CN102134191A - Process method for producing ethyl acetate by catalytic rectification - Google Patents
Process method for producing ethyl acetate by catalytic rectification Download PDFInfo
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- CN102134191A CN102134191A CN2010106007608A CN201010600760A CN102134191A CN 102134191 A CN102134191 A CN 102134191A CN 2010106007608 A CN2010106007608 A CN 2010106007608A CN 201010600760 A CN201010600760 A CN 201010600760A CN 102134191 A CN102134191 A CN 102134191A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process method for producing ethyl acetate by catalytic rectification. The process method is implemented by catalytic reaction of acetic acid and ethanol in a catalytic rectification tower, wherein the acetic acid is added from the upper part of a catalytic rectification section, the ethanol is added from a tower kettle, and crude ester with low ethanol content is obtained on a tower top, thereby reducing the energy consumption of subsequent crude ester rectification; the crude ester is added from the middle part of the rectification tower, the finished ethyl acetate with a purity of more than 99.95% is obtained at the bottom of the rectification tower, and the materials on the top of the rectification tower are returned back to the catalytic rectification tower; and the materials at the bottom of the catalytic rectification tower is not separated out, and partial materials can be recycled to the catalytic rectification section. By utilizing the process method, the content of the ethanol in the crude ester is reduced to the greatest extent, and the recycle of the ethanol in a system is reduced, and the energy consumption is saved; a solid acid catalyst is used, thereby reducing the requirements on equipment materials and saving the equipment cost; and the catalyst can be regenerated and has no pollution on the environment, thus the process method is strong in practicability and can be used for achieving large-scale production.
Description
Technical field
The present invention relates to a kind of processing method of catalytic distillation production ethyl acetate, be specifically related to catalytic rectifying tower and use solid acid catalyst to prepare the technology of ethyl acetate in high purity.
Technical background
Ethyl acetate is a kind of important organic solvent, is widely used in industries such as organic synthesis, coating, medicine, spices, caking agent.Traditional acetic acid, ethyl esterification method synthesizing ethyl acetate adopt sulfuric acid to make catalyzer, have that sulfuric acid corrosion resistance is strong, side reaction is many, the by product difficult treatment reaches shortcomings such as environment pollute.
Catalytic distillation is a kind of novel separating technology with wide application prospect.Chemical reaction and rectifying separation process are finished in catalytic rectifying tower simultaneously.When having overcome the use sulfuric acid catalyst, ethanol and acetic acid can only add the tower still, the high shortcoming of pure content in the thick ester that cat head obtains.Acetic acid autocatalysis rectifying section top adds on the column plate of catalytic distillation section or filling in the filler of solid acid catalyst, and it is more thorough that ethanol is got at the tower internal reaction, thereby obtain the very low thick ester of pure content, reduces the circulation of ethanol in system, saves energy consumption.
Summary of the invention
The object of the invention is to solve in the prior art pure content height in the thick ester, adopt sulfuric acid to make catalyzer, to the demanding shortcoming of the material of equipment, adopt catalytic rectification process, ethanol is reacted completely as far as possible, and alcoholic acid content can be reduced to below 0.3% in the thick ester that obtains, and adopts the solid acid as catalyst, to equipment material require lowly, can realize large-scale production.
The invention provides a kind of processing method of catalytic distillation production ethyl acetate, the synthesizing ethyl acetate under the effect of solid acid catalyst with ethanol and acetic acid, then through refining, recycling step:
1) acetic acid adds from the top of catalytic distillation section, and ethanol adds from the tower still, obtain azeotrope that ethyl acetate and water forms from the catalytic distillation section after, after rectifying section is through separation, enter phase splitter, obtain thick ester and water respectively; Acetic acid autocatalysis rectifying section top adds, and the ethanol synthesis of rising is tending towards fully, and ethanol content is very low in the thick ester that obtains, and ethanol, acetic acid all can only add the tower still when having overcome the use sulfuric acid catalyst, the high shortcoming of pure content in the thick ester of cat head.
2) the thick ester that will obtain is adopted to follow-up treating tower 102, treating tower bottom extraction finished product ethyl acetate (purity 〉=99.95%), and top material returns catalytic rectifying tower;
3) catalytic rectifying tower 101 bottoms can not extraction, also can partly be circulated to the catalytic distillation section.
4) recovery tower 103 reclaims catalytic rectifying tower 101 and treating tower 102 cat head aqueous phase ethanol and ethyl acetate.
Described solid acid catalyst is a strongly acidic cation-exchange, and corrodibility is low, and is low to the equipment material requirement, can realize scale operation.
Described catalytic rectifying tower 101 reflux ratios are 2～3.8: 1.
The mol ratio of described ethanol and acetic acid is 1～1.1: 1.
The condition of described catalytic rectifying tower operating process is: 0.1～0.15Mpa (absolute pressure), 67～105 ℃.
Described catalytic rectifying tower 101 comprises rectifying section, catalytic distillation section and tower still.Top of tower to acetic acid adds inlet and is rectifying section, and it is the catalytic distillation section that acetic acid adds inlet following.Described rectifying section can be a column plate, also can be filler; The catalytic distillation section can be installed the catalytic distillation column plate, also can load the filler that contains catalyzer; Tower still loading catalyst, similar is in fixed-bed reactor.
The present invention carries out catalyzed reaction by acetic acid and ethanol to generate ethyl acetate in catalytic rectifying tower.By the reactive distillation effect, reduce alcoholic acid content in the thick ester effectively, treating tower 102 bottoms can obtain the ethyl acetate of purity 〉=99.95%.The present invention has reduced the pure content in the thick ester to greatest extent, has reduced ethanol and has circulated in system, saves energy consumption; Adopt solid acid catalyst, reduced requirement, saved equipment cost, and catalyzer is renewable equipment material, environmentally safe, practical.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention mainly comprises catalytic rectifying tower 101, treating tower 102, recovery tower 103; Catalytic rectifying tower 101 tops of tower to acetic acid adds inlet and is rectifying section;
It is the catalytic distillation section that catalytic rectifying tower 101 acetic acid add inlet following, and the catalytic distillation column plate is installed, and perhaps filling contains the filler of catalyzer, and ethanol and acetic acid generate the reaction of ethyl acetate mainly to carry out in this zone;
Described catalytic rectifying tower 101 all is liquid phase feedings.Described catalytic rectifying tower 101 rectifying sections can be tray column or packing tower.
The step of processing method of the present invention:
1) acetic acid adds from catalytic rectifying tower 101 tops, and ethanol adds from the tower still, and catalytic rectifying tower 101 tops obtain the azeotrope of ethyl acetate and water, after phase-splitting, obtain thick ester and water respectively;
2) the thick ester that will obtain is adopted to follow-up treating tower 102, treating tower 102 bottom extraction finished product ethyl acetate, and top material returns 101 towers;
3) catalytic rectifying tower 101 bottoms can not extraction, also can partly be circulated to the catalytic distillation section; Recovery tower 103 top materials (ethanol and a spot of ethyl acetate) return treating tower 102, bottom discharge water;
4) catalytic rectifying tower 101 and treating tower 102 top waters all enter recovery tower 103.
Application Example:
Adopt Fig. 1 technical process, the condition of catalytic rectifying tower 101 operating process is: tower top pressure 0.1Mpa (absolute pressure), tower still pressure 0.15Mpa (absolute pressure), 67 ℃ of tower top temperatures; 105 ℃ of tower still temperature.
Catalytic rectifying tower 101 raw materials components mole ratio ethanol: acetic acid=1.02: 1;
Catalytic rectifying tower 101 reflux ratios=3;
Treating tower 102 reflux ratios=2;
Recovery tower 103 reflux ratios=1.8;
Result such as following table 1:
Adopt above-mentioned example, it is 99.95% ethyl acetate that treating tower 102 bottoms can obtain purity.
Claims (5)
1. the processing method of a catalytic distillation production ethyl acetate, ethanol and acetic acid is synthesizing ethyl acetate under the effect of strongly acidic cation-exchange catalyzer, after the ethyl acetate that reaction generates and water formation azeotrope distillate from the top of catalytic rectifying tower (101) through phase splitter, obtain thick ester, it is characterized in that:
1) acetic acid adds from the top of the catalytic distillation section of catalytic rectifying tower (101), and ethanol adds from the tower still, obtain azeotrope that ethyl acetate and water forms from the catalytic distillation section after, after rectifying section is through separation, enter phase splitter, obtain thick ester and water respectively;
2) the thick ester that will obtain is adopted to follow-up treating tower (102), treating tower (102) bottom extraction finished product ethyl acetate, and top material returns catalytic rectifying tower (101);
3) catalytic rectifying tower (101) but bottom extraction or part are circulated to the catalytic distillation section;
4) recovery tower (103) reclaims catalytic rectifying tower (101) and treating tower (102) cat head aqueous phase ethanol and ethyl acetate.
2. processing method according to claim 1, the mol ratio that it is characterized in that described ethanol and acetic acid is 1～1.1: 1.
3. processing method according to claim 1 is characterized in that the condition of described catalytic rectifying tower operating process is: 0.1～0.15Mpa, 67～105 ℃.
4. processing method according to claim 1 is characterized in that described catalytic rectifying tower (101) comprises rectifying section, catalytic distillation section and tower still, and top of tower to acetic acid adds inlet and is rectifying section, and it is the catalytic distillation section that acetic acid adds inlet following; Described rectifying section can be column plate or filler; The catalytic distillation section can be installed the filler that catalytic distillation column plate or filling contain catalyzer; Tower still loading catalyst, similar is in fixed-bed reactor.
5. processing method according to claim 1 is characterized in that described treating tower (102) and recovery tower (103) are tray column or packing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106007608A CN102134191B (en) | 2010-12-22 | 2010-12-22 | Process method for producing ethyl acetate by catalytic rectification |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106007608A CN102134191B (en) | 2010-12-22 | 2010-12-22 | Process method for producing ethyl acetate by catalytic rectification |
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| CN102134191A true CN102134191A (en) | 2011-07-27 |
| CN102134191B CN102134191B (en) | 2013-03-06 |
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| CN2010106007608A Expired - Fee Related CN102134191B (en) | 2010-12-22 | 2010-12-22 | Process method for producing ethyl acetate by catalytic rectification |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274932A (en) * | 2013-06-05 | 2013-09-04 | 沈阳化工大学 | Method for recovering organic acids from dilute acid solution |
| CN104557524A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of ethyl acetate |
| CN109534997A (en) * | 2018-10-25 | 2019-03-29 | 兖矿鲁南化工有限公司 | The system and technique of the consummate ethyl acetate of rapidly extracting after a kind of pressurization lactate synthesis |
| CN113045417A (en) * | 2019-12-29 | 2021-06-29 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by green catalytic method |
| CN113651691A (en) * | 2021-09-15 | 2021-11-16 | 河北工业大学 | Method for preparing asymmetric oxalate through catalytic rectification |
| CN114478250A (en) * | 2021-12-27 | 2022-05-13 | 浙江联盛化学股份有限公司 | Preparation method of methyl ethyl carbonate and co-production of diethyl carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837183A (en) * | 2006-04-19 | 2006-09-27 | 广西壮族自治区化工研究院 | Method for reaction rectification coupling continuous preparation of and series acetate |
-
2010
- 2010-12-22 CN CN2010106007608A patent/CN102134191B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837183A (en) * | 2006-04-19 | 2006-09-27 | 广西壮族自治区化工研究院 | Method for reaction rectification coupling continuous preparation of and series acetate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274932A (en) * | 2013-06-05 | 2013-09-04 | 沈阳化工大学 | Method for recovering organic acids from dilute acid solution |
| CN104557524A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of ethyl acetate |
| CN104557524B (en) * | 2013-10-22 | 2016-06-15 | 中国石油化工股份有限公司 | A kind of production method of ethyl acetate |
| CN109534997A (en) * | 2018-10-25 | 2019-03-29 | 兖矿鲁南化工有限公司 | The system and technique of the consummate ethyl acetate of rapidly extracting after a kind of pressurization lactate synthesis |
| WO2020083118A1 (en) * | 2018-10-25 | 2020-04-30 | 兖矿鲁南化工有限公司 | System and process for rapid extraction and refining of ethyl acetate after synthesis by pressurized esterification |
| KR20210050511A (en) * | 2018-10-25 | 2021-05-07 | 옌쾅 루난 케미컬스 컴퍼니 리미티드 | System and method for rapid extraction and purification of ethyl acetate after compression esterification synthesis |
| KR102484021B1 (en) | 2018-10-25 | 2023-01-03 | 옌쾅 루난 케미컬스 컴퍼니 리미티드 | System and method for rapid extraction and purification of ethyl acetate after pressurized esterification synthesis |
| CN113045417A (en) * | 2019-12-29 | 2021-06-29 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by green catalytic method |
| CN113045417B (en) * | 2019-12-29 | 2023-04-07 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by catalytic method |
| CN113651691A (en) * | 2021-09-15 | 2021-11-16 | 河北工业大学 | Method for preparing asymmetric oxalate through catalytic rectification |
| CN114478250A (en) * | 2021-12-27 | 2022-05-13 | 浙江联盛化学股份有限公司 | Preparation method of methyl ethyl carbonate and co-production of diethyl carbonate |
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| CN102134191B (en) | 2013-03-06 |
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