into iodate quaternary phosphine and bromination quaternary phosphine.
For the quaternary phosphine catalyzer that can be used among the present invention, can mention disclosed compound among the JP-B-58-22448, for example trityl group phosphonium iodide, triphenyl propyl group phosphonium iodide, triphenyl benzyl phosphonium iodide and tributyl-methyl phosphonium phosphonium iodide.This iodate quaternary phosphine is preferably dropped in the reaction system, so that the mol ratio of itself and oxyethane is 0.001 to 0.05 times.In addition, when using bromination quaternary phosphine catalyzer, can use bromination catalyst, and its preferable amount equals iodate quaternary phosphine catalyzer corresponding to above-mentioned iodate quaternary phosphine catalyzer.
In the present invention, alkaline carbonate can be used as promotor and coexists as in the reaction system, so can improve the formation efficiency that forms ethylene glycol.For alkaline carbonate is coexisted as in the reaction system, can add basic metal such as sodium or potassium, oxyhydroxide, carbonate or the supercarbonate of preferred potassium, when only adding any in the alkali metal compound, it will be present in the reaction system with carbonate form.In the case, preferably include alkaline carbonate, preferred salt of wormwood is so that the mol ratio of itself and iodate quaternary phosphine is 0.01 to 1.
Water can be reduced to stoichiometry or lower according to reaction system to the amount of oxyethane.Yet its consumption is preferably 1.0 to 10.0 times (by mole) of oxyethane.In addition, for carbonic acid gas,, under usual conditions, be 0.1 to 5.0mol for its consumption of every moles of ethylene oxide almost obtaining enough effects with amount below the oxyethane equimolar amount.Yet this ratio needn't strict limit.
Temperature of reaction changes at the composition of reaction starting stage etc. according to the type of the type of alkylene oxide, catalyzer, reaction soln, but reaction is carried out in 50 to 180 ℃ of scopes usually.Pressure changes according to the amount of carbonic acid gas, temperature of reaction etc., and can further change according to the reaction progress, but carries out in 0.5 to 5.0MPa scope usually.
The type of reactor does not have particular restriction, as long as it is for can make gas-liquid reaction steadily.In addition, the number of reactors of choosing and the residence time should reach required transformation efficiency.In addition, when producing ethylene glycol, can increase reactor according to the needs of the ethylene carbonate in the hydrolysis reaction solution.
In the reaction soln that autoreactor draws off, by fractionation by distillation water and most of ethylene glycol.The residual liquid (catalyst solution) that comprises catalyzer will be recirculated in the reactor, and catalyzer will be used for reaction once more like this.
The mode that efficient recovery iodate or bromination quaternary phosphine catalyzer and its recirculation are used from reaction system
Under the situation about in the reaction soln that the catalyzer autoreactor is drawn off, reclaiming, catalyst concn is very little, and catalyzer in statu quo will be difficult to separate out, therefore, preferably remove water contained in the reaction soln and ethylene glycol, (will remove ethylene glycol catalyzer afterwards) then once more and mix with water.
Reclaiming with catalyst solution under the situation of catalyzer, can reclaim catalyzer by this solution itself is mixed with water, but preferably further remove contained ethylene glycol, then mixing and reclaim catalyzer with water by distillation for the rate of recovery that improves catalyzer.
In other words, in this reaction, from this reactions steps, be discharged to small part reaction soln or catalyst solution, and remove and anhydrate and aklylene glycol, or aklylene glycol, make the mol ratio of aklylene glycol contained in the solution and catalyzer be 20 times at the most thus, when mol ratio during greater than this numerical value, preferably at the most during twice, then mix with water once more.
When the mol ratio of aklylene glycol and catalyzer is lower than 20 times, simply mixing water so that catalyzer separate out and reclaim.
When the liquid that draws off from reactions steps mixed with water, can exist wherein needed to cool off so that the situation that the iodate quaternary phosphine is separated out.In other words, the solubility with temperature of iodate quaternary phosphine in water or ethylene glycol reduces and diminishes.
The reaction soln that draws off from reactions steps is generally 100 to 180 ℃, preferably with this reaction soln cooling, so that the mixed temperature of this solution and water becomes 30 ℃ at the most, preferred 0 to 20 ℃, can more effectively separate out the iodate quaternary phosphine thus.Whether need this cooling to determine with the temperature of wanting blended water and combined amount according to the temperature of reaction soln.
In addition, for guaranteeing to separate out, preferably not only will cool off, and will add or initially add seed crystal, the effect of separating out under stable condition will become big thus.
In addition, if from the liquid that reactions steps draws off, remove to the product ethylene glycol of the preferred main amount of small part, for example to make catalyst concentration like this be to be 40wt% at least if remove ethylene glycol (it can be moisture), then this liquid is mixed with water, then the iodate quaternary phosphine can be separated out under needn't cooling off, but preferably it is cooled to 40 ℃ at the most, can effectively separates out thus.
Want the amount of blended water, according to amount, the muriatic amount of the amount of iodate quaternary phosphine in the reaction soln, ethylene glycol, whether cool off, the organic efficiency of required iodate quaternary phosphine etc. changes, but if the blended water yield is too little, then filtration is tending towards difficulty, and the efficient of dissolving chlorination quaternary phosphine reduces.On the other hand, if the blended water yield is too big, separate then behind the iodate quaternary phosphine that the amount of contained iodate quaternary phosphine is tending towards increasing in the liquid phase.Usually, the water yield that will add in primary treatment is defined as suitably at least in 0.1 times of liquid to be processed, preferred 0.1 to 5 times of scope.
With solids constituent from after liquid phase can be used as washing reaction solution, catalyst solution once more or the water of isolating catalyzer from ethylene glycol.In the case.If it is used as washing water repeatedly, the concentration that then is used for the contained Lvization quaternary phosphine of the water that washs will raise, therefore the concentration of contained Lvization quaternary phosphine will raise in the iodate quaternary phosphine that will reclaim like this, after using it for washing 1 to 5 time, it be replaced with fresh water and wash.
Also can use a kind of like this method under no any problem, promptly in the method, washing reaction solution carries out repeatedly progressively to become the washing water with low Lvization quaternary phosphine concentration.
In a specific embodiments of this operation, during beginning water or iodate quaternary phosphine slurry are dropped in the reactor, and to wherein dropping into reaction soln or catalyst solution and water continuously or intermittently, and thus obtained mixture drawn off continuously or intermittently, so can pass through the wherein contained precipitate of filtered and recycled.
In addition, for from reaction soln, separating ethylene glycol, can carry out operation by the underpressure distillation separating alcohol.Also water can be separated with ethylene glycol.
Mix the precipitate that so obtains with water by reaction soln and be generally and have iodide content 90wt% and the chloride content high reactivity iodate quaternary phosphine catalyzer of 10wt% at the most at least, and can effectively be recirculated in the reactions steps and re-use.
In addition, separating liquid after the iodate quaternary phosphine precipitate, to comprise muriate be the Lvization quaternary phosphine.This Lvization quaternary phosphine for example can be converted into the iodate quaternary phosphine by a kind of like this method, promptly in the method isolating liquid being carried out dehalogenation with OH type anionite-exchange resin handles, then with the hydroiodic acid HI neutralization, or with the anionite-exchange resin of iodine replacement chlorion directly is exchanged for iodide ion.Like this, catalyzer is renewable, and the regenerated catalyst that so obtains can be recirculated in the reactions steps and re-uses.
In the present invention uses, partial reaction solution can be from the reactor of continuous operation continuously or be interrupted and draw off, then reclaim iodate quaternary phosphine catalyzer, the iodate quaternary phosphine catalyzer of recovery can be recirculated in the reactor.In the case, be used to reclaim the amount of reaction soln of iodate quaternary phosphine catalyzer and/or the amount of catalyst solution and do not have particular restriction.Yet, for keeping high-level reaction efficiency in the scope of cost recovery of removing muriate and excessively do not increase catalyzer, preferably when the weight ratio of muriate in the reactor and iodide becomes 0.01 to 1.0, continuously or be interrupted and draw off to handle with reaction soln.The amount that draws off does not have particular restriction, but is preferably about 0.1 to 100wt%, and the amount of reaction soln amount or catalyst solution of pressing is calculated.
Reaction system Lvization quaternary phosphine is converted into iodate and/or bromination quaternary phosphine, reclaims and be recirculated into the embodiment that re-uses in the reaction system then
According to the present invention, comprise the ratio of chlorination contained in the mixture to be processed that contains the chlorination quaternary phosphine and iodate quaternary phosphine or ratio, growth position or the aftertreatment (for example whether having pre-reclaimer operation) as described below formed according to chlorine in the method for producing ethylene glycol and iodine change.The exist ratio and the concentration of chlorination in the mixture to be processed and iodate quaternary phosphine do not have particular restriction.Yet, consider the efficient of reclaimer operation, the ratio of muriate and iodide is high more good more.In other words, Lvization quaternary phosphine and the ratio of iodate quaternary phosphine in mixture to be processed are preferably at least 1/20, more preferably at least 1/10 (mol ratio), and the Lvization quaternary phosphine is preferably 0.1wt% at least at mixture concentration to be processed, especially preferably 1wt% at least.
As implementing an object lesson of the present invention, obtain the method for mixture to be processed below can mentioning and add each method in the method for iodide, they describe order, but should understand and not mean that the present invention is limited by following method.
Application examples I
As the liquid that contains catalyzer, will draw off at the partially liq in the method for producing ethylene glycol.As long as it is the liquid that contains the catalyzer that is present in this method, there is not particular restriction for the removed position of this liquid.As mentioned above, the reaction that is formed ethylene glycol by oxyethane is a two-step reaction, comprises that oxyethane and carbonic acid gas form the reaction of ethylene carbonate and the hydrolysis reaction that ethylene carbonate forms ethylene glycol.Therefore, when this reaction is undertaken by the reactor that is provided with in placed in-line two steps, the liquid from this production method can be drawn off from arbitrary reactor maybe can from two reactors, draw off.
When liquid when reactor outlet draws off, be the rate of recovery of raising iodate quaternary phosphine in one step of back, preferred chlorination and iodate quaternary phosphine concentration height in mixture to be processed, therefore, in the case, the preferred water, ethylene glycol or the ethylene carbonate that remove as solvent of steaming is to concentrate.Distillation can be undertaken by distillation tower, but also can use simple vaporizer.Should concentrate and proceed at least 1/20 times (by mole) that the concentration of iodate quaternary phosphine in mixture to be processed becomes solvent and get final product.Consider the thermotolerance of quaternary alkylphosphonium salt, this concentration operation preferably under reduced pressure preferably at 400 torrs (53.2Pa) at the most, carries out under 60 to 210 ℃ of preferred temperature.
The highly enriched catalyst solution that obtains by the distillation concentrated reaction solution comprises the Lvization quaternary phosphine of iodate quaternary phosphine and the formation by the iodate quaternary phosphine in the technology of chlorination production ethylene glycol.Here, catalyst solution is for taking out from technology and spissated a kind of reaction soln, or the catalyst solution for drawing off from distillation tower, and this distillation tower is used for catalyst solution is separated with water, ethylene glycol and ethylene carbonate in technology.
The iodide that use as being used to reclaim the iodate quaternary phosphine can use any iodide, if its be can dissociation in water also can with the ionic compound of Lvization quaternary phosphine ion-exchange, it can be chosen suitably by those skilled in the art.Yet, consider solvability, toxicity, price etc., for example can preferably use an alkali metal salt such as sodium salt or sylvite or hydracid.
Inorganic iodide can be any iodide, if its be can dissociation in water also can with the ionic compound of Lvization quaternary phosphine ion-exchange.Yet, consider solvability, toxicity, price etc., preferred as alkali salt such as sodium salt or sylvite.
The add-on of iodide can with the equivalent at least of the Lvization quaternary phosphine that exists in the mixture to be processed.Preferred range is 0.5 to 10mol, and more preferably 1 to 5mols, by the every mole of Lvization quaternary phosphine that exists in the mixture to be processed.If the iodide amount that adds then improves the rate of recovery, but will lose excessive iodide more than necessary.
Iodide can solid or the form of the organic solvent solution or the aqueous solution add.Yet, in service in industry, consider the operability preferred liquid, therefore, preferably add with organic solvent solution or aqueous solution form.
For the aqueous solution, the amount of water can be the amount that is enough to dissolve iodide, and this amount depends on the iodide that will use.For example, will use therein under the situation of potassiumiodide, its saturation solubility in water is 60%, and therefore can add the concentration of the such potassiumiodide of entry in mixture to be processed will be at most this level.Usually it is added with the aqueous solution form with concentration 1 to 60%.
The device that iodide is added mixture to be processed can be any vessel form, but the preferred container with whipping appts that uses is to promote ion exchange reaction.
By this operation, the Lvization quaternary phosphine that exists in the mixture to be processed will be converted into the iodate quaternary phosphine, and it will be separated out in water by already present iodate quaternary phosphine in mixture to be processed.Separate out temperature and be preferably low temperature, the iodate quaternary phosphine that remains in like this in the water will be seldom.Separate out preferably under 0 to 30 ℃ of temperature and carry out.
The iodate quaternary phosphine of separating out will carry out filtered and recycled.Filter method does not have particular restriction, for example only all can use by the conventional filtration and the centrifugation of strainer.
Iodate quaternary phosphine with recovered in solid form can comprise the Lvization quaternary phosphine of about 10wt% and the iodide of adding sometimes.Under this concentration, itself can be recirculated in the reactions steps of preparation ethylene glycol.Yet,, can before recirculation is used, it be washed with water to improve the purity of iodate quaternary phosphine if necessary.Water after being used to wash comprises the iodate quaternary phosphine, and this water can be used for washing next time or can will add the water of the above-mentioned iodide in the mixture to be processed once more as dissolving.
The iodate quaternary phosphine that reclaims for example dissolves in the ethylene glycol, and can this be recirculated in the reaction system.
The embodiment that Lvization quaternary phosphine wherein is converted into the iodate quaternary phosphine that will reclaim has been described above.This operation also can be carried out in organic solvent.Below, operating in the organic solvent of butter wherein separated out in description carry out, thus the Lvization quaternary phosphine is converted into an embodiment of the iodate quaternary phosphine that will reclaim.
In the highly enriched catalyst solution that obtains, ethylene glycol and/or ethylene carbonate exist as solvent.Therefore, to this catalyst solution, can implement butter of the present invention and separate out operation.But adding wherein, another low organic solvent of solubleness of butter (forming by the adding iodide) also is effective.In addition, ethylene glycol in preferably will this highly enriched catalyst solution and/or ethylene carbonate are further removed to obtain to be substantially free of the solid of solvent, this solid is dissolved in another organic solvent once more, so can further reduce the solubleness of butter, will further improve precipitation efficiency like this.
For organic solvent used herein, it preferably has the performance of high dissolving quaternary alkylphosphonium salt, has the performance of low dissolving butter simultaneously.As preferred solvent, for example can mention aliphatic halogenated hydrocarbons, ketone, alcohol, nitrile, acid amides and carbamide compound.
Wherein, alcohol can be for example ethanol, the 1-propyl alcohol, the 2-propyl alcohol, the 1-butanols, the 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1, the 1-dimethyl ethanol, the 1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 3-methyl isophthalic acid-butanols, 2-methyl-1-butene alcohol, 1,1-dimethyl-1-propyl alcohol, the 1-hexanol, the 2-hexanol, the 3-hexanol, 2-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, the 1-enanthol, the 2-enanthol, the 3-enanthol, the 4-enanthol, the 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, 1 nonyl alcohol, the 2-nonyl alcohol, 1-decanol, the 1-hendecanol, the 1-dodecanol, 1, the 6-hexylene glycol, cyclopentanol, hexalin, benzylalcohol or phenylethyl alcohol etc.
Aliphatic halogenated hydrocarbons can be for example methylene dichloride, chloroform, 1,2-ethylene dichloride, 1, vinyl trichloride, 1,2 cbloropropane isopropyl chloride, 1,3-propylene dichloride, glyceryl trichloride or 1,6-dichloro hexane etc.
Nitrile can be for example acetonitrile, propionitrile, butyronitrile, adiponitrile or benzonitrile.Acid amides can be for example dimethyl formamide or N,N-DIMETHYLACETAMIDE.Carbamide compound can be for example tetramethyl-urea or 1,3-methylimidazole quinoline-2-ketone.This ketone can be for example acetone, methylethylketone or methyl isopropyl Ketone.Carbonic ether can be for example ethylene carbonate, Texacar PC or butylene carbonate etc.
For organic solvent, can use wherein a kind of solvent separately, maybe can be used in combination with form of mixtures its two or more.The amount of the organic solvent that adds does not have particular restriction, but is generally chlorination in the mixture to be processed and 1 to 10 times of iodate quaternary phosphine gross weight.
For example, sodium iodide can very easily be dissolved in the acetone, therefore is preferred combination.In addition, potassiumiodide can very easily be dissolved in the ethylene glycol, and therefore such combination also is preferred.Yet, in the case, needn't require iodide to be dissolved in the organic solvent fully.Even if the saturated meltage of iodide is very little, after adding mixture to be processed, iodide will consume by reacting with the Lvization quaternary phosphine, and dissolving will further be carried out to replenish this consumption.Therefore, the amount that exceeds solubleness will be reacted the formation butter.The requirement of selecting iodide and organic solvent be iodide with the butter of this iodide and Lvization quaternary phosphine reaction formation in organic solvent, exist molar solubility poor.For this combination, for example can mention the combination of butanols or ethylene glycol and potassiumiodide.
The device that is used for iodide are added mixture to be processed can be any vessel form, but the preferred container with whipping device that uses is to promote ion exchange reaction.
By this operation, the Lvization quaternary phosphine De quaternary alkylphosphonium salt that exists in the mixture to be processed will be converted into the iodate quaternary phosphine, and chlorine will form with butter and separate out simultaneously.Separating out temperature does not have particular restriction, can determine the solubleness of the boiling point of the organic solvent of the dependency of solvent temperature, use or viscosity, He quaternary alkylphosphonium salt according to butter.Usually, separate out under 0 to 50 ℃ normal temperature and carry out.The reaction of iodide and chlorine quaternary phosphine will be carried out very soon when the viscosity of solvent is hanged down.Yet, have under the low situation of the solubleness of high viscosity or iodide at solvent, preferably prolong mixing time.This reaction was preferably finished in 3 hours at 1 minute.To be converted into iodide with transformation efficiency at least 90% by this operation Lvization quaternary phosphine De quaternary alkylphosphonium salt in organic solvent, meanwhile, butter will be separated out.
With the butter of separating out by removing by filter.Filter method does not have particular restriction, for example only all can use by the conventional filtration of strainer and centrifugation etc.
In the filtrate after the filtering separation butter, with the iodate quaternary phosphine as catalyst dissolution.Therefore, remove organic solvent by evaporating from then in the filtrate, iodate quaternary phosphine and iodide (when excessive adding) will be with recovered in solid form.Removing organic solvent is undertaken by conventional vaporizer.As mentioned above, consider the thermotolerance of the iodate quaternary phosphine of recovery, as required, thisly remove organic solvent by evaporation and preferably carrying out under 200 ℃ at the most in temperature by decompression.
So the purity of the iodate quaternary phosphine that reclaims is at least 90% (iodide and the remaining solvent that do not comprise excessive adding), therefore it in statu quo or to be dissolved in suitable solvent such as solution form recirculation in the ethylene glycol such as the reactions steps can be re-used.Yet, before preferably in being recirculated into reactions steps, re-using the solid that reclaims is washed with water to remove remaining iodide and solvent.Wash for this water, form slurry in the solid that the washing water adding can be reclaimed, it can be filtered and centrifugation.In the case, consider the solution loss of washing water, the amount that preferably makes the washing water that will add is the twice at the most of the solid weight that will reclaim.
As the other method of removing the butter in the above-mentioned technology, can not filter under the butter, remove by similar operations and desolvate, carry out above-mentioned water washing then so that butter is soluble in water and remove.
Can mention that following method is as another embodiment of the present invention.
Application examples II
In application examples I, reclaim in advance, wherein add entry and mix with high concentration catalyst solution, wherein the concentration of iodate quaternary phosphine is at least 1/20 (by mole) of ethylene glycol, or, then cool off so that iodate quaternary phosphine selectivity is separated out and reclaimed with its concentrated concentration so far.Here if the water yield of Jia Ruing is chosen wantonly, but too little, then can not obtain enough effects of separating out, and therefore must add at least 0.1 times of dissolved iodate quaternary phosphine weight.The upper limit that adds the water yield does not have particular restriction, but handles volume in order excessively not improve, and its amount preferably is adjusted to about at the most 5 times of dissolved dissolved iodate quaternary phosphine weight.This temperature of separating out operation is preferably low, and the residual quantity of iodate quaternary phosphine in water will be very little like this.This operation is preferably carried out under 0 to 30 ℃ of temperature.
Behind the iodate quaternary phosphine that recovery is separated out, in the remainder water solution, will there be undecomposed iodate quaternary phosphine and Lvization quaternary phosphine.Remaining this solution can be used as mixture to be processed after reclaiming the iodate quaternary phosphine, if need and can concentrate it, adds iodide then to carry out the Lvization quaternary phosphine to the conversion of iodate quaternary phosphine with separate out.Consider the organic efficiency of the transformation efficiency and the iodate quaternary phosphine of Lvization quaternary phosphine, preferably concentrate, so that the concentration of the Lvization quaternary phosphine in mixture to be processed becomes 1wt% at least before the adding iodide.
The type of the iodide that add, concentration and adding method, the filter method of precipitate, aftertreatment etc. can be identical with above-mentioned application examples I.
Yet in the case, water is present in the reaction system, and iodide can solid form add, and so will reduce the consumption of water, and can reduce the solution loss of iodate quaternary phosphine in waste water.
In addition, after reclaiming in advance, can separate out operation by using mixture according to following acquisition to carry out butter as mixture to be processed, promptly this mixture is by evaporation and remove in the aqueous solution that contains chlorination and iodate quaternary phosphine preferred at least 90%, more preferably at least 99% water and obtain.In other words, the mixture that will handle is dissolved in the organic solvent, and meltage is 1 to 10 times of summation of chlorination in the mixture to be processed and iodate quaternary phosphine, and to wherein adding iodide.The type of the iodide that add, concentration and adding method, the filter method of precipitate, aftertreatment etc. can be identical with the method for above-mentioned application examples I.
In addition, in the method, can add the iodide aqueous solution and replace the water that adds so that the iodate quaternary phosphine is separated out in high concentration catalyst solution, it will be unnecessary adding iodide in the case in one step of back.
Under each situation, by carry out removing organic solvent the organic solvent solution after solid-liquid separates from precipitate, can further reclaim the iodate quaternary phosphine to butter, it can be re-used with the iodate quaternary phosphine that reclaims earlier again.
Can mention that following method is as another embodiment.
Application examples III
In application examples 1, with highly enriched catalyst solution (wherein the concentration of iodate quaternary phosphine be ethylene glycol 1/20 or be concentrated into this concentration) further concentrate, and solvent that will at least 90% steams and removes.In the case, resistates (distillation residue) will solidify when cooling.The solidified resistates with the water washing of appropriate amount, so is eluted to the quaternary phosphine of the Lvization in the resistates in the water and removes.Equally in the case, the temperature of the water that is used to wash is preferably low, and the meltage of iodate quaternary phosphine in washing water will be very little like this.Washing is preferably carried out under 0 to 30 ℃.
The water yield that is used to wash does not have particular restriction.Yet, consider detersive efficiency and the loss of iodate quaternary phosphine in waste water, it is preferably 0.5 to 10 times of the solid residue weight that will wash.Do not require that the water that is used to wash is pure water, in present method, can use recirculated water.Especially preferably the aqueous solution that contains the iodate quaternary phosphine is because can reduce the solution loss of iodate quaternary phosphine in water thus.
In the water after washing, the Lvization quaternary phosphine of wash-out and the iodate quaternary phosphine of oligodynamical will be had.
It can be used as mixture to be processed, as mentioned above, it can be concentrated on demand, adds iodide then to carry out the Lvization quaternary phosphine to the conversion of iodate quaternary phosphine with separate out.Equally in the case, the concentration of Lvization quaternary phosphine in mixture to be processed is preferably 1wt% at least before adding iodide, and the type of the iodide that add, concentration and adding method, the filter method of precipitate, aftertreatment etc. can be identical with the method for above-mentioned application examples I.
Equally in the case, water has been present in the system, and iodide can add by solid form, can reduce the consumption of water thus, and can reduce the solution loss of iodate quaternary phosphine in waste water.
In addition, carry out washing operation therein, the water after will washing adds in wherein the aforesaid method as mixture to be processed with iodide, can carry out a kind of mode of aforesaid method as shortening with the iodide aqueous solution as washing water.In the case, the concentration of the iodide aqueous solution that use can be such concentration, and promptly the concentration in the water of iodide after washing will be the concentration in above-mentioned adding and the admixture.
Can separate out operation by using mixture according to following acquisition to carry out butter as mixture to be processed, promptly this mixture is by evaporation and remove in the aqueous solution that contains chlorination and iodate quaternary phosphine preferred at least 90%, more preferably at least 99% water and obtain.In other words, the mixture that will handle is dissolved in the organic solvent, and meltage is 1 to 10 times of summation of chlorination in the mixture to be processed and iodate quaternary phosphine, and to wherein adding iodide.
The type of the iodide that add, concentration and adding method, the filter method of precipitate, aftertreatment etc. can be identical with the method for above-mentioned application examples I.
In addition, equally in the method, the available iodide aqueous solution replaces bath water, and it will be unnecessary therefore adding iodide in the case in one step of back.
Under each situation, by carry out removing organic solvent the organic solvent solution after solid-liquid separates from precipitate, can further reclaim the iodate quaternary phosphine to butter, it can be re-used with the iodate quaternary phosphine that reclaims earlier again.
In addition, can with highly enriched catalyst solution (wherein the concentration of iodate quaternary phosphine be ethylene glycol 1/20 or be concentrated into this concentration) further concentrate, and steam remove at least 90% solvent after, solution remained under at least 90 ℃ the temperature, so can keep liquid state.Water is added wherein, then be cooled to 0 to 40 ℃, so can separate out the iodate quaternary phosphine.In addition, can drop in chilled water or the slurry with above-mentioned concentration residue only or with water and separate out.Equally, in the case, after separating and reclaiming the iodate quaternary phosphine of separating out, in the residual aqueous solution, will there be undecomposed iodate and Lvization quaternary phosphine.
It can be used as mixture to be processed, as mentioned above, it can be concentrated on demand, adds iodide then to carry out the Lvization quaternary phosphine to the conversion of iodate quaternary phosphine with separate out.
Equally in the case, the concentration of Lvization quaternary phosphine in mixture to be processed is preferably 1wt% at least before adding iodide, and the type of the iodide that add, concentration and adding method, the filter method of precipitate, aftertreatment etc. can be identical with the method for above-mentioned application examples I.
Equally in the case, water has been present in the system, and iodide can add by solid form, can reduce the consumption of water thus, and can reduce the solution loss of iodate quaternary phosphine in waste water.
In addition, carry out a kind of mode of aforesaid method, can use the iodide aqueous solution place of water of heating as shortening.
Can separate out operation by using mixture according to following acquisition to carry out butter as mixture to be processed, promptly this mixture is by evaporation and remove in the aqueous solution that contains chlorination and iodate quaternary phosphine preferred at least 90%, more preferably at least 99% water and obtain.In other words, the mixture that will handle is dissolved in the organic solvent, and meltage is 1 to 10 times of summation of chlorination in the mixture to be processed and iodate quaternary phosphine, and to wherein adding iodide.
The type of the iodide that add, concentration and adding method, the filter method of precipitate, aftertreatment etc. can be identical with the method for above-mentioned application examples I.
Equally in the method, the available iodide aqueous solution replaces bath water, and it will be unnecessary therefore adding iodide in the case in one step of back.
In all embodiments, the present invention also is applicable to chlorination and the iodate quaternary phosphine that remains in the separating liquid behind the butter that solid-liquid separation is separated out by the adding iodide.In other words, also can add iodide repeatedly and remove butter until reaching the required rate of recovery.
In the embodiment of this invention, near small part reaction soln and/or catalyst solution are from the reaction method of operate continuously continuously or be interrupted and draw off, and concentrate as required and/or pre-treatment after, carry out conversion and the recovery iodate quaternary phosphine of Lvization quaternary phosphine, then the iodate quaternary phosphine catalyst recycle that reclaims is gone in the reactor to the iodate quaternary phosphine.In the case, there is not particular restriction for reclaiming the reaction soln that the iodate quaternary phosphine draws off and/or the amount of catalyst solution.Yet in the scope that does not excessively increase the cost that reclaims catalyzer, keeping reaction efficiency to be in high level by removing the dechlorination quaternary phosphine, when the weight ratio in reactor became 0.01 to 1.0 when Lvization quaternary phosphine and iodide, continuously preferred or interruption drew off reaction soln and/or the catalyst solution that is used to handle.Unloading output does not have particular restriction, but preferably in about 0.1 to 100wt% scope, by the amount of reaction soln or catalyst solution in each individual system.
Embodiment
The present invention further describes reference example.Yet, should understand the present invention and not mean that and limited by these embodiment.
Embodiment 1-1
Be forced into 2.0MPa with carbonic acid gas, in first reactor of 1 hour 100 ℃ of following residence time, drop into 5 weight parts/hr iodate tributyl Jia Ji Phosphonium as catalyzer, 0.8 weight part/hr salt of wormwood and 78 weight parts/hr parent material aqueous solution of ethylene oxide (60wt%), obtain to comprise the reaction soln of ethylene carbonate and ethylene glycol (EG) thus.This solution is transferred to (2 hours residence time) in second reactor with its entire amount under 150 ℃ of pressure 0.5MPa, temperature, makes contained ethylene carbonate hydrolysis thus to obtain the aqueous glycol solution that 66.5 weight parts/hr contains catalyzer.
The reaction soln that obtains is distilled down at pressure 11kPa (80mmHg) by the vacuum tower 140 ℃ of column bottom temperatures, at the bottom of tower, obtain dehydration liquid thus, and, evaporate most of ethylene glycol thus and reclaim the catalyst solution that 13 weight parts/hr has catalyst concentration from base of evaporator with handling down at pressure 8kPa (60mmHg) in the further 140 ℃ of vacuum-evaporators operated down of this liquid.The catalyst solution that reclaims goes in first reactor to re-use as catalyst recycle.The catalyst solution of operation after 1 year is composed as follows continuously:
The composition of catalyst solution
Ethylene glycol: about 59wt%
Iodide (iodate quaternary phosphine): about 33wt%
Muriate (Lvization quaternary phosphine): about 6wt%
Salt of wormwood: about 2wt%
After reaching above-mentioned composition, change operation, like this this catalyst solution of part is drawn off with speed 0.02 weight part/hr.The catalyst solution (hereinafter referred to as " unloading liquid A ") that draws off is dropped in the rinsing vessel, and under 3 torrs (400Pa) and 128 ℃ of conditions, remove about 93wt% ethylene glycol contained in the liquid.
The liquid of removing behind the ethylene glycol (hereinafter referred to as " concentrated liquid A ") is remained under 95 ℃, and adds the 3wt% potassium iodide aqueous solution, and with this mixture stir and mix under be cooled to 20 ℃, it was placed 1 hour.Here the muriate equimolar amount among potassiumiodide of Jia Ruing and the concentrated liquid A, the water yield of use and concentrated liquid A etc. are heavy.
Precipitate is separated by vacuum filter and analyze, this precipitate like this composed as follows.This shows that it can effectively separate contained 90wt% iodide and muriate among the unloading liquid A as iodate quaternary phosphine catalyzer.
The composition of precipitate
Water: about 18wt%
Ethylene glycol: about 2wt%
Iodide (iodate quaternary phosphine): about 80wt%
Muriate (Lvization quaternary phosphine): about 2wt%
Salt of wormwood: 1wt% at the most
Be dissolved in this precipitate in the ethylene glycol and be recirculated into reactor.
Therefore, this operates in when carrying out catalyst recovery and recirculation and carries out continuously, so can operate continuously effectively under reactionless efficient reduction problem in the method for producing ethylene glycol.
Embodiment 1-2
In embodiment 1-1, replace potassium iodide aqueous solution to add separating as concentrated liquid A and remove among the concentrated liquid A after the ethylene glycol with the distilled water of same amount, and carry out similar operations so that solid is separated out.
Precipitate is separated and analysis.Confirm that so this precipitate comprises the iodide of the 94wt% among the unloading liquid A and the muriate of about 13wt%, and can from muriate, effectively separate iodate quaternary phosphine catalyzer.
In isolating liquid from precipitate (hereinafter referred to as " separating liquid A "), about 6wt% iodide and about 87wt% muriate among the dissolving unloading liquid A.In this separating liquid A, add the potassiumiodide that its amount (by mole) is 1.2 times of muriates in the liquid in the 50wt% water-soluble form, and this mixture was placed 1 hour down at 20 ℃.This precipitate is separated and analysis, so confirm in this precipitate, can effectively separate as the 50wt% muriate among the unloading liquid A of iodate quaternary phosphine catalyzer.
Embodiment 1-3
With the separating liquid A distillation that obtains among the embodiment 1-2, and steaming removes the water of the 50wt% among the separating liquid A to concentrate.In this concentrated liquid, add the potassiumiodide that its amount (by mole) is 1.2 times of muriates in the liquid in the 50wt% water-soluble form, and this mixture was placed 1 hour down at 20 ℃.This precipitate is separated and analysis, so confirm in this precipitate, can effectively separate as the 75wt% muriate among the unloading liquid A of iodate quaternary phosphine catalyzer.
Embodiment 2-1
Be forced into 2.0MPa with carbonic acid gas, in first reactor of 1 hour 100 ℃ of following residence time, drop into 5 weight parts/hr iodate tributyl Jia Ji Phosphonium as catalyzer, 0.8 weight part/hr salt of wormwood and 78 weight parts/hr parent material aqueous solution of ethylene oxide (60wt%), obtain to comprise the reaction soln of ethylene carbonate and ethylene glycol (EG) thus.This solution is transferred to (2 hours residence time) in second reactor with its entire amount under 150 ℃ of pressure 0.5MPa, temperature, makes contained ethylene carbonate hydrolysis thus to obtain the aqueous glycol solution that 66.5 weight parts/hr contains catalyzer.
The reaction soln that obtains is passed through in the vacuum tower of 140 ℃ of column bottom temperatures in pressure 11kPa (80mmHg) distillation down, at the bottom of tower, obtain dehydration liquid thus, and, evaporate most of ethylene glycol thus and reclaim the catalyst solution that 13 weight parts/hr has catalyst concentration from base of evaporator with handling down at pressure 8kPa (60mmHg) in the further 140 ℃ of vacuum-evaporators operated down of this liquid.The catalyst solution that reclaims goes in first reactor to re-use as catalyst recycle.The catalyst solution of operation after 1 year is composed as follows continuously:
The composition of catalyst solution
Ethylene glycol: about 59wt%
Iodide (iodate quaternary phosphine): about 33wt%
Muriate (Lvization quaternary phosphine): about 6wt%
Salt of wormwood: about 2wt%
After reaching above-mentioned composition, change operation, like this this catalyst solution of part is drawn off with speed 0.02 weight part/hr.The catalyst solution (hereinafter referred to as " unloading liquid A ") that draws off is dropped in the rinsing vessel, and under 3 torrs (400Pa) and 128 ℃ of conditions, remove about 93wt% ethylene glycol contained in the liquid.The liquid of removing behind the ethylene glycol (hereinafter referred to as " concentrated liquid A ") is remained under 95 ℃, and the water of adding and concentrated product A same amount.This mixture is cooled to 20 ℃ in stirring with under mixing, it was placed 1 hour.
Precipitate (hereinafter referred to as " precipitate A ") is passed through its separation of vacuum separation, and analyze acquisition filtrate (hereinafter referred to as " filtrate A "), this filtrate A's like this is composed as follows, and it is the muriatic a kind of filtrate of about 80wt% that contains among the unloading liquid A.
The composition of filtrate A
Water: about 78wt%
Ethylene glycol: about 7wt%
Iodide (iodate quaternary phosphine): about 1wt%
Muriate (Lvization quaternary phosphine):
About 10wt%
Salt of wormwood: 4wt%
On the other hand, analyze the composed as follows of above-mentioned precipitate A this precipitate like this.This show its be comprise among the unloading liquid A the 90wt% iodide
The composition A of precipitate
Water: about 16wt%
Ethylene glycol: about 1wt%
Iodide (iodate quaternary phosphine): about 80wt%
Muriate (Lvization quaternary phosphine): about 2wt%
Salt of wormwood: 1wt% at the most
Water contained among the filtrate A and ethylene glycol are removed by the vaporizer of operating down at 140 ℃.Remove anhydrate and ethylene glycol in, pressure is reduced, kept 5 torrs (660Pa) at last 30 minutes.By this operation, the quantitative change of contained water and ethylene glycol is 10wt% at the most in the distillation leftover.To so remove anhydrate and the resistates of ethylene glycol in, add the acetone of identical weight.Then, the liquid that obtains is transferred in the container that agitator is housed, and adds the sodium iodide of solid form, add-on is contained muriatic 1.2 times (by moles), then at room temperature stirs 1 hour.To separate out precipitate that operation forms by this butter and separate by vacuum filter and analyze, so in this precipitate, have the muriatic sodium-chlor of 98wt% at least that is equivalent among the filtrate A.On the other hand, to separate the filtrate (hereinafter referred to as " liquor B ") that obtains by solid-liquid and be added in 5 torrs (660Pa), 110 ℃ down in the vaporizer of operation, and steam to remove in the liquor B acetone and the ethylene glycol of all amounts basically, the solid that obtains is mixed with the water of identical weight and wash, follow by vacuum filter and carry out the solid-liquid separation.Analyze the solid (hereinafter referred to as " solid B ") that obtains, find that it has following composition.
Solid is formed B
Water: about 17wt%
Ethylene glycol: 1wt% at the most
Iodide (iodate quaternary phosphine): about 81wt%
Muriate (Lvization quaternary phosphine): 1wt% at the most
Sodium iodide: about 1wt%
Have this solid B and a kind of mixture of above-mentioned precipitate A bonded and comprise iodide and the muriate of about 98wt% contained among the unloading liquid A, as the iodate quaternary phosphine, it is dissolved in the ethylene glycol of identical weight and is recirculated in the reactor and re-uses.
Therefore, when carrying out catalyst recovery and recirculation, operation is proceeded, and can not have continuous effective operation under the problem that reaction efficiency reduces thus in producing the method for ethylene glycol.
Embodiment 2-2
In embodiment 2-1, separating and removing after the ethylene glycol among the concentrated product A of institute, the propyl carbinol that adds identical weight is as being used for the dissolved organic solvent.This solution is transferred in the container that agitator is housed, and the potassiumiodide of contained muriate identical weight in adding and the liquid, then at room temperature mixed 2 hours.
Precipitate is separated and analysis through vacuum filter, so in this precipitate, exist to be equivalent to the muriatic Repone K of 95wt% at least contained among the concentrated product A.
On the other hand, filtrate is added in the vaporizer of 5 torrs (660Pa), 110 ℃ of following operations, all measure butanols and ethylene glycol basically in the evaporated filtrate.The filtrate that obtains is mixed with the water of identical weight and wash, follow by vacuum filter and carry out the solid-liquid separation.The solid that analyze to obtain finds that it has following composition, and it is to contain the iodide that draw off the about 95wt% among the filtrate A and the solid of muriatic iodate quaternary phosphine form.
Solid is formed
Water: about 18wt%
Ethylene glycol: 2wt%
Iodide (iodate quaternary phosphine): about 80wt%
Muriate (Lvization quaternary phosphine): 1wt% at the most
Potassiumiodide: about at the most 1wt%
This solid is dissolved in the ethylene glycol of identical weight and is recirculated in the reactor and re-use.
Therefore, when carrying out catalyst recovery and recirculation, operation is proceeded, and can not have continuous effective operation under the problem that reaction efficiency reduces thus in producing the method for ethylene glycol.
Comparative example 1
In embodiment 1-1, draw off 100g dehydration reaction solution from the vacuum distilling tower bottom.The wherein contained ethylene glycol and the ratio of catalyzer are 87%.To the water that wherein adds identical weight, and this mixture is cooled to 0 ℃, but do not form precipitate.
Embodiment 1-4
In the filtrate that in embodiment 1-2, obtains, be incorporated as the potassiumiodide of the 1 times of molar weight of muriate in the liquid, and this mixture was placed 1 hour down at 20 ℃ with 50wt% aqueous solution form.Separate precipitate and analysis.The result confirms, in this precipitate, effectively in the separating filtrate about 87wt% muriate as iodate quaternary phosphine catalyzer.
Industrial applicibility
According to the present invention, producing alkylene derivative such as aklylene glycol such as ethylene glycol, or in the method for alkylene carbonates such as ethylene carbonate, comprise with alkylene oxide such as oxirane and water or carbon dioxide in the presence of carbon dioxide by iodate and/or bromination quaternary phosphine catalyst reaction, can from reaction system, effectively reclaim iodate or bromination quaternary phosphine catalyst and it is recycled use, maybe the Lvization quaternary phosphine that forms in the reaction system effectively can be converted into iodate and/or bromination quaternary phosphine, it can be recirculated in the reaction system and re-use. The Lvization quaternary phosphine that so can prevent low catalytic activity is accumulated in reaction system, it can be transformed simultaneously high catalytic activity iodate and/or bromination quaternary phosphine and with its recirculation use, so can and in long-time, carry out constantly and effectively forming the reaction of alkylene derivative with the maintenance of the catalytic activity in reaction system high level.
The present invention is based on Japanese patent application No.2003-031391 (February 7 2003 applying date), Japanese patent application No.2003-078178 (March 20 2003 applying date) and Japanese patent application No.2003-088281 (March 27 2003 applying date), introduce it here all as a reference.
Claims (7)
1. method of producing alkylene derivative, comprise alkylene oxide and water reactions steps in the presence of carbonic acid gas by iodate or bromination quaternary phosphine catalyst reaction formation aklylene glycol, it is characterized in that from removing this aklylene glycol partial reaction solution and/or the catalyst solution at least, so that the mol ratio of aklylene glycol and catalyzer becomes 20 times at the most, then mix to reclaim catalyzer with water
Wherein said reaction soln is effusive liquid from reactor and/or the liquid that draws off from reactor; Described catalyst solution is for dividing liquid dried up and aklylene glycol or alkylene carbonates catalyst concentration from reaction soln by distillation.
2. according to the method for claim 1, it is characterized in that the mol ratio of aklylene glycol and catalyzer is 2 times at the most.
3. according to 1 or 2 method, it is characterized in that mixing the service temperature that reclaims catalyzer with water is 30 ℃ at the most.
4. according to the method for claim 2, it is characterized in that the blended water yield is at least 0.1 times, by the catalyst weight that reclaims.
5. according to the method for claim 2, it is characterized in that mixing water after, carry out solid-liquid and separate, with this catalyzer with solids constituent from after be recirculated in the reactions steps.
6. according to the method for claim 2, it is characterized in that alkylene oxide is an oxyethane.
7. according to the method for claim 5, wherein will separate isolating liquid and use as the water cycle of washing catalyst by solid-liquid.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP031391/03 | 2003-02-07 | ||
| JP2003031391A JP4333153B2 (en) | 2003-02-07 | 2003-02-07 | Method for producing alkylene glycol |
| JP2003078178A JP4273799B2 (en) | 2003-03-20 | 2003-03-20 | Method for producing alkylene derivative |
| JP078178/03 | 2003-03-20 | ||
| JP2003088281A JP4273802B2 (en) | 2003-03-27 | 2003-03-27 | Method for producing alkylene derivative |
| JP088281/03 | 2003-03-27 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800033584A Division CN1313424C (en) | 2003-02-07 | 2004-02-09 | Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1974509A CN1974509A (en) | 2007-06-06 |
| CN1974509B true CN1974509B (en) | 2010-05-19 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101531408A Expired - Lifetime CN1974509B (en) | 2003-02-07 | 2004-02-09 | Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative |
| CNB2004800033584A Expired - Lifetime CN1313424C (en) | 2003-02-07 | 2004-02-09 | Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800033584A Expired - Lifetime CN1313424C (en) | 2003-02-07 | 2004-02-09 | Method for producing alkylene derivative and method for regenerating catalyst for producing alkylene derivative |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4333153B2 (en) |
| CN (2) | CN1974509B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2480446C2 (en) * | 2007-12-06 | 2013-04-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method of producing alkylene glycol |
| TWI457317B (en) * | 2008-05-20 | 2014-10-21 | Shell Int Research | Process for the production of alkylene carbonate |
| BR112012012895B1 (en) | 2009-11-30 | 2018-01-02 | Mitsubishi Chemical Corporation | METHOD FOR PRODUCING ETHYLENE AND ETHYLENE GLYCOL CARBONATE. |
| CN102858727B (en) * | 2010-04-28 | 2014-09-24 | 三菱化学株式会社 | Process for production of alkylene carbonates and/or alkylene glycols |
| US10124330B2 (en) | 2011-06-14 | 2018-11-13 | Equinor Energy As | Method and apparatus for the removal of polyvalent cations from mono ethylene glycol |
| EA039838B1 (en) * | 2018-12-10 | 2022-03-18 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Process for the preparation of ethylene glycol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400559A (en) * | 1982-06-14 | 1983-08-23 | The Halcon Sd Group, Inc. | Process for preparing ethylene glycol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5419905A (en) * | 1977-07-15 | 1979-02-15 | Showa Denko Kk | Preparation of alkylene glycols |
-
2003
- 2003-02-07 JP JP2003031391A patent/JP4333153B2/en not_active Expired - Lifetime
-
2004
- 2004-02-09 CN CN2006101531408A patent/CN1974509B/en not_active Expired - Lifetime
- 2004-02-09 CN CNB2004800033584A patent/CN1313424C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400559A (en) * | 1982-06-14 | 1983-08-23 | The Halcon Sd Group, Inc. | Process for preparing ethylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2000-128814A 2000.05.09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004262767A (en) | 2004-09-24 |
| CN1313424C (en) | 2007-05-02 |
| CN1974509A (en) | 2007-06-06 |
| CN1745051A (en) | 2006-03-08 |
| JP4333153B2 (en) | 2009-09-16 |
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