CN1097654A - Cerium base solid catalyst during glycol series monoether acetate is synthetic - Google Patents
Cerium base solid catalyst during glycol series monoether acetate is synthetic Download PDFInfo
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- CN1097654A CN1097654A CN 94105066 CN94105066A CN1097654A CN 1097654 A CN1097654 A CN 1097654A CN 94105066 CN94105066 CN 94105066 CN 94105066 A CN94105066 A CN 94105066A CN 1097654 A CN1097654 A CN 1097654A
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Abstract
The present invention is a kind of glycol monoether acetate and synthetic cerium salt solid catalyst of diethylene glycol monoether acetic ether of being used for.It basic composition is cerous sulfate, ferrous sulfate, cobaltous sulfate, nickelous sulfate, is to be formed through mixing, calcining, crushing screening by above-mentioned substance.It is synthetic to carry out glycol monoether acetate and diethylene glycol monoether acetic ether with catalyst provided by the invention, use sulfuric acid to compare with tradition, can improve target product selectivity to 100%, simplify production technology, shorten the production cycle and be no more than 4 hours, save equipment investment, save energy consumption, equipment is not had the burn into environmentally safe as catalyst.
Description
The present invention relates to a kind of esterification solid catalyst, particularly relate to a kind of glycol monoether acetate and the diethylene glycol monoether acetic ether cerium base solid catalyst in synthetic.
At present, producing glycol monoether acetate and diethylene glycol monoether acetic ether 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 domestic unique production ethylene glycol monoethyl ether acetate adopts sulfuric acid as esterification catalyst exactly, its reaction conversion ratio is 94～99%, but also has following problem:
(1), have side reaction to take place in producing, target product selectivity is 95～98%;
(2), complex manufacturing (needing alkali neutralization, washing etc.), the production cycle reaches 24 hours;
(3), investment of production equipment volume height;
(4), catalyst sulfuric acid corrosion production equipment;
(5), environmental pollution is arranged;
(6), energy consumption height.
The objective of the invention is to select a kind of cerium base solid catalyst, as glycol monoether acetate and the synthetic esterification catalyst of diethylene glycol monoether acetic ether, 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.
Main points of the present invention: the present invention is to provide a kind of cerium base solid catalyst, its basic composition and percentage by weight are:
Cerous sulfate: 50～90%(wt)
Ferrous sulfate: 5～25%(wt)
Cobaltous sulfate: 3～15%(wt)
Nickelous sulfate: 2～10%(wt)
Wherein the Main Ingredients and Appearance cerous sulfate can form stronger B acid site in course of reaction, and esterification is had obvious catalysis, and other component is a co-catalyst, plays synergy in course of reaction.
This catalyst preferred weight percent is as follows:
Cerous sulfate: 60～80%(wt)
Ferrous sulfate: 10～20%(wt)
Cobaltous sulfate: 5～12%(wt)
Nickelous sulfate: 5～8%(wt)
More than each composition can select chemical pure crystalloid medicine for use, the Preparation of catalysts method is: mechanical mixture is even in proportion with above-mentioned each catalytic component, calcining is 24 hours under 500 ℃ of conditions, be cooled to room temperature, formed solid particulate thing is pulverized back 0.12～0.15mm and is sieved, and promptly forms 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 acetic ether:
A, material ratio:
The mol ratio of acetic acid and ethylene glycol mono-ether or diethylene glycol monoether is 1.5～2.5, is preferably 1.8～2.2;
Acetic acid is 0.1～0.3 with the mol ratio of band aqua, is preferably 0.15～0.25, and the band aqua can be one or more in normal hexane, carbon tetrachloride, benzene, toluene or the dimethylbenzene.The effect of band aqua is to take reaction product water out of reaction system, and balance is moved to target product.
Catalyst consumption is 1.5%～6.5% of an acetic acid 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 3.5 hours, 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 glycol monoethyl ether and acetic acid, the synthesizing glycol monomethyl ether acetate;
2, be raw material with ethylene glycol monoethyl ether and acetic acid, synthesizing glycol list ethyl ether acetate ester;
3, be raw material with ethylene glycol monobutyl ether and acetic acid, synthesizing glycol monobutyl ether acetate ester;
4, be raw material with diethylene glycol monomethyl ether and acetic acid, synthetic diethylene glycol monomethyl ether acetate;
5, be raw material with diethylene glycol monoethyl ether and acetic acid, synthetic diethylene glycol ether acetate alone;
6, be raw material with diethylene glycol monobutyl ether and acetic acid, synthetic diethylene glycol monobutyl ether acetate;
Cerium base solid catalyst provided by the present invention is 95～99% to the conversion ratio of synthetic glycol monoether acetate and diethylene glycol monoether acetic ether (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 4 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) this catalyst does not have corrosiveness to production equipment;
5) esterification that adopts this catalyst to carry out does not have factory effluent discharging, non-environmental-pollution;
6) reaction of this catalyst institute catalysis can be saved energy consumption 30%.
Embodiment 1:
Reaction mass is formed (weight portion):
90 parts of acetic acid
76 parts of glycol monoethyl ethers
18 parts of benzene
1.5 parts of catalyst
Wherein catalyst consists of: cerous sulfate 80%(wt), ferrous sulfate 10%(wt), cobaltous sulfate 5%(wt), nickelous sulfate 5%(wt).
The Preparation of catalysts method is seen the invention main points.
Various materials are added in the reaction vessel, be heated to 110 ℃ of reaction temperatures, along with the carrying out of course of reaction, be warming up to 150 ℃ gradually, reaction was carried out 2.5 hours, will react the synthetic mixture filtering recovering catalyst then, and filtrate rectifying is promptly got product.Reaction conversion ratio is 98%, target product selectivity 100%.
Actual example 2:
Reaction mass is formed:
90 parts of acetic acid
90 parts of ethylene glycol monoethyl ethers
18 parts of benzene
1.5 parts of catalyst
Wherein catalyst consists of: cerous sulfate 60%(wt), ferrous sulfate 20%(wt), cobaltous sulfate 12%(wt), nickelous sulfate 8%(wt).
Various materials are added in the reaction vessel, be heated to reaction temperature reaction 2.5 hours, will react the synthetic mixture filtering recovering catalyst then, filtrate rectifying is promptly got product.Reaction conversion ratio 99%, target product selectivity 100%.
Actual example 3:
Reaction mass is formed:
90 parts of acetic acid
120 parts of ethylene glycol monobutyl ethers
18 parts of benzene
3 parts of catalyst
Wherein catalyst consists of: cerous sulfate 70%(wt), ferrous sulfate 15%(wt), cobaltous sulfate 10%(wt), nickelous sulfate 5%(wt).
Various materials are added in the reaction vessel, be heated to reaction temperature reaction 3.0 hours, will react the synthetic mixture filtering recovering catalyst then, filtrate rectifying is promptly got product.Reaction conversion ratio 96%, target product selectivity 100%.
Actual example 4:
Reaction mass is formed:
90 parts of acetic acid
120 parts of diethylene glycol monomethyl ethers
22 parts of toluene
3 parts of catalyst
Wherein catalyst consists of: cerous sulfate 73%(wt), ferrous sulfate 12%(wt), cobaltous sulfate 8%(wt), nickelous sulfate 7%(wt).
Various materials are added in the reaction vessel, be heated to reaction temperature reaction 3.5 hours, will react the synthetic mixture filtering recovering catalyst then, filtrate rectifying is promptly got product.Reaction conversion ratio 96%, target product selectivity 100%.
Actual example 5:
Reaction mass is formed:
90 parts of acetic acid
134 parts of ethylene glycol monoethyl ethers
22 parts of toluene
3 parts of catalyst
Wherein catalyst consists of: cerous sulfate 65%(wt), ferrous sulfate 18%(wt), cobaltous sulfate 11%(wt), nickelous sulfate 6%(wt).
Various materials are added in the reaction vessel, be heated to reaction temperature reaction 3.5 hours, will react the synthetic mixture filtering recovering catalyst then, filtrate rectifying is promptly got product.Reaction conversion ratio 97%, target product selectivity 100%.
Actual example 6:
Reaction mass is formed:
90 parts of acetic acid
162 parts of ethylene glycol monobutyl ethers
22 parts of toluene
3 parts of catalyst
Wherein catalyst consists of: cerous sulfate 72%(wt), ferrous sulfate 16%(wt), cobaltous sulfate 7%(wt), nickelous sulfate 5%(wt).
Various materials are added in the reaction vessel, be heated to reaction temperature reaction 3.5 hours, will react the synthetic mixture filtering recovering catalyst then, filtrate rectifying is promptly got product.Reaction conversion ratio 95%, target product selectivity 100%.
Claims (4)
1, a kind of glycol monoether acetate and synthetic catalyst of diethylene glycol monoether acetic ether of being used for is characterized in that it being a kind of cerium base solid catalyst, its basic composition and percentage by weight:
Cerous sulfate: 50～90% (wt)
Ferrous sulfate: 5～25% (wt)
Cobaltous sulfate: 3～15% (wt)
Nickelous sulfate: 2～10% (wt).
2, catalyst according to claim 1 is characterized in that, this method for preparing catalyst is:
Mechanical mixture is even in proportion with described each catalytic component of claim 1, and calcining is 24 hours under 500 ℃ of conditions, is cooled to room temperature, and after formed solid particulate thing was pulverized, 0.12～0.15mm sieved, and promptly forms catalyst.
3, catalyst according to claim 1 is characterized in that, percentage by weight is:
Cerous sulfate: 60～80%(wt)
Ferrous sulfate: 10～20%(wt)
Cobaltous sulfate: 5～12%(wt)
Nickelous sulfate: 5～8%(wt).
4, use the described catalyst of claim 1 to carry out glycol monoether acetate and diethylene glycol monoether acetic ether synthetic reaction, it is characterized in that, reaction condition control is as follows:
A, material ratio:
The mol ratio of acetic acid and ethylene glycol mono-ether or diethylene glycol monoether is 1.5～2.5, is preferably 1.8～2.2;
Acetic acid is 0.1～0.3 with the mol ratio of band aqua, is preferably 0.15～0.25;
Catalyst consumption is 1.5%～6.5% of an acetic acid 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 3.5 hours, the mixture filtering recovering catalyst with in the container promptly got product with filtrate rectifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94105066 CN1048653C (en) | 1994-05-16 | 1994-05-16 | Cerium base solid catalyst in synthesizing glycol series monoether acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94105066 CN1048653C (en) | 1994-05-16 | 1994-05-16 | Cerium base solid catalyst in synthesizing glycol series monoether acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1097654A true CN1097654A (en) | 1995-01-25 |
| CN1048653C CN1048653C (en) | 2000-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94105066 Expired - Fee Related CN1048653C (en) | 1994-05-16 | 1994-05-16 | Cerium base solid catalyst in synthesizing glycol series monoether acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048653C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061901C (en) * | 1997-03-12 | 2001-02-14 | 厦门大学 | Supported solid-acid catalyst for producing butyl acetic ether |
| CN1079283C (en) * | 1998-11-13 | 2002-02-20 | 北京化工大学 | Load type laminated zirconium sulfate catalyst and its application in preparation of aliphatic alcohol ether acetate |
-
1994
- 1994-05-16 CN CN 94105066 patent/CN1048653C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061901C (en) * | 1997-03-12 | 2001-02-14 | 厦门大学 | Supported solid-acid catalyst for producing butyl acetic ether |
| CN1079283C (en) * | 1998-11-13 | 2002-02-20 | 北京化工大学 | Load type laminated zirconium sulfate catalyst and its application in preparation of aliphatic alcohol ether acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1048653C (en) | 2000-01-26 |
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