CN105315236A - Method of producing 3,4-epoxy-1-butylene - Google Patents
Method of producing 3,4-epoxy-1-butylene Download PDFInfo
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Abstract
The invention relates to a method of producing 3,4-epoxy-1-butylene and mainly solves the problem that a method in the prior art is low in raw material conversion rate, is serious in waste and is low in production yield. The synthetic method includes the following steps: a) performing a reaction to isopropyl benzene and air to obtain a hydrogen peroxide isopropyl benzene oxidized liquid; b) controlling the weight percentage ratio of organic acid to be not more than 0.3%, the weight percentage ratio of alkali metal ions or alkali earth metal ions to be not more than 0.1% and the weight percentage ratio of water to be not more than 0.5% in the hydrogen peroxide isopropyl benzene oxidized liquid; c) performing an epoxidation reaction to the hydrogen peroxide isopropyl benzene oxidized liquid with 1,3-butadiene to generate the 3,4-epoxy-1-butylene and [alpha],[alpha]-dimethyl benzyl alcohol; and d) performing a reaction between the [alpha],[alpha]-dimethyl benzyl alcohol and hydrogen to generate isopropyl benzene, and feeding the isopropyl benzene back to the step a) as the raw material for producing the hydrogen peroxide isopropyl benzene. The method can solves technical problems and can be used in industrial production of the 3,4-epoxy-1-butylene.
Description
Technical field
The present invention relates to a kind of method of producing 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
It is low that technical problem to be solved by this invention is that prior art exists feed stock conversion, and the problem that waste is serious and product yield is low, provides a kind of production 3,4-epoxy-1-butylene method newly.It is high that the method has catalyst activity, noresidue in product, and feed stock conversion is high, good stability, and 3,4-epoxy-1-butylene selectivity is high, environmental protection and the feature without joint product.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing 3,4-epoxy-1-butylene, comprises the following steps:
A) isopropyl benzene and air generation peroxidation, obtain hydrogen phosphide cumene oxidation solution;
B) organic acid in hydrogen phosphide cumene oxidation solution is removed, basic metal or alkaline-earth metal ions, and water, organic acid weight percentage is wherein made to be not more than 0.3%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 0.1%, and the weight percentage of water is not more than 0.5%;
C) through step b) the hydrogen phosphide cumene oxidation solution and 1 that processes, 3-divinyl is under the effect of catalyzer, selective oxidation reduction reaction is there is under liquid-phase condition, wherein 1,3-divinyl is oxidized to 3,4-epoxy-1-butylene, hydrogen phosphide cumene is reduced into α, alpha-alpha-dimethyl benzylalcohol;
D) α, alpha-alpha-dimethyl benzylalcohol and hydrogen generation hydrogenolysis generate isopropyl benzene; The isopropyl benzene generated is circulated to step a) as the raw material preparing hydrogen phosphide cumene oxidation solution.
In technique scheme, preferably, step reaction conditions a) is: temperature of reaction 0 ~ 200 DEG C, reaction pressure 0.1 ~ 5.0MPa.More preferably, temperature of reaction 50 ~ 150 DEG C, reaction pressure 0.1 ~ 2.0MPa.
In technique scheme, preferably, control organic acid weight percentage in hydrogen phosphide cumene oxidation solution and be not more than 0.1%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 500ppm, and the weight percentage of water is not more than 0.2%.More preferably, control organic acid weight percentage in hydrogen phosphide cumene oxidation solution and be not more than 600ppm, the weight percentage of basic metal or alkaline-earth metal ions is not more than 200ppm, and the weight percentage of water is not more than 0.1%.
In technique scheme, preferably, described organic acid is selected from least one in formic acid, acetic acid, propionic acid, oxalic acid, propanedioic acid, lactic acid or phenol.
In technique scheme, preferably, step c) reaction conditions is: temperature of reaction 25 ~ 160 DEG C, reaction pressure 0.1 ~ 10.0MPa, the mol ratio 1 ~ 20 of 1,3-butadiene and hydrogen phosphide cumene, the weight space velocity of hydrogen phosphide cumene 0.05 ~ 20.0 hour
-1, catalyzer used is titanium-containing meso-porous or macroporous silica catalytic material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO
2.More preferably, temperature of reaction is 40 ~ 130 DEG C, and reaction pressure is 0.5 ~ 8.0MPa, and the mol ratio of 1,3-butadiene and hydrogen phosphide cumene is 2 ~ 15, and the weight space velocity of hydrogen phosphide cumene is 0.1 ~ 15.0 hour
-1.
In technique scheme, preferably, steps d) reaction conditions be: temperature of reaction 80 ~ 400 DEG C, reaction pressure 0.1 ~ 6.0MPa.
In technique scheme, preferably, in described hydrogen phosphide cumene oxidation solution, the concentration expressed in percentage by weight of hydrogen phosphide cumene is 1 ~ 90%.More preferably, 10 ~ 80%.
In the inventive method, step is a) oxidation step, and adopt molecular oxygen that cumene oxidation is become hydrogen phosphide cumene, 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 air-oxidation system of any additive.Under normal circumstances, the temperature of reaction of oxidation step and pressure are preferably 50 ~ 150 DEG C and 0.1 ~ 2.0MPa respectively.Temperature is too low, and reaction efficiency is low, maybe cannot carry out; Too high temperature then easily causes hydrogen phosphide cumene decompose or produce other by product.
In the inventive method, step b) be depickling, dealkalize metal or alkaline-earth metal ions and decompression concentrate step.Wherein depickling removes the organic acid in the hydrogen phosphide cumene oxidation solution that produces in oxidation step.In oxidation step, along with the carrying out of reaction, some micromolecular organic acids can be produced, as formic acid, acetic acid, propionic acid, oxalic acid, propanedioic acid, lactic acid or phenol etc.Organic acid both can adopt organic solvent extraction technology to remove, and the aqueous solution of the oxyhydroxide of basic metal, alkaline-earth metal or ammonia or carbonate also can be adopted to carry out washing and remove and (be generally NaCO
3or the aqueous solution of NaOH), or adopt micromolecular organic amine, as methylamine, ethamine, propylamine, quadrol etc. remove, or directly adopt water to wash.In oxidation solution, so inevitably in turn introduce basic metal or alkaline-earth metal ions and water.Basic metal or alkaline-earth metal ions (are generally Na
+) remove and can adopt water-washing method, then remove water wherein by drying treatment.By depickling, de-Na
+and the process of decompression concentrate, be supplied in the hydrogen phosphide cumene oxidation solution of epoxidation step, organic acid weight content is preferably≤0.1%, is more preferably≤600ppm; Na
+weight content be preferably≤500ppm, be more preferably≤200ppm; The weight content of water is preferably≤0.2%, be more preferably≤0.1%.
In hydrogen phosphide cumene oxidation solution, the mensuration of organic acid content can adopt the mode of ion chromatography or acid base titration, and the mensuration of basic metal or alkaline-earth metal ions content can adopt ion chromatography, and water-content can adopt vapor-phase chromatography to measure.
Step c) in, as the 1,3-butadiene of selective oxidation reduction reaction raw material, to its purity without particular requirement, generally 1,3-butadiene purity is greater than 80 volume %.The form of mixtures that hydrogen phosphide cumene is generally formed with itself and isopropyl benzene as the oxygen carrier of selective oxidation reduction reaction uses, and generally selects its concentration to be 1 ~ 90 % by weight, and preferably 10 ~ 80 % by weight.Concentration is too low, redox reaction 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 redox catalyst, easily causes catalyst deactivation.Selective redox 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 isopropyl benzene, can avoid like this introducing extra material, increase separating energy consumption.Selective oxidation reduction reaction temperature is preferably 40 ~ 130 DEG C.Temperature is crossed low reaction and is difficult to carry out, and temperature is too high, easily causes hydrogen phosphide cumene to decompose, and by product increases.Reaction pressure is in a liquid state to maintain reaction raw materials, is preferably 0.5 ~ 8.0MPa.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.Selective oxidation reduction 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 Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO
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): (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.Wherein, in catalyzer, titanium content is 0.1 ~ 20%, preferably 0.2 ~ 10%.
In order to ensure α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis can carry out smoothly, improves the utilization ratio of hydrogen phosphide cumene, reduces the loss of isopropyl benzene, will improve the transformation efficiency of hydrogen phosphide cumene as far as possible, reduces its content in the reaction product.In general, after rectifying separation goes out 1,3-butadiene and 3,4-epoxy-1-butylene, in the cumene solution of benzylalcohol being supplied to hydrogenolysis step, the weight content of hydrogen phosphide cumene should control below 3%.This can be realized by the activity improving catalyzer, also can have been come by methods such as rectifying, absorption, extractions.Pay the utmost attention to the content that the methods such as the activity of employing raising catalyzer, rectifying and absorption reduce hydrogen phosphide cumene.
Hydrogenolysis step is in the presence of a catalyst by α that selective oxidation reduction step produces, alpha-alpha-dimethyl benzylalcohol hydrogenolysis generates isopropyl benzene, this reaction is carried out under gas-solid-liquid three-phase condition in solvent, and solvent is inertia to reactant and product and is liquid state at reaction conditions.Selected solvent 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 isopropyl benzene, can avoid like this introducing extra material, increase separating energy consumption.Used catalyst Ni-based, copper base, the palladium bases etc. comprised on carriers such as being carried on activated alumina, silicon oxide, zeolite molecular sieve and gac have the catalytic material of catalytic hydrogenolysis function.The temperature and pressure of hydrogenolysis is preferably 80 ~ 400 DEG C and 0.1 ~ 6.0MPa respectively.Hydrogenolysis both can carry 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.
The present inventor finds, the excessive concentration of Organic Acid and Base metal or alkaline-earth metal ions and water in hydrogen phosphide cumene oxidation solution, can have a strong impact on the selectivity of selective oxidation reduction reaction and the work-ing life of catalyzer.Organic acid weight percentage in control hydrogen phosphide cumene oxidation solution is only had to be not more than 0.1%, the weight percent concentration of basic metal or alkaline-earth metal ions is not more than 500ppm, the weight percent concentration of water is not more than 0.2%, the carrying out of guarantee redox reaction highly selective; Also can ensure that catalyzer has longer work-ing life, catalyzer can improve 100% duration of service simultaneously; In addition, the inventive method, outside object product 3,4-epoxy-1-butylene, does not have other joint product to generate, and the isopropyl benzene as initial raw material can use at system internal recycle, and Technical Economy is good, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
At 105 DEG C, 0.4MPa, control tail oxygen volume content lower than under 5% condition, isopropyl benzene and air carry out oxidizing reaction, obtain hydrogen phosphide cumene (CHP) oxidation solution that weight concentration is 20 ~ 24%.
Employing NaOH weight content is the solution washing hydrogen phosphide cumene oxidation solution of 2%, and wherein the volume ratio of oxidation solution and alkali lye is 3:1, removes organic acid wherein.Then use deionized water wash oxidation solution, remove the Na residual because of alkali cleaning
+, wherein the volume ratio of oxidation solution and deionized water is 3:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, concentrate temperature 75 DEG C, obtains the oxidation solution that hydrogen phosphide cumene concentration is 50 % by weight, while concentrate because of washing the water that remains also be removed to a certain extent.After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 90ppm, H
2the weight content of O is 200ppm, Na
+weight content be 55ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 50 % by weight) under Ti-HMS catalyzer (weight percentage of Ti is 1.6%) exists, with 1 in fixed-bed reactor, 3-divinyl carries out selective redox reaction generation 3,4-epoxy-1-butylene and α, alpha-alpha-dimethyl benzylalcohol.Weight space velocity=4 hour of wherein 1,3-butadiene/CHP=5:1 (mole), CHP
-1, temperature of reaction 100 DEG C, reaction pressure 3.0MPa.
Reaction mixture is passed into butadiene recovery column to reclaim excessive 1,3-butadiene and recycle, wherein butadiene recovery column operates at ambient pressure, tower top temperature-4.5 DEG C, bottom temperature 150 DEG C, normal pressure.Tower reactor is containing 3,4-epoxy-1-butylene, α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters 3,4-epoxy-1-butylene knockout towers, and this tower operates at ambient pressure, tower top temperature 66 DEG C, bottom temperature 160 DEG C.
3,4-epoxy-1-butylene knockout tower tower reactor is containing α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters benzylalcohol hydrogenolysis device.α, alpha-alpha-dimethyl benzylalcohol is at 0.5%Pd/Al
2o
3there is lower hydrogenolysis and generate isopropyl benzene in catalyzer.Temperature of reaction is 160 DEG C, and reaction pressure is 2.0MPa, H
2/ α, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 3:1, α, and the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 hours
-1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene.Reaction result is as shown in table 1.
[embodiment 2]
At 100 DEG C, 0.3MPa, control tail oxygen volume content lower than under 5% condition, isopropyl benzene and air carry out oxidizing reaction, obtain hydrogen phosphide cumene (CHP) oxidation solution that weight concentration is 20 ~ 24%.
Adopt Na
2cO
3weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, removes organic acid wherein.Then use deionized water wash oxidation solution, remove the Na residual because of alkali cleaning
+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, concentrate temperature 70 C, obtains the oxidation solution that hydrogen phosphide cumene concentration is 40 % by weight, while concentrate because of washing the water that remains also be removed to a certain extent.After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 100ppm, H
2the weight content of O is 250ppm, Na
+weight content be 40ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 40 % by weight) under Ti-MCM-41 catalyzer (weight percentage of Ti is 2.0%) exists, with 1 in fixed-bed reactor, 3-divinyl carries out selective redox reaction generation 3,4-epoxy-1-butylene and α, alpha-alpha-dimethyl benzylalcohol.Weight space velocity=4.5 hour of wherein 1,3-butadiene/CHP=5:1 (mole), CHP
-1, temperature of reaction 98 DEG C, reaction pressure 2.8MPa.
Divinyl reclaims and product separation process same [embodiment 1].
3,4-epoxy-1-butylene knockout tower tower reactor is containing α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters benzylalcohol hydrogenolysis device.α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis under 0.2%Pd/C catalyzer exists generates isopropyl benzene.Temperature of reaction is 150 DEG C, and reaction pressure is 2.0MPa, H
2/ α, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 3:1, α, and the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 hours
-1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene.Reaction result is as shown in table 1.
[embodiment 3]
At 98 DEG C, 0.3MPa, control tail oxygen volume content lower than under 5% condition, isopropyl benzene and air carry out oxidizing reaction, obtain hydrogen phosphide cumene (CHP) oxidation solution that weight concentration is 20 ~ 24%.
Employing NaOH weight content is the solution washing hydrogen phosphide cumene oxidation solution of 2%, and wherein the volume ratio of oxidation solution and alkali lye is 3:1, removes organic acid wherein.Then use deionized water wash oxidation solution, remove the Na residual because of alkali cleaning
+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, concentrate temperature 80 DEG C, obtains the oxidation solution that hydrogen phosphide cumene concentration is 60 % by weight, while concentrate because of washing the water that remains also be removed to a certain extent.After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 70ppm, H
2the weight content of O is 100ppm, Na
+weight content be 30ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 60 % by weight) under Ti-TUD-1 catalyzer (weight percentage of Ti is 1.5%) exists, with 1 in fixed-bed reactor, 3-divinyl carries out selective redox reaction generation 3,4-epoxy-1-butylene and α, alpha-alpha-dimethyl benzylalcohol.Weight space velocity=4 hour of wherein 1,3-butadiene/CHP=6:1 (mole), CHP
-1, temperature of reaction 100 DEG C, reaction pressure 3.5MPa.
Divinyl reclaims and product separation process same [embodiment 1].
3,4-epoxy-1-butylene knockout tower tower reactor is containing α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters benzylalcohol hydrogenolysis device.α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis under 0.2%Pd/C catalyzer exists generates isopropyl benzene.Temperature of reaction is 165 DEG C, and reaction pressure is 2.4MPa, H
2/ α, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 2:1, α, and the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 hours
-1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene.Reaction result is as shown in table 1.
[embodiment 4]
At 100 DEG C, 0.3MPa, control tail oxygen volume content lower than under 5% condition, isopropyl benzene and air carry out oxidizing reaction, obtain hydrogen phosphide cumene (CHP) oxidation solution that weight concentration is 20 ~ 24%.
Employing NaOH weight content is the solution washing hydrogen phosphide cumene oxidation solution of 2%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, removes organic acid wherein.Then use deionized water wash oxidation solution, remove the Na residual because of alkali cleaning
+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, concentrate temperature 80 DEG C, obtains the oxidation solution that hydrogen phosphide cumene concentration is 55 % by weight, while concentrate because of washing the water that remains also be removed to a certain extent.After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 75ppm, H
2the weight content of O is 110ppm, Na
+weight content be 40ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 55 % by weight) under Ti-SBA-15 catalyzer (weight percentage of Ti is 3.0%) exists, with 1 in fixed-bed reactor, 3-divinyl carries out selective redox reaction generation 3,4-epoxy-1-butylene and α, alpha-alpha-dimethyl benzylalcohol.Weight space velocity=4.5 hour of wherein 1,3-butadiene/CHP=7:1 (mole), CHP
-1, temperature of reaction is 100 DEG C, and reaction pressure is 3.5MPa.
Divinyl reclaims and product separation process same [embodiment 1].
3,4-epoxy-1-butylene knockout tower tower reactor is containing α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters benzylalcohol hydrogenolysis device.α, alpha-alpha-dimethyl benzylalcohol is at 0.2%Pd/Al
2o
3there is lower hydrogenolysis and generate isopropyl benzene in catalyzer.Temperature of reaction is 165 DEG C, and reaction pressure is 2.3MPa, H
2/ α, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 3:1, α, and the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 hours
-1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene.Reaction result is as shown in table 1.
[embodiment 5]
At 102 DEG C, 0.3MPa, control tail oxygen volume content lower than under 5% condition, isopropyl benzene and air carry out oxidizing reaction, obtain hydrogen phosphide cumene (CHP) oxidation solution that weight concentration is 20 ~ 24%.
Adopt Na
2cO
3weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, removes organic acid wherein.Then use deionized water wash oxidation solution, remove the Na residual because of alkali cleaning
+, wherein the volume ratio of oxidation solution and deionized water is 3:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, concentrate temperature 80 DEG C, obtains the oxidation solution that hydrogen phosphide cumene concentration is 55 % by weight, while concentrate because of washing the water that remains also be removed to a certain extent.After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 80ppm, H
2the weight content of O is 120ppm, Na
+weight content be 45ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 55 % by weight) under Ti-KIT-1 catalyzer (weight percentage of Ti is 2.6%) exists, with 1 in fixed-bed reactor, 3-divinyl carries out selective redox reaction generation 3,4-epoxy-1-butylene and α, alpha-alpha-dimethyl benzylalcohol.Weight space velocity=4 hour of wherein 1,3-butadiene/CHP=6:1 (mole), CHP
-1, temperature of reaction is 100 DEG C, and reaction pressure is 3.5MPa.
Divinyl reclaims and product separation process same [embodiment 1].
3,4-epoxy-1-butylene knockout tower tower reactor is containing α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters benzylalcohol hydrogenolysis device.α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis under 0.2%Pd/C catalyzer exists generates isopropyl benzene.Temperature of reaction is 155 DEG C, and reaction pressure is 2.2MPa, H
2/ α, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 3:1, α, and the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 hours
-1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene.Reaction result is as shown in table 1.
[embodiment 6]
At 95 DEG C, 0.2MPa, control tail oxygen volume content lower than under 5% condition, isopropyl benzene and air carry out oxidizing reaction, obtain hydrogen phosphide cumene (CHP) oxidation solution that weight concentration is 20 ~ 24%.
Adopt Na
2cO
3weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, removes organic acid wherein.Then use deionized water wash oxidation solution, remove the Na residual because of alkali cleaning
+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, concentrate temperature 80 DEG C, obtains the oxidation solution that hydrogen phosphide cumene concentration is 50 % by weight, while concentrate because of washing the water that remains also be removed to a certain extent.After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 80ppm, H
2the weight content of O is 120ppm, Na
+weight content be 40ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 50 % by weight) at Ti-SiO
2under catalyzer (weight percentage of Ti is 1.0%) exists, in fixed-bed reactor, carry out selective redox reaction generation 3,4-epoxy-1-butylene and α with 1,3-butadiene, alpha-alpha-dimethyl benzylalcohol.Weight space velocity=4 hour of wherein 1-butylene/CHP=8:1 (mole), CHP
-1, temperature of reaction 100 DEG C, reaction pressure 3.2MPa.
Divinyl reclaims and product separation process same [embodiment 1].
3,4-epoxy-1-butylene knockout tower tower reactor is containing α, and the material of alpha-alpha-dimethyl benzylalcohol and isopropyl benzene etc. enters benzylalcohol hydrogenolysis device.α, alpha-alpha-dimethyl benzylalcohol is at 0.5%Pd/Al
2o
3there is lower hydrogenolysis and generate isopropyl benzene in catalyzer.Temperature of reaction is 160 DEG C, and reaction pressure is 2.0MPa, H
2/ α, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 3:1, α, and the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 hours
-1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene.Reaction result is as shown in table 1.
[comparative example 1]
With [embodiment 1], just not carrying out alkali cleaning to oxidation solution, is 800ppm, H comprising phenol at interior organic acid weight content
2the weight content of O is 300ppm, Na
+weight content reach 55ppm, its reaction result is in table 2.
[comparative example 2]
With [embodiment 1], just not washing the oxidation solution after alkali cleaning, is 100ppm, H comprising phenol at interior organic acid weight content
2the weight content of O is 200ppm, Na
+weight content reach 400ppm, its reaction result is in table 2.
[comparative example 3]
With [embodiment 1], just not carrying out decompression concentrate to the oxidation solution after alkali cleaning, washing, is 100ppm, H comprising phenol at interior organic acid weight content
2the weight content 0.2%, Na of O
+weight content be 80ppm.The concentration of hydrogen phosphide cumene oxidation solution is 22.0 % by weight.Its reaction result is in table 2.
[comparative example 4]
With [embodiment 1], just not carrying out alkali cleaning, washing to oxidation solution, is 750ppm, H comprising phenol at interior organic acid weight content
2the weight content of O is 100ppm, Na
+weight content reach 90ppm, its reaction result is in table 2.
Table 1
Note: CHP-hydrogen phosphide cumene, EPB-3,4-epoxy-1-butylene.
Table 2
Note: CHP-hydrogen phosphide cumene, EPB-3,4-epoxy-1-butylene.
Can see from the above results, through depickling, de-Na
+and the hydrogen phosphide cumene oxidation solution of decompression concentrate process, control organic acid weight percentage and be not more than 0.3%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 0.1%, and the weight percentage of water is not more than 0.5%.Especially control organic acid weight percentage and be not more than 600ppm, the weight percentage of basic metal or alkaline-earth metal ions is not more than 200ppm, and the weight percentage of water is not more than 0.1%.High yield, highly selective 1,3-butadiene catalysis epoxidation can be become 3,4-epoxy-1-butylene, and catalyzer has satisfactory stability.
Claims (10)
1. produce the method for 3,4-epoxy-1-butylene for one kind, comprise the following steps:
A) isopropyl benzene and air generation peroxidation, obtain hydrogen phosphide cumene oxidation solution;
B) organic acid in hydrogen phosphide cumene oxidation solution is removed, basic metal or alkaline-earth metal ions, and water, organic acid weight percentage is wherein made to be not more than 0.3%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 0.1%, and the weight percentage of water is not more than 0.5%;
C) through step b) the hydrogen phosphide cumene oxidation solution and 1 that processes, 3-divinyl is under the effect of catalyzer, selective oxidation reduction reaction is there is under liquid-phase condition, wherein 1,3-divinyl is oxidized to 3,4-epoxy-1-butylene, hydrogen phosphide cumene is reduced into α, alpha-alpha-dimethyl benzylalcohol;
D) α, alpha-alpha-dimethyl benzylalcohol and hydrogen generation hydrogenolysis generate isopropyl benzene; The isopropyl benzene generated is circulated to step a) as the raw material preparing hydrogen phosphide cumene oxidation solution.
2. produce the method for 3,4-epoxy-1-butylene according to claim 1, it is characterized in that step reaction conditions a) is: temperature of reaction 0 ~ 200 DEG C, reaction pressure 0.1 ~ 5.0MPa.
3. produce the method for 3,4-epoxy-1-butylene according to claim 2, it is characterized in that step reaction conditions a) is: temperature of reaction 50 ~ 150 DEG C, reaction pressure 0.1 ~ 2.0MPa.
4. produce 3 according to claim 1, the method of 4-epoxy-1-butylene, it is characterized in that controlling organic acid weight percentage in hydrogen phosphide cumene oxidation solution is not more than 0.1%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 500ppm, and the weight percentage of water is not more than 0.2%.
5. produce 3 according to claim 4, the method of 4-epoxy-1-butylene, it is characterized in that controlling organic acid weight percentage in hydrogen phosphide cumene oxidation solution is not more than 600ppm, the weight percentage of basic metal or alkaline-earth metal ions is not more than 200ppm, and the weight percentage of water is not more than 0.1%.
6. produce the method for 3,4-epoxy-1-butylene according to claim 1, it is characterized in that described organic acid is selected from least one in formic acid, acetic acid, propionic acid, oxalic acid, propanedioic acid, lactic acid or phenol.
7. produce 3 according to claim 1, the method of 4-epoxy-1-butylene, it is characterized in that step c) reaction conditions is: temperature of reaction 25 ~ 160 DEG C, reaction pressure 0.1 ~ 10.0MPa, 1, the mol ratio 1 ~ 20 of 3-divinyl and hydrogen phosphide cumene, the weight space velocity of hydrogen phosphide cumene 0.05 ~ 20.0 hour
-1, catalyzer used is titanium-containing meso-porous or macroporous silica catalytic material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO
2.
8. produce the method for 3,4-epoxy-1-butylene according to claim 7, it is characterized in that temperature of reaction is 40 ~ 130 DEG C, reaction pressure is 0.5 ~ 8.0MPa, the mol ratio of 1,3-butadiene and hydrogen phosphide cumene is 2 ~ 15, and the weight space velocity of hydrogen phosphide cumene is 0.1 ~ 15.0 hour
-1.
9. produce the method for 3,4-epoxy-1-butylene according to claim 1, it is characterized in that steps d) reaction conditions be: temperature of reaction 80 ~ 400 DEG C, reaction pressure 0.1 ~ 6.0MPa.
10. produce the method for 3,4-epoxy-1-butylene according to claim 1, it is characterized in that the concentration expressed in percentage by weight of hydrogen phosphide cumene in described hydrogen phosphide cumene oxidation solution is 1 ~ 90%.
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