CN103936586A - Production method of ethyl acetate - Google Patents
Production method of ethyl acetate Download PDFInfo
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- CN103936586A CN103936586A CN201410210485.7A CN201410210485A CN103936586A CN 103936586 A CN103936586 A CN 103936586A CN 201410210485 A CN201410210485 A CN 201410210485A CN 103936586 A CN103936586 A CN 103936586A
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- ethyl acetate
- acetic acid
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- ethanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to a production method of ethyl acetate, which comprises the following steps: acetic acid and concentrated sulfuric acid are added into an esterification kettle, and heated to 110-120 DEG C while controlling the pressure at 40-60 KPa; ethanol and acetic acid are uniformly mixed in a mol ratio of (1.3-0.9):1, and sent into the esterification kettle to generate ethyl acetate and water; the products ethyl acetate and water and the raw material ethanol are sent into a rectification tower in the form of azeotropes; the acetic acid with higher boiling point flows back into the esterification kettle, and the azeotropes with lower boiling point are distilled out of the top of the rectification tower and cooled by a condenser to obtain a condensate; the condensate enters a phase splitter to be subjected to collection and phase splitting; the water phase enters the recycling section; and the ester phase is divided into two parts, wherein one part participates in the reflux, and the other part is used for dehydration and refinement. The azeotropic composition of the two-element and three-element azeotropes are changed by pressurization, so that the content of water in the azeotropes increases, and water can be conveniently distilled out; and meanwhile, under the pressurization action, the density of the distilled gas is increased, the productivity of the equipment is enhanced, and the energy consumption is lowered.
Description
Technical field
The present invention relates to a kind of production method of ethyl acetate, be specifically related to a kind of production method of the esterification rectifying production ethyl acetate of pressurizeing.
Background technology
Ethyl acetate (Ethyl Acetate, EA), claims again vinyl acetic monomer, is a branch of acetic acid downstream derived product.The category that it belongs to chemical solvents, is a kind of important green organic solvent, has good solubility property, is a kind of quick-dry type industrial solvent.Ethyl acetate is widely used in the production of the polymkeric substance such as fiber, rubber, resin and medicine intermediate; Also can be used for producing used in copy machines liquid nitrocellulose ink; In textile industry, be used as freshener; In foodstuffs industry, be used as the fragrance extraction agent of special modification alcohol; In perfume industry, be most important spice additive, can be used as the component of deodorant tune.In addition, ethyl acetate also can be used as tackiness agent solvent, paint thinner and manufacture the raw material of medicine, dyestuff.
The method of production ethyl acetate in the world roughly has following several at present: acetate ethanol direct esterification, acetaldehyde condensation method, alcohol dehydrogenase method, ethene and acetic acid direct addition method, catalytic rectification process.The traditional technology of synthesizing ethyl acetate is the continuous esterification method production line using 98% the vitriol oil as catalyzer, and acetic acid and ethanol carry out esterification in reactor, generates ethyl acetate and water.The water carrying in the water that esterification generates and raw material needs and ethyl acetate formation azeotrope could steam from esterifying kettle.In technique, because the content ratio of water in reaction is much larger than the content ratio of water in azeotrope, esterification tower top needs larger backflow, or need another ethyl acetate of supplementing a part of high-content even finished product ester in reactor to break molecular balance, reactive distillation is produced continual and steady, therefore, the rectifying energy consumption of esterification column is higher, accounts for the more than 60% of whole production technique.
Summary of the invention
The object of the present invention is to provide a kind of production technique that improves the thick product production capacity of ethyl acetate and reduce energy consumption.
The technical solution adopted in the present invention is:
A production method for ethyl acetate, comprises the following steps
(1) in esterifying kettle, add acetic acid and the catalyzer vitriol oil, be heated to 110 ~ 120 DEG C, control pressure 40 ~ 60 KPa;
(2) ethanol and acetic acid are sent in mixing tank by a certain percentage, after mixing, entered esterifying kettle, generate ethyl acetate and water;
(3) product-ethyl acetate, water and feed ethanol enter rectifying tower with azeotrope form by gas phase pipe after heating evaporation, azeotrope separates in rectifying tower, the acetic acid that boiling point is high flows back in esterifying kettle, low-boiling azeotrope steams from rectifying tower top, is cooled to phlegma through condenser;
(4) phlegma enters into from condenser that phase splitter is collected, phase-splitting, and water enters recycle section, and ester is divided into two portions mutually, and a part of ethyl acetate is squeezed into rectifying tower through pump and participated in refluxing, and a part of ethyl acetate is refined for dehydration.
Wherein: in step (1), the add-on of acetic acid is 1/5 ~ 3/4 of esterifying kettle liquid level, and the add-on of the vitriol oil is to add 0.5% ~ 2.5% of quality of acetic acid.
Pressure distillation has changed the azeotropic composition of ethyl ester and water, for making the content of water in azeotrope that ethyl ester and water forms high, the ethyl ester amount of required backflow is little, reduce evaporation energy consumption, contriver has carried out preferably above-mentioned steps (1), preferably, in above-mentioned steps (1), the add-on of acetic acid is 1/2 of esterifying kettle liquid level, the add-on of the vitriol oil is that to add 1.0% of quality of acetic acid, temperature of reaction be 115 DEG C, and pressure-controlling is 49 KPa.
The ethanol of sending in step (2) and the mol ratio of acetic acid are 1.3 ~ 0.9:1, and esterification temperature is 110 ~ 120 DEG C; Preferably, the ethanol of sending in step (2) and the mol ratio of acetic acid are 1.1:1, and esterification temperature is 115 DEG C, concentration >=99.5% of acetic acid used, concentration >=95% of ethanol used.
In step (3), the temperature at rectifying tower top is 80 ~ 90 DEG C; Preferably, in step (3), the temperature at rectifying tower top is 82 DEG C.
Take after above technical scheme, beneficial effect of the present invention is:
(1) by having changed the azeotropic composition of binary and ternary azeotrope under pressurized state, the content of water in azeotrope is raise, be conducive to steaming of water.
(2) without adding in addition high-content ethyl acetate and needing the amount of the ethyl acetate refluxing to reduce.
(3) simultaneously due to pressurization, the density that steams gas is increased, can increase the production capacity of equipment, and steam consumption reduction, Energy Intensity Reduction.
Brief description of the drawings
Fig. 1 is the process flow sheet of production method of the present invention;
Number in the figure is as follows: 1-mixing tank, 2-esterifying kettle, 3-rectifying tower, 4-condenser, 5-phase splitter, 6-pump.
Embodiment
By reference to the accompanying drawings 1, the present invention will be further described.
In esterifying kettle (2), add acetic acid and the sulfuric acid of certain liquid level, then heating, ethanol and acetic acid are sent into mixing tank (1) by certain molar ratio, after mixing, mixing tank (1) enters esterifying kettle (2), in esterifying kettle (2), under acetic acid and the katalysis of ethanol at sulfuric acid, generate ethyl acetate and water.The ternary azeotrope that ethanol of complete reaction does not form with water, ethyl acetate, the binary azeotrope that ethyl ester, water form are simultaneously together with acetic acid, after heating, enter rectifying tower (3), the boiling point of acetic acid is higher, after rectifying tower (3) rectifying, get back to esterifying kettle (2), steam thing and enter overhead condenser (4), after condensation, enter phase splitter (5), ester is divided into two portions mutually, a part participates in refluxing through pump (6), and a part of extraction is refining for dehydration; Water enters recovery tower, the ethyl acetate of dissolving in recycle-water and ethanol.Whole system is by the weighing apparatus depressor control pressure being connected with phase splitter (5), to ensure that evaporate rectifying completes under pressurized state.
embodiment 1
In esterifying kettle, add the acetic acid of 1/3 liquid level and the sulfuric acid of acetic acid total amount 1.5%, be heated to 115 DEG C.Ethanol and the acetic acid in molar ratio ratio of 1.1:1 are sent into mixing tank, and wherein acetate concentration is more than 99.5%, and alcohol concn is more than 95%, enters esterifying kettle after mixing tank mixes.In esterifying kettle, acetic acid and ethanol, under the katalysis of sulfuric acid, control 115 DEG C of temperature of reaction, and reaction pressure 40KPa generates ethyl acetate and water.The ternary azeotrope that ethanol of complete reaction does not form with water, ethyl acetate, the binary azeotrope that ethyl ester, water form are simultaneously together with acetic acid, after heating, enter rectifying tower, control 80 DEG C of top temperature, the boiling point of acetic acid is higher, after rectifying tower rectifying, gets back to esterifying kettle, steams thing and enters overhead condenser, after condensation, enter phase splitter, ester layer segment refluxes, and part extraction is refining for dehydration; Water enters recovery tower, the ethyl acetate of dissolving in recycle-water and ethanol.Result: ester composition of layer is: ethyl acetate: 94.7%, water: 3.2%, alcohol: 2.1%, steam consumption reduces by 15%.
embodiment 2
In esterifying kettle, add the acetic acid of 1/2 liquid level and the sulfuric acid of acetic acid total amount 1.0%, be heated to 115 DEG C.Ethanol and the acetic acid in molar ratio ratio of 1.1:1 are sent into mixing tank, and wherein acetate concentration is more than 99.5%, and alcohol concn is more than 95%, enters esterifying kettle after mixing tank mixes.In esterifying kettle, acetic acid and ethanol, under the katalysis of sulfuric acid, control 115 DEG C of temperature of reaction, and reaction pressure 49KPa generates ethyl acetate and water.The ternary azeotrope that ethanol of complete reaction does not form with water, ethyl acetate, the binary azeotrope that ethyl ester, water form are simultaneously together with acetic acid, after heating, enter rectifying tower, control 82 DEG C of top temperature, the boiling point of acetic acid is higher, after rectifying tower rectifying, gets back to esterifying kettle, steams thing and enters overhead condenser, after condensation, enter phase splitter, ester layer segment refluxes, and part extraction is refining for dehydration; Water enters recovery tower, the ethyl acetate of dissolving in recycle-water and ethanol.Result: ester composition of layer is: ethyl acetate: 94.5%, water: 3.5%, alcohol: 2%, water layer composition is ethyl acetate: 8%; Water: 87%; Alcohol: 5%, steam consumption reduces by 17%.
embodiment 3
In esterifying kettle, add the acetic acid of 1/2 liquid level and the sulfuric acid of acetic acid total amount 1.0%, be heated to 120 DEG C.Ethanol and the acetic acid in molar ratio ratio of 1.1:1 are sent into mixing tank, and wherein acetate concentration is more than 99.5%, and alcohol concn is more than 95%, enters esterifying kettle after mixing tank mixes.In esterifying kettle, acetic acid and ethanol, under the katalysis of sulfuric acid, control 120 DEG C of temperature of reaction, and reaction pressure 60KPa generates ethyl acetate and water.The ternary azeotrope that ethanol of complete reaction does not form with water, ethyl acetate, the binary azeotrope that ethyl ester, water form are simultaneously together with acetic acid, after heating, enter rectifying tower, control 90 DEG C of top temperature, the boiling point of acetic acid is higher, after rectifying tower rectifying, gets back to esterifying kettle, steams thing and enters overhead condenser, after condensation, enter phase splitter, ester layer segment refluxes, and part extraction is refining for dehydration; Water enters recovery tower, the ethyl acetate of dissolving in recycle-water and ethanol.Result: ester composition of layer is: ethyl acetate: 94.3%, water: 3.6%, alcohol: 2.1%, steam consumption reduces by 14%.
Claims (8)
1. a production method for ethyl acetate, is characterized in that, comprises the following steps:
1) in esterifying kettle, add acetic acid and the vitriol oil, be heated to 110 ~ 120 DEG C, control pressure 40 ~ 60 KPa;
2) ethanol and acetic acid are mixed by a certain percentage and sends into esterifying kettle, generate ethyl acetate and water;
3) product-ethyl acetate, water and feed ethanol enter rectifying tower with azeotrope form by gas phase pipe after heating evaporation, azeotrope separates in rectifying tower, the acetic acid that boiling point is high flows back in esterifying kettle, and low-boiling azeotrope steams from rectifying tower top, is cooled to phlegma through condenser;
4) phlegma enters into that phase splitter is collected, phase-splitting, and water enters recycle section, and ester is divided into two portions mutually, and a part of ethyl acetate is squeezed into rectifying tower and participated in refluxing, and a part of ethyl acetate is refined for dehydration.
2. the production method of ethyl acetate as claimed in claim 1, is characterized in that, the temperature of reaction of step (1) is 115 DEG C, and pressure is 49 KPa.
3. the production method of ethyl acetate as claimed in claim 1, is characterized in that, in step (1), the add-on of acetic acid is 1/5 ~ 3/4 of esterifying kettle liquid level, and the add-on of the vitriol oil is to add 0.5% ~ 2.5% of quality of acetic acid.
4. the production method of ethyl acetate as claimed in claim 3, is characterized in that, in step (1), the add-on of acetic acid is 1/2 of esterifying kettle liquid level, and the add-on of the vitriol oil is to add 1.0% of quality of acetic acid.
5. the production method of ethyl acetate as claimed in claim 1, is characterized in that, in step (2), the mol ratio of ethanol and acetic acid is 1.3 ~ 0.9:1, and esterification temperature is 110 ~ 120 DEG C.
6. the production method of ethyl acetate as claimed in claim 5, is characterized in that, the ethanol of sending in step (2) and the mol ratio of acetic acid are 1.1:1, and esterification temperature is 115 DEG C.
7. the production method of ethyl acetate as claimed in claim 1, is characterized in that, in step (3), the temperature at rectifying tower top is 80 ~ 90 DEG C.
8. the production method of ethyl acetate as claimed in claim 7, is characterized in that, in step (3), the temperature at rectifying tower top is 82 DEG C.
Priority Applications (1)
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| CN201410210485.7A CN103936586A (en) | 2014-05-19 | 2014-05-19 | Production method of ethyl acetate |
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| CN201410210485.7A CN103936586A (en) | 2014-05-19 | 2014-05-19 | Production method of ethyl acetate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377891A (en) * | 2020-03-24 | 2020-07-07 | 浙江恒澜科技有限公司 | Device and method for preparing 2,5-furandicarboxylic acid from hexoic diacid (salt) through coupling of dehydration cyclization reaction and azeotropic distillation water removal |
| CN111606874A (en) * | 2020-05-28 | 2020-09-01 | 浙江恒澜科技有限公司 | Method and device for preparing 2,5-furandicarboxylic acid by microwave-induced strengthening and azeotropic distillation dewatering combined technology |
| CN111718260A (en) * | 2019-03-19 | 2020-09-29 | 潍坊奥通药业有限公司 | Continuous esterification process based on acyclovir intermediate production mother liquor |
| CN111943840A (en) * | 2020-07-27 | 2020-11-17 | 浙江建业化工股份有限公司 | Treatment process of n-propyl acetate bed charge |
| CN112358397A (en) * | 2020-11-24 | 2021-02-12 | 浙江台州市联创环保科技股份有限公司 | Equipment and method for rectifying and separating ethyl acetate and ethanol azeotrope |
| CN115108910A (en) * | 2022-08-09 | 2022-09-27 | 珠海谦信新材料有限公司 | Synthesis and heat coupling process of ethyl acetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616398A (en) * | 2004-09-14 | 2005-05-18 | 上海吴泾化工有限公司 | Esterizing tower reaction separating flow new process for producing ethyl acetate |
| CN1706794A (en) * | 2005-04-25 | 2005-12-14 | 上海吴泾化工有限公司 | Continuous catalyst-adding operation method for esterification reactor |
| CN103739486A (en) * | 2013-11-26 | 2014-04-23 | 泰兴金江化学工业有限公司 | Production method for ethyl acetate crude product |
-
2014
- 2014-05-19 CN CN201410210485.7A patent/CN103936586A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616398A (en) * | 2004-09-14 | 2005-05-18 | 上海吴泾化工有限公司 | Esterizing tower reaction separating flow new process for producing ethyl acetate |
| CN1706794A (en) * | 2005-04-25 | 2005-12-14 | 上海吴泾化工有限公司 | Continuous catalyst-adding operation method for esterification reactor |
| CN103739486A (en) * | 2013-11-26 | 2014-04-23 | 泰兴金江化学工业有限公司 | Production method for ethyl acetate crude product |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718260A (en) * | 2019-03-19 | 2020-09-29 | 潍坊奥通药业有限公司 | Continuous esterification process based on acyclovir intermediate production mother liquor |
| CN111377891A (en) * | 2020-03-24 | 2020-07-07 | 浙江恒澜科技有限公司 | Device and method for preparing 2,5-furandicarboxylic acid from hexoic diacid (salt) through coupling of dehydration cyclization reaction and azeotropic distillation water removal |
| CN111606874A (en) * | 2020-05-28 | 2020-09-01 | 浙江恒澜科技有限公司 | Method and device for preparing 2,5-furandicarboxylic acid by microwave-induced strengthening and azeotropic distillation dewatering combined technology |
| CN111943840A (en) * | 2020-07-27 | 2020-11-17 | 浙江建业化工股份有限公司 | Treatment process of n-propyl acetate bed charge |
| CN111943840B (en) * | 2020-07-27 | 2022-08-23 | 浙江建业化工股份有限公司 | Treatment process of n-propyl acetate bed charge |
| CN112358397A (en) * | 2020-11-24 | 2021-02-12 | 浙江台州市联创环保科技股份有限公司 | Equipment and method for rectifying and separating ethyl acetate and ethanol azeotrope |
| CN112358397B (en) * | 2020-11-24 | 2024-01-16 | 浙江台州市联创环保科技股份有限公司 | Equipment and method for rectifying and separating ethyl acetate and ethanol azeotrope |
| CN115108910A (en) * | 2022-08-09 | 2022-09-27 | 珠海谦信新材料有限公司 | Synthesis and heat coupling process of ethyl acetate |
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Application publication date: 20140723 |