CN101553479A - 生产碳酸亚烷酯的方法和由此生产的碳酸亚烷酯在生产烷烃二醇和二烷基碳酸酯中的应用 - Google Patents
生产碳酸亚烷酯的方法和由此生产的碳酸亚烷酯在生产烷烃二醇和二烷基碳酸酯中的应用 Download PDFInfo
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- -1 alkylene carbonate Chemical compound 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 41
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- 235000011089 carbon dioxide Nutrition 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- QOQHDJZWGSAHFL-UHFFFAOYSA-N butylphosphanium;bromide Chemical class [Br-].CCCC[PH3+] QOQHDJZWGSAHFL-UHFFFAOYSA-N 0.000 claims description 5
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
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- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
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- C07C69/96—Esters of carbonic or haloformic acids
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
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- 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
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Abstract
在如下方法中通过在鏻催化剂存在下使环氧烷与二氧化碳反应生产碳酸亚烷酯,其中:(a)将环氧烷、二氧化碳和鏻催化剂连续地引入到反应区中,从反应区中抽出包含碳酸亚烷酯和用过的鏻催化剂的产品物流,(b)从产品物流中分离碳酸亚烷酯和包含用过的鏻催化剂的物流,(c)将在步骤(b)中分离的碳酸亚烷酯作为产品回收,(d)使至少一部分包含用过的鏻催化剂的物流进行纯化,得到纯化的鏻催化剂,和(e)将纯化的鏻催化剂任选与另一部分包含用过的鏻催化剂的物流组合再循环到反应区中。
Description
技术领域
本发明涉及生产碳酸亚烷酯的方法和由此生产的碳酸亚烷酯在生产烷烃二醇和二烷基碳酸酯中的应用。
背景技术
生产碳酸亚烷酯的方法是已知的。WO-A 2005/003113公开了其中在适合的催化剂存在下使二氧化碳与环氧烷接触的方法。所公开的催化剂是四烷基鏻化合物。所述说明书公开了所使用的催化剂已经被再循环。所述说明书还公开了如果催化剂被再循环用于在醇特别是丙二醇(1,2-丙二醇)中制备碳酸亚烷酯,则所述催化剂是非常稳定的。
US-A 4,434,105也公开了制备碳酸亚烷酯的方法。公开了各种催化剂。该文献还描述了催化剂在反应完成之后可被再利用。
在连续法中,包含碳酸亚烷酯和催化剂的反应产物必须经过后处理(work-up treatment)。这种后处理通常包括一个或多个蒸馏步骤,用以使产品与催化剂分离。已经发现,如果催化剂被再利用而没有采取适宜的步骤除去再循环催化剂中的污染物,则催化剂活性降低。这些污染物包括鏻催化剂的分解产物。上述文献中都没有提供避免任何这种污染物积累的方法。
现在已经发现可以通过从产品中纯化至少一部分催化剂保持催化剂活性。
发明内容
因此,本发明提供通过在鏻催化剂存在下使环氧烷与二氧化碳反应生产碳酸亚烷酯的方法,在所述方法中
(a)将环氧烷、二氧化碳和鏻催化剂连续地引入到反应区中,从反应区中抽出包含碳酸亚烷酯和用过的鏻催化剂的产品物流,
(b)从产品物流中分离碳酸亚烷酯和包含用过的鏻催化剂的物流,
(c)将在步骤(b)中分离的碳酸亚烷酯作为产品回收,
(d)使至少一部分包含用过的鏻催化剂的物流进行纯化,得到纯化的鏻催化剂,和
(e)将纯化的鏻催化剂再循环到反应区中。
本发明的方法允许催化剂可以在连续法中长期使用。已经发现其原因可能与在制备碳酸亚烷酯过程中在催化剂中形成分解产物有关。已经发现鏻催化剂的污染物包括氧化膦。通过将用过的催化剂纯化,可以有效地除去氧化膦,使得活性催化剂可以再循环到步骤(a)的反应区中。本发明方法另外的优点在于所述方法先解决了对包括用以从所述方法抽出受污染催化剂的排放物流的需要。
所述催化剂是鏻化合物。这种催化剂从例如US-A 5,153,333、US-A 2,994,705、US-A 4,434,105、WO-A 99/57108、EP-A 776,890和WO-A 2005/003113已知。优选地,所述催化剂是式R4PHal的卤化膦,其中Hal表示卤素,每个R可以相同或不同且可以选自烷基、烯基、环状脂族或芳族基团。基团R适当地包含1-12个碳原子。在R为C1-8烷基时得到好的结果。最优选地,基团R选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、和叔丁基。优选地,卤素离子是溴离子或碘离子。表现出来的是溴化物和碘化物比相应的氯化物更稳定。最优选的鏻催化剂是四(正丁基)溴化鏻。本发明方法另外的优点在于无需含卤素的催化剂流出物流的高成本处理。用过的鏻催化剂的纯化可以以多种方式实现。有可能对用过的催化剂进行提取、结晶吸附或其它分离技术。优选对用过的催化剂进行蒸馏。
已经发现用过的催化剂在长时间暴露于较高温度时倾向于形成分解产物。因此,优选在相对低的温度下进行蒸馏。为此,适当地在低于大气压力下进行蒸馏。通过使用低于大气压的压力,催化剂组合物中的污染物被蒸馏,留下作为蒸馏残余物的纯化的鏻催化剂。优选蒸馏温度不超过250℃。更优选地,蒸馏温度范围为50-200℃,最优选为100-180℃。用于这种蒸馏温度的适合的压力为0.1-0.0001巴(10-0.01kPa)。优选地,压力范围为0.05-0.0005巴(5,000-5Pa)。
令人惊讶的是,即使在经历这些蒸馏条件之后,这些鏻催化剂显示出它们的活性完全恢复了。
鏻催化剂倾向于是固体材料。所述催化剂可作为固体再循环到反应区中。还有可能将催化剂转化为熔融物并将熔融的催化剂再循环到反应区中。然而,因为溶剂的存在表现出对催化剂的稳定作用,优选在溶剂存在下将纯化的鏻催化剂再循环到反应区中。溶剂可以是含羰基的化合物,特别是醛,如WO-A 2005/051939中公开的。更优选地,溶剂是醇。可以选择许多醇以提高鏻催化剂的稳定性。所述醇可以是单价的、二价的、或多价的。醇可以包括被一个或多个羟基取代的脂族C1-12链。还可以使用适当地具有6-12个碳原子的芳族醇或烷基芳族醇。还可以使用聚亚烷基二醇或其单烷基醚。也可使用混合物。
优选地,使用的醇选自C1-6单链烷醇、C2-6烷烃二醇、C3-6烷烃多元醇(包括甘油)、苯酚、C1-6烷基取代的苯酚、C6-12环脂族醇、及其混合物。非常适合的是C2-6烷烃多元醇,特别是1,2-乙二醇、1,2-丙二醇、山梨醇、及其混合物。使用乙二醇或丙二醇还有一个另外的优点是当将碳酸亚烷酯转化为亚烷基二醇(烷烃二醇)时,亚烷基二醇用作鏻催化剂的溶剂。山梨醇为鏻催化剂提供优异的稳定性。可能有利的是使用1,2-乙二醇或1,2-丙二醇与山梨醇的组合物。
为了补充任何分解的催化剂,有效的是向反应区加入补充的鏻催化剂。补充的鏻催化剂可以在工艺中存在有催化剂的任何位置加入。适当地,任何补足用鏻催化剂通过直接加入到反应区中或通过加入到要被再循环的纯化的鏻催化剂物流中而添加到工艺中。
在本发明方法中,至少一部分含用过的鏻催化剂的物流进行纯化步骤。有可能使全部物流经过这种纯化,由此使所有的催化剂进行纯化。然而,优选只使其部分进行纯化。通过这样做,避免了污染物的积累。此外,已经表明,如果鏻催化剂包含少量的这种污染物,则这种污染物对催化剂活性没有有害作用。显而易见,不是所有催化剂都必须连续纯化提供了显著的经济利益。适当地,包含用过的鏻催化剂的物流的1-90wt%、更优选2-50wt%、最优选5-25wt%进行纯化。优选另一部分包含用过的鏻催化剂的物流也与纯化的鏻催化剂一起被再循环到反应区中。更优选地,将这一物流的所有剩余部分再循环到反应区中。尽管可能不需要排放物流,但是有可能采用少量的排放物流。
包含用过的鏻催化剂的物流适当地包含一些碳酸亚烷酯。碳酸亚烷酯保证了用过的鏻催化剂处于液态,由此促进其输送,例如再循环。此外,已经发现醇和碳酸亚烷酯的组合物对催化剂有稳定作用。因此,如果只有一部分用过的鏻催化剂进行纯化,则剩余部分的用过的催化剂(适当地与碳酸亚烷酯组合)被再循环到反应区中。如果纯化的鏻催化剂已经被溶解于醇,则可以适当地将这些物流合并,使得用过的鏻催化剂、纯化的鏻催化剂、醇和碳酸亚烷酯的混合物被再循环到反应区中。如果在包含用过的鏻催化剂的物流中存在有碳酸亚烷酯,则在纯化步骤中将碳酸亚烷酯与任何含磷污染物和催化剂分离。这可以在其中在不同的塔板得到不同级分的蒸馏塔中实现。然而,还有可能在两个专用步骤中实现,其中在第一步骤中将碳酸亚烷酯与催化剂和任何重质污染物分离,并且随后使污染物与催化剂分离,以得到纯化的鏻催化剂。后一种方式的优点在于可以对每个分离采用最佳的蒸馏条件。
在本发明方法中转化的环氧烷适当地是C2-4环氧烷,特别是环氧乙烷或环氧丙烷或其混合物。
在反应区中鏻催化剂的量可以方便地表示为每摩尔环氧烷的催化剂摩尔数。由于副产品量降低,本发明方法适当地在每摩尔环氧烷至少0.0001摩尔鏻催化剂存在下进行。优选地,存在的鏻催化剂的量使得其范围为每摩尔环氧丙烷0.0001-0.1摩尔鏻催化剂、更优选为0.001-0.05、和最优选为0.003-0.03摩尔鏻催化剂。
二氧化碳与环氧烷的反应是可逆的。这意味着形成的碳酸亚烷酯可以转化回到二氧化碳和环氧烷。二氧化碳和环氧烷之间的摩尔比可以低到0.5∶1,更适当地为0.75∶1。考虑到该反应的可逆性,优选确保至少轻微过量的二氧化碳,例如1.0∶1-10∶1,更优选1.01∶1-2∶1,最优选1.01∶1-1.2∶1。确定二氧化碳过量的合适的方法是在提高二氧化碳压力下进行反应并通过计量给料二氧化碳保持压力恒定。总的压力范围适当地为5-200巴;二氧化碳分压优选为5-70巴,更优选7-50巴,和最优选10-30巴。
反应温度可以选自宽的范围。适当地,温度选自30-300℃。较高温度的优点在于反应速率提高。然而,如果反应温度太高,则可能发生副反应,即碳酸亚烷酯降解为二氧化碳和丙醛或丙酮、不期望的环氧烷与任何烷烃二醇(如果存在的话)的反应,或者可能促进不期望的鏻催化剂分解。因此,温度适当地选自100-220℃。
本领域技术人员能够酌情采用其它反应条件。可以选择环氧烷和二氧化碳在反应区内的停留时间而没有过度的负荷。停留时间通常可以在5分钟到24小时之间变化,优选为10分钟到10小时。环氧烷的转化率适当地为至少95%,更优选至少98%。取决于温度与压力,可以改变停留时间。催化剂浓度也可以在宽的范围内变化。适合的浓度包括1-25wt%,基于总的反应混合物。使用基于总的反应混合物为2-8wt%的催化剂浓度可以得到好的结果。
对于碳酸亚烷酯和醇的相对量,本领域技术人员可以在宽的范围内改变其比例。采用0.1-10、特别是0.2-5、更优选0.5-2的碳酸亚烷酯与醇的重量比已经得到非常好的结果。考虑到反应区中环氧烷和醇之间的不期望的反应的可能性,醇的量适当地保持在相对低的水平,例如基于反应区中环氧烷、二氧化碳、碳酸亚烷酯和醇的重量为1-25wt%。优选地,醇量范围为5-20wt%。
在本发明方法中生产的碳酸亚烷酯可以适当地用于生产烷烃二醇和二烷基碳酸酯。因此,本发明也提供制备烷烃二醇和二烷基碳酸酯的方法,包括使链烷醇和碳酸亚烷酯经酯交换催化剂反应,和从得到的反应混合物回收烷烃二醇和二烷基碳酸酯,其中所述碳酸亚烷酯是通过本发明的方法制备的。链烷醇适当地为C1-4醇。优选地,链烷醇是甲醇、乙醇或异丙醇。
酯交换反应本身是已知的。在本申请中参考US-A 4,691,041,其公开了通过经非均相催化剂体系的酯交换生产乙二醇和碳酸二甲酯的方法,非均相催化剂体系特别地是具有叔胺、季铵、磺酸和羧酸官能团的离子交换树脂;浸渍到二氧化硅中的碱金属和碱土金属硅酸盐;和铵离子交换的沸石。US-A 5,359,118和US-A 5,231,212公开了用于经多种催化剂制备碳酸二烷基酯的连续法,所述催化剂包括碱金属化合物,特别是碱金属氢氧化物或醇化物,例如氢氧化钠或甲醇钠;铊化合物;含氮碱,例如三烷基胺;膦;;胂;硫或硒化合物;和锡、钛或锆的盐。根据WO-A 2005/003113,碳酸亚烷酯与链烷醇的反应经非均相催化剂例如氧化铝进行。在这个文献中,建议与烷烃二醇一起除去鏻催化剂,即在碳酸亚烷酯转化为烷烃二醇之后与烷烃二醇一起除去鏻催化剂。然而,根据本发明,优选在早期分离醇,如果存在的话。根据本发明,优选将醇从包含碳酸亚烷酯和用过的鏻催化剂的产品物流中分离。这样,再循环的醇量可以保持在最小值。此外,从碳酸亚烷酯产品中除去可能在反应过程中作为副产物形成的任何轻质卤化物,因此不会妨碍任何随后的工艺步骤。优选使用烷烃二醇作为溶剂,在其存在下将纯化的鏻催化剂再循环到其中二氧化碳和环氧烷反应以产生碳酸亚烷酯的反应区中。这样,避免了非必要的醇的存在。
根据以上所述,本发明另外提供了通过在鏻催化剂存在下使环氧烷与二氧化碳反应生产碳酸亚烷酯的方法,在所述方法中
(a)将环氧烷、二氧化碳和鏻催化剂连续地引入到反应区中,从反应区中抽出包含碳酸亚烷酯和用过的鏻催化剂的产品物流,和
(b)从产品物流中分离碳酸亚烷酯和包含用过的鏻催化剂的物流。分离可以适当地通过蒸馏实现。任选地在与更轻的醇分离之后,碳酸亚烷酯产品通常作为塔顶产品回收。塔底产品包含用过的鏻催化剂和一些碳酸亚烷酯。然后根据本发明的方法使部分该塔底物流经单独的蒸馏段纯化。将如此得到的纯化的鏻催化剂适当地溶解于烷烃二醇并且将溶液与剩余部分的包含用过的鏻催化剂和碳酸亚烷酯的物流合并。得到的碳酸亚烷酯、醇、用过的鏻催化剂和纯化的鏻催化剂的组合物被再循环到反应区中。
具体实施方式
通过以下实施例进一步阐述本发明。
实施例
实施例1
为了表明可以纯化用过的鏻催化剂,进行以下实验。
使包含约75wt%的碳酸丙二酯和25wt%的用过的鏻催化剂组合物的用过的催化剂溶液(100ml)在圆底玻璃瓶中进行蒸馏。用过的催化剂组合物包含18.2摩尔%的三丁基氧化膦,其余是四丁基溴化鏻。通过在65℃和2mbar(200Pa)下真空蒸馏除去第一级分。这个级分主要由碳酸丙二酯组成。残余物在冷却时固化并在加热时再次熔融。熔融物在160℃和1mbar(100Pa)下进行蒸馏。回收主要由三丁基氧化膦组成的第二级分。保留在瓶中的残余物固化,并且主要由四丁基溴化鏻组成。分析表明残余物包含1.7摩尔%的三丁基氧化膦。
实施例2
为了表明纯化的鏻催化剂已经恢复其催化活性,进行两个实验。在两个实验中,都将120g环氧丙烷引入到1升反应釜中。反应釜用CO2加压并且加热到150℃。引入另外的CO2,直到达到20巴的压力。将250mg溴化鏻催化剂在5g 1,2-丙二醇中的溶液引入到反应釜中。引入另外的10g 1,2-丙二醇。通过将CO2计量给料到反应釜保持压力恒定在20bar。在五小时之后,终止CO2引入,并且使反应釜冷却。测定两个实验中的碳酸丙二酯的量、转化率和选择性。
两个实验以同样方式进行,唯一的不同之处在于在实验1中催化剂取自实施例1的残余物,而在实验2中,使用新鲜的高纯度四丁基溴化鏻(得自Fluka)。结果表示在下表中。
表
实验编号 | 碳酸丙二酯g | 转化率% | 选择性% |
1 | 187.8 | 90.7 | 99.7 |
2 | 190.5 | 90.6 | 99.8 |
Claims (12)
1.通过在鏻催化剂存在下使环氧烷与二氧化碳反应生产碳酸亚烷酯的方法,在所述方法中
(a)将环氧烷、二氧化碳和鏻催化剂连续地引入到反应区中,从反应区中抽出包含碳酸亚烷酯和用过的鏻催化剂的产品物流,
(b)从产品物流中分离碳酸亚烷酯和包含用过的鏻催化剂的物流,
(c)将在步骤(b)中分离的碳酸亚烷酯作为产品回收,
(d)使至少一部分包含用过的鏻催化剂的物流进行纯化,得到纯化的鏻催化剂,和
(e)将纯化的鏻催化剂再循环到反应区中。
2.权利要求1的方法,其中催化剂是式R4PHal的卤化鏻,其中Hal表示卤素,和每个R可以相同或不同且可以选自烷基、烯基、环状脂族或芳族基团。
3.权利要求2的方法,其中催化剂是四(正丁基)溴化鏻。
4.权利要求1-3任一项的方法,其中使被纯化的包含用过的鏻催化剂的物流的一部分进行蒸馏。
5.权利要求4的方法,其中蒸馏温度为50-200℃,最优选为100-180℃。
6.权利要求4或5的方法,其中蒸馏的压力为0.1-0.0001巴(10-0.01kPa)。
7.权利要求1-6任一项的方法,其中在溶剂存在下使纯化的鏻催化剂再循环到反应区中。
8.权利要求1-7任一项的方法,其中使包含用过的鏻催化剂的物流的1-90wt%、更优选2-50wt%、最优选5-25wt%进行纯化。
9.权利要求1-8任一项的方法,其中将另一部分包含用过的鏻催化剂的物流再循环到反应区。
10.权利要求1-9任一项的方法,其中将用过的鏻催化剂、纯化的鏻催化剂、醇和碳酸亚烷酯的混合物再循环到反应区中。
11.制备烷烃二醇和二烷基碳酸酯的方法,包括使链烷醇和碳酸亚烷酯经酯交换催化剂反应,和从得到的反应混合物回收烷烃二醇和二烷基碳酸酯,其中所述碳酸亚烷酯通过权利要求1-10任一项的方法制备。
12.权利要求11的方法,其中烷烃二醇用作溶剂,在其存在下将纯化的鏻催化剂再循环到反应区中。
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WO (1) | WO2007104730A1 (zh) |
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CN102442910A (zh) * | 2010-10-08 | 2012-05-09 | 拜尔材料科学股份公司 | 由碳酸二烷基酯制备碳酸二芳基酯的方法 |
CN103028440A (zh) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | 用于制备碳酸亚烷酯的大孔型树脂催化剂 |
CN105377829A (zh) * | 2013-07-19 | 2016-03-02 | 丸善石油化学株式会社 | 环状碳酸酯的连续制造方法 |
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TWI457317B (zh) * | 2008-05-20 | 2014-10-21 | Shell Int Research | 碳酸伸烷酯之製造方法 |
WO2009141377A1 (en) * | 2008-05-20 | 2009-11-26 | Shell Internationale Research Maatschappij B.V. | Process for preparing an 1,2-alkylene carbonate |
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2007
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- 2007-03-12 AU AU2007224469A patent/AU2007224469A1/en not_active Abandoned
- 2007-03-12 KR KR1020087024405A patent/KR20080110782A/ko not_active Application Discontinuation
- 2007-03-12 RU RU2008140313/04A patent/RU2008140313A/ru not_active Application Discontinuation
- 2007-03-12 EP EP07726784A patent/EP1994018B1/en not_active Not-in-force
- 2007-03-12 JP JP2008558796A patent/JP5551876B2/ja not_active Expired - Fee Related
- 2007-03-12 ES ES07726784T patent/ES2396866T3/es active Active
- 2007-03-12 CN CN2007800075665A patent/CN101553479B/zh not_active Expired - Fee Related
- 2007-03-12 BR BRPI0708285-1A patent/BRPI0708285A2/pt not_active Application Discontinuation
- 2007-03-12 WO PCT/EP2007/052270 patent/WO2007104730A1/en active Application Filing
- 2007-03-12 US US11/684,873 patent/US20070213542A1/en not_active Abandoned
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102442910A (zh) * | 2010-10-08 | 2012-05-09 | 拜尔材料科学股份公司 | 由碳酸二烷基酯制备碳酸二芳基酯的方法 |
CN103028440A (zh) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | 用于制备碳酸亚烷酯的大孔型树脂催化剂 |
CN103028440B (zh) * | 2011-09-29 | 2015-06-10 | 中国石油化工股份有限公司 | 用于制备碳酸亚烷酯的大孔型树脂催化剂 |
CN105377829A (zh) * | 2013-07-19 | 2016-03-02 | 丸善石油化学株式会社 | 环状碳酸酯的连续制造方法 |
US9586927B2 (en) | 2013-07-19 | 2017-03-07 | Maruzen Petrochemical Co., Ltd. | Method for continuously producing cyclic carbonate |
CN105377829B (zh) * | 2013-07-19 | 2017-11-28 | 丸善石油化学株式会社 | 环状碳酸酯的连续制造方法 |
Also Published As
Publication number | Publication date |
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BRPI0708285A2 (pt) | 2011-05-24 |
JP2014088387A (ja) | 2014-05-15 |
JP2009530240A (ja) | 2009-08-27 |
US20070213542A1 (en) | 2007-09-13 |
WO2007104730A1 (en) | 2007-09-20 |
EP1994018A1 (en) | 2008-11-26 |
JP5551876B2 (ja) | 2014-07-16 |
EP1994018B1 (en) | 2012-11-28 |
AU2007224469A1 (en) | 2007-09-20 |
KR20080110782A (ko) | 2008-12-19 |
CN101553479B (zh) | 2013-11-27 |
JP5726278B2 (ja) | 2015-05-27 |
TWI387584B (zh) | 2013-03-01 |
MX2008011415A (es) | 2008-09-18 |
TW200800882A (en) | 2008-01-01 |
CA2641997A1 (en) | 2007-09-20 |
ES2396866T3 (es) | 2013-02-28 |
RU2008140313A (ru) | 2010-04-20 |
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