CN103664492A - Alkylation method for methylbenzene and methyl alcohol - Google Patents
Alkylation method for methylbenzene and methyl alcohol Download PDFInfo
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- CN103664492A CN103664492A CN201210325137.5A CN201210325137A CN103664492A CN 103664492 A CN103664492 A CN 103664492A CN 201210325137 A CN201210325137 A CN 201210325137A CN 103664492 A CN103664492 A CN 103664492A
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 86
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 22
- 230000029936 alkylation Effects 0.000 title claims abstract description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 42
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 238000007069 methylation reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 claims description 18
- 150000002576 ketones Chemical class 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000011987 methylation Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 2
- 150000003738 xylenes Chemical class 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920004935 Trevira® Polymers 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- -1 carbonium ion Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FHYUCVWDMABHHH-UHFFFAOYSA-N toluene;1,2-xylene Chemical compound CC1=CC=CC=C1.CC1=CC=CC=C1C FHYUCVWDMABHHH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an alkylation method for methylbenzene and methyl alcohol, which mainly solves the problem that arene products comprise oxygenated chemical impurities and the byproduct wastewater is meta-acidic in the prior art. The alkylation method combines methylbenzene methylation and removal of oxygenated chemicals, and comprises the steps of a) enabling mixed raw material of methylbenzene and methyl alcohol to contact with a catalyst in a methylation reactor, and reacting so as to produce a material flow I; b) allowing the material flow I to enter a downstream reactor for removing oxygenated chemicals, and reacting so as to produce a material flow II; c) carrying out heat exchange and cooling on the material flow II, then feeding into an oil-water separator, discharging byproduct water at the lower layer out, and allowing an oil phase at the upper layer to overflow downstream so as to be taken as a material flow III; and d) allowing the material flow III to enter a steam stripping tower, discharging light components before benzene out from the top of the tower, taking heavy components after benzene obtained by a tower kettle as a material flow IV, adding into an aromatics integrated unit, and separating paraxylene out. The alkylation method can well solve the problem and can be used in industrial production for producing mixed xylenes or paraxylene through alkylation reaction of methylbenzene and methyl alcohol.
Description
Technical field
The present invention relates to a kind of alkylation of toluene methanol method of eliminating oxygenatedchemicals impact, particularly about a kind of can be by the method for the by-product alcohols in methylbenzene methanol methylation reaction product, aldehydes, ketone and carboxylic-acid Impurity removal.
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 benzene and dimethylbenzene, therefore causes toluene relative surplus; 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 is changed into greatest extent to market requirement p-Xylol vigorous, high added value is 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 and methanol alkylation are the p-Xylol new process of production that economic benefit is larger, can improve substantially toluene 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.This 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.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; Safely, the carboxylic-acid impurity such as by-product acetic acid are dissolved in by-product water slave unit, can heavy corrosion reactor downstream have the Location Detection of Medium Transportation Pipeline of liquid phase water appearance and relevant tower.
Summary of the invention
Technical problem to be solved by this invention is in aromatic hydrocarbon product, to contain oxygenatedchemicals impurity, and the problem of byproduct wastewater slant acidity provides a kind of new alkylation of toluene methanol method.The method, for the methylbenzene methanol industrial production that methylates, has aromatic hydrocarbon product quality and is not subject to the advantages such as oxygenatedchemicals impurity effect, byproduct wastewater anacidity corrodibility.
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 alkylation of toluene methanol method, 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, toluene contacts with catalyzer in methylation reaction device with methanol mixed raw material, after reaction, generate stream I, wherein catalyzer used by weight percentage, comprises following component: (a) at least one in 40wt% ~ 90wt% ZSM-5 zeolite or MCM-22 molecular sieve; (b) at least one in the lanthanide series rare-earth elements of 0.01wt% ~ 5.0wt%; (c) binding agent of 15wt% ~ 80wt%;
B) stream I enters downstream oxygenatedchemicals and removes reactor, and weight space velocity is 0.5 ~ 10 hour
-1, after reaction, generate logistics II;
C) stream I I through heat exchange and cooling after enter water-and-oil separator, lower floor's by-product water is disposed to out-of-bounds, upper oil phase overflow is to downstream, as stream I II;
D) stream I II enters stripping tower, and before benzene, light constituent drains into out-of-bounds by tower top, and heavy constituent after tower reactor benzene, as stream I V, is incorporated in Aromatic Hydrocarbon United Plant, isolates p-Xylol.
In technique scheme, preferred technical scheme, contains alcohols, ketone, aldehydes and carboxylic-acid oxygenatedchemicals in stream I, and the weight content of the alcohols in stream I V, ketone, aldehydes and carboxylic-acid oxygenatedchemicals is all less than 0.5ppm; The weight content of the ketone in stream I II and carboxylic-acid oxygenatedchemicals is all less than 0.5ppm; Be disposed to the pH value preferable range of by-product water out-of-bounds for being greater than 5.0; The tower top temperature preferable range of stripping tower is 110 ~ 130 ℃, and tower top pressure preferable range is 0.4 ~ 0.6MPa.
Preferred technical scheme, before benzene, light constituent is C
1~ C
5alkane, alkene, and the oxygenatedchemicals such as acetaldehyde, methyl alcohol, preferred technical scheme, tower reactor benzene later restructuring is divided into C
6~ C
14aromatic hydrocarbons, alkane and alkene.Preferred technical scheme, in catalyzer, lanthanide series rare-earth elements is selected from least one in lanthanum, cerium, praseodymium, neodymium, and binding agent is selected from least one in silicon oxide, aluminum oxide, kaolin.Preferred technical scheme, catalyzer used by weight percentage, comprises following component: (a) 40wt% ~ 90wt% ZSM-5 zeolite and MCM-22 molecular sieve, wherein the weight ratio of two kinds of molecular sieves is 0.1 ~ 10:1; (b) at least one in the lanthanide series rare-earth elements of 0.01wt% ~ 5.0wt%; (c) binding agent of 15wt% ~ 80wt%.Preferred technical scheme, it is 1 ~ 8 hour that stream I enters the weight space velocity that downstream oxygenatedchemicals removes reactor
-1.
Using toluene 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 reactor, 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; The carboxylic acid dissolving in by-product water is completely converted, and aqueous pH values guarantees more than 5.0, has eliminated the risk to pipeline and tower corrosion.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 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 alkylation of toluene methanol process flow diagram.
In Fig. 1,1 is methylation reaction device, and 2 for oxygenatedchemicals removes reactor, and 3 is water-and-oil separator, and 4 is stripping tower.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Method for preparing catalyst: at least one in 40wt% ~ 90wt% ZSM-5 zeolite or MCM-22 zeolite molecular sieve and γ-Al of 15wt% ~ 80wt%
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 loads at least one in the lanthanide series rare-earth elements of 0.01wt% ~ 5.0wt% in catalyst body, to obtain methylation catalyst.
In methylation reaction device, catalyzer is 3wt%La
2o
3/ 60wt%MCM-22/37wt% γ-Al
2o
3, toluene: methyl alcohol (mol ratio)=2:1, toluene by weight air speed 1 hour
-1, temperature of reaction 370
oc, reaction pressure 0.5MPa; The factor of considering methylation reaction heat release, oxygenatedchemicals removes reactor reaction temperature 400
oc, reaction pressure is still 0.5Mpa, aromatic hydrocarbons weight of material air speed is 4 hours
-1; Liquid product is after water-and-oil separator separation, and oil phase enters stripping tower and carries out light constituent separation, stripping tower top temperature 118
oc, stripping tower pressure on top surface 0.45MPa.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 1 below:
Table 1
| ? | Stream I (wtppm) | Stream I I (wtppm) | Stream I II (wtppm) | Stream I V (wtppm) |
| Acetaldehyde | 5 | 9 | 7 | ≤0.5 |
| Methyl alcohol | 560 | 520 | 45 | ≤0.5 |
| Acetone | 42 | ≤0.5 | ≤0.5 | ≤0.5 |
| Butanone | 18 | ≤0.5 | ≤0.5 | ≤0.5 |
| Acetic acid | 89 | ≤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; The byproduct wastewater pH value of water-and-oil separator bottom discharge is 5.3.
[embodiment 2]
In methylation reaction device, catalyzer is 5wt%
2ceO
2/ 50wt%ZSM-5/45wt% γ-Al
2o
3, toluene: methyl alcohol (mol ratio)=3:1, toluene by weight air speed 4 hours
-1, temperature of reaction 440
oc, reaction pressure 3MPa; The factor of considering methylation reaction heat release, oxygenatedchemicals removes reactor reaction temperature 460
oc, reaction pressure is still 3Mpa, aromatic hydrocarbons weight of material air speed is 6 hours
-1; Liquid product is after water-and-oil separator separation, and oil phase enters stripping tower and carries out light constituent separation, stripping tower top temperature 124
oc, stripping tower pressure on top surface 0.51MPa.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 2 below:
Table 2
| ? | Stream I (wtppm) | Stream I I (wtppm) | Stream I II (wtppm) | Stream I V (wtppm) |
| |
4 | 6 | 4 | ≤0.5 |
| Methyl alcohol | 123 | 104 | 12 | ≤0.5 |
| Acetone | 62 | ≤0.5 | ≤0.5 | ≤0.5 |
| Butanone | 25 | ≤0.5 | ≤0.5 | ≤0.5 |
| Acetic acid | 6 | ≤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; The byproduct wastewater pH value of water-and-oil separator bottom discharge is 5.6.
[embodiment 3]
In methylation reaction device, catalyzer is 2wt%MgO/4wt%
2ceO
2/ 70wt%ZSM-5/ 24wt% γ-Al
2o
3, toluene: methyl alcohol (mol ratio)=2:1, toluene by weight air speed 4 hours
-1, temperature of reaction 450
oc, reaction pressure 0.6MPa; The factor of considering methylation reaction heat release, oxygenatedchemicals removes reactor reaction temperature 470
oc, reaction pressure is still 0.6Mpa, aromatic hydrocarbons weight of material air speed is 8 hours
-1; Liquid product is after water-and-oil separator separation, and oil phase enters stripping tower and carries out light constituent separation, stripping tower top temperature 120
oc, 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) | Stream I V (wtppm) |
| |
2 | 6 | 3 | ≤0.5 |
| Methyl alcohol | 86 | 78 | 7 | ≤0.5 |
| Acetone | 75 | ≤0.5 | ≤0.5 | ≤0.5 |
| Butanone | 30 | ≤0.5 | ≤0.5 | ≤0.5 |
| Acetic acid | 5 | ≤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; The byproduct wastewater pH value of water-and-oil separator bottom discharge is 5.5.
Claims (10)
1. an alkylation of toluene methanol method, 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, toluene contacts with catalyzer in methylation reaction device with methanol mixed raw material, after reaction, generate stream I, wherein catalyzer used by weight percentage, comprises following component: (a) at least one in 40wt% ~ 90wt% ZSM-5 zeolite or MCM-22 molecular sieve; (b) at least one in the lanthanide series rare-earth elements of 0.01wt% ~ 5.0wt%; (c) binding agent of 15wt% ~ 80wt%;
B) stream I enters downstream oxygenatedchemicals and removes reactor, and weight space velocity is 0.5 ~ 10 hour
-1, after reaction, generate logistics II;
C) stream I I through heat exchange and cooling after enter water-and-oil separator, lower floor's by-product water is disposed to out-of-bounds, upper oil phase overflow is to downstream, as stream I II;
D) stream I II enters stripping tower, and the light constituent before benzene drains into out-of-bounds by tower top, and the later heavy constituent of benzene that tower reactor obtains, as stream I V, is incorporated in Aromatic Hydrocarbon United Plant, isolates p-Xylol.
2. alkylation of toluene methanol method according to claim 1, it is characterized in that containing alcohols, ketone, aldehydes and carboxylic-acid oxygenatedchemicals in stream I, the weight content of the alcohols in stream I V, ketone, aldehydes and carboxylic-acid oxygenatedchemicals is all less than 0.5ppm.
3. alkylation of toluene methanol method according to claim 1, is characterized in that ketone in stream I II and the weight content of carboxylic-acid oxygenatedchemicals are all less than 0.5ppm.
4. alkylation of toluene methanol method according to claim 1, the pH value that it is characterized in that being disposed to by-product water is out-of-bounds greater than 5.0.
5. alkylation of toluene methanol method 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. alkylation of toluene methanol method according to claim 1, is characterized in that in step d), the light constituent before benzene is C
1~ C
5alkane, alkene, and acetaldehyde, methyl alcohol oxygenatedchemicals.
7. alkylation of toluene methanol method according to claim 1, is characterized in that the later restructuring of benzene that in step d), tower reactor obtains is divided into C
6~ C
14aromatic hydrocarbons, alkane and alkene.
8. alkylation of toluene methanol method according to claim 1, is characterized in that, in catalyzer, lanthanide series rare-earth elements is selected from least one in lanthanum, cerium, praseodymium, neodymium, and binding agent is selected from least one in silicon oxide, aluminum oxide, kaolin.
9. alkylation of toluene methanol method according to claim 8, it is characterized in that, catalyzer used by weight percentage, comprises following component: (a) 40wt% ~ 90wt% ZSM-5 zeolite and MCM-22 molecular sieve, and wherein the weight ratio of two kinds of molecular sieves is 0.1 ~ 10:1; (b) at least one in the lanthanide series rare-earth elements of 0.01wt% ~ 5.0wt%; (c) binding agent of 15wt% ~ 80wt%.
10. alkylation of toluene methanol method according to claim 1, is characterized in that it is 1 ~ 8 hour that stream I enters the weight space velocity that downstream oxygenatedchemicals removes reactor
-1.
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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 |
| WO2019125831A1 (en) * | 2017-12-22 | 2019-06-27 | Exxonmobil Chemical Patents Inc. | Catalysts for producing paraxylene by methylation of benzene and/or toluene |
| 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 |
| CN112661589A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Method and system for producing p-xylene from toluene |
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| JP2022172200A (en) * | 2017-12-22 | 2022-11-15 | エクソンモービル・ケミカル・パテンツ・インク | Catalysts for producing paraxylene by methylation of benzene and/or toluene |
| 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 |
| CN112661589A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Method and system for producing p-xylene from toluene |
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