CN109694296B - Method for preparing aromatic hydrocarbon by methanol conversion - Google Patents

Method for preparing aromatic hydrocarbon by methanol conversion Download PDF

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Publication number
CN109694296B
CN109694296B CN201710982555.4A CN201710982555A CN109694296B CN 109694296 B CN109694296 B CN 109694296B CN 201710982555 A CN201710982555 A CN 201710982555A CN 109694296 B CN109694296 B CN 109694296B
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catalyst
fluidized bed
regenerator
regenerated catalyst
regeneration medium
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CN109694296A (en
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李晓红
齐国祯
金永明
王艳学
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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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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44Noble metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The invention relates to a method for preparing aromatic hydrocarbon by catalytic conversion of methanol, which mainly solves the problems of low yield of the aromatic hydrocarbon and serious hydrothermal deactivation of a catalyst in the prior art. The method comprises the steps of enabling a methanol raw material to enter a fluidized bed reactor to be in contact reaction with a modified ZSM-5 catalyst to obtain a product containing aromatic hydrocarbon and a spent catalyst, enabling the spent catalyst after steam stripping to enter a riser regenerator to be in contact with a regeneration medium I to be burnt at 500-600 ℃, enabling an outlet of the riser regenerator to be connected with at least one group of closed cyclone separators, enabling a semi-regenerated catalyst obtained through separation of the closed cyclone separators to enter the fluidized bed regenerator to be in contact with a regeneration medium II to be continuously burnt at 630-700 ℃ to obtain a regenerated catalyst, enabling the regenerated catalyst to enter a degassing tank, and enabling a degassed product to return to the fluidized bed regenerator.

Description

Method for preparing aromatic hydrocarbon by methanol conversion
Technical Field
The invention relates to a method for preparing aromatic hydrocarbon by catalytic conversion of methanol.
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 catalytic reforming and steam cracking process is the main production process of arene and belongs to the field of petroleum production technology. China has relatively rich coal resources. With the successful development of high-efficiency and long-period methanol catalyst and methanol device upsizing technology in recent years, the production cost of coal-based methanol is greatly reduced, which provides a cheap raw material source for the production of downstream products (olefin, aromatic hydrocarbon and the like) of methanol. Therefore, the production of aromatic hydrocarbons from methanol is considered.
The technology was first reported in 1977 by Chang et al (Journal of Catalysis, 1977, 47, 249) by Mobil corporation that methanol and its oxygenates were converted over a ZSM-5 molecular sieve catalyst to produce aromatics and the likeA process for producing hydrocarbons. 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 adopted ZSM-5 molecular sieve containing 2.7 wt% of phosphorus as catalyst, the reaction temperature was 400-450 ℃, and the space velocity of methanol and dimethyl ether was 1.3 hours-1
There are many related reports and patents in this field. The patent of the catalyst for preparing aromatic hydrocarbon by methanol: chinese patents CN102372535, CN102371176, CN102371177, CN102372550, CN102372536, CN102371178, CN102416342, CN101550051, U.S. Pat. No. 4,4615995, U.S. Pat. No. 5/0099249A 1, etc. The patent in the aspect of the process for preparing aromatic hydrocarbon by methanol: US patents US4686312, CN 101244969, CN1880288, CN101602646, CN101823929, CN101671226, CN101607858, CN102199069, CN102199446, CN1880288, CN102146010, CN104326859, CN105457568, CN105457569, CN105457570, CN105461497 and the like.
Among them, patents CN105457568, CN105457569, CN105457570 and CN105461497 introduce a double regeneration fluidized bed technology for reducing the problem of hydrothermal deactivation of the catalyst. In these techniques, the first regenerator is a fast bed or a turbulent bed and regenerates at 500 to 600 ℃, but the hydrogen-burning or carbon-burning effect of the first regenerator is not clear, the water partial pressure in the second regenerator cannot be precisely controlled under the high-temperature regeneration condition, and it is difficult to suppress the hydrothermal deactivation of the catalyst to the maximum extent.
Therefore, the prior patent technologies have the problems of serious hydrothermal deactivation of the catalyst and low yield of the aromatic hydrocarbon. The invention provides a technical scheme pertinently and solves the problems.
Disclosure of Invention
The invention aims to solve the technical problem of low aromatic hydrocarbon yield in the prior art, and provides a method for preparing aromatic hydrocarbon by catalytic conversion of methanol, which has the advantage of high aromatic hydrocarbon yield.
In order to solve the problems, the technical scheme adopted by the invention is as follows: the method comprises the following steps that a methanol raw material enters a fluidized bed reactor to be in contact reaction with a modified ZSM-5 catalyst to obtain a product containing aromatic hydrocarbon and a spent catalyst, the spent catalyst after steam stripping enters a riser regenerator to be in contact with a regeneration medium I to be burnt at 500-600 ℃, the outlet of the riser regenerator is connected with at least one group of closed cyclone separators, a semi-regenerated catalyst obtained by separation of the closed cyclone separators enters the fluidized bed regenerator to be in contact with a regeneration medium II to be continuously burnt at 630-700 ℃ to obtain a regenerated catalyst, the regenerated catalyst enters a degassing tank, and a degassed product returns to the fluidized bed regenerator; the temperature of the degassed regenerated catalyst is 450-550 ℃; returning 50-90% of the degassed regenerated catalyst to the riser regenerator; returning 10-50% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 1-5 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is not more than 0.08; the volume percentage content of oxygen in the regeneration medium I is 21-30%.
In the above technical solution, preferably, the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is not more than 0.06. In one embodiment of the present invention, it is 0.02.
In the above technical solution, preferably, the degassing tank is provided with at least one heat collector, and the degassing medium is nitrogen.
In the above technical solution, preferably, the heat collector is an internal heat collector or an external heat collector.
In the technical scheme, preferably, the temperature of a catalyst bed layer of the fluidized bed reactor is 420-550 ℃, and the weight space velocity of the raw material is 0.2-15 hours-1The reaction gauge pressure is 0 to 1 MPa.
In the technical scheme, preferably, the temperature of a catalyst bed layer of the fluidized bed reactor is 480-530 ℃, and the weight space velocity of the raw material is 0.6-10 hours-1The reaction gauge pressure is 0.02-0.8 MPa.
In the technical scheme, the temperature in the riser regenerator is preferably 500-570 ℃. In one embodiment of the present invention, the temperature is 550 ℃.
In the technical scheme, the residence time of the catalyst in the riser regenerator is preferably 2-4 seconds. In one embodiment of the present invention, it is 3 s.
In the technical scheme, the temperature in the fluidized bed regenerator is preferably 630-680 ℃. In one embodiment of the present invention, the temperature is 650 ℃.
In the above technical solution, preferably, in an embodiment of the present invention, 70% of the degassed regenerated catalyst returns to the riser regenerator; after degassing, 30% of the regenerated catalyst was returned to the fluidized bed reactor.
In the above technical scheme, preferably, the modifying element of the modified ZSM-5 molecular sieve catalyst is at least one of Zn, La, P, Ga, Mn, Ag, and Cu, and the content of the modifying element is 0.01 to 15% by weight of the catalyst.
In the above technical solution, preferably, the carbon content of the regenerated catalyst is lower than 0.4% in terms of catalyst mass percent.
In the above technical solution, preferably, the mass percentage of methanol in the methanol raw material is at least 10%.
In the above technical solution, preferably, the regeneration medium i and the regeneration medium ii enter the riser regenerator and the fluidized bed regenerator after being dehydrated.
In the above technical solution, preferably, the water partial pressure of the regeneration medium i and the regeneration medium ii at 20 ℃ is not higher than 2 kpa.
The regeneration medium is an oxygen-containing gas, typically a mixture of air, air and nitrogen.
The yield of aromatic hydrocarbon per pass carbon base is the mass of aromatic hydrocarbon/(methanol feed rate x 14/32) x 100% in the product
The invention provides a technical scheme of double regenerators, wherein a first regenerator is a riser reactor and mainly completes a hydrogen burning process, a second regenerator completes a carbon burning process, and when a semi-regenerated catalyst is regenerated in the second regenerator, the generated water partial pressure is lower than the water partial pressure which obviously causes hydrothermal deactivation of the catalyst. By the measure, the hydrothermal deactivation phenomenon of the metal modified ZSM series catalyst can be effectively weakened, the activity of the catalyst is maintained, and the higher yield of the aromatic hydrocarbon is obtained.
By adopting the technical scheme of the invention, the single-pass carbon-based yield of the aromatic hydrocarbon can be maintained above 65 weight percent all the time after the operation is carried out for 1000 hours,
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; 2 is a riser regenerator; 3 is a fluidized bed regenerator; 4 is a degassing tank; 5 is a stripper; 6 is a degassing tank inclined pipe; 7 is a regeneration inclined tube; 8 is a return inclined tube of the degassing tank; 9 is a to-be-grown inclined tube; 10 is a stripper inclined tube; 11 is a fluidized bed regenerator cyclone separator; 12 is a closed cyclone separator; 13 is a cyclone separator of the fluidized bed reactor; a heat collector 14; 15 is a methanol raw material; 16 is regeneration medium I; 17 is regeneration medium II, 18 flue gas; 19 is a reaction product; 20 is a degassed product; 21 is a stripped product; 22 is a stripping medium; 23 is a degassing medium.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
The method comprises the following steps that a methanol raw material enters a fluidized bed reactor to be in contact reaction with a modified ZSM-5 catalyst to obtain a product containing aromatic hydrocarbon and a spent catalyst, the spent catalyst after steam stripping enters a riser regenerator to be in contact with a regeneration medium I to be burnt at 500 ℃, an outlet of the riser regenerator is connected with a group of closed cyclone separators, a semi-regenerated catalyst obtained by separation of the closed cyclone separators enters a fluidized bed regenerator to be in contact with a regeneration medium II to be continuously burnt at 630 ℃ to obtain a regenerated catalyst, the regenerated catalyst enters a degassing tank, and a degassed product returns to the fluidized bed regenerator; the temperature of the regenerated catalyst after degassing is 450 ℃; returning 50% of the degassed regenerated catalyst to the riser regenerator; returning 50% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 5 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is 0.08; the volume percentage of oxygen in the regeneration medium I was 21%. The carbon content of the regenerated catalyst was 0.38% by mass of the catalyst. The degassing tank is provided with a built-in heat collector. And the regeneration medium I and the regeneration medium II enter the riser regenerator and the fluidized bed regenerator after being dehydrated. The water partial pressure of the regeneration medium I and the regeneration medium II at the temperature of 20 ℃ is 1.9 kilopascal.
The temperature of the catalyst bed layer of the fluidized bed reactor is 420 ℃, and the weight space velocity of the raw material is 0.2 h-1The reaction gauge pressure was 0 MPa.
The mass percentage of the methanol in the methanol raw material is 10 percent. A Zn-La-P-ZSM-5 catalyst is adopted, and the mass percentage of the catalyst is that the Zn element content is 7%, the La element content is 5%, and the P element content is 3%.
The result shows that the aromatic hydrocarbon single-pass carbon-based yield can be maintained above 52 weight percent after 1000 hours of operation.
[ example 2 ]
According to the conditions and the steps described in the example 1, the spent catalyst enters a riser regenerator and contacts with a regeneration medium I to be burnt at the temperature of 600 ℃, the semi-regenerated catalyst enters a fluidized bed regenerator and contacts with a regeneration medium II to be continuously burnt at the temperature of 700 ℃, and the temperature of the degassed regenerated catalyst is 550 ℃; returning 90% of the degassed regenerated catalyst to the riser regenerator; returning 10% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 1 second; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is 0.06; the volume percentage of oxygen in the regeneration medium I is 30%. The carbon content of the regenerated catalyst was 0.01% by mass of the catalyst. The degassing tank is provided with an external heat collector. The water partial pressure of the regeneration medium I and the regeneration medium II is 0.5 kilopascal at the temperature of 20 ℃.
The temperature of the catalyst bed of the fluidized bed reactor is 550 ℃, and the weight space velocity of the raw material is 15 hours-1The reaction gauge pressure was 1 MPa.
The mass percentage of the methanol in the methanol raw material is 100 percent. Adopts Zn-ZSM-5 catalyst, and the Zn element content is 0.01 percent by mass percent of the catalyst.
The result shows that the single-pass carbon-based yield of the aromatic hydrocarbon can be maintained above 55 weight percent after 1000 hours of operation.
[ example 3 ]
According to the conditions and the steps described in the example 1, the spent catalyst enters a riser regenerator to be contacted with a regeneration medium I to be burnt at the temperature of 550 ℃, the semi-regenerated catalyst enters a fluidized bed regenerator to be contacted with a regeneration medium II to be continuously burnt at the temperature of 650 ℃, and the temperature of the degassed regenerated catalyst is 500 ℃; returning 70% of the degassed regenerated catalyst to the riser regenerator; returning 30% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 3 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is 0.02; the volume percentage of oxygen in the regeneration medium I is 25%. The carbon content of the regenerated catalyst was 0.05% by mass of the catalyst. The degassing tank is provided with an external heat collector. The water partial pressure of the regeneration medium I and the regeneration medium II is 0.1 kilopascal at the temperature of 20 ℃.
The temperature of the catalyst bed of the fluidized bed reactor is 500 ℃, and the weight space velocity of the raw material is 2.8 hours-1The reaction gauge pressure was 0.25 MPa.
The mass percentage of the methanol in the methanol raw material is 100 percent. A Zn-P-ZSM-5 catalyst is adopted, and the content of Zn element is 1.5 percent and the content of P element is 2.1 percent in percentage by mass of the catalyst.
The result shows that the single-pass carbon-based yield of the aromatic hydrocarbon can be maintained above 65 weight percent after 1000 hours of operation.
[ example 4 ]
According to the conditions and the steps described in the example 1, the spent catalyst enters a riser regenerator to be contacted with a regeneration medium I to be burnt at the temperature of 580 ℃, the semi-regenerated catalyst enters a fluidized bed regenerator to be contacted with a regeneration medium II to be continuously burnt at the temperature of 690 ℃, and the temperature of the degassed regenerated catalyst is 480 ℃; returning 55% of the degassed regenerated catalyst to the riser regenerator; returning 45 percent of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 5 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is 0.07; the volume percentage of oxygen in the regeneration medium I was 21%. The carbon content of the regenerated catalyst was 0.1% by mass of the catalyst. The degassing tank is provided with an external heat collector. The water partial pressure of the regeneration medium I and the regeneration medium II at the temperature of 20 ℃ is 0.2 kilopascal and 0.8 kilopascal respectively.
The temperature of the catalyst bed of the fluidized bed reactor is 470 ℃, and the weight space velocity of the raw material is 12 hours-1The reaction gauge pressure was 0.9 MPa.
The mass percentage of the methanol in the methanol raw material is 90 percent. A Zn-Ga-ZSM-5 catalyst is adopted, and the Zn element content is 3.5 percent and the Ga element content is 2.4 percent in percentage by mass of the catalyst.
The result shows that the aromatic hydrocarbon single-pass carbon-based yield can be maintained above 58 wt% after running for 1000 hours.
[ example 5 ]
According to the conditions and the steps described in the example 1, the spent catalyst enters a riser regenerator and contacts with a regeneration medium I to be burnt at the temperature of 570 ℃, the semi-regenerated catalyst enters a fluidized bed regenerator and contacts with a regeneration medium II to be continuously burnt at the temperature of 680 ℃, and the temperature of the degassed regenerated catalyst is 530 ℃; returning 85% of the degassed regenerated catalyst to the riser regenerator; returning 15% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 2 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is 0.01; the volume percentage of oxygen in the regeneration medium I was 21%. The carbon content of the regenerated catalyst was 0.05% by mass of the catalyst. The degassing tank is provided with two built-in heat collectors. The water partial pressure of the regeneration medium I and the regeneration medium II at the temperature of 20 ℃ is 0.1 kilopascal and 0.6 kilopascal respectively.
The temperature of the catalyst bed layer of the fluidized bed reactor is 530 ℃, and the weight space velocity of the raw material is 5 hours-1The reaction gauge pressure was 0.3 MPa.
The mass percentage of the methanol in the methanol raw material is 98 percent, and the mass percentage of the water is 2 percent. A Zn-Ag-ZSM-5 catalyst is adopted, and the Zn element content is 4.2 percent and the Ag element content is 1.1 percent in percentage by mass of the catalyst.
The result shows that the aromatic hydrocarbon single-pass carbon-based yield can be maintained above 60 wt% after running for 1000 hours.
[ example 6 ]
According to the conditions and the steps described in the example 1, the spent catalyst enters a riser regenerator to be contacted with a regeneration medium I to be scorched at the temperature of 500 ℃, the semi-regenerated catalyst enters a fluidized bed regenerator to be contacted with a regeneration medium II to be continuously scorched at the temperature of 630 ℃, and the temperature of the degassed regenerated catalyst is 530 ℃; returning 85% of the degassed regenerated catalyst to the riser regenerator; returning 15% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 4 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is 0.03; the volume percentage of oxygen in the regeneration medium I was 21%. The carbon content of the regenerated catalyst was 0.2% by mass of the catalyst. The degassing tank is provided with two built-in heat collectors. The water partial pressure of the regeneration medium I and the regeneration medium II at the temperature of 20 ℃ is 0.05 Pa and 0.3 Pa respectively.
The temperature of the catalyst bed of the fluidized bed reactor is 480 ℃, and the weight space velocity of the raw material is 0.6 h-1The reaction gauge pressure was 0.02 MPa.
The mass percentage of the methanol in the methanol raw material is 100 percent. A Zn-Ag-ZSM-5 catalyst is adopted, and the Zn element content is 3.8 percent and the Ag element content is 1.5 percent in percentage by mass of the catalyst.
The result shows that the aromatic hydrocarbon single-pass carbon-based yield can be maintained above 60 wt% after running for 1000 hours.
Comparative example 1
The starting materials, procedures and catalyst of example 2 were used except that the partial pressure of water at 20 ℃ in regeneration medium I and regeneration medium II was greater than 2 kPa. The results show that the yield of the aromatic hydrocarbon single-pass carbon base can be maintained to be more than 55 weight percent within 200 hours of operation, and then the yield of the aromatic hydrocarbon single-pass carbon base is gradually reduced, and the yield of the aromatic hydrocarbon single-pass carbon base is reduced to 49 weight percent when the operation is carried out for 1000 hours.
Comparative example 2
The raw materials, the steps and the catalyst in the embodiment 2 are adopted, except that the catalyst to be regenerated enters a riser regenerator and contacts with a regeneration medium I to be burnt at 480 ℃, and the residence time of the catalyst in the riser regenerator is 0.8 second; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst was 0.09. Other conditions were the same as in example 2. The results show that the yield of the aromatic hydrocarbon single-pass carbon base can be maintained to be more than 55 weight percent within 400 hours of operation, and then the yield of the aromatic hydrocarbon single-pass carbon base is gradually reduced, and the yield of the aromatic hydrocarbon single-pass carbon base is reduced to 47 weight percent when the operation is carried out for 1000 hours.
Comparative example 3
The starting material and catalyst of example 2 were used, except that a fluidized bed regenerator was used, the regeneration temperature was 670 ℃ and the partial pressure of water at 20 ℃ of the regeneration medium was 0.5 kPa. The results show that the yield of the aromatic hydrocarbon single-pass carbon base can be maintained to be more than 55 weight percent within 300 hours of operation, and then the yield of the aromatic hydrocarbon single-pass carbon base is gradually reduced, and the yield of the aromatic hydrocarbon single-pass carbon base is reduced to 46 weight percent when the operation is carried out for 1000 hours.
Comparative example 4
The feed and catalyst of example 2 were used except that two fluidized bed regenerators were used. The results show that the yield of the aromatic hydrocarbon single-pass carbon base can be maintained to be more than 55 weight percent within 400 hours of operation, and then the yield of the aromatic hydrocarbon single-pass carbon base is gradually reduced, and the yield of the aromatic hydrocarbon single-pass carbon base is reduced to 52 weight percent when the operation is carried out for 1000 hours.
Comparative example 5
The feed and catalyst of example 2 were used except that 100% of the regenerated catalyst was returned to the fluidized bed reactor after degassing. The results show that the single-pass carbon-based yield of the aromatic hydrocarbon can only be maintained at about 45 wt%.

Claims (9)

1. A method for preparing aromatic hydrocarbon through catalytic conversion of methanol comprises the steps that a methanol raw material enters a fluidized bed reactor to be in contact reaction with a modified ZSM-5 catalyst to obtain a product containing the aromatic hydrocarbon and a spent catalyst, the spent catalyst after steam stripping enters a riser regenerator to be contacted with a regeneration medium I to be burnt at 500-600 ℃, the outlet of the riser regenerator is connected with at least one group of closed cyclone separators, a semi-regenerated catalyst obtained through separation by the closed cyclone separators enters the fluidized bed regenerator to be contacted with a regeneration medium II to be continuously burnt at 630-700 ℃ to obtain a regenerated catalyst, the regenerated catalyst enters a degassing tank, and a degassed product returns to the fluidized bed regenerator;
the temperature of the degassed regenerated catalyst is 450-550 ℃; returning 50-90% of the degassed regenerated catalyst to the riser regenerator; returning 10-50% of the degassed regenerated catalyst to the fluidized bed reactor; the residence time of the catalyst in the riser regenerator is 1-5 seconds; the mass ratio of hydrogen to carbon elements of coke on the semi-regenerated catalyst is not more than 0.08; the volume percentage content of oxygen in the regeneration medium I is 21-30%; the water partial pressure of the regeneration medium I and the regeneration medium II is not higher than 2 kilopascals at the temperature of 20 ℃.
2. The method of claim 1, wherein the mass ratio of hydrogen to carbon in the coke on the semi-regenerated catalyst is not greater than 0.06.
3. The method for preparing aromatic hydrocarbon through catalytic conversion of methanol according to claim 1, wherein the degassing tank is provided with at least one heat collector, and the degassing medium is nitrogen.
4. The method for preparing aromatic hydrocarbons through catalytic conversion of methanol according to claim 3, wherein the heat collector is an internal heat collector or an external heat collector.
5. The method for preparing aromatic hydrocarbon through catalytic conversion of methanol according to claim 1, wherein the temperature of a catalyst bed layer of a fluidized bed reactor is 420-550 ℃, and the weight space velocity of the raw material is 0.2-15 hours-1The reaction gauge pressure is 0 to 1 MPa.
6. The method for preparing aromatic hydrocarbons through catalytic conversion of methanol according to claim 1, wherein the modifying element of the modified ZSM-5 molecular sieve catalyst is at least one of Zn, La, P, Ga, Mn, Ag and Cu, and the content of the modifying element is 0.01-15% by weight of the catalyst.
7. The method of claim 1, wherein the carbon content of the regenerated catalyst is less than 0.4% by mass of the catalyst.
8. The method for preparing aromatic hydrocarbons through catalytic conversion of methanol according to claim 1, wherein the mass percentage of methanol in the methanol raw material is at least 10%.
9. The method for preparing aromatic hydrocarbons through catalytic conversion of methanol according to claim 1, wherein the regeneration medium I and the regeneration medium II enter the riser regenerator and the fluidized bed regenerator after being dehydrated.
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