CN107827746A - A kind of method of catalytic distillation synthesis mixed ester - Google Patents
A kind of method of catalytic distillation synthesis mixed ester Download PDFInfo
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- CN107827746A CN107827746A CN201711169250.8A CN201711169250A CN107827746A CN 107827746 A CN107827746 A CN 107827746A CN 201711169250 A CN201711169250 A CN 201711169250A CN 107827746 A CN107827746 A CN 107827746A
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- catalytic distillation
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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
- 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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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention discloses a kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, using storng-acid cation exchange resin as catalyst, using catalytic distillation tower as reactor, catalytic distillation back flow reaction is carried out, is finally separated and can obtain the mixing fat of ethyl acetate and butyl acetate.This method is formed azeotropic mixture using butyl acetate and fourth alcohol and water, the water of the generation of reaction is all taken out of from tower top using the strong band outlet capacity of butyl acetate.The acetic acid content in the conversion ratio and catalytic distillation tower reactor of alcohols reactant can be improved, influence of the product water to course of reaction in tower can be eliminated again.Ester aqueous mixtures are essentially in overhead product, the content of acetic acid is very low, and the difficulty of such ethyl acetate and butyl acetate subsequent purification work substantially reduces, and simplifies production procedure, improves production efficiency, reduces energy consumption.
Description
Technical field
The invention belongs to organic chemical synthesis field, more particularly to a kind of method of catalytic distillation synthesis mixed ester, specifically
It is related to the method for the simultaneously synthesizing ethyl acetate of catalytic distillation and butyl acetate.
Background technology
Catalytic distillation (CD, catalytic distillation) technology be heterogeneous catalytic reaction with separated same
The chemical process being coupled in one equipment, the process make chemical reaction and separated be obtained for reinforcing.As one kind
Heterogeneous reaction still-process, the catalyst of existing catalytic distillation uses solid catalyst, and is filled into the form of certain
In tower, catalysis and filler double action can be played.During catalytic distillation technology, reaction product can be isolated instead in time
Region is answered, according to the principle of reversible reaction, the conversion ratio of reactant can be improved, strengthen course of reaction, increase yield, meanwhile,
The selectivity of course of reaction is improved, with production, can simplification of flowsheet, reduce energy consumption, reduce operating cost.
Therefore, catalytic distillation technology is widely used in a series of chemical reaction process.
The core of catalytic reaction is catalyst, and in existing catalytic distillation technology, catalyst is with catalyst structure
Form occurs.As the critical component for realizing catalytic distillation technology, catalyst structure is most study in catalytic distillation technology
One of key content.Typically 1.0~3.0mm of granular size solid granular catalyst is wrapped up with Web materials, processing system
Into the catalyst structure of a shaping type.
Catalyst structure, which is used for catalytic distillation technology, to be needed to meet following condition：(1) catalysis is controlled in catalyst structure
The amount of agent and the amount of product are adapted；(2) catalyst can effective haptoreaction thing；(3) vehicle repair major can be allowed in catalyst structure
Middle contact is good；(4) liquid need to be evenly distributed in component, and hydrodynamics is good, and pressure drop is low, and liquid holdup meets the requirement of reaction；
(5) easily install, change and regenerate the catalyst in component.
In recent years, application of the catalytic distillation technology in esterification system is further extensive, and this has benefited from esterification
The heterogeneous catalysis that function admirable continuously emerges, meanwhile, catalytic distillation technology can also play its advantage and overcome traditional handicraft
Shortcoming.
Catalytic distillation technology is used widely in the industrialized production of methyl acetate.Society's hamming is catalyzed with H β zeolites
Agent, use catalytic distillation technology in catalytic distillation tower (being Ф 30mm highly for 2000mm tower diameters) using lactic acid and n-butanol as original
Expect direct synthesizing lactic acid N-butyl, continuous feed, n-butyl lactate can in the mass content of tower reactor after catalytic distillation process stabilization
Up to 97.14%.
From conception nearly 40 years till now is proposed, scholars people constantly change catalytic distillation technology to this technology
Enter, continue to optimize, the understanding of catalytic distillation technology process is also constantly being deepened.Steamed although acid esterification reaction system is catalysis
Technology is evaporated using one of earliest reaction system, but still there are many technical issues that need to address.
(1) in terms of catalyst structure, the catalyst requirement used is solid catalyst, and is graininess, catalyst structure
The specification and performance of part are difficult to be processed into consistent pattern, and catalytic amount, carrier performance and tower void rate are difficult to unification.
(2) material for wrapping up catalyst structure easily corrodes, and Anticorrosion is difficult to solve, and catalyst filling is changed difficult.
(3) due to forming polynary azeotropic mixture in esterification system, reaction product can not fully enter tower top or bottom of towe, urge
Changing the technical advantage of distillation can not be played very well.Such as in the esterification system of acetic acid and ethanol, what product water was formed
Minimum azeotropic mixture can not all take it from tower top out of, partly into bottom of towe, separates the invigoration effect to reaction and is affected.
The content of the invention
The present invention be directed to above-mentioned prior art problem, there is provided a kind of simultaneously synthesizing ethyl acetate of new catalytic distillation technology with
The mixing fat method of butyl acetate, this method have catalyst need not be made component, solid catalyst species more extensively, can
Using plate column or packed tower, the distinguishing features such as catalyst regenerative operation is simple.
In order to realize the purpose of the present invention, technical scheme is as follows：
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, with highly acid
Cationic ion-exchange resin is catalyst, using catalytic distillation tower as reactor, carries out catalytic distillation back flow reaction, the product of generation is complete
Portion steams from tower top, is finally separated and can obtain the mixing fat of ethyl acetate and butyl acetate.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
Storng-acid cation exchange resin be D072, D002, D008, LS-50, NKC-9, one kind in LT-3.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
Raw material in acetic acid, ethanol, the mol ratio of n-butanol be 2-4:0.8-1:0.5-1.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
Catalyst amount for add quality of acetic acid 0.5-10%.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
The temperature of catalytic distillation back flow reaction be：60-96℃；Reaction time is：60-240min；Reflux ratio is：0.5-3.5
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
Catalyst also include catalyst preheating step；Described catalyst preheating step is the salt that catalyst is first used to 1-7%
Acid solution (mass fraction) impregnates 5-24h, and after filtering, pH=6 is washed to distillation, then is washed 4~6 times with absolute ethyl alcohol, puts
Enter be placed in baking oven after constant temperature 8-24h it is standby in drying basin.It can be carried on the basis of original by the activity of pretreatment catalyst
High 3-8% catalytic efficiency.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
Oven temperature be 60-140 DEG C.After temperature is more than 140 DEG C, its catalytic performance is decreased obviously.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
Catalyst pretreatment after also include catalyst is crushed after cross 200 mesh sieves be immersed in concentration be 0.01-0.05mol/L Fe3+
In solion, soak time is 4-24 hours, filters out vacuum drying 12-36 hours at latter 60-85 DEG C.After catalyst crushes,
Particle diameter diminishes surface area increase, and effective contact area of catalyst and reactant increases, improves reaction rate, be advantageous to react
Progress.Separately through Fe3+After processing, catalytic activity slightly improves.
The method for synthesizing mixed ester as the further improvement of technical scheme, a kind of catalytic distillation described in any of the above,
Described catalyst is reused 10-15 times.After 10 times are reused, the catalytic activity of catalyst does not substantially reduce, weight
Multiple performance is preferable.
As the further improvement of technical scheme, a kind of above-described method of catalytic distillation synthesis mixed ester is described
The conversion per pass of ethanol be more than 95%, the conversion per pass of butanol is more than 97%.
The invention has the advantages that：
1. by the analysis to two synthesizing ethyl acetate, Synthesis of Butyl Acetate reaction systems, according in reaction system two
The composition and boiling point difference of member or ternary azeotrope, using the strong band outlet capacity of butyl acetate, using butyl acetate and butanol and
Water forms azeotropic mixture, the water of the generation of reaction is all taken out of from tower top.The acetic acid content in tower reactor can be improved, can be eliminated again
Influence of the product water to course of reaction in tower.Ester-aqueous mixtures are essentially in overhead product, the content of acetic acid is very low, so
Ethyl acetate and the difficulty of butyl acetate subsequent purification work substantially reduce, and simplify production procedure, are carried than traditional production technology
High efficiency 5-10%, reduce energy consumption 20-30%.
2. using the band outlet capacity of butyl acetate, the content of ester in overhead product is improved, reduces tower reactor product reclaimed water and second
The content of acid butyl ester, meanwhile, the resin catalyst after acetic acid and crushing recycles in tower, maximumlly recycles second
Acid, operation cost is reduced, greatly reduce the discharge of waste water.
3. in this catalytic distillation technology, solid catalyst does not have to be processed into catalyst structure, the catalyst in tower and vapour-
Liquid two is in contact, and catalytic efficiency improves 10-20% than existing catalytic distillation technology, recycles, catalyst regenerative operation
Simply, change simple.Technical disadvantages existing for overcoming traditional esterifications technique, reduce production equipment cost.
4. this method, compared with existing esterification technology, the relatively conventional esterification technique of conversion per pass of ethanol improves
8-12%, the conversion ratio of butanol improve 5-10%.
Brief description of the drawings
Accompanying drawing 1 is process chart of the invention.
In figure：1. catalytic distillation tower；2. reflux ratio controller；3 phase separators.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, second in raw material
Acid, ethanol, the mol ratio of n-butanol are 2:0.8:0.5；Using storng-acid cation exchange resin D072 as catalyst, catalyst is used
Measure to add the 0.5% of quality of acetic acid.Using catalytic distillation tower as reactor, catalytic distillation back flow reaction, the temperature of reaction are carried out
For：60℃；Reaction time is：60min；Reflux ratio is：0.5, catalyst is reused 10 times.Finally carrying out phase separation can obtain
To ethyl acetate and the mixing fat of butyl acetate.The conversion per pass that reaction terminates rear ethanol is more than 95.2%, the one way of butanol
Conversion ratio is more than 97.5%.
Embodiment 2
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, second in raw material
Acid, ethanol, the mol ratio of n-butanol are 2.3:0.85:0.6；Using storng-acid cation exchange resin D002 as catalyst, catalysis
Agent dosage is the 2% of addition quality of acetic acid.Using catalytic distillation tower as reactor, catalytic distillation back flow reaction, the temperature of reaction are carried out
Spend and be：70℃；Reaction time is：100min；Reflux ratio is：1, catalyst is reused 11 times.Finally it is separated
Obtain the mixing fat of ethyl acetate and butyl acetate.The conversion per pass that reaction terminates rear ethanol is more than 95.6%, the list of butanol
Journey conversion ratio is more than 97.4%.
Embodiment 3
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, second in raw material
Acid, ethanol, the mol ratio of n-butanol are 2.7:0.9:0.7；Using storng-acid cation exchange resin D008 as catalyst, catalyst
Dosage is the 4% of addition quality of acetic acid.Using catalytic distillation tower as reactor, catalytic distillation back flow reaction, the temperature of reaction are carried out
For：80℃；Reaction time is：140min；Reflux ratio is：2, catalyst is reused 12 times.Finally carrying out phase separation can obtain
To ethyl acetate and the mixing fat of butyl acetate.The conversion per pass that reaction terminates rear ethanol is more than 95.3%, the one way of butanol
Conversion ratio is more than 97.6%.
Embodiment 4
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, second in raw material
Acid, ethanol, the mol ratio of n-butanol are 3:0.95:0.8；Using storng-acid cation exchange resin LS-50 as catalyst, catalyst
Dosage is the 6% of addition quality of acetic acid.Using catalytic distillation tower as reactor, catalytic distillation back flow reaction, the temperature of reaction are carried out
For：90℃；Reaction time is：180min；Reflux ratio is：3, catalyst is reused 13 times.Finally carrying out phase separation can obtain
To ethyl acetate and the mixing fat of butyl acetate.The conversion per pass that reaction terminates rear ethanol is more than 95.1%, the one way of butanol
Conversion ratio is more than 97%.
Embodiment 5
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, second in raw material
Acid, ethanol, the mol ratio of n-butanol are 3.5:1:0.9；Using storng-acid cation exchange resin NKC-9 as catalyst, catalyst
Dosage is the 8% of addition quality of acetic acid.Using catalytic distillation tower as reactor, catalytic distillation back flow reaction, the temperature of reaction are carried out
For：96℃；Reaction time is：220min；Reflux ratio is：3.5, catalyst is reused 14 times.Finally it is separated
Obtain the mixing fat of ethyl acetate and butyl acetate.The conversion per pass that reaction terminates rear ethanol is more than 95.8%, the list of butanol
Journey conversion ratio is more than 98%.
Embodiment 6
A kind of method of catalytic distillation synthesis mixed ester, this method is using ethanol, n-butanol, acetic acid as raw material, second in raw material
Acid, ethanol, the mol ratio of n-butanol are 4:0.9:1；Using storng-acid cation exchange resin LT-3 as catalyst, catalyst amount
To add the 10% of quality of acetic acid.Using catalytic distillation tower as reactor, catalytic distillation back flow reaction is carried out, the temperature of reaction is：
85℃；Reaction time is：240min；Reflux ratio is：2.5, catalyst is reused 15 times.Finally it is separated i.e. available
The mixing fat of ethyl acetate and butyl acetate.The conversion per pass that reaction terminates rear ethanol is more than 95.5%, and the one way of butanol turns
Rate is more than 97.6%.
The embodiment 7 of improvement project
On the basis of embodiment 1-6, the mixing of similarity condition is carried out after being pre-processed to used catalyst again
It is prepared by fat.
The pretreatment of catalyst is：Catalyst is first impregnated into 5-24h, filtering with 1-7% hydrochloric acid solution (mass fraction)
Afterwards, pH=6 is washed to distillation, then is washed 4~6 times with absolute ethyl alcohol, be put into constant temperature 8- in the baking oven that temperature is 60-140 DEG C
It is placed in after 24h standby in drying basin.Then carry out preparing with the mixing fat of embodiment 1-6 similarity conditions again.
Experiment proves：Urging for 3-8% can be improved on the basis of original by the activity of the catalyst of the preprocess method
Change efficiency.Reaction time is：60-180min；When making catalyst with D072, the conversion per pass that reaction terminates rear ethanol is more than
96.1%, the conversion per pass of butanol is more than 97.3%.When making catalyst with D002, reaction terminates the conversion per pass of rear ethanol
More than 96.4%, the conversion per pass of butanol is more than 97.1%；When making catalyst with D008, the one way that reaction terminates rear ethanol turns
Rate is more than 96.2%, and the conversion per pass of butanol is more than 97%；When making catalyst with LS-50, reaction terminates the list of rear ethanol
Journey conversion ratio is more than 96.3%, and the conversion per pass of butanol is more than 97.2%；When making catalyst with NKC-9, reaction terminates rear second
The conversion per pass of alcohol is more than 96.8%, and the conversion per pass of butanol is more than 97.8%；When making catalyst with LT-3, reaction terminates
The conversion per pass of ethanol is more than 96.5% afterwards, and the conversion per pass of butanol is more than 97.1%.
The embodiment 8 of improvement project
On the basis of the embodiment 7 of improvement project, after being pre-processed to used catalyst just, further to urging
Agent carries out secondary pretreatment again, and the catalyst obtained after secondary pretreatment carries out the mixing fat with embodiment 1-6 similarity conditions
Prepare.
The pretreated after-treatment of catalyst is：Will pretreated catalyst crush after cross 200 mesh sieves be immersed in it is dense
Spend the Fe for 0.01mol/L-0.05mol/L3+In solion, soak time is 4-24 hours, filters out vacuum at latter 60-85 DEG C
Dry 12-36 hours.
Experiment proves：The catalyst powder of pretreatment is after broken, and particle diameter diminishes surface area increase, and catalyst and reactant have
Contact area increase is imitated, improves reaction rate, is advantageous to the progress of reaction.Separately through Fe3+After processing, catalytic activity is improved.
After the secondary pretreatment of catalyst, prepared with the mixing fat of embodiment 1-6 similarity conditions, as a result show：D072 makees catalyst
When, the conversion per pass that reaction terminates rear ethanol is more than 97.2%, and the conversion per pass of butanol is more than 97.7%；D002 is catalyzed
During agent, the conversion per pass that reaction terminates rear ethanol is more than 96.9%, and the conversion per pass of butanol is more than 97.3%；D008 is urged
During agent, the conversion per pass that reaction terminates rear ethanol is more than 97.2%, and the conversion per pass of butanol is more than 97.5%；LS-50
When making catalyst, the conversion per pass that reaction terminates rear ethanol is more than 96.7%, and the conversion per pass of butanol is more than 97.5%；
When NKC-9 makees catalyst, the conversion per pass that reaction terminates rear ethanol is more than 98.1%, and the conversion per pass of butanol is more than
97.3%；When LT-3 makees catalyst, the conversion per pass that reaction terminates rear ethanol is more than 97.6%, and the conversion per pass of butanol is big
In 97.4%.
Claims (10)
- A kind of 1. method of catalytic distillation synthesis mixed ester, it is characterised in that：Using ethanol, n-butanol, acetic acid as raw material, with strong acid Property cationic ion-exchange resin be catalyst, using catalytic distillation tower as reactor, carry out catalytic distillation back flow reaction, the product of generation All steamed from tower top, be finally separated and can obtain the mixing fat of ethyl acetate and butyl acetate.
- A kind of 2. method of catalytic distillation synthesis mixed ester according to claim 1, it is characterised in that：Described highly acid Cationic ion-exchange resin is D072, D002, D008, LS-50, NKC-9, one kind in LT-3.
- A kind of 3. method of catalytic distillation synthesis mixed ester according to claim 1 or 2, it is characterised in that：Described original Acetic acid, ethanol, the mol ratio of n-butanol are 2-4 in material:0.8-1:0.5-1.
- A kind of 4. method of catalytic distillation synthesis mixed ester according to claim 3, it is characterised in that：Described catalyst Dosage is to add the 0.5-10% of quality of acetic acid.
- A kind of 5. method of catalytic distillation synthesis mixed ester according to claim 1, it is characterised in that：Described catalysis is steamed The temperature for evaporating back flow reaction is：60-96℃；Reaction time is：60-240min；Reflux ratio is：0.5-3.5
- A kind of 6. method of catalytic distillation synthesis mixed ester according to claim 2, it is characterised in that：Described catalyst Also include catalyst preheating step；Described catalyst preheating step is the hydrochloric acid solution (matter that catalyst is first used to 1-7% Measure fraction) dipping 5-24h, after filtering, pH=6 is washed to distillation, then washed 4~6 times with absolute ethyl alcohol, it is put into baking oven permanent It is placed in after warm 8-24h standby in drying basin.
- A kind of 7. method of catalytic distillation synthesis mixed ester according to claim 6, it is characterised in that：Described baking oven temperature Spend for 60-140 DEG C.
- A kind of 8. method of catalytic distillation synthesis mixed ester according to claim 6, it is characterised in that：Described catalyst Also the Fe that concentration is 0.01mol/L-0.05mol/L is immersed in after pretreatment including crossing 200 mesh sieves after catalyst is crushed3+Ion In solution, soak time is 4-24 hours, filters out vacuum drying 12-36 hours at latter 60-85 DEG C.
- 9. the method that mixed ester is synthesized according to a kind of any described catalytic distillations of claim 6-8, it is characterised in that：Described Catalyst is reused 10-15 times.
- A kind of 10. method of catalytic distillation synthesis mixed ester according to claim 1, it is characterised in that：Described ethanol Conversion per pass be more than 95%, the conversion per pass of butanol is more than 97%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369396A (en) * | 2018-11-30 | 2019-02-22 | 福州大学 | A kind of method that direct esterification prepares high-purity ethylene acetate |
| CN112047838A (en) * | 2019-07-20 | 2020-12-08 | 江门谦信化工发展有限公司 | Relay type ethyl acetate industrial preparation process |
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| WO2012021965A1 (en) * | 2010-08-20 | 2012-02-23 | Enerkem, Inc. | Production of acetates from acetic acid and alcohols |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226884A (en) * | 1997-03-26 | 1999-08-25 | 英国石油化学品有限公司 | Ester co-production |
| WO2012021965A1 (en) * | 2010-08-20 | 2012-02-23 | Enerkem, Inc. | Production of acetates from acetic acid and alcohols |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369396A (en) * | 2018-11-30 | 2019-02-22 | 福州大学 | A kind of method that direct esterification prepares high-purity ethylene acetate |
| CN112047838A (en) * | 2019-07-20 | 2020-12-08 | 江门谦信化工发展有限公司 | Relay type ethyl acetate industrial preparation process |
| CN112047838B (en) * | 2019-07-20 | 2023-04-07 | 江门谦信化工发展有限公司 | Relay type ethyl acetate industrial preparation process |
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