CN105272942A - 3,4-epoxy-1-butene preparation method - Google Patents
3,4-epoxy-1-butene preparation method Download PDFInfo
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Abstract
The present invention relates to a 3,4-epoxy-1-butene preparation method. A purpose of the present invention is mainly to solve the problems of low raw material conversion rate, low product yield and serious waste in the prior art. The technical scheme comprises the following steps that: a) ethylbenzene and air are subjected to a peroxidation reaction to obtain a hydrogen peroxide ethylbenzene oxidation liquid; b) the hydrogen peroxide ethylbenzene oxidation liquid and 1,3-butadiene are subjected to a selective oxidation reaction under a liquid phase condition under the effect of a catalyst to generate 3,4-epoxy-1-butene, alpha-methylbenzyl alcohol and acetophenone; c) the alpha-methylbenzyl alcohol is subjected to dehydration to generate styrene; and d) the acetophenone is subjected to hydrogenation to generate alpha-methylbenzyl alcohol, the generated alpha-methylbenzyl alcohol returns to the step c), and the alpha-methylbenzyl alcohol returned to the step c) and the alpha-methylbenzyl alcohol generated in the step b) are subjected to hydrogenation to generate styrene. With the technical scheme, the problem in the prior art is well solved, and the method can be used for preparation of 3,4-epoxy-1-butene and co-production of styrene in the industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of 3,4-epoxy-1-butylene.
Background technology
3,4-epoxy-1-butylene (EPB) is a kind of novel fine-chemical intermediate, by 1,3-epoxidized butadiene is combined to, there is wide market potential, due to this compound both aerobic ring, have double bond again, be a kind of rare intermediate containing two kinds of important functional groups, seldom have organic intermediate to have so wide purposes.But for a long time because production cost is too high, do not obtain market always and pay attention to.
By 3,4-epoxy-1-butylene sets out and can prepare hundreds of important subsequent product, relate to multiple fields such as bulk chemical, fine chemicals and special chemical article, being the best synthesis material of various pharmaceutical intermediate, chipal compounds, BACN, functional high molecule material, is fine chemicals in short supply both at home and abroad.Such as, set out from 3,4-epoxy-1-butylene, hundreds of chemical such as dihydrofuran, tetrahydrofuran (THF), BDO, cyclopropylamine, butylene acetic ester/carbonic ether, halogenated epoxy butane can be derived.The Development and Production of pharmaceutical intermediate has become new industry and the focus industry of domestic chemical circles in recent years, cyclopropylamine is as important medicinal fine-chemical intermediate, domestic market presents the situation that supply falls short of demand, the increase of cyclopropylamine throughput will greatly promote the development of broad-spectrum antibiotics Ciprofloxacin of new generation again, and the application of cyclopropylamine in medicine, agricultural chemicals and organic synthesis is popularized rapidly, this also requires that the production of 3,4-epoxy-1-butylene must be got caught up in.
In addition, 3,4-epoxy-1-butylene through halogenation, sulfuration, with acetic acid and CO
2the reactions such as addition, can synthetic time series halogenation (replacement) vinyl epoxy compound, carbonic ether, acetate monomers, through oligomerisation or copolyreaction, prepare the functional high molecule materials such as various block polyether, polyester, fire retardant material, Novel lubricating material, photoactive coating or tackiness agent.Their outstanding advantages is, these polymerisates still retain C=C double bond or epoxide group, can modification further.
The technique that 1,3-butadiene catalysis epoxidation produces 3,4-epoxy-1-butylene can be divided into two classes: one is carry out gas phase selective epoxidation with molecular oxygen, and this is also industrialization technology unique except ethylene epoxidizing in alkene.The active period studied it is 1996 ~ 2007 years, and this technique 1,3-butadiene transformation efficiency is 14 ~ 18%, 3,4-epoxy-1-butylene selectivity is 87 ~ 90%.US5081096 adopts the Ag catalyzer similar with ethylene epoxidizing, with K, Rb and Cs for auxiliary agent.US5138077 adopts Ag-Tl/Al
2o
3catalyzer, 1,3-butadiene transformation efficiency is 14.5%, 3,4-epoxy-1-butylene selectivity is 90.0%.US6011163 adopts low-carbon alkanes and hydrocarbon compoud containing fluorine to be thinner, with Ag-Cs/ α-Al
2o
3for catalyzer, 1,3-butadiene transformation efficiency is 17.5%, 3,4-epoxy-1-butylene selectivity is 87.6%.The Lanzhou Chemistry and Physics Institute of the Chinese Academy of Sciences has carried out the research of 1,3-butadiene epoxidation system 3,4-epoxy-1-butylene, shows the research of catalyzer, at the Ag/ α-Al that Ba, Cs, Cl promote
2o
3catalyzer can obtain higher 1,3-butadiene transformation efficiency and 3,4-epoxy-1-butylene selectivity, the interaction of Cs-Ag can promote that oxygenate kind is inserted in divinyl and form epoxide (Journal of Molecular Catalysis, 20 (04), 2006; Journal of Molecular Catalysis, 21 (01), 2007).In molecular oxygen selective oxidation 1,3-divinyl system 3, in the reaction of 4-epoxy-1-butylene, due to 1,3-butadiene conversion and 3,4-epoxy-1-butylene selectivity is low, 1, the waste of 3-divinyl is serious, along with 1,3-butadiene resource is day by day in short supply, price constantly rises, recent research steering take superoxide as oxygenant, adopts homogeneous catalyst by divinyl highly selective (99%), the exploratory study being converted into 3,4-epoxy-1-butylene high conversion (80% ~ 90%).Although homogeneous catalyst is active high, good product selectivity, catalyzer easily remains in the product, and the separation of catalyzer also can make technique more complicated, increases production cost.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists feed stock conversion and product yield is low, wastes serious problem, provides a kind of preparation method of 3,4-epoxy-1-butylenes newly.It is high that the method has catalyst activity, and feed stock conversion is high, good stability, and 3,4-epoxy-1-butylene yield is high, the feature of environmental protection.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of 3,4-epoxy-1-butylene, comprises the following steps:
A) ethylbenzene and air carry out peroxidation, obtain hydrogen peroxide ethylbenzene oxidation liquid;
B) hydrogen peroxide ethylbenzene oxidation liquid and 1,3-butadiene are under the effect of catalyzer, epoxidation reaction occurs under liquid-phase condition and generates 3,4-epoxy-1-butylene, α-methylbenzylalcohol and methyl phenyl ketone;
C) α-methylbenzylalcohol dehydration reaction generates vinylbenzene;
D) methyl phenyl ketone and hydrogen generation hydrogenation reaction generate α-methylbenzylalcohol; The α-methylbenzylalcohol that this step generates gets back to c) step, and hydrogenation generates vinylbenzene together with the α-methylbenzylalcohol that b) step generates.
In technique scheme, preferably, step reaction conditions a) is: temperature of reaction 0 ~ 250 DEG C, reaction pressure 0.1 ~ 5.0MPa.More preferably, temperature of reaction 50 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0MPa.
In technique scheme, preferably, step b) reaction conditions be: temperature of reaction 25 ~ 160 DEG C, reaction pressure 0.1 ~ 8.0MPa, the mol ratio 1 ~ 15 of 1,3-butadiene and hydrogen peroxide ethylbenzene, the weight space velocity of hydrogen peroxide ethylbenzene 0.01 ~ 20 hour
-1.More preferably, temperature of reaction 40 ~ 140 DEG C, reaction pressure 0.5 ~ 6.0MPa, the mol ratio 2 ~ 12 of 1,3-butadiene and hydrogen peroxide ethylbenzene, the weight space velocity of hydrogen peroxide ethylbenzene 0.05 ~ 15 hour
-1.
In technique scheme, preferably, step b) catalyzer used is heterogeneous titanium-containing meso-porous or macroporous silica catalytic material.More preferably, catalyzer used is heterogeneous titanium-containing meso-porous or macroporous silica catalyzer Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO
2.
In technique scheme, preferably, step c) reaction conditions be: temperature of reaction 50 ~ 400 DEG C, reaction pressure 0 ~ 5.0MPa, the weight space velocity of α-methylbenzylalcohol is 0.1 ~ 10.0 hour
-1.More preferably, temperature of reaction 100 ~ 350 DEG C, reaction pressure 0.1 ~ 3.0MPa, the weight hourly space velocity of α-methylbenzylalcohol is 0.3 ~ 5.0 hour
-1.
In technique scheme, preferably, steps d) reaction conditions be: temperature of reaction 50 ~ 350 DEG C, reaction pressure 0.1 ~ 6.0MPa, H
2be 1 ~ 10 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 0.1 ~ 10.0 hour
-1.More preferably, temperature of reaction 100 ~ 300 DEG C, reaction pressure 0.5 ~ 4.0MPa, H
2be 2 ~ 6 with the mol ratio of methyl phenyl ketone, the weight hourly space velocity of methyl phenyl ketone is 0.3 ~ 6.0 hour
-1.
In technique scheme, preferably, in described hydrogen peroxide ethylbenzene oxidation liquid, the concentration expressed in percentage by weight of hydrogen peroxide ethylbenzene is 1 ~ 50%.
In the inventive method, step is a) oxidation step, and adopt molecular oxygen that ethylbenzene oxidation is become hydrogen peroxide ethylbenzene, this is a classical free radical reaction.Molecular oxygen used both can be that air also can adopt oxygen-rich air.This reaction both can be carried out under the existence of catalyzer or additive, also can when efficiently carrying out without when any catalyzer or additive.Used catalyst or additive are generally basic metal, alkaline-earth metal, the oxyhydroxide of ammonia or carbonate, but consider from the aftertreatment angle of oxidation solution, preferentially adopt containing the ethylbenzene air oxidation system of any additive.Under normal circumstances, the temperature of reaction of oxidation step and pressure are respectively 0 ~ 250 DEG C and 0.1 ~ 5.0MPa, are preferably 50 ~ 200 DEG C and 0.1 ~ 2.0MPa.Temperature is too low, and reaction efficiency is low, maybe cannot carry out; Too high temperature then easily causes hydrogen peroxide ethylbenzene decompose or produce other by product.
In the inventive method, step b) be epoxidation step, the form of mixtures that hydrogen peroxide ethylbenzene is generally formed with itself and ethylbenzene as the oxygen carrier of epoxidation reaction uses, and generally selects its weight concentration to be 1 ~ 50%, and preferably 10 ~ 40%.Concentration is too low, epoxidation inefficiency, less economical; Excessive concentration, then reaction heat effect is obvious, and reaction heat removes difficulties, and too high concentration causes the too high levels of benzylalcohol and other by product in product, unfavorable to the performance of epoxidation catalyst, easily cause catalyst deactivation, and too high concentration also easily causes decomposition reaction to occur.Epoxidation reaction is carried out under liquid-phase condition in solvent, and the solvent adopted is liquid under temperature of reaction and pressure, and it is inertia to reactant and product.The solvent adopted comprises benzene and the substituted benzene such as the paraffinic hydrocarbonss such as hexane, hexanaphthene, heptane, octane, nonane, decane, undecane, dodecane and benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropyl benzene, preferred ethylbenzene, can avoid like this introducing extra material, increase separating energy consumption.Epoxidation reaction temperature is 25 ~ 160 DEG C, is preferably 40 ~ 140 DEG C.Temperature is crossed low reaction and is difficult to carry out, and temperature is too high, easily causes hydrogen peroxide ethylbenzene to decompose, and by product increases.Reaction pressure is in a liquid state to maintain reaction raw materials, and preferably 0.1 ~ 8.0MPa, is more preferably 0.5 ~ 6.0MPa.Hypotony easily causes material to be vaporized, and cannot ensure to carry out under liquid-phase condition, and hypertonia then causes reaction heat to increase, and power consumption increases, and affects economy.The mol ratio of 1,3-butadiene and hydrogen peroxide ethylbenzene is 1 ~ 15, preferably 2 ~ 12, and the air speed of hydrogen peroxide ethylbenzene is 0.01 ~ 20.0 hour
-1preferably 0.05 ~ 15.0 hour
-1.Epoxidation reaction both can be carried out in slurry bed reactor, also can carry out in fixed-bed reactor.But from the angle of large-scale commercial production, preferably adopt fixed-bed reactor.Catalyzer used is titanium-containing meso-porous or macroporous silica catalytic material, preferably has titaniferous porous silica Si catalyst Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO of mesoporous or large pore property
2.
In technique scheme, Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO catalyzer adopts post-synthesis preparation, first synthesizes pure silicon HMS, MCM-41, TUD-1, SBA-15, KIT-1 mesoporous material or selects suitable macro-pore SiO
2powder.
The preparation method of the former powder of pure silicon HMS is as follows: take general formula as RNH
2organic amine be template agent, wherein R is the chain alkylene containing 5 ~ 40 carbon atoms, with silicon ester or amorphous silica for silicon source, take alcohol and water as solvent, adopts hydrothermal synthesis method preparation.Wherein, described silicon ester is selected from positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four n-propyl, positive silicic acid four isopropyl ester or positive silicic acid four butyl ester; Described RNH
2middle R is preferably the straight-chain paraffin base containing 10 ~ 20 carbon atoms; Described alcohol is selected from least one in methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl alcohol, allyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexalin, ethylene glycol or propylene glycol.With molar ratio computing, silicon source: template: water: alcohol=1:(0.05 ~ 0.5): (10 ~ 60): (3 ~ 15).
The preparation method of the former powder of silica MCM-41 is as follows: take cetyl trimethylammonium bromide as template, with silicon ester or amorphous silica for silicon source, take water as solvent, adopts hydrothermal synthesis method to prepare in alkaline environment.Wherein, described silicon ester is selected from positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four n-propyl, positive silicic acid four isopropyl ester or positive silicic acid four butyl 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 the former powder of pure silicon TUD-1 is as follows: be template with trolamine, is silicon source, is solvent, adopts hydrothermal synthesis method to prepare in alkaline environment with alcohol and water with silicon ester.Wherein, described silicon ester is selected from positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four n-propyl, positive silicic acid four isopropyl ester or positive silicic acid four butyl ester; Described alcohol is selected from methyl alcohol, ethanol, n-propyl alcohol or Virahol, and described alkali is 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): (0.1 ~ 0.5).
The preparation method of the former powder of pure silicon SBA-15 is as follows: adopt triblock copolymer (PEO-PPO-PEO), with silicon ester be silicon source in strong acidic environment, hydrothermal synthesis method prepare.Wherein, described silicon ester is selected from positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four n-propyl, positive silicic acid four isopropyl ester or positive silicic acid four butyl ester, and the preferred volumetric molar concentration of described acid is the hydrochloric acid soln of 0.5 ~ 3.5 mol/L.With molar ratio computing, silicon source: PEO-PPO-PEO:H
2o:HCl=1:(0.005 ~ 0.04): (20 ~ 100): (3 ~ 10).
The preparation method of the former powder of pure silicon KIT-1 is as follows: be template agent with cetyl trimethylammonium bromide, take silicon ester as silicon source, and under EDTA (sodium ethylene diamine tetracetate) and water exist, prepared by hydrothermal synthesis method.Wherein, described silicon ester is selected from positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four n-propyl, positive silicic acid four isopropyl ester or positive silicic acid four butyl ester.With molar ratio computing, silicon source: template: EDTA: water=1:(0.1 ~ 0.4): (0.5 ~ 1.5): (20 ~ 100).
The former powder of at least one be selected from the pure silicon mesoporous silicon oxide of HMS, MCM-41, TUD-1, SBA-15, KIT-1 or macroporous silica and binding agent are shaped to carrier; The consumption of former powder is 50 ~ 99 % by weight;
With halogenated titanium or titanic acid ester for titanium source, adopt organic solvent with liquid-phase grafting form, or be that carrier gas adopts gas phase graft form with dry gas, the active titanium species with four-coordination be implanted in the carrier framework of gained, obtain titaniferous porous silica Si catalyst.Preferred employing organosilicon reagent, to the further surface grafting silanization treatment of catalyzer carried after titanium, makes it have the hydrophobic property of height.Described organosilicon is selected from least one in halosilanes, silazane or silylamine.Catalyzer and the organosilyl way of contact, can flood the catalyst Precursors organic silicon solution be dissolved in organic solvent, also can with the organosilicon steam grafting process be scattered in dry gas.Be 0.05 ~ 30% at the described weight percentage with titanium in the titaniferous porous silica Si catalyst of very hydrophobic characteristic.
In the inventive method, step c) be α-methylbenzylalcohol dehydrating step, dehydrating step in the presence of a catalyst α-methylbenzylalcohol dehydration is generated vinylbenzene.Used catalyst comprises the various catalytic material with dehydrating function, as activated alumina, zeolite molecular sieve etc.Dehydration reaction both can be carried out in slurry bed reactor, also can carry out in fixed-bed reactor.The temperature and pressure of dehydration reaction is 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.
Steps d) be hydrogenation of acetophenone step, used catalyst comprises Raney's nickel catalyst, gac, aluminum oxide or silica supported Ni-based, copper base or palladium base etc. have the catalytic material of shortening function, temperature of reaction 50 ~ 350 DEG C, preferably 100 ~ 300 DEG C; Reaction pressure 0.1 ~ 6.0MPa, preferably 0.5 ~ 4.0MPa; H
2be 1 ~ 10 with the mol ratio of methyl phenyl ketone, preferably 2 ~ 6; The weight space velocity of methyl phenyl ketone 0.1 ~ 10.0 hour
-1, preferably 0.3 ~ 6.0 hour
-1.Hydrogenation reaction both can be carried out in slurry bed reactor, also can carry out in fixed-bed reactor.
The inventive method is outside object product 3,4-epoxy-1-butylene, and also have joint product vinylbenzene to generate, Technical Economy is good, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
At 160 DEG C, 0.4MPa, control tail oxygen volume content lower than under 5% condition, ethylbenzene and air carry out peroxidation, obtain the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10%, obtain through vacuum concentrate hydrogen peroxide ethylbenzene (EBHP) oxidation solution that weight concentration is 30%.
By above-mentioned weight concentration be 30% hydrogen peroxide ethylbenzene oxidation liquid at Ti-HMS catalyzer, (weight percentage of titanium is 1.6%.) under existence, in fixed-bed reactor and 1,3-butadiene carry out epoxidation reaction and generate 3,4-epoxy-1-butylene, α-methylbenzylalcohol and a small amount of methyl phenyl ketone.Wherein 1,3-butadiene/EBHP=4 (mol ratio), weight space velocity=3 hour of EBHP
-1, temperature of reaction is 105 DEG C, and reaction pressure is 3.5MPa.
Reaction mixture is passed into 1,3-butadiene recovery tower to reclaim excessive 1,3-butadiene and recycle, this tower operates at ambient pressure, tower top temperature-4.5 DEG C, bottom temperature 140 DEG C.Tower reactor enters 3,4-epoxy-1-butylene knockout towers containing the material of 3,4-epoxy-1-butylene, α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene etc., and this tower operates at ambient pressure, tower top temperature 65 DEG C, bottom temperature 160 DEG C.Thick 3, the 4-epoxy-1-butylene cuts of tower top obtain pure 3,4-epoxy-1-butylenes through further rectifying separation.Tower reactor enters dehydration reactor containing the logistics of α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene, and α-methylbenzylalcohol is at γ-Al
2o
3there is lower dehydration and generate vinylbenzene in catalyzer, dehydration reaction temperature is 200 DEG C, reaction pressure 0.5MPa, α-methylbenzylalcohol weight space velocity 1.0 hours
-1.Reacted mixture enters styrene separating tower, and this tower operates at reduced pressure conditions, tower top pressure 80mmHg, tower top temperature 50 DEG C, bottom temperature 110 DEG C.Vinylbenzene and ethylbenzene are extracted as overhead fraction, obtain pure styrene through further rectifying separation; Tower reactor enters hydrogenation of acetophenone reactor containing the cut of methyl phenyl ketone and changes into α-methylbenzylalcohol, and used catalyst is 5%Ni/Al
2o
3, temperature of reaction 160 DEG C, pressure 2.5MPa, H
2be 3:1 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 2.0 hours
-1, the α-methylbenzylalcohol of generation and aforesaid α-methylbenzylalcohol merge and enter dehydration reactor and change into vinylbenzene.Reaction result is as shown in table 1.
[embodiment 2]
At 150 DEG C, 0.3MPa, control tail oxygen volume content lower than under 5% condition, ethylbenzene and air carry out peroxidation, obtain the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10%, obtain through vacuum concentrate hydrogen peroxide ethylbenzene (EBHP) oxidation solution that weight concentration is 28%.
Be that the hydrogen peroxide ethylbenzene oxidation liquid of 28% is under Ti-MCM41 catalyzer (weight percentage of titanium is 2.0%) exists by above-mentioned weight concentration, with 1 in fixed-bed reactor, 3-divinyl carries out epoxidation reaction and generates 3,4-epoxy-1-butylene, α-methylbenzylalcohol and a small amount of methyl phenyl ketone.Wherein 1,3-butadiene/EBHP=4 (mol ratio), weight space velocity=3 hour of EBHP
-1, temperature of reaction is 105 DEG C, and reaction pressure is 3.5MPa.
Reaction mixture is passed into butadiene recovery column to reclaim excessive 1,3-butadiene and recycle, 1,3-butadiene reclaim and 3,4-epoxy-1-butylene rectifying separation together [embodiment 1].Tower reactor enters dehydration reactor containing the logistics of α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene, and α-methylbenzylalcohol dehydration under ZSM-5 exists generates vinylbenzene, and dehydration reaction temperature is 200 DEG C, reaction pressure 0.5MPa, α-methylbenzylalcohol weight space velocity 1.0 hours
-1.Reacted mixture enters styrene separating tower, and cinnamic rectifying separation is with [embodiment 1].Styrene separating tower tower reactor enters hydrogenation of acetophenone reactor containing the cut of methyl phenyl ketone and changes into α-methylbenzylalcohol, and used catalyst is 0.5%Pd/C, temperature of reaction 150 DEG C, pressure 2.0MPa, H
2be 3:1 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 2.0 hours
-1, the α-methylbenzylalcohol of generation and aforesaid α-methylbenzylalcohol merge and enter dehydration reactor and change into vinylbenzene.Reaction result is as shown in table 1.
[embodiment 3]
At 155 DEG C, 0.35MPa, control tail oxygen volume content lower than under 5% condition, ethylbenzene and air carry out peroxidation, obtain the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10%, obtain through vacuum concentrate hydrogen peroxide ethylbenzene (EBHP) oxidation solution that weight concentration is 30%.
Be that the hydrogen peroxide ethylbenzene oxidation liquid of 30% is under Ti-TUD-1 catalyzer (weight percentage of titanium is 1.5%) exists by above-mentioned weight concentration, with 1 in fixed-bed reactor, 3-divinyl carries out epoxidation reaction and generates 3,4-epoxy-1-butylene, α-methylbenzylalcohol and a small amount of methyl phenyl ketone.Wherein 1,3-butadiene/EBHP=4 (mol ratio), weight space velocity=3 hour of EBHP
-1, temperature of reaction is 105 DEG C, and reaction pressure is 3.5MPa.
Reaction mixture is passed into butadiene recovery column to reclaim excessive 1,3-butadiene and recycle, 1,3-butadiene reclaim and 3,4-epoxy-1-butylene rectifying separation together [embodiment 1].Tower reactor enters dehydration reactor containing the logistics of α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene, and α-methylbenzylalcohol dehydration under ZSM-5 exists generates vinylbenzene, and dehydration reaction temperature is 200 DEG C, reaction pressure 0.5MPa, α-methylbenzylalcohol weight space velocity 1.0 hours
-1.Reacted mixture enters styrene separating tower, and cinnamic rectifying separation is with [embodiment 1].Styrene separating tower tower reactor enters hydrogenation of acetophenone reactor containing the cut of methyl phenyl ketone and ethylbenzene and changes into α-methylbenzylalcohol, and used catalyst is 8%Ni/SiO
2, temperature of reaction 155 DEG C, pressure 2.5MPa, H
2be 3:1 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 2.0 hours
-1, the α-methylbenzylalcohol of generation and aforesaid α-methylbenzylalcohol merge and enter dehydration reactor and change into vinylbenzene.Reaction result is as shown in table 1.
[embodiment 4]
At 160 DEG C, 0.4MPa, control tail oxygen volume content lower than under 5% condition, ethylbenzene and air carry out peroxidation, obtain the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10%, obtain through vacuum concentrate hydrogen peroxide ethylbenzene (EBHP) oxidation solution that weight concentration is 30%.
Be that the hydrogen peroxide ethylbenzene oxidation liquid of 30% is under Ti-SBA-15 catalyzer (weight percentage of titanium is 3.0%) exists by above-mentioned weight concentration, with 1 in fixed-bed reactor, 3-divinyl carries out epoxidation reaction and generates 3,4-epoxy-1-butylene, α-methylbenzylalcohol and a small amount of methyl phenyl ketone.Wherein 1,3-butadiene/EBHP=4 (mol ratio), weight space velocity=3 hour of EBHP
-1, temperature of reaction is 105 DEG C, and reaction pressure is 3.5MPa.
Reaction mixture is passed into butadiene recovery column to reclaim excessive 1,3-butadiene and recycle, 1,3-butadiene reclaim and 3,4-epoxy-1-butylene rectifying separation together [embodiment 1].Tower reactor enters dehydration reactor containing the logistics of α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene, and α-methylbenzylalcohol is at γ-Al
2o
3there is lower dehydration and generate vinylbenzene in catalyzer, dehydration reaction temperature is 200 DEG C, reaction pressure 0.5MPa, α-methylbenzylalcohol weight space velocity 1.0 hours
-1.Reacted mixture enters styrene separating tower, and cinnamic rectifying separation is with [embodiment 1].Styrene separating tower tower reactor enters hydrogenation of acetophenone reactor containing the cut of methyl phenyl ketone and changes into α-methylbenzylalcohol, and used catalyst is 5%Ni/Al
2o
3, temperature of reaction 160 DEG C, pressure 2.5MPa, H
2be 3:1 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 2.0 hours
-1, the α-methylbenzylalcohol of generation and aforesaid α-methylbenzylalcohol merge and enter dehydration reactor and change into vinylbenzene.Reaction result is as shown in table 1.
[embodiment 5]
At 150 DEG C, 0.3MPa, control tail oxygen volume content lower than under 5% condition, ethylbenzene and air carry out peroxidation, obtain the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10%, obtain through vacuum concentrate hydrogen peroxide ethylbenzene (EBHP) oxidation solution that weight concentration is 30%.
Be that the hydrogen peroxide ethylbenzene oxidation liquid of 30% is under Ti-KIT-1 catalyzer (weight percentage of titanium is 2.6%) exists by above-mentioned weight concentration, with 1 in fixed-bed reactor, 3-divinyl carries out epoxidation reaction and generates 3,4-epoxy-1-butylene, α-methylbenzylalcohol and a small amount of methyl phenyl ketone.Wherein 1,3-butadiene/EBHP=4 (mol ratio), weight space velocity=3 hour of EBHP
-1, temperature of reaction is 105 DEG C, and reaction pressure is 3.5MPa.
Reaction mixture is passed into butadiene recovery column to reclaim excessive 1,3-butadiene and recycle, 1,3-butadiene reclaim and 3,4-epoxy-1-butylene rectifying separation together [embodiment 1].Tower reactor enters dehydration reactor containing the logistics of α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene, and α-methylbenzylalcohol dehydration under ZSM-5 exists generates vinylbenzene, and dehydration reaction temperature is 200 DEG C, reaction pressure 0.5MPa, α-methylbenzylalcohol weight hourly space velocity 1.0 hours
-1.Reacted mixture enters styrene separating tower, and cinnamic rectifying separation is with [embodiment 1].Styrene separating tower tower reactor enters hydrogenation of acetophenone reactor containing the cut of methyl phenyl ketone and changes into α-methylbenzylalcohol, and used catalyst is 0.5%Pd/C, temperature of reaction 150 DEG C, pressure 0.5MPa, H
2be 3:1 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 2.0 hours
-1, the α-methylbenzylalcohol of generation and aforesaid α-methylbenzylalcohol merge and enter dehydration reactor and change into vinylbenzene.Reaction result is as shown in table 1.
[embodiment 6]
At 155 DEG C, 0.35MPa, control tail oxygen volume content lower than under 5% condition, ethylbenzene and air carry out peroxidation, obtain the hydrogen peroxide ethylbenzene oxidation liquid that weight concentration is 10%, obtain through vacuum concentrate hydrogen peroxide ethylbenzene (EBHP) oxidation solution that weight concentration is 30%.
Be that the hydrogen peroxide ethylbenzene oxidation liquid of 30% is at Ti-SiO by above-mentioned weight concentration
2under catalyzer (weight percentage of titanium is 1.0%) exists, in fixed-bed reactor, carry out epoxidation reaction with 1,3-butadiene generate 3,4-epoxy-1-butylene, α-methylbenzylalcohol and a small amount of methyl phenyl ketone.Wherein 1,3-butadiene/EBHP=4 (mol ratio), weight space velocity=3 hour of EBHP
-1, temperature of reaction is 105 DEG C, and reaction pressure is 3.5MPa.
Reaction mixture is passed into butadiene recovery column to reclaim excessive 1,3-butadiene and recycle, 1,3-butadiene reclaim and 3,4-epoxy-1-butylene rectifying separation together [embodiment 1].Tower reactor enters dehydration reactor containing the logistics of α-methylbenzylalcohol, methyl phenyl ketone and ethylbenzene, and α-methylbenzylalcohol dehydration under ZSM-5 exists generates vinylbenzene, and dehydration reaction temperature is 200 DEG C, reaction pressure 0.5MPa, α-methylbenzylalcohol weight space velocity 1.0 hours
-1.Reacted mixture enters styrene separating tower, and cinnamic rectifying separation is with [embodiment 1].Styrene separating tower tower reactor enters hydrogenation of acetophenone reactor containing the cut of methyl phenyl ketone and changes into α-methylbenzylalcohol, and used catalyst is 8%Ni/SiO
2, temperature of reaction 155 DEG C, pressure 2.5MP, H
2be 3:1 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 2.0 hours
-1, the α-methylbenzylalcohol of generation and aforesaid α-methylbenzylalcohol merge and enter dehydration reactor and change into vinylbenzene.Reaction result is as shown in table 1.
Table 1
Note: EBHP-hydrogen peroxide ethylbenzene, EPB-3,4-epoxy-1-butylene.
As seen from Table 1, between the whole reaction period, EBHP transformation efficiency maintains more than 98.8%, and 3,4-epoxy-1-butylene selectivity maintains more than 99.1%, does not have waste residue to generate, and produces containing organic waste water hardly.
[comparative example 1]
5.0gAg-Ba-Cs-Cl/AlO is added in stainless steel fixed-bed reactor
3catalyzer (wherein the weight content of the weight content of Ag to be the weight content of 10.0%, Ba be 0.05%, Cs is 0.05%), 1,3-butadiene and air are reacted by beds after mixing.Wherein 1,3-butadiene/O
2the volume space velocity (GHSV)=2000 hour of=1 (mol ratio), mixing raw material
-1, temperature of reaction is 230 DEG C, reaction pressure normal pressure.When reacting beginning, butadiene conversion=30%, EPB selectivity=88.5%, when reaction is constantly little to 200 further, butadiene conversion is down to 15%, EPB selectivity and is down to 85.0%.
[comparative example 2]
5.0gAg-CsCl/AlO is added in stainless steel fixed-bed reactor
3catalyzer (wherein the weight content of Ag is the weight content of 15.0%, CsCl is 0.1%), 1,3-butadiene and air are reacted by beds after mixing.Wherein 1,3-butadiene/O
2the volume space velocity (GHSV)=2000 hour of=1 (mol ratio), mixing raw material
-1, temperature of reaction is 230 DEG C, reaction pressure normal pressure.When reacting beginning, butadiene conversion=20%, EPB selectivity=90.0%, when reaction is constantly little to 200 further, butadiene conversion is down to 10%, EPB selectivity and is down to 87.5%.
Claims (10)
1. the preparation method of an epoxy-1-butylene, comprises the following steps:
A) ethylbenzene and air carry out peroxidation, obtain hydrogen peroxide ethylbenzene oxidation liquid;
B) hydrogen peroxide ethylbenzene oxidation liquid and 1,3-butadiene are under the effect of catalyzer, epoxidation reaction occurs under liquid-phase condition and generates 3,4-epoxy-1-butylene, α-methylbenzylalcohol and methyl phenyl ketone;
C) α-methylbenzylalcohol dehydration reaction generates vinylbenzene;
D) methyl phenyl ketone and hydrogen generation hydrogenation reaction generate α-methylbenzylalcohol; The α-methylbenzylalcohol that this step generates gets back to c) step, and hydrogenation generates vinylbenzene together with the α-methylbenzylalcohol that b) step generates.
2. the preparation method of 3,4-epoxy-1-butylenes according to claim 1, is characterized in that step reaction conditions a) is: temperature of reaction 0 ~ 250 DEG C, reaction pressure 0.1 ~ 5.0MPa.
3. the preparation method of 3,4-epoxy-1-butylenes according to claim 2, is characterized in that step reaction conditions a) is: temperature of reaction 50 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0MPa.
4. according to claim 13, the preparation method of 4-epoxy-1-butylene, it is characterized in that step b) reaction conditions be: temperature of reaction 25 ~ 160 DEG C, reaction pressure 0.1 ~ 8.0MPa, 1, the mol ratio 1 ~ 15 of 3-divinyl and hydrogen peroxide ethylbenzene, the weight space velocity of hydrogen peroxide ethylbenzene 0.01 ~ 20 hour
-1; Catalyzer used is heterogeneous titanium-containing meso-porous or macroporous silica catalytic material.
5. according to claim 43, the preparation method of 4-epoxy-1-butylene, it is characterized in that step b) reaction conditions be: temperature of reaction 40 ~ 140 DEG C, reaction pressure 0.5 ~ 6.0MPa, 1, the mol ratio 2 ~ 12 of 3-divinyl and hydrogen peroxide ethylbenzene, the weight space velocity of hydrogen peroxide ethylbenzene 0.05 ~ 15 hour
-1; Catalyzer used is heterogeneous titanium-containing meso-porous or macroporous silica catalyzer Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO
2.
6. the preparation method of 3,4-epoxy-1-butylenes according to claim 1, is characterized in that step c) reaction conditions be: temperature of reaction 50 ~ 400 DEG C, reaction pressure 0 ~ 5.0MPa, the weight space velocity of α-methylbenzylalcohol is 0.1 ~ 10.0 hour
-1.
7. the preparation method of 3,4-epoxy-1-butylenes according to claim 6, is characterized in that step c) reaction conditions be: temperature of reaction 100 ~ 350 DEG C, reaction pressure 0.1 ~ 3.0MPa, the weight hourly space velocity of α-methylbenzylalcohol is 0.3 ~ 5.0 hour
-1.
8. the preparation method of 3,4-epoxy-1-butylenes according to claim 1, is characterized in that steps d) reaction conditions be: temperature of reaction 50 ~ 350 DEG C, reaction pressure 0.1 ~ 6.0MPa, H
2be 1 ~ 10 with the mol ratio of methyl phenyl ketone, the weight space velocity of methyl phenyl ketone is 0.1 ~ 10.0 hour
-1.
9. the preparation method of 3,4-epoxy-1-butylenes according to claim 8, is characterized in that steps d) reaction conditions be: temperature of reaction 100 ~ 300 DEG C, reaction pressure 0.5 ~ 4.0MPa, H
2be 2 ~ 6 with the mol ratio of methyl phenyl ketone, the weight hourly space velocity of methyl phenyl ketone is 0.3 ~ 6.0 hour
-1.
10. the preparation method of 3,4-epoxy-1-butylenes according to claim 1, is characterized in that the concentration expressed in percentage by weight of hydrogen peroxide ethylbenzene in described hydrogen peroxide ethylbenzene oxidation liquid is 1 ~ 50%.
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|---|---|---|---|---|
| CN113559923A (en) * | 2021-07-23 | 2021-10-29 | 陕西师范大学 | VOx/Zr-TUD-1 catalyst and method for preparing fluorine-containing epoxy oligomer-based styrene by catalytic dehydrogenation of VOx/Zr-TUD-1 catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678548A (en) * | 2002-08-27 | 2005-10-05 | 国际壳牌研究有限公司 | Process for the preparation of styrene or substituted styrene |
| CN101348472A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing epoxide |
| CN101535248A (en) * | 2006-11-13 | 2009-09-16 | 国际壳牌研究有限公司 | Process for the liquid phase oxidation of ethylbenzene into ethylbenzene hydroperoxide |
-
2014
- 2014-07-24 CN CN201410355468.2A patent/CN105272942B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678548A (en) * | 2002-08-27 | 2005-10-05 | 国际壳牌研究有限公司 | Process for the preparation of styrene or substituted styrene |
| CN101535248A (en) * | 2006-11-13 | 2009-09-16 | 国际壳牌研究有限公司 | Process for the liquid phase oxidation of ethylbenzene into ethylbenzene hydroperoxide |
| CN101348472A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing epoxide |
Non-Patent Citations (7)
| Title |
|---|
| XIAOMING ZHANG ET AL: "Catalytic monoepoxidation of butadiene over titanium silicate molecular sieves TS-1", 《CATALYSIS LETTERS》 * |
| 吴平易等: "介孔分子筛孔中过渡金属的组装及其催化应", 《化学进展》 * |
| 李为民等: "《石油化工概论》", 30 June 2013, 中国石化出版社 * |
| 李学峰等: "介孔材料在烯烃环氧化中的催化应用", 《化学进展》 * |
| 王寿峰等: "锰配合物催化1, 3-丁二烯环氧化合成环氧丁烯", 《分子催化》 * |
| 王绍梅等: "钛硅溶胶后移植法制备Ti-KIT-1介孔分子筛", 《安阳师范学院学报》 * |
| 赵忠奎等: "《高效反应技术与绿色化学》", 31 July 2012, 中国石化出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113559923A (en) * | 2021-07-23 | 2021-10-29 | 陕西师范大学 | VOx/Zr-TUD-1 catalyst and method for preparing fluorine-containing epoxy oligomer-based styrene by catalytic dehydrogenation of VOx/Zr-TUD-1 catalyst |
| CN113559923B (en) * | 2021-07-23 | 2023-08-29 | 陕西师范大学 | VOx/Zr-TUD-1 catalyst and method for preparing fluorine-containing epoxy oligomer-based styrene by catalytic dehydrogenation |
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