CN102464632A - Method for preparing epoxy chloropropane - Google Patents
Method for preparing epoxy chloropropane Download PDFInfo
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- CN102464632A CN102464632A CN2010105520841A CN201010552084A CN102464632A CN 102464632 A CN102464632 A CN 102464632A CN 2010105520841 A CN2010105520841 A CN 2010105520841A CN 201010552084 A CN201010552084 A CN 201010552084A CN 102464632 A CN102464632 A CN 102464632A
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- hydrogen peroxide
- epoxy chloropropane
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Abstract
The invention relates to a method for preparing epoxy chloropropane. The problems of low conversion rate and low epoxidation selectivity of hydrogen peroxide when the epoxy chloropropane is produced in the prior art are solved. The hydrogen peroxide and chloropropene serve as raw materials, and under the condition that: the reaction temperature is 40 to 90 DEG C, the weight ratio between the hydrogen peroxide and the chloropropene is 0.02 to 0.2, and the weight ratio between a catalyst and the hydrogen peroxide is 0.1 to 1.2, the hydrogen peroxide and the chloropropene are reacted for 1 to 5 hours. The preparation method for the catalyst comprises the following steps of: mixing an inorganic silicon source, an organic silicon source, a titanium source, an organic template agent, an alkali compound and water; and after crystallizing the mixture for 1 to 30 days at 160 to 220 DEG C, and filtering, washing and drying the crystal to obtain the catalyst. The problems are better solved through the technical scheme and the method can be applied to the industrial production of the epoxy chloropropane.
Description
Technical field
The present invention relates to a kind of method for preparing epoxy chloropropane.
Background technology
The industrialized production technology of epoxy chloropropane has propenyl chloride method and propylene acetate method.The former is industrial classical way, and it is about more than 90% to account for global ECH aggregated capacity; And being merely enterprise of several family, the latter adopts.The propylene high-temperature chlorination succeeded in developing and was applied to industrial production first by Shell company in 1948.Its technological process mainly comprises propylene high-temperature chlorination system propenyl chloride, propenyl chloride hypochlorination synthesizing dichloropropanol and three reaction members of dichlorohydrine saponification synthesizing epoxy chloropropane.The characteristics of propylene high-temperature chlorination be production process flexibly, technical maturity, stable operation; Except producing epoxy chloropropane; Also can produce important organic synthesis intermediates such as glycerine, propenyl chloride; By-product D-D mixture (1,3-dichloropropylene and 1,2-propylene dichloride) also is the important intermediate of synthetic pesticide.Shortcoming is that the equipment corrosion that causes of raw material chlorine is serious, the material of purified propylene and reactor drum is required high, and energy consumption is big, and the chlorine consumption is high, and by product is many, and product yield is low.The investment of administering the three wastes accounts for 15%～20% of gross investment, makes that the epoxy chloropropane production cost is higher.
At present, both at home and abroad to H
2O
2Make oxygenant, adopt titanium-silicon molecular sieve catalyst, the research of preparing epichlorohydrin by chloropropene epoxidation is very active.It is catalyzer with the HTS that document US 4833260 discloses a kind of, directly alkene (comprising haloolefin) is carried out the method that epoxidation is produced epoxide with hydrogen peroxide.It is high to have catalyst activity and selectivity, reaction conditions gentle (generally being 40～50 ℃), hydrogen peroxide conversion and higher, the pollution-free (H of epoxy chloropropane productive rate
2O
2Be transformed into H
2Advantage such as O).But do not contain organosilicon in the skeleton of titanium-silicon molecular sieve catalyst, influenced the catalytic performance of catalyzer.
Summary of the invention
Hydrogen peroxide conversion was low when technical problem to be solved by this invention was prior art production epoxy chloropropane, and the problem that hydrogen peroxide epoxidation selectivity is low provides a kind of new method for preparing epoxy chloropropane.This method has the hydrogen peroxide conversion height, the characteristics that hydrogen peroxide epoxidation selectivity is high.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method for preparing epoxy chloropropane; With hydrogen peroxide and propenyl chloride is raw material; In temperature of reaction is 40～90 ℃, and the weight ratio of hydrogen peroxide and propenyl chloride is 0.02～0.2, and the weight ratio of catalyzer and hydrogen peroxide is to react under 0.1～1.2 condition to obtain said epoxy chloropropane in 1～5 hour;
Wherein, Said Preparation of catalysts method may further comprise the steps: inorganic silicon source, organosilicon source, titanium source, organic formwork agent, basic cpd and water are mixed, and reaction mixture is with molar ratio computing inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: (0.01～0.05): (0.01～0.03): (0.03～0.15): (0.4～2.0): (20～100); Said mixture crystallization under 160～220 ℃ of conditions of temperature was obtained said catalyzer through filtration, washing, drying after 1～30 day.
In the technique scheme, said inorganic silicon source is selected from least a in silicon sol, silicon ester or the solid oxidation silicon.The organosilicon source is two (triethoxy is silica-based) methane.The titanium source is selected from TiCl
4, TiCl
3, TiOCl
2Or TiOSO
4In at least a.Organic formwork agent is selected from least a in TPAOH, 4-propyl bromide, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide or the tetraethyl ammonium hydroxide.Basic cpd is selected from least a in ammoniacal liquor, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, tetramethylenediamine, hexanediamine, diethylamine, tripropyl amine or the Tributylamine.Said propenyl chloride is selected from chlorallylene, 2-methyl-chlorallylene or 2-ethyl-chlorallylene.With molar ratio computing, inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: the preferable range of water is 1: (0.02～0.04): (0.015～0.025): (0.06～0.12): (0.8～1.6): (50～70).The crystallization temperature preferable range is 170～200 ℃, and the crystallization time preferable range is 3～5 days.The temperature of reaction preferable range is 40～70 ℃, and the reaction times preferable range is 1～3 hour, and the weight ratio preferable range of hydrogen peroxide and propenyl chloride is 0.06～1.6, and the weight ratio preferable range of catalyzer and hydrogen peroxide is 0.4～0.9.The reaction preferred version of hydrogen peroxide and propenyl chloride is for reacting under the condition that exists at organic solvent, and the weight ratio of hydrogen peroxide and organic solvent is 0.01～0.1, and preferable range is 0.04～0.07.Said organic solvent is selected from methyl alcohol, ethanol, 1, ammediol, 1, at least a in 2-Ucar 35 or the 1-butanols.
The present invention has been owing to used organosilicon source and inorganic silicon source simultaneously in the process of synthetic catalyst, so synthesized and have organosilyl titanium-silicon molecular sieve catalyst, and wherein partly there is Si-CH in skeletal structure of compound
2-Si structure has replaced the Si-O-Si structure in the conventional microvoid structure, and therefore this material has good hydrophobicity, helps contacting of reaction substrate propenyl chloride and catalyzer, has improved hydrogen peroxide conversion.Adopt the inventive method, 60 ℃ of temperature of reaction, under the condition of normal pressure, hydrogen peroxide conversion is 85%, and the epoxidised selectivity of hydrogen peroxide is 97%, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With silicon sol (40 weight %), two (triethoxy is silica-based) methane, TiCl
4, TPAOH, ammoniacal liquor and water mixes by stoichiometric ratio, wherein each component mol ratio of raw material is the inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.01: 0.01: 0.03: 0.4: 20.160 ℃ of crystallization 1 day, product obtained containing skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 0.2 gram and contain organosilicon titanium-silicon molecular sieve catalyst, 20 gram methanol solvates, 5 gram propenyl chlorides, be warmed up to 50 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 1 hour down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 85.3%, and the epoxidised selectivity of hydrogen peroxide is 97.2%.
[embodiment 2]
With solid silica (2000 order), two (triethoxy is silica-based) methane, TiCl
3, 4-propyl bromide, ethamine and water mixes by stoichiometric ratio, wherein each component mol ratio of raw material is the inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.05: 0.03: 0.15: 2.0: 100.170 ℃ of crystallization 5 days, product obtained containing skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 0.1 gram and contain organosilicon titanium-silicon molecular sieve catalyst, 10 gram chlorallylenes, be warmed up to 40 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 2 hours down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 86.4%, and the epoxidised selectivity of hydrogen peroxide is 96.5%.
[embodiment 3]
With tetraethoxy, two (triethoxy is silica-based) methane, TiOCl
2, TBAH, Tri N-Propyl Amine and water mix by stoichiometric ratio, and wherein each component mol ratio of raw material is the inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.03: 0.02: 0.09: 1.2: 60.180 ℃ of crystallization 10 days, product obtained containing skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 0.4 gram and contain organosilicon titanium-silicon molecular sieve catalyst, 40 gram alcohol solvents, 20 gram 2-methyl-chlorallylenes, be warmed up to 60 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 3 hours down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 85.8%, and the epoxidised selectivity of hydrogen peroxide is 96.2%.
[embodiment 4]
Methyl silicate, two (triethoxy is silica-based) methane, tetrabutyl titanate, Tetrabutyl amonium bromide, n-Butyl Amine 99 and water are mixed by stoichiometric ratio, and wherein each component mol ratio of raw material is the inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.02: 0.02: 0.06: 0.8: 40.190 ℃ of crystallization 20 days, product obtained containing skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 0.6 gram and contain organosilicon titanium-silicon molecular sieve catalyst, 60 grams 1,2-propylene glycol solvent, 30 gram 2-ethyl-chlorallylenes then are warmed up to 70 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 4 hours down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 85.6%, and the epoxidised selectivity of hydrogen peroxide is 97.3%.
[embodiment 5]
Silicon sol (40 weight %), two (triethoxy is silica-based) methane, tetraethyl titanate, tetraethylammonium bromide, quadrol and water are mixed by stoichiometric ratio, and wherein each component mol ratio of raw material is the inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.04: 0.02: 0.12: 1.6: 80.200 ℃ of crystallization 30 days, product obtained containing skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 0.8 gram and contain organosilicon titanium-silicon molecular sieve catalyst, 80 grams 1, ammediol solvent, 40 gram propenyl chlorides are warmed up to 80 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 5 hours down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 86.2%, and the epoxidised selectivity of hydrogen peroxide is 97.8%.
[embodiment 6]
Silicon sol (40 weight %), organosilicon source, tetrabutyl titanate, tetraethyl ammonium hydroxide, tetramethylenediamine and water are mixed by stoichiometric ratio, and wherein each component mol ratio of raw material is the inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.01: 0.02: 0.07: 0.7: 50.220 ℃ of crystallization 3 days, product obtained containing skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 1.2 grams and contain organosilicon titanium-silicon molecular sieve catalyst, 100 gram 1-butanols solvents, 50 gram propenyl chlorides, be warmed up to 90 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 2 hours down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 85.9%, and the epoxidised selectivity of hydrogen peroxide is 97.4%.
[comparative example 1]
With silicon sol (40 weight %), TiCl
4, TPAOH, ammoniacal liquor and water mixes by stoichiometric ratio, wherein each component mol ratio of raw material is the inorganic silicon source: titanium source: organic formwork agent: basic cpd: water=1: 0.01: 0.03: 0.4: 20.160 ℃ of crystallization 1 day, product was not contained skeleton organic group MFI HTS through filtration, washing, drying.
In 250 milliliters of there-necked flasks, add the above-mentioned synthetic of 0.2 gram and do not contain skeleton organic group MFI titanium-silicon molecular sieve catalyst, 20 gram methanol solvates, 10 gram propenyl chlorides, be warmed up to 50 ℃, add 3 gram mass marks again and be 30% H
2O
2Solution, agitation condition reacted 1 hour down, and reaction finishes the back and is cooled to 7 ℃ with frozen water cooling there-necked flask.At last, spinning goes out sieve catalyst and product solution.Hydrogen peroxide conversion is 80.7%, and the epoxidised selectivity of hydrogen peroxide is 94.6%.
Claims (9)
1. method for preparing epoxy chloropropane; With hydrogen peroxide and propenyl chloride is raw material; In temperature of reaction is 40～90 ℃; The weight ratio of hydrogen peroxide and propenyl chloride is 0.02～0.2, and the weight ratio of catalyzer and hydrogen peroxide is to react under 0.1～1.2 condition to obtain said epoxy chloropropane in 1～5 hour;
Wherein, Said Preparation of catalysts method may further comprise the steps: inorganic silicon source, organosilicon source, titanium source, organic formwork agent, basic cpd and water are mixed, and reaction mixture is with molar ratio computing inorganic silicon source: organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: (0.01～0.05): (0.01～0.03): (0.03～0.15): (0.4～2.0): (20～100); Said mixture crystallization under 160～220 ℃ of conditions of temperature was obtained said catalyzer through filtration, washing, drying after 1～30 day.
2. according to the said method for preparing epoxy chloropropane of claim 1, it is characterized in that said inorganic silicon source is selected from least a in silicon sol, silicon ester or the solid oxidation silicon; The organosilicon source is two (triethoxy is silica-based) methane; The titanium source is selected from TiCl
4, TiCl
3, TiOCl
2Or TiOSO
4In at least a; Organic formwork agent is selected from least a in TPAOH, 4-propyl bromide, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide or the tetraethyl ammonium hydroxide; Basic cpd is selected from least a in ammoniacal liquor, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, tetramethylenediamine, hexanediamine, diethylamine, tripropyl amine or the Tributylamine.
3. according to the said method for preparing epoxy chloropropane of claim 1, it is characterized in that said propenyl chloride is selected from chlorallylene, 2-methyl-chlorallylene or 2-ethyl-chlorallylene.
4. according to the said method for preparing epoxy chloropropane of claim 1; It is characterized in that with molar ratio computing the inorganic silicon source: the organosilicon source: titanium source: organic formwork agent: basic cpd: water=1: (0.02～0.04): (0.015～0.025): (0.06～0.12): (0.8～1.6): (50～70).
5. according to the said method for preparing epoxy chloropropane of claim 1, it is characterized in that crystallization temperature is 170～200 ℃, crystallization time is 3～5 days.
6. according to the said method for preparing epoxy chloropropane of claim 1; It is characterized in that temperature of reaction is 40～70 ℃; Reaction times is 1～3 hour, and the weight ratio of hydrogen peroxide and propenyl chloride is 0.06～1.6, and the weight ratio of catalyzer and hydrogen peroxide is 0.4～0.9.
7. according to the said method for preparing epoxy chloropropane of claim 1, it is characterized in that hydrogen peroxide and propenyl chloride react under the condition that organic solvent exists, the weight ratio of hydrogen peroxide and organic solvent is 0.01～0.1.
8. according to the said method for preparing epoxy chloropropane of claim 7, the weight ratio that it is characterized in that hydrogen peroxide and organic solvent is 0.04～0.07.
9. according to the said method for preparing epoxy chloropropane of claim 1, it is characterized in that said organic solvent is selected from methyl alcohol, ethanol, 1, ammediol, 1, at least a in 2-Ucar 35 or the 1-butanols.
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| CN201010552084.1A CN102464632B (en) | 2010-11-17 | 2010-11-17 | Method for preparing epoxy chloropropane |
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Cited By (3)
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| CN104888855A (en) * | 2015-04-03 | 2015-09-09 | 江南大学 | Molybdenyl acetylacetonate solid catalyst used for alkene epoxidation reaction and preparation method thereof |
| CN113426480A (en) * | 2021-05-25 | 2021-09-24 | 武汉理工大学 | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve |
| CN114702463A (en) * | 2022-03-29 | 2022-07-05 | 浙江皇马科技股份有限公司 | Method for preparing methyl epichlorohydrin |
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| CN114702463A (en) * | 2022-03-29 | 2022-07-05 | 浙江皇马科技股份有限公司 | Method for preparing methyl epichlorohydrin |
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