CN108017488B - Method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw material - Google Patents

Method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw material Download PDF

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CN108017488B
CN108017488B CN201610973694.6A CN201610973694A CN108017488B CN 108017488 B CN108017488 B CN 108017488B CN 201610973694 A CN201610973694 A CN 201610973694A CN 108017488 B CN108017488 B CN 108017488B
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alcohol
product
ether
bed reactor
catalyst
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CN108017488A (en
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李晓红
钟思青
金永明
王菊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw materials, which mainly solves the problem of low yield of the aromatic hydrocarbon in the prior art. According to the technical scheme, alcohol and/or ether raw materials enter a fluidized bed reactor I to obtain a reaction product I, the reaction product I enters a separation unit I to obtain a gas-phase product, a water-phase product and an aromatic hydrocarbon product I, at least one part of the gas-phase product enters a fluidized bed reactor II to react to obtain a reaction product II, the reaction product II enters a separation unit II to obtain a light hydrocarbon product, a heavy hydrocarbon product and an aromatic hydrocarbon product II, at least one part of the heavy hydrocarbon product enters an aromatization reactor to obtain a reaction product III, the reaction product III enters the separation unit I, and the fluidized bed reactor I and the fluidized bed reactor II share a regenerator.

Description

Method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw material
Technical Field
The invention relates to a method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw materials.
Background
Aromatic hydrocarbons (especially triphenyl, Benzene, Toluene, Xylene, i.e., BTX) are important basic organic synthesis feedstocks. Driven by the demand for downstream derivatives, the market demand for aromatics continues to increase.
The steam cracking process using liquid hydrocarbons (such as naphtha, diesel oil, secondary processing oil) as raw materials is the main production process of aromatic hydrocarbons. The process belongs to the production technology of petroleum routes, and in recent years, the cost of raw materials is continuously increased due to the limited supply and higher price of petroleum resources. Due to the factors, the technology for preparing aromatic hydrocarbon by replacing raw materials draws more and more extensive attention. China has relatively rich coal resources. With the successful development of high-efficiency and long-period methanol catalyst and methanol device large-scale technology in recent years, the production cost of coal-based methanol and/or dimethyl ether is greatly reduced, and a cheap raw material source is provided for the production of downstream products (olefin, aromatic hydrocarbon and the like) of methanol and/or dimethyl ether. Therefore, the production of aromatic hydrocarbons from methanol and/or dimethyl ether as a raw material is considered.
This technology was first reported in 1977 by Chang et al (Journal of Catalysis, 1977, 47, 249) by Mobil corporation to prepare hydrocarbons such as aromatic hydrocarbons by conversion of methanol and its oxygenates over a ZSM-5 molecular sieve catalyst. In 1985, Mobil corporation in its applied US1590321, first published the research result of preparing aromatic hydrocarbon by converting methanol and dimethyl ether, the research adopts ZSM-5 molecular sieve containing 2.7 wt% of phosphorus as catalyst, the reaction temperature is 400-450 ℃, and the airspeed of methanol and dimethyl ether is 1.3h-1。
Chinese patents 201010111821.4, 200910090002.3, 200810102684.0, 200910135643.6 and 200910089699.2 adopt a reactor, the reactor only has a reaction zone, and a single reaction temperature is adopted. Liquefied gas and ethylene in light hydrocarbon generated by methanol aromatization reaction in the system proposed by the Chinese patent 201410447321.6 are returned to the methanol aromatization reactor for further conversion. The oil phase hydrocarbons with the carbon number of less than 7 obtained by separating the product of the alcohol/ether aromatization reaction device in the system proposed by Chinese patent 201410106062.0 enter the alcohol/ether aromatization reaction device for further reaction. The oxygen-containing compound is easy to generate thermal cracking reaction at the temperature higher than 500 ℃ to generate methane and carbon monoxide with low added values, and simultaneously, the coke content is increased. To reduce this part of the reaction, the reaction temperature is generally below 500 ℃, while the reaction temperature suitable for the low carbon hydrocarbon aromatization reaction is above 500 ℃, thus leading to the problem of lower aromatic selectivity of the prior art.
According to the method disclosed in the Chinese patent 200610012703.1, gas-phase low-carbon hydrocarbon obtained by methanol in the first-stage reaction enters a second-stage reactor, and the reaction is continued at the temperature of 250-500 ℃, wherein the two stages of catalysts are different. According to the method introduced in the Chinese patent 200910089698.8, propylene is separated from a product generated by the reaction of methanol or/and dimethyl ether in the fixed bed reactor, and the propylene enters the second fixed bed reactor to react at the temperature of 250-350 ℃. The second stage or the second reactor of the method has lower reaction temperature and low selectivity of aromatic hydrocarbon.
In the method introduced in chinese patent 20100108008.1, methanol is firstly subjected to alkylation reaction, and all reaction products enter an aromatization reactor to finally obtain ethylene, propylene, butylene, benzene, toluene and xylene. The method has low selectivity of aromatic hydrocarbon due to the existence of low-carbon olefin in the final product.
The method introduced in the Chinese patent 201010146915.5 does not discharge carbon dioxide hydrocarbon, adopts Zn and Mo modified ZSM-5 and ZSM-35 catalysts, and does not introduce the selectivity of aromatic hydrocarbon in the light hydrocarbon aromatization process.
The above patent technologies all have the problem of low selectivity of aromatic hydrocarbon. The invention provides a technical scheme pertinently and solves the problems.
Disclosure of Invention
The invention aims to solve the technical problem that in the prior art, the aromatic selectivity is low when a non-aromatic hydrocarbon product obtained by aromatization of an alcohol and/or ether raw material continues to be aromatized, and provides a method for preparing aromatic hydrocarbon by catalytic conversion of the alcohol and/or ether raw material.
In order to solve the problems, the technical scheme adopted by the invention is as follows: feeding an alcohol and/or ether raw material (7) into a fluidized bed reactor I (1) to obtain a reaction product I (8), feeding the reaction product I (8) into a separation unit I (5) to obtain a gas-phase product (11), a water-phase product (12) and an aromatic hydrocarbon product I (13), feeding at least one part of the gas-phase product (11) into a fluidized bed reactor II (3) to react to obtain a reaction product II (14), feeding the reaction product II (14) into a separation unit II (6) to obtain a light hydrocarbon product (15), a heavy hydrocarbon product (16) and an aromatic hydrocarbon product II (18), feeding at least one part of the heavy hydrocarbon product (16) into an aromatization reactor (4) to obtain a reaction product III (17), and feeding the reaction product III (17) into the separation unit I (5); the light hydrocarbon product (15) comprises at least a portion of C2 alkanes.
In the above technical solution, preferably, the light hydrocarbon product (15) includes all of the C2 alkanes in the reaction product ii (14).
In the above solution, preferably, the heavy hydrocarbon product (16) does not comprise C2 olefins.
In the above technical solution, preferably, the fluidized bed reactor i (1) and the fluidized bed reactor ii (3) share the regenerator (2).
In the above technical scheme, preferably, the fluidized bed reactor I (1) and the fluidized bed reactor II (3) adopt the same catalyst, and the catalyst is a ZSM-5 molecular sieve catalyst.
In the technical scheme, preferably, the temperature of a catalyst bed layer of the fluidized bed reactor I (1) is 420-550 ℃, and the weight space velocity is 0.2-6 h-1The reaction pressure is 0 to 0.5 MPa in terms of gauge pressure.
In the technical scheme, preferably, the temperature of the catalyst bed layer of the fluidized bed reactor II (3) is 480-600 ℃, and the weight space velocity is 0.2-5 h-1The reaction pressure is 0 to 0.5 MPa in terms of gauge pressure.
In the technical scheme, preferably, the active component of the catalyst II adopted by the aromatization reactor (4) comprises at least one selected ZSM-5, ZSM-23, ZSM-11, β molecular sieve, MCM-22 molecular sieve or a composite molecular sieve formed by the molecular sieves, the catalyst load comprises at least one selected element in Zn, P, Ga, La, Ag, Cu, Mn and Mg, and the content of each element loaded by the catalyst is 0.01-15% by mass percent.
In the technical scheme, preferably, the temperature of a catalyst bed layer in the aromatization reactor (4) is 500-600 ℃, and the weight space velocity is 0.3-5 h-1The reaction pressure is 0 to 0.5 MPa in terms of gauge pressure.
In the above technical solution, preferably, the light hydrocarbon product (15) includes hydrogen, methane and carbon two hydrocarbons, and the heavy hydrocarbon product (16) includes non-aromatic hydrocarbons with more than three carbon atoms.
In the above technical scheme, preferably, the aromatization reactor (4) is an adiabatic fixed bed reactor or a tubular fixed bed reactor or an isothermal fixed bed reactor.
In the above technical scheme, preferably, the aromatization reactor (4) is provided with at least two reactors, at least one reactor is opened and one reactor is prepared, the reaction and the regeneration are switched, and the regeneration period is 10-720 hours.
In the above technical solution, preferably, the regeneration conditions are: the regeneration temperature is 450-650 ℃, the regeneration medium is oxygen-containing gas, and the volume content of oxygen is 0.1-21%.
In the technical scheme, preferably, 10-100% of the gas-phase product (11) enters the fluidized bed reactor II (3) by weight; 10-100% by weight of the heavy hydrocarbon product (16) enters the aromatization reactor (4).
In the technical scheme, the temperature of the catalyst bed layer of the aromatization fluidized bed reactor I (1) is preferably 470-530 ℃.
In the technical scheme, preferably, the catalyst I is a modified ZSM-5 catalyst; the modified element comprises at least one of Zn, P, Ga, La and Ag; the total content of the modified elements is 0.01-10% by mass of the catalyst.
In the technical scheme, the catalyst II is preferably a ZSM-5 molecular sieve catalyst loaded with Zn, Ga and La, and the total content of the loaded metal is 0.1-10% in percentage by mass of the catalyst.
In the above technical solution, preferably, the alcohol and/or ether raw material (7) includes methanol, ethanol, n-propanol, isopropanol, and C4～C20At least one of alcohol, methyl ethyl ether, dimethyl ether, diethyl ether and diisopropyl ether; the mass percentage of the oxygen-containing compound is at least 10%.
Research shows that 35-45% of carbon-based C1-C6 low-carbon hydrocarbons exist in the products of the alcohol and/or ether raw material aromatization process, and if the low-carbon hydrocarbons further undergo aromatization reaction, the aromatic selectivity of the alcohol and/or ether raw material aromatization process can be effectively improved. Because a large amount of dehydrogenation and hydrogen transfer reactions exist in the aromatization process of the alcohol and/or ether raw materials, the alkane, especially propane, in the low-carbon hydrocarbon has high content, and the content of the propane can reach more than 30 percent. The low-carbon hydrocarbon mixture obtained in the aromatization process of the alcohol and/or ether raw material is a mixture of C1-C6 olefin and alkane. The carbon-hydrogen bond and carbon-carbon bond in the low-carbon alkane have high stability, and dehydrogenation activation is needed to generate low-carbon alkene in the aromatization reaction, so the aromatization of the low-carbon alkane is more difficult. In addition, the lower the carbon number of the C1-C6 is, the more difficult the activation becomes, and the less aromatization reaction is likely to occur. Therefore, the aromatization performance of various low-carbon hydrocarbons in the low-carbon hydrocarbon mixture obtained in the aromatization process of the alcohol and/or ether raw material is greatly different. If only one catalyst and reaction conditions are adopted, the selectivity of aromatic hydrocarbon of low-carbon hydrocarbon which is easy to perform aromatization reaction is reduced, or the low-carbon hydrocarbon which is difficult to perform aromatization reaction is greatly enriched in a reactor due to low aromatization conversion rate, so that the economy is reduced. In order to avoid the phenomenon and improve the aromatic selectivity of the aromatization of the low-carbon hydrocarbon obtained in the aromatization process of the alcohol and/or ether raw material, the technical scheme of the invention discharges methane and carbon dioxide hydrocarbons with higher aromatization difficulty in the low-carbon hydrocarbon obtained by the reaction of the alcohol and/or ether raw material in the fluidized bed reactor I, and non-aromatic hydrocarbons with more than three carbon atoms enter the fluidized bed reactor II under milder reaction conditions, wherein the hydrocarbon which is easier to undergo aromatization reaction completes the conversion to the aromatic hydrocarbon, and the remaining hydrocarbon which is harder to undergo aromatization reaction continuously enters the aromatization reactor under relatively harsh reaction conditions. By adopting the technical scheme of the invention, the yield of the arene carbon base reaches 78.2 weight percent, the yield of the BTX carbon base reaches 62.6 weight percent, and a better technical effect is achieved.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
In FIG. 1, 1 is a fluidized bed reactor I; 2 is a regenerator; 3 is a fluidized bed reactor II; 4 is an aromatization reactor; 5 is a separation unit I; 6 is a separation unit II; 7 is an alcohol and/or ether feedstock; 8 is a reaction product I; 9 is main wind; 10 is flue gas; 11 is a gas phase product; 12 is an aqueous phase product; 13 is an aromatic hydrocarbon product I; 14 is a reaction product II; 15 is a light hydrocarbon product; 16 is a heavy hydrocarbon product; 17 is a reaction product III; 18 is an aromatic product II.
The method comprises the steps that an alcohol and/or ether raw material 7 enters a fluidized bed reactor I1 to obtain a reaction product I8, the reaction product I8 enters a separation unit I5 to obtain a gas-phase product 11, a water-phase product 12 and an aromatic hydrocarbon product I13, the gas-phase product 11 completely enters a fluidized bed reactor II 3 to react to obtain a reaction product II 14, the reaction product II 14 enters a separation unit II 6 to obtain a light hydrocarbon product 15, a heavy hydrocarbon product 16 and an aromatic hydrocarbon product II 18, the heavy hydrocarbon product 16 completely enters an aromatization reactor 4 to obtain a reaction product III 17, and the reaction product III 17 enters the separation unit I5.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
The raw materials with the weight percentage of 95% of methanol enter a fluidized bed reactor I (1) to obtain a reaction product I (8), the reaction product I (8) enters a separation unit I (5) to obtain a gas phase product (11), a water phase product (12) and an aromatic hydrocarbon product I (13), the gas phase product (11) completely enters a fluidized bed reactor II (3) to react to obtain a reaction product II (14), the reaction product II (14) enters a separation unit II (6) to obtain a light hydrocarbon product (15), a heavy hydrocarbon product (16) and an aromatic hydrocarbon product II (18), the heavy hydrocarbon product (16) completely enters an aromatization reactor (4) to obtain a reaction product III (17), and the reaction product III (17) enters the separation unit I (5). The light hydrocarbon product (15) contained all of the C2 alkanes in reaction product II (14). The heavy hydrocarbon product (16) contains no C2 olefins.
The fluidized bed reactor I (1) and the fluidized bed reactor II (3) adopt a P modified Zn-ZSM-5 molecular sieve catalyst, and the Zn loading mass percentage content is 0.1%. The temperature of the catalyst bed layer of the fluidized bed reactor I (1) is 420 ℃, and the weight space velocity is 0.2h-1The reaction pressure is normal pressure. The temperature of the catalyst bed layer of the fluidized bed reactor II (3) is 480 ℃, and the weight space velocity is 0.2h-1The reaction pressure is normal pressure.
The aromatization reactor (4) adopts a ZSM-5 molecular sieve catalyst loaded with Zn, Ga and La, and the total content of loaded metals is 0.01 percent in terms of the mass percent of the catalyst; the temperature of the catalyst bed layer is 500 ℃, and the weight space velocity is 0.3h-1The reaction pressure is normal pressure. The aromatization reactor (4) is an adiabatic fixed bed reactor, two reactors are arranged, one is opened and the other is prepared, the reaction and the regeneration are switched, and the regeneration period is 10 hours; the regeneration conditions are as follows: the regeneration temperature is 450 ℃, the regeneration medium is oxygen-containing gas, and the volume content of oxygen is 0.1%.
The light hydrocarbon product (15) is hydrogen, methane and carbon two hydrocarbons, and the heavy hydrocarbon product (16) is non-aromatic hydrocarbon with more than three carbon atoms.
The results showed that the yield of aromatic hydrocarbon carbon groups was 65.5 wt% and the yield of BTX carbon groups was 52.4 wt%.
[ example 2 ]
According to the conditions and procedures described in example 1, a feedstock containing 10% by weight of methanol is fed into a fluidized bed reactor I (1) to produce a reaction product I (8); 10% by weight of the gas-phase product (11) is fed to the fluidized-bed reactor II (3); 10% by weight of the heavy hydrocarbon product (16) enters the aromatization reactor (4). The light hydrocarbon product (15) contained all of the C2 alkanes in reaction product II (14). The heavy hydrocarbon product (16) contains no C2 olefins.
The fluidized bed reactor I (1) and the fluidized bed reactor II (3) adopt a P modified Zn-ZSM-5 molecular sieve catalyst, and the Zn loading mass percentage content is 10%. The temperature of the catalyst bed layer of the fluidized bed reactor I (1) is 550 ℃, and the weight space velocity is 6h-1The reaction pressure was 0.5 MPa in gauge pressure. The temperature of the catalyst bed layer of the fluidized bed reactor II (3) is 600 ℃, and the weight space velocity is 5h-1The reaction pressure was 0.5 MPa in gauge pressure.
The aromatization reactor (4) adopts a ZSM-5 molecular sieve catalyst loaded with Zn, Ga and La, and the total content of loaded metals is 15 percent in terms of the mass percentage of the catalyst; the temperature of the catalyst bed layer is 600 ℃, and the weight space velocity is 5h-1The reaction pressure was 0.5 MPa in gauge pressure. The aromatization reactor (4) is a tubular fixed bed reactor, two tubular fixed bed reactors are arranged, one is opened, the other is prepared, the reaction and the regeneration are switched, and the regeneration period is 720 hours; the regeneration conditions are as follows: the regeneration temperature is 650 ℃, the regeneration medium is oxygen-containing gas, and the oxygen volume content is 21%.
The results showed that the yield of aromatic hydrocarbon carbon groups was 72.8 wt% and the yield of BTX carbon groups was 56.8 wt%.
[ example 3 ]
According to the conditions and procedures described in example 1, a feedstock containing 10% by weight of methanol is fed into a fluidized bed reactor I (1) to produce a reaction product I (8); 100% by weight of the gas-phase product (11) is fed into a fluidized-bed reactor II (3); 100% by weight of the heavy hydrocarbon product (16) enters the aromatization reactor (4). The light hydrocarbon product (15) contained all of the C2 alkanes in reaction product II (14). The heavy hydrocarbon product (16) contains no C2 olefins.
The fluidized bed reactor I (1) and the fluidized bed reactor II (3) adopt P modificationThe Zn-ZSM-5 molecular sieve catalyst has the Zn loading mass percentage content of 5 percent. The temperature of the catalyst bed layer of the fluidized bed reactor I (1) is 500 ℃, and the weight space velocity is 2h-1The reaction pressure was 0.2 MPa in gauge pressure. The temperature of the catalyst bed layer of the fluidized bed reactor II (3) is 550 ℃, and the weight space velocity is 2h-1The reaction pressure was 0.2 MPa in gauge pressure.
The aromatization reactor (4) adopts a ZSM-5 molecular sieve catalyst loaded with Zn, Ga and La, and the total content of loaded metals is 5 percent in terms of the mass percentage of the catalyst; the temperature of the catalyst bed layer is 550 ℃, and the weight space velocity is 1.5h-1The reaction pressure was 0.2 MPa in gauge pressure. The aromatization reactor (4) is an adiabatic fixed bed reactor, two reactors are arranged, one is opened and the other is prepared, the reaction and the regeneration are switched, and the regeneration period is 200 hours; the regeneration conditions are as follows: the regeneration temperature is 560 ℃, the regeneration medium is oxygen-containing gas, and the oxygen volume content is 10%.
The results showed that the yield of the aromatic hydrocarbon carbon group was 78.2 wt% and the yield of the BTX carbon group was 62.6 wt%.
[ example 4 ]
The starting materials, conditions and procedures described in example 3 were followed.
The fluidized bed reactor I (1) and the fluidized bed reactor II (3) adopt a P modified Zn-ZSM-5 molecular sieve catalyst, and the Zn loading mass percentage content is 3%.
The aromatization reactor (4) adopts a ZSM-5 molecular sieve catalyst loaded with Zn, Ga and La, and the total content of the loaded metal is 10 percent by mass of the catalyst.
The results showed that the yield of the aromatic hydrocarbon carbon groups was 73.4 wt% and the yield of the BTX carbon groups was 58.7 wt%.
[ example 5 ]
The starting materials, catalysts and procedure described in example 3 were followed. 80% by weight of the gas-phase product (11) is fed to the fluidized-bed reactor II (3); 80% by weight of the heavy hydrocarbon product (16) enters the aromatization reactor (4).
The results showed that the yield of the aromatic hydrocarbon carbon groups was 76.8 wt% and the yield of the BTX carbon groups was 61.4 wt%.
[ example 6 ]
The catalyst, conditions and procedure described in example 3 were followed. Raw materials with the total weight percentage of 70 percent of methanol and ethanol (the weight ratio of methanol to ethanol is 1:1) enter a fluidized bed reactor I (1) to obtain a reaction product I (8).
The results showed that the yield of aromatic hydrocarbon carbon groups was 71.8 wt% and the yield of BTX carbon groups was 56.7 wt%.
[ example 7 ]
The catalyst, reaction conditions and procedure described in example 3 were followed. The light hydrocarbon product (15) contained 70% of the C2 paraffins in reaction product II (14), with the remaining C2 paraffins in reaction product II (14) going to the heavy hydrocarbon product (16).
The results showed that the yield of the aromatic hydrocarbon carbon groups was 75.3 wt% and the yield of the BTX carbon groups was 59.5 wt%.
[ COMPARATIVE EXAMPLE 1 ]
Following the catalyst, reaction conditions and procedures described in example 3, the light hydrocarbon product (15) contained no C2 alkanes, and the C2 alkanes in reaction product ii (14) went to the heavy hydrocarbon product (16). The results showed that the yield of aromatic hydrocarbon carbon groups was 60.2 wt% and the yield of BTX carbon groups was 48.9 wt%.
[ COMPARATIVE EXAMPLE 2 ]
Following the catalyst, reaction conditions and procedures described in example 3, the heavy hydrocarbon product (16) comprises C2 olefins. The results showed that the yield of aromatic hydrocarbon carbon groups was 69.2 wt% and the yield of BTX carbon groups was 55.4 wt%.

Claims (15)

1. A method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw materials is characterized in that alcohol and/or ether raw materials (7) enter a fluidized bed reactor I (1) to obtain a reaction product I (8), the reaction product I (8) enters a separation unit I (5) to obtain a gas-phase product (11), a water-phase product (12) and an aromatic hydrocarbon product I (13), at least one part of the gas-phase product (11) enters a fluidized bed reactor II (3) to react to obtain a reaction product II (14), the reaction product II (14) enters a separation unit II (6) to obtain a light hydrocarbon product (15), a heavy hydrocarbon product (16) and an aromatic hydrocarbon product II (18), at least one part of the heavy hydrocarbon product (16) enters an aromatization reactor (4) to obtain a reaction product III (17), and the reaction product III (17) enters the separation unit I (5); the light hydrocarbon products (15) included all the C2 alkanes in reaction product II (14), and the heavy hydrocarbon products (16) contained no C2 alkenes.
2. The method for preparing aromatic hydrocarbons by catalytic conversion of alcohol and/or ether feedstocks according to claim 1, wherein the fluidized bed reactor i (1) and the fluidized bed reactor ii (3) share the regenerator (2).
3. The method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw materials according to claim 1, characterized in that the fluidized bed reactor I (1) and the fluidized bed reactor II (3) adopt the same catalyst, and the catalyst is a ZSM-5 molecular sieve catalyst.
4. The method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw materials as claimed in claim 1, wherein the temperature of the catalyst bed of the fluidized bed reactor I (1) is 420-550 ℃, and the weight space velocity is 0.2-6 h-1The reaction pressure is 0 to 0.5 MPa in terms of gauge pressure.
5. The method for preparing aromatic hydrocarbon by catalytic conversion of alcohol and/or ether raw materials according to claim 1, wherein the temperature of a catalyst bed layer of a fluidized bed reactor II (3) is 480-600 ℃, and the weight space velocity is 0.2-5 h-1The reaction pressure is 0 to 0.5 MPa in terms of gauge pressure.
6. The method for preparing the aromatic hydrocarbon by the catalytic conversion of the alcohol and/or ether raw material according to claim 1, wherein the active component of the catalyst II adopted by the aromatization reactor (4) comprises at least one selected from ZSM-5, ZSM-23, ZSM-11, β molecular sieves, MCM-22 molecular sieves or composite molecular sieves formed among the molecular sieves, the catalyst load comprises at least one element selected from Zn, P, Ga, La, Ag, Cu, Mn and Mg, and the content of each element loaded by the catalyst is 0.01-15% by mass of the catalyst.
7. The method of claim 1, wherein the aromatic hydrocarbon is produced by catalytic conversion of the alcohol and/or ether feedstockThe temperature of a catalyst bed layer in the aromatization reactor (4) is 500-600 ℃, and the weight space velocity is 0.3-5 h-1The reaction pressure is 0 to 0.5 MPa in terms of gauge pressure.
8. The process for the catalytic conversion of an alcohol and/or ether feedstock to aromatics according to claim 1, wherein the light hydrocarbon products (15) include hydrogen, methane, and carbon-two hydrocarbons, and the heavy hydrocarbon products (16) include non-aromatics over three carbons.
9. The method for preparing aromatic hydrocarbons by catalytic conversion of an alcohol and/or ether feedstock as claimed in claim 1, wherein the aromatization reactor (4) is an adiabatic fixed bed reactor or a tubular fixed bed reactor or an isothermal fixed bed reactor.
10. The method for preparing aromatic hydrocarbons by catalytic conversion of alcohol and/or ether raw materials according to claim 1, characterized in that the aromatization reactor (4) is provided with at least two reactors, at least one of which is opened and prepared, and the reaction and regeneration are switched, and the regeneration period is 10-720 hours.
11. The method for producing aromatic hydrocarbons by catalytic conversion of an alcohol and/or ether feedstock according to claim 2, wherein the regeneration conditions are: the regeneration temperature is 450-650 ℃, the regeneration medium is oxygen-containing gas, and the volume content of oxygen is 0.1-21%.
12. The method for preparing the aromatic hydrocarbon by the catalytic conversion of the alcohol and/or ether raw material as claimed in claim 1, wherein 10-100% of the gas phase product (11) by weight enters a fluidized bed reactor II (3); 10-100% by weight of the heavy hydrocarbon product (16) enters the aromatization reactor (4).
13. The method for preparing the aromatic hydrocarbon by the catalytic conversion of the alcohol and/or ether raw material as claimed in claim 1, wherein the temperature of the catalyst bed of the fluidized bed reactor I (1) is 470-530 ℃.
14. The method for preparing the aromatic hydrocarbon through catalytic conversion of the alcohol and/or ether raw material according to claim 6, wherein the catalyst II is a ZSM-5 molecular sieve catalyst loaded with Zn, Ga and La, and the total content of the loaded metals is 0.1-10% in percentage by mass of the catalyst.
15. The method for producing aromatic hydrocarbons by catalytic conversion of an alcohol and/or ether feedstock according to claim 1, wherein the alcohol and/or ether feedstock (7) comprises at least one of methanol, ethanol, n-propanol, isopropanol, C4-C20 alcohols, methyl ethyl ether, dimethyl ether, diethyl ether, and diisopropyl ether; the mass percentage of the oxygen-containing compound is at least 10%.
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