CN102372588A - Method for preparing moving bed of para-xylene by aromatics alkylation - Google Patents
Method for preparing moving bed of para-xylene by aromatics alkylation Download PDFInfo
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- CN102372588A CN102372588A CN2010102615515A CN201010261551A CN102372588A CN 102372588 A CN102372588 A CN 102372588A CN 2010102615515 A CN2010102615515 A CN 2010102615515A CN 201010261551 A CN201010261551 A CN 201010261551A CN 102372588 A CN102372588 A CN 102372588A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for preparing a moving bed of para-xylene by aromatics alkylation, which mainly solves the problems of insufficient catalyst stability and difficult realization of continuous production in the prior art. According to the invention, a moving-bed reactor is employed, a catalyst to be regenerated from the bottom of the moving bed enters into a catalyst regenerator, the regenerated catalyst returns to the moving-bed reactor for circular utilization. The technical scheme better solves the problems, and can be used in industrial production of preparing para-xylene by aromatics alkylation.
Description
Technical field
The present invention relates to a kind of moving bed process of alkylating aromatic hydrocarbon system p-Xylol.
Background technology
P-Xylol is a kind of important Organic Chemicals; Main application is through the synthetic terephthalic acid of oxidation; Carry out polycondensation with terepthaloyl moietie again and produce macromolecular material polyethylene terephthalate (being terylene); Terylene then is excellent property, the great polyester material of demand, is widely used in weaving and wrapping material field.
At present; The most frequently used p-Xylol working method is toluene disproportionation and C9 aromatic transalkylation in the industry; Owing to receive thermodynamics equilibrium limit; Usually only contain 24% the p-Xylol of having an appointment in the C8 aronmatic product that this method obtains, and the p-Xylol demand will account for more than 60% on the YLENE demand market, so this concentration is formed the demand that can not satisfy the industrial polyester material produce.For obtaining the high density p-Xylol and improve the p-Xylol yield, mixed C 8 aromatics need pass through isomerizing and fractionation by adsorption or Crystallization Separation combination technique and further handle, and follow-up processing has brought the loss of raw material and the lifting of cost.
In view of this; Numerous investigators are devoted to develop new p-Xylol synthetic technology; Be desirably in production link and just can cross the product that obtains high p-Xylol content, methylbenzene shape selective disproportionation, toluene and methanol shape selective alkylation are such technology, and wherein industriallization has also been succeeded in developing and stepped into to the methylbenzene shape selective disproportionation technology; Its characteristics are rich p-Xylol and the benzene of producing; Toluene and methanol shape selective alkylation technology then low yield benzene are not even produced benzene, and have therefore improved the utilization ratio of methylbenzene raw material, adapt to the present situation of current domestic benzene glut the market especially.
Owing to introduced methyl alcohol in alkylation reaction system, methyl alcohol the coking reaction very easily takes place under alkylation reaction condition and causes catalyst deactivation, this problem is the difficult problem of restriction alkylation of toluene methanol technical development always.
Alkylation reaction of arene technology generally adopts fixed bed reaction technology, and US4377718 and US4761513 have announced similar alkylation of toluene technology, and wherein the different positions of alkylating reagent between fixed bed adds.But because alkylation catalyst deactivation is fast, fixed bed reaction technology needs the frequent regeneration of switching.In addition, because the alkylated reaction thermal discharge is big, adopt fixed bed to be prone to cause the local temperature runaway of reactor drum, operational difficulty.
CN1326430A discloses a kind of fluid-bed aromatics alkylation technology; Introduce aromatic hydrocarbons in the fluidized bed reaction zone first location; Fluidized bed reaction zone is introduced with alkylating reagent in one or more positions in the first location downstream, and this technology can obtain high toluene conversion and high methyl utilization ratio.But fluidized-bed process increases catalyst abrasion and energy consumption, and its preparation is had relatively high expectations.Moving bed process is to solve the insufficient effective ways of catalyst stability; Be not applied to alkylating aromatic hydrocarbon system YLENE field at present; And the moving bed process that is used for other catalytic process is existing; Like a kind of catalysis conversion method that on moving-bed, carries out gasoline and liquefied gas that patent CN101195762A announces, this method is compared with fixed-bed process, can improve the stability of catalyzer significantly; And compare with fluidized-bed, the physical strength of the catalyzer particularly requirement of abrasion index can reduce greatly.
The moving bed process of alkylating aromatic hydrocarbon system p-Xylol of the present invention; Its separate part adopts existing mature technology; Wherein the separation system of head product comprises lightness-removing column, benzene/methylbenzene regenerating column and benzenol hydrorefining, after this system separates, obtains carbon six following light constituents, benzene/methylbenzene, C8 aronmatic and carbon nine and above heavy aromatics product.C8 aronmatic is further separated conversion could obtain highly purified p-Xylol product; Its operating process and operational condition are according to Chinese patent (application number: 200480035152.X); Fractionation by adsorption step in this process can be replaced by the Crystallization Separation step, and the Crystallization Separation step can be with reference to Chinese patent (application number: 95197157.3) carry out; Also can be replaced by absorption-crystallization combination process, concrete scheme can be with reference to Chinese patent (application number: 92111073.1).
The catalyzer that uses in the moving bed process of the present invention is solid acid catalyst; Having the tart solid material all can obtain to use in the method; Like aluminum oxide, heteropolyacid, solid super-strong acid, molecular sieve etc.; Wherein the most frequently used is the molecular screen material of silicon-aluminum containing, and suitable molecular screen material comprises ZSM-5, ZSM-11, ZSM-12, ZSM-23, EU-1, MCM-22, USY, Mordenite, Beta, SAPO-5, SAPO-11, SAPO-31, SAPO-34 etc., can on the basis of molecular screen material, carry out suitable modification; Improving the performance of catalyzer, common modifying method comprises (water) thermal treatment, oxide carried etc.
The used performance index of the present invention define as follows:
Summary of the invention
To be solved by this invention be in the prior art catalyst stability not enough, be difficult to realize the quantity-produced problem, a kind of moving bed process of new alkylating aromatic hydrocarbon system p-Xylol is provided.This method can realize the online activation of catalyzer and recycle, and therefore overcome in the past in the bed technology because of the catalyst deactivation regenerated difficult problem of will frequently stopping, and that has guaranteed to produce carries out continuously.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of moving bed process of alkylating aromatic hydrocarbon system p-Xylol may further comprise the steps:
A) aroamtic hydrocarbon raw material is mixed with alkylating reagent heating vaporization, obtain reaction raw material I, wherein aroamtic hydrocarbon raw material is selected from toluene or benzene and toluene mixture, and alkylating reagent is selected from methyl alcohol or methyl alcohol and dme mixture;
B) reaction raw material I is sent into moving-burden bed reactor, the alkylation catalyst of silicon-aluminum containing molecular sieve is contacted with reaction raw material I in the process of moving down and alkylated reaction takes place, obtain reaction effluent II;
C) reaction effluent II can obtain to be rich in oil phase reaction effluent III, gas-phase reaction elute IV and the water elute V of YLENE through the Oil, Water, Gas three phase separation, and wherein gas-phase reaction elute IV and water elute V discharge after separation and environmental protection treatment;
D) oil phase reaction effluent III obtains containing unconverted aromatic fraction, mixing carbon eight cuts and the carbon nine above heavy arene cuts of benzene and toluene through separation;
E) mix carbon eight cuts and get into absorption, crystallization or absorption/crystallization combination and separation and isomerizing system, obtain the p-Xylol product;
F) unconverted aromatic fraction is refluxed, merge the entering fluidized-bed reactor with reaction mixture I and transform;
That g) comes out from moving-bed bottom treats regenerated catalyst, is carried separating hopper and promoting gas to reclaimable catalyst by lift line and separates the back and get into catalyst regenerator from the top, and the catalyzer that gets into revivifier contacts with regeneration gas and carries out coke burning regeneration;
H) catalyzer after the regeneration is drawn from the revivifier lower part outlet, separates hopper through lift line and regenerated catalyst and returns moving-burden bed reactor and recycle from top.
In the technique scheme, the molar percentage of contained benzene is 0.1～99.9% in benzene and the toluene mixture; To account for the per-cent of methyl total mole number be 0.1～99.9% to the contained methyl mole number of dme in methyl alcohol and the dme mixture; The ratio range of contained methyl total mole number of alkylating reagent and aromatic hydrocarbons total mole number is 0.1～10: 1, is preferably 0.2～1: 1; The alkylation reaction of arene condition is following: 300～500 ℃ of temperature of reaction, reaction pressure 0.1～5.0MPa, hydrogen/aromatic hydrocarbons mol ratio 0～8, aromatic hydrocarbons weight space velocity 0.5～10.0h
-1Catalyst regeneration system is divided into place's scorch region and secondary scorch region, and the inlet resurgent gases of first scorch region is 0.05～0.5% in the volume percent oxygen level, and temperature is 300～450 ℃; The inlet resurgent gases of secondary scorch region is 0.3～6.0% in the volume percent oxygen level, and temperature is 400～550 ℃.
In the moving bed process of above-mentioned alkylating aromatic hydrocarbon system p-Xylol; The catalyzer of inactivation can return reactive system through recycling after the regeneration system rapidly activation; The catalyst regeneration cycle can decide according to its deactivation rate, and the catalyst loss that causes because of reasons such as wearing and tearing can solve through the additional of live catalyst.Therefore, above scheme can adapt to the catalyzer that deactivation rate differs, and can solve poor catalyst stability in the prior art preferably, be difficult to realize the quantity-produced problem.
Through embodiment the present invention is described further below.
Embodiment
[comparative example]
Adopting fixed-bed reactor, is alkylating reagent with methyl alcohol, and toluene is aromatic feed, and methyl alcohol and toluene material merge gasification, feed reactor drum and alkylation catalyst contact reacts then.Reaction conditions is: catalyzer tonburden 2000 grams, and 400 ℃ of feed temperatures, the toluene by weight air speed is 4.0h
-1, methyl and toluene mole ratio are 0.5, do not face hydrogen, and reaction pressure is 0.5MPa, and used alkylation catalyst contains the Al of weight percent 20%
2O
3Properties-correcting agent and 10% La
2O
3Properties-correcting agent, surplus heavy be Hydrogen ZSM-5 molecular sieve (silica alumina ratio SiO
2/ Al
2O
3=50).The reaction evaluating result lists in table 1 and compares.
[embodiment 1]
Toluene is mixed with methyl alcohol heating vaporization, obtain reaction raw material I; Reaction raw material I feeds moving-burden bed reactor; The alkylation catalyst of silicon-aluminum containing molecular sieve is in contact with it in the process of moving down and alkylated reaction takes place, obtain reaction effluent II, reaction conditions is: catalyzer tonburden 2000 grams; 400 ℃ of feed temperatures, toluene by weight air speed are 4.0h
-1, methyl alcohol and toluene mole ratio are 0.5, do not face hydrogen, and reaction pressure is 0.5MPa, and used alkylation catalyst contains the Al of weight percent 20%
2O
3Properties-correcting agent and 10% La
2O
3Properties-correcting agent, surplus heavy be Hydrogen ZSM-5 molecular sieve (silica alumina ratio SiO
2/ Al
2O
3=50); Reaction effluent II can obtain to be rich in oil phase reaction effluent III, gas-phase reaction elute IV and the water elute V of YLENE through the Oil, Water, Gas three phase separation, and wherein gas-phase reaction elute IV and water elute V discharge after separation and environmental protection treatment; Oil phase reaction effluent III obtains containing unconverted aromatic fraction, mixing carbon eight cuts and the carbon nine above heavy arene cuts of benzene and toluene through separation; Mix carbon eight cuts and get into absorption, crystallization or absorption/crystallization combination and separation and isomerizing system, obtain the p-Xylol product; Unconverted aromatic fraction is refluxed, merge the entering fluidized-bed reactor with reaction mixture I and transform; The reclaimable catalyst that comes out from the moving-bed bottom; Carry separating hopper and promoting gas by lift line and separate the back and get into catalyst regenerator from the top to reclaimable catalyst; The catalyzer that gets into revivifier contacts with regeneration gas and carries out coke burning regeneration, and regeneration condition is: the inlet resurgent gases of first scorch region is 0.2% in the volume percent oxygen level, and temperature is 400 ℃; The inlet resurgent gases of secondary scorch region is 3.0% with the volume percent oxygen level, and temperature is 520 ℃; Catalyzer after the regeneration is drawn from the revivifier lower part outlet, separates hopper through lift line and regenerated catalyst and returns moving-burden bed reactor and recycle from top.The reaction evaluating result lists in table 1 and compares.
Table 1
[embodiment 2～5]
Carry out alkylation reaction of arene according to embodiment 1 described step and condition, but the catalyst regeneration condition is done some adjustment, concrete regeneration condition and evaluation result are listed in table 2 and are compared.
Table 2
[embodiment 6～9]
Carry out alkylation reaction of arene according to embodiment 1 described step and condition; But aromatic feed is selected benzene and toluene mixture; The concrete composition of aromatic feed is listed in table 3 with the reaction evaluating result and is compared, and alkylating reagent is close to all and transforms, and below will not explain.
Table 3
[embodiment 10～13]
Carry out alkylation reaction of arene according to embodiment 7 said steps and condition; But alkylating reagent is selected methyl alcohol and dme mixture; Contained methyl of alkylating reagent and aromatic feed mol ratio are 0.5, and alkylating reagent composition and reaction evaluating result list in table 4 and compare.
Table 4
[embodiment 14～17]
Carry out alkylation reaction of arene according to embodiment 12 said steps and condition, but change alkylating reagent and aromatic feed ratio, concrete charging proportioning and reaction evaluating result list in table 5 and compare.
Table 5
[embodiment 18～23]
Carry out alkylation reaction of arene according to embodiment 12 said steps and condition, and the alkylated reaction parameter is adjusted, concrete reaction conditions and evaluation result are listed in table 6 and are compared.
Table 6
We find the data of contrast the foregoing description, adopt fixed bed to carry out alkylated reaction, catalyzer after through 26 hours evaluation, active existing a large amount of losses, toluene conversion is merely initial 55%; And adopt the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to the invention; Through the technology of 24 hour regeneration period, make catalyzer after 200 hours evaluation, activity remains unchanged basically; Thereby can realize continuous production, obtain effect preferably.
Claims (7)
1. the moving bed process of an alkylating aromatic hydrocarbon system p-Xylol may further comprise the steps:
A) aroamtic hydrocarbon raw material is mixed with alkylating reagent heating vaporization, obtain reaction raw material I, wherein aroamtic hydrocarbon raw material is selected from toluene or benzene and toluene mixture, and alkylating reagent is selected from methyl alcohol or methyl alcohol and dme mixture;
B) reaction raw material I is sent into moving-burden bed reactor, the alkylation catalyst of silicon-aluminum containing molecular sieve is contacted with reaction raw material I in the process of moving down and alkylated reaction takes place, obtain reaction effluent II;
C) reaction effluent II can obtain to be rich in oil phase reaction effluent III, gas-phase reaction elute IV and the water elute V of YLENE through the Oil, Water, Gas three phase separation, and wherein gas-phase reaction elute IV and water elute V discharge after separation and environmental protection treatment;
D) oil phase reaction effluent III obtains containing unconverted aromatic fraction, mixing carbon eight cuts and the carbon nine above heavy arene cuts of benzene and toluene through separation;
E) mix carbon eight cuts and get into absorption, crystallization or absorption/crystallization combination and separation and isomerizing system, obtain the p-Xylol product;
F) unconverted aromatic fraction is refluxed, merge the entering fluidized-bed reactor with reaction mixture I and transform;
That g) comes out from moving-bed bottom treats regenerated catalyst, is carried separating hopper and promoting gas to reclaimable catalyst by lift line and separates the back and get into catalyst regenerator from the top, and the catalyzer that gets into revivifier contacts with regeneration gas and carries out coke burning regeneration;
H) catalyzer after the regeneration is drawn from the revivifier lower part outlet, separates hopper through lift line and regenerated catalyst and returns moving-burden bed reactor and recycle from top.
2. the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to claim 1, the molar percentage that it is characterized in that contained benzene in benzene and the toluene mixture is 0.1～99.9%.
3. the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to claim 1 is characterized in that the per-cent that the contained methyl mole number of dme in methyl alcohol and the dme mixture accounts for the methyl total mole number is 0.1～99.9%.
4. the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to claim 1 is characterized in that the ratio range of contained methyl total mole number of alkylating reagent and aromatic hydrocarbons total mole number is 0.1～10: 1.
5. the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to claim 4 is characterized in that the ratio range of contained methyl total mole number of alkylating reagent and aromatic hydrocarbons total mole number is 0.2～1: 1.
6. the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to claim 1; It is characterized in that the alkylation reaction of arene condition is following: 300～500 ℃ of temperature of reaction; Reaction pressure 0.1～5.0MPa, hydrogen/aromatic hydrocarbons mol ratio 0～8, aromatic hydrocarbons weight space velocity 0.5～10.0h
-1
7. the moving bed process of alkylating aromatic hydrocarbon system p-Xylol according to claim 1; It is characterized in that catalyst regeneration system is divided into place's scorch region and secondary scorch region; Just the inlet resurgent gases of scorch region is 0.05～0.5% in the volume percent oxygen level, and temperature is 300～450 ℃; The inlet resurgent gases of secondary scorch region is 0.3～6.0% in the volume percent oxygen level, and temperature is 400～550 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585416A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Method for alkylation reaction between oxygen-containing component and aromatic hydrocarbon |
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|---|---|---|---|---|
| CN101417235A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院大连化学物理研究所 | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin |
| CN101456784A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417235A (en) * | 2007-10-24 | 2009-04-29 | 中国科学院大连化学物理研究所 | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin |
| CN101456784A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585416A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Method for alkylation reaction between oxygen-containing component and aromatic hydrocarbon |
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