CN102875321B - Method for continuous production of p-xylene through aromatic hydrocarbon alkylation - Google Patents
Method for continuous production of p-xylene through aromatic hydrocarbon alkylation Download PDFInfo
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- CN102875321B CN102875321B CN201110195360.8A CN201110195360A CN102875321B CN 102875321 B CN102875321 B CN 102875321B CN 201110195360 A CN201110195360 A CN 201110195360A CN 102875321 B CN102875321 B CN 102875321B
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Abstract
The invention relates to a method for the continuous production of p-xylene through aromatic hydrocarbon alkylation to mainly solve problems comprising many methanol side reactions, bad catalyst stability and difficult realization of the continuous production in the prior art. The method which allows a reaction to be carried out through the series connection of at least two reactors comprises the following steps: 1, mixing a carrying gas with an aromatic hydrocarbon raw material to obtain a reaction mixture I; 2, allowing the reaction mixture I to sequentially flow to the last reactor from the first reactor; 3, dividing an alkylation reagent into at least two parts, mixing the alkylation reagent with the reaction mixture I at the inlet of each of the reactors, and allowing the obtained new mixture to enter the reactors to contact and react with an alkylation catalyst in order to obtain a reaction product rich in xylene; and 4, letting one of the series reactors into a regeneration gas system through material switching to carry out the regeneration of the alkylation catalyst. The technical scheme of the sequential regeneration of all the reactors well solves the problems, and can be applied to the industrial production of p-xylene through the aromatic hydrocarbon alkylation.
Description
Technical field
The present invention relates to a kind of method of alkylating aromatic hydrocarbon continuous seepage 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 (PET), terylene is then excellent property, the great polyester material of demand, is widely used in weaving and wrapping material field.
At present, industrial take toluene as the most popular method of raw material production p-Xylol is toluene disproportionation and C9 aromatic 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 also been succeeded in developing and has been stepped into industrialization, its feature is rich product p-Xylol and benzene, and toluene and methanol shape selective alkylation technique then low yield benzene even do not produce benzene, and therefore drastically increase the utilization ratio of methylbenzene raw material.But introduce methyl alcohol due to alkylation 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.
For suppressing methyl alcohol side reaction, existing report is set about from two aspects substantially, and namely catalyzer improves and process optimization.In catalyzer improvement, patent CN1933907A proposes the method processing zeolite catalyst with the solution that phosphorous acid fluid dissolves alumina obtains, and the catalyzer after process, while obtaining higher Selectivity for paraxylene, has good stability; Patent CN1593759A selects modified Nano ZSM-5 molecular sieve, through the oxide modifying of metal and silicon, achieve good toluene methylation catalytic reaction effect, after evaluating through 200 hours, toluene conversion maintains more than 25%, and dimethylbenzene para-isomeride selectivity reaches more than 94%.Process optimization aspect, Saudi Basic Industries Corp., by optimization reactor driving condition (CN1775715A) and the way of adding water (CN1898185A) in the feed, extends the parallel-adder settle-out time of alkylation of toluene methanol reaction; Patent CN1759081A adopts the method shortening reactant and catalyst contact time to extend catalyst life, and concrete grammar is improved reactant feed rate, reduces catalyst bed size, uses the support of the catalyst of similar foam and adds thinner in reactant.
Present invention employs the reaction process being different from above-mentioned report, multiple reactors in series is carried out alkylated reaction, alkylating reagent methyl alcohol so can be made to have multiple opening for feed, thus reduce the ratio of each reactor inlet methyl alcohol and aromatic hydrocarbons, reduce the partial concn of methyl alcohol, methyl alcohol side reaction is inhibited.The key of this reaction process is the number of tandem reactor, is the combination of horizontal arrangement, longitudinal stack or two kinds of modes, does not all affect effect, and just affect the overall floor space of device as each reactor.Within the specific limits, the number of tandem reactor is more, and methyl alcohol partial concn is lower, and side reaction control effects is better; But too much reactor can increase facility investment and operation easier, thus loses more than gain in economy.The present invention for representative is set forth with 6 reactors in series, does not represent the present invention and is confined to 6 reactors in series.
Summary of the invention
To be solved by this invention be many, the poor catalyst stability of methyl alcohol side reaction in prior art, be difficult to realize quantity-produced problem, a kind of method of new alkylating aromatic hydrocarbon continuous seepage p-Xylol is provided.The method can significantly improve alkylation efficiency, extending catalyst stability, and can realize the continuous seepage of p-Xylol.
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 alkylating aromatic hydrocarbon continuous seepage p-Xylol, it is characterized in that at least two reactors in series to react together, comprises the following steps:
A) carrier gas is mixed with aroamtic hydrocarbon raw material, obtain reaction mixture I;
B) reaction mixture I is successively from first reactor stream to last reactor;
C) alkylating reagent is divided at least two strands, mixes with reaction mixture I at the entrance of each reactor respectively, then enter reactor and alkylation catalyst contact reacts, obtain the reaction product being rich in dimethylbenzene;
D) switched the access resurgent gases system made in tandem reactor by material, carry out alkylation catalyst regeneration, each reactor regenerates successively.
In above-mentioned reaction process, the number of tandem reactor is 2 ~ 20; Aroamtic hydrocarbon raw material is the mixture of benzene, toluene or benzene and toluene, and in benzene and toluene mixture, the mole percent level of benzene is 0.1 ~ 99.9%; Carrier gas is the gas mixture of hydrogen, nitrogen or hydrogen and nitrogen, and in hydrogen and nitrogen mixture, hydrogen volume degree is 0.1 ~ 99.9%, and alkylated reaction can run under the condition not having carrier gas; Alkylating reagent is the mixture of methyl alcohol or water and methyl alcohol, and in water and carbinol mixture, the OK range of water and methanol molar ratio is 1: 10 ~ 20: 1, is preferably 1: 1 ~ 10: 1; Alkylation reaction of arene condition is as follows: temperature of reaction 300 ~ 500 DEG C, reaction pressure 0.1 ~ 4.0MPa, aromatic hydrocarbons weight space velocity 0.5 ~ 10.0h
-1, aromatic hydrocarbons and alkylating reagent mol ratio are 0.5 ~ 10, and carrier gas and aromatic hydrocarbons mol ratio are 0 ~ 8; Alkylation catalyst is the solid-acid material of load silicon oxide, and solid-acid material is selected from crystal aluminosilicate or phosphorous crystal aluminosilicate; Crystal aluminosilicate preferred version is selected from ZSM-5 molecular sieve; Phosphorous crystal aluminosilicate preferred version is selected from SAPO-11 molecular sieve; In resurgent gases, the volumn concentration of oxygen is 0.5 ~ 25%, and regeneration temperature is 400 ~ 600 DEG C, and resurgent gases volume space velocity is 10 ~ 5000h
-1.
In above-mentioned alkylating aromatic hydrocarbon method, alkylating reagent methyl alcohol is divided into multiply charging, and therefore methyl alcohol be lowered in the concentration of reactor each several part or dividing potential drop, and thus side reaction is inhibited; In reaction system, introduce water can make the concentration of methyl alcohol reduce further, also can play the effect suppressing coking; The methyl alcohol in batches added and its states of matter of water and temperature are variable, can play the effect of cold shock in the aromatic alkylation processes that heat release is violent, the temperature of reaction system are controlled more stable, and therefore further increase the work-ing life of catalyzer; In this reaction system, also introduce a set of regeneration system rapidly, can in-situ regeneration be carried out when the active deficiency of some reactor catalysts, and not affect the normal operation of other reactors.Adopt above method, effectively can suppress methyl alcohol side reaction, extending catalyst life-span, and the continuation that can maintain reaction unit while catalyst regeneration runs, and achieves the continuous seepage of p-Xylol, achieves good effect.Use ratio of methanol reaches 68%, and react toluene conversion after 1000 hours and still remain on more than 35%, catalyst regeneration is functional, achieves continuous seepage, achieves good technique effect.
The specific performance index definition of alkylation reaction of arene is as follows:
Accompanying drawing explanation
Fig. 1 is the signal of alkylating aromatic hydrocarbon continuous reproduction process flow process, and for 6 reactors in series, in figure, F-1 is aromatic feed, and F-2 is alkylating reagent charging, and F-3 is resurgent gases entrance, and F-4 is carrier gas inlet; R-1 ~ 6 are reactor numbering; V-1 ~ 18 are switching valve numbering; E is regeneration tail gas exhaust outlet; P is product exit.
Concrete operations flow process is as follows: initial reaction stage, arene stream F-1 and carrier gas F-4 passes into reactor R-1 through V-2, V-3, V-4, R-2, V-6, V-8, R-3, V-9, V-10, R-4, V-12, V-14, R-5, V-15, V-16 and P is flowed through successively again from R-1 outlet, reaction product P leads to aromatics seperation system, now F-2 passes into reactor R-1 ~ 5 respectively by V-1, V-5, V-7, V-11 and V-13, and reactor R-6 does not have charging and discharging, through a reaction time, when system aromatic conversion is not enough, each valve is switched, include R-6 in alkylation reaction system, R-1 switches to regeneration system, now arene stream F-1 and circulating carried F-4 flows through V-2 successively, V-4, R-2, V-6, V-8, R-3, V-9, V-10, R-4, V-12, V-14, R-5, V-15, V-16, R-6, V-18 and P, equally, reaction product P leads to aromatics seperation system, F-2 passes through V-5, V-7, V-11, V-13 and V-17 passes into reactor R-2 ~ 6 respectively, F-3 enters R-1 by V-1 and carries out catalyst regeneration, regeneration tail gas is by V-3 also E discharge by the road.The catalyst regeneration of R-2 ~ 6 by that analogy.
Below by embodiment, the invention will be further described.
Embodiment
[embodiment 1 ~ 4]
Carrier gas mixed with aromatic hydrocarbons and vaporize, obtain reaction mixture I, wherein carrier gas is hydrogen, and aromatic hydrocarbons is respectively the mixture of benzene, toluene and benzene and toluene; Reaction mixture I flows to R-5 from R-1 successively, respectively with the alkylation catalyst contact reacts of silicon-aluminum containing molecular sieve in each reactor; Alkylating reagent methyl alcohol is divided into five strands of equivalent, introduces each reactor respectively, contact with other reactants and alkylation catalyst, reaction conditions is: each reactor charge 10 grams of catalyzer, and temperature of reaction 400 DEG C, aromatic hydrocarbons weight space velocity is 4.0h
-1, aromatic hydrocarbons and methanol molar ratio are 2, and hydrogen and aromatic hydrocarbons mol ratio are 3, and reaction pressure is 0.5MPa, and alkylation catalyst used contains the SiO of weight percent 15%
2properties-correcting agent, Hydrogen ZSM-5 molecular sieve (the silica alumina ratio SiO of 75%
2/ Al
2o
3=50) reaction product being rich in dimethylbenzene, is obtained at tandem reactor end; Contrast each embodiment initial reaction performance, catalyzer does not regenerate.React sampling analysis after 2 hours, concrete appreciation condition and data results list in table 1.
Table 1
* toluene is as product, and its selectivity is 48.37%.
Table 1 data declaration partly or entirely replaces toluene with benzene, and also can carry out alkylated reaction and produce p-Xylol, but in aromatic hydrocarbons, benzene content is higher, transformation efficiency is lower, and this is because benzene alkylation difficulty is higher than alkylation of toluene.
[embodiment 5 ~ 8]
Carry out alkylation reaction of arene according to step described in embodiment 1 and condition, wherein the condition such as carrier gas composition adjusts, and respectively at reaction sampling analysis after 2 hours and 100 hours, concrete appreciation condition and data results are listed in table 2 and contrasted.
Table 2
Table 2 data show with nitrogen partial or after all replacing hydrogen as carrier gas, less on the impact of catalyzer initial performance, however comparatively large on catalyst stability impact, and in carrier gas, hydrogen content is lower, catalyst deactivation is faster, and under not having the condition of carrier gas, catalyst deactivation is faster.
[embodiment 9 ~ 12]
Carry out alkylation reaction of arene according to step described in embodiment 1 and condition, wherein alkylating reagent becomes the mixture of water and methyl alcohol, and respectively at reaction sampling analysis after 2 hours and 200 hours, concrete appreciation condition and data results are listed in table 3 and contrasted.
Table 3
According to reaction result listed by table 3, at the evaluation initial stage, methyl alcohol water content is less on alkylation properties impact, but larger to the activity influence of long-term assessment rear catalyst.Suitable water content can reduce catalyst deactivation speed, increases the service life.
[embodiment 13 ~ 14]
Alkylation reaction of arene is carried out according to step described in embodiment 10 and condition, the ratio that wherein alkylating reagent distributes in six reactors is inequality, respectively at reaction sampling analysis after 2 hours and 200 hours, concrete appreciation condition and data results list in table 4, and contrast with the data of embodiment 10.
Table 4
Listed by table 4, the feeding manner changing alkylating reagent is comparatively large on reactivity worth impact, and methyl alcohol distribution means that is even or that successively decrease all can obtain good catalyst stability.
[embodiment 15 ~ 20]
Carry out alkylation reaction of arene according to step described in embodiment 10 and condition, change alkylation reaction condition, react sampling analysis after 2 hours, concrete appreciation condition and data results are listed in table 5 and are contrasted.
Table 5
Can draw to draw a conclusion according to the data of table 5, toluene conversion and use ratio of methanol all significantly improve at a higher temperature, improving reaction pressure also can make catalyst activity slightly improve, the effect of carrier gas air input is less obvious, improves methanol feeding amount and then while raising toluene conversion, use ratio of methanol is declined.
[embodiment 21 ~ 24]
Regenerated by the catalyzer evaluated through 200 hours of embodiment 10, then reappraise, evaluation procedure and condition are with embodiment 10, and react sampling analysis after 2 hours, concrete regeneration condition and evaluation result are in table 6.
Table 6
Regeneration tests result shows, ensures suitable temperature and amount of oxygen, and after can making catalyst regeneration, performance is well recovered.
[embodiment 25]
Alkylated reaction is carried out according to the step of embodiment 18 and condition, alkylated reaction is used for unlike front 5 reactors, 6th reactor initial stage leaves unused, and come into operation when reactor 1 regenerates, regeneration condition is with embodiment 23, each reactor regenerates successively, and switch reactor regeneration latter 2 hours sampling analysis, concrete operations conditions and data results lists in table 7.
Table 7
As shown in Table 7, reactor R-1 ~ 6 switch regeneration samsara, and amount to reaction more than 1000 hours, smooth running, regenerated catalyst is functional, and toluene conversion is about 36%, and use ratio of methanol is about 68%; Dimethylbenzene selective more than 65%, in dimethylbenzene, para-isomeride selectivity is about 80%.
[comparative example]
Simultaneous test adopts single reactor and the alkylation reaction condition identical with embodiment 25, and loadings is 50 grams, the charging of methyl alcohol sub-thread, and does not carry out the regeneration of catalyzer.Data results lists in table 8.
Table 8
Contrast table 7 and table 8 data can find, when single reactor and sub-thread methanol feeding, catalyst activity reduction is significantly accelerated, after reacting more than 70 hour, namely toluene conversion drops to about 30%, and after 120 hours, transformation efficiency only retains about 16%, and use ratio of methanol is starkly lower than tandem process.Therefore, the technique that multiple reactors in series provided by the present invention also switches regeneration is the effective ways realizing toluene methylation continuous and stable production really, and can control methyl alcohol side reaction, improves catalyst stability.
Claims (1)
1. a method for alkylating aromatic hydrocarbon continuous seepage p-Xylol,
Its technical process is as shown in Fig. 1 in Figure of description: F-1 is aromatic feed, and F-2 is alkylating reagent charging, and F-3 is resurgent gases entrance, and F-4 is carrier gas inlet, R-1 ~ 6 are reactor numbering, V-1 ~ 18 are switching valve numbering, E is regeneration tail gas exhaust outlet, P is product exit, initial reaction stage, arene stream F-1 and carrier gas F-4 passes into reactor R-1 through V-2, V-3, V-4, R-2, V-6, V-8, R-3, V-9, V-10, R-4, V-12, V-14, R-5, V-15, V-16 and P is flowed through successively again from R-1 outlet, reaction product P leads to aromatics seperation system, now F-2 passes into reactor R-1 ~ 5 respectively by V-1, V-5, V-7, V-11 and V-13, and reactor R-6 does not have charging and discharging, through a reaction time, when system aromatic conversion is not enough, each valve is switched, include R-6 in alkylation reaction system, R-1 switches to regeneration system, now arene stream F-1 and circulating carried F-4 flows through V-2 successively, V-4, R-2, V-6, V-8, R-3, V-9, V-10, R-4, V-12, V-14, R-5, V-15, V-16, R-6, V-18 and P, equally, reaction product P leads to aromatics seperation system, F-2 passes through V-5, V-7, V-11, V-13 and V-17 passes into reactor R-2 ~ 6 respectively, F-3 enters R-1 by V-1 and carries out catalyst regeneration, regeneration tail gas is by V-3 also E discharge by the road, the catalyst regeneration of R-2 ~ 6 by that analogy,
Concrete operations processing condition are as follows: carrier gas mixed with aromatic hydrocarbons and vaporize, obtain reaction mixture I, wherein carrier gas is hydrogen, and aromatic hydrocarbons is respectively toluene; Reaction mixture I flows to R-5 from R-1 successively, respectively with the alkylation catalyst contact reacts of silicon-aluminum containing molecular sieve in each reactor; Alkylating reagent methyl alcohol is divided into five strands of equivalent, introduces each reactor respectively, contact with other reactants and alkylation catalyst, reaction conditions is: each reactor charge 10 grams of catalyzer, and temperature of reaction 400 DEG C, aromatic hydrocarbons weight space velocity is 4.0h
-1, aromatic hydrocarbons and methanol molar ratio are 2, and hydrogen and aromatic hydrocarbons mol ratio are 3, and reaction pressure is 0.5MPa, and alkylation catalyst used contains the SiO of weight percent 15%
2properties-correcting agent, Hydrogen ZSM-5 molecular sieve (the silica alumina ratio SiO of 75%
2/ Al
2o
3=50) reaction product being rich in dimethylbenzene, is obtained at tandem reactor end; Contrast each embodiment initial reaction performance, catalyzer does not regenerate; React sampling analysis after 2 hours, reaction result is: toluene conversion is 28.37mol%.Dimethylbenzene selective is 66.26%, and Selectivity for paraxylene is 84.62%, and use ratio of methanol is 53.36mol%.
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| CN106854128B (en) * | 2016-11-28 | 2019-11-22 | 陕西煤化工技术工程中心有限公司 | A kind of method that toluene produces paraxylene with methanol |
| CN110746256A (en) * | 2019-11-07 | 2020-02-04 | 常州瑞华化工工程技术股份有限公司 | Method for improving methylation rate by methylation of benzene and/or toluene |
| CN115259984B (en) * | 2022-07-14 | 2024-02-02 | 中国科学院山西煤炭化学研究所 | Method for preparing alkylbenzene by alkylation of benzene and synthesis gas |
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| US4377718A (en) * | 1980-07-25 | 1983-03-22 | Teijin Petrochemical Industries Ltd. | Process for producing p-xylene |
| CN1051902A (en) * | 1989-11-11 | 1991-06-05 | 上海高桥石油化工公司化工厂 | Catalyst regeneration process in the synthesizing ethyl benzene method |
| CN101622327A (en) * | 2007-01-19 | 2010-01-06 | 埃克森美孚化学专利公司 | Adopt the liquid-phase alkylation of multiple catalyzer |
| WO2010138504A1 (en) * | 2009-05-28 | 2010-12-02 | Saudi Basic Industries Corporation | Aromatic alkylation process |
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| CN101417233A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院大连化学物理研究所 | Fixed bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4377718A (en) * | 1980-07-25 | 1983-03-22 | Teijin Petrochemical Industries Ltd. | Process for producing p-xylene |
| CN1051902A (en) * | 1989-11-11 | 1991-06-05 | 上海高桥石油化工公司化工厂 | Catalyst regeneration process in the synthesizing ethyl benzene method |
| CN101622327A (en) * | 2007-01-19 | 2010-01-06 | 埃克森美孚化学专利公司 | Adopt the liquid-phase alkylation of multiple catalyzer |
| WO2010138504A1 (en) * | 2009-05-28 | 2010-12-02 | Saudi Basic Industries Corporation | Aromatic alkylation process |
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