CN102746093B - Heavy aromatics hydrocracking is utilized to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene - Google Patents
Heavy aromatics hydrocracking is utilized to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene Download PDFInfo
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- CN102746093B CN102746093B CN201110099977.XA CN201110099977A CN102746093B CN 102746093 B CN102746093 B CN 102746093B CN 201110099977 A CN201110099977 A CN 201110099977A CN 102746093 B CN102746093 B CN 102746093B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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
Abstract
The present invention relates to a kind of method utilizing heavy aromatics hydrocracking to increase production BTX aromatic hydrocarbons and trimethylbenzene, mainly solve heavy aromatics added value low, the technical problem that separation of produced trimethylbenzene monomer cost is higher from the heavy aromatics containing the first and second benzene, propyl benzene and butylbenzene.The present invention by adopting the Hydrogen binder free ten-ring zeolite of Supported Pt Nanoparticles or palladium to be catalyzer, temperature of reaction be 320 ~ 450 DEG C, reaction pressure is 2.0 ~ 4.0Mpa, the weight hourly space velocity of hydrocarbon raw material is 1.0 ~ 4.0 hours
-1, hydrogen/hydrocarbon raw material, than with under mole counting the reaction conditions of 3 ~ 10: 1, carries out the technical scheme of hydrocracking reaction, solves this problem preferably, can be used in the industrial production of BTX aromatic hydrocarbons and trimethylbenzene to heavy aromatics.
Description
Technical field
The present invention relates to a kind of method utilizing heavy aromatics hydrocracking to increase production 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 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 carbon seven 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, comprise the every field such as plastics, coating, softening agent, medicine, synthon, particularly producing the use properties in the fine chemicals such as high-temperature resin, speciality coating, softening agent, solidifying agent with uniqueness, improve economic benefit.And domestic reformation C9 aromatic industrial scale is all smaller, because the reasons such as technology and equipment successively stop production, 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 and unsym-trimethyl benzene 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 traditional heavy aromatics added value is low, and from containing the higher problem of separation of produced trimethylbenzene monomer cost the heavy aromatics of the first and second benzene, propyl benzene and butylbenzene, provide a kind of heavy aromatics hydrocracking that utilizes newly to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene.The method has reaction product and is easily separated, and production cost is lower, and added value of product is high, and heavy aromatics obtains the advantage of high value added utilization.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method utilizing heavy aromatics hydrocracking to increase production BTX aromatic hydrocarbons and trimethylbenzene, with carbon nine and above heavy aromatics and hydrogen for raw material, aromatic hydrocarbons weight content wherein in C9 aromatic except trimethylbenzene is greater than 2%, 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 is in mole than under the condition of 3 ~ 10: 1, raw material and catalyst exposure are obtained by reacting BTX aromatic hydrocarbons, wherein B is benzene, T is toluene, X is dimethylbenzene, and the aromatic hydrocarbons weight content in reaction effluent in C9 aromatic except trimethylbenzene is less than 0.5%, and catalyzer used comprises following component with weight parts: 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 of Hydrogen binder free ten-ring zeolites; 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 is 350 ~ 420 DEG C, reaction pressure is 2.4 ~ 3.5Mpa, the weight hourly space velocity of reformation heavy aromatics 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, is preferably 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; Aromatic hydrocarbons weight content optimum in reaction effluent in C9 aromatic except trimethylbenzene is 0.01 ~ 0.3%.
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.
The present invention relates to the method utilizing heavy aromatics hydrocracking to increase production BTX aromatic hydrocarbons and trimethylbenzene.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 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 present invention utilizes heavy aromatics hydrocracking to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene, with the mixture of heavy aromatics and hydrogen for raw material, adopting the efficient dual-function catalyst of binder free Zeolite support carried noble metal, 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 is than with under mole counting the condition of 3 ~ 10: 1, in aromatic hydrocarbons in reaction effluent in C9 aromatic except trimethylbenzene, weight content is less than 0.3%, BTX aromatic hydrocarbons yield reaches 46.4%, reaction product obtains trimethylbenzene monomer after rectifying separation, and increase production BTX aromatic hydrocarbons, achieve good technique effect.
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.Use a of reduction activation, b catalyzer carries out reaction examination, and the heavy aromatics reaction raw materials composition of employing counts the aromatic hydrocarbons of 6-8 carbon with weight percent: 1.79%; Sym-trimethylbenzene: 12.15%; Unsym-trimethyl benzene: 38.35%; Hemimellitene: 3.95%; Other 9 carbon aromatic hydrocarbons except trimethylbenzene: 38.05%; 10 above hydrocarbon of carbon: 5.71%, reaction conditions and reaction result list in table 1, as can be seen from table 1 reaction result, good by reaction heavy aromatics carbon more than two alkyl removal effect, can be separated trimethylbenzene monomer, and increase production BTX aromatic hydrocarbons from 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.Use the c of reduction activation, d, e catalyzer carries out reaction examination, and use c ~ e catalyzer of reduction activation in fixed-bed reactor, carry out reaction examination, 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.At hydrogen pressure 2.8MPa, H
2/ oil volume is than 400, and temperature in 360 DEG C, weight hourly space velocity WHSV is 2.0 hours
-1reaction result list in table 2.
[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.Use the f of reduction activation, g catalyzer carries out reaction examination, the heavy aromatics reaction raw materials composition adopted and reaction conditions are with embodiment 3, reaction conditions and reaction result list in table 2, as can be seen from table 2 reaction result, good by reaction heavy aromatics carbon more than two alkyl removal effect, trimethylbenzene monomer can be separated from product, and increase production BTX aromatic hydrocarbons.
[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.The h catalyzer of reduction activation is used to carry out reaction examination, the heavy aromatics reaction raw materials composition adopted and reaction conditions are with embodiment 3, reaction conditions and reaction result list in table 2, as can be seen from table 2 reaction result, good by reaction heavy aromatics carbon more than two alkyl removal effect, trimethylbenzene monomer can be separated from product, and increase production BTX aromatic hydrocarbons.
The evaluation result of table 1 catalyzer a and b under differential responses condition
The evaluation result of table 2 catalyzer c-h
Claims (8)
1. the method utilizing heavy aromatics hydrocracking to increase production BTX aromatic hydrocarbons and trimethylbenzene, with carbon nine and above heavy aromatics and hydrogen for raw material, aromatic hydrocarbons weight content wherein in C9 aromatic except trimethylbenzene is greater than 2%, 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 is in mole than under the condition of 3 ~ 10: 1, raw material and catalyst exposure are obtained by reacting BTX aromatic hydrocarbons, wherein B is benzene, T is toluene, X is dimethylbenzene, and the aromatic hydrocarbons weight content in reaction effluent in C9 aromatic except trimethylbenzene is less than 0.5%, and catalyzer used comprises following component with weight parts: 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 of Hydrogen binder free ten-ring zeolites; The crushing strength of binder free zeolite is greater than 40N/, and zeolite weight content is greater than 95%.
2. utilize heavy aromatics hydrocracking to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that temperature of reaction is 350 ~ 420 DEG C, reaction pressure is 2.4 ~ 3.5Mpa, the weight hourly space velocity of hydrocarbon raw material is 1.0 ~ 3.0 hours
-1, hydrogen/hydrocarbon raw material is in mole than for 4 ~ 8: 1.
3. utilize heavy aromatics hydrocracking to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that heavy aromatics is from reformate, pyrolysis gasoline, petroleum naphtha and catalytically cracked gasoline.
4. utilize heavy aromatics hydrocracking to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that the ten-ring zeolite selected in catalyzer is at least one of ZSM-5 or ZSM-11 zeolite.
5. utilize heavy aromatics hydrocracking to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that the SiO of binder free ten-ring zeolite
2/ Al
2o
3mol ratio is 20 ~ 200.
6. utilize heavy aromatics hydrocracking to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that the consumption being selected from least one in Pt or Pd with weight parts is 0.01 ~ 0.5 part.
7. utilize the hydrocracking of reformation heavy aromatics to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that in catalyzer also containing at least one be selected from Zn, La, Sn, Pb or Bi, its consumption counts 0 ~ 1 part with parts by weight, and non-vanishing.
8. utilize the hydrocracking of reformation heavy aromatics to increase production the method for BTX aromatic hydrocarbons and trimethylbenzene according to claim 1, it is characterized in that the aromatic hydrocarbons weight content optimum in reaction effluent in C9 aromatic except trimethylbenzene is 0.01 ~ 0.3%.
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