CN109942357A - A kind of low-boiling point alcohol continuous esterification rectification process - Google Patents
A kind of low-boiling point alcohol continuous esterification rectification process Download PDFInfo
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- CN109942357A CN109942357A CN201910302010.3A CN201910302010A CN109942357A CN 109942357 A CN109942357 A CN 109942357A CN 201910302010 A CN201910302010 A CN 201910302010A CN 109942357 A CN109942357 A CN 109942357A
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Abstract
The invention belongs to fine chemistry industry synthesis technology fields, provide a kind of low-boiling point alcohol continuous esterification rectification process.Technique of the invention is in the esterification reaction process of low-boiling point alcohol, alcohol in the middle part of into esterification column stripping section constantly gasifies, with carboxylic acid, the abundant mass-and heat-transfer of sulfuric acid catalyst, esterification occurs, and mass transfer, heat transfer are carried out in each rectifying theoretical tray by alcohol and remove the water of reaction generation from tower top, crude product carboxylate obtains simultaneously continuously producing in tower reactor, realizes continuous production and water removal in tower equipment, product yield and feed stock conversion are promoted, cost is considerably reduced.Alcohol-aqueous mixtures that esterification column overhead is taken out of are further separated through rectifying column, and overhead extraction ethyl alcohol realizes alcohol and recycles.Crude product carboxylate finally realizes product through product rectifying column and continuously post-processes through continuous neutralization, centrifuge separation, isolated organic phase.
Description
Technical field
The invention belongs to fine chemistry industry synthesis technology fields, and in particular to a kind of low-boiling point alcohol continuous esterification essence
Evaporate technique.
Background technique
Organic matter containing carboxylic acid and the esterification of alcohol type organic be it is important in organic synthesis react, be synthesizing ester product
Main method, reaction process at a certain temperature, occurred using carboxylic acid type organic and alcohol under the catalytic action of catalyst
Esterification, while esterification is a kind of reversible reaction, reaction has equilibrium conversion, and conversion ratio is lower, and raw material can not
Reaction completely, it is therefore, industrial generally by high temperature distillation, water in reaction product is removed, reaction-ure conversion-age is promoted.
But for the esterification of low boiling point alcohols, such as methanol, ethyl alcohol, in distillation removal process, alcohols feedstock can be with
Azeotropic occurs for water, and raw material alcohols is also evaporated while removing water, can not achieve the conversion ratio for improving raw material.
Existing esterification technique passes through what intermittent reaction form was realized in a kettle, and there are production efficiency low cost is high
Problem, since reaction time of esterification is longer, so the residence time in the reactor generally in several hours, cannot achieve anti-
It answers and realizes successive reaction in device.
It is existing using the concentrated sulfuric acid as in catalyst esterification technique, using the inorganic bases neutralization reaction such as sodium hydroxide, ammonium hydroxide
The remaining concentrated sulfuric acid afterwards separates organic phase progress rectifying and obtains product after reaction, reaction process generallys use intermittent processing
Mode, long processing period are at high cost.
Summary of the invention
It is low existing low boiling point alcohols esterification reaction process conversion ratio, aiming at the problem that cannot achieve serialization, the present invention mentions
Going out a kind of low-boiling point alcohol continuous esterification rectification process and technique, it can effectively remove the water generated in reaction process,
Being carried out continuously for esterification is realized in packed tower, is improved esterification conversion ratio and yield, is reduced manufacturing cost
And manipulation strength.And realize the continuous production of post-processing.
Technical solution of the present invention:
A kind of low-boiling point alcohol continuous esterification rectification process, including crude product ester rectifying column, return tank, sulfuric acid catalyst are high
Position slot, carboxylic acid head tank, catalyst-carboxylic acid blending tank, alcohol head tank, esterification column, rectifying column, alcohol surge tank, alcohol storage tank, static state
Reactor, centrifugal extractor and storage tank；
Sulfuric acid catalyst in the sulfuric acid catalyst head tank is added continuously to urge with the carboxylic acid in carboxylic acid head tank
After being sufficiently mixed preheating in agent-carboxylic acid blending tank, into the middle part of the rectifying section and stripping section of esterification column；Alcohol in alcohol head tank
In the middle part of the preheated stripping section for being passed into esterification column；Sulfuric acid catalyst head tank, carboxylic acid head tank, alcohol head tank, catalyst-carboxylic
Acid-mixed closes pot bottom and is provided with flow control instrument；Esterification column overhead extraction material is alcohol-aqueous mixtures, is passed through back after preheated
A part of alcohol is passed into rectifying column by stream tank carries out further rectifying, and another part alcohol is from esterification column overhead reflux to esterification column
It is internal；Alcohol after rectifying is produced through the top of the distillation column using return tank, and the alcohol after a part of rectifying enters alcohol surge tank, then into
Enter in alcohol storage tank, the ethyl alcohol after purification is squeezed into alcohol head tank again and is recycled；Alcohol after another part rectifying is from rectifying column
The reaction was continued in overhead reflux to rectifying column；
The esterification crude product and lye that esterification column tower bottom obtains are in batch reactor neutralization reaction, except sulphur in deesterify crude product
Acid, material continuously separates in centrifugal extractor after neutralization, and the organic matter after separation enters crude product ester rectifying column, through crude product ester essence
Tower top obtains esterification products after evaporating tower rectifying；Esterification products after return tank, a part enter storage tank in, another part from
Crude product the top of the distillation column, which enters in crude product ester rectifying column, continues to participate in reaction.
The lye is ammonium hydroxide or sodium hydroxide solution.
The low-boiling point alcohol is methanol or ethyl alcohol.
The beneficial effects of the present invention are: the present invention is in the esterification reaction process of low-boiling point alcohol, into esterification column stripping section
The alcohol at middle part constantly gasifies, and with carboxylic acid, the abundant mass-and heat-transfer of sulfuric acid catalyst, esterification occurs, and by alcohol in each rectifying
Mass transfer, heat transfer are carried out in theoretical tray by the water of reaction generation from tower top removal, crude product carboxylate is obtained in tower reactor and continuously adopted
Out, continuous production and water removal are realized in tower equipment, are promoted product yield and feed stock conversion, are considerably reduced into
This.Alcohol-aqueous mixtures that esterification column overhead is taken out of are further separated through rectifying column, overhead extraction ethyl alcohol, realize alcohol circulation benefit
With.Through continuous neutralization, centrifuge separation, isolated organic phase finally realizes product through product rectifying column and connects crude product carboxylate
Continuous post-processing.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of type of the present invention.
In figure: 1 crude product ester rectifying column；2 return tanks；3 sulfuric acid catalyst head tanks；4 carboxylic acid head tanks；5 catalyst-carboxylic acid
Blending tank；6 alcohol head tanks；7 esterification columns；8 rectifying columns；9 alcohol surge tanks；10 alcohol storage tanks；11 batch reactors；12 Centrifugical extractions
Machine；13 storage tanks.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
A kind of low-boiling point alcohol continuous esterification rectification process, including crude product ester rectifying column 1, return tank 2, sulfuric acid catalyst
Head tank 3, carboxylic acid head tank 4, catalyst-carboxylic acid blending tank 5, alcohol head tank 6, esterification column 7, rectifying column 8, alcohol surge tank 9, alcohol
Storage tank 10, batch reactor 11, centrifugal extractor 12 and storage tank 13；
The esterification column 7 includes tower reactor, rectification process section and overhead reflux section, and rectification process section includes rectifying section and mention
Section is evaporated, filler is provided in rectifying section and stripping section, it is anti-that mass transfer, heat transfer and esterification occur in filler for carboxylic acid, pure and mild catalyst
It answers；
Sulfuric acid catalyst in the sulfuric acid catalyst head tank 3 proportionally connects with the carboxylic acid in carboxylic acid head tank 4
It is continuous be added to be sufficiently mixed in catalyst-carboxylic acid blending tank 5 after, into the middle part of the rectifying section and stripping section of esterification column 7；Alcohol
Alcohol in head tank 6 is passed into the middle part of the stripping section of esterification column 7 according to alcohol and carboxylic acid molar ratio for 2:1-8:1；Sulfuric acid catalyst
Head tank 3, carboxylic acid head tank 4, alcohol head tank 6, catalyst -5 bottom of carboxylic acid blending tank are provided with flow control instrument, ester
Change the temperature of 7 tower reactor of tower at 65-100 DEG C；7 overhead extraction material of esterification column be alcohol-aqueous mixtures, it is preheated to 40-70 DEG C again
A part of alcohol is passed into rectifying column 8 through return tank 2 and carries out further rectifying, another part alcohol is from 7 overhead reflux of esterification column
To esterification column 7；For alcohol after rectifying through 8 overhead extraction of rectifying column using return tank 2, the alcohol after a part of rectifying enters alcohol
Surge tank 9 enters back into alcohol storage tank 10, and the ethyl alcohol after purification is squeezed into alcohol head tank 6 again and is recycled；Another part rectifying
The reaction was continued out of rectifying column 8 overhead reflux to rectifying column 8 for alcohol afterwards；
The esterification crude product and ammonium hydroxide that 7 tower bottom of esterification column obtains are in 11 neutralization reaction of batch reactor, except in deesterify crude product
Sulfuric acid, material continuously separates in centrifugal extractor 12 after neutralization, and the organic matter after separation enters crude product ester rectifying column 1, through thick
Tower top obtains esterification products after 1 rectifying of product ester rectifying column；For esterification products after return tank 2, a part enters storage tank 13
In, another part enters in crude product ester rectifying column 1 from 1 tower top of crude product ester rectifying column continues to participate in reaction.
Claims (3)
1. a kind of low-boiling point alcohol continuous esterification rectification process, which is characterized in that the low-boiling point alcohol continuous esterification rectifying
System includes crude product ester rectifying column (1), return tank (2), sulfuric acid catalyst head tank (3), carboxylic acid head tank (4), catalyst-carboxylic
Sour blending tank (5), alcohol head tank (6), esterification column (7), rectifying column (8), alcohol surge tank (9), alcohol storage tank (10), batch reactor
(11), centrifugal extractor (12) and storage tank (13)；
The esterification column (7) includes tower reactor, rectification process section and overhead reflux section, and rectification process section includes rectifying section and stripping
It is provided with filler in section, rectifying section and stripping section, mass transfer, heat transfer and esterification occur in filler for carboxylic acid, pure and mild catalyst；
Sulfuric acid catalyst in the sulfuric acid catalyst head tank (3) proportionally connects with the carboxylic acid in carboxylic acid head tank (4)
It is continuous be added to be sufficiently mixed in catalyst-carboxylic acid blending tank (5) after, into the rectifying section and stripping section of esterification column (7)
Portion；Alcohol in alcohol head tank (6) is passed into the middle part of the stripping section of esterification column (7) according to alcohol and carboxylic acid molar ratio for 2:1-8:1；Sulphur
Acid catalyst head tank (3), carboxylic acid head tank (4), alcohol head tank (6), catalyst-carboxylic acid blending tank (5) bottom are provided with
Flow control instrument, the temperature of esterification column (7) tower reactor is at 65-100 DEG C；Esterification column (7) overhead extraction material is alcohol-water mixing
Object, a part of alcohol is passed into the further rectifying of progress in rectifying column (8) through return tank (2) again by preheated to 40-70 DEG C, another
Part alcohol is internal from esterification column (7) overhead reflux to esterification column (7)；Alcohol after rectifying through rectifying column (8) overhead extraction using
Return tank (2), the alcohol after a part of rectifying enter alcohol surge tank (9), enter back into alcohol storage tank (10), the ethyl alcohol after purification is again
It squeezes into alcohol head tank (6) and is recycled；Alcohol after another part rectifying is interior from rectifying column (8) overhead reflux to rectifying column (8)
The reaction was continued；
The esterification crude product and ammonium hydroxide that esterification column (7) tower bottom obtains are in batch reactor (11) neutralization reaction, except in deesterify crude product
Sulfuric acid, material continuously separates in centrifugal extractor (12) after neutralization, and the organic matter after separation enters crude product ester rectifying column (1),
Tower top obtains esterification products after crude product ester rectifying column (1) rectifying；After return tank (2), a part enters deposits esterification products
In storage tank (13), another part enters in crude product ester rectifying column (1) from 1 tower top of crude product rectifying column continues to participate in reaction.
2. low-boiling point alcohol continuous esterification rectification process according to claim 1, which is characterized in that the lye is
Ammonium hydroxide or sodium hydroxide solution.
3. low-boiling point alcohol continuous esterification rectification process according to claim 1 or 2, which is characterized in that described is low
Boiling point alcohol is methanol or ethyl alcohol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910302010.3A CN109942357A (en) | 2019-04-16 | 2019-04-16 | A kind of low-boiling point alcohol continuous esterification rectification process |
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| CN201910302010.3A CN109942357A (en) | 2019-04-16 | 2019-04-16 | A kind of low-boiling point alcohol continuous esterification rectification process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232007A (en) * | 2022-06-16 | 2022-10-25 | 浙江建业化工股份有限公司 | Production method of plasticizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326923A (en) * | 2000-06-02 | 2001-12-19 | 唐山市冀东溶剂厂 | Method for continuously producing butyl acetate |
| CN1844076A (en) * | 2006-03-20 | 2006-10-11 | 江阴市百川化学工业有限公司 | Method for mass producing butyl acetate by reactive distillation method and using sulfuric acid as catalyst |
-
2019
- 2019-04-16 CN CN201910302010.3A patent/CN109942357A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326923A (en) * | 2000-06-02 | 2001-12-19 | 唐山市冀东溶剂厂 | Method for continuously producing butyl acetate |
| CN1844076A (en) * | 2006-03-20 | 2006-10-11 | 江阴市百川化学工业有限公司 | Method for mass producing butyl acetate by reactive distillation method and using sulfuric acid as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 姚蒙正等: "《精细化工产品合成原理》", 31 December 2000 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232007A (en) * | 2022-06-16 | 2022-10-25 | 浙江建业化工股份有限公司 | Production method of plasticizer |
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