CN1161963A - Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide - Google Patents
Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide Download PDFInfo
- Publication number
- CN1161963A CN1161963A CN 96100528 CN96100528A CN1161963A CN 1161963 A CN1161963 A CN 1161963A CN 96100528 CN96100528 CN 96100528 CN 96100528 A CN96100528 A CN 96100528A CN 1161963 A CN1161963 A CN 1161963A
- Authority
- CN
- China
- Prior art keywords
- reaction
- epoxidation
- alkene
- organic hydroperoxide
- molybdenum dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Epoxy Compounds (AREA)
Abstract
This invention discloses a method for producing epoxy compound. Olefine along with organic hydrogen peroxide under the action of catalyst and a certain reaction condition, the olefine is formed into epoxy compound through epoxidation and the organic hydrogen peroxide is quantitatively converted into corresponding alcohol. It is suitable for the epoxidation reaction of gas, liquid and solid state olefine containing 2-30 carbon atoms. The invented method has high reaction activity, no environmental pollution, and the alcohol produced may be further developed for utilization. The reaction conversion rate is 100% and the selectivity may reach 96%.
Description
The present invention relates to a kind of method that generates the epoxidation compound with imido grpup dialkoxy molybdenum dioxide catalyst olefine selective epoxidation reaction.It belongs to field of chemical technology, and its international Patent classificating number is C07.
Oxyethane is to adopt silver catalyst catalyzed ethylene and the direct epoxidation of oxygen to produce.But the reaction preference of propylene oxide and the direct catalysis epoxidation of other many epoxide is very poor, and they mainly are to use the chlorohydrination mass production, but this method is seriously polluted, and a large amount of by products is not utilized and does not have any economic worth.
Kollar and Wallington are at its patent of invention U.S.3,351, disclosing in 635 with the soluble metal title complex comes catalyzing propone and organic hydroperoxide epoxidation to generate propylene oxide, its best result is that the transformation efficiency of organic hydroperoxide is up to 93.5%, and the selectivity that generates propylene oxide is 99.1%.But in its disclosed embodiment, the propylene consumption is excessive greatly with respect to the consumption of oxygenant.
Shum and Cooper be at its patent of invention U.S.4, discloses the method that generates epoxide with two (glycol ether) ether molybdenum dioxide catalyzed alkene and organic hydroperoxide epoxidation in 772,731.The transformation efficiency of the organic hydroperoxide in this reaction process is 100%, and the selectivity that generates propylene oxide is 94%.Also have some other disclosed catalytic reaction processes in addition, but, influenced the transformation efficiency and the selectivity of catalytic epoxidation because of use catalyzer unstable deposition of easily decomposing in reaction process.
The purpose of this invention is to provide a method that generates epoxide with the epoxidation reaction of olefines of imido grpup dialkoxy molybdenum dioxide catalyst.To reach the selectivity that has very high organic hydroperoxide transformation efficiency and generate epoxide with present method epoxidation of olefins.
Be the technical measures that realize that the object of the invention is taked: the present invention's organic hydroperoxide is an oxygenant, and imido grpup dialkoxy molybdenum dioxide makes olefin epoxide turn to epoxide as catalyzer.Alkene and organic hydroperoxide are under the effect of catalyzer, and alkene generates epoxide through epoxidation, and organic hydroperoxide then is converted into corresponding alcohol quantitatively.
Catalysis epoxidation method of the present invention is applicable to the epoxidation Reaction of Alkenes that contains 2-30 carbon atom.Alkenes compounds specifically can be described as ethene, propylene, n-butene, iso-butylene, various amylene, various hexene, various heptene, various octene, various dodecylene, tetrahydrobenzene, tetrahydrotoluene, vinylbenzene, vinyl toluene.Also applicable to the epoxidation reaction that has substituent alkene of functional group and polyunsaturated vegetable oil, for example: vinylcarbinol, acrylate, methacrylic ester, Semen Maydis oil, soybean oil, Oleum Gossypii semen, Viscotrol C and sweet oil.It is applicable to various steam states, liquid state and solid-state epoxidation Reaction of Alkenes.
Organic hydroperoxide of the present invention is that molecular formula is arbitrary organic hydroperoxide of ROOH, and substituent R is the arbitrary alkyl that contains 3-20 carbon atom.When wherein using tertbutyl peroxide, hydrogen peroxide ethylbenzene and hydrogen phosphide cumene, the result of the epoxidised reaction of olefin catalytic is better.
Catalyzer of the present invention is β, β-imido grpup dialkoxy molybdenum dioxide compounds, has following structure:
R wherein
1-R
4, R
5, R
6-R
9Each group can be identical, also can be different, can be hydrogen atom, can be the alkyl that contains 1-10 carbon atom also, can contain functional groups such as hydroxyl, halogen, carboxyl, carbonyl or ester group in the substituted hydrocarbon radical.Wherein work as R
1=R
6=CH
3, CH
3CH
2, phenyl; R
5=H, CH
3, CH
3CH
2, n-C
4H
9, phenyl; When all the other are hydrogen atom, catalytic effect the best of catalyzer.
The method of catalyzing expoxidation of olefines of the present invention is applicable to quite wide reaction conditions.Activity according to reaction substrate can be selected different reaction conditionss with other factors.The range of reaction temperature of catalysis epoxidation is-20-200 ℃, and the optimal reaction temperature scope is 40-150 ℃.The reaction pressure scope is from normal pressure to 100 normal atmosphere.Reaction times played from 1 minute any time, and the optimum reacting time scope is 10 minutes-5 hours.The reacting material ratio scope of alkene and organic hydroperoxide is 0.2: 1-20: 1, and optimum range is 1: 1-6: 1.
Compared with the prior art, the technique effect that reached of the present invention:
The alcohol of catalytic epoxidation method non-environmental-pollution of the present invention, generation can further develop, the reactive behavior of catalyzed reaction is very high, reacting material ratio (mol ratio) at alkene and organic hydroperoxide is 4: 1 o'clock, and transformation efficiency is 100%, and selectivity is 96%.When material ratio (mol ratio) when being low to moderate 1.5: 1, still have very high transformation efficiency and selectivity, transformation efficiency can reach 100%, and selectivity is 89%.
Catalytic epoxidation process of the present invention should be carried out under controlled condition, is applicable to the production technique of batch reactor production technique and mobile tubulose reactor.
Below in conjunction with embodiment the present invention is further described.
Embodiment 1: add 10 gram tetrahydrobenzene, 27 and restrain isopropyl benzene, hydroxyl cumene solution, 20 gram benzene and 30 milligrams of β, the β-imido grpup diisopropoxy molybdenum dioxide that contain 45.1% hydrogen phosphide cumene in a reactor, then under the normal pressure nitrogen atmosphere, 80 ℃ of stirring reactions 5 hours.The transformation efficiency of hydrogen phosphide cumene is 98%, and the selectivity that generates the cyclohexene ring oxide compound is 92%, and based on hydrogen phosphide cumene, the productive rate of cyclic ethylene epoxide is 90%.
Embodiment 2: have in the autoclave of oscillating agitator one, add t-butanol solution, 160 gram propylene and 0.1 gram β, β-imido grpup diisopropoxy molybdenum dioxide that 100 grams contain 46% tertbutyl peroxide.React time enough then under 110 ℃, 45 normal atmosphere, the transformation efficiency of tertbutyl peroxide is 100%, and the selectivity that generates propylene oxide is 96%.Based on tertbutyl peroxide, the productive rate of propylene oxide is 96%.
Embodiment 3: have in the tripping still of oscillating agitator one, add the t-butanol solution that 240 grams contain 46% tertbutyl peroxide, 150 gram propylene and 0.1 gram β, β-imido grpup diisopropoxy molybdenum dioxide.Then the enough time of reaction under 100 ℃, 40 normal atmosphere, the transformation efficiency of tertbutyl peroxide is 100%, and the selectivity that generates propylene oxide is 89%.The productive rate of propylene oxide is 89%.
Claims (3)
1. one kind with imido grpup dialkoxy molybdenum dioxide catalyzing expoxidation of olefines novel method, it is characterized in that: method of the present invention be with alkene and organic hydroperoxide under imido grpup dialkoxy molybdenum dioxide catalyst action, under the certain reaction condition, alkene generates epoxide through epoxidation, organic hydroperoxide is converted into corresponding alcohol quantitatively, and it is applicable to steam state, liquid state and solid-state containing 〉=2 epoxidation Reaction of Alkenes to 30 carbon atoms; The reaction mass mol ratio is 4: 1 o'clock, and transformation efficiency is 100%, and selectivity is 96%, and when molar ratio of material was low to moderate 1.5: 1, transformation efficiency was 100%, and selectivity is 89%;
2. by the described alkene epoxidation novel method of claim 1, it is characterized in that: the range of reaction temperature of catalysis epoxidation for 〉=-20 to 200 ℃, the optimal reaction temperature scope is 〉=40 to 150 ℃, the reaction pressure scope is from normal pressure to 100 normal atmosphere, when reaction times is between taking office from 1 minute, the optimum reacting time scope is 〉=10 minutes to 5 hours, and the reacting material ratio scope of alkene and organic hydroperoxide is 〉=0.2: 1 to 20: 1, optimum range is 〉=1: 1 to 6: 1;
3. by the described alkene epoxidation novel method of claim 1, it is characterized in that: contain 〉=steam state, liquid state and the solid-state alkene of 2 to 30 carbon atoms, they are ethene, propylene, n-butene, iso-butylene, amylene, hexene, heptene, octene, dodecylene, tetrahydrobenzene, tetrahydrotoluene, vinylbenzene, vinyl toluene; Also go for having substituent alkene of functional group and polyunsaturated vegetable oil, as vinylcarbinol, acrylate, methacrylic ester, Semen Maydis oil, soybean oil, Oleum Gossypii semen, Viscotrol C and sweet oil; The organic hydroperoxide that the present invention adopts is that molecular formula is arbitrary organic hydroperoxide of ROOH, and substituent R is to contain 〉=arbitrary alkyl of 3 to 20 carbon atoms; Wherein, during with usefulness tertbutyl peroxide, hydrogen peroxide ethylbenzene and hydrogen phosphide cumene, the result of olefin catalytic epoxidation reaction is better.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96100528 CN1161963A (en) | 1996-04-08 | 1996-04-08 | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96100528 CN1161963A (en) | 1996-04-08 | 1996-04-08 | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1161963A true CN1161963A (en) | 1997-10-15 |
Family
ID=5116638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96100528 Pending CN1161963A (en) | 1996-04-08 | 1996-04-08 | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1161963A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295625A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol |
| CN102295626A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing 1,2-cyclohexene oxide and alpha, alpha-dimethyl benzyl simultaneously |
| CN103012324A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Propylene epoxidation reaction method |
| CN103012325A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Method for producing propylene epoxide through propylene epoxidation reaction |
| CN103012486A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103539762A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for producing epoxypropane by propylene epoxidation |
-
1996
- 1996-04-08 CN CN 96100528 patent/CN1161963A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295625A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol |
| CN102295626A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing 1,2-cyclohexene oxide and alpha, alpha-dimethyl benzyl simultaneously |
| CN102295625B (en) * | 2010-06-24 | 2014-01-22 | 中国石油化工股份有限公司 | Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol |
| CN103012324A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Propylene epoxidation reaction method |
| CN103012325A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Method for producing propylene epoxide through propylene epoxidation reaction |
| CN103012486A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103012324B (en) * | 2011-09-22 | 2014-09-10 | 中国石油化工股份有限公司 | Propylene epoxidation reaction method |
| CN103012325B (en) * | 2011-09-22 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing propylene epoxide through propylene epoxidation reaction |
| CN103012486B (en) * | 2011-09-22 | 2015-10-21 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103539762A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for producing epoxypropane by propylene epoxidation |
| CN103539762B (en) * | 2012-07-12 | 2016-01-13 | 中国石油化工股份有限公司 | Epoxidation of propylene produces the method for propylene oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5214168A (en) | Integrated process for epoxide production | |
| CN106964337B (en) | A kind of preparation method of epoxidation catalyst and epoxidation catalyst and its application of preparation | |
| CN1602303A (en) | Organic chemical oxidation during hydrogen peroxide production | |
| CN1926124B (en) | Improved catalytic process for the preparation of epoxides from alkenes | |
| JP2895605B2 (en) | Epoxidation of olefinically unsaturated compounds | |
| CN101139326A (en) | Method for preparing cyclohexanol and epoxide | |
| CN103193589A (en) | Method for preparing epoxy compound, cyclohexanol and cyclohexanone by co-oxidation synthesis | |
| US6160137A (en) | Method for producing propylene oxide | |
| US6429323B1 (en) | Method for continuous production of propylene oxide and other alkene oxides | |
| GB1585012A (en) | Process for the epoxidation of olefins | |
| CN1161963A (en) | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide | |
| US6960693B2 (en) | Oxidation reaction process catalyzed by phase-transfer catalyst controlling reaction | |
| WO2001070714A1 (en) | Process for producing propylene oxide | |
| CN100544821C (en) | A kind of molybdenum-vanadium-tellurium-niobium catalytic agent that is used for the reaction of selective oxidation of propane system acrylic acid and preparation method thereof | |
| KR100911230B1 (en) | Process for preparation of propylene oxide | |
| AU2001275684A1 (en) | Oxirane production method | |
| JP2007533608A (en) | Method for preparing alkylene oxide | |
| CN1307167C (en) | Method for recovering propylene oxide | |
| EP0074259A1 (en) | Catalytic epoxidation of olefins | |
| WO2003024901A1 (en) | Process for producing cumene | |
| CN102442978B (en) | Alkene epoxidation method | |
| US5670674A (en) | Production of oxirane compounds | |
| US4093636A (en) | Epoxidation of olefinic compounds | |
| US3507809A (en) | Preparation of epoxidation catalyst solution | |
| CN108689966A (en) | A kind of preparation method of propylene oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |