CN101823929B - System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether - Google Patents

System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether Download PDF

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CN101823929B
CN101823929B CN2010101469155A CN201010146915A CN101823929B CN 101823929 B CN101823929 B CN 101823929B CN 2010101469155 A CN2010101469155 A CN 2010101469155A CN 201010146915 A CN201010146915 A CN 201010146915A CN 101823929 B CN101823929 B CN 101823929B
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separated
aromatic hydrocarbons
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gas
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CN101823929A (en
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魏飞
骞伟中
汤效平
黄晓凡
杨伟
恽忪
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Tsinghua University
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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 system and a process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether and belongs to the technical field of aromatic hydrocarbon production. The methanol or the dimethyl ether serving as a raw material firstly reacts in an aromatization reactor; a reaction product is separated; H2, methane, mixed C8 aromatic hydrocarbon and partial C9s + hydrocarbons serving as products are output from the system; and C2+ non-aromatic hydrocarbon and aromatic hydrocarbons except the mixed C8 aromatic hydrocarbon and the partial C9s + hydrocarbons are take as a circular material flow and return to corresponding reactors for further aromatization reaction. By separating and recycling the product obtained in the process of aromizing the methanol or the dimethyl ether, the system and the process improve the yield and selectivity of the aromatic hydrocarbon; and moreover, the process is flexible, and target products can be changed according to market demands.

Description

The system of a kind of methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon and technique
Technical field
The present invention relates to a kind of system and technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon, belong to the Aromatics Production Technology field.
Background technology
Aromatic hydrocarbons refers to contain the hydro carbons of phenyl ring, and the triphen in aromatic hydrocarbons (benzene, toluene and dimethylbenzene also claim BTX) is organic chemical industry's basic material, is widely used in synthon, synthetic resins, synthetic rubber and various fine chemicals.The source of aromatic hydrocarbons is mainly by catalytic reforming process, naphtha cracking technique, low-carbon (LC) aromatization of hydrocarbons and aromatic hydrocarbons conversion process in petrochemical industry at present; Small part is only arranged from the coal tar in Coal Chemical Industry, rely on larger to oil.Also cause concern with coal-based methanol, dme aromatics process processed in recent years, but also be in development still there is no industrialized unit fortune dress.
China belongs to the country of petroleum resources shortage, the oil that annual consumption at present is 3 to 400,000,000 tons, and throughput can only maintain 1.8 hundred million tons of left and right, causes thus China's oil import interdependency to strengthen year by year.On the other hand, rich coal resources in China, in recent years, burning hot situation appearred in China Coal Chemical Industry, the various places various Coal Chemical Engineering Projects that start one after another.As comparatively ripe coal chemical technology, coal-based synthesizing methanol, dme become the optimumitem of most coal chemical industry enterprises.Design and construction situation for China's methyl alcohol, dme project, although various statistical information there are differences, but consistent conclusion is within the following short period, the production capacity of methyl alcohol, dme will far surpass actual demand, by 2010, after first large-scale methyl alcohol, dme device capbility discharge, the appearance of methyl alcohol, dme production capacity surplus situation will be inevitable.In view of the growing aromatic hydrocarbons demand of present China, actively develop the technical study by coal-based methanol, dme preparing aromatic hydrocarbon, not only opened up a technological line for coal/conversion of natural gas aromatic hydrocarbons processed, for China's methyl alcohol, dme find an outlet that reality is feasible; And satisfying the market reduces aromatic hydrocarbons production to the degree of dependence of petroleum to the demand of aromatic hydrocarbons.
Obtain aromatic hydrocarbons by methyl alcohol, dme, see at first MTG (the Methanol to Gasoline) technology of U.S. Mobil company exploitation, 20 century 70 Mobil companies have developed the ZSM-5 zeolite catalyzer, make methyl alcohol, dimethyl ether conversion become stop bracket gasoline, its product contains 30% aromatic hydrocarbons in forming.1985, Mobil company is in the US Patent No. P4590321 of its application, announced first the result of study of methyl alcohol, dimethyl ether conversion aromatic hydrocarbons processed, this research adopt phosphorous for the ZSM-5 molecular sieve of 2.7wt% be catalyzer, temperature of reaction is 400～450 ℃, methyl alcohol, dme weight space velocity 1.3h -1The result demonstration, the ZSM-5 catalyzer that process phosphorus is modified is at higher hydrocarbon (the ZSM-5 molecular sieve catalyzer that all is better than non-modified aspect C5～selectivity C9), a plurality of indexs such as selectivity of aromatic hydrocarbons.But its primary product is still the low-carbon (LC) hydro carbons of C1～C4, and total aromaticity content is not high.1986, Mobil company applied for US Patent No. P4686312, has announced a kind of multistage reaction process that the low-carbon oxygen-containing compound is converted into the product that is rich in aromatic hydrocarbons; At first methyl alcohol, dme are converted into take the preparing low carbon hydrocarbons class as main product in the first paragraph reactor, aromatization further occurs in these products under the effect of catalyzer in second stage reactor, and obtain to be rich in the product of aromatic hydrocarbons (benzene,toluene,xylene and heavy arene).2002, the United States Patent (USP) Pub.No.US2002/0099249A1 of Chevron Phillips company announced and has a kind ofly adopted two kinds of molecular sieve catalysts by the set out technology of combination producing aromatic hydrocarbons of methyl alcohol, dme; Wherein the first catalyzer is the sial phosphorus molecular sieve, and the second catalyzer is to contain metallic zinc and from the molecular sieve catalyst of IIIA family or group vib element.Adopt above-mentioned two kinds of molecular sieve catalysts, and make up in a certain way, this invention has obtained a kind of effective ways of methyl alcohol, dimethyl ether conversion preparing aromatic hydrocarbon, particularly BTX.
Methyl alcohol, dme aromatization technology mainly contain fixed bed methyl alcohol, dme aromatic hydrocarbons processed (MTA) technology of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences and methyl alcohol, dme aromatic hydrocarbons processed (FMTA) technology of Tsing-Hua University at home.The Shanxi coalification patent CN 1880288A in to adopt methyl alcohol, dme be raw material, modified ZSM-5 is catalyzer, be take aromatic hydrocarbons as main product with methyl alcohol, dimethyl ether conversion, through refrigerated separation, gas-phase product lower carbon number hydrocarbons and liquid product are separated, liquid product is through extracting and separating, obtain aromatic hydrocarbons and non-aromatics, the further aromizing of low-carbon (LC) hydro carbons.Therefore but in the alkane aromatization process, hydrogen has a strong impact on aromizing productive rate and the selectivity of alkane, and the gas-phase product of methyl alcohol, dme aromizing directly being entered the technique that the low-carbon (LC) aromatizing reaction of hydrocarbons carries out aromatization is not optimum process.The devices and methods therefor of a kind of methyl alcohol, the regeneration of dme aromatization process catalyzer successive reaction is disclosed in the patent CN 101244969A of Tsing-Hua University, adopting fluidization is aromatic hydrocarbons with the hydrocarbon conversion of methyl alcohol, dme or C1～C2, but this patent has only been considered the main reaction of methyl alcohol, dme aromizing, do not relate to the utilization of recycle stock, so the total arenes yield of methyl alcohol, dme aromatization process is on the low side.
By upper surface analysis as can be known, up to the present, the research of methyl alcohol, dme aromizing mainly concentrates on the improvement to catalyzer, except the Shanxi coalification the product of methyl alcohol, dme aromatization process has been carried out simple gas-liquid separation, still do not consider methyl alcohol, dme aromatization process product separation and by product such as low-carbon (LC) hydro carbons etc. the recycle mode, be fit to methyl alcohol, the system of dme aromizing and the report of technique of suitability for industrialized production.
Summary of the invention
The present invention is directed to and do not take into full account methyl alcohol, dme aromatization process product separation and the methyl alcohol of by-product recovery utilization and the present situation of dme technology of aromatization at present, a kind of methyl alcohol of product separation and by product recycle, system and technique of dme preparing aromatic hydrocarbon of comprising is provided, by the separation of product and the recycle of by product, thus yield and the selectivity of raising target product aromatic hydrocarbons.
Technical scheme of the present invention has following several:
The first technical scheme provided by the invention is: a kind of system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon is characterized in that described system comprises:
A. aromatization reactor is used for methyl alcohol or dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator, being used for to be gas-phase product, oil-phase product and water from reactor 1 product separation out;
C. a low carbon olefin hydrocarbon reactor, be used for being converted into from the low-carbon alkene of solution-air-gas-phase product that the liquid triphase separator is separated take aromatic hydrocarbons as main product;
D. gas-liquid separator, be used for will from low carbon olefin hydrocarbon reactor 2 generate take aromatic hydrocarbons as main product separation as gas-phase product and oil-phase product;
E. a gas phase separator, be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that gas-liquid separator is separated 2+ low-carbon (LC) hydrocarbon mixture;
F. a hydrogen methane separation device, be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator is separated;
G. low-carbon (LC) hydro carbons reactor is used for the C that will separate from gas phase separator 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator to be separated;
H. aromatic hydrocarbons-non-aromatics separator, be used for the oil-phase product that solution-air-liquid triphase separator and gas-liquid separator are separated further is separated into aromatic component and non-aromatic component, the non-aromatics product of separating enters low carbon olefin hydrocarbon reactor and participates in reaction;
I. an aromatic hydrocarbons separator 10, be used for the aromatic component that aromatic hydrocarbons-the non-aromatics separator is separated is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic component;
J. aromatic disproportion reactor is used for benzene, toluene and the C that will separate from the aromatic hydrocarbons separator 9+ aromatic hydrocarbons is converted into take mixed C 8 aromatic hydrocarbons as main product by disproportionation reaction, and this product enters solution-air-liquid triphase separator to be separated.
Employing is characterized in that as a kind of technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon of system as described in the first technical scheme, and this technique is carried out as follows:
A. methyl alcohol or dme enter aromatization reactor, participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator, and water is discharged system;
B. the gas-phase product by solution-air-the liquid triphase separator is separated described in step a enters low carbon olefin hydrocarbon reactor and participates in reaction, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～15hr -1Reacted product enters gas-liquid separator and is separated into gas-phase product and oil-phase product after condensation, enter gas phase separator by gas-liquid separator gas-phase product out and be separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture enters aromatic hydrocarbons-non-aromatics separator by gas-liquid separator liquid product out;
C. the hydrogen methane mixture of being separated by gas phase separator described in step b enters hydrogen methane separation device, is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator to be separated;
E. the oil-phase product of being separated by solution-air-liquid triphase separator and gas-liquid separator enters aromatic hydrocarbons-non-aromatics separator, is separated into non-aromatic component and aromatic component, and non-aromatic component returns to low carbon olefin hydrocarbon reactor and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-the non-aromatics separator is separated described in step e enters the aromatic hydrocarbons separator and is separated into benzene and toluene mixture, and mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons, benzene and toluene mixture and part C 9+ aromatic hydrocarbons enters disproportionation reactor 4 and reacts, and temperature of reaction is 400～600 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～20hr -1Mixed C 8 aromatic hydrocarbons and residue C 9+ discharge system as product; Or the aromatic component by aromatic hydrocarbons-non-aromatics separator 9 is separated described in step e enters the aromatic hydrocarbons separator and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons is discharged system as product respectively.
The second technical scheme provided by the invention is: a kind of system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon is characterized in that described system comprises:
A. aromatization reactor is used for methyl alcohol or dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator, being used for to be gas-phase product, oil-phase product and water from aromatization reactor product separation out;
C. a gas phase separator, be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that solution-air-liquid/gas separator is separated 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device, be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator is separated;
E. low-carbon (LC) hydro carbons reactor is used for the C that will separate from gas phase separator 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator to be separated;
F. an aromatic hydrocarbons-non-aromatics separator, be used for the oil-phase product that solution-air-the liquid triphase separator is separated further is separated into aromatic component and non-aromatic component, and the non-aromatics product of separating enters low-carbon (LC) hydro carbons reactor and participates in reaction;
G. an aromatic hydrocarbons separator, be used for the aromatic component that aromatic hydrocarbons-the non-aromatics separator is separated is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic component;
H. aromatic disproportion reactor 4 is used for benzene, toluene and the C that will separate from the aromatic hydrocarbons separator 9+ aromatic hydrocarbons is converted into take mixed C 8 aromatic hydrocarbons as main product by disproportionation reaction, and this product enters solution-air-liquid triphase separator to be separated.
Employing is characterized in that as a kind of technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon of system as described in the second technical scheme, and this technique is carried out as follows:
A. methyl alcohol or dme enter aromatization reactor, participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator, and water is discharged system;
B. the gas-phase product by solution-air-the liquid triphase separator is separated described in step a enters gas phase separator and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
C. the hydrogen methane mixture of being separated by gas phase separator described in step b enters hydrogen methane separation device, is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator to be separated;
E. enter aromatic hydrocarbons-non-aromatics separator by the oil-phase product that solution-air-the liquid triphase separator is separated, be separated into non-aromatic component and aromatic component, non-aromatic component returns to low-carbon (LC) hydro carbons reactor and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-the non-aromatics separator is separated described in step e enters the aromatic hydrocarbons separator and is separated into benzene and toluene mixture, and mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons, benzene and toluene mixture and part C 9+ aromatic hydrocarbons enters disproportionation reactor and reacts, and temperature of reaction is 400～600 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～20hr -1Mixed C 8 aromatic hydrocarbons and residue C9+ discharge system as product; Or the aromatic component by aromatic hydrocarbons-the non-aromatics separator is separated described in step e enters the aromatic hydrocarbons separator and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons is discharged system as product respectively.
The third technical scheme provided by the invention is: a kind of system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon is characterized in that described system comprises:
A. aromatization reactor is used for methyl alcohol or dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator, being used for to be gas-phase product, oil-phase product and water from aromatization reactor product separation out;
C. a gas phase separator, be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that solution-air-liquid/gas separator is separated 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device, be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator is separated;
E. low-carbon (LC) hydro carbons reactor is used for the C that will separate from gas phase separator 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator to be separated;
F. an aromatic hydrocarbons-non-aromatics separator, be used for the oil-phase product that solution-air-the liquid triphase separator is separated further is separated into aromatic component and non-aromatic component, and the non-aromatics product of separating enters low-carbon (LC) hydro carbons reactor and participates in reaction;
G. an aromatic hydrocarbons separator, be used for the aromatic component that aromatic hydrocarbons-the non-aromatics separator is separated is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic component, isolated benzene, toluene and C 9+ aromatic component returns to methyl alcohol or dme aromatization reactor 1 participates in reaction, and perhaps as the output of products system, isolated mixed C 8 aromatic hydrocarbons are as the output of products system.
Employing is characterized in that as a kind of technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon of system as described in the third technical scheme, and this technique is carried out as follows:
A. methyl alcohol or dme enter aromatization reactor 1, participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator, and water is discharged system;
B. the gas-phase product by solution-air-the liquid triphase separator is separated described in step a enters gas phase separator and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
C. the hydrogen methane mixture of being separated by gas phase separator described in step b enters hydrogen methane separation device, is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator 7 described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator to be separated;
E. enter aromatic hydrocarbons-non-aromatics separator by the oil-phase product that solution-air-the liquid triphase separator is separated, be separated into non-aromatic component and aromatic component, non-aromatic component returns to low-carbon (LC) hydro carbons reactor and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-the non-aromatics separator is separated described in step e enters the aromatic hydrocarbons separator and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons, isolated benzene, toluene and part C 9+ aromatic component returns to aromatization reactor and participates in reaction, perhaps as the output of products system, and isolated mixed C 8 aromatic hydrocarbons and residue C 9+ as the output of products system.
Described aromatization reactor, low carbon olefin hydrocarbon reactor, low-carbon (LC) hydro carbons reactor and aromatic disproportion reactor are fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or with the circulating fluid bed reactor of revivifier.
Described gas phase separator separates with hydrogen, methane the separation method that adopts with other low-carbon (LC) hydro carbons be absorption and desorption or pressure-variable adsorption or rectifying, when the method for described employing absorption and desorption is separated, its absorption agent employing gasoline, carbonatoms are 1～4 alcohols, ethers, ketone, or adopt that this technique self generates≤the liquid phase hydro carbons of C9, preferably this technique self generate≤the liquid phase hydro carbons of C9 is as low-carbon (LC) hydro carbons absorption agent.
The present invention compares with present existing methyl alcohol, dme technology of aromatization, have the following advantages and the high-lighting effect: 1. the present invention by separation and the by product recycle of product in methyl alcohol, dme aromatization process, has improved yield and the selectivity of target product aromatic hydrocarbons; 2. the present invention can select different flow processs according to the difference of target product, and technique is flexible; 3. hydrogen and low-carbon (LC) separation of hydrocarbons in the gas-phase product that methyl alcohol, dme aromizing is produced, hydrogen is as the output of products device, by adopting this technique, not only improved the economic benefit of process, and improved aromatics yield and the selectivity of low-carbon (LC) hydro carbons aromatization process; 4. in the gas-phase product sepn process, adopt this explained hereafter self generate≤the liquid phase hydro carbons of C9 with low-carbon (LC) hydro carbons and Hydrogen Separation, not only saves cost as absorption agent, also avoided the pollution of adopting external gasoline that native system is brought.
Description of drawings
Fig. 1 is system and the process flow sheet of methyl alcohol provided by the invention or dimethyl ether conversion preparing aromatic hydrocarbon the first embodiment.
Fig. 2 is system and the process flow sheet of methyl alcohol provided by the invention or dimethyl ether conversion preparing aromatic hydrocarbon the second embodiment.
Fig. 3 is system and the process flow sheet of methyl alcohol provided by the invention or the third embodiment of dimethyl ether conversion preparing aromatic hydrocarbon.
In figure: the 1-aromatization reactor; The 2-low carbon olefin hydrocarbon reactor; 3-low-carbon (LC) hydro carbons reactor; 4-aromatic disproportion reactor; 5-solution-air-liquid triphase separator; The 6-gas-liquid separator; The 7-gas phase separator; 8-hydrogen methane separation device; 9-aromatic hydrocarbons-non-aromatics separator; 10-aromatic hydrocarbons separator.
Embodiment
Be described further below in conjunction with system, technique and the embodiment of accompanying drawing to methyl alcohol provided by the present invention or dimethyl ether conversion preparing aromatic hydrocarbon.
The present invention is directed to the methyl alcohol that does not take into full account methyl alcohol, dme aromatization process product separation and by-product recovery at present and utilize, the present situation of dme technology of aromatization, a kind of methyl alcohol of product separation and by product recycle, system and technique of dme preparing aromatic hydrocarbon of comprising is provided, by the recycle of by product, improved yield and the selectivity of target product aromatic hydrocarbons.Below in conjunction with accompanying drawing and specific embodiment, several technical schemes provided by the present invention are further described:
Fig. 1 is system and the process flow sheet of methyl alcohol provided by the invention or dimethyl ether conversion preparing aromatic hydrocarbon the first embodiment, and described system comprises:
A. aromatization reactor 1 is used for methyl alcohol, dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator 5, being used for to be gas-phase product, oil-phase product and water from reactor 1 product separation out;
C. a low carbon olefin hydrocarbon reactor 2, be used for being converted into from the low-carbon alkene of solution-air-gas-phase product that liquid triphase separator 5 is separated take aromatic hydrocarbons as main product;
D. gas-liquid separator 6, be used for will from low carbon olefin hydrocarbon reactor 2 generate take aromatic hydrocarbons as main product separation as gas-phase product and oil-phase product;
E. a gas phase separator 7, be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that gas-liquid separator 6 is separated 2+ low-carbon (LC) hydrocarbon mixture;
F. a hydrogen methane separation device 8, be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator 7 is separated;
G. low-carbon (LC) hydro carbons reactor 3 is used for the C that will separate from gas phase separator 7 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator 5 to be separated;
H. aromatic hydrocarbons-non-aromatics separator 9, be used for the oil-phase product that solution-air-liquid triphase separator 5 and gas-liquid separator 6 are separated further is separated into aromatic component and non-aromatic component, the non-aromatics product of separating enters low carbon olefin hydrocarbon reactor 2 and participates in reaction;
I. an aromatic hydrocarbons separator 10, be used for the aromatic component that aromatic hydrocarbons-non-aromatics separator 9 is separated is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic component;
J. aromatic disproportion reactor 4 is used for benzene, toluene and the C that will separate from aromatic hydrocarbons separator 10 9+ aromatic hydrocarbons is converted into take mixed C 8 aromatic hydrocarbons as main product by disproportionation reaction, and this product enters solution-air-liquid triphase separator 5 to be separated.
A kind of said system that adopts is by the technique of methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon as shown in Figure 1, and this technique is carried out as follows:
A. methyl alcohol, dme enter aromatization reactor 1, participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator 5 and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator 9, and water is discharged system;
B. the gas-phase product by solution-air-liquid triphase separator 5 is separated described in step a enters low carbon olefin hydrocarbon reactor 2 and participates in reaction, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～15hr -1Reacted product enters gas-liquid separator 6 and is separated into gas-phase product and oil-phase product after condensation, enter gas phase separator 7 by gas-liquid separator 6 gas-phase product out and be separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture enters aromatic hydrocarbons-non-aromatics separator 9 by gas-liquid separator 6 liquid product out;
C. the hydrogen methane mixture of being separated by gas phase separator 7 described in step b enters hydrogen methane separation device 8, is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator 7 described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor 3 and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator 5 to be separated;
E. the oil-phase product of being separated by solution-air-liquid triphase separator 5 and gas-liquid separator 6 enters aromatic hydrocarbons-non-aromatics separator 9, is separated into non-aromatic component and aromatic component, and non-aromatic component returns to low carbon olefin hydrocarbon reactor 2 and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-non-aromatics separator 9 is separated described in step e enters aromatic hydrocarbons separator 10 and is separated into benzene and toluene mixture, and mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons, benzene and toluene mixture and part C 9+ aromatic hydrocarbons enters disproportionation reactor 4 and reacts, and temperature of reaction is 400～600 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～20hr -1 Mixed C 8 aromatic hydrocarbons and residue C 9+ discharge system as product; Or the aromatic component by aromatic hydrocarbons-non-aromatics separator 9 is separated described in step e enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons is discharged system as product respectively.
Fig. 2 is system and the process flow sheet of methyl alcohol provided by the invention or dimethyl ether conversion preparing aromatic hydrocarbon the second embodiment, and described system comprises:
A. aromatization reactor 1 is used for methyl alcohol, dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator 5, being used for to be gas-phase product, oil-phase product and water from reactor 1 product separation out;
C. a gas phase separator 7, be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that solution-air-liquid/gas separator 5 is separated 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device 8, be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator 7 is separated;
E. low-carbon (LC) hydro carbons reactor 3 is used for the C that will separate from gas phase separator 7 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator 5 to be separated;
F. an aromatic hydrocarbons-non-aromatics separator 9, be used for the oil-phase product that solution-air-liquid triphase separator 5 is separated further is separated into aromatic component and non-aromatic component, and the non-aromatics product of separating enters low-carbon (LC) hydro carbons reactor 3 and participates in reaction;
G. an aromatic hydrocarbons separator 10, be used for the aromatic component that aromatic hydrocarbons-non-aromatics separator 9 is separated is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic component;
H. aromatic disproportion reactor 4 is used for benzene, toluene and the C that will separate from aromatic hydrocarbons separator 10 9+ aromatic hydrocarbons is converted into take mixed C 8 aromatic hydrocarbons as main product by disproportionation reaction, and this product enters solution-air-liquid triphase separator 5 to be separated.
A kind of said system that adopts is by the technique of methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon as shown in Figure 2, and this technique is carried out as follows:
A. methyl alcohol, dme enter aromatization reactor 1, participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator 5 and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator 9, and water is discharged system;
B. the gas-phase product by solution-air-liquid triphase separator 5 is separated described in step a enters gas phase separator 7 and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
C. the hydrogen methane mixture of being separated by gas phase separator 7 described in step b enters hydrogen methane separation device 8, is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator 7 described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor 3 and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator 5 to be separated;
E. enter aromatic hydrocarbons-non-aromatics separator 9 by the oil-phase product that solution-air-liquid triphase separator 5 is separated, be separated into non-aromatic component and aromatic component, non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-non-aromatics separator 9 is separated described in step e enters aromatic hydrocarbons separator 10 and is separated into benzene and toluene mixture, and mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons, benzene and toluene mixture and part C 9+ aromatic hydrocarbons enters disproportionation reactor 4 and reacts, and temperature of reaction is 400～600 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～20hr -1 Mixed C 8 aromatic hydrocarbons and residue C9+ discharge system as product; Or the aromatic component by aromatic hydrocarbons-non-aromatics separator 9 is separated described in step e enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons is discharged system as product respectively.
Fig. 3 is system and the process flow sheet of methyl alcohol provided by the invention or the third embodiment of dimethyl ether conversion preparing aromatic hydrocarbon, and described system comprises:
A. aromatization reactor 1 is used for methyl alcohol, dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator 5, being used for to be gas-phase product, oil-phase product and water from reactor 1 product separation out;
C. a gas phase separator 7, be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that solution-air-liquid/gas separator 5 is separated 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device 8, be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator 7 is separated;
E. low-carbon (LC) hydro carbons reactor 3 is used for the C that will separate from gas phase separator 7 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator 5 to be separated;
F. an aromatic hydrocarbons-non-aromatics separator 9, be used for the oil-phase product that solution-air-liquid triphase separator 5 is separated further is separated into aromatic component and non-aromatic component, and the non-aromatics product of separating enters low-carbon (LC) hydro carbons reactor 3 and participates in reaction;
G. an aromatic hydrocarbons separator 10, be used for the aromatic component that aromatic hydrocarbons-non-aromatics separator 9 is separated is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic component, isolated benzene, toluene and C 9+ aromatic component returns to aromatization reactor 1 and participates in reaction, and perhaps as the output of products system, isolated mixed C 8 aromatic hydrocarbons are as the output of products system.
A kind of technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon of system, is characterized in that as shown in Figure 3, and this technique is carried out as follows:
A. methyl alcohol, dme enter aromatization reactor 1, participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator 5 and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator 9, and water is discharged system;
B. the gas-phase product by solution-air-liquid triphase separator 5 is separated described in step a enters gas phase separator 7 and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
C. the hydrogen methane mixture of being separated by gas phase separator 7 described in step b enters hydrogen methane separation device 8, is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator 7 described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor 3 and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator 5 to be separated;
E. enter aromatic hydrocarbons-non-aromatics separator 9 by the oil-phase product that solution-air-liquid triphase separator 5 is separated, be separated into non-aromatic component and aromatic component, non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-non-aromatics separator 9 is separated described in step e enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+ aromatic hydrocarbons, isolated benzene, toluene and part C 9+ aromatic component returns to aromatization reactor 1 and participates in reaction, perhaps as the output of products system, and isolated mixed C 8 aromatic hydrocarbons and residue C 9+ as the output of products system.
Described aromatization reactor 1, low carbon olefin hydrocarbon reactor 2, low-carbon (LC) hydro carbons reactor 3 and aromatic disproportion reactor 4 are for fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or with the circulating fluid bed reactor of revivifier.
Described gas phase separator 7 separates with hydrogen, methane the separation method that adopts with other low-carbon (LC) hydro carbons be absorption and desorption or pressure-variable adsorption or rectifying, when the method for described employing absorption and desorption is separated, its absorption agent employing gasoline, carbonatoms are 1～4 alcohols, ethers, ketone, or adopt that this technique self generates≤the liquid phase hydro carbons of C9, preferably this technique self generate≤the liquid phase hydro carbons of C9 is as low-carbon (LC) hydro carbons absorption agent.
Embodiment 1
Methyl alcohol enters aromatization reactor 1 (aromatization reactor employing fixed bed) and participate in reaction under the effect of Zn-ZSM-5 catalyzer, and temperature of reaction is 470 ℃, and reaction pressure is 0.05MPa, and weight space velocity is 0.6hr -1Reacted material enters solution-air-liquid/gas separator 5 and is divided into gas-phase product, oil-phase product and water, gas-phase product enters low-carbon alkene aromatization reactor 2, reactor is fixed-bed reactor, catalyzer is the Zn-ZSM-5 molecular sieve catalyst, temperature of reaction is 450 ℃, reaction pressure is 0.1MPa, and weight space velocity is 1hr -1Reacted material enters gas-liquid separator 6 and is divided into gas-phase product and oil-phase product after condensation, gas-phase product enters gas phase separator 7, adopts the method for absorption and desorption with hydrogen methane and other C 2+ low-carbon (LC) hydro carbons separates, and absorption agent employing boiling range is the gasoline of 80-180 ℃.Hydrogen adopts the method for membrane sepn to separate with methane.The low-carbon (LC) hydro carbons of hydrogen does not enter low-carbon (LC) hydro carbons aromatization reactor 3 and carries out aromatization, and reactor is fixed-bed reactor, and catalyzer is the Zn-ZSM-5 molecular sieve catalyst, and temperature of reaction is 580 ℃, and reaction pressure is 0.3MPa, and weight space velocity is 0.62hr -1Reacted product returns to solution-air-liquid/gas separator 5 to be separated, and the oil-phase product of being separated by solution-air-liquid/gas separator 5 and gas-liquid separator 6 enters aromatic hydrocarbons-non-aromatics separator 9 and separates and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low carbon olefin hydrocarbon reactor 2 and participates in reaction, and aromatic component enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene, toluene and 50% C 9+ entering aromatic disproportion reactor 4 to participate in reaction, catalyzer is the Zn-P-ZSM-5 molecular sieve catalyst, and temperature of reaction is 400 ℃, and reaction pressure is 0.1MPa, and weight space velocity is 2hr -1Reacted product returns to solution-air-liquid/gas separator 5, the C of mixed C 8 aromatic hydrocarbons and residue 50% 9+ discharge system as product.The final product of this technique distributes as shown in table 1.
Embodiment 2
Methyl alcohol enters aromatization reactor 1 (aromatization reactor employing fixed bed) and participate in reaction under the effect of Ag-ZSM-5 catalyzer, and temperature of reaction is 450 ℃, and working pressure is 0.14MPa, and weight space velocity is 0.7hr -1Reacted material enters solution-air liquid/gas separator 5 and is divided into gas-phase product, oil-phase product and water, gas-phase product enters and directly enters gas phase separator 7, the benzene that the employing reaction generates and the mixture of toluene are as absorption agent, and absorption temperature is 40 ℃, and absorption pressure is 2MPa.Hydrogen adopts the method for membrane sepn to separate with methane.The low-carbon (LC) hydro carbons of hydrogen does not enter low-carbon (LC) hydro carbons aromatization reactor 3 and carries out aromatization, and reactor is fixed-bed reactor, and catalyzer is the Mo-ZSM-5 molecular sieve catalyst, and temperature of reaction is 600 ℃, and reaction pressure is 1MPa, and weight space velocity is 0.1hr -1Reacted product returns to solution-air-liquid/gas separator 5 to be separated, and the oil-phase product of being separated by solution-air-liquid/gas separator 5 enters aromatic hydrocarbons-non-aromatics separator 9 and separates and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction, and aromatic component enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene, toluene and 60% C 9+ entering aromatic disproportion reactor 4 to participate in reaction, the catalyzer that aromatic disproportion reactor 4 adopts is Ga-P-ZSM-5, and temperature of reaction is 500 ℃, and reaction pressure is 0.5MPa, and weight space velocity is 5hr -1Reacted product returns to solution-air-liquid/gas separator 5, the C of mixed C 8 aromatic hydrocarbons and residue 40% 9+ discharge system as product.Above-mentioned aromatization reactor 1, low-carbon (LC) hydro carbons reactor 2 and aromatic disproportion reactor 4 all adopt moving-burden bed reactor.The final product of this technique distributes as shown in table 1.
Embodiment 3
Methyl alcohol enters aromatization reactor 1 (aromatization reactor employing fluidized-bed) and participate in reaction under the effect of Ga-P-ZSM-5 catalyzer, and temperature of reaction is 550 ℃, and reaction pressure is 0.5MPa, and weight space velocity is 5hr -1Reacted material enters solution-air-liquid/gas separator 5 and is divided into gas-phase product, oil-phase product and water.Directly enter gas phase separator 7 with hydrogen and methane and C from solution-air-liquid/gas separator 5 gas-phase product out 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for rectifying to separate.Hydrogen adopts the method for pressure-variable adsorption to separate with methane.The C of hydrogen not 2+ low-carbon (LC) hydrocarbon material flow enters low-carbon (LC) hydro carbons reactor 3 and carries out aromatization.Low-carbon (LC) hydro carbons aromatization reactor 3 is fixed-bed reactor, and catalyzer is the Zn-P-ZSM-35 molecular sieve catalyst, and temperature of reaction is 580 ℃, and reaction pressure is 0.2MPa, and weight space velocity is 0.62hr -1Reacted product returns to solution-air-liquid/gas separator 5 to be separated, and separates by solution-air-liquid/gas separator 5 oil-phase product that obtains and enters aromatic hydrocarbons-non-aromatics separator 9 and separate and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction, and BTX aromatics enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene and toluene return to aromatization reactor 1 as recycle stream and participate in reaction.C 9+ and mixed C 8 aromatic hydrocarbons as output of products.Adopt above-mentioned technological process, the material balance of its whole system is as shown in table 1.
Embodiment 4:
Material benzenemethanol enters circulating fluidized bed aromatization of methanol reactor through being preheating to after 160 ℃ from the sparger of fluidized-bed reactor bottom, catalyzer after regeneration loops back reactor from revivifier, methyl alcohol contacts in fluidized-bed with catalyzer, catalyzer is Zn-P-ZSM-5, temperature of reaction is 550 ℃, reaction pressure is 0.2MPa, and weight space velocity is 0.4hr -1Reacted oil gas enters after the cyclonic separation of reactor head and enters solution-air-liquid/gas separator 5 through condensation and separate, and returning to revivifier after stripping, the catalyzer of having tied the carbon inactivation carries out charcoal regeneration, catalyst recycle after regeneration is returned reactor 1, and so far circulation is completed.Wherein the catalyst regeneration medium is air, and regeneration temperature is 650 ℃, and regeneration pressure is 0.11MPa.
Enter solution-air-liquid/gas separator 5 by the reacted product of aromatization reactor 1 and be divided into gas-phase product, oil-phase product and water.Directly enter gas phase separator 7 with hydrogen and methane and C from solution-air-liquid/gas separator 5 gas-phase product out 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for pressure-variable adsorptions with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separately.Hydrogen adopts the method for pressure-variable adsorption to separate in hydrogen methane separation device 8 with methane.The C of hydrogen not 2+ low-carbon (LC) hydrocarbon material flow enters low-carbon (LC) hydro carbons reactor 3 and carries out aromatization.Low-carbon (LC) hydro carbons aromatization reactor 3 is fixed-bed reactor, and catalyzer is the Zn-P-ZSM-35 molecular sieve catalyst, and temperature of reaction is 580 ℃, and reaction pressure is 0.2MPa, and weight space velocity is 5hr -1Reacted product returns to solution-air-liquid/gas separator 5 to be separated, and separates by solution-air-liquid/gas separator 5 oil-phase product that obtains and enters aromatic hydrocarbons-non-aromatics separator 9 and separate and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction, and BTX aromatics enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene and toluene and 30% C 9+ return to aromatization reactor 1 as recycle stream to participate in reaction.70% C 9+ and mixed C 8 aromatic hydrocarbons as output of products.Adopt above-mentioned technological process, the material balance of its whole system is as shown in table 1.
Embodiment 5:
Material benzenemethanol enters the circulating fluidized bed aromatization reactor through being preheating to after 200 ℃ from the sparger of fluidized-bed aromatization reactor 1 bottom, catalyzer after regeneration loops back reactor from revivifier, methyl alcohol contacts in fluidized-bed with catalyzer, catalyzer is Ga-P-ZSM-5, and temperature of reaction is that 480 ℃, reaction pressure are that 0.2MPa, weight space velocity are 0.4hr -1The catalyzer of knot carbon inactivation returns to revivifier and carries out charcoal regeneration after stripping, the catalyst recycle after regeneration is returned reactor 1, and so far circulation is completed.Wherein the catalyst regeneration medium is air, and regeneration temperature is 650 ℃, and regeneration pressure is 0.11MPa.
Enter solution-air-liquid/gas separator 5 by the reacted product of aromatization reactor 1 and be divided into gas-phase product, oil-phase product and water.Directly enter gas phase separator 7 with hydrogen and methane and C from solution-air-liquid/gas separator 5 gas-phase product out 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for rectifying to separate.Hydrogen adopts the method for absorption and desorption to separate with methane, the aromatic hydrocarbons that absorption agent generates for reaction.The C of hydrogen not 2The circulating fluidized bed low-carbon (LC) hydro carbons reactor 3 that+low-carbon (LC) hydrocarbon material flow enters with revivifier carries out aromatization, and the catalyzer after regeneration loops back reactor from revivifier.C 2+ low-carbon (LC) hydrocarbon material flow contacts in fluidized-bed with catalyzer, and catalyzer is the Zn-P-ZSM-35 molecular sieve catalyst, and temperature of reaction is that 600 ℃, reaction pressure are that 0.2MPa, weight space velocity are 1hr -1Reacted oil gas enters solution-air-liquid/gas separator 5 after the cyclonic separation of reactor head separates, and returning to revivifier after stripping, the catalyzer of having tied the carbon inactivation carries out charcoal regeneration, catalyst recycle after regeneration is returned reactor 3, and so far circulation is completed; Wherein the catalyst regeneration medium is air, and regeneration temperature is 620 ℃, and regeneration pressure is 0.11MPa.Separating by solution-air-liquid/gas separator 5 oil-phase product that obtains enters aromatic hydrocarbons-non-aromatics separator 9 and separates and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction, and BTX aromatics enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene, toluene and 40% C 9+ return to aromatization reactor as recycle stream to participate in reaction.The C of residue 60% 9+ and mixed C 8 aromatic hydrocarbons as output of products.Adopt above-mentioned technological process, the material balance of its whole system is as shown in table 1.
Embodiment 6:
Material benzenemethanol enters the circulating fluidized bed aromatization reactor through being preheating to after 200 ℃ from the sparger of fluidized-bed aromatization reactor 1 bottom, catalyzer after regeneration loops back reactor from revivifier, methyl alcohol contacts in fluidized-bed with catalyzer, catalyzer is Mo-P-ZSM-5, and temperature of reaction is that 500 ℃, reaction pressure are that 0.7MPa, weight space velocity are 0.4hr -1The catalyzer of knot carbon inactivation returns to revivifier and carries out charcoal regeneration after stripping, the catalyst recycle after regeneration is returned reactor 1, and so far circulation is completed.Wherein the catalyst regeneration medium is air, and regeneration temperature is 650 ℃, and regeneration pressure is 0.5MPa.
Enter solution-air-liquid/gas separator 5 by the reacted product of aromatization reactor 1 and be divided into gas-phase product, oil-phase product and water.Directly enter gas phase separator 7 with hydrogen and methane and C from solution-air-liquid/gas separator 5 gas-phase product out 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for rectifying to separate.Hydrogen adopts the method for absorption and desorption to separate with methane, the aromatic hydrocarbons that absorption agent generates for reaction.The C of hydrogen not 2+ low-carbon (LC) hydrocarbon material flow enters fluidized-bed low-carbon (LC) hydro carbons reactor 3 and carries out aromatization.C 2+ low-carbon (LC) hydrocarbon material flow contacts in fluidized-bed with catalyzer, and catalyzer is the Mo-P-ZSM-5 molecular sieve catalyst, and temperature of reaction is that 600 ℃, reaction pressure are that 0.7MPa, weight space velocity are 1hr -1Reacted oil gas enters solution-air-liquid/gas separator 5 after the cyclonic separation of reactor head separates, and returning to revivifier after stripping, the catalyzer of having tied the carbon inactivation carries out charcoal regeneration, catalyst recycle after regeneration is returned reactor 3, so far circulation is completed, and shares a revivifier at this aromatization reactor 1 and low-carbon (LC) hydro carbons reactor 3.Separating by solution-air-liquid/gas separator 5 oil-phase product that obtains enters aromatic hydrocarbons-non-aromatics separator 9 and separates and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction, and BTX aromatics enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene, toluene and 80% C 9+ return to aromatization reactor as recycle stream to participate in reaction.The C of residue 20% 9+ and mixed C 8 aromatic hydrocarbons as output of products.Adopt above-mentioned technological process, the material balance of its whole system is as shown in table 1.
Table 1 aromatization of methanol process product distributes, wt%
Figure GSA00000083587200131
Embodiment 7:
Dme enters fluidized-bed aromatization reactor 1 as raw material and participate in reaction under the effect of Zn-P-ZSM-5 catalyzer, and temperature of reaction is 450 ℃, and reaction pressure is 0.5MPa, and weight space velocity is 0.5hr -1Reacted material enters solution-air-liquid/gas separator 5 and is divided into gas-phase product, oil-phase product and water.Directly enter gas phase separator 7 with hydrogen and methane and C from solution-air-liquid/gas separator 5 gas-phase product out 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for absorption and desorptions, adopts methyl alcohol as absorption agent.Hydrogen adopts the method for pressure-variable adsorption to separate in hydrogen methane separation device 8 with methane.The C of hydrogen not 2+ low-carbon (LC) hydrocarbon material flow enters low-carbon (LC) hydro carbons reactor 3 and carries out aromatization.Low-carbon (LC) hydro carbons aromatization reactor 3 is fixed-bed reactor, and catalyzer is the Zn-P-ZSM-35 molecular sieve catalyst, and temperature of reaction is 580 ℃, and reaction pressure is 1MPa, and weight space velocity is 1hr -1Reacted product returns to solution-air-liquid/gas separator 5 to be separated, and separates by solution-air-liquid/gas separator 5 oil-phase product that obtains and enters aromatic hydrocarbons-non-aromatics separator 9 and separate and obtain non-aromatic component and aromatic component; Non-aromatic component returns to low-carbon (LC) hydro carbons reactor 3 and participates in reaction, and BTX aromatics enters aromatic hydrocarbons separator 10 and is separated into benzene, toluene, mixed C 8 aromatic hydrocarbons and C 9+, benzene and toluene return to methyl alcohol, dme aromatization participation reaction as recycle stream.C 9+ and mixed C 8 aromatic hydrocarbons as output of products.Adopt said system and technological process, the mass yield of mixed C 8 is 70.52%.
Above-described embodiment is the part preferred embodiment, and protection domain of the present invention is as the criterion with the claim of application.Those skilled in the art can be by the methyl alcohol of using for reference the present invention's proposition, system and the technique of dimethyl ether conversion preparing aromatic hydrocarbon, and the links such as appropriate change raw material, processing parameter realize.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and content.

Claims (10)

1. system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon is characterized in that described system comprises:
A. an aromatization reactor (1) is used for methyl alcohol or dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator (5), being used for to be gas-phase product, oil-phase product and water from aromatization reactor (1) product separation out;
C. a low carbon olefin hydrocarbon reactor (2), be used for being converted into from the low-carbon alkene of solution-air-gas-phase product that liquid triphase separator (5) is separated take aromatic hydrocarbons as main product;
D. a gas-liquid separator (6), be used for will from low carbon olefin hydrocarbon reactor (2) generate take aromatic hydrocarbons as the product separation led as gas-phase product and oil-phase product;
E. a gas phase separator (7), be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that separate gas-liquid separator (6) 2+ low-carbon (LC) hydrocarbon mixture;
F. a hydrogen methane separation device (8), be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator (7) is separated;
G. a low-carbon (LC) hydro carbons reactor (3) is used for the C that will separate from gas phase separator (7) 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator (5) to be separated;
H. aromatic hydrocarbons-non-aromatics separator (9), be used for the oil-phase product that solution-air-liquid triphase separator (5) and gas-liquid separator (6) are separated further is separated into aromatic component and non-aromatic component, the non-aromatics product of separating enters low carbon olefin hydrocarbon reactor (2) and participates in reacting;
I. an aromatic hydrocarbons separator (10), be used for the aromatic component that aromatic hydrocarbons-non-aromatics separator (9) is separated is separated into benzene, toluene, mixed C 8Aromatic hydrocarbons and C 9+ aromatic component;
J. an aromatic disproportion reactor (4) is used for benzene, toluene and the C that will separate from aromatic hydrocarbons separator (10) 9+ aromatic hydrocarbons is converted into mixed C by disproportionation reaction 8Aromatic hydrocarbons is main product, and this product enters solution-air-liquid triphase separator (5) to be separated.
2. the technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon that adopts the described system of claim 1, is characterized in that, this technique is carried out as follows:
A. methyl alcohol or dme enter aromatization reactor (1), participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator (5) and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator (9), and water is discharged system;
B. the gas-phase product by solution-air-liquid triphase separator (5) is separated described in step a enters low carbon olefin hydrocarbon reactor (2) and participates in reaction, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～15hr -1Reacted product enters gas-liquid separator (6) and is separated into gas-phase product and oil-phase product after condensation, enter gas phase separator (7) by gas-liquid separator (6) gas-phase product out and be separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture enters aromatic hydrocarbons-non-aromatics separator (9) by gas-liquid separator (6) liquid product out;
C. the hydrogen methane mixture of being separated by gas phase separator (7) described in step b enters hydrogen methane separation device (8), is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator (7) described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor (3) and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator (5) to be separated;
E. the oil-phase product of being separated by solution-air-liquid triphase separator (5) and gas-liquid separator (6) enters aromatic hydrocarbons-non-aromatics separator (9), be separated into non-aromatic component and aromatic component, non-aromatic component returns to low carbon olefin hydrocarbon reactor (2) and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-non-aromatics separator (9) is separated described in step e enters aromatic hydrocarbons separator (10) and is separated into benzene and toluene mixture, and mixed C 8Aromatic hydrocarbons and C 9+ aromatic hydrocarbons, benzene and toluene mixture and part C 9+ aromatic hydrocarbons enters disproportionation reactor (4) and reacts, and temperature of reaction is 400～600 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～20hr -1Mixed C 8Aromatic hydrocarbons and residue C 9+ discharge system as product; Or the aromatic component by aromatic hydrocarbons-non-aromatics separator (9) is separated described in step e enters aromatic hydrocarbons separator (10) and is separated into benzene, toluene, mixed C 8Aromatic hydrocarbons and C 9+ aromatic hydrocarbons is discharged system as product respectively.
3. system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon is characterized in that described system comprises:
A. an aromatization reactor (1) is used for methyl alcohol or dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator (5), being used for to be gas-phase product, oil-phase product and water from aromatization reactor (1) product separation out;
C. a gas phase separator (7), be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that separate solution-air-liquid/gas separator (5) 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device (8), be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator (7) is separated;
E. a low-carbon (LC) hydro carbons reactor (3) is used for the C that will separate from gas phase separator (7) 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator (5) to be separated;
F. aromatic hydrocarbons-non-aromatics separator (9), be used for the oil-phase product that solution-air-liquid triphase separator (5) is separated further is separated into aromatic component and non-aromatic component, the non-aromatics product of separating enters low-carbon (LC) hydro carbons reactor (3) and participates in reaction;
G. an aromatic hydrocarbons separator (10), be used for the aromatic component that aromatic hydrocarbons-non-aromatics separator (9) is separated is separated into benzene, toluene, mixed C 8Aromatic hydrocarbons and C 9+ aromatic component;
H. an aromatic disproportion reactor (4) is used for benzene, toluene and the C that will separate from aromatic hydrocarbons separator (10) 9+ aromatic hydrocarbons is converted into mixed C by disproportionation reaction 8Aromatic hydrocarbons is main product, and this product enters solution-air-liquid triphase separator (5) to be separated.
4. one kind is adopted the technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon of system as claimed in claim 3, it is characterized in that, this technique is carried out as follows:
A. methyl alcohol or dme enter aromatization reactor (1), participate in reaction under the effect of catalyzer, and temperature of reaction is 400～550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator (5) and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator (9), and water is discharged system;
B. the gas-phase product by solution-air-liquid triphase separator (5) is separated described in step a enters gas phase separator (7) and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
C. the hydrogen methane mixture of being separated by gas phase separator (7) described in step b enters hydrogen methane separation device (8), is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator (7) described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor (3) and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator (5) to be separated;
E. enter aromatic hydrocarbons-non-aromatics separator (9) by the oil-phase product that solution-air-liquid triphase separator (5) is separated, be separated into non-aromatic component and aromatic component, non-aromatic component returns to low-carbon (LC) hydro carbons reactor (3) and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-non-aromatics separator (9) is separated described in step e enters aromatic hydrocarbons separator (10) and is separated into benzene and toluene mixture, and mixed C 8Aromatic hydrocarbons and C 9+ aromatic hydrocarbons, benzene and toluene mixture and part C 9+ aromatic hydrocarbons enters disproportionation reactor (4) and reacts, and temperature of reaction is 400～600 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～20hr -1Mixed C 8Aromatic hydrocarbons and residue C 9+ discharge system as product; Or the aromatic component by aromatic hydrocarbons-non-aromatics separator (9) is separated described in step e enters aromatic hydrocarbons separator (10) and is separated into benzene, toluene, mixed C 8Aromatic hydrocarbons and C 9+ aromatic hydrocarbons is discharged system as product respectively.
5. system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon is characterized in that described system comprises:
A. an aromatization reactor (1) is used for methyl alcohol or dimethyl ether conversion for take aromatic hydrocarbons as main product;
B. solution-air-liquid triphase separator (5), being used for to be gas-phase product, oil-phase product and water from reactor (1) product separation out;
C. a gas phase separator (7), be used for and will further be separated into hydrogen methane mixture and C from the gas-phase product that separate solution-air-liquid/gas separator (5) 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device (8), be separated into hydrogen and methane for the hydrogen methane mixture that gas phase separator (7) is separated;
E. a low-carbon (LC) hydro carbons reactor (3) is used for the C that will separate from gas phase separator (7) 2+ low-carbon (LC) hydrocarbon mixture is converted into take aromatic hydrocarbons as main product, and this product enters solution-air-liquid triphase separator (5) to be separated;
F. aromatic hydrocarbons-non-aromatics separator (9), be used for the oil-phase product that solution-air-liquid triphase separator (5) is separated further is separated into aromatic component and non-aromatic component, the non-aromatics product of separating enters low-carbon (LC) hydro carbons reactor (3) and participates in reaction;
G. an aromatic hydrocarbons separator (10), be used for the aromatic component that aromatic hydrocarbons-non-aromatics separator (9) is separated is separated into benzene, toluene, mixed C 8Aromatic hydrocarbons and C 9+ aromatic component, isolated benzene, toluene and C 9+ aromatic component returns to aromatization reactor (1) and participates in reaction, perhaps as the output of products system, and isolated mixed C 8Aromatic hydrocarbons is as the output of products system.
6. the technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon that adopts the described system of claim 5, is characterized in that, this technique is carried out as follows:
A. methyl alcohol or dme enter aromatization reactor (1), participate in reaction under the effect of catalyzer, and temperature of reaction is 400-550 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid triphase separator (5) and is separated into gas-phase product, oil-phase product and water, and oil-phase product enters aromatic hydrocarbons-non-aromatics separator (9), and water is discharged system;
B. the gas-phase product by solution-air-liquid triphase separator (5) is separated described in step a enters gas phase separator (7) and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
C. the hydrogen methane mixture of being separated by gas phase separator (7) described in step b enters hydrogen methane separation device (8), is separated into hydrogen and methane, discharges system as product;
D. the C that is separated by gas phase separator (7) described in step b 2+ low-carbon (LC) hydrocarbon mixture enters low-carbon (LC) hydro carbons reactor (3) and reacts, and temperature of reaction is 400～650 ℃; Reaction pressure is 0.05～1MPa; Weight space velocity is 0.1～10hr -1Reacted product enters solution-air-liquid/gas separator (5) to be separated;
E. enter aromatic hydrocarbons-non-aromatics separator (9) by the oil-phase product that solution-air-liquid triphase separator (5) is separated, be separated into non-aromatic component and aromatic component, non-aromatic component returns to low-carbon (LC) hydro carbons reactor (3) and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-non-aromatics separator (9) is separated described in step e enters aromatic hydrocarbons separator (10) and is separated into benzene, toluene, mixed C 8Aromatic hydrocarbons and C 9+ aromatic hydrocarbons, isolated benzene, toluene and part C 9+ aromatic component returns to aromatization reactor (1) and participates in reaction, perhaps as the output of products system, and isolated mixed C 8Aromatic hydrocarbons and residue C 9+ as the output of products system.
7. a kind of system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon as claimed in claim 1 is characterized in that: described low carbon olefin hydrocarbon reactor (2) adopts fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or with the circulating fluid bed reactor of revivifier.
8. the system by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon as described in claim 1 or 3 is characterized in that: described aromatization reactor (1), low-carbon (LC) hydro carbons reactor (3) and aromatic disproportion reactor (4) adopt fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or with the circulating fluid bed reactor of revivifier.
9. as claim 2,4 or 6 described a kind of techniques by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon, it is characterized in that: it is absorption and desorption method, pressure swing adsorption process or rectification method that described gas phase separator (7) is separated the separation method that adopts.
10. a kind of technique by methyl alcohol or dimethyl ether conversion preparing aromatic hydrocarbon as claimed in claim 9, it is characterized in that: when described gas phase separator (7) adopted the absorption and desorption method to separate, it was 1～4 alcohols, ethers, ketone or the liquid phase hydro carbons that adopts described technique self generation≤C9 that absorption agent used adopts gasoline, carbonatoms.
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Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN104549441A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Small-crystal-grain ZSM-5 methanol aromatization catalyst
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US9783460B2 (en) 2013-12-20 2017-10-10 Exxonmobil Chemical Patents Inc. Process for converting oxygenates to aromatic hydrocarbons
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US10196325B2 (en) 2015-01-15 2019-02-05 Exxonmobil Chemical Patents Inc. Process for converting syngas to aromatics and catalyst system suitable therefor
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4885421A (en) * 1987-12-08 1989-12-05 Harandi Mohsen N Multistage reactor system for production of fuels
US5191142A (en) * 1991-12-23 1993-03-02 Amoco Corporation Process for converting methanol to olefins or gasoline
WO2001077046A1 (en) * 2000-04-11 2001-10-18 Exxonmobil Chemical Patents, Inc. Process for producing chemicals from oxygenate
CN101177373A (en) * 2006-11-07 2008-05-14 中国科学院大连化学物理研究所 Method for producing propylene by conversion of carbinol or dimethyl ether
CN101270016A (en) * 2006-12-29 2008-09-24 环球油品公司 Aromatics co-production in a methanol-to-propylene unit
CN101580449A (en) * 2008-05-15 2009-11-18 中国石油天然气股份有限公司 Method and device for preparing aromatics through methane aromatization

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4885421A (en) * 1987-12-08 1989-12-05 Harandi Mohsen N Multistage reactor system for production of fuels
US5191142A (en) * 1991-12-23 1993-03-02 Amoco Corporation Process for converting methanol to olefins or gasoline
WO2001077046A1 (en) * 2000-04-11 2001-10-18 Exxonmobil Chemical Patents, Inc. Process for producing chemicals from oxygenate
CN101177373A (en) * 2006-11-07 2008-05-14 中国科学院大连化学物理研究所 Method for producing propylene by conversion of carbinol or dimethyl ether
CN101270016A (en) * 2006-12-29 2008-09-24 环球油品公司 Aromatics co-production in a methanol-to-propylene unit
CN101580449A (en) * 2008-05-15 2009-11-18 中国石油天然气股份有限公司 Method and device for preparing aromatics through methane aromatization

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