CN102302950A - Catalyst system for synthesizing oxyacid ester by oxidative carbonylation and use method thereof - Google Patents
Catalyst system for synthesizing oxyacid ester by oxidative carbonylation and use method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 150000002148 esters Chemical class 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000005832 oxidative carbonylation reaction Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 150000004699 copper complex Chemical class 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 18
- -1 copper halide Chemical class 0.000 claims description 18
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 16
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 5
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010533 azeotropic distillation Methods 0.000 claims description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 claims description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 150000001879 copper Chemical class 0.000 abstract 2
- 229910001220 stainless steel Inorganic materials 0.000 description 19
- 239000010935 stainless steel Substances 0.000 description 19
- 238000005303 weighing Methods 0.000 description 19
- 230000006315 carbonylation Effects 0.000 description 12
- 238000005810 carbonylation reaction Methods 0.000 description 12
- 238000011160 research Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical group C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and discloses a catalyst system for synthesizing oxyacid esters by oxidative carbonylation and a use method thereof. The catalyst system consists of a divalent copper salt and a solvent, and a copper complex with catalytic activity is formed by the complex reaction of the copper salt and the solvent at a certain temperature and time. The catalyst system belongs to a homogeneous system, is easy for liquid phase circulation, has the advantages of high activity, good circulation performance, simple process flow, small corrosivity and the like, and has a good industrial application prospect.
Description
Technical field
The invention belongs to chemical technology field; Relate to a kind of catalyst system and method for using thereof that is used for oxidation carbonyl synthesizing oxygen-containing acid esters; Specifically be a kind of reaction that is used for synthetic other organic acid esters of carbonic ester coproduction of oxidation of alcohols carbonylation, by mantoquita and solvent original position synthetic catalyst and method for using thereof.
Background technology
Alcohols carbonylation research just began as far back as the 1950's, and studying maximum is methanol carbonylation (Falbe J.New Syntheses with Carbonate Monoxide, 1980).Germanization scholar Peppe W. finds at first to use that carbonyl Co makes catalyst, halogen is made auxiliary agent, under high pressure methanol carbonyl synthesis of acetic acid (Peppe W.et al.Ann.Chem, 1953); Because this discovery; BASF AG adopts the Co-I homogeneous catalysis system to set up industrialized unit (Hohenschutz H nineteen sixty; Et al.Hydrocarbon Process.1966), but this severe reaction conditions (pressure is up to 7MPa), so fail further industrial applications; The end of the sixties, the Paulik F E of Monsanto company adopted carbonyl Rh to make catalyst; Successfully developed low pressure Rh-I catalyst system of new generation (Paulik F E, et al.Chem.Commun, 1968); And set up industrialized unit in 1970; Along with its excellent economy, this method has become the center that world's acetate and acetic anhydride manufacture are attracted attention, and the related development technology is the emphasis and the focus of Chinese scholars and business research always.In recent years, more rich China has obtained significant progress especially for coal resources, international major company such as BASF Aktiengesellchaft (CN1466489A, 2004) and Celanese Int Corp (CN1926089A, 2007 of high level research alcohols carbonylation; CN101918350A, 2010) etc. all applied for related patent U.S. Patent No., domestic Southwest Chemical Research and Design Institute (CN1843624A, 2006), chemistry institute of the Chinese Academy of Sciences (CN1939586A, 2007 in China; CN101182340A, 2008) and Jiangsu Suo Pu group company (CN101362103A, 2009) etc. also represented China's proprietary technology of pure carbonylation.But widely used carbonylating catalyst remains noble metal Rh system or Ir system, and its reserves limited, cost an arm and a leg, reclaim always the puzzling industrialization development of carbonylation of shortcomings such as difficulty.
These deficiencies to existing catalyst system; People hope to find a kind of non-precious metal catalyst system that is used for carbonylation; And the correlative study progress is slower, but the carbonylation base metal catalyst system and catalyzing in the presence of aerobic has been obtained remarkable achievement recently, makes that the research of carbonylation important branch-alcohol oxidation carbonylation is very popular at present; The Italian Enichem company (IT1252070,1995 that wherein are worth mentioning; US5536864,1996 etc.) taking the lead in CuCl is catalyst, has realized the industrialization of methanol oxidation carbonyl Synthesis of dimethyl carbonate (important green chemical of 21 century) the eighties in 20th century; U.S. Texaco company (US4667053,1987 afterwards; US4785130,1988; US4879266,1989; ) and Dow chemical company (US5004827,1991; US5349102,1994; US5387708,1995), German Bayer company (US5821377,1998; US5739258,1998; WO0037413,2000; ), Japanese UBE company (US5162563,1992; JP2007084470,2007), and Chinese patent (CN1197792A, 1998; CN1333086A, 2002; CN1642892A, 2005; CN1724159A, 2006; CN101664697A; 2010 etc.) then exist corrosion and unsettled deficiency to carry out improving research for the CuCl catalyst system and catalyzing; All obtained the effect of improving in various degree; And the catalyst that above patent is used all is the basis with the CuCl of poor stability, has essence technical problems such as equipment corrosion and poor stability.
Chinese patent CN1169624C (2004), CN100388978C (2008), CN101856625A (2010) are to above deficiency; Use stability cupric system preferably instead; Organic amine salt, organophosphorated salt and high molecular polymer that employing contains N or P atom are part; This composition catalyst obviously reduces corrosion on Equipment property; Particularly this research group (CN100388978C CN101856625A) adopts common the quaternary ammonium salt Huo quaternary alkylphosphonium salt that contains N or P atom and copper halide or zinc complex reaction, has proposed a kind of serial organometallic complex catalyst that is used for pure oxidation carbonyl synthesizing carbonate ester originally; Increase dissolubility and cupric activity of catalyst, but all had defectives such as Preparation of Catalyst complicacy.
Existing pure carbonylation catalyst system and catalyzing exists the monovalence copper catalyst poor stability and the cupric complex that belong to precious metal, alcohol oxidation carbonylation to prepare shortcomings such as complicacy mostly.
Summary of the invention
The objective of the invention is provides a kind of catalyst system that is used for oxidation carbonyl synthesizing oxygen-containing acid esters to above-mentioned technical problem.
Another object of the present invention provides the method for using of above-mentioned catalyst system.
The objective of the invention is to realize through following technical proposal:
A kind of catalyst system that is used for oxidation carbonyl synthesizing oxygen-containing acid esters, this system react the copper complex with catalytic activity that form through uniform temperature and time by mantoquita and solvent complex by cupric salt and solvent composition.
Described catalyst system, wherein cupric salt is one or more in copper halide, copper carbonate, copper sulphate, copper nitrate or the copper acetate, wherein copper halide is preferably CuCl
2, CuBr
2Solvent is N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone, 1,3-dimethyl-imidazolinone, one or more in the methyl-sulfoxide.
Described catalyst system, wherein the temperature of mantoquita and solvent complex reaction is 60～180 ℃, the reaction time is 0.5～3h.
Described catalyst system, wherein the reaction of mantoquita and solvent complex is synthetic for original position.
Said caltalyst ties up to the application in the oxidation carbonyl synthesizing oxygen-containing acid esters.
Said catalyst system is used for the method for using of oxidation carbonyl synthesizing oxygen-containing acid esters, and concrete steps are: at first a certain amount of cupric salt, solvent and raw alcohol are added in the agitated reactor and use N
2The displacement emptying fully mixes it with 100～1000 rev/mins rotating speeds stirrings, is heated to 60～180 ℃ of original positions that keep 0.5～3h to accomplish catalyst and synthesizes; Feed the N in the CO gas displacement agitated reactor then
2And keep certain pressure, feed O more continuously
2Beginning oxidation carbonyl carries out the esters of oxyacids synthetic reaction, the CO and the O of continuous supplement consumed in the course of reaction
2, keeping the interior stagnation pressure of agitated reactor is 0.5～8.0MPa, and temperature is 10～200 ℃, and the course of reaction total duration is 0.5～8h.
Described method for using, wherein raw alcohol is methyl alcohol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, 1, one or more in 2-propane diols, n-butanol, the tert-butyl alcohol.
Described method for using, the cupric salt mass fraction that wherein adds in the agitated reactor is 5%～30%, and the solvent quality mark is 30%～60%, and the raw alcohol mass fraction is 35%～65%; The process conditions of esters of oxyacids synthetic reaction: pressure is 2.5～3.5MPa, and temperature is 80～120 ℃, and the reaction time is 2～6h.
Described method for using, product and catalyst separation recovery method were after wherein reaction finished: agitated reactor liquid adopts conventional distillation and/or special extract rectification, obtains carbonic ester product and other organic acid esters joint product, and reclaims unreacted alcohol; Mantoquita-solvent catalyst system is able to the liquid phase circulation, directly is used for catalytic reaction next time.
Described method for using, wherein special extract rectification is one or more in compression rectification, extracting rectifying, the azeotropic distillation; Carbonic ester is one or more in dimethyl carbonate, diethyl carbonate, ethylene carbonate, dipropyl carbonate, propene carbonate, the dibutyl carbonate; Other organic acid esters are one or more in methyl acetate, ethyl acetate, ethyl propionate, the propyl butyrate.
Beneficial effect of the present invention:
The present invention is at preceding binomial patent application (CN100388978C; CN101856625A) on the basis; Effect characteristics (the CN101565361A for preparing halogen ion and solvent in the reaction of carbonyls according to pure oxidation; 2009), use for reference Braun R D and propose copper halide, mainly be [CuX in the dinethylformamide solvent at N
4]
2-Structure (Braun R D.ZAnorg Allg Chem, 1976) and Dunn and Buffagni are reported in N, and dinethylformamide or N all are with this complex MCl in the N-dimethylacetamide solvent
4-nX
nThere is (William E B, et al.Inorg Chem, 1962) literature method in form; Copper halide, specific solvent and the mutual effect of reaction substrate alcohol have systematically been studied; Confirm seed collecting cupric and specific solvent original position synthetic (copper complex of formation does not separate out, directly carries out catalytic reaction), promptly at certain condition; Pass through chemical reaction; Original position generates one or more wild phases in complex, and pure oxidation carbonyl synthesizing oxygen-containing acid esters is had advantages of high catalytic activity, thereby accomplishes the present invention.
Mantoquita and solvent catalyst system preparation technology that the present invention proposes are simple, and low in raw material cost is easy to get, catalytic activity high, good cycle.Simultaneously, catalyst system is realized homogeneous catalysis and liquid phase circulation easily, and catalyst transport is convenient, and technological operation is simple, and serviceability is good repeatedly, has prospects for commercial application.
(1) adopts cheap, abundant copper to replace noble metal catalyst, effectively reduce the production cost of pure carbonyl synthesizing oxygen-containing acid esters.
(2) be reflected at organic solvent and carry out under existing, mild condition, wider range, easy to control.
(3) post processing is simple, and catalyst system loops back the debit just, has better industrial application prospects.
(4) whole process is good to environment, and not having pollution, byproduct of reaction is water and CO
2, be a kind of green chemical synthesis method.
The specific embodiment
Below through embodiment the present invention is done further elaboration.
The performance evaluation of catalyst system and catalyzing adopts alcohol conversion and ester selectivity to describe; With the reactant alcohol is benchmark; Conversion ratio is meant the conversion per pass that chromatography reaction front and back alcohol matter quantitative changeization calculates, and selectivity is the ratio that reaction conversion becomes alcohol matter amount with total amount of alcohol conversion of ester.
Liquid product is analyzed with gas chromatographic analysis and GC-MS, and gas-phase product is analyzed with gas chromatographic analysis and Ovshinsky appearance.
Below each embodiment condition and the operating process do not mentioned can be undertaken by following total embodiment, sintetics that different embodiment relate to and byproduct kind are relevant with mantoquita, solvent, the raw alcohol of selection:
With cupric salt (one or more in copper halide, copper carbonate, copper sulphate, copper nitrate or the copper acetate), solvent (N, dinethylformamide, N; The N-dimethylacetylamide, N-methyl pyrrolidone, 1; The 3-dimethyl-imidazolinone; In the methyl-sulfoxide one or more) and in raw alcohol (methyl alcohol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, 1, one or more in 2-propane diols, n-butanol, the tert-butyl alcohol) the adding agitated reactor (the cupric salt mass fraction is 5%～30%, and the solvent quality mark is 30%～60%; The raw alcohol mass fraction is 35%～65%), use N
2The displacement emptying fully mixes it with 100～1000 rev/mins rotating speeds stirrings, is heated to 60～180 ℃ of original positions that keep 0.5～3h to accomplish catalyst and synthesizes; Feed the N in the CO gas displacement agitated reactor then
2And keep certain pressure, feed O more continuously
2Beginning oxidation carbongl group synthesis reaction, the CO and the O of continuous supplement consumed in the course of reaction
2, keeping the interior stagnation pressure of agitated reactor is that (be preferably 2.5～3.5MPa), reaction temperature is 10～200 ℃ (being preferably 80～120 ℃) to 0.5～8.0MPa, and the course of reaction total duration is that 0.5～8h (is preferably 2～6h).After reaction finishes; Product and catalyst separation recovery method are: agitated reactor liquid adopts conventional distillation and/or special extract rectification (one or more in compression rectification, extracting rectifying, the azeotropic distillation); Obtain carbonic ester product (one or more in dimethyl carbonate, diethyl carbonate, ethylene carbonate, dipropyl carbonate, propene carbonate, the dibutyl carbonate etc.) and other organic acid esters (one or more in methyl acetate, ethyl acetate, ethyl propionate, the propyl butyrate etc.) joint product, and reclaim unreacted alcohol; Mantoquita-solvent catalyst system is able to the liquid phase circulation, directly is used for catalytic reaction next time.
Embodiment 1
Take by weighing 15g CuBr
2, 100mL solvent N, N-dimethylacetylamide, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, use N
2Air in the metathesis reactor stirs with the rotating speed of 500 commentaries on classics/min that to make it fully be mixed and heated to 100 ℃ of original positions that keep 1h to accomplish catalyst synthetic.Feed the N in the CO gas displacement agitated reactor then
2And keep certain pressure, feed suitable O continuously
2The beginning carbongl group synthesis reaction, the CO and the O of continuous supplement consumed in the course of reaction
2, keep the pressure of stagnation pressure 2.5～3.5MP in the agitated reactor, reaction temperature is 120 ℃, reaction continues 4h.Collection still liquid is used gas chromatographic analysis, conversion of methanol 21.7%, the selectivity 76.2% of dimethyl carbonate, the selectivity 23.8% of methyl acetate after being cooled to room temperature.After reaction finished, agitated reactor liquid adopted conventional distillation and/or special extract rectification (one or more in compression rectification, extracting rectifying, the azeotropic distillation), obtains dimethyl carbonate product and methyl acetate joint product, and reclaims unreacted alcohol; Mantoquita-solvent catalyst system is able to the liquid phase circulation, directly is used for catalytic reaction next time.
Embodiment 2
Take by weighing 15g CuCl
2, 100mL solvent N; N-dimethylacetylamide, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, conversion of methanol 19.7%; The selectivity 26.5% of dimethyl carbonate, the selectivity 73.2% of methyl acetate.
Embodiment 3
Take by weighing 15g Cu (NO
3)
2, 100mL solvent N; N-dimethylacetylamide, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, conversion of methanol 11.9%; The selectivity 75.6% of dimethyl carbonate, the selectivity 19.6% of methyl acetate.
Embodiment 4
Take by weighing 15g CuSO
4, 100mL solvent N; N-dimethylacetylamide, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, conversion of methanol 8.0%; The selectivity 63.1% of dimethyl carbonate, the selectivity 28.4% of methyl acetate.
Embodiment 5
Take by weighing 15g Cu (OAc)
2, 100mL solvent N; N-dimethylacetylamide, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, conversion of methanol 18.6%; The selectivity 35.9% of diethyl carbonate, the selectivity 61.8% of methyl acetate.
Embodiment 6
Take by weighing 30g CuBr
2, 100mL solvent N; N-dimethylacetylamide, 100mL ethanol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, ethanol conversion 36.2%; The selectivity 51.7% of diethyl carbonate, the selectivity 48.3% of ethyl acetate.
At this; The performance that recycles for the examination catalyst moves to rectifying column with fluid product and carries out simple rectifying, steams unreacted raw polyol and product; The remaining solvent that contains catalyst turns back in the agitated reactor; Additional raw polyol reacts again, so recycles 6 times, and experimental result is seen table 1.
Table 1 catalyst circulation is used experimental result
| Cycle-index | Ethanol conversion, % | The selectivity of diethyl carbonate, % | The selectivity of ethyl acetate, % |
| 1 | 36.2 | 51.7 | 48.3 |
| 2 | 27.3 | 50.4 | 49.6 |
| 3 | 27.4 | 62.3 | 37.7 |
| 4 | 26.1 | 64.5 | 35.5 |
| 5 | 25.0 | 68.5 | 31.5 |
| 6 | 25.7 | 67.6 | 32.4 |
Embodiment 7
Take by weighing 30g CuBr
2, 100mL solvent N, N-dimethylacetylamide, 100mL ethylene glycol add in the 1000mL stainless steel autoclave, other process conditions are identical with embodiment 1, the conversion ratio 34.4% of ethylene glycol, the selectivity 31.8% of ethylene carbonate.
Embodiment 8
Take by weighing 15g CuBr
2, 100mL solvent N; Dinethylformamide, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, conversion of methanol 15.1%; The selectivity 49.4% of dimethyl carbonate, the selectivity 26.7% of methyl acetate.
Embodiment 9
Take by weighing 15g CuBr
2, 100mL solvent 1; 3-dimethyl-imidazolinone, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, conversion of methanol 14.7%; The selectivity 50.9% of dimethyl carbonate, the selectivity 40.4% of methyl acetate.
Embodiment 10
Take by weighing 15g CuBr
2, 100mL solvent N-methyl pyrrolidone, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, other process conditions are identical with embodiment 1, conversion of methanol 21.2%, the selectivity 74.3% of dimethyl carbonate, the selectivity 23.1% of methyl acetate.
Embodiment 11
Take by weighing 30g CuBr
2, 100mL solvent N; N-dimethylacetylamide, 100mL normal propyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, the conversion ratio 35.5% of normal propyl alcohol; The selectivity 65.9% of dipropyl carbonate, the selectivity 34.1% of ethyl propionate.
Embodiment 12
Take by weighing 30g CuBr
2, 100mL solvent N; N-dimethylacetylamide, 100mL isopropyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, the conversion ratio 21.7% of isopropyl alcohol; The selectivity 53.3% of dipropyl carbonate, the selectivity 46.7% of ethyl propionate.
Embodiment 13
Take by weighing 30g CuBr
2, 100mL solvent N, N-dimethylacetylamide, 100mL1,2-propane diols add in the 1000mL stainless steel autoclave, other process conditions are identical with embodiment 1,1, the conversion ratio 34.1% of 2-propane diols, the selectivity 57.7% of propene carbonate.
Embodiment 14
Take by weighing 30g CuBr
2, 100mL solvent N; N-dimethylacetylamide, 100mL n-butanol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, the conversion ratio 42.1% of n-butanol; The selectivity 36.4% of dibutyl carbonate, the selectivity 63.6% of propyl butyrate.
Embodiment 15
Take by weighing 30g CuBr
2, 100mL solvent N; N-dimethylacetylamide, the 100mL tert-butyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, the conversion ratio 19.8% of the tert-butyl alcohol; The selectivity 50.9% of dibutyl carbonate, the selectivity 49.1% of propyl butyrate.
Comparative Examples 1
Take by weighing 15g CuBr
2, 100mL solvent H
2O, 100mL methyl alcohol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, and conversion of methanol is almost 0, detect less than dimethyl carbonate in the still liquid of reaction back.Explain that the system that mantoquita and water form does not almost have catalytic activity.
Comparative Examples 2
Take by weighing 15g CuBr
2, 100mL solvent N, N-dimethylethanolamine, 100mL ethanol add in the 1000mL stainless steel autoclave, other process conditions are identical with embodiment 1; Ethanol conversion 5.1%; The selectivity 10% of diethyl carbonate, consume oxygen is more in the course of reaction, produces a large amount of accessory substances.Mantoquita and N are described, the system catalytic activity that the N-dimethylethanolamine forms is very low.
Comparative Examples 3
Take by weighing 15g ZnBr
2, 100mL solvent N; N-dimethylacetylamide, 100mL ethanol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, and ethanol conversion is almost 0; Detect less than diethyl carbonate in the still liquid, show that zinc salt/dicyandiamide solution does not possess catalytic activity to this reaction.
Comparative Examples 4
Take by weighing 15g K
2CO
3, 100mL solvent N; Dinethylformamide, 100mL ethanol add in the 1000mL stainless steel autoclave, and other process conditions are identical with embodiment 1, and ethanol conversion is almost 0; Detect less than diethyl carbonate in the still liquid, show that sylvite/dicyandiamide solution does not possess catalytic activity to this reaction.
Claims (10)
1. a catalyst system that is used for oxidation carbonyl synthesizing oxygen-containing acid esters is characterized in that this system by cupric salt and solvent composition, reacts the copper complex with catalytic activity that forms through uniform temperature and time by mantoquita and solvent complex.
2. catalyst system according to claim 1 is characterized in that described cupric salt is one or more in copper halide, copper carbonate, copper sulphate, copper nitrate or the copper acetate, and wherein copper halide is preferably CuCl
2, CuBr
2Solvent is N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone, 1,3-dimethyl-imidazolinone, one or more in the methyl-sulfoxide.
3. catalyst system according to claim 1 is characterized in that the temperature of mantoquita and solvent complex reaction is 60～180 ℃, and the reaction time is 0.5～3h.
4. catalyst system according to claim 1 is characterized in that the reaction of mantoquita and solvent complex is synthetic for original position.
5. claim 1,2,3 or 4 said caltalysts tie up to the application in the oxidation carbonyl synthesizing oxygen-containing acid esters.
6. the said catalyst system of claim 1 is used for the method for using of oxidation carbonyl synthesizing oxygen-containing acid esters, and concrete steps are: at first a certain amount of cupric salt, solvent and raw alcohol are added in the agitated reactor and use N
2The displacement emptying fully mixes it with 100～1000 rev/mins rotating speeds stirrings, is heated to 60～180 ℃ of original positions that keep 0.5～3h to accomplish catalyst and synthesizes; Feed the N in the CO gas displacement agitated reactor then
2And keep certain pressure, feed O more continuously
2Beginning oxidation carbonyl carries out the esters of oxyacids synthetic reaction, the CO and the O of continuous supplement consumed in the course of reaction
2, keeping the interior stagnation pressure of agitated reactor is 0.5～8.0MPa, and temperature is 10～200 ℃, and the course of reaction total duration is 0.5～8h.
7. method for using according to claim 6 is characterized in that raw alcohol is methyl alcohol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, 1, one or more in 2-propane diols, n-butanol, the tert-butyl alcohol.
8. method for using according to claim 6, the cupric salt mass fraction that it is characterized in that adding in the agitated reactor is 5%～30%, and the solvent quality mark is 30%～60%, and the raw alcohol mass fraction is 35%～65%; The process conditions of esters of oxyacids synthetic reaction: pressure is 2.5～3.5MPa, and temperature is 80～120 ℃, and the reaction time is 2～6h.
9. method for using according to claim 6; It is characterized in that reaction finishes the back product and the catalyst separation recovery method is: agitated reactor liquid adopts conventional distillation and/or special extract rectification; Obtain carbonic ester product and other organic acid esters joint product, and reclaim unreacted alcohol; Mantoquita-solvent catalyst system is able to the liquid phase circulation, directly is used for catalytic reaction next time.
10. method for using according to claim 9 is characterized in that special extract rectification is one or more in compression rectification, extracting rectifying, the azeotropic distillation; Carbonic ester is one or more in dimethyl carbonate, diethyl carbonate, ethylene carbonate, dipropyl carbonate, propene carbonate, the dibutyl carbonate; Other organic acid esters are one or more in methyl acetate, ethyl acetate, ethyl propionate, the propyl butyrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115108911A (en) * | 2022-05-26 | 2022-09-27 | 南京工业大学 | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792453A (en) * | 2005-12-26 | 2006-06-28 | 南京工业大学 | Complex catalyst for synthesizing carbonic ester by alcohol homogeneous oxidation carbonylation and preparation process and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792453A (en) * | 2005-12-26 | 2006-06-28 | 南京工业大学 | Complex catalyst for synthesizing carbonic ester by alcohol homogeneous oxidation carbonylation and preparation process and use method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Russian Journal of General Chemistry》 20091231 L. V. Stepakova et al. Organic Solvent Effect on the Solution-Solid Phase Equilibria in the Systems CuCl2-L-H2O (L = DMSO, DMF, Acetonitrile) at 25°С 第1053-1056页 1-10 第79卷, 第6期 * |
| L. V. STEPAKOVA ET AL.: "Organic Solvent Effect on the Solution–Solid Phase Equilibria in the Systems CuCl2–L-H2O (L = DMSO, DMF, Acetonitrile) at 25°С", 《RUSSIAN JOURNAL OF GENERAL CHEMISTRY》, vol. 79, no. 6, 31 December 2009 (2009-12-31), pages 1053 - 1056 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108911A (en) * | 2022-05-26 | 2022-09-27 | 南京工业大学 | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide |
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