CN106140297A - A kind of resin esterification catalyst and preparation method thereof - Google Patents
A kind of resin esterification catalyst and preparation method thereof Download PDFInfo
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- CN106140297A CN106140297A CN201510115471.1A CN201510115471A CN106140297A CN 106140297 A CN106140297 A CN 106140297A CN 201510115471 A CN201510115471 A CN 201510115471A CN 106140297 A CN106140297 A CN 106140297A
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- catalyst
- cationic ion
- resin
- exchange resin
- esterification
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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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Abstract
The invention discloses a kind of resin esterification catalyst and preparation method thereof, utilize this method can prepare the solid catalyst that can be applicable to esters synthesis；It is carrier that described catalyst uses 732 type cationic ion-exchange resins, AlCl3For modified maceration extract, it is 0.015g/mL that the impregnation concentration being used controls, and dip time is 20h, and the catalyst obtaining can be efficient, and the esterification of high selective catalysis acetic acid and n-butanol, acetic acid conversion reaches 67.3%.Catalyst performance stabilised, after using 5 times continuously, acetic acid conversion remains to be maintained at more than 60%.
Description
Technical field
The present invention relates to a kind of resin esterification catalyst and preparation method thereof, especially a kind of esterification being applied to acetic acid and n-butanol and design
Catalyst and preparation method thereof.
Background technology
N-butyl acetate is a kind of important Organic chemical products, is widely used in the industries such as synthetic perfume, industrial production, pharmacy.On synthetic perfume,
N-butyl acetate is used for preparing the type essence such as banana, pineapple, candy；In industrial production, can serve as manufacture nitrocotton, cellulose lacquer coating,
Artificial leather, coated paper, plastics polisher, the solvent etc. of synthetic resin；Pharmaceutically, may be used to produce erythromycin or polyurethanes etc..
Such production of chemicals current is essentially all and uses the traditional processing technology making catalyst with the concentrated sulfuric acid.Owing to butyl acetate boiling point is higher, instead
During Ying the catalyst concentrated sulfuric acid easily make reactant or product be dehydrated, the side reaction such as carbonization.After reaction terminates, product to neutralize through alkali, water
The concentrated sulfuric acid is removed in eccysis, and subsequent purification process is more complicated；Water-washing process can lose portioned product and unreacting material, and produce a large amount of production waste water.
In order to remove the salt after neutralizing washing, needing vapour phase discharging at final product tower, the energy consumption causing is higher.
Storng-acid cation exchange resin is the catalyst for esterification reaction of a class better performances, and easily separates with product, can overcome sulphuric acid catalysis technique
Numerous shortcomings.But usual reaction rate is relatively slow, not as good as the concentrated sulfuric acid, it is therefore desirable to meet Production requirement to its modification.
Strong-acid type 732 cationic ion-exchange resin be with styrene-divinylbenzene polymerization polymer spheres as basic framework, by the concentrated sulfuric acid, chlorosulfonic acid
Obtain Deng the spheroid sulfonation with polymer, be that current applications is the widest, the maximum a kind of cationic ion-exchange resin of consumption.This catalyst is at Aquo System
Esterification in show good catalytic performance, but its resistance to elevated temperatures difference, acid strength is not high, and Lewis acid is drawn by researchers by load
Enter inside sulfonate resin, make in Lewis acid and sulfonate resinAcid is grouped together into high activated catalyst.Load Lewis acid
The acidity of cationic ion-exchange resin higher, make reaction just can carry out at low temperatures.The new acid site that modified resin is formed will not be by other metals
Ion exchanges, and which solves cationic ion-exchange resin when commercial Application, and its acidic-group is replaced and inactivated by metal ion contained in raw material
Problem.
For this phenomenon, Liu Fuan etc. (Journal of Molecular Catalysis 7 (1993) 385) thinks, the cation in Lewis acid can be with 732 type cations
2 sulfonic group complexings of the resin in exchanger resin, slough HCl and form a new strong any proton center, with Lewis acid synergy, make
The acid strength of modified cationic ion-exchange resin strengthens, and improves its catalysis activity.Zhang Feng etc. (catalysis journal 6 (2010) 666) use ZnCl2
Impregnating 732 cationic ion-exchange resins, being catalyzed the synthesis of acetic acid and N-butyl under the conditions of microwave radiation technology, acetic acid conversion has reached 64.5%, obtains
Catalyst performance stabilised, even if still being able to show very strong Protic Acid Catalyzed effect in aqueous phase system.Therefore, strong Lewis acid conduct is used
The preparation of modifier modification 732 type cationic ion-exchange resin has very big industrial application value in order to the catalyst of synthesizing ester chemicals.
Content of the invention
Corrosivity existing for the catalyst that existing production n-butyl acetate is used is strong, is not easily recycled, the problems such as recycling rate of waterused is low, this
Invention provides the esterification catalyst preparation method of a kind of efficient stable.This catalyst is applied in the reaction of acetic acid and butanol, improves the positive fourth of acetic acid
The selectivity of ester.
A kind of efficient esterification catalyst, with 732 type cationic ion-exchange resins as carrier, with Al3+For active component, impregnation concentration is
0.01～0.03g/mL, preferably 0.015g/mL；Dip time is 10～40h, preferably 20h.
In the inventive method, under described cationic ion-exchange resin performance indications enter: water content 45～50%, CEC >=4.5mmol/g (does),
Wet apparent density 0.77～0.87g/mL, effective grain size 0.40～0.60mm, expansion rate (Na+→H+)≤10%.
A kind of esterification catalyst of the present invention, including following content: cationic ion-exchange resin is acidified by (1), obtains H type cationic ion-exchange resin；
(2) H type cationic ion-exchange resin and the solution using deionized water to prepare being joined dipping in container, filtering, washing, to neutral, obtains
Esterification catalyst.
Maceration extract employed in the present invention is AlCl3Solution, its concentration is 0.01～0.03g/mL, preferably 0.015g/mL；
Dip time employed in the present invention is l0～40h, preferably 20h.
Catalyst of the present invention can apply in the reactive distillation production process of acetic acid and butanol, and preferable process conditions are: reaction temperature 80～160 DEG C,
It is preferably 100～130 DEG C.Catalyst of the present invention is applicable to successive reaction or intermittent reaction.
Detailed description of the invention
Further illustrate the effect of the present invention below by embodiment and comparative example.The cationic ion-exchange resin performance indications using in embodiment are as follows:
Water content 47%, wet apparent density 0.79g/mL, effective grain size 0.45mm.
The preparation of H type cationic ion-exchange resin: Na type cationic ion-exchange resin is soaked 5 hours in 1mol/L hydrochloric acid solution, uses deionized water
It is washed till pH=6, low temperature drying, obtain H type cationic ion-exchange resin.
Embodiment: by 5g over dry H type cationic ion-exchange resin dipping and the AlCl that concentration is 0.15g/mL3In solution, filter after impregnating 20 hours,
It is washed with deionized water to without Cl-, dry for standby.
By the acetic acid of catalyst and 0.5mol, 0.5mol n-butanol joins in the there-necked flask with thermometer, and heating mantle control temperature exists
Between 90～130 DEG C, mechanical agitation, connect water knockout drum, condensing reflux, stop reaction after 2 hours, detect product content, acetic acid conversion is 67.3%.
By catalyst filtration, low temperature drying, repeating above experiment 4 times, conversion ratio is respectively 65.2%, and 63.4%, 61.9%, 60.3%.
Comparative example: by the acetic acid of 5g over dry H type cationic ion-exchange resin and 0.5mol, 0.5mol n-butanol joins three mouthfuls of burnings with thermometer
In Ping, heating mantle control temperature is between 90～130 DEG C, and mechanical agitation, connection water knockout drum, condensing reflux, stopping reaction after 2 hours, detection is produced
Product content, acetic acid conversion is 47.1%.
From contrast it can be seen that catalyst after Fu Zai has very big lifting on catalytic performance, and still can keep being catalyzed after repeatedly utilizing
Activity.
Claims (8)
1. resin esterification catalyst and preparation method thereof, the resin obtaining can efficient catalytic synthesizing n-butyl acetate.It is characterized in that, described
Method use AlCl3Solution impregnation is through pretreated 732 type cationic ion-exchange resins；The catalyst using described method to prepare can be in temperature
The esterification of efficient catalytic acetic acid and n-butanol under the conditions of with, the consumption of catalyst is the 3% of raw material gross mass in the reaction；Compared to inorganic acid
With other solid acid catalysts, the catalyst preparation process that described method prepares is simple, and little to equipment corrosion, catalytic performance is good, and recycling rate of waterused is high.
2. method according to claim 1, it is characterised in that the 732 type cationic ion-exchange resins being used are for passing through washing, to eluate not
Have yellow again, pH value be 6 technical grade resin be raw material.
3. method according to claim 1, it is characterised in that the AlCl being used3In solution, Al3+For active component, impregnation concentration is
0.01～0.03g/mL, preferably 0.015g/mL.
4. method according to claim 1, it is characterised in that dip time is 10～40h, preferably 20h.
5. method according to claim 1, it is characterised in that under described cationic ion-exchange resin performance indications enter: water content 45～50%,
CEC >=4.5mmol/g (does), wet apparent density 0.77～0.87g/mL, effective grain size 0.40～0.60mm, expansion rate (Na+ → H+)≤10%.
6. method according to claim 1, it is characterised in that include following content: cationic ion-exchange resin is acidified by (1), obtains hydrogen
Type cationic ion-exchange resin；(2) hydrogen type cation exchange resin is added simultaneously in container leaching with the prior solution using deionized water to prepare
Stain, filters, and washing, to neutral, obtains esterification catalyst.
7. method according to claim 1, it is characterised in that catalyst amount is the 2%～10% of material liquid total amount, preferably 5%.
8. method according to claim 1, it is characterised in that the catalyst obtained by described method is applicable to reactive distillation system or normal pressure constant temperature
System, still can ensure catalytic effect after recycled for multiple times.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2014106545632 | 2014-11-18 | ||
| CN201410654563 | 2014-11-18 |
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| Publication Number | Publication Date |
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| CN106140297A true CN106140297A (en) | 2016-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510115471.1A Pending CN106140297A (en) | 2014-11-18 | 2015-03-17 | A kind of resin esterification catalyst and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298837A (en) * | 2020-03-16 | 2020-06-19 | 江苏国立化工科技有限公司 | Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier |
| CN114409537A (en) * | 2022-03-28 | 2022-04-29 | 山东新和成药业有限公司 | Preparation method of acetate compound and catalyst adopted by preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229787A (en) * | 1998-03-19 | 1999-09-29 | 尹昌树 | Method of using natural materials for synthetizing acetic ester |
| WO2011011137A1 (en) * | 2009-07-21 | 2011-01-27 | Exxonmobil Chemical Patents Inc. | Process for the preparation of keto acid esters useful as pvc plasticizers |
| CN103435481A (en) * | 2013-09-13 | 2013-12-11 | 江苏华伦化工有限公司 | Production method of ethylene glycol diacetate (EGDA) |
-
2015
- 2015-03-17 CN CN201510115471.1A patent/CN106140297A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229787A (en) * | 1998-03-19 | 1999-09-29 | 尹昌树 | Method of using natural materials for synthetizing acetic ester |
| WO2011011137A1 (en) * | 2009-07-21 | 2011-01-27 | Exxonmobil Chemical Patents Inc. | Process for the preparation of keto acid esters useful as pvc plasticizers |
| CN103435481A (en) * | 2013-09-13 | 2013-12-11 | 江苏华伦化工有限公司 | Production method of ethylene glycol diacetate (EGDA) |
Non-Patent Citations (3)
| Title |
|---|
| 《针织工程手册》编委会编: "《针织工程手册-染整分册》", 28 February 1995, 中国纺织出版社 * |
| 李永光等: "强酸性阳离子交换树脂催化剂在酯化反应中的应用", 《日用化学工业》 * |
| 杨辉荣等: "羧酸酯催化合成的新方法", 《精细化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298837A (en) * | 2020-03-16 | 2020-06-19 | 江苏国立化工科技有限公司 | Preparation method of modified solid acid catalyst with hydrocarbon resin as carrier |
| CN114409537A (en) * | 2022-03-28 | 2022-04-29 | 山东新和成药业有限公司 | Preparation method of acetate compound and catalyst adopted by preparation method |
| CN114409537B (en) * | 2022-03-28 | 2022-05-31 | 山东新和成药业有限公司 | Preparation method of acetate compound and catalyst adopted by preparation method |
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Application publication date: 20161123 |