CN108689966A - A kind of preparation method of propylene oxide - Google Patents
A kind of preparation method of propylene oxide Download PDFInfo
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- CN108689966A CN108689966A CN201810486113.5A CN201810486113A CN108689966A CN 108689966 A CN108689966 A CN 108689966A CN 201810486113 A CN201810486113 A CN 201810486113A CN 108689966 A CN108689966 A CN 108689966A
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- propylene
- propylene oxide
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- hydrogen peroxide
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- 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
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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
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of propylene oxide, its main feature is that the Titanium Sieve Molecular Sieve with MSE topological structures is used to carry out in the reaction system of propylene and hydrogen peroxide catalyzing and synthesizing propylene oxide for catalyst, the weight ratio of the propylene and catalysts and solvents is 1:0.03~0.15:1~15;The catalyst is the assembly of Ti-MSE molecular sieves or the molecular sieve containing Ti-MSE;The solvent is arbitrary one or more kinds of mixing in water, acetone, acetonitrile, methanol, ethyl alcohol, isopropanol and the tert-butyl alcohol.The present invention has catalytic activity good compared with prior art, and post-processing is easy, and propylene oxide yield is up to 93%, and selecting property is up to 99%, and environmental-friendly, reaction condition is mild, and there is certain industrialization promotion to use foreground and significant economic value.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, especially one kind using Titanium Sieve Molecular Sieve as catalyst, propylene and
Hydrogen peroxide is the propylene oxide process of reaction system.
Background technology
Propylene oxide is a kind of important Organic Chemicals, and nearly 3/4ths propylene oxide is for producing polyether polyols
Alcohol, and synthesis of polyurethane is further processed;Remaining a quarter is then used to produce propylene glycol, alcohol ether, propene carbonate etc. other
Fine chemicals.Currently, industrially the method for production propylene oxide mainly has:Chlorohydrination, ethylbenzene hydroperoxide method, tertiary butyl mistake
Hydrogen oxide method, isopropyl benzene hydroperoxide method and hydrogen peroxide direct oxidation method.The chlorohydrination meeting a large amount of chlorine-contained wastewater of by-product, not only
The pollution of environment can be caused, and there is stronger corrosivity to equipment, gradually by more environment-friendly ethylbenzene hydroperoxide
The oxidation technologies such as method, tert-butyl hydroperoxide method, isopropyl benzene hydroperoxide method, hydrogen peroxide direct oxidation method are substituted.
Hydrogen peroxide direct oxidation method is respectively using propylene and hydrogen peroxide as raw material and oxidant, in urging for Titanium Sieve Molecular Sieve
Change effect is lower to produce propylene oxide, has the characteristics that reaction condition is mild, activity is high, selectivity is good, pollution-free, is a kind of environment
Friendly Synthesis of Propylene Oxide.
Patent (US 4833260) discloses a kind of using the TS-1 Titanium Sieve Molecular Sieve of MFI topological structures as catalyst synthesis ring
The method of Ethylene Oxide, document (Studies in Surface Science and Catalysis, 2007, Vol.170,
p1236-1243;Journal of Catalysis, 2016, Vol.342, p173-183) it reports with MWW topological structures
Ti-MWW Titanium Sieve Molecular Sieve is the method for catalyst synthesizing epoxypropane.Recently, with the development of Titanium Sieve Molecular Sieve synthetic technology,
The titanium-silicon molecular sieve catalyst material that more and more structure novels, duct open is developed, and is expected to be pushed further into epoxy
The development of oxide production process.
Document (Green Chemistry, 2016, Vol.18, p735-741) reports a kind of titanium silicon with MSE structures
The preparation of molecular sieve and its performance in catalysis of phenol hydroxylating, however, so far not about the titanium silicon of MSE structures point
The report of son sieve catalysis propylene synthesizing epoxypropane.Titanium Sieve Molecular Sieve based on MSE structures is excellent in liquid phase oxidation reaction
Catalytic performance, it, which is expected to efficiently to be catalyzed propylene ring oxidation reaction, prepares propylene oxide.
Invention content
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of propylene oxide preparation method, using tool
It is that the reaction system of catalyst and propylene and hydrogen peroxide carries out catalyzing and synthesizing epoxy third to have the Titanium Sieve Molecular Sieve of MSE topological structures
Alkane, high selectivity, catalytic activity is good, environmental-friendly, and post-processing is easy, and propylene oxide yield is up to 93%, and selecting property is up to
99%, reaction condition is mild, has expanded the application field of molecular sieve, provides novel, environmental-friendly propylene oxide synthesis way
There is diameter certain industrialization promotion to use foreground and significant economic value.
Realizing the specific technical solution of the object of the invention is:A kind of preparation method of propylene oxide, its main feature is that using tool
It is that catalyst carries out catalyzing and synthesizing epoxy in the reaction system of propylene and hydrogen peroxide to have the Titanium Sieve Molecular Sieve of MSE topological structures
Propane, specific prepare include the following steps:
A steps:It is 1 by weight by propylene and catalysts and solvents:0.03~0.15:1~15 is stirred into reaction
System, the catalyst are the assembly of Ti-MSE molecular sieves or the molecular sieve containing Ti-MSE;The solvent be water, acetone, acetonitrile,
Arbitrary one or more kinds of mixing in methanol, ethyl alcohol, isopropanol and the tert-butyl alcohol;
B step:By reaction system at a temperature of 30~120 DEG C, the peroxidating that mass concentration is 2~65% is added dropwise
Hydrogen, time for adding are 0.1~3 hour, and the reaction was continued 0.1~3 hour after being added dropwise, mole of the hydrogen peroxide and propylene
Than being 1:1~5;
Step c:After reaction, catalyst is filtered out, filtrate detaches through distillation, and it is propylene oxide to obtain product.
The reaction temperature is preferably 50~80 DEG C;The time for adding is preferably 0.1~2 hour.
The mass concentration of the hydrogen peroxide is preferably 5~40%, and the molar ratio of hydrogen peroxide and propylene is preferably 1:1~
3。
The present invention has catalytic activity good compared with prior art, and post-processing is easy, and propylene oxide yield is up to 93%,
Selecting property is up to 99%, and environmental-friendly, reaction condition is mild, has certain industrialization promotion with foreground and significant economy
Value.
Specific implementation mode
The preparation of the present invention and application are described in further detail below by way of specific embodiment.
Embodiment 1
The first step:0.1g Ti-MSE molecular sieve catalysts and the 10g tert-butyl alcohols and 2g propylene steams are added in reactor,
The reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 60 DEG C, it is 30% that 2.5ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 0.5 hour, be added dropwise after the reaction was continued 1 hour.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
1.30g product propene oxides, yield 92.6% are obtained, propylene oxide is selectively 99.0%.
Embodiment 2
The first step:0.1g Ti-MSE molecular sieve catalysts and 5g acetone and 1g propylene steams are added in reactor, stirred
The reaction system uniformly obtained.
Second step:When the temperature of reaction system is risen to 60 DEG C, it is 30% that 0.8ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 0.5 hour, be added dropwise after the reaction was continued 1.5 hours.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
0.41g product propene oxides, yield 91.0% are obtained, propylene oxide is selectively 98.2%.
Embodiment 3
The first step:0.1g Ti-MSE molecular sieve catalysts and the 10g tert-butyl alcohols and 2g propylene steams are added in reactor,
The reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 75 DEG C, it is 30% that 2ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding are 1.5 hours, and the reaction was continued 0.5 hour after being added dropwise.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
1.05g product propene oxides, yield 93.5% are obtained, propylene oxide is selectively 99.2%.
Embodiment 4
The first step:It is catalyst and uncle 10g by the assembly of 0.08g Ti-MSE molecular sieves and 0.02g TS-1 molecular sieves
Butanol and 2g propylene steams are added in reactor, the reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 60 DEG C, it is 40% that 2.5ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 1.5 hours, be added dropwise after the reaction was continued 0.5 hour.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
1.31g product propene oxides, yield 93.2% are obtained, propylene oxide is selectively 99.5%.
Embodiment 5
The first step:0.1g Ti-MSE molecular sieve catalysts and the 20g tert-butyl alcohols and 2g propylene steams are added in reactor,
The reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 60 DEG C, it is 30% that 2.5ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 0.5 hour, be added dropwise after the reaction was continued 1 hour.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
1.32g product propene oxides, yield 94.0% are obtained, propylene oxide is selectively 99.5%.
Embodiment 6
The first step:It is catalyst and 10g by the assembly of 0.07g Ti-MSE molecular sieves and 0.03g Ti-MWW molecular sieves
The tert-butyl alcohol and 2g propylene steams are added in reactor, the reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 60 DEG C, it is 30% that 1.7ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 1.5 hours, be added dropwise after the reaction was continued 0.5 hour.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
0.88g product propene oxides, yield 92.2% are obtained, propylene oxide is selectively 99.5%.
Embodiment 7
The first step:It is catalyst and 10g second by the assembly of 0.05g Ti-MSE molecular sieves and 0.05gTi-MOR molecular sieves
Nitrile and 2g propylene steams are added in reactor, the reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 60 DEG C, it is 30% that 1.7ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 1.5 hours, be added dropwise after the reaction was continued 1.5 hours.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
0.88g product propene oxides, yield 92.2% are obtained, propylene oxide is selectively 99.5%.
Embodiment 8
The first step:0.1g Ti-MSE molecular sieve catalysts and the 10g tert-butyl alcohols and 2g propylene steams are added in reactor,
The reaction system being uniformly mixing to obtain.
Second step:When the temperature of reaction system is risen to 80 DEG C, it is 30% that 1.8ml mass concentrations are added dropwise into reaction system
Hydrogen peroxide, time for adding be 2.0 hours, be added dropwise after the reaction was continued 0.5 hour.
Third walks:After completion of the reaction, routinely filter method isolates catalyst, then routinely distillation procedure, separation
0.95g product propene oxides, yield 93.4% are obtained, propylene oxide is selectively 99.5%.
Ti-MSE molecular sieves in the various embodiments described above according to literature method (Chemical Communication, 2008,
Vol.5, p6224-6226) it prepares, the analysis of reactants and products uses gas-chromatography (Shimadzu GC2014, Rt-Wax capillary
Column 30m × 0.25mm × 0.25 μm), using cyclopentanone as internal standard, the method for temperature programming is quantified, propylene oxide yield and choosing
Selecting property is calculated according to following formula:
Only the present invention will be further described for the above various embodiments, and not to limit patent of the present invention, all is this hair
Bright equivalence enforcement is intended to be limited solely by within the right of patent of the present invention.
Claims (3)
1. a kind of preparation method of propylene oxide, it is characterised in that use the Titanium Sieve Molecular Sieve with MSE topological structures for catalysis
Agent carries out catalyzing and synthesizing propylene oxide in the reaction system of propylene and hydrogen peroxide, and specific prepare includes the following steps:
A steps:It is 1 by weight by propylene and catalysts and solvents: 0.03 ~ 0.15:1 ~ 15 is stirred
At reaction system, the catalyst is the assembly of Ti-MSE molecular sieves or the molecular sieve containing Ti-MSE;The solvent be water,
Arbitrary one or more kinds of mixing in acetone, acetonitrile, methanol, ethyl alcohol, isopropanol and the tert-butyl alcohol;
B step:By reaction system at a temperature of 30 ~ 120 DEG C, the hydrogen peroxide that mass concentration is 2 ~ 65 % is added dropwise,
Time for adding is 0.1 ~ 3 hour, and the reaction was continued 0.1 ~ 3 hour after being added dropwise, mole of the hydrogen peroxide and propylene
Than being 1: 1 ~ 5;
Step c:After reaction, catalyst is filtered out, filtrate detaches through distillation, and it is propylene oxide to obtain product.
2. the preparation method of propylene oxide according to claim 1, it is characterised in that the reaction temperature is preferably 50 ~ 80
℃;The time for adding is preferably 0.1 ~ 2 hour.
3. the preparation method of propylene oxide according to claim 1, it is characterised in that the mass concentration of the hydrogen peroxide is excellent
It is selected as 5 ~ 40 %, the molar ratio of hydrogen peroxide and propylene is preferably 1: 1 ~ 3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970684A (en) * | 2019-04-26 | 2019-07-05 | 江苏扬农化工集团有限公司 | A kind of method that oxidizing process removes aldehyde type impurities in propylene oxide |
Citations (7)
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|---|---|---|---|---|
| JPH08225556A (en) * | 1994-11-16 | 1996-09-03 | Arco Chem Technol Lp | Improved method of epoxidation catalyzed by titanium silicalite |
| CN1709574A (en) * | 2005-04-18 | 2005-12-21 | 华东师范大学 | Titanium-silicon molecular sieve catalyst with MWW structure, and its preparing method and use |
| CN101274922A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Preparation for epoxypropane |
| CN102558100A (en) * | 2012-01-20 | 2012-07-11 | 中国天辰工程有限公司 | Method for catalyzing propene epoxidation by taking Titanium Silicalite-1(TS-1) as catalyst |
| US20130018196A1 (en) * | 2010-03-25 | 2013-01-17 | Dow Global Technologies Llc | Process for producing propylene oxide using a pretreated epoxidation catalyst |
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|---|---|---|---|---|
| JPH08225556A (en) * | 1994-11-16 | 1996-09-03 | Arco Chem Technol Lp | Improved method of epoxidation catalyzed by titanium silicalite |
| CN1709574A (en) * | 2005-04-18 | 2005-12-21 | 华东师范大学 | Titanium-silicon molecular sieve catalyst with MWW structure, and its preparing method and use |
| CN101274922A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Preparation for epoxypropane |
| US20130018196A1 (en) * | 2010-03-25 | 2013-01-17 | Dow Global Technologies Llc | Process for producing propylene oxide using a pretreated epoxidation catalyst |
| CN102558100A (en) * | 2012-01-20 | 2012-07-11 | 中国天辰工程有限公司 | Method for catalyzing propene epoxidation by taking Titanium Silicalite-1(TS-1) as catalyst |
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| Y. KUBOTA，ET AL.: "High-Performance Catalysts with MSE-Type Zeolite Framework", 《TOP CATAL》 * |
| YOSHIHIRO KUBOTA，ET AL.: "Synthesis and catalytic performance of Ti-MCM-68 for effective oxidation reactions", 《CHEM. COMMUN.》 * |
| 颜佳颖: "MWW和MSE结构钛硅分子筛的后处理合成及催化性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970684A (en) * | 2019-04-26 | 2019-07-05 | 江苏扬农化工集团有限公司 | A kind of method that oxidizing process removes aldehyde type impurities in propylene oxide |
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