CN104557425A - Catalyst distillation method for producing paraxylene through aryl alkylation - Google Patents
Catalyst distillation method for producing paraxylene through aryl alkylation Download PDFInfo
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Abstract
The invention relates to a catalyst distillation method for producing paraxylene through aryl alkylation, and aims at solving the technical problems of large side reaction and easy inactivation of a catalyst in the prior art. The problems are well solved by adopting the technical scheme that the method comprises the following steps: performing alkylation reaction for synthesis gas serving as an alkylation agent and arene serving as a raw material in the presence of a bifunctional catalyst in a reaction distillation tower to obtain a mixture I rich in paraxylene; feeding liquid collected from the bottom part of the reaction distillation tower into a reboiler at the bottom of the tower; transferring into the reaction distillation tower to continuously react; feeding other liquid products recovered from the tower bottom into a methylbenzene rectifying column; mixing the separated light components and some gas-phase products to obtain a mixture II; reflowing the mixture II into the reaction distillation tower; feeding products flowing from the bottom of the methylbenzene rectifying column into a xylene rectifying tower; removing heavy aromatics above C9 to obtain a paraxylene product; cooling the gas-phase product on the top part of the reaction distillation tower and then feeding into a gas-phase, water-phase and oil-phase separator, reflowing the gas phase and the oil phase to the reaction distillation tower, and treating and draining the water phase. The method is applicable to the industrial production of paraxylene.
Description
Technical field
The present invention relates to the catalytic distillation method that a kind of alkylating aromatic hydrocarbon produces p-Xylol.
Background technology
P-Xylol is a kind of important Organic Chemicals, main application is through oxidative synthesis terephthalic acid, carry out polycondensation again with ethylene glycol and produce macromolecular material polyethylene terephthalate (i.e. terylene), terylene is then excellent property, the great polyester material of demand, is widely used in weaving and wrapping material field.
P-Xylol generally can obtain from coal tar, reformate and pyrolysis gasoline, but its amount is less, far can not meet actual needs.Industrial the most frequently used p-Xylol production method is toluene disproportionation and transalkylation, owing to limiting by thermodynamic(al)equilibrium, in the C8 aronmatic product that the method obtains usually only containing have an appointment 24% p-Xylol, and p-Xylol demand will account for more than 60% on dimethylbenzene market, therefore this concentration composition can not meet the demand of industrial polyester material produce.For obtaining high density p-Xylol and improving p-Xylol yield, mixed C 8 aromatics need process further through isomerization and fractionation by adsorption or Crystallization Separation combination technique, and follow-up process brings the loss of raw material and the lifting of cost.In view of this, numerous investigator is devoted to develop new p-Xylol synthetic technology, be desirably in production link and just can cross the product obtaining high p-Xylol content, methylbenzene shape selective disproportionation, toluene and methanol shape selective alkylation are such technology, wherein methylbenzene shape selective disproportionation technology has been succeeded in developing and has been realized industrialization, its feature is rich product p-Xylol and benzene, toluene and methanol shape selective alkylation technique then low yield benzene even do not produce benzene, and therefore improve the utilization ratio of methylbenzene raw material, the special present situation adapting to Present Domestic benzene glut the market.But introduce methyl alcohol due to reaction system, very easily there is coking reaction and cause catalyst deactivation in methyl alcohol, this problem is a difficult problem for restriction alkylation of toluene methanol technical development always under alkylation reaction condition.
At present, toluene methylation process generally adopts fixed-bed reactor, and toluene and methyl alcohol, normally according to suitable ratio, after fully mixing in advance, by heater heats to certain temperature, are introduced in fixed-bed reactor together.While the main reaction that toluene methylation occurs, also can there is many side reactions.Especially the methyl alcohol that reactive behavior is higher easily forms alkene, changes into various hydro carbons and even carbon deposit through the reaction such as polymerization, cracking, aromizing, side reaction also create a large amount of reaction heat, cause the temperature difference of reactor bed larger, catalyst deactivation aggravates.In addition, in fixed-bed reactor, due to generate xylene products can not in time and methylating reagent separate, make dimethylbenzene and methylating reagent occur to react heavy aromaticss such as generating a large amount of carbon nine, carbon ten further.
Patent CN1291968A discloses a kind of reaction distillation method of producing dimethylbenzene, toluene and methyl alcohol carry out alkylated reaction and generate dimethylbenzene in reactive distillation column, for suppressing the side reaction of methyl alcohol, the method adopts the way of low reaction temperatures (<300 DEG C), high toluene and methanol mol ratio (>10:1) and methyl alcohol multiple feed.But higher toluene and methanol mol ratio result in lower toluene per pass conversion and the big cycle volume of material simultaneously.In addition, because methyl alcohol and toluene adverse current are by beds, methyl alcohol skewness in beds is easily caused also to occur that local is superfluous, is unfavorable for the control of side reaction.
Patent CN1355779A then discloses a kind of method by toluene and/or benzene and synthetic gas dimethylbenzene, the methylating agent such as synthesis gas reaction methanol or dme on composite catalyst, the methylating agent generated simultaneously with toluene and/or benzene generation methylation reaction and be consumed, thus the dosage that makes to methylate in beds remains on lower concentration.The local of methylating reagent in beds can be avoided superfluous by this way, thus suppress the side reaction of methylating reagent, extend the life-span of reaction system.But dimethylbenzene could not be separated by the method immediately, dimethylbenzene and methylating reagent be the further heavy aromatics such as alkylated reaction Formed nine or carbon ten easily.
Summary of the invention
Technical problem to be solved by this invention is that the method for producing p-Xylol in prior art exists the problems such as the many and catalyst life of alkylating agent skewness, side reaction is short, the invention provides the catalytic distillation method that a kind of new alkylating aromatic hydrocarbon produces p-Xylol, the method effectively can improve the per pass conversion of aroamtic hydrocarbon raw material, suppress side reaction, and the advantage in extending catalyst work-ing life.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol, comprises following several step:
A) take synthetic gas as alkylating reagent, aromatic hydrocarbons is raw material, and alkylated reaction occurs synthetic gas and the aromatic hydrocarbons dual-function catalyst in reactive distillation column, generates the mixture I being rich in p-Xylol;
B) p-Xylol mixture coagulated becomes liquid to collect at the bottom of reactive distillation column tower, reactive distillation column overhead collection gas-phase product;
C) liquid portion collected at the bottom of reactive distillation column tower enters the reboiler at the bottom of tower, then enters reactive distillation column, continues reaction; Other liquid products reclaimed at the bottom of tower flow through toluene rectifying tower, remove light constituent toluene and benzene, the light constituent deviate from and gas-phase product mixing, and form mixture II, mixture II is back to reactive distillation column; Toluene rectifying tower bottom stream passes into xylene distillation tower, except carbon elimination more than nine heavy aromatics, obtains para-xylene product;
D) described reactive distillation column top gas phase product enters gas phase, aqueous phase, oil phase triphase separator after cooling, and gas phase and oil phase are back to reactive distillation column, and aqueous phase discharges after treatment.
In technique scheme, preferred technical scheme, the synthetic gas as alkylating reagent comprises CO or CO
2in at least one and H
2the gas mixture of composition; Aroamtic hydrocarbon raw material is the miscellany of toluene, benzene and the two arbitrary proportion thereof.There is alkylated reaction in synthetic gas and the aromatic hydrocarbons dual-function catalyst in reactive distillation column, generate the mixture I being rich in p-Xylol.Reactive distillation column comprise be positioned at middle part reaction zone, the second rectification zone under first rectification zone and reaction zone of reaction distillation top of tower, be filled with the dual-function catalyst of synthesising gas systeming carbinol and alkylation of toluene in reaction zone.
Preferred technical scheme, dual-function catalyst comprises: the first component being selected from one or more in Cu, Zn, Cr, Mn, Zr, Ti, Co, Ni, Ga, Fe metallic element and/or its oxide compound; With the second component of one or more be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, Beta, MOR, MCM-22, SAPO-11 molecular sieve.The SiO of above-mentioned molecular sieve
2/ Al
2o
3mol ratio preferable range is 20 ~ 500, and molecular sieve catalyst used is through selectivity process in advance, treatment process is one or more in carrying alkali metal oxide compound, alkaline earth metal oxide, rare-earth oxide, P contained compound, boron-containing compound and silicon-containing compound.First component and the second component compound of dual-function catalyst can adopt the preparation methods such as mechanically mixing, pickling process, coprecipitation method.With alkylation catalyst weight percent meter, the first component be selected from Cu, Zn, Cr, Mn, Zr, Ti, Ni, Ga, Fe metallic element and/or its oxide compound one or more, content preferable range is 0 ~ 10; Second component is selected from one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, Beta, MOR, MCM-22 molecular sieve, and content preferable range is 20 ~ 90.
In above-mentioned catalytic distillation technology, introduce after aroamtic hydrocarbon raw material preheating from upper end, reaction zone, synthetic gas and aromatic hydroxy compound react with alkylation of toluene in reaction zone adverse current and catalyst exposure concurrent GCMS computer cyclostrophicization.P-Xylol mixture coagulated becomes liquid to collect at the bottom of reactive distillation column tower, reactive distillation column overhead collection gas-phase product.Top gaseous phase product enters gas phase, aqueous phase, oil phase triphase separator after condenser, and oil phase is directly back to reactive distillation column, and aqueous phase discharges after treatment.Gas phase mixture first removes heavy component through a rectifying tower, then by conversion of methane device, and then pass into reactive distillation column.A product liquid part of collecting at the bottom of tower is back to reactive distillation column through reboiler, all the other first flow through toluene rectifying tower and remove light constituent toluene and benzene, the light constituent deviate from is used to wash gas-phase product, then reactive distillation column is back to, toluene rectifying tower bottom stream then passes into xylene distillation tower except carbon elimination nine and above heavy aromatics thereof, finally obtains para-xylene product.
Concrete Synthetic holography and alkylation reaction condition as follows: temperature of reaction preferable range is 250 ~ 550 DEG C, more preferably 300 ~ 500 DEG C; Reaction pressure preferable range is 1.0 ~ 10.0 MPa, more preferably 1.0 ~ 5.0 MPa; Aromatic hydrocarbons weight space velocity preferable range is 0.5 ~ 8.0 h
-1, more preferably 1 ~ 5.0 h
-1; In aromatic hydrocarbons and synthetic gas, the mol ratio preferable range of hydrogen is 0.001 ~ 100, more preferably 0.1 ~ 10.
In the present invention, xylene product constantly removes from reactive distillation column, facilitates the further conversion of aroamtic hydrocarbon raw material; And due to the timely separation of dimethylbenzene, in reactor, xylene concentration is low, the heavy aromatics product generated by the further alkylation of dimethylbenzene is than few a lot of in fixed bed; Adopt the online synthesizing alkylated reagent of synthetic gas, can avoid on the one hand in beds, occurring that the local of alkylating agent is superfluous, suppress the generation of its side reaction, on the other hand, unconverted synthetic gas can be used as thinner and inhibitor, slow down the generation of carbon deposit, and take away the reaction heat in catalyst bed by the circulation of synthetic gas, be conducive to constant temperature method; In addition, alkylated reaction continuous consumption methyl alcohol can also promote the further conversion of synthetic gas.Due to above-mentioned advantage, this reactive distillation process can be used for aromatic alkylation processes, and Selectivity for paraxylene, between 80% ~ 95%, obtains good effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is reactive distillation column; 2 is reboiler; 3 is preheater; 4 is preheater; 5 is condenser; 6 is gun barrel; 7 is tower top hydrocarbon gas knockout tower; 8 is tower top hydrocarbon gas washing tower; 9 is toluene rectifying tower; 10 is reboiler; 11 is xylene distillation tower; 12 is reboiler; 13 is aroamtic hydrocarbon raw material charging; 14 is synthetic gas charging; 15 is the charging of toluene rectifying tower; 16 is the discharging of dimethylbenzene tower reactor; 17 is para-xylene product discharging; 18 is that toluene rectifying tower tower top toluene and a small amount of light constituent reflux; 19 is washing tower charging; 20 is emission gases; 21 is circulation and stress synthetic gas; 22 is cleaner; 23 is recovered overhead liquid hydrocarbon; 24 is tower top discharge water; 25 is reflux liquid hydrocarbon after washing.
Reaction is carried out in reactive distillation column 1.Reactive distillation column comprises the reaction zone at middle part, the second rectification zone under first rectification zone and reaction zone of reaction distillation top of tower, is filled with the dual-function catalyst of synthesising gas systeming carbinol and alkylation of toluene in reaction zone.The synthetic gas 22 of synthetic gas 14 and backflow after preheater 3 from continuously feeding below reaction zone, aroamtic hydrocarbon raw material 13 is introduced from upper end, reaction zone after preheater 4 preheating, synthetic gas and aromatic hydroxy compound are in reaction zone counter current contact and alkylated reaction occurs, and obtain mixture I.P-Xylol mixture coagulated becomes liquid to collect at the bottom of reactive distillation column tower, reactive distillation column overhead collection gas-phase product.The liquid wherein collected at the bottom of part tower returns reactive distillation column 1 from the reboiler 2 at the bottom of reactive distillation column tower.The material not returning reactive distillation column 1 sends into toluene rectifying tower 9 through pipeline 15, and toluene and a small amount of light constituent send into reactive distillation column 1 and washing tower 8 through overhead line 18 and 19 respectively.Part toluene rectifying tower materials at bottom of tower sends into rectifying tower 9 again through reboiler 10.And dimethylbenzene and heavy aromatics component send into xylene distillation tower 11 at the bottom of tower, dimethylbenzene reclaims from tower top 17, and part xylene distillation tower materials at bottom of tower again sends into rectifying tower 11 after reboiler 12 heats, and heavy aromatics component 16 to reclaim at the bottom of tower.The gas-phase product of the method enters gun barrel 6 after condenser 5 cools, and is divided into aqueous phase, oil phase and gas phase.Oil phase 23 returns reactive distillation column 1, water is discharged from pipeline 24, and gas phase is sent into knockout tower 7 and reclaimed synthetic gas, and the synthetic gas of backflow first removes methane by cleaner 22, send into reactive distillation column 1 again, residual gas product is discharged through pipeline 20 after washing in washing tower 8.
Below by embodiment, the invention will be further described.
Embodiment
[embodiment 1]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is formed according to the ratio mechanically mixing of weight ratio 2:1 by copper-based catalysts and the solid acid catalyst containing ZSM-5 molecular sieve, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 300 ~ 500 DEG C, reaction pressure 1.0 ~ 5.0 MPa, data results lists in table 1.
Aromatics conversion rate in table 1 is the overall conversion of toluene and benzene, and dimethylbenzene selective refers to the ratio of xylene products in all aromatic product, aromatic hydrocarbons composition in basis product, and formula is as follows:
Table 1
[embodiment 2]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is obtained according to the ratio co-precipitation of weight ratio 2:1 by nickel/copper-based catalysts and the solid acid catalyst containing ZSM-5 molecular sieve, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 300 ~ 500 DEG C, reaction pressure 1.0 ~ 5.0 MPa, data results lists in table 2, and reactivity worth method of calculation are in detail with reference to embodiment 1.
Table 2
[embodiment 3]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is formed according to the ratio mechanically mixing of weight ratio 2:1 by copper-based catalysts and the solid acid catalyst containing MCM-22 molecular sieve, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 250 ~ 500 DEG C, reaction pressure 1.0 ~ 5.0 MPa, data results lists in table 3, and reactivity worth method of calculation are in detail with reference to embodiment 1.
Table 3
[embodiment 4]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is obtained according to the ratio co-precipitation of weight ratio 2:1 by nickel/copper-based catalysts and the solid acid catalyst containing MCM-22 molecular sieve, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 250 ~ 300 DEG C, reaction pressure 2.5 ~ 5.0 MPa, data results lists in table 4, and reactivity worth method of calculation are in detail with reference to embodiment 1.
Table 4
[embodiment 5]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is formed according to the ratio mechanically mixing of weight ratio 2:1 by copper-based catalysts and the solid acid catalyst containing ZSM-5 molecular sieve, total filling amount 1000 grams, toluene by weight air speed 6.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 250 ~ 300 DEG C, reaction pressure 2.5 ~ 5.0 MPa, data results lists in table 5, and reactivity worth method of calculation are in detail with reference to embodiment 1.
Table 5
[embodiment 6]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is formed according to the ratio mechanically mixing of weight ratio 2:1 by copper-based catalysts and the solid acid catalyst containing ZSM-5 molecular sieve, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO, CO that mol ratio is 1:1:1
2with H
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 250 ~ 300 DEG C, reaction pressure 2.5 ~ 5.0 MPa, data results lists in table 6, and reactivity worth method of calculation are in detail with reference to embodiment 1.
Table 6
[embodiment 7]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is by copper-based catalysts and formed by the ratio mechanically mixing of the ZSM-5 molecular sieve catalyzer of MgO selectivity process according to weight ratio 2:1, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 300 ~ 500 DEG C, reaction pressure 1.0 ~ 5.0 MPa, data results lists in table 7.
Table 7
[embodiment 8]
Adopt flow process as shown in Figure 1 to carry out alkylation of toluene reaction evaluating, catalyzer is by copper-based catalysts and formed by the ratio mechanically mixing of the ZSM-5 molecular sieve catalyzer of phosphoric acid selectivity process according to weight ratio 2:1, total filling amount 1000 grams, toluene by weight air speed 2.0 h
-1, synthetic gas consists of CO and the H that mol ratio is 1:1
2, H
2be 1:1 with toluene mole ratio, temperature of reaction 300 ~ 500 DEG C, reaction pressure 1.0 ~ 5.0 MPa, data results lists in table 8.
Table 8
[comparative example 1]
This comparative example illustrates that the alkylating aromatic hydrocarbon that the technical program adopts produces the catalytic distillation method of p-Xylol compared with the fixed-bed approach of routine, and catalyst stability is higher.Adopt the identical catalyzer as embodiment 8 and reaction evaluating condition, 500 DEG C, 5.0 MPa time, the technical program stability can reach 500 hours, and conventional fixed-bed approach stability reaches 350 hours.
Claims (10)
1. alkylating aromatic hydrocarbon produces a catalytic distillation method for p-Xylol, comprises following several step:
A) take synthetic gas as alkylating reagent, aromatic hydrocarbons is raw material, and alkylated reaction occurs synthetic gas and the aromatic hydrocarbons dual-function catalyst in reactive distillation column, generates the mixture I being rich in p-Xylol;
B) p-Xylol mixture coagulated becomes liquid to collect at the bottom of reactive distillation column tower, reactive distillation column overhead collection gas-phase product;
C) liquid portion collected at the bottom of reactive distillation column tower enters the reboiler at the bottom of tower, then enters reactive distillation column, continues reaction; Other liquid products reclaimed at the bottom of tower flow through toluene rectifying tower, remove light constituent toluene and benzene, the light constituent deviate from and gas-phase product mixing, and form mixture II, mixture II is back to reactive distillation column; Toluene rectifying tower bottom stream passes into xylene distillation tower, except carbon elimination more than nine heavy aromatics, obtains para-xylene product;
D) described reactive distillation column top gas phase product enters gas phase, aqueous phase, oil phase triphase separator after cooling, and gas phase and oil phase are back to reactive distillation column, and aqueous phase discharges after treatment.
2. alkylating aromatic hydrocarbon according to claim 1 produces the catalytic distillation method of p-Xylol, it is characterized in that the gas phase that step d) refluxes and oil mixture first remove heavy component through rectifying tower, again by conversion of methane device, finally pass into reactive distillation column again.
3. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 1, it is characterized in that the synthetic gas as alkylating reagent comprises CO or CO
2in at least one and H
2the gas mixture of composition; Aroamtic hydrocarbon raw material is the miscellany of toluene, benzene and the two arbitrary proportion thereof.
4. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 1, it is characterized in that the middle part of reactive distillation column is reaction zone, reaction distillation top of tower is the first rectification zone, be the second rectification zone under reaction zone, be filled with the dual-function catalyst of synthesising gas systeming carbinol and alkylation of toluene in reaction zone.
5. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 1, it is characterized in that described dual-function catalyst comprises: the first component being selected from one or more in Cu, Zn, Cr, Mn, Zr, Ti, Co, Ni, Ga, Fe metallic element and/or its oxide compound; With the second component of one or more be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, Beta, MOR, MCM-22, SAPO-11 molecular sieve.
6. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 5, it is characterized in that, with dual-function catalyst weight percent meter, first component be selected from Cu, Zn, Cr, Mn, Zr, Ti, Ni, Ga, Fe metallic element and/or its oxide compound one or more, content is 0 ~ 10; Second component is selected from one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, Beta, MOR, MCM-22 molecular sieve, and content is 20 ~ 90; The SiO of described molecular sieve
2/ Al
2o
3mol ratio is about 20 ~ 500.
7. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 5, the second component that it is characterized in that in dual-function catalyst adopt in alkalimetal oxide, alkaline earth metal oxide, rare-earth oxide, P contained compound, boron-containing compound and silicon-containing compound one or more carry out selectivity process.
8. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 5, it is characterized in that the first component and second component can adopt the preparation methods such as mechanically mixing, pickling process, coprecipitation method.
9. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 1, introduce below reaction zone after it is characterized in that synthetic gas preheating, introduce from upper end, reaction zone after aroamtic hydrocarbon raw material preheating, synthetic gas and aromatic hydroxy compound react with alkylation of toluene in reaction zone adverse current and catalyst exposure concurrent GCMS computer cyclostrophicization.
10. alkylating aromatic hydrocarbon produces the catalytic distillation method of p-Xylol according to claim 1, it is characterized in that alkylation reaction condition is as follows: temperature of reaction 200 ~ 550 DEG C, reaction pressure 1.0 ~ 10.0 MPa, aromatic hydrocarbons weight space velocity 0.5 ~ 8.0 h
-1, in aromatic hydrocarbons and synthetic gas, the mol ratio of hydrogen is 0.001 ~ 100.
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| CN105218431A (en) * | 2015-10-22 | 2016-01-06 | 安徽国星生物化学有限公司 | A kind of synthetic method of 2-picoline |
| CN110743609A (en) * | 2019-11-21 | 2020-02-04 | 厦门大学 | Combined catalyst and preparation method thereof, and method for preparing dimethylbenzene by carbon dioxide hydrogenation coupling toluene alkylation |
| CN111072445A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Process for synthesizing xylene from toluene and methanol |
| CN114436736A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Catalytic reaction system for heavy aromatic hydrocarbon conversion and method for catalyzing heavy aromatic hydrocarbon conversion |
| CN114716290A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Process system and process method for producing p-xylene in high yield from mixed aromatics |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218431A (en) * | 2015-10-22 | 2016-01-06 | 安徽国星生物化学有限公司 | A kind of synthetic method of 2-picoline |
| CN111072445A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Process for synthesizing xylene from toluene and methanol |
| CN111072445B (en) * | 2018-10-18 | 2022-07-12 | 中国石油化工股份有限公司 | Process for synthesizing xylene from toluene and methanol |
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| CN114436736A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Catalytic reaction system for heavy aromatic hydrocarbon conversion and method for catalyzing heavy aromatic hydrocarbon conversion |
| CN114436736B (en) * | 2020-10-19 | 2024-01-26 | 中国石油化工股份有限公司 | Catalytic reaction system for heavy aromatics conversion and method for catalyzing heavy aromatics conversion |
| CN114716290A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Process system and process method for producing p-xylene in high yield from mixed aromatics |
| CN114716290B (en) * | 2020-12-22 | 2024-04-05 | 中国石油化工股份有限公司 | Process system and process method for producing paraxylene by mixed aromatic hydrocarbon |
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