CN101287690A - A method of making aromatic products - Google Patents
A method of making aromatic products Download PDFInfo
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- CN101287690A CN101287690A CNA2006800384109A CN200680038410A CN101287690A CN 101287690 A CN101287690 A CN 101287690A CN A2006800384109 A CNA2006800384109 A CN A2006800384109A CN 200680038410 A CN200680038410 A CN 200680038410A CN 101287690 A CN101287690 A CN 101287690A
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Abstract
A method of making an alkylaromatic compound comprises contacting an alkylatable aromatic hydrocarbon and a polyalkylaromatic compound in a transalkylation system to yield an alkylaromatic compound wherein at least a portion of the polyalkylaromatic compound has been formed by contacting an alkylatable aromatic hydrocarbon and an olefin at a location that is remote from the transalkylation system. The method may further comprise further reacting the alkylaromatic compound to produce one or more aromatic products.
Description
Technical field
The present invention relates to prepare the method for Alkylaromatics from alkylatable aromatic hydrocarbon and many Alkylaromatics.In certain embodiments, the invention further relates to by making Alkylaromatics further react the method for preparing aromatic product.
Background technology
Can be with aromatic alkylation to form Alkylaromatics, described Alkylaromatics can further react to form aromatic product such as alkenyl aromatic compound, phenolic compound and/or other products.The product of alkylation system also can comprise many Alkylaromatics, can make described many Alkylaromatics carry out transalkylation to obtain the monoalkylation aromatic substance, and described monoalkylation aromatic substance is further reacted to form aromatic product.
At U.S.3, disclose by making alkylatable aromatic hydrocarbon alkylation in 525,776, subsequently the method that the alkenyl aromatic hydrocarbon is produced in the monoalkylation aromatic substance dehydrogenation that obtains.Disclosed method comprises uses alkylation reactor, transalkylation reactor and dehydrogenation reactor.This method provides the separation of many alkylaromatics and they is recycled to transalkylation reactor they are converted into monoalkylation aromatic hydrocarbons, described monoalkylation aromatic hydrocarbons can be experienced dehydrogenation step suitably to obtain alkenyl aromatic compound.
U.S.4,169,111 disclose the alkylation of benzene and ethene in alkylation zone.A part of diethylbenzene that will produce in alkylation zone is recycled to this alkylation zone to improve catalyst life.Remaining diethylbenzene and other multi-ethyl phenenyl are fed to transalkylation reactor to be converted into ethylbenzene.
Summary of the invention
The objective of the invention is to improve the economy of preparation aromatic product.Another object of the present invention is the amount that is reduced in the alkylatable aromatic hydrocarbon of transporting to another position from a position in the preparation chain of aromatic product.
Another purpose of the present invention provides measure, the low-cost alkene of producing in some geographical position by this measure away from the alkyl aromatic reactive system can be economically as the indirect input of this alkyl aromatic reactive system.In the present context, the alkyl aromatic reactive system provides the Alkylaromatics reaction to generate the system of one or more aromatic products.
Therefore according to the present invention, a kind of method is provided, this method is included in alkylatable aromatic hydrocarbon is contacted with many Alkylaromatics to obtain Alkylaromatics, wherein forms the many Alkylaromatics of at least a portion by alkylatable aromatic hydrocarbon is contacted with alkene.
According to another embodiment of the invention, a kind of method is provided, this method is included in and makes the Alkylaromatics reaction to obtain alkenyl aromatic compound in the reactive system, wherein form at least a portion Alkylaromatics by alkylatable aromatic hydrocarbon is contacted with many Alkylaromatics in trans alkylation system, described many Alkylaromatics form in the position away from described trans alkylation system.
According to another embodiment of the present invention, a kind of method is provided, this method is included in and makes the Alkylaromatics reaction to obtain phenolic compound in the reactive system, wherein form at least a portion Alkylaromatics by alkylatable aromatic hydrocarbon is contacted with many Alkylaromatics in trans alkylation system, described many Alkylaromatics form in the position away from described trans alkylation system.
Description of drawings
Fig. 1 is the sketch of embodiment of the inventive method of preparation aromatic product.
The inventive method provides the economic vantage point away from the alkyl aromatic reactive system in the olefin feedstock source of preparation alkyl aromatic ingredient requirement.Make alkylation system can obtain many advantages away from the position of alkyl aromatic reactive system and/or away from trans alkylation system.Such advantage is the use that the favourable raw material of cost can be provided at each assembly that the location arrangements based on various raw material availabilities prepares chain.Therefore for example, the position of alkylation system can be near the source of the favourable alkene of cost, the favourable alkene of wherein this cost is imported with the raw material of doing alkylation system, and the final user of the close alkyl aromatic reactive system product in the position of alkyl aromatic reactive system, its position may be away from source olefins.
The inventive method can comprise following processing step: make alkylatable aromatic hydrocarbon carry out alkylation to form many Alkylaromatics, make many Alkylaromatics carry out transalkylation subsequently, described Alkylaromatics is further reacted to obtain one or more aromatic products to form Alkylaromatics.Alkylation can comprise delivers to alkylation reactor with the raw material that comprises alkylatable aromatic hydrocarbon and alkene, and it provides the production of many Alkylaromatics.
Alkylatable aromatic hydrocarbon to the raw material of alkylation reactor can comprise any suitable alkylatable aromatic hydrocarbon, and it comprises various substituted benzene compounds and benzene.The example of this alkylatable aromatic hydrocarbon comprises benzene, toluene, ethylbenzene, propyl benzene, butylbenzene, dimethylbenzene, diethylbenzene, two propyl benzene, two butylbenzene and high-molecular weight alkylaromatic hydrocarbons more.The alkylatable aromatic substance that is preferably used as the raw material of alkylation reactor is selected from following aromatic substance: benzene, toluene, ethylbenzene and propyl benzene.Benzene is most preferred alkylatable aromatic hydrocarbon.
To can comprise with the alkene that alkylatable aromatic hydrocarbon is fed to alkylation reactor can with any monoolefine of the alkylatable aromatic hydrocarbon reaction of alkylation reactor raw material, described raw material comprises the monoolefine of 2-5 carbon atom.The object lesson of possible alkene comprises the mixture of ethene, propylene, butylene, amylene and any combination thereof such as the mixture of ethene and propylene.Therefore, the alkylation reactor raw material can comprise alkene, and described alkene can comprise ethene or propylene or ethene and propylene.Alkene can comprise internal olefin and/or alpha-olefin.Internal olefin can comprise 2-butylene and/or 2-amylene.Alpha-olefin can comprise ethene, propylene and/or 1-butylene.
As mentioned above, alkylation system can comprise the alkylation reactor that is used to receive raw material for alkylation; Obtain many Alkylaromatics with it.This alkylation reactor can be to be suitable for providing any suitable equipment that contact of raw material for alkylation with alkylation catalyst under the alkylating reaction conditions of alkylatable aromatic hydrocarbon of alkylation system raw material.This equipment can comprise catalysis-distillation equipment.Therefore usually, the alkylation reactor equipment that is provided at contact raw material for alkylation suitable alkylation reaction condition under and the container that can comprise the reaction zone of determining to comprise alkylation catalyst.
The one side of the inventive method is to form many Alkylaromatics with alkylatable aromatic hydrocarbon alkylation.The many Alkylaromatics of term are represented the benzene molecular that replaces, wherein at least two of the phenyl ring six carbon atom alkyl that contain bonding as used herein.Therefore, many Alkylaromatics can comprise by two alkyl or three phenyl ring that alkyl replaces.Use alkylation step (it forms contrast with obtaining the monoalkyl aromatic substance, preferentially obtains many Alkylaromatics) that tangible economy, safety and other advantage can be provided.Such advantage is that its allows at it is that the position in the close source of olefin feedstock is advantageously arranged alkylation system economically, though this source may be geographically away from the source of alkylatable aromatic hydrocarbon with away from the position of alkyl aromatic reactive system.The inventive method is transported to the alkylation system place and provides these advantages as the amount of the alkylatable aromatic hydrocarbon of raw material by lowering the requirement; This is because the alkylatable aromatic hydrocarbon of using has alkene by the alkylated reaction load.
The alkylation degree of alkylatable aromatic hydrocarbon feedstock is high more, the alkylatable aromatic hydrocarbon feedstock that requirement is transported to the alkylation place more less and the conveying by many Alkylaromatics of producing by alkylation system, the alkene that is transported to transalkylation place and alkylaromatic hydrocarbon point of response from the alkylation place is many more.For this situation is described, with reference now to the synoptic diagram of Fig. 1, its aromatic product that has provided according to the inventive method embodiment prepares chain 10.Comprise alkylation system 12 in preparation chain 10, it provides the alkylation of alkylatable aromatic hydrocarbon by alkene.Alkene is fed to alkylation system 12 and alkylatable aromatic hydrocarbon is fed to alkylation system 12 by pipeline 16 by pipeline 14.Many Alkylaromatics are obtained and are transported to integration system 20 by handling equipment 26 from alkylation system 12, and it comprises trans alkylation system 22 and alkyl aromatic reactive system 24.Alkylatable aromatic hydrocarbon is fed to trans alkylation system 22 by pipeline 28.Obtain the aromatic product logistics from alkyl aromatic reactive system 24 by pipeline 30.This product stream can comprise one or more aromatic products.
Understanding requires one mole of alkene and one mole of alkylatable aromatic hydrocarbon for the every mole of aromatic product that produces in the material balance based on the stoichiometry productive rate (ignoring loss of yield) that passes through whole preparation chain 10.If the alkylatable aromatic hydrocarbon feedstock alkylation that will arrive alkylation system 12 is to form many Alkylaromatics such as dialkyl aromatic compound rather than monoalkyl aromatic substance, then inciting somebody to action still less for the every mole of aromatic product that produces by integration system 20, the alkylatable aromatic hydrocarbon of mole number is fed to alkylation system 12 to obtain the still less monoalkyl aromatic substance of mole number by alkylation with from alkylation system 12.But the minimizing of amount that will be fed to the alkylatable aromatic hydrocarbon of alkylation system 12 must be remedied by the alkylatable aromatic hydrocarbon of the equimolar amount of the trans alkylation system 22 that is fed to integration system 20.An advantage of this explanation the inventive method is to adopt alkylation step to be used for the alkylatable aromatic hydrocarbon amount that alkylation step requires with reduction, therefore increase the amount of alkene of every mole of alkylatable aromatic hydrocarbon of reacting in the alkylation step simultaneously, by improving position with alkylation system near source olefins but provide possible economic benefits away from the possibility in alkylatable aromatic hydrocarbon source.Under such situation, with substantially only be that the monoalkylation reaction is compared the time when alkylation step, the volume of the desired alkylatable aromatic hydrocarbon volume that will be transported to alkylation system and many Alkylaromatics of carrying from alkylation system is reduced by alkylated reaction.
For further specifying the useful feature of the inventive method, refer again to Fig. 1.Only obtain under the situation of monoalkyl aromatic substance from alkylation system 12 therein in the stoichiometry mode, for every mole of monoalkyl aromatic substance that obtains from alkylation system 12, make one mole of alkene and one mole of alkylatable aromatic hydrocarbon reaction, every mole of monoalkyl aromatic substance with to adding integration system 20 obtains one mole of aromatic product.The result that this is required typically; But employing the inventive method, what more wish is to form contrast with the monoalkyl aromatic substance to obtain many Alkylaromatics from alkylation system 12; With such productive rate of the many Alkylaromatics that are used to self-alkylation system 12, less alkylatable aromatic hydrocarbon consumes in alkylation system 12 to provide given aromatic product overall yield by preparation chain 10.Then by will for the alkylatable aromatic hydrocarbon of the residue that the productive rate of aromatic product requires introduce integration system 20 trans alkylation system 22 and with its adding.
In an example that uses benzene to transform, obtain at alkylation system 12 under the situation of dialkyl benzene, indicate for every mole of aromatic product that obtains through the mol balance of preparation chain 10, half (1/2) mole benzene is fed to alkylation system 12 to obtain half (1/2) mole dialkyl benzene with one mole of alkene.This half mole of dialkyl benzene is fed to trans alkylation system 22 with half (1/2) mole benzene, thereby transalkylation reaction wherein provides the one mole of monoalkylated benzenes that is fed to alkyl aromatic reactive system 24, obtains one mole of aromatic product.
Another example that uses benzene to transform is when alkylation system 12 obtains trialkyl benzene.In the case, indicate for every mole of aromatic product that obtains, 1/3rd (1/3) moles of benzene are fed to alkylation system 12 to obtain 1/3rd (1/3) moles of trialkyl benzene with one mole of alkene through the mol balance of preparation chain 10.These/3rd moles of trialkyl benzene are fed to trans alkylation system 22 with 2/3rds (2/3) moles of benzene, thereby transalkylation reaction provides the one mole of monoalkylated benzenes that is fed to alkyl aromatic reactive system 24, obtains one mole of aromatic product.
As can recognizing from above discussion, for the aromatic product through 10 productions of preparation chain of giving determined number, the inventive method allows the use of alkylatable aromatic hydrocarbon to be transformed into another position from a position.This reaches by operation alkylation system in help producing the operator scheme of many Alkylaromatics with respect to the monoalkyl aromatic substance.To make conversion of olefines be form that can easier conveying to alkylatable aromatic hydrocarbon molecule and compare with the situation when the manufacture order Alkylaromatics only by this loading of alkene, and the amount for the alkylatable aromatic hydrocarbon of alkylated reaction requirement is minimized.Therefore, the advantage of the inventive method is that the geographical position of alkylation system 12 can be near source olefins, particularly near low-cost source olefins, but away from alkylatable aromatic hydrocarbon or alkyl aromatic reactive system or the two through the Jiyuan.Trans alkylation system 22 can be arranged in such geographical position then, the more approaching alkylatable aromatic hydrocarbon in this geographical position through the Jiyuan or the aromatic product source of requirement, it is away from above-mentioned source olefins.
Any suitable alkylation catalyst known in the art can be used for alkylation step, but will be appreciated that many technical literatures have instructed that to need alkylation catalyst in conventional alkylation system be selectively to the productive rate or the monoalkylation of single alkylating aromatic hydrocarbon, and the polyalkylated amount of generation is minimized.But, for present method, compare with the instruction of expressing in many prior aries, need alkylation catalyst preferentially to provide many alkylations of alkylatable aromatic hydrocarbon to obtain many Alkylaromatics.Suitable alkylation catalyst is disclosed in patent such as U.S.3, and 525,776, U.S.3,751,504, U.S.3,763,259, U.S.4,169,111, U.S.4,393,262, U.S.4,876,408, U.S.5,081,323, U.S.5,177,280, U.S.5,243,116, U.S.5,530,170 and U.S.6,670,517, all these documents are hereby incorporated by.
The alkylation catalyst that is preferably used as the inventive method alkylation catalyst is that the productive rate to many Alkylaromatics has selectivity, and make the productive rate of undesirable by product such as ethene, propylene or butene low polymers or polymkeric substance minimized those.Undesirable side reaction comprise wherein a part of alkyl group side chain compartition those and wherein can cause those of ring such as indane and indenes closed loop.
Usually, alkylation catalyst can comprise hydrogen halide, halogenation boron, metal halide (for example halogenide of aluminium, zinc, iron or copper) and crystalline aluminosilicate, and all these materials have a detailed description in above-mentioned patent.In metal halide compound, preferably Freed pleasure-Kerafyrm thatch type catalytic cpd such as aluminum chloride.Some alkylation catalysts of more wishing that are used for the inventive method comprise crystalline aluminosilicate as at least a its component.The various adequate types crystalline aluminosilicates that are used for alkylation catalyst of the present invention have a detailed description and they can comprise that restricted index is about 1 to about 12 mesopore zeolite as being called those of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57 in above-mentioned patent.The mole that is used for the silicon-dioxide of zeolite of alkylation catalyst and aluminum oxide can surpass 12: 1 and preferred it above 30: 1.
Alkylation catalyst can comprise U.S. patent No.6,670, the ZSM-5 zeolite catalyst of the silica bound described in 517 or U.S. patent No.5, mesopore zeolite or the U.S. patent No.5 described in 530,170 by the siliceous material selectionization, 243, sour modified zeolite described in 116 or U.S. patent No.5, sealumination modified Y zeolite described in 177,280 or U.S. patent No.5, beta-zeolite catalyst described in 081,323.
An aspect of of the present present invention is about alkylation reaction condition, and the alkylation system raw material that comprises alkylatable aromatic hydrocarbon and alkene is contacted with alkylation catalyst so that the many alkylations of alkylatable aromatic hydrocarbon with respect to monoalkylation preferentially to be provided.In alkylatable aromatic hydrocarbon by alkene under the polyalkylated situation, alkylation reaction condition comprises alkylatable aromatic hydrocarbon low relatively in the alkylation system raw material and olefin molar ratio (alkylatable aromatic hydrocarbon and olefin molar ratio are hereinafter referred to as " alkylation ratio "), and this is because low alkylation ratio promotes many alkylations of alkylatable aromatic hydrocarbon.But in the prior art alkylation process, because many alkylations retarding effect of high alkylation ratio need have high alkylation ratio usually in the alkylation system raw material.The example of this inappropriate high alkylation ratio is to surpass 8.5: 1 high alkylation ratio or surpass 3: 1 alkylation ratio.
Can be to the low alkylation ratio of the raw material of alkylation step by reducing and the advantage that further provides with the cost of circular correlation separating of excessive alkylatable aromatic hydrocarbon with respect to common process.Owing to handle and circulation alkylatable aromatic hydrocarbon more in a small amount, also have the possibility that reduces the alkylation system equipment cost.
Can influence the alkylation ratio of the alkylation system raw material of requirement to the selectivity of many Alkylaromatics productive rate and its other catalytic performance although recognize alkylation catalyst, but normally this ratio should promote many alkylations of alkylatable aromatic hydrocarbon and typically it less than about 2.8: 1.But in order to operate alkylation system better, the alkylation ratio should be less than 2.5: 1 with preferably less than 2: 1.Most preferably, for the best productive rate of many Alkylaromatics, the alkylation ratio was less than 1.5: 1.
Usually, the alkene mole number of every mole of alkylatable aromatic hydrocarbon reaction can be at least 1.5 in many alkylated reactions, and the alkene mole number of the alkylatable aromatic hydrocarbon reaction of preferred every molar reactive can be at least 1.8 and most preferably at least or about 2.
The lower limit of alkylation ratio is determined by the actual process of considering following factor: the performance performance of alkylation catalyst, the separating power of process system and separate relevant cost with component.What excessively low alkylation ratio can promote alkene does not wish polymerization.Therefore, the alkylation ratio in the alkylation system raw material can surpass 0.1: 1 and be preferred above 0.2: 1.Most preferably the alkylation ratio in the alkylation system raw material was above 0.5: 1.Consider above situation, the alkylation ratio in the alkylation system raw material can be about 0.1: 1 to about 2.8: 1, more specifically 0.2: 1 to 2.5: 1.Preferably, this ratio is 0.5: 1 to 2: 1.
Alkylated reaction can carry out under liquid-phase condition or gas phase condition or blended liquid and gas phase condition, and certainly condition is that alkylation reaction condition makes and brings out many alkylations of alkylatable aromatic hydrocarbon.The amount of the monoalkylation reaction of generation is minimized, promote the amount of many alkylated reactions of generation simultaneously.On the meaning of directivity, higher temperature of reaction conditions favouring in many alkylations and lower temperature of reaction conditions favouring in monoalkylation.
The polyalkylated typical vapor phase alkylation condition that is used for alkylatable aromatic hydrocarbon and alkene can comprise about 340 ℃ (644 °F) to the alkylated reaction temperature of 480 ℃ (896), about normal atmosphere to about 20, the alkylated reaction pressure of 000kPa (2900psig) and about 0.5hr
-1To about 10hr
-1The weight hourly space velocity (WHSV) based on the alkene of alkylation system raw material.The mol ratio of alkylatable aromatic hydrocarbon and alkene as mentioned above.Understand the polyalkylated vapor phase alkylation condition that is used for alkylatable aromatic hydrocarbon and alkene and may be different from above those disclosed.
The polyalkylated typical liquid phase alkylation reaction condition that is used for alkylatable aromatic hydrocarbon and alkene can comprise about 25 ℃ (77 °F) to the alkylated reaction temperature of 450 ℃ (842), about normal atmosphere to about 20, the alkylated reaction pressure of 600kPa (3000psig) and about 0.5hr
-1To about 10hr
-1The weight hourly space velocity (WHSV) based on the alkene of alkylation system raw material.The mol ratio of alkylatable aromatic hydrocarbon and alkene as mentioned above.Understand the polyalkylated liquid phase alkylation reaction condition that is used for alkylatable aromatic hydrocarbon and alkene and may be different from above those disclosed.
The feature that is used for the inventive method of alkylation system is that physics is away from trans alkylation system.In fact, this respect of the present invention allows the physical location of alkylation system advantageously near low price alkene feed source, even the feed of alkylatable aromatic hydrocarbon may be limited when in these positions.Therefore, the position that relates to alkylation system herein means that away from the statement of other process system typically alkylation system is not communicated with trans alkylation system or alkyl aromatic reactive system fluid at least.Therefore, lacking fluid is communicated with and does not allow many Alkylaromatics to trans alkylation system or alkyl aromatic reactive system or to the direct transfer of two systems.Opposite because alkylation system than distant positions, its many Alkylaromatics must be transferred to by any suitable handling equipment and use the position of many Alkylaromatics as the trans alkylation system of transalkylation raw material.
Have the separation alkylation system of 80km (50 miles) and the distance of trans alkylation system at least in can meaning of mentioning of this consideration, but this distance can be greater than 300km (186 miles) or even greater than 800km (497 miles) than distant positions.In some cases, position far away may be even greater than the distance of 1500km (923 miles).
Imagine suitable handling equipment and comprise that use is transported to any of the various device of another physical location or method with fluid from a physical location, it comprises and for example uses assembling to be suitable for comprising any combination with groove truck, barge or ships that transport, railway jar or tank car, pipeline and the above-mentioned measure of the container of transporting fluid.Shifting by pipeline under the situation of many Alkylaromatics, typically many Alkylaromatics are being transported to jar or container and were used for before many Alkylaromatics are used as the transalkylation raw material its storage.
Be transported to trans alkylation system and comprise many Alkylaromatics as the alkylation products of transalkylation raw material.The many Alkylaromatics of term can comprise following compound: diethylbenzene, triethyl-benzene, tetrem benzene, five ethylbenzene, six ethylbenzene, two propyl benzene, diisopropylbenzene(DIPB), three propyl benzene, tri-isopropyl benzene, four propyl benzene, four isopropyl benzenes, five propyl benzene, five isopropyl benzenes, six propyl benzene, six isopropyl benzenes, two butylbenzene, three butylbenzene, four butylbenzene, five butylbenzene and six butylbenzene.But the many Alkylaromatics of more generally these are diethylbenzene, triethyl-benzene, diisopropylbenzene(DIPB) and tri-isopropyl benzene.
As the amount of many Alkylaromatics in the alkylation products of transalkylation raw material can for about 5wt% to about 80wt% or even extremely about 90wt% or 95wt% or 100wt%.Many Alkylaromatics content of preferred alkyl product is high as far as possible, so it may be 10-80wt%, preferably 15-80wt% and more preferably 20-75wt%.The monoalkyl aromatic substance also can exist, but the existence of these compounds is that amounts undesirable and these compounds existence usually are less than the 75wt% of alkylation products, preferably less than 50wt% with most preferably less than 30wt%.
The transalkylation step comprises the transalkylation reactor that above-mentioned many Alkylaromatics and alkylatable aromatic hydrocarbon as the transalkylation raw material are fed to trans alkylation system, and its transalkylation of many Alkylaromatics that alkylation products is provided is to obtain the monoalkyl aromatic substance.
As mentioned above, alkylation products preferably comprises many Alkylaromatics of real mass.More preferably, in the trans alkylation system raw material, there are the excessive many Alkylaromatics of stoichiometry.The amount of introducing the olefin(e) compound of transalkylation reactor with many Alkylaromatics and alkylatable aromatic hydrocarbon is minimized, so that favourable transalkylation reaction conditions to be provided.Therefore, the transalkylation reactor raw material should comprise the olefin(e) compound of non-real mass.Preferably arrive the 20wt% of the amount of alkene of transalkylation reactor less than the raw material gross weight that arrives transalkylation reactor.
As mentioned above, trans alkylation system comprises transalkylation reactor, and it is used to receive many Alkylaromatics and alkylatable aromatic hydrocarbon as the transalkylation raw material, and obtains comprising the transalkylation product of most of monoalkyl aromatic substance.Transalkylation reactor can be to be suitable for any suitable equipment that the trans alkylation system raw material is contacted with transalkylation catalyst under reaction conditions, and this reaction conditions is suitable for the many Alkylaromatics of trans alkylation system raw material and the transalkylation of alkylatable aromatic hydrocarbon.Therefore, usually, transalkylation reactor is provided at the equipment of contact transalkylation raw material under the suitable transalkylation reaction conditions and can comprises the container of the reaction zone of determining to comprise transalkylation catalyst.
May comprise or may not comprise one or more centrifugal stations with the alkyl aromatic reactive system and one or more reaction workshop section is relevant with all or the equipment of subordinate at this understanding trans alkylation system of mentioning and the alkylation system of in fact mentioning.Therefore, when mentioning the transalkylation product at this, understanding it can be the transalkylation reactor effluent, and its processing of having carried out separation or a series of isolated or purified or any other form is to provide the product that is suitable for use as alkyl aromatic reactive system raw material.Equally, referred in this term such as alkylation products or similar term should be understood to represent alkylation reactor effluent self or expression have been carried out separating or the processing of a series of isolated or purified or any other form with the alkylation reactor effluent of the product of transalkylation raw material that the transalkylation reactor that is suitable for use as trans alkylation system is provided.
Any suitable transalkylation catalyst known in the art can be used for the transalkylation step and recognizes that the catalyzer that can be used for abovementioned alkylization suitably also can be used as transalkylation catalyst suitably.Therefore, those above-mentioned alkylation catalysts also are can be as the same catalyst of transalkylation catalyst.Preferred zeolite transalkylation catalyst is described in detail in U.S. patent No.6,670,517.
Transalkylation reaction conditions is similar in appearance to the alkylation reaction condition that early defines, wherein the transalkylation reaction temperature is that 25 ℃ (77 °F) are to 480 ℃ (896 °F), transalkylation reaction pressure is extremely about 20 for about normal atmosphere, 000kPa (2900psig) and be 0.5hr based on the weight hourly space velocity (WHSV) of the summation of many Alkylaromatics and alkylatable aromatic hydrocarbon feedstock
-1To 10hr
-1
As mentioned above, Alkylaromatics can be further processed in the alkyl aromatic reactive system or further react to obtain one or more products.The one side of the inventive method is the place of alkylaromatic hydrocarbon reactive system, and the position of this system can and separate with it away from the place of alkylation system.The feature of preferred alkyl transfer system and alkyl aromatic reactive system is the part of integration system, wherein they is connected in identical geographical position or combine to make the alkyl aromatic reactive system easily to receive not need as the transalkylation product of its raw material the distance of carrying the transalkylation product bigger.Trans alkylation system and alkyl aromatic reactive system operability are connected to be provided at two fluid flow communications between the system, especially, make fluid flow communication allow the transalkylation product is directly introduced the alkyl aromatic reactive system from trans alkylation system.
The specific embodiments of alkyl aromatic reactive system comprises further reacts to produce the system of alkenyl aromatic compound Alkylaromatics.The example of these systems is the dehydrogenation system of producing vinylbenzene and hydrogen, the system that produces cinnamic SM/PO type process and produce alpha-methyl styrene or p-methylstyrene.Other embodiment comprises further reacts to produce the system of phenolic compound Alkylaromatics.The example of these systems is to form cumene hydroperoxide and adopt acid catalyst to make hydroperoxide decomposition with the system that produces phenol and acetone with form sec-butylbenzene hydroperoxide and adopt the system of acid treatment hydroperoxide with production phenol and methylethylketone then then.
In addition, possible is that Alkylaromatics is not further processed.Some embodiments of alkyl aromatic reactive system below are described in further detail.
In one embodiment, the alkyl aromatic reactive system comprises the dehydrogenation system that obtains alkenyl aromatic compound and hydrogen.In the case, preferably alkene is ethene; Preferred many Alkylaromatics comprise diethylbenzene and/or triethyl-benzene; With preferred transalkylation product be ethylbenzene.In preferred dehydrogenation system, the dehydrogenation reactor of dehydrogenation system can provide any suitable equipment that contacts of transalkylation product and dehydrogenation catalyst, with generally include the dehydrogenation reactor container, it determines dehydrogenation reaction zone and can comprise dehydrogenation catalyst particles that this dehydrogenation catalyst particles is seated in usually together to form the dehydrogenation catalyst bed.
Dehydrogenation catalyst can be any known iron or Iron oxide based catalysts, and it can be used for the dehydrogenation of Alkylaromatics suitably.These dehydrogenation catalysts comprise those catalyzer that contain ferriferous oxide.The ferriferous oxide of dehydrogenation catalyst can be for any form with from any source of the suitable iron oxide material that is provided for the ferriferous oxide based dehydrogenation catalyst or obtain by any method.A kind of required especially ferriferous oxide based dehydrogenation catalyst comprises potassium oxide and ferriferous oxide.
The ferriferous oxide of ferriferous oxide based dehydrogenation catalyst can be various forms, and it comprises one or more ferriferous oxides such as iron oxide yellow (pyrrhosiderite, FeOOH), iron oxide black (magnetite, Fe
3O
4) and red iron oxide (rhombohedral iron ore, Fe
2O
3) (comprising synthetic rhombohedral iron ore or regenerated ferriferous oxide), or it can combine with potassium oxide to form potassium ferrite (K
2Fe
2O
4), or it can combine to form one or more by general formula (K with potassium oxide
2O) x (Fe
2O
3) y represent comprise iron and potassium mutually.
Typical ferriferous oxide based dehydrogenation catalyst comprises as Fe
2O
3The 10-98wt% ferriferous oxide that calculates and at the most 40wt% as K
2The potassium that O calculates.The promoter metals that it is oxide compound that the ferriferous oxide based dehydrogenation catalyst can further comprise one or more common forms.These promoter metals can be selected from any two or more the mixture in Sc, Y, La, Mo, W, Ce, Rb, Ca, Mg, V, Cr, Co, Ni, Mn, Cu, Zn, Cd, Al, Sn, Bi, rare earth and they.In promoter metals, preferably be selected from any two or more those of mixture in Ca, Mg, Mo, W, Ce, La, Cu, Cr, V and they.Most preferably be Ca, Mg, W, Mo and Ce.
Can be suitably can in following patent publication us, find: U.S. patent disclosure No.2003/0144566A1, U.S. patent No.5,689,023, U.S. patent No.5 as the description of the typical ferriferous oxide based dehydrogenation catalyst of dehydrogenation catalyst, 376,613, U.S. patent No.4,804,799, U.S. patent No.4,758,543, U.S. patent No.6,551,958 B1 and EP 0,794,004 B1, all these patent publication us are hereby incorporated by.
Iron oxide based catalysts prepares by any method known to those skilled in the art.Usually, the ferriferous oxide based dehydrogenation catalyst that comprises potassium oxide and ferriferous oxide can be by following operation preparation: mix the component of iron containing compounds and potassium-containing compound, with these component moulding to form particle and this particle of calcining.Also can be with the compound that contains promoter metals with the iron content component with contain the potassium component and mix.
Catalyst component can be shaped to particle such as extrudate, pellet, tablet, ball, ball, saddle, trilobal thing, quatrefoil thing etc.A kind of preferred method of preparation iron based dehydrogenation catalyst is catalyst component and water or softening agent or both are mixed and can to extrude the paste moulding, from this paste formation extrudate.Dry then and calcining extrudate.Calcining is preferably carried out in oxidizing atmosphere such as air and under the temperature of 1200 ℃ at the most (but being preferably 500-1100 ℃, most preferably 700-1050 ℃).
Recognize that dehydrogenation reactor or dehydrogenation reactor system can comprise more than a dehydrogenation reactor or reaction zone.If use more than a dehydrogenation reactor, they can be operated by serial or parallel connection, or they can be operated independently of one another or under identical or different processing condition.
Dehydrogenation condition can comprise about 500 ℃ to about 1000 ℃, preferred 525-750 ℃ and 550-700 ℃ dehydrogenation reactor temperature in most preferably.Therefore, first temperature of dehydrogenation catalyst bed can be about 500 ℃ to about 1000 ℃, more specifically 525-750 ℃ and 550-700 ℃ the most particularly.
Reaction pressure relatively low and can for from vacuum pressure to about 172kPa (25psia).Liquid hourly space velocity (LHSV) can be about 0.01hr
-1To about 10hr
-1And preferred 0.1hr
-1To 2hr
-1Term " liquid hourly space velocity " is defined as in standard state (promptly 0 ℃ and 1kPa absolute pressure) if the dehydrogenation feed of the measuring cumulative volume of the liquid volume flow of ethylbenzene beds divided by the volume of beds or when having two or more beds for example down as used herein.When vinylbenzene prepares by ethylbenzene dehydrogenation, need the steam of employing 0.1 to 20 and the mol ratio of ethylbenzene to use steam usually as thinner.Steam also can be as the thinner that adopts other dehydrogenatable hydrocarbon.
In another embodiment of alkyl aromatic reactive system, provide the dehydrogenation of transalkylation product can comprise so-called SM/PO (styrene monomer/propylene oxide) process system with the dehydrogenation system that obtains styrene product.In the case, preferably alkene is ethene; Preferred many Alkylaromatics comprise that diethylbenzene and/or triethyl-benzene and preferred transalkylation product are ethylbenzene.SM/PO technology provides the oxidation of ethylbenzene, the ethylbenzene that the transalkylation product for example is provided by the oxidation of oxygen to obtain ethylbenzene hydroperoxide, make the reaction of this ethylbenzene hydroperoxide and propylene to form propylene oxide and pure by product, handle this alcohol by product with the production styrene product.
SM/PO technology is known in the art.In the oxidation step of SM/PO technology, the liquid-phase oxidation that ethylbenzene becomes ethylbenzene hydroperoxide 100-160 ℃, suitably under 130-150 ℃ the temperature and, carry out under the pressure of 2-3 crust suitably at the 1-4 crust.Oxidation typically adopts air to carry out as being used for the oxygen source of oxidizing gas, wraps oxygen containing any fluid suitably but also can use.The main by product that forms in this of SM/PO technology is a methyl phenyl ketone in stage, its can hydrogenation for being used for dehydrating step to produce cinnamic 1-phenylethyl alcohol.
In the epoxidation step of SM/PO technology, make the reaction of ethylbenzene hydroperoxide and propylene to obtain propylene oxide and 1-phenylethyl alcohol or to replace the 1-phenylethyl alcohol.In this epoxidation step, can adopt homogeneous catalyst or heterogeneous catalyst.As homogeneous catalyst, adopt molybdenum compound usually, and be used as heterogeneous catalyst usually based on the catalyzer of the titanium on the silica supports.
To carry out epoxidised condition be known in the art and typically comprise 75-150 ℃ temperature and the pressure and the reaction mediums of 80 crust are liquid phase at the most.In epoxidation step, alkyl aryl hydroperoxide is contacted to obtain oxirane compound and hydroxyalkyl aryl with alkene.The catalyzer that can be used for this step suitably comprises the titanium on silicon-dioxide and/or silicate.Preferred catalyzer is described in EP-B-345856, and the disclosure of the document is hereby incorporated by.Reaction under proper temperature and pressure, is carried out under 0-200 ℃, preferred 25-200 ℃ temperature usually especially.Accurate pressure is not crucial, as long as it is enough to keep reaction mixture under the liquid condition.Normal atmosphere may be gratifying.Usually, pressure can be about 1 to about 100 * 10
5N/m
2
Normally, at first will carry out separating treatment from the effluent of epoxidation step to remove the propylene oxide of formation, the residual stream that will comprise the 1-phenylethyl alcohol is thereafter carried out one or more further separating treatment suitably especially removing ethylbenzene, thereby is used further to the stage early of technology.The logistics experience dehydrating step that contains the 1-phenylethyl alcohol that will finally obtain then.
It also is known in the art that the 1-phenylethyl alcohol becomes cinnamic dehydration.It can carry out in gas phase or in liquid phase or in gas phase He in the liquid phase.Suitable dehydration catalyst comprises for example acid material such as aluminum oxide, soda alumina, pure aluminium silicate and H-type synthetic zeolite.Dehydration conditions also is known and generally includes for liquid-phase dehydration 100-210 ℃ temperature of reaction with for gas-phase dehydration 210-320 ℃, 280-310 ℃ temperature of reaction typically.Pressure is generally 0.1 to crust.Obtain comprising cinnamic dehydrogenation product from the dehydrating step of SM/PO process system.
In another embodiment of alkyl aromatic reactive system, the phynol/acetone preparation system provides the propyl benzene of transalkylation product to transform to obtain comprising phenol or acetone or their both phynol/acetone products.In the case, preferably alkene is propylene; Preferred many Alkylaromatics comprise that diisopropylbenzene(DIPB) and/or tri-isopropyl benzene and preferred transalkylation product are isopropyl benzenes.The phynol/acetone preparation system can be any treatment system that the conversion of isopropyl benzene to phenol is provided suitably well known by persons skilled in the art.But, preferably provide the aerial oxidation of isopropyl benzene forming the system of cumene hydroperoxide, cumene hydroperoxide under acidic conditions compartition to form phenol and acetone.Therefore, the phynol/acetone preparation system can comprise two steps, and one of them step is that oxidation step and another step are hydroperoxide compartition steps.
The cumene oxidation step is carried out in the presence of alkaline medium and under oxidation reaction condition in liquid phase usually.With oxygen-containing gas such as air under suitable oxidizing temperature and pressure condition by or bubbling pass through isopropyl benzene.Usually, it is 1-10 with oxidative pressure that oxidizing temperature is 40-180 ℃, 000kPa (1-100 crust) absolute pressure.Can use those skilled in the art known and be applicable to that isopropyl benzene sees U.S. patent No.6 to an any other method of the oxidation of cumene hydroperoxide and a description of this suitable method for oxidation, 043,399, this patent is hereby incorporated by.
The cumene hydroperoxide experience hydroperoxide compartition step that will obtain from the first step of phynol/acetone preparation system then, thus in the presence of suitable acid compound, cumene hydroperoxide is transformed by acid catalyzed compartition reaction.Typically, sulfuric acid is the appropriate acid of catalysis compartition reaction, but can use the acid of other type and even have an acid active solid heterogeneous catalyzer.Usually, it is 1-10 with the compartition reaction pressure that the compartition temperature of reaction is 40-180 ℃, 000kPa (100 crust) absolute pressure.
Known and any method that be suitable for the compartition of cumene hydroperoxide of those skilled in the art can be used for second step of phynol/acetone preparation system.The example of the whole bag of tricks that can use suitably is included in U.S. patent No.4, and 490,565, U.S. patent No.4,567,304, U.S. patent No.5,371,305 and U.S. patent No.6, those that describe in 225,513, all these documents are hereby incorporated by.
Obtain the phynol/acetone product from the phynol/acetone preparation system.Term phynol/acetone product means any or multiple product logistics of obtaining from the cumene hydroperoxide acid catalysis compartition step of phynol/acetone preparation system and the single product stream that can comprise entire reaction effluent logistics (it comprises phenol and acetone) or obtain from separating of the various components of compartition reaction effluent logistics so that phenol product logistics or product acetone logistics or other logistics such as residual stream to be provided as used herein.
In another embodiment, some or all of isopropyl benzenes can be substituted by sec-butylbenzene.The aromatic product that obtains can comprise phenol and one or more product streams can comprise methylethylketone and acetone in addition.In the case, preferably alkene is 1-butylene and/or 2-butylene; Preferred many Alkylaromatics comprise that many butylbenzenes and preferred transalkylation product are sec-butylbenzenes.
The inventive method can comprise uses alkylation system making first alkylatable aromatic hydrocarbon and the olefine reaction under suitable alkylation reaction condition, thereby forms the alkylation products that comprises a large amount of many Alkylaromatics.Trans alkylation system is used for making the second alkylatable aromatic hydrocarbon and the reaction of many Alkylaromatics under suitable transalkylation reaction conditions, thereby forms the transalkylation product that comprises Alkylaromatics.Dehydrogenation system can be used for dehydrogenation transalkylation product, thereby obtains dehydrogenation product.The dehydrogenation system of the inventive method can further be positioned at away from the position of alkylation system and trans alkylation system and can unite with dehydrogenation system, and therefore, trans alkylation system and alkylation system are separated.The first and second alkylatable aromatic hydrocarbons can comprise benzene.
The inventive method can comprise that the raw material for alkylation that will comprise benzene and ethene is fed to alkylation system, obtain comprising the multi-ethyl phenenyl product of multi-ethyl phenenyl by alkylation system, after this step, benzene and multi-ethyl phenenyl product are fed to trans alkylation system as the transalkylation raw material, obtain comprising the transalkylation product of ethylbenzene by trans alkylation system.Then the transalkylation product is fed to dehydrogenation system as dehydrogenation feed, obtains comprising cinnamic styrene product by dehydrogenation system.This embodiment of the present invention can comprise further the multi-ethyl phenenyl product is transported to trans alkylation system by handling equipment that the position of trans alkylation system is away from the alkylation system that wherein carries out the transalkylation step.Trans alkylation system also can be united with dehydrogenation system, and therefore, trans alkylation system can be separated with alkylation system.
The inventive method can comprise by the alkyl aromatic raw material that is provided for the alkyl aromatic dehydrogenation unit from the method for the first alkylatable aromatic hydrocarbon and olefin production vinyl aromatic compounds, the position of this alkyl aromatic dehydrogenation unit is away from the position of many alkylation, and wherein alkyl aromatic dehydrogenation unit and transalkylation are united.Thereby this method is included in and makes the described first alkylatable aromatic hydrocarbon alkylation to form many alkyl aromatics product under many alkylation reaction conditions, and it comprises a large amount of many Alkylaromatics.Many alkyl aromatics product is transported to position far away, thereby it obtains alkyl aromatic raw material and the alkyl aromatic raw material dehydrogenation feed as the alkyl aromatic dehydrogenation unit as the transalkylation raw material of transalkylation there, thereby obtain dehydrogenation product.
Can in the scope of described disclosure and appended claims, reasonably change, improve and adjust and do not deviate from scope of the present invention.
Claims (10)
1. method comprises:
Alkylatable aromatic hydrocarbon is contacted with many Alkylaromatics obtaining Alkylaromatics,
Wherein, alkylatable aromatic hydrocarbon forms the many Alkylaromatics of at least a portion by being contacted with alkene.
2. the method for claim 1 further comprises described Alkylaromatics is further reacted to obtain alkenyl aromatic compound.
3. claim 1 or 2 method, wherein further reaction comprises the dehydrogenation reaction that obtains alkenyl aromatic compound and hydrogen.
4. the method for claim 1 further comprises described Alkylaromatics is further reacted to obtain phenolic compound.
5. each method of claim 1-4, wherein said alkylatable aromatic hydrocarbon comprises benzene.
6. each method of claim 1-5, wherein said alkene comprises ethene.
7. each method of claim 1-5, wherein said alkene comprises propylene.
8. claim 2 or 4 method, wherein said trans alkylation system is communicated with the reactive system fluid that wherein carries out described further reaction.
9. method comprises:
Make Alkylaromatics reaction obtaining alkenyl aromatic compound or phenolic compound,
Wherein in trans alkylation system, form at least a portion Alkylaromatics and formed many Alkylaromatics in position away from described trans alkylation system by alkylatable aromatic hydrocarbon is contacted with many Alkylaromatics.
10. the method for claim 9, wherein said reaction comprises the dehydrogenation reaction that obtains alkenyl aromatic compound and hydrogen.
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| US71770605P | 2005-09-16 | 2005-09-16 | |
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