CN1100614C - Solid catalyst for synthesizing glycol monoether acetate - Google Patents
Solid catalyst for synthesizing glycol monoether acetate Download PDFInfo
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- CN1100614C CN1100614C CN98114195A CN98114195A CN1100614C CN 1100614 C CN1100614 C CN 1100614C CN 98114195 A CN98114195 A CN 98114195A CN 98114195 A CN98114195 A CN 98114195A CN 1100614 C CN1100614 C CN 1100614C
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- acetate
- catalyst
- titanium
- ether
- diethylene glycol
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Abstract
The present invention relates to a solid catalyst for synthesizing glycol monoether acetic ester. The catalyst is composed of 20 to 50 wt% of active substance and 50 to 80 wt% of carrier, wherein the active substance adopts titanium salt, such as titanium sulfate, titanium tetrachloride or titanium nitrate, and the carrier adopts silicon dioxide, hydrogen type ZSM-5, activated clay or diatomite. The present invention inhibits the occurrence of side reaction during the process of the production, improves the selectivity of a target product, shortens production period and reduces investment of production equipment. At the same time, the problems of corrosion of production equipment, environment pollution, high energy consumption of production, etc. are avoided.
Description
The present invention relates to a kind of esterification solid catalyst, particularly relate to the titanium base solid 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 94～99%, but also there is 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 titanium base solid 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 present invention is to provide a kind of titanium base solid catalyst, it basic composition is:
Titanium sulfate (or titanium tetrachloride, Titanium Nitrate) 20～50% (wt)
Silica 50～80% (wt)
Or Hydrogen ZSM-5 50～80% (wt)
Or atlapulgite 50～80% (wt)
Or diatomite 50～80% (wt)
Main component Ti (SO for example wherein
4)
2, in course of reaction, can form stronger B acid site, esterification there is apparent catalytic action, other component is a co-catalyst, plays synergy in course of reaction.
This catalyst preferred weight percent is as follows:
Titanium sulfate (or titanium tetrachloride, Titanium Nitrate) 40～50% (wt)
Silica 50～60% (wt)
Or Hydrogen ZSM-5 50～60% (wt)
Or atlapulgite 50～60% (wt)
Or diatomite 50～60% (wt)
More than each constituent can select chemical pure medicine for use, the Preparation of catalysts method is: with titanium sulfate (or titanium salts such as titanium tetrachloride, Titanium Nitrate) is raw material, earlier titanium salt is dissolved in the distilled water, add carrier silica (or Hydrogen ZSM-5 or atlapulgite or diatomite) crystallization, dry its surface moisture in proportion, in 100 ℃～500 ℃ vacuum drying or roasting 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid catalyst.
Use this catalyst to carry out glycol monoether acetate and the synthetic reaction condition of 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, balance is moved to target product, catalyst consumption is 1.5%～6.5% of an acetate weight, 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.
Titanium base solid 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), reaches the effect of sulfuric acid as esterification catalyst, and has following remarkable result:
(1) this catalyst is 100% to the selectivity of target product;
(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 (weight ratio):
90 parts of acetate
76 parts of EGMEs
18 parts of benzene
3.8 parts of catalyst
Wherein Preparation of catalysts is as follows:
Earlier with 4 parts of Ti (SO
4)
2Be dissolved in 50 parts of distilled water, add 4 parts of carrier Hydrogen ZSM-5 (SiO
2/ Al
2O
3=25) in 373K crystallization, dry its surface moisture, in 200 ℃ of vacuum drying or roasting 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid 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%, target product selectivity 100%.
Embodiment 2
Reaction mass is formed (weight ratio):
36 parts of acetate
45 parts of ethylene glycol ethyl ethers
18 parts of benzene
1 part of catalyst
Wherein Preparation of catalysts is as follows:
Earlier with 4 parts of Ti (Cl
4)
2Be dissolved in 50 parts of distilled water, add 4 parts of carrier silica (the A-200 Fumed Silica that vapor phase method is produced) in 373K crystallization, dry its surface moisture, in 200 ℃ of vacuum drying or roasting 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid 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 99.2%, target product selectivity 100%.
Embodiment 3
Reaction mass is formed (weight ratio):
36 parts of acetate
59 parts of ethylene glycol ethyl ethers
18 parts of benzene
3 parts of catalyst
Wherein Preparation of catalysts is as follows:
Earlier with 4 parts of Ti (NO
3)
4Be dissolved in 50 parts of distilled water, add 4 parts of carrier Hydrogen ZSM-5 (SiO
2/ Al
2O
3=38) in 373K crystallization, dry its surface moisture, in 200 ℃ of vacuum drying or roasting 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid 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 99.2%, target product selectivity 100%.
Embodiment 4
Reaction mass is formed (weight ratio):
96 parts of acetate
120 parts of diethylene glycol ethers
12 parts of benzene
3.8 parts of catalyst
Wherein Preparation of catalysts is as follows:
Earlier with 4 parts of Ti (SO
4)
2Be dissolved in 50 parts of distilled water, add 6 parts of carrier Hydrogen ZSM-5 (SiO
2/ Al
2O
3=50) in 373K crystallization, dry its surface moisture, in 250 ℃ of vacuum drying or roasting 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid 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 96.5%, target product selectivity 100%.
Embodiment 5
Reaction mass is formed (weight ratio):
36 parts of acetate
67 parts of diethylene glycol ethers
18 parts of benzene
2 parts of catalyst
Wherein Preparation of catalysts is as follows:
Earlier with 4 parts of Ti (SO
4)
2Be dissolved in 50 parts of distilled water, add 4 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 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid 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 97.2%, target product selectivity 100%.
Embodiment 6
Reaction mass is formed (weight ratio):
36 parts of acetate
81 parts of diethylene glycol ethers
18 parts of benzene
2 parts of catalyst
Wherein Preparation of catalysts is as follows:
Earlier with 4 parts of TiCl
4Be dissolved in 50 parts of distilled water, add 6 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 1～3 hour, be cooled to room temperature, formed solid particulate thing crushing screening to 200 order promptly forms the titanium base solid 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 95.2%, target product selectivity 100%.
Claims (4)
1. ethylene glycol series monoether acetate solid catalyst for synthesizing, it is characterized in that this catalyst is made up of active material and carrier, active material is the titanium salt that is selected from titanium sulfate, titanium tetrachloride or Titanium Nitrate, and carrier is silica, Hydrogen ZSM-5, atlapulgite or diatomite; Weight percentage is active material 20-50%, carrier 50-80%.
2. according to the described ethylene glycol series monoether acetate of claim 1 solid catalyst for synthesizing, it is characterized in that active material 40-50%, carrier 50-60%.
3. the described Preparation of catalysts method of claim 1 is characterized in that titanium salt is dissolved in the distilled water, adds carrier in proportion, crystallization, drying, and at 100-500 ℃ of vacuum baking 1-3 hour, cool to room temperature promptly got product.
4. the purposes of the described catalyst of claim 1, it is applicable to following reaction:
With EGME and acetate is raw material, the synthesizing glycol methyl ether acetate;
With ethylene glycol ethyl ether and acetate is raw material, synthesizing glycol ether acetic acid esters;
With butyl glycol ether and acetate is raw material, the synthesizing butyl cellosolve acetic acid esters;
With diethylene glycol dimethyl ether and acetate is raw material, synthetic diethylene glycol dimethyl ether acetic acid esters;
With diethylene glycol ether and acetate is raw material, synthetic diethylene glycol ether acetic acid esters;
With diethylene glycol butyl ether and acetate is raw material, synthetic diethylene glycol butyl ether acetic acid esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114195A CN1100614C (en) | 1998-07-29 | 1998-07-29 | Solid catalyst for synthesizing glycol monoether acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114195A CN1100614C (en) | 1998-07-29 | 1998-07-29 | Solid catalyst for synthesizing glycol monoether acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243036A CN1243036A (en) | 2000-02-02 |
| CN1100614C true CN1100614C (en) | 2003-02-05 |
Family
ID=5223870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114195A Expired - Fee Related CN1100614C (en) | 1998-07-29 | 1998-07-29 | Solid catalyst for synthesizing glycol monoether acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1100614C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654354B (en) * | 2009-08-28 | 2011-09-21 | 北京中煤矿山工程有限公司 | Soluble glass slurry taking water-soluble ester as curing agent |
| CN101654355B (en) * | 2009-08-28 | 2011-09-21 | 北京中煤矿山工程有限公司 | Chemical soluble glass slurry for reinforcing and preventing leakage |
| CN101654614B (en) * | 2009-08-28 | 2011-09-21 | 北京中煤矿山工程有限公司 | Water glass slurry for grouting on mine working surface |
| CN102059131A (en) * | 2010-12-14 | 2011-05-18 | 华东理工大学 | Novel titanium salt catalyst and catalytic esterification reaction thereof |
| CN102775301B (en) * | 2012-08-06 | 2015-07-22 | 南京林业大学 | Method for synthesizing aliphatic dibasic acid alkoxy ethyl ester by using ZSM-5 molecular sieve to catalyze |
| CN105646221A (en) * | 2014-11-14 | 2016-06-08 | 辽宁奥克化学股份有限公司 | A preparing method of 2-butoxyethyl acetate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU662540A1 (en) * | 1978-01-09 | 1979-05-15 | Уфимский Нефтяной Институт | Method of obtaining 1,3-dichlorpropenes |
| SU1245564A1 (en) * | 1982-06-24 | 1986-07-23 | Ордена Трудового Красного Знамени Институт Нефтехимических Процессов Им.Ю.Г.Мамедалиева | Method of producing secondary butylbenzol |
| CN1039418A (en) * | 1988-06-08 | 1990-02-07 | 国际壳牌研究有限公司 | A kind of preparation method of oxirane compound |
| CN1128749A (en) * | 1995-02-07 | 1996-08-14 | 胜一化工股份有限公司 | Propanediol monoalkyl ether ester compound and prepn. method thereof |
-
1998
- 1998-07-29 CN CN98114195A patent/CN1100614C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU662540A1 (en) * | 1978-01-09 | 1979-05-15 | Уфимский Нефтяной Институт | Method of obtaining 1,3-dichlorpropenes |
| SU1245564A1 (en) * | 1982-06-24 | 1986-07-23 | Ордена Трудового Красного Знамени Институт Нефтехимических Процессов Им.Ю.Г.Мамедалиева | Method of producing secondary butylbenzol |
| CN1039418A (en) * | 1988-06-08 | 1990-02-07 | 国际壳牌研究有限公司 | A kind of preparation method of oxirane compound |
| CN1128749A (en) * | 1995-02-07 | 1996-08-14 | 胜一化工股份有限公司 | Propanediol monoalkyl ether ester compound and prepn. method thereof |
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| Publication number | Publication date |
|---|---|
| CN1243036A (en) | 2000-02-02 |
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