CN105693513B - A kind of method of the secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures - Google Patents
A kind of method of the secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures Download PDFInfo
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- CN105693513B CN105693513B CN201610226103.9A CN201610226103A CN105693513B CN 105693513 B CN105693513 B CN 105693513B CN 201610226103 A CN201610226103 A CN 201610226103A CN 105693513 B CN105693513 B CN 105693513B
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- hydrocarbon mixtures
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- methanol
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- butyl acetate
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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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/06—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by azeotropic distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
Abstract
The invention discloses the method for a kind of secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures, it is characterised in that includes following process：First alcohol and water is added as entrainer in sec-butyl acetate and C8 hydrocarbon mixtures, three-phase azeotropic distillation separation is carried out in rectifying column, tower reactor obtains the sec-butyl acetate of content more than 99%, and tower top obtains methanol, water, the ternary azeotrope of C8 hydrocarbon mixtures；Gained ternary azeotrope is carried out plus water extracts, aqueous phase is methanol aqueous solution, and organic phase is C8 hydrocarbon mixtures.The present invention isolates qualified sec-butyl acetate and C8 hydrocarbon mixtures using three-phase azeotropic distillation and liquid-liquid extraction from byproduct mixed ester, can obtain the sec-butyl acetate more than more than 99%, turn waste into wealth, be advantageous to the significantly decline of production cost.
Description
Technical field
The invention belongs to chemical field, it is related to a kind of secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures
Method, the more particularly to a kind of secondary butyl ester of separating acetic acid and C8 hydrocarbon from the byproduct mixed ester of esterification production sec-butyl acetate technique
The method of class mixture.
Background technology
Sec-butyl acetate is as a kind of solvent of environmental-protecting performance, mainly using the suitable anti-butylene in C4 resources directly and second
Esterification generation sec-butyl acetate.This esterification industry has obtained substantial amounts of application at home in recent ten years.But in acetic acid
In the generating process of secondary butyl ester, while a kind of byproduct can be generated mixed ester, it is mainly sec-butyl acetate and C8 hydro carbons
Mixture.All manufacturing enterprises domestic at present all do not carry out reprocessing processing to it, but directly as byproduct, as
Oily low price of warming oneself by a fire is handled.Sec-butyl acetate is as a kind of solvent of environmental-protecting performance, and market price is at more than 4,000 yuan, C8 hydrocarbon mixtures
Separate can be used to formulated gasolines, can also reach more than 3,000 yuan, and be used as oil of warming oneself by a fire, the price that can only have 1,000 yuan or so.Therefore
Caused mixed ester in the generating process of sec-butyl acetate is processed, reclaims sec-butyl acetate and the mixing of C8 hydro carbons
Thing, improves product yield and economic benefit is particularly important.
The content of the invention
The purpose of the present invention is exactly that caused byproduct mixed ester in existing esterification generation sec-butyl acetate technique is carried out
Processing, there is provided one kind isolates sec-butyl acetate and C8 hydrocarbon using three-phase azeotropic distillation and liquid-liquid extraction from byproduct mixed ester
The method of class mixture, the sec-butyl acetate more than more than 99% is obtained, so as to reclaim product, reduce energy consumption, economize on resources.
The technical solution adopted by the present invention is：A kind of secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures
Method, it is characterised in that include following process：First alcohol and water is added as azeotropic in sec-butyl acetate and C8 hydrocarbon mixtures
Agent, three-phase azeotropic distillation separation is carried out in rectifying column, tower reactor obtains the sec-butyl acetate of content more than 99%, and tower top obtains first
Alcohol, water, the ternary azeotrope of C8 hydrocarbon mixtures；Gained ternary azeotrope is carried out plus water extracts, aqueous phase is methanol aqueous solution,
Organic phase is C8 hydrocarbon mixtures.
Present invention additionally comprises the methanol aqueous solution obtained after extraction to carry out rectifying recovery first alcohol and water, and methanol loop is used for altogether
Rectifying is boiled, water circulation is used to extract methanol.
Sec-butyl acetate and C8 hydrocarbon mixture of the present invention is to generate sec-butyl acetate technique along anti-butylene and acid esterification
Byproduct mixed ester.
During three-phase azeotropic distillation of the present invention, the operating pressure in rectifying column is to depressurize, or normal pressure, or pressurization, preferably normal pressure.
The selection range of the reflux ratio of rectifying column of the present invention is 2~10, preferably 5.
C8 hydrocarbon mixtures, the mass ratio of water are methanol in methanol of the present invention, raw material to be separated：C8 hydrocarbon mixtures：Water
=2~3：1：0.2~0.5.
The ratio of the quality and the methanol-C8 hydrocarbon mixture gross masses that add water in the present invention plus water extraction process is 5%~
200%, preferably 20%~100%；Extraction time is 0.1~5h, preferably 0.5~2h；
The present invention selects first alcohol and water as entrainer in the separation of sec-butyl acetate and C8 hydrocarbon mixtures, methanol,
Water, C8 hydrocarbon mixtures form minimum azeotropic mixture, just mixing before the azeotropic temperature of sec-butyl acetate and C8 hydrocarbon mixtures
C8 hydrocarbon mixtures in thing are separated.
Beneficial effects of the present invention：1st, effective Resource recovery, from the mixture of sec-butyl acetate and C8 hydrocarbon mixtures
Qualified sec-butyl acetate product is isolated, is turned waste into wealth, is advantageous to the significantly decline of production cost；
2nd, separation process is fairly simple, is divided into two steps, first, azeotropic distillation, two being liquid-liquid extraction, operational control is easy；
3rd, the present invention is alternatively arranged as the demand of sec-butyl acetate product purification, when the acetic acid of pharmaceutically demand more than 99.9%
It secondary butyl ester, can be refined using this method, separate the trace impurity inside product.
Embodiment
Below by embodiment, the present invention is described in detail：
Embodiment 1：
Take mixed ester（Sec-butyl acetate and C8 hydrocarbon mixtures）600 grams（Enter gas chromatographic analysis, wherein sec-butyl acetate
Content 64.8%, C8 hydrocarbon mixtures 35.2%）, 450 grams of methanol, 90 grams of water, then three kinds of materials are mixed, added
In the kettle of glass rectification test device, then all devices of glass rectification test device are installed and debugged, then heated
Mixed material in kettle, when temperature in the kettle rises to 70 degree, come to life in kettle, the condensed device of material vaporization to tower top in tower is cold
But be liquid, in most of reflux column, produce a part of material, the reflux ratio for regulating rectifying column is 5, kettle temperature simultaneously slowly on
Rise, the material of overhead extraction can produce layering, and lower floor is the mixed solution of first alcohol and water, and upper strata is methanol and C8 hydrocarbon mixtures
Mixture, early stage, temperature in the kettle be less than 100 degree when, the mixed solution of lower layer methanol and water can be returned in kettle.
In distillation process, sampling tracking point is carried out to the upper oil phase methanol and the mixture of C8 hydrocarbon mixtures condensed in kettle and on top
Analysis, when temperature in the kettle rises to 116 degree, first stop backflow, then slowly reduce electrical heating, to the last stop.Adopt kettle material
Gas chromatographic analysis is carried out, obtains 357 grams of the sec-butyl acetate of content 99.46%；558 grams of the oil phase material that tower top is isolated, water
185 grams of phase materials, oil phase material add 600 grams of water, stratification are then carried out, after 1 hour, lower floor's aqueous phase material and above
The aqueous phase material mixing separated, then put glass trial assembly and put back into receipts methanol, finally obtain 433 grams of methanol；The oil phase being obtained by extraction
Totally 234 grams of material, enters vapour chromatograph, wherein sec-butyl acetate content 3.73%, C8 hydrocarbon mixtures content 96.26%,
Because of 26 grams of volatilizing loss during material experiment.
Embodiment 2：
Take mixed ester（Sec-butyl acetate and C8 hydrocarbon mixtures）1000 grams（Enter gas chromatographic analysis, wherein acetic acid Zhong Ding
Ester content 66.2%, C8 hydrocarbon mixtures 33.8%）, 1000 grams of methanol, 300 grams of water, then three kinds of materials are mixed, then
Add in the kettle of glass rectification test device, then all devices of glass rectification test device are installed and debugged, then carry out
Mixed material in heating kettle, when temperature in the kettle rises to 70 degree, come to life in kettle, the material vaporization to tower top in tower is condensed
Device is cooled to liquid, in most of reflux column, produces a part of material, and the reflux ratio for regulating rectifying column is 5, and kettle temperature is simultaneously slow
Slow to rise, the material of overhead extraction can produce layering, and lower floor is the mixed solution of first alcohol and water, and upper strata is that methanol and C8 hydro carbons mix
The mixture of compound, early stage, when temperature in the kettle is less than 100 degree, the mixed solution of lower layer methanol and water can be returned to kettle
It is interior.In distillation process, the upper oil phase methanol and the mixture of C8 hydrocarbon mixtures condensed in kettle and on top is sampled
Trace analysis, when temperature in the kettle rises to 116 degree, first stop backflow, then slowly reduce electrical heating, to the last stop.Adopt tower
Kettle material carries out gas chromatographic analysis, obtains 632 grams of the sec-butyl acetate of content 99.66%；The oil phase material that tower top is isolated
952 grams, 681 grams of aqueous phase material, oil phase material adds 500 grams of water, stratification is then carried out, after 1 hour, lower floor's aqueous-phase material
Material and the aqueous phase material mixing above separated, then put glass trial assembly and put back into receipts methanol, finally obtain 982 grams of methanol；Extract
Totally 326 grams of the oil phase material arrived, enter vapour chromatograph, wherein sec-butyl acetate content 2.77%, C8 hydrocarbon mixture contents
97.23%, because of 60 grams of volatilizing loss during material experiment.
Embodiment 3：
Take mixed ester（Sec-butyl acetate and C8 hydrocarbon mixtures）400 grams（Enter gas chromatographic analysis, wherein sec-butyl acetate
Content 62.3%, C8 hydrocarbon mixtures 37.6%）, 380 grams of methanol, 60 grams of water, then three kinds of materials are mixed, added
In the kettle of glass rectification test device, then all devices of glass rectification test device are installed and debugged, then heated
Mixed material in kettle, when temperature in the kettle rises to 70 degree, come to life in kettle, the condensed device of material vaporization to tower top in tower is cold
But be liquid, in most of reflux column, produce a part of material, the reflux ratio for regulating rectifying column is 5, kettle temperature simultaneously slowly on
Rise, the material of overhead extraction can produce layering, and lower floor is the mixed solution of first alcohol and water, and upper strata is methanol and C8 hydrocarbon mixtures
Mixture, early stage, temperature in the kettle be less than 100 degree when, the mixed solution of lower layer methanol and water can be returned in kettle.
In distillation process, sampling tracking point is carried out to the upper oil phase methanol and the mixture of C8 hydrocarbon mixtures condensed in kettle and on top
Analysis, when temperature in the kettle rises to 116 degree, first stop backflow, then slowly reduce electrical heating, to the last stop.Adopt kettle material
Gas chromatographic analysis is carried out, obtains 237 grams of the sec-butyl acetate of content 99.44%；455 grams of the oil phase material that tower top is isolated, water
123 grams of phase materials, oil phase material add 450 grams of water, stratification are then carried out, after 1 hour, lower floor's aqueous phase material and above
The aqueous phase material mixing separated, then put glass trial assembly and put back into receipts methanol, finally obtain 368 grams of methanol；The oil phase being obtained by extraction
Totally 141 grams of material, enters vapour chromatograph, wherein sec-butyl acetate content 3.55%, C8 hydrocarbon mixtures content 96.45%,
Because of 34 grams of volatilizing loss during material experiment.
Embodiment of the present invention, the description only carried out to the preferred embodiment of the present invention, not to this hair
Bright spirit and scope are defined, and on the premise of design philosophy of the present invention is not departed from, engineers and technicians are to this in this area
The all variations and modifications that the technical scheme of invention is made, all should fall into protection scope of the present invention, and the present invention is claimed
Technology contents, all record in detail in the claims.
Claims (6)
1. the method for a kind of secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures, it is characterised in that include as follows
Process：
First alcohol and water is added as entrainer in sec-butyl acetate and C8 hydrocarbon mixtures, and three-phase azeotropic essence is carried out in rectifying column
Cut is from tower reactor obtains the sec-butyl acetate of content more than 99%, and tower top obtains methanol, water, the ternary azeotropic of C8 hydrocarbon mixtures
Thing；
Gained ternary azeotrope is carried out plus water extracts, aqueous phase is methanol aqueous solution, and organic phase is C8 hydrocarbon mixtures.
2. according to the method for claim 1, it is characterised in that：The methanol aqueous solution for also including obtaining after extraction uses rectifying
Method reclaims first alcohol and water, and methanol loop is used for azeotropic distillation, and water circulation is used to extract methanol.
3. according to the method for claim 1, it is characterised in that：Sec-butyl acetate and the C8 hydrocarbon mixture is along anti-fourth
The byproduct mixed ester of alkene and acid esterification generation sec-butyl acetate technique.
4. according to the method for claim 1, it is characterised in that：The reflux ratio of the rectifying column is 2~10.
5. according to the method for claim 4, it is characterised in that：The reflux ratio of the rectifying column is 5.
6. according to the method for claim 1, it is characterised in that：C8 hydrocarbon mixtures, water in the methanol, raw material to be separated
Mass ratio be methanol：C8 hydrocarbon mixtures：Water=2~3：1：0.2~0.5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610226103.9A CN105693513B (en) | 2016-04-13 | 2016-04-13 | A kind of method of the secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures |
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| CN201610226103.9A CN105693513B (en) | 2016-04-13 | 2016-04-13 | A kind of method of the secondary butyl ester of three-phase azeotropic distillation separating acetic acid and C8 hydrocarbon mixtures |
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| CN105693513A CN105693513A (en) | 2016-06-22 |
| CN105693513B true CN105693513B (en) | 2018-03-30 |
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| CN106831420A (en) * | 2016-12-20 | 2017-06-13 | 惠州宇新化工有限责任公司 | A kind of secondary butyl ester of azeotropic distillation separating acetic acid and C8The method of alkene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481307A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Method for separating acetic acid and sec-butyl acetate from reaction products |
| CN101486640A (en) * | 2009-01-13 | 2009-07-22 | 湖南瑞源石化股份有限公司 | Preparation of sec-butyl acetate |
| CN103980115A (en) * | 2014-06-03 | 2014-08-13 | 湖南瑞源石化股份有限公司 | Method for recycling acetic acid sec-butyl ester from reaction product during preparation of acetic acid sec-butyl ester with high efficiency |
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- 2016-04-13 CN CN201610226103.9A patent/CN105693513B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481307A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Method for separating acetic acid and sec-butyl acetate from reaction products |
| CN101486640A (en) * | 2009-01-13 | 2009-07-22 | 湖南瑞源石化股份有限公司 | Preparation of sec-butyl acetate |
| CN103980115A (en) * | 2014-06-03 | 2014-08-13 | 湖南瑞源石化股份有限公司 | Method for recycling acetic acid sec-butyl ester from reaction product during preparation of acetic acid sec-butyl ester with high efficiency |
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