CN105294603B - The method for producing epoxychloropropane - Google Patents
The method for producing epoxychloropropane Download PDFInfo
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- CN105294603B CN105294603B CN201410314287.5A CN201410314287A CN105294603B CN 105294603 B CN105294603 B CN 105294603B CN 201410314287 A CN201410314287 A CN 201410314287A CN 105294603 B CN105294603 B CN 105294603B
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Abstract
The present invention relates to a kind of method for producing epoxychloropropane, the problem of mainly solving prior art, waste water, waste residue amount to be present big, seriously polluted, and equipment corrosion is strong.The present invention is by using comprising the following steps：A) ethylbenzene carries out peroxidization with air, obtains hydrogen peroxide ethylbenzene oxidation liquid；B) with chloropropene in the presence of catalyst epoxidation reaction generation epoxychloropropane, α xylyl alcohols and acetophenone occur under liquid-phase condition for hydrogen peroxide ethylbenzene oxidation liquid；C) α xylyl alcohols dehydration generation styrene；D) with hydrogen hydrogenation reaction generation α xylyl alcohols occur for acetophenone；The α xylyl alcohols of step generation return to c) step, preferably solves the problem with the technical scheme for being hydrogenated to styrene together with the α xylyl alcohols of b) step generation, available in the industrial production for preparing epoxychloropropane, co-production styrene.
Description
Technical field
The present invention relates to a kind of method for producing epoxychloropropane.
Background technology
Epoxychloropropane is that a kind of important Organic Chemicals and fine chemical product, purposes are quite varied.Using it as
Epoxy resin made from raw material has that caking property is strong, resistant to chemical etching, shrinkage factor is low, chemical stability is good, excellent in cushion effect
And dielectric properties it is excellent the features such as, have in industries such as coating, adhesive, reinforcing material, cast material and electronics laminated products
It is widely applied.In addition, epoxychloropropane can be additionally used in synthetic glycerine, nitroglycerine, fiberglass, electric insulation product, surface
Activating agent, medicine, agricultural chemicals, coating, sizing material, ion exchange resin, plasticizer, (contracting) glycerol derivatives, chlorohydrin rubber etc. are more
Kind product.
Conventional epoxy chloropropane production method mainly has two kinds of propylene high-temperature chloridising and acetate propylene ester process.Propylene high-temperature
Chloridising by Shell companies in First Successful Development in 1948, the technical process mainly include propylene high-temperature chlorination chloropropene,
Chloropropene chlorohydrination synthesizing dichloropropanol and dichlorohydrin saponification synthesizing epoxy three reaction members of chloropropane.The method production process
Flexibly, technical maturity, stable operation, but shortcoming are that equipment corrosion caused by raw material chlorine is serious, to purified propylene and reactor
Material require high, energy consumption is big, and chlorine consumption is high, and accessory substance is more, and product yield is low, and waste water, waste residue amount are big, seriously polluted.
Acetate propylene ester process is developed respectively by the academy of sciences of the former Soviet Union and Japanese Showa electrician company the 1980s
Success.The technical process mainly includes propylene, oxygen and acetic acid reaction synthesis allyl acetate, acetate propylene ester hydrolysis allyl
Alcohol, allyl alcohol and chlorine synthesizing dichloropropanol, dichlorohydrin generate epoxychloropropane totally four reaction members through saponification.With tradition
Propylene high-temperature chloridising compare, be that reaction condition is gentle the characteristics of acetate propylene ester process, easily controllable, material consumption, energy consumption, pair
Product, wastewater flow rate have all declined, and major defect is technological process length, and catalyst life is short, low production efficiency, investment cost
It is high.
With the development of biodiesel, when producing biodiesel, there are a large amount of glycerine to be generated as accessory substance, therefore, with
Glycerine is that the technique of raw material production epoxychloropropane is also arisen at the historic moment.The technical process of glycerine legal system epoxychloropropane mainly includes
Glycerin chlorination refining dichlorohydrin (WO 2005054167, WO 2006020234, EP 1771403) and dichlorohydrin saponification ring
Two reaction members of oxygen chloropropane.Because dichlorohydrin saponification epoxychloropropane is important in the acrylonitrile-chlorinated method of conventional high-temperature
Link, technology maturation, so, glycerin chlorination refining dichlorohydrin is the core of the technology.With the development of biomass energy, in life
The glycerine of generation material diesel oil when institute by-product is more and more, and this provides raw material sources for producing epoxy chloropropane through glycerine method.But
Due to making raw material using hydrogen chloride during glycerin chlorination refining dichlorohydrin, equipment corrosion is serious, and dichlorohydrin saponification
Epoxychloropropane process processed makees saponification agent using white lime, and course of reaction produces a large amount of calcium chloride waste residues and containing organic chloride
Waste water, environmental pollution are serious.
The content of the invention
The technical problems to be solved by the invention are that prior art has waste water, a waste residue amount big, seriously polluted, equipment corrosion
A kind of the problem of property is strong, there is provided new production epoxychloropropane method.This method has catalyst activity height, feed stock conversion
Height, stability is good, epoxychloropropane high income, it is green the characteristics of.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of method for producing epoxychloropropane,
Comprise the following steps：
A) ethylbenzene carries out peroxidization with air, obtains hydrogen peroxide ethylbenzene oxidation liquid；
B) with chloropropene in the presence of catalyst epoxidation occurs under liquid-phase condition for hydrogen peroxide ethylbenzene oxidation liquid anti-
Epoxychloropropane, α-methylbenzylalcohol and acetophenone should be generated；
C) α-methylbenzylalcohol dehydration generation styrene；
D) with hydrogen hydrogenation reaction generation α-methylbenzylalcohol occurs for acetophenone；The α-methylbenzylalcohol of step generation returns to c)
Step, styrene is hydrogenated to together with the α-methylbenzylalcohol of b) step generation.
In above-mentioned technical proposal, it is preferable that step a) reaction condition is：0~250 DEG C of reaction temperature, reaction pressure 0.1
~5.0MPa.It is highly preferred that 50~200 DEG C of reaction temperature, 0.1~2.0MPa of reaction pressure.
In above-mentioned technical proposal, it is preferable that step b) reaction condition is：25~180 DEG C of reaction temperature, reaction pressure
0.1~10.0MPa, the mol ratio 1~20 of chloropropene and hydrogen peroxide ethylbenzene, the weight space velocity 0.1~20 of hydrogen peroxide ethylbenzene
Hour-1.It is highly preferred that 40~150 DEG C, 0.5~8.0MPa of reaction pressure of reaction temperature, chloropropene rubs with hydrogen peroxide ethylbenzene
That ratio 2~15, the weight space velocity of hydrogen peroxide ethylbenzene 0.3~10.0 hour-1.Catalyst used is that multiphase is titanium-containing meso-porous or big
Hole silica catalysis material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2。
In above-mentioned technical proposal, it is preferable that step c) reaction condition is：50~400 DEG C of reaction temperature, reaction pressure 0
~5.0MPa, the weight space velocity of α-methylbenzylalcohol is 0.1~10.0 hour-1.It is highly preferred that 100~350 DEG C of reaction temperature, instead
0.1~3.0MPa of pressure is answered, the weight space velocity of α-methylbenzylalcohol is 0.3~5.0 hour-1。
In above-mentioned technical proposal, it is preferable that step d) reaction condition is：50~350 DEG C of reaction temperature, reaction pressure
0.1~6.0MPa, H2Mol ratio with acetophenone is 1~10, and the weight space velocity of acetophenone is 0.1~10.0 hour-1.More preferably
Ground, 80~300 DEG C of reaction temperature, reaction pressure 0.5~5.0MPa, H2Mol ratio with acetophenone is 2~6, the weight of acetophenone
It is 0.3~6.0 hour to measure air speed-1。
In above-mentioned technical proposal, it is preferable that the weight percent of hydrogen peroxide ethylbenzene in the hydrogen peroxide ethylbenzene oxidation liquid
Concentration is 1~50%.
In the inventive method, step a) is peroxidation step, using molecular oxygen by ethylbenzene oxidation into hydrogen peroxide ethylbenzene, this
It is a classical radical reaction.Molecular oxygen used can be air or use oxygen-enriched air.The reaction both can be with
Carry out, can also efficiently be carried out in the case of without any catalyst or additive in the presence of catalyst or additive.Institute
It is generally the hydroxide or carbonate of alkali metal, alkaline-earth metal, ammonia with catalyst or additive, but from the post processing of oxidation solution
Angle considers, preferential using the ethylbenzene air oxidation system without any additive.Under normal circumstances, the reaction temperature of oxidation step
Degree and pressure are respectively 0~250 DEG C and 0.1~5.0MPa, preferably 50~200 DEG C and 0.1~2.0MPa.Temperature is too low, instead
Answer efficiency low, or can not carry out；And too high temperature then easily causes hydrogen peroxide ethylbenzene to decompose or produce other accessory substances.
In the inventive method, step b) is epoxidation step, the carrier of oxygen one of the hydrogen peroxide ethylbenzene as epoxidation reaction
As the form of mixtures that is formed with itself and ethylbenzene use, be typically chosen its weight concentration as 1~50%, preferably 10~40%.
Concentration is too low, and epoxidation efficiency is low, less economical；Excessive concentration, then reaction heat effect is obvious, and reaction heat removes difficulties, and
It is unfavorable to the performance of epoxidation catalyst and too high concentration causes the too high levels of benzylalcohol and other accessory substances in product, hold
Catalyst inactivation is easily caused, and too high concentration also easily causes decomposition reaction.Epoxidation reaction is under liquid-phase condition
Carried out in solvent, used solvent is liquid under reaction temperature and pressure, and it is inertia to reactant and product.
Used solvent includes alkane and benzene, the first such as hexane, hexamethylene, heptane, octane, nonane, decane, hendecane, dodecane
The benzene such as benzene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene and substituted benzene, preferably ethylbenzene, it can so avoid introducing
Extra material, increase separating energy consumption.Epoxidation reaction temperature is 25~180 DEG C, preferably 40~150 DEG C.Temperature is too low anti-
It should be difficult to, temperature is too high, easily causes hydrogen peroxide ethylbenzene to decompose, accessory substance increase.Reaction pressure is former with maintenance reaction
Material is in a liquid state, preferably 0.1~10.0MPa, more preferably 0.5~8.0MPa.Hypotony easily causes material to vaporize, nothing
Method ensures to carry out under liquid-phase condition, and hypertonia then causes reaction heat to increase, and power consumption increases, and influences economy.Chlorine
The mol ratio of propylene and hydrogen peroxide ethylbenzene is 1~20, preferably 2~15, and the air speed of hydrogen peroxide ethylbenzene is small for 0.1~20.0
When-1, preferably 0.3~10.0 hour-1.Epoxidation reaction can both be carried out in slurry bed reactor, can also be anti-in fixed bed
Answer in device and carry out.But from the angle of large-scale industrial production, it is preferred to use fixed bed reactors.Catalyst used be containing
Titanium is mesoporous or macroporous silica catalysis material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-
SiO2。
In above-mentioned technical proposal, Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO are urged
Agent is prepared using post-synthesis, synthesizes pure silicon HMS, MCM-41, TUD-1, SBA-15, KIT-1 mesoporous material or choosing first
Select suitable macro-pore SiO2Powder.
The preparation method of pure silicon HMS original powder is as follows：Using formula as RNH2Organic amine be template agent, wherein R is containing 5~40
The chain alkylene of individual carbon atom, using esters of silicon acis or amorphous silica as silicon source, using alcohol and water as solvent, using hydrothermal synthesis method
Prepare.Wherein, the esters of silicon acis is selected from positive quanmethyl silicate, tetraethyl orthosilicate, the n-propyl of positive silicic acid four, the isopropyl of positive silicic acid four
Ester or the butyl ester of positive silicic acid four；The RNH2Middle R is preferably the linear paraffin base containing 10~20 carbon atoms；The alcohol is selected from first
Alcohol, ethanol, normal propyl alcohol, isopropanol, vinyl alcohol, allyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, amylalcohol, cyclohexanol, second two
At least one of alcohol or propane diols.With molar ratio computing, silicon source:Template:Water:Alcohol=1:(0.05~0.5):(10~60):
(3~15).
The preparation method of silica MCM-41 original powder is as follows：Using cetyl trimethylammonium bromide as template, with esters of silicon acis
Or amorphous silica is silicon source, using water as solvent, prepared in alkaline environment using hydrothermal synthesis method.Wherein, the silicon
Acid esters is selected from positive quanmethyl silicate, tetraethyl orthosilicate, the n-propyl of positive silicic acid four, the isopropyl ester of positive silicic acid four or the fourth of positive silicic acid four
Ester.With molar ratio computing, silicon source:Template:Water:Alkali=1:(0.05~0.35):(15~40):(0.1~0.4).
The preparation method of pure silicon TUD-1 original powder is as follows：Using triethanolamine as template, using esters of silicon acis as silicon source, with alcohol and
Water is solvent, is prepared in alkaline environment using hydrothermal synthesis method.Wherein, the esters of silicon acis is selected from positive quanmethyl silicate, positive silicon
Sour tetra-ethyl ester, the n-propyl of positive silicic acid four, the isopropyl ester of positive silicic acid four or the butyl ester of positive silicic acid four；The alcohol is selected from methanol, ethanol, positive third
Alcohol or isopropanol, the alkali are selected from tetraethyl ammonium hydroxide.With molar ratio computing, silicon source:Template:Water:Alcohol:Alkali=1:(0.3~
3.0):(5~30):(0.5~5.0):(0.1~0.5).
The preparation method of pure silicon SBA-15 original powder is as follows：Using triblock copolymer (PEO-PPO-PEO), using esters of silicon acis as
For silicon source in strong acidic environment, prepared by hydrothermal synthesis method.Wherein, the esters of silicon acis is selected from positive quanmethyl silicate, positive silicic acid tetrem
Ester, the n-propyl of positive silicic acid four, the isopropyl ester of positive silicic acid four or the butyl ester of positive silicic acid four, the acid preferably molar concentration are rubbed for 0.5~3.5
You/liter hydrochloric acid solution.With molar ratio computing, silicon source:PEO-PPO-PEO:H2O:HCl=1:(0.005~0.04):(20~
100):(3~10).
The preparation method of pure silicon KIT-1 original powder is as follows：Using cetyl trimethylammonium bromide as template agent, using esters of silicon acis as
Silicon source, in the presence of EDTA (sodium ethylene diamine tetracetate) and water, prepared by hydrothermal synthesis method.Wherein, the esters of silicon acis is selected from positive silicon
Sour four methyl esters, tetraethyl orthosilicate, the n-propyl of positive silicic acid four, the isopropyl ester of positive silicic acid four or the butyl ester of positive silicic acid four.With molar ratio computing,
Silicon source:Template:EDTA:Water=1:(0.1~0.4):(0.5~1.5):(20~100).
By in pure silicon mesoporous silicon oxide or macroporous silica selected from HMS, MCM-41, TUD-1, SBA-15, KIT-1
At least one former powder and binding agent be shaped to carrier；The dosage of former powder is 50~99 weight %；
Using halogenated titanium or titanate esters as titanium source, organic solvent is used in the form of liquid-phase grafting, or using dry gas as load
Gas uses gas phase graft form, the active titanium species with four-coordination is implanted in the carrier framework of gained, it is more to obtain titaniferous
Hole SiO 2 catalyst.It is preferred that using organosilicon reagent to carry titanium after the further surface grafting silanization treatment of catalyst,
Make it have the hydrophobic property of height.The organosilicon is selected from least one of halosilanes, silazane or silylamine.Urge
The way of contact of agent and organosilicon, catalyst Precursors can be impregnated with the organic silicon solution being dissolved in organic solvent,
It can be handled with the organosilicon steam grafting being scattered in dry gas.It is porous in the described titaniferous with very hydrophobic characteristic
The weight percentage of titanium is 0.1~20% in SiO 2 catalyst.Wherein, it is 6 that the organic solvent, which is selected from carbon number,
~20 chain hydrocarbon, cyclic hydrocarbon and aromatic hydrocarbons；The dry gas is selected from air, nitrogen, helium, neon, argon gas, xenon, methane, hydrogen
At least one of gas, carbon monoxide or carbon dioxide.
In the inventive method, step c) is α-methylbenzylalcohol dehydration, and dehydration is in the presence of a catalyst will
α-methylbenzylalcohol dehydration generation styrene.Used catalyst includes the various catalysis materials with dehydrating function, such as active oxidation
Aluminium, zeolite molecular sieve etc..Dehydration can both be carried out in slurry bed reactor, can also be entered in fixed bed reactors
OK.The temperature and pressure of dehydration be respectively 50~400 DEG C and 0~5.0MPa, preferably 100~350 DEG C and 0.1~
3.0MPa；The weight space velocity of α-methylbenzylalcohol is 0.1~10.0 hour-1, preferably 0.3~5.0 hour-1。
In the inventive method, step d) is hydrogenation of acetophenone step, and used catalyst includes Raney's nickel catalyst, activity
Charcoal, aluminum oxide or silica supported Ni-based, copper-based or palladium base etc. have the catalysis material of catalytic hydrogenation function, reaction temperature 50
~350 DEG C, preferably 80~300 DEG C；0.1~6.0MPa of reaction pressure, preferably 0.5~5.0MPa；H2With the mol ratio of acetophenone
For 1~10, preferably 2~6；The weight space velocity of acetophenone 0.1~10.0 hour-1, preferably 0.3~6.0 hour-1.Hydrogenation reaction was both
It can carry out, can also be carried out in fixed bed reactors in slurry bed reactor.
The inventive method is in addition to purpose product epoxychloropropane, and also joint product styrene generates, and Technical Economy is good,
Achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
In 160 DEG C, 0.4MPa, control tail oxygen volume content is less than under the conditions of 5%, and ethylbenzene carries out peroxidation with air
Should, the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10% is obtained, the peroxide that weight concentration is 30% is made through vacuum concentrate
Change hydrogen ethylbenzene (EBHP) oxidation solution.
By above-mentioned weight concentration be 30% hydrogen peroxide ethylbenzene oxidation liquid in Ti-HMS catalyst, (Ti weight percent contains
Measure as in the presence of 1.6%), in fixed bed reactors and chloropropene carries out epoxidation reaction generation epoxychloropropane, Alpha-Methyl
Benzylalcohol and a small amount of acetophenone.Wherein chloropropene/EBHP=4:1 (mole), EBHP weight space velocity=3.0 hour-1, reaction temperature
For 105 DEG C, reaction pressure 3.5MPa.
Reaction mixture is passed through into the excessive chloropropene of chloropropene recovery tower recovery to recycle, the tower is grasped at ambient pressure
Make, 45 DEG C of tower top temperature, 150 DEG C of bottom temperature.Thing of the tower reactor containing epoxychloropropane, α-methylbenzylalcohol, acetophenone and ethylbenzene etc.
Material enters epoxychloropropane knockout tower, and the tower operates under reduced pressure, tower top pressure 90mmHg, 50 DEG C of tower top temperature, bottom temperature
130℃.The thick epoxychloropropane cut of tower top passes through the isolated pure epoxy chloropropane of further rectifying.Tower reactor benzyl containing Alpha-Methyl
The logistics of alcohol, acetophenone and ethylbenzene enters dehydration reactor, and α-methylbenzylalcohol is in γ-Al2O3Dehydration generation benzene in the presence of catalyst
Ethene, dehydration temperature are 200 DEG C, reaction pressure 0.5MPa, the weight space velocity of α-methylbenzylalcohol 1.0 hours-1.It is reacted
Mixture enters styrene separating tower, and the tower operates at reduced pressure conditions, tower top pressure 80mmHg, 50 DEG C of tower top temperature, tower reactor
110 DEG C of temperature.Styrene and ethylbenzene are from overhead extraction, by further separating to obtain refined styrene, tower reactor evaporating containing acetophenone
Divide into hydrogenation of acetophenone reactor and change into α-methylbenzylalcohol, used catalyst 5%Ni/Al2O3, 150 DEG C of reaction temperature,
Pressure 2.0MP, H2Mol ratio with acetophenone is 3:1, the weight space velocity of acetophenone is 2.0 hours-1, the α-methylbenzylalcohol of generation
Dehydration reactor, which is combined into, with foregoing α-methylbenzylalcohol changes into styrene.Reaction result is as shown in table 1.
【Embodiment 2】
In 150 DEG C, 0.3MPa, control tail oxygen volume content is less than under the conditions of 5%, and ethylbenzene carries out peroxidation with air
Should, the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10% is obtained, the peroxide that weight concentration is 28% is made through vacuum concentrate
Change hydrogen ethylbenzene (EBHP) oxidation solution.
By above-mentioned weight concentration be 28% hydrogen peroxide ethylbenzene oxidation liquid in Ti-MCM-41 catalyst (Ti weight hundred
Point content in the presence of 2.0%), in fixed bed reactors and chloropropene carry out epoxidation reaction generation epoxychloropropane, α-
Xylyl alcohol and a small amount of acetophenone.Wherein chloropropene/EBHP=4:1 (mole), EBHP weight space velocity=3.0 hour-1, reaction
Temperature is 105 DEG C, reaction pressure 3.5MPa.
Reaction mixture is passed through into the excessive chloropropene of chloropropene recovery tower recovery to recycle, chloropropene recovery and epoxy
Chloropropane rectifying separation is same【Embodiment 1】.Logistics of the tower reactor containing α-methylbenzylalcohol, acetophenone and ethylbenzene enters dehydration reactor,
α-methylbenzylalcohol is dehydrated generation styrene in the presence of ZSM-5 catalyst, and dehydration temperature is 200 DEG C, reaction pressure
0.5MPa, the weight space velocity of α-methylbenzylalcohol 1.0 hours-1.Reacted mixture enters styrene separating tower, the essence of styrene
Cut is from same【Embodiment 1】.Cut of the styrene separating tower tower reactor containing acetophenone into hydrogenation of acetophenone reactor change into α-
Xylyl alcohol, used catalyst 0.5%Pd/C, 150 DEG C of reaction temperature, pressure 2.0MP, H2Mol ratio with acetophenone is 3:
1, the weight space velocity of acetophenone is 2.0 hours-1, the α-methylbenzylalcohol of generation and foregoing α-methylbenzylalcohol are combined into dehydration instead
Device is answered to change into styrene.Reaction result is as shown in table 1.
【Embodiment 3】
In 155 DEG C, 0.35MPa, control tail oxygen volume content is less than under the conditions of 5%, and ethylbenzene carries out peroxidation with air
Should, the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10% is obtained, the peroxide that weight concentration is 30% is made through vacuum concentrate
Change hydrogen ethylbenzene (EBHP) oxidation solution.
By above-mentioned weight concentration be 30% hydrogen peroxide ethylbenzene oxidation liquid in Ti-TUD-1 catalyst (Ti weight percent
Content be 1.5%) in the presence of, in fixed bed reactors and chloropropene carry out epoxidation reaction generation epoxychloropropane, α-first
Base benzylalcohol and a small amount of acetophenone.Wherein chloropropene/EBHP=4:1 (mole), EBHP weight space velocity=3 hour-1, reaction temperature
For 105 DEG C, reaction pressure 3.5MPa.
Reaction mixture is passed through into the excessive chloropropene of chloropropene recovery tower recovery to recycle, chloropropene recovery and epoxy
Chloropropane rectifying separation is same【Embodiment 1】.Logistics of the tower reactor containing α-methylbenzylalcohol, acetophenone and ethylbenzene enters dehydration reactor,
α-methylbenzylalcohol is dehydrated generation styrene in the presence of ZSM-5 catalyst, and dehydration temperature is 200 DEG C, reaction pressure
0.5MPa, the weight space velocity of α-methylbenzylalcohol 1.0 hours-1.Reacted mixture enters styrene separating tower, the essence of styrene
Cut is from same【Embodiment 1】.Cut of the styrene separating tower tower reactor containing acetophenone into hydrogenation of acetophenone reactor change into α-
Xylyl alcohol, used catalyst 8Ni%Ni/SiO2, 150 DEG C of reaction temperature, pressure 2.2MP, H2Mol ratio with acetophenone is
3:1, the weight space velocity of acetophenone is 2.0 hours-1, the α-methylbenzylalcohol of generation and foregoing α-methylbenzylalcohol are combined into dehydration
Reactor changes into styrene.Reaction result is as shown in table 1.
【Embodiment 4】
In 160 DEG C, 0.4MPa, control tail oxygen volume content is less than under the conditions of 5%, and ethylbenzene carries out peroxidation with air
Should, the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10% is obtained, the peroxide that weight concentration is 30% is made through vacuum concentrate
Change hydrogen ethylbenzene (EBHP) oxidation solution.
By above-mentioned weight concentration be 30% hydrogen peroxide ethylbenzene oxidation liquid in Ti-SBA-15 catalyst (Ti weight hundred
Point content in the presence of 3.0%), in fixed bed reactors and chloropropene carry out epoxidation reaction generation epoxychloropropane, α-
Xylyl alcohol and a small amount of acetophenone.Wherein chloropropene/EBHP=4:1 (mole), EBHP weight space velocity=3 hour-1, reaction temperature
Spend for 105 DEG C, reaction pressure 3.5MPa.
Reaction mixture is passed through into the excessive chloropropene of chloropropene recovery tower recovery to recycle, chloropropene recovery and epoxy
Chloropropane rectifying separation is same【Embodiment 1】.Logistics of the tower reactor containing α-methylbenzylalcohol, acetophenone and ethylbenzene enters dehydration reactor,
α-methylbenzylalcohol is in γ-Al2O3Dehydration generation styrene in the presence of catalyst, dehydration temperature are 200 DEG C, reaction pressure
0.5MPa, the weight space velocity of α-methylbenzylalcohol 1.0 hours-1.Reacted mixture enters styrene separating tower, the essence of styrene
Cut is from same【Embodiment 1】.Cut of the styrene separating tower tower reactor containing acetophenone into hydrogenation of acetophenone reactor change into α-
Xylyl alcohol, used catalyst 5%Ni/Al2O3, 150 DEG C of reaction temperature, pressure 2.0MP, H2Mol ratio with acetophenone is
3:1, the weight space velocity of acetophenone is 2.0 hours-1, the α-methylbenzylalcohol of generation and foregoing α-methylbenzylalcohol are combined into dehydration
Reactor changes into styrene.Reaction result is as shown in table 1.
【Embodiment 5】
In 155 DEG C, 0.3MPa, control tail oxygen volume content is less than under the conditions of 5%, and ethylbenzene carries out peroxidation with air
Should, the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10% is obtained, the peroxide that weight concentration is 28% is made through vacuum concentrate
Change hydrogen ethylbenzene (EBHP) oxidation solution.
By above-mentioned weight concentration be 28% hydrogen peroxide ethylbenzene oxidation liquid in Ti-KIT-1 catalyst (Ti weight percent
Content be 2.6%) in the presence of, in fixed bed reactors and chloropropene carry out epoxidation reaction generation epoxychloropropane, α-first
Base benzylalcohol and a small amount of acetophenone.Wherein chloropropene/EBHP=4:1 (mole), EBHP weight space velocity=3.0 hour-1, reaction temperature
Spend for 105 DEG C, reaction pressure 3.5MPa.
Reaction mixture is passed through into the excessive chloropropene of chloropropene recovery tower recovery to recycle, chloropropene recovery and epoxy
Chloropropane rectifying separation is same【Embodiment 1】.Logistics of the tower reactor containing α-methylbenzylalcohol, acetophenone and ethylbenzene enters dehydration reactor,
α-methylbenzylalcohol is dehydrated generation styrene in the presence of ZSM-5 catalyst, and dehydration temperature is 200 DEG C, reaction pressure
0.5MPa, α-methylbenzylalcohol weight (hourly) space velocity (WHSV) 1.0h-1.Reacted mixture enters styrene separating tower, the rectifying point of styrene
From same【Embodiment 1】.Cut of the styrene separating tower tower reactor containing acetophenone changes into Alpha-Methyl into hydrogenation of acetophenone reactor
Benzylalcohol, used catalyst 0.5%Pd/C, 150 DEG C of reaction temperature, pressure 2.0MP, H2Mol ratio with acetophenone is 3:1, benzene
The weight space velocity of ethyl ketone is 2.0 hours-1, the α-methylbenzylalcohol of generation and foregoing α-methylbenzylalcohol are combined into dehydration reactor
Change into styrene.Reaction result is as shown in table 1.
【Embodiment 6】
In 155 DEG C, 0.35MPa, control tail oxygen volume content is less than under the conditions of 5%, and ethylbenzene carries out peroxidation with air
Should, the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10% is obtained, the peroxide that weight concentration is 30% is made through vacuum concentrate
Change hydrogen ethylbenzene (EBHP) oxidation solution.
By above-mentioned weight concentration be 30% hydrogen peroxide ethylbenzene oxidation liquid in Ti-SiO2Catalyst (Ti weight percent
Content be 1.0%) in the presence of, in fixed bed reactors and chloropropene carry out epoxidation reaction generation epoxychloropropane, α-first
Base benzylalcohol and a small amount of acetophenone.Wherein chloropropene/EBHP=4:1 (mole), EBHP weight space velocity=3.0 hour-1, reaction temperature
Spend for 105 DEG C, reaction pressure 3.5MPa.
Reaction mixture is passed through into the excessive chloropropene of chloropropene recovery tower recovery to recycle, chloropropene recovery and epoxy
Chloropropane rectifying separation is same【Embodiment 1】.Logistics of the tower reactor containing α-methylbenzylalcohol, acetophenone and ethylbenzene enters dehydration reactor,
α-methylbenzylalcohol is dehydrated generation styrene in the presence of ZSM-5 catalyst, and dehydration temperature is 200 DEG C, reaction pressure
0.5MPa, the weight space velocity of α-methylbenzylalcohol is 1.0 hours-1.Reacted mixture enters styrene separating tower, styrene
Rectifying separation is same【Embodiment 1】.Cut of the styrene separating tower tower reactor containing acetophenone changes into hydrogenation of acetophenone reactor
α-methylbenzylalcohol, used catalyst 8Ni%Ni/SiO2, 150 DEG C of reaction temperature, pressure 2.2MP, H2With the mol ratio of acetophenone
For 3:1, the weight space velocity of acetophenone is 2.0 hours-1, the α-methylbenzylalcohol of generation is combined into de- with foregoing α-methylbenzylalcohol
Water reactor changes into styrene.Reaction result is as shown in table 1.
Table 1
Note：EBHP- hydrogen peroxide ethylbenzene, ECH- epoxychloropropane.
As seen from Table 1, during whole reaction, the selectivity of epoxychloropropane more than 98.9%,
EBHP conversion ratios generate without waste residue more than 97.8%, are nearly free from the waste water containing organic matter.
【Comparative example 1】
460 grams of chloropropenes and 5000 grams of water are added in the pressure vessel with frp lining, stirring, then pass to 450
Gram chlorine, rise temperature carry out chlorohydrin action 2 hours to 60 DEG C, obtain anti-containing 1,3- dichlorohydrins and 2,3- dichlorohydrin
Answer mixture.It is then slowly added into and contains 1200 grams of Ca (OH)2The aqueous solution carry out saponification, be made containing the anti-of epoxychloropropane
Answer mixture.Through gas chromatographic analysis, epichlorohydrin content is 380 grams in final reaction mixture, in terms of chloropropene, ring
The yield of oxygen chloropropane is 70%, meanwhile, produce about 11 kilograms of waste water and 1300 grams of CaCl containing organic chloride and inorganic matter2
Waste residue.
【Comparative example 2】
460 grams of glycerol stocks and 5 g of adipic acid catalyst are added in the pressure vessel with frp lining, under agitation
Temperature is raised to 120 DEG C, is passed through 400 grams of HCl gas reactions 8 hours, generates the anti-of 1,3- dichlorohydrins and 2,3- dichlorohydrin
Answer mixture.Addition contains 210 grams of Ca (OH)2The aqueous solution to caused dichlorohydrin carry out saponification generation epoxy chloropropionate
Alkane.Through gas chromatographic analysis, epichlorohydrin content is 312 grams in final reaction mixture, in terms of glycerine, epoxychloropropane
Yield be 67.5%, while produce about 5 kilograms of waste water and 610 grams of CaCl containing organic chloride and inorganic matter2Waste residue.
Claims (10)
1. a kind of method for producing epoxychloropropane, comprises the following steps：
A) ethylbenzene carries out peroxidization with air, obtains hydrogen peroxide ethylbenzene oxidation liquid；
B) with chloropropene in the presence of catalyst epoxidation reaction life occurs under liquid-phase condition for hydrogen peroxide ethylbenzene oxidation liquid
Into epoxychloropropane, α-methylbenzylalcohol and acetophenone, the catalyst is that multiphase is titanium-containing meso-porous or macroporous silica is catalyzed material
Expect Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2；
C) α-methylbenzylalcohol dehydration generation styrene；
D) with hydrogen hydrogenation reaction generation α-methylbenzylalcohol occurs for acetophenone；The α-methylbenzylalcohol of step generation returns to c) step
Suddenly, generation styrene is dehydrated with together with the α-methylbenzylalcohol of b) step generation,
Wherein, in step b), Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO catalysis
Agent is prepared using post-synthesis,
Pure silicon HMS, MCM-41, TUD-1, SBA-15, KIT-1 mesoporous material or the suitable macro-pore SiO of selection are synthesized first2Powder；
Then by pure silicon mesoporous silicon oxide or macroporous silica selected from HMS, MCM-41, TUD-1, SBA-15, KIT-1
At least one former powder and binding agent be shaped to carrier；The dosage of former powder is 50~99 weight %；
And using halogenated titanium or titanate esters as titanium source, organic solvent is used in the form of liquid-phase grafting, or using dry gas as load
Gas uses gas phase graft form, the active titanium species with four-coordination is implanted in the carrier framework of gained, obtains after carrying titanium
Catalyst；
And organosilicon reagent is used to the further surface grafting silanization treatment of catalyst after carrying titanium to obtain the multiphase
Titanium-containing meso-porous or macroporous silica catalysis material.
2. the method for epoxychloropropane is produced according to claim 1, it is characterised in that step a) reaction condition is：Reaction
0~250 DEG C of temperature, 0.1~5.0MPa of reaction pressure.
3. the method for epoxychloropropane is produced according to claim 2, it is characterised in that step a) reaction condition is：Reaction
50~200 DEG C of temperature, 0.1~2.0MPa of reaction pressure.
4. the method for epoxychloropropane is produced according to claim 1, it is characterised in that step b) reaction condition is：Reaction
25~180 DEG C, 0.1~10.0MPa of reaction pressure of temperature, the mol ratio 1~20 of chloropropene and hydrogen peroxide ethylbenzene, hydrogen peroxide
The weight space velocity of ethylbenzene 0.1~20 hour-1。
5. the method for epoxychloropropane is produced according to claim 4, it is characterised in that step b) reaction condition is：Reaction
40~150 DEG C, 0.5~8.0MPa of reaction pressure of temperature, the mol ratio 2~15 of chloropropene and hydrogen peroxide ethylbenzene, hydrogen peroxide
The weight space velocity of ethylbenzene 0.3~10.0 hour-1。
6. the method for epoxychloropropane is produced according to claim 1, it is characterised in that step c) reaction condition is：Reaction
50~400 DEG C, 0~5.0MPa of reaction pressure of temperature, the weight space velocity of α-methylbenzylalcohol is 0.1~10.0 hour-1。
7. the method for epoxychloropropane is produced according to claim 6, it is characterised in that step c) reaction condition is：Reaction
100~350 DEG C, 0.1~3.0MPa of reaction pressure of temperature, the weight space velocity of α-methylbenzylalcohol is 0.3~5.0 hour-1。
8. the method for epoxychloropropane is produced according to claim 1, it is characterised in that step d) reaction condition is：Reaction
50~350 DEG C of temperature, reaction pressure 0.1~6.0MPa, H2Mol ratio with acetophenone is 1~10, the weight space velocity of acetophenone
For 0.1~10.0 hour-1。
9. the method for epoxychloropropane is produced according to claim 8, it is characterised in that step d) reaction condition is：Reaction
80~300 DEG C of temperature, reaction pressure 0.5~5.0MPa, H2Mol ratio with acetophenone is 2~6, and the weight space velocity of acetophenone is
0.3~6.0 hour-1。
10. the method for the production epoxychloropropane according to claim 1, it is characterised in that the hydrogen peroxide ethylbenzene oxygen
The concentration expressed in percentage by weight for changing hydrogen peroxide ethylbenzene in liquid is 1~50%.
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| CN1030580A (en) * | 1987-04-16 | 1989-01-25 | 三井东圧化学株式会社 | The preparation method of Epicholorohydrin |
| CN1310698A (en) * | 1998-07-20 | 2001-08-29 | 国际壳牌研究有限公司 | Process for the preparation of styrene and propylene oxide |
| CN102757407B (en) * | 2011-04-26 | 2014-04-16 | 中国石油化工股份有限公司 | Allyl chloride epoxidation method for preparing epichlorohydrin |
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