CN1240667C - Method for synthesizing methyl propyl carbonate and dipropyl carbonate through catalysis in gas phase and solid phase - Google Patents
Method for synthesizing methyl propyl carbonate and dipropyl carbonate through catalysis in gas phase and solid phase Download PDFInfo
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- CN1240667C CN1240667C CN 200410033108 CN200410033108A CN1240667C CN 1240667 C CN1240667 C CN 1240667C CN 200410033108 CN200410033108 CN 200410033108 CN 200410033108 A CN200410033108 A CN 200410033108A CN 1240667 C CN1240667 C CN 1240667C
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- methylcarbonate
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- dipropyl carbonate
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Abstract
The present invention relates to a method for synthesizing methylpropyl carbonic ester and dipropyl carbonate by catalysis in a gas phase and a solid phase, which is characterized in that nitrate or acetate of transition metal or alkaline earth metal is used as an active constituent precursor, and the active constituent precursor is immersed and calcined to obtain a supported catalyst; a carrier for preparing the catalyst can be active aluminum oxide or diatomite or a beta-molecular sieve, control reaction temperature is from 393K to 443K, the pressure of a reactor is from 1.0 to 1.2MPa, and the catalyst is prepared by an ester exchange reaction. The method for synthesizing methylpropyl carbonic ester and dipropyl carbonate, which is provided by the present invention, has the advantages of moderate reaction conditions, high conversion rates of a raw material, easy separation of the catalyst, cleanness, no pollution, continuous operation of an entire reaction system, etc.
Description
Technical field
The present invention relates to the method for a kind of gas and solid phase catalyzing synthesizing methyl propyl carbonate and dipropyl carbonate.
Background technology
Dialkyl carbonate has electrochemical stability preferably in electrochemical field because of it, higher flash-point and lower fusing point obtain practical application in lithium ion battery, wherein dipropyl carbonate has bigger molecular weight because of it than methylcarbonate and diethyl carbonate, its flash-point, oxidation resistance is improved, thereby make the electrochemical stability of lithium-ion battery electrolytes and the also corresponding (Barker that is improved of security of battery, Jeremy, etal, Carbonaceous electrode andcompatible electrolyte [P], U S Patent, 5 643 695,1997; Zhuan Quanchao, Wushan etc., the research of lithium ion battery organic electrolyte, the 7th volume fourth phase of calendar year 2001), contain propyl group in the molecule of methyl-propyl carbonic ether and dipropyl carbonate in addition, carbonyl, propoxy-isoreactivity group, therefore also very important intermediate in organic synthesis, traditional synthetic method uses phosgene (carbonyl chloride) to make carbonylation agent mostly, but this synthesis technique is seriously polluted, require very high to production environment, and the hydrogenchloride that by-product corrodibility is very strong, also very high to equipment requirements, therefore people are devoted to develop the oligosaprobic new synthetic line of a kind of low toxicity always, along with Green Chemistry and environmental friendliness CHEMICAL DEVELOPMENT, this new green chemical of methylcarbonate comes out, because it is nontoxic chemical, more because the superiority of himself structure, it both can make carbonylation agent, or good methylating reagent, can replace phosgene, methyl-sulfate, deleterious reagent such as monochloro methane, be that raw material forms a new synthetic matrix (S.Memoli in organic synthesis with the methylcarbonate, M.Selva, Dimethylcarbonate for eco-friendlymethylation reactions, Chemosphere 43 (2001) 115-121; JayP.Parrish, Perspectives on Alkyl Carbonates in OrganicSynthesis, Tetrahedron 56 (2000) 8207-8237; Yoshio Ono, Dimethylcarbonate for environmentally bengin reactions, Catalysis Today35 (1997) 15-25), the production of China's methylcarbonate begins to take shape Just because of this, for development methylcarbonate downstream industry provides good condition (Tao Ruifeng, the methylcarbonate market status and development prospect, chemical industry Technological Economy, 2003 21 the tenth phases of volume; Liu Yong, Zhang Xigong, the methylcarbonate market status and technical progress, meticulous and specialty chemicals, 2003 the 3/4th phases), adopt methylcarbonate to make carbonylation agent and propyl alcohol gas and solid phase catalyzing synthesizing methyl propyl carbonate and dipropyl carbonate, can reduce environmental pollution greatly, catalyzer is easy to Separation and Recovery, reduced the cost of product aftertreatment, and the methyl alcohol of by-product still is the raw material of oxidative carbonylation Synthesis of dimethyl carbonate, has improved utilization ratio of raw materials, for the Green Chemistry of development cleanliness without any pollution has been opened up a new road.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with methylcarbonate and propyl alcohol, under the condition that loaded catalyst exists, gas-solid by methylcarbonate and propyl alcohol is the method for transesterification reaction catalytic synthesis of methyl propyl carbonate and dipropyl carbonate mutually, the transformation efficiency of methylcarbonate is higher in this method, realizes continuous production simultaneously easily.
Technical scheme of the present invention is as follows:
The method of a kind of gas and solid phase catalyzing synthesizing methyl propyl carbonate and dipropyl carbonate, its special feature is, with methylcarbonate and propyl alcohol is raw material, employing is the loaded catalyst of active ingredient presoma preparation with the acetate of the nitrate of transition metal or transition metal or the nitrate of alkaline-earth metal or the acetate of alkaline-earth metal, control reaction temperature 393K～443K, reactor pressure 1.0～1.2MPa carries out transesterification reaction and makes;
Wherein the mol ratio of raw material propyl alcohol and methylcarbonate is 2～5: 1;
Wherein catalyzer is to be the active ingredient presoma with the nitrate of transition metal or the acetate of transition metal or the nitrate of alkaline-earth metal or the acetate of alkaline-earth metal, with activated alumina or diatomite or beta molecular sieve as carrier, through dipping, the resulting loaded catalyst of roasting;
Active ingredient presoma in the catalyzer can be any one in lime acetate, zinc acetate, lead acetate, venus crystals, cobaltous acetate, manganous acetate, magnesium nitrate, nickelous nitrate, the strontium nitrate, and this active ingredient presoma accounts for 5～40% of carrier quality.
The method of synthesizing methyl propyl carbonate provided by the invention and dipropyl carbonate has that reaction conditions gentleness, feed stock conversion height, catalyzer are easy to separate, cleanliness without any pollution, whole reaction system are realized advantages such as continuous operation.
Embodiment
Embodiment 1
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 72.0%, and the selectivity of methyl-propyl carbonic ether is 61.6%, and the selectivity of dipropyl carbonate is 38.4%.
Embodiment 2
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, Na β is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 10% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 54.8%, and the selectivity of methyl-propyl carbonic ether is 83.9%, and the selectivity of dipropyl carbonate is 16.1%.
Embodiment 3
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, H β is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 40% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 47.2%, and the selectivity of methyl-propyl carbonic ether is 92.2%, and the selectivity of dipropyl carbonate is 7.8%.
Embodiment 4
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, diatomite is carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 40% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 34.8%, and the selectivity of methyl-propyl carbonic ether is 96.2%, and the selectivity of dipropyl carbonate is 3.8%.
Embodiment 5
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 5% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.2MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 66.5%, and the selectivity of methyl-propyl carbonic ether is 65.0%, and the selectivity of dipropyl carbonate is 35.0%.
Embodiment 6
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 10% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 443K, and reactor pressure is 1.0MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 66.5%, and the selectivity of methyl-propyl carbonic ether is 64.1%, and the selectivity of dipropyl carbonate is 35.9%.
Embodiment 7
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 40% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 70.3%, and the selectivity of methyl-propyl carbonic ether is 63.3%, and the selectivity of dipropyl carbonate is 36.7%.
Embodiment 8
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 0.9ml/h, propyl alcohol 4.1ml/h (mol ratio of propyl alcohol and methylcarbonate is 5: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 78.5%, and the selectivity of methyl-propyl carbonic ether is 54.6%, and the selectivity of dipropyl carbonate is 45.4%.
Embodiment 9
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.8ml/h, propyl alcohol 3.2ml/h (mol ratio of propyl alcohol and methylcarbonate is 2: 1), temperature of reaction is 403K, and reactor pressure is 1.2MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 61.2%, and the selectivity of methyl-propyl carbonic ether is 69.6%, and the selectivity of dipropyl carbonate is 30.4%.
Embodiment 10
It is the active ingredient presoma that catalyzer adopts with the zinc acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used zinc acetate quality is 20% of a carrier quality, is carrying out activity rating on the fixed-bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 393K, and reactor pressure is 1.0MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 65.5%, and the selectivity of methyl-propyl carbonic ether is 59.7%, and the selectivity of dipropyl carbonate is 40.3%.
Embodiment 11
It is the active ingredient presoma that catalyzer adopts with the lead acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used lead acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.0MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 50.2%, and the selectivity of methyl-propyl carbonic ether is 74.2%, and the selectivity of dipropyl carbonate is 25.8%.
Embodiment 12
It is the active ingredient presoma that catalyzer adopts with the venus crystals, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used venus crystals quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.2MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 36.7%, and the selectivity of methyl-propyl carbonic ether is 92.8%, and the selectivity of dipropyl carbonate is 7.2%.
Embodiment 13
It is the active ingredient presoma that catalyzer adopts with the nickelous nitrate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used nickelous nitrate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 57.5%, and the selectivity of methyl-propyl carbonic ether is 78.3%, and the selectivity of dipropyl carbonate is 21.7%.
Embodiment 14
It is the active ingredient presoma that catalyzer adopts with the cobaltous acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used cobaltous acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 413K, and reactor pressure is 1.0MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 59.8%, and the selectivity of methyl-propyl carbonic ether is 77.6%, and the selectivity of dipropyl carbonate is 22.4%.
Embodiment 15
It is the active ingredient presoma that catalyzer adopts with the manganous acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used manganous acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 54.7%, and the selectivity of methyl-propyl carbonic ether is 85.4%, and the selectivity of dipropyl carbonate is 14.6%.
Embodiment 16
It is the active ingredient presoma that catalyzer adopts with the magnesium nitrate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used magnesium nitrate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 423K, and reactor pressure is 1.2MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 65.2%, and the selectivity of methyl-propyl carbonic ether is 75.1%, and the selectivity of dipropyl carbonate is 24.9%.
Embodiment 17
It is the active ingredient presoma that catalyzer adopts with the lime acetate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used lime acetate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), reactor pressure is 1.1MPa, and temperature of reaction is 403K, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 69.2%, and the selectivity of methyl-propyl carbonic ether is 67.1%, and the selectivity of dipropyl carbonate is 32.9%.
Embodiment 18
It is the active ingredient presoma that catalyzer adopts with the strontium nitrate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used strontium nitrate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 59.0%, and the selectivity of methyl-propyl carbonic ether is 80.0%, and the selectivity of dipropyl carbonate is 20.0%.
Embodiment 19
It is the active ingredient presoma that catalyzer adopts with the Bismuth trinitrate, activated alumina is a carrier, obtain loaded catalyst through dipping, roasting, used Bismuth trinitrate quality is 20% of a carrier quality, is fixedly carrying out activity rating on the flowing bed reactor continuously, and control condition is methylcarbonate 1.1ml/h, propyl alcohol 3.9ml/h (mol ratio of propyl alcohol and methylcarbonate is 3: 1), temperature of reaction is 403K, and reactor pressure is 1.1MPa, and the gas phase air speed is 600h
-1, estimate 6 hours, the methylcarbonate transformation efficiency is 57.7%, and the selectivity of methyl-propyl carbonic ether is 79.0%, and the selectivity of dipropyl carbonate is 21.0%.
Claims (5)
1, the method for a kind of gas and solid phase catalyzing synthesizing methyl propyl carbonate and dipropyl carbonate is characterized in that:
With methylcarbonate and propyl alcohol is raw material, employing is the loaded catalyst of active ingredient presoma preparation with the acetate of the nitrate of transition metal or transition metal or the nitrate of alkaline-earth metal or the acetate of alkaline-earth metal, control reaction temperature 393K～443K, reactor pressure 1.0～1.2MPa carries out transesterification reaction and makes.
2, the method for gas and solid phase catalyzing synthesizing methyl propyl carbonate as claimed in claim 1 and dipropyl carbonate is characterized in that:
The mol ratio of raw material propyl alcohol and methylcarbonate is 2～5: 1.
3, the method for gas and solid phase catalyzing synthesizing methyl propyl carbonate as claimed in claim 1 or 2 and dipropyl carbonate is characterized in that:
Described catalyzer is that the acetate with the nitrate of the acetate of the nitrate of transition metal or transition metal or alkaline-earth metal or alkaline-earth metal is the active ingredient presoma, with activated alumina or diatomite or beta molecular sieve as carrier, through dipping, the resulting loaded catalyst of roasting.
4, the method for gas and solid phase catalyzing synthesizing methyl propyl carbonate as claimed in claim 3 and dipropyl carbonate is characterized in that:
Described active ingredient presoma is any one in lime acetate, zinc acetate, lead acetate, venus crystals, cobaltous acetate, manganous acetate, magnesium nitrate, nickelous nitrate, the strontium nitrate.
5, the method for gas and solid phase catalyzing synthesizing methyl propyl carbonate as claimed in claim 4 and dipropyl carbonate is characterized in that:
Described active ingredient presoma accounts for 5～40% of carrier quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410033108 CN1240667C (en) | 2004-04-03 | 2004-04-03 | Method for synthesizing methyl propyl carbonate and dipropyl carbonate through catalysis in gas phase and solid phase |
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| CN 200410033108 CN1240667C (en) | 2004-04-03 | 2004-04-03 | Method for synthesizing methyl propyl carbonate and dipropyl carbonate through catalysis in gas phase and solid phase |
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| CN1240667C true CN1240667C (en) | 2006-02-08 |
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| CN102203052B (en) * | 2008-09-01 | 2013-12-11 | 宇部兴产株式会社 | Method for producing asymmetric chain carbonate |
| CN103521266B (en) * | 2013-08-30 | 2015-05-06 | 重庆大学 | Composite catalyst for synthesizing dimethyl carbonate and preparation method of dimethyl carbonate |
| CN105251496A (en) * | 2015-09-18 | 2016-01-20 | 四川泸天化股份有限公司 | Catalyst and method preparing dimethyl carbonate by using catalyst |
| CN109433183B (en) * | 2018-11-01 | 2021-09-03 | 河南科技学院 | Bimetal composite oxide catalyst, preparation method and application |
| CN110128274B (en) * | 2019-05-28 | 2022-02-22 | 中国科学院成都有机化学有限公司 | Method for synthesizing diphenyl carbonate by dimethyl carbonate ester exchange |
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