CN1732139A - Process for producing cumene - Google Patents
Process for producing cumene Download PDFInfo
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- CN1732139A CN1732139A CN 200380107455 CN200380107455A CN1732139A CN 1732139 A CN1732139 A CN 1732139A CN 200380107455 CN200380107455 CN 200380107455 CN 200380107455 A CN200380107455 A CN 200380107455A CN 1732139 A CN1732139 A CN 1732139A
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Abstract
This present invention relates to a process for producing cumene, characterized by subjecting cumyl alcohol and hydrogen to the action of a dehydration catalyst to obtain a mixture comprising the alpha-methylstyrene and water generated and hydrogen and subjecting the mixture to the action of a hydrogenation catalyst.
Description
Technical field
The present invention relates to the manufacture method of cumene.
Background technology
The manufacture method of known cumene is: in the presence of dehydration catalyst, make the cumic alcohol dehydration, become alpha-methyl styrene, then in the presence of hydrogenation catalyst, make the alpha-methyl styrene hydrogenation become cumene (for example, European Chemical News Volume 74Number 19475-11 March 2001).But known method may not necessarily satisfy low cost and make cumene efficiently.
Summary of the invention
The invention provides a kind of low cost and make the method for cumene efficiently.
That is, the present invention relates to the manufacture method of cumene, it is characterized in that, cumic alcohol and hydrogen are offered dehydration catalyst, obtain containing the alpha-methyl styrene He Shui of generation and the mixture of hydrogen; And this mixture offered hydrogenation catalyst.
Embodiment
Among the present invention, in the presence of dehydration catalyst, the cumic alcohol dehydration becomes alpha-methyl styrene and water, at this moment, withered alcohol and water must be offered dehydration catalyst.
Dehydration catalyst can list, acid such as sulfuric acid, phosphoric acid, tosic acid, metal oxides such as activated alumina, titanium dioxide, zirconium white, silica alumina, zeolite, consider and separating of reaction solution of preferred solid catalyst, consider catalyst life, selectivity etc., preferred activated alumina.
Dehydration reaction is undertaken by cumic alcohol is contacted with dehydration catalyst usually, but owing to proceed hydrogenation reaction among the present invention after dehydration reaction, also hydrogen is offered dehydration catalyst.
Dehydration reaction can preferably use solvent to implement in liquid phase carrying out in the presence of gas phase or liquid phase or the solvent or not.Solvent should be for not having active material to the reactant based products basically.Solvent also can be made of the material in the cumic alcohol solution that is present in use.For example, cumic alcohol is during with the mixture that constitutes as the cumene of product, and not special interpolation solvent can be with its surrogate as solvent.In addition, useful solvent can list, alkane (for example octane, decane, dodecane), aromatic series monocyclic compound (for example benzene, ethylbenzene, toluene) etc.The dehydration reaction temperature is generally 50～450 ℃, preferred 150～300 ℃.In general pressure is that 10～10000kPa is favourable.Use the catalyzer of slurry or fixed bed form can advantageously implement dehydration reaction.
Among the present invention, alpha-methyl styrene and the water that obtains in the dehydration reaction is offered hydrogenation catalyst, the alpha-methyl styrene hydrogenation becomes cumene.
The hydrogenation solvent can list the solid catalyst that contains the periodic table of elements 10 families or 11 family's metals.Specifically nickel, palladium, platinum, copper be can list, nuclear hydrogenation reaction, the yield height that can suppress aromatic nucleus considered, preferred palladium or copper.Cu-series catalyst can enumerate copper, how to draw copper, copper chromium, copper zinc, copper chromium zinc, copper silicon-dioxide, copper aluminum oxide etc.Palladium catalyst can list palladium aluminum oxide, palladium silicon-dioxide, palladium carbon etc.
Usually can carry out hydrogenation reaction by alpha-methyl styrene and water are contacted with hydrogenation catalyst, but owing to after dehydration reaction, proceed hydrogenation reaction among the present invention, in the mixture that in dehydration reaction, obtains, except alpha-methyl styrene and water, also the water that generates is offered water catalyst.Hydrogenation reaction can be carried out in the presence of solvent or not in liquid phase or gas phase, preferably uses solvent to implement.Solvent should be for not having active material to reactant and product basically.Solvent also can be made of the material in the alpha-methyl styrene solution that is present in use.For example, alpha-methyl styrene is during with the mixture that constitutes as the cumene of product, and not special interpolation solvent can be with its surrogate as solvent.In addition, useful solvent can list, alkane (for example octane, decane, dodecane), aromatic series monocyclic compound (for example benzene, ethylbenzene, toluene) etc.The hydrogenation reaction temperature is generally 0～500 ℃, preferred 30～400 ℃.In general pressure is that 10～10000kPa is favourable.
The invention is characterized in, cumic alcohol and hydrogen are offered dehydration catalyst, the mixture that will contain the alpha-methyl styrene He Shui of generation and hydrogen offers hydrogenation catalyst and makes cumene.
It is preferred embodiment as follows.
Use the catalyzer of fixed bed form to utilize the liquid phase continuous processing to help implementing the present invention.The reactor of continuous processing has disconnected thermal reactor, isothermal reactor, and isothermal reactor need be used for the equipment of heat extraction, therefore preferred disconnected thermal reactor.When breaking thermal reactor, the dehydration reaction of cumic alcohol is thermo-negative reaction, and therefore the simultaneous temperature that carries out in reaction reduces, and the hydrogenation reaction of alpha-methyl styrene is an exothermic reaction, and therefore the simultaneous temperature that carries out in reaction raises.Thermal value is bigger as a result, and therefore, temperature out is higher than reactor inlet temperature.Be as the criterion selective reaction temperature and pressure according to the not aggegation of water that contains in the alpha-methyl styrene solution after the dehydration reaction.Preferred 150 to 300 ℃ of temperature of reaction, reaction pressure preferred 100 is to 2000kPa.When temperature is lower than 150 ℃, when pressure is higher than 2000kPa, at dehydration reaction outlet water-setting collection, the performance of hydrogenation catalyst is reduced sometimes.And during hypertonia, unfavorable to the molecular balance of dehydration reaction.Temperature is higher than 300 ℃, when pressure is lower than 100kPa, produce a large amount of gas phase portion sometimes, and dirt etc. cause that disadvantageous situation such as catalyst life reduction occurs.
Can be from the inlet of fixed-bed reactor, be the inlet of dehydration catalyst, or the inlet of hydrogenation catalyst supplies with hydrogen, considered by the activity and the machine complexity of dehydration catalyst, preferably only supplied with by the fixed-bed reactor inlet.That is, often be present in the dehydration reaction district by making hydrogen, the gasification of the moisture that produces of promoting to dewater, balance dehydration transformation efficiency rises, than not existing hydrogen to obtain high conversion constantly efficiently.The water that produces in the dehydration reaction will be by hydrogenation catalyst, and by turning round with aforesaid not level of agglutination, water removal device is not set especially can turn round at low cost.
As long as the amount of dehydration catalyst can fully transform cumic alcohol, preferred cumic alcohol transformation efficiency is more than 90%.As long as the amount of hydrogenation catalyst can fully transform alpha-methyl styrene, preferred alpha-methyl styrene transformation efficiency is more than 98%.Consider cost, preferred dehydration catalyst and hydrogenation catalyst are filled in single fixed-bed reactor rather than the multistage reactor.Can separate by several beds in the reactor, also can be not separated.Under the indiscrete situation, dehydration catalyst can directly contact with hydrogenation catalyst, but also can do partition with the inertia weighting material.
Method of the present invention preferably is applicable to dehydration procedure and hydrogenation operation in the manufacturing process of following cyclopropane.That is, in following operation, can utilize aforesaid method to carry out the hydrogenation of the dehydration of cumic alcohol and the resulting alpha-methyl styrene that dewaters.
Oxidation operation: obtain the operation of cumene hydroperoxide by cumene oxidation,
Epoxidation process: in the liquid phase, under the existence of epoxidation catalyst, make the cumene solution that contains cumene hydroperoxide and excessive propylene reaction, obtain the operation of propylene oxide and cumic alcohol thus,
Dehydration procedure: in the presence of dehydration catalyst, by the cumic alcohol that obtains in the epoxidation process being dewatered obtain the operation of alpha-methyl styrene, and
The hydrogenation operation: in the presence of hydrogenation catalyst, the alpha-methyl styrene hydrogenation becomes cumene, as the feedstock recycle of the oxidation operation operation to oxidation operation.
Oxidation operation is the operation that obtains cumene hydroperoxide by cumene oxidation.Usually, can carry out the oxidation of cumene by the autoxidation of oxygen-containing gass such as air or oxygen condensed air.This oxidizing reaction can not use additive to implement, and also can use the such additive of alkali.Common temperature of reaction is 50～200 ℃, reaction pressure at normal atmosphere between the 5Mpa.Under the situation of the oxidation style of use additive, as alkaline reagents, can use the alkaline metal cpds of NaOH, KOH and so on, alkali earth metallic compound or Na
2CO
3, NaHCO
3And so on alkaline carbonate or ammonium and (NH
4) CO
3, alkali metal carbon acid ammonium salt etc.
Epoxidation process is in the liquid phase, under the existence of epoxidation catalyst, make the cumene hydroperoxide that obtains in the oxidation operation and excessive propylene reaction, obtains the operation of propylene oxide and cumic alcohol thus.
Consider and the separating of reactant that the preferred solid catalyst of catalyzer is considered to obtain object, the preferably solid catalyst that is made of the Si oxide that contains titanium under high yield and the high selectivity.These catalyzer preferably contain with Si oxide chemical bonded Ti, are so-called Ti-SiO 2 catalyst.Can list, for example, on silica supports, support the material of Ti compound, utilize coprecipitation method or sol-gel method and Si oxide compound material, or contain zeolite compound of Ti etc.
The cumene hydroperoxide of using as the raw material of epoxidation process can be thin or dense refining thing or non-refining thing.
By being contacted with catalyzer with cumene hydroperoxide, propylene carries out epoxidation reaction.Use solvent in liquid phase, to implement reaction.Solvent is a liquid under the temperature in when reaction and pressure, and should be for not having active material basically for reactant and product.Solvent also can be made of the material in the cumene hydroperoxide solution that is present in use.For example, cumene hydroperoxide is during with the mixture that constitutes as the cumene of product, and not special interpolation solvent can be with its surrogate as solvent.In addition, useful solvent can list, aromatic series monocyclic compound (for example benzene, toluene, chlorobenzene, orthodichlorobenzene) and alkane (for example octane, decane, dodecane) etc.
Epoxidation reaction temperature is generally 0～200 ℃, preferred 25～200 ℃.Pressure is that the abundant pressure that makes reaction mixture fully remain on liquid state gets final product.In general pressure is that 10～10000kPa is favourable.
Solid catalyst can advantageously be implemented with the form of slurry or fixed bed.When large-scale industry is operated, preferably use fixed bed.In addition, can utilize batch process, semi-continuous process, continuous processing to wait implements.
The mol ratio that is supplied to the propylene/cumene hydroperoxide of epoxidation process is preferably 2/1～50/1.Should be frequently 2/1 when too small, speed of response can reduce sometimes, deterioration of efficiency, and should be frequently 50/1 when excessive, the amount of the propylene of recirculation is excessive, needs a large amount of energy sometimes in recovery process.
As mentioned above, dehydration procedure and hydrogenation operation by the cumic alcohol that obtains in the epoxidation process being dewatered obtain alpha-methyl styrene, and then obtain cumene by hydrogenation, as the feedstock recycle of oxidation operation to oxidation operation.
Embodiment
The present invention will be described below by embodiment.
Embodiment 1
Be dehydration catalyst and be in the single reaction vessel of hydrogenation catalyst that catalyzer one side of dewatering certainly makes the cumene solution and the hydrogen that contain 25 weight % cumic alcohols flow through with up-flow being filled with successively with 60 weight % Cu/SiO 2s with the activated alumina.The pressure of this moment is 1MPaG, and temperature is 205 ℃ at reactor inlet, and 1.5 moles of the hydrogen of use are doubly to cumic alcohol, and gas line speed is 14cm/sec (being scaled normal temperature and pressure).The cumic alcohol transformation efficiency of activated alumina outlet is 99%, and the transformation efficiency of the alpha-methyl styrene of Cu/SiO 2 outlet is 99%, and whole cumene selection rate is 99%.
Embodiment 2
Removing reaction pressure is 1.4MPaG, uses 2.0 moles times beyond the hydrogen of cumic alcohol, implements with embodiment 1 the samely.The cumic alcohol transformation efficiency of activated alumina outlet is 99%, and the transformation efficiency of the alpha-methyl styrene of Cu/SiO 2 outlet is 99%, and whole cumene selection rate is 99%.
Embodiment 3
Be dehydration catalyst and be in the single reaction vessel of hydrogenation catalyst that catalyzer one side of dewatering certainly makes the cumene solution and the hydrogen that contain 25 weight % cumic alcohols flow through with up-flow being filled with successively with 0.05 weight % palladium/aluminum oxide with the activated alumina.The pressure of this moment is 1.4MPaG, and temperature is 205 ℃ at reactor inlet, and 1.5 moles of the hydrogen of use are doubly to cumic alcohol, and gas line speed is 14cm/sec (being scaled normal temperature and pressure).The cumic alcohol transformation efficiency of activated alumina outlet is 99%, and the transformation efficiency of the alpha-methyl styrene of palladium/aluminum oxide outlet is 99%, and whole cumene selection rate is 99%.
Industrial applicibility
As mentioned above, the present invention can provide the method for low cost and high efficiency manufacture cumene.
Claims (6)
1. the manufacture method of cumene is characterized in that, cumic alcohol and hydrogen are offered dehydration catalyst, obtains containing the alpha-methyl styrene He Shui of generation and the mixture of hydrogen; And this mixture offered hydrogenation catalyst.
2. the method for claim 1, wherein dehydration catalyst is an activated alumina.
3. the method for claim 1, wherein hydrogenation catalyst is the catalyzer that contains the metal of the periodic table of elements 10 families or 11 families.
4. method as claimed in claim 3, wherein, metal is palladium or copper.
5. the method for claim 1, wherein dehydration catalyst and hydrogenation catalyst are filled in the single fixed bed flow-through reactor.
6. the manufacture method of propylene oxide comprises:
Oxidation operation: obtain the operation of cumene hydroperoxide by cumene oxidation,
Epoxidation process: in the liquid phase, under the existence of epoxidation catalyst, make the cumene solution that contains cumene hydroperoxide and excessive propylene reaction, obtain the operation of propylene oxide and cumic alcohol thus,
Dehydration procedure: in the presence of dehydration catalyst, by the cumic alcohol that obtains in the epoxidation process being dewatered obtain the operation of alpha-methyl styrene,
The hydrogenation operation: in the presence of hydrogenation catalyst, the alpha-methyl styrene hydrogenation becomes cumic alcohol, as the feedstock recycle of oxidation operation operation to oxidation operation:
Wherein, comprise and utilize each described method of claim 1～5 to carry out the hydrogenation of the alpha-methyl styrene that dehydration and dehydration obtained of cumic alcohol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002371731 | 2002-12-24 | ||
| JP371731/2002 | 2002-12-24 | ||
| JP197750/2003 | 2003-07-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1732139A true CN1732139A (en) | 2006-02-08 |
| CN1325450C CN1325450C (en) | 2007-07-11 |
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ID=35964222
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200380107455 Expired - Fee Related CN1325450C (en) | 2002-12-24 | 2003-12-16 | Process for producing cumene |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679149B (en) * | 2007-05-23 | 2013-02-20 | 环球油品公司 | Process for producing cumene |
| CN102964199A (en) * | 2011-09-01 | 2013-03-13 | 中国石油化工股份有限公司 | Method for selective hydrogenation of methyl-alpha-methyl styrene |
| CN104109139A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Epoxypropane synthesis method |
| CN104277013A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Method for preparing epoxybutane |
| CN105315237A (en) * | 2014-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Synthetic method of 3,4-epoxy-1-butylene |
| WO2021058019A1 (en) | 2019-09-29 | 2021-04-01 | 中国石油化工股份有限公司 | Catalyst for use in production of cumene, and preparation method therefor and use thereof |
| CN113651664A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Method for conversion of benzyl alcohol |
-
2003
- 2003-12-16 CN CN 200380107455 patent/CN1325450C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679149B (en) * | 2007-05-23 | 2013-02-20 | 环球油品公司 | Process for producing cumene |
| CN102964199A (en) * | 2011-09-01 | 2013-03-13 | 中国石油化工股份有限公司 | Method for selective hydrogenation of methyl-alpha-methyl styrene |
| CN102964199B (en) * | 2011-09-01 | 2014-12-03 | 中国石油化工股份有限公司 | Method for selective hydrogenation of methyl-alpha-methyl styrene |
| CN104109139A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Epoxypropane synthesis method |
| CN104277013A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Method for preparing epoxybutane |
| CN105315237A (en) * | 2014-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Synthetic method of 3,4-epoxy-1-butylene |
| CN105315237B (en) * | 2014-07-03 | 2017-11-21 | 中国石油化工股份有限公司 | The synthetic method of the butylene of 3,4 epoxy 1 |
| WO2021058019A1 (en) | 2019-09-29 | 2021-04-01 | 中国石油化工股份有限公司 | Catalyst for use in production of cumene, and preparation method therefor and use thereof |
| CN113651664A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Method for conversion of benzyl alcohol |
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|---|---|
| CN1325450C (en) | 2007-07-11 |
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