CN103159591A - Technique of synthesizing ethanol with acetic acid - Google Patents
Technique of synthesizing ethanol with acetic acid Download PDFInfo
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- CN103159591A CN103159591A CN201110424387XA CN201110424387A CN103159591A CN 103159591 A CN103159591 A CN 103159591A CN 201110424387X A CN201110424387X A CN 201110424387XA CN 201110424387 A CN201110424387 A CN 201110424387A CN 103159591 A CN103159591 A CN 103159591A
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Abstract
The invention aims to solve the problem that conversion rate of acetic acid is low in the prior techniques and corrosion resistant material equipment is needed because the acetic acid cannot convert completely in hydrogenation reaction. The technical scheme includes: acetic acid and hydrogen are used as raw materials to synthesize ethanol, acetic ester is produced from esterification reaction of acetic acid and monohydric alcohol, ethanol and corresponding monohydric alcohol are produced from acetic ester and hydrogen, the monohydric alcohol reacts with acetic acid in the esterification reaction step, and the ethanol is sent to a rectifying tower to refine. The technique of synthesizing ethanol with acetic acid has the advantages that cheap copper catalyst is used in the reaction, material of hydrogenation equipment do not have to be corrosion resistant, acetic ester including monohydric alcohol and water is used as raw material, hydrogen is added to the acetic ester to synthesize ethanol, and the problem that conversion rate of acetic acid in the prior technique is solved.
Description
Technical field
The present invention relates to the technique of a kind of acetic acid ethanol processed, specifically a kind ofly take acetic acid as raw material, through the technique of esterification repeated hydrogenation synthesizing alcohol.
Background technology
Ethanol is a kind of important Organic chemical products, be widely used in the industries such as food, chemical industry, medicine, dyestuff, national defence, ethanol can also substitute the detonation suppressor of tetraethyllead as gasoline, and can be entrained in gasoline as vehicle-use alcohol gasoline as fuel.In world wide, 60% of ethanol production is used as vehicle fuel at present.
The production method of ethanol is divided into fermentation method and chemical synthesis, and Ethanol Production by Fermentation is mainly that to take the food crop such as corn, cassava, wheat, Chinese sorghum be raw material, under the effect of microorganism, through fermentation, distillation, makes.The ethene that chemical synthesis is produced the current main employing petroleum cracking gained of ethanol is raw material, through the chemical reaction synthesizing alcohol.Due to the China's oil scarcity of resources, limited popularization and the development of chemosynthesis ethanol in China, so the alcohol production of China 96.5% all adopts fermentation method.One ton of ethanol of fermentative Production need consume 3.3 tons of corns and 1.5 tons of coals, and the price of ethanol per ton is more than 8000 yuan, and Ethanol Production by Fermentation is China's discharge organic contamination object height, a serious industry of environmental pollution.Development along with fuel ethanol industrial, the problem of the Ethanol Production by Fermentation that the grain of take is raw material becomes increasingly conspicuous, Food Security is related to the stability and harmony of stablizing of national economy and society, therefore develop non-grain route synthesizing alcohol, particularly with the set out technique of synthesizing alcohol of coal resources, will be one and there is important economic implications and the route of strategic importance.
Patent CN102229520 discloses the method that the direct gas phase hydrogenation of a kind of acetic acid prepares ethanol, but the pressure that reacts required is high, and the reaction used catalyst contains precious metal.Patent USP7863489 discloses the catalyzer of a kind of acetic acid direct hydrogenation ethanol processed, but the transformation efficiency of acetic acid is lower, is only 85% left and right, and adopts equally noble metal catalyst.In the process that is raw material direct hydrogenation synthesizing alcohol at acetic acid, because acetic acid in reaction can not transform fully, and acetic acid has certain corrodibility, the acetic acid of therefore take is stricter to the requirement of conversion unit as the direct synthesizing alcohol of raw material, needs certain corrosion resistant material.
Summary of the invention
the present invention is intended to solve acetic acid low conversion rate in current prior art, and because acetic acid can not transform fully and need corrosion resistant material equipment in hydrogenation process.
Technical scheme of the present invention is that to take acetic acid, hydrogen be the raw material synthesizing alcohol, at first acetic acid and monohydroxy-alcohol generation esterification generate acetic ester, then the acetic ester repeated hydrogenation generates ethanol and corresponding monohydroxy-alcohol, and then monohydroxy-alcohol is returned to esterification step and acetic acid reaction, it is refining that ethanol is sent into rectifying tower.Reaction formula is as follows:
CH
3COOH + ROH → CH
3COOR + H
2O
CH
3COOR + 2H
2 → CH
3CH
2OH + ROH
Total reaction CH
3cOOH+2H
2→ CH
3cH
2oH+H
2o
(R is alkyl, as-CH
3,-C
2h
5,-C
3h
7deng)
This technique mainly is comprised of equipment such as esterifier, rough segmentation tower, vaporization tower, hydrogenator, rectifying tower and necessary condenser, interchanger, valve, pipeline, fresh feed pump, hydrogen gas compressors.At first the product of esterification generation containing acetic ester occurs in acetic acid and monohydroxy-alcohol in esterifier, generate containing the acetic ester product in the rough segmentation tower by unreacted complete acetic acid separated, isolated acetic acid is back in esterifier and continues reaction, send into the vaporization tower and separate the thick ester product obtained, thick ester product mainly contains acetic ester, and a small amount of water and the complete monohydroxy-alcohol of unreacted, the temperature of controlling the vaporization tower reaches the bubble point of thick ester product, then thick ester is sent into to hydrogenator and hydrogen reaction, Cu-series catalyst is housed in hydrogenator, controlling reaction pressure is 0.5-5.0 MPa, temperature of reaction is 180-300
oc, the mol ratio of hydrogen and acetic ester is 10-100, the liquid air speed of acetic ester is 0.1-1 h
-1.Reaction obtains the thick pure product containing ethanol by gas-liquid separation.
If what monohydroxy-alcohol adopted is ethyl acetate, the thick pure product of a part directly can be back to esterifier, for the acetic acid reaction synthesizing ethyl acetate.The thick pure product of remaining another part is sent into rectifying tower and is obtained smart ethanol.
If what monohydroxy-alcohol adopted is not ethyl acetate, as methyl acetate, propyl acetate, butylacetate etc., need methyl alcohol, propyl alcohol, butanols and separation of ethanol in thick pure product, wherein separate the methyl alcohol, propyl alcohol, the butanols that obtain and be back to esterifier, for and the acetic acid reaction synthesizing acetic ester, and ethanol is sent into, rectifying tower is refining obtains smart ethanol.
Adopt technical process of the present invention, acetic acid at first esterification generates acetic ester, then isolate unreacted acetic acid and be back to esterifier in the rough segmentation tower, therefore back adds hydrogen partial affects without acetic acid, so catalyzer can the lower Cu-series catalyst of use cost, the material of hydrogenation unit is also without corrosion resistant material.
Adopt technical process of the present invention, the available acetic ester containing the monobasic alcohol and water is that raw material is directly used in the hydrogenation synthesizing alcohol.
Adopt technical process of the present invention, the acetic acid esterified synthesis for ethyl acetate, vinyl acetic monomer repeated hydrogenation synthesizing alcohol then, the selectivity of ethanol is more than 95%, the space-time yield of ethanol is greater than 1200 g kg
-1h
-1.
Adopt technical process of the present invention, the acetic acid synthesized methyl esters of acetic acid esterified, propyl acetate, N-BUTYL ACETATE, then ritalin, propyl acetate, N-BUTYL ACETATE repeated hydrogenation synthesizing alcohol, the selectivity of ethanol is more than 47%, the space-time yield of ethanol is greater than 600 g kg
-1h
-1.
The invention has the beneficial effects as follows: catalyzer can the lower Cu-series catalyst of use cost; The material of hydrogenation unit is also without corrosion resistant material; The available acetic ester containing the monobasic alcohol and water is that raw material is directly used in the hydrogenation synthesizing alcohol; Overcome the problem of the low conversion rate of acetic acid in the prior art, during from the vinyl acetic monomer synthesizing alcohol, selectivity has reached more than 95%.
The accompanying drawing explanation
Fig. 1 be acetic acid and ethanol through esterification synthesizing alcohol schematic flow sheet, wherein 1-12 is pipeline, I is esterifier, II is the rough segmentation tower, III is the vaporization tower, IV is hydrogenator, V is gas-liquid separator, VI is rectifying tower.
Fig. 2 be acetic acid and monohydroxy-alcohol through esterification synthesizing alcohol schematic flow sheet, wherein 1-11 is pipeline, I is esterifier, II is the rough segmentation tower, III is the vaporization tower, IV is hydrogenator, V is gas-liquid separator, VI is rectifying tower.
Embodiment
Below in conjunction with embodiment, foregoing invention content of the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
Flow process of the present invention as shown in Figure 1, acetic acid 1 enters esterifier I by the road, react generation vinyl acetic monomer product with the coarse ethanol from pipeline 9 under the effect of an acidic catalyst, the product containing vinyl acetic monomer generated 2 enters rough segmentation tower II by the road, in the rough segmentation tower, by unreacted, complete acetic acid separated out, so 4 is back in esterifier I by the road again.The thick ester of isolating in the rough segmentation tower containing vinyl acetic monomer 3 enters vaporization tower III by the road, thick ester from pipeline 3 in vaporization tower III mixes and is heated to the bubble point of thick ester with hydrogen, and then 5 enter hydrogenator IV by the road, under the effect of Cu-series catalyst, react, reacted logistics mainly contains ethanol, the hydrogen that water and unreacted are complete, vinyl acetic monomer, this logistics 6 enters gas-liquid separator V by the road, after gas-liquid separation, hydrogen by the road 7 be back to vaporization tower III together with hydrogen make-up from pipeline 12, and the logistics that condensation is got off mainly contains ethanol, the vinyl acetic monomer that water and unreacted are complete, this logistics 8 flows out and is divided into two portions by the road, wherein a part 9 is back to esterifier I by the road, another part logistics 10 enters rectifying tower VI by the road, ethanol after rectifying 11 takes out by the road.In esterifier, acetic acid and ethanol react under an acidic catalyst effect, generate the product containing vinyl acetic monomer, then the product containing vinyl acetic monomer enters the rough segmentation tower, the azeotrope that ethyl acetate, second alcohol and water form steams from tower top, it consists of (weight percent) 82.6% ethyl acetate, 8.4% ethanol, 9.0% water.The thick ester of this composition is sent into to the vaporization tower, in vaporization, be heated to bubble point in tower, then enter in hydrogenator and hydrogen reaction, 15 g Cu-series catalysts are housed in hydrogenator, temperature of reaction is 270
oc, reaction pressure is 2.0 MPa, and the mol ratio of hydrogen and ethyl acetate is 30, and the selectivity of reaction result ethanol is 96.8%, and the space-time yield of ethanol is 1315.6 g kg
-1h
-1.
Temperature of reaction in embodiment 1 is become to 180
oc, reaction pressure becomes 0.5 MPa, and the mol ratio of hydrogen and ethyl acetate is 100, and the selectivity of reaction result ethanol is 98.2%, and the space-time yield of ethanol is 412.7 g kg
-1h
-1.
Temperature of reaction in embodiment 1 is become to 300
oc, reaction pressure becomes 5.0 MPa, and the mol ratio of hydrogen and ethyl acetate is 10, and the selectivity of reaction result ethanol is 95.3%, and the space-time yield of ethanol is 1633.6 g kg
-1h
-1.
Embodiment 4
The flow process of this reaction as shown in Figure 2, acetic acid 1 enters esterifier I by the road, react generation acetic ester (as ritalin, propyl acetate, N-BUTYL ACETATE) product with the monohydroxy-alcohol (as methyl alcohol, propyl alcohol, butanols) from pipeline 9 under the effect of an acidic catalyst, the product containing acetic ester generated 2 enters rough segmentation tower II by the road, in the rough segmentation tower, by unreacted, complete acetic acid separated out, then 4 is back in esterifier I by the road again.The thick ester of isolating in the rough segmentation tower containing acetic ester 3 enters vaporization tower III by the road, thick ester from pipeline 3 in vaporization tower III mixes and is heated to the bubble point of thick ester with hydrogen, and then 5 enter hydrogenator IV by the road, under the effect of Cu-series catalyst, react, reacted logistics mainly contains ethanol, monohydroxy-alcohol, the hydrogen that water and unreacted are complete, acetic ester, this logistics 6 enters gas-liquid separator V by the road, after gas-liquid separation, hydrogen by the road 7 be back to vaporization tower III together with hydrogen make-up from pipeline 11, and the logistics that condensation is got off mainly contains ethanol, monohydroxy-alcohol, the acetic ester that water and unreacted are complete, this logistics 8 enters rectifying tower VI by the road, ethanol after rectifying 10 takes out by the road, monohydroxy-alcohol 9 is back to esterifier I by the road.In esterifier, acetic acid and methyl alcohol react under an acidic catalyst effect, generate the product containing ritalin, then the product containing ritalin enters the rough segmentation tower, overhead product tower top containing methyl acetate after separating steams, it consists of (weight percent) 99.0% methyl acetate, 0.9% methyl alcohol, 0.1% water.The thick ester of this composition is sent into to the vaporization tower, in vaporization, be heated to bubble point in tower, then enter in hydrogenator and hydrogen reaction, 15 g Cu-series catalysts are housed in hydrogenator, temperature of reaction is 270
oc, reaction pressure is 2.0 MPa, and the mol ratio of hydrogen and ethyl acetate is 30, and the selectivity of reaction result ethanol is 47.8%, and the space-time yield of ethanol is 657.3 g kg
-1h
-1.
By the acetic acid in embodiment 4 and the acetic acid synthesized methyl esters of methanol esterification, replace to acetic acid and the acetic acid synthesized propyl ester of n-propyl alcohol esterification, the selectivity of reaction result ethanol is 48.1%, the space-time yield of ethanol is 662.3 g kg
-1h
-1.
By the acetic acid in embodiment 4 and the acetic acid synthesized methyl esters of methanol esterification, replace to acetic acid and propyl carbinol esterification Synthesis of n-Butyl Acetate, the selectivity of reaction result ethanol is 48.1%, the space-time yield of ethanol is 662.3 g kg
-1h
-1.The selectivity of reaction result ethanol is 47.1%, and the space-time yield of ethanol is 641.7 g kg
-1h
-1.
Claims (10)
1. the technological process of production with acetic acid ethanol processed, it is characterized in that: acetic acid and monohydroxy-alcohol esterification, synthetic mixture enters rough segmentation tower simple separation, the thick ester that mainly contains the complete monohydroxy-alcohol of acetic ester, a small amount of water and unreacted obtained, in hydrogenator under catalyst action with hydrogen reaction, produce ethanol, monohydroxy-alcohol, water and unreacted acetic ester.
2. technical process as claimed in claim 1 is characterized in that: described catalyzer is Cu-series catalyst.
3. technical process as claimed in claim 1 is characterized in that: the equipment of employing mainly comprises esterifier, rough segmentation tower, vaporization tower, hydrogenator, rectifying tower and necessary condenser, interchanger, valve, pipeline, fresh feed pump and hydrogen gas compressor.
4. technical process as described as any one in claim 1-3 is characterized in that: hydrogenator is shell and tube heat exchange type reactor or adiabatic reactor.
5. technical process as described as any one in claim 1-4 is characterized in that: the temperature of controlling the vaporization tower reaches the bubble point of thick ester product.
6. technical process as described as any one in claim 1-5 is characterized in that: monohydroxy-alcohol is methyl alcohol, propyl alcohol or butanols.
7. technical process as claimed in claim 6 is characterized in that: the ethanol in the ethanol of generation, monohydroxy-alcohol, water and unreacted acetic ester is with after monohydroxy-alcohol separates, and it is refining that ethanol is sent into rectifying tower, and monohydroxy-alcohol returns to esterifier and acetic acid reaction.
8. technical process as described as any one in claim 1-4 is characterized in that: described monohydroxy-alcohol is ethanol.
9. technical process as claimed in claim 8 is characterized in that: part ethanol returns to esterifier and acetic acid reaction.
10. production technique as described as any one in claim 1-9, it is characterized in that: the reaction pressure of hydrogenation reaction is 0.5-5.0 MPa, temperature of reaction is 180-300
oc, the mol ratio of hydrogen and acetic ester is 10-100, the liquid air speed of acetic ester is 0.1-1 h
-1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193583A (en) * | 2014-08-05 | 2014-12-10 | 河北美邦工程科技有限公司 | Method for co-production of cyclohexanol and absolute ethyl alcohol |
| CN104649862A (en) * | 2015-02-05 | 2015-05-27 | 天津大学 | Method and equipment for producing ethanol product by taking ethyl acetate as raw material |
| CN104844419A (en) * | 2015-05-04 | 2015-08-19 | 上海华谊（集团）公司 | Energy integration method for producing ethyl alcohol through acetic acid esterification and hydrogenation |
| CN106995363A (en) * | 2016-01-25 | 2017-08-01 | 河南顺达化工科技有限公司 | A kind of hydrogenation coupled technique for preparing ethanol of acetic acid |
| CN107892643A (en) * | 2017-12-01 | 2018-04-10 | 南京科技职业学院 | A kind of method by production of acetic acid ethanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093162A (en) * | 2010-12-13 | 2011-06-15 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093162A (en) * | 2010-12-13 | 2011-06-15 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester |
Non-Patent Citations (1)
| Title |
|---|
| 李扬等: "醋酸酯化合成乙醇工艺及经济性分析", 《精细化工原料及中间体》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193583A (en) * | 2014-08-05 | 2014-12-10 | 河北美邦工程科技有限公司 | Method for co-production of cyclohexanol and absolute ethyl alcohol |
| CN104649862A (en) * | 2015-02-05 | 2015-05-27 | 天津大学 | Method and equipment for producing ethanol product by taking ethyl acetate as raw material |
| CN104844419A (en) * | 2015-05-04 | 2015-08-19 | 上海华谊（集团）公司 | Energy integration method for producing ethyl alcohol through acetic acid esterification and hydrogenation |
| CN106995363A (en) * | 2016-01-25 | 2017-08-01 | 河南顺达化工科技有限公司 | A kind of hydrogenation coupled technique for preparing ethanol of acetic acid |
| CN106995363B (en) * | 2016-01-25 | 2018-07-10 | 河南顺达化工科技有限公司 | A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid |
| CN107892643A (en) * | 2017-12-01 | 2018-04-10 | 南京科技职业学院 | A kind of method by production of acetic acid ethanol |
| CN107892643B (en) * | 2017-12-01 | 2020-12-15 | 南京科技职业学院 | Method for producing ethanol from acetic acid |
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Address after: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610225 Patentee after: Southwest Chemical Research & Design Institute Co., Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610225 Patentee before: Xinan Chemical Research & Design Inst. |