CN109694306B - Method for preparing dimethylbenzene by efficiently converting methanol - Google Patents

Method for preparing dimethylbenzene by efficiently converting methanol Download PDF

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CN109694306B
CN109694306B CN201710982628.XA CN201710982628A CN109694306B CN 109694306 B CN109694306 B CN 109694306B CN 201710982628 A CN201710982628 A CN 201710982628A CN 109694306 B CN109694306 B CN 109694306B
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CN109694306A (en
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李晓红
钟思青
王菊
王艳学
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C07—ORGANIC CHEMISTRY
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    • 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
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    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline 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
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • 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
    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron

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Abstract

The invention relates to a method for preparing dimethylbenzene by efficiently converting methanol, which mainly solves the problem of low selectivity of dimethylbenzene in the prior art. The raw material containing methanol enters a methanol reaction zone of an aromatization unit, and a hydrocarbon product I which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit by utilizing a gas-solid ultrashort contact mode; the hydrocarbon product I mainly containing aromatic hydrocarbon comprises a methane-hydrogen mixture with the mass percent of less than 3 percent and C with the mass percent of less than 5 percent10 +Aromatic hydrocarbons; the separation unit separates to obtain a methane-hydrogen mixture C2 +Light hydrocarbon mixture, benzene, toluene, xylene, carbon nonaarene and C10 +Aromatic hydrocarbons; c2 +The light hydrocarbon mixture returns to the light hydrocarbon reaction zone of the aromatization unit, and a product II which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit; the technical proposal that toluene and carbon nonaromatic hydrocarbon enter a disproportionation unit and the obtained disproportionation product returns to a separation unit better solves the problem and can be used in the industrial production of aromatic hydrocarbon.

Description

Method for preparing dimethylbenzene by efficiently converting methanol
Technical Field
The invention relates to a method for preparing dimethylbenzene by efficiently converting 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 for aromatics, especially xylene, continues to grow.
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, it is considered to produce aromatic hydrocarbons and xylene from methanol.
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 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. For example, patents for methanol to aromatics catalysts: CN102372535, CN102371176, CN102371177, CN102372550, CN102372536, CN102371178, CN102416342, CN101550051, US4615995, US2002/0099249A1 and the like. The patent in the aspect of the process for preparing aromatic hydrocarbon by methanol: US4686312, CN 101244969, CN1880288, CN101602646, CN101823929, CN101671226, CN101607858, CN102199069, CN102199446, CN1880288, CN102146010, CN104326859, CN105457568, CN105457569, CN105457570, CN105461497 and the like.
Liquefied gas and ethylene in light hydrocarbon generated by methanol aromatization reaction in the system proposed by the Chinese patent CN104326859 are returned to the methanol aromatization reactor for further conversion. The oil phase hydrocarbons with the carbon number of below 7 obtained by separating the product of the alcohol/ether aromatization reaction device in the system proposed by Chinese patent CN103864565 enter the alcohol/ether aromatization reaction device for further reaction. In the process of preparing aromatic hydrocarbon from oxygen-containing compound, it is believed that the oxygen-containing compound, such as methanol and ethanol, is first dehydrated under acid catalysis to generate low carbon hydrocarbon, and the low carbon hydrocarbon is further subjected to aromatization reaction to obtain aromatic hydrocarbon. The suitable reaction temperature of the low-carbon hydrocarbon aromatization reaction is higher than that of the oxygen-containing compound dehydration reaction, and the two reactions are difficult to be considered by adopting a single reaction temperature. 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.
CN1880288 (using different catalysts), CN101607858 (using different catalysts), CN102775261 (using different catalysts), CN102146010 (fixed bed reactor), and CN101823929 propose using two reactors, and the gas phase product obtained by the reaction in the first reactor partially or totally enters the second reactor for further reaction. Wherein the two reactors of patents CN1880288, CN101607858 and CN102775261 respectively adopt different types of catalysts; the patents CN101607858 and CN102146010 adopt two fixed bed reactors; the C2+ low-carbon hydrocarbon mixture separated from the product of the aromatization reactor of the CN101823929 patent enters a low-carbon hydrocarbon reactor for aromatization, the process flow is complex, and the energy consumption is high.
CN103394312 proposes a multi-stage fluidized bed apparatus and method for preparing aromatic hydrocarbon by alcohol/ether catalytic conversion, wherein a horizontal porous distribution plate divides the fluidized bed into multiple catalyst loading stages. The multi-stage fluidized bed apparatus described in this patent is of the same diameter from top to bottom. When the multi-section fluidized bed is a four-section fluidized bed, the temperature of the first catalyst filling section and the temperature of the second catalyst filling section are both controlled to be 450-500 ℃, the temperature of the third catalyst filling section and the temperature of the fourth catalyst filling section are controlled to be 420-450 ℃, and the temperature is lower. The only feed to the multistage fluidized bed apparatus of this patent is the alcohol/ether feed. These conditions limit that the aromatics selectivity of the process is not high.
CN101671226 discloses a process for preparing xylene by aromatization of methanol, which takes a metal-modified molecular sieve composite material as a catalyst, methanol reacts with one or a mixture of more than one of C1-C12 hydrocarbons, and the yield of xylene single-pass carbon base can reach 37.21% by the synergistic reaction of aromatization and alkylation of methanol and hydrocarbons.
The above patent technologies all have the problems of low aromatic selectivity and low xylene selectivity. The invention provides a technical scheme pertinently and solves the problems.
Disclosure of Invention
The invention aims to solve the technical problem of low selectivity of the dimethylbenzene in the prior art, and provides a method for preparing the dimethylbenzene by efficiently converting methanol.
In order to solve the problems, the technical scheme adopted by the invention is as follows: raw materials containing methanol enter a methanol reaction zone of an aromatization unit, and a hydrocarbon product I which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit by utilizing a gas-solid ultrashort contact mode; the hydrocarbon product I mainly containing aromatic hydrocarbon comprises a methane-hydrogen mixture with the mass percent of less than 3 percent and C with the mass percent of less than 5 percent10 +Aromatic hydrocarbons; the separation unit separates to obtain a methane-hydrogen mixture C2 +Light hydrocarbon mixture, benzene, toluene, xylene, carbon nonaarene and C10 +Aromatic hydrocarbons; said C is2 +The light hydrocarbon mixture returns to the light hydrocarbon reaction zone of the aromatization unit, and a product II which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit; the toluene and the carbon nonaromatic hydrocarbon enter a disproportionation unit, and an obtained disproportionation product returns to a separation unit; the reaction conditions of the methanol reaction zone are as follows: the temperature of a catalyst bed layer is 450-520 ℃, the reaction pressure is 0-0.6 MPa in terms of gauge pressure, and the weight space velocity of methanol is 1-10 hours-1(ii) a The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of a catalyst bed layer is 480-600 ℃, the reaction pressure is 0-1 MPa calculated by gauge pressure, and the weight space velocity of light hydrocarbon is 0.3-10 hours-1(ii) a The methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode comprises gas-solid cross flow contact, gas-solid cyclone flow contact and gas-solid cocurrent flow downward contact, and the contact time of a gas-phase material and a catalyst is less than 1 second.
In the above technical solution, preferably, the methane-hydrogen mixture includes hydrogen, methane and ethane, the mass percentage of ethylene is less than 3%, and C3 +The total mass percentage of the hydrocarbons is less than 1 percent.
In the above technical solution, preferably, the methane-hydrogen mixture, benzene, xylene and C10 +The aromatic hydrocarbon enters a subsequent flow path, and the subsequent flow path comprises the aromatic hydrocarbonA combination unit.
In the above technical solution, preferably, C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is more than 10%, the mass percentage of propane is less than 70%, and the mass percentage of ethane is less than 3%.
In the above technical scheme, preferably, the catalyst in the methanol reaction zone is a modified ZSM-5 catalyst, the modifying element is at least one of Zn, La, P, Ga, Mn, and Ag, and the content of the modifying element is 0.01 to 15% by weight of the catalyst.
In the technical scheme, preferably, the modifying elements are P and Zn, and the ratio of P to Zn is 10: 1-1: 1.
In the technical scheme, more preferably, the ratio of P to Zn is 7: 1-3: 1.
In the above technical scheme, preferably, the light hydrocarbon reaction zone adopts a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.
In the above technical solution, preferably, the reaction conditions of the methanol reaction zone are as follows: the temperature of a catalyst bed layer is 470-500 ℃, the reaction pressure is 0.05-0.4 MPa calculated by gauge pressure, and the space velocity of the methanol weight is 3-7 hours-1。
In the above technical solution, preferably, the reaction conditions of the light hydrocarbon reaction zone are: the temperature of a catalyst bed layer is 530-580 ℃, the reaction pressure is 0.05-0.6 MPa calculated by gauge pressure, and the weight space velocity of light hydrocarbon is 1-8 hours-1。
In the above technical solution, preferably, the contact time of the gas phase material and the catalyst is 0.24-0.7 second.
In the above technical scheme, preferably, the catalyst In the light hydrocarbon reaction zone is a modified ZSM-5 catalyst, the modifying element is at least one of Zn, La, P, Ga, and In, and the content of the modifying element is 0.01 to 18% by weight of the catalyst.
In the above technical solution, preferably, the reaction conditions of the disproportionation unit are: the catalyst is ZSM-5, the reaction temperature is 300-450 ℃, the reaction gauge pressure is 0.1-20 MPa, and the mass ratio of toluene to carbon nonaarene is 0.2-5: 1.
In the above technical scheme, preferably, the gas-solid ultrashort contact mode of the methanol reaction zone is gas-solid cross flow contact, and the included angle between the gas phase feeding direction and the solid catalyst flowing direction is 10-90 °.
In the above technical solution, preferably, the mass percentage of methanol in the methanol raw material is at least 10%.
The invention adopts a gas-solid ultrashort contact mode to effectively inhibit hydrogen, methane, ethane and C in the process of preparing aromatic hydrocarbon by catalytic conversion of methanol10 +The generation of heavy aromatics is combined with C under the condition of low selectivity of byproducts in the process of preparing aromatics by converting methanol2 +Light hydrocarbon mixture aromatization and toluene and carbon nine aromatics disproportionation are carried out to obtain xylene to the maximum extent. By adopting the technical scheme of the invention, the yield of the xylene carbon group reaches 53.8 percent by weight, and a better technical effect is achieved.
Drawings
FIG. 1 is a schematic flow chart of the present invention. In fig. 1, 1 is an aromatization unit; 2 is a separation unit; 3 is a disproportionation unit; 4 is a raw material containing methanol; 5 is an aromatization unit reaction product; 6 is a methane-hydrogen mixture; 7 is C2 +A light hydrocarbon mixture; 8 is benzene; 9 is xylene; 10 is toluene; 11 is a carbon nonaarene; 12 is C10 +Aromatic hydrocarbons; 13 is a disproportionation reaction product.
Detailed Description
[ example 1 ]
The method comprises the following steps that a methanol raw material with the mass percentage of 100% of methanol enters a methanol reaction zone of an aromatization unit, and a hydrocarbon product I which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit in a gas-solid ultrashort contact mode; the hydrocarbon product I mainly containing aromatic hydrocarbon comprises 0.5 percent of methane-hydrogen mixture and 2.4 percent of C by mass10 +Aromatic hydrocarbons; the separation unit separates to obtain a methane-hydrogen mixture C2 +Light hydrocarbon mixture, benzene, toluene, xylene, carbon nonaarene and C10 +Aromatic hydrocarbons; c2 +The light hydrocarbon mixture returns to the light hydrocarbon reaction zone of the aromatization unit, and the aromatic hydrocarbon is mainly producedThe substance II enters a separation unit; toluene and carbon nonaarene enter a disproportionation unit, and the obtained disproportionation product returns to a separation unit. The methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode is gas-solid cross flow contact, the contact time of the gas phase material and the catalyst is 0.99 seconds, and the included angle between the gas phase feeding direction and the solid catalyst flowing direction is 10 degrees. The light hydrocarbon reaction zone adopts a fixed bed reactor. Methane hydrogen mixture, benzene, xylene and C10 +And (4) enabling the aromatic hydrocarbon to enter a subsequent aromatic hydrocarbon combination unit. The reaction conditions in the methanol reaction zone were: the temperature of a catalyst bed layer is 450 ℃, the reaction pressure is 0 MPa in terms of gauge pressure, and the space velocity of the methanol weight is 1 hour-1. The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of the catalyst bed layer is 480 ℃, the reaction pressure is 0 MPa calculated by gauge pressure, and the weight space velocity of light hydrocarbon is 0.3 h-1. The reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 300 ℃, the reaction gauge pressure is 0.1 MPa, and the mass ratio of the toluene to the carbon nonaarene is 0.2: 1.
The methane-hydrogen mixture comprises hydrogen, methane and ethane, the mass percentage of ethylene is 2.99 percent, and C3 +The total mass percent of the hydrocarbons is 0.99%. C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is 10.1%, the mass percentage of propane is 69.9%, and the mass percentage of ethane is 2.99%.
The methanol reaction zone adopts a Zn-La-P-ZSM-5 catalyst, 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 light hydrocarbon reaction zone adopts a Zn-La-Ga-ZSM-5 catalyst, and the mass percentage of the catalyst is that the Zn element content is 8%, the La element content is 5%, and the Ga element content is 5%.
The results showed a xylene carbon based yield of 45.8 wt%.
[ example 2 ]
According to the conditions and steps described in example 1, a methanol raw material with 10 percent of methanol mass percent enters a methanol reaction zone of an aromatization unit to react to obtain a hydrocarbon product I with aromatic hydrocarbon as the main component; the hydrocarbon product I mainly containing aromatic hydrocarbon comprises the following components in percentage by mass2.99 percent of methane-hydrogen mixture and 4.99 percent of C by mass10 +An aromatic hydrocarbon. The methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode is gas-solid cross flow contact, the contact time of the gas phase material and the catalyst is 0.05 second, and the included angle between the gas phase feeding direction and the solid catalyst flowing direction is 90 degrees. The light hydrocarbon reaction zone adopts a moving bed reactor. Methane hydrogen mixture, benzene, xylene and C10 +The aromatic hydrocarbon enters a subsequent flow.
The reaction conditions in the methanol reaction zone were: the temperature of the catalyst bed layer is 520 ℃, the reaction pressure is 0.6 MPa in terms of gauge pressure, and the weight space velocity of the methanol is 10 hours-1. The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of the catalyst bed layer is 600 ℃, the reaction pressure is 1 MPa in terms of gauge pressure, and the weight space velocity of light hydrocarbon is 10 hours-1. The reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 450 ℃, the reaction gauge pressure is 20 MPa, and the mass ratio of the toluene to the carbon nonaromatic hydrocarbon is 5: 1.
The methane-hydrogen mixture comprises hydrogen, methane and ethane, the mass percentage of ethylene is 0.1 percent, and C3 +The total mass percent of the hydrocarbons is 0.01 percent. C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is 20%, the mass percentage of propane is 50%, and the mass percentage of ethane is 1%.
The methanol reaction zone adopts a Zn-ZSM-5 catalyst, and the Zn element content is 0.01 percent by mass of the catalyst. The light hydrocarbon reaction zone adopts Ga-ZSM-5 catalyst, and the content of Ga element is 0.01 percent by mass percent of the catalyst.
The results showed a xylene carbon based yield of 47.1 wt%.
[ example 3 ]
According to the conditions and steps described in the embodiment 1, a methanol raw material with the mass percent of methanol of 98 percent enters a methanol reaction zone of an aromatization unit to react to obtain a hydrocarbon product I with aromatic hydrocarbon as the main component; the hydrocarbon product I mainly containing aromatic hydrocarbon comprises 1.4 percent of methane-hydrogen mixture and 3 percent of C10 +An aromatic hydrocarbon.The methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode is gas-solid cross flow contact, the contact time of the gas phase material and the catalyst is 0.5 second, and the included angle between the gas phase feeding direction and the solid catalyst flowing direction is 60 degrees. The light hydrocarbon reaction zone adopts a fluidized bed reactor. Methane hydrogen mixture, benzene, xylene and C10 +And (4) enabling the aromatic hydrocarbon to enter an aromatic hydrocarbon combination device.
The reaction conditions in the methanol reaction zone were: the temperature of a catalyst bed layer is 480 ℃, the reaction pressure is 0.15 MPa in terms of gauge pressure, and the weight space velocity of the methanol is 3 hours-1. The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of a catalyst bed layer is 580 ℃, the reaction pressure is 0.2 MPa in terms of gauge pressure, and the weight space velocity of light hydrocarbon is 2 hours-1. The reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 380 ℃, the reaction gauge pressure is 10 MPa, and the mass ratio of the toluene to the carbon nonaromatic hydrocarbon is 3: 1.
The methane-hydrogen mixture comprises hydrogen, methane and ethane, the mass percentage of ethylene is 1.3 percent, and C3 +The total mass percent of hydrocarbons is 0.3%. C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is 60%, the mass percentage of propane is 20%, and the mass percentage of ethane is 2.3%.
The methanol reaction zone adopts a Zn-P-Mn-ZSM-5 catalyst, and the mass percentage of the catalyst is that the Zn element content is 1.5%, the P element content is 2.1%, and the Mn element content is 3.8%. The light hydrocarbon reaction zone adopts a Zn-Ag-La-Ga-ZSM-5 catalyst, and the mass percentage of the catalyst is that the Zn element content is 3.4%, the Ag element content is 1.2%, the La element content is 4.7%, and the Ga element content is 2.8%.
The results showed 53.8 wt% yield of xylene carbon groups.
[ example 4 ]
Following the catalyst, conditions and procedure described in example 3,
only the methanol reaction zone is in a fluidized form, the gas-solid ultra-short contact mode is gas-solid cyclone contact, and the contact time of the gas phase material and the catalyst is 0.24 s. The reaction conditions in the methanol reaction zone were: catalyst bedThe layer temperature was 500 ℃, the reaction pressure was 0.4 MPa in gauge pressure, and the space velocity of methanol weight was 7 hours-1. The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of a catalyst bed layer is 580 ℃, the reaction pressure is 0.6 MPa calculated as gauge pressure, and the weight space velocity of light hydrocarbon is 8 hours-1. The reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 420 ℃, the reaction gauge pressure is 15 MPa, and the mass ratio of the toluene to the carbon nonaromatic hydrocarbon is 4: 1.
The methane-hydrogen mixture comprises hydrogen, methane and ethane, the mass percentage of ethylene is 0.5 percent, and C3 +The total mass percent of the hydrocarbons is 0.05%. C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is 40%, the mass percentage of propane is 30%, and the mass percentage of ethane is 1.4%.
The results showed a xylene carbon based yield of 50.2 wt%.
[ example 5 ]
According to the catalyst, conditions and steps described in the embodiment 3, the methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode is gas-solid cocurrent downward contact, and the contact time of the gas-phase material and the catalyst is 0.7 second. The reaction conditions in the methanol reaction zone were: the temperature of the catalyst bed layer is 470 ℃, the reaction pressure is 0.05 MPa in gauge pressure, and the weight space velocity of the methanol is 3 hours-1. The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of a catalyst bed layer is 530 ℃, the reaction pressure is 0.05 MPa calculated by gauge pressure, and the weight space velocity of light hydrocarbon is 1 hour-1. The reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 360 ℃, the reaction gauge pressure is 5 MPa, and the mass ratio of the toluene to the carbon nonaromatic hydrocarbon is 1: 1.
The methane-hydrogen mixture comprises hydrogen, methane and ethane, the mass percentage of ethylene is 0.1 percent, and C3 +The total mass percent of the hydrocarbons is 0.01 percent. C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is 70%, the mass percentage of propane is 15%, and the mass percentage of ethane is 0.6%.
The results showed a xylene carbon based yield of 50.9 wt%.
[ example 6 ]
The feed, procedure and catalyst of example 3 were used. The reaction conditions in the methanol reaction zone were: the temperature of the catalyst bed layer is 540 ℃, the reaction pressure is 0.7 MPa in terms of gauge pressure, and the weight space velocity of the methanol is 12 hours-1. The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of a catalyst bed layer is 620 ℃, the reaction pressure is 1.1 MPa in terms of gauge pressure, and the weight space velocity of light hydrocarbon is 12 hours-1. The reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 460 ℃, the reaction gauge pressure is 22 MPa, and the mass ratio of the toluene to the carbon nonaarene is 8: 1. The results showed that the xylene carbon based yield was 43.8 wt%.
Comparative example 1
The feed, procedure and catalyst of example 1 were used. The methanol reaction zone does not adopt a gas-solid ultrashort contact mode, and the reaction conditions are as follows: the temperature of the catalyst bed layer is 480 ℃, the reaction pressure is 0.2 MPa in terms of gauge pressure, and the weight space velocity of the methanol is 1.5 hours-1. The obtained hydrocarbon product I mainly containing aromatic hydrocarbon comprises 4.1 percent of methane-hydrogen mixture and 7.8 percent of C by mass10 +An aromatic hydrocarbon. The results showed a xylene carbon based yield of 42.2 wt%.
Comparative example 2
The feed, procedure and catalyst of example 1 were used. The methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode is gas-solid cross flow contact, the contact time of the gas phase material and the catalyst is 1.2 seconds, and the included angle between the gas phase feeding direction and the solid catalyst flowing direction is 95 degrees. The obtained hydrocarbon product I mainly containing aromatic hydrocarbon comprises 3.2 mass percent of methane-hydrogen mixture and 6.4 mass percent of C10 +An aromatic hydrocarbon. The results showed a xylene carbon based yield of 43.7 wt%.
Comparative example 3
The feed, procedure and catalyst of example 1 were used. The aromatization unit has no light hydrocarbon reaction zone, and C obtained by separation2 +The light hydrocarbon mixture does not return to the light hydrocarbon reaction zone of the aromatization unit. ResultsThe xylene carbon based yield was found to be 35.7 wt%.

Claims (10)

1. A method for preparing dimethylbenzene by methanol high-efficiency conversion comprises the steps that a raw material containing methanol enters a methanol reaction zone of an aromatization unit, and a hydrocarbon product I which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit by utilizing a gas-solid ultrashort contact mode; the hydrocarbon product I mainly containing aromatic hydrocarbon comprises a methane-hydrogen mixture with the mass percent of less than 3 percent and C with the mass percent of less than 5 percent10 +Aromatic hydrocarbons; the separation unit separates to obtain a methane-hydrogen mixture C2 +Light hydrocarbon mixture, benzene, toluene, xylene, carbon nonaarene and C10 +Aromatic hydrocarbons; said C is2 +The light hydrocarbon mixture returns to the light hydrocarbon reaction zone of the aromatization unit, and a product II which is obtained by reaction and mainly contains aromatic hydrocarbon enters a separation unit; the toluene and the carbon nonaromatic hydrocarbon enter a disproportionation unit, and an obtained disproportionation product returns to a separation unit;
the reaction conditions of the methanol reaction zone are as follows: the temperature of a catalyst bed layer is 450-520 ℃, the reaction pressure is 0-0.6 MPa in terms of gauge pressure, and the weight space velocity of methanol is 1-10 hours-1；
The reaction conditions of the light hydrocarbon reaction zone are as follows: the temperature of a catalyst bed layer is 480-600 ℃, the reaction pressure is 0-1 MPa calculated by gauge pressure, and the weight space velocity of light hydrocarbon is 0.3-10 hours-1；
The methanol reaction zone is in a fluidized form, the gas-solid ultrashort contact mode comprises gas-solid cross flow contact, gas-solid cyclone flow contact and gas-solid cocurrent flow downward contact, and the contact time of a gas-phase material and a catalyst is less than 1 second.
2. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein the methane-hydrogen mixture comprises hydrogen, methane and ethane, the mass percentage of ethylene is less than 3%, and C3 +The total mass percentage of the hydrocarbons is less than 1 percent.
3. The methanol composition of claim 1Process for the production of xylenes by reforming, characterized in that said methane-hydrogen mixture, benzene, xylenes and C10 +And (4) the aromatic hydrocarbon enters a subsequent flow, and the subsequent flow comprises an aromatic hydrocarbon combination unit.
4. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein C is C2 +The total mass percentage of ethylene, propylene and butylene in the light hydrocarbon mixture is more than 10%, the mass percentage of propane is less than 70%, and the mass percentage of ethane is less than 3%.
5. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein the catalyst in the methanol reaction zone is a modified ZSM-5 catalyst, the modifying element is at least one of Zn, La, P, Ga, Mn and Ag, and the content of the modifying element is 0.01-15% by weight of the catalyst.
6. The method for preparing xylene through efficient conversion of methanol according to claim 1, characterized in that a fixed bed reactor, a fluidized bed reactor and a moving bed reactor are adopted as the light hydrocarbon reaction zone.
7. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein the catalyst In the light hydrocarbon reaction zone is a modified ZSM-5 catalyst, the modified element is at least one of Zn, La, P, Ga and In, and the content of the modified element is 0.01-18% by weight of the catalyst.
8. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein the reaction conditions of the disproportionation unit are as follows: the catalyst is ZSM-5, the reaction temperature is 300-450 ℃, the reaction gauge pressure is 0.1-20 MPa, and the mass ratio of toluene to carbon nonaarene is 0.2-5: 1.
9. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein the gas-solid ultrashort contact mode of the methanol reaction zone is gas-solid cross flow contact, and the included angle between the gas phase feeding direction and the solid catalyst flowing direction is 10-90 °.
10. The method for preparing xylene through efficient methanol conversion according to claim 1, wherein the mass percentage of methanol in the methanol raw material is at least 10%.
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