CN1485305A - Process for preparing alkylbenzene with low energy consumption - Google Patents
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- CN1485305A CN1485305A CNA021307938A CN02130793A CN1485305A CN 1485305 A CN1485305 A CN 1485305A CN A021307938 A CNA021307938 A CN A021307938A CN 02130793 A CN02130793 A CN 02130793A CN 1485305 A CN1485305 A CN 1485305A
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Abstract
A process of manufacturing alkylbenzene with low energy consumption comprises benzen and alkene as the raw material are putting into an alkylation reactor for alkylation, alkylating products from the outlet of the alkylation reactor entering 0-5 polyalkylbenzene transfer reactors then back to the liquid-phrase alkylation reactor; after separating, obtaining benzene, monoalkyl benzene, polyalkylbenzene and heavy componenst, some benzene is back to the alkylation reactor, the rest benzene and polyalkylbenzene entering the transalkylation reactor for transalylation, the products of transalylation and products of alkylation are separated. The method lowers the concentration of polyalkylbenzene in alkylating products, reduces operating load of a polyalkylbenzene tower and transalylation, thus saves the amount of benzene in transalylation and energy consumption.
Description
Technical field
The present invention relates to a kind of method for preparing hydrocarbon from the less hydrocarbon of carbon atom quantity.More particularly, be a kind of method from low-carbon alkene and benzene production alkylbenzene.
Background technology
Ethylbenzene is important Organic Chemicals, is mainly used in production vinylbenzene, and 99% ethylbenzene has only 1% to use it for anything else all as cinnamic raw material in the world, as solvent, production diethylbenzene and anthraquinone etc.Therefore, the demand of ethylbenzene almost all depends on cinnamic production.It is predicted that in the period of 1998～2005, the vinylbenzene consumption in the whole world will be with annual 4.2% speed increase, the cinnamic consumption of China is with 8.7% speed increase.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%, and their demand will be with annual 3%～4% speed increment.Because the market requirement growing, be that the alkylation production technique development of raw material is rapid with benzene and olefine reaction.
The production of ethylbenzene is AlCl at first
3Method technology, isopropyl benzene production are solid phosphoric acid method technology.Because its catalyzer is to the deep-etching of equipment with to the severe contamination of environment, at present by the technology by catalyzer is replaced with the molecular sieve.And molecular sieve vapor-phase alkylation method is because the temperature of reaction height, and the xylene content height is replaced by the molecular sieve liquid phase method gradually.People claim that the molecular sieve liquid phase method is an environmentally friendly technology condition relaxes, selectivity is good, impurity is few because this technology has, pollution-free, do not have an advantage such as corrosion.Recently this technology has become ethylbenzene, isopropyl benzene is produced ideal method.At present, this Technology is mature on the whole, and cuts down the consumption of energy, and reducing material consumption is the developing direction of this technology.
USP4,891,458 disclose on beta-zeolite catalyst, have at least a part of liquid phase to exist down, and aromatic hydrocarbons such as benzene carry out alkylated reaction with C2～C4 alkene, and the transalkylation reaction generation is arranged in the alkylation reactor.Therefore alkylate is through after distilling, isolated polyalkylbenzene, mainly be that dialkyl benzene, trialkyl benzene etc. loop back alkylation reactor and carry out transalkylation reaction, perhaps in the transalkylation reactor that other establishes, carry out transalkylation reaction, the monoalkylated benzenes yield is increased with aromatic hydrocarbons such as benzene.The catalyzer that this patent requires to use is beta-zeolite catalyst, and the mol ratio of aromatic hydrocarbons and alkene is 4: 1 at least, otherwise catalyzer is with rapid deactivation.
USP4,922,053 disclosed benzene and ethene carry out the technology of vapor phase alkylation production ethylbenzene and carry out in bed alkylation reactor more than.The part of the isolated many ethylbenzene in alkylate process distillation back loops back first section bed or other one or more snippets bed at alkylation reactor top, has increased the ethylbenzene yield, and has reduced the generation of byproducts such as dimethylbenzene.
USP5,336,821 disclose in alkylating aromatic hydrocarbon is produced, and as the production of ethylbenzene, isopropyl benzene, a part of alkylate goes out the technology of carrying out recovery of heat by an indirect heat exchanger behind the alkylation reactor.Wherein a kind of implementation method is after the portion of product that alkylation reactor exports is passed through indirect heat exchanger, to loop back alkylation reactor.The alkylation catalyst of this technology is advisable with zeolite catalyst.
USP4,008,290 discloses the technology that a kind of isopropyl benzene is produced.Benzene and propylene are behind alkylated reaction, and its product is divided into two strands: one loops back the inlet of alkylation reactor; Another thigh goes separation system.Isolating product is isopropyl benzene, diisopropylbenzene(DIPB) and tri-isopropyl benzene, excessive benzene.Excessive benzene is divided into two strands: one loops back the inlet of alkylation reactor; Another strand carries out transalkylation reaction with after diisopropylbenzene(DIPB) and tri-isopropyl benzene mix.This patent is thought because alkylate loops back the inlet of alkylation reactor, has improved the benzene/alkene ratio of alkylated reaction, is beneficial to the isopropyl benzene generation, and has limited the generation of propylene polymerization and coke.But, to compare with former no circulation technology, diisopropylbenzene(DIPB) and tri-isopropyl benzene growing amount increase.
USP6,008,422 discloses a kind of 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.Third part removes to isolate target product.This technology makes each layer catalyzer move under the condition of optimum temps, byproduct formation amount minimum, thereby prolonged life of catalyst.
When FR2795404 pointed out that ethylbenzene or isopropyl benzene are produced in reaction on EUO type catalyzer, alkylated reaction carried out with transalkylation reaction.EUO type catalyzer is made up of one of Si and Al, Fe, Ga, four kinds of elements of B.Alkylation reactor outlet product is divided into three strands: two strands all loop back the alkylation reactor inlet, and one removes to isolate target product.Loop back the alkylation reactor inlet owing to contain the alkylate of a large amount of benzene, reduced and gone isolating benzene amount, saved energy consumption.
CN1128249A disclose a kind of in the presence of zeolite catalyst the method for the liquid phase alkylation process of benzene.It 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, be 1.5～8 in benzene and olefin molar ratio, carry out under the reaction conditions of recycle stock and reactor discharging weight ratio 1.5～12.This technology is specially adapted to the preparation of ethylbenzene and isopropyl benzene.The characteristics of this patent are with the recycle stock of partially alkylated outlet material as the Returning reactor inlet, can control the reaction bed temperature rise effectively and guarantee the dissolving of alkene in reaction mass; And reduced the operating load of benzene recovery tower, saved energy consumption.
CN1217310A discloses a kind of alkylbenzene production technique, it is characterized in that partly circulating by the alkylation reactor outlet material in a multistage bed reactor, makes benzene feedstock and alkene carry out the technology of alkylated reaction.
The common feature of above-mentioned prior art is the alkylated reaction effluent not to be added to handle go to reclaim benzene and circulation, but when benzene/when alkene ratio reduced, polyalkylbenzene concentration increased, has therefore increased the energy consumption of load and the benzene tower and the polyalkylbenzene tower of transalkylation reaction.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of processing method of production alkylbenzene of less energy-consumption.
Method provided by the invention comprises:
Benzene feedstock and raw material olefin enter the alkylation reactor that is made of the multistage reaction zone, alkylated reaction takes place under the effect of alkylation catalyst, loop back the liquid phase alkylation reaction device from alkylation reactor outlet or the intersegmental alkylated reaction effluent that comes out through x polyalkylbenzene conversion reactor, the alkylated reaction effluent that exports out from alkylation reactor carries out transalkylation reaction through y polyalkylbenzene conversion reactor earlier, obtain benzene through separation then, monoalkylated benzenes, polyalkylbenzene and heavy constituent, wherein part benzene returns alkylation reactor, residue benzene and polyalkylbenzene enter transalkylation reactor, under the effect of transalkylation catalyst transalkylation reaction takes place, the transalkylation reaction effluent comes along with the alkylated reaction effluent and separates.
Behind the alkylate process polyalkylbenzene conversion reactor, the monoalkylated benzenes product concentration improves, and the monoalkylated benzenes productive rate is improved; Polyalkylbenzene concentration reduces, and has alleviated the operating load of polyalkylbenzene tower, has alleviated the operating load of transalkylation part simultaneously, thereby has reduced the consumption of the benzene of transalkylation part, has saved energy consumption.
Description of drawings
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing 1 is the processing method synoptic diagram of the production alkylbenzene of less energy-consumption provided by the present invention.
Accompanying drawing 2～8th, the position view of polyalkylbenzene conversion reactor.
Embodiment
Method provided by the invention is so concrete enforcement:
Benzene feedstock and raw material olefin enter the alkylation reactor that is made of the multistage reaction zone, alkylated reaction takes place under the effect of alkylation catalyst, loop back the liquid phase alkylation reaction device from alkylation reactor outlet or the intersegmental alkylated reaction effluent that comes out through x polyalkylbenzene conversion reactor, the alkylated reaction effluent that exports out from alkylation reactor carries out transalkylation reaction through y polyalkylbenzene conversion reactor earlier, obtain benzene through separation then, monoalkylated benzenes, polyalkylbenzene and heavy constituent, wherein part benzene returns alkylation reactor, residue benzene and polyalkylbenzene enter transalkylation reactor, under the effect of transalkylation catalyst transalkylation reaction takes place, the transalkylation reaction effluent comes along with the alkylated reaction effluent and separates.
Benzene and alkene react in the liquid phase alkylation reaction device, contain benzene and alkylbenzene in the alkylate.The outer circulation of liquid phase alkylation reaction device partly adds x the polyalkylbenzene conversion reactor that zeolite catalyst is housed, and makes the round-robin alkylate directly enter the liquid phase alkylation reaction device again after carrying out transalkylation reaction on this reactor.Elder generation was through y the polyalkylbenzene conversion reactor that zeolite catalyst is housed before the liquid phase alkylation reaction effluent went to separate.In technique scheme, x is 0～5 integer, and y is 0～5 integer, but x+y ≠ 0.
The polyalkylbenzene conversion reactor can be the reactor of fixed bed, suspension bed or other form of a plurality of serial or parallel connections, preferably placed in-line fixed-bed reactor, beds can be one or more snippets, single polyalkylbenzene conversion reactor bed number is advisable preferably 3～6 sections with 2～12 sections.Alkylate can enter the polyalkylbenzene conversion reactor with upflowing, downflow system or from the reactor side.The preferably upflowing charging of the flow direction of logistics also can be a downflow system in the reactor.Alkylate enters has at least a part of liquid phase to exist in the polyalkylbenzene conversion reactor; If full gas phase, need carry out condensation to the alkylate of gas phase after, enter the polyalkylbenzene conversion reactor.Transalkylation reaction in the polyalkylbenzene conversion reactor is carrying out under the Partial Liquid Phase condition at least, preferably full liquid phase.
Transalkylation reaction in the polyalkylbenzene conversion reactor is carrying out under the Partial Liquid Phase condition at least.The liquid phase alkylation reaction device has multiply logistics circulation time, has one logistics at least by the polyalkylbenzene conversion reactor; In the time of can being provided with the centre heat collector on the recycle stream, the polyalkylbenzene conversion reactor all can before and after middle heat collector, the polyalkylbenzene conversion reactor also can directly be connected on liquid phase alkylation reaction device rear portion, make whole alkylates be divided into two portions through behind this reactor, wherein a part loops back the liquid phase alkylation reaction device, and another part goes separation system to isolate target product; Also can be added on the stream thigh of alkylate of separate part; Or on the recycle stream and remove to establish respectively in the isolating logistics polyalkylbenzene conversion reactor.
The processing condition of polyalkylbenzene conversion reactor are: temperature of reaction is 150～450 ℃, preferably 180～300 ℃; Reaction pressure is 1.0～12.0MPa, preferably 1.5～6.0MPa; The benzene alkene mol ratio of producing the benzene feedstock of alkylate and raw material olefin is 1～30 preferred below 10, most preferably below 5.Alkylate passes through the volume space velocity 1～24/h of polyalkylbenzene conversion reactor, preferred 1～15/h, optimum 1～12/h.
The benzene alkene mol ratio of producing the benzene feedstock of alkylate and raw material olefin is 1～30 preferred below 10, most preferably below 5.Alkylate passes through the volume space velocity 1～24/h of polyalkylbenzene conversion reactor, preferred 1～15/h, optimum 1～12/h.
The reaction bed catalyst system therefor of polyalkylbenzene conversion reactor is to be the main catalyzer of forming with the zeolite, the described zeolite of described zeolite is y-type zeolite, β zeolite, nanometer β zeolite, MCM series zeolite or its mixture, and wherein MCM series comprises MCM-22, MCM-36, MCM-49, MCM-56 zeolite catalyst or its mixture.Optimum catalyzer is the y-type zeolite catalyzer.
The Recycle design of above-mentioned liquid phase alkylation reaction device outer circulation part can be to draw one or more strands of alkylates from the outlet of liquid phase alkylation reaction device to loop back reactor inlet; Also can be that first section bed or other a certain section or several sections beds that one or more strands of alkylates are recycled to the bottom of liquid phase alkylation reaction device are drawn in liquid phase alkylation reaction device outlet, can also be to be recycled to the inlet of drawing arbitrary conversion zone before the logistics from drawing one or more strands of logistics between the conversion zone of reactor.
Liquid phase alkylation reaction device reaction conditions is: temperature of reaction is 100～400 ℃, preferably 150～300 ℃; Reaction pressure is 1.0～12.0MPa, preferably 1.5～6.0MPa; The benzene alkene mol ratio of benzene feedstock and raw material olefin is 1～30, and is preferred 2～25, most preferably 3～10; The weight ratio (recycle ratio) of the load of recycle stock amount and the reaction zone section of drawing (not conforming to the recycle stock amount) is 0.001～20, and is preferred 0.05～10, most preferably 0.05～6.
The condition of transalkylation reaction is: temperature of reaction is 100～400 ℃, preferably 150～280 ℃; Reaction pressure is 1.0～12.0MPa, preferably 1.5～6.0MPa; The mol ratio of phenyl and alkyl is 1～40 in the material, and is preferred 2～20, most preferably is 3～15.
The alkylation catalyst and the transalkylation catalyst that use respectively in above-mentioned liquid phase alkylation reaction device and the transalkylation reactor can be the catalyzer that contains different zeolites, also can be the catalyzer that contains super acids, heteropolyacid or load-type solid acid, described zeolite be faujusite, mordenite, zeolite L, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-20 zeolite, β zeolite, nanometer β zeolite, MCM-22, MCM-36, MCM-49, MCM-56 zeolite or its mixture.Optimum catalyzer is Y zeolite catalyzer, beta-zeolite catalyst and MCM-22 zeolite catalyst.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction.
Accompanying drawing 1 is the processing method synoptic diagram of the production alkylbenzene of less energy-consumption provided by the present invention, but does not limit the present invention.In accompanying drawing 1, the alkylated reaction recycle stream is earlier through two polyalkylbenzene conversion reactor 8a, 8b, and elder generation was through two polyalkylbenzene conversion reactor 8a, 8c before the alkylated reaction effluent went to separate.
The flow process of this method is as follows: respectively from the fresh benzene of pipeline 1,26, reclaim that benzene mixes after pipeline 27 with mix from alkene, the circulation alkylate of pipeline 3,13 respectively after, enter liquid phase alkylation reaction device 6 through pipeline 5 and react.The outlet product part of this reactor enters polyalkylbenzene conversion reactor 8a through pipeline 7 successively as recycle stock and carries out transalkylation reaction.The product of reactor 8a is divided into two-way, wherein one the tunnel enters polyalkylbenzene conversion reactor 8b through pipeline 9, and the product of reactor 8b is back to the inlet of liquid phase alkylation reaction device 6 successively through pipeline 11, recycle pump 12, pipeline 13, pipeline 5; The product of another road reactor 8a enters polyalkylbenzene conversion reactor 8c through pipeline 10, and the product of reactor 8c enters interchanger 15 heat exchange after pipeline 16 enters benzene tower 17 through pipeline 14.Enter liquid phase alkylation reaction device 6 from the alkene of pipeline 2 and 3 by pipeline 5 and on first section beds, react, its product again with part olefin from pipeline 2 and 4, enter second section beds again and react.
Alkylation reaction product, transalkylation reaction product from pipeline 16,38 enters benzene tower 17 respectively, and the isolated benzene of cat head enters return tank of top of the tower 19 through pipeline 18.A part of benzene in the return tank of top of the tower successively through pipeline 24,25,26 with after fresh benzene from pipeline 1 mixes as the benzene raw materials of alkylated reaction.Another part benzene enters transalkylation reactor 37 through pipeline 24,25,35, interchanger 15, pipeline 36 successively, as the benzene raw materials of transalkylation reaction.The alkane non-condensable gas that the benzene return tank of top of the tower is discharged and a small amount of benzene enter dealkylate tower 21 through pipeline 20.Through pipeline 22 dischargers, the benzene at the bottom of dealkylate tower 21 towers is through pipeline 23 and Returning reacting system after recovery benzene from pipeline 24 mixes from the isolated alkane non-condensable gas of the cat head of dealkylate tower 21.The material that contains monoalkylated benzenes and polyalkylbenzene that goes out from benzene tower 17 tower bottom flows enters monoalkylated benzenes tower 29 through pipeline 28, and wherein through pipeline 30 take-up gears, the bottoms material enters polyalkylbenzene tower 32 through pipeline 31 to the monoalkylated benzenes product from cat head.Isolated heavy constituent are through pipeline 34 take-up gears at the bottom of the polyalkylbenzene Tata, the polyalkylbenzene that steams from cat head through pipeline 33 with enter transalkylation reactor 37 through pipeline 35, interchanger 15, pipeline 36 successively after recovery benzene raw materials from pipeline 25 mixes.The product of transalkylation reactor outlet is introduced benzene tower 17 through pipeline 38, carries out Separation and Recovery with alkylation reaction product.
Accompanying drawing 2～8th, the position view of polyalkylbenzene conversion reactor, separate part is all identical with accompanying drawing 1 with the transalkylation part.
In accompanying drawing 2, polyalkylbenzene conversion reactor 8a, 8c lay respectively at after the outlet of liquid phase alkylation reaction device 6, before the interchanger 15, the polyalkylbenzene conversion reactor are not set before the recycle pump 12.The alkylated reaction recycle stream is earlier through a polyalkylbenzene conversion reactor 8a, and elder generation was through two polyalkylbenzene conversion reactor 8a, 8c before the alkylated reaction effluent went to separate.
In accompanying drawing 3, polyalkylbenzene conversion reactor 8a, 8b lay respectively at after the outlet of liquid phase alkylation reaction device 6, before the recycle pump 12, the polyalkylbenzene conversion reactor are not set before the interchanger 15.The alkylated reaction recycle stream is earlier through two polyalkylbenzene conversion reactor 8a, 8b, and elder generation was through a polyalkylbenzene conversion reactor 8a before the alkylated reaction effluent went to separate.
In accompanying drawing 4, polyalkylbenzene conversion reactor 8b, 8c lay respectively at before the recycle pump 12, before the interchanger 15, the polyalkylbenzene conversion reactor are not set after the outlet of liquid phase alkylation reaction device 6.The alkylated reaction recycle stream is earlier through a polyalkylbenzene conversion reactor 8b, and elder generation was through a polyalkylbenzene conversion reactor 8c before the alkylated reaction effluent went to separate.
In accompanying drawing 5, polyalkylbenzene conversion reactor 8 is positioned at after the outlet of liquid phase alkylation reaction device 6, before the interchanger 15, the polyalkylbenzene conversion reactor is not set before the recycle pump 12.The alkylated reaction recycle stream is earlier through a polyalkylbenzene conversion reactor 8, and elder generation was through a polyalkylbenzene conversion reactor 8 before the alkylated reaction effluent went to separate.
In accompanying drawing 6, polyalkylbenzene conversion reactor 8 is positioned at before the interchanger 15, after the outlet of liquid phase alkylation reaction device 6, the polyalkylbenzene conversion reactor is not set before the recycle pump 12.Elder generation was through a polyalkylbenzene conversion reactor 8 before the alkylated reaction effluent went to separate.
In accompanying drawing 7, polyalkylbenzene conversion reactor 8 is positioned at before the recycle pump 12, after the outlet of liquid phase alkylation reaction device 6, the polyalkylbenzene conversion reactor is not set before the interchanger 15.The alkylated reaction recycle stream is earlier through a polyalkylbenzene conversion reactor 8.
In accompanying drawing 8, polyalkylbenzene conversion reactor 8 is positioned at after the outlet of liquid phase alkylation reaction device 6, before the interchanger 15, the polyalkylbenzene conversion reactor is not set before the recycle pump 12.Recycle stream is the inlet that returns liquid phase alkylation reactor 6 from the intersegmental extraction of liquid phase alkylation reaction device 6 behind recycle pump 12.Elder generation was through a polyalkylbenzene conversion reactor 8 before the alkylated reaction effluent went to separate.
Alkylation process provided by the invention is applicable to all kinds of alkylated reactions of benzene, and particularly suitable hangs down benzene/alkene than being the alkylated reaction of alkylating agent with ethene and propylene under the condition.The characteristics of this technology are that the outer circulation in the liquid phase alkylation reaction device partly adds one or more polyalkylbenzene conversion reactors that zeolite catalyst is housed, make the round-robin alkylate directly after carrying out transalkylation reaction on this reactor, enter the liquid phase alkylation reaction device again, so it has the following advantages:
1, behind the alkylate process polyalkylbenzene conversion reactor, transalkylation reaction takes place, the monoalkylated benzenes product concentration improves, and the monoalkylated benzenes productive rate is improved;
2, behind the alkylate process polyalkylbenzene conversion reactor, transalkylation reaction takes place, polyalkylbenzene concentration reduces, and has alleviated the operating load of polyalkylbenzene tower, has alleviated the operating load of transalkylation part simultaneously.Thereby reduced the consumption of the benzene of transalkylation part, saved energy consumption.
3, in the current alkylbenzene production in order to reach the purpose of saving energy consumption, material consumption, adopt the method that reduces benzene/alkene ratio usually.But along with the reduction of benzene/alkene ratio, the monoalkylated benzenes product selectivity descends, and the polyalkylbenzene selectivity rises, and has increased the operating load of transalkylation part.After adopting the polyalkylbenzene conversion reactor, recycle stream enters this reactor, polyalkylbenzene generation transalkylation reaction, and concentration reduces, and the monoalkylated benzenes product concentration increases.Alleviate the operating load of transalkylation part, saved energy consumption.This technology is specially adapted to low benzene alkene and produces ethylbenzene or isopropyl benzene than benzene under the condition and olefine reaction.
4, the liquid phase alkylation reaction device is owing to loop back partially alkylated product to reactor itself, and making single basic benzene concentration rising in the reactor has increased the chance that alkene and monoalkylated benzenes react.Compared with former no circulation technology, polyalkylbenzene concentration is slightly high in the liquid phase alkylation reaction device.And the introducing of polyalkylbenzene conversion reactor has just in time solved this problem of this type of reactor.
The following examples will give further instruction to present method, but therefore not limit present method.
Embodiment 1
The fixed-bed reactor of simulating every section equivalent ethylene feed, forming by 7 sections alkylation catalyst AEB-2 (producing) bed by the Chang Ling catalyst plant.Benzene/the ethylene molar ratio of every section bed is 24: 1, and eight sections total benzene/ethylene ratio moles are 3.4: 1.Its simulation process is as follows.The simulation of first section bed: benzene and ethene carry out alkylated reaction after entering reactor by 24: 1 mol ratio under liquid-phase condition.After reaction finished, catalyzer was dismantled.Second section bed simulation: with first section product is raw material, loads onto same fresh catalyzer again, feeds the ethene with the epimere same amount.The rest may be inferred, with the raw material of second from the bottom section product as final stage, loads onto same fresh catalyzer again, and the ethene of feeding and epimere same amount condition under obtains alkylate in benzene/ethylene molar ratio at 3.4: 1.The reaction of each section bed is 250 ℃ of temperature, and reaction pressure is 3.5MPa, first section benzene feedstock volume space velocity 12h
-1, later every section bed charging air speed increases 0.18h
-1
It is the polyalkylbenzene conversion reactor of the main polyalkylbenzene conversion catalyst AEB-2 that forms that the feeding of final stage gained alkylate is equipped with the β zeolite, and the catalyst loading volume is 8mL, and particle diameter is 20～40 orders.Reactor is the stainless steel tube of internal diameter 12.5mm, and logistics enters reactor with upflowing.Reaction conditions is as follows: 250 ℃ of temperature, pressure 3.5MPa, volume space velocity 3h
-1
Test-results shows that the transformation efficiency of diethylbenzene has reached 7.55%, and the transformation efficiency of triethyl-benzene has reached 29.01%, and ethylbenzene selectivity is 98.00%.So alkylate has improved the ethylbenzene yield after polyalkylbenzene transforms, reduced many ethylbenzene concentrations, and be more suitable for of the production of low benzene alkene than ethylbenzene under the condition.
The alkylate that obtains with embodiment 1 is charging, carries out transalkylation reaction, simulation polyalkylbenzene conversion reactor on polyalkylbenzene conversion catalyst AEB-1 (being produced by Wenzhou catalyst plant) catalyzer of Y zeolite for main composition.200 ℃～250 ℃ of temperature of reaction, reaction pressure 3.5MPa, feed volume air speed 3/h, catalyst loading volume are 8mL, particle diameter is 20～40 orders.Reactor is the stainless steel tube of internal diameter 12.5mm, and logistics enters reactor with upflowing.
Test-results shows that in mimic polyalkylbenzene conversion reactor, when temperature of reaction was 220 ℃, the transformation efficiency of diethylbenzene had reached 15.41%, and the transformation efficiency of triethyl-benzene has reached 64.34%, and ethylbenzene selectivity is 97.77%.In general, ethylbenzene concentration rises, diethylbenzene and triethyl-benzene density loss.
Claims (9)
1, a kind of processing method of production alkylbenzene of less energy-consumption, benzene feedstock and raw material olefin enter the alkylation reactor that is made of the multistage reaction zone, alkylated reaction takes place under the effect of alkylation catalyst, it is characterized in that looping back the liquid phase alkylation reaction device through x polyalkylbenzene conversion reactor from alkylation reactor outlet or the intersegmental alkylated reaction effluent that comes out, the alkylated reaction effluent that exports out from alkylation reactor carries out transalkylation reaction through y polyalkylbenzene conversion reactor earlier, obtain benzene through separation then, monoalkylated benzenes, polyalkylbenzene and heavy constituent, wherein part benzene returns alkylation reactor, residue benzene and polyalkylbenzene enter transalkylation reactor, under the effect of transalkylation catalyst transalkylation reaction takes place, the transalkylation reaction effluent comes along with the alkylated reaction effluent and separates.
2, according to the method for claim 1, it is characterized in that x is 0～5 integer, y is 0～5 integer, but x+y ≠ 0.
3, according to the method for claim 1, it is characterized in that described polyalkylbenzene conversion reactor catalyst system therefor is is the main catalyzer of forming with the zeolite, described zeolite is y-type zeolite, β zeolite, nanometer β zeolite, MCM series zeolite or its mixture.
4,, it is characterized in that described MCM series zeolite comprises MCM-22, MCM-36, MCM-49, MCM-56 according to the method for claim 3.
5, according to the method for claim 1, it is characterized in that the processing condition of described polyalkylbenzene conversion reactor are: 150～450 ℃ of temperature of reaction, reaction pressure are 1.0～12.0MPa, volume space velocity 1～24/h.
6, according to the method for claim 1, it is characterized in that alkylation reaction condition is: 100～400 ℃ of temperature of reaction, reaction pressure are 1.0～12.0MPa, and the benzene alkene mol ratio of benzene feedstock and raw material olefin is 1～30.
7, according to the method for claim 1, it is characterized in that transalkylation reaction conditions is: temperature of reaction is 100～400 ℃, and reaction pressure is 1.0～12.0MPa, and the mol ratio of phenyl and alkyl is 1～40 in the material.
8, according to the method for claim 1, it is characterized in that the alkylation catalyst and the transalkylation catalyst that use respectively in alkylation reactor and the transalkylation reactor are the catalyzer that contains different zeolites, described zeolite is faujusite, mordenite, zeolite L, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-20 zeolite, β zeolite, nanometer β zeolite, MCM-22, MCM-36, MCM-49, MCM-56 zeolite or its mixture.
9,, it is characterized in that the alkylation catalyst and the transalkylation catalyst that use respectively in alkylation reactor and the transalkylation reactor are the catalyzer that contains super acids, heteropolyacid or load-type solid acid according to the method for claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983434A (en) * | 2015-02-11 | 2016-10-05 | 中国科学院大连化学物理研究所 | Preparation method and use of binder-free ZSM-11 molecular sieve-based catalyst |
| RU191347U1 (en) * | 2018-12-10 | 2019-08-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | DEVICE FOR SEPARATION OF BENZENE ALKYLATION REACTION PRODUCTS |
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2002
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983434A (en) * | 2015-02-11 | 2016-10-05 | 中国科学院大连化学物理研究所 | Preparation method and use of binder-free ZSM-11 molecular sieve-based catalyst |
| CN105983434B (en) * | 2015-02-11 | 2019-07-05 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of the ZSM-11 molecular sieve catalyst of binder free |
| RU191347U1 (en) * | 2018-12-10 | 2019-08-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | DEVICE FOR SEPARATION OF BENZENE ALKYLATION REACTION PRODUCTS |
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