CN104109075A - High-xylene-selectivity toluene disproportionation method - Google Patents

High-xylene-selectivity toluene disproportionation method Download PDF

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CN104109075A
CN104109075A CN201310129886.5A CN201310129886A CN104109075A CN 104109075 A CN104109075 A CN 104109075A CN 201310129886 A CN201310129886 A CN 201310129886A CN 104109075 A CN104109075 A CN 104109075A
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toluene
dimethylbenzene
mcm
catalyzer
reaction
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祁晓岚
王月梅
孔德金
陈秉
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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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Abstract

The invention relates to a high-xylene-selectivity toluene disproportionation method. The technical problems of high benzene selectivity, low xylene selectivity, and low productivity and high energy consumption caused by high hydrogen/hydrocarbon mole ratio existing in the prior art are mainly solved. The method is characterized in that a toluene raw material contacts with a catalyst in a fixed bed reactor and undergoes a toluene disproportionation reaction under critical hydrogen conditions to prepare xylene and benzene, wherein the reaction conditions comprise a reaction temperature of 300-500DEG C, a reaction pressure of 0.1-5.0MPa, a molar ratio of hydrogen/toluene of 0.2-4 and a charging air speed of 1-8h<-1>, and the catalyst comprises 30-90 parts by weight of an MWW structured molecular sieve with the SiO2/Al2O3 molar ratio of 10-200, and 10-70 parts by weight of a binder. The method well solves the problems, and can be used in the industrial production of benzene and xylene by disproportionating toluene.

Description

There is the toluene disproportionation process of dimethylbenzene highly selective
Technical field
The present invention relates to a kind of toluene disproportionation process, particularly there is the toluene disproportionation process of dimethylbenzene highly selective.
Background technology
Aromatic hydrocarbons is important Organic Chemicals, is all to derive from petrochemical industry conventionally.Wherein, benzene and dimethylbenzene are mainly from catalytic reforming, pyrolysis gasoline and toluene disproportionation and transalkylation reaction.In three kinds of isomer of dimethylbenzene, p-Xylol (PX) is important Organic Chemicals, and mainly for the production of pure terephthalic acid (PTA), PTA is again the raw material of producing polyester.Because PX demand is growing, directly from reformate and extracting pyrolysis gasoline with separate PX and far can not satisfy the demands.In benzene, toluene and dimethylbenzene, the source of toluene is the most sufficient, but its purposes can not show a candle to benzene and dimethylbenzene, therefore cause toluene relative surplus.Toluene is mainly derived from reformer, pyrolysis gasoline and cinnamic by-product, also contains a large amount of toluene in the aromatic hydrocarbons that gelatin liquefaction or coal gasification process make, and within 2011, global toluene production capacity has reached 2,954 ten thousand tons.In China, toluene mainly as the raw material of gasoline component, disproportionation benzene processed and dimethylbenzene, produce the Chemicals such as nitrotoluene, phenylformic acid, Tolylamine, Benzene Chloride, tolylene diisocyanate cresols and be used as solvent.Due to environmental protection pressure, the demand of toluene aspect solvent will be subject to certain restriction.
Industrialized p-Xylol production technology mainly contains two kinds at present, and a kind of by producing p-Xylol technique through fractionation by adsorption, isomerization after toluene disproportionation and transalkylation, the second is selective disproportionation of toluene crystallization separation process.The former is balanced the xylol of composition through disproportionation and transalkylation, though the latter's energy production high purity PX, toluene conversion is low.For adapting to energy-saving and cost-reducing requirement, improve the economic benefit of Aromatic Hydrocarbon United Plant, develop new volume increase PX production line imperative.
Toluene disproportionation unit is integral part indispensable in Aromatic Hydrocarbon United Plant, and it can be converted into dimethylbenzene and the benzene that value is higher relatively inexpensive toluene, has logistics conversion hinge and effective vital role of adjusting aroamtic hydrocarbon raw material and product structure.Toluene disproportionation process mainly contains two classes, comprises toluene and the C of transalkylation performance 9the disproportionation of A aromatic hydrocarbons and alkyl transfering process and only process the toluene disproportionation process of toluene.
The advantage of disproportionation and alkyl transfering process is to utilize toluene and heavy aromatics to be converted into benzene and dimethylbenzene, typical process is as " Tatoray " and " S-TDT " technique, along with the update of catalyzer, processing power also improves gradually, as empty scooter 1.7 h of HLD-001 catalyzer -1, the air speed of HAT-099 catalyzer and MXT-01 catalyzer reaches 2.5 h -1, hydrogen hydrocarbon mol ratio also drops to 3-4 simultaneously, and total conversion rate maintains more than 45%.
The toluene disproportionation process of only processing toluene comprises methylbenzene shape selective disproportionation technique and selective disproportionation technique not, adopt selective disproportionation of toluene technology as MSTDP, MTPX technique, PX-Plus and SD technique etc., can obtain the Mixed XYLENE that PX content is greater than 90%, break thermodynamic(al)equilibrium, can be up to 3.5-4.0 h with hourly space velocity -1, but transformation efficiency is only 30% left and right.This technique need coordinate Crystallization Separation could further embody its superiority.If dimethylbenzene separates or undertaken by fractionation by adsorption, because toluene internal circulating load is higher, improve by PX selectivity the advantage of bringing separating energy consumption to reduce and will give a discount.The existing non-shape toluene disproportionation technology of selecting all exists low-speed, high hydrogen hydrocarbon mol ratio (hereinafter to be referred as hydrogen-hydrocarbon ratio) to cause the technical problem that production capacity is low, energy consumption is high.
It is catalyzer that CN 101124186 A adopt nickel modified mordenite, needs first catalyzer to be carried out to good cure with inactivate activity nickel, then just can carry out toluene disproportionation process.And this catalyzer comprises the precious metal such as platinum, palladium, Catalyst Production cost is improved.Be 47% for making toluene conversion, the hydrogen-hydrocarbon ratio needing is 3:1.
It is catalyzer that CN 101687729 A adopt nickel modified mordenite, and its charging air speed LHSV is 1 ~ 4.5 h -1, 300 ~ 450 DEG C of temperature of reaction, reaction pressure 30 ~ 45 bar, hydrogen-hydrocarbon ratio is 3:1 at least.Meanwhile, this catalyzer also needs prevulcanized processing.
CN 102123947 A have developed containing niobium mordenite catalyst, and for toluene disproportionation process, in product, non-aromatic compound selective is less than 0.75%.
Toluene disproportionation process refers to that two molecule toluene generate the reaction of a part benzene and a part dimethylbenzene, and the toluene disproportionation of 2 moles generates the dimethylbenzene of 1 mole and the benzene of 1 mole in theory, and in product, the mol ratio X/B of dimethylbenzene and benzene should be 1.But in real reaction system, be usually attended by side reaction, as toluene hydro-dealkylation, reaction generates benzene and methane, and toluene benzene ring hydrogenation generates methylcyclohexane, aromatic ring scission reaction etc.Therefore, under normal circumstances toluene disproportionation process often the selectivity of benzene apparently higher than dimethylbenzene selective, make X/B much smaller than 1.See benzene relative surplus from market angle, supply falls short of demand for dimethylbenzene, therefore wishes to reduce as far as possible side reaction to improve dimethylbenzene selective.
In conventional toluene disproportionation catalyst active ingredient, mordenite has one dimension twelve-ring channel architecture, and strength of acid is high, is therefore conducive to occur the side reaction such as hydro-dealkylation and cracking, and therefore dimethylbenzene yield is not high.ZSM-5 has two-dimentional ten-ring cross channel structure, and strength of acid is higher, is extended influence, and the reaction of toluene hydro-dealkylation more easily occurs.
The molecular sieve with MWW structure comprises that MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1 and ITQ-2 etc. are several, and its crystal is generally sheet or dish shape, and (Wu has friendly relations, Xu Ning, the structure of MCM-22 family molecular sieves and catalytic performance, chemistry circular, 2004,67, w102).
MCM-22 has two not connected multidimensional pore canal system.Article one, being two-dimentional sinusoidal reticulated channel, is ten-ring aperture; Another is all ten-ring, but contains large supercage.Supercage is cut open as twelve-ring along level, and cage size is 0.71 × 0.71 × 1.82 nm.The sinusoidal pore canal system of MCM-22 is netted, has a large amount of point of crossing, is similar to ZSM-5.Molecule can have various ways to spread in duct.But due to aperture ovalize, the diffusion of molecule is had to stronger restriction, in catalyzed reaction, may show very strong shape selectivity.
Catalyzer taking MCM-22 as carrier is converted into the fields such as alkene and aromatic hydrocarbons, catalytic cracking, isomerisation of olefin, hydro carbons alkylation at alkane and has shown good catalytic performance.
In EP 0800497, taking benzene and ethene as raw material, compared with Y, Beta, ZSM-5 equimolecular sieve, carry out liquid phase alkylation reaction on MCM-22, MCM-49 and MCM-56 time, show higher ethylbenzene selectivity.USP 5258565 also discloses MCM-36 molecular sieve is prepared ethylbenzene technology for benzene and ethylene alkylation.ZL 200410000957.2 discloses a kind of halogen-containing MCM-22 zeolite catalyst, during for benzene liquid phase alkylation reaction, can improve ethylbenzene selectivity.The rare ethene of the disclosed one of CN101352690 and molecular sieve catalyst for producing phenylethane from alkylation of benzene, be made up of MCM-22 or MCM-49.
USP 5557024 adopts MCM-56 to prepare the molecular sieve catalyst of isopropyl benzene as a kind of high reactivity benzene and propylene liquid-phase alkylation, is 20 ~ 30 h in propylene air speed -1time can obtain more than 90% propylene conversion.
5258566 of USP disclose the technology that benzene and long chain olefin alkylation on MCM-36 molecular sieve are prepared chain alkyl aromatic hydrocarbon, and monoalkylation benzene selective can reach 81%.USP 5401896 adopts MCM-49 also to obtain good result as benzene and long chain olefin alkylation catalyzer.
CN101940943A discloses the form selected methylation catalyzer of a kind of toluene and the synthetic p-Methylisopropylbenzene of propylene, comprises the ZSM-35 through liquid-phase silicone deposition surface modification, Beta, MCM-22 zeolite.
It is that catalyzer carries out alkene and isoparaffin alkylated reaction to improving gasoline octane rating that USP 5254792 adopts MCM-22 and MCM-49, has obtained good effect.It is the alkylated reaction that catalyzer carries out isoparaffin and normal olefine that 5258569 of USP adopt MCM-36.
For increasing gasoline octane rating, reduce harmful gas emission in motor-vehicle tail-gas, need in gasoline, add MTBE (tertiary butyl ether), ETBE (Ethyl Tertisry Butyl Ether) etc. as gasoline dope, this needs a large amount of iso-butylenes as raw material, and one of feasible approach is abundant butene-1 resource to be carried out to skeletal isomerization obtain iso-butylene.Document (" Appl. Catal., A:General ", 1996,158:561 ~ 569) report, MCM-22 has very high activity, selectivity and stability, 1.15 in this reaction), in the time that the conversion rate control of n-butene is below 50%, selective isobutene is the highest.
ZL 99112884.2 adopt modified MC M-22 molecular sieve be catalyzer for direct synthesis of arene with methane, can highly selective benzene processed.CN1401431 discloses a kind of methane aromatization catalyst, and this catalyzer for supporting active ingredient WO on MCM-49 zeolite 3or MoO 3, the wherein SiO of MCM-49 2/ Al 2o 3than being 20～100.Its methane aromatization raw material is pure methane or methane, carbon dioxide gas mixture, and in the aromatic product that can obtain, benzene proportion can approach 90%.
At present, not yet there is the molecular sieve with MWW structure as the report of toluene disproportionation catalyst.
Summary of the invention
Technical problem to be solved by this invention be for overcome toluene disproportionation in prior art prepare in benzene and dimethylbenzene technology, exist cause the selectivity of benzene high owing to there is side reaction, dimethylbenzene selective is low, cause product X/B much smaller than 1, cause dimethylbenzene target product production capacity low, the technical problem that energy consumption is high, a kind of new toluene disproportionation process with dimethylbenzene highly selective is provided, the method is for toluene disproportionation process, under the condition of low hydrogen-hydrocarbon ratio, there is dimethylbenzene selective and benzene selective is suitable, in product, the mol ratio X/B of dimethylbenzene and benzene is greater than 0.9, the feature that toluene conversion is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of toluene disproportionation process with dimethylbenzene highly selective, under hydro condition, methylbenzene raw material contacts with catalyzer by fixed-bed reactor and carries out toluene disproportionation process and prepare dimethylbenzene and benzene, its reaction conditions is: 300～500 DEG C of temperature of reaction, reaction pressure 0.1～5.0 MPa, hydrogen/toluene mole ratio 0.2～4, charging air speed 1～8 h -1; Catalyzer used, in parts by weight, comprises the SiO of 30～90 parts 2/ Al 2o 3mol ratio is 10～200 the molecular sieve with MWW structure and the binding agent of 10～70 parts.
In technique scheme, the molecular sieve preferred version with MWW structure is at least one being selected from MCM-22, MCM-36, MCM-49, MCM-56.Binding agent preferred version is at least one being selected from aluminum oxide, pseudo-boehmite, kaolin or montmorillonite.The molecular sieve with MWW structure more preferably scheme is at least one being selected from MCM-22, MCM-49, MCM-56.There is the SiO of MWW structure molecular screen 2/ Al 2o 3mol ratio preferable range is 15～100.There is the SiO of MWW structure molecular screen 2/ Al 2o 3mol ratio more preferably scope is 20～80; SiO 2/ Al 2o 3mol ratio more preferably scope is 25～60.
Preferably technical scheme is, also comprises at least one modifying element being selected from periodic table of elements VIII family in catalyzer, and in the parts by weight of catalyzer, the content of modifying element is 0.01 ~ 10 part.Preferred technical scheme is, the modifying element in catalyzer is nickel, and in the parts by weight of catalyzer, the content of modifying element is 0.1 ~ 5 part; There is the molecular sieve SiO of MWW structure 2/ Al 2o 3mol ratio is 25～60.Preferred technical scheme is, the modifying element in catalyzer is cobalt, and in the parts by weight of catalyzer, the content of modifying element is 0.1 ~ 5 part.
In technique scheme, temperature of reaction preferable range is 350～450 DEG C, and reaction pressure preferable range is 0.5～4.0 MPa, and hydrogen/toluene mole ratio preferable range is 0.5～3, and charging air speed preferable range is 2～6 h -1.Temperature of reaction more preferably scope is 360～440 DEG C, and reaction pressure more preferably scope is 1.0～3.5 MPa, and hydrogen/toluene mole ratio more preferably scope is 0.6～2.5, and charging air speed more preferably scope is 2～6 h -1.Preferred technical scheme is that in product, the mol ratio X/B of dimethylbenzene and benzene is greater than 0.9.
 
The present invention, because employing has the molecular sieve of MWW structure as the active ingredient of catalyzer, is not the MCM-22 molecular sieve with MWW structure yet, has two not connected multidimensional pore canal system, and one is two-dimentional sinusoidal reticulated channel, is ten-ring aperture; Another is all ten-ring, but contains large supercage, and supercage is cut open as twelve-ring along level, and cage size is 0.71 × 0.71 × 1.82 nm.The sinusoidal pore canal system of MCM-22 is netted, has a large amount of point of crossing, and molecule can have various ways to spread in duct.But due to aperture ovalize, the diffusion of molecule is had to stronger restriction, in catalyzed reaction, may show very strong shape selectivity.MCM-22 molecular sieve is that the catalyzer of active ingredient is converted into the fields such as alkene and aromatic hydrocarbons, catalytic cracking, isomerisation of olefin, hydro carbons alkylation at alkane and has shown good catalytic performance.
Adopt the toluene disproportionation process with dimethylbenzene highly selective provided by the invention, 300～500 DEG C of temperature of reaction, reaction pressure 0.1～5.0MPa, toluene feed air speed 1～8 h -1, under hydrogen/toluene mole ratio 0.2～4 condition, X/B reaches as high as 0.99, and toluene conversion reaches as high as 47.5%, and benzene and C8 aromatic hydrocarbons (B+C8) selectivity reach as high as 88.5%, have obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but therefore do not limit the scope of the invention.
 
Embodiment
[embodiment 1]
Get respectively SiO 2/ Al 2o 3mol ratio is 40 grams of 60 grams, 20 Hydrogen MCM-22 molecular sieve and pseudo-boehmites, adds 5 milliliters, chemical pure nitric acid and 50 grams of Ni(NO that concentration is 10% after mixing 3) 2solution, carries out extruded moulding after mediating evenly, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyst A.
 
[embodiment 2]
Get respectively SiO 2/ Al 2o 3mol ratio is 15 grams of 85 grams, 92 Hydrogen MCM-22 molecular sieve and kaolin, adds 5 milliliters, chemical pure nitric acid and 50 grams of Co(NO that concentration is 40% after mixing 3) 2solution, carries out extruded moulding after mediating evenly, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyst B.
 
[embodiment 3]
Get respectively SiO 2/ Al 2o 3mol ratio is 30 grams, 70 grams, 40 Hydrogen MCM-49 molecular sieve and aluminum oxide, adds 2 milliliters, chemical pure nitric acid, 50 milliliters of deionized waters after mixing, and carries out extruded moulding after mediating evenly, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyzer C.
 
[embodiment 4]
Get respectively SiO 2/ Al 2o 3mol ratio is 60 grams of 40 grams, 25 Hydrogen MCM-49 molecular sieve and pseudo-boehmites, after mixing, add 2 milliliters, chemical pure nitric acid, 50 milliliters of deionized waters, after mediating evenly, carry out extruded moulding, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyzer D.
 
[embodiment 5]
Get respectively SiO 2/ Al 2o 3mol ratio is 30 grams of 70 grams, 40 Hydrogen MCM-36 molecular sieve and pseudo-boehmites, after mixing, add 2 milliliters, chemical pure nitric acid, 50 milliliters of deionized waters, after mediating evenly, carry out extruded moulding, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyzer E.
 
[embodiment 6]
Get respectively SiO 2/ Al 2o 3mol ratio is 30 grams of 70 grams, 54 Hydrogen MCM-56 molecular sieve and pseudo-boehmites, after mixing, add 2 milliliters, chemical pure nitric acid, 50 milliliters of deionized waters, after mediating evenly, carry out extruded moulding, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyzer F.
 
[embodiment 7]
Get respectively SiO 2/ Al 2o 3mol ratio is 40 grams of 60 grams, 20 Hydrogen MCM-22 molecular sieve and pseudo-boehmites, after mixing, add 2 milliliters, chemical pure nitric acid, 50 milliliters of deionized waters, after mediating evenly, carry out extruded moulding, 120 DEG C dry after 4 hours, 600 DEG C of roastings 4 hours, make catalyzer F.
The concrete composition of each embodiment is in table 1.
Table 1
[embodiment 8～14]
Catalyst A ~ the G making with embodiment 1 ~ 7 carries out toluene disproportionation process Performance at fixed-bed reactor, and appreciation condition is: taking pure toluene as raw material, and 10 grams of loaded catalysts, toluene feed weight space velocity is 2.5 hours -1, 400 DEG C of temperature of reaction, reaction pressure 3.0 MPa, hydrogen is with raw molecule than 2.0, and evaluation result is as shown in table 2.
Toluene conversion, the toluene amount of wt %=100 × react away/the enter toluene amount of reactor.
Selectivity, the toluene amount that the benzene (B) of wt %=100 × generation and dimethylbenzene (X) are measured/reacted away.
X/B, the benzene mole number of dimethylbenzene mole number/generation that mol/mol=generates.
Table 2
Embodiment Catalyzer numbering Toluene conversion Selectivity X/B
8 A 46.1 81.5 0.98
9 B 47.5 77.8 0.92
10 C 44.7 80.5 0.96
11 D 39.8 82.3 0.98
12 E 43.8 81.0 0.94
13 F 42.7 80.2 0.91
14 G 41.7 79.8 0.95
[embodiment 15～20]
Taking pure toluene as raw material, investigated the toluene disproportionation process performance of catalyst A at fixed-bed reactor, 10 grams of loaded catalysts, differential responses condition and reaction result are listed in table 3.
Table 3
Embodiment 15 16 17 18 19 20
Temperature of reaction/DEG C 320 360 380 400 420 480
Reaction pressure/MPa 0.5 2.0 3.0 3.0 3.0 4.0
Charging air speed/h -1 1.1 1.5 2.0 3.0 4.0 7.5
Hydrogen hydrocarbon mol ratio 0.5 1.0 1.5 2.5 3.0 3.8
X/B 0.99 0.98 0.98 0.98 0.95 0.91
Toluene conversion 25.1 33.4 39.7 44.1 43.4 45.3
Selectivity 88.5 86.3 84.4 83.1 81.0 71.5

Claims (9)

1. one kind has the toluene disproportionation process of dimethylbenzene highly selective, under hydro condition, methylbenzene raw material contacts with catalyzer by fixed-bed reactor and carries out toluene disproportionation process and prepare dimethylbenzene and benzene, its reaction conditions is: 300～500 DEG C of temperature of reaction, reaction pressure 0.1～5.0 MPa, hydrogen/toluene mole ratio 0.2～4, charging air speed 1～8 h -1; Catalyzer used, in parts by weight, comprises the SiO of 30～90 parts 2/ Al 2o 3mol ratio is 10～200 the molecular sieve with MWW structure and the binding agent of 10～70 parts.
2. the toluene disproportionation process with dimethylbenzene highly selective according to claim 1, at least one in MCM-22, MCM-36, MCM-49, MCM-56 of the molecular screening that it is characterized in that having MWW structure; Binding agent is selected from least one in aluminum oxide, pseudo-boehmite, kaolin or montmorillonite; There is the SiO of MWW structure molecular screen 2/ Al 2o 3mol ratio is 15～100.
3. the toluene disproportionation process with dimethylbenzene highly selective according to claim 1, at least one in MCM-22, MCM-49, MCM-56 of the molecular screening that it is characterized in that having MWW structure, has the SiO of MWW structure molecular screen 2/ Al 2o 3mol ratio is 20～80.
4. the toluene disproportionation process with dimethylbenzene highly selective according to claim 1, it is characterized in that also comprising in catalyzer at least one modifying element being selected from periodic table of elements VIII family, in the parts by weight of catalyzer, the content of modifying element is 0.01 ~ 10 part.
5. the toluene disproportionation process with dimethylbenzene highly selective according to claim 4, is characterized in that the modifying element in catalyzer is nickel, and in the parts by weight of catalyzer, the content of modifying element is 0.1 ~ 5 part; There is the molecular sieve SiO of MWW structure 2/ Al 2o 3mol ratio is 25～60.
6. the toluene disproportionation process with dimethylbenzene highly selective according to claim 4, is characterized in that the modifying element in catalyzer is cobalt, and in the parts by weight of catalyzer, the content of modifying element is 0.1 ~ 5 part.
7. the toluene disproportionation process with dimethylbenzene highly selective according to claim 1, is characterized in that 350～450 DEG C of temperature of reaction, reaction pressure 0.5～4.0 MPa, hydrogen/toluene mole ratio 0.5～3, charging air speed 2～6 h -1.
8. according to the toluene disproportionation process with dimethylbenzene highly selective described in claim 1 or 7, it is characterized in that in product, the mol ratio X/B of dimethylbenzene and benzene is greater than 0.9.
9. the toluene disproportionation catalyst with dimethylbenzene highly selective according to claim 1, is characterized in that 360～440 DEG C of temperature of reaction, reaction pressure 1.0～3.5 MPa, hydrogen/toluene mole ratio 0.6～2.5, charging air speed 2～6 h -1.
CN201310129886.5A 2013-04-16 2013-04-16 High-xylene-selectivity toluene disproportionation method Pending CN104109075A (en)

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Publication number Priority date Publication date Assignee Title
CN106866338A (en) * 2017-03-31 2017-06-20 新疆大学 The method for promoting toluene low temperature disproportionated reaction
CN106866338B (en) * 2017-03-31 2019-07-16 新疆大学 Promote the method for toluene low temperature disproportionated reaction

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