CN102746091B - Method for producing BTX (benzene, toluene and xylol) aromatic hydrocarbons and trimethylbenzene from heavy aromatic hydrocarbons - Google Patents
Method for producing BTX (benzene, toluene and xylol) aromatic hydrocarbons and trimethylbenzene from heavy aromatic hydrocarbons Download PDFInfo
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- CN102746091B CN102746091B CN201110099947.9A CN201110099947A CN102746091B CN 102746091 B CN102746091 B CN 102746091B CN 201110099947 A CN201110099947 A CN 201110099947A CN 102746091 B CN102746091 B CN 102746091B
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Abstract
The invention relates to a method for producing BTX aromatic hydrocarbons and trimethylbenzene from 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 trimethylbenzene monomers from the heavy aromatic hydrocarbons. According to the invention, hydrogen type binder-free ten-membered ring zeolite loading 0.005-0.5 parts by mass of Pt or Pd is adopted as a catalyst, hydrogen and the heavy aromatic hydrocarbons which are raw materials undergo hydrocracking treatment, so BTX aromatic hydrocarbon yield increase and separating production of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene are realized. The method well solves the problems, and can be used for the industrial production for the yield increases of the BTX aromatic hydrocarbons and the trimethylbenzene.
Description
Technical field
The present invention relates to a kind of method that heavy aromatics produces BTX aromatic hydrocarbons and trimethylbenzene.
Background technology
Heavy arene comprises carbon more than nine aromatic hydrocarbons of steam cracking device and refinery continuous reformer by-product, 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, C9 aromatic in continuous reformer heavy aromatics is generally used for the production of producing p-Xylol (PX) with toluene transalkylation, 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 heavy aromatics added value is low, and the flow process being separated trimethylbenzene monomer from heavy aromatics is complicated, the technical problems such as product purity is low, and productive rate is lower.A kind of new heavy aromatics is provided to produce the method for BTX aromatic hydrocarbons and trimethylbenzene.The method has that reaction is simple, and product is easily separated, and flow process is short, sym-trimethylbenzene and oblique presentation rate high, 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 heavy aromatics produces the method for BTX aromatic hydrocarbons and 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 10 ~ 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, sym-trimethylbenzene and unsym-trimethyl benzene respectively; 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, dimethylbenzene, the aromatics of sym-trimethylbenzene and unsym-trimethyl benzene, 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, sym-trimethylbenzene tower materials at bottom of tower passes into unsym-trimethyl benzene tower, unsym-trimethyl benzene product are obtained from unsym-trimethyl benzene column overhead, materials at bottom of tower part cycle is as raw material, all the other discharges.
The present invention relates to heavy aromatics and produce BTX aromatic hydrocarbons and the method for 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 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.
The efficient dual-function catalyst that the invention provides a kind of binder free Zeolite support carried noble metal for the method for heavy aromatics hydrocracking volume increase BTX aromatic hydrocarbons and trimethylbenzene, 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
-1hydrogen/hydrocarbon raw material reacts than under mole counting the reaction conditions of 3 ~ 10: 1, aromatic hydrocarbons weight content in reaction effluent in C9 aromatic except trimethylbenzene is less than 0.5%, BTX aromatic hydrocarbons yield reaches 59.2%, adopt the separation process shown in accompanying drawing 1, BTX aromatic hydrocarbons and highly purified sym-trimethylbenzene and unsym-trimethyl benzene 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, unsym-trimethyl benzene 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, 4 is high score tank, and 5 is hydrogen rich off gas, and 6 is gas stripping column, 7 cannot not be solidifying tail gas, and 8 is liquid light hydrocarbon, and 9 is BTX recovery tower, 10 is BTX aromatic hydrocarbons, 11 is sym-trimethylbenzene tower, and 12 is sym-trimethylbenzene, and 13 is unsym-trimethyl benzene tower, 14 is unsym-trimethyl benzene, and 15 is heavy tail oil.
Fig. 1 idiographic flow 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 enters unsym-trimethyl benzene tower 13, unsym-trimethyl benzene column overhead obtains unsym-trimethyl benzene 14, unsym-trimethyl benzene tower materials at bottom of tower discharge unit heavy ends 15, 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; 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.In fixed-bed reactor, use a of reduction activation, b catalyzer is at hydrogen pressure 2.8MPa, H
2/ oil volume, than 400, reacts temperature in 360 DEG C, weight hourly space velocity WHSV=2.0 hour
-1when, is checked and rated, and heavy aromatics raw material composition weight percent counts dimethylbenzene: 7.49%; 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 more than 10 carbon: 18.22%.Reaction result lists in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene, unsym-trimethyl benzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene and unsym-trimethyl benzene 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 003%, 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 and reaction conditions are with embodiment 1, and reaction result is in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene, unsym-trimethyl benzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene and unsym-trimethyl benzene 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 and reaction conditions are with embodiment 1, and reaction result is in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene, unsym-trimethyl benzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene and unsym-trimethyl benzene 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 and reaction conditions are with embodiment 1, and reaction result is in table 1.Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene, unsym-trimethyl benzene according to the cracking of Fig. 1 heavy arene hydrogenation, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene and unsym-trimethyl benzene product.
Table 1 catalyzer a ~ h evaluation result
Claims (1)
1. heavy aromatics produces a method for BTX aromatic hydrocarbons and trimethylbenzene, takes 250 grams of White Carbon blacks, 100 grams of SiO
2/ Al
2o
3mol ratio is the ZSM-5 zeolite of 125, adds 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 adding 500 gram weight per-cents 40% again and become cylindric shape to carry out drying; The 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/, and ZSM-5/ZSM-11 cocrystallization zeolite weight content is 98.1%, and the product of preparation 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 0.001% 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 and reaction conditions are:
Heavy aromatics raw material composition weight percent counts dimethylbenzene: 7.49%; 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 more than 10 carbon: 18.22%;
At hydrogen pressure 2.8MPa, H
2/ oil volume, than 400, reacts temperature in 360 DEG C, weight hourly space velocity WHSV=2.0 hour
-1,
Reaction result is as follows:
Produce the technical process of BTX aromatic hydrocarbons and sym-trimethylbenzene, unsym-trimethyl benzene according to heavy arene hydrogenation cracking, be separated and obtain BTX aromatic hydrocarbons and sym-trimethylbenzene and unsym-trimethyl benzene product;
Described technical process is enter reactor (3) after heavy aromatics (1) and hydrogen (2) mix 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 enters unsym-trimethyl benzene tower (13), unsym-trimethyl benzene column overhead obtains unsym-trimethyl benzene (14), unsym-trimethyl benzene tower materials at bottom of tower discharge unit heavy ends (15), all the other loop back reactor (3) and continue reaction.
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| CN103772121B (en) * | 2012-10-25 | 2015-08-12 | 中国石油化工股份有限公司 | The method of C9 and above heavy arene component cracking fecund trimethylbenzene |
| CN103351887B (en) * | 2013-07-08 | 2015-06-10 | 常熟市联邦化工有限公司 | Process for preparing high temperature heat transfer oil base oil by using C10 heavy aromatic residual oil |
| CN107226772B (en) * | 2017-06-19 | 2020-08-21 | 中海油天津化工研究设计院有限公司 | From C9+Method for preparing dimethylbenzene and coproducing durene from heavy aromatics |
| CN107365240A (en) * | 2017-06-19 | 2017-11-21 | 中海油天津化工研究设计院有限公司 | One kind is by C9+The method that heavy aromatics prepares BTX coproduction durols |
| CN110803974A (en) * | 2019-11-12 | 2020-02-18 | 江苏正丹化学工业股份有限公司 | Mesitylene step-by-step cryogenic crystallization separation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348405A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing light arene and light alkane from hydrocarbon raw material |
| CN101347742A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials |
| CN101768039A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for lightening and transalkylation of C9 and heavier aromatic hydrocarbons |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045208B (en) * | 2006-03-27 | 2010-05-12 | 中国石油化工股份有限公司 | Dealkylation and alkyl-transfering catalyst for C9 or more heavy aromatic hydrocarbons |
| CN100553777C (en) * | 2006-08-11 | 2009-10-28 | 中国石油化工股份有限公司 | The aromatic hydrocarbons transalkylation of high selectivity and dealkylation catalyst |
| CN101121144B (en) * | 2006-08-11 | 2010-09-01 | 中国石油化工股份有限公司 | Catalyst for aromatics alkyl transferring and dealkylation to synthesis benzene and xylene |
| CN101172924B (en) * | 2006-11-02 | 2010-09-01 | 中国石油化工股份有限公司 | High selectivity arene alkyl transfer and dealkylation xylol production increase reaction method |
| TWI478768B (en) * | 2007-07-18 | 2015-04-01 | China Petro Chemical Technologydevelopment Company | Catalysts and methods for the production of light aromatics and light alkanes from hydrocarbon feedstocks |
-
2011
- 2011-04-20 CN CN201110099947.9A patent/CN102746091B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348405A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing light arene and light alkane from hydrocarbon raw material |
| CN101347742A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials |
| CN101768039A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for lightening and transalkylation of C9 and heavier aromatic hydrocarbons |
Non-Patent Citations (1)
| Title |
|---|
| 重整重芳烃催化加氢裂解反应工艺条件的探究;唐之勤等;《化学反应工程与工艺》;20110225;第27卷(第1期);第1-5页 * |
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