CN107827692A - A kind of method that ethylbenzene is produced with high concentration ethylene gas - Google Patents

A kind of method that ethylbenzene is produced with high concentration ethylene gas Download PDF

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CN107827692A
CN107827692A CN201710293859.XA CN201710293859A CN107827692A CN 107827692 A CN107827692 A CN 107827692A CN 201710293859 A CN201710293859 A CN 201710293859A CN 107827692 A CN107827692 A CN 107827692A
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benzene
ethylbenzene
reaction
tower
gas
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CN107827692B (en
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和成刚
徐志刚
张文明
张晶
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CHANGZHOU RUIHUA CHEMICAL ENGINEERING TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to a kind of method that ethylbenzene is produced with high concentration ethylene gas, including following technique：The dense ethene dry gas of raw material is divided into multiply and correspondingly enters multiple absorption towers；It is absorbent that first absorption tower, which is additionally provided benzene feedstock,；Handled from the gaseous phase materials that absorption tower comes out into vapor phase alkylation device；And liquid material is reacted into liquid phase alkylation reaction device；Discharging after liquid phase alkylation reaction separates two strands, wherein first strand of material returns to this grade of absorption tower makees absorbent as absorbent, second strand of material into next stage absorption tower；One returns to last absorption tower to the material eventually formed after share split is reacted, and another stock then enters benzene recovery tower；Material of the extraction rich in ethylbenzene enters ethylbenzene recovery tower formation ethylbenzene distillate in benzene recovery tower.The present invention mainly uses liquid phase production technology, and reaction temperature is relatively low, has the advantages that energy-saving and environmental protection, and conversion rate of products is high, and the control of caused xylene content is in below 100PPM, good product quality.

Description

A kind of method that ethylbenzene is produced with high concentration ethylene gas
Technical field
The invention belongs to the dry gas and benzene alkylation of the component containing high concentration ethylene（Also referred to as " hydrocarbonylation "）The method for producing ethylbenzene, Mainly include dry gas and absorb liquid phase reactor technique, the process of alkylation liquid separated.
Background technology
Ethylbenzene is important industrial chemicals, is mainly used in dehydrogenation and manufactures industrial chemicals monomer styrene, styrene is The raw material of polystyrene and copolymer, market dosage are big.At present, the production of ethylbenzene mainly uses the production of benzene alkylation with ethylene Method, benzene and ethene are synthesized in the presence of acidic catalyst by Friedel-Crafts alkylated reactions, its reaction equation It is as follows：
The ethylbenzene of generation can also further carry out more alkylated reactions with ethene, generate diethylbenzene and more ethylbenzene.
Diethylbenzene and more ethylbenzene in reaction product carries out transalkylation after rectifying separates, using with benzene（Also referred to as " anti-hydrocarbon Change "）Method obtain in ethylbenzene return system, be referred to as turning alkylated reaction in the said process present invention, used equipment claims To turn alkylation reactor.
Different according to ethylene source, the production technology of ethylbenzene is divided into pure ethylene technique（Feed ethylene is polymer grade ethylene）And Dilute ethene（Raw material is the dry gas containing ethene, refers generally to catalytic cracked dry gas）Technique；, can according to the difference of alkylated reaction phase To be divided into liquid phase method technique and gas-phase process, because reaction condition is gentle, the ethylbenzene than gas-phase process produces liquid phase method technique Quality is good, energy and material consumption is low, is all the preferred process route of industrialization no matter to pure ethylene or dilute ethylene unit.It is new in the world Build pure ethylene method Benzene Device and use liquid phase method process route, but for dilute ethene dry gas raw material, due to containing in dry gas The light components such as hydrogen, methane, ethane, nitrogen, existing reaction process can not realize that alkylation reactor operates under liquid-phase condition, And liquid phase method catalyst is in the presence of having gas phase, it is easy to inactivate, therefore domestic industrialized dilute ethene dry gas at present The all gas-phase process routes of Benzene Device processed.Gas phase reaction temperature is high, the impurity composition such as the dimethylbenzene of reaction product, propyl benzene It is more, final production ethylbenzene product poor quality.But the feed ethylene of dilute ethylene process is typically derived from the dry of catalytic cracking unit Gas, general dry gas are used as fuel, and the market price is converted according to its calorific value and fuel, so the price advantage of raw material dry gas is bright Aobvious, dry gas method Benzene Device produces ethylbenzene using ethene therein, improves its added value, there is certain economic benefit.If Liquid phase method technique can be succeeded in developing to dilute ethylene raw, no matter then in the cost of raw material or product quality, all with important meaning Justice.But due to the problems such as ethylene concentration is low, PROCESS FOR TREATMENT is difficult, catalyst is immature, the industrialization of dry gas liquid phase method is not implemented.
In addition with the development and application of methanol-to-olefins technology, light hydrocarbon cracking alkene technology, more dilute second are brought Alkene resource, dilute ethene dry gas direct alkylation ethylbenzene technology can be not provided with the deep cooling process for separating in alkene production, avoid The with high investment and high energy consumption of the part, so methanol-to-olefins technology, the tail gas of light hydrocarbon cracking alkene technology directly produce second Benzene also turns into study hotspot.The ethene dry gas of two kinds of process by-products has certain difference, methanol-to-olefins skill with catalytic cracked dry gas Art, light hydrocarbon cracking alkene technology dry gas in Ethylene mass concentration reach 65% or so, more conventional 15% or so catalytic cracking is done High 4 times or so of the ethylene concentration of gas, to distinguish catalytic cracked dry gas, temporarily it is defined as " dense ethene dry gas ".Because ethene is dense Degree increases substantially, and carrying out liquid phase method technique for dense ethene dry gas raw material provides certain condition.
With the purity requirement more and more higher of downstream styrene product, how each research unit is to improve the production of dry gas method ethylbenzene Product quality has done substantial amounts of research work, has focused largely on the improvement of process optimization, catalyst performance, fail to reach with Pure ethylene liquid phase method ethylbenzene quality is suitable, and main cause fails to reach liquid-phase reaction condition.The more technique of document report is second Alkene content is less（Ethylene contents 6-30%）Dry gas vapor phase method production technology.
Patent CN101768043A reports for work a kind of dilute ethylene production ethylbenzene process method, using dilute in refinery dry gas Ethene is raw material, through washing and selectively removing propylene after segmentation enter alkylation reaction device, in the presence of a zeolite catalyst with Benzene carries out alkylation reaction, 280-450 DEG C of reaction temperature；Reaction pressure 0.4-3.0MPa；After alkylation reaction product vapor-liquid separation, tail For gas through low temperature absorption discharger, product liquid isolates recycle benzene, ethylbenzene, propyl benzene, diethylbenzene and again through piece-rate system successively Component；Diethylbenzene with benzene is mixed into dealkylation reaction device to carry out dealkylation reaction and is further converted to over a molecular sieve catalyst Ethylbenzene.Conversion of ethylene is not less than 99%, and the overall selectivity for generating ethylbenzene is not less than 99%, and tail gas carries the benzene rate of recovery and is not less than 99.5%.The technique is conventional dry gas ethylbenzene production technology, in product ethylbenzene xylene content 800 to 1000ppm or so, compared with Dimethylbenzene 100ppm contents have the difference close to the order of magnitude in pure ethylene method ethylbenzene.
Patent CN101993331A, CN102040458A reports a kind of pure ethylene or the side of dry gas and producing phenylethane from alkylation of benzene Method, mainly solve in the prior art to exist in pure ethylene or dry gas and benzene vapor phase alkylation, 300~430 DEG C of reaction temperature, 0.5~2.8MPa of reaction pressure, xylene impurities content is high in product ethylbenzene, ethylbenzene purity is low, poor catalyst stability, regeneration The problem of cycle and short service life.The present invention by using different SiO2/Al2O3 mol ratios ZSM-5 molecular sieve catalyst, Dry gas enters the distribution of beds, controls every section of beds inlet temperature and reactor head stream inlet temperature phase Difference is no more than ± 5 DEG C of technical scheme, and the xylene content reduced in ethylbenzene drops to 500ppm by original 850ppm, although The magazine component such as dimethylbenzene decreases, but ethylbenzene quality is still poor.
Patent CN102875316A reports a kind of method of dry gas and producing phenylethane from alkylation of benzene, by using with dry gas and benzene For reaction raw materials, reaction raw materials contact with catalyst occurs vapor phase alkylation generation ethylbenzene；Catalyst used is with weight Percentages contain various combinations, and the catalyst is handled by high-temperature vapor, and steam treatment condition is in normal pressure, temperature Under the conditions of 400~800 DEG C, steam treatment 1~20 hour solves poor catalyst stability, the problem of regeneration period is short, not Improvement is made to catalyst performance.
Patent CN103772125A reports produce the combined method of ethylbenzene with oil refinery dry gas.By be combined with ethane cracking, The technologies such as oil absorbs, alkylation, solve the problems, such as that prior art raw material is single and utilization rate is not high, it is proposed that a kind of efficiently profit With the ethene in oil refinery dry gas, the novel combined method for producing ethylbenzene of ethane component.Main function is the raising of ethylbenzene production capacity, And do not consider that cracking produces other influences of magazine component to alkylated reaction.
Patent CN201110105517.3 reports for work a kind of for containing containing ethylene raw with being removed in benzene preparing ethylbenzene by reaction technique The method of heavy hydrocarbon in ethylene raw, enter absorption-desorption apparatus containing ethylene raw, stripping gas containing ethylene raw is cooled to 5~40 Enter liquid distributing device after DEG C, the stripping gas that liquid distributing device top comes out, which goes out device, to carry out heavy hydrocarbon recovery or make fuel gas, through liquid separation Stripping gas lime set afterwards containing absorbent and heavy hydrocarbon is come out from liquid distributing device bottom, and a part, which returns to absorption-desorption apparatus circulation, to be made With the tail gas absorber for the product separate section that another part is delivered in process for preparing ethylbenzene containing ethylene raw isolates contained absorption Agent and heavy hydrocarbon, the absorbent isolated return to absorption-desorption apparatus and recycled.This method is only improved into alkylation reactor Ethylene concentration, reduces the accessory substance of reaction, does not change the problem of reaction impurity growing amount itself is big.
Above patent is that dry gas gas phase legal system ethylbenzene is reported, the content of the impurity such as dimethylbenzene has certain reduction in product, But production high-purity benzene ethene, the requirement to material ethylbenzene can not be reached.In addition, the external catalysis for being related to dry gas method ethylbenzene Rectification process is reported, but catalyst operates in the liquid phase environment of complexity, and the life-span is shorter, and designs benzene alkene than big, point Improved from energy consumption, although improving ethylbenzene quality, the stability and device economic performance of catalyst by catalytic rectification process Have much room for improvement.Analyzed more than and liquid phase reaction process is different, it can be seen that dry gas liquid phase method technique is that solve dry gas ethylbenzene The rational routes of poor product quality, while the raising of product quality can reduce the steam consumption of fractionation, reduce plant energy consumption.
The content of the invention
It is an object of the invention to propose a dry gas that can be utilized containing high concentration ethylene with benzene to enter under liquid-phase condition Row alkylated reaction produces the technique of ethylbenzene, the property of dense ethene dry gas is taken into full account, using the liquid phase reactor work of absorbing reaction Skill, solves ethylbenzene product purity problem.
The process that the present invention is implemented is as follows：
A kind of method that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that including following technique：
（1）：The dense ethene dry gas of raw material is divided into multiply, multiple absorptions are correspondingly arranged for the dense ethene dry gas share split quantity of raw material Tower, the dense ethene dry gas of multiply corresponds under flow control respectively enters multiple absorption towers, and benzene feedstock is divided into two strands；
（2）First strand of dense ethene dry gas, which corresponds to, enters the first absorption tower, and the absorbent at the top of the first absorption tower is one benzene feedstock And alkylated reaction goes out material；First burst of ethylene-rich liquid material after being absorbed by the first absorption tower out enters protection reactor Impurity elimination；The first gas phase come out from the first absorption tower goes out after material heating is alkylated reaction into vapor phase alkylation device Processing；
Reaction mass after removal of impurities enters the first catalyst reaction bed of liquid phase alkylation reaction device, makees in molecular sieve catalyst Liquid phase alkylation reaction is carried out under；
（3）The reaction generated after the reaction of the first catalyst reaction bed is discharged after heat exchange cooling is crossed, and temperature is generally 150-230 DEG C, two strands of materials are separated, wherein first strand of material returns to the absorption at the top of the first absorption tower as the first absorption tower Agent, second strand of material enter absorbent of the second absorption tower as second absorption tower；
Second strand of dense ethene dry gas material comes out the second burst of ethylene-rich liquid material formed from second absorption tower and enters liquid-phase alkylation Second catalyst reaction bed of reactor carries out liquid phase alkylation reaction, and the second gas phase come out from second absorption tower goes out material Enter vapor phase alkylation device after heating and carry out reaction treatment；
（4）The reaction discharging two generated after the reaction of the second catalyst reaction bed separates two strands of materials after heat exchange cools, First strand of material returns to the absorbent at the top of second absorption tower as second absorption tower, and second strand of material is made into the 3rd absorption tower For the absorbent on the 3rd absorption tower；
（5）If the 3rd strand and the dense ethene dry gas material reference step of carried interest below（3）And step（4）Carry out corresponding to reaction and Distribution, the tailing that one last material is formed after alkylated reaction are then again divided into two strands, and first strand of material returns last Absorption tower at the top of absorbent as the absorption tower, second strand of material then enter benzene recovery tower；
（6）Benzene is distillated in benzene recovery tower to feed back in the reaction system of benzene feedstock with liquid form, while in benzene recovery tower Material of the extraction rich in ethylbenzene enters in ethylbenzene recovery tower；
（7）Ethylbenzene distillate is formed in ethylbenzene recovery tower, other productions are then sent into propyl benzene recovery tower, in propyl benzene recovery tower Tower top forms propyl benzene byproduct distillate, then enters in the production that propyl benzene recovery tower bottom of towe is formed in more ethylbenzene recovery towers；
（8）Include the distillate of benzene, diethylbenzene and a small amount of triethylbenzene (TEB) component in tower top formation in more ethylbenzene recovery towers, this is distillated Thing enters after reclaiming benzene therein into tail gas recovery tower turns alkylation reactor, and turn alkylation instead with one benzene feedstock Should, the discharging for turning to be formed after alkylated reaction then enters in benzene recovery tower.
Recycle benzene utilization is formed in order to further reclaim benzene, while improves the rate of recovery of ethene, the vapor-phase alkylation is anti- Answer device to carry out entering stabilizer after the discharging after reaction treatment carries out cooling treatment, enter tail gas stablizing column overhead and separating gas phase Recovery tower is discharged after reclaiming benzene therein as fuel, enters benzene recovery tower in the liquid phase that stabilizer separates.
It is described to pass through liquid phase alkylation reaction shape for the absorptivity on absorption tower and the transformation efficiency of liquid phase alkylation reaction Into discharging in, with two strands of material ratios for entering next stage absorption tower be 1 into this grade of absorption tower:9-99.
Proposed by the present invention is that a kind of dry gas specifically for high concentration ethylene produces ethylbenzene process, using ethene and other The reaction of component and benzene and the difference of solubility property, realize that benzene and the liquid phase ethylene of dissolving react step by step, and discharge unreacted Fixed gas, finally realize that benzene and the ethene alkylated reaction under liquid-phase condition generate ethylbenzene, dry gas source can be methanol system The gas phase that alkene and the non-deep cooling of light hydrocarbon cracking device are processed forms or the mixture in other sources, in mixture Other compositions can be the components such as H2, methane, ethane, nitrogen, propane, propylene.
This patent is directed to dense ethene dry gas, and wherein ethylene concentration is more than or equal to 40%, preferably 60%-98%, due to ethylene concentration Height, impurity influence small on ethylene absorption, it is not necessary to will contain dense ethene dry gas and be pre-processed, and be directly entered absorbing reaction device, enter Row liquid phase alkylation reaction, save the pretreatment energy consumption of conventional dilute ethene dry gas vapor phase method, participate in the dry gas of this reaction 95% with On ethene can dissolve after enter Liquid-phase reactor in handle, ethene converts completely.It is unabsorbed dry containing a small amount of ethene In gas, 360 DEG C or so are heated to by heating furnace, into Gas-phase reactor, by the substantially all conversion of residual ethylene.
This patent uses catalyst of the beta-molecular sieve as liquid phase alkylation reaction, preferred molecular sieve catalyst UOP EBZ500 etc., catalyst adapt to the requirement of ethylene liquid phase alkylation reaction, and can receive to absorb the fixed gas and alkane of dissolving Hydrocarbon.Reaction pressure is usually controlled in the range of 1.0-5.6MPa in the liquid phase alkylation reaction of the present invention, preferably 2.8- 3.6MPa, reaction temperature are usually controlled in the range of 160-290 DEG C, preferably 205-240 DEG C, and olefin feed weight air speed is 0.1- 3.6h-1, preferably 0.6-0.8h-1, composition benzene is 1 with composition olefin molar ratio：2-26, preferably：1：2.5-4.In the present invention once The conversion of ethylene of alkylated reaction is more than 99.9%, and ethylbenzene is more than 86% relative to ethylene selectivity, and dimethylbenzene is given birth in total ethylbenzene Into 10~100PPM of proportion of amount.Wherein, into the benzene in the benzene feedstock in the first absorption tower and the dense ethene dry gas of raw material In alkene mol ratio be 1：2-26.
Dense ethene dry gas gas will be contained in this patent and be divided into multiply, be usually segmented into 2-12 stocks, preferably 4-6 stocks, this Sample may insure that the absorbent containing benzene, ethylbenzene can largely absorb the ethene of addition, so that it is guaranteed that more than 95% ethene is in liquid phase Alkylation reaction is reacted, within the impurity 100PPM such as control dimethylbenzene.
Absorption tower is that packed tower or plate tower, pressure tower are usually controlled in the range of 0.6-5.2MPa in this patent, excellent 2.7-3.6MPa is selected, absorbent is alkylated reaction benzene feedstock and generation ethylbenzene, the mixture of diethylbenzene, wherein in benzene feedstock The mass concentration of benzene is 20%-99%, preferably 64%-98%, anti-into liquid-phase catalyst bed directly as reaction raw materials after absorption Should.
Reactor is protected to use alkylation catalyst or alkaline nitrogen absorber as guard catalyst in the present invention, mainly The poisonous substance of alkylation catalyst in elimination reaction material, such as basic nitrogen compound, prevent material to liquid phase alkylation reaction device Cause poisoning and deactivation.Catalyst adapts to raw material neutral and alkali nitrogen 0.1-8PPM requirement, after overprotection adsorption reaction, in discharging Basic nitrogen is less than 0.05PPM, and protection reaction pressure is usually controlled in the range of 1.0-5.6MPa, preferably 3.0-3.6MPa, Reaction temperature is usually controlled in the range of 100-240 DEG C, preferably 180-200 DEG C.
This technique is alkylated reaction under ethene liquid-phase condition, it is allowed to which other a small amount of heavier olefins of dense ethene dry gas are deposited Heavier olefins alkylate will not increase impurity content in ethylbenzene, it is allowed to which heavier olefins such as propylene content are within 10%, preferably 1-1000PPM, it is not necessary to pre-process, being alkylated the propyl benzene of generation can reclaim in separate section, and can further refined raw Into product isopropylbenzene.
The separative element of this patent, according to the high low setting separation sequence of relative volatility, recycling is isolated first Reaction mass benzene, then obtain major product ethylbenzene, then obtain byproduct propyl benzene or isopropylbenzene, finally obtain diethylbenzene conduct Turn the raw material of alkylation.N-proplbenzene in isopropylbenzene is influenceed for the change of adaptive response process conditions, this patent sets isopropylbenzene Treating column, it is necessary to when, part propyl benzene be sent into treating column carry out refinement treatment and obtain isopropylbenzene, after processing in isopropylbenzene just Propyl benzene content reaches industry top grade product standard in below 300PPM（SH-T 1744-2004）.
The separative element tower recovered overhead low-pressure steam of this patent, including stabilizer, benzene recovery tower, ethylbenzene recovery tower, Propyl benzene recovery tower, more ethylbenzene recovery towers, isopropyl benzene column, steam grade are 0.04-1.6MPa, preferably 0.2-0.3MPa, and tower top returns The low low-pressure steam feeder steam pipe system received, it can make as the styrene units production of ethylbenzene styrene combined unit With.
The present invention mainly uses liquid phase production technology, and reaction temperature is relatively low, has the advantages that energy-saving and environmental protection, product conversion Rate is high, and the control of caused xylene content is in below 100PPM, good product quality.
Figure of description
Fig. 1 is the process chart of the present invention；
Wherein 1 absorption tower, 2 liquid phase alkylation reaction devices, 3 protection reactors, 4 heating furnaces, 5 vapor phase alkylation devices, 6 stabilizers, 7 tail gas absorbers, 8 benzene recovery towers, 9 ethylbenzene recovery towers, 10 propyl benzene recovery towers, 11 isopropylbenzene treating columns, 12 More ethylbenzene recovery towers, 13 turns of alkylation reactors.
Embodiment
Embodiment 1, as shown in Figure 1：
Dense ethene dry gas is divided into 4 strands first, enters absorption tower under flow control respectively, first strand of dense ethene dry gas material enters Enter the first absorption tower 1-1, absorption tower 1-1 top adds benzene feedstock and alkylated reaction discharging is used as absorbent, absorbs dense second 95% and above ethene and other a small amount of hydro carbons and fixed gas, the ethylene-rich liquid formed after absorption in alkene dry gas initially enter Protection reactor 3 removes impurity composition therein, subsequently into the first catalyst reaction bed of liquid phase alkylation reaction device 2, Under molecular sieve catalyst UOP EBZ500 effects, ethene and benzene alkylation reaction generation ethylbenzene, reaction discharging is by heat exchange drop Temperature is divided into two strands, and what one accounted for gross weight 92% enters second absorption tower, and what one accounted for gross weight 8% enters the first absorption tower； Because reaction discharging contains certain alkane and fixed gas in itself in second absorption tower, absorbed in tower in dense ethene dry gas Outside 95% ethene, a small amount of alkane and fixed gas reach absorption and desorption in second absorption tower and balanced, the ethylene-rich liquid after absorption, then The second catalyst reaction bed into liquid phase alkylation reaction device 2 carries out liquid phase reactor, and reaction discharging is again divided into two strands, and one What stock accounted for gross weight 91% enters the 3rd absorption tower, and what one accounted for gross weight 7% enters second absorption tower；According to identical reaction stream Journey passes through remaining absorption tower and reactor catalyst bed, until dense ethene dry gas all by absorbing reaction after the completion of, from liquid Outflow reaction unit at the top of 4th catalyst reaction bed of phase alkylation reactor 2, the material equally flowed out drop by heat exchange Temperature is divided into two strands, and one, which accounts for the 95% of gross weight and enters benzene recovery tower 8, handles reaction mass, and one accounts for the 5% of gross weight and enters the Four absorption towers；
The benzene containing gasification and a small amount of unreacted ethene dry gas from the gas phase discharging at the top of four absorption towers, gas phase discharging warp Cross after heating furnace is heated to 360 DEG C, be at high temperature totally converted a small amount of ethene in tail gas into dry gas vapor phase method reactor, Gas phase reaction is discharged after cooling, and rough segmentation processing is carried out into stabilizer 6, enters tail gas from the gas phase discharging of the tower top of stabilizer 6 After recovery tower 7 reclaims material benzene therein, fuel is used as from the discharge of the top of tail gas recovery tower 7, in the liquid phase that stabilizer 6 separates then Into benzene recovery tower 8.
The benzene feedstock that alkylation reaction needs in the present embodiment is sent into benzene column and entered in device, eventually passes through following for fractionation unit It is divided into two bursts of logistics after the supercharging of ring benzene pump, wherein one logistics enters absorption tower 1 as absorbent dissolving ethene so that into the The mol ratio of the benzene in benzene feedstock in one absorption tower and the alkene in the dense ethene dry gas of raw material is 1：3；Its another burst of logistics is made To turn alkylated reaction benzene feedstock, more ethylbenzene for sending with tail gas recovery tower 7, which enter, to be turned alkylation reactor 13 and carries out turning alkyl Change reaction, the discharging feeding benzene recovery tower 8 for turning alkylated reaction is handled.Alkylation reaction and the material for turning alkylation reaction generation Benzene, ethylbenzene, diethylbenzene and a small amount of propyl benzene, Residual oil etc. are mainly contained, all reaction masses are imported at benzene recovery tower 8 Reason.
The tower top of benzene recovery tower 8 distillates benzene, and reaction workshop section is fed back to as being alkylated and turn alkylated reaction using liquid form Benzene feedstock, its bottom of towe then produces the material rich in ethylbenzene into ethylbenzene recovery tower 9.In ethylbenzene recovery tower 9, tower top distillates Refined ethylbenzene product of the thing as this unit, bottom of towe production are sent into propyl benzene recovery tower 10, evaporated in the tower top of propyl benzene recovery tower 10 Go out propyl benzene of the thing as by-product, the propyl benzene byproduct material can enter in isopropylbenzene treating column 11, can obtain reaching top grade product The refined isopropylbenzene of standard, the bottom of towe production of propyl benzene recovery tower 10 are sent into more ethylbenzene recovery towers 12.In more ethylbenzene recovery towers 12 The component such as diethylbenzene and a small amount of triethylbenzene (TEB) reclaims benzene therein in being distillated by tower top into tail gas absorber 7 after, feeding turns alkyl Change in reactor 13 and carry out transalkylation reaction, tower bottoms is delivered to out-of-bounds in more ethylbenzene recovery towers 12.
As shown in figure 1, embodiment two, the specific implementation process of the present embodiment are, raw material dry gas source fills for light hydrocarbon cracking Put, normal operating flow is 17202kg/h, mass fraction of ethylene 48.7%, and scale produces about 240,000 tons of ethylbenzene per year.Design liquid phase Alkylation reactor diameter of phi 2000, using 4 sections of absorbing reaction techniques, liquid phase alkylation reaction section catalyst ethylene air speed 0.6kg catalyst/kg ethene .h, every section of 2m of catalyst packing height, amount to catalyst amount 25.4m3.Process chart is shown in figure 1, the dense ethene dry gas of raw material, reaction stream data, product ethyl-benzene level such as table 1-3.
The raw material crude ethylene specification of table 1
Component Mass fraction Flow kg/h Volume fraction
H2 2.70% 459 24.88%
CO 0.15% 29 0.10%
N2 0.60% 97 0.39%
CH4 24.40% 4200 28.10%
C2H6 23.40% 4021 14.37%
C2H4 48.80% 8385 32.12%
C3 and more than 0.05% 9 0.01%
The key reaction of table 2 and separation logistics data table
Logistics number 1 2 3 4 5
Temperature, DEG C 25 205 225 158 179
Pressure, KPaA 3356 4480 4480 3100 4480
Flow, kg/h 17202.00 143831.67 143831.67 77387.69 58863.93
Mass fraction wt%
Methane 24.36 0.32 0.32 0.08 0.26
Nitrogen 0.60 0.00 0.00 0.00 0.00
Hydrogen 2.69 0.01 0.01 0.00 0.01
Ethene 48.70 1.34 0.00 0.00 0.00
Ethane 23.36 0.78 0.78 0.37 0.68
Propylene 0.05 0.00 0.00 0.00 0.00
Propane 0.02 0.00 0.00 0.00 0.00
Butane 0.01 0.01 0.01 0.01 0.01
Butylene 0.01 0.01 0.01 0.01 0.02
It is non-aromatic 0.00 0.15 0.15 0.15 0.12
Benzene 0.00 92.96 89.72 99.25 62.18
Toluene 0.00 0.06 0.06 0.06 0.05
Ethylbenzene 0.00 3.58 7.34 0.06 29.83
Dimethylbenzene 0.00 0.00 0.00 0.00 0.00
Propyl benzene 0.00 0.00 0.00 0.00 0.00
First and second benzene 0.00 0.00 0.00 0.00 0.00
Butylbenzene 0.00 0.00 0.00 0.00 0.00
Diethylbenzene 0.00 0.63 1.29 0.00 5.52
Triethylbenzene (TEB) 0.00 0.13 0.26 0.00 1.12
Residual oil 0.00 0.02 0.04 0.00 0.18
Water 0.00 0.00 0.00 0.01 0.00
Continuous upper table
Logistics number 6 7 8 9 10
Temperature, DEG C 339 181 222 97 146
Pressure, KPaA 820 3100 3100 220 1100
Flow, kg/h 47115.62 23680.39 23680.47 31462.88 7110.73
Mass fraction
Methane 8.78 0.05 0.05 0.00 0.00
Nitrogen 0.22 0.00 0.00 0.00 0.00
Hydrogen 0.98 0.00 0.00 0.00 0.00
Ethene 0.00 0.00 0.00 0.00 0.00
Ethane 8.40 0.32 0.32 0.00 0.00
Propylene 0.00 0.00 0.00 0.00 0.00
Propane 0.01 0.00 0.00 0.00 0.00
Butane 0.04 0.01 0.01 0.00 0.00
Butylene 0.00 0.00 0.00 0.00 0.00
It is non-aromatic 0.13 0.15 0.15 0.00 0.00
Benzene 66.09 67.74 55.57 0.06 0.00
Toluene 0.03 0.07 0.07 0.12 0.00
Ethylbenzene 13.75 1.70 32.90 99.80 0.00
Dimethylbenzene 0.01 0.00 0.00 0.01 0.00
Propyl benzene 0.03 0.00 0.00 0.01 0.00
First and second benzene 0.01 0.00 0.00 0.00 0.00
Butylbenzene 0.12 0.30 0.30 0.00 1.02
Diethylbenzene 1.28 24.92 8.72 0.00 83.18
Triethylbenzene (TEB) 0.06 4.74 1.90 0.00 15.80
Residual oil 0.02 0.00 0.00 0.00 0.00
Water 0.01 0.00 0.00 0.00 0.00
The product ethylbenzene specification of table 3
Component Unit Specification
Outward appearance Colourless transparent liquid
Density (20 DEG C) g/cm3 0.868
Benzene wt% 0.06
Toluene wt% 0.11
Ethylbenzene wt% 99.8
Diethylbenzene ppmwt 5
Dimethylbenzene ppmwt 96
Isopropylbenzene ppmwt 260
Due to using liquid phase production technology, relatively low 180-280 DEG C of its reaction temperature, caused xylene content control in the present embodiment System is in below 100PPM, good product quality.And by catalyst and optimization of process conditions, reach energy conservation object, with existing dry gas Gas-phase process compares：1）Within 100PPM, device material consumption reduces for impurity concentration such as dimethylbenzene control in ethylbenzene product；2) Plant energy consumption reduces by 50% or so.
The basic principles, principal features and advantages of the present invention have been shown and described above.The technical staff of the industry should Understand, above-described embodiment do not limit in any form, such as in the present invention dense ethene dry gas share split quantity, concentration etc., such as All technical schemes obtained by the way of equivalent substitution or equivalent transformation, are all fallen within protection scope of the present invention.

Claims (11)

  1. A kind of 1. method that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：
    （1）The dense ethene dry gas of raw material is divided into multiply, multiple absorption towers are correspondingly arranged for the dense ethene dry gas share split quantity of raw material, The dense ethene dry gas of multiply corresponds under flow control respectively enters multiple absorption towers, and benzene feedstock is divided into two strands；
    （2）First strand of dense ethene dry gas, which corresponds to, enters the first absorption tower, and the absorbent at the top of the first absorption tower is one benzene feedstock And alkylated reaction goes out material；First burst of ethylene-rich liquid material after being absorbed by the first absorption tower out enters protection reactor Impurity elimination；The first gas phase come out by the first absorption tower goes out material and merged with the gas phase discharging on other absorption towers, enters after heating Vapor phase alkylation device is alkylated reaction treatment；
    Reaction mass after removal of impurities enters the first catalyst reaction bed of liquid phase alkylation reaction device, makees in molecular sieve catalyst Liquid phase alkylation reaction is carried out under；
    （3）The reaction generated after the reaction of the first catalyst reaction bed is discharged after heat exchange cooling is crossed, and temperature is generally 150-230 DEG C, two strands of materials are separated, wherein first strand of material returns to the absorption at the top of the first absorption tower as the first absorption tower Agent, second strand of material enter absorbent of the second absorption tower as second absorption tower；
    Second strand of dense ethene dry gas material comes out the second burst of ethylene-rich liquid material formed from second absorption tower and enters liquid-phase alkylation Second catalyst reaction bed of reactor carries out liquid phase alkylation reaction, and the second gas phase come out from second absorption tower goes out material Merge with the gas phase discharging on other absorption towers, vapor phase alkylation device is entered after heating and carries out reaction treatment；
    （4）The reaction discharging two generated after the reaction of the second catalyst reaction bed separates two strands of materials after heat exchange cools, First strand of material returns to the absorbent at the top of second absorption tower as second absorption tower, and second strand of material is made into the 3rd absorption tower For the absorbent on the 3rd absorption tower；
    （5）If the 3rd strand and the dense ethene dry gas material reference step of carried interest below（3）And step（4）Carry out corresponding to reaction and Distribution, the tailing that one last material is formed after alkylated reaction are then again divided into two strands, and first strand of material returns last Absorption tower at the top of absorbent as the absorption tower, second strand of material then enter benzene recovery tower；
    （6）Benzene is distillated in benzene recovery tower to feed back in the reaction system of benzene feedstock with liquid form, while in benzene recovery tower Material of the extraction rich in ethylbenzene enters in ethylbenzene recovery tower；
    （7）Ethylbenzene distillate is formed in ethylbenzene recovery tower, other productions are then sent into propyl benzene recovery tower, in propyl benzene recovery tower Tower top forms propyl benzene byproduct distillate, then enters in the production that propyl benzene recovery tower bottom of towe is formed in more ethylbenzene recovery towers；
    （8）Include the distillate of benzene, diethylbenzene and a small amount of triethylbenzene (TEB) component in tower top formation in more ethylbenzene recovery towers, this is distillated Thing enters after reclaiming benzene therein into tail gas recovery tower turns alkylation reactor, and turn alkylation instead with one benzene feedstock Should, the discharging for turning to be formed after alkylated reaction then enters in benzene recovery tower.
  2. 2. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：The dense ethene is done The concentration of gas is more than or equal to 40%, by weight percentage.
  3. 3. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：In the benzene feedstock The concentration of benzene is 20%-99%, by weight percentage.
  4. 4. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：Absorbed into first The mol ratio of the benzene in benzene feedstock in tower and the alkene in the dense ethene dry gas of raw material is 1：2-26.
  5. 5. the method according to claim 4 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：Absorbed into first The mol ratio of the benzene in benzene feedstock in tower and the alkene in the dense ethene dry gas of raw material is 1：2.5-4.
  6. 6. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：The liquid phase Change in reaction：Reaction pressure control is usually controlled in the range of 160-290 DEG C in 1.0-5.6MPa, reaction temperature, alkene Weight space velocity is 0.1-3.6h-1。
  7. 7. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：It is described to contain dense second Alkene dry gas is divided into 4-6 stocks.
  8. 8. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：The molecular sieve is urged Agent is beta-molecular sieve.
  9. 9. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：The gas phase alkyl Enter stabilizer after changing the discharging progress cooling treatment after reactor carries out reaction treatment, gas phase entrance is separated stablizing column overhead Tail gas recovery tower is discharged after reclaiming benzene therein as fuel, enters benzene recovery tower in the liquid phase that stabilizer separates.
  10. 10. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：Isopropylbenzene is set Treating column, propyl benzene byproduct distillate is sent into treating column progress refinement treatment and obtains refined isopropylbenzene.
  11. 11. the method according to claim 1 that ethylbenzene is produced with high concentration ethylene gas, it is characterised in that：It is described to pass through liquid In the discharging that phase alkylated reaction is formed, it is with two strands of weight of material ratios for entering next stage absorption tower into this grade of absorption tower 1：9-99.
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CN110218140A (en) * 2019-06-28 2019-09-10 常州瑞凯化工装备有限公司 A kind of method of light hydrocarbon cracking production high-quality ethylbenzene
CN111574318A (en) * 2020-06-04 2020-08-25 常州瑞华化工工程技术股份有限公司 Energy-saving reaction process for producing ethylbenzene from pure ethylene
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
CN115304448A (en) * 2022-07-21 2022-11-08 中石化广州工程有限公司 Process and device for preparing ethylbenzene by ethylene-containing dry gas-liquid phase method
CN115353439A (en) * 2022-07-21 2022-11-18 中石化广州工程有限公司 Process and device for producing ethylbenzene by ethylene-containing dry gas-liquid phase method
CN115368197A (en) * 2022-07-21 2022-11-22 中石化广州工程有限公司 Process and device for producing ethylbenzene by ethylene-containing dry gas-liquid phase method

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CN110218140A (en) * 2019-06-28 2019-09-10 常州瑞凯化工装备有限公司 A kind of method of light hydrocarbon cracking production high-quality ethylbenzene
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CN115304448A (en) * 2022-07-21 2022-11-08 中石化广州工程有限公司 Process and device for preparing ethylbenzene by ethylene-containing dry gas-liquid phase method
CN115353439A (en) * 2022-07-21 2022-11-18 中石化广州工程有限公司 Process and device for producing ethylbenzene by ethylene-containing dry gas-liquid phase method
CN115368197A (en) * 2022-07-21 2022-11-22 中石化广州工程有限公司 Process and device for producing ethylbenzene by ethylene-containing dry gas-liquid phase method

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