CN103664488A - Arene methanol alkylation method for removing oxygen-containing compound impurities - Google Patents
Arene methanol alkylation method for removing oxygen-containing compound impurities Download PDFInfo
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Abstract
The invention relates to an arene methanol alkylation method for removing oxygen-containing compound impurities, which is mainly used for solving the problem that oxygen-containing compound impurities exist in an arene product in the prior art. The method provided by the invention solves the problem relatively well by adopting the following technical scheme: a) the mixed raw material of benzene or toluene and methanol contacts with a composite catalyst in a composite bed reactor to generate a material flow I; b) the material flow I is subjected to heat exchange and cooling before entering an oil-water separator, the lower-layer byproduct water is discharged outside, and the upper-layer oil phase overflows to the downstream part as a material flow II; c) the material flow II enters a stripping tower, the light component is discharged outside through the tower top, the heavy component is combined into an arene combination device as a material flow III, and the p-xylene is separated out. The method can be applied to the industrial production of producing mixed xylene or p-xylene through the alkylation reaction of arene such as benzene or toluene and methanol.
Description
Technical field
The present invention relates to a kind of aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity, particularly about a kind of can be by the method for by-product alcohols, aldehydes, ketone and carboxylic-acid impurity removal in benzene or toluene and methyl alcohol methylation reaction product.
Background technology
P-Xylol is very important petrochemical complex basic organic, in fields such as trevira, medicine, agricultural chemicals, dye well solvents, all has purposes extremely widely.At present, the PX throughput in the whole world is over 3,000 ten thousand tons/year, and production capacity is still maintaining sustained and rapid growth, expecting 2011 yearly capacities will be over 4,000 ten thousand ton, wherein the throughput in Asia and consumers demand occupy the first in the world, 2011, Asia estimated to reach nearly 2,400 ten thousand tons to the demand of PX.And China is as most important p-Xylol Production and consumption state in the world, will reach 9,920,000 tons to 2011 annual requirements, production capacity will reach more than 8,800,000 tons.
Source with toluene in industry triphen is the most sufficient, but its industrial use can not show a candle to dimethylbenzene, therefore causes toluene relative surplus; In recent years, domestic Chemical Industry is fast-developing, and Aromatic Hydrocarbon in Gasoline content's index constantly reduces, and superfluous trend has also appearred in benzaldehyde product; And p-Xylol all has purposes extremely widely in fields such as trevira, medicine, agricultural chemicals, dye well solvents, but this product only accounts for 4.2% in pyrolysis gasoline, is 7.5% in reformate, C
8in BTX aromatics, be 22-26%, output wretched insufficiency.Therefore, toluene and benzene are changed into market requirement p-Xylol vigorous, high added value is to greatest extent an important research direction in petrochemical technology always.
Toluene is converted into dimethylbenzene, then dimethylbenzene is converted into this process of p-Xylol by separated with isomerization, be the main method that p-Xylol is produced always.The traditional method that wherein toluene is converted into dimethylbenzene is toluene disproportionation process, in order effectively to utilize the above Heavy Aromatic Hydrocarbons of carbon nine, develops into toluene disproportionation and heavy aromatics alkyl transfering process.At present, the disproportionation processes of pure toluene charging has all been abandoned by nearly all producer, and replaces the alkyl transfering process that can process heavy aromatics.Realize in recent years industrialized toluene dimethylbenzene technique processed, also has selective disproportionation of toluene technique, the advantage of this technology is to produce the dimethylbenzene product that is rich in p-Xylol, therefore significantly reduce energy consumption and the material consumption of separation and isomerization process, be applicable to toluene resource abundance and the relatively low enterprise of heavy aromatics processing pressure.Compare with above-mentioned two kinds of toluene dimethylbenzene process processed, toluene or benzene and methanol alkylation are the p-Xylol new process of production that economic benefit is larger, can improve substantially toluene or benzene utilization ratio.And the methylating reagent methyl alcohol using is important Coal Chemical Industry product, the great significance of this technology to domestic Chemical Industry in future.
Methylbenzene methanol methylation reaction (MTX) refers to take methyl alcohol as raw material for alkylation, increases a methyl on toluene aromatic ring, thereby generates the process of dimethylbenzene.Phenylcarbinol methylation reaction (BTX) refers to take methyl alcohol as raw material for alkylation, increases a methyl on the aromatic ring of benzene, thereby generates the process of toluene and dimethylbenzene.MTX reaction is a St reaction in benzene being undertaken by carbonium ion mechanism, process is: methyl alcohol is activated in catalyst B acid site, with the toluene adsorbing a little less than the attack of methyl carbonium ion, inducing action due to methyl on phenyl ring, main o-Xylol and the p-Xylol of generating, less m-xylene produces another product water simultaneously.BTX reaction is also the St reaction in benzene being undertaken by carbonium ion mechanism, and target product is toluene and dimethylbenzene.Meanwhile, due to the introducing of methyl alcohol, also can there is the side reactions such as carbonylation, alkene and etherificate in methyl alcohol self.
The technical characterstic that methylates of domestic Dalian Inst of Chemicophysics, Chinese Academy of Sciences is when producing dimethylbenzene by the rich low-carbon alkene that produces of methyl alcohol side reaction, patent CN1721378 and CN101417233 have introduced the fluidized-bed of co-producing light olefins and the technique of moving-bed and catalyzer, have also proposed to react the modified technique of online silicon modification for the problem of catalyzer shape selectivity loss in reaction process.
External each large petrochemical enterprise, as U.S. GTC company, ExxonMobil company, Saudi Aribian Basic Industry Company, British Petroleum Company p.l.c. etc. have carried out a large amount of research to toluene methylation technology.The research work coverage of ExxonMobil company aspect toluene methylation is the widest, has included catalyzer and reaction process.Aspect catalyzer, the said firm adopts high silica ZSM-5 molecular sieve as active main body in its patent CN97198340, then through phosphorus modification, and process by high-temperature water vapor, catalyzer shape selectivity is significantly improved, in dimethylbenzene, Selectivity for paraxylene is more than 90%, and now toluene conversion is about 30%, and use ratio of methanol is 60%; Its another piece of patent US5563310 adopts the modification of IVB family metal oxide to obtain high activated catalyst, in toluene and methanol mol ratio, it is the generation Mixed XYLENE that methylates under 4-8/1 and 200-235 ℃ of cold condition, toluene conversion is up to 11.8%, and dimethylbenzene yield is up to 9.7%.Process aspect the said firm has carried out multiple trial, relates to fluidized-bed process, reaction distillation technique and adopts the recombining process that synthetic gas and toluene are raw material.
The catalyst technology of Saudi Aribian Basic Industry Company (SABIC) also be take ZSM-5 molecular sieve as basis, adopts phosphorus modification, and think this catalyzer without steam-treated is also able to take aqueous reaction technique dealuminzation hardly.Its patent CN200410068466 has also introduced the driving technique of its uniqueness, i.e. high-speed, the low hydrogen hydrocarbon process of temperature raising progressively when, and claim that catalyst stability is more than 500 hours.
Yet, after contacting with catalyzer under hot conditions, methanol feedstock there is multiple reaction, also can bring a series of problem.From aromatic hydrocarbon product quality control, the carboxylic-acid impurity such as the ketones such as the aldehydes such as methyl alcohol and by-product acetaldehyde, by-product acetone, by-product acetic acid are dissolved in liquid phase aromatic product, threaten the normal running of adsorption separation unit, disproportionation unit and isomerization unit in the Aromatic Hydrocarbon United Plant of downstream.
Summary of the invention
Technical problem to be solved by this invention is the problem that contains oxygenatedchemicals impurity in aromatic hydrocarbon product, and a kind of new aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity is provided.The method, for toluene or the phenylcarbinol industrial production that methylates, has advantages of that aromatic hydrocarbon product quality is not subject to oxygenatedchemicals impurity effect.
In order to solve the problems of the technologies described above, the technical solution used in the present invention comprises the following steps: a kind of aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity, comprises the following steps:
A) at 350 ℃ ~ 480 ℃ of temperature, weight space velocity, it is 0.5 ~ 5 hour
-1, pressure is under 0.1 ~ 3MPa condition, benzene or toluene and methanol mixed raw material, by composite bed reactor, contacts with composite catalyst, resultant of reaction flows I;
B) stream I through heat exchange and cooling after enter water-and-oil separator, the lower floor's by-product water after separation is disposed to out-of-bounds, upper oil phase overflow is to downstream, as stream I I;
C) stream I I enters stripping tower, separated C
6light constituent drained into out-of-bounds by tower top in the past, the C that tower reactor obtains
6and later heavy constituent, as stream I II, be incorporated in Aromatic Hydrocarbon United Plant, isolate p-Xylol;
Wherein, composite catalyst is methylation catalyst and oxygenatedchemicals Removal of catalyst.
In technique scheme, contain alcohols, ketone, aldehydes and carboxylic-acid oxygenatedchemicals in stream I, the weight content of the alcohols in stream I II, ketone, aldehydes and carboxylic-acid oxygenatedchemicals is all less than 0.5ppm; The weight content of the ketone in stream I I and carboxylic-acid oxygenatedchemicals is all less than 0.5ppm; The tower top temperature of stripping tower is 110 ~ 130 ℃, and tower top pressure is 0.4 ~ 0.6MPa.
Preferred technical scheme, in step c), separated C
6light constituent was C in the past
1~ C
5alkane, alkene, and the oxygenatedchemicals such as acetaldehyde, methyl alcohol, in step c), the C that tower reactor obtains
6and heavy constituent comprises C later
6~ C
14aromatic hydrocarbons, alkane and alkene.Methylation catalyst is: (a) at least one in 40% ~ 90% ZSM-5 zeolite or MCM-22 zeolite molecular sieve; (b) 0.01 ~ 5.0% MgO, La
2o
3, CaO and SiO
2in at least one; (c) 15 ~ 80% binding agent.Oxygenatedchemicals Removal of catalyst is: (a) 10% ~ 95% La
2o
3, ZnO, ZrO
2, CaO, MgO, TiO
2and Cr
2o
3in at least one; (b) 5 ~ 90% binding agent.
Using toluene or benzene and methyl alcohol as raw material, by alkylated reaction, can High-efficient Production be rich in the BTX aromatics of p-Xylol, reach the object of adjusting aromatic hydrocarbon product structure, increasing p-Xylol output.At oxygenatedchemicals, remove in bed, carboxylic-acid impurity generation de-carbonyl reaction, the boiling point of reaction product is lower than benzene; Ketone impurity generation decomposition reaction generates hydro carbons, carbonic acid gas, and the boiling point of reaction product is also significantly reduced to below benzene boiling point.In stripping tower, the lower boiling alcohols, aldehydes and the ketone that in aromatic hydrocarbon oil, only contain drain into out-of-bounds from stripping tower top, guarantee to enter alcohols, ketone, aldehydes and carboxylic-acid weight oxygenate content in the BTX aromatics of Aromatic Hydrocarbon United Plant and are all less than 0.5ppm.Operational path of the present invention, can eliminate again the disadvantageous effect of oxygenatedchemicals to aromatic hydrocarbons quality and equipment safety generation with the p-Xylol of toluene or benzene and the industrial urgent need of methanol production, and facility investment and running cost are low, have obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the methylbenzene methanol of the eliminating oxygenatedchemicals impact process flow diagram that methylates.
In Fig. 1,1 for methylate/oxygenatedchemicals removes composite bed reactor, and 2 is water-and-oil separator, and 3 is stripping tower.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
The preparation method of methylation catalyst: at least one in 40% ~ 90% ZSM-5 zeolite or MCM-22 zeolite molecular sieve and γ-Al of 15 ~ 80%
2o
3after binding agent fully mixes, add suitable quantity of water kneading and compacting, dry with 550
oafter C roasting, obtain catalyst body.Pickling process, ion exchange method and chemical deposition by extensive employing are by 0.01 ~ 5.0% MgO, La
2o
3, CaO and SiO
2in at least one load to and in catalyst body, obtain methylation catalyst.
The preparation method of oxygenatedchemicals Removal of catalyst: 10% ~ 95% La
2o
3, ZnO, ZrO
2, CaO, MgO, TiO
2and Cr
2o
3at least one in oxide compound and γ-Al of 5 ~ 90%
2o
3, after silicon oxide or clay bond fully mix, add suitable quantity of water kneading and compacting, dry and 450
oafter C roasting, obtain oxygenatedchemicals Removal of catalyst.
In reactor, load respectively toluene methylation catalyzer and oxygenatedchemicals Removal of catalyst from top to bottom, the mass ratio of upper and lower bed is 5:1.Toluene: methyl alcohol (mol ratio)=2:1, toluene by weight air speed 1 hour
-1, 370 ℃ of temperature of reaction, reaction pressure 0.5MPa; Liquid product is after water-and-oil separator separation, and oil phase enters stripping tower and carries out light constituent separation, 118 ℃ of stripping tower top temperatures, stripping tower pressure on top surface 0.45MPa.As shown in schematic flow sheet, stream I, the oxygenatedchemicals analytical resultss such as the acetaldehyde in II and III, methyl alcohol, acetone, butanone and acetic acid are as shown in table 1:
Table 1
| ? | Stream I (wtppm) | Stream I I (wtppm) | Stream I II (wtppm) |
| Acetaldehyde | 8 | 8 | ≤0.5 |
| Methyl alcohol | 510 | 41 | ≤0.5 |
| Acetone | ≤0.5 | ≤0.5 | ≤0.5 |
| Butanone | ≤0.5 | ≤0.5 | ≤0.5 |
| Acetic acid | ≤0.5 | ≤0.5 | ≤0.5 |
The toluene methylation product that removes reactor, water-and-oil separator and stripping tower through oxygenatedchemicals, the content of acetaldehyde, methyl alcohol, acetone, butanone and acetic acid is all reduced to below 0.5wtppm.
[embodiment 2]
In reactor, load respectively Benzylation catalyzer and oxygenatedchemicals Removal of catalyst from top to bottom, the mass ratio of upper and lower bed is 1:4.Toluene: methyl alcohol (mol ratio)=3:1, benzene weight space velocity 2 hours
-1, 400 ℃ of temperature of reaction, reaction pressure 1MPa; Liquid product is after water-and-oil separator separation, and oil phase enters stripping tower and carries out light constituent separation, 124 ℃ of stripping tower top temperatures, stripping tower pressure on top surface 0.51MPa.As shown in schematic flow sheet, stream I, the oxygenatedchemicals analytical resultss such as the acetaldehyde in II and III, methyl alcohol, acetone, butanone and acetic acid are as shown in table 2 below.
Table 2
| ? | Stream I (wtppm) | Stream I I (wtppm) | Stream I II (wtppm) |
| Acetaldehyde | 15 | 13 | ≤0.5 |
| Methyl alcohol | 806 | 65 | ≤0.5 |
| Acetone | ≤0.5 | ≤0.5 | ≤0.5 |
| Butanone | ≤0.5 | ≤0.5 | ≤0.5 |
| Acetic acid | ≤0.5 | ≤0.5 | ≤0.5 |
The toluene methylation product that removes reactor, water-and-oil separator and stripping tower through oxygenatedchemicals, the content of acetaldehyde, methyl alcohol, acetone, butanone and acetic acid is all reduced to below 0.5wtppm.
[embodiment 3]
In reactor, load respectively methylbenzene selective methylation catalyst and oxygenatedchemicals Removal of catalyst from top to bottom, the mass ratio of upper and lower bed is 1:1.Toluene: methyl alcohol (mol ratio)=2:1, toluene by weight air speed 4 hours
-1, temperature of reaction 450
oc, reaction pressure 0.6MPa; Liquid product is after water-and-oil separator separation, and oil phase enters stripping tower and carries out light constituent separation, 120 ℃ of stripping tower top temperatures, stripping tower pressure on top surface 0.50MPa.As shown in schematic flow sheet, stream I, II, the oxygenatedchemicals analytical resultss such as the acetaldehyde in III and IV, methyl alcohol, acetone, butanone and acetic acid are as shown in table 3 below.
Table 3
| ? | Stream I (wtppm) | Stream I I (wtppm) | Stream I II (wtppm) |
| Acetaldehyde | 9 | 7 | ≤0.5 |
| Methyl alcohol | 106 | 18 | ≤0.5 |
| Acetone | ≤0.5 | ≤0.5 | ≤0.5 |
| Butanone | ≤0.5 | ≤0.5 | ≤0.5 |
| Acetic acid | ≤0.5 | ≤0.5 | ≤0.5 |
The toluene methylation product that removes reactor, water-and-oil separator and stripping tower through oxygenatedchemicals, the content of acetaldehyde, methyl alcohol, acetone, butanone and acetic acid is all reduced to below 0.5wtppm.
Claims (9)
1. an aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity, comprises the following steps:
A) at 350 ℃ ~ 480 ℃ of temperature, weight space velocity, it is 0.5 ~ 5 hour
-1, pressure is under 0.1 ~ 3MPa condition, benzene or toluene and methanol mixed raw material, by composite bed reactor, contacts with composite catalyst, resultant of reaction flows I;
B) stream I through heat exchange and cooling after, enter water-and-oil separator, the lower floor's by-product water after separation is disposed to out-of-bounds, upper oil phase overflow is to downstream, as stream I I;
C) stream I I enters stripping tower, separated C
6light constituent drained into out-of-bounds by tower top in the past, the C that tower reactor obtains
6and later heavy constituent, as stream I II, be incorporated in Aromatic Hydrocarbon United Plant, isolate p-Xylol;
Wherein, composite catalyst is methylation catalyst and oxygenatedchemicals Removal of catalyst.
2. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, is characterized in that the weight content of alcohols, ketone, aldehydes and carboxylic-acid oxygenatedchemicals in stream I II is all less than 0.5ppm.
3. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, is characterized in that ketone in stream I I and the weight content of carboxylic-acid oxygenatedchemicals are all less than 0.5ppm.
4. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, loads respectively methylation catalyst and oxygenatedchemicals Removal of catalyst from top to bottom in composite bed reactor, and both weight ratios are 1:9 ~ 9:1.
5. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, the tower top temperature that it is characterized in that stripping tower is 110 ~ 130 ℃, tower top pressure is 0.4 ~ 0.6MPa.
6. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, is characterized in that in step c), separated C
6light constituent comprised C in the past
1~ C
5alkane, alkene, and acetaldehyde and methyl alcohol oxygenatedchemicals.
7. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, is characterized in that in step c) the C that tower reactor obtains
6and heavy constituent comprises C later
6~ C
14aromatic hydrocarbons, alkane and alkene.
8. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, it is characterized in that methylation catalyst, in weight percentage, comprise following component: (a) at least one in 40% ~ 90% ZSM-5 zeolite or MCM-22 zeolite molecular sieve; (b) 0.01 ~ 5.0% MgO, La
2o
3, CaO and SiO
2in at least one; (c) 15 ~ 80% silicon oxide or alumina binder.
9. the aromatic hydrocarbons methanol alkylation method that removes oxygenatedchemicals impurity according to claim 1, is characterized in that
Oxygenatedchemicals Removal of catalyst, in weight percentage, comprises following component: (a) 10% ~ 95% La
2o
3, ZnO, ZrO
2, CaO, MgO, TiO
2and Cr
2o
3in at least one; (b) 5 ~ 90% silicon oxide or alumina binder.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608794A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for removing oxygen-containing organic compound impurity from aromatic hydrocarbons material flow |
| CN111635780A (en) * | 2020-06-04 | 2020-09-08 | 浙江大学 | Method for producing BTX (benzene-toluene-xylene) from coal tar |
| CN112521244A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and device for reducing by-products in circulating hydrogen in hydro-static bed reaction system |
| CN112521243A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and system for long-period running toluene-methanol methylation reaction |
| CN112619696A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Composite bed hydrocracking catalyst system and preparation method and application thereof |
| CN114426456A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Combined process for benzene and heavy aromatic transalkylation and toluene methylation |
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|---|---|---|---|---|
| CN106608794A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for removing oxygen-containing organic compound impurity from aromatic hydrocarbons material flow |
| CN106608794B (en) * | 2015-10-22 | 2019-10-11 | 中国石油化工股份有限公司 | The method of oxygen-containing organic compound impurity in Arene removal logistics |
| CN112521244A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and device for reducing by-products in circulating hydrogen in hydro-static bed reaction system |
| CN112521243A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Method and system for long-period running toluene-methanol methylation reaction |
| CN112521243B (en) * | 2019-09-19 | 2023-07-04 | 中国石油化工股份有限公司 | Method and system for long-period running toluene methanol methylation reaction |
| CN112521244B (en) * | 2019-09-19 | 2023-08-04 | 中国石油化工股份有限公司 | Method and device for reducing byproducts in circulating hydrogen in hydrogen-contacting fixed bed reaction system |
| CN112619696A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Composite bed hydrocracking catalyst system and preparation method and application thereof |
| CN112619696B (en) * | 2019-10-09 | 2022-12-09 | 中国石油化工股份有限公司 | Composite bed hydrocracking catalyst system and preparation method and application thereof |
| CN111635780A (en) * | 2020-06-04 | 2020-09-08 | 浙江大学 | Method for producing BTX (benzene-toluene-xylene) from coal tar |
| CN111635780B (en) * | 2020-06-04 | 2021-05-14 | 浙江大学 | Method for producing BTX (benzene-toluene-xylene) from coal tar |
| CN114426456A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Combined process for benzene and heavy aromatic transalkylation and toluene methylation |
| CN114426456B (en) * | 2020-10-10 | 2024-08-30 | 中国石油化工股份有限公司 | Combined process for benzene and heavy aromatic transalkylation and toluene methylation |
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