CN102453002A - Method for preparing epoxypropane - Google Patents
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- CN102453002A CN102453002A CN2010105242282A CN201010524228A CN102453002A CN 102453002 A CN102453002 A CN 102453002A CN 2010105242282 A CN2010105242282 A CN 2010105242282A CN 201010524228 A CN201010524228 A CN 201010524228A CN 102453002 A CN102453002 A CN 102453002A
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Abstract
The invention relates to a method for producing epoxypropane, in particular to a process for preparing epoxypropane by an organic peroxide method, with methylcyclohexane as an initial hydrocarbon. The method comprises the following three steps: 1. oxidizing methylcyclohexane in a liquid phase to obtain methyl cyclohexyl hydrogen peroxide; 2. subjecting the methyl cyclohexyl hydrogen peroxide to react with propylene to obtain epoxypropane and methylcyclohexanol; and 3. dehydrating and hydro-converting the methylcyclohexanol to methylcyclohexane, and returning to the first oxidation reaction step for recycling.
Description
Technical field
The present invention relates to the working method of petrochemical materials, relate more specifically to the working method of propylene oxide.
Background technology
Propylene oxide is after Vestolen PP 7052, vinyl cyanide, the third-largest verivate of propylene, because of its have tension force very big contain the oxygen triatomic ring, chemical property is very active, has purposes widely, is mainly used in to produce Ucar 35, polyethers etc.
Traditional Synthesis of Propylene Oxide mainly contains chlorohydrination and organo-peroxide oxidation style.
Chlorohydrination: chlorohydrination is an industrial-scale production propylene oxide technology the earliest, is also using so far.This technology is with hypochlorous acid (the chlorine aqueous solution) and propylene reaction, generates propylene chlorohydrin, and dehydrochlorination under the effect of calcium hydroxide generates propylene oxide then.The advantage of this technology is that technology is simple, small investment of production equipment.Unsurmountable shortcoming is to produce a large amount of by product and waste water.Under the general technology condition, 1 ton of propylene oxide of every production needs to consume 0.85 ton of propylene, and 0.12 ton of by-product propylene dichloride produces 50～80 tons of waste water, and wherein the content of dichloro propyl ether is 400mg/L in the waste water.Each item index improves to some extent in recent years, and above data can reach respectively: consume 0.815 ton of propylene, and 0.08 ton of by-product propylene dichloride, the content of dichloro propyl ether is 40mg/L in the waste water.But by-product and wastewater problem remain the vital defective of this technology.
The organo-peroxide method: the organo-peroxide method is at first with molecular oxygen a kind of hydrocarbon (to be called later on: starting hydrocarbon) be oxidized to the alkyl hydrogen peroxide; With this alkyl hydrogen peroxide propylene oxidation is become propylene oxide then; This alkyl hydrogen peroxide then changes into corresponding alcohol, and reaction formula is following:
According to the difference of used starting hydrocarbon, and the different treatment method of co-product alcohol, industrial application has following three kinds of technologies at present.
The Trimethylmethane method: with the Trimethylmethane is starting hydrocarbon; With molecular oxygen oxidation of isobutane is become the isobutyl-hydrogen peroxide; Obtain propylene oxide with isobutyl-hydrogen peroxide oxidation propylene then; The isobutyl-hydrogen peroxide changes into the trimethyl carbinol, as co-product, or trimethyl carbinol dehydration is generated iso-butylene as co-product with the trimethyl carbinol.The advantage of this method is when obtaining propylene oxide, Trimethylmethane to be changed into the trimethyl carbinol or iso-butylene, and tertbutyl peroxide is relatively stable, can carry out epoxidation reaction with higher concentration.Shortcoming is to need a large amount of Trimethylmethanes, and the oxidation of the first step Trimethylmethane need carry out under higher temperature, owing to need remain on liquid-phase oxidation, so required pressure is also than higher.The first step reaction is carried out under the condition of 3.0MPa～4.0MPa generally at 140 ℃.
The ethylbenzene method: with ethylbenzene is starting hydrocarbon, with molecular oxygen ethylbenzene oxidation is become ethylbenzene hydroperoxide, obtains propylene oxide with the ethylbenzene hydroperoxide propylene oxide then, and ethylbenzene hydroperoxide changes into methyl phenyl carbinol simultaneously, and further dehydration becomes vinylbenzene as co-product.The advantage of this technology is to obtain vinylbenzene simultaneously as co-product.Shortcoming also be because with vinylbenzene as co-product, 1 ton of propylene oxide of every production needs 2.2 tons of vinylbenzene of coproduction, not only will consider the investment of vinylbenzene workshop section, also will consider the vinylbenzene market requirement and price.The oxidation of ethylbenzene needs higher temperature in addition, and generally 155 ℃ of oxidations, the ethylbenzene hydroperoxide selectivity is low, and the ethylbenzene hydroperoxide instability resolves into methyl phenyl carbinol and methyl phenyl ketone etc. easily.In the epoxidation of propylene step, the concentration of ethylbenzene hydroperoxide is lower, needs a large amount of propylene to recycle etc., all is the shortcoming of this technology.
Cumene method: the cumene method of succeeding in developing in recent years is to be starting hydrocarbon with the isopropyl benzene, with air the isopropyl benzene initial oxidation is become dicumyl peroxide, obtains propylene oxide with the dicumyl peroxide propylene oxide then, and dicumyl peroxide changes into dimethyl benzyl alcohol.Subsequently the dimethyl benzyl alcohol dehydration hydrogenation being transformed into isopropyl benzene recycles as starting hydrocarbon.The advantage of this technology is not have co-product, therefore needn't consider the question of market of co-product.Because cumene oxidation becomes dicumyl peroxide easier, only need about 110 ℃, to get final product, simultaneously so condition more relaxes.Can control higher dicumyl peroxide concentration and less propylene/superoxide ratio in the epoxidation process.Shortcoming is that the dicumyl peroxide ratio is easier to decompose, and as resolving into phenol, acetone, the dimethyl benzyl alcohol dehydration hydrogenation is converted into the process of isopropyl benzene, and being actually earlier, dehydration generates phenylallene, hydrogenation then.Therefore the easy polymerization of phenylallene, and also hydrogenation simultaneously of phenyl ring need to select hydrogenation, generally need carry out hydrogenation at low temperatures with Pt or Pd catalyzer.
With industrial process, the propylene hydrogen peroxide oxidation method that is carrying out the industrial application trial run also is the method for relatively being paid close attention to except that above.This method is under the effect of titanium-containing molecular sieve catalyst, obtains propylene oxide with the hydrogen peroxide oxidation propylene.The advantage of this method is that oxygenant is selected ydrogen peroxide 50 for use, and ydrogen peroxide 50 changed into water after epoxidation was accomplished, and did not have other co-product, the production technique comparative maturity of ydrogen peroxide 50, and ydrogen peroxide 50 is accumulating more easily under certain condition.Shortcoming is that the production process of ydrogen peroxide 50 also needs hydrogen and oxygen; Identical with the basic raw material of the above-mentioned superoxide method that does not have coproduction, need other solubilizing agent in addition in the epoxidization reaction process, be solvent generally with methyl alcohol etc.; Under the effect of catalyzer; Cause the propylene oxide open loop to generate Ucar 35 or further polymerization generation poly Ucar 35 in the reaction process easily, cause the catalyzer rapid deactivation, need often regeneration.
Other also has certain methods to be in different stepss such as laboratory study or pilot scale research.Like the hydrogen-oxygen direct oxidation method, be with hydrogen and oxygen direct oxidation propylene production propylene oxide under the effect of Pt-HTS.Be actually hydrogen and oxygen online generation ydrogen peroxide 50 on the Pt catalyzer, ydrogen peroxide 50 becomes propylene oxide with propylene oxidation immediately under the effect of HTS then.It is the Perfected process that the propylene oxide research field is being pursued always that propylene directly prepares propylene oxide with molecular oxygen oxidation, many investigators is arranged always in this process of exploration, but never breakthrough.
More than in the novel process of various preparation propylene oxide, the organo-peroxide method propylene oxide process of dioxygen water law and no co-product is current two kinds of technological processs that everybody relatively has an optimistic view of.
The typical process of hydrogen peroxide oxidation method is: with the working fluid that the air or oxygen oxidation is made up of high boiling point aromatic hydrocarbons and octyl phosphate equal solvent and starting hydrocarbon 2-ethyl hydrogen anthranol, 2-ethyl hydrogen anthranol wherein is oxidized to 2-ethyl-anthraquinone, generates ydrogen peroxide 50 simultaneously.Water extraction ydrogen peroxide 50 and evaporation and concentrating obtain certain density ydrogen peroxide 50 then.The back is under the effect of TS sieve catalyst again, and in methanol solvate, the hydrogen peroxide oxidation propylene becomes propylene oxide.The working fluid hydrogenation under the effect of palladium catalyst that contains 2-ethyl-anthraquinone is reduced into 2-ethyl hydrogen anthranol with wherein 2-ethyl-anthraquinone, and working fluid restores.
The typical process of the organo-peroxide method of no co-product is: convert it into the hydrocarbon hydrogen peroxide with the atmospheric oxidation starting hydrocarbon; Under the effect of catalyzer, propylene oxidation is become propylene oxide then with this hydrocarbon hydrogen peroxide; Said hydrocarbon hydrogen peroxide changes into corresponding alcohol; At last this dehydration of alcohols is hydroconverted into the starting hydrocarbon of initial use, recycles.
Summary of the invention
The technical problem that the present invention will solve is: in order to overcome the deficiency of prior art; The invention provides a kind of technology of new preparation propylene oxide; Specifically with methylcyclohexane as starting hydrocarbon; Develop a kind of organo-peroxide method propylene oxide production novel process of not having co-product, this technology has also overcome the many shortcomings in many traditional organo-peroxide methods except that the advantage with general organo-peroxide method.
Use Trimethylmethane to compare with original technology as starting hydrocarbon, with methylcyclohexane during as starting hydrocarbon, because of boiling point, the flash-point of methylcyclohexane all high.Security is better in the process of the first step oxidizing reaction, and needed pressure is also lower when making it remain on liquid state, as under required temperature of reaction, keep stagnation pressure just can keep material in liquid state at 2.0MPa or below the 1.0MPa.The boiling point of methylcyclohexane neither be too high, need carry out concentration or other step later on need handle the time in the first step oxidizing reaction, and is also more convenient, need not severe condition such as very high temperature or vacuum tightness.
Use ethylbenzene relatively with original technology as starting hydrocarbon; Methylcyclohexane is oxidized to corresponding superoxide more easily than ethylbenzene; And the superoxide that is generated is more stable; Therefore the peroxide concentrations that its oxidizing reaction temperature is lower, reaction preference is higher, obtain product is higher, and efficiency of equipment is higher.
Use isopropyl benzene to compare with original technology as starting hydrocarbon; Owing to there is not the influence of phenyl ring; So it is lower that related peroxide breakdown generates the amount of by product, and methylcyclohexane is lower than isopropyl benzene boiling point, some follow-up treatment step operations are convenient; More superior is that methylcyclohexane is formed by the toluene hydrogenation, more cheap and easy to get than isopropyl benzene.
Technical scheme of the present invention is:
A kind of preparation method of propylene oxide comprises three reactions step:
The first step, oxidizing reaction: methylcyclohexane is used molecular oxygen oxidation in liquid phase, the part methyl cyclohexane oxidation is become the methylcyclohexyl hydrogen peroxide;
Second step; Propylene ring oxidation reaction: under the oxidation catalyst of cyclopropene effect; Methylcyclohexyl hydrogen peroxide and propylene that the first step oxidizing reaction is obtained react; In liquid phase, propylene oxidation is become propylene oxide, the methylcyclohexyl hydrogen peroxide changes into methyl-cyclohexanol in reaction process simultaneously;
The 3rd step, hydrogenolysis: after second step, the propylene ring oxidation reaction product was isolated propylene oxide, under the hydrogenolysis catalyst effect with the methyl cyclohexane dehydration of alcohols, be hydroconverted into methylcyclohexane, return the first step oxidation step and recycle.
Reaction formula of the present invention is like (1) formula:
Concrete technical scheme of the present invention is:
The first step, oxidizing reaction:
Molecular oxygen described in the said the first step oxidizing reaction provides with one of following form: air, oxygen-denuded air or oxygen-rich air;
Said oxygen-denuded air is meant: oxygen level is lower than the gas of oxygen level in the air;
Said oxygen-rich air is meant: oxygen level is higher than the gas of oxygen level in the air.
Said the first step oxidizing reaction temperature is 50 ℃～200 ℃, preferred 80 ℃～150 ℃, and more preferably 100 ℃～145 ℃;
Said the first step oxidation pressure is gauge pressure 0MPa～2.0MPa, preferred 0.3MPa～1.0MPa.
Said oxidizing reaction can be carried out with mode intermittently in tank reactor, also can in tank reactor or tower reactor, carry out in a continuous manner, and reaction result is not had the internals influence.
Methylcyclohexane is that part transforms in the oxidizing reaction, and in the reaction output liquid of said the first step oxidizing reaction, the mass concentration of methylcyclohexyl hydrogen peroxide is 3%～50%, preferred 10%～25%.
Oxidizing reaction is carried out with free radical mechanism, and reaction generally occurs in the tertiary carbon atom position.Temperature is too low, and oxidation rate is too slow, and the required reaction times is oversize; Temperature is too high, increases though generate the speed of methylcyclohexyl superoxide, and the speed of the methylcyclohexyl peroxide breakdown that generates also can increase, and causes reaction preference to descend.Simultaneous temperature is too high, and keep material needs higher pressure in liquid state.Reaction pressure is advisable in liquid state to keep reaction mass, and hypertonia not only increases energy expenditure, and reaction result is not had very good influence.
The used oxygenant of this oxidizing reaction is a molecular oxygen, comes from air, or oxygen-rich air, or oxygen-denuded air.So-called oxygen-rich air is meant that the oxygen level in the gas is higher than the gas of airborne oxygen level, and so-called oxygen deprivation is meant that the oxygen level in the gas is lower than the gas of airborne oxygen level.Use oxygen-rich air to make oxygenant, can improve the speed of response of oxidizing reaction, but increase the danger of reaction process, generally will control oxygen level and methylcyclohexane steam content in the reaction end gas, make it to form explosive mixture and be advisable.Use oxygen-denuded air as oxygenant, can improve the process security, but oxidation rate can reduce, the reaction times can prolong.From the basic security consideration of economy, preferred air is as oxygenant.
The consumption and the speed of air do not have strict restriction; Confirming according to conditions such as the character of reaction mass, temperature of reaction, pressure, generally is the control condition of the concentration of the methylcyclohexyl hydrogen peroxide that generates in transformation efficiency or the reaction output object of control methylcyclohexane as the air consumption.When the transformation efficiency of methylcyclohexane is low, the concentration of also promptly reacting methylcyclohexyl hydrogen peroxide in the output object is low, and the selectivity that then generates the methylcyclohexyl hydrogen peroxide is high, but the utilising efficiency of reactor drum is low; Transformation efficiency is too high, and the methylcyclohexyl hydrogen peroxide of generation can decompose, and causes the purpose product selectivity to descend.
This oxidizing reaction does not generally need catalyzer.
Second step, propylene ring oxidation reaction:
The said second step propylene ring oxidation reaction temperature is 30 ℃～150 ℃, preferred 60 ℃～125 ℃;
The said second step propylene ring oxidation reaction pressure is gauge pressure 0.5MPa～6.0MPa, preferred 0.8MPa～5.0MPa, more preferably 1.0MPa～3.0MPa.
What the second step propylene ring oxidation reaction was used reacts the solution that contains methylcyclohexyl hydrogen peroxide 3%～50% that is generally that obtains by the first step; All the other are unconverted methylcyclohexane and some by products of in the first step reaction process, forming; Like alcohol, ketone etc., in the lump as solvent.If the concentration of methylcyclohexyl hydrogen peroxide is low excessively, can increase the material treatment capacity, reduce the production efficiency of reactor drum.If the excessive concentration of methylcyclohexyl hydrogen peroxide, except having certain danger, the epoxidation reaction excessive velocities, normally carrying out of influence reaction influences the purpose product selectivity simultaneously.Therefore, can carry out being used further to this step propylene ring oxidation reaction after suitable the concentrating if the concentration of the methylcyclohexyl hydrogen peroxide that obtains of the first step is not enough.If it is too high that the first step obtains in the oxidation products acid content, can also remove the purification of acid, generally adopt neutralization or deacidite absorption etc.
The propylene ring oxidation reaction temperature is too high, and the decomposition rate of methylcyclohexyl hydrogen peroxide is bigger, influences its utilising efficiency, if temperature of reaction is too low, speed of response can be slow excessively, thereby reduces production efficiency of equipment.
The pressure of propylene ring oxidation reaction is dissolved in the principle in the reaction solution according to the propylene that can make significant quantity and decides.Hypertonia does not have remarkable favourable influence to reaction, but increases energy expenditure.Hypotony, propylene is low in the solubleness of reaction solution, is unfavorable for the carrying out that reacts.
The reaction times of propylene ring oxidation reaction does not have special requirement; Many-sided factors such as kind according to temperature of reaction, reaction pressure and catalyzer are confirmed, are to confirm foundation with the selectivity that reaches ideal methylcyclohexyl hydrogen peroxide conversion, propylene oxide.The transformation efficiency of generalized case methylcyclohexyl hydrogen peroxide is controlled at more than 90% is advisable, and preferably is controlled at more than 95%.
In the said second step propylene ring oxidation reaction, the oxidation catalyst of cyclopropene consumption is the 10ppm～5000ppm of propylene ring oxidation reaction material total mass, preferred 50ppm～1000ppm, more preferably 100ppm～500ppm.
The key factor of propylene ring oxidation reaction is an oxidation catalyst of cyclopropene.Can use the reaction of said hydrocarbon hydrogen peroxide of any effectively catalysis and propylene to generate the catalyzer of propylene oxide in the technology of the present invention.
Be that said oxidation catalyst of cyclopropene is: effectively catalyzing propone and said methylcyclohexyl hydroperoxidation generate the catalyzer of propylene oxide in the said second step propylene ring oxidation reaction.
Said second the step propylene ring oxidation reaction described in oxidation catalyst of cyclopropene, generally be contain be selected from following at least a element be the catalyzer of active ingredient: Mo, V, Ti, Zr, Nb, W, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir and Re; Preferably contain be selected from following at least a element be the catalyzer of active ingredient: Mo, Ti, Ru and Ir.
Said second the step propylene ring oxidation reaction described in oxidation catalyst of cyclopropene, be contain be selected from following at least a element be the catalyzer of main active ingredient: Mo, V, Ti, Zr, Nb, W, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir and Re.
Preferably, said second oxidation catalyst of cyclopropene of step in the propylene ring oxidation reaction adds reaction system with the form of the soluble compound of said main active ingredient, and perhaps the form with the soluble complexes of said main active ingredient adds reaction system;
The soluble compound or the complex compound of said main active ingredient are meant, in the usage quantity scope of catalyzer, can be dissolved in the compound or the complex compound that form homogeneous phase solution in the described second step propylene ring oxidation reaction system.
The soluble compound of said oxidation catalyst of cyclopropene master active ingredient is: the naphthenate of the soap of said oxidation catalyst of cyclopropene master active ingredient or said oxidation catalyst of cyclopropene master active ingredient.
The soluble compound of said oxidation catalyst of cyclopropene master active ingredient is at least a in following: lipid acid molybdenum, cycloalkanes molybdenum, lipid acid ruthenium, naphthenic acid ruthenium, lipid acid iridium and naphthenic acid iridium.
The soluble complexes of said oxidation catalyst of cyclopropene master active ingredient is: said oxidation catalyst of cyclopropene master active ingredient and the complex compound that contains the organic cpds part formation that is selected from least a atom among O, the N.
The described organic cpds part that is selected from least a atom among O, the N that contains is at least a in following: terepthaloyl moietie, Ucar 35, quadrol, tn, thanomin, Yi Bingchunan and methyl ethyl diketone.
When catalyzer uses with the form of the soluble compound of said main active ingredient or complex compound; Catalyst consumption representes generally do not having special demands with the massfraction of main active ingredient in the reaction system, concentration crosses that low then speed of response is too slow; Concentration is high; Speed of response increases, but excessive concentration, need are considered the economic problems of catalyst recovery.Therefore general control 10ppm～5000ppm, preferred 50ppm～1000ppm, more preferably 100ppm～500ppm.
The catalyzer of said epoxidation reaction also can add reaction system with the form of the insoluble compound of main active ingredient, is a kind of common type like the oxide compound of main active ingredient.At this moment; The oxide compound of main active ingredient can use separately; Also can load on the carriers such as silicon oxide, aluminum oxide and use; More can use, like silicate with regular pore structure, silico-aluminate or the aluminate of main active ingredient with silicon oxide and/or aluminum oxide formation with the form that formation such as the oxide compound of these main active ingredients and silicon oxide, aluminum oxide have an xln of regular pore structure.
Also promptly can also be preferred,
Said second oxidation catalyst of cyclopropene of step in the propylene ring oxidation reaction, be that component A and B component form, go on foot undissolved crystalline solid material in the epoxidation reaction system said second;
Described component A is a kind of in following: the oxide compound of the oxide compound of the oxide compound of the oxide compound of the oxide compound of Mo, the oxide compound of V, Ti, the oxide compound of Zr, Nb, the oxide compound of W, Fe, the oxide compound of Co, Ni, the oxide compound of Ru, the oxide compound of Rh, the oxide compound of Pd, the oxide compound of Pt, the oxide compound of Ir and the oxide compound of Re;
Described B component is a kind of in following: the oxide compound of the oxide compound of Si, the oxide compound of Al and P;
Oxidation catalyst of cyclopropene in the preferred said second step propylene ring oxidation reaction is: titaniferous silicate, titaniferous silico-aluminate, contain the silicate of molybdenum or contain the silico-aluminate of molybdenum.
When using insoluble catalyzer, generally adopt slurry type reactors or fixed-bed reactor, wherein fixed-bed reactor since its move easily and catalyst separating and more preferred easily.
The 3rd step, hydrogenolysis:
Said the 3rd step hydrogenolysis temperature is 30 ℃～500 ℃, preferred 100 ℃～400 ℃, and more preferably 150 ℃～350 ℃;
Said the 3rd step hydrogenolysis pressure is gauge pressure 0MPa～10.0MPa, preferred 0.1MPa～8.0MPa, more preferably 0.5MPa～4.5MPa.
After the reaction of second step was accomplished, said superoxide methylcyclohexyl hydrogen peroxide became propylene oxide with propylene oxidation, and self changes into corresponding methyl-cyclohexanol.After isolating propylene oxide, said alcohol carries out the 3rd step hydrogenolysis together with solvent, and said alcohol is transformed into corresponding alkane, i.e. the used starting hydrocarbon methylcyclohexane of the first step reaction.
This hydrogenolysis is in having polyhydroxylated molecule, to carry out under dehydration and the effect of carbon-carbon double bond hydrogenation dual-function catalyst.
Hydrogenolysis catalyst is meant described in said the 3rd step hydrogenolysis: the catalyzer that has catalytic alcohol intramolecular dehydration function and catalyzed carbon carbon double-bond hydrogenation function simultaneously.
Hydrogenolysis catalyst is to be made up of the suitable metal with catalyzed carbon carbon double-bond hydrogenation function of a kind of solid acid catalyst load described in said the 3rd step hydrogenolysis;
Said solid acid comprises at least a in following: silicon oxide, aluminum oxide, oxidation sial, Si-Al molecular sieve and phosphate aluminium molecular sieve;
Said metal with catalyzed carbon carbon double-bond hydrogenation function is selected from least a in following: Pt, Pd, Ru, Co, Fe, Ni, Cu, Ag and Cr, at least a among preferred Pt, Pd, the Ni.
Said the 3rd step hydrogenolysis generally adopts slurry bed or fixed-bed reactor to carry out, in view of operation and catalyst separating convenient during, preferably carry out with the fixed bed pattern.
The invention has the beneficial effects as follows:
Having invented a kind of is the novel process of raw material production propylene oxide with hydrogen, molecular oxygen and propylene.This technology uses methylcyclohexane to be starting hydrocarbon, through oxidation, epoxidation, three reactions step of hydrogenolysis, propylene is changed into propylene oxide, and the starting hydrocarbon methylcyclohexane recycles.The used starting hydrocarbon of this technology is more cheap and easy to get, and it is safer that each goes on foot the reaction conditions milder, and the purpose selectivity of product of each step reaction is better, and production efficiency is higher, and production cost is lower.
Embodiment
Embodiment 1
The first step, oxidizing reaction:
Be equipped with in the 500ml stainless steel cauldron of stirring and condensation reflux unit; Add reaction raw materials methylcyclohexane 200ml; Sealed reactor, under nitrogen atmosphere, be warmed up to and constant temperature 135 ℃ of temperature of reaction, conditioned reaction pressure is to gauge pressure 0.4MPa; Speed bubbling air with 400ml/min carries out oxidation, stirring velocity 500rmp.Reaction times, the reaction solution of collection was as the raw material of second step reaction when being 10h.
Whenever during experiment, get liquid material sample in the reaction kettle through thief hole, with the concentration of methylcyclohexyl hydrogen peroxide in the traditional iodimetric analysis institute sample thief at a distance from 1h.The reaction initial stage, the concentration of methylcyclohexyl hydrogen peroxide increases with the prolongation in reaction times, after reaching finite concentration, prolongs the reaction times again, and the concentration of methylcyclohexyl hydrogen peroxide can descend.Concentration numerical value during with methylcyclohexyl hydrogen peroxide maximum concentration and reaction times are as reaction result.When the reaction times was 10h, the methylcyclohexyl concentration of hydrogen peroxide in the reaction solution reached the highest under the condition of present embodiment, was 19.3%.
Second step, epoxidation reaction:
In the stainless steel cauldron of 300ml; Add the reaction solution 70g that contains the methylcyclohexyl hydrogen peroxide that above-mentioned the first step oxidizing reaction obtains; Wherein the mass content of methylcyclohexyl hydrogen peroxide is 19.3%; Catalyzer be 2 ethyl hexanoic acid and ammonium molybdate be mixed with contain the solution that molybdenum is 6wt%, add-on is that the mass content of molybdenum in reaction solution is 350ppm.Sealed reactor adds propylene 30g through test tank.Be warmed up to 115 ℃ of temperature of reaction, to gauge pressure 2.2MPa, 500rmp stirs reaction 1.5h down with nitrogen conditioned reaction pressure.Cool to room temperature, the analytical reaction product.With iodimetric analysis residue methylcyclohexyl concentration of hydrogen peroxide, analyze each organic amount with the gc marker method, obtain the selectivity of methylcyclohexyl hydrogen peroxide conversion and propylene oxide.The present embodiment result is: the transformation efficiency of methylcyclohexyl hydrogen peroxide is 98.1%, and the selectivity of propylene oxide is 95.5%.Collecting reaction product; Go out purpose product propylene oxide and unreacted propylene through rectifying separation; Obtaining with methylcyclohexane and methyl-cyclohexanol is the solution of staple; Be called the surplus liquid of the second step reaction decylization Ethylene Oxide, as the raw material of three-step reaction, wherein the mass content of methylcyclohexyl alcohol is 18.2%.
The 3rd step, hydrogenolysis:
In the 300ml stainless steel cauldron, add the surplus liquid 120g of the described second step reaction decylization Ethylene Oxide, wherein the mass content of methylcyclohexyl alcohol is 18.2%, adds the Pd/ γ-Al that contains palladium 0.5wt%
2O
3Catalyzer 1.0g; Use nitrogen and hydrogen exchange reaction kettle successively, be warmed up to 150 ℃ of temperature of reaction then, logical hydrogen is also regulated pressure to reaction pressure gauge pressure 0.5MPa; Under the stirring of 500rpm, carry out hydrogenolysis, up to the system that observes no longer till the consuming hydrogen.Drop to room temperature, sampling analysis.The result is 94.9% for the transformation efficiency of methylcyclohexyl alcohol, and the selectivity of purpose product methylcyclohexane is 99.1%.
Embodiment 2: the first step oxidizing reaction
Be equipped with in the 500ml stainless steel cauldron of stirring and condensation reflux unit, add methylcyclohexane 200ml, sealing; Under nitrogen atmosphere, be warmed up to and constant temperature 100 ℃ of temperature of reaction; Conditioned reaction pressure is to gauge pressure 0.3MPa, and feeding oxygen level with the speed of 400ml/min is 30% gas, i.e. oxygen-rich air; Carry out oxidation, stirring velocity 500rmp.Reaction times, the methylcyclohexyl concentration of hydrogen peroxide in the reaction solution reached the highest when being 12h, was 12.5%.Collect the raw material of reaction solution as the second step epoxidation reaction.
Embodiment 3: the first step oxidizing reaction
Be equipped with in the 500ml stainless steel cauldron of stirring and condensation reflux unit, add methylcyclohexane 200ml, sealing; Under nitrogen atmosphere, be warmed up to and constant temperature 145 ℃ of temperature of reaction; Conditioned reaction pressure is to gauge pressure 1.0MPa, and feeding oxygen level with the speed of 400ml/min is 15% gas, i.e. oxygen-denuded air; Carry out oxidation, stirring velocity 500rmp.Reaction times, the methylcyclohexyl concentration of hydrogen peroxide in the reaction solution reached the highest when being 8h, was 22.4%.Collect the raw material of reaction solution as the second step epoxidation reaction.
Embodiment 4: the second steps epoxidation reaction
In the stainless steel cauldron of 300ml; Add the reaction solution 70g that contains the methylcyclohexyl hydrogen peroxide that embodiment 1 the first step oxidizing reaction obtains; Wherein the mass content of methylcyclohexyl hydrogen peroxide is 19.3%; Catalyzer be naphthenic acid and ammonium molybdate be mixed with contain the solution that molybdenum is 8wt%, add-on is that the mass content of molybdenum in reaction solution is 500ppm.Sealed reactor adds propylene 30g through test tank.Be warmed up to 100 ℃ of temperature of reaction, to gauge pressure 1.0MPa, 500rmp stirs reaction 3h down with nitrogen conditioned reaction pressure.Cool to room temperature, the analytical reaction product.With iodimetric analysis residue methylcyclohexyl concentration of hydrogen peroxide,, obtain the methylcyclohexyl hydrogen peroxide conversion and to the selectivity of propylene oxide with each organic amount of gc marker method analysis.The present embodiment result is: the transformation efficiency of methylcyclohexyl hydrogen peroxide is 95.7%, and the selectivity of propylene oxide is 95.6%.
Embodiment 5: the second steps epoxidation reaction
In the stainless steel cauldron of 300ml; Add the reaction solution 70g that contains the methylcyclohexyl hydrogen peroxide that embodiment 1 the first step oxidizing reaction obtains; Wherein the mass content of methylcyclohexyl hydrogen peroxide is 19.3%; Catalyzer be Yi Bingchunan and ammonium molybdate be mixed with contain the solution that molybdenum is 6wt%, add-on is that the mass content of molybdenum in reaction solution is 200ppm.Sealed reactor adds propylene 30g through test tank.Be warmed up to 125 ℃ of temperature of reaction, to gauge pressure 3.0MPa, 500rmp stirs reaction 1.5h down with nitrogen conditioned reaction pressure.Cool to room temperature, the analytical reaction product.With iodimetric analysis residue methylcyclohexyl concentration of hydrogen peroxide,, obtain the methylcyclohexyl hydrogen peroxide conversion and to the selectivity of propylene oxide with each organic amount of gc marker method analysis.The present embodiment result is: the transformation efficiency of methylcyclohexyl hydrogen peroxide is 98.8%, is 96.9% to the selectivity of propylene oxide.Collecting reaction product goes out purpose product propylene oxide and unreacted propylene through rectifying separation, and obtaining with methylcyclohexane and methylcyclohexyl methyl alcohol is the solution of staple, is called the surplus liquid of the second step reaction decylization Ethylene Oxide, as the raw material of three-step reaction.
Embodiment 6: the second steps epoxidation reaction
In the stainless steel cauldron of 300ml; Add the reaction solution 70g that contains the methylcyclohexyl hydrogen peroxide that embodiment 1 the first step oxidizing reaction obtains; Wherein the mass content of methylcyclohexyl hydrogen peroxide is 19.3%; The solution that contains ruthenium 5wt% of catalyzer for being mixed with methyl ethyl diketone and methyl ethyl diketone ruthenium, add-on is that the mass content of ruthenium in reaction solution is 350ppm.Sealed reactor adds propylene 30g through test tank.Be warmed up to 60 ℃ of temperature of reaction, to gauge pressure 0.8MPa, 500rmp stirs reaction 2.5h down with nitrogen conditioned reaction pressure.Cool to room temperature, the analytical reaction product.With iodimetric analysis residue methylcyclohexyl concentration of hydrogen peroxide,, obtain the methylcyclohexyl hydrogen peroxide conversion and to the selectivity of propylene oxide with each organic amount of gc marker method analysis.The present embodiment result is: the transformation efficiency of methylcyclohexyl hydrogen peroxide is 98.9%, and the selectivity of propylene oxide is 97.7%.
Embodiment 7: the second steps epoxidation reaction
In the stainless steel cauldron of 300ml; Add the reaction solution 70g that contains the methylcyclohexyl hydrogen peroxide that embodiment 1 the first step oxidizing reaction obtains; Wherein the mass content of methylcyclohexyl hydrogen peroxide is 19.3%; Catalyzer is the solution that contains iridium 5wt% of Yi Bingchunan and iridous chloride configuration, and add-on is that the mass content of iridium in reaction solution is 150ppm.Sealed reactor adds propylene 30g through test tank.Be warmed up to 90 ℃ of temperature of reaction, to gauge pressure 5.6MPa, 500rmp stirs reaction 3h down with nitrogen conditioned reaction pressure.Cool to room temperature, the analytical reaction product.With iodimetric analysis residue methylcyclohexyl concentration of hydrogen peroxide,, obtain the methylcyclohexyl hydrogen peroxide conversion and to the selectivity of propylene oxide with each organic amount of gc marker method analysis.The present embodiment result is: the transformation efficiency of methylcyclohexyl hydrogen peroxide is 87.6%, and the selectivity of propylene oxide is 85.3%.
Embodiment 8: the second steps epoxidation reaction
In the stainless steel cauldron of 300ml; Add the reaction solution 100g that contains the methylcyclohexyl hydrogen peroxide that embodiment 2 obtains; Wherein the mass content of methylcyclohexyl hydrogen peroxide is 12.5%; Catalyzer be 2 ethyl hexanoic acid and ammonium molybdate be configured to contain the solution that molybdenum is 6wt%, add-on is that the mass content of molybdenum in reaction solution is 350ppm.Sealed reactor adds propylene 30g through test tank.Be warmed up to 115 ℃ of temperature of reaction, to gauge pressure 2.2MPa, 500rmp stirs reaction 1.5h down with nitrogen conditioned reaction pressure.Cool to room temperature, the analytical reaction product.With iodimetric analysis residue methylcyclohexyl concentration of hydrogen peroxide,, obtain the methylcyclohexyl hydrogen peroxide conversion and to the selectivity of propylene oxide with each organic amount of gc marker method analysis.The present embodiment result is: the transformation efficiency of methylcyclohexyl hydrogen peroxide is 87.6%, and the selectivity of propylene oxide is 85.3%.
Embodiment 9: the second steps epoxidation reaction
Prepare catalyzer earlier
At room temperature, the 25g cetyl trimethylammonium bromide is mixed with the 90g deionized water with the aqueous solution 25g that contains the 20wt% TMAH, stirred 30 minutes; The mixture that adds the positive quanmethyl silicate of 42g, 2.2g titanium isopropylate and 25ml Virahol then stirred 5 hours at ambient temperature.Isolate solid product, be washed with water to neutrality, at 70 ℃ of drying under reduced pressure, 550 ℃ of roastings 4 hours in retort furnace then obtain white solid.The above-mentioned white solid of 5g is mixed with 3.0g hexamethyldisilazane and 60g toluene, and reflux 2 hours is filtered and also use the toluene wash solid product, and 120 ℃ of drying under reduced pressure 2 hours must titaniferous epoxidation catalyst.This catalyst structure is the titaniferous silicate with regular pore structure, and specific surface area is 1100m
2/ g.
Carry out epoxidation reaction
The catalyzer 1.0g that adds the present embodiment preparation in the stainless steel cauldron of 300ml, and the reaction solution 70g that contains methylcyclohexyl hydrogen peroxide 22.4wt% that obtains of embodiment 3, propylene 30g.Be warmed up to 95 ℃ of temperature of reaction, conditioned reaction pressure is gauge pressure 2.5MPa, 2.5 hours reaction times, agitator speed 500r/min.Reaction result: the transformation efficiency 96.5% of methylcyclohexyl hydrogen peroxide, the selectivity 97.3% of propylene oxide.
Embodiment 10: the second steps epoxidation reaction
With titaniferous epoxidation catalyst compressing tablet, fragmentation, the sieve diameter of embodiment 9 preparation is that the particle of 0.5～1.0mm is subsequent use.At internal diameter is the above-mentioned catalyzer of filling 2.0g in the stainless steel fixed-bed reactor of 10mm.Be warmed up to 95 ℃ of temperature of reaction, reacting system pressure be adjusted to gauge pressure 3.0MPa with nitrogen.With volume pump reaction solution and the propylene that embodiment 1 the first step oxidizing reaction obtains measured input reactor respectively from the top of fixed-bed reactor then.Total feed liquid air speed 2.5h
-1, in molar ratio, propylene: methylcyclohexyl hydrogen peroxide=10: 1.Reaction product is sampling analysis after cooling, decompression.Reaction result: the transformation efficiency 96.7% of methylcyclohexyl hydrogen peroxide, the selectivity 95.8% of propylene oxide.
Embodiment 11: the three steps hydrogenolysis
In the 300ml stainless steel cauldron, add the surplus liquid 120g of the said second step reaction decylization Ethylene Oxide of embodiment 1, wherein the mass content of methylcyclohexyl alcohol is 18.2%, adds the Pt/SiO of platiniferous 0.5wt%
2Catalyzer 1.0g uses nitrogen and hydrogen exchange reaction kettle successively, is warmed up to 200 ℃ of temperature of reaction then, and logical hydrogen and conditioned reaction pressure carry out hydrogenolysis to gauge pressure 2.0MPa under the stirring of 500rpm, up to the system that observes no longer till the consuming hydrogen.Drop to room temperature, sampling analysis.The result is 98.6% for the transformation efficiency of methylcyclohexyl alcohol, and the selectivity of methylcyclohexane is 98.2%.
Embodiment 12: the three steps hydrogenolysis
In the 300ml stainless steel cauldron, add the surplus liquid 120g of the said second step reaction decylization Ethylene Oxide of embodiment 1, wherein the mass content of methylcyclohexyl alcohol is 18.2%, adds Ni/ γ-Al of nickeliferous 0.5wt%
2O
3Catalyzer 3.5g uses nitrogen and hydrogen exchange reaction kettle successively, is warmed up to 350 ℃ of temperature of reaction then, and logical hydrogen and conditioned reaction pressure carry out hydrogenolysis to gauge pressure 4.5MPa under the stirring of 500rpm, up to the system that observes no longer till the consuming hydrogen.Drop to room temperature, sampling analysis.The result is 95.7% for the transformation efficiency of methylcyclohexyl alcohol, and the selectivity of methylcyclohexane is 96.8%.
Embodiment 13: the three steps hydrogenolysis
In the 300ml stainless steel cauldron; Add the surplus liquid 120g of the said second step reaction decylization Ethylene Oxide that embodiment 5 obtains; Wherein the mass content of methylcyclohexyl alcohol is 17.5%, adds the Pd-Ag/HZSM-5 catalyzer 1.0g that contains palladium 0.5wt%, argentiferous 0.05wt%, uses nitrogen and hydrogen exchange reaction kettle successively; Be warmed up to 320 ℃ of temperature of reaction then; Logical hydrogen and conditioned reaction pressure carry out hydrogenolysis to gauge pressure 1.0MPa under the stirring of 500rpm, up to the system that observes no longer till the consuming hydrogen.Drop to room temperature, sampling analysis.The result is 98.8% for the transformation efficiency of methylcyclohexyl alcohol, and the selectivity of methylcyclohexane is 99.3%.
Embodiment 14: the three steps hydrogenolysis
With particle diameter is the Pd/ γ-Al that contains palladium 0.5wt% of 1mm
2O
3Catalyzer 2.0g, the stainless steel fixed-bed reactor of the internal diameter 12mm that packs into.The surplus liquid of the said second step reaction decylization Ethylene Oxide that reaction feed obtains for embodiment 1 second step epoxidation reaction.Add the metering input from reactor drum top through volume pump, hydrogen also adds from reactor head with the speed of 60ml/min, forms and drip fluidized bed response behaviour.Liquid air speed 2.0h
-1, 300 ℃ of temperature of reaction, reaction pressure gauge pressure 2.0MPa.Product flows out from reactor bottom, after condensation separation, gets the liquid-like analysis.The result is the transformation efficiency 98.6% of methyl-cyclohexanol, the selectivity 98.8% of methylcyclohexane.
Claims (18)
1. the preparation method of a propylene oxide comprises following three reactions step:
The first step, oxidizing reaction: methylcyclohexane is used molecular oxygen oxidation in liquid phase, the part methyl cyclohexane oxidation is become the methylcyclohexyl hydrogen peroxide;
Second step; Propylene ring oxidation reaction: under the oxidation catalyst of cyclopropene effect; Methylcyclohexyl hydrogen peroxide and propylene that the first step oxidizing reaction is obtained react; In liquid phase, propylene oxidation is become propylene oxide, the methylcyclohexyl hydrogen peroxide changes into methyl-cyclohexanol in reaction process simultaneously;
The 3rd step, hydrogenolysis: after second step, the propylene ring oxidation reaction product was isolated propylene oxide, under the hydrogenolysis catalyst effect with the methyl cyclohexane dehydration of alcohols, be hydroconverted into methylcyclohexane, return the first step oxidation step and recycle.
2. the preparation method of propylene oxide according to claim 1 is characterized in that:
Molecular oxygen described in the said the first step oxidizing reaction provides with one of following form: air, oxygen-denuded air or oxygen-rich air;
Said oxygen-denuded air is meant: oxygen level is lower than the gas of oxygen level in the air;
Said oxygen-rich air is meant: oxygen level is higher than the gas of oxygen level in the air.
3. the preparation method of propylene oxide according to claim 1 is characterized in that:
Said the first step oxidizing reaction temperature is 50 ℃～200 ℃, preferred 80 ℃～150 ℃, and more preferably 100 ℃～145 ℃;
Said the first step oxidation pressure is gauge pressure 0MPa～2.0MPa, preferred 0.3MPa～1.0MPa.
4. according to the preparation method of the described propylene oxide of one of claim 1 to 3, it is characterized in that:
In the reaction output liquid of said the first step oxidizing reaction, the mass concentration of methylcyclohexyl hydrogen peroxide is 3%～50%, preferred 10%～25%.
5. the preparation method of propylene oxide according to claim 1 is characterized in that:
The said second step propylene ring oxidation reaction temperature is 30 ℃～150 ℃, preferred 60 ℃～125 ℃;
The said second step propylene ring oxidation reaction pressure is gauge pressure 0.5MPa～6.0MPa, preferred 0.8MPa～5.0MPa, more preferably 1.0MPa～3.0MPa.
6. the preparation method of propylene oxide according to claim 1 is characterized in that:
In the said second step propylene ring oxidation reaction, the oxidation catalyst of cyclopropene consumption is the 10ppm～5000ppm of propylene ring oxidation reaction material total mass, preferred 50ppm～1000ppm, more preferably 100ppm～500ppm.
7. according to the preparation method of the described propylene oxide of one of claim 1 to 6, it is characterized in that:
In the said second step propylene ring oxidation reaction, said oxidation catalyst of cyclopropene is: effectively catalyzing propone and said methylcyclohexyl hydroperoxidation generate the catalyzer of propylene oxide.
8. the preparation method of propylene oxide according to claim 7 is characterized in that:
Said second the step propylene ring oxidation reaction described in oxidation catalyst of cyclopropene, be contain be selected from following at least a element be the catalyzer of main active ingredient: Mo, V, Ti, Zr, Nb, W, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir and Re.
9. the preparation method of propylene oxide according to claim 8 is characterized in that:
Said second oxidation catalyst of cyclopropene of step in the propylene ring oxidation reaction adds reaction system with the form of the soluble compound of said main active ingredient, and perhaps the form with the soluble complexes of said main active ingredient adds reaction system;
The soluble compound or the complex compound of said main active ingredient are meant, in the usage quantity scope of catalyzer, can be dissolved in the compound or the complex compound that form homogeneous phase solution in the described second step propylene ring oxidation reaction system.
10. the preparation method of propylene oxide according to claim 9 is characterized in that:
The soluble compound of said oxidation catalyst of cyclopropene master active ingredient is: the naphthenate of the soap of said oxidation catalyst of cyclopropene master active ingredient or said oxidation catalyst of cyclopropene master active ingredient.
11. the preparation method of propylene oxide according to claim 10 is characterized in that:
The soluble compound of said oxidation catalyst of cyclopropene master active ingredient is at least a in following: lipid acid molybdenum, cycloalkanes molybdenum, lipid acid ruthenium, naphthenic acid ruthenium, lipid acid iridium and naphthenic acid iridium.
12. the preparation method of propylene oxide according to claim 8 is characterized in that:
The soluble complexes of said oxidation catalyst of cyclopropene master active ingredient is: said oxidation catalyst of cyclopropene master active ingredient and the complex compound that contains the organic cpds part formation that is selected from least a atom among O, the N.
13. the preparation method of propylene oxide according to claim 12 is characterized in that:
The described organic cpds part that is selected from least a atom among O, the N that contains is at least a in following: terepthaloyl moietie, Ucar 35, quadrol, tn, thanomin, Yi Bingchunan and methyl ethyl diketone.
14. the preparation method according to the described propylene oxide of one of claim 1 to 13 is characterized in that:
Said second oxidation catalyst of cyclopropene of step in the propylene ring oxidation reaction, be that component A and B component form, go on foot undissolved crystalline solid material in the epoxidation reaction system said second;
Described component A is a kind of in following: the oxide compound of the oxide compound of the oxide compound of the oxide compound of the oxide compound of Mo, the oxide compound of V, Ti, the oxide compound of Zr, Nb, the oxide compound of W, Fe, the oxide compound of Co, Ni, the oxide compound of Ru, the oxide compound of Rh, the oxide compound of Pd, the oxide compound of Pt, the oxide compound of Ir and the oxide compound of Re;
Described B component is a kind of in following: the oxide compound of the oxide compound of Si, the oxide compound of Al and P;
Oxidation catalyst of cyclopropene in the preferred said second step propylene ring oxidation reaction is: titaniferous silicate, titaniferous silico-aluminate, contain the silicate of molybdenum or contain the silico-aluminate of molybdenum.
15. the preparation method of propylene oxide according to claim 1 is characterized in that:
Said the 3rd step hydrogenolysis temperature is 30 ℃～500 ℃, preferred 100 ℃～400 ℃, and more preferably 150 ℃～350 ℃;
Said the 3rd step hydrogenolysis pressure is gauge pressure 0MPa～10.0MPa, preferred 0.1MPa～8.0MPa, more preferably 0.5MPa～4.5MPa.
16. the preparation method according to the described propylene oxide of one of claim 1 to 15 is characterized in that:
Hydrogenolysis catalyst is meant described in said the 3rd step hydrogenolysis: the catalyzer that has catalytic alcohol intramolecular dehydration function and catalyzed carbon carbon double-bond hydrogenation function simultaneously.
17. the preparation method of propylene oxide according to claim 16 is characterized in that:
Hydrogenolysis catalyst is to be made up of the suitable metal with catalyzed carbon carbon double-bond hydrogenation function of a kind of solid acid catalyst load described in said the 3rd step hydrogenolysis;
Said solid acid comprises at least a in following: silicon oxide, aluminum oxide, oxidation sial, Si-Al molecular sieve and phosphate aluminium molecular sieve;
Said metal with catalyzed carbon carbon double-bond hydrogenation function is selected from least a in following: Pt, Pd, Ru, Co, Fe, Ni, Cu, Ag and Cr, at least a among preferred Pt, Pd, the Ni;
Said the 3rd step hydrogenolysis adopts slurry type reactors or fixed-bed reactor.
18. the preparation method of propylene oxide according to claim 1 is characterized in that:
Comprise following three reactions step:
The first step, oxidizing reaction: methylcyclohexane is used molecular oxygen oxidation in liquid phase, the part methyl cyclohexane oxidation is become the methylcyclohexyl hydrogen peroxide;
Molecular oxygen described in the said the first step oxidizing reaction provides with one of following form: air, oxygen-denuded air or oxygen-rich air;
Said the first step oxidizing reaction temperature is 100 ℃～145 ℃;
The gauge pressure pressure of said the first step oxidizing reaction is 0.3MPa～1.0MPa;
In the reaction output liquid of said the first step oxidizing reaction, the mass concentration of methylcyclohexyl hydrogen peroxide is 10%～25%;
Second step; Propylene ring oxidation reaction: under the oxidation catalyst of cyclopropene effect; Methylcyclohexyl hydrogen peroxide and propylene that the first step oxidizing reaction is obtained react; In liquid phase, propylene oxidation is become propylene oxide, the methylcyclohexyl hydrogen peroxide changes into methyl-cyclohexanol in reaction process simultaneously;
The said second step propylene ring oxidation reaction temperature is 60 ℃～125 ℃;
The said second step propylene ring oxidation reaction pressure is gauge pressure 1.0MPa～3.0MPa;
In the said second step propylene ring oxidation reaction, the oxidation catalyst of cyclopropene consumption is the 100ppm～500ppm of propylene ring oxidation reaction material total mass;
Said second oxidation catalyst of cyclopropene of step in the propylene ring oxidation reaction adds reaction system with the form of the soluble compound of said main active ingredient, and perhaps the form with the soluble complexes of said main active ingredient adds reaction system; The soluble compound of said oxidation catalyst of cyclopropene master active ingredient is at least a in following: lipid acid molybdenum, cycloalkanes molybdenum, lipid acid ruthenium, naphthenic acid ruthenium, lipid acid iridium and naphthenic acid iridium; The soluble complexes of said oxidation catalyst of cyclopropene master active ingredient is: said oxidation catalyst of cyclopropene master active ingredient and the complex compound that contains the organic cpds part formation that is selected from least a atom among O, the N; The described organic cpds part that is selected from least a atom among O, the N that contains is at least a in following: terepthaloyl moietie, Ucar 35, quadrol, tn, thanomin, Yi Bingchunan and methyl ethyl diketone;
Perhaps said second oxidation catalyst of cyclopropene of step in the propylene ring oxidation reaction is: titaniferous silicate, titaniferous silico-aluminate, contain the silicate of molybdenum or contain the silico-aluminate of molybdenum; Adopt fixed-bed reactor;
The 3rd step, hydrogenolysis: after second step, the propylene ring oxidation reaction product was isolated propylene oxide, under the hydrogenolysis catalyst effect with the methyl cyclohexane dehydration of alcohols, be hydroconverted into methylcyclohexane, return the first step oxidation step and recycle;
Said the 3rd step hydrogenolysis temperature is 150 ℃～350 ℃;
Said the 3rd step hydrogenolysis pressure is gauge pressure 0.5MPa～4.5MPa;
Hydrogenolysis catalyst is to be made up of the suitable metal with catalyzed carbon carbon double-bond hydrogenation function of a kind of solid acid catalyst load described in said the 3rd step hydrogenolysis; Said solid acid comprises at least a in following: silicon oxide, aluminum oxide, oxidation sial, Si-Al molecular sieve and phosphate aluminium molecular sieve; Said metal with catalyzed carbon carbon double-bond hydrogenation function is selected from least a in following: Pt, Pd and Ni.
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| CN104327016A (en) * | 2014-11-05 | 2015-02-04 | 河北美邦工程科技有限公司 | Method for preparing epoxypropane |
| CN106699695A (en) * | 2016-10-31 | 2017-05-24 | 中石化南京工程有限公司 | Production method of propylene oxide |
| CN106699696A (en) * | 2016-10-31 | 2017-05-24 | 中石化南京工程有限公司 | Coproduction method of epoxypropane and cyclohexanone |
| CN107488099A (en) * | 2017-08-10 | 2017-12-19 | 中石化南京工程有限公司 | A kind of method for producing expoxy propane and cyclohexanol |
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| CN106699695B (en) * | 2016-10-31 | 2019-05-03 | 中石化南京工程有限公司 | A kind of production method of propylene oxide |
| CN106699695A (en) * | 2016-10-31 | 2017-05-24 | 中石化南京工程有限公司 | Production method of propylene oxide |
| CN106699696A (en) * | 2016-10-31 | 2017-05-24 | 中石化南京工程有限公司 | Coproduction method of epoxypropane and cyclohexanone |
| CN106699696B (en) * | 2016-10-31 | 2019-05-03 | 中石化南京工程有限公司 | A kind of co-production of propylene oxide and cyclohexanone |
| CN107488099A (en) * | 2017-08-10 | 2017-12-19 | 中石化南京工程有限公司 | A kind of method for producing expoxy propane and cyclohexanol |
| CN107488099B (en) * | 2017-08-10 | 2019-05-07 | 中石化南京工程有限公司 | A method of producing propylene oxide and cyclohexanol |
| CN107744834A (en) * | 2017-08-30 | 2018-03-02 | 江南大学 | A kind of supported palladium Raney nickel synthesized for alkene epoxidation and Bisphenol F and preparation method |
| CN107744834B (en) * | 2017-08-30 | 2020-06-09 | 江南大学 | Supported palladium-nickel catalyst for olefin epoxidation and bisphenol F synthesis and preparation method thereof |
| CN109225197A (en) * | 2018-10-23 | 2019-01-18 | 福州大学 | A kind of preparation method of propylene oxygen gas-phase epoxidation catalyst |
| CN112742395A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrogenation dealdehyding catalyst and preparation method and application thereof |
| CN112742395B (en) * | 2019-10-31 | 2023-04-07 | 中国石油化工股份有限公司 | Hydrogenation dealdehyding catalyst and preparation method and application thereof |
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