CN104549456B - Heavy aromatic lightening catalyst and preparation method thereof - Google Patents
Heavy aromatic lightening catalyst and preparation method thereof Download PDFInfo
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- CN104549456B CN104549456B CN201310512276.3A CN201310512276A CN104549456B CN 104549456 B CN104549456 B CN 104549456B CN 201310512276 A CN201310512276 A CN 201310512276A CN 104549456 B CN104549456 B CN 104549456B
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- 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
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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 invention relates to a heavy aromatic lightening catalyst and a preparation method thereof and mainly aims at solving the problems that the conversion level of heavy aromatic is low, the yield of mononuclear aromatic is low, the selectivity is low and the catalyst deactivation rate is high in the prior art. The heavy aromatic lightening catalyst comprises the following components in percentage by weight: 30-70% of an MCM-41 molecular sieve containing a BEA-type zeolite structural unit, 29.5-69.9% of at least one of gamma-alumina, eta-alumina and pseudo boehmite, which serves as a binding agent, and 0.1-0.5% of at least one metal selected from Pt, Pd and Ir. By adopting the technical scheme, the problems are well solved, and the heavy aromatic lightening catalyst can be applied to industrial production of lightening heavy aromatic into the mononuclear aromatic.
Description
Technical field
The present invention relates to a kind of heavy aromatics lightening catalyst and preparation method thereof.
Background technology
Heavy aromatics refers to the c of by-product in oil and the coal course of processing9Above aromatic hydrocarbons.Heavy aromatics is grasped through simple rectification at present
Make, separate the higher durol of bid value, isodurene, naphthalene, methyl naphthalene etc., remaining small part is used for producing solvent naphtha or work
For the blending component of gasoline, most of as low price fuel, raw material availability is low, both waste of resource, also serious environment pollution, damages
Evil health is it is difficult to play the due economic benefit of Heavy Aromatic Hydrocarbons.It is therefore to meet the oil demand that economic development brings
Growth, by develop heavy oil deep conversion technology, volume increase high added value light-end products will be 21 century oil refining industry
Significant development strategy.All to maximize processing heavy aromatics, improve mixed xylenes yield is the various techniques of heavy aromatics lighting
Target, improves air speed simultaneously, increases device disposal ability.Domestic and international industrialized technique at present, actual treatment heavy aromatics,
Particularly c10And its ability of above heavy aromatics still is apparent not enough, following technique research and development should be as emphasis.In recent years to triphen
In strong demand, increment is rapid, and will produce the situation that supply falls short of demand, and how by developing heavy oil deep conversion, volume increase is high additional
The light-end products such as the triphen of value are various countries petrochemical industry worker problems in the urgent need to address.
Usp4,341,622 discloses a kind of method that utilization heavy reformate produces btx.The method adopts restricted index
For 1～12, silica/alumina molar ratio (silica alumina ratio) be more than 12, the zeolite of low acid activity be catalyst, so that reformate is existed
React under conditions of 427～540 DEG C, then product separated is obtained benzene, toluene and dimethylbenzene.Described catalyst contains
The viii race noble metal of hydro-dealkylation function, preferably platinum, the silica alumina ratio of zeolite used is preferably greater than 200, more preferably greater than
500, preferred zeolite is zsm-5.The zeolite selecting high silica alumina ratio is to reduce zeolite acidity, retains dimethylbenzene as far as possible in reaction
In be not converted.
Us2007062848a1 discloses one kind and first will carry out selective opening and de- alkane after polycyclic aromatic hydrocarbon fractional saturation again
The method to obtain light aromatics for the base.The method can meet in feed stream polycyclic aromatic hydrocarbon content in more than 20wt%, saturation rank
Duan Wendu at 300～500 DEG C, pressure 2～10mpa；Open loop phase temperature at 200～600 DEG C, pressure 1～12mpa.Due to two
Section catalyst is contained in same reactor, it requires that logistics needs to ensure that certain time of staying could obtain preferable conversion
Rate, therefore air speed are relatively low.
Cn1472181a discloses a kind of heavy aromatics lightening catalyst, including 0.01～2.0 weight % viii race metal and
Complex carrier, described complex carrier includes the zsm-5 zeolite of 30～70 weight %, the modenite of 5～20 weight % and 10～65 weights
The aluminium oxide of amount %.This catalyst is used for heavy aromatic hydrocarbon light, can improve c9 +Aromatics conversion rate and the yield of benzene and dimethylbenzene,
And reduce carbon distribution.
Cn1082539c discloses a kind of heavy arenes lightening catalyst and the separation method of lighting product.Described urge
Agent by the platinum of 0.05～0.3 weight % or palladium, 20～59 weight % there is the zeolite of mor structure, the zsm-5 zeolite of 20～50 weight %
Aluminium oxide composition with 20～40 weight %.By the raw material of the heavy arene containing c9+ under the conditions of 350～450 DEG C, 0.3～3.5mpa
Carry out with above-mentioned catalyst contacting, gained lighting product through fractional distillation can get btx and sym-trimethylbenzene., pseudocumene, equal four
The Organic Ingredientss such as toluene.
Cn1048425c discloses a kind of heavy arenes lightening catalyst and lightening method.This catalyst is with 30～70
The zsm-5 zeolite of weight % and γ-or η-al of 30～70 weight %2o3For carrier, load the stannum and 0.05～0.3 of 0.1～0.5 weight %
The platinum of weight % or the palladium composition of 0.2～0.8 weight %.When 350～450 DEG C, 0.5～3.5mpa, weight space velocity 1～5-1, hydrogen/hydrocarbon body
Long-pending than under conditions of 500～1200, this catalyst has higher activity and stability and relatively low hydrogen consumption.
Content of the invention
One of the technical problem to be solved be in order to overcome catalyst present in prior art for weight fragrant
During hydrocarbon lighting reaction, heavy aromatics conversion level is low, and mononuclear aromatics yield is low and selectivity is low, fast the asking of catalyst deactivation rate
Topic, provides a kind of new catalyst for heavy aromatics lighting.This catalyst has heavy aromatics conversion level height, mononuclear aromatics
Yield and selectivity high, the slow advantage of catalyst deactivation rate.
The two of the technical problem to be solved are to provide a kind of weight virtue corresponding with solving one of technical problem
The preparation method of hydrocarbon lightening catalyst.
The three of the technical problem to be solved are to provide a kind of weight virtue corresponding with solving one of technical problem
The purposes of hydrocarbon lightening catalyst.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of heavy aromatics lighting catalysis
Agent, in terms of catalyst weight percent, including following components:
A) 30～70% mcm-41 molecular sieve containing bea type zeolite building units；
B) 29.5～69.9% at least one being selected from gama-alumina, η-aluminium oxide or boehmite are bonding
Agent；
C) 0.1～0.5% it is selected from least one metal in pt, pd or ir or its oxide.
In technique scheme, in used catalyst composition, the mcm-41 molecular sieve containing bea type zeolite building units is
For Hydrogen or ammonium type molecular sieve, in molecular sieve, sodium weight content is less than 2%, and its mole consists of n sio2: al2o3, n in formula=
30～60.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of heavy aromatics lighting catalysis
The preparation method of agent, comprises the following steps:
1. by the desired amount of mcm-41 molecular sieve containing bea type zeolite building units with the desired amount of selected from gamma oxidation
At least one binding agent in aluminum, η-aluminium oxide or boehmite carry out kneading, molding, be dried after, at 450～650 DEG C
Roasting 0.5～24h obtains catalyst carrier；
2. by the precursor solution of the desired amount of at least one metal in pt, pd or ir or its oxide in 30
～50 DEG C are impregnated into 0.5～24h in catalyst carrier, obtain finished product catalysis in 300～450 DEG C of roasting 0.5～24h after drying
Agent.
In technique scheme, in catalyst carrier preparation process, preferred version is, adds and presses carrier dry basis 2
～5% extrusion aid, extrusion aid is at least one in sesbania powder or Oleum Verniciae fordii；Add the one-tenth pressing carrier dry basis 3～6%
Colloid, gelatinizing agent be selected from hydrochloric acid, nitric acid, acetic acid, tartaric acid, at least one in citric acid or oxalic acid and water volume ratio 1:1～
1:5.
In technique scheme, the precursor solution preferred version of metal pt used is chloroplatinic acid；The forerunner of metal pd
Thing solution preferred version is at least one in Palladous nitrate. or Palladous chloride.；The precursor solution preferred version of metal ir is chlorine iridium
Acid.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of side of heavy aromatics lighting
Method, raw material heavy aromatics mixture is mixed with hydrogen, passes through beds, in 350 ~ 440 DEG C of reaction temperature, instead
Answer pressure 4 ~ 7 mpa, weight (hourly) space velocity (WHSV) degree 0.5 ~ 6 hr-1, any one with above-mentioned under the conditions of hydrogen/hydrocarbon mol ratio 4.0 ~ 8.0
Catalyst contact described in kind, heavy aromatics is converted into the mononuclear aromatics comprising benzene,toluene,xylene.
In technique scheme, preferred technical scheme is that reaction temperature is 350 ~ 390 DEG C, reaction pressure is 5 ~ 6
Mpa, weight (hourly) space velocity (WHSV) degree are 1 ~ 2 hr-1, hydrogen/hydrocarbon mol ratio be 6.0 ~ 7.0.
The catalyst that the present invention provides can be used for the industry that heavy aromatics lightweight turns to the mononuclear aromatics such as benzene, toluene and dimethylbenzene
In production.
Make due to employing the mcm-41 mesoporous molecular sieve containing bea type zeolite building units in framing structure in the present invention
For catalyst acid center, the presence of the bea type zeolite building units of crystalline state, overcome the unformed hole of conventional mcm-41 molecular sieve
Wall leads to the shortcoming of hydrothermal stability difference, improves the stability of catalyst, and the presence of macropore has and divides greatly beneficial to heavy arene
The acid site that son enters in duct carries out ring-opening reaction, and the product molecule after conversion quickly can be spread with passing hole channel, thus prolonging
Delay the deactivation rate of catalyst；There is by load the precious metal element of hydrogenating function, control its load capacity in a reasonable model
Enclose, the degree of unsaturation of Polycyclic Aromatic Hydrocarbon Mixture raw material can be effectively improved, help deep conversion heavy aromatics molecule；Catalyst acid
The rational proportion of center and metallic element makes will to retain as far as possible in lighting course of reaction original monocyclic in raw material stream
Aromatic component, and by heavy aromatics to the mononuclear aromatics conversion of lightweight, so that the yield of mononuclear aromatics and selectivity maximize, obtain
Preferable technique effect.
The present invention carries out the Performance of heavy aromatics lighting reaction, reactor inside diameter using supercritical fixed bed reactors
12 millimeters of ф, 800 millimeters of length, stainless steel.Using electrical heating, temperature automatic control.Reactor bottom fills ф 2～3
Millimeter bead is supporter, 5 grams of catalyst filling in reactor, and 2～3 millimeters of beades of ф are filled on top, are made for raw material pre-
Heat and vaporization are used.Raw material heavy aromatics mixture is mixed with hydrogen, passes through beds, in reaction temperature 350
~ 440 DEG C, reaction pressure 4 ~ 7 mpa, weight (hourly) space velocity (WHSV) degree 0.5 ~ 6 hr-1, under conditions of hydrogen/hydrocarbon mol ratio 4.0 ~ 8.0 with
Catalyst is contacted, and makes heavy aromatics be converted into the mononuclear aromatics such as benzene,toluene,xylene.
Heavy aromatics mixture is autogamy raw material, and experimental data is calculated as follows.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The preparation method of the mcm-41 molecular sieve of the zeolite building units of type containing bea: by 60g beta zeolite 100ml salt
After processing 1h in 50 DEG C in acid solution (0.2mol/l), add silica white, hydrochloric acid, cetyl trimethylammonium bromide
(ctab), alkylphenol polyoxyethylene (op-10) and deionized water make the mol ratio of thing phase in solution is 1sio2:
0.25ctab:0.04op-10:1.98hcl:160h2O, in addition, wbeta/wsio2(g/g)=0.50, by solution in 100 after stirring 2h
It is dried through filtration washing after DEG C hydrothermal treatment consists 48h, and in 500 DEG C of nitrogen atmosphere roasting 1h, 500 DEG C of air atmosphere roasting 5h are standby
With.
By butt weight be 50 g type containing bea zeolite building units mcm-41 molecular sieve (making by oneself) and 50 g γ-al2o3
(industrial goods) add blender to uniform, then add 3 g sesbania powders, 5 g volume ratio 1:1 hno in mixture3Solution and
40 g deionized waters, grind and uniformly make the dough being suitable to extrude.Extruded by mould, shape is in elongated cylinder
(diameter 1.7 mm), dries after 550 DEG C of roasting 4 h for 120 DEG C, be then cut into consistent size carrier granular (1.7 ×
4.0 mm), it is designated as z1.
Chloroplatinic acid wiring solution-forming is impregnated to carrier granular at 40 DEG C, the amount containing pt in impregnation liquid is carrier butt
The 0.2% of weight, dipping 8h after drying, in 450 DEG C of roasting 3 h, finished product catalyst a.
[embodiment 2～10]
The preparation method being provided according to embodiment 1 and process, by changing metal front in carrier composition and impregnation liquid
The species of thing and content, are prepared for a series of finished catalysts, are shown in Table 1.
Table 1
[embodiment 11-19]
Catalyst a～the j being obtained with embodiment 1～10 (highest response pressure on supercritical fixed bed reactors
10mpa, the use of temperature is room temperature～600 DEG C) investigate and heavy aromatics mixture is converted into btx (wherein b is benzene, and t is toluene, and x is
Dimethylbenzene) etc. mononuclear aromatics ability.Table 2 is to evaluate raw material composition.Catalyst packing 5 g, in 370 DEG C of reaction temperature, reaction
Pressure 5.5mpa, weight (hourly) space velocity (WHSV) degree 1.0hr-1, contacted with catalyst under the conditions of hydrogen/hydrocarbon mol ratio 6.0, product is carried out
Reclaim and component detection, conversion results are shown in Table 3.
Table 2
| Raw material forms | Non-aromatic | Benzene | Toluene | Ethylbenzene | Dimethylbenzene | Decahydronaphthalene | Naphthane | Naphthalene |
| Content (wt%) | 0.02 | 24.54 | 24.61 | 5.00 | 0.02 | 14.81 | 15.25 | 15.75 |
Table 3
| Catalyst is numbered | Total conversion (wt%) | Mononuclear aromatics selectivity (wt%) | Btx selectivity (wt%) |
| a | 59.9 | 76.2 | 51.3 |
| b | 61.6 | 75.1 | 50.6 |
| c | 58.7 | 77.0 | 53.4 |
| d | 63.2 | 74.3 | 49.7 |
| e | 64.0 | 74.0 | 49.1 |
| f | 66.7 | 73.2 | 49.0 |
| g | 55.3 | 80.1 | 55.8 |
| h | 59.0 | 77.5 | 53.2 |
| i | 65.1 | 73.7 | 48.9 |
| j | 62.6 | 74.7 | 49.2 |
[embodiment 20～24]
Investigated heavy aromatics mixture on supercritical fixed bed reactors with catalyst a～e that embodiment 1～5 is obtained
It is converted into the ability of the mononuclear aromatics such as btx.Catalyst packing 5g, in 380 DEG C of reaction temperature, reaction pressure 6mpa, weight (hourly) space velocity (WHSV)
Spend 1.0 hr-1, contacted with catalyst under the conditions of hydrogen/hydrocarbon mol ratio 6.5, product is reclaimed and component detection, will
Conversion results are shown in Table 4.
Table 4
| Catalyst is numbered | Total conversion (wt%) | Mononuclear aromatics selectivity (wt%) | Btx selectivity (wt%) |
| a | 62.4 | 78.0 | 52.6 |
| b | 63.6 | 77.1 | 51.1 |
| c | 62.5 | 78.6 | 53.9 |
| d | 63.0 | 76.8 | 50.5 |
| e | 62.1 | 78.3 | 52.7 |
[embodiment 25～29]
Investigated heavy aromatics mixture on supercritical fixed bed reactors with catalyst a～e that embodiment 1～5 is obtained
It is converted into the ability of the mononuclear aromatics such as btx.Catalyst packing 5 g, in 370 DEG C of reaction temperature, reaction pressure 5.5mpa, weighs space-time
Speed 2.0 hr-1, contacted with catalyst under the conditions of hydrogen/hydrocarbon mol ratio 6.0, product is reclaimed and component detection,
Conversion results are shown in Table 5.
Table 5
| Catalyst is numbered | Total conversion (wt%) | Mononuclear aromatics selectivity (wt%) | Btx selectivity (wt%) |
| a | 58.0 | 78.1 | 52.5 |
| b | 58.6 | 77.5 | 51.8 |
| c | 57.5 | 78.9 | 54.4 |
| d | 58.3 | 77.8 | 50.8 |
| e | 57.1 | 78.3 | 50.3 |
[embodiment 30～34]
Investigated heavy aromatics mixture on supercritical fixed bed reactors with catalyst a～e that embodiment 1～5 is obtained
It is converted into the ability of the mononuclear aromatics such as btx.Catalyst packing 5 g, in 370 DEG C of reaction temperature, reaction pressure 6mpa, weight (hourly) space velocity (WHSV)
Spend 1.0 hr-1, contacted with catalyst under the conditions of hydrogen/hydrocarbon mol ratio 6.5, product is reclaimed and component detection, will
Conversion results are shown in Table 6.
Table 6
| Catalyst is numbered | Total conversion (wt%) | Mononuclear aromatics selectivity (wt%) | Btx selectivity (wt%) |
| a | 59.8 | 75.7 | 51.9 |
| b | 61.8 | 75.9 | 50.2 |
| c | 58.3 | 76.3 | 52.8 |
| d | 62.9 | 72.8 | 49.9 |
| e | 63.5 | 74.5 | 49.5 |
[embodiment 35～39]
Investigated heavy aromatics mixture on supercritical fixed bed reactors with catalyst a～e that embodiment 1～5 is obtained
It is converted into the ability of the mononuclear aromatics such as btx.Catalyst packing 5 g, in 380 DEG C of reaction temperature, reaction pressure 6mpa, weight (hourly) space velocity (WHSV)
Spend 2.0 hr-1, contacted with catalyst under the conditions of hydrogen/hydrocarbon mol ratio 6.5, product is reclaimed and component detection, will
Conversion results are shown in Table 7.
Table 7
| Catalyst is numbered | Total conversion (wt%) | Mononuclear aromatics selectivity (wt%) | Btx selectivity (wt%) |
| a | 60.9 | 78.5 | 52.9 |
| b | 61.6 | 77.9 | 52.0 |
| c | 60.8 | 79.0 | 54.3 |
| d | 60.6 | 77.1 | 51.6 |
| e | 59.9 | 78.7 | 53.7 |
Claims (10)
1. a kind of heavy aromatics lightening catalyst, in terms of catalyst weight percent, including following components:
A) 30～70% mcm-41 molecular sieve containing bea type zeolite building units；
B) 29.5～69.9% at least one being selected from gama-alumina, η-aluminium oxide or boehmite are binding agent；
C) 0.1～0.5% it is selected from least one metal in pt, pd or ir or its oxide.
2. heavy aromatics lightening catalyst according to claim 1 is it is characterised in that containing bea type zeolite building units
Mcm-41 molecular sieve is Hydrogen or ammonium type molecular sieve, and in molecular sieve, sodium weight content is less than 2%.
3. heavy aromatics lightening catalyst according to claim 1 is it is characterised in that containing bea type zeolite building units
Mcm-41 molecular sieve mole consists of n sio2: al2o3, n=30～60 in formula.
4. the preparation method of the heavy aromatics lightening catalyst described in claim 1, comprises the following steps:
1. by the desired amount of mcm-41 molecular sieve containing bea type zeolite building units with the desired amount of selected from gama-alumina,
At least one binding agent in η-aluminium oxide or boehmite carry out kneading, molding, be dried after, in 450～650 DEG C of roastings
0.5～24h obtains catalyst carrier；
2. by the precursor solution of the desired amount of at least one metal in pt, pd or ir or its oxide in 30～50
DEG C it is impregnated into 0.5～24h in catalyst carrier, obtain finished catalyst in 300～450 DEG C of roasting 0.5～24h after drying.
5. the preparation method of heavy aromatics lightening catalyst according to claim 4 is it is characterised in that catalyst carrier system
Add the extrusion aid pressing carrier dry basis 2～5% during standby；Add in catalyst carrier preparation process and be selected from hydrochloric acid, nitre
At least one acid solution in acid, acetic acid, tartaric acid, citric acid or oxalic acid is gelatinizing agent.
6. the preparation method of heavy aromatics lightening catalyst according to claim 5 is it is characterised in that extrusion aid is sesbania
At least one in powder or Oleum Verniciae fordii.
7. the preparation method of heavy aromatics lightening catalyst according to claim 5 is it is characterised in that with carrier dry basis
Gauge, in catalyst carrier preparation process add 3～6 weight % gelatinizing agent, in gelatinizing agent, selected from hydrochloric acid, nitric acid, acetic acid,
The volume ratio of at least one and water in tartaric acid, citric acid or oxalic acid is 1:1～1:5.
8. the preparation method of heavy aromatics lightening catalyst according to claim 4 is it is characterised in that described metal pt
Precursor solution be chloroplatinic acid；The precursor solution of metal pd is at least one in Palladous nitrate. or Palladous chloride.；Metal ir's
Precursor solution is chloro-iridic acid.
9. a kind of method of heavy aromatics lighting, raw material heavy aromatics mixture is mixed with hydrogen, passes through catalyst bed
Layer, in 350 ~ 440 DEG C of reaction temperature, reaction pressure 4 ~ 7 mpa, weight (hourly) space velocity (WHSV) degree 0.5 ~ 6 hr-1, hydrogen/hydrocarbon mol ratio
Contact with any one described catalyst in claim 1 ~ 3 under the conditions of 4.0 ~ 8.0, heavy aromatics be converted into comprise benzene, toluene,
The mononuclear aromatics of dimethylbenzene.
10. heavy aromatics lighting according to claim 9 method it is characterised in that 350 ~ 390 DEG C of reaction temperature, reaction
Pressure 5 ~ 6mpa, weight (hourly) space velocity (WHSV) degree 1 ~ 2 hr-1, contact with catalyst under conditions of hydrogen/hydrocarbon mol ratio 6.0 ~ 7.0.
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| CN107115887A (en) * | 2017-06-19 | 2017-09-01 | 中国海洋石油总公司 | A kind of method for preparing catalyst for being used to crack heavy aromatics |
| CN110639545B (en) * | 2018-06-27 | 2022-07-12 | 中国石油化工股份有限公司 | Heavy distillate oil selective hydrogenation catalyst and application thereof |
| CN113209816A (en) * | 2020-01-21 | 2021-08-06 | 中国石油化工股份有限公司 | Catalyst grading method for catalytic oxidation of sulfur-containing VOCs and method for catalytic oxidation of sulfur-containing VOCs |
| CN112007691A (en) * | 2020-09-18 | 2020-12-01 | 中海油天津化工研究设计院有限公司 | Platinum-palladium bimetallic catalyst and preparation method and application thereof |
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| CN1488578A (en) * | 2003-08-07 | 2004-04-14 | 复旦大学 | Mesoporous molecular sieve cortaining beta zeolite secondary constitutional unit and preparing method thereof |
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| 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 |
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| CN1488578A (en) * | 2003-08-07 | 2004-04-14 | 复旦大学 | Mesoporous molecular sieve cortaining beta zeolite secondary constitutional unit and preparing method thereof |
| CN102107144A (en) * | 2009-12-24 | 2011-06-29 | 中国石油化工股份有限公司 | Method for preparing C8 aromatic isomerization catalyst |
| CN103121896A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons |
| CN103121912A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing dimethylbenzene through methylation and transalkylation |
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