CA1297123C - Process for cosynthesis of ethylene glycol and dimethyl carbonate - Google Patents
Process for cosynthesis of ethylene glycol and dimethyl carbonateInfo
- Publication number
- CA1297123C CA1297123C CA000532588A CA532588A CA1297123C CA 1297123 C CA1297123 C CA 1297123C CA 000532588 A CA000532588 A CA 000532588A CA 532588 A CA532588 A CA 532588A CA 1297123 C CA1297123 C CA 1297123C
- Authority
- CA
- Canada
- Prior art keywords
- zirconium
- methanol
- titanium
- carbonate
- tin
- 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 - Fee Related
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 169
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 zirconium alkoxides Chemical class 0.000 claims description 20
- 239000002815 homogeneous catalyst Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Chemical class 0.000 claims description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 2
- 208000036366 Sensation of pressure Diseases 0.000 claims description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 2
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- TWRYZRQZQIBEIE-UHFFFAOYSA-N tetramethoxystannane Chemical compound [Sn+4].[O-]C.[O-]C.[O-]C.[O-]C TWRYZRQZQIBEIE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003755 zirconium compounds Chemical group 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZUWXYYNYQIKFSJ-UHFFFAOYSA-N zirconium(2+);dinitrate Chemical compound [Zr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZUWXYYNYQIKFSJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- PLONEVHFXDFSLA-UHFFFAOYSA-N ethyl hexanoate;tin(2+) Chemical compound [Sn+2].CCCCCC(=O)OCC PLONEVHFXDFSLA-UHFFFAOYSA-N 0.000 claims 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000005809 transesterification reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- BNUFVLQIPHELMH-UHFFFAOYSA-N 1,3-dioxolan-2-one;methanol Chemical compound OC.O=C1OCCO1 BNUFVLQIPHELMH-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 150000000180 1,2-diols Chemical class 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000005910 alkyl carbonate group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- SZRVNOQINZUPBH-UHFFFAOYSA-M CC([O-])C.[Ti].C(C)C(C(=O)[O-])CCCC.[Sn+2] Chemical compound CC([O-])C.[Ti].C(C)C(C(=O)[O-])CCCC.[Sn+2] SZRVNOQINZUPBH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 description 1
- 229910007938 ZrBr4 Inorganic materials 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WZRZKFUVOSDSBQ-UHFFFAOYSA-N butane-1,2-diol;carbonic acid Chemical compound OC(O)=O.CCC(O)CO WZRZKFUVOSDSBQ-UHFFFAOYSA-N 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- KLGVAUJELUIWKZ-UHFFFAOYSA-N dimethyl carbonate;ethane-1,2-diol Chemical compound OCCO.COC(=O)OC KLGVAUJELUIWKZ-UHFFFAOYSA-N 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical class C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IKGXNCHYONXJSM-UHFFFAOYSA-N methanolate;zirconium(4+) Chemical compound [Zr+4].[O-]C.[O-]C.[O-]C.[O-]C IKGXNCHYONXJSM-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- YTEWOCYAXODONQ-UHFFFAOYSA-N oxygen(2-) zirconium(3+) nitrate Chemical compound [O-2].[Zr+3].[N+](=O)([O-])[O-] YTEWOCYAXODONQ-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- XLMQAUWIRARSJG-UHFFFAOYSA-J zirconium(iv) iodide Chemical compound [Zr+4].[I-].[I-].[I-].[I-] XLMQAUWIRARSJG-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
PROCESS FOR COSYNTHESIS OF ETHYLENE
GLYCOL AND DIMETHYL CARBONATE
(D#80,611-F) ABSTRACT OF THE DISCLOSURE
A process is disclosed for the cosynthesis of ethylene glycol and dimethyl carbonate by reacting methanol and ethylene carbonate in the presence of a catalyst selected from the group consisting of zirconium, titanium and and tin.
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pg:EX9I/e
GLYCOL AND DIMETHYL CARBONATE
(D#80,611-F) ABSTRACT OF THE DISCLOSURE
A process is disclosed for the cosynthesis of ethylene glycol and dimethyl carbonate by reacting methanol and ethylene carbonate in the presence of a catalyst selected from the group consisting of zirconium, titanium and and tin.
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pg:EX9I/e
Description
g7~3 PROCESS FOR COSYNTHESIS OF ETHYLENE
GLYCOE AND DIMETHYL CARBONATE
(D#80,611-F) This invention concerns a process for cosynthesis of ethylene glycol and dimethyl carbonate by the transesterification reaction of ethylene carbonate and methanol in the presence of homogeneous and heterogeneous catalysts from the group consisting of zirconium, titanium, tin oxides, salts and complexes. In addition to the fact that substantially fewer moles of methanol are needed in the methanol-ethylene carbonate feedstock per mole of dimethyl carbonate produced, this invention is advantageous in that the catalysts are in many cases found to perform better than sodium carbonate, which has been used in the art.
BACKGROUND OF THE INVENTION
Generally the prior art reports that the transesterification of aliphatic hydroxy compounds with carbonic acid, aliphatic diesters and aromatic diesters occurs readily in the presence of a basic catalyst and is a convenient method of synthesis of higher carbonates.
Several references deal with the transesterification of glycol carbonates using an aliphatic alcohol. Most demonstrate the use of methanol and ethylene carbonate.
U. S. Patent No. 4,307,032 discloses a process for the preparation of a dialkyl carbonate by contacting a glycol carbonate of a 1,2-diol containing 2 to 4 carbon atoms with a ~.
~, Q~ ~1 ~ ~
dV
selected alcohol to form the corresponding carbonate of said alcohol at a temperature of between 50 and 250C, in the presence of an improved catalyst which is a thallium compound, allowing the reaction to take place under milder conditions. Thallium is however expensive and very toxic.
In another process disclosed in U. S. Patent No. 4,181,676 there is taught a method for preparation of dialXyl carbonate by contacting a glycol carbonate of a 1,2-diol having 2 to 4 carbon atoms with a selected group of alcohols at an elevat-ed temperature in the presence of an alkali metal or alkali metal compound wherein the improvement comprises employing less than 0.01 percent by weight of alkali metal or alkali metal compound based on the weight of the reaction mixture.
It is known that alkyl carbonates of the type ROCOOR
can be obtained from alcohols and cyclic carbonates corresponding to the above formula through a transesterification reaction in the presence of alkali alcoholates or hydrates; however, moderate amounts of inorganic compounds are produced by these reactions and must be removed by methods which may unfavorably affect the general economy of the process.
In U. S. Patent 4,0~2,884 this problem was addressed and it was found that dialkyl carbonates can be prepared by reacting alcohols with cyclic carbonates in the presence of organic bases, which makes it unnecessary to remove inorganic f ~ ;.
', ' ~, ., ' ' . ' :
- ~LZ9~7~23 compounds and allows the catalyst to be totally recovered by means of simple distillation. The preferred organic base is a tertiary aliphatic amine.
U. S. Patent 4,349,486 teaches a monocarbonate transesterification process comprising contacting a beta-fluoroaliphatic carbonate, a compound selected from the class of monohydroxy aliphatic alcohols, monohydroxy phenols and ortho-positioned dihydroxy aromatic compounds in the presence of a base. This invention claims to greatly reduce undesirable side reactions and only small amounts of carbonic acid-aliphatic-aromatic mixed diester are associated with the isolated aromatic monocarbonate reaction.
The Gilpin and Emmons Patent, referred to above, dis-cusses problems associated with the separation of the methanol, dimethyl carbonate azeotrope and teaches one solution, wherein dimethyl carbonate is isolated from the azeotrope by a com-bination of low temperature crystallization and fractional distillation.
In another article in the J. Or~. Chem. 49(b) 1122-1125 ~1984) Cella and Bacon discuss the results of their work. Among other things, they found that the alkylation of alkali metal bicarbonate and carbonate salts with alkyl halides in dipolar aprotic solvents and phase-transfer catalysts produces alkyl carbonates in good yields. The major limitation of this method : , ~
:. .
is the failure of activated aryl halides or electronegatively substituted alkyl halides to produce carbonates due to the facility with which the intermediate alkoxy carbonate salts decompose.
Disadvantages of the methods discussed above include in many cases the fact that it is necessary to use a large amount of methanol feedstock relative to the amount of dimethyl carbonate produced. Also, in many cases, alkali metal halides are coproduced and these halides present disposal problems.
It would be a substantial advance in the art to devise an efficient process for co-producing dimethyl carbonate and ethylene glycol, which was homogenous and did not necessitate difficult product-catalyst separations. The dimethyl carbonate produced by this novel process can be used as a gasoline extender.
SUMMA~Y OF THE INVENTION
This invention concerns a process for the cosynthesis of ethylene glycol and dimethyl carbonate from ethylene carbonate and methanol by reacting ethylene carbonate and methanol in the presence of a homogeneous or heterogeneous catalyst selected from the group consisting of zirconium, titanium and tin oxides, salts or complexes thereof, at a temperature of from 20C to 200C and . . , ,;
.- : . :
,, ,. :: ' 971:~3 an operative pressure of zero to 5000 psig, until the desired products are formed.
A particular advantage of these systems over the prior art is the high selectivities to dimethyl carbonate (DMC) and ethylene glycol (EG)-basis the ethylene carbonate (EC) and methanol (MeOH) charged. These selectivities are illustrated in the accompanying Example I for the zirconium acetylacetonate catalyst and Example X for the zirconium diperchlorate oxide catalyst precursor.
DETAILED DESCRIPTION OF THE INVENTION
In the narrower and more preferred practice of this invention dimethyl carbonate and ethylene glycol are prepared simultaneously by a transesterification process which comprises reacting ethylene carbonate and methanol in the presence of a homogeneous zirconium, titanium or tin catalyst, at a temperature of between 50C and 150C, and a pressure of at least 50 psig, until the desired products are formed.
Starting materials employed in the process are an aliphatic alcohol and an aliphatic carbonate. Alcohols which work in the process of this invention include the monohydric alcohols containing one to 14 carbon atoms, including methanol, ethanol, isopropanol and isobutanol. Methanol is the preferred alcohol. Alkylene carbonates which will work in the process of this invention include the carbonate derivatives of 1,2-diols .
~ ~ .
,...... ' ~
;; :: , , .~
- 12~71~3 containing two to 10 carbon atoms per molecule, including ethylene carbonate, 1,2-propylene carbonate and 1,2-butanediol carbonate. Ethylene carbonate is the preferred alkylene car~onate feedstock for this process. The preferred starting materials are illustrated in the accompanying examples. Recovery of the desired ethylene glycol and dimethyl carbonate can generally be carried out by distillation and crystallization.
More specifically, methanol and ethylene carbonate are pumped into a tubular reactor upflow at a flow rate of 0.1 to 100 liquid hourly space velocity (LHSV). The reactor temperature is held at between 20 and 200C and a back pressure of zero to 5000 psi is maintained thorughout the experiment.
The homogeneous catalyst systems suitable for the practice of this invention generally comprise a zirconium, titanium or tin compound. The compound can be in the form of a salt or complex.
The zirconium-containing catalyst compound comprises a salt of zirconium or a complex. Suitable examples include zirconium salts of strong (mineral) acids, such as zirconium tetrachloride, ZrC14, zirconium bromide, ZrBr4, zirconium fluo-ride, zirconium nitrate, zirconium sulfate, Zr(SO4)2 4H2O, zirconium mixed halides and zirconium tetraiodide, zirconium alkoxides such as zirconium methoxide, zirconium ethoxide and zirconium isopropoxide, zirconium salts of weak acids such as , : ,~ : . :
":, .
' ~;
~L29~7~Z3 zirconium acetate and zirconium acetylacetonate, Zr(02C5H7)4, as well as zirconium compounds containiny the zirconyl moiety, as for example, zirconium diperchlorate oxide, ZrO(CL04)2 8H20 and zirconium oxide nitrate, ZrO(N03)2 X H20.
The preferred zirconium catalyst precursors are zirconium acetylacetonate and zirconium diperchlorate oxide.
The titanium-containing catalyst compound may likewise comprise a salt of titanium or a complex. Suitable examples include titanium methoxide; other titanium alkoxides such as titanium isopropoxide, titanium acetate and titanium acetylacetonate also work. The preferred titanium compound is titanium isopropoxide.
Suitable tin-containing catalyst precursors for ECtMeOH
transesterification include compounds such as tin(II) 2-ethylhexanoate, tin methoxide, dimethyltin salts, dibutyltin acetate and tributyltin chloride. The preferred tin compound is tin(II) 2-ethylhexanoate.
Also in some cases, the analogous zirconium, titanium and tin heterogeneous catalyst precursors may also be effective.
Examples of suitable heterogeneous catalysts for the desired ethylene carbonate methanol transesterification include zirconium oxide, ZrO2, and titanium oxide. Said heterogeneous zirconium or titanium catalysts may be in the form of pellets, extrudates, , .
.
:
~Z~7~Z3 granules or powders. Also effective may be zirconium carbide, zirconium nitride and zirconium silicate.
A particularly effective catalyst for the cosynthesis of dimethyl carbonate and ethylene glycol is a solution of zirconium diperchlorate oxide dissolved in the ethylene carbonate-methanol feed mix. This reaction solution is illus-trated in accompanying Example X.
During the cosynthesis of ethylene glycol and dimethyl carbonate by the reaction of ethylene carbonate with methanol, a large excess of methanol is normally employed in the prior art.
Usually the initial molar ratio of methanol to ethylene carbonate is in the range of 5 or greater, and preferably at least 10.
This preferred ratio range is illustrated by U. S. Pat-ent 3,803,201 (1974). In the practice of this invention, by contrast, the initial weight ratio of ethylene carbonate to methanol is preferably 2 to 5. Such a range of weight ratios is illustrated by the accompanying examples.
Potential advantages to operating at this ethylene carbonate-to-methanol weight ratio include:
a) More efficient transesterification.
b) Lower levels of methanol required to be recycled after the transesterification step.
Ethylene glycol-dimethyl carbonate synthesis using the homogeneous catalyst described SUPRA can be conducted at reaction ,', :
~2~Z3 temperatures in the range from 20 to 200C. The preferred operating temperature range is 50-150~C.
The reaction can be conducted under atmospheric pres-sure. A pressure reactor is nevertheless required in the case of low-boiling point components if the reaction is to be carried out in the upper temperature range and in the liquid phase. The pressure is not critical. In general the reaction is allowed to proceed under the autogenous pressure of the reactants. However, the reaction can also be carried out under elevated pressure r for example, under an inert atmosphere. A pressure of zero to 5000 psig is appropriate here. An operating pressure of greater than 50 psig is suitable and the preferred pressure was in the range of 50 to 150 psi.
The residence time for the ethylene carbonate and methanol reactants in the tubular reac'cor may vary over a wide range according to the temperature of reaction, the molar ratios of carbonate/alcohol feedstocks, etc. Using the homogeneous catalysts of this invention, the necessary residence time in the reactor may range from 0.01 hours to 10 hours, although it may be extended beyond 10 hours without danger of additional by-products being formed. The preferred residence time is in the range of 0.1 to 5 hours.
The desired products of this process according to the invention are ethylene glycol and dimethyl carbonate.
-. . .
-- ~LZ971~3 By-products include diethylene glycol, l,l~dimethoxyethane, 1,2-dimethoxyethane, methyl 1,3-dioxolane, glycol monomethyl ether and dimethyl ether.
Products have been identified in this work by gas chromatography (gc), NMR, IR and gc-IR or a combination of these techniques. Zirconium and titanium analyses were by atomic absorption IAA). All liquid product analyses have, for the most part, been by gc; all temperatures are in degrees centigrade and all pressures in pounds per square inch gauge.
The following examples illustrate the novel process of this invention. The examples are only for illustrating the invention and are not considered to be limiting:
EXAMPLE I
This example illustrates the cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol, in good selectivity, using a homogeneous zirconium catalyst derived from zirconium acetylacetonate dissolved in the EC/MeOH feed mix. ~he weight ratio of ethylene carbonate to methanol is 2:3.
To a 1 kg mixture of ethylene carbonate (EC) and methanol (typical composition: 59.0% MeOH, 41.0~ EC) was added 50g of zirconium acetylacetonate. The mixture was stirred to dissolve the zirconium salt, cooled in wet ice and the clear ' .
97~3 solution pumped through a 50 cc capacity, stainless steel, tubular reactor upflow at a rate of 25 cc/hr. The reactor temperature was held at 130C and a back-pressure of 100 psi was maintained throughout the experiment. After feeding the ethylene carbonate-methanol mix for several (3-8) hours, the liquid effluent was sampled at regular time intervals and analyzed by gas-liquid chromatography.
Typically, this liquid effluent had the following composition:
10.8 wt~ dimethyl carbonate (DMC) 6.9 wt% ethylene glycol (EG) 30.4 wt% ethylene carbonate (EC) 50.1 wt% methanol (MeOH) Estimated molar selectivity to DMC, basic EC convert-ed =
10.8/90 x 100 = >98%
(41.0-30.4)/88 Estimated molar selectivity to DMC, basic MeOH convert-ed =
10.8/90x2 _ x 100 = 86%
(59.0-50.1)/32 , .. : . . ~ .
- ;
: ` , ~, .
~', ' ' , .
g~lZ3 EG selectivity basis EC converted:
6.9/62 x 100 = 92%
~41.0-30.4)/88 EG selectivity basis MeOH converted:
6.9/62 x 2 x 100 = 78 (59.0-50.1)/32 where DMC, FW = 90.0; EC, FW = 88.0; EGr FW = 62.0; MeOH, FW = 32Ø
EXAMPLES II to IX
Table 1 shows the cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol using a variety of homogeneous zirconium, titanium and tin catalyst sys-tems. Here the most effective catalyst precursors are:
zirconium acetylacetonate tin(II) 2-ethylhexanoate titanium isopropoxide ,, " ... ..
,~ :
: .. ,.. :
, DIMETHYL C~RBONATE/ETHYLENE GLYCOL COSYNTHESISa Reactor Feed Temp. Rate Liquid Product (wt%) Example Catalyst _ ( cc/hr DMC EG EC MeOH
II Zirconium tetra- 130 25 5.6 3.6 41.2 46.0 chloride " 150 25 8.7 5.0 31.6 47.4 III Zirconiu ~ iso- 100 100 2.1 1.8 38.0 54.0 propoxide IV Zirconiumbacetyl- 110 100 5.5 4.0 36.9 51.8 acetonate 150 25 11.4 7.6 31.8 47.0 V Titani ~ isopro- 100 100 4.7 1.8 30.4 52.9 poxide Vl Titanium ~catyl- 110 25 0.1 0.1 52.5 46.1 acetonate ' " 130 25 0.3 0.2 55.5 42.9 " 150 25 1.0 0.6 49.4 47.8 VII Tin~II) 2cethyl- 100 100 5.8 2.2 35.1 55.8 hexanoate VIII Dibutyltin acetate100 100 1.5 0.4 40.1 56.9 IX Tributyltin chloride100 100 0.2 40.6 57.6 aRun in continuous, 50cc capacity, tubular reactor, upflow at 25 cc/hr. liquid flow rate 100 psi pressure, feed composition: 59% MeOH, 41% EC.
Solution in EC/MeO~ was filtered prior to use.
CSome catalyst precipitation during run.
dFeed composition: 52.5% MeOH, 47.5% EC.
, , :
., . : ,: . .
:: , , ,:
: , , - . . ..
~ ~Z~7~3 X MPLE X
This example illustrates khe cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol, in good selectivity, using a homogeneous zirconium diperchlorate oxide catalyst precursor.
To a 1 kg mixture of ethylene carbonate and methanol t66.6% MeOH, 33.3 l/EC) was added 50 g of zirconium diperchlorate oxide, ZrO(C104)2 8H2O. The mixture was stirred to dissolve the zirconyl salt (1.3~ Zr), cooled in wet ice, and fed to the 50 cc tubular reactor at a rate of 25 cc/hr. using the procedures of Example I. The reactor temperature was held at 100C, and a back pressure of 100 psi was maintained throughout the experiment.
Typical liquid effluent showed the following composi-tion:
10.4 wt% dimethyl carbonate 9.0 wt% ethylene glycol 24.2 wt% ethylene carbonate 54.2 wt~ methanol The reactor temperature was then raised to 130C. Typ-ical liquid product now showed the following composition:
14.8 wt% dimethyl carbonate 9.0 wt% ethylene glycol 14.9 wt% ethylene carbonate 53.1 wt~ methanol .: ~
,.~ ' ' ~Z97123 In the latter experiment:
Estimated molar selectivity to DMC, basis EC converted = 89~.
Estimated molar selectivity to D~C, basis MeOH conver~e~ = 76%.
Estimated molar selectivity to EG, basis EC converted = >98%.
Estimated molar selectivity to EG, basis MeOH converted = 95~.
EXAMPLE XI
This example also illustrates dimethyl carbonate/
ethylene glycol cosynthesis, but uses a homogeneous zirconyl nitrate catalyst precursor.
To a 1 kg mixture of ethylene carbonate and methanol ~57.0% MeOH, 38.5% EC) was added 50 g of zirconium dinitrate ox-ide, ZrO(NO3)2 X H2O). The mixture was stirred to dissolve the zirconyl salt (1.5~ Zr), cooled in wet ice, and fed to the 50 cc reactor at a rate of 25 cc/hr., as in Example I. The reactor temperature was held at 130C, and a back pressure of 100 psi was maintained throughout the experiment.
Typical liquid effluent showed the following composi-tion:
4.8 wt~ dimethyl carbonate 8.3 wt% ethylene glycol 27.3 wt% ethylene carbonate 56.0 wt% methanol .
, ...
,~ . :: . . ,: .
::-, . , .:, .
~, , ::
, . . - , , :. '~ ~ ` ' ''' ~29~~Z3 The reactor temperature was then raised to 150C. Un-der these conditions the liqui.d product showed the following com-posltlon:
6.8 wt% carbonate 14.0 wt% ethylene glycol 24.1 wt% ethylene carbonate 52.5 wt~ methanol EXAMPLE XII
This example illustrates the cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol, in good selectivity, using a hetergeneous zirconium oxide catalyst.
To the 50 cc tubular reactor of Example I, packed with 3.2 mm pellets of zirconium oxide ~98% ZrO2), is pumped a so-lution of ethylene carbonate plus methanol (67.6% MeOH, 31.9% EC) at a rate of 50 cc/hr. Reactor temperature was held at 130C, the back pressure was 100 psi. Typlcal liquid effluent showed the following composition.
3.8 wt% dimethyl carbonate 2.7 wt% ethylene glycol 29.9 wt% ethylene carbonate 63.1 wt% methanol ..
:~ . ; '.
'~
,, ,.
'` ` ':
~2~7123 The reactor temperature was then raised to 160C. Typ-ical liquid product under equillibrium conditions, using this higher reactor temperature were as follows:
7.9 wt% dimethyl carbonate 5.2 wt~ ethylene glycol 25.2 wt% ethylene carbonate 60.8 wt~ methanol No zirconium could be detected in the product liquid, basis atomic absorption analyses (AA).
-.
: ,:
, ', : .: -... .
- ~ . . .. .
- : :
..
- :
,: . . : "
GLYCOE AND DIMETHYL CARBONATE
(D#80,611-F) This invention concerns a process for cosynthesis of ethylene glycol and dimethyl carbonate by the transesterification reaction of ethylene carbonate and methanol in the presence of homogeneous and heterogeneous catalysts from the group consisting of zirconium, titanium, tin oxides, salts and complexes. In addition to the fact that substantially fewer moles of methanol are needed in the methanol-ethylene carbonate feedstock per mole of dimethyl carbonate produced, this invention is advantageous in that the catalysts are in many cases found to perform better than sodium carbonate, which has been used in the art.
BACKGROUND OF THE INVENTION
Generally the prior art reports that the transesterification of aliphatic hydroxy compounds with carbonic acid, aliphatic diesters and aromatic diesters occurs readily in the presence of a basic catalyst and is a convenient method of synthesis of higher carbonates.
Several references deal with the transesterification of glycol carbonates using an aliphatic alcohol. Most demonstrate the use of methanol and ethylene carbonate.
U. S. Patent No. 4,307,032 discloses a process for the preparation of a dialkyl carbonate by contacting a glycol carbonate of a 1,2-diol containing 2 to 4 carbon atoms with a ~.
~, Q~ ~1 ~ ~
dV
selected alcohol to form the corresponding carbonate of said alcohol at a temperature of between 50 and 250C, in the presence of an improved catalyst which is a thallium compound, allowing the reaction to take place under milder conditions. Thallium is however expensive and very toxic.
In another process disclosed in U. S. Patent No. 4,181,676 there is taught a method for preparation of dialXyl carbonate by contacting a glycol carbonate of a 1,2-diol having 2 to 4 carbon atoms with a selected group of alcohols at an elevat-ed temperature in the presence of an alkali metal or alkali metal compound wherein the improvement comprises employing less than 0.01 percent by weight of alkali metal or alkali metal compound based on the weight of the reaction mixture.
It is known that alkyl carbonates of the type ROCOOR
can be obtained from alcohols and cyclic carbonates corresponding to the above formula through a transesterification reaction in the presence of alkali alcoholates or hydrates; however, moderate amounts of inorganic compounds are produced by these reactions and must be removed by methods which may unfavorably affect the general economy of the process.
In U. S. Patent 4,0~2,884 this problem was addressed and it was found that dialkyl carbonates can be prepared by reacting alcohols with cyclic carbonates in the presence of organic bases, which makes it unnecessary to remove inorganic f ~ ;.
', ' ~, ., ' ' . ' :
- ~LZ9~7~23 compounds and allows the catalyst to be totally recovered by means of simple distillation. The preferred organic base is a tertiary aliphatic amine.
U. S. Patent 4,349,486 teaches a monocarbonate transesterification process comprising contacting a beta-fluoroaliphatic carbonate, a compound selected from the class of monohydroxy aliphatic alcohols, monohydroxy phenols and ortho-positioned dihydroxy aromatic compounds in the presence of a base. This invention claims to greatly reduce undesirable side reactions and only small amounts of carbonic acid-aliphatic-aromatic mixed diester are associated with the isolated aromatic monocarbonate reaction.
The Gilpin and Emmons Patent, referred to above, dis-cusses problems associated with the separation of the methanol, dimethyl carbonate azeotrope and teaches one solution, wherein dimethyl carbonate is isolated from the azeotrope by a com-bination of low temperature crystallization and fractional distillation.
In another article in the J. Or~. Chem. 49(b) 1122-1125 ~1984) Cella and Bacon discuss the results of their work. Among other things, they found that the alkylation of alkali metal bicarbonate and carbonate salts with alkyl halides in dipolar aprotic solvents and phase-transfer catalysts produces alkyl carbonates in good yields. The major limitation of this method : , ~
:. .
is the failure of activated aryl halides or electronegatively substituted alkyl halides to produce carbonates due to the facility with which the intermediate alkoxy carbonate salts decompose.
Disadvantages of the methods discussed above include in many cases the fact that it is necessary to use a large amount of methanol feedstock relative to the amount of dimethyl carbonate produced. Also, in many cases, alkali metal halides are coproduced and these halides present disposal problems.
It would be a substantial advance in the art to devise an efficient process for co-producing dimethyl carbonate and ethylene glycol, which was homogenous and did not necessitate difficult product-catalyst separations. The dimethyl carbonate produced by this novel process can be used as a gasoline extender.
SUMMA~Y OF THE INVENTION
This invention concerns a process for the cosynthesis of ethylene glycol and dimethyl carbonate from ethylene carbonate and methanol by reacting ethylene carbonate and methanol in the presence of a homogeneous or heterogeneous catalyst selected from the group consisting of zirconium, titanium and tin oxides, salts or complexes thereof, at a temperature of from 20C to 200C and . . , ,;
.- : . :
,, ,. :: ' 971:~3 an operative pressure of zero to 5000 psig, until the desired products are formed.
A particular advantage of these systems over the prior art is the high selectivities to dimethyl carbonate (DMC) and ethylene glycol (EG)-basis the ethylene carbonate (EC) and methanol (MeOH) charged. These selectivities are illustrated in the accompanying Example I for the zirconium acetylacetonate catalyst and Example X for the zirconium diperchlorate oxide catalyst precursor.
DETAILED DESCRIPTION OF THE INVENTION
In the narrower and more preferred practice of this invention dimethyl carbonate and ethylene glycol are prepared simultaneously by a transesterification process which comprises reacting ethylene carbonate and methanol in the presence of a homogeneous zirconium, titanium or tin catalyst, at a temperature of between 50C and 150C, and a pressure of at least 50 psig, until the desired products are formed.
Starting materials employed in the process are an aliphatic alcohol and an aliphatic carbonate. Alcohols which work in the process of this invention include the monohydric alcohols containing one to 14 carbon atoms, including methanol, ethanol, isopropanol and isobutanol. Methanol is the preferred alcohol. Alkylene carbonates which will work in the process of this invention include the carbonate derivatives of 1,2-diols .
~ ~ .
,...... ' ~
;; :: , , .~
- 12~71~3 containing two to 10 carbon atoms per molecule, including ethylene carbonate, 1,2-propylene carbonate and 1,2-butanediol carbonate. Ethylene carbonate is the preferred alkylene car~onate feedstock for this process. The preferred starting materials are illustrated in the accompanying examples. Recovery of the desired ethylene glycol and dimethyl carbonate can generally be carried out by distillation and crystallization.
More specifically, methanol and ethylene carbonate are pumped into a tubular reactor upflow at a flow rate of 0.1 to 100 liquid hourly space velocity (LHSV). The reactor temperature is held at between 20 and 200C and a back pressure of zero to 5000 psi is maintained thorughout the experiment.
The homogeneous catalyst systems suitable for the practice of this invention generally comprise a zirconium, titanium or tin compound. The compound can be in the form of a salt or complex.
The zirconium-containing catalyst compound comprises a salt of zirconium or a complex. Suitable examples include zirconium salts of strong (mineral) acids, such as zirconium tetrachloride, ZrC14, zirconium bromide, ZrBr4, zirconium fluo-ride, zirconium nitrate, zirconium sulfate, Zr(SO4)2 4H2O, zirconium mixed halides and zirconium tetraiodide, zirconium alkoxides such as zirconium methoxide, zirconium ethoxide and zirconium isopropoxide, zirconium salts of weak acids such as , : ,~ : . :
":, .
' ~;
~L29~7~Z3 zirconium acetate and zirconium acetylacetonate, Zr(02C5H7)4, as well as zirconium compounds containiny the zirconyl moiety, as for example, zirconium diperchlorate oxide, ZrO(CL04)2 8H20 and zirconium oxide nitrate, ZrO(N03)2 X H20.
The preferred zirconium catalyst precursors are zirconium acetylacetonate and zirconium diperchlorate oxide.
The titanium-containing catalyst compound may likewise comprise a salt of titanium or a complex. Suitable examples include titanium methoxide; other titanium alkoxides such as titanium isopropoxide, titanium acetate and titanium acetylacetonate also work. The preferred titanium compound is titanium isopropoxide.
Suitable tin-containing catalyst precursors for ECtMeOH
transesterification include compounds such as tin(II) 2-ethylhexanoate, tin methoxide, dimethyltin salts, dibutyltin acetate and tributyltin chloride. The preferred tin compound is tin(II) 2-ethylhexanoate.
Also in some cases, the analogous zirconium, titanium and tin heterogeneous catalyst precursors may also be effective.
Examples of suitable heterogeneous catalysts for the desired ethylene carbonate methanol transesterification include zirconium oxide, ZrO2, and titanium oxide. Said heterogeneous zirconium or titanium catalysts may be in the form of pellets, extrudates, , .
.
:
~Z~7~Z3 granules or powders. Also effective may be zirconium carbide, zirconium nitride and zirconium silicate.
A particularly effective catalyst for the cosynthesis of dimethyl carbonate and ethylene glycol is a solution of zirconium diperchlorate oxide dissolved in the ethylene carbonate-methanol feed mix. This reaction solution is illus-trated in accompanying Example X.
During the cosynthesis of ethylene glycol and dimethyl carbonate by the reaction of ethylene carbonate with methanol, a large excess of methanol is normally employed in the prior art.
Usually the initial molar ratio of methanol to ethylene carbonate is in the range of 5 or greater, and preferably at least 10.
This preferred ratio range is illustrated by U. S. Pat-ent 3,803,201 (1974). In the practice of this invention, by contrast, the initial weight ratio of ethylene carbonate to methanol is preferably 2 to 5. Such a range of weight ratios is illustrated by the accompanying examples.
Potential advantages to operating at this ethylene carbonate-to-methanol weight ratio include:
a) More efficient transesterification.
b) Lower levels of methanol required to be recycled after the transesterification step.
Ethylene glycol-dimethyl carbonate synthesis using the homogeneous catalyst described SUPRA can be conducted at reaction ,', :
~2~Z3 temperatures in the range from 20 to 200C. The preferred operating temperature range is 50-150~C.
The reaction can be conducted under atmospheric pres-sure. A pressure reactor is nevertheless required in the case of low-boiling point components if the reaction is to be carried out in the upper temperature range and in the liquid phase. The pressure is not critical. In general the reaction is allowed to proceed under the autogenous pressure of the reactants. However, the reaction can also be carried out under elevated pressure r for example, under an inert atmosphere. A pressure of zero to 5000 psig is appropriate here. An operating pressure of greater than 50 psig is suitable and the preferred pressure was in the range of 50 to 150 psi.
The residence time for the ethylene carbonate and methanol reactants in the tubular reac'cor may vary over a wide range according to the temperature of reaction, the molar ratios of carbonate/alcohol feedstocks, etc. Using the homogeneous catalysts of this invention, the necessary residence time in the reactor may range from 0.01 hours to 10 hours, although it may be extended beyond 10 hours without danger of additional by-products being formed. The preferred residence time is in the range of 0.1 to 5 hours.
The desired products of this process according to the invention are ethylene glycol and dimethyl carbonate.
-. . .
-- ~LZ971~3 By-products include diethylene glycol, l,l~dimethoxyethane, 1,2-dimethoxyethane, methyl 1,3-dioxolane, glycol monomethyl ether and dimethyl ether.
Products have been identified in this work by gas chromatography (gc), NMR, IR and gc-IR or a combination of these techniques. Zirconium and titanium analyses were by atomic absorption IAA). All liquid product analyses have, for the most part, been by gc; all temperatures are in degrees centigrade and all pressures in pounds per square inch gauge.
The following examples illustrate the novel process of this invention. The examples are only for illustrating the invention and are not considered to be limiting:
EXAMPLE I
This example illustrates the cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol, in good selectivity, using a homogeneous zirconium catalyst derived from zirconium acetylacetonate dissolved in the EC/MeOH feed mix. ~he weight ratio of ethylene carbonate to methanol is 2:3.
To a 1 kg mixture of ethylene carbonate (EC) and methanol (typical composition: 59.0% MeOH, 41.0~ EC) was added 50g of zirconium acetylacetonate. The mixture was stirred to dissolve the zirconium salt, cooled in wet ice and the clear ' .
97~3 solution pumped through a 50 cc capacity, stainless steel, tubular reactor upflow at a rate of 25 cc/hr. The reactor temperature was held at 130C and a back-pressure of 100 psi was maintained throughout the experiment. After feeding the ethylene carbonate-methanol mix for several (3-8) hours, the liquid effluent was sampled at regular time intervals and analyzed by gas-liquid chromatography.
Typically, this liquid effluent had the following composition:
10.8 wt~ dimethyl carbonate (DMC) 6.9 wt% ethylene glycol (EG) 30.4 wt% ethylene carbonate (EC) 50.1 wt% methanol (MeOH) Estimated molar selectivity to DMC, basic EC convert-ed =
10.8/90 x 100 = >98%
(41.0-30.4)/88 Estimated molar selectivity to DMC, basic MeOH convert-ed =
10.8/90x2 _ x 100 = 86%
(59.0-50.1)/32 , .. : . . ~ .
- ;
: ` , ~, .
~', ' ' , .
g~lZ3 EG selectivity basis EC converted:
6.9/62 x 100 = 92%
~41.0-30.4)/88 EG selectivity basis MeOH converted:
6.9/62 x 2 x 100 = 78 (59.0-50.1)/32 where DMC, FW = 90.0; EC, FW = 88.0; EGr FW = 62.0; MeOH, FW = 32Ø
EXAMPLES II to IX
Table 1 shows the cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol using a variety of homogeneous zirconium, titanium and tin catalyst sys-tems. Here the most effective catalyst precursors are:
zirconium acetylacetonate tin(II) 2-ethylhexanoate titanium isopropoxide ,, " ... ..
,~ :
: .. ,.. :
, DIMETHYL C~RBONATE/ETHYLENE GLYCOL COSYNTHESISa Reactor Feed Temp. Rate Liquid Product (wt%) Example Catalyst _ ( cc/hr DMC EG EC MeOH
II Zirconium tetra- 130 25 5.6 3.6 41.2 46.0 chloride " 150 25 8.7 5.0 31.6 47.4 III Zirconiu ~ iso- 100 100 2.1 1.8 38.0 54.0 propoxide IV Zirconiumbacetyl- 110 100 5.5 4.0 36.9 51.8 acetonate 150 25 11.4 7.6 31.8 47.0 V Titani ~ isopro- 100 100 4.7 1.8 30.4 52.9 poxide Vl Titanium ~catyl- 110 25 0.1 0.1 52.5 46.1 acetonate ' " 130 25 0.3 0.2 55.5 42.9 " 150 25 1.0 0.6 49.4 47.8 VII Tin~II) 2cethyl- 100 100 5.8 2.2 35.1 55.8 hexanoate VIII Dibutyltin acetate100 100 1.5 0.4 40.1 56.9 IX Tributyltin chloride100 100 0.2 40.6 57.6 aRun in continuous, 50cc capacity, tubular reactor, upflow at 25 cc/hr. liquid flow rate 100 psi pressure, feed composition: 59% MeOH, 41% EC.
Solution in EC/MeO~ was filtered prior to use.
CSome catalyst precipitation during run.
dFeed composition: 52.5% MeOH, 47.5% EC.
, , :
., . : ,: . .
:: , , ,:
: , , - . . ..
~ ~Z~7~3 X MPLE X
This example illustrates khe cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol, in good selectivity, using a homogeneous zirconium diperchlorate oxide catalyst precursor.
To a 1 kg mixture of ethylene carbonate and methanol t66.6% MeOH, 33.3 l/EC) was added 50 g of zirconium diperchlorate oxide, ZrO(C104)2 8H2O. The mixture was stirred to dissolve the zirconyl salt (1.3~ Zr), cooled in wet ice, and fed to the 50 cc tubular reactor at a rate of 25 cc/hr. using the procedures of Example I. The reactor temperature was held at 100C, and a back pressure of 100 psi was maintained throughout the experiment.
Typical liquid effluent showed the following composi-tion:
10.4 wt% dimethyl carbonate 9.0 wt% ethylene glycol 24.2 wt% ethylene carbonate 54.2 wt~ methanol The reactor temperature was then raised to 130C. Typ-ical liquid product now showed the following composition:
14.8 wt% dimethyl carbonate 9.0 wt% ethylene glycol 14.9 wt% ethylene carbonate 53.1 wt~ methanol .: ~
,.~ ' ' ~Z97123 In the latter experiment:
Estimated molar selectivity to DMC, basis EC converted = 89~.
Estimated molar selectivity to D~C, basis MeOH conver~e~ = 76%.
Estimated molar selectivity to EG, basis EC converted = >98%.
Estimated molar selectivity to EG, basis MeOH converted = 95~.
EXAMPLE XI
This example also illustrates dimethyl carbonate/
ethylene glycol cosynthesis, but uses a homogeneous zirconyl nitrate catalyst precursor.
To a 1 kg mixture of ethylene carbonate and methanol ~57.0% MeOH, 38.5% EC) was added 50 g of zirconium dinitrate ox-ide, ZrO(NO3)2 X H2O). The mixture was stirred to dissolve the zirconyl salt (1.5~ Zr), cooled in wet ice, and fed to the 50 cc reactor at a rate of 25 cc/hr., as in Example I. The reactor temperature was held at 130C, and a back pressure of 100 psi was maintained throughout the experiment.
Typical liquid effluent showed the following composi-tion:
4.8 wt~ dimethyl carbonate 8.3 wt% ethylene glycol 27.3 wt% ethylene carbonate 56.0 wt% methanol .
, ...
,~ . :: . . ,: .
::-, . , .:, .
~, , ::
, . . - , , :. '~ ~ ` ' ''' ~29~~Z3 The reactor temperature was then raised to 150C. Un-der these conditions the liqui.d product showed the following com-posltlon:
6.8 wt% carbonate 14.0 wt% ethylene glycol 24.1 wt% ethylene carbonate 52.5 wt~ methanol EXAMPLE XII
This example illustrates the cosynthesis of dimethyl carbonate and ethylene glycol from ethylene carbonate plus methanol, in good selectivity, using a hetergeneous zirconium oxide catalyst.
To the 50 cc tubular reactor of Example I, packed with 3.2 mm pellets of zirconium oxide ~98% ZrO2), is pumped a so-lution of ethylene carbonate plus methanol (67.6% MeOH, 31.9% EC) at a rate of 50 cc/hr. Reactor temperature was held at 130C, the back pressure was 100 psi. Typlcal liquid effluent showed the following composition.
3.8 wt% dimethyl carbonate 2.7 wt% ethylene glycol 29.9 wt% ethylene carbonate 63.1 wt% methanol ..
:~ . ; '.
'~
,, ,.
'` ` ':
~2~7123 The reactor temperature was then raised to 160C. Typ-ical liquid product under equillibrium conditions, using this higher reactor temperature were as follows:
7.9 wt% dimethyl carbonate 5.2 wt~ ethylene glycol 25.2 wt% ethylene carbonate 60.8 wt~ methanol No zirconium could be detected in the product liquid, basis atomic absorption analyses (AA).
-.
: ,:
, ', : .: -... .
- ~ . . .. .
- : :
..
- :
,: . . : "
Claims (12)
1. A process for cosynthesis of ethylene glycol and di-methyl carbonate which comprises reacting ethylene carbonate and methanol in the presence of a homogeneous catalyst selected from the group consisting of soluble salts of zirconium, titanium and tin or complexes thereof, at a temperature of 20° to 200°C and a pressure of from 0 to 5000 psig until the desired products are formed.
2. The process of Claim 1 wherein the homogeneous catalyst is a salt or complex of zirconium from the group consisting of zirconium salts of strong mineral acids, zirconium alkoxides, zirconium salts of weak acids and zirconyl compounds.
3. The process of Claim 2 wherein the homogeneous catalyst is a zirconium compound selected from the group consisting of zirconium acetylacetonate, zirconium diperchlorate oxide, zircon-ium methoxide, zirconium dinitrate oxide, zirconium tetrachloride and zirconium isopropoxide.
4. The process of Claim 1 wherein the homogeneous catalyst is a salt or complex of titanium from the group consisting of titanium acetylacetonate, titanium isopropoxide and titanium meth-oxide.
5. The process of Claim 1 wherein the homogeneous catalyst is a salt or complex of tin from the group consisting of tin 2-ethylhexanoate, tin methoxide, dibutyltin acetate and tributyltin chloride.
6. The process of Claim 1 wherein the operating tem-perature is between 50° and 150°C.
7. The process of Claim 1 wherein the operating pres-sure is between zero and 5000 psig.
8. The process of Claim 1 wherein the weight ratio of methanol to ethylene carbonate is in the range of 2:1 to 5:1.
9. The process of Claim 1 for cosynthesis of dimethyl carbonate and ethylene glycol which comprises feeding methanol and ethylene carbonate to a tubular reactor while maintaining a weight ratio of methanol to ethylene carbonate of between 2:1 to 5:1, in the presence of a soluble zirconium, titanium or tin salt or complex, while maintaining the reactor at a temperature of between 50° and 150°C and a pressure of at least 50 psig.
10. A process for cosynthesis of ethylene glycol and dimethyl carbonate by reacting ethylene carbonate and methanol containing a homogeneous catalyst dissolved therein from the group consisting of zirconium acetylacetonate, zirconium diperchlorate oxide, titanium isopropoxide and tin(II) ethylhexanoate, at a temperature of 20° to 200°C and a pressure of from 0 to 5000 psig.
11. The process of Claim 1 wherein the cosynthesis of ethy-lene glycol and dimethyl carbonate from ethylene carbonate plus methanol is conducted in the presence of a heterogeneous catalyst selected from the group consisting of the oxides of zirconium and titanium.
12. The process of Claim 11 wherein the heterogeneous cata-lyst is zirconium oxide.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US891,093 | 1986-07-31 | ||
US06/891,093 US4661609A (en) | 1986-07-31 | 1986-07-31 | Process for cosynthesis of ethylene glycol and dimethyl carbonate |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1297123C true CA1297123C (en) | 1992-03-10 |
Family
ID=25397604
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000532588A Expired - Fee Related CA1297123C (en) | 1986-07-31 | 1987-03-20 | Process for cosynthesis of ethylene glycol and dimethyl carbonate |
Country Status (5)
Country | Link |
---|---|
US (1) | US4661609A (en) |
EP (1) | EP0255252B1 (en) |
JP (1) | JPS6341432A (en) |
CA (1) | CA1297123C (en) |
DE (1) | DE3781742T2 (en) |
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DE4105554A1 (en) * | 1991-02-22 | 1992-08-27 | Bayer Ag | METHOD FOR PRODUCING DIALKYL CARBONATES |
JP2631803B2 (en) * | 1992-11-25 | 1997-07-16 | 株式会社日本触媒 | Method for producing dialkyl carbonate |
US6594688B2 (en) * | 1993-10-01 | 2003-07-15 | Collaboration Properties, Inc. | Dedicated echo canceler for a workstation |
US5489703A (en) * | 1995-05-19 | 1996-02-06 | Amoco Corporation | Reaction extraction of alkyl carbonate |
EP1086940B1 (en) | 1998-06-10 | 2007-05-02 | Asahi Kasei Chemicals Corporation | Method for continuously producing a dialkyl carbonate and a diol |
US6365767B1 (en) | 1999-05-28 | 2002-04-02 | Exxonmobil Chemical Patents Inc. | Process for co-production of dialkyl carbonate and alkanediol |
US6207850B1 (en) | 1999-11-03 | 2001-03-27 | Mobil Oil Corporation | Process for co-production of dialkyl carbonate and alkanediol |
US6407279B1 (en) | 1999-11-19 | 2002-06-18 | Exxonmobil Chemical Patents Inc. | Integrated process for preparing dialkyl carbonates and diols |
US6162940A (en) * | 1999-12-14 | 2000-12-19 | Mobil Oil Corporation | Process for co-production of dialkyl carbonate and alkanediol |
JP3659109B2 (en) * | 2000-01-19 | 2005-06-15 | 三菱化学株式会社 | Co-production method of ethylene glycol and carbonate |
US6342623B1 (en) | 2000-02-04 | 2002-01-29 | Exxonmobil Chemical Patents Inc. | Process for co-production of dialkyl carbonate and alkanediol |
US6166240A (en) * | 2000-02-22 | 2000-12-26 | Mobil Oil Corporation | Process for co-production of dialkyl carbonate and alkanediol |
UA76478C2 (en) * | 2001-07-09 | 2006-08-15 | Лонза Інк. | In situ methods of preparing quaternary ammonium alkylcarbonates |
US6573396B2 (en) | 2001-10-12 | 2003-06-03 | Exxonmobil Chemical Patents Inc. | Co-production of dialkyl carbonates and diols with treatment of hydroxy alkyl carbonate |
US6620959B1 (en) | 2002-04-16 | 2003-09-16 | Exxonmobil Chemical Patents Inc. | Process for the production of unsymmetric and/or symmetric dialkyl carbonates and diols |
AU2005254380A1 (en) * | 2004-06-17 | 2005-12-29 | Asahi Kasei Chemicals Corporation | Process for producing dialkyl carbonate and diol |
KR100895602B1 (en) * | 2005-09-20 | 2009-05-06 | 아사히 가세이 케미칼즈 가부시키가이샤 | Process for production of dialkyl carbonate and diol |
US7378540B2 (en) * | 2005-10-21 | 2008-05-27 | Catalytic Distillation Technologies | Process for producing organic carbonates |
US8058465B2 (en) * | 2005-11-25 | 2011-11-15 | Asahi Kasei Chemicals Corporation | Process for industrially producing dialkyl carbonate and diol |
CN101312933B (en) * | 2005-11-25 | 2012-02-29 | 旭化成化学株式会社 | Industrial preparation method for dialkyl carbonate and diol |
US20090326257A1 (en) * | 2005-12-12 | 2009-12-31 | Shinsuke Fukuoka | Process for industrially producing dialkyl carbonate and diol |
TWI308911B (en) * | 2005-12-13 | 2009-04-21 | Asahi Kasei Chemcials Corp | Process for industrially producing dialkyl carbonate and diol |
TW200732291A (en) * | 2005-12-14 | 2007-09-01 | Asahi Kasei Chemicals Corp | Process for production of dialkyl carbonate and diol in industrial scale and with high yield |
TWI314549B (en) | 2005-12-26 | 2009-09-11 | Asahi Kasei Chemicals Corp | Industrial process for separating out dialkyl carbonate |
TW200738601A (en) * | 2005-12-27 | 2007-10-16 | Asahi Kasei Chemicals Corp | Industrial process for production of dialkyl carbonate and diol |
DE102009030680A1 (en) | 2009-06-26 | 2010-12-30 | Bayer Materialscience Ag | Process for the preparation of dialkyl carbonates from alkylene carbonates and alcohols |
IT1396205B1 (en) | 2009-10-13 | 2012-11-16 | Eni Spa | COMPOSITION OF GASOLINE INCLUDING DIETHYL CARBONATE FROM BIOETHANOL. |
DE102009053370A1 (en) | 2009-11-14 | 2011-05-19 | Bayer Materialscience Ag | Process for the purification of dialkyl carbonates |
IT1397623B1 (en) | 2009-12-16 | 2013-01-18 | Eni Spa | COMPOSITION OF GAS OIL INCLUDING DIETYL CARBONATE FROM BIOETHANOL AND VEGETABLE OIL |
IT1396959B1 (en) | 2009-12-18 | 2012-12-20 | Eni Spa | COMPOSITION OF DIESEL INCLUDING BIODIESEL AND DIETYL CARBONATE FROM BIOETHANOL |
DE102010006657A1 (en) | 2010-02-03 | 2011-08-04 | Bayer MaterialScience AG, 51373 | Process for the preparation of dialkyl carbonates |
CN103525874B (en) * | 2012-07-03 | 2015-06-10 | 深圳市绿微康生物工程有限公司 | Method for preparing dimethyl carbonate |
US9475751B2 (en) | 2012-11-21 | 2016-10-25 | Covestro Deutschland Ag | Process for producing dialkyl carbonates |
US9518003B1 (en) | 2013-07-30 | 2016-12-13 | E3Tec Service, Llc | Method of producing high-concentration alkyl carbonates using carbon dioxide as feedstock |
CN106478421B (en) | 2015-08-31 | 2019-09-13 | 亚申科技(浙江)有限公司 | DMC Processes |
US9656943B2 (en) | 2015-10-20 | 2017-05-23 | Chang Chun Plastics Co. Ltd. | Process for producing dimethyl carbonate |
US10131620B2 (en) | 2015-10-20 | 2018-11-20 | Chang Chun Plastics Co., Ltd. | Process for producing dimethyl carbonate |
CN107417719B (en) * | 2017-05-08 | 2022-11-25 | 华东理工大学 | Application of titanium chelate as reaction catalyst for synthesizing benzyl carbonate or diphenyl carbonate by ester exchange |
CN110105174B (en) * | 2019-05-22 | 2021-10-08 | 胜华新能源科技(东营)有限公司 | Method for producing ethylene glycol by using ethylene carbonate and methanol as raw materials |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3803201A (en) * | 1971-02-22 | 1974-04-09 | Dow Chemical Co | Synthesis of dimethyl carbonate |
DE2736063A1 (en) * | 1977-08-10 | 1979-02-22 | Bayer Ag | Process for the preparation of aromatic carbonic acid esters |
DE2740251A1 (en) * | 1977-09-07 | 1979-03-22 | Bayer Ag | PROCESS FOR THE PRODUCTION OF DIALKYLCARBONATES |
DE2740243A1 (en) * | 1977-09-07 | 1979-03-15 | Bayer Ag | PROCESS FOR THE PRODUCTION OF DIALKYLCARBONATES |
DE2740242C3 (en) * | 1977-09-07 | 1980-03-06 | Bayer Ag, 5090 Leverkusen | Process for the production of dimethyl carbonate |
JPS5463023A (en) * | 1977-10-26 | 1979-05-21 | Mitsubishi Chem Ind Ltd | Ester exchange of carbonate |
US4552704A (en) * | 1983-12-27 | 1985-11-12 | General Electric Company | Process for the production of aromatic carbonates |
-
1986
- 1986-07-31 US US06/891,093 patent/US4661609A/en not_active Expired - Fee Related
-
1987
- 1987-03-20 CA CA000532588A patent/CA1297123C/en not_active Expired - Fee Related
- 1987-07-08 DE DE8787306054T patent/DE3781742T2/en not_active Expired - Fee Related
- 1987-07-08 EP EP87306054A patent/EP0255252B1/en not_active Expired - Lifetime
- 1987-07-22 JP JP62181292A patent/JPS6341432A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
DE3781742D1 (en) | 1992-10-22 |
EP0255252A3 (en) | 1989-02-15 |
JPS6341432A (en) | 1988-02-22 |
EP0255252A2 (en) | 1988-02-03 |
DE3781742T2 (en) | 1993-03-18 |
EP0255252B1 (en) | 1992-09-16 |
US4661609A (en) | 1987-04-28 |
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