CN101823929A - 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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CN101823929A
CN101823929A CN201010146915A CN201010146915A CN101823929A CN 101823929 A CN101823929 A CN 101823929A CN 201010146915 A CN201010146915 A CN 201010146915A CN 201010146915 A CN201010146915 A CN 201010146915A CN 101823929 A CN101823929 A CN 101823929A
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separator
separated
aromatic hydrocarbons
product
gas
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CN101823929B (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

A kind of methyl alcohol or dimethyl ether conversion are produced the system and the technology of aromatic hydrocarbons
Technical field
The present invention relates to a kind ofly produce the system and the technology of aromatic hydrocarbons, belong to the aromatic hydrocarbons production technical field by methyl alcohol or dimethyl ether conversion.
Background technology
Aromatic hydrocarbons refers to contain the hydro carbons of phenyl ring, and the triphen in the aromatic hydrocarbons (benzene, toluene and dimethylbenzene also claim BTX) is organic chemical industry's a 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 technology, low-carbon (LC) aromatization of hydrocarbons and aromatic hydrocarbons conversion process in the petrochemical complex industry at present; Small part is only arranged from the coal tar in the Coal Chemical Industry, rely on bigger oil.Also cause concern with coal-based methanol, dme system aromatic hydrocarbons technology in recent years, but also be in development still do not have industrialized unit fortune dress.
China belongs to the country of petroleum resources shortage, the annual at present oil that consumes 3 to 400,000,000 tons, and throughput can only maintain about 1.8 hundred million tons, causes China's oil import interdependency to strengthen year by year thus.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 Industry projects that start one after another.As comparatively sophisticated coal chemical technology, coal-based synthesizing methanol, dme become the first-selected project of most coal chemical industry enterprises.Planning and construction situation for China's methyl alcohol, dme project, although various statistical information there are differences, but consistent conclusion is in 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 of producing aromatic hydrocarbons by coal-based methanol, dme, not only opened up a technological line, for China's methyl alcohol, dme find an outlet that reality is feasible for coal/conversion of natural gas system aromatic hydrocarbons; And satisfy the demand of market to aromatic hydrocarbons, reduce the degree of dependence of aromatic hydrocarbons production to petroleum.
Obtain aromatic hydrocarbons by methyl alcohol, dme, see MTG (the Methanol to Gasoline) technology of U.S. Mobil company exploitation at first, the seventies in 20th century, Mobil company developed the ZSM-5 zeolite catalyst, make methyl alcohol, dimethyl ether conversion become stop bracket gasoline, its product contains 30% aromatic hydrocarbons in forming.1985, Mobil company is in the U.S. Pat P4590321 of its application, announced the result of study of methyl alcohol, dimethyl ether conversion system aromatic hydrocarbons first, 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 shows that the ZSM-5 catalyzer that process phosphorus is modified is at higher hydrocarbon (the ZSM-5 molecular sieve catalyst 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 still is the low-carbon (LC) hydro carbons of C1～C4, and total aromaticity content is not high.1986, Mobil company applied for U.S. Pat P4686312, had 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; Methyl alcohol, dme at first are converted into the product based on the preparing low carbon hydrocarbons class in first section reactor, aromatization further takes place 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 first kind of catalyzer is the sial phosphorus molecular sieve, and second kind of 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 methyl alcohol, dimethyl ether conversion is produced aromatic hydrocarbons, particularly a kind of effective ways of BTX.
Methyl alcohol, dme aromatization technology mainly contain methyl alcohol, dme system aromatic hydrocarbons (FMTA) technology of fixed bed methyl alcohol, dme system aromatic hydrocarbons (MTA) technology and the Tsing-Hua University of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences at home.The Shanxi coalification patent CN 1880288A in to adopt methyl alcohol, dme be raw material, modified ZSM-5 is a catalyzer, methyl alcohol, dimethyl ether conversion are the product based on aromatic hydrocarbons, 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 the aromizing productive rate and the selectivity of alkane, and the gas-phase product of methyl alcohol, dme aromizing directly being entered the technology that the low-carbon (LC) aromatizing reaction of hydrocarbons carries out aromatization is not optimum process.A kind of methyl alcohol, dme aromatization process catalyzer successive reaction regenerated devices and methods therefor are disclosed among 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 last 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 that the Shanxi coalification the product of methyl alcohol, dme aromatization process has been carried out the simple gas-liquid separation, do not consider still that methyl alcohol, dme aromatization process product separate and the recycle mode of by product such as low-carbon (LC) hydro carbons etc., be fit to methyl alcohol, the system of dme aromizing and the report of technology of suitability for industrialized production.
Summary of the invention
The present invention is directed to and do not take into full account methyl alcohol, the separation of dme aromatization process product and the methyl alcohol of by-product recovery utilization and the present situation of dme technology of aromatization at present, provide a kind of and comprise that product separates and the methyl alcohol of by product recycle, system and the technology that dme is produced aromatic hydrocarbons, by the separation of product and the recycle of by product, thus the yield and the selectivity of raising target product aromatic hydrocarbons.
Technical scheme of the present invention has following several:
First kind of technical scheme provided by the invention is: a kind ofly produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that described system comprises:
A. an aromatization reactor is used for methyl alcohol or dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator, the product that is used for coming out from reactor 1 is separated into gas-phase product, oil-phase product and water;
C. low carbon olefin hydrocarbon reactor is used for the low-carbon alkene from solution-air-gas-phase product that the liquid triphase separator is separated is converted into product based on aromatic hydrocarbons;
D. a gas-liquid separator is used for and will be separated into gas-phase product and oil-phase product from the product based on aromatic hydrocarbons of low carbon olefin hydrocarbon reactor 2 generations;
E. gas phase separator, the gas-phase product that is used for separating from gas-liquid separator further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
F. hydrogen methane separation device, the hydrogen methane mixture that is used for gas phase separator is separated is separated into hydrogen and methane;
G. a 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 the product based on aromatic hydrocarbons, 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 is 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. an 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 product based on mixed C 8 aromatic hydrocarbons by disproportionation reaction, and this product enters solution-air-liquid triphase separator to be separated.
Employing is produced the technology of aromatic hydrocarbons as a kind of of system as described in first kind of technical scheme by methyl alcohol or dimethyl ether conversion, it is characterized in that this technology 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 the 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, the gas-phase product that is come out by gas-liquid separator enters gas phase separator and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture, the liquid product that is come out by gas-liquid separator enters aromatic hydrocarbons-non-aromatics separator;
C. the hydrogen methane mixture of being separated by gas phase separator described in the step b enters hydrogen methane separation device, is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator described in the 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 low carbon olefin hydrocarbon reactor and participates in reaction;
F. the aromatic component by aromatic hydrocarbons-the non-aromatics separator is separated described in the 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 portion 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 the 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.
Second kind of technical scheme provided by the invention is: a kind ofly produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that described system comprises:
A. an aromatization reactor is used for methyl alcohol or dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator, the product that is used for coming out from aromatization reactor is separated into gas-phase product, oil-phase product and water;
C. gas phase separator, the gas-phase product that is used for separating from solution-air-liquid/gas separator further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
D. hydrogen methane separation device, the hydrogen methane mixture that is used for gas phase separator is separated is separated into hydrogen and methane;
E. a 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 the product based on aromatic hydrocarbons, and this product enters solution-air-liquid triphase separator to be separated;
F. an aromatic hydrocarbons-non-aromatics separator is 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 is 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. an 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 product based on mixed C 8 aromatic hydrocarbons by disproportionation reaction, and this product enters solution-air-liquid triphase separator to be separated.
Employing is produced the technology of aromatic hydrocarbons as a kind of of system as described in second kind of technical scheme by methyl alcohol or dimethyl ether conversion, it is characterized in that this technology 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 the 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 the step b enters hydrogen methane separation device, is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator described in the 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 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 the 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 portion 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 the 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 ofly produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that described system comprises:
A. an aromatization reactor is used for methyl alcohol or dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator, the product that is used for coming out from aromatization reactor is separated into gas-phase product, oil-phase product and water;
C. gas phase separator, the gas-phase product that is used for separating from solution-air-liquid/gas separator further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
D. hydrogen methane separation device, the hydrogen methane mixture that is used for gas phase separator is separated is separated into hydrogen and methane;
E. a 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 the product based on aromatic hydrocarbons, and this product enters solution-air-liquid triphase separator to be separated;
F. an aromatic hydrocarbons-non-aromatics separator is 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 is 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 methyl alcohol or dme aromatization reactor 1 participates in reaction, and perhaps as the product output system, isolated mixed C 8 aromatic hydrocarbons are as the product output system.
Employing is produced the technology of aromatic hydrocarbons as a kind of of system as described in the third technical scheme by methyl alcohol or dimethyl ether conversion, it is characterized in that this technology 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 the 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 the step b enters hydrogen methane separation device, is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator 7 described in the 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 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 the 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 portion C 9+ aromatic component returns aromatization reactor and participates in reaction, perhaps as the product output system, and isolated mixed C 8 aromatic hydrocarbons and residue C 9+ as the product output system.
Described aromatization reactor, low carbon olefin hydrocarbon reactor, low-carbon (LC) hydro carbons reactor and aromatic disproportion reactor are the circulating fluid bed reactor of fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or band revivifier.
Described gas phase separator is separated hydrogen, methane the separation method that is adopted and is adsorbed or rectifying for absorbing desorb or transformation with other low-carbon (LC) hydro carbons, when the method for described employing absorption desorb is separated, its absorption agent employing gasoline, carbonatoms are 1～4 alcohols, ethers, ketone, or adopt that this technology self generates≤the liquid phase hydro carbons of C9, preferably this technology 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 has improved the yield and the selectivity of target product aromatic hydrocarbons by the separation and the by product recycle of product in methyl alcohol, the dme aromatization process; 2. the present invention can select different flow processs according to the difference of target product, and technology is flexible; 3. hydrogen separates with the low-carbon (LC) hydro carbons in the gas-phase product that methyl alcohol, dme aromizing are produced, hydrogen is as the product take-off equipment, by adopting this technology, not only improved the economic benefit of process, and improved the 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 produces system and the process flow sheet of first kind of embodiment of aromatic hydrocarbons for methyl alcohol provided by the invention or dimethyl ether conversion.
Fig. 2 produces system and the process flow sheet of second kind of embodiment of aromatic hydrocarbons for methyl alcohol provided by the invention or dimethyl ether conversion.
Fig. 3 produces system and the process flow sheet of the third embodiment of aromatic hydrocarbons for methyl alcohol provided by the invention or dimethyl ether conversion.
Among the 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
System, technology and the embodiment of methyl alcohol provided by the present invention or dimethyl ether conversion being produced aromatic hydrocarbons below in conjunction with accompanying drawing are described further.
The present invention is directed to and do not take into full account methyl alcohol, the methyl alcohol that dme aromatization process product separates and by-product recovery is utilized, the present situation of dme technology of aromatization at present, provide a kind of and comprised that product separates and the methyl alcohol of by product recycle, system and the technology that dme is produced aromatic hydrocarbons, by the recycle of by product, improved the 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 that methyl alcohol provided by the invention or dimethyl ether conversion are produced first kind of embodiment of aromatic hydrocarbons, and described system comprises:
A. an aromatization reactor 1 is used for methyl alcohol, dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator 5, the product that is used for coming out from reactor 1 is separated into gas-phase product, oil-phase product and water;
C. low carbon olefin hydrocarbon reactor 2 is used for the low-carbon alkene from solution-air-gas-phase product that liquid triphase separator 5 is separated is converted into product based on aromatic hydrocarbons;
D. a gas-liquid separator 6 is used for and will be separated into gas-phase product and oil-phase product from the product based on aromatic hydrocarbons of low carbon olefin hydrocarbon reactor 2 generations;
E. gas phase separator 7, the gas-phase product that is used for separating from gas-liquid separator 6 further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
F. hydrogen methane separation device 8, the hydrogen methane mixture that is used for gas phase separator 7 is separated is separated into hydrogen and methane;
G. a low-carbon (LC) hydro carbons reactor 3 is used for the C that separates from gas phase separator 7 2+ low-carbon (LC) hydrocarbon mixture is converted into the product based on aromatic hydrocarbons, 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 is 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. 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 product based on mixed C 8 aromatic hydrocarbons by disproportionation reaction, and this product enters solution-air-liquid triphase separator 5 to be separated.
A kind of as shown in Figure 1 said system that adopts is produced the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, and this technology 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 the 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, the gas-phase product that is come out by gas-liquid separator 6 enters gas phase separator 7 and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture, the liquid product that is come out by gas-liquid separator 6 enters aromatic hydrocarbons-non-aromatics separator 9;
C. the hydrogen methane mixture of being separated by gas phase separator 7 described in the step b enters hydrogen methane separation device 8, is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator 7 described in the 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 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 the 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 portion 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 the 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 that methyl alcohol provided by the invention or dimethyl ether conversion are produced second kind of embodiment of aromatic hydrocarbons, and described system comprises:
A. an aromatization reactor 1 is used for methyl alcohol, dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator 5, the product that is used for coming out from reactor 1 is separated into gas-phase product, oil-phase product and water;
C. gas phase separator 7, the gas-phase product that is used for separating from solution-air-liquid/gas separator 5 further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
D. hydrogen methane separation device 8, the hydrogen methane mixture that is used for gas phase separator 7 is separated is separated into hydrogen and methane;
E. a low-carbon (LC) hydro carbons reactor 3 is used for the C that separates from gas phase separator 7 2+ low-carbon (LC) hydrocarbon mixture is converted into the product based on aromatic hydrocarbons, and this product enters solution-air-liquid triphase separator 5 to be separated;
F. an aromatic hydrocarbons-non-aromatics separator 9 is 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 is 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. 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 product based on mixed C 8 aromatic hydrocarbons by disproportionation reaction, and this product enters solution-air-liquid triphase separator 5 to be separated.
A kind of as shown in Figure 2 said system that adopts is produced the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, and this technology 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 the 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 the step b enters hydrogen methane separation device 8, is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator 7 described in the 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 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 the 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 portion 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 the 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 that methyl alcohol provided by the invention or dimethyl ether conversion are produced the third embodiment of aromatic hydrocarbons, and described system comprises:
A. an aromatization reactor 1 is used for methyl alcohol, dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator 5, the product that is used for coming out from reactor 1 is separated into gas-phase product, oil-phase product and water;
C. gas phase separator 7, the gas-phase product that is used for separating from solution-air-liquid/gas separator 5 further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
D. hydrogen methane separation device 8, the hydrogen methane mixture that is used for gas phase separator 7 is separated is separated into hydrogen and methane;
E. a low-carbon (LC) hydro carbons reactor 3 is used for the C that separates from gas phase separator 7 2+ low-carbon (LC) hydrocarbon mixture is converted into the product based on aromatic hydrocarbons, and this product enters solution-air-liquid triphase separator 5 to be separated;
F. an aromatic hydrocarbons-non-aromatics separator 9 is 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 is 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 aromatization reactor 1 and participates in reaction, and perhaps as the product output system, isolated mixed C 8 aromatic hydrocarbons are as the product output system.
The a kind of of system produces the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion as shown in Figure 3, it is characterized in that this technology 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 the 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 the step b enters hydrogen methane separation device 8, is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator 7 described in the 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 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 the 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 portion C 9+ aromatic component returns aromatization reactor 1 and participates in reaction, perhaps as the product output system, and isolated mixed C 8 aromatic hydrocarbons and residue C 9+ as the product output system.
Described aromatization reactor 1, low carbon olefin hydrocarbon reactor 2, low-carbon (LC) hydro carbons reactor 3 and aromatic disproportion reactor 4 are the circulating fluid bed reactor of fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or band revivifier.
Described gas phase separator 7 is separated hydrogen, methane the separation method that is adopted and is adsorbed or rectifying for absorbing desorb or transformation with other low-carbon (LC) hydro carbons, when the method for described employing absorption desorb is separated, its absorption agent employing gasoline, carbonatoms are 1～4 alcohols, ethers, ketone, or adopt that this technology self generates≤the liquid phase hydro carbons of C9, preferably this technology 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 that absorbs desorb with hydrogen methane and other C 2+ low-carbon (LC) hydro carbons separates, and absorption agent employing boiling range is 80-180 ℃ a gasoline.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 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 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 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 technology 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 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 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 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 technology 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.The gas-phase product that comes out from solution-air-liquid/gas separator 5 directly enters gas phase separator 7 with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for rectifying to separate.Hydrogen adopts the method for transformation absorption 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 solution-air-liquid/gas separator 5 to be separated, and separates the oil-phase product that obtains by solution-air-liquid/gas separator 5 and enters aromatic hydrocarbons-non-aromatics separator 9 and separate and obtain non-aromatic component and aromatic component; Non-aromatic component returns 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 aromatization reactor 1 as recycle stream and participate in reaction.C 9+ export as product with mixed C 8 aromatic hydrocarbons.Adopt above-mentioned technological process, the material balance of its total system is as shown in table 1.
Embodiment 4:
The sparger from the fluidized-bed reactor bottom enters circulating fluidized bed aromatization of methanol reactor to material benzenemethanol after 160 ℃ through being preheating to, 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 revivifier behind stripping, the catalyzer of having tied the carbon inactivation carries out charcoal regeneration, catalyst recycle after the regeneration is returned reactor 1, and circulation is so far finished.Wherein the catalyst regeneration medium is an air, and regeneration temperature is 650 ℃, and regeneration pressure is 0.11MPa.
Enter solution-air-liquid/gas separator 5 by aromatization reactor 1 reacted product and be divided into gas-phase product, oil-phase product and water.The gas-phase product that comes out from solution-air-liquid/gas separator 5 directly enters gas phase separator 7 with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for transformations absorption with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separately.Hydrogen adopts the method for transformation absorption 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 solution-air-liquid/gas separator 5 to be separated, and separates the oil-phase product that obtains by solution-air-liquid/gas separator 5 and enters aromatic hydrocarbons-non-aromatics separator 9 and separate and obtain non-aromatic component and aromatic component; Non-aromatic component returns 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 aromatization reactor 1 as recycle stream to participate in reaction.70% C 9+ export as product with mixed C 8 aromatic hydrocarbons.Adopt above-mentioned technological process, the material balance of its total system is as shown in table 1.
Embodiment 5:
The sparger from fluidized-bed aromatization reactor 1 bottom enters the circulating fluidized bed aromatization reactor to material benzenemethanol after 200 ℃ through being preheating to, 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 revivifier and carries out charcoal regeneration behind stripping, the catalyst recycle after the regeneration is returned reactor 1, and circulation is so far finished.Wherein the catalyst regeneration medium is an air, and regeneration temperature is 650 ℃, and regeneration pressure is 0.11MPa.
Enter solution-air-liquid/gas separator 5 by aromatization reactor 1 reacted product and be divided into gas-phase product, oil-phase product and water.The gas-phase product that comes out from solution-air-liquid/gas separator 5 directly enters gas phase separator 7 with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for rectifying to separate.Hydrogen adopts the method that absorbs desorb 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 the band 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 revivifier behind stripping, the catalyzer of having tied the carbon inactivation carries out charcoal regeneration, catalyst recycle after the regeneration is returned reactor 3, and circulation is so far finished; Wherein the catalyst regeneration medium is an air, and regeneration temperature is 620 ℃, and regeneration pressure is 0.11MPa.Separating the oil-phase product that obtains 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 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 aromatization reactor as recycle stream to participate in reaction.The C of residue 60% 9+ export as product with mixed C 8 aromatic hydrocarbons.Adopt above-mentioned technological process, the material balance of its total system is as shown in table 1.
Embodiment 6:
The sparger from fluidized-bed aromatization reactor 1 bottom enters the circulating fluidized bed aromatization reactor to material benzenemethanol after 200 ℃ through being preheating to, 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 revivifier and carries out charcoal regeneration behind stripping, the catalyst recycle after the regeneration is returned reactor 1, and circulation is so far finished.Wherein the catalyst regeneration medium is an air, and regeneration temperature is 650 ℃, and regeneration pressure is 0.5MPa.
Enter solution-air-liquid/gas separator 5 by aromatization reactor 1 reacted product and be divided into gas-phase product, oil-phase product and water.The gas-phase product that comes out from solution-air-liquid/gas separator 5 directly enters gas phase separator 7 with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method for rectifying to separate.Hydrogen adopts the method that absorbs desorb 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 revivifier behind stripping, the catalyzer of having tied the carbon inactivation carries out charcoal regeneration, catalyst recycle after the regeneration is returned reactor 3, so far circulation is finished, at this aromatization reactor 1 and low-carbon (LC) hydro carbons reactor 3 shared revivifiers.Separating the oil-phase product that obtains 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 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 aromatization reactor as recycle stream to participate in reaction.The C of residue 20% 9+ export as product with mixed C 8 aromatic hydrocarbons.Adopt above-mentioned technological process, the material balance of its total 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.The gas-phase product that comes out from solution-air-liquid/gas separator 5 directly enters gas phase separator 7 with hydrogen and methane and C 2+ low-carbon (LC) hydro carbons separates, and gas phase separator 7 adopts the method that absorbs desorbs, adopts methyl alcohol as absorption agent.Hydrogen adopts the method for transformation absorption 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 solution-air-liquid/gas separator 5 to be separated, and separates the oil-phase product that obtains by solution-air-liquid/gas separator 5 and enters aromatic hydrocarbons-non-aromatics separator 9 and separate and obtain non-aromatic component and aromatic component; Non-aromatic component returns 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 methyl alcohol, dme aromatization participation reaction as recycle stream.C 9+ export as product with mixed C 8 aromatic hydrocarbons.Adopt said system and technological process, the mass yield of mixed C 8 is 70.52%.
The foregoing description 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 technology that dimethyl ether conversion is produced aromatic hydrocarbons, and 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 regarded as being included in spirit of the present invention, scope and the content.

Claims (10)

1. produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion for one kind, it is characterized in that described system comprises:
A. an aromatization reactor (1) is used for methyl alcohol or dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator (5), the product that is used for coming out from aromatization reactor (1) is separated into gas-phase product, oil-phase product and water;
C. a low carbon olefin hydrocarbon reactor (2) is used for the low-carbon alkene from solution-air-gas-phase product that liquid triphase separator (5) is separated is converted into product based on aromatic hydrocarbons;
D. a gas-liquid separator (6) is used for and will be separated into gas-phase product and oil-phase product from the product based on aromatic hydrocarbons of low carbon olefin hydrocarbon reactor (2) generation;
E. a gas phase separator (7), the gas-phase product that is used for separating from gas-liquid separator (6) further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
F. a hydrogen methane separation device (8) is used for the hydrogen methane mixture that gas phase separator (7) is separated is separated into hydrogen and methane;
G. a low-carbon (LC) hydro carbons reactor (3) is used for the C that separates from gas phase separator (7) 2+ low-carbon (LC) hydrocarbon mixture is converted into the product based on aromatic hydrocarbons, 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) is 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. an aromatic disproportion reactor (4) is used for the benzene, toluene and the C that separate from aromatic hydrocarbons separator (10) 9+ aromatic hydrocarbons is converted into product based on mixed C 8 aromatic hydrocarbons by disproportionation reaction, and this product enters solution-air-liquid triphase separator (5) to be separated.
One kind adopt the described system of claim 1 produce the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that this technology 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 the 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, the gas-phase product that is come out by gas-liquid separator (6) enters gas phase separator (7) and is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture, the liquid product that is come out by gas-liquid separator (6) enters aromatic hydrocarbons-non-aromatics separator (9);
C. the hydrogen methane mixture of being separated by gas phase separator (7) described in the step b enters hydrogen methane separation device (8), is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator (7) described in the 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 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 the 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 portion 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 the 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.
3. produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion for one kind, it is characterized in that described system comprises:
A. an aromatization reactor (1), be used for or be converted into product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator (5), the product that is used for coming out from aromatization reactor (1) is separated into gas-phase product, oil-phase product and water;
C. a gas phase separator (7), the gas-phase product that is used for separating from solution-air liquid/gas separator (5) further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device (8) is used for the hydrogen methane mixture that gas phase separator (7) is separated is separated into hydrogen and methane;
E. a low-carbon (LC) hydro carbons reactor (3) is used for the C that separates from gas phase separator (7) 2+ low-carbon (LC) hydrocarbon mixture is converted into the product based on aromatic hydrocarbons, and this product enters solution-air-liquid triphase separator (5) to be separated;
F. an aromatic hydrocarbons-non-aromatics separator (9) is 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) is 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. an aromatic disproportion reactor (4) is used for the benzene, toluene and the C that separate from aromatic hydrocarbons separator (10) 9+ aromatic hydrocarbons is converted into product based on mixed C 8 aromatic hydrocarbons by disproportionation reaction, and this product enters solution-air-liquid triphase separator (5) to be separated.
An employing as system as described in the claim 3 produce the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that this technology 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 the 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 the step b enters hydrogen methane separation device (8), is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator (7) described in the 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 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 the 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 portion 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 the 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.
5. produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion for one kind, it is characterized in that described system comprises:
A. an aromatization reactor (1) is used for methyl alcohol or dimethyl ether conversion are the product based on aromatic hydrocarbons;
B. solution-air-liquid triphase separator (5), the product that is used for coming out from reactor (1) is separated into gas-phase product, oil-phase product and water;
C. a gas phase separator (7), the gas-phase product that is used for separating from solution-air-liquid/gas separator (5) further is separated into hydrogen methane mixture and C 2+ low-carbon (LC) hydrocarbon mixture;
D. a hydrogen methane separation device (8) is used for the hydrogen methane mixture that gas phase separator (7) is separated is separated into hydrogen and methane;
E. a low-carbon (LC) hydro carbons reactor (3) is used for the C that separates from gas phase separator (7) 2+ low-carbon (LC) hydrocarbon mixture is converted into the product based on aromatic hydrocarbons, and this product enters solution-air-liquid triphase separator (5) to be separated;
F. an aromatic hydrocarbons-non-aromatics separator (9) is 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) is 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 aromatization reactor (1) and participates in reaction, and perhaps as the product output system, isolated mixed C 8 aromatic hydrocarbons are as the product output system.
One kind adopt the described system of claim 5 produce the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that this technology 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 the 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 the step b enters hydrogen methane separation device (8), is separated into hydrogen and methane, discharges system as product;
D. the C that separates by gas phase separator (7) described in the 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 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 the 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 portion C 9+ aromatic component returns aromatization reactor (1) and participates in reaction, perhaps as the product output system, and isolated mixed C 8 aromatic hydrocarbons and residue C 9+ as the product output system.
7. as claimed in claim 1ly a kind ofly produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion, it is characterized in that: described low carbon olefin hydrocarbon reactor (2) adopts the circulating fluid bed reactor of fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or band revivifier.
8. describedly produce the system of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion as claim 1 or 3, it is characterized in that: described aromatization reactor (1), low-carbon (LC) hydro carbons reactor (3) and aromatic disproportion reactor (4) adopt the circulating fluid bed reactor of fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor or band revivifier.
9. describedly a kind ofly produce the technology of aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion as claim 2,4 or 6, it is characterized in that: described gas phase separator (7) is separated the separation method that adopted for absorbing desorption method, pressure swing adsorption process or rectification method.
10. a kind of technology of producing aromatic hydrocarbons by methyl alcohol or dimethyl ether conversion as claimed in claim 9, it is characterized in that: when described gas phase separator (7) adopted the absorption desorption method to separate, it was 1～4 alcohols, ethers, ketone or the liquid phase hydro carbons that adopts described technology self generation≤C9 that used absorption agent adopts gasoline, carbonatoms.
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CN112694381B (en) * 2019-10-23 2023-11-24 中国石油化工股份有限公司 Device and method for preparing high added value product from low-carbon olefin

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