CN100412038C - Homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method and system - Google Patents
Homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method and system Download PDFInfo
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- CN100412038C CN100412038C CNB200410086218XA CN200410086218A CN100412038C CN 100412038 C CN100412038 C CN 100412038C CN B200410086218X A CNB200410086218X A CN B200410086218XA CN 200410086218 A CN200410086218 A CN 200410086218A CN 100412038 C CN100412038 C CN 100412038C
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Abstract
The present invention relates to a continuous reaction method and a system for oxidizing alkene with a boiling point with oxydol through homogeneous catalysis. The present invention eliminates most of water (water in oxydol and water generated in reaction) in a system by utilizing the azeotropy of water and components (solvent) in reaction liquid), the epoxide yield is improved, production efficiency is improved, and serialization is realized, and gaseous alkene can be added continuously. Meanwhile, products are separated continuously, and homogeneous catalysts are not separated from the reaction system and can be recycled. The system is mainly composed of a reactor, a condenser, a rectifying tower, a water-oil separator and a vaporizer. The separation of epoxy compounds and the recovery of alkene and benzene (namely solvent) are carried out in reaction products of the reaction system, partial unreacted raw materials, generated products and water are distilled through the heat energy of reaction and the solvent (namely benzene) in reaction, and catalysts are not separated. The reaction system realizes the serialization of the process that epoxy compounds are prepared by oxidizing alkene with a boiling point with oxydol.
Description
Technical field
The present invention relates to the reactive system of a kind of low boiling point olefin with hydrogen peroxide epoxidation continuous production epoxy compounds, belonging to low boiling point olefin and hydrogen peroxide is raw material, is catalyzer with assorted many tungsten phosphates, the technology of oxidation continuous production epoxy compounds.
Background technology
Epoxy compounds is very important organic intermediate.At present, except that oxyethane can directly be produced by atmospheric oxidation ethene, the production method of the epoxy compounds of other alkene all was by indirect oxidation method, chlorohydrination or the preparation of peracid method, exists problems such as joint product and environmental pollution respectively.Hydrogen peroxide is a kind of very oxygen source of cleaning, in recent years, with the hydrogen peroxide is oxygen source, the research of catalyzing expoxidation of olefines is a lot, but because the epoxy compounds of low boiling point olefin is water-soluble bigger, is being in the oxygen source reaction system with the hydrogen peroxide therefore, all need a large amount of polar organic solvents to suppress the side effect of water, therefore, the reaction system efficiency ratio is lower, is difficult to realize industrial applications.
For realizing high-level efficiency, the serialization production of said process, at first needing provides alkene and hydrogen peroxide to reactor continuously, reaction product in the simultaneously continuous extraction reactor, and from product separating ring oxygen compound, unreacted alkene and solvent, alkene and solvent benzol are recycled, and catalyzer need not separate, can be recycled.
Summary of the invention
The object of the present invention is to provide a kind of homogeneous catalysis low boiling point olefin hydrogen peroxide continuous production reaction method, this method has catalyzer need not separate, can be recycled, the characteristics that refuse and pollutant emission are few.
Another object of the present invention is to provide a kind of system that is used to realize aforementioned production method.
In order to achieve the above object, its key step of production method provided by the invention is:
A) in 30% hydrogen peroxide of 2.0-3.0kg: the 60-70L solvent: the ratio of 250-350g catalyzer adds in the reactor, is warming up to 70-80 ℃, by the benzene in the solvent water in the hydrogen peroxide that adds is taken out of, and benzene returns reactor and proceeds reaction; Described solvent is that tributyl phosphate, tricresyl phosphate fourth are fine, hydrochloric ether, dioxane or pyridine and benzene are 1 by volume: 3-3: 1 mixture;
B) be warming up to 85-90 ℃ again, press material flow 30-33mol/h, hydrogen peroxide flow 2-2.5kg/h enters reactor; Described raw material is the alkene of boiling point≤35 ℃, as: propylene, iso-butylene, butylene, ethene or vinylchlorid;
C) epoxy of unreacted alkene, generation, water and benzene carry out rectifying, and unreacted alkene is recycled to reactor through vaporization;
D) epoxy of Sheng Chenging advances the product storage tank through condensation, and water separates back benzene and is recycled to reactor with benzene.
Provided by the inventionly be used to realize that the reactive system of aforesaid method mainly is made of reactor, condenser, rectifying tower, water-oil separator, gasifier etc.Specifically, reactive system formation of the present invention is:
Reactor is used for the catalyzed reaction of hydrogen peroxide and raw material;
First condenser, the one end is connected with reactor, accepts the benzene and the water that steam from reactor; The other end is connected with a water-oil separator, makes benzene and aqueous phase separation, and the benzene after the separation returns the reactor that is connected with first condenser, and water is discharged by water-oil separator;
Rectifying tower is connected with reactor, accepts the unreacted alkene that steams from reactor, epoxy, water and the benzene of generation; Water wherein is with after benzene separates by the water-oil separator that is connected with rectifying tower, the benzene Returning reactor, and water is discharged by water-oil separator;
Second condenser, the one end is connected with rectifying tower, accepts isolating epoxy product in the rectifying tower;
The 3rd condenser, the one end is connected with rectifying tower, accepts unreacted alkene in the rectifying tower; The other end is connected with a vaporizer, and this vaporizer is sent in the reactor after unreacted alkene is vaporized.
Wherein the working temperature of first condenser is 50 to 60 ℃.
Wherein the working temperature of second condenser is-25 to 50 ℃.
Wherein the working temperature of the 3rd condenser is-25 to 40 ℃.
Description of drawings
Fig. 1 is a production system synoptic diagram provided by the invention.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing.
Example 1, with 2.5kg concentration 30% hydrogen peroxide adds prepackage 70L solvents (tributyl phosphate and benzene mixed solvent) and 300g catalyzer through pipeline 101 reactor 1, be warming up to 80 ℃, take the water in the hydrogen peroxide that adds out of system through pipeline 104 by benzene, by first condenser 2 (temperature of this first condenser 2 is 50 ℃), enter water-oil separator 4, benzene flows back in the reactor 1 through pipeline 107.Then, be warming up to 85 ℃, the flow of control iso-butylene is 30.3mol/h, concentration is the flow 2kg/h of 30% hydrogen peroxide, enter reactor 1 through pipeline 102 and 101 respectively, the epoxy of unreacted alkene, generation, water and benzene enter rectifying tower 3 by pipeline 104, unreacted alkene from rectifying tower 3 by pipeline 108 by the 3rd condenser 2 " (this condenser temperature is controlled at 0 ℃); condensation enters vaporizer 5 through pipeline 109 and vaporizes, and gets back to reactor 1 by pipeline 103,102 then.Product methyl propylene oxide by rectifying tower 3 along pipeline 105 through second condenser 2 ' (this condenser temperature is controlled at 5 ℃), advance the product storage tank, water in the rectifying tower 3 and benzene enter water-oil separator 4 through pipeline 106, benzene wherein flows back to reactor 1 by pipeline 107.The methyl propylene oxide reaches 96.5% to the selectivity of hydrogen peroxide, and the yield of methyl propylene oxide is 89%.
Claims (6)
1. homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method, its key step is:
A) in 30% hydrogen peroxide of 2.0-3.0kg: the 60-70L solvent: the ratio of 250-350g catalyzer adds in the reactor, is warming up to 70-80 ℃, by the benzene in the solvent water in the hydrogen peroxide that adds is taken out of, and benzene returns reactor and proceeds reaction; Described solvent is that tributyl phosphate, tricresyl phosphate butyronitrile, hydrochloric ether, dioxane or pyridine and benzene are 1 by volume: 3-3: 1 mixture;
B) be warming up to 85-90 ℃ again, press material flow 30-33mol/h, hydrogen peroxide flow 2-2.5kg/h enters reactor; Described raw material is the alkene of boiling point≤35 ℃;
C) epoxy compounds of unreacted alkene, generation, water and benzene carry out rectifying, and unreacted alkene is recycled to reactor through vaporization;
D) epoxy compounds of Sheng Chenging advances the product storage tank through condensation, and water separates back benzene and is recycled to reactor with benzene.
2. the method for claim 1 is characterized in that, the alkene described in the step b is propylene, iso-butylene, butylene, ethene or vinylchlorid.
3. a reactive system that is used to realize the described method of claim 1 mainly is made up of reactor, condenser, rectifying tower, water-oil separator, gasifier, wherein:
Reactor is used for the catalyzed reaction of hydrogen peroxide and raw material;
First condenser, the one end is connected with reactor, accepts the benzene and the water that steam from reactor; The other end is connected with a water-oil separator, makes benzene and aqueous phase separation, and the benzene after the separation returns the reactor that is connected with first condenser, and water is discharged by water-oil separator;
Rectifying tower is connected with reactor, accepts the unreacted alkene that steams from reactor, epoxy compounds, water and the benzene of generation; Water wherein is with after benzene separates by the water-oil separator that is connected with rectifying tower, the benzene Returning reactor, and water is discharged by water-oil separator;
Second condenser, the one end is connected with rectifying tower, accepts isolating epoxy compounds product in the rectifying tower;
The 3rd condenser, the one end is connected with rectifying tower, accepts unreacted alkene in the rectifying tower; The other end is connected with a vaporizer, and this vaporizer is sent in the reactor after unreacted alkene is vaporized.
4. the system of claim 3 is characterized in that, the working temperature of first condenser is 50 to 60 ℃.
5. the system of claim 3 is characterized in that, the working temperature of second condenser is-25 to 50 ℃.
6. the system of claim 3 is characterized in that, the working temperature of the 3rd condenser is-25 to 40 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200410086218XA CN100412038C (en) | 2004-10-27 | 2004-10-27 | Homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method and system |
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| CN100412038C true CN100412038C (en) | 2008-08-20 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103373904B (en) * | 2012-04-27 | 2015-03-18 | 中国石油化工股份有限公司 | Synthesis method of benzenediol |
| CN103373902B (en) * | 2012-04-27 | 2015-03-18 | 中国石油化工股份有限公司 | Method for hydroxylating aromatic hydrocarbon to prepare corresponding phenol or diphenol |
| CN104672178A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院大连化学物理研究所 | Continuous reaction method for catalyzing epoxidation of hydrogen peroxide oxyalkylene |
| CN112920143A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Reaction device for controlling dehydration in phase transfer catalytic reaction process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003146977A (en) * | 2001-11-08 | 2003-05-21 | Nippon Shokubai Co Ltd | Method for producing epoxy compound |
| CN1534030A (en) * | 2003-03-28 | 2004-10-06 | 中国石油化工股份有限公司 | Production method of epoxy chloropropane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003146977A (en) * | 2001-11-08 | 2003-05-21 | Nippon Shokubai Co Ltd | Method for producing epoxy compound |
| CN1534030A (en) * | 2003-03-28 | 2004-10-06 | 中国石油化工股份有限公司 | Production method of epoxy chloropropane |
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