CN100478324C - Method of catalytic synthesizing ethyl propyl carbonic acid ester - Google Patents
Method of catalytic synthesizing ethyl propyl carbonic acid ester Download PDFInfo
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- CN100478324C CN100478324C CNB2006101615973A CN200610161597A CN100478324C CN 100478324 C CN100478324 C CN 100478324C CN B2006101615973 A CNB2006101615973 A CN B2006101615973A CN 200610161597 A CN200610161597 A CN 200610161597A CN 100478324 C CN100478324 C CN 100478324C
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Abstract
The invention discloses a catalyzing and synthesizing method of ethyl propyl ester carbonate, which is characterized by the following: selecting alkaline metal or alkaline metal salt or hydroxide as catalyst as well as active aluminium oxide or active charcoal immersed by alkaline metal or alkaline metal salt or hydroxide; adopting DEC and normal propyl alcohol as raw material; improving the transmitting rate of normal propyl alcohol to 84% and selectivity of ethyl propyl ester carbonate to 98.69%.
Description
Technical field
The present invention relates to process for catalytic synthesis, refer in particular to a kind of method of catalytic synthesizing ethyl propyl carbonic acid ester.
Background technology
Because the whole world is for the close attention of the energy, environmental protection aspect, and fast developments such as mobile communication, notebook, Video Camera and various portable power tools, press for have high-energy-density, chemical power source that safe and reliable, life-span is long, but in today of social civilization high development, require this electrical source of power to have the clean and pollution features of smaller of environment, and the chemical power source of secondary high-energy-density just can satisfy this requirement, as lithium ion battery, it is a secondary cell with fastest developing speed after NI-G, nickel metal hydride battery.The ionogen common solvent of novel high-energy secondary cells such as the lithium ion battery of non-water system is generally all kinds of carbonic ethers, this kind solvent has characteristics such as specific inductivity height, electrochemical stability be good, can improve the energy density and the loading capacity of battery, more can improve safety performance and increase the service life.Institute of the present invention synthetic ethyl propyl carbonic acid ester has bigger molecular weight and higher dielectric constant because of it, therefore its flash-point, oxidation resistance all are greatly improved, thus the security that can better improve the electrochemical stability and the battery of lithium-ion battery electrolytes.Mostly the method for traditional synthetic dialkyl carbonate is to adopt the phosgene of severe toxicity etc. is carbonylation agent, and this not only brings more potential safety hazard to production process, but also can cause problems such as environmental pollution.And the present invention proposes is carbonylation agent with the diethyl carbonate, has not only solved the problem of raw material greenization, and the byproduct methyl alcohol of this reaction still produces the raw material of diethyl carbonate, thereby makes raw material obtain utilization to greatest extent.
Summary of the invention
Purpose of the present invention just provides the method for a kind of green, efficient catalytic synthesizing ethyl propyl carbonic acid ester.Concrete scheme is as follows:
A kind of method of catalytic synthesizing ethyl propyl carbonic acid ester, its special feature is that with diethyl carbonate and n-propyl alcohol be raw material, in temperature of reaction is 100～150 ℃, the mol ratio of diethyl carbonate and n-propyl alcohol is 1: 1～4: 1, reaction times is 1～5 hour, and catalyst levels is to synthesize under 1%～10% the condition of raw materials quality.
Oxyhydroxide, carbonate, acetate with basic metal or alkaline-earth metal are catalyzer.
Or be carrier with activated alumina, gac, oxyhydroxide, carbonate, acetate with basic metal or alkaline-earth metal are that active ingredient is carried out the vacuum impregnation processing, treatment process is as follows: at first with oxyhydroxide, carbonate, the acetate wiring solution-forming of basic metal or alkaline-earth metal, liquor capacity and carrier bulk are close.Then gac, zeolite molecular sieve or aluminum oxide are added wherein, stir ,-0.05～-flooded 12～24 hours under the vacuum part of 0.085Mpa, take out 100～150 ℃ of oven dry in back, standby.Wherein the active ingredient quality accounts for 5%～30% of catalyzer total mass.
The method of the synthesizing ethyl propyl carbonic acid ester that the present invention proposes has advantages of nontoxic raw materials, the reaction conditions gentleness, and method for preparing catalyst is simple, the efficient advantages of higher.
Embodiment
Embodiment 1
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with potassium hydroxide, consumption is 3% of a raw materials quality, 100 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 39.8%, and the ethyl propyl carbonic acid ester selectivity is 100%.
Embodiment 2
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with potassium hydroxide, consumption is 3% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 42.6%, and the ethyl propyl carbonic acid ester selectivity is 97.8%.
Embodiment 3
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with potassium hydroxide, consumption is 3% of a raw materials quality, 150 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 47.89%, and the ethyl propyl carbonic acid ester selectivity is 95.1%.
Embodiment 4
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with potassium hydroxide, consumption is 3% of a raw materials quality, 130 ℃ of temperature of reaction, 5 hours reaction times.
The n-propyl alcohol transformation efficiency is 43.1%, and the ethyl propyl carbonic acid ester selectivity is 96.5%.
Embodiment 5
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with potassium hydroxide, consumption is 10% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 76.5%, and the ethyl propyl carbonic acid ester selectivity is 94.17%.
Embodiment 6
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with potassium hydroxide, consumption is 1% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 23.9%, and the ethyl propyl carbonic acid ester selectivity is 100%.
Embodiment 7
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 1: 1 is a catalyzer with sodium hydroxide, consumption is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 25.8%, and the ethyl propyl carbonic acid ester selectivity is 66.5%.
Embodiment 8
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 2: 1 is a catalyzer with sodium hydroxide, consumption is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 67.2%, and the ethyl propyl carbonic acid ester selectivity is 98.7%.
Embodiment 9
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with salt of wormwood, consumption is 3% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 9.8%, and the ethyl propyl carbonic acid ester selectivity is 100%.
Embodiment 10
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with the potassium acetate, consumption is 3% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 26.8%, and the ethyl propyl carbonic acid ester selectivity is 99.7%.
Embodiment 11
With the gac is carrier, is that active ingredient is carried out the vacuum impregnation processing with salt of wormwood, and treatment process is as follows: at first with the salt of wormwood wiring solution-forming, liquor capacity and carrier bulk are close.Then gac is added wherein, stir ,-0.05～-flooded 12～24 hours under the vacuum part of 0.085Mpa, take out 100～150 ℃ of oven dry in back, get final product.Wherein the active ingredient quality accounts for 15% of catalyzer total mass.
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1 is a catalyzer with the activated carbon supported salt of wormwood of gained, catalyst levels is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 5.3%, and the ethyl propyl carbonic acid ester selectivity is 100%.
Embodiment 12
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1, activated carbon supported potassium hydroxide with the preparation of embodiment 11 is catalyzer, wherein the active ingredient quality accounts for 10% of catalyzer total mass, catalyst levels is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 10.9%, and the ethyl propyl carbonic acid ester selectivity is 100%.
Embodiment 13
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1, activated carbon supported potassium hydroxide with the preparation of embodiment 11 is catalyzer, wherein the active ingredient quality accounts for 30% of catalyzer total mass, catalyst levels is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 34.6%, and the ethyl propyl carbonic acid ester selectivity is 98.7%.
Embodiment 14
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1, activated carbon supported potassium hydroxide with the preparation of embodiment 11 is catalyzer, wherein the active ingredient quality accounts for 5% of catalyzer total mass, catalyst levels is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 6.9%, and the ethyl propyl carbonic acid ester selectivity is 100%.
Embodiment 15
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1, activated alumina load salt of wormwood with the preparation of embodiment 11 is catalyzer, wherein the active ingredient quality accounts for 20% of catalyzer total mass, catalyst levels is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 83.9%, and the ethyl propyl carbonic acid ester selectivity is 80.27%.
Embodiment 16
Diethyl carbonate (analytical pure) and n-propyl alcohol cumulative volume 30mL, mol ratio 4: 1, zeolite molecular sieve NaY load salt of wormwood with the preparation of embodiment 11 is catalyzer, wherein the active ingredient quality accounts for 10% of catalyzer total mass, catalyst levels is 5% of a raw materials quality, 130 ℃ of temperature of reaction, 1 hour reaction times.
The n-propyl alcohol transformation efficiency is 15.6%, and the ethyl propyl carbonic acid ester selectivity is 60.3%.
Claims (2)
1, a kind of method of catalytic synthesizing ethyl propyl carbonic acid ester is characterized in that:
With diethyl carbonate and n-propyl alcohol is raw material, and temperature of reaction is 100～150 ℃, the proportioning raw materials diethyl carbonate: the mol ratio of n-propyl alcohol is 1: 1～4: 1, and the reaction times is 1～5 hour, and catalyst levels is 1%～10% of a raw materials quality;
Wherein catalyzer is oxyhydroxide, carbonate or the acetate of basic metal or alkaline-earth metal, or the gac that adopts the salt of basic metal or alkaline-earth metal or oxyhydroxide or acetate dip treating to cross, the loaded catalyst of activated alumina and zeolite molecular sieve.
2, the method for a kind of catalytic synthesizing ethyl propyl carbonic acid ester according to claim 1, it is characterized in that: the preparation method of described loaded catalyst is: at first with oxyhydroxide, carbonate, the acetate wiring solution-forming of basic metal or alkaline-earth metal, liquor capacity and carrier bulk are close; Then gac, aluminum oxide are added wherein, stir ,-0.05～-flooded 12～24 hours under the vacuum condition of 0.085Mpa, take out 100～150 ℃ of oven dry in back, get final product; Wherein the active ingredient quality accounts for 5%～30% of catalyzer total mass.
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| CN101985418B (en) * | 2010-08-16 | 2013-01-02 | 江苏天音化工有限公司 | Method for preparing 2-methoxy-1-propanol ether acetate |
| CN103483200B (en) * | 2013-09-16 | 2016-02-17 | 河北工业大学 | A kind of method of transesterify Catalysts of Preparing Methyl Ethyl Carbonate |
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Non-Patent Citations (2)
| Title |
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| 碳酸二乙酯合成方法综述. 潘鹤林.上海化工，第20卷第3期. 2001 |
| 碳酸二乙酯合成方法综述. 潘鹤林.上海化工，第20卷第3期. 2001 * |
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Address after: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee after: Jiangsu Polytechnic University Address before: 213016 Department of science and technology, Jiangsu Polytechnic University, Baiyun Road, Jiangsu, Changzhou Patentee before: Jiangsu Polytechnic University |
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