CN104672178A - Continuous reaction method for catalyzing epoxidation of hydrogen peroxide oxyalkylene - Google Patents
Continuous reaction method for catalyzing epoxidation of hydrogen peroxide oxyalkylene Download PDFInfo
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- CN104672178A CN104672178A CN201310643173.0A CN201310643173A CN104672178A CN 104672178 A CN104672178 A CN 104672178A CN 201310643173 A CN201310643173 A CN 201310643173A CN 104672178 A CN104672178 A CN 104672178A
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- Prior art keywords
- reactor
- hydrogen peroxide
- reaction
- mixed solvent
- benzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a continuous reaction method for catalyzing the epoxidation of hydrogen peroxide oxyalkylene. The method comprises the following steps: carrying out azeotropic treatment on water and components (solvent) in reaction liquid so as to remove most of water (water in hydrogen peroxide) in a system and then form an anhydrous hydrogen peroxide solution; adding olefin and a phase transfer catalyst, carrying out epoxidation reaction at certain temperature, and cooling the obtained object; and separating and recovering the catalyst for two times by using a horizontal screw decanter centrifuge and a butterfly separator, wherein the catalyst can be recycled; and carrying out further rectification and separation on a liquid phase obtained by separating, so as to obtain a product; and recycling a mixed solvent again.
Description
Technical field
The present invention relates to a kind of catalysis hydrogen peroxide oxidation alkene epoxidation successive reaction flow process, belong to small-numerator olefin and hydrogen peroxide for raw material, with phase-transfer catalyst, catalysis epoxidation produces the technology of epoxy compounds.
Background technology
Epoxy compounds is a kind of very important organic intermediate.At present, except oxyethane directly can be produced by atmospheric oxidation ethene, the production method of the epoxy compounds of other alkene is all standby by indirect oxidation method, chlorohydrination or peracid legal system, there is the problem such as joint product and environmental pollution respectively.
1988, people's reported first such as Carlo Venturello heteropolyacid quaternary ammonium salt EPOXIDATION OF ALKENES CATALYZED BY, heteropolyacid quaternary ammonium salt [R in reaction process
4n
+]
3{ PO
4[WO (O
2)
2]
4}
3-for catalytic active species, aqueous hydrogen peroxide solution is oxygenant, and benzene is solvent.CN100412038C discloses a kind of homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method and system, and its reactive system is comparatively complicated and be difficult to balance.
For realizing high-level efficiency, the continuous prodution of said process, the multiple reactors in series of this flow scheme design uses, and uses horizontal screw centrifuge and butterfly separating machine well to solve separation and recovery of catalyst problem, whole system is run continuously.
Summary of the invention
The object of the present invention is to provide a kind of successive reaction flow process of catalysis hydrogen peroxide oxidation alkene epoxidation, the method well solves separation and recovery of catalyst problem, can be recycled.The key step of production method provided by the invention is:
A) in 80-100kg mass concentration 27.5-50% hydrogen peroxide: the ratio of 850-950 kilogram of mixed solvent adds in reactor, be warming up to 70-80 DEG C, water-band in the hydrogen peroxide added gone out by the benzene in solvent or toluene, benzene or toluene return in reactor and proceed reaction; Described solvent is tributyl phosphate, trioctyl phosphate, tricresyl phosphate butyronitrile or dioxane and benzene or toluene is the mixture of 1:3-3:1 by volume;
B) temperature is made to remain on 40-90 DEG C, by H
2o
2be that 1:2-1:5 adds alkene with olefin molar ratio;
C) the epoxidation reaction time is 2-8 hour;
D) system temperature is made to be cooled to 0-20 DEG C after reaction;
E) the rear system material of reaction is by horizontal screw centrifuge and butterfly separating machine twice Separation and Recovery catalyzer;
F) centrifugal catalyzer is recycled again by being transported in reactor by slush pump after adding mixed solvent;
G) the further rectifying separation of the centrifugal liquid phase obtained obtains product;
H) mixed solvent can add the use of hydrogen peroxide Posterior circle again.
Use multiple reactors in series to form in reaction process provided by the invention, first reactor completes the process of water in benzene in mixed solvent or toluene removing hydrogen peroxide, and benzene or refluxing toluene return first reactor, and water is separated from the first reactor; The mixture of hydrogen peroxide and mixed solvent enters the second reactor, and this mixture is anhydrous system, adds catalyzer and alkene carries out epoxidation reaction at 40-90 DEG C in the second reactor.In the second reactor, reaction enters the 3rd reactor after terminating, and be cooled to 0-20 DEG C, in the 3rd reactor, material is by horizontal screw centrifuge and butterfly separating machine twice Separation and Recovery catalyzer.Be transported in the second reactor by slush pump after the centrifugal catalyzer obtained adds a certain amount of mixed solvent and use.The further rectifying separation of the centrifugal liquid phase obtained obtains product, and the mixed solvent of rectifying gained enters the first reactor cycles and uses.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Example 1, the hydrogen peroxide being 50% by 100 kilograms of concentration add first reactor of prepackage 950 kilograms of solvents (tributyl phosphate and toluene Mixed Solvent), be warming up to 80 DEG C, by toluene, the water-band in the hydrogen peroxide added is gone out system, pass through condenser, enter water-oil separator, toluene flows back to the first reactor.After diversion ratio is greater than 98%, system material enters the second reactor, the temperature of reaction of the second reactor is 50 DEG C, add 14.5 kg catalyst, be filled with 250 kilograms of butylene, react 5 hours, reaction terminates rear material and enters the 3rd reactor, material is made to be cooled to 15 DEG C, be separated for twice catalyst recirculation uses through horizontal screw centrifuge and butterfly separating machine successively, the further rectifying separation product of liquid phase after centrifugation and material, obtain butylene oxide ring 74.1 kilograms, butylene oxide ring yield is 90%, and butylene and the mixed solvent of recovery recycle.
Claims (5)
1. catalysis hydrogen peroxide oxidation alkene epoxidation continuous reaction method, its key step is:
A) in 80-100kg mass concentration 27.5-50% hydrogen peroxide: the ratio of 850-950 kilogram of mixed solvent adds in reactor, be warming up to 70-80 DEG C, water-band in the hydrogen peroxide added gone out by the benzene in solvent or toluene, benzene or toluene return in reactor and proceed reaction; Described mixed solvent is tributyl phosphate, trioctyl phosphate, tricresyl phosphate butyronitrile or dioxane and benzene or toluene is the mixture of 1:3-3:1 by volume;
B) temperature is made to remain on 40-90 DEG C, by H
2o
2be that 1:2-1:5 adds alkene with olefin molar ratio;
C) the epoxidation reaction time is 2-8 hour;
D) system temperature is made to be cooled to 0-20 DEG C after reaction;
E) the rear system material of reaction is by horizontal screw centrifuge and butterfly separating machine twice Separation and Recovery catalyzer;
F) centrifugal catalyzer is recycled again by being transported in reactor by slush pump after adding mixed solvent;
G) the further rectifying separation of the centrifugal liquid phase obtained obtains product;
H) mixed solvent can add the use of hydrogen peroxide Posterior circle again.
2. the method for claim 1, is characterized in that: the alkene described in step b is propylene, butylene, iso-butylene, ethene or vinylchlorid.
3. the method for claim 1, it is characterized in that: the reactor described in step a is composed in series by three single reactors, first reactor completes the process of water in benzene in mixed solvent or toluene removing hydrogen peroxide, benzene or refluxing toluene return first reactor, and water is separated from the first reactor; The mixture of hydrogen peroxide and mixed solvent enters the second reactor, and this mixture is anhydrous system, adds catalyzer and alkene carries out epoxidation reaction at 40-90 DEG C in the second reactor;
After described reaction in the second reactor terminates, material enters the 3rd reactor cooling to 0-20 DEG C.
4. method as claimed in claim 3, is characterized in that: in the 3rd described reactor, material is by horizontal screw centrifuge and butterfly separating machine twice Separation and Recovery catalyzer;
Be transported to reaction in the second reactor by slush pump after the described centrifugal catalyzer obtained adds mixed solvent to use.
5. the method for claim 1, is characterized in that: the further rectifying separation of the described centrifugal liquid phase obtained obtains product; The mixed solvent of described rectifying gained enters the first reactor cycles and uses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310643173.0A CN104672178A (en) | 2013-12-03 | 2013-12-03 | Continuous reaction method for catalyzing epoxidation of hydrogen peroxide oxyalkylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310643173.0A CN104672178A (en) | 2013-12-03 | 2013-12-03 | Continuous reaction method for catalyzing epoxidation of hydrogen peroxide oxyalkylene |
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|---|---|
| CN104672178A true CN104672178A (en) | 2015-06-03 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310643173.0A Pending CN104672178A (en) | 2013-12-03 | 2013-12-03 | Continuous reaction method for catalyzing epoxidation of hydrogen peroxide oxyalkylene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108073143A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of reaction control phase transfer catalyst precipitation process catalyst particle size regulates and controls method |
| CN112479914A (en) * | 2020-11-24 | 2021-03-12 | 蚌埠丰原医药科技发展有限公司 | Device and method for continuously producing acetaminophen |
Citations (5)
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|---|---|---|---|---|
| US20030092921A1 (en) * | 2001-06-05 | 2003-05-15 | Stangland Eric E. | Method of making gold-titania catalyst for oxidation of hydrocarbons |
| CN1765854A (en) * | 2004-10-27 | 2006-05-03 | 中国科学院大连化学物理研究所 | Homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method and system |
| CN1809547A (en) * | 2003-06-18 | 2006-07-26 | 德古萨股份公司 | Process for the epoxidation of propene |
| CN101613329A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of preparation method of propylene oxide |
| CN102471298A (en) * | 2009-08-05 | 2012-05-23 | 陶氏环球技术有限责任公司 | Process for producing an oxirane |
-
2013
- 2013-12-03 CN CN201310643173.0A patent/CN104672178A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030092921A1 (en) * | 2001-06-05 | 2003-05-15 | Stangland Eric E. | Method of making gold-titania catalyst for oxidation of hydrocarbons |
| CN1809547A (en) * | 2003-06-18 | 2006-07-26 | 德古萨股份公司 | Process for the epoxidation of propene |
| CN1765854A (en) * | 2004-10-27 | 2006-05-03 | 中国科学院大连化学物理研究所 | Homogeneous catalysis low boiling point olefin hydrogen peroxide continuous reaction method and system |
| CN101613329A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of preparation method of propylene oxide |
| CN102471298A (en) * | 2009-08-05 | 2012-05-23 | 陶氏环球技术有限责任公司 | Process for producing an oxirane |
Non-Patent Citations (1)
| Title |
|---|
| 周志刚: "钛硅分子筛催化环己烯环氧化", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, 15 December 2011 (2011-12-15) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108073143A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of reaction control phase transfer catalyst precipitation process catalyst particle size regulates and controls method |
| CN108073143B (en) * | 2016-11-18 | 2020-03-17 | 中国科学院大连化学物理研究所 | Method for regulating and controlling catalyst granularity in reaction control phase transfer catalyst precipitation process |
| CN112479914A (en) * | 2020-11-24 | 2021-03-12 | 蚌埠丰原医药科技发展有限公司 | Device and method for continuously producing acetaminophen |
| CN112479914B (en) * | 2020-11-24 | 2023-05-09 | 蚌埠丰原医药科技发展有限公司 | Device and method for continuously producing acetaminophen |
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