CN1265940A - Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate - Google Patents
Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate Download PDFInfo
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- CN1265940A CN1265940A CN 99112715 CN99112715A CN1265940A CN 1265940 A CN1265940 A CN 1265940A CN 99112715 CN99112715 CN 99112715 CN 99112715 A CN99112715 A CN 99112715A CN 1265940 A CN1265940 A CN 1265940A
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Abstract
The supported type heteropolyacid catalyst in glycol series monoether acetate synthesis is characterized by that said catalyst is composed of porous carrier supported heteropolyacid, and the heteropolyacid is selected from one or several kinds of phosphato-tungstic acid, phosphomolybdic acid, silicotungstic acid and silicon-molybdic acid, it is 20-60% of total mass of said catalyst, the porous carrier is selected from one of silica gel, silicon dioxide produced by gas phase method, hydrogen type ZSM-5 molecular sieve, active carbon, active clay, diatomite and titanium dioxide. Said invention can inhibit production of side reaction in the course of production, raise selectivity of target product, shorten production period, reduce investment of production equipment, at the same time can prevent corrosion of production equipment, reduce environmental pollution and reduce energy consumption.
Description
The present invention relates to a kind of catalyst for esterification reaction, particularly relate to the carried heteropoly acid catalyst in a kind of glycol monoether acetate and the diethylene glycol monoether acetate synthetic reaction.
At present, producing glycol monoether acetate and diethylene glycol monoether acetate both at home and abroad all adopts sulfuric acid as esterification catalyst, although this kind reaction system has higher reaction conversion ratio, auxiliary agent chemical plant, Yixing, Jiangsu as the domestic production ethyl cellosolve acetate adopts sulfuric acid as esterification catalyst exactly, its reaction conversion ratio is 94～99%, but also has following problem:
(1) because dehydration, esterification and the oxidation of sulfuric acid cause a series of side reactions in the process of esterification.The existence of small amounts of ether, sulfuric ester, unsaturated compound and carbonyls is arranged in the post reaction mixture, and target product selectivity 95～98% has caused the refining of product and has reclaimed the difficulty of unreacting material;
(2) post processing of product will cause reaction process complexity, the generation three wastes, product to run off through alkali neutralization, washing to remove the sulfuric acid as catalyst;
(3) sulfuric acid severe corrosion equipment causes the equipment regular update, and production cost improves;
(4) owing to use sulfuric acid, it is improper to use in the operation, endangers personal safety easily;
(5) environmental pollution is arranged;
(6) energy consumption height.
The objective of the invention is to select a kind of carried heteropoly acid catalyst, esterification catalyst as a kind of glycol monoether acetate and diethylene glycol monoether acetate in synthetic, the side reaction that suppresses in the production process takes place, improve target product selectivity, shorten the production cycle, reduce investment of production equipment, avoid producing problems such as the environmental pollution of production equipment burn into, energy consumption height simultaneously.
The invention provides the carried heteropoly acid catalyst of a kind of ethylene glycol series monoether acetate in synthetic, it is characterized in that: this catalyst is made up of the porous carrier carried heteropoly acid, heteropoly acid is selected from one or more of phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, accounts for 20～60% of catalyst gross mass; Porous carrier is selected from a kind of of silica that silicic acid glue, vapor phase method produces, Hydrogen ZSM-5 molecular sieve, active carbon, atlapulgite, diatomite, titanium dioxide.
Main component phosphotungstic acid for example wherein, in course of reaction, can form stronger B acid site, but because of its specific area very little, the surface acid amount seldom, reactant can not enter its body phase preferably, reactivity is less, find after deliberation, utilize heteropoly acid in water, to have the characteristics of fine solubility, can be loaded by heteropoly acid in porous (as silica gel, the silica that vapor phase method is produced, Hydrogen ZSM-5 equimolecular sieve, active carbon, atlapulgite, diatomite etc.) on the carrier, utilize the high-specific surface area of porous carrier, make the more carried heteropoly acid catalyst of surface acid amount.Studies show that they have significant catalytic action to esterification, in course of reaction, play collaborative co-catalyst effect.
The heavy percentage of the preferred matter of this catalyst is as follows:
Phosphotungstic acid (or phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid) 40～50%
Silica gel 50～60%
Or the silica 50～60% of vapor phase method production
Or Hydrogen ZSM-5 equimolecular sieve 50～60%
Or active carbon 50～60%
Or atlapulgite 50～60%
Or diatomite 50～60%
Or titanium dioxide 50～60%
More than each constituent can select chemical pure medicine for use, the Preparation of catalysts method is: with phosphotungstic acid (or phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid) is raw material, earlier phosphotungstic acid is dissolved in the distilled water, add carrier (silica of producing as silica gel, vapor phase method, Hydrogen ZSM-5 equimolecular sieve, active carbon, atlapulgite, diatomite, titanium dioxide etc.) crystallization, dry its surface moisture in proportion, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid catalyst.
It is as follows to use this catalyst to carry out the synthetic reaction condition control of glycol monoether acetate and diethylene glycol monoether acetate:
A. material ratio:
The mol ratio of acetate and ethylene glycol mono-ether or diethylene glycol monoether is 1.1～1.8, is preferably 1.1～1.5; Acetate is 0.15～0.3 with the mol ratio of band aqua, be preferably 0.20～0.25, the band aqua can be one or more in benzene,toluene,xylene, benzinum, butyl oxide, n-butyl acetate, carbon tetrachloride, n-hexane or the cyclohexane, the effect of band aqua is to take reactants water out of reaction system, and balance is moved to target product; Catalyst consumption is 1.5%～6.5% of a quality of acetic acid, is preferably 3.5%～4.5%.
B. reaction process process:
The catalyst and the reaction mass that prepare are once added in the conventional esterification container according to material ratio given among the above-mentioned A, be heated to 110～150 ℃ of reaction temperatures, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.
Catalyst provided by the invention can be used for following reaction:
1. be raw material with EGME and acetate, the synthesizing glycol methyl ether acetate;
2. be raw material with ethylene glycol ethyl ether and acetate, synthesizing glycol ether acetic acid esters;
3. be raw material with butyl glycol ether and acetate, the synthesizing butyl cellosolve acetic acid esters;
4. be raw material with diethylene glycol dimethyl ether and acetate, synthetic diethylene glycol dimethyl ether acetic acid esters;
5. be raw material with diethylene glycol ether and acetate, synthetic diethylene glycol ether acetic acid esters;
6. be raw material with diethylene glycol butyl ether and acetate, synthetic diethylene glycol butyl ether acetic acid esters.
Carried heteropoly acid catalyst provided by the present invention is 95～99.5% to the conversion ratio of synthetic glycol monoether acetate and diethylene glycol monoether acetate (being target product), reach the effect of sulfuric acid, and have following remarkable result as esterification catalyst:
(1) this catalyst to the selectivity of target product near 100%;
(2) adopt this catalyst to simplify production technology, the production cycle is no more than 1.5 hours;
(3) adopt this catalyst can reduce with sulfuric acid and make equipment such as the set alkali neutralization of catalyst, washing, shortened process is saved equipment investment 50%;
(4) adopt this catalyst that production equipment is not had corrosiveness;
(5) adopt this catalyst to carry out esterification non-wastewater discharge, non-environmental-pollution;
(6) adopt the reaction of this catalyst institute catalysis to can save energy 40%.
Embodiment 1
Reaction mass is formed (mass ratio):
90 parts of acetate
76 parts of EGMEs
18 parts of benzene
2 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier 3 parts of phosphotungstic acids are dissolved in 25 parts of distilled water, add 5 parts of carrier Hydrogen ZSM-5 (SiO
2/ Al
2O
3=38) in 373 K crystallization, dry its surface moisture, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid catalyst.
Various materials are added in the conventional esterification container, be heated to 107～125 ℃ of reaction temperatures, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.Reaction conversion ratio is 99.5%, and target product selectivity is near 100%.
Embodiment 2
Reaction mass is formed (mass ratio):
36 parts of acetate
45 parts of ethylene glycol ethyl ethers
18 parts of benzene
2 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier 1 part of phosphomolybdic acid is dissolved in 25 parts of distilled water, add 2 parts of carrier silica (the A-200 Fumed Silica that vapor phase method is produced) in 373K crystallization, dry its surface moisture, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid catalyst.
Various materials are added in the conventional esterification container, be heated to 115～140 ℃ of reaction temperatures, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.Reaction conversion ratio is 98.2%, and target product selectivity is near 100%.
Embodiment 3
Reaction mass is formed (mass ratio):
36 parts of acetate
59 parts of butyl glycol ethers
18 parts of benzene
3 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier 3 parts of silicomolybdic acid are dissolved in 25 parts of distilled water, add 5 parts of carrier Hydrogen ZSM-5 (SiO
2/ Al
2O
3=38) in 373K crystallization, dry its surface moisture, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid catalyst.
Various materials are added in the conventional esterification container, be heated to 125～160 ℃ of reaction temperatures, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.Reaction conversion ratio is 97.2%, and target product selectivity is near 100%.
Embodiment 4
Reaction mass is formed (mass ratio):
90 parts of acetate
120 parts of diethylene glycol dimethyl ethers
28 parts of benzene
3.8 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier 1 part of phosphotungstic acid is dissolved in 25 parts of distilled water, adds 5 parts of carrier Hydrogen ZSM-5 (SiO
2/ Al
2O
3=50) in 373K crystallization, dry its surface moisture, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid catalyst.
Various materials are added in the conventional esterification container, be heated to reaction temperature, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.Reaction conversion ratio is 96.5%, and target product selectivity is near 100%.
Embodiment 5
Reaction mass is formed (mass ratio):
36 parts of acetate
67 parts of diethylene glycol ethers
18 parts of benzene
3 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier 1 part of phosphotungstic acid is dissolved in 25 parts of distilled water, add 5 parts of carrier atlapulgites (through what make with extra care) in 373K crystallization, dry its surface moisture, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid catalyst.
Various materials are added in the conventional esterification container, be heated to reaction temperature, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.Reaction conversion ratio is 97.2%, and target product selectivity is near 100%.
Embodiment 6
Reaction mass is formed (mass ratio):
36 parts of acetate
81 parts of diethylene glycol butyl ether
18 parts of benzene
3 parts of catalyst
Wherein the Preparation of catalysts method is seen the invention main points.
Earlier 2 parts of silico-tungstic acids and 2 parts of phosphotungstic acids are dissolved in 3.6 parts of distilled water, add 17 fens butyl titanates, stir, in 373K crystallization, dry its surface moisture, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, formed solid particulate thing is pulverized, and promptly forms carried heteropoly acid [PW
12+ SiW
12]/TiO
2Catalyst, this catalyst has certain service life.
Various materials are added in the conventional esterification container, be heated to reaction temperature, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.Reaction conversion ratio is 95.2%, target product selectivity 100%.
Claims (4)
1. the carried heteropoly acid catalyst during an ethylene glycol series monoether acetate synthesizes, it is characterized in that: this catalyst is made up of the porous carrier carried heteropoly acid, heteropoly acid is selected from one or more of phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, accounts for 20～60% of catalyst gross mass; Porous carrier is selected from a kind of of silica that silicic acid glue, vapor phase method produces, Hydrogen ZSM-5 molecular sieve, active carbon, atlapulgite, diatomite, titanium dioxide.
2. the carried heteropoly acid catalyst in synthesizing according to the described ethylene glycol series monoether acetate of claim 1, it is characterized in that: the content of active component heteropoly acid is 40～50% weight.
3. the preparation method of the carried heteropoly acid catalyst during the described ethylene glycol series monoether acetate of claim 1 synthesizes, it is characterized in that: each component is mixed in proportion, in 100 ℃～500 ℃ vacuum drying or roasting 1～4 hour, be cooled to room temperature, the solid particulate thing that forms pulverize and promptly to get catalyst.
4. the application of the described catalyst of claim 1 in glycol monoether acetate and diethylene glycol monoether acetate synthetic reaction is characterized in that: reaction condition control is as follows:
A. material ratio
The mol ratio of acetate and ethylene glycol mono-ether or diethylene glycol monoether is 1.1～1.8, and acetate is 0.15～0.3 with the mol ratio of band aqua, and catalyst consumption is 1.5%～6.5% of a quality of acetic acid;
B. reaction process process
The catalyst and the reaction mass that prepare are once added in the conventional esterification container according to material ratio given among the above-mentioned A, be heated to 110～150 ℃ of reaction temperatures, after question response carried out 1 hour, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112715A CN1120049C (en) | 1999-03-03 | 1999-03-03 | Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112715A CN1120049C (en) | 1999-03-03 | 1999-03-03 | Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate |
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| Publication Number | Publication Date |
|---|---|
| CN1265940A true CN1265940A (en) | 2000-09-13 |
| CN1120049C CN1120049C (en) | 2003-09-03 |
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|---|---|---|---|
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Cited By (6)
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|---|---|---|---|---|
| CN100441495C (en) * | 2003-12-19 | 2008-12-10 | 华东师范大学 | Silicon gel coated poly metal oxygen-containing cluster compound nano particle material and its preparing method |
| CN103691484A (en) * | 2013-12-17 | 2014-04-02 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN104190468A (en) * | 2014-08-04 | 2014-12-10 | 南京师范大学 | Catalyst for synthesizing high-monoester-content methacrylate hydroxyethyl phosphate, preparation method of catalyst and catalytic synthesis process thereof |
| CN109265340A (en) * | 2018-11-19 | 2019-01-25 | 深圳市前海博扬研究院有限公司 | A kind of glycol ChanShuDing ether carboxylate and preparation method thereof |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919255A (en) * | 1972-11-03 | 1975-11-11 | Eastman Kodak Co | Production of 2,2-disubstituted propiolactones |
| US5189201A (en) * | 1992-03-25 | 1993-02-23 | Showa Denko K.K. | Process for preparation of lower fatty acid ester |
| US5300703A (en) * | 1993-04-05 | 1994-04-05 | Texaco Chemical Company | Alkylphenol synthesis using heteropoly acid catalysts |
| US5488178A (en) * | 1995-03-08 | 1996-01-30 | Texaco Chemical Inc. | Ditertiary butyl peroxide preparation from tertiary butyl hydroperoxide |
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1999
- 1999-03-03 CN CN99112715A patent/CN1120049C/en not_active Expired - Fee Related
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| CN100441495C (en) * | 2003-12-19 | 2008-12-10 | 华东师范大学 | Silicon gel coated poly metal oxygen-containing cluster compound nano particle material and its preparing method |
| CN103691484A (en) * | 2013-12-17 | 2014-04-02 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN104190468A (en) * | 2014-08-04 | 2014-12-10 | 南京师范大学 | Catalyst for synthesizing high-monoester-content methacrylate hydroxyethyl phosphate, preparation method of catalyst and catalytic synthesis process thereof |
| CN104190468B (en) * | 2014-08-04 | 2016-08-24 | 南京师范大学 | A kind of catalyst, preparation method and catalysis synthesizing technology thereof for the synthesis of high monoester content hydroxy ethyl phosphate |
| CN109265340A (en) * | 2018-11-19 | 2019-01-25 | 深圳市前海博扬研究院有限公司 | A kind of glycol ChanShuDing ether carboxylate and preparation method thereof |
| CN110938207A (en) * | 2019-12-10 | 2020-03-31 | 烟台开发区金宏化工有限公司 | Preparation method of hydrogen-containing silicone oil |
| CN110938207B (en) * | 2019-12-10 | 2022-02-22 | 烟台开发区金宏化工有限公司 | Preparation method of hydrogen-containing silicone oil |
| CN115582115A (en) * | 2022-10-18 | 2023-01-10 | 陕西煤业化工技术研究院有限责任公司 | Catalyst, device and method for preparing methyl o-methylbenzoate |
| CN115582115B (en) * | 2022-10-18 | 2024-03-01 | 陕西煤业化工技术研究院有限责任公司 | Catalyst, device and method for preparing methyl o-methylbenzoate |
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