CN102267859B - Method for producing ethylbenzene by using ethylene - Google Patents
Method for producing ethylbenzene by using ethylene Download PDFInfo
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- CN102267859B CN102267859B CN2011101629924A CN201110162992A CN102267859B CN 102267859 B CN102267859 B CN 102267859B CN 2011101629924 A CN2011101629924 A CN 2011101629924A CN 201110162992 A CN201110162992 A CN 201110162992A CN 102267859 B CN102267859 B CN 102267859B
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Abstract
The invention discloses a method for producing ethylbenzene by using ethylene, which comprises the following steps: (1) dividing a gas mixture containing ethylene and inert component into N parts, and conveying the N parts of gas mixture into the bottom of the Nth section of an alkylation reactor from a gas phase inlet through pipes, wherein the gas mixture is contacted with an absorbing agent from the absorbing agent inlet on the top of the alkylation reactor in an absorbing section, the alkylation reactor has N absorbing sections and N reaction sections, and the ethylbenzene and polyethylbenzene mass content in the absorbing agent is 30 to 90 percent; and (2) allowing the absorbing agent which carry ethylene to flow downward to react in the reaction section to form ethylbenzene and polyethylbenzene, wherein the absorbing agent passes through all absorbing sections and reaction sections in the alkylation reactor in turn, and the gas phase and liquid phase alkylation liquid, which are obtained after reaction, are conveyed to a subsequent section. In the invention, the conversion rate and recovery rate of ethylene are increased obviously, and the complete reaction can be guaranteed; the contact of gas phase ethylene with a catalyst is avoided completely, so the coking and inactivation of the catalyst can be delayed; and the method can meet the needs of the industrial field.
Description
Technical field
The present invention relates to produce the method for alkylbenzene, more particularly, is absorption, catalysis, the distillating method of producing ethylbenzene.
Background technology
Production technique master's ethylbenzene of ethylbenzene is to produce cinnamic raw material, and vinylbenzene be except that ethene trimerization monomer the propylene, can be used for producing the monomer of a series of macromolecular materials, these materials comprise polystyrene, synthetic rubber, the main basic product of these petrochemical compleies of ABS resin.At present, the cinnamic output in the whole world was 3,100 ten thousand tons in 2010, correspondingly, and about 3,400 ten thousand tons of ethylbenzene output.
The ethylbenzene molecular formula is C
8H
10, molecular weight is 106.17g/mol.Outward appearance is a colourless transparent liquid, and aromatic odour is arranged.
Ethylbenzene be benzene and ethene under the effect of an acidic catalyst, by Friedel-Crafts alkylated reaction synthetic, its reaction formula is as follows:
The ethylbenzene that generates also can further carry out many alkylated reactions with ethene, generates diethylbenzene and many ethylbenzene.
Reaction product is after rectifying separation, and alkylation reactor is returned in many ethylbenzene (mainly being diethylbenzene) circulation and benzene carries out transalkylation reaction (or carrying out) in independent transalkylation reactor, obtains ethylbenzene.
From present technology, ethylbenzene mainly makes by benzene alkylation with ethylene, and AlCl be arranged
3Method and homogeneous phase AlCl
3Method, the Alkar method, gas molecule in space sieve catalysis method, liquid phase molecular sieve catalytic method, and catalytic distillation technology etc.
U.S. Dow chemical company succeeded in developing with AlCl in nineteen thirty-five
3Technology for Catalyst Production ethylbenzene.AlCl
3Be dissolved in benzene, in ethylbenzene and the many ethyl benzene mixtures, generate complex compound and also form catalyzer complexing phase, contact with ethylene gas together mutually with other liquid aromatic hydrocarbons and alkylated reaction takes place.Its typical process condition is: 80～130 ℃ of temperature of reaction, pressure normal pressure be to 0.15MPa, benzene/ethylene molar ratio about 3, more complete to guarantee the ethene single step reaction, generate ethylbenzene and many ethylbenzene, many ethylbenzene of while and benzene generation transalkylation reaction, conversion of ethylene is near 100%.Alkylation yield 97.5%.
This production technique is because reaction process medium corrodibility is strong, and is very high to the requirement of equipment, and particularly the water requirement is very strict to raw material impurity content, and in addition, catalyst levels is big, and energy consumption, material consumption are all than higher, and this technology is eliminated just gradually.
At the beginning of the seventies, Monsanto company discovers, AlCl
3The complex compound that forms with many ethylbenzene can be dissolved in rapidly in benzene-ethylbenzene-many ethylbenzene mixed solution, thereby only forms homogeneous phase solution, and catalytic activity improves greatly.And the more traditional AlCl of catalyst levels
3Method reduces significantly, and its representative condition is: benzene alkene is than 1.2,140～200 ℃ of temperature of reaction, pressure 0.7～0.9, alkylation yield 97%.This technology began to drop into suitability for industrialized production by Monsanto and Lummus company in 1974.
The advantage of this technology is an alkylation yield height, AlCl
3Catalyst levels is few, but since this technology owing to still adopt AlCl
3As catalyzer, still there is the problem of equipment corrosion and sewage disposal, so this technology also belongs to superseded technology, only be used for traditional AlCl
3The transformation of method equipment, existing tens covering devices in the whole world adopt homogeneous phase AlCl
3Technology, 3,000,000 tons/year of overall throughputs.
The Alkar gas phase process is realized industrialization in nineteen sixty by Uop Inc., and BF is adopted in reaction
3Be catalyzer, ethene and benzene gas-phase reaction, its principal feature are that available low-concentration ethane is a raw material, and raw material ethylene concentration scope is 3～100%.Catalytic cracked dry gas or coke oven tail gas all can be unstripped gas.But for H in the unstripped gas
2S, CO
2And H
2Impurity such as O need strictness to remove, and are less than 0.0001%, but just normal running.Reaction medium does not have corrosion, catalyst activity height, but selectivity is poor slightly, thereby aftertreatment energy consumption, material consumption are higher.Reaction conditions is 3.5MPa, 120 ℃.At present, this technology has not had new device.
Mobil company succeeds in developing the ZSM-5 zeolite molecular sieve with shape selective catalysis effect the seventies.The ZSM-5 molecular sieve has the cross bore web frame, and the port size size is the most suitable to aromatic hydrocarbons processing.In producing reactions such as ethylbenzene, p-Xylol, obtained good application.This technology has avoided using AlCl
3Problems such as environmental pollution that causes as catalyzer and equipment corrosion.1980, the U.S.'s first cover vapor-phase alkylation device was put into serial production.
Its typical process condition is: alkylation reactor is multistage insulation formula (4～6 sections), unstripped gas segmentation cold shock is to remove reaction heat, reaction medium benzene and ethene are gas phase, adsorb and reaction at catalyst surface, 370～420 ℃ of temperature of reaction, pressure 1.4～2.8MPa, weight ethylene air speed (WHSV) is 2～5gEg
-1Cathr
-1, the total mol ratio 5～20 of benzene/ethene, conversion of ethylene 99.8%, ethylbenzene selectivity can reach 99.5%.
This process catalyst consumption is few, and equipment does not have corrosion, environmental nonpollution, and characteristics such as ethylbenzene yield height; Higher owing to its temperature of reaction in addition, thus the capacity usage ratio height, but byproduct steam; Flow process is short, less investment, and the existing covering device more than 30 in the whole world is used this technology at present, and annual production is more than 1,000 ten thousand tons.
The eighties, Unocal company succeeds in developing y-type zeolite and liquid phase alkylation process, and signs license licensed licenser licence by Lummus company.Afterwards, catalyzer and the Technology patent right of Unocal purchased by Uop Inc., and catalyzer is made by Uop Inc., thereby renames as Lummus/UOP technology, also claims Lummus/Unocal/UOP (L/U/U) technology.Recently, the EBZ-500 zeolite catalyst of Uop Inc.'s exploitation demonstrates higher activity and selectivity.Compare with gas-phase process, the major advantage of liquid phase method technology is: (1) is reflected at 3.5～4.0Mpa, 250～320 ℃, benzene/ethene amount of substance ratio is to carry out under 8～10 conditions.Certain pressure makes reaction mass remain on liquid phase state; Excessive benzene can improve ethylbenzene selectivity again, reduces the generation of by products such as diethylbenzene; Then do not need the process furnace heating after temperature of reaction reduces, reactor material needn't be used the high-temperature alloy steel as vapor phase process, and gets final product with general carbon steel.(2) the y-type zeolite catalyzer is adopted in reaction, and the macropore three-dimensional channel is arranged on its structure, has good alkylation and transalkylation activity.Various materials flow through zeolite cavity easily in the reactor, wash away the knot charcoal that accumulates in the zeolite cavity, thereby reduce the charcoal rate of finishing.The catalyst regeneration cycle is more than 2 years, life expectancy 8～10 years.(3), thereby make the total recovery of ethylbenzene can reach 99% because many ethylbenzene carry out transalkylation reaction in the reactor that the y-type zeolite catalyzer is housed separately; Ethylbenzene purity can reach 99.85%.(4) flow process is shorter, and the table of equipment number is few, does not have corrosion, and " three wastes " discharging is few, pollution-free substantially.Because armamentarium adopts carbon steel material, investment cost is relatively low.
Since the operation of the nineteen ninety first cover 210kt/a of Japan styrene monomer company device, existing 3 are enclosed within Japan, 1 is enclosed within China's operation, also has 13 covering devices to be in the construction period, and throughput does not wait from 100kt/a to 530kt/a
[11]
Chemical Research ε tLicensing company and Lummus company succeed in developing catalytic distillation system ethylbenzene production technique, i.e. CDTECH technology at the end of the eighties.This technology is that the liquid phase sieve technology is combined with catalytic rectification process, carries out catalyzed reaction and distillation procedure simultaneously.The catalyzer that adopts is Y type (or β type) molecular sieve, and reactor is a rectifying tower, and catalyzer is arranged at the rectifying section of rectifying tower, the heating of tower still, and the overhead benzene total reflux, ethylbenzene is from the discharging of tower still.150～170 ℃ of temperature of reaction, pressure 1.0～2.0MPa, the total mol ratio 1～2 of benzene alkene, conversion of ethylene is near 100%, and ethylbenzene selectivity is more than 99%, and the catalyst regeneration cycle can reach 2 years.
The catalytic rectification process principal feature is and reaction heat can be directly used in separation that reduced isolating thermal load, energy consumption is low; The easy coking of catalyst for alkylation reaction and the inactivation of general benzene and ethene carry out but be reflected in the liquid phase, can in time burnt precursor be shifted out, and help prolonging life of catalyst; Reduce the chance of side reactions such as alkylated reaction and isomerization generation dimethylbenzene further take place again, can make ethylbenzene in time leave reaction zone, improve the selectivity of ethylbenzene.
USP4,849,569 have proposed a kind of catalytic distillation technology, promptly in reaction, finish separating of reactant and resultant, and utilize reaction heat to carry out fractionation by distillation, made full use of the process energy, and owing to reaction product is successively removed, destroy chemical equilibrium, improved the transformation efficiency of reactant and the yield of purpose product.But the member of its filling is catalyzer to be added the Stainless Steel Cloth parcel with woven fiber glass form, and labour intensity is big and mass-transfer efficiency is low, and reaction effect is undesirable.
CN1064475A has proposed a kind of cartridge type catalytic reaction distillation technology in bulk, is characterized in that fixed-bed reactor are put into distillation tower forms conversion zone, and with each bed temperature of Quench Material control between bed, this technology does not make full use of the reaction liberated heat.
USP5,476,978 catalytic distillation technologies that propose are applied to alkylation process, but many alkyl thing content height in its product.Reaction conversion ratio, selectivity are not high.Need complicated follow-up transalkylation and separating technology.
CN1085644C proposes to produce the catalytic distillation method of alkylbenzene, this method is to be undertaken by in four sections or five sections catalytic distillation towers that constitute at one, this catalytic distillation tower is followed successively by from top to bottom: first rectifying section, first conversion zone, second rectifying section, second conversion zone, stripping section, wherein first rectifying section can not established, benzene and alkene carry out alkylated reaction at catalytic distillation tower first conversion zone, and the by product polyalkylbenzene must carry out transalkylation reaction in catalytic distillation tower second reaction.This method can make alkylated reaction, transalkylation reaction carry out simultaneously in same catalytic distillation tower, has improved the selectivity of conversion of olefines rate and alkylbenzene, has simplified technical process.
CN100582071C has proposed the dividing wall type catalytic rectifying tower, has mentioned being used for alkylation process.
The raw material ethene of ethylbenzene production has multiple source: the polymer grade ethylene that cracker comes ethene (ethylene content 12-20%) in the FCC dry gas, ethanol dehydration chemical grade ethene lighter hydrocarbons cracking system chemical grade ethene the ethene or the like of methanol-to-olefins, raw material route all is a polymer grade ethylene in the world at present, the utilization of FCC dry gas is China's unique technique route, is used by other countries hardly.
Ethylbenzene process has the Technological Economy competitive power at present, and only the FCC dry gas comes vapor phase process to produce ethylbenzene, and polymerization-grade polymer grade ethylene liquid phase method ethylbenzene device, and new device nearly all was the liquid phase method device in nearly 5 years.The obvious different rank of content owing to ethene in the ethylene raw, 10-30%, 30-80%, the 80-99.95% polymer grade ethylene all is diverse on the used ins and outs, and many patents are known as and can be adapted to all raw materials and do not meet the science reason, clearly because the difference of ethylene concentration, the solubleness of ethene in benzene, reaction heat effect are to the influence of system, and residual ethylene content, vent gas treatment and recovery are widely different in fact in the tail gas.But the ethylene production ethylbenzene basic technology of 10-90% can be identical, and difference is only different at the yield of ethene.When ethylene content greater than 80% the time, in present liquid-phase catalysis technology, total mol ratio of benzene and ethene is about 3-6, ethene is divided into the 2-10 thigh, benzene is not cut apart, so local, the mol ratio of benzene and ethene is at 20-100, ethene and other gases (methane hydrogen ethane etc.) can be dissolved in the middle of the benzene fully, thereby can finish the alkylated reaction of ethene and benzene in liquid phase.But for the ethylene gas of ethylene content 10-80%, more reasonably technology must be arranged obviously, could economical rationality use it to produce ethylbenzene.
Summary of the invention
The objective of the invention is to propose a kind of method, to overcome the above-mentioned defective that prior art exists with ethylene production ethylbenzene.
Method of the present invention comprises the steps:
(1) contains the gaseous mixture of ethene and inert component such as nitrogen etc., be divided into N part, enter the bottom of alkylation reactor N absorber portion respectively by pipeline, flow from bottom to top, with from the absorption agent at alkylation reactor top in the absorber portion counter current contact, ethene and inert component are absorbed agent and absorb;
In the described absorption agent, the mass content of ethylbenzene and many ethylbenzene is 30～90%, and surplus is a benzene, preferably 40～70%, more preferably 50～60%, the yield that can guarantee ethene is greater than 90%, better greater than 95%, thereby can utilize the ethene resource fully.
The mass ratio of ethylbenzene and many ethylbenzene is: ethylbenzene: many ethylbenzene=1: 0.05～0.5;
Described many ethylbenzene is diethylbenzene and triethyl-benzene, and the mass ratio of diethylbenzene and triethyl-benzene is: diethylbenzene: triethyl-benzene=1: 0.05～0.5;
(2) absorption agent that has absorbed ethene flows downward, and enters next-door neighbour's conversion zone thereunder, under catalyst action, and the benzene in the absorption agent, ethylbenzene and diethylbenzene etc. and dissolved ethene, reaction generates more than one in ethylbenzene and the many ethylbenzene;
Described catalyzer is Y molecular sieve or beta-molecular sieve;
Absorption agent is in alkylation reactor, pass through each absorber portion and conversion zone successively, in conversion zone, be dissolved in ethene in the absorption agent and almost completely be converted in ethylbenzene or the many ethylbenzene more than one, thereby make absorption agent recover receptivity again, can carry out the absorption and the reaction of next stage ethene;
Reacted gas phase and liquid phase alkylation liquid are sent to follow-up workshop section respectively, handle.
So be provided with, can ensure to react completely, and can avoid the ethene contact catalyst of gas phase fully, thereby delay the coking and the inactivation of catalyzer that can satisfy the needs of industry member, this is one of free-revving engine of the present invention.
Absorption and reaction are carried out under following processing condition: pressure 2.5MPa-5.0MPa, 17 ℃ of 0-240 of temperature, the mol ratio 20-30 of benzene and ethene, the mol ratio 5-20 of ethylbenzene and ethene;
Reacting section catalyst ethene air speed is 0.3-0.8kg catalyzer/kg ethene .h, is preferably 0.5-0.6kg catalyzer/kg ethene .h;
Absorption and reaction are carried out under following processing condition: pressure 2.5MPa-5.0MPa, 17 ℃ of 0-240 of temperature, the mol ratio 20-30 of benzene and ethene, the mol ratio 5-20 of ethylbenzene and ethene;
Adopt above-mentioned method, conversion of ethylene can reach 99.95%, and the ethylene recovery rate is greater than 90%;
Conversion of ethylene is defined as follows:
Enter the ethene flow of reactor-the leave ethene flow of reactor)/the ethene flow X100% of reactor entered;
The ethylene recovery rate is defined as follows:
Ethene flow in the tail gas of ethene flow-separating device in the dry gas of access to plant)/dry gas of access to plant in ethene flow X100%;
The present invention will contain ethylene gas and be divided into aliquot, be in order to ensure the ethene that absorbs as much as possible with the ethylene absorbent that contains the benzene composition in the gas phase, thereby guarantee the rate of recovery of ethene.Different with general benzene alkylation reaction, in general benzene gas phase or liquid-phase alkylation, only use benzene usually, ethylbenzene usually only contains therein and is no more than 1% mass percent.Among the present invention, the absorption agent that uses benzene, ethylbenzene, many ethylbenzene etc. to form, rather than only use above-mentioned benzene.Usually in the absorption agent mass content of ethylbenzene and many ethylbenzene greater than 30%, better in the absorption agent mass content of ethylbenzene and many ethylbenzene greater than 50%, the mass content of ethylbenzene and many ethylbenzene is greater than 60% in the best absorption agent, so be provided with can guarantee ethene yield greater than 90%, better greater than 95%, thereby can utilize the ethene resource fully.
Secondly, because main the forming of absorption agent by benzene, ethylbenzene, and amount of ethylbenzene is more than the amount of benzene, so in alkylated reaction, the ethylene alkylation of benzene and the ethylene alkylation of ethylbenzene all are very significant, thereby produce ethylbenzene and many ethylbenzene of significant quantity, the content of many ethylbenzene is greater than the technology of routine significantly.
So dispose technology, can't make the total energy consumption of technology increase significantly.Its reason is, usually in the technology of using Y molecular sieve or beta-molecular sieve, the benzene of alkylated reaction and ethylene ratio (mol) are generally between 3.5-6, the mol ratio of transalkylation reaction phenyl and vinyl is 2-10, it can be that 2-2.5 moves steadily in the long term in the mol ratio of phenyl and vinyl that molecular sieve catalyst has been arranged, thereby can't increase the internal circulating load of benzene in large quantities, and the ground mass percent of ethylbenzene reaches 30-60% in the alkylation liquid of assurance arrival benzene tower, thereby has guaranteed the efficient and energy-conservation of sepn process.Compare with liquid phase alkylation process with existing vapor-phase alkylation, the ethylbenzene of high density like this, the mol ratio that is equivalent to benzene/ethene in the benzene alkylation reaction is 1.5-3, and obviously the mol ratio than benzene/ethene in the benzene alkylation reaction in the existing technology is 3.5-6, and significant advance is arranged.
Once more, the alkylated reaction of benzene and ethene, the alkylated reaction of ethylbenzene and ethene all is thermopositive reaction, and stronger heat effect is arranged.In vapor-phase alkylation technology, reaction need be divided into multistage, and, absorb heat by cold dry gas and cool off reaction product to keep temperature of reaction (CN1055075C) at the cold dry gas of intersegmental adding; When the ethylene concentration in the dry gas surpassed 40%, the cold benzene vapour that also must add a part was to keep temperature of reaction.In liquid phase method technology, general temperature rise by the reaction of each section of control, the mode of taking heat away with waste heat boiler again after stream temperature raises keeps temperature of reaction (CN200580051066.2).In the present invention, after each section reaction, the temperature of liquid-phase reaction product can raise, the reactant flow that heats up, having more material is evaporated in the mixed gas that contains ethene and goes, reduce the temperature of liquid phase stream by the mode that absorbs evaporation, thereby kept temperature of reaction within the reasonable range that catalyzer can bear.
Adopt method of the present invention, not only can significantly improve the conversion of ethylene and the rate of recovery, and can ensure and react completely, and can avoid the ethene contact catalyst of gas phase fully, thereby delayed the coking and the inactivation of catalyzer, can satisfy the needs of industry member.
Description of drawings
Fig. 1 is the schema with ethylene production ethylbenzene.
Fig. 2 is the conversion zone of reactor and the structural representation of absorber portion.
Fig. 3 is the conversion zone cross sectional representation.
Embodiment
Referring to Fig. 1 and Fig. 2, method of the present invention comprises the steps:
(1) contains the gaseous mixture of ethene and inert component such as nitrogen etc., be divided into N part, enter the bottom of the N absorber portion 2 of alkylation reactor 100 respectively from gas phase inlet 10 by pipeline, flow from bottom to top, with from the absorption agent of alkylation reactor 100 top absorption agents inlet 16 in absorber portion 2 counter current contact, ethene and inert component, other reaction mediums that may also contain trace are absorbed agent and absorb such as propylene and butylene etc.;
Described alkylation reactor 100 is provided with N absorber portion 2 and N conversion zone 1;
Preferably, contain the gaseous mixture of ethene and inert component, be divided into 4～8 parts, alkylation reactor 100 is provided with 4～8 absorber portions 2 and 4～8 conversion zones 1, and absorber portion 2 is identical with the quantity of conversion zone 1;
In the described absorption agent, the mass content of ethylbenzene and many ethylbenzene is 30～90%, and surplus is a benzene, preferably 30～70%, more preferably 40～60%, the yield that can guarantee ethene is greater than 90%, better greater than 95%, thereby can utilize the ethene resource fully.
The mass ratio of ethylbenzene and many ethylbenzene is: ethylbenzene: many ethylbenzene=1: 0.05～0.5;
Described many ethylbenzene is diethylbenzene and triethyl-benzene, and the mass ratio of diethylbenzene and triethyl-benzene is: diethylbenzene: triethyl-benzene=1: 0.05～0.5;
(2) absorption agent that has absorbed ethene flows downward, and enters next-door neighbour's conversion zone thereunder 1, under catalyst action, and the benzene in the absorption agent, ethylbenzene and diethylbenzene etc. and dissolved ethene, reaction generates ethylbenzene and many ethylbenzene;
Described catalyzer is Y molecular sieve or beta-molecular sieve; Can adopt＜petrochemical complex the method preparation of 1999 years No4P215 bibliographical informations, or adopt commercially produced product, be the product of EBZ-500 as Uop Inc.'s trade mark; Or the trade mark of Sinopec company is the AEB-6 catalyzer.
Absorption agent is in alkylation reactor 100, pass through each absorber portion 2 and conversion zone 1 successively, in conversion zone, be dissolved in ethene in the absorption agent and almost completely be converted in ethylbenzene or the many ethylbenzene more than one, thereby make absorption agent recover receptivity again, can carry out the absorption and the reaction of next stage ethene;
So be provided with, can ensure to react completely, and can avoid the ethene contact catalyst of gas phase fully, thereby delay the coking and the inactivation of catalyzer that can satisfy the needs of industry member, this is one of free-revving engine of the present invention.
Absorption and reaction are carried out under following processing condition: pressure 2.5MPa-5.0MPa, 17 ℃ of 0-240 of temperature, the mol ratio 20-30 of benzene and ethene, the mol ratio 5-20 of ethylbenzene and ethene;
Reacting section catalyst ethene air speed is 0.3-0.8kg catalyzer/kg ethene .h, is preferably 0.5-0.6kg catalyzer/kg ethene .h;
(3) reacted gas phase mainly contains residual ethylene and rare gas element, is sent into the middle part of stabilizer tower 200 by pipeline 22 by the gaseous phase outlet 19 of alkylation reactor 100;
Reacted liquid phase alkylation liquid, mainly contain benzene, ethylbenzene and many ethylbenzene, liquid phase outlet 17 by the bottom of alkylation reactor 100 is discharged, part enters stabilizer tower 200 by pipeline 24 from the middle part, part enters alkylation reactor 100 through pipeline 29 from 16 circulations of the absorption agent at alkylation reactor 100 tops inlet by pipeline 23;
Wherein: the quality that enters alkylation reactor 100 is the 0-50% of total amount, preferably 20～30%;
In stabilizer tower 200, separate the gas of sucking-off, be the gas phase inert component in the liquid phase and the ethene of complete reaction not, discharge by the tail gas outlet 26 at stabilizer tower 200 tops, be sent to follow-up recovery process 500, reactant or reaction product such as benzene in the recovery tail gas and ethylbenzene;
(4) deviate from the liquid phase alkylation liquid of gas, contain a large amount of ethylbenzene and many ethylbenzene, flow out from the stabilizer tower liquid phase outlet 27 of stabilizer tower 200 bottoms, part enters benzene tower 300 by pipeline 28 from the liquid phase alkylation liquid of benzene tower 300 inlet 31, and part enters alkylation reactor 100 from absorption agent inlet 16 circulations at alkylation reactor 100 tops;
The quality that enters benzene tower 300 is the 0-60% of total hydrocarbonylation liquid measure, preferred 30～50%;
The processing condition of stabilizer tower: pressure 0.6-1.5MPa, tower top temperature 40-60 ℃, column bottom temperature 160-200 ℃;
(5) fresh benzene enters benzene tower 300 by benzene inlet 30 from top, and in the benzene tower 300, the material that enters is separated, and condensing is discharged from the benzene tower gaseous phase outlet 32 of cat head, is sent to follow-up recovery process 500;
Recycle benzene is discharged from the benzene outlet 35 on the top of benzene tower 300, part enters alkylation reactor 100 from absorption agent inlet 16 circulations at alkylation reactor 100 tops, part is sent to transalkylation reactor 400, the quality that is sent to alkylation reactor 100 is the 40-95% of global cycle benzene amount, preferred 80～95%; The tower base stream of benzene tower 300 is sent to follow-up separation circuit from benzene Tata bottom outlet 33 by pipeline, separating obtained product ethylbenzene and many ethylbenzene;
The processing condition of benzene tower 300: pressure 0.6-0.8MPa, tower top temperature 150-180 ℃, column bottom temperature 210-240 ℃, reflux ratio 1.2-2;
Further, the tower base stream of benzene tower 300 enters ethylbenzene tower 600 to be separated, and ethylbenzene is discharged from the ethylbenzene tower gaseous phase outlet 38 at ethylbenzene tower top, and the ethylbenzene tower liquid phase outlet 39 of many ethylbenzene at the bottom of the tower discharged;
The processing condition of ethylbenzene tower 600: pressure 0.18-0.3MPa, tower top temperature 150-180 ℃, column bottom temperature 210-240 ℃, reflux ratio 0.6-2;
Further, many ethylbenzene stream that ethylbenzene tower liquid phase outlet 39 is discharged are sent to many ethylbenzene towers 700 and separate, many ethylbenzene are discharged from many ethylbenzene towers gaseous phase outlet 40 of cat head, part enters transalkylation reactor 400 by pipeline from the transalkylation reactor material inlet 42 of bottom, part is sent into the absorption agent inlet 16 at alkylation reactor 100 tops by pipeline 37, circulation enters alkylation reactor 100, and the ethylbenzene tar outlet 41 of ethylbenzene tar at the bottom of many ethylbenzene tower 700 towers discharged;
The material that enters transalkylation reactor 400 is 10～90% of a total mass, preferred 10～30%;
The processing condition of many ethylbenzene towers: pressure 20-80kPa (absolute pressure), tower top temperature 40-60 ℃, column bottom temperature 200-240 ℃, reflux ratio 0.2-1;
Further, in transalkylation reactor 400, diethylbenzene and triethyl-benzene etc. are under the effect of transalkylation catalyst, generate ethylbenzene with the benzene reaction, the alkylation liquid that contains benzene, ethylbenzene, many ethylbenzene is discharged from the transalkylation reactor outlet 31 at transalkylation reactor 400 tops, is sent to benzene tower 300 and recycles;
The transalkylation reaction processing condition:
Transalkylation catalyst adopts commercially produced product, is the product of EBZ-500 as Uop Inc.'s trade mark; Or the trade mark of Sinopec company is the AEB-1 catalyzer.
Pressure 3.0-5.0MPa, temperature 180-260 ℃, the mol ratio of transalkylation reaction phenyl and vinyl is 2-10, preferred 2-3.
Referring to Fig. 1～Fig. 3, described alkylation reactor 100 comprises: the housing 3 of column, absorber portion 2 and conversion zone 1, gas phase inlet 10, gaseous phase outlet 19, absorption agent inlet 16 and liquid phase outlet 17;
Described absorber portion 2 and conversion zone 1 alternate combination are arranged in the described housing 3;
Described conversion zone 1 comprises: be provided with import distribution hole central well down take 101, be provided with dividing plate 102, upper bed board 103, the lower bed board 104 of liquid phase inlet 105 and be provided with the outer downtake 107 in outlet distribution hole;
Upper bed board 103 is connected with the top of outer downtake 107, and lower bed board 104 is connected with the bottom of outer downtake 107, constitutes catalytic bed 106, is provided with the gap between liquid phase exit plate 107 and the housing 3, is liquid phase outlet flow 98;
Described dividing plate 102 is arranged between absorber portion 2 and the conversion zone 1, and two ends are connected with housing 3 inwalls;
The upper end of described central well down take 101 is connected with liquid phase inlet 105, and catalytic bed 106 is passed in the lower end, is fixed on housing 3 inwalls by supporting clapboard 108;
Described gas phase inlet 10 is arranged on absorber portion 2 bottoms, and described gaseous phase outlet 19 is arranged on absorber portion 2 tops;
Absorption agent contacts with the gas that enters at absorber portion 2, absorption ethene wherein etc., enter central well down take 101 then, enter catalytic bed 106 by import distribution hole, logistics is passed catalytic bed and is flowed, react, by outlet distribution hole, enter next absorber portion then by liquid phase outlet flow 98;
So being provided with is exactly in order thoroughly to cut apart gas phase and liquid phase, thereby avoids the coking and the inactivation of catalyzer, can satisfy industrial requirements.
Certain dry gas liquid phase ethylbenzene device, the flow process of employing Fig. 1, scale is produced 100000 tons in ethylbenzene per year.
Wherein:
Absorber portion adopts 8 theoretical stages;
The catalyzer ethene air speed of conversion zone 1 is 0.5kg catalyzer/kg ethene .h, every section 2m of loaded catalyst
3, amount to catalyst levels 10m
3
Processing condition and logistics data such as table 1.Thing stream number in the table 1 is each parts number among Fig. 1.
In the table 1, other refer to the total amount of the rare gas element except that ethene in the dry gas.
Table 1
| The |
10 | 16 | 22 | 24 | 27 | 28 | 29 | 30 |
| Pressure MPa | 3.9 | 4.0 | 3.0 | 3.0 | 0.9 | 0.9 | 0.9 | 1.0 |
| Temperature ℃ | 90 | 185 | 155 | 204 | 181 | 181 | 181 | 40 |
| Flow kg/h | 20041 | 140696 | 48262 | 112475 | 144440 | 35053 | 109388 | 14255 |
| Ethene | 5641 | 450 | 3.8 |
| Other | 14400 | 13340 | 2095.2 | 1517 | 15 | |||
| Benzene | 82142 | 25326 | 44362 | 67762 | 16444 | 51317 | 14240 | |
| Ethylbenzene | 51909 | 8768 | 59569 | 68337 | 16584 | 51753 | ||
| Many ethylbenzene | 5168 | 378 | 6445 | 6824 | 1666 | 5168 |
Continuous table 1
| The |
31 | 32 | 33 | 37 | 38 | 39 | 40 | 42 |
| Pressure MPa | 3.8 | 0.71 | 0.75 | 4.0 | 0.2 | 0.22 | 4.0 | 3.8 |
| Temperature ℃ | 220 | 142 | 238 | 163 | 163 | 229 | 102 | 220 |
| Flow kg/h | 8550 | 825 | 25368 | 5302 | 19082 | 6286 | 3249 | 8550 |
| Ethene | 4.4 | |||||||
| Other | ||||||||
| Benzene | 4243 | 743 | 12 | 5220 | 12 | 5220 | ||
| Ethylbenzene | 2694 | 19087 | 26 | 19024 | 63 | 63 | 89 | |
| Many ethylbenzene | 1408 | 4362 | 4362 | 3037 | 3037 |
According to calculating, conversion of ethylene can reach 99.95%, and the ethylene recovery rate is greater than 90%.
Claims (8)
1. the method with ethylene production ethylbenzene is characterized in that: comprise the steps:
(1) contains the gaseous mixture of ethene and inert component, be divided into N part, enter the bottom of the N absorber portion (2) of alkylation reactor (100) respectively from gas phase inlet (10) by pipeline, flow from bottom to top, with from the absorption agent of alkylation reactor (100) top absorption agent inlet (16) in absorber portion (2) counter current contact;
Described alkylation reactor (100) is provided with N absorber portion (2) and N conversion zone (1);
In the described absorption agent, the mass content of ethylbenzene and many ethylbenzene is 30～90%, and surplus is a benzene;
(2) absorption agent that has absorbed ethene flows downward, and enters next-door neighbour's conversion zone thereunder (1), under catalyst action, and the benzene in the absorption agent, ethylbenzene and diethylbenzene and dissolved ethene, reaction generates more than one in ethylbenzene and the many ethylbenzene;
Absorption agent passes through each absorber portion (2) and conversion zone (1) successively in alkylation reactor (100), in conversion zone, be dissolved in conversion of ethylene in the absorption agent and be in ethylbenzene or the many ethylbenzene more than one;
Reacted gas phase and liquid phase alkylation liquid are sent to follow-up workshop section respectively, handle;
(3) reacted gas phase is sent into the middle part of stabilizer tower (200) by pipeline (22) by the gaseous phase outlet (19) of alkylation reactor (100);
Reacted liquid phase alkylation liquid, liquid phase outlet (17) by the bottom of alkylation reactor (100) is discharged, part enters stabilizer tower (200) by pipeline (24) from the middle part, part by pipeline (23) through pipeline (29) from the absorption agent at alkylation reactor (100) top enter the mouth (16) circulate and enter alkylation reactor (100);
In stabilizer tower (200), separate the gas of sucking-off, discharge by the tail gas outlet (26) at stabilizer tower (200) top;
(4) deviate from the liquid phase alkylation liquid of gas, flow out from the stabilizer tower liquid phase outlet (27) of stabilizer tower (200) bottom, part enters benzene tower (300) by pipeline (28) from the liquid phase alkylation liquid of benzene tower (300) inlet (31), and part circulates from the absorption agent inlet (16) at alkylation reactor (100) top and enters alkylation reactor (100);
The processing condition of stabilizer tower: pressure 0.6-1.5MPa, tower top temperature 40-60 ℃, column bottom temperature 160-200 ℃;
(5) fresh benzene enters benzene tower (300) by benzene inlet (30) from top, and condensing is not discharged from the benzene tower gaseous phase outlet (32) of cat head, is sent to follow-up recovery process (500);
Recycle benzene is discharged from the benzene outlet (35) on the top of benzene tower (300), part enters alkylation reactor (100) from absorption agent inlet (16) circulation at alkylation reactor (100) top, part is sent to transalkylation reactor (400), the tower base stream of benzene tower (300) is sent to follow-up separation circuit from benzene Tata bottom outlet (33) by pipeline, separating obtained product ethylbenzene and many ethylbenzene;
Described alkylation reactor (100) comprising: the housing of column (3), absorber portion (2) and conversion zone (1), gas phase inlet (10), gaseous phase outlet (19), absorption agent inlet (16) and liquid phase outlet (17);
Described absorber portion (2) and the alternate combination of conversion zone (1) are arranged in the described housing (3);
Described conversion zone (1) comprising: be provided with import distribution hole central well down take (101), be provided with dividing plate (102), upper bed board (103), the lower bed board (104) of liquid phase inlet (105) and be provided with the outer downtake (107) that exports the distribution hole;
Upper bed board (103) is connected with the top of outer downtake (107), lower bed board (104) is connected with the bottom of outer downtake (107), constitute catalytic bed (106), be provided with the gap between liquid phase exit plate (107) and the housing (3), be liquid phase outlet flow (98);
Described dividing plate (102) is arranged between absorber portion (2) and the conversion zone (1), and two ends are connected with housing (3) inwall;
The upper end of described central well down take (101) is connected with liquid phase inlet (105), and catalytic bed (106) is passed in the lower end, is fixed on housing (3) inwall by supporting clapboard (108);
Described gas phase inlet (10) is arranged on absorber portion (2) bottom, and described gaseous phase outlet (19) is arranged on absorber portion (2) top;
Absorption agent inlet (16) is arranged on the top of housing (3), and liquid phase outlet (17) is arranged on the bottom of housing (3);
The gaseous mixture that contains ethene and inert component is divided into 4～8 parts, and alkylation reactor (100) is provided with 4～8 absorber portions (2) and 4～8 conversion zones (1), and absorber portion (2) is identical with the quantity of 4～8 conversion zones (1);
Described catalyzer is Y molecular sieve or beta-molecular sieve.
2. method according to claim 1, it is characterized in that, the tower base stream of benzene tower (300) enters ethylbenzene tower (600) to be separated, and ethylbenzene is discharged from the ethylbenzene tower gaseous phase outlet (38) at ethylbenzene tower top, and the ethylbenzene tower liquid phase outlet (39) of many ethylbenzene at the bottom of the tower discharged.
3. method according to claim 2, it is characterized in that, many ethylbenzene stream that ethylbenzene tower liquid phase outlet (39) is discharged are sent to many ethylbenzene towers (700) and separate, many ethylbenzene are discharged from many ethylbenzene towers gaseous phase outlet (40) of cat head, part enters transalkylation reactor (400) by pipeline from the transalkylation reactor material inlet (42) of bottom, part is sent into the absorption agent inlet (16) at alkylation reactor (100) top by pipeline (37), circulation enters alkylation reactor (100), and the ethylbenzene tar outlet (41) of ethylbenzene tar at the bottom of many ethylbenzene towers (700) tower discharged.
4. method according to claim 3, it is characterized in that, in transalkylation reactor (400), diethylbenzene and triethyl-benzene are under the effect of transalkylation catalyst, generate ethylbenzene with the benzene reaction, the alkylation liquid that contains benzene, ethylbenzene, many ethylbenzene is discharged from the transalkylation reactor outlet (31) at transalkylation reactor (400) top, is sent to benzene tower (300) and recycles.
5. method according to claim 1 is characterized in that, in the described absorption agent, the mass content of ethylbenzene and many ethylbenzene is 30～70%, and surplus is a benzene.
6. method according to claim 1 is characterized in that, in the step (3), the quality that enters alkylation reactor (100) is 20～30% of a total amount.
7. method according to claim 1 is characterized in that, in the step (4), the quality that enters benzene tower (300) is 30～50% of total hydrocarbonylation liquid measure.
8. method according to claim 1 is characterized in that, in the step (5), the quality that is sent to alkylation reactor (100) is the 40-95% of global cycle benzene amount.
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| CN102875287A (en) * | 2012-09-03 | 2013-01-16 | 李小燕 | Method and device for producing various products with methyl alcohols |
| CN107827692B (en) * | 2017-04-28 | 2021-06-29 | 常州瑞华化工工程技术股份有限公司 | Method for producing ethylbenzene by using high-concentration ethylene gas |
| CN108299143A (en) * | 2017-12-27 | 2018-07-20 | 北方华锦化学工业股份有限公司 | Ethylbenzene vapor phase alkylation device opens, stop during recovered material method |
| CN112321379B (en) * | 2020-10-22 | 2023-05-09 | 北京惠尔三吉绿色化学科技有限公司 | Energy-saving and environment-friendly method for preparing ethylbenzene from dry gas |
| CN114671732A (en) * | 2022-04-07 | 2022-06-28 | 中石化广州工程有限公司 | Process for preparing ethylbenzene by ethylene-containing dry gas-liquid phase method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5176883A (en) * | 1985-01-07 | 1993-01-05 | Chemical Research & Licensing Company | Alkylation of organic aromatic compounds |
| CN101417920A (en) * | 2007-10-26 | 2009-04-29 | 环球油品公司 | The C2 that FCC-produces and the incorporate production of ethylbenzene |
| CN101768043A (en) * | 2008-12-31 | 2010-07-07 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene by reaction of dilute ethylene and benzene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5176883A (en) * | 1985-01-07 | 1993-01-05 | Chemical Research & Licensing Company | Alkylation of organic aromatic compounds |
| CN101417920A (en) * | 2007-10-26 | 2009-04-29 | 环球油品公司 | The C2 that FCC-produces and the incorporate production of ethylbenzene |
| CN101768043A (en) * | 2008-12-31 | 2010-07-07 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene by reaction of dilute ethylene and benzene |
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