CN103041863A - Method for preparing ethyl acetate by metal-organic framework-loading phosphotungstic acid catalyst - Google Patents
Method for preparing ethyl acetate by metal-organic framework-loading phosphotungstic acid catalyst Download PDFInfo
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- CN103041863A CN103041863A CN201210517120XA CN201210517120A CN103041863A CN 103041863 A CN103041863 A CN 103041863A CN 201210517120X A CN201210517120X A CN 201210517120XA CN 201210517120 A CN201210517120 A CN 201210517120A CN 103041863 A CN103041863 A CN 103041863A
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Abstract
The invention discloses a method for preparing ethyl acetate by a metal-organic framework-loading phosphotungstic acid catalyst. The method comprises the steps of: dissolving phosphotungstic acid into distilled water at room temperature to prepare a solution with the concentration being 0.01-0.06mol/L; soaking a metal-organic framework into the solution for 1 hour; then baking for 2-6 hours at the temperature of 120-200 DEG C; and stirring once every other 20-30min in a baking process to prepare a catalyst, wherein the mass percent of phosphotungstic acid in the prepared catalyst is 1-15%. The prepared catalyst is applied to reactive distillation and catalysis of acetic acid and preparation of ethyl acetate by ethanol, not only the process conversion rate and the product yield are increased, but also a process flow is simplified, and equipment and operating costs are reduced.
Description
Technical field
The present invention relates to a kind of method for preparing ethyl acetate, use phosphotungstic acid/metallic organic framework supported solid catalyst, adopt reaction rectification technique, prepare the method for ethyl acetate take acetic acid and ethanol as the raw material esterification.
Background technology
Ethyl acetate (EA) has another name called ethyl acetate, it is a kind of important downstream product of acetic acid, has excellent dissolubility, quick-drying, main as producing coating (paint and enamel paint) in industry, adhesive, ethyl cellulose, artificial leather, the solvent of malthoid colouring agent and staple fibre etc., also can be used as adhesive and be used for printing-ink, the production of olivet etc., be used for medicine as extractant, the production of organic acid product etc., can be used as in addition and produce pineapple, banana, fruit essence and the whiskeys such as strawberry, the raw material of milk wet goods spices, purposes is very extensive, and development prospect is good.
The acetic acid esterified method is the modal production method of ethyl acetate, is in the presence of catalyst (being generally sulfuric acid), and acetic acid and ethanol generation esterification generate ethyl acetate.This method exists reaction temperature high, and the acetic acid utilization rate is low, and side reaction easily occurs, and product treatment is difficult, catalyst is strong to equipment corrosion, the shortcomings such as waste liquor contamination environment and production cost height.To react in recent years and separation coupling technology, particularly the novel reaction distillation technology novel process that is applied to production of ethyl can overcome numerous shortcomings that traditional direct esterification technique exists.Reaction rectification technique is chemical reaction to be separated two processes organically combine with rectifying, finishes simultaneously a kind of novel reaction technology of reaction and separation process in same equipment.Liao An equality in 1997 has been studied with cation exchange resin as catalyst reactive distillation synthesizing ethyl acetate, and 2000, Ye Qing etc. studied and done catalyst rectifying with natural mordenite zeolite and prepare ethyl acetate.Heteropolyacid catalyst is just becoming the study hotspot of present environmental friendliness chemistry as the chief component of green catalysis.The present invention overcomes the numerous shortcomings that exist in traditional direct esterification technique in conjunction with the novel environment-friendly process of the reactive distillation synthesizing ethyl acetate of advantage exploitation take heteropoly acid as catalyst of distillation technology and heteropoly acid.
Summary of the invention
The object of the present invention is to provide a kind of high activity, environmentally benign catalysts is used for solving problems of the prior art.With catalyst synthesizing ethyl acetate of the present invention, in the conversion ratio that improves ethanol, kept the high selectivity of ethyl acetate.Another object of the present invention is to provide a kind of preparation method of above-mentioned catalyst.The present invention also aims to provide the application of a kind of above-mentioned catalyst in synthesizing ethyl acetate.
The concrete preparation method of catalyst of the present invention comprises as follows:
At room temperature, phosphotungstic acid is dissolved in distilled water is configured to the solution that concentration is 0.01 ~ 0.06mol/L, and impregnating metal organic backbone carrier, soak after 1 hour, 120 ~ 200 ℃ of lower roastings 2 ~ 6 hours, each 20 ~ 30min stirs once in roasting process, so that phosphotungstic acid loads on the metallic organic framework uniformly, the quality percentage composition of phosphotungstic acid is 1 ~ 15% in the catalyst of making; Use the above-mentioned phosphotungstic acid for preparing/metallic organic framework supported solid catalyst, adopt reaction rectification technique, esterification acetic acid and ethanol prepare ethyl acetate.Reaction condition is as follows, calculates in molar ratio, and acetic acid: the charge proportion of ethanol is 1:1, and reaction temperature is 150 ℃, reflux ratio: 1 ~ 2, and feed rate: 20 ~ 60mL/h.
The present invention adopts distillation technology, take phosphotungstic acid/metallic organic framework as the catalyst synthesizing ethyl acetate, with traditional take sulfuric acid as catalyst, catalytic reaction compares with the synthesizing ethyl acetate technique that rectifying is carried out separately and has the following advantages: 1) simplified flow process, reduced installation cost and operating cost; 2) because this reaction is exothermic reaction, reaction heat all is provided as the part of distillation process institute calorific requirement, has saved energy; 3) for this reversible reaction, because the continuous separation of product makes balance move to positive direction, increased the yield of process conversion ratio and product; 4) because the employing carried heteropoly acid is catalyst, reduced the corrosion of equipment and the pollution of environment.
The specific embodiment
The present invention will be further described below in conjunction with the implementation example
Embodiment 1
The metallic organic framework load contains the preparation of 1.2% phosphotungstic acid catalyst: the 3g phosphotungstic acid is dissolved in the distilled water of 100ml, be immersed in again in the 250g metallic organic framework after l hour, the mass percentage content of phosphotungstic acid is 1.2% in the catalyst, with the phosphotungstic acid of metallic organic framework load 120 ℃ of lower roastings 2 hours, in roasting process, stir once every 20min, make the catalyst that contains 1.2% phosphotungstic acid of metallic organic framework load.
The continuous reaction rectification tower, rectifying section is the filled section, 8 theoretical plates are arranged, 5 theoretical plates of conversion zone, stripping section has 2 theoretical plates, load rolling metal θ ring in rectifying section and the stripping section, the catalyst that contains 1.2% phosphotungstic acid of the metallic organic framework load that conversion zone filling l00g makes, carry out reactive distillation under the normal pressure, reactive distillation cat head temperature is 65 ℃, 150 ℃ of tower reactor temperature, just having begun to add cumulative volume at the bottom of the still is that 250ml acid alcohol mole is the mixed liquor of 2:1, the mol ratio 1:1 of charging acetic acid and ethanol, ethanol feed rate 20ml/h, reflux ratio is l, the phase composition of cat head ester is calculated in mass percent by analysis, ethyl acetate 84.96%, ethanol content 9.33%, water content 5.8%.
Embodiment 2
The continuous reaction rectification tower, rectifying section is the filled section, 8 theoretical plates are arranged, 5 theoretical plates of conversion zone, stripping section has 2 theoretical plates, load rolling metal θ ring in rectifying section and the stripping section, conversion zone is loaded the catalyst that contains 1.2% phosphotungstic acid of the metallic organic framework load that l00g makes with same method among the embodiment 1, carry out reactive distillation under the normal pressure, reactive distillation cat head temperature is 65 ℃, 150 ℃ of tower reactor temperature, just having begun to add cumulative volume at the bottom of the still is that 250ml acid alcohol mole is the mixed liquor of 2:1, the mol ratio 1:1 of charging acetic acid and ethanol, ethanol feed rate 40ml/h, reflux ratio is l, the phase composition of cat head ester is calculated in mass percent by analysis, ethyl acetate 81.32%, ethanol content 13.42%, water content 5.26%.
Embodiment 3
The metallic organic framework load contains the preparation of 7% phosphotungstic acid catalyst: the 5g phosphotungstic acid is dissolved in the distilled water of 50ml, be immersed in again in the 93g metallic organic framework after 1 hour, the mass percentage content of phosphotungstic acid is 5% in the catalyst, with the phosphotungstic acid of metallic organic framework load 180 ℃ of lower roastings 2 hours, in roasting process, stir once every 20min, make the catalyst that contains 7% phosphotungstic acid of metallic organic framework load.
The continuous reaction rectification tower, rectifying section is the filled section, 8 theoretical plates are arranged, 5 theoretical plates of conversion zone, stripping section has 2 theoretical plates, load the draw ring glass fiber in rectifying section and the stripping section, conversion zone is loaded the catalyst that contains 4.7% phosphotungstic acid of the metallic organic framework load that l00g makes with same method in the EXAMPLE l, carry out reactive distillation under the normal pressure, reactive distillation cat head temperature is 65 ℃, 150 ℃ of tower reactor temperature, just having begun to add cumulative volume at the bottom of the still is that 250ml acid alcohol mole is the mixed liquor of 2:1, the mol ratio 1:1 of charging acetic acid and ethanol, ethanol feed rate 60ml/h, reflux ratio is l, the phase composition of cat head ester is calculated in mass percent by analysis, ethyl acetate 75.21%, ethanol content 17.52%, water content 6.27%.
Embodiment 4
The metallic organic framework load contains the preparation of 10% phosphotungstic acid catalyst: the 10g phosphotungstic acid is dissolved in the distilled water of 100ml, be immersed in again in the 90g metallic organic framework after l hour, the mass percentage content of phosphotungstic acid is 90% in the catalyst, with the phosphotungstic acid of metallic organic framework load 120 ℃ of lower roastings 6 hours, in roasting process, stir once every 30min, make the catalyst that contains 10% phosphotungstic acid of metallic organic framework load.
The continuous reaction rectification tower, rectifying section is the filled section, 8 theoretical plates are arranged, 5 theoretical plates of conversion zone, stripping section has 2 theoretical plates, load rolling metal θ ring in rectifying section and the stripping section, the catalyst that contains 10% phosphotungstic acid of the metallic organic framework load that conversion zone filling l00g makes, carry out reactive distillation under the normal pressure, reactive distillation cat head temperature is 65 ℃, 150 ℃ of tower reactor temperature, just having begun to add cumulative volume at the bottom of the still is that 250ml acid alcohol mole is the mixed liquor of 2:1, the mol ratio 1:1 of charging acetic acid and ethanol, ethanol feed rate 20ml/h, reflux ratio is 2, the phase composition of cat head ester is calculated in mass percent by analysis, ethyl acetate 84.75%, ethanol content 6.27%, water content 8.98%.
Embodiment 5
The continuous reaction rectification tower, rectifying section is the filled section, 8 theoretical plates are arranged, 5 theoretical plates of conversion zone, stripping section has 2 theoretical plates, load rolling metal θ ring in the grain section of heating up in a steamer and the stripping section, conversion zone is loaded the catalyst that contains 14% phosphotungstic acid of the metallic organic framework load that l00g makes with same method among the embodiment 4, carry out reactive distillation under the normal pressure, reactive distillation cat head temperature is 65 ℃, 150 ℃ of tower reactor temperature, just having begun to add cumulative volume at the bottom of the still is that 250ml acid alcohol mole is the mixed liquor of 2:1, the mol ratio 1:1 of charging acetic acid and ethanol, ethanol feed rate 40ml/h, reflux ratio is 2, the phase composition of cat head ester is calculated in mass percent by analysis, ethyl acetate 86.35%, ethanol content 7.96%, water content 5.69%.
Embodiment 6
The load of reactive metal organic backbone contains the preparation of 15% phosphotungstic acid catalyst: the l5g phosphotungstic acid is dissolved in the distilled water of 100ml, be immersed in again in the 85g reactive metal organic backbone after l hour, the mass percentage content of phosphotungstic acid is 10% in the catalyst, with the phosphotungstic acid of reactive metal organic backbone load 200 ℃ of lower roastings 6 hours, in roasting process, stir once every 30min, make the catalyst that contains 15% phosphotungstic acid of reactive metal organic backbone load.
The continuous reaction rectification tower, rectifying section is the filled section, 8 theoretical plates are arranged, 5 theoretical plates of conversion zone, stripping section has 2 theoretical plates, load rolling metal θ ring in rectifying section and the stripping section, the catalyst that contains 15% phosphotungstic acid of the reactive metal organic backbone load that conversion zone filling l00g makes, carry out reactive distillation under the normal pressure, reactive distillation cat head temperature is 65 ℃, 150 ℃ of tower reactor temperature, just having begun to add cumulative volume at the bottom of the still is that 250ml acid alcohol mole is the mixed liquor of 2:1, the mol ratio 1:1 of charging acetic acid and ethanol, ethanol feed rate 20ml/h, reflux ratio is 2, the phase composition of cat head ester is calculated in mass percent by analysis, ethyl acetate 90.14%, ethanol content 5.44%, water content 4.42%.
Claims (1)
1. a metallic organic framework load phosphotungstic acid catalyst prepares the method for ethyl acetate, it is characterized in that: at room temperature, phosphotungstic acid is dissolved in distilled water is configured to the solution that concentration is 0.01 ~ 0.06mol/L, metallic organic framework is impregnated in the mentioned solution, flood after 1 hour, 120 ~ 200 ℃ of lower roastings 1 ~ 5 hour, in roasting process, stir once every 10 ~ 30min, the quality percentage composition of phosphotungstic acid is 5 ~ 10% in the catalyst; Use above-mentioned be prepared into to catalyst, adopt reaction rectification technique, catalysis acetic acid and ethanol prepare ethyl acetate, reaction condition is as follows, calculates in molar ratio, and acetic acid: the charge proportion of ethanol is 1:1, reaction temperature is 150 ℃, reflux ratio: 1 ~ 2, and feed rate: 20 ~ 60mL/h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769036A (en) * | 2014-02-26 | 2014-05-07 | 东北师范大学 | Preparation method for polyacid @ MIL-101 composite material and application of polyacid @ MIL-101 composite material |
| CN104857988A (en) * | 2015-05-07 | 2015-08-26 | 盐城工学院 | Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof |
| CN108262073A (en) * | 2018-01-15 | 2018-07-10 | 重庆科技学院 | A kind of application of metal organic framework load phosphotungstic acid catalyst, preparation method and Synthesis of Adipic Acid Catalyzed |
| CN111054441A (en) * | 2019-11-25 | 2020-04-24 | 浙江大学 | Preparation method and application of silicotungstic acid shell-coated and core-embedded zeolite imidazole framework |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798264A (en) * | 2010-03-25 | 2010-08-11 | 江苏大学 | Method for preparing ethyl acetate by using alumina supported phosphotungstic acid as catalyst |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798264A (en) * | 2010-03-25 | 2010-08-11 | 江苏大学 | Method for preparing ethyl acetate by using alumina supported phosphotungstic acid as catalyst |
Non-Patent Citations (2)
| Title |
|---|
| LIK H.WEE,ET AL: "Heteropolyacid encapsulated in Cu3(BTC)2 nanocrystals: An effective esterification catalyst[J]", 《CATALYSIS TODAY》 * |
| 刘勇晶等: "磷钨酸催化反应精馏合成乙酸乙酯的研究[J]", 《化学与生物工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769036A (en) * | 2014-02-26 | 2014-05-07 | 东北师范大学 | Preparation method for polyacid @ MIL-101 composite material and application of polyacid @ MIL-101 composite material |
| CN104857988A (en) * | 2015-05-07 | 2015-08-26 | 盐城工学院 | Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof |
| CN108262073A (en) * | 2018-01-15 | 2018-07-10 | 重庆科技学院 | A kind of application of metal organic framework load phosphotungstic acid catalyst, preparation method and Synthesis of Adipic Acid Catalyzed |
| CN108262073B (en) * | 2018-01-15 | 2020-09-25 | 重庆科技学院 | Metal organic framework supported phosphotungstic acid catalyst, preparation method and application of catalyst in catalytic synthesis of adipic acid |
| CN111054441A (en) * | 2019-11-25 | 2020-04-24 | 浙江大学 | Preparation method and application of silicotungstic acid shell-coated and core-embedded zeolite imidazole framework |
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Application publication date: 20130417 |