CN1294114C - Method for producing acetic ether - Google Patents
Method for producing acetic ether Download PDFInfo
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- CN1294114C CN1294114C CNB2004100122927A CN200410012292A CN1294114C CN 1294114 C CN1294114 C CN 1294114C CN B2004100122927 A CNB2004100122927 A CN B2004100122927A CN 200410012292 A CN200410012292 A CN 200410012292A CN 1294114 C CN1294114 C CN 1294114C
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Abstract
The present invention discloses a method for producing ethyl acetate. The method uses acetic acid and ethanol as raw materials, the charging ration of reaction raw materials (namely acetic acid and ethanol) is 1 to 1.5, LaZSM-5 solid acid or heteropoly acid of phosphorus and molybdenum or TiO2/SO4<-2>-HZSM-5 or phosphotungstic acid or methanesulfonic acid is used as catalysts, extraction agents are composed of glycerol, ethylene glycol, potassium acetate, sodium acetate trihydrate, sodium chloride and potassium chloride, reaction temperature is from 80 to 140 DGE C, refined ethyl acetate is used as refluxing media, and the reflux ratio is between 1.5 and 2.0. The present invention has the advantages of reduced content of alcohol in crude ester in esterification reaction, lightened segregational load of dewatering towers, reduced quantity of extracted top ester of dewatering towers, basically no pollution to the environment and lightened post-treatment work of effulent, the disadvantages of large productive energy consumption, large raw material consumption and serious equipment corrosion of existing technologies are overcome, the problem of equipment corrosion by high-temperature extractive distillation is avoided, and finally, the purity of ethyl acetate can reach 99.99%.
Description
Technical field
The present invention relates to a kind of method of production ethyl acetate, belong to reaction of organic chemical industry's compound and separation technology field.
Background technology
Ethyl acetate is good organic solvent, and pleasant fragrance is arranged, and therefore purposes is extremely widely arranged in foodstuffs industry and coatings industry.The production technology of ethyl acetate has experienced the history in more than 100 year, has passed through improvement many times and has reached its maturity.For example, to make the method for raw material production ethyl acetate be method commonly used for disclosed employing acetate and ethanol in the prior art, this method is made catalyzer with sulfuric acid, in synthesizing ethyl acetate, generate the water of a part, in this method, selection of catalysts is even more important, the most traditional catalyzer is a sulfuric acid, its advantage is the catalytic activity height, and is with low cost, and shortcoming is because vitriolic severe corrosive and oxidisability make equipment corrosion serious, there are a series of by products to generate simultaneously, all bring certain difficulty for the refining of product and raw material recovery, and the aftertreatment of reactant will be through neutralization, washing is to remove sulfuric acid, complex process and contaminate environment.
Summary of the invention
The method that the purpose of this invention is to provide a kind of production ethyl acetate, this method adopts acetate and ethanol to make the raw material production ethyl acetate, selecting solid acid for use is catalyzer, reaction of acetate and alcoholic acid and rectifying are carried out simultaneously, acetate or ethanol energy primitive reaction are complete, thereby simplify subsequent reactions thing process for refining greatly, reduced energy consumption, overcome the shortcoming that conventional art exists.
The objective of the invention is to realize by following technical scheme: a kind of method of production ethyl acetate, make raw material with acetate and ethanol, in the presence of solid catalyst, react, catalyzer is selected LaZSM-5 solid acid or phosphato-molybdic heteropolyacid or TiO for use
2/ SO
4 -2-HZSM-5 or phospho-wolframic acid or methylsulfonic acid, extraction agent is a composite extractant, form by glycerol, ethylene glycol, Potassium ethanoate, sodium-acetate, sodium-chlor, Repone K, its fit quality ratio is 11: 2: 0.1: 0.1: 0.1: 0.1, reaction raw materials acetate and alcoholic acid raw materials components mole ratio are 1-1.5, temperature of reaction is 80-140 ℃, reaction pressure normal pressure-0.3Mpa, reflux medium adopts the purified ethyl acetate, reflux ratio is between 1.5-2.0, and wherein reaction raw materials catalyzed reaction and rectifying in catalytic rectifying tower carries out simultaneously.
Particularly, method of the present invention comprises two parts: reactive distillation processes and extraction process, and details are as follows:
A. reactive distillation processes
Acetate is added by tower middle and upper part 1/4-1/2, utilize the good combination destruction azeotropic of acetate and water to form, catch the small amount of ethanol that rises simultaneously, reach and reduce product alcoholic acid content, cat head steams thing after condenser condenses, is divided into oil phase and water through water-and-oil separator, after water is told, thick ester enters extraction tower and carries out extracting and refining, and reflux adopts the product behind the extracting and refining, reflux ratio 1.5-2.
B. extraction process
Adopt composite extractant, be made up of glycerol, ethylene glycol, Potassium ethanoate, sodium-acetate etc., add with the top of certain input speed by tower, the space between extraction agent import and the cat head is as last breeze way, ester after being used for the separating and extracting agent and extracting is taken out of from cat head by ester to avoid extraction agent.The thick ester of esterification reaction tower extraction is added by the bottom of tower with certain input speed, and the space between at the bottom of thick ester import and the tower goes out from the tower tail band to avoid ester to be extracted agent as breeze way down, and whole extraction process carries out under 15-20 ℃.The smart ester purity of cat head extraction can reach 99.99%.Portioned product enters reaction fractionating tower as phegma.
Among the present invention, be added with one section catalytic bed of filling the ion exchange resin after handling, can reach the purpose of not having alcohol in the thick ester in the reactor exit.
In still liquid, insert the glass spring filler, acid alcohol feed-pipe outlet is fixed on center at the bottom of the still, the ester alcohol mixture charging that reaction generates, through the circuitous king-post that enters into of the heavy obstruct of top filler, promptly increased the residence time of ethanol in still liquid, make it fully to react to be converted into ester, can reduce the pure content in the overhead product.
Add one section filler catalytic bed in the reactor exit, utilize the temperature of tower middle and lower part and content higher acid carrying out secondary reaction that micro ethanol is reacted away and reach the purpose of falling alcohol.
Among the present invention, adopt smart ester rather than thick ester to reflux,, have than higher band outlet capacity because seldom impure in the smart ester at cat head.
Add the empty adapter bonnet of a joint in extraction pillar upper end, do not load material as breeze way, the benefit of reducing is to make the ethyl acetate flow velocity after the extraction slack-off, helping extraction agent separates, the feed entrance point of extraction agent is changed into the lower end of adapter bonnet, and the feed entrance point of thick ethyl acetate is in the extractant feed lower end.
The obtained technical progress of the present invention is: adopt the coupling of reaction and rectifying, it is advantageous that and can be directly used in sepn process to reaction heat, thereby cut down the consumption of energy; Than being easier to control reaction temperature, there is not tangible focus, do not need cooling apparatus yet; The transformation efficiency height is avoided the reaction earlier of one or more raw materials, is separated, and then circulation reacts, separates, and can simplify flow process, cuts down the consumption of energy; Under centrifugation, make moisture in time leave catalytic reaction zone, make and react carry out more thorough, make objectionable impurities can not enter beds simultaneously, thereby can prolong the operational cycle of catalyzer; Make ethyl acetate in time leave reaction zone, avoided the generation of side reaction, improve selectivity.
Description of drawings
What Fig. 1 provided is process flow sheet of the present invention.
The implication of each label representative is as follows among the figure:
1, there-necked flask 2, reaction bed 3, more options opening for feed 4, catalytic filler 5, full cooler 6, phase splitter 7, header tank 8, under meter 9, glass filler 10, down cushioning pocket 11, extracting rectifying post 12, go up cushioning pocket 13, glass filler A, smart ester B, extraction agent C, backflow D, useless extraction agent E, thick ester F, mixing raw material.
Embodiment
Following examples are in order to explanation the present invention
Embodiment 1
The successive reaction rectifying tower, rectifying section is the filled section, and 19 theoretical stages are arranged, stripping section has 9 theoretical stages, carries out reactive distillation under the normal pressure, and charging acetic acid and alcoholic acid mol ratio are 1: 1, reactive distillation cat head temperature is 75 ℃, tower still temperature is 130 ℃, and raw material acetic acid and ethanol add at the bottom of by still, and reflux ratio is 1.5, the phase composite of cat head ester is in mass percent by analysis, ethyl acetate 93.75%, ethanol content 0.18%, water-content 5.31% other about 0.76%.After extraction tower was purified, the ester phase composite was in mass percent, ethyl acetate 99.98%, ethanol content 0.01%, water-content 0.01%.
Embodiment 2
The successive reaction rectifying tower, rectifying section is the filled section, and 22 theoretical stages are arranged, stripping section has 10 theoretical stages, carries out reactive distillation under the normal pressure, and charging acetic acid and alcoholic acid mol ratio are 1: 1, reactive distillation cat head temperature is 73 ℃, tower still temperature is 130 ℃, and raw material acetic acid and ethanol add at the bottom of by still, and reflux ratio is 1.5, the phase composite of cat head ester is in mass percent by analysis, ethyl acetate 94.15%, ethanol content 0.14%, water-content 5.12% other about 0.59%.After extraction tower was purified, the ester phase composite was in mass percent, ethyl acetate 99.95%, and ethanol content 0.04%, other is about 0.01% years old.
Embodiment 3
The successive reaction rectifying tower, rectifying section is the filled section, and 25 theoretical stages are arranged, stripping section has 10 theoretical stages, carries out reactive distillation under the normal pressure, and charging acetic acid and alcoholic acid mol ratio are 1: 1, reactive distillation cat head temperature is 73 ℃, tower still temperature is 140 ℃, and raw material acetic acid and ethanol add at the bottom of by still, and reflux ratio is 1.8, the phase composite of cat head ester is in mass percent by analysis, ethyl acetate 93.24%, ethanol content 0.18%, water-content 5.10% other about 1.48%.After extraction tower was purified, the phase composite of cat head ester was in mass percent, ethyl acetate 99.99%, and ethanol content 0.008%, other is about 0.002% years old.
Claims (4)
1, a kind of method of production ethyl acetate is a raw material with acetate and ethanol, it is characterized in that: reaction raw materials acetate and alcoholic acid raw materials components mole ratio are 1-1.5, and catalyzer is selected LaZSM-5 solid acid or phosphato-molybdic heteropolyacid or TiO for use
2/ SO
4 -2-HZSM-5 or phospho-wolframic acid or methylsulfonic acid, extraction agent is a composite extractant, form by glycerol, ethylene glycol, Potassium ethanoate, sodium-acetate, sodium-chlor, Repone K, its fit quality ratio is 11: 2: 0.1: 0.1: 0.1: 0.1, temperature of reaction 80-140 ℃, reflux medium adopts the purified ethyl acetate, and reflux ratio is between 1.5-2.0, and production process comprises reactive distillation processes and extraction process:
A. reactive distillation processes
Acetate is added by tower middle and upper part 1/4-1/2, and cat head steams thing after condenser condenses, is divided into oil phase and water through water-and-oil separator, and after water was told, thick ester entered extraction tower and carries out extracting and refining, and reflux adopts the product behind the extracting and refining, reflux ratio 1.5-2;
B. extraction process:
Composite extractant is added by the top of tower, space between composite extractant import and the cat head is as last breeze way, the thick ester of esterification reaction tower extraction adds with the bottom by tower, space conduct between at the bottom of thick ester import and the tower is breeze way down, whole extraction process carries out under 15-20 ℃, ethyl acetate product is by the cat head extraction, and portioned product enters reaction fractionating tower as phegma.
2, by the method for the described production ethyl acetate of claim 1, it is characterized in that in still liquid, inserting the glass spring filler, the outlet of acid alcohol feed-pipe is fixed on center at the bottom of the still.
3, the method for production ethyl acetate according to claim 1 is characterized in that being added with in the reactor exit one section filler catalytic bed.
4, the method for production ethyl acetate according to claim 1 is characterized in that in extracting rectifying post upper end the empty adapter bonnet of one joint being arranged, and the feed entrance point of extraction agent is in the lower end of adapter bonnet, and the feed entrance point of thick ethyl acetate is in the extractant feed lower end.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100122927A CN1294114C (en) | 2004-05-21 | 2004-05-21 | Method for producing acetic ether |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100122927A CN1294114C (en) | 2004-05-21 | 2004-05-21 | Method for producing acetic ether |
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| CN1580031A CN1580031A (en) | 2005-02-16 |
| CN1294114C true CN1294114C (en) | 2007-01-10 |
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| CNB2004100122927A Expired - Fee Related CN1294114C (en) | 2004-05-21 | 2004-05-21 | Method for producing acetic ether |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544562B (en) * | 2009-05-07 | 2013-03-13 | 中国科学院大连化学物理研究所 | Zeolite molecular sieve catalysis method for synthesizing sec-butyl acetate from acetic acid and butylenes. |
| CN102671682B (en) * | 2012-06-05 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethyl acetate, and preparation method and application of catalyst |
| CN102701971A (en) * | 2012-06-26 | 2012-10-03 | 太仓市周氏化学品有限公司 | Environment-friendly synthetic method for preparing ethyl acetate |
| CN104987297A (en) * | 2015-06-09 | 2015-10-21 | 响水县现代化工有限责任公司 | Preparation method for propanamide |
| CN105642361A (en) * | 2016-01-12 | 2016-06-08 | 广西新天德能源有限公司 | Immobilized catalyst for producing ethyl acetate by reaction distillation coupling method and preparation method thereof |
| CN105753691A (en) * | 2016-03-30 | 2016-07-13 | 广西新天德能源有限公司 | Method for utilizing molecular sieve supported catalyst to prepare acetic ether |
| CN108675929A (en) * | 2018-03-23 | 2018-10-19 | 广西金茂生物化工有限公司 | A kind of production technology of ethyl acetate |
| CN108314622A (en) * | 2018-05-04 | 2018-07-24 | 南通百川新材料有限公司 | A kind of new acetic acid ethyl ester extracting system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325840A (en) * | 2001-04-20 | 2001-12-12 | 清华大学 | Process for preparing ethyl acetate |
| CN1433395A (en) * | 1999-10-14 | 2003-07-30 | 苏舍化学技术有限公司 | Method of producing ethyl acetate and equipment for carrying out this method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433395A (en) * | 1999-10-14 | 2003-07-30 | 苏舍化学技术有限公司 | Method of producing ethyl acetate and equipment for carrying out this method |
| CN1325840A (en) * | 2001-04-20 | 2001-12-12 | 清华大学 | Process for preparing ethyl acetate |
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