CN1026781C

CN1026781C - Preparation of cumene through alkylation of aromatic compound and preparation phenol through cumene

Info

Publication number: CN1026781C
Application number: CN 89109031
Authority: CN
Inventors: 荒木信太郎; 松永藤尚; 福原浩
Original assignee: Mitsui Petrochemical Industries Ltd
Current assignee: Mitsui Chemicals Inc
Priority date: 1988-11-28
Filing date: 1989-11-28
Publication date: 1994-11-30
Anticipated expiration: 2004-11-28
Also published as: CN1043120A

Abstract

In a first form, a process is provided for preparing phenol by converting acetone by-produced by the cumene process into isopropanol, and alkylating benzene with the isopropanol and optional propylene, thereby forming phenol without acetone by-product. And cumene is prepared by alkylating benzene in the presence of a zeolite catalyst using isopropanol or a mixture of isopropanol and propylene as an alkylating agent. Further provided is the continuous alkylation of benzene with isopropanol wherein a reaction mixture is divided into first and second portions, with the first portion being recycled to the reactor and the second portion being taken out as a reaction product.

Description

Preparation of cumene through alkylation of aromatic compound and preparation phenol through cumene

The present invention relates to prepare isopropyl benzene, prepare phenol and adopt the alkylation of alcohol as the aromatic substance of alkylating agent by isopropyl benzene by the alkylation of aromatic substance.

The commercial of alkylating aromatic substance that aromatic alkylation is obtained is important intermediate raw material.For example, be a kind of very important reactant by the isopropyl benzene that the reaction of benzene and propylene is obtained for synthesizing of phenol.

Isopropyl benzene is normally made the alkylation of benzene by propylene, on the problem of this alkylation process, has done many researchs.For example, Japanese Unexamined Patent Publication No 40419/1982 has disclosed the employing lewis acid catalyst and carried out alkylation under liquid-phase condition, U.S. Patent number 2,375, and 724 have disclosed the use of solid phosphoric acid catalyst.

Isopropyl benzene also can make by the alkylation of Virahol to benzene, and as disclosing in Japanese Unexamined Patent Publication No 159427/1983 and 159430/1983, it is well-known adopting the reaction of solid peracid under gas phase condition.Reaction under liquid-phase condition has also been proposed.For example, U.S. Patent number 4,011,278 have disclosed at silica-alumina ratio and have been adjusted to alkylation in the presence of 40 the H-mordenite catalyst.

These are used for isopropyl benzene synthetic method several problems, for example, adopts lewis acidic alkylation process to need the existence of alcohols, and this is because in reactive system, and catalyzer is easily by the water deactivation, and to adopt alcohols to carry out alkylation be impossible.Adopt the vapor-phase alkylation of Virahol impracticable in fact, this by low alkylation transformation efficiency and often regenerated catalyst to compensate bad the causing of rapid change of its short-life catalyzer.Adopt the liquid-phase alkylation of Virahol to have high alkylation transformation efficiency, but its actual efficiency is shady, this is because the percentage recovery rate of its final product is not shown.For commercial production, this method has the problem that needs overcome, and promptly in order to refuse water, needs to adopt expensive catalysts, such as the H-mordenite of ZSM-5 zeolite with high oxidation silica alumina ratio and dealuminzation.

In the prior art, make the reaction of benzene and propylene with make isopropyl benzene, oxidation isopropyl benzene with make Cumene Hydroperoxide 80 and with Cumene Hydroperoxide 80 through being that phenol and acetone are well-known with acid cleavage.The conventional phenol preparation method that these steps combine is so-called isopropyl benzene or isopropyl benzene-phynol method.

It also is a kind of old well-known technology that acetone is hydrogenated to Virahol.At present, this technology still is widely used in mensuration and other purposes of hydrogenation catalyst catalytic activity.For example, normally they examine and determine acetone hydrogenation ability the activity of Raney nickel catalyst by comparison.Multiple advanced person's method is suggested, and this has obtained announcement in Japanese Unexamined Patent Publication No 12729/1987 and 77338/1987.

About adopting Virahol to carry out the alkylation of benzene, it is well-known adopting the reaction of solid peracid under gas phase condition, and this has obtained announcement in Japanese Unexamined Patent Publication No 159427/1983 and 159430/1983.Also proposed the reaction under liquid-phase condition,, this has been disclosed in 278 at U.S. Patent number 4,011.

About as the acetone of by product in the cumene method re-use (for example by being converted into Virahol) aspect, useful suggestion is not proposed.

Usually be referred to as the phenol preparation method of cumene method, its characteristics are to have produced by product acetone, and this is favourable from some aspect, but are disadvantageous from other aspects.More particularly, its favourable part is: making two kinds of products in a single preparation facilities simultaneously, to produce each product in than the device that is separating more effective.But see that conversely if the ratio of prepared phenol and acetone unbalanced words for its business demand, the little a kind of material of requirement is mass production in vain.

As known to this field, in these years the supply of acetone is excessive.Therefore, the production of acetone by product is considered to a critical defect of cumene method now.Although having found the major applications of acetone is the parent material as the preparation methyl methacrylate, because the parent material of preparation methyl methacrylate has turned to another kind of material, the requirement of acetone descends.

In this case, a kind of phenol preparation method that does not produce acetone and other by products of the development of demand although proposed a plurality of suggestions, does not have a kind of method to prepare phenol with gratifying recovery rate.

In addition, in the step with preparation phenol by benzene and propylene production isopropyl benzene, the impurity in the propylene causes a shortcoming usually, and Here it is, and the propylene that is used for the isopropyl benzene preparation normally adopts crude oil to produce as parent material.Yet crude oil comprises sulphur compound and each heavy metal species, and these impurity are entrained in the propylene as trace impurity in the propylene manufacturing processed sometimes.For example, in propylene, suppressed the effect of catalyzer (aluminum chloride-HCl coordination compound) in the isopropyl benzene preparation process, hindered the isopropyl benzene synthetic normally to carry out thus as the carbonyl sulfide (COS) of sulphur compound or as the As of beavy metal impurity.Therefore, carry out strict purification process in advance to prevent that propylene is by these contaminating impurities.Yet the type and the quantity of these impurity are changing, and this not only depends on the crude oil source, but also depends on the difference that is prepared the treatment condition of propylene by crude oil.This irregularity has caused the propylene purification process to have complicated and harsh especially step.

Therefore, in order to alleviate the heavy burden of step in the propylene purification process, wish to set up a kind of method that is used to prepare the propylene that does not comprise these impurity with high stable purity.

About the alkylation of aromatic substance, it is known in this field that many methods are arranged.For example, adopt the alkylation of alkene to be widely used in industry, become a kind of of important industrial technology,, also proposed various suggestions for adopting alcohols to carry out alkylating method.

It is as described below to be used to adopt alcohols that aromatic substance is carried out alkylating several prior art processes.

(1) Japanese Unexamined Patent Publication No 159430/1983 has disclosed and has a kind ofly prepared 1 in the presence of the zeolite catalyst of oxide modifying, the method for 4-dialkyl benzene compound.

(2) Japanese Unexamined Patent Publication No 263934/1986 disclosed a kind of in the presence of ZSM-5 type zeolite catalyst by alkylation of toluene being prepared the method for right-dimethylbenzene with methyl alcohol.

(3) Japanese Unexamined Patent Publication No 216128/1983 and 159427/1983 has disclosed in the presence of the mordenite type zeolite catalyst of proton exchange by making benzene or alkylbenzene and a kind of alcohol reaction prepare the method for monoalkylated benzenes or dialkyl benzene.

(4) U.S. Patent number 4,011, and 278 have disclosed a kind of method of alcohols with various aromatic alkylations that adopt in the presence of ZSM-5 type zeolite catalyst.

All these methods all are to increase the percentage yield of final Alkylaromatics by improving catalyzer.

Alkylation by aromatic substance makes normally difficulty of a kind of desirable compound.More particularly, alkylation product have usually compared with beginning reactant stronger alkylation activity, thereby further alkylation can be carried out and form more high-grade alkylate, thereby has brought obstacle to selective alkylation.For this reason, proposed many suggestions, reached selective alkylation by improving catalyzer.

In the alkylation process of aromatic substance, reactivity depends on the acid properties and the shape of catalyst system therefor.It has been generally acknowledged that the acid properties control speed of reaction of catalyzer, the shape control selectivity of catalyzer.

It should be noted that and adopt the alkylation process of alcohols to produce water.Usually, in the presence of water, the acidity with catalyzer of acid properties dies down, even can have the forfeiture of catalytic activity, particularly when used catalyzer is solid peracid.Therefore, under the situation that can form water, adopt various measures, comprise being used to increase the employing of reactive harsh reaction conditions and the employing of water-fast catalyzer.

Yet, at (for example strongly acidic catalyst of modification) under the reaction conditions of this harshness or in the presence of improved catalyzer, the selectivity of required compound has reduced, and this is that perhaps the dehydration of alcohols has caused the generation of olefin by-products because formed highly alkylating product.

For of the alkylation of above-mentioned employing alcohols, also do not finish the technology that can optionally produce the viable commercial of required reaction product as the aromatic substance of alkylating reagent.

Therefore, an object of the present invention is to provide modification method a kind of novelty, that do not form preparation phenol by product, that reach commercial acceptable yield.

The problem of cumene method is a large amount of acetone by products rather than low phenol yield.By the by product acetone conversion being become Virahol, with Virahol benzene alkylation and the propylene and the Virahol one that adopt to replenish are used from alkylation (if obtainable Virahol uses up), the inventor has solved the problems referred to above.In conjunction with these steps, the inventor has finished a kind of method for preparing phenol that does not form the acetone by product.

And then, adopt by method for hydrogenation to change and the Virahol institute synthetic isopropyl benzene that comes does not comprise any sulphur compound and heavy metal, and the latter is contained in the alkylation process that adopts usually the benzene that propylene carried out that makes as parent material with crude oil from acetone.

In a kind of form of the present invention, described purpose can by with the following step suitably in conjunction with obtaining:

(a) with Virahol and/or propylene benzene alkylation is come synthesizing iso-propylbenzene,

(b) will become Cumene Hydroperoxide 80 from the cumene oxidation of step (a),

(c) with the acid cleavage of hydrogen over hydrogenation isopropyl benzene with synthesizing phenol and acetone, and

(d) will be hydrogenated to Virahol from the acetone of step (c) so that be recycled to step (a).

Method in first kind of form of the present invention has guaranteed only to prepare phenol with the compound that contains 3 carbon atoms from benzene, oxygen and hydrogen.

Another object of the present invention provides the improving one's methods of novelty that has the isopropyl benzene of high yield and minimum amount of by-products with Virahol preparation.

In second kind of form of the present invention, a kind of method for preparing isopropyl benzene is provided, it comprises: in the presence of zeolite catalyst with alkylating reagent with benzene alkylation, wherein said alkylating reagent is the mixture of Virahol or Virahol and propylene.

Preferably, described zeolite is that a kind of silica-alumina ratio is 4/1 to less than 10/1 proton exchange Y type skeleton zeolite.

It is a kind of with the method for Virahol with benzene alkylation that another purpose of the present invention is to provide, and can increase selectivity thus and synthesize final product.

In the third mode, the invention provides a kind of in reactor with the method for Virahol with benzene alkylation, it comprises: in the future the reaction mixture separated into two parts A and the B that comprise alkene of autoreactor, be recycled to reactor with part A with the fresh alkyl reactant of part B same amount, and the part B that will be left takes out reactive system as mixture of reaction products.

Only figure (Fig. 1) has schematically described the reactive system that is applicable to that the present invention puts into practice.

The phenol preparation method of first kind of mode of the present invention is shown a successive processes by typical earth surface, and it comprises the following steps:

The step (a) to (d) that is included in the described method will obtain detailed description.

Step (a)

Step (a) is one with the step of benzene alkylation with synthesizing iso-propylbenzene.

Although in the present invention, benzene alkylation step (a) is classified into step (a-1), (a-2), (a-3) and (a-4), and the alkylating reagent that is used for these benzene alkylation step can be independent propylene, the mixture of Virahol or propylene and Virahol separately.

At first, will the use of the alkylating reagent (comprising the alkylating reagent that is made of Virahol) that mainly comprises Virahol be described.

With Virahol and the propylene that replenishes to the process of benzene alkylation with the preparation isopropyl benzene in, a kind of solid-state acidic substance are used as catalyzer.Useful catalysts comprises common solid peracid such as activated earth, silicon-dioxide and silica-alumina; Metal oxide such as titanium dioxide, zinc oxide and zirconium white; It is various that selection causes the zeolite that people pay attention to as catalyst shape in recent years; And with the compound of metal ion to these Zeolite modifyings.Adopt (auxiliary) propylene that replenishes of Virahol both can under gas phase condition, carry out, also can under liquid-phase condition, carry out the alkylation of benzene.Temperature of reaction is preferable in 100 to 450 ℃ of scopes, is preferably in 150 to 300 ℃ of scopes.Reaction atmosphere can be decompression, normal atmosphere or pressurized atmosphere, and when requiring liquid phase reaction, pressurization is necessary for keeping liquid phase.

The mol ratio of benzene and Virahol is preferable in 20/1 to 1/10 scope, is preferably in 5/1 to 2/1 scope.When also adopting propylene, the mol ratio of benzene and Virahol and propylene is preferably such, make those mol ratios in 20/1 to 1/10 scope with the material of 3 carbon atoms (Virahol adds propylene) and benzene, be more preferably under in 5/1 to 2/1 scope, and the mol ratio of Virahol and propylene is preferably in 5/1 to 1/10 scope in 3/1 to 1/100 scope.

In the present invention, adopt alkylation process that Virahol carries out benzene can batch type or continuous mode carry out.Owing to the form that solid catalyst can be different is used, thereby, fluidised bed system can be adopted,, fixed bed system can be adopted for pellet type catalyst for fine catalyst.For easily with the simplicity of reaction product catalyst separating and reactor, preferred fixed bed system.

In this kind form alkylated reaction, except the final product isopropyl benzene, some more senior alkylating products and water form as by product.Therefore, the reaction mixture that alkylating is produced carries out fractionation, is separated into unreacted propylene, unreacted benzene, isopropyl benzene, more senior alkylate and water.Unreacted benzene and the alkylating product of height are recycled to alkylation step to be used for further alkylation.

Secondly, will the main alkylation process that adopts propylene be described.

The alkylation of the benzene of main employing propylene (comprise and only use propylene) can be the alkylation step of well-known cumene method.Be used for that catalyst for reaction generally is the aluminum chloride coordination compound between benzene and propylene, it can be by making aluminum chloride absorbing hydrogen chloride gas at a solvent in such as isopropyl benzene.

The mol ratio of benzene and propylene is preferably in 1/1 to 10/1 scope, is preferably in 1.2/1 to 6/1 scope.The aluminum chloride coordination compound catalyst amounts that adds is preferably 0.01 to 5%(weight), the best is 0.1 to 1%(weight, is benchmark with aluminum chloride).In this reaction, hydrogen chloride gas can coexist as reactive system, thereby stablizes the coordination compound catalyzer.

Form isopropyl benzene alkylation process can 30 to 200 ℃, be preferably under 60 to 160 ℃ of temperature and normal atmosphere to 15kg-f/cm ²Carry out under the pressure.Can batch type, half batch type or continuous mode carry out described reaction.

In this kind mode alkylated reaction, except the final product isopropyl benzene, some more senior alkylating product and water have also been formed as by product.Therefore, the reaction mixture of alkylating gained is carried out fractionation, be separated into unreacted propylene, unreacted benzene, isopropyl benzene, more senior alkylation product and water.Unreacted benzene and more senior alkylating product are recycled to alkylation step to be used for further alkylation.

Step (b)

Step (b) be one will be from the cumene oxidation of step (a) isopropyl benzene be transformed into the step of Cumene Hydroperoxide 80.

By step in the inventive method (b) or (b-2) expression cumene oxidation can 60 to 150 ℃, be preferably under 90 to 130 ℃ of temperature, 1 to 10kg/cm ²Under the pressure, adopt molecular oxygen to carry out.Molecular oxygen can be used as oxygen, air or is obtained by the oxygen mixture of inert gas dilution.For oxidising process is successfully carried out, can in reactive system, add basic cpd and be adjusted to optimum level, promptly in 8.5 to 10.5 scopes with pH value with system.Used basic cpd comprises yellow soda ash, salt of wormwood and potassium hydroxide aqueous solution.When oxygenizement was carried out, basic cpd can add by intermittent mode on a small quantity, thereby kept best reactive system pH value in whole process.The required reaction times of this oxidising process does not specifically limit, but can be to its selection so that final product or Cumene Hydroperoxide 80 reach maximum selectivity.

The preferable initiator that adds in reactive system is to start oxidising process reposefully.The example of initiator comprises azo-compound, such as α, and α '-Diisopropyl azodicarboxylate and α, α ' azo dicyclohexyl nitrile.The Cumene Hydroperoxide 80 that is produced by cumene oxidation also is a kind of preferable initiator.The amount of initiator that adds in the system is preferably about 0.1 to 5%(weight), be preferably about 0.5% to 2%(weight), be benchmark with the reactant.

Oxygenizement can with batch type, continuously or half batch type mode carry out.

Step (c)

It is the step of phenol and acetone with the Cumene Hydroperoxide 80 acid cleavage that step (c) is one.

In the reaction mixture from step (b), the Cumene Hydroperoxide 80 concentration of existence is generally about 20 to 30%(weight).Reaction mixture preferably should be concentrated by for example distillation, thereby mixture is being increased to 60 to 85%(weight with the concentration of Cumene Hydroperoxide 80 before acid cleavage).Such concentration process can carry out under certain temperature of 150 ℃, is preferably under 100 ℃ and carries out.Concentrating to cause the thermolysis of Cumene Hydroperoxide 80 unhappyly under the high-temperature very much, thereby causing low final product or phenol recovery rate.As long as reach effective concentration, for the safe handling superoxide, described temperature is preferably low as far as possible.

In the cracking of step (c), adopt a kind of acidic cpd as catalyzer, used here catalyzer comprises strong acid, such as sulfuric acid, hydrochloric acid and hydrofluoric acid.Included heteropolyacid in addition is such as phospho-wolframic acid and phospho-molybdic acid.Also can adopt solid acid such as ion exchange resin and silica-alumina.The catalyst amounts that adds is preferably about 0.01 to 5%(weight), be preferably 0.1 to 2%(weight, be benchmark with reaction mixture concentration).

In addition, described acid cleavage adopts a kind of solvent as reaction medium.The example of this solvent comprises aromatic hydrocarbon, such as benzene,toluene,xylene and isopropyl benzene; The aliphatic carbons hydrogen compound is such as hexane, heptane, hexanaphthene and methylcyclohexane; Alcohols is such as methyl alcohol, ethanol, propyl alcohol and butanols; Ketone is such as acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK); And ethers, such as Di Iso Propyl Ether and dibutyl ether.Make because acetone is the acid cleavage by Cumene Hydroperoxide 80, thereby it is best reaction medium.Used amount of solvents is preferably about 1 to 20 times of the reaction mixture enriched material weight that stands acid cleavage, is more preferred from about 2 to 10 times.

Acid cleavage both can be carried out in a continuous manner, also can half batch mode carry out.The batch type operation is not best, and this is because the Cumene Hydroperoxide 80 solution of high density can contact with acid catalyst, thereby causes too fast cracking.

When acid cleavage finishes, reaction mixture is concentrated to reclaim acetone.As the reaction medium of acid cleavage, simultaneously, the corresponding remaining acetone of quantity that produces with acid cleavage by Cumene Hydroperoxide 80 is dropped into subsequently step (d) so that propionic acid is hydrogenated to Virahol by once more for partially recycled acetone.The enriched material of removing acetone is carried out rectifying to reclaim final product or phenol.

Step (d)

Step (d) is the step that the acetone of a step (c) is hydrogenated to the Virahol that is recycled to step (a).

Catalyzer, normally Raney nickel catalyst is used to acetone is hydrogenated in the step of Virahol.Useful also have nickel family catalyzer, the reduced nickel agent that becomes through reduction such as the nickel oxide that is carried on diatomite, aluminum oxide, the silicon-dioxide etc.; Copper family catalyzer is such as copper-chromium, Raney nickel-copper, copper-zinc; And platinum group catalyst, such as metals such as the platinum on activated carbon, aluminium and other carriers, palladium, ruthenium, rhodiums, these catalyzer are known as hydrogenation catalyst.Described temperature of reaction can be in room temperature to 200 ℃ scope.For commercial acceptable response speed, temperature of reaction can be in 60 to 150 ℃ of scopes.

Come from economic consideration, too high temperature of reaction is undesirable, because this can trigger the over-hydrogenation of acetone, causes the Virahol recovery rate that reduces.Hydrogenation can be undertaken by liquid phase reaction or gas-phase reaction.Therefore, described pressure can be at normal atmosphere to 80kg/cm ²In the scope, be preferably 5 to 50kg/cm ²Used hydrogen is 1/2 to 10/1 for the mol ratio of acetone reactant, is preferably 1/1 to 5/1.

Hydrogenation can carried out under the existence condition under the reaction medium existence condition or not.Here used examples of solvents comprises alcohols, such as methyl alcohol, ethanol, propyl alcohol and butanols.The useful Virahol that also has as the acetone hydrogenated products.Useful di-alcohols in addition is such as ethylene glycol, propylene glycol, glycol ether and triglycol; And ethers, such as Di Iso Propyl Ether, dibutyl ether, glycol dimethyl ether, diglyme and triglyme.Also can adopt aprotonic solvent, for example dimethyl formamide, N,N-DIMETHYLACETAMIDE, acetonitrile and methyl-sulphoxide.Useful saturated hydrocarbon in addition is such as hexane, heptane, pentamethylene and hexanaphthene.In the hydrogenation practice, as solvent, water also is preferable.

Step of hydrogenation can be batch type or continous way.According to the shape of used special catalyst, when adopting fine catalyst, reaction can be carried out in fluidized-bed, and maybe when adopting pellet type catalyst, reaction can be carried out in fixed bed.Simple for catalyzer and isolating convenience of reaction mixture and reactor, fixed bed reaction is preferable.

When the hydrogenation of acetone is when carrying out in fixed bed, hydrogen can gas-liquid convection or gas-liquid and stream mode contact with reaction mixture.Liquids and gases stream can use to dirty-gas downward stream mode to upper reaches or liquid to upper reaches-gas to upper reaches, liquid to dirty-gas by liquid.In order to increase speed of reaction, the liquid-gas downward stream mode that is referred to as trickle bed is preferable.

If desired, the Virahol from step (d) need be able to be recycled to step (a) as a kind of product extraction system.

Have above-mentioned combining step (a) and (b), (c) and the inventive method (d) and can make phenol with rational product yield by benzene through compound with 3 carbon atoms, and need not consider the demand of acetone, the latter is formed by conventional cumene method as by product in other cases.

In second kind of shape, the invention provides a kind of by benzene alkylation being prepared the method for isopropyl benzene with the mixture of Virahol or Virahol and propylene.The present invention adopts a kind of zeolite catalyst to be used for this benzene alkylation reaction.Described catalyzer preferably silica-alumina ratio be 4/1 to less than 10/1, be preferably 5/1 to Y type skeleton zeolite less than 8/1 proton exchange.Described catalyzer can be Powdered or particulate state.

The mol ratio of Virahol and benzene is preferably 1/10 to 10/1, is preferably 2/1 to 5/1.When the mixture with Virahol and propylene was used as alkylating reagent, the mol ratio of Virahol/propylene mixtures and benzene was preferably 1/10 to 10/1, is preferably 2/1 to 5/1, and the mol ratio of propylene and Virahol is up to 1/1 simultaneously, is preferably up to 2/10.

Range of reaction temperature is preferably 150 to 350 ℃, is preferably 220 to 250 ℃.Reaction pressure can be decompression, normal atmosphere or supercharging, although pressurization is necessary for keeping liquid phase in carrying out liquid phase reaction.In the present invention practice, the alkylation of benzene can be intermittently or continuous mode carry out.About the catalyzer form,, can adopt fluidised bed system, and, can adopt fixed bed system for pellet type catalyst for fine catalyst.Simple for the facility of reaction product and catalyst separating and reactor, preferable employing fixed bed system.

For different material, the percentage recovery rate of alkylating can depend on that promptly described material is Virahol or Virahol/propylene mixtures respectively by following expression formula definition.

Alkylation recovery rate=(isopropyl benzene ¹2 * diisopropylbenzene(DIPB) ¹3 * tri-isopropyl benzene)/Virahol charging capacity * 100%

Alkylation recovery rate=(isopropyl benzene ¹2 * diisopropylbenzene(DIPB) ¹3 * tri-isopropyl benzene)/(Virahol ¹Propylene) * 100%

Now, will describe the third form of the present invention, although engage in the alkylation research of the aromatic substance that adopts alcohols always, the inventor can not find out the optimum reaction condition that alkylate is effectively produced.The inventor finds that a kind of reason that alkylate can not be produced with high recovery rate is: the dehydration that has produced alcohols in initial alkylated reaction.The dehydration of alcohols has formed alkene.In fact, find that a lot of alkene are dissolved in reaction soln, reaction has formed the alkylate of low recovery rate thus.

In addition, adopting alkene also is known as the alkylating reagent of aromatic alkylation effect.In the process of seeking the alkene that generates as by product is used for alkylating method during initial reaction, the inventor has found the present invention.

In the third form of the present invention, provide a kind of being used for to adopt the alkylating reagent that exists with a kind of alcohol " Virahol " form that a kind of aromatic substance " benzene " is carried out continuous alkylating method at a reactor, this method comprises the following steps: that in the future the reaction mixture that comprises alkene of autoreactor is divided into first and second part A and B, make the ratio (A/B) of first part and second section greater than 1, the A of first part is re-circulated to reactor, remaining second section B is taken out reactive system as a kind of mixture of reaction products.

This method makes the alcohol as the alkylating reagent input optionally to be consumed by alkylated reaction, and makes the ratio that is converted into the alcohol of alkene by side reaction reach minimum.Therefore, can improve the percentage recovery rate of alkylate, and without any inconvenience.

Surprisingly, we also find, have in selectivity under the situation of remarkable increase to have obtained desirable monoalkylated product, and at this moment because in whole alkylate, the ratio of more senior alkylating product is reduced to minimum.

Referring to Fig. 1, illustrate a reactive system that is used for the inventive method.

Reactive system as shown in Figure 1 comprises that one comprises the feed pot 1 of the alkylation material that the form of mixtures with aromatic substance and a kind of alcohol exists, be connected to cylindrical reactor 3 on the batch can 1 by a service 2, and be connected to oil/water separator 6 on the reactor 3 by a product discharge tube 4 and pressure regulator valve wherein 5.Described reactor 3 has apical pore and bottom outlet 12 and 13, and they are interconnected by a recirculation conduit 9.Service 2 is continuously on the recirculation conduit 9 adjacent with apical pore 12, and discharge tube 4 is connected on the recirculation conduit 9 adjacent with bottom outlet 13.Feed pipe 2 comprises that one is used for the fresh feed pump 10 that pump advances solution, and recirculation conduit 9 comprises that one is used for the recirculating pump 11 with reaction soln recirculation.

The reactor 3 that is filled with the following solid catalyst that will describe is accepted a part of reaction soln of the recirculation conduit 9 of flowing through that gives off from the filler of service 2 with by reactor bottom outlet 13 at its apical pore 12.Will be by the reaction soln separated into two parts of reactor bottom outlet 13 taking-ups.First part is recycled to reactor through recirculation conduit 9, and second section is displaced into oil/water separator 6 through discharge tube 4, and there, the water 8 that it is divided into reaction product 7 and forms is then with its extraction system.

For initiation reaction, reaction material is imported the recirculation conduit 9 of reactor 3 and ligation device apical pore and bottom outlet 12 and 13.Start recirculating pump 11, with a part of reaction soln once more from bottom outlet 13 pumps to apical pore 12.By this way the solution in the reactor 3 is constantly circulated by recirculation conduit.To be adjusted to certain flow rate A by way of first part's reaction soln stream of recirculating pump 11 and recirculation conduit 9.Reactor 3 is adjusted to predetermined condition, continues the recirculation reaction soln simultaneously.When reaction conditions reaches the predetermined condition of alkylated reaction generation, start take away pump 10, thereby begin the alkylation feed liquid of the form of mixtures that is aromatic substance and a kind of alcohol in jar 1 is delivered to reactor 3 through service 2 and recirculation conduit 9.The alkylation materials flow is adjusted to certain flow rate B, thereby accumulates total stream (A+B) through feed and recirculation conduit 2 and 9 materials flows to reactor 3.Because reactor 3 has been equipped with solution when the reaction beginning, so the additional supply of alkylation material can make the inside reactor pressurization in the reactor, cause that pressure rises.Thereby, be open at the pressure regulator valve 5 in the discharge tube 4, emitting a part of reaction soln, thereby inside reactor is remained under the predetermined pressure.Turn of tidal stream to the second section reaction soln of discharge tube 4 is adjusted to the flow velocity identical with the flow velocity B of alkylation material.

By control pump and valve, make the ratio of flow velocity A and B in predetermined scope, so just reached purpose of the present invention.

Below will be in more detail the present invention's method be described.

In the present invention's practice, adopt a kind of solid catalyst.The normally acid solid matter of useful catalysts comprises silica-alumina, activated earth, zeolite, strong-acid ion exchange resin and metal oxide.Zeolite catalyst comprises that the zeolite, ZSM-5 type zeolite, proton exchange mordenite type zeolite, y-type zeolite, US-Y type zeolite of oxide modifying and those further use metal ion-modified zeolite.Useful metal oxide example comprises the oxide compound of metals such as the oxide compound of oxide compound, titanium and zirconium of metalloids such as iron, cobalt, nickel, chromium and vanadium, niobium, antimony.

Here used catalyzer can be Powdered or particulate state, certainly, for the convenience of reaction mixture and catalyst separating, preferably selects pellet type catalyst for use.

Temperature of reaction is preferably 100 to 350 ℃, is preferably 150 to 300 ℃.Reaction pressure does not specifically limit, as long as enough inside reactor can be remained on liquid phase.

In practice of the present invention, it equals the flow velocity of the second section reaction soln of being discharged by reactive system through the flow velocity B(of the flow velocity A of first part's reaction soln of reactive system and the new alkylation material of supplying with in circulation) ratio be critical.The ratio of A/B should be greater than 1, and is preferable in 2 to 100 scopes, is preferably 2 to 50.When A/B than less than 1 the time, it is invalid that the inventive method becomes.When A/B than for up to 2 the time, the inventive method is just just effective.When A/B than greater than 100 the time, do not obtain further improvement, this uneconomical use that shows pump has unnecessarily increased its load.

The alkylating reagent quantity of supplying with among the present invention can be 0.1 to 20hr ^-1In the scope, be preferably 0.5 to 10hr ^-1(liquid hourly space velocity).

In practice of the present invention, described alkylation material is the mixture of aromatic substance and alcohol.Aromatic substance can be 1/1 to 12/1 with the mol ratio of alcohol, is preferably 2/3 to 8/1.

In many kinds alcohol and aromatic substance combination, commercially the most important thing is the alkylation of adopting Virahol that benzene is carried out.

In practice of the present invention, a kind of solvent can be added the mixture of alcohol and aromatic substance.Useful solvent is that those are the inert solvent to relevant alkylated reaction.This example comprises hydrocarbon cosolvent, such as pentane, hexane, heptane, pentamethylene and hexanaphthene.

Method of the present invention helps the reaction of successive type.The type of reactor that is used for successive reaction can be a kind of fluidised bed system concerning fine catalyst, concerning pellet type catalyst, can be a kind of fixed bed system.

Example

Provided example of the present invention below, it is as elaboration, rather than as restriction.

Following example relates to the preparation of phenol.

Example 1

With the alkylation of Virahol to benzene

At an internal diameter is the 25.4mm(1 inch) and length be the middle part of the upright stainless steel reaction post of the 500mm 50mlUS-Y type zeolite of packing into.The reactor mol ratio of packing into is 5/1 the benzene and the mixture of Virahol, and Virahol carries out recirculation by the following step of hydrogenation that will describe.Reactor heating, when reaching 230 ℃, at reactor bottom with the flow velocity of 50ml/hr with additional material supply response device.Reaction was carried out 15 hours, and keeping reaction pressure simultaneously is 25kg/cm ²

During handling, do not find gas evolution.We have obtained a kind of reaction product that comprises isolating organic phase and water.With vapor-phase chromatography the organic phase of reaction product is analyzed, found that Virahol and propylene conversion are 99.4%, the recovery rate of isopropyl benzene is 17.7%, and diisopropylbenzene(DIPB) (DIPB) recovery rate is 0.7%, and the alkylation recovery rate that with the Virahol is benchmark is 93.8%.Be dissolved with 0.35%(weight in the organic phase) propylene.

THE AUTOXIDATION OF CUMENE

One the 120 gram isopropyl benzenes of packing in blast pipe, alkali supplying opening, thief hole, thermometer sheath, reflux exchanger and strong mixer and the 500ml stainless steel autoclave, 30 gram 5% aqueous sodium carbonates and 0.5 gram α, α '-Diisopropyl azodicarboxylate initiator are housed.Air in the autoclave is used purging with nitrogen gas earlier, and forming nitrogen pressure then is 5kg/cm ²As initial pressure.When being stirred, the material in the autoclave begins heating.When internal temperature reaches 110 ℃, begin to blast air.In the beginning air blast, increase agitator and rotating speed rpm to guarantee enough gas-to-liquid contact.Blast air with cumene oxidation by speed with 30l/hr.When carrying out oxidizing reaction, take out the reaction mixture sample off and on by thief hole, to check the pH value of reaction mixture.A small amount of 5% aqueous sodium carbonate is pumped into reactor through the alkali supplying opening, is 9 to 10 thereby reaction mixture is remained on the pH value.

After beginning 10 hours from air blast, termination reaction.Reaction mixture is taken out autoclave and is divided into oil phase and water.Analyze oil phase to determine the content of Cumene Hydroperoxide 80 by liquid chromatograph chromatography, find that described oil phase comprises 26%(weight) Cumene Hydroperoxide 80.

The acid cleavage of Cumene Hydroperoxide 80.

To concentrate under 100 ℃ and 160mmHg vacuum tightness from the oil phase of cumene oxidation, unreacted isopropyl benzene is removed in distillation.When oil phase concentrates about 3 times, stop concentration operation.Thereby oil phase comprises about 78%(weight) Cumene Hydroperoxide 80.

Agitator, dropping funnel, thermometer overcoat are housed and return in the 500ml four neck flasks of liquid cooling condenser one and add the 150ml acetone and the 2 gram vitriol oils.100 gram Cumene Hydroperoxide 80 enriched materials are housed in the dropping funnel.To put into temperature be that 80 ℃ water-bath is so that acetone constantly refluxes the material in the stirred flask simultaneously with watering bottle.

When acetone refluxes, the Cumene Hydroperoxide 80 enriched material is added dropwise to flask from funnel.The quantity of observing backflow acetone is to regulate the rate of addition of enriched material.After all the Cumene Hydroperoxide 80 enriched material adds, continue to make reaction to carry out and 30 minutes.When reaction finishes, by liquid chromatograph chromatography reaction mixture is analyzed, found remaining few Cumene Hydroperoxide 80, promptly transformation efficiency is near 100%.We find that the phenol amount of generation is transformed corresponding to 95% Cumene Hydroperoxide 80.

Powdered sodium carbonate is added reaction mixture with the neutralisation of sulphuric acid catalyzer.By filtering solid is removed from the reaction mixture that has neutralized, concentrated filtrate to be to reclaim acetone.The amounts of acetone that reclaims comprises the acetone material and 28.5 grams derive from the acetone of Cumene Hydroperoxide 80 through the acid cleavage gained.The hydrogenation of acetone

At internal diameter is the 25.4mm(1 inch) and length be to add 50 grams (24ml) in the upright stainless steel reaction pipe of 500mm to form fritter shape Raney nickel alloy (R-20L is made by Nikko Rika K.K. Corp.).In reaction tubes, add entry, then the 20% caustic soda aqueous solution is gently pumped into reaction tubes with the activation Raney nickel catalyst.Because discharge heat during catalyst activation, the internal temperature of reactor has raise.The flow velocity of control soda lye makes the inside reactor temperature be no more than 60 ℃.After pumping into 0.5 liter soda lye, input water is to replace described material with rinsing reactor stopping composition.The control rinsing becomes neutrality up to the water that flows out from reactor, when rinsing finishes, replaces water to import with the filling reactor with pump Virahol, begins reactor is heated.

When internal temperature reaches 125 ℃, begin reaction by at reactor bottom propyl alcohol and hydrogen being sent into reactor with the flow velocity of 19g/hr and 16l/hr respectively, the pressure of reactor remains on 20kg/cm ²

The reaction mixture that to discharge reactor by a gas-liquid separator at the top is divided into reaction liquid and hydrogen.Reaction liquid and hydrogen are discharged with the flow velocity of 18.9g/hr and 8.1l/hr respectively.

Continue above-mentioned reaction, constantly supply with acetone and hydrogen simultaneously, resulting Virahol is recycled to alkylation step.When reaction finished in 9 hours, by vapor-phase chromatography and liquid chromatography reaction liquid and hydrogen are analyzed respectively, find remaining 1%(weight in the reaction liquid) acetone, and remaining component only is made of Virahol.Gaseous emission and analysis revealed exist 0.73% methane, 0.02% ethane and 0.07% propane.Calculate reaction efficiency according to these results, find that acetone conversion is 99.0%, the Virahol recovery rate is 98.7%.

The alkylating reagent that resulting Virahol can be used as the benzene alkylation effect reuses.

Example 2

Adopt the alkylation of Virahol and propylene to benzene

At an internal diameter is the 25.4mm(1 inch) and length be the centre of the upright stainless steel reaction post of the 500mm 50mlUS-Y type zeolite of packing into.The adding mol ratio is 50/9/1 benzene, Virahol and propylene mixtures material in reactor, and reactor is heated.When temperature reaches 230 ℃, in the bottom of reactor additional material is supplied with to reactor with the flow velocity of 50ml/hr.Successive reaction 15 hours remains on 25kg/cm with reaction pressure simultaneously ²During handling, do not find gas evolution.We have obtained the reaction product of a kind of separated organic phase and water.With vapor-phase chromatography the organic phase of reaction product is analyzed, found that Virahol and propylene conversion are 99.4%, the recovery rate of isopropyl benzene is 16.9%, and the DIPS recovery rate is 4.2%, is that the alkylation recovery rate of benchmark is 92.7% with Virahol and propylene.Be dissolved with 0.62%(weight in the described organic phase) propylene.

Subsequently, carry out the following step in the mode identical with example 1.

THE AUTOXIDATION OF CUMENE

The acid cleavage of Cumene Hydroperoxide 80

The hydrogenation of acetone

The final remnants that obtain have 1.0%(weight) reaction soln of acetone, remaining material is made of Virahol merely.The analysis revealed of gaseous emission exists 0.00% methane, 0.00% ethane and 0.01% propane.Calculate reaction efficiency according to these analytical resultss, find that acetone conversion is 99.0%, the Virahol recovery rate is 99.0%.

The alkylating reagent that the Virahol of gained can be used as the benzene alkylation effect reuses.

Example 3

Adopt the alkylation of propylene to benzene

1 78 gram benzene and the aluminum chloride coordination compoundes of packing in the 1 liter glass autoclave of the agitating vane that is coated with tetrafluoroethylene and thermometer overcoat will be arranged.Calculate with aluminum chloride, the aluminum chloride coordination compound amount of filling is 0.08 gram, and this mol ratio corresponding to aluminum chloride coordination compound and propylene is 1/1000.Autoclave is immersed in the oil bath, the internal temperature of autoclave is remained on 100 ℃, and fully stir.

Increase progressively the propylene that adds 25.2 gram gaseous phases in autoclave, promptly added propylene at about 90 minutes in the clock time, the internal pressure with autoclave remains on 3kg-f/cm simultaneously ²Termination reaction when propylene is supplied with end.Reaction mixture is taken out from autoclave, with vapor-phase chromatography reaction mixture is analyzed, is found that it comprises 25.1%(weight) isopropyl benzene, 13.3%(weight) between-diisopropylbenzene(DIPB), 7.4%(weight) p-Diisopropylbenzene and 7.9%(weight) tri-isopropyl benzene.Total recovery rate of isopropyl benzene, diisopropylbenzene(DIPB) and tri-isopropyl benzene is 99%(with the weight of propylene material is benchmark).

By distillation, reaction mixture is separated into the product of unreacted benzene, isopropyl benzene, higher isopropylation.Product that will more senior isopropylation send back to initial or alkylation step being used for transalkylation, thereby be translated into isopropyl benzene.

Adopt the isopropyl benzene of 120 gram gained, produce Virahol according to cumene oxidation, acid cleavage and the acetone step of hydrogenation identical with example 1.The alkylating reagent that the Virahol of gained can be used as the benzene alkylation effect reuses, and this is identical with example 1.

Show that thus phenol can not produce the acetone by product simultaneously by following series of steps combination system is got:

(b) with the cumene oxidation or the Cumene Hydroperoxide 80 of step (a),

(c) be phenol and acetone with the Cumene Hydroperoxide 80 acid cleavage,

(d) acetone in the step (c) is hydrogenated to Virahol, and Virahol is recycled to step (a).

Following example relates to the preparation of isopropyl benzene.

Example 4

At an internal diameter is the 25.4mm(1 inch), length is that the ratio that is loaded into the 50ml silica-alumina in the middle of the upright stainless steel reaction post of 500mm is 7 proton exchange y-type zeolite.With mol ratio is that the mixture of 5/1 benzene and Virahol adds reactor and to its heating.When reaching 230 ℃,, in reactor, add additional material in the bottom of reactor with the flow velocity of 50ml/hr.Successive reaction 15 hours remains on 25kg/cm with reactor pressure simultaneously ²Treating processes in, do not find gas evolution.We have obtained a kind of reaction product that comprises isolating organic phase and water.When reaction finished in 15 hours, with the organic phase of gc analysis reaction product, find that the transformation efficiency of Virahol is 99.4%, the isopropyl benzene yield is 19.8%, the recovery rate of diisopropylbenzene(DIPB) (DIPB) is 5.1%, and the alkylation recovery rate that with the Virahol is benchmark is 97.4%.

Example 5

At an internal diameter is the 25.4mm(1 inch) and length be that the ratio that adds the 50ml silica-alumina in the middle of the upright stainless steel reaction post of 500mm is 7 proton exchange y-type zeolite.Adding mol ratio in reactor is 3/1 benzene and isopropyl acetone mixture and heats it.When reaching 230 ℃,, in reactor, supply with interpolation (adding) material at reactor bottom with the flow velocity of 50ml/hr.Reaction was carried out 200 hours continuously, simultaneously reaction pressure was remained on 25kg/cm ²In treating processes, do not find gas evolution.We have obtained a kind of reaction product that comprises isolating organic phase and water.When reaction finished in 15 hours, with the organic phase of gc analysis reaction product, find that the transformation efficiency of Virahol is 99.7%, the recovery rate of isopropyl benzene is 21.5%, and the DIPB recovery rate is 11.8%, and alkylation recovery rate (is benchmark with the Virahol) is 94.5%.

Example 6

At an internal diameter is the 25.4mm(1 inch) and length be that ratio that the upright stainless steel reaction post middle part of 500mm adds the 50ml silica-alumina is 7 proton exchange y-type zeolite.Adding mol ratio in reactor is 50/9/1 benzene, Virahol and propylene mixtures material and heats it.When reaching 230 ℃, in reactor, supply with addition material in the bottom of reactor with the flow velocity of 50ml/hr.Successive reaction 15 hours remains on 25kg/cm with reaction pressure simultaneously ²In treating processes, do not observe gas evolution.We have obtained a kind of reaction product that comprises isolating organic phase and water.When reaction finished in 15 hours, with the organic phase of gc analysis reactant, find that Virahol and propylene conversion are 99.4%, the recovery rate of isopropyl benzene is 17.7%, the DIPB recovery rate is 3.7%, and alkylation recovery rate (is benchmark with Virahol and propylene) is 93.8%.Be dissolved with 0.35%(weight in the organic phase) propylene.

Reference examples 1

With 6N hydrochloric acid conventional H-mordenite is handled, the ratio that obtains silica-alumina is 40 dealuminium mordenite catalyst.

At an internal diameter is the 25.4mm(1 inch) and length be to be loaded into the described catalyzer of 50ml in the upright stainless steel reaction post of 500mm.To be filled into mol ratio in reactor be 5/1 benzene and isopropanol mixture material and heat it.When temperature reaches 23 ℃, in reactor, supply with addition material at reactor bottom with the flow velocity of 50ml/hr.Reaction was carried out 15 hours, simultaneously reaction pressure was remained on 25kg/cm ²In treating processes, do not find gas evolution.We have obtained a kind of reaction product that comprises isolating organic phase and water.By the organic phase of gc analysis reaction product, find that the transformation efficiency of Virahol is 9%, the recovery rate of isopropyl benzene is 16.3%, and the DIPB recovery rate is 4.5%, and alkylation recovery rate (is benchmark with the Virahol) is 88.5%.

Can see that from above-mentioned example the mixture that the use of zeolite catalyst has guaranteed to adopt Virahol or Virahol and propylene can make isopropyl benzene from benzene, and obtain high yield as alkylating reagent.

Following example relates to the alkylation of aromatic substance.

Example 7

Adopt reactive system as shown in Figure 1.At an internal diameter is the 25.4mm(1 inch) and length be that centre in the upright stainless steel reaction post of 500mm is mounted with 50mlUS-Y zeolite (TSZ-351PAH1 is made by TosoK.K. company, and diameter is the noodles shape of 1.5mm).Be added to reactor with benzene.Start recirculating pump, thus with the flow velocity of 700ml/hr with reaction soln recirculation.The inside reactor temperature is controlled at 230 ℃, and pressure-controlling is at 25kg-f/cm ²G, supplying with mol ratio with the flow velocity of 50ml/hr in reactor is 5/1 the benzene and the mixture reaction agent material of Virahol.With the charging flow velocity that is equivalent to benzene/isopropanol mixture a part of reaction mixture is discharged by the discharge tube of being shunted by the recirculation conduit of vicinity reactor bottom, reaction was carried out 8 hours, continuous simultaneously supply benzene/isopropanol mixture.

In last 1 hour, the reaction mixture amount that row releases is 42.8 grams.Because this reaction mixture is the mixture of a kind of oil phase and water, thus with oil phase with contain aqueous phase separation.Oil phase is analyzed by capillary gas chromatography, finds that the transformation efficiency of Virahol is 99.9%, and alkylation recovery rate (is benchmark with the Virahol) is 98.4%.

Alkylate comprises 21.8% isopropyl benzene, 3.3% diisopropylbenzene(DIPB) and 0.1% tri-isopropyl benzene, shows that the isopropyl benzene selectivity is 89.5%.In this alkylated reaction, the percentage rate of formation of propylene by product is 0.7%.

Reference examples 2

Repeat the process of example 7, difference is not start recirculating pump.

The result shows that the transformation efficiency of Virahol is 99.8%, and alkylating recovery rate (is benchmark with the Virahol) is 97.0%.The percentage rate of formation of propylene by product is 2.6% in this alkylated reaction.

Alkylate comprises 19.8% isopropyl benzene, 5.1% diisopropylbenzene(DIPB) and 0.2% tri-isopropyl benzene, and the reaction preference that shows isopropyl benzene is 83.4%.

Example 8

Repeat the process of example 7, difference is to replace described catalyzer by H-mordenite type zeolite (by the TSZ-640 of TosoK.K. production).The result shows that alkylation recovery rate (is benchmark with the Virahol) is 98.3%.The selectivity that alkylate is reacted into isopropyl benzene is 78.9%.

Reference examples 3

Repeat the process of example 8, difference is not have circulating reaction solution.The result shows that the alkylation recovery rate is that the reaction preference of 87.6% isopropyl benzene is 73.7%.

Example 9

Repeat the process of example 7, difference is by mol ratio to be 3/1 benzene and isopropanol mixture surrogate response material.The result shows that the alkylation recovery rate is 96.0%, and the reaction preference of isopropyl benzene is 80.8%.

Reference examples 4

Repeat the process of example 9, difference is not have circulating reaction solution.The result shows that the alkylation recovery rate is 85.4%, and the isopropyl benzene selectivity is 54.1%.The propylene amount that produces as by product is that 14.6%(is a benchmark with the Virahol that loads).

Example 10-11

The process of weight example 7 changes the flow velocity of reaction mixture recycling part simultaneously.The result of its result and example 7 and reference examples 2 sees the literary composition back as table 1() shown in.

As can be seen from Table 1, when the ratio of the recycling part of reaction mixture increased, the reaction preference of isopropyl benzene had also increased.

The third form of the present invention provides a kind of alkylation that adopts a kind of alcohol as the aromatic substance of alkylating reagent, wherein with a part of mixture of reaction products recirculation, thus olefin by-products is sent back to reactor to be used for further alkylation.Alkylating recovery rate (is benchmark with alcohol) obtains increasing, and the selectivity of monoalkylated product also significantly increases in the alkylate.

Although described some preferred embodiments, according to the above description, also can make many improvement and variation to it.Therefore, should be understood that in the scope of appended claims, can implement the present invention with the different mode of top specifically described mode.

Table 1

The alkylation isopropyl benzene of reaction mixture anti-

The recirculation flow velocity, the A recovery rate is answered selectivity

Example (ml/hr) is (mol%) A/B (mol%)

CE2 - 97.0 83.4 -

E10 360 97.4 84.7 7.2

E7 700 98.4 89.5 14

E11 1270 98.9 91.1 25.4

Claims

1, a kind of method for preparing phenol is characterized in that may further comprise the steps:

(a) under 150-350 ℃ of temperature, in the presence of zeolite catalyst, with the mixture of Virahol or Virahol and propylene with the benzene alkanisation with synthesizing iso-propylbenzene, the mol ratio of described benzene and described Virahol and/or propylene is 1/10 to 10/1,

(b) will become Cumene Hydroperoxide 80 from the cumene oxidation of step (a),

(c) hydroperoxidation different third is carried out acid cleavage with synthesizing phenol and acetone,

(d) under the temperature of room temperature to 200 ℃, will be hydrogenated to isopropyl acetone from the acetone of step (c), and

(e) mixture with Virahol or Virahol and propylene is recycled to step (a).

2, the method for claim 1, wherein said zeolite are a kind of silicon oxide and the ratio of aluminum oxide is 4 to less than 10 proton exchange Y type skeleton zeolite.

3, the method for claim 1, wherein the described THE AUTOXIDATION OF CUMENE of step (b) is the temperature and 9.8 * 10 60-150 ℃ of scope ⁴-9.8 * 10 ⁵Carry out oxidation with molecular oxygen under the pressure of Pa scope.

4, the method for claim 1, wherein the acid cleavage of the described Cumene Hydroperoxide 80 of step (c) is under≤150 ℃ temperature, reacts with at least a acid that is selected from strong acid, heteropolyacid and solid peracid.

5, the method for claim 1, wherein the hydrogenation of the described acetone of step (d) is in the presence of hydrogenation catalyst, from normal atmosphere to 7.8 * 10 ⁶Carry out under the pressure of Pa, the mol ratio of hydrogen/acetone is 1/2 to 10/1.

6, the method for claim 1, wherein the reaction product of step (a) comprises unreacted benzene, senior alkyl product and the olefin by-products from Virahol; Wherein

The reaction product separated into two parts of described step (a), the ratio of first part and second section is greater than 1,

Described first part is recycled to step (a),

Described second section enters step (b), increases alkylating percentage yield thus, and makes the olefin by-products that forms from Virahol reduce to minimum.

7, method as claimed in claim 6, the ratio of wherein said first part and second section is in 2/1 to 100/1 scope.