CN103772122A - P-diethylbenzene preparation method through ethylbenzene disproportionation - Google Patents
P-diethylbenzene preparation method through ethylbenzene disproportionation Download PDFInfo
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- CN103772122A CN103772122A CN201210412541.6A CN201210412541A CN103772122A CN 103772122 A CN103772122 A CN 103772122A CN 201210412541 A CN201210412541 A CN 201210412541A CN 103772122 A CN103772122 A CN 103772122A
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Abstract
The invention relates to a p-diethylbenzene preparation method through ethylbenzene disproportionation and mainly solves the problems that in the reaction in which the p-diethylbenzene is prepared through ethylbenzene disproportionation, the p-diethylbenzene selectivity is low and the yield is low in the prior art. The method provided by the invention takes ethylbenzene as raw materials, and a gas inertial to reaction as a carrier gas, under the conditions that the reaction temperature is 300-500 DEG C, the reaction pressure is 0-1MPa, the space velocity is 1-10 hour<-1> and the molar ratio of the carrier gas to the ethylbenzene is (1:1)-(5:1), the reaction raw materials are in contact with a catalyst to generate the p-diethylbenzene and benzene. The catalyst comprises the following component in part by weight: a) 5-95 parts of silicone modified core-shell zeolite, b) 5-95 parts of a binding agent, wherein the core-shell zeolite has a core phase of ZSM-5 and a shell layer of Silicalite-1, with a silicon dioxide layer covering outside the shell layer, the problem is solved. Therefore, the method can be used for the industrial production where the p-diethylbenzene is prepared through ethylbenzene disproportionation.
Description
Technical field
The present invention relates to a kind of ethylbenzene disproportionation and prepare p-Diethylbenzene method.
Background technology
P-Diethylbenzene is requisite parsing agent in p-Xylol adsorptive separation technology process, and it is synthetic has very important social benefit and practical value.The industrial requirements that p-Diethylbenzene is resolved agent as p-Xylol is that its purity is greater than 95%.But because the boiling point of p-Diethylbenzene, adjacent diethylbenzene and NSC 62102 is close, adopt rectificating method from mixing the p-Diethylbenzene product of purifying diethylbenzene, separating energy consumption is high, and purity is also difficult to reach requirement.CN200410020397.7 adopts ethylbenzene to react with ethanol alkylation to synthesize p-Diethylbenzene, the method for the ethanol ethylbenzene alkylation p-Diethylbenzene processed that US4950835 has also reported.
Alkylation relatively, the reaction mass composition of disproportionation synthetic route is comparatively simple, and production technique is simplified, without being suspected to have stronger competitive power and magnetism.For Kaeding, phosphorus, magnesium-modified HZSM-5 molecular sieve were catalyzer (J. Catal. 1985,95 (2), 512-519), temperature of reaction 698 ~ 798K, ethylbenzene weight space velocity 30.2 hours
-1, hydrogen weight space velocity 0.24 hour
-1, pressure ~ 0.8MPa condition under carry out disproportionation reaction, conversion of ethylbenzene 14.7 ~ 22.5%, p-Diethylbenzene productive rate 3.44 ~ 6.77%, p-Diethylbenzene selectivity 99.3 ~ 99.8%.Because temperature of reaction is high, air speed is large, and operate under hydrogen is faced in pressurization, in technique, increased difficulty.
ZSM-5 is a kind of molecular sieve catalyst of excellent property, and its strength of acid and sour distribution can in very large range regulate and control, and therefore 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 addition, its aperture is bigger, if be directly used in the catalyzer of producing p-Diethylbenzene, can produce a large amount of isomer.Therefore can be by molecular sieve outer surface is modified, to improve the selectivity of molecular sieve shape selective catalytic reaction.
U.S. Pat 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.Adopt this catalyst series, very little on the impact of reactive behavior.
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, only need a load for micron ZSM-5, 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 in 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 in reaction that ethylbenzene disproportionation prepares p-Diethylbenzene, and the problem that p-Diethylbenzene selectivity is low, yield is low provides the method for the synthetic p-Diethylbenzene of a kind of new ethanol and ethylbenzene alkylation.The method has higher selectivity and yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ethylbenzene disproportionation is prepared the method for p-Diethylbenzene, take ethylbenzene as raw material, take to reaction be inertia gas as carrier gas, be 300 ~ 500 ℃ in temperature of reaction, reaction pressure is 0 ~ 1 MPa, and air speed is 1 ~ 10 hour
-1, the mol ratio of carrier gas and ethylbenzene is that under the condition of (1:1) ~ (5:1), reaction raw materials contacts with catalyzer, generates p-Diethylbenzene and benzene; Wherein catalyzer used, 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 ~ 420 ℃, and more preferably scope is 350 ~ 400 ℃; Weight space velocity preferable range is 2 ~ 8 hours
-1, more preferably scope is 3 ~ 5 hours
-1.Carrier gas preferred version is nitrogen.The mol ratio preferable range of carrier gas and ethylbenzene is (1:1) ~ (3.5:1).
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 ℃, 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, because the core-shell molecular sieve that adopts silicon modification is made 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, effectively modulation outer surface acidity matter, thus in ethylbenzene disproportionation is prepared p-Diethylbenzene reaction, there is certain selectivity and do not affect the activity of catalyzer.But, be only inadequate by eliminating outer surface acidity, 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
2to the obstruction in duct, thereby effectively reduce the loss of the catalytic activity in modifying process.Be 370 ℃ in temperature of reaction, air speed is 3 hours
-1condition under, being chosen in more than 95% of p-Diethylbenzene, the yield of diethylbenzene is more than 15%, 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
3it is the preparation as active constituent catalyst of 150 ZSM-5 molecular sieve.
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 ion-exchange 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.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
3it is the preparation as active constituent catalyst of 150 ZSM-5 molecular sieve.
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.Be 14% of core-shell molecular sieve weight through the silicon dioxide layer of weighing.
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.Be 7% of core-shell molecular sieve weight through the silicon dioxide layer of weighing.
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.Be 21% of core-shell molecular sieve weight through the silicon dioxide layer of weighing.
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 ion-exchange 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.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.Be 14% of core-shell molecular sieve weight through the silicon dioxide layer of weighing.
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 ion-exchange 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.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.Be 14% of core-shell molecular sieve weight through the silicon dioxide layer of weighing.
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]
Ethylbenzene disproportionation is prepared p-Diethylbenzene and is reacted carrying out in fixed-bed reactor.Get 2 grams of catalyzer, take ethylbenzene as raw material, nitrogen is carrier gas, and the mol ratio of nitrogen and hydrocarbon is 3:1, and feed liquid weight space velocity is 3 hours
-1, 370 ℃ of temperature of reaction.4 hours sampling analysis of charging record diethylbenzene yield and p-Diethylbenzene selectivity, as shown in table 1.
Table 1
| Embodiment | P-Diethylbenzene selectivity % | Diethylbenzene yield % |
| Comparative example 1 | 28.3 | 16.1 |
| Comparative example 2 | 71.2 | 13.1 |
| Comparative example 3 | 91.5 | 8.3 |
| Embodiment 1 | 98.3 | 11.5 |
| Embodiment 2 | 95.9 | 12.1 |
| Embodiment 3 | 95.2 | 11.6 |
| Embodiment 4 | 95.6 | 12.7 |
| Embodiment 5 | 97.7 | 10.9 |
[embodiment 7]
Get catalyzer prepared by 2 grams [embodiment 1], take ethylbenzene as raw material, nitrogen is carrier gas, and the mol ratio of nitrogen and hydrocarbon is 5:1, and feed liquid weight space velocity is 3 hours
-1, 350 ℃ of temperature of reaction.It is 10.3% that 4 hours sampling analysis of charging record diethylbenzene yield, p-Diethylbenzene selectivity 96.1%.
[embodiment 8]
Get catalyzer prepared by 2 grams [embodiment 2], take ethylbenzene as raw material, nitrogen is carrier gas, and the mol ratio of nitrogen and hydrocarbon is 3:1, and feed liquid weight space velocity is 3 hours
-1, 400 ℃ of temperature of reaction.It is 12.4% that 4 hours sampling analysis of charging record diethylbenzene yield, p-Diethylbenzene selectivity 95.3%.
[embodiment 9]
Get catalyzer prepared by 2 grams [embodiment 3], take ethylbenzene as raw material, the mol ratio of nitrogen and hydrocarbon is 3:1, and feed liquid weight space velocity is 5 hours
-1, 420 ℃ of temperature of reaction.It is 10.1% that 4 hours sampling analysis of charging record diethylbenzene yield, p-Diethylbenzene selectivity 98.1%.
[embodiment 10]
Get catalyzer prepared by 2 grams [embodiment 4], take ethylbenzene as raw material, nitrogen is carrier gas, and the mol ratio of nitrogen and hydrocarbon is 1:1, and feed liquid weight space velocity is 4 hours
-1, 370 ℃ of temperature of reaction.It is 10.8% that 4 hours sampling analysis of charging record diethylbenzene yield, p-Diethylbenzene selectivity 96.7%.
Claims (10)
1. ethylbenzene disproportionation is prepared a method for p-Diethylbenzene, take ethylbenzene as raw material, take to reacting the gas that is inertia as carrier gas, is 300 ~ 500 ℃ in temperature of reaction, and reaction pressure is 0 ~ 1 MPa, and air speed is 1 ~ 10 hour
-1, the mol ratio of carrier gas and ethylbenzene is that under the condition of (1:1) ~ (5:1), reaction raw materials contacts with catalyzer, generates p-Diethylbenzene and benzene; Wherein catalyzer used, 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;
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. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 1, it 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. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 2, it 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. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 1, it is characterized in that described binding agent is selected from least one in silicon sol or silicon oxide.
5. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 1, it is characterized in that temperature of reaction is 320 ~ 420 ℃, and weight space velocity is 2 ~ 8 hours
-1.
6. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 5, it is characterized in that temperature of reaction is 350 ~ 400 ℃.
7. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 1, it is characterized in that weight space velocity is 2 ~ 8 hours
-1.
8. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 7, it is characterized in that weight space velocity is 3 ~ 5 hours
-1.
9. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 1, it is characterized in that carrier gas is nitrogen.
10. ethylbenzene disproportionation is prepared the method for p-Diethylbenzene according to claim 1, and the mol ratio that it is characterized in that carrier gas and ethylbenzene is (1:1) ~ (3.5:1).
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