CN103121983A - Allyl chloride epoxidation method - Google Patents
Allyl chloride epoxidation method Download PDFInfo
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- CN103121983A CN103121983A CN2011103673565A CN201110367356A CN103121983A CN 103121983 A CN103121983 A CN 103121983A CN 2011103673565 A CN2011103673565 A CN 2011103673565A CN 201110367356 A CN201110367356 A CN 201110367356A CN 103121983 A CN103121983 A CN 103121983A
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Abstract
The invention relates to an allyl chloride epoxidation method and mainly solves problems of no multi-channel existing in a catalyst and low activity of the catalyst in the prior art. In a homogeneous or a water / oil two-phase reaction medium, on the condition of 20 DEG C to 60 DEG C, by the catalysis of a composite material catalytic with TS-2 zeolites, an oxygen source and the allyl chloride are reacted for 1 to 5 hours. The molar ratio of the allyl chloride to the oxygen source is 0.5-20, and the molar ratio of the allyl chloride to the catalytic is 1-10. According to the technical scheme, the method effectively solves the problems and can be used in industrial production of the allyl chloride epoxidation.
Description
Technical field
The present invention relates to a kind of method of chloro propylene epoxidation reaction.
Background technology
The industrialized production technology of epoxy chloropropane has propenyl chloride method and propylene acetate method.The former is industrial classical way, accounts for global ECH aggregated capacity approximately more than 90%; And the latter is only adopted by several enterprises.The propylene high-temperature chlorination process by Shell company in First Successful Developments in 1948 and be applied to industrial production.Its technological process mainly comprises propylene high-temperature chlorination propenyl chloride processed, propenyl chloride hypochlorination synthesizing dichloropropanol and three reaction members of dichlorohydrine saponification synthesizing epoxy chloropropane.The characteristics of propylene high-temperature chlorination process be production process flexibly, technical maturity, stable operation, except producing epoxy chloropropane, also can produce the important organic synthesis intermediates such as glycerine, propenyl chloride, by-product D-D mixture (1,3-dichloropropylene and 1,2-propylene dichloride) be also 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 is required high, and energy consumption is large, 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 the epoxy chloropropane production cost 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.Document US4833260 discloses a kind of take HTS as catalyzer, directly alkene (comprising haloolefin) is carried out the method that epoxidation is produced epoxide with hydrogen peroxide.Has catalyst activity and selectivity high, reaction conditions gentle (being generally 40～50 ℃), hydrogen peroxide conversion and the epoxy chloropropane productive rate is higher, pollution-free (H
2O
2Be transformed into H
2The advantage such as O).But because its catalyst pores structure is single, catalytic performance is still waiting further raising, and is therefore structurally-modified to satisfy the requirement of this respect by catalyzer is carried out, and more and more causes the concern of chemist.In recent years organic molecule is combined with inorganic oxide, synthetic novel porous material with special construction and character is subject to extensive concern.Wherein the composite holes material is also one of them study hotspot.Compare with common material, the composite holes material is conducive to the material transfer diffusion, thereby shows wide application prospect at absorption, separation and catalytic field.Patent CN 101525137A and CN 101723393 A have reported respectively the preparation method of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material.Prepared material all has integrated macro morphology, has high specific surface area and flourishing gap structure.But also have the problem of not introducing micro porous molecular sieve, we solve problems by the method at this large pore material hole wall growth micro porous molecular sieve.
Summary of the invention
Technical problem to be solved by this invention is that catalyzer does not contain multistage pore canal, and catalyst activity hangs down problem, a kind of method that provides new chloro propylene epoxidation to react.The method is used for the chloro propylene epoxidation reaction, has catalyzer and contains multistage pore canal, the advantage that catalyst activity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of chloro propylene epoxidation, it is characterized in that in homogeneous phase or water/oily two phase reaction medium, containing to react under the catalysis of the composite catalyst of TS-2 molecular sieve at oxygen source and propenyl chloride under 20 ℃～60 ℃ conditions and generating the product epoxy chloropropane in 0.5～3 hour, wherein the mol ratio of propenyl chloride and oxygen source is 0.5～20, and the mol ratio of propenyl chloride and catalyzer is 1～10.
In technique scheme, the described matrix material that contains the TS-2 molecular sieve, have three and overlap the duct on three-dimensional space: first set is the co-continuous macroporous structure that connects, and the aperture is at 0.05～8 micron; The second cover is to consist of in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and the aperture is adjustable continuously between 2～8 nanometers; The 3rd cover is the micropore canals of TS-2 molecular sieve.Described oxygen source preferred version is for being selected from hydrogen peroxide or alkyl peroxide, the wherein said hydrogen peroxide preferred version concentration that is weight percentage is 5～90% aqueous hydrogen peroxide solution, and described alkyl peroxide preferred version is for being selected from tertbutyl peroxide, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexyl hydroperoxide.Described reaction medium preferred version is to be selected from least a in alcoholic solvent, alkanes solvent, aromatic hydrocarbon solvent, esters solvent, ether solvent, ketones solvent, nitrile solvents or halogenated hydrocarbon solvent; Wherein said alcoholic solvent preferred version is to be selected from least a in methyl alcohol, ethanol, n-propyl alcohol, Virahol or the trimethyl carbinol; Described alkanes solvent preferred version is at least a in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon that is selected from C5～C18; Described aromatic hydrocarbon solvent preferred version is to be selected from least a in benzene, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene; Described esters solvent preferred version is to be selected from least a in fatty acid ester, aromatic esters, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate or trioctyl phosphate; Described ether solvent preferred version is to be selected from least a in alkyl ether, aromatic base ethers or aromatic alkyl ethers; Described ketones solvent preferred version is to be selected from least a in dialkyl group ketone, aryl alkyl ketone; Described nitrile solvents preferred version is to be selected from least a in acetonitrile or Bian nitrile; Described halogenated hydrocarbon solvent preferred version is to be selected from least a in halogenated alkane or halogenated aryl hydrocarbon.
The described TS-2 molecular sieves compound material method for preparing catalyst that contains, comprise the following steps: the inductor R1 that a) will be separated, structure directing agent R2, acid catalyst and water mix, add the mixture in silicon source and titanium source 0～30 ℃ of fully hydrolysis, the mixture quality ratio consists of: R1/SiO
2=0.3～1.0; R2/SiO
2=0.3～2.0; H
2O/SiO
2=4～7; H
+/ SiO
2=0.1～0.35; TiO
2/ SiO
2=0.01～0.15; B) said mixture is poured in mould, at 20～80 ℃ of gels, continued standing aging 0.1～48 hour; C) with the aging after product demoulding, 20～100 ℃ of dryings, be 1～7 day time of drying, then makes mesoporous macroporous structure amorphous ti silica material after 0.5～24 hour 450～800 ℃ of roastings, and its specific surface is up to 750～1000 meters
2/ gram, pore volume are 0.9～1.8 meter
2/ gram has two and overlaps the duct on three-dimensional space: a cover is the co-continuous macroporous structure that connects, and the aperture is at 0.05～8 micron; Another set of is to consist of in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and the aperture is adjustable continuously between 2～8 nanometers; D) the mesoporous macroporous structure oxide material that will make is put into the tetrabutyl phosphonium bromide amine aqueous solution and was soaked 0.1～48 hour, then puts into the top of hydrothermal reaction kettle, and still bottom is water, and gas phase crystallization 1～3 day namely obtains a kind of matrix material of the TS-2 of containing molecular sieve.The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, polyoxyethylene or polyethylene oxide at least a, its molecular-weight average is 3000～100000; Structure directing agent R2 is selected from least a in triblock copolymer, chain alkyl trimethylammonium halogenation ammonia, citric acid, tartrate, oxysuccinic acid or lactic acid; Wherein triblock copolymer is polyoxyethylene-poly-oxypropylene polyoxyethylene, and its molecular-weight average is 1500～10000; The general formula of chain alkyl trimethylammonium halogenation ammonia is (CH
3)
nN
+(CH
3)
3X
-, n=8～18, X is Cl or Br.The silicon source is selected from least a in methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate.The titanium source is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4Or general formula is (R
2O)
4At least a in the organic titanate of Ti, wherein R
2Alkyl for 1-4 carbon atom.Acid catalyst is at least a in nitric acid, phosphoric acid, hydrochloric acid or acetic acid.Preferred 0.1～24 hour of its gel digestion time.Its ageing products is preferred 2～10 hours of 450～800 ℃ of roasting time, continues to extend roasting time little on the reaction structure impact.
In technique scheme, control respectively mesoporous and generation macropore owing to having adopted two template in synthetic, the inductor R1 that wherein is separated plays in sol-gel process and causes the effect that the co-continuous macropore that is separated and then leads generates, and structure directing agent R2 mainly plays the space occupy-place or generate the lead effect of regular mesoporous generation of mesomorphic phase by interacting with the silicon titanium species.Method by the gas phase crystallization is synthetic TS-2 molecular sieve in the macropore duct, simultaneously by to the modulation of silicon source and titanium source category, Template Types, add-on and reaction conditions, can be respectively mesoporous macroporous structure and the pore size distribution of product be regulated and controled effectively.Its macro morphology size of the matrix material that contains the TS-2 molecular sieve of the inventive method preparation depends on the pattern of the mould that uses, and specific surface is up to 750～1000 meters
2/ gram, pore volume are 0.9～1.8 meter
2/ gram.Have three and overlap the duct on three-dimensional space: first set is the co-continuous macroporous structure that connects, and the aperture is at 0.05～8 micron; The second cover is to consist of in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and the aperture is adjustable continuously between 2～8 nanometers; The 3rd cover is the micropore canals of TS-2 molecular sieve.With catalyzer of the present invention, be used for the chloro propylene epoxidation reaction, after 1 hour, it is H as a result 50 ℃ of reactions
2O
2Transformation efficiency is more than 95%, than the H of prior art
2O
2Transformation efficiency can improve more than 2%, has obtained technique effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Hydrochloric acid soln 13 grams of weighing 1 mol/L, add 1.6 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000, P123) stirring and dissolving under room temperature adds polyoxyethylene glycol (molecular weight 10000) 0.8 gram in mixing solutions, change in frozen water mixing bath to continue to stir 5 minutes.Add 4 gram methyl silicates and 0.1 gram tetrabutyl titanate in mixing solutions, after vigorous stirring 10 minutes, mixed solution is poured in mould sealed, standing 5 hours of room temperature, the demoulding after taking out, drying at room temperature, 550 ℃ of roastings 5 hours, get mesoporous macropore combined porous structure amorphous ti silica material, the mesoporous macroporous structure amorphous ti silica material of system is put into the tetrabutyl phosphonium bromide ammonium solution soaked 24 hours, then put into the top of hydrothermal reaction kettle, the still bottom is water, gas phase crystallization 1 day namely obtains containing the matrix material of TS-2 molecular sieve.The texture parameter of concrete product is: 875 meters of specific surface areas
2/ gram, pore volume are 1.3 centimetres
3/ gram, 1 micron of macropore diameter, mesoporous aperture 7 nanometers.
Add above-mentioned synthetic catalyzer, the 100 ml methanol solvents of 5 mmoles, the propenyl chloride of 5 mmoles in 250 milliliters of there-necked flasks, be warmed up to 50 ℃, then to add the massfraction of 0.5 mmole be 30% H
2O
2Solution, under agitation condition, reaction is 1 hour, and reaction is cooled to 7 ℃ with the cooling there-necked flask of frozen water after finishing.At last, centrifugation goes out molecular sieve catalyst and product solution.The same circulating reaction of catalyzer that reclaims four times, reaction result is as shown in table 1.
Table 1
| The catalyst recirculation number of times | H 2O 2Transformation efficiency, % | The transformation efficiency of propylene, % | The epoxy chloropropane selectivity, % |
| Live catalyst | 96.2 | 8.8 | 96.7 |
| I | 95.3 | 7.6 | 94.1 |
| II | 96.6 | 8.2 | 95.3 |
| III | 95.7 | 7.8 | 96.4 |
| IV | 96.4 | 8.4 | 96.6 |
[embodiment 2]
Add above-mentioned synthetic catalyzer, the 100 ml methanol solvents of 0.5 mmole, the propenyl chloride of 5 mmoles in 250 milliliters of there-necked flasks, be warmed up to 20 ℃, then to add the massfraction of 0.25 mmole be 30% H
2O
2Solution, under agitation condition, reaction is 2 hours, and reaction is cooled to 7 ℃ with the cooling there-necked flask of frozen water after finishing.At last, centrifugation goes out molecular sieve catalyst and product solution.H
2O
2Transformation efficiency 95.4%, the transformation efficiency 7.6% of propylene, epoxy chloropropane selectivity 96.3%.
[embodiment 3]
Add above-mentioned synthetic catalyzer, the 100 ml methanol solvents of 1.5 mmoles, the propenyl chloride of 5 mmoles in 250 milliliters of there-necked flasks, be warmed up to 30 ℃, then to add the massfraction of 5 mmoles be 30% H
2O
2Solution, under agitation condition, reaction is 3 hours, and reaction is cooled to 7 ℃ with the cooling there-necked flask of frozen water after finishing.At last, centrifugation goes out molecular sieve catalyst and product solution.H
2O
2Transformation efficiency 96.1%, the transformation efficiency 8.1% of propylene, epoxy chloropropane selectivity 95.4%.
[embodiment 4]
Add above-mentioned synthetic catalyzer, the 100 ml methanol solvents of 3 mmoles, the propenyl chloride of 5 mmoles in 250 milliliters of there-necked flasks, be warmed up to 40 ℃, then to add the massfraction of 3 mmoles be 30% H
2O
2Solution, under agitation condition, reaction is 4 hours, and reaction is cooled to 7 ℃ with the cooling there-necked flask of frozen water after finishing.At last, centrifugation goes out molecular sieve catalyst and product solution.H
2O
2Transformation efficiency 96.7%, the transformation efficiency 8.2% of propylene, epoxy chloropropane selectivity 96.4%.
[embodiment 5]
Add above-mentioned synthetic catalyzer, the 100 ml methanol solvents of 1 mmole, the propenyl chloride of 5 mmoles in 250 milliliters of there-necked flasks, be warmed up to 60 ℃, then to add the massfraction of 1 mmole be 30% H
2O
2Solution, under agitation condition, reaction is 5 hours, and reaction is cooled to 7 ℃ with the cooling there-necked flask of frozen water after finishing.At last, centrifugation goes out molecular sieve catalyst and product solution.H
2O
2Transformation efficiency 95.8%, the transformation efficiency 7.7% of propylene, epoxy chloropropane selectivity 96.2%.
[embodiment 6]
Change solvent, the oxygen source of reaction system, all the other conditions are identical with embodiment 1, and the result of epoxidation reaction is as shown in table 2.
Table 2
| Solvent | Oxygen source | H 2O 2Transformation efficiency, % | Propylene conversion, % | The epoxy chloropropane selectivity, % |
| The trimethyl carbinol | 35% superoxol | 95.4 | 8.4 | 96.5 |
| Acetone | 65% superoxol | 97.8 | 8.5 | 97.3 |
| Chloroform | 50% superoxol | 96.1 | 7.8 | 96.2 |
[Comparative Examples 1]
Press each Step By Condition of embodiment 1, just catalyzer is TS-2 molecular sieve (self-control), and reaction result is H
2O
2Transformation efficiency be 93.0%, the transformation efficiency of propenyl chloride is 6.4%, the selectivity of epoxy chloropropane is 92.5%.
Claims (3)
1. the method for a chloro propylene epoxidation, it is characterized in that in homogeneous phase or water/oily two phase reaction medium, containing to react under the catalysis of the composite catalyst of TS-2 molecular sieve at oxygen source and propenyl chloride under 20 ℃～60 ℃ conditions and generating the product epoxy chloropropane in 0.5～3 hour, wherein the mol ratio of propenyl chloride and oxygen source is 0.5～20, and the mol ratio of propenyl chloride and catalyzer is 1～10.
2. the method for chloro propylene epoxidation according to claim 1, the matrix material that it is characterized in that containing the TS-2 molecular sieve have three cover ducts on three-dimensional space: first set is the co-continuous macroporous structure that connects, and the aperture is at 0.05～8 micron; The second cover is to consist of in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and the aperture is adjustable continuously between 2～8 nanometers; The 3rd cover is the micropore canals of TS-2 molecular sieve.
3. the method for chloro propylene epoxidation claimed in claim 1, it is characterized in that described oxygen source is selected from hydrogen peroxide or alkyl peroxide, the wherein said hydrogen peroxide concentration that is weight percentage is 5～90% aqueous hydrogen peroxide solution, and described alkyl peroxide is selected from tertbutyl peroxide, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexyl hydroperoxide, described reaction medium is selected from alcoholic solvent, the alkanes solvent, aromatic hydrocarbon solvent, esters solvent, ether solvent, ketones solvent, at least a in nitrile solvents or halogenated hydrocarbon solvent, wherein said alcoholic solvent is selected from methyl alcohol, ethanol, n-propyl alcohol, at least a in Virahol or the trimethyl carbinol, described alkanes solvent is selected from the straight-chain paraffin of C5～C18, at least a in branched paraffin or naphthenic hydrocarbon, described aromatic hydrocarbon solvent is selected from benzene, toluene, ethylbenzene, dimethylbenzene, at least a in trimethylbenzene, described esters solvent is selected from fatty acid ester, aromatic esters, trimethyl phosphite 99, triethyl phosphate, the tricresyl phosphate propyl ester, at least a in tributyl phosphate or trioctyl phosphate, described ether solvent is selected from least a in alkyl ether, aromatic base ethers or aromatic alkyl ethers, described ketones solvent is selected from least a in dialkyl group ketone, aryl alkyl ketone, described nitrile solvents is selected from least a in acetonitrile or Bian nitrile, and described halogenated hydrocarbon solvent is selected from least a in halogenated alkane or halogenated aryl hydrocarbon.
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Cited By (2)
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|---|---|---|---|---|
| CN106967010A (en) * | 2016-01-13 | 2017-07-21 | 中国石油化工股份有限公司 | A kind of chloropropene method for oxidation |
| CN107954838A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of method for preparing the chloro- 2- propyl alcohol of 1,3- bis- |
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2011
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967010A (en) * | 2016-01-13 | 2017-07-21 | 中国石油化工股份有限公司 | A kind of chloropropene method for oxidation |
| CN106967010B (en) * | 2016-01-13 | 2019-08-16 | 中国石油化工股份有限公司 | A kind of chloropropene method for oxidation |
| CN107954838A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of method for preparing the chloro- 2- propyl alcohol of 1,3- bis- |
| CN107954838B (en) * | 2016-10-18 | 2021-10-08 | 中国石油化工股份有限公司 | Method for preparing 1, 3-dichloro-2-propanol |
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