CN102746092B - Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons - Google Patents

Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons Download PDF

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CN102746092B
CN102746092B CN201110099967.6A CN201110099967A CN102746092B CN 102746092 B CN102746092 B CN 102746092B CN 201110099967 A CN201110099967 A CN 201110099967A CN 102746092 B CN102746092 B CN 102746092B
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trimethylbenzene
sym
aromatic hydrocarbons
zeolite
tower
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CN102746092A (en
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王德举
刘仲能
王燕波
郭友娣
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons to mainly solve technical problems of low added value of the heavy aromatic hydrocarbons, and complex flow, low product purity, low yield and the like in separation of 1,3,5-trimethylbenzene monomers from the heavy aromatic hydrocarbons. According to the method, hydrogen type binder-free ten-membered ring zeolite loading 0.005-0.5% by mass of Pt or Pd is adopted as a catalyst, hydrogen and the heavy aromatic hydrocarbons which are raw materials undergo hydrocracking treatment, and 1,2,4-trimethylbenzene and heavy aromatic hydrocarbons having boiling points greater than the boiling point of the 1,2,4-trimethylbenzene in products are returned to a reactor, so BTX aromatic hydrocarbon yield increase and 1,3,5-trimethylbenzene separation production are realized. The method well solves the problems, and can be used for the industrial production for yield increases of the BTX (benzene, toluene and xylol) aromatic hydrocarbon and the 1,3,5-trimethylbenzene.

Description

The method of heavy aromatics hydrocracking separation of produced sym-trimethylbenzene
Technical field
The present invention relates to a kind of method of heavy aromatics hydrocracking separation of produced sym-trimethylbenzene.
Background technology
Heavy arene comprises carbon more than nine aromatic hydrocarbons of steam cracking device and refinery continuous reformer by-product, is mainly carbon nine and C10 aromartic, is valuable petrochemical complex resource, heavy arene of particularly reforming.Along with the operation in succession of China's large petrochemical plant continuous reformer in recent years, the increase of production amplitude of reformation heavy arene is very fast, continuous reformer heavy aromatics is (C9 aromatic in continuous reformer heavy aromatics is generally used for and produces PX with toluene disproportionation, isomerization) except being applied to the production of p-Xylol (PX), also have considerable part to enter heavy aromatics comprehensive utilization production and carry out process application, for extracting the component such as sym-trimethylbenzene, unsym-trimethyl benzene, hemimellitene, the first and second benzene wherein.
External just starting after isolating unsym-trimethyl benzene the 1950's from reformation C9 aromatic utilizes this part resource to produce fine chemical product on a large scale, its Application Areas is day by day widened to define and is compared rounded system, comprises the every field such as plastics, coating, softening agent, medicine, synthon.This part heavy aromatics has specific molecular structure feature and develops its use properties particularly unique in the fine chemicals such as production high-temperature resin, speciality coating, softening agent, solidifying agent in some goods, improves economic benefit.And the R & D and manufacture scale of domestic reformation C9 aromatic is all smaller, some enterprise is due to the reasons such as technology and equipment successively stopping production, and some devices not yet reach large production equipment scale.The utilization ratio of current China reformation C9 aromatic is also lower, and a considerable amount of heavy aromatics fusion has been burnt in the oil, and this is the waste in a utilization of resources.
C9 aromatic has nine kinds of isomerss, can have sym-trimethylbenzene, unsym-trimethyl benzene, m-methyl ethylbenzene and p-methyl-ethylbenzene after being separated industrially as product.Wherein with unsym-trimethyl benzene and sym-trimethylbenzene added value maximum.From prior art, producing the difficult point being separated trimethylbenzene is there is many materials such as C9 aromatic isomer and butylbenzene such as the first and second benzene, propyl benzene in raw material, and the boiling point of part carbon nine and above aromatic hydrocarbons (the first and second benzene, butylbenzene) and trimethylbenzene are closely.CN1139095A has invented one from C 9the method producing sym-trimethylbenzene is separated, the C that the first and second benzene weight contents are greater than 22% in BTX aromatics 9bTX aromatics raw material is after first rectifying, containing sym-trimethylbenzene, unsym-trimethyl benzene and neighbour, the blending fraction section of p-methyl-ethylbenzene is by as reaction raw materials, add the trimethyl carbinol, the vitriol oil, aluminum chloride and hydrochloric acid as reaction additive, through alkylated reaction and settlement treatment, first and second benzene are converted into high boiling material, then reactant is carried out rectifying separation, the final sym-trimethylbenzene product obtaining purity and be greater than 98%.Except trimethylbenzene except the C of heavy aromatics generally containing high level of reformer 9aromatic hydrocarbons, its content is generally greater than 30%, CN1313269A and the heavy aromatics from refinery reformer is needed carry out continuous rectification through two packing towers and isolate the higher unsym-trimethyl benzene fraction of purity, but can not obtain higher degree sym-trimethylbenzene.CN1974500A adopts three tower serial flow process counterweight bulk wight aromatic hydrocarbons to be separated, can the enriched mesitylene of higher unsym-trimethyl benzene co-production more than 35% purity of production purity, and sym-trimethylbenzene purity is lower.Therefore, in prior art, the technical process of separation of produced sym-trimethylbenzene is longer, complex process, and yield is lower, and production cost is higher, and industrial application difficulty is large.
Zeolite powder particularly nano zeolite powder can form dust in actual applications, inconvenient operation, there is the weakness such as difficult recovery, easy in inactivation and gathering, also can jeopardize the health of operator, because too high pressure drop zeolite powder is not suitable for fixed-bed reactor in catalyzed reaction yet.Therefore zeolite molecular sieve powder must be made the particle with certain physical strength and shape, this process often needs to add binding agent, the binding agent of frequent employing comprises some oxide compounds and some clay minerals such as aluminum oxide, silicon-dioxide, titanium dioxide, the introducing of binding agent can reduce the content of effective zeolite component, cause adsorptive capacity to decline, effective surface area is reduced.Because binding agent constituent part can enter zeolite cavity or blocking portion zeolite aperture, therefore diffusional limitation is introduced, adsorptive power is caused to weaken, adsorption selectivity is deteriorated, sorption and desorption speed declines, in catalyzed reaction, then cause active reduction, selectivity declines, and Binder Composition also may cause some side reactions undesirably occurred.Binder free zeolite molecular sieve refers to not containing inert binder in zeolitic molecular sieve particle, the main zeolite block of material with definite shape and size relying on the interaction self-supporting between zeolite grain to exist.Binder free zeolitic material mesolite weight content is greater than 95%, and crushing strength is greater than 40N/, and available effective surface area is comparatively large, in catalyzed reaction, have better properties.
Summary of the invention
Technical problem to be solved by this invention is that mainly to solve heavy aromatics added value low, the flow process being separated sym-trimethylbenzene monomer from heavy aromatics is complicated, the technical problems such as product purity is low, and productive rate is lower, provide a kind of method of new heavy aromatics hydrocracking separation of produced sym-trimethylbenzene.It is simple that the method has reaction, and product is easily separated, and flow process is short, and sym-trimethylbenzene productive rate is high, and product added value is high, and heavy aromatics obtains the advantage of high value added utilization.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of heavy aromatics hydrocracking separation of produced sym-trimethylbenzene, comprises the following steps successively:
A) with carbon nine and above heavy aromatics and hydrogen for raw material passes in reaction zone, the aromatic hydrocarbons weight content wherein in C9 aromatic except trimethylbenzene is greater than 2%;
B) it is 1.0 ~ 4.0 hours in the weight hourly space velocity of temperature of reaction 320 ~ 450 DEG C, reaction pressure 2.0 ~ 4.0Mpa, hydrocarbon raw material in the reaction region -1, hydrogen/hydrocarbon raw material reacts than mole to count raw material and catalyst exposure under the condition of 3 ~ 10: 1, and obtain effluent I, the aromatic hydrocarbons weight content wherein in C9 aromatic except trimethylbenzene is less than 0.5%;
C) effluent I is by gas-liquid separation and distillation tower, reclaims light paraffins, lightweight BTX aromatic hydrocarbons and sym-trimethylbenzene respectively, and cut circulation more than unsym-trimethyl benzene and unsym-trimethyl benzene boiling point returns to reaction zone and reacts; In BTX aromatic hydrocarbons, B is benzene, and T is toluene, and X is dimethylbenzene;
Catalyst wherein used comprises following component: a) 0.005 ~ 0.5 part is selected from the precious metal of at least one in Pt or Pd; B) 99.5 ~ 100 parts is Hydrogen binder free ten-ring zeolite.The crushing strength of binder free zeolite is greater than 40N/, and zeolite weight content is greater than 95%.
In technique scheme, preferred reaction conditions is temperature of reaction 350 ~ 420 DEG C, the weight hourly space velocity of reaction pressure 2.4 ~ 3.5Mpa, hydrocarbon raw material is 1.0 ~ 3.0 hours -1, hydrogen/hydrocarbon raw material is than mole to count 4 ~ 8: 1; Heavy aromatics from reformate, pyrolysis gasoline, petroleum naphtha and catalytically cracked gasoline, preferred reformation heavy aromatics raw material; The ten-ring zeolite selected in catalyzer is at least one in ZSM-5 or ZSM-11 zeolite, the SiO of binder free ten-ring zeolite 2/ Al 2o 3mol ratio is 20 ~ 200; The consumption that catalyzer is selected from least one in Pt or Pd with weight parts load is 0.01 ~ 0.5 part; Also containing at least one be selected from Zn, La, Sn, Pb or Bi in catalyzer, its consumption by weight number is > 0 ~ 1 part.
Binder free zeolite is with sodium form preparation synthesis, then carry out ion-exchange with the acid solution such as ammonium salt solution or hydrochloric acid, carry out roasting after exchange and be converted into h-type zeolite, then introduced at least one metal of Pt or Pd by ion-exchange or dipping method, use Palladous chloride, Palladous nitrate, ammonium palladic chloride, ammonium palladous chloride, platinum nitrate, Platinic chloride, ammonium chloroplatinate, ammonium chloroplatinite, dichloro four ammonium closes the aqueous solution of platinum at least one as precursor.Binder free h-type zeolite is introduced after Pt or Pd, carries out drying being less than at 200 DEG C, then calcines dried catalyzer at 300 ~ 600 DEG C.
At described step c) in be separated into benzene respectively according to the boiling point of compound, toluene, the aromatics of dimethylbenzene and sym-trimethylbenzene, be specially effluent I and pass into high score tank, tower top obtains hydrogen rich off gas, the low material of tower enters gas stripping column, stripper overhead is not coagulated tail gas and liquid light hydrocarbon, gas stripping column tower base stream is passed in BTX benzene-toluene-xylene recovery tower, from BTX recovery tower recovered overhead BTX aromatic hydrocarbons, BTX recovery tower materials at bottom of tower passes into sym-trimethylbenzene tower, sym-trimethylbenzene product are obtained from sym-trimethylbenzene column overhead, the low material of tower returns circulation and returns to reaction zone and react, part heavy ends discharges.
The present invention relates to the method for heavy aromatics hydrocracking separation of produced sym-trimethylbenzene and the catalyzer for this method.Along with the progress of Petroleum Processing Technology, the heavy aromatics output of catalytic reforming unit and the output of pyrolysis gasoline improve constantly.From prior art, producing the difficult point being separated trimethylbenzene is exist in raw material to comprise the first and second benzene, the C9 aromatic isomer such as propyl benzene and butylbenzene are at interior many materials, part carbon nine and above aromatic hydrocarbons (the first and second benzene, butylbenzene) boiling point and trimethylbenzene closely, therefore the flow process being separated trimethylbenzene monomer is longer, complex process, invest large energy consumption high, product yield is low, the problems such as economic target difference, therefore be difficult to be used, so develop aromatics seperation purification new technology as early as possible, improve and development sym-trimethylbenzene production technology, reduce production cost, improve the technological competitiveness of domestic sym-trimethylbenzene industry, meet the demand of domestic and international market.
According to the present invention, the acid carrier of catalyzer uses with the form of binder free ten-ring duct zeolite.The acidity of Zeolite support is most important in hydrocracking reaction, and first alkylbenzene many carbon carbochain carries out protonated on B acid site, removes many carbon carbochain through cracking, and it is comparatively easy to react; And on L acid site, many carbon carbochain of alkylbenzene be then formed free radical therefrom between chain rupture, reaction is difficulty comparatively.Binder free Zeolites Zeolites content is high, and containing highdensity B acid site, it is more easy therefore to remove for many carbon carbochain of alkylbenzene.The pore passage structure of zeolite is also vital for the impact of de-alkyl, different zeolites has different pore passage structures, wherein ten-ring structural zeolite has very high removal activity to the ethyl of heavy arene and propyl group, but only has the transformation efficiency of medium trimethylbenzene.In above-mentioned hydrocracking reaction, the such as alkene intermediates such as ethene, propylene can be produced, should promptly cause catalyst deactivation to prevent olefinic polymerization from impelling coke to be formed or cause the character of aromatic component in product to be deteriorated with light aromatics generation alkylated reaction by hydrotreated lube base oil.Therefore, there is the hydrogenating function that acid sites matches in catalyzer, should metallic element containing group VIII in the periodic table of elements with hydrogenation.Metal component Pt or Pd all has good hydrogenation effect, should consider the problem that acidity of catalyst center and hydrogenation metal center match and adapt to raw material in catalyst preparing.Acid sites by the silica/alumina mole ratio of adjustment zeolite molecular sieve or can be mediated by modification, and the hydrogenation activity of metal center can be adjusted by the dispersity of content of metal, loaded metal.The raw material suppressing metal hydrogenation performance component may be contained for raw material is comparatively complicated, the pyrolysis gasoline raw material of such as sulfur compound, can consider Pt, Pd two kinds of metal composite together, this all can have good sulfur resistance than being used alone any one metal of Pt, Pd thus keeping good Hydrogenation.Pt, Pd two kinds of metal composite can produce mutually electro ultrafiltration or chemical action, instead of separately exist in catalyzer, thus provide excellent hydrogenation and sulfur resistance.Catalyzer of the present invention adopts binder free ten-ring zeolite as acidic components, there is sour density large, the feature that aperture is unobstructed, metal hydrogenation component has the moderate feature of Hydrogenation, can the heavy aromatics such as effective elimination first and second benzene, propyl benzene and butylbenzene, thus be conducive to the rectifying separation of trimethylbenzene monomer, can be separated from reaction effluent and obtain highly purified trimethylbenzene monomer, and BTX aromatic hydrocarbons can be increased production.And circulate unsym-trimethyl benzene and above aromatic hydrocarbons, isomerization reaction and heavy aromatics that unsym-trimethyl benzene can occur take off the reaction such as alkyl and transalkylation generation sym-trimethylbenzene, so can improve the output of sym-trimethylbenzene further.
The invention provides a kind of method of efficient dual-function catalyst for heavy aromatics hydrocracking separation of produced sym-trimethylbenzene of binder free Zeolite support carried noble metal, with heavy aromatics and hydrogen for raw material is 1.0 ~ 4.0 hours in the weight hourly space velocity of temperature of reaction 320 ~ 450 DEG C, reaction pressure 2.0 ~ 4.0Mpa, hydrocarbon raw material -1, hydrogen/hydrocarbon raw material reacts than under mole counting the reaction conditions of 3 ~ 10: 1, and the aromatic hydrocarbons weight content in reaction effluent in C9 aromatic except trimethylbenzene is less than 0.5%, BTX aromatic hydrocarbons yield and reaches 62.8%; And unsym-trimethyl benzene or circulation unsym-trimethyl benzene and the above heavy aromatics of the unsym-trimethyl benzene boiling point raw material as hydrocracking that circulates further, in product, sym-trimethylbenzene improves further, adopt the separation process shown in accompanying drawing 1, BTX aromatic hydrocarbons and highly purified sym-trimethylbenzene product can be obtained, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that BTX aromatic hydrocarbons and sym-trimethylbenzene are produced in heavy arene hydrogenation cracking.
In Fig. 1,1 attaches most importance to aroamtic hydrocarbon raw material, and 2 is hydrogen feed, and 3 is hydrocracking reactor, and 4 is high score tank, and 5 is hydrogen rich off gas, 6 is gas stripping column, and 7 cannot not be solidifying tail gas, and 8 is liquid light hydrocarbon, and 9 is BTX recovery tower, 10 is BTX aromatic hydrocarbons, and 11 is sym-trimethylbenzene tower, and 12 is sym-trimethylbenzene, and 13 is heavy tail oil.
Fig. 1 concrete technology flow process is enter reactor 3 after heavy aromatics 1 and hydrogen 2 mix preheating, and product enters high score tank 4, discharge unit hydrogen rich off gas 5 after product separation, and all the other circulations are mixed into reactor 3 with raw hydrogen 2; High score tank 4 bottoms material enters gas stripping column 6, gas stripping column tower top is not coagulated tail gas 7 and liquid light hydrocarbon 8, gas stripping column materials at bottom of tower enters BTX recovery tower 9, BTX recovery tower tower top obtains BTX aromatic hydrocarbons 10, BTX recovery tower materials at bottom of tower enters sym-trimethylbenzene tower 11, sym-trimethylbenzene column overhead obtains sym-trimethylbenzene 12, sym-trimethylbenzene tower materials at bottom of tower discharge unit heavy ends 13, and all the other loop back reactor 3 and continue reaction.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1 ~ 2]
Adhesiveless ZSM-5 zeolite (SiO 2/ Al 2o 3mol ratio is 60) with reference to Chinese patent CN100384735C preparation, the adhesiveless ZSM-5 zeolite crushing strength of preparation is greater than 75N/, ZSM-5 zeolite weight content is 98.5%, and product and ammonium nitrate solution carry out ion-exchange, carries out roasting and be converted into h-type zeolite after exchange.The Pt of dip loading the mass ratio range 0.05% and Zn of 0.25% on Hydrogen adhesiveless ZSM-5 zeolite, at 450 DEG C, calcining obtains catalyzer a in 4 hours, a catalyzer after reduction activation reacts in fixed-bed reactor, and heavy aromatics raw material counts dimethylbenzene 7.49% with weight percent; Isopropyl benzene 2.39%; N-proplbenzene 4.00%; M-methyl ethylbenzene 15.40%; P-methyl-ethylbenzene 4.07%; Sym-trimethylbenzene 5.03%; O-methylethylbenzene 6.82%; Unsym-trimethyl benzene 26.86%; Hemimellitene 8.43%; Indane 0.94%; Hydrocarbon 18.22% more than 10 carbon, the appreciation condition of catalyzer a and reaction result are in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene product.
The Pd of dip loading the mass ratio range 0.3% and Pb of 0.05% on Hydrogen adhesiveless ZSM-5 zeolite, at 450 DEG C, calcining obtains catalyzer b in 4 hours, b catalyzer after reduction activation reacts in fixed-bed reactor, heavy aromatics raw material is with embodiment 1, and the appreciation condition of catalyzer b and reaction result are in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene product.
[embodiment 3 ~ 5]
Adhesiveless ZSM-5 zeolite (SiO 2/ Al 2o 3mol ratio is 20) with reference to Chinese patent CN100384735C preparation, the adhesiveless ZSM-5 zeolite crushing strength of preparation is greater than 65N/, ZSM-5 zeolite weight content is 99.6%, and product and ammonium nitrate solution carry out ion-exchange, carries out roasting and be converted into h-type zeolite after exchange.The Pt of dip loading the mass ratio range 0.005% and Sn of 0.01% on Hydrogen adhesiveless ZSM-5 zeolite, at 450 DEG C, calcining obtains catalyzer c in 4 hours; The La of the Pd of dip loading mass ratio range 0.5%, the Zn of 0.01% and 1.0% on Hydrogen adhesiveless ZSM-5 zeolite, at 450 DEG C, calcining obtains catalyzer d in 4 hours; The Sn of the Pt of dip loading mass ratio range 0.03%, the Bi of 0.02% and 0.2% on Hydrogen adhesiveless ZSM-5 zeolite, at 450 DEG C, calcining obtains catalyzer e in 4 hours.Catalyzer after reduction activation reacts in fixed-bed reactor, and heavy aromatics raw material is with embodiment 1, and the appreciation condition of catalyzer and reaction result are in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene product.
[embodiment 6 ~ 7]
Binderless ZSM-5-11 zeolite (SiO 2/ Al 2o 3mol ratio is 45) with reference to Chinese patent CN101348261A preparation, binderless ZSM-5-11 zeolite crushing strength of preparation is greater than 80N/, ZSM-11 zeolite weight content is 97.9%, and product and ammonium nitrate solution carry out ion-exchange, carries out roasting and be converted into h-type zeolite after exchange.The Pt of dip loading the mass ratio range 0.06% and Zn of 0.2% on Hydrogen binderless ZSM-5-11 zeolite, at 450 DEG C, calcining obtains catalyzer f in 4 hours; The Pt of dip loading the mass ratio range 0.2% and Bi of 0.20% on Hydrogen binderless ZSM-5-11 zeolite, at 450 DEG C, calcining obtains catalyzer g in 4 hours.Catalyzer after reduction activation reacts in fixed-bed reactor, and heavy aromatics raw material is with embodiment 1, and the appreciation condition of catalyzer and reaction result are in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene product.
[embodiment 8]
Take 250 grams of White Carbon blacks, 100 grams of ZSM-5 zeolite (SiO 2/ Al 2o 3mol ratio is 125), add 12 grams of sesbania powder, 16 grams of Tai-Ace S 150 [Al 2(SO 4) 318H 2o], 10 grams of NaOH carry out kneading with the silicon sol (weight percent 40%) adding 500 grams again and become cylindric shape to carry out drying.TBAH (TBAOH) solution being 8% by the cylindric presoma of 40 grams of above-mentioned preparations and 80 gram mass percentage concentrations respectively mixes and is placed in crystallizing kettle and at 160 DEG C, carries out hydrothermal treatment consists 4 days.Product with distilled water wash dry after in air atmosphere in 550 DEG C of roastings.The XRD figure spectrum of product all shows that crystalline phase is ZSM-5/ZSM-11 cocrystallization zeolite, and baseline straightening, prepares the SiO of product 2/ Al 2o 3mol ratio is determined as 185.Adhesiveless ZSM-5/ZSM-11 cocrystallization zeolite the crushing strength of preparation is greater than 40N/, ZSM-5/ZSM-11 cocrystallization zeolite weight content is 98.1%, product with prepare product and ammonium nitrate solution carries out ion-exchange, carry out roasting after exchange and be converted into h-type zeolite.The Pt of dip loading the mass ratio range 0.001% and Pd of 0.1% on Hydrogen adhesiveless ZSM-5/ZSM-11 zeolite, at 450 DEG C, calcining obtains catalyzer h in 4 hours.Catalyzer after reduction activation reacts in fixed-bed reactor, and heavy aromatics raw material is with embodiment 1, and the appreciation condition of catalyzer and reaction result are in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene product.

Claims (1)

1. a method for heavy aromatics hydrocracking separation of produced sym-trimethylbenzene, SiO 2/ Al 2o 3mol ratio is that binderless ZSM-5-11 zeolite of 45 is with reference to Chinese patent CN101348261A preparation, binderless ZSM-5-11 zeolite crushing strength of preparation is greater than 80N/, ZSM-11 zeolite weight content is 97.9%, product and ammonium nitrate solution carry out ion-exchange, carry out roasting and be converted into h-type zeolite after exchange; The Pt of dip loading the mass ratio range 0.06% and Zn of 0.2% on Hydrogen binderless ZSM-5-11 zeolite, at 450 DEG C, calcining obtains catalyzer f in 4 hours; Catalyzer after reduction activation reacts in fixed-bed reactor, and heavy aromatics raw material counts dimethylbenzene 7.49% with weight percent; Isopropyl benzene 2.39%; N-proplbenzene 4.00%; M-methyl ethylbenzene 15.40%; P-methyl-ethylbenzene 4.07%; Sym-trimethylbenzene 5.03%; O-methylethylbenzene 6.82%; Unsym-trimethyl benzene 26.86%; Hemimellitene 8.43%; Indane 0.94%; Hydrocarbon 18.22% more than 10 carbon, appreciation condition and the reaction result of catalyzer are as follows:
Concrete technology flow process is: enter reactor (3) after heavy aromatics (1) and hydrogen (2) mixing preheating, product enters high score tank (4), discharge unit hydrogen rich off gas (5) after product separation, all the other circulations are mixed into reactor (3) with raw hydrogen (2); High score tank (4) bottoms material enters gas stripping column (6), gas stripping column tower top is not coagulated tail gas (7) and liquid light hydrocarbon (8), gas stripping column materials at bottom of tower enters BTX recovery tower (9), BTX recovery tower tower top obtains BTX aromatic hydrocarbons (10), BTX recovery tower materials at bottom of tower enters sym-trimethylbenzene tower (11), sym-trimethylbenzene column overhead obtains sym-trimethylbenzene (12), sym-trimethylbenzene tower materials at bottom of tower discharge unit heavy ends (13), all the other loop back reactor (3) and continue reaction;
Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene according to above-mentioned heavy arene hydrogenation cracking, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene product.
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