CN1328231C - Modified method for producing alkylbenzene - Google Patents
Modified method for producing alkylbenzene Download PDFInfo
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- CN1328231C CN1328231C CNB2004100711160A CN200410071116A CN1328231C CN 1328231 C CN1328231 C CN 1328231C CN B2004100711160 A CNB2004100711160 A CN B2004100711160A CN 200410071116 A CN200410071116 A CN 200410071116A CN 1328231 C CN1328231 C CN 1328231C
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Abstract
The present invention relates to an improved production method for alkylbenzene. Benzene and alkene which are raw materials enter a multi-section alkylation reactor system which can replace an alkylation reaction zone to react; at least a stream of reaction effluents are led out from spaces between every two reaction zones of the alkylation reactor or an outlet of the reactor to be used as a circulation material flow, and the effluents independently or simultaneously flow back to an inlet of any reaction zone before the circulation material flow leading-out section in an external circulation mode; benzene, monoalkyl benzene, polyalkylbenzene and heavy components can be obtained after the reaction the effluents are separated, wherein the benzene and the polyalkylbenzene enter an alkyl transfer reactor to carry out alkyl transfer reaction under the function of an alkyl transfer catalyst, and partially or all reaction effluents can be circulated into the alkylation reactor as well as can be completely separated. Because the method establishes a multi-section alkylation reactor which can replace an alkylation reaction zone, the operation can be more flexible, and the method is more suitable for the operating conditions of low benzene-alkene ratio and high air speed; thus, the operating cycle of the device is effectively extended.
Description
Technical field
The present invention relates to a kind ofly prepare the method for hydrocarbon from the less hydrocarbon of carbon atom quantity, more particularly, is a kind of method of producing alkylbenzene from low-carbon alkene and benzene.
Background technology
Ethylbenzene is important Organic Chemicals, is mainly used in production vinylbenzene.The vinylbenzene of producing by the method for ethylbenzene catalytic dehydrogenation accounts for 90% of its throughput.In recent years, cinnamic purposes constantly enlarges, and demand is growing, and by 2000, cinnamic in the world ultimate production was increased to 2,000 ten thousand tons/year.Isopropyl benzene is a raw material of producing phenol, acetone, and the device that adopts cumene method to produce phenol, acetone accounts for more than 90%.Once prediction, their demand will be with annual 3%～4% speed increment.Therefore, be that the alkylation production technique development of raw material is very fast with alkene and benzene.
Because traditional alkylbenzene production technique-AlCl
3Method and solid phosphoric acid method have shortcomings such as deep-etching, high pollution, and the method for present industrial production ethylbenzene, isopropyl benzene is comprised molecular sieve vapor-phase alkylation method and molecular sieve liquid-phase alkylation method mostly by the processing method by catalyzer substitutes with the molecular sieve.Especially the molecular sieve liquid phase method few, pollution-free with its reaction conditions mitigation, selectivity height, impurity, do not have characteristics such as corrosion, become the environmentally friendly technology that each major company competitively develops and promotes in recent years.
CN1128249A discloses a kind of in the presence of zeolite catalyst, is the method for the liquid-phase alkylation production alkylbenzene of raw material with alkene and benzene.This method is in one section recirculation reactor that contains zeolite catalyst, with by fresh benzene, to reclaim the mixture that the part effluent behind benzene, fresh alkene and the alkylated reaction forms be raw material, carries out alkylated reaction under the reaction conditions that suits.This method only adopts the reactor of one section beds, with the recycle stock of section port material as the Returning reactor inlet, controls the reaction bed temperature rise and guarantee that alkene dissolves in reaction mass by adjusting its flow.The problem that this method does not exist each reaction zone to mate mutually, its deficiency is: the alkylbenzene and the easy coking heavy constituent impurity that contain higher concentration in the alkylation reactor outlet material, loop back reactor inlet and make alkylbenzene and heavy constituent excessive concentration in the reactor inlet material, the direction that can cause on the one hand during with olefine reaction reacting to generating polyalkylbenzene is carried out, and influences the selectivity of purpose product monoalkylated benzenes; Coking deactivation that on the other hand can accelerator activator.
CN1217310A discloses a kind of alkylbenzene production technique, this technology is in the presence of alkylation catalyst, benzene feedstock enters in the reactor that contains two sections alkylation catalysts at least, and the benzene feedstock that enters first section of alkylation reactor at least generates alkylbenzene with the raw material ethylene reaction that enters each section of alkylation reactor.An alkylated reaction effluent liquid part is returned alkylation reactor with external circulation mode, and another part enters transalkylation reactor with after polyalkylbenzene from the polyalkylbenzene tower mixes, and generates alkylbenzene under the effect of molecular sieve catalyst.Each section of alkylation reactor adopts intermediate heat segmentation heat-obtaining, controls the temperature of each conversion zone.The problem of this flow process mainly contains two: the alkylbenzene and the easy coking heavy constituent impurity that 1. contain higher concentration in the alkylation reactor outlet material, being back to reactor inlet makes and alkylbenzene and heavy constituent excessive concentration in the reactor inlet material will influence the selectivity of purpose product monoalkylated benzenes; And the coking deactivation of meeting accelerator activator.2. because first section catalyzer contact reacts material at first, and adsorbed more detrimental impurity, and the detrimental impurity of second section and the absorption of catalyzer afterwards is less relatively, causes second section catalyzer of first section catalyst deactivation velocity ratio to want fast.Because recycle stock is to return first section inlet, when this section catalyzer elder generation inactivation,, cause the operating time of each section to be difficult for coupling mutually with the reaction that influences second section.
CN1428319A discloses a kind of production method of alkylbenzene.Benzene feedstock and alkene enter the alkylation reactor reaction that is made of the multistage reaction zone, from drawing one reaction effluent between the conversion zone of alkylation reactor at least as recycle stream, turn back to the inlet of the arbitrary conversion zone before the recycle stream section of drawing individually or simultaneously with external circulation mode, contain benzene and alkylbenzene in the recycle stream.This invention can reduce the generation of polyalkylbenzene effectively, improves the selectivity of purpose product monoalkylated benzenes; Can reduce heavy seeds content in the reaction feed effectively, delay the coking and deactivation of catalyzer; Low benzene alkene be can adapt to more than processing condition, operation energy consumption and investment reduced; Has reduced because of the influence to the whole alkylated reaction system operation cycle of the difference of deactivation rate in selective reaction zone more neatly.But owing to be subjected to the restriction of operational condition, the operational cycle of each reaction zone can't mate fully mutually.
CN1285810A discloses a kind of particularly method of ethylbenzene and isopropyl benzene of Alkylaromatics of producing.This method is reacted benzene and polyalkylbenzene mixing raw material introducing transalkylation reaction zone earlier, and then, the effluent of transalkylation reaction zone directly enters alkylation zone with alkene again, and reaction generates monoalkylated benzenes and polyalkylbenzene under the effect of alkylation catalyst.First of alkene is introduced the downstream of point in transalkylation reaction zone.This patent wherein one what is claimed is a part that will comprise the total effluent of alkylation and be recycled to transalkylation or alkylation zone.The deficiency of this method is: transalkylated product is directly sent into alkylation zone without separating, wherein monoalkylated benzenes and polyalkylbenzene content are higher, unfavorable to the purpose product selectivity, owing in the transalkylated product more heavies is arranged, will greatly influence the life-span of alkylation catalyst in addition.
USP6,008,422 discloses a kind of liquid phase alkylation reaction of arene technology of carrying out in many beds alkylation reactor.The product of alkylated reaction is divided into three parts: first part loops back the inlet of alkylation reactor, loops back one section of reactor or several sections beds after the second section condensation, and third part removes to isolate target product.This patent also exists the CN1217310A similar problem.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of improved alkylbenzene production method, set up the cycle of operation of alternative alkylation reaction zone with extension fixture.
Method provided by the invention comprises:
(1), the alkylation of benzene and alkene
Benzene feedstock, raw material olefin, alkylated reaction recycle stream and optional transalkylation reaction effluent enter the built-up type alkylation reactor system that is made of a plurality of beds, this system comprises alternative alkylation reaction zone and irreplaceable alkylation reaction zone, alkylated reaction takes place in above-mentioned material under the effect of alkylation catalyst, separate the alkylated reaction effluent and obtain benzene, monoalkylated benzenes, polyalkylbenzene and heavy constituent;
(2), the part of alkylated reaction effluent circulation
Draw from the outlet of arbitrary conversion zone of built-up type alkylation reactor system, recycle stream turns back to the inlet of the arbitrary conversion zone before the recycle stream section of drawing individually or simultaneously with external circulation mode;
(3), switch alternative alkylation reaction zone
When stopping using during alkylation catalyst deactivation in alternative alkylation reaction zone, benzene feedstock, raw material olefin, alkylated reaction recycle stream and optional transalkylation reaction effluent enter all the other alkylation reaction zone reactions; Behind the alkylation catalyst after the alkylation catalyst of inactivation in alternative alkylation reaction zone is replaced by fresh and/or regeneration, in alternative alkylation reaction zone incision alkylated reaction system;
(4), the transalkylation of benzene and polyalkylbenzene
Enter transalkylation reactor from isolating benzene of step (1) and polyalkylbenzene, under the effect of transalkylation catalyst, transalkylation reaction takes place;
(5), the processing of transalkylation reaction effluent
The transalkylation reaction effluent can have three kinds of whereabouts: the one, and all be circulated to built-up type alkylation reactor system and proceed alkylated reaction, the 2nd, a part is circulated to built-up type alkylation reactor system and proceeds alkylated reaction, another part goes to separate, and the 3rd, all go to separate;
(6), product separates
Alkylated reaction effluent and optional transalkylation reaction effluent carry out fractionation together and obtain benzene, monoalkylated benzenes, polyalkylbenzene and heavy constituent, wherein a benzene part of Hui Shouing is returned the built-up type alkylation reactor system of step (1), another part is as the raw material of transalkylation, polyalkylbenzene is also as the raw material of transalkylation, monoalkylated benzenes is that purpose product alkylbenzene goes out device, and heavy constituent go out device as by product.
Method provided by the invention adopts reaction effluent partly to circulate, and the method for setting up alternative alkylation reaction zone, make operation more flexible, be applicable to the operating mode of low benzene alkene ratio and high-speed more, prolonged the cycle of operation of device effectively, simultaneously, the characteristics of invention CN1428319A have also been continued to keep.
Description of drawings
Accompanying drawing 1～5 is the alkylbenzene production method principle flow chart of interchangeable alkylation reaction zone provided by the invention when alkylated reaction system different positions.
Accompanying drawing 6 is an alkylbenzene production method idiographic flow synoptic diagram provided by the invention.
Embodiment
Method provided by the invention is so concrete enforcement:
Benzene feedstock, raw material olefin, alkylated reaction recycle stream and optional transalkylation reaction effluent enter the built-up type alkylation reactor system that is made of a plurality of beds, this system comprises alternative alkylation reaction zone and irreplaceable alkylation reaction zone, and above-mentioned material under the effect of alkylation catalyst alkylated reaction takes place.Alkylation reaction condition is: 80～350 ℃ preferred 120～300 ℃ of temperature; Preferred 1.0～the 6.0MPa of pressure 0.1～12.0MPa; The mol ratio of benzene feedstock and raw material olefin (benzene alkene than) is 0.1～50 preferred 1～30 most preferably 1.2～15; Every section bed inlet benzene alkene mol ratio is 1～80 preferred 3～60 most preferably 6～40; Mol ratio 0.1～100 preferred 1～40 optimum of phenyl and alkyl chooses 2～30 in the reaction mass.Separate the alkylated reaction effluent and obtain benzene, monoalkylated benzenes, polyalkylbenzene and heavy constituent.
Recycle stream is drawn from the outlet of the arbitrary conversion zone of built-up type alkylation reactor system, turns back to the inlet of the recycle stream section of drawing arbitrary conversion zone before individually or simultaneously with external circulation mode.The weight ratio (abbreviation recycle ratio) of the load of recycle stock amount and the reaction zone section of drawing (not containing the recycle stock amount) is 0.001～30 preferred 0.05～15 most preferably 0.05～10.The present invention also can draw one reaction effluent as recycle stream at least from last conversion zone outlet of alkylation reactor.
When stopping using during alkylation catalyst deactivation in alternative alkylation reaction zone, benzene feedstock, raw material olefin, alkylated reaction recycle stream and optional transalkylation reaction effluent enter all the other alkylation reaction zone reactions; Behind the alkylation catalyst after the alkylation catalyst of inactivation in alternative alkylation reaction zone is replaced by fresh and/or regeneration, in alternative alkylation reaction zone incision alkylated reaction system.The reaction conditions of interchangeable alkylation zone is: 80～350 ℃ preferred 120～300 ℃ of temperature; Preferred 1.0～the 6.0MPa of pressure 0.1～12.0MPa; The mol ratio of benzene feedstock and raw material olefin (benzene alkene than) is 0.1～50 preferred 1～30 most preferably 1.2～15; Every section bed inlet benzene alkene mol ratio is 1～80 preferred 3～60 most preferably 6～40, and mol ratio 0.1～100 preferred 1～40 optimum of phenyl and alkyl chooses 2～30 in the reaction mass.
Isolating polyalkylbenzene and benzene enter in the transalkylation reactor, carry out transalkylation reaction under the effect of transalkylation catalyst, and transalkylation reaction conditions is: temperature is 80～350 ℃ preferred 100～280 ℃; Pressure is the preferred 1.0～6.0MPa of 0.1～12.0MPa; The mol ratio of phenyl and alkyl is that 0.1～80 preferred 1～40 optimum chooses 2～30 in the reaction mass.
Alkylated reaction effluent and optional transalkylation reaction effluent carry out fractionation together and obtain benzene, monoalkylated benzenes, polyalkylbenzene and heavy constituent, wherein a benzene part of Hui Shouing is returned alkylation reactor, another part is as the raw material of transalkylation, polyalkylbenzene is also as the raw material of transalkylation, monoalkylated benzenes is that purpose product alkylbenzene goes out device, and heavy constituent go out device as by product.
The described built-up type alkylation reactor system that is made of a plurality of beds is made up of 2～40 bed serial or parallel connections, this reactor assembly both can be a reactor of being made up of the multistage bed, but the multistage reaction zone that also a plurality of single hop reactors are formed is gone back the multistage reaction zone of at least one single hop bed reactor and at least one multistage bed reactor composition.Logistics in the reactor flows to preferably upflowing, also can be downflow system.Reactor can be the reactor of fixed bed, suspension bed, slurry bed, moving-bed or other form.Fixed-bed reactor preferably.Can also parallel connection between a plurality of reactors or the mode of series and parallel use but preferably series connection.
Built-up type alkylation reactor system comprises alternative alkylation reaction zone and irreplaceable alkylation reaction zone, wherein interchangeable alkylation reaction zone by 1～39 preferred 1～20 most preferably 2～15 beds constitute, it both can be a reactor of forming by the multistage bed, also by a plurality of single hops or multistage reactors in series or the reaction zone that composes in parallel, the reaction zone that constitutes with parallel way can be simultaneously or independent one the tunnel is connected with irreplaceable alkylation reaction zone.Interchangeable alkylation reaction zone is in arbitrary position of multistage alkylation reactor upstream, midstream and downstream separately, also can be arranged on any two or three positions in the upstream, midstream and downstream of alkylation reaction zone to interchangeable alkylation reaction zone simultaneously.Logistics in the alkylation reactor flows to preferably upflowing, also can be downflow system.Reactor can be the reactor of fixed bed, suspension bed, slurry bed, moving-bed or other form, preferably fixed-bed reactor.
The bed of each section both can be connected between each section of alkylation reaction zone and interchangeable alkylation reaction zone, also can be in parallel, but be optimum with the series connection.
Employed in the present invention alkylation and transalkylation catalyst, it can be the catalyzer that contains different zeolites, as faujusite, mordenite, zeolite L, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-20 zeolite, β zeolite, MCM-22, MCM-36, MCM-49, MCM-56 zeolite etc., also can be the catalyzer that contains super acids, heteropolyacid or load-type solid acid.In alkylation and transalkylation reaction system, and interchangeable alkylation reaction zone, all can load one or more of above-mentioned catalyzer of identical or different type.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.Be graphic simplicity, interchanger, return tank and respective lines all do not mark in the drawings.
Accompanying drawing 1～5 is the alkylbenzene production method principle flow chart of interchangeable alkylation reaction zone provided by the invention when alkylated reaction system different positions.
Interchangeable alkylation reaction zone is arranged on the upstream of alkylated reaction system in the accompanying drawing 1, and alkylation reactor 5 is for being positioned at replaceable alkylation reaction zone of alkylated reaction system upstream.
The technical process of accompanying drawing 1 is as follows: fresh benzene, the recovery benzene from pipeline 22,21 mixes after pipeline 2 respectively, with the alkylation recycle stream of pipeline 3, successively after the part olefin of pipeline 1,30, entering alkylation reactor 5 through pipeline 4 reacts, the outlet product of this reactor enters alkylation reactor 9 through pipeline 8 and carries out alkylated reaction through pipeline 6 and successively through the part olefin of pipeline 1,31.Reaction mass is from bottom to top by first section bed of catalyzer and react, and enters reactor 9 from second section, the 3rd section, the 4th section and the 5th section beds ingress respectively from the part alkene of pipeline 32,33,34,35 and reacts.Its product enters product separation device 14 through pipeline 10,13 successively.Be back to alkylation reactor 5 inlets through pipeline 3,4 from second section beds extension material of reactor 9 successively as recycle stock.Heat collector (not drawing among the figure) all can be set, to control each section between each section of reactor 9 in suitable temperature of reaction.
After mixing from the alkylate of pipeline 10,11, transalkylation reaction product respectively, enter product separation device 14 through pipeline 13.Non-condensable gas goes out device through pipeline 15.The benzene of separating is divided into 2 parts through pipeline 16, wherein a part is mixed benzene raw materials as alkylated reaction through pipeline 21 with fresh benzene from pipeline 22, another part then enters transalkylation reactor 12 through pipeline 20, as the benzene raw materials of transalkylation reaction.The monoalkylated benzenes product is derived through pipeline 17, heavy constituent are derived through pipeline 19, polyalkylbenzene is mixed into transalkylation reactor 12 through pipeline 18 and benzene raw materials from pipeline 16, transalkylation reactor 12 effluents, enter product separation device 14 through pipeline 13 and carry out Separation and Recovery together with after alkylation reaction product from pipeline 10 mixes through pipeline 11.
Interchangeable alkylation reaction zone is arranged on the upstream and downstream of alkylated reaction system simultaneously in the accompanying drawing 2, and alkylation reactor 5,23 is respectively the interchangeable alkylation reaction zone of alkylated reaction system upstream and downstream.
In the accompanying drawing 3, alkylation reactor 5 is interchangeable alkylation reaction zone, and this reaction zone is positioned at the middle part of whole alkylated reaction system.
In the accompanying drawing 4, alkylation reactor 6 is interchangeable alkylation reaction zone, and this reaction zone is positioned at the downstream of whole alkylated reaction system.
In the accompanying drawing 5, alkylation reactor 5 and 7 is interchangeable alkylation reaction zone of two parallel connections, can be individually or simultaneously and alkylated reaction system serial operation.This reaction zone is positioned at the upstream of whole alkylated reaction system.
The technical process of accompanying drawing 2-5 except that interchangeable alkylation reaction zone alkylated reaction alliance difference, transalkylation is all identical with flow processs such as product separation, no longer the technical process of accompanying drawing 2-5 is described in detail herein.
Accompanying drawing 6 is an alkylbenzene production method idiographic flow synoptic diagram provided by the invention.
The technical process of accompanying drawing 6 is described in detail as follows: respectively from the fresh benzene of pipeline 28,20, reclaim benzene through pipeline 2, alkylation recycle stream with pipeline 3, successively after the part olefin of pipeline 1,30, entering alkylation reactor 5 through pipeline 4 reacts, the outlet product of this reactor enters alkylation reactor 8 through pipeline 7 and carries out alkylated reaction through pipeline 6 and successively through the part olefin of pipeline 1,31.The discharging part of reactor 8 is back to the inlet of reactor 5 as recycle stock through pipeline 3, another part then through pipeline 9 with after the part olefin of pipeline 1,32, enter alkylation reactor 10 successively.Through first section bed and the reaction after, reaction product again with successively through the part olefin of pipeline 1,33, on second section bed, react; The discharging that reactor is second section with successively through the part olefin of pipeline 1,34, enter the 3rd section bed and the reaction; The 3rd section reaction product again with through the part olefin of pipeline 1,35 successively, on the 4th section bed, react.The product of reactor 10 enters benzene tower 16 through pipeline 12,13 successively.Between alkylation reactor 5,8 and each section of 10 interchanger and heat collector are set, to control the suitable temperature of reaction of each section.Alkylation reactor 5, can be isolated with the alkylated reaction system when needing as interchangeable alkylation reaction zone, and promptly the mixture of fresh benzene, recovery benzene, alkylation recycle stream, alkene enters reactor 8 through pipeline 11,7 successively.
After mixing from the alkylate of pipeline 12,14, transalkylation reaction product respectively, enter benzene tower 16 through pipeline 13, the isolated benzene of cat head, a part is mixed benzene raw materials as alkylated reaction through pipeline 19,20 successively with fresh benzene from pipeline 28, another part then enters transalkylation reactor 15 through pipeline 19,22 and 29, as the benzene raw materials of transalkylation reaction.In addition, also can extract recovery benzene out as reaction raw materials from benzene tower rectifying section side line.The alkane non-condensable gas that return tank of top of the tower is discharged and a small amount of benzene are isolated the alkane non-condensable gas through the dealkylate tower, remaining benzene and recovery benzene mixing Returning reacting system (not expressing among the figure).The material that contains monoalkylated benzenes and polyalkylbenzene that is gone out by benzene tower 16 tower bottom flows enters monoalkylated benzenes tower 17 through pipeline 21, and wherein the monoalkylated benzenes product is derived from cat head through pipeline 24, and the bottoms material enters polyalkylbenzene tower 18 through pipeline 23.Isolate heavy constituent 27 at the bottom of the polyalkylbenzene Tata, the polyalkylbenzene that cat head steams mixes after pipeline 29 enters transalkylation reactor 15 with benzene raw materials from pipeline 22 through pipeline 26, transalkylation reactor 15 effluents through pipeline 14 with enter benzene tower 16 after alkylate from pipeline 12 mixes and carry out Separation and Recovery.
Alkylation process provided by the invention is applicable to all kinds of alkylated reactions of benzene, and being specially adapted to ethene and propylene is the alkylated reaction of alkylating agent.The present invention is on the basis of former invention CN1428319A, sets up the alkylation reaction zone that can replace in the alkylated reaction system.Therefore, except that continuing to keep the advantage of invention CN1428319A, also have the following advantages:
1, adopts the reaction zone material partly to circulate and replaceable alkylation reaction zone process combined flow process, interchangeable reaction zone decaying catalyst is changed in good time, make the operating time of each conversion zone be easier to coupling and control mutually.
2, conversion zone be can select and adjust neatly, the operating time of whole alkylated reaction system and the normal operation of device do not influenced because of the conversion zone deactivation rate is different.
3, can adapt to the processing condition of low benzene alkene ratio, long periods of time in order more, the while reduces the hop count of reactor effectively.By adjusting flow, feed entrance point, reaction hop count and the interchangeable reaction zone of recycle stock, reach and reduce the purpose that reactive system benzene alkene compares, cuts down the consumption of energy, reduces investment, long-term operation.
4, the flexible operation of interchangeable alkylation reaction zone, flow process is simple.
5, by trace analysis to the catalyzer of interchangeable reaction zone, in time understand the running condition of catalyzer, in time find the problem in the device running.
6, improve the selectivity of product monoalkylated benzenes, help the long term life of catalyzer.
7, acceptable material can not carry out pre-treatment and directly enters alkylation reactor, has saved investment.
The following examples will give further instruction to present method, but therefore not limit present method.
The alkylation catalyst and the transalkylation catalyst trade mark used among the embodiment are respectively AEB-2 and AEB-1, are produced by Chang Ling catalyst plant and Wenzhou catalyst plant respectively.
Embodiment 1
Press the flow process of accompanying drawing 6, benzene and ethylene reaction generate ethylbenzene.Alkylation reactor 5 is the reactor of interchangeable conversion zone.Alkylation reactor 5, alkylation reactor 8 and alkylation reactor 10 catalyst system therefors are identical alkylation catalyst, 180～250 ℃ of temperature of reaction, reaction pressure 3.5MPa, benzene feedstock alkene than be 3.5, the circulation weight ratio is to react under 0.6 the reaction conditions, conversion of ethylene is 100%, ethylbenzene selectivity is 87%, ethylization selectivity 〉=99%.Many ethylbenzene of benzene and recovery react in the transalkylation reactor of transalkylation catalyst is housed.Its reaction conditions is: the mol ratio of 170～250 ℃ of temperature of reaction, reaction pressure 3.0MPa, phenyl and alkyl is 12.The per pass conversion of diethylbenzene is 87.3% in the reactant, ethylbenzene selectivity 100%.Transalkylation reaction product is sent into the distillation system separation together with alkylate and is obtained benzene, ethylbenzene and many ethylbenzene etc.Xylene content in the ethylbenzene is less than 50ppm, and the overall selectivity that generates ethylbenzene is greater than 99.5%.
After catalyzer lost efficacy for some reason in the alkylation reactor 5, this reactor and reactive system can be isolated, draw off catalyst regeneration.Through pipeline 11, after ethene through pipeline 1 and 31 mixes, enter alkylation reactor 8 from the recovery benzene of the circulation alkylation liquid of pipeline 3 and pipeline 2.Alkylation reactor 8 and alkylation reactor 10 110～250 ℃ of temperature of reaction, reaction pressure 3.5MPa, benzene feedstock alkene than be 3.5, the circulation weight ratio is to react under 0.6～1 the reaction conditions, conversion of ethylene is 100%, ethylbenzene selectivity is 87.0%, ethylization selectivity 〉=99%.Transalkylation partial reaction condition and rectifying condition are constant.
Press the flow process of accompanying drawing 6, benzene and propylene reaction generate isopropyl benzene.Alkylation reactor 5 is the reactor of interchangeable conversion zone.Alkylation reactor 5, alkylation reactor 8 and alkylation reactor 10 catalyst system therefors are identical alkylation catalyst, 150～210 ℃ of temperature of reaction, reaction pressure 3.2MPa, benzene alkene than be 2.5, the circulation weight ratio is to react under 0.4 the condition, propylene conversion is 100%, the isopropyl benzene selectivity is 89%, isopropylation selectivity 〉=99%.The diisopropylbenzene(DIPB) of benzene and recovery reacts in the transalkylation reactor of transalkylation catalyst is housed.Its reaction conditions is: 160～240 ℃ of temperature of reaction, reaction pressure 2.6MPa.The per pass conversion of isopropyl benzene is 80% in the reactant, and the selectivity of isopropyl benzene is greater than 99%.Transalkylation reaction product is sent into the distillation system separation together with alkylate and is obtained benzene, isopropyl benzene and diisopropylbenzene(DIPB) etc.The overall selectivity that generates isopropyl benzene is greater than 99.5%.
Behind catalyst deactivation in the alkylation reactor 5, this reactor is cut out.From the circulation alkylation liquid of pipeline 3 and the recovery benzene process pipeline 11 of pipeline 2, after the propylene of pipeline 1 and 31 mixes, enter reactor 8. Alkylation reactor 8 and 10 150～210 ℃ of temperature of reaction, reaction pressure 3.2MPa, benzene feedstock alkene than be 2.5, the circulation weight ratio is to react under 0.5～1 the condition, propylene conversion is 100%, the isopropyl benzene selectivity is 89.0%, isopropylation selectivity 〉=99%.Transalkylation partial reaction condition and rectifying condition are constant.
Claims (6)
1, a kind of improved alkylbenzene production method is characterized in that this method comprises:
(1), the alkylation of benzene and alkene
Benzene feedstock, raw material olefin, alkylated reaction recycle stream and optional transalkylation reaction effluent enter the built-up type alkylation reactor system that is made of a plurality of beds, this system comprises alternative alkylation reaction zone and irreplaceable alkylation reaction zone, alkylated reaction takes place in above-mentioned material under the effect of alkylation catalyst, separate the alkylated reaction effluent and obtain benzene, monoalkylated benzenes, polyalkylbenzene and heavy constituent;
(2), the part of alkylated reaction effluent circulation
Draw from the outlet of arbitrary conversion zone of built-up type alkylation reactor system, recycle stream turns back to the inlet of the arbitrary conversion zone before the recycle stream section of drawing individually or simultaneously with external circulation mode;
(3), switch alternative alkylation reaction zone
When stopping using during alkylation catalyst deactivation in alternative alkylation reaction zone, benzene feedstock, raw material olefin, alkylated reaction recycle stream and optional transalkylation reaction effluent enter all the other alkylation reaction zone reactions; Behind the alkylation catalyst after the alkylation catalyst of inactivation in alternative alkylation reaction zone is replaced by fresh and/or regeneration, in alternative alkylation reaction zone incision alkylated reaction system;
(4), the transalkylation of benzene and polyalkylbenzene
Enter transalkylation reactor from isolating benzene of step (1) and polyalkylbenzene, under the effect of transalkylation catalyst, transalkylation reaction takes place;
(5), the processing of transalkylation reaction effluent
The transalkylation reaction effluent has three kinds of whereabouts: the one, and all be circulated to built-up type alkylation reactor system and proceed alkylated reaction, the 2nd, a part is circulated to built-up type alkylation reactor system and proceeds alkylated reaction, another part goes to separate, and the 3rd, all go to separate;
(6), product separates
Alkylated reaction effluent and optional transalkylation reaction effluent carry out fractionation together and obtain benzene, monoalkylated benzenes, polyalkylbenzene and heavy constituent, wherein a benzene part of Hui Shouing is returned the built-up type alkylation reactor system of step (1), another part is as the raw material of transalkylation, polyalkylbenzene is also as the raw material of transalkylation, monoalkylated benzenes is that purpose product alkylbenzene goes out device, and heavy constituent go out device as by product.
2, according to the method for claim 1, it is characterized in that the described built-up type alkylation reactor system that is made of a plurality of beds is made up of 2～40 bed serial or parallel connections, this reactor assembly is a reactor of being made up of the multistage bed, or the multistage reaction zone of a plurality of single hop reactors compositions, or the multistage reaction zone of at least one single hop bed reactor and at least one multistage bed reactor composition.
3, according to the method for claim 1, it is characterized in that described interchangeable alkylation reaction zone is made of 1～39 bed, it is a reactor of forming by the multistage bed, or by a plurality of single hops or multistage reactors in series or the reaction zone that composes in parallel, the reaction zone that constitutes with parallel way or simultaneously or independent a tunnel connect with irreplaceable alkylation reaction zone.
4, according to the method for claim 1, it is characterized in that described interchangeable alkylation reaction zone is in arbitrary position of multistage alkylation reactor upstream, midstream and downstream separately, perhaps interchangeable alkylation reaction zone is arranged on any two or three positions in the upstream, midstream and downstream of alkylation reaction zone simultaneously.
5, according to the method for claim 1, it is characterized in that described alkylation reaction condition is: 80～350 ℃ of temperature, pressure 0.1～12.0MPa, the mol ratio 0.1～50 of benzene feedstock and raw material olefin, every section bed inlet benzene alkene mol ratio 1～80, the mol ratio 0.1～100 of phenyl and alkyl in the reaction mass.
6, according to the method for claim 1, it is characterized in that described transalkylation reaction conditions is: temperature is 80～350 ℃, and pressure is 0.1～12.0MPa, the mol ratio 0.1～80 of phenyl and alkyl in the reaction mass.
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| CNB2004100711160A CN1328231C (en) | 2004-07-29 | 2004-07-29 | Modified method for producing alkylbenzene |
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| CN106635140B (en) * | 2015-10-28 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of alkylation reaction method |
| CN113544112B (en) * | 2019-02-04 | 2024-01-23 | 中国石油化工股份有限公司 | Dealkylation and transalkylation of mixed phenols to make cresols |
| CN112694386A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by taking coal-based acetylene as raw material |
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| CN1428319A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Production method of alkylbenzene |
| CN1514816A (en) * | 2001-06-08 | 2004-07-21 | ŵ�����˹ɷ�����˾ | Process for catalytic alkylation of hydrocarbons |
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| CN1428319A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Production method of alkylbenzene |
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