CN103664490A - Method for toluene alkylation with methanol - Google Patents
Method for toluene alkylation with methanol Download PDFInfo
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- CN103664490A CN103664490A CN201210325066.9A CN201210325066A CN103664490A CN 103664490 A CN103664490 A CN 103664490A CN 201210325066 A CN201210325066 A CN 201210325066A CN 103664490 A CN103664490 A CN 103664490A
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Abstract
The invention relates to a method for toluene alkylation with methanol and the method is mainly used for solving the problem of the prior art that the reactivity is obviously reduced while the selectivity is improved during the toluene alkylation with methanol. The method is characterized in that toluene and methanol are adopted as raw materials and contacted with a catalyst to produce xylene and water, wherein the catalyst adopted comprises the following components in parts by weight: a) 5 to 95 parts of silicon modified core-shell molecular sieve, and 5 to 95 parts of adhesive, wherein the nuclear phase of the silicon modified core-shell molecular sieve is an ZSM molecular sieve, the core shell is an Silicalite-1 molecular sieve, and a silicon dioxide layer covers outside the core shell; the weight ratio of core to shell is (0.01-3):1; the silicon dioxide layer accounts for 1-30wt% of the core-shell molecular sieve. According to the technical scheme, the problem in the prior art can be better solved and the method is applicable to the industrial production of toluene alkylation with methanol.
Description
Technical field
The present invention relates to a kind of alkylation of toluene methanol method.
Background technology
P-Xylol is the important source material of synthetic polyester fibers, at present industrial main employing toluene disproportionation and C
9aromatic hydrocarbons transalkylation, xylene isomerization and toluene select the methods such as disproportionation to produce.Because the p-Xylol content in its product is subject to thermodynamic control, the equilibrium concentration of p-Xylol in all xylene isomers only accounts for approximately 24%, and between isomer, boiling point approaches, and separation condition is harsh, and equipment requirements is high.In toluene selective disproportionation reaction, need could generate more than 85% p-Xylol of one mole of purity with two moles of toluene, toluene utilization ratio is lower.And at toluene, react with methanol alkylation in the p-Xylol technique of directly synthetic high density, toluene utilization ratio is high, and product is easy to separation, thereby this technique has good exploitation value.
Alkylation of toluene methanol reaction is with conventionally all adopting acidic molecular sieve to make catalyzer, and the strength of acid of ZSM-5 and sour distribution can in very large range regulate and control, so ZSM-5 is the molecular screen material extensively adopting in research.But, the acid sites of ZSM-5 molecular sieve outside surface is disadvantageous to selecting shaped reaction conventionally, in molecular sieve crystal, there is alkylated reaction and generate p-Xylol in toluene and methyl alcohol, p-Xylol spreads out from the duct of ZSM-5 at first, but there is acidic site in molecular sieve outer surface, particularly the ratio of small crystal grain molecular sieve outer surface acidity position is larger, and p-Xylol further isomery under the effect at outer surface acidity center turns to m-xylene and o-Xylol.In prior art, can be by molecular sieve outer surface being modified to reduce the generation of this reaction, to improve the selectivity of molecular sieve shape selective catalytic reaction.
US Patent No. 4088605, US4788374 and US4868146 have reported the molecular sieve shell at ZSM-5 or ZSM-3 outside surface crystallization total silicon, and this shell can not affect under the prerequisite of nuclear phase molecular sieve pore passage diffusion and Acidity, modulation outer surface properties.
CN1927463A relates to a kind of method of modifying ZSM-5 zeolite outer surface acidity by chemical reaction deposit.The feature of the method is that estersil reacts in airtight container with molecular sieve at 140-170 ℃, then carries out coolingly, and roasting makes.The effect of the method and benefit are that the utilization ratio of estersil is high, for micron ZSM-5, only need a load, the contraposition of catalyzer is selected to reach more than 90%, and needs twice chemical reaction deposit for nano-ZSM-5, and para-selectivity can reach more than 90%.But the method is when modifying outside acidity, and meeting Partial Blocking duct, causes catalyst activity greatly to reduce.
Summary of the invention
Technical problem to be solved by this invention is that prior art is carried out alkylation of toluene methanol when reaction, is improving the optionally active obvious problem that declines of simultaneous reactions, and a kind of method of new alkylation of toluene methanol is provided.The method has when having compared with highly selective, the active less advantage that declines.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of alkylation of toluene methanol, take toluene and methyl alcohol as raw material, the gas that reaction is to inertia of take is carrier gas, in temperature of reaction, be 300 ~ 500 ℃, reaction pressure is 0 ~ 1 MPa, and air speed is 1 ~ 10 hour
-1, the mol ratio of toluene and methyl alcohol is (10:1) ~ (1:3), the mol ratio of carrier gas and methylbenzene methanol total amount is that under the condition of (1:1) ~ (5:1), reaction raw materials contacts with catalyzer, generates dimethylbenzene and water; Catalyzer used wherein, comprises following component in parts by weight:
A) core-shell molecular sieve of the silicon modification of 5 ~ 95 parts;
B) binding agent of 5 ~ 95 parts;
Wherein, the nuclear phase of the core-shell molecular sieve of described silicon modification is ZSM-5 molecular sieve, and shell is Silicalite-1 molecular sieve, and shell is coated with silicon dioxide layer outward; Wherein, the weight ratio of core/shell is (0.01 ~ 3): 1; Silicon dioxide layer is 1 ~ 30% of core-shell molecular sieve weight.
In technique scheme, nuclear phase ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2o
3preferable range is 10 ~ 350, and more preferably scope is 20 ~ 300.The weight ratio preferable range of core/shell is (0.02 ~ 2): 1, and more preferably scope is (0.03 ~ 1.5): 1.Silicon dioxide layer weight preferable range is 2 ~ 25% of core-shell molecular sieve weight, and more preferably scope is 3 ~ 22%.In catalyzer, binding agent preferred version is at least one being selected from silicon sol or silicon oxide.Temperature of reaction preferable range is 320 ~ 480 ℃, and more preferably scope is 350 ~ 450 ℃.In raw material, the mol ratio of toluene and methyl alcohol is that preferable range is (8:1) ~ (1:2), and more preferably scope is (6:1) ~ (1:1).Carrier gas preferred version is nitrogen.
The preparation method of the catalyzer in the present invention is as follows: the binding agent of the core-shell molecular sieve of silicon modification and aequum is carried out to kneading, moulding, dry, roasting, obtain catalyzer finished product.Wherein, the preparation method of the core-shell molecular sieve of silicon modification comprises the following steps:
1) preparation shell liquid: tetraethoxy, organic formwork agent R and water are mixed to mole the consisting of of mixture: H
2o/SiO
2=20 ~ 120, R/SiO
2=0.01 ~ 0.3; Wherein, organic formwork agent R is selected from least one in TPAOH, 4-propyl bromide, methylamine, ethamine, propylamine or butylamine;
2) nuclear phase ZSM-5 molecular sieve is added in above-mentioned shell liquid, in 130 ~ 210 ℃ of crystallization 1 ~ 36 hour, through cooling, filter, dry, obtain core-shell molecular sieve; Wherein, the weight ratio of nuclear phase ZSM-5 molecular sieve and shell liquid is 1:(5 ~ 250);
3) core-shell molecular sieve is mixed with silicon source, in 140 ~ 180 ℃ of crystallization 1 ~ 10 hour, roasting products therefrom, obtain the core-shell molecular sieve of described silicon modification; Wherein, the weight ratio in core-shell molecular sieve and silicon source is 1:(1 ~ 2); Described silicon source, in parts by weight, comprises following component:
A) 1 ~ 100 part be selected from least one in tetraethoxy, positive silicic acid propyl ester or butyl silicate;
B) 0 ~ 99 part be selected from least one dispersion agent in normal hexane, hexanaphthene, normal heptane, suberane, octane or cyclooctane.
In technique scheme, in step 1), a mole composition preferable range for mixture is: H
2o/SiO
2=30 ~ 100, R/SiO
2=0.03 ~ 0.2.Step 2) in, crystallization temperature preferable range is 140 ~ 200 ℃, and crystallization time preferable range is 2 ~ 24 hours.In step 3), crystallization temperature preferable range is 150 ~ 170 ℃, and crystallization time preferable range is 2 ~ 9 hours.In step 3), in parts by weight, at least one the consumption preferable range being selected from tetraethoxy, positive silicic acid propyl ester or butyl silicate is 5 ~ 95 parts, and the consumption preferable range that is selected from least one dispersion agent in normal hexane, hexanaphthene, normal heptane, suberane, octane or cyclooctane is 5 ~ 95 parts.
In the inventive method, owing to adopting the core-shell molecular sieve of silicon modification, make catalyst activity main body, this main body is at nuclear phase ZSM-5 molecular sieve surface growth total silicon Silicalite-1 shell, shell is not affecting under the prerequisite of nuclear phase molecular sieve pore passage diffusion and Acidity, effective modulation outer surface acidity matter, thus in alkylation of toluene methanol reaction, there is certain selectivity.Yet, by eliminating outer surface acidity, be only inadequate, also need aperture to modify and just can reach the selectivity that industrial application requires.The present invention is by core-shell molecular sieve is carried out to silicon modification, and the template in core-shell molecular sieve shell can effectively prevent from depositing SiO in the process of silicon modification
2obstruction to duct, thus the loss of the catalytic activity in modifying process effectively reduced.In methylbenzene methanol mol ratio, be 6:1, temperature of reaction is 380 ℃, and air speed is 3 hours
-1condition under, being chosen in more than 90% of p-Xylol, the loss of catalyst activity is less than 18%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[comparative example 1]
[comparative example 1] is used for illustrating SiO
2/ Al
2o
3be that 150 ZSM-5 molecular sieve is as the preparation of active constituent catalyst.
Take silicon sol as binding agent, by 10 grams of Hydrogen ZSM-5 molecular sieves, 6 grams of silicon sol, 0.1 gram of sesbania powder and 2 ml waters, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[comparative example 2]
[comparative example 2] is used for illustrating that nuclear phase is SiO
2/ Al
2o
3be 150 ZSM-5 molecular sieve, shell is that the core-shell molecular sieve of Silicalite-1 is as the preparation of active constituent catalyst mutually.
The TPAOH of 50 gram 25%, 260 grams of tetraethoxys, 1574 grams of water are mixed and are made into shell liquid, stir 4 hours, in shell liquid, each component mol ratio is H
2o/SiO
2=70, R/SiO
2=0.05.By 10 grams of good SiO of ion-exchange
2/ Al
2o
3be that 150 Hydrogen ZSM-5 molecular sieve adds in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 ℃ of crystallization 8 hours.When crystallization finishes, chilling, filters, and washing, is drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.13:1, and its XRD analysis result conforms to data in literature.
Get 10 grams of these core-shell molecular sieves, 6 grams of silicon sol, 0.1 gram of sesbania powder and 2 ml waters, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[comparative example 3]
[comparative example 3] is used for illustrating the SiO of silicon modification
2/ Al
2o
3be that 150 ZSM-5 molecular sieve is as the preparation of active constituent catalyst.
5 grams of tetraethoxys and 5 grams of hexanaphthenes are mixed, add 10 grams of Hydrogen ZSM-5 molecular sieves, in crystallizing kettle in 170 ℃ of crystallization 6 hours.After crystallization finishes, chilling, sample is in 120 ℃ of dried overnight, then 550 ℃ of roastings 5 hours.Repeating said process once again, obtain the molecular sieve of silicon modification, is 28% of molecular sieve weight through the silicon dioxide layer of weighing.Get 10 grams of these molecular sieves, 6 grams of silicon sol, 0.1 gram of sesbania powder and 2 ml waters, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[embodiment 1]
The TPAOH of 25 gram 25%, 130 grams of tetraethoxys, 787 grams of water are mixed and are made into shell liquid, stir 4 hours, in shell liquid, each component mol ratio is H
2o/SiO
2=70, R/SiO
2=0.05.By 5 grams of SiO
2/ Al
2o
3be that 150 Hydrogen ZSM-5 molecular sieve adds in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 ℃ of crystallization 8 hours.After crystallization finishes, chilling, filtration, wash, be drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.13:1, and its XRD analysis result conforms to data in literature.
2.5 grams of tetraethoxys and 2.5 grams of hexanaphthenes are mixed, add the core-shell molecular sieve of above-mentioned not roasting, in crystallizing kettle in 170 ℃ of crystallization 6 hours.After crystallization finishes, chilling, sample, in 120 ℃ of dried overnight, then 550 ℃ of roastings 5 hours, obtains the molecular sieve of silicon modification.Through the silicon dioxide layer of weighing, be 14% of core-shell molecular sieve weight.
Get the molecular sieve of 5 grams of above-mentioned silicon modifications, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml water, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[embodiment 2]
The TPAOH of 25 gram 25%, 130 grams of tetraethoxys, 787 grams of water are mixed and are made into shell liquid, stir 4 hours, in shell liquid, each component mol ratio is H
2o/SiO
2=70, R/SiO
2=0.05.By 5 grams of SiO
2/ Al
2o
3be that 150 Hydrogen ZSM-5 molecular sieve adds in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 ℃ of crystallization 8 hours.After crystallization finishes, chilling, filtration, wash, be drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.13:1, and its XRD analysis result conforms to data in literature.
1.3 grams of tetraethoxys and 3.7 grams of hexanaphthenes are mixed, add the core-shell molecular sieve of above-mentioned not roasting, in crystallizing kettle in 170 ℃ of crystallization 6 hours.After crystallization finishes, chilling, sample, in 120 ℃ of dried overnight, then 550 ℃ of roastings 5 hours, obtains the molecular sieve of silicon modification.Through the silicon dioxide layer of weighing, be 7% of core-shell molecular sieve weight.
Get the molecular sieve of 5 grams of above-mentioned silicon modifications, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml water, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[embodiment 3]
The TPAOH of 25 gram 25%, 103 grams of tetraethoxys, 787 grams of water are mixed and are made into shell liquid, stir 4 hours, in shell liquid, each component mol ratio is H
2o/SiO
2=89, R/SiO
2=0.06.By 5 grams of SiO
2/ Al
2o
3be that 150 Hydrogen ZSM-5 molecular sieve adds in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 ℃ of crystallization 8 hours.After crystallization finishes, chilling, filtration, wash, be drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.16:1, and its XRD analysis result conforms to data in literature.
3.7 grams of tetraethoxys and 1.3 grams of hexanaphthenes are mixed, add the core-shell molecular sieve of above-mentioned not roasting, in crystallizing kettle in 170 ℃ of crystallization 6 hours.After crystallization finishes, chilling, sample, in 120 ℃ of dried overnight, then 550 ℃ of roastings 5 hours, obtains the molecular sieve of silicon modification.Through the silicon dioxide layer of weighing, be 21% of core-shell molecular sieve weight.
Get the molecular sieve of 5 grams of above-mentioned silicon modifications, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml water, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[embodiment 4]
The TPAOH of 35 gram 25%, 45 grams of tetraethoxys, 272 grams of water are mixed and are made into shell liquid, stir 4 hours, in shell liquid, each component mol ratio is H
2o/SiO
2=70, R/SiO
2=0.2.By 5 grams of good SiO of ion-exchange
2/ Al
2o
3be that 150 Hydrogen ZSM-5 molecular sieve adds in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 ℃ of crystallization 8 hours.When crystallization finishes, chilling, filters, and washing, is drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.38:1, and its XRD analysis result conforms to data in literature.
2.5 grams of tetraethoxys and 2.5 grams of hexanaphthenes are mixed, add the core-shell molecular sieve of above-mentioned not roasting, in crystallizing kettle in 170 ℃ of crystallization 6 hours.After crystallization finishes, chilling, sample, in 120 ℃ of dried overnight, then 550 ℃ of roastings 5 hours, obtains the molecular sieve of silicon modification.Through the silicon dioxide layer of weighing, be 14% of core-shell molecular sieve weight.
Get the molecular sieve of 5 grams of above-mentioned silicon modifications, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml water, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[embodiment 5]
The TPAOH of 25 gram 25%, 103 grams of tetraethoxys, 787 grams of water are mixed and are made into shell liquid, stir 4 hours, in shell liquid, each component mol ratio is H
2o/SiO
2=89, R/SiO
2=0.06.By 5 grams of good SiO of ion-exchange
2/ Al
2o
3be that 150 Hydrogen ZSM-5 molecular sieve adds in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 ℃ of crystallization 8 hours.When crystallization finishes, chilling, filters, and washing, is drying to obtain core-shell molecular sieve H.The weight ratio of core/shell is 0.16:1, and its XRD analysis result conforms to data in literature.
2.5 grams of tetraethoxys and 2.5 grams of hexanaphthenes are mixed, add the core-shell molecular sieve of above-mentioned not roasting, in crystallizing kettle in 170 ℃ of crystallization 6 hours.After crystallization finishes, chilling, sample, in 120 ℃ of dried overnight, then 550 ℃ of roastings 5 hours, obtains the molecular sieve of silicon modification.Through the silicon dioxide layer of weighing, be 14% of core-shell molecular sieve weight.
Get the molecular sieve of 5 grams of above-mentioned silicon modifications, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml water, mix kneading, extruded moulding, 550 ℃ of roastings 5 hours.
[embodiment 6]
It is to carry out in fixed-bed reactor that toluene reacts with methanol alkylation.Get 2 grams of catalyzer, reaction raw materials mol ratio is toluene: methyl alcohol=6:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 3, and feed liquid weight space velocity is 3 hours
-1, 380 ℃ of temperature of reaction.4 hours sampling analysis of charging record toluene conversion and Selectivity for paraxylene, as shown in table 1.
Table 1
| Embodiment | Selectivity for paraxylene % | Toluene conversion % | Catalyst activity loss % |
| Comparative example 1 | 23.7 | 13.4 | - |
| Comparative example 2 | 62.7 | 12.3 | 8.2 |
| Comparative example 3 | 90.4 | 6.2 | 53.4 |
| Embodiment 1 | 96.7 | 11.7 | 12.6 |
| Embodiment 2 | 93.1 | 12.3 | 8.2 |
| Embodiment 3 | 92.6 | 12.1 | 9.7 |
| Embodiment 4 | 90.3 | 12.7 | 5.2 |
| Embodiment 5 | 92.5 | 11.2 | 16.4 |
[embodiment 7]
Get catalyzer prepared by 2 grams [embodiment 1], reaction raw materials mol ratio is toluene: methyl alcohol=2:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 5, and feed liquid weight space velocity is 3 hours
-1, 380 ℃ of temperature of reaction.It is 30.7% that 4 hours sampling analysis of charging record toluene conversion, Selectivity for paraxylene 92.9%, and catalyst activity loss is 14.3%.
[embodiment 8]
Get catalyzer prepared by 2 grams [embodiment 2], reaction raw materials mol ratio is toluene: methyl alcohol=2:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 5, and feed liquid weight space velocity is 3 hours
-1, 420 ℃ of temperature of reaction.It is 36.7% that 4 hours sampling analysis of charging record toluene conversion, Selectivity for paraxylene 90.9%, and catalyst activity loss is 12.9%.
[embodiment 9]
Get catalyzer prepared by 2 grams [embodiment 3], reaction raw materials mol ratio is toluene: methyl alcohol=1:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 3, and feed liquid weight space velocity is 3 hours
-1, 450 ℃ of temperature of reaction.It is 75.2% that 4 hours sampling analysis of charging record toluene conversion, Selectivity for paraxylene 90.1%, and catalyst activity loss is 13.7%.
[embodiment 10]
Get catalyzer prepared by 2 grams [embodiment 4], reaction raw materials mol ratio is toluene: methyl alcohol=1:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 3, and feed liquid weight space velocity is 2 hours
-1, 350 ℃ of temperature of reaction.It is 68.7% that 4 hours sampling analysis of charging record toluene conversion, Selectivity for paraxylene 93.4%, and catalyst activity loss is 17.2%.
Claims (9)
1. a method for alkylation of toluene methanol, take toluene and methyl alcohol as raw material, and the gas that reaction is to inertia of take is carrier gas, in temperature of reaction, is 300 ~ 500 ℃, and reaction pressure is 0 ~ 1 MPa, and air speed is 1 ~ 10 hour
-1, the mol ratio of toluene and methyl alcohol is (10:1) ~ (1:3), the mol ratio of carrier gas and methylbenzene methanol total amount is that under the condition of (1:1) ~ (5:1), reaction raw materials contacts with catalyzer, generates dimethylbenzene and water; Catalyzer used wherein, comprises following component in parts by weight:
A) core-shell molecular sieve of the silicon modification of 5 ~ 95 parts;
B) binding agent of 5 ~ 95 parts;
Wherein, the nuclear phase of the core-shell molecular sieve of described silicon modification is ZSM-5 molecular sieve, and shell is Silicalite-1 molecular sieve, and shell is coated with silicon dioxide layer outward; Wherein, the weight ratio of core/shell is (0.01 ~ 3): 1; Silicon dioxide layer is 1 ~ 30% of core-shell molecular sieve weight.
2. the method for alkylation of toluene methanol according to claim 1, is characterized in that in the core-shell molecular sieve of silicon modification nuclear phase ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2o
3be 10 ~ 350, the weight ratio of core/shell is (0.02 ~ 2): 1, and silicon dioxide layer is 2 ~ 25% of core-shell molecular sieve weight.
3. the method for alkylation of toluene methanol according to claim 2, is characterized in that in the core-shell molecular sieve of silicon modification nuclear phase ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2o
3be 20 ~ 300, the weight ratio of core/shell is (0.03 ~ 1.5): 1, and silicon dioxide layer is 3 ~ 22% of core-shell molecular sieve weight.
4. the method for alkylation of toluene methanol according to claim 1, is characterized in that described binding agent is selected from least one in silicon sol or silicon oxide.
5. the method for alkylation of toluene methanol according to claim 1, is characterized in that temperature of reaction is 320 ~ 480 ℃.
6. the method for alkylation of toluene methanol according to claim 5, is characterized in that temperature of reaction is 350 ~ 450 ℃.
7. the method for alkylation of toluene methanol according to claim 1, the mol ratio that it is characterized in that toluene and methyl alcohol in raw material is (8:1) ~ (1:2).
8. the method for alkylation of toluene methanol according to claim 7, the mol ratio that it is characterized in that toluene and methyl alcohol in raw material is (6:1) ~ (1:1).
9. the method for alkylation of toluene methanol according to claim 1, is characterized in that carrier gas is nitrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019062815A1 (en) * | 2017-09-30 | 2019-04-04 | 株式会社模范 | Catalyst for directly preparing p-xylene by using syngas, preparation thereof, and applications thereof |
| CN112675906A (en) * | 2021-01-12 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | Toluene methanol alkylation reaction catalyst, and synthesis method and application thereof |
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