CN103041846A - Alkylated catalyst containing modified ZSM-11 zeolite and application of alkylated catalyst - Google Patents
Alkylated catalyst containing modified ZSM-11 zeolite and application of alkylated catalyst Download PDFInfo
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Abstract
The invention discloses an alkylated catalyst containing modified ZSM-11 zeolite and an application of the alkylated catalyst. The alkylated catalyst comprises the following components in percentage by weight: 30-85 percent of ZSM-11 zeolite, 10-60 percent of binding agent, 0.1-10 percent of alkali metal oxide, 1-20 percent of ZSM-11 zeolite modified additive SiO2 and 0.5-30 percent of ZSM-11 zeolite modified additive alkali metal oxide. The catalyst composition disclosed by the invention is used in a methylbenzene alkylation process for synthesizing p-methyl methylbenzene from methylbenzene and ethylene and is favorable in catalytic reaction effect.
Description
Technical field
The present invention relates to a kind of alkylation catalyst and application thereof that contains modified ZSM-5-11 zeolite, be especially in use in the synthetic form selected methylation catalyst to methyl-ethyl benzene of toluene and ethene.
Background technology
P-methylstyrene can be obtained to the methyl-ethyl benzene dehydrogenation, after polymerization, the polymethylstyrene novel plastic can be produced.This polymer is at proportion, heat resistance, and the aspects such as transparency and shrinkage factor all are better than existing polystyrene plastics.In addition p-methylstyrene can with other monomer copolymerization, can improve heat resistance and the anti-flammability of some polymer, can be used in a large number engineering plastics, the manufacturing of the aspects such as phthalic resin coating, thereby in widespread attention.Also do not obtain for a long time the satisfactory method to methyl-ethyl benzene of high concentration, obtain the product of contraposition, a kind of well behaved shape-selective catalyst must be arranged, acid site intensity is suitable in pore size, grain size and the hole of requirement zeolite catalyst, and the acidity of outer surface is inhibited, might make the alkylation of toluene reaction break the thermodynamical equilibrium CONCENTRATION DISTRIBUTION of contraposition methyl-ethyl benzene, a position methyl-ethyl benzene, ortho position methyl-ethyl benzene product, mainly generate the contraposition methyl-ethyl benzene.Catalytic theory infers that the ZSM-5 molecular sieve think through chemical modification can make toluene and ethene vapor phase alkylation break through the restriction of thermodynamical equilibrium, can obtain 90% above concentration to methyl-ethyl benzene, and basically do not generate neighbour, a position methyl-ethyl benzene.In recent years, the research of this problem has caused the broad interest of each company and scientific research institution, and obtained certain progress, if can obtain further success, to produce dramatic change to the production technology to methyl-ethyl benzene, to energy savings, simplified apparatus, reduce production costs the very important meaning of having increased economic efficiency.
US5698756 uses methyl-silicone oil polymer (Dow-550) that the HZSM-5 molecular sieve of Si/Al=26 is carried out modification, the silicone oil polymer of each load 7.8%, and modification is 4 times altogether.Then in sodium nitrate solution the exchange three times, under 200 ℃, carry out drying again and catalyst.The evaluating catalyst condition is: 450 ℃ of temperature, toluene air speed 5 h
-1, benzene alkene is than 4, stagnation pressure 0.7MPa; Be to have obtained overall selectivity to methyl-ethyl benzene in 15.45% the situation greater than 77% effect in toluene conversion, but also have the methyl-ethyl benzene product at a certain amount of position and ortho position.
CN1103607A provides ethene and toluene reaction in a kind of catalytic cracked dry gas to produce shape selective catalysis agent to methyl-ethyl benzene.The agent of this kind shape selective catalysis is a kind of Pentasil type catalyst that contains rare earth, and select suitable chemical modifier to carry out modification: molecular sieve is carried out the dipping modifications such as aluminium and magnesium, the amount of its oxide modifier is not less than 0.25%.With modified catalyst at 350 ℃ ~ 420 ℃ of temperature, mass space velocity 0.3 ~ 0.5 h
-1, benzene alkene is checked and rated catalyst under the reaction condition of reaction pressure 0.1 ~ 1MPa than 4 ~ 6, can obtain conversion of ethylene more than 85% and 90% above selective to methyl-ethyl benzene.
Above document has all promoted the para-selectivity of product to methyl-ethyl benzene preferably, but the toluene conversion of product overall selectivity is still lower, can't satisfy the demand of actual production, thereby has limited its industrial applications.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalyst that contains modified ZSM-5-11 zeolite and synthetic to the application in the methyl-ethyl benzene at toluene and ethene, it is not high to have solved in the prior art toluene conversion, selectively lower to methyl-ethyl benzene, the problems such as the side reaction such as disproportionated reaction and isomerization reaction is serious, thus the effect of alkylation of toluene reaction improved.
The present invention contains the alkylation catalyst of modified ZSM-5-11 zeolite, in catalyst weight percentage, has following composition: ZSM-11 zeolite 30% ~ 85%, adhesive 10%～60%, alkali metal oxide 0.1%～10%, ZSM-11 Zeolite modifying auxiliary agent silica 1 %～20%, ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide 0.5% ~ 30%.
In the carbon monoxide-olefin polymeric of the present invention, modified additive silica and modified additive rare-earth oxide load on the ZSM-11 zeolite, and order is elder generation's loaded modified auxiliary agent rare-earth oxide, then loaded modified auxiliary agent silica.Loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, and with the ZSM-11 zeolite of silicon-containing organic compound processing rare-earth oxide modification, then drying and roasting gets final product.
In the catalyst of the present invention, ZSM-11 zeolite SiO
2/ Al
2O
3Mol ratio is 20 ~ 500, is preferably 30 ~ 200, more preferably 50 ~ 100, and by weight percentage, the content of ZSM-11 zeolite in catalyst is preferably 40% ~ 70%, and more preferably 50% ~ 60%.
In the catalyst of the present invention, the content of ZSM-11 Zeolite modifying auxiliary agent silica is preferably 2% ~ 10%, and more preferably 3% ~ 8%.The thulium of ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide is selected from one or more in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and the lutetium, is preferably lanthanum or/and cerium; In catalyst weight percentage, the content of rare-earth oxide is preferably 1% ~ 15%, and more preferably 2% ~ 10%.
In the carbon monoxide-olefin polymeric of the present invention, adhesive is aluminium oxide or silica, is preferably silica; By weight percentage, its content in catalyst is preferably 15% ~ 50%.
In the carbon monoxide-olefin polymeric of the present invention, alkali metal oxide be the oxide of sodium or/and the oxide of potassium, by weight percentage, its content in catalyst is preferably 0.5% ~ 5%, more preferably 1% ~ 3%.
The present invention contains modified ZSM-5-11 zeolite catalyst composition and is applied to toluene and ethylene selectivity alkylation and generates in the methyl-ethyl benzene course of reaction, the concrete technology condition can adjusted in a big way, for example, volume space velocity 0.5 h when hydrogen partial pressure 0.5MPa ~ 5.0MPa, 360 ℃ ~ 500 ℃ of reaction temperatures, toluene liquid
-1~ 10.0h
-1, toluene/ethylene molar ratio 1:1 ~ 10:1, hydrogen to oil volume ratio 200:1 ~ 1000:1(hydrogen and the volume ratio of toluene under standard conditions), optimum condition is: volume space velocity 2 h when hydrogen partial pressure 1MPa ~ 3MPa, 380 ℃ ~ 460 ℃ of reaction temperatures, toluene liquid
-1~ 5h
-1, toluene/ethylene molar ratio 3:1 ~ 5:1, hydrogen to oil volume ratio 300:1 ~ 500:1.
The present invention selects the ZSM-11 zeolite, after rare-earth oxide modification and liquid-phase silicone deposition surface modification, adds suitable alkali metal compound, has prepared final catalyst.Catalyst of the present invention catalyzes and synthesizes methyl-ethyl benzene carrying out alkylation of toluene take ethene as raw material, when can obtain higher toluene conversion, can greatly suppress the side reactions such as transalkylation, has improved in the product selective to methyl-ethyl benzene.Can be used for synthetic production technology to methyl-ethyl benzene, the energy decrease is to operation easier and the energy consumption of the separative element of the product of methyl-ethyl benzene.It is not high that the carbon monoxide-olefin polymeric that contains modified ZSM-5-11 zeolite of the present invention has solved in the prior art toluene conversion, selectively lower to methyl-ethyl benzene, the problems such as the side reaction such as disproportionated reaction and isomerization reaction is serious, thus the effect of alkylation of toluene reaction improved.
The specific embodiment
The preparation process of catalyst of the present invention mainly comprises following steps:
(1) rare earth compound is loaded on the ZSM-11 zeolite, through super-dry and roasting, obtain the ZSM-11 zeolite of rare-earth oxide modification;
(2) with the ZSM-11 zeolite that contains the rare-earth oxide modification that the solution impregnation step (1) that changes silicon compound makes, through super-dry and roasting, obtain silicon-rare earth modified ZSM-11 zeolite;
(3) modified ZSM-5-11 zeolite, adhesive, alkali compounds, extrusion aid and the abundant kneading of water that make of step (2) becomes plastic paste, and extruded moulding through super-dry and roasting, obtains catalyst of the present invention.
In the step (1), rare earth compound loads on the molecular sieve can adopt ion-exchange, infusion process or kneading method, when wherein adopting ion-exchange or infusion process, the used compounds containing rare earth of solution of preparation compounds containing rare earth are selected from chloride and/or nitrate, more preferably nitrate.When adopting kneading method, be that compounds containing rare earth are fully mixed with molecular sieve, compounds containing rare earth are to be selected from oxide, chloride, nitrate, sulfate and the carbonate one or more, are preferably oxide and/or nitrate, more preferably nitrate.
The described modifier of step (2) is silicon-containing organic compound, is preferably the polyphenyl methylsiloxane, solvent can be can solvent modified dose organic matter or inorganic matter, be preferably organic hydrocarbon, such as n-hexane etc.
The described adhesive of step (3) is for making the material of material forming, and for example aluminium oxide or silica are preferably silica, is the precursor of aluminium oxide or silica when using, such as aluminium hydroxide, Ludox, white carbon etc.Described alkali compounds is that NaOH is or/and potassium hydroxide.Described extrusion aid is the material that is conducive to extruded moulding, can be selected from graphite, starch, cellulose and the sesbania powder one or more, is preferably the sesbania powder, and by weight percentage, the amount of its adding is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
Drying condition described in step (1), (2) and (3) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and step (1), step (2) and the described drying condition of step (3) can be identical, also can be different.The roasting condition of step (1), (2) and (3) is 400 ℃ ~ 800 ℃ and keeps 0.5h ~ 10.0h that step (1), step (2) and the described roasting condition of step (3) can be identical, also can be different.
Catalyst of the present invention is to adopt the medium-sized fixed bed reactors of 100ml to estimate, and loaded catalyst is 100ml, and appreciation condition is: volume space velocity 4.0h when hydrogen partial pressure 1.3MPa, 390 ℃ of reaction temperatures, toluene liquid
-1, toluene/ethylene molar ratio 4, hydrogen to oil volume ratio 400.Catalyst runs was carried out constituent analysis to tail gas and product liquid after 8 hours, calculated the selective of the conversion ratio of ethene and p-methyl-ethylbenzene, and concrete computational methods are as follows:
Further specify the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited among the following embodiment.
[embodiment 1](if following do not have special indicate, degree all is weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1) getting silica alumina ratio (silica/alumina molar ratio, lower with) is 80 ZSM-11 zeolite 300 grams, makes 450 milliliters take the lanthanum nitrate hexahydrates of lanthana content as 50 grams.Above-mentioned solution and the ZSM-11 zeolite that contains lanthanum nitrate fully mixed, after 110 ℃ of oven dry, the 500 ℃ of roastings in 4 hours, obtain consisting of of sample: lanthana/ZSM-11=1/6.
The ZSM-11(350 gram of the lanthana modification that (2) makes with (1) step), then flood with 500 milliliters of the hexane solutions take silica content as the polyphenyl methylsiloxane of 25 grams for preparing, leave standstill behind the dipping, thorough to solvent evaporates, 550 ℃ of lower roastings, obtain consisting of of sample: SiO after dry
2/ La
2O
3/ ZSM-11=0.5/1/6.
(3) modified ZSM-5 that makes with (2) step-11(400 gram), 117.5 gram white carbons (binding agent), 7.6 gram NaOH, 20 gram sesbania powder become plastic paste with the abundant kneading of an amount of water, extruded moulding (1.5 millimeters of diameters), through 120 ℃ of dryings of 8 hours and 550 ℃ of roastings of 3 hours, obtain catalyst of the present invention, it consists of: Na
2O/SiO
2/ La
2O
3/ ZSM-11/ binding agent=0.15/0.5/1/6/2.35(catalyst percentage consists of: Na
2O:1.5%, SiO
2: 5%, La
2O
3: 10%, ZSM-11:60%, binding agent: 23.5%), be numbered E-1, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment2]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silica alumina ratio of employed ZSM-11 zeolite is 38, the consisting of of the catalyst that obtains: Na
2O:1.5%, SiO
2: 5%, La
2O
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-2, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment3]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the employed lanthanum compound that contains is lanthanum chloride, and employed binding agent is Ludox, the consisting of of the catalyst that obtains: Na
2O:1.5%, SiO
2: 5%, La
2O
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-3, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment4]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the composition of catalyst is different, the consisting of of the catalyst that obtains: Na
2O:0.5%, SiO
2: 3.5%, La
2O
3: 6%, ZSM-11:50%, binding agent: 40%, be numbered E-4, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment5]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the composition of catalyst is different, the consisting of of the catalyst that obtains: Na
2O:1%, SiO
2: 6%, La
2O
3: 9%, ZSM-11:70%, binding agent: 14%, be numbered E-5, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment6]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silica alumina ratio of employed ZSM-11 zeolite is 120, and employed rare earth metal is lanthanum and cerium, and catalyst form different, the consisting of of the catalyst that obtains: Na
2O:1%, SiO
2: 4%, La
2O
3: 1.8%, Ce
2O
3: 3.2%, ZSM-11:55%, binding agent: 35%, be numbered E-6, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment7]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the composition of catalyst is different, obtains consisting of of catalyst: Na
2O:5%, SiO
2: 4%, La
2O
3: 1%, ZSM-11:35%, binding agent: 55%, be numbered E-7, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment8]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, difference is that employed thulium compound is lanthanum chloride, directly mix with molecular sieve, obtain modified ZSM-5-11 zeolite through oven dry and calcination process, the consisting of of the catalyst that obtains: Na
2O:1.5%, SiO
2: 5%, La
2O
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-8, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment9]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the temperature and time of the drying that adopts in the preparation process and roasting is different, and actual conditions is: the treatment conditions of (1) step sample be 200 ℃ 2 hours, 380 ℃ 8 hours; (2) treatment conditions of step be 80 ℃ 16 hours, 580 ℃ 3 hours; (3) treatment conditions of step be 50 ℃ 48 hours, 490 ℃ 6 hours.Obtain catalyst of the present invention, it consists of: Na
2O:1.5%, SiO
2: 5%, La
2O
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-9, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[Comparative Examples 1]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is molecular sieve without thulium and siliceous deposits modification, and form different, the consisting of of the catalyst that obtains: Na
2O:2%, ZSM-11:60%, binding agent: 38%, be numbered C-1, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[Comparative Examples 2]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is molecular sieve without the siliceous deposits modification, and form different, the consisting of of the catalyst that obtains: Na
2O:2%, La
2O
3: 10%, ZSM-11:60%, binding agent: 28%, be numbered C-2, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
The evaluation result of table 1 different catalysts
| The embodiment numbering | Catalyst | Toluene conversion, % | P-methyl-ethylbenzene is selective, % |
| 1 | E-1 | 24.1 | 97.8 |
| 2 | E-2 | 24.2 | 97.5 |
| 3 | E-3 | 23.7 | 97.7 |
| 4 | E-4 | 23.6 | 98.3 |
| 5 | E-5 | 24.2 | 97.4 |
| 6 | E-6 | 23.4 | 98.2 |
| 7 | E-7 | 22.5 | 98.8 |
| 8 | E-8 | 24.0 | 98.1 |
| 9 | E-9 | 24.3 | 98.6 |
| The comparative example numbering | - | - | - |
| 1 | C-1 | 24.2 | 78.6 |
| 2 | C-2 | 24.6 | 87.0 |
Annotate: the evaluating catalyst process conditions are: volume of toluene air speed 4.0h
-1, 390 ℃ of temperature, pressure 1.3MPa, toluene/ethylene ratio 4.0 (mol/mol), hydrogen to oil volume ratio 400,8 hours time.
Show from the result of table 1, the present invention selects the ZSM-11 zeolite, after liquid-phase silicone deposition surface modification, added the catalyst that makes behind the rare-earth oxide, catalyze and synthesize methyl-ethyl benzene carrying out alkylation of toluene take ethene as raw material, when can obtain higher toluene conversion, can greatly suppress the side reactions such as transalkylation, improve in the product selective to methyl-ethyl benzene.Can be used for synthetic production technology to methyl-ethyl benzene, the energy decrease is to operation easier and the energy consumption of the separative element of the product of methyl-ethyl benzene.
Claims (10)
1. alkylation catalyst that contains modified ZSM-5-11 zeolite, it is characterized in that in catalyst weight percentage, has following composition: ZSM-11 zeolite 30% ~ 85%, adhesive 10%～60%, alkali metal oxide 0.1%～10%, ZSM-11 Zeolite modifying auxiliary agent silica 1 %～20%, ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide 0.5% ~ 30%.
2. according to catalyst claimed in claim 1, it is characterized in that: ZSM-11 Zeolite modifying auxiliary agent silica and ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide load on the ZSM-11 zeolite, order is elder generation's loaded modified auxiliary agent rare-earth oxide, then loaded modified auxiliary agent silica.
3. according to catalyst claimed in claim 2, it is characterized in that: loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, and with the ZSM-11 zeolite of silicon-containing organic compound processing rare-earth oxide modification, then drying and roasting gets final product.
4. according to catalyst claimed in claim 1, it is characterized in that: the SiO of ZSM-11 zeolite
2/ Al
2O
3Mol ratio is 20 ~ 500, by weight percentage, and the content 40% ~ 70% of ZSM-11 zeolite in catalyst.
5. according to catalyst claimed in claim 1, it is characterized in that: the content of ZSM-11 Zeolite modifying auxiliary agent silica is 2% ~ 10%.
6. according to catalyst claimed in claim 1, it is characterized in that: the thulium of ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide is selected from one or more in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and the lutetium, is preferably lanthanum or/and cerium; In catalyst weight percentage, the content of rare-earth oxide is 1% ~ 15%.
7. according to catalyst claimed in claim 1, it is characterized in that: adhesive is aluminium oxide or silica, and by weight percentage, the content of adhesive in catalyst is 15% ~ 50%.
8. according to catalyst claimed in claim 1, it is characterized in that: alkali metal oxide be the oxide of sodium or/and the oxide of potassium, by weight percentage, the content of alkali metal oxide in catalyst is 0.5% ~ 5%.
9. the described catalyst of the arbitrary claim of claim 1 to 8 generates the application in the methyl-ethyl benzene course of reaction at toluene and ethylene selectivity alkylation.
10. according to application claimed in claim 9, it is characterized in that: it is that 0.5MPa ~ 5.0MPa, reaction temperature are 360 ℃ ~ 500 ℃, volume space velocity is 0.5 h during toluene liquid that toluene and ethylene selectivity alkylation generate hydrogen partial pressure to the methyl-ethyl benzene reaction
-1~ 10.0h
-1, toluene/ethylene molar ratio is 1:1 ~ 10:1, hydrogen to oil volume ratio is 200:1 ~ 1000:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106607078A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst used for preparing paraxylene and propylene from oxygen-containing compounds, and preparation method and applications thereof |
| CN106669828A (en) * | 2016-11-28 | 2017-05-17 | 宣城市聚源精细化工有限公司 | Preparation method of catalyst applied to alkylation reaction of toluene and tertiary butanol |
| CN107754848A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | C8 aronmatic shape selective catalysis synthesizes p-methyl-ethylbenzene catalyst |
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| CN101940943A (en) * | 2010-09-28 | 2011-01-12 | 同济大学 | Shape-selective alkylation catalyst for synthesizing p-cymene with toluene and propylene as raw materials |
| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
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| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607078A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst used for preparing paraxylene and propylene from oxygen-containing compounds, and preparation method and applications thereof |
| CN106607078B (en) * | 2015-10-21 | 2019-02-19 | 中国石油化工股份有限公司 | The catalyst of oxygenatedchemicals paraxylene and propylene, preparation method and applications |
| CN107754848A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | C8 aronmatic shape selective catalysis synthesizes p-methyl-ethylbenzene catalyst |
| CN107754848B (en) * | 2016-08-23 | 2020-12-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing p-methyl ethyl benzene by shape-selective catalysis of carbon octaene |
| CN106669828A (en) * | 2016-11-28 | 2017-05-17 | 宣城市聚源精细化工有限公司 | Preparation method of catalyst applied to alkylation reaction of toluene and tertiary butanol |
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| CN103041846B (en) | 2014-10-15 |
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