CN113926395A - Reaction device and method for preparing aromatic hydrocarbon through catalytic conversion of methanol - Google Patents

Reaction device and method for preparing aromatic hydrocarbon through catalytic conversion of methanol Download PDF

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Publication number
CN113926395A
CN113926395A CN202010608744.7A CN202010608744A CN113926395A CN 113926395 A CN113926395 A CN 113926395A CN 202010608744 A CN202010608744 A CN 202010608744A CN 113926395 A CN113926395 A CN 113926395A
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bed
zone
catalyst
conversion
turbulent
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李晓红
俞志楠
郑毅骏
王莉
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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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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • 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

Abstract

The invention relates to a reaction device for preparing aromatic hydrocarbon by catalytic conversion of methanol, which comprises a turbulent bed reaction zone, a fast bed conversion zone, a lifting zone and a two-dense bed; the fast bed conversion zone is positioned in the turbulent bed reaction zone and the second dense bed, the upper outlet of the fast bed conversion zone is connected with the lifting zone and the connecting part is positioned in the second dense bed, and the lower inlet of the fast bed conversion zone is positioned in the catalyst bed layer of the turbulent bed reaction zone; the lower inlet of the lift zone is connected to the upper outlet of the turbulent bed reaction zone, the dense bed is arranged outside the lift zone, and the connection between the lift zone and the turbulent bed reaction zone is positioned in the dense bed. The method firstly converts the methanol into light hydrocarbon rich in olefin and partial aromatic hydrocarbon in a fast bed reaction zone with high selectivity, and the light hydrocarbon rich in olefin is subjected to aromatization reaction in a turbulent bed reaction zone continuously, so that the method can be used in the industrial production of the aromatic hydrocarbon.

Description

Reaction device and method for preparing aromatic hydrocarbon through catalytic conversion of methanol
Technical Field
The invention relates to a reaction device for preparing aromatic hydrocarbon through catalytic conversion of methanol and a method for preparing aromatic hydrocarbon through catalytic conversion of methanol by adopting the reaction device.
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, firstly published the research result of preparing aromatic hydrocarbon by converting methanol and dimethyl ether, and the research adopts ZSM-5 molecular sieve containing 2.7 wt% of phosphorus as a catalyst, the reaction temperature is 400-450 ℃, and the space velocity of methanol and dimethyl ether is 1.3 h-1.
There have been many reports and patents related to this field. For example, in the system proposed in chinese patent CN104326859, liquefied gas and ethylene in light hydrocarbon generated by methanol aromatization reaction 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 patent technologies all have the problems of low yield and low selectivity of aromatic hydrocarbon, and the invention provides a technical scheme pertinently to solve the problems.
Disclosure of Invention
The invention provides a reaction device and a method for preparing aromatic hydrocarbon through catalytic conversion of methanol, aiming at the technical problem of low aromatic hydrocarbon selectivity in the prior art. The device and the method have the advantage of high selectivity of aromatic hydrocarbon, and can be used in industrial production of aromatic hydrocarbon.
The invention provides a reaction device for preparing aromatic hydrocarbon by catalytic conversion of methanol, which comprises a turbulent bed reaction zone (1), a fast bed conversion zone (2), a lifting zone (5) and a dense bed (3); the fast bed conversion zone (2) is positioned in the turbulent bed reaction zone (1) and the two dense beds (3), the upper outlet of the fast bed conversion zone (2) is connected with the lifting zone (5) and the connection part is positioned in the two dense beds (3), and the lower inlet of the fast bed conversion zone (2) is positioned in the catalyst bed layer of the turbulent bed reaction zone (1); the lower inlet of the lift zone (5) is connected to the upper outlet of the turbulent bed reaction zone (1), the dense bed (3) is arranged outside the lift zone (5), and the connection of the lift zone (5) and the turbulent bed reaction zone (1) is located within the dense bed (3).
According to some embodiments of the invention, the reaction apparatus comprises at least one fast bed conversion zone (2); the included angle between the at least one fast bed conversion zone (2) is 360/n degrees by taking the number of the fast bed conversion zones (2) as n; n is less than 20, preferably 2 to 10.
According to some embodiments of the invention, the reaction apparatus further comprises a regeneration tube chute (6), a spent tube chute (7), a circulation tube chute (8), a turbulent bed reaction zone cyclone (9), a dense bed cyclone (10), a light hydrocarbon feed distributor (12), a methanol feed distributor (11), and a methanol feed tube (4).
According to the preferred embodiment of the invention, the turbulent bed reaction zone cyclone separator (9) is positioned in the turbulent bed reaction zone (1) and the outlet of the turbulent bed reaction zone cyclone separator is connected with the two dense beds (3), the two dense bed cyclone separators (10) are positioned in the two dense beds (3), the regeneration inclined tube (6) is connected with the turbulent bed reaction zone (1), the to-be-regenerated inclined tube (7) is connected with the two dense beds (3), and the circulating inclined tube (8) is respectively connected with the two dense beds (3) and the turbulent bed reaction zone (1).
According to a preferred embodiment of the present invention, the light hydrocarbon feed distributor (12) is located inside the turbulent bed reaction zone (1) below the junction of the regeneration ramps (6) and the turbulent bed reaction zone (1), and the methanol feed distributor (11) is located inside the fast bed conversion zone (2) and is connected to the methanol feed line (4).
According to a preferred embodiment of the invention, the junction of the regeneration chute (6) and the turbulent bed reaction zone (1) is located below the methanol feed pipe (4).
In another aspect, the present invention provides a method for preparing aromatic hydrocarbons by catalytic conversion of methanol, which employs the reaction apparatus according to the first aspect of the present invention, and includes the following steps:
s1), enabling a light hydrocarbon raw material (14) to enter a turbulent bed reaction area (1) to be in contact reaction with a catalyst, enabling an obtained semi-spent catalyst and a light hydrocarbon conversion product (17) to ascend, enabling a part of the semi-spent catalyst to enter a fast bed conversion area (2), enabling a part of the semi-spent catalyst to enter a secondary dense bed (3) through a lifting area (5), and enabling the light hydrocarbon conversion product (17) to enter the secondary dense bed (3);
s2), feeding the methanol raw material (13) into a fast bed conversion zone (2), contacting and reacting with a semi-spent catalyst, and feeding the catalyst and reaction products obtained by the reaction into a dense bed (3) through a lifting zone (5);
s3), circulating part of the spent catalyst in the dense bed (3) to enter the turbulent bed reaction zone (1), and feeding part of the spent catalyst to a regeneration device for regeneration;
s4) returning the regenerated catalyst (15) obtained by regeneration to the turbulent bed reaction zone (1);
s5) separating the product in the dense bed (3) to obtain an aromatization product (18) and entering a subsequent separation system.
According to a preferred embodiment of the present invention, the step S1 includes:
light hydrocarbon raw materials (14) enter a turbulent bed reaction area (1) through a light hydrocarbon feeding distributor (12) to be in contact reaction with a catalyst, the obtained semi-spent catalyst and light hydrocarbon conversion products (17) go upwards, part of the semi-spent catalyst enters a fast bed conversion area (2), part of the semi-spent catalyst enters a secondary dense bed (3) through a lifting area (5), and the light hydrocarbon conversion products (17) enter the secondary dense bed (3) through a turbulent bed reaction area cyclone separator (9).
According to a preferred embodiment of the present invention, the step S2 includes:
a methanol raw material (13) enters a fast bed conversion zone (2) through a methanol feeding pipe (4) and a methanol feeding distributor (11) to contact and react with a semi-spent catalyst, and the catalyst and a reaction product obtained by the reaction enter a dense bed (3) through a lifting zone (5);
according to a preferred embodiment of the present invention, the step S3 includes:
part of spent catalyst in the secondary dense bed (3) enters the turbulent bed reaction zone (1) through a circulating inclined tube (8), and part of spent catalyst enters a regenerator for regeneration through a regeneration inclined tube (7);
according to a preferred embodiment of the present invention, the step S4 includes:
the regenerated catalyst (15) obtained by the regeneration of the regenerator returns to the turbulent bed reaction zone (1) through a regeneration inclined tube (6);
according to a preferred embodiment of the present invention, the step S5 includes:
the product in the double dense bed (3) is separated by a double dense bed cyclone separator (10) to obtain an aromatization product (18) which enters a subsequent separation system.
According to some embodiments of the invention, the catalyst density in the fast bed conversion zone (2) is 20 to 100Kg/m3Preferably 50 to 90Kg/m3The gas linear speed is 3-10 m/s, preferably 3.5-6 m/s, and the catalyst temperature is 470-530 ℃, preferably 480-500 ℃.
According to some embodiments of the invention, the density of the catalyst in the turbulent reaction zone (1) is 200 to 400Kg/m3Preferably 250 to 350, the gas linear speed is 0.5 to 1.2m/s, preferably 0.7 to 1.1m/s, and the catalyst temperature is 500 to 580 ℃, preferably 520 to 560 ℃.
According to a preferred embodiment of the present invention, the light hydrocarbon feedstock (14) is a non-aromatic hydrocarbon mixture of carbon two to carbon six, other than ethane, obtained by subjecting the aromatization product (18) to a separation system.
According to a preferred embodiment of the invention, the regenerated catalyst has a carbon content of less than 0.1%, preferably less than 0.05%, based on the total mass of the catalyst.
According to a preferred embodiment of the present invention, the catalyst is a ZSM-5 catalyst.
According to some embodiments of the present invention, methanol conversion and aromatics carbon-based selectivity in the present invention may be calculated as follows:
methanol conversion rate (mass flow of methanol feed-mass flow of methanol in product)/mass flow of methanol feed x 100%.
The selectivity to aromatics on carbon basis is the mass flow of aromatics in the product/(mass flow of methanol feed × methanol conversion × 14/32) × 100%.
The invention has the following advantages:
according to the technical scheme for preparing the aromatic hydrocarbon by catalytic conversion of the methanol, the methanol is converted step by step to obtain high aromatic hydrocarbon selectivity. Firstly, methanol is converted into light hydrocarbon rich in olefin and partial aromatic hydrocarbon in a fast bed reaction zone with high selectivity, and the light hydrocarbon rich in olefin is subjected to aromatization reaction in a turbulent bed reaction zone. The fast bed reaction zone and the turbulent bed reaction zone are coupled in a fluidized bed reactor, the process flow is simple, and the reaction conditions and the catalyst activity required by methanol conversion and light hydrocarbon aromatization are met.
Drawings
FIG. 1 is a schematic flow diagram of a reaction device for preparing aromatic hydrocarbons by catalytic conversion of methanol:
in FIG. 1, 1 is a turbulent bed reaction zone; 2 is a fast bed conversion zone; 3 is a dense bed; 4 is a methanol feed line; 5 is a lifting area; 6 is a regeneration inclined tube; 7 is a to-be-grown inclined tube; 8 is a circulating inclined pipe; 9 is turbulent bed reaction zone cyclone separator; 10 is a double dense bed cyclone separator; 11 is a methanol feeding distributor; 12 is a light hydrocarbon feeding distributor; 13 is a methanol raw material; 14 is light hydrocarbon raw material; 15 is a regenerant; 16 is a spent agent; 17 is a light hydrocarbon conversion product; 18 is an aromatization product.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
As shown in fig. 1, the reaction device for preparing aromatic hydrocarbon by catalytic conversion of methanol comprises a turbulent bed reaction zone (1), a fast bed conversion zone (2), a lifting zone (5), a secondary dense bed (3), a regeneration inclined tube (6), a to-be-generated inclined tube (7), a circulation inclined tube (8), a turbulent bed reaction zone cyclone separator (9), a secondary dense bed cyclone separator (10), a light hydrocarbon feeding distributor (12), a methanol feeding distributor (11) and a methanol feeding tube (4); the fast bed conversion zone (2) is positioned in the turbulent bed reaction zone (1) and the dense bed (3), the upper outlet of the fast bed conversion zone (2) is connected with the lifting zone (5) and the connection part is positioned in the dense bed (3), and the lower inlet of the fast bed conversion zone (2) is positioned in the catalyst bed layer of the turbulent bed reaction zone (1); the lower inlet of the lifting region (5) is connected with the upper outlet of the turbulent bed reaction region (1), the two dense beds (3) are arranged outside the lifting region (5), and the connecting part of the lifting region (5) and the turbulent bed reaction region (1) is positioned in the two dense beds (3); the turbulent bed reaction zone cyclone separator (9) is positioned in the turbulent bed reaction zone (1), the outlet of the turbulent bed reaction zone cyclone separator is connected with the two dense beds (3), the two dense bed cyclone separator (10) is positioned in the two dense beds (3), the regeneration inclined tube (6) is connected with the turbulent bed reaction zone (1), the inclined tube to be generated (7) is connected with the two dense beds (3), and the circulating inclined tube (8) is respectively connected with the turbulent bed reaction zone (1) and the two dense beds (3); the light hydrocarbon feeding distributor (12) is positioned in the turbulent bed reaction zone (1) and below the joint of the regeneration inclined tube (6) and the turbulent bed reaction zone (1), and the methanol feeding distributor (11) is positioned in the fast bed conversion zone (2) and is connected with the methanol feeding pipe (4); the junction of the regeneration chute (6) and the turbulent bed reaction zone (1) is located below the methanol feed line (4).
Wherein, light hydrocarbon raw materials (14) enter a turbulent bed reaction zone (1) through a light hydrocarbon feeding distributor (12) to be in contact reaction with a catalyst, the obtained semi-spent catalyst and light hydrocarbon conversion products (17) go upwards, part of the semi-spent catalyst enters a fast bed conversion zone (2), part of the semi-spent catalyst enters a secondary dense bed (3) through a lifting zone (5), and the light hydrocarbon conversion products (17) enter the secondary dense bed (3) through a turbulent bed reaction zone cyclone separator (9); a methanol raw material (13) enters a fast bed conversion zone (2) through a methanol feeding pipe (4) and a methanol feeding distributor (11), and a catalyst and a reaction product obtained by reaction enter a dense bed (3) through a lifting zone (5); part of spent catalyst in the secondary dense bed (3) enters the turbulent bed reaction zone (1) through a circulating inclined tube (8), and part of spent catalyst enters a regenerator for regeneration through a regeneration inclined tube (7); the regenerated catalyst (15) obtained by the regeneration of the regenerator returns to the turbulent bed reaction zone (1) through a regeneration inclined tube (6); the aromatization product (18) enters a subsequent separation system through a two-dense-bed cyclone separator (10).
[ example 1 ]
An apparatus as shown in FIG. 1 was used in which the number of fast bed conversion zones (2) was 2 and the angle between the fast bed conversion zones (2) was 180 °. A light hydrocarbon raw material (14) enters a turbulent bed reaction zone (1) through a light hydrocarbon feeding distributor (12) to be in contact reaction with a catalyst, a semi-spent catalyst and a light hydrocarbon conversion product (17) obtained by the reaction go upwards, a part of the semi-spent catalyst enters a fast bed conversion zone (2), a part of the semi-spent catalyst enters a secondary dense bed (3) through a lifting zone (5), and the light hydrocarbon conversion product (17) enters the secondary dense bed (3) through a turbulent bed reaction zone cyclone separator (9); a methanol raw material (13) enters a fast bed conversion zone (2) through a methanol feeding pipe (4) and a methanol feeding distributor (11), and a catalyst and a reaction product obtained by reaction enter a dense bed (3) through a lifting zone (5); part of spent catalyst in the secondary dense bed (3) enters the turbulent bed reaction zone (1) through a circulating inclined tube (8), and part of spent catalyst enters a regenerator for regeneration through a regeneration inclined tube (7); the regenerated catalyst (15) obtained by the regeneration of the regenerator returns to the turbulent bed reaction zone (1) through a regeneration inclined tube (6); the aromatization product (18) enters a subsequent separation system through a two-dense-bed cyclone separator (10).
The reaction conditions used were: the density of the catalyst in the fast bed conversion zone (2) is 80Kg/m3Gas linear speed 4m/s and catalyst temperature 500 ℃; the density of the catalyst in the turbulent bed reaction zone (1) is 350Kg/m3Gas linear speed 0.9m/s, catalyst temperature 550 ℃; the light hydrocarbon raw material (14) is a non-aromatic hydrocarbon mixture of carbon two to carbon six, which is obtained by a separation system from an aromatization product (18) except ethane; the regenerated catalyst has carbon content of 0.08 percent based on the total mass of the catalyst; adopts Zn modified ZSM-5 catalyst.
The conversion of methanol was 99.0 wt.% and the selectivity to aromatic carbon groups was 77.2 wt.%.
[ example 2 ]
The same as in example 1, except that the number of fast bed conversion zones (2) was 1.
The methanol conversion rate is 98.5 wt% and the selectivity of aromatic hydrocarbon to carbon group is 75.6 wt%.
[ example 3 ]
The same as in example 1, except that the number of the fast bed conversion zones (2) was 3, the angle between the fast bed conversion zones (2) was 120 °.
The methanol conversion rate is 99.7 wt% and the selectivity of aromatic hydrocarbon to carbon group is 77.3 wt%.
[ example 4 ]
The same as in example 1, except that the number of the fast bed conversion zones (2) was 20, the angle between the fast bed conversion zones (2) was 18 °.
The methanol conversion rate was found to be 99.9 wt% and the selectivity to aromatic carbon groups was found to be 78.2 wt%.
[ example 5 ]
Same as example 1, except that the catalyst density in the fast bed conversion zone (2) was 20Kg/m3Gas linear speed 10m/s and catalyst temperature 530 ℃; the density of the catalyst in the turbulent bed reaction zone (1) is 200Kg/m3Gas linear speed 1.2m/s, catalyst temperature 580 ℃.
The methanol conversion rate is 99.9 wt% and the selectivity of the aromatic hydrocarbon to carbon group is 76.4 wt%.
[ example 6 ]
Same as example 1, except that the catalyst density in the fast bed conversion zone (2) was 100Kg/m3Gas linear speed 3m/s, catalyst temperature 470 ℃; the density of the catalyst in the turbulent bed reaction zone (1) is 400Kg/m3Gas linear speed 0.5m/s, catalyst temperature 500 ℃.
The methanol conversion rate was found to be 98.7 wt% and the selectivity to aromatic carbon groups was found to be 74.9 wt%.
[ example 7 ]
Same as example 1, except that the catalyst density in the fast bed conversion zone (2) was 60Kg/m3Gas linear velocity 5m/s, catalyst temperature 490℃。
The methanol conversion rate is 99.6 wt% and the selectivity of aromatic hydrocarbon to carbon group is 76.8 wt%.
[ example 8 ]
The same as in example 1, except that; the density of the catalyst in the turbulent bed reaction zone (1) is 300Kg/m3Gas linear speed 1m/s and catalyst temperature 520 ℃.
The methanol conversion rate is 99.5 wt% and the selectivity of aromatic hydrocarbon to carbon group is 77.9 wt%.
[ example 9 ]
The same as in example 1 except that the catalyst was regenerated, the carbon content was 0.07% based on the total mass of the catalyst.
The methanol conversion rate is 99.2 wt% and the selectivity of aromatic hydrocarbon to carbon group is 77.7 wt%.
[ COMPARATIVE EXAMPLE 1 ]
The same as in example 1, except that no fast bed conversion zone was provided. The methanol raw material (13) enters the turbulent bed reaction zone (1) to contact and react with the catalyst.
The methanol conversion rate is 99.2 wt% and the selectivity of aromatic hydrocarbon to carbon group is 56.8 wt%.

Claims (10)

1. A reaction device for preparing aromatic hydrocarbon by catalytic conversion of methanol comprises a turbulent bed reaction zone (1), a fast bed conversion zone (2), a lifting zone (5) and a dense bed (3); the fast bed conversion zone (2) is positioned in the turbulent bed reaction zone (1) and the two dense beds (3), the upper outlet of the fast bed conversion zone (2) is connected with the lifting zone (5) and the connection part is positioned in the two dense beds (3), and the lower inlet of the fast bed conversion zone (2) is positioned in the catalyst bed layer of the turbulent bed reaction zone (1); the lower inlet of the lift zone (5) is connected to the upper outlet of the turbulent bed reaction zone (1), the dense bed (3) is arranged outside the lift zone (5), and the connection of the lift zone (5) and the turbulent bed reaction zone (1) is located within the dense bed (3).
2. A reactor device according to claim 1, characterized in that it comprises at least one fast bed conversion zone (2); the included angle between the at least one fast bed conversion zone (2) is 360/n degrees by taking the number of the fast bed conversion zones (2) as n; n is less than 20.
3. The reaction apparatus according to claim 1 or 2, further comprising a regeneration tube chute (6), a spent tube chute (7), a circulation tube chute (8), a turbulent bed reaction zone cyclone (9), a dense bed cyclone (10), a light hydrocarbon feed distributor (12), a methanol feed distributor (11), and a methanol feed tube (4).
4. A reactor according to any one of claims 1 to 3, characterized in that the turbulent bed reaction zone cyclone (9) is located in the turbulent bed reaction zone (1) and its outlet is connected to the dense bed (3), the dense bed cyclone (10) is located in the dense bed (3), the regeneration chute (6) is connected to the turbulent bed reaction zone (1), the spent chute (7) is connected to the dense bed (3), and the recycle chute (8) is connected to the dense bed (3) and the turbulent bed reaction zone (1), respectively; preferably, the light hydrocarbon feed distributor (12) is located inside the turbulent bed reaction zone (1) below the junction of the regeneration chute (6) and the turbulent bed reaction zone (1), and the methanol feed distributor (11) is located inside the fast bed reforming zone (2) and connected to the methanol feed line (4).
5. A method for preparing aromatic hydrocarbon by catalytic conversion of methanol, which adopts the reaction device as claimed in any one of claims 1-4, and comprises the following steps:
s1), enabling a light hydrocarbon raw material (14) to enter a turbulent bed reaction area (1) to be in contact reaction with a catalyst, enabling an obtained semi-spent catalyst and a light hydrocarbon conversion product (17) to ascend, enabling a part of the semi-spent catalyst to enter a fast bed conversion area (2), enabling a part of the semi-spent catalyst to enter a secondary dense bed (3) through a lifting area (5), and enabling the light hydrocarbon conversion product (17) to enter the secondary dense bed (3);
s2), feeding the methanol raw material (13) into a fast bed conversion zone (2), contacting and reacting with a semi-spent catalyst, and feeding the catalyst and reaction products obtained by the reaction into a dense bed (3) through a lifting zone (5);
s3), circulating part of the spent catalyst in the dense bed (3) to enter the turbulent bed reaction zone (1), and feeding part of the spent catalyst to a regeneration device for regeneration;
s4) returning the regenerated catalyst (15) obtained by regeneration to the turbulent bed reaction zone (1);
s5) separating the product in the dense bed (3) to obtain an aromatization product (18) and entering a subsequent separation system.
6. The method according to claim 5, wherein the method comprises the following step S1 comprising:
light hydrocarbon raw materials (14) enter a turbulent bed reaction area (1) through a light hydrocarbon feeding distributor (12) to be in contact reaction with a catalyst, the obtained semi-spent catalyst and light hydrocarbon conversion products (17) go upwards, part of the semi-spent catalyst enters a fast bed conversion area (2), part of the semi-spent catalyst enters a secondary dense bed (3) through a lifting area (5), and the light hydrocarbon conversion products (17) enter the secondary dense bed (3) through a turbulent bed reaction area cyclone separator (9).
7. The process according to claim 5 or 6, wherein the catalyst density in the fast bed conversion zone (2) is 20 to 100Kg/m3The gas linear speed is 3-10 m/s, and the catalyst temperature is 470-530 ℃.
8. The reaction process according to any one of claims 5 to 7, wherein the density of the catalyst in the turbulent bed reaction zone (1) is 200 to 400Kg/m3The gas linear speed is 0.5-1.2 m/s, and the catalyst temperature is 500-580 ℃.
9. The process of any one of claims 5-8, wherein the light hydrocarbon feedstock (14) is a non-aromatic mixture of carbon two to carbon six, other than ethane, separated from the aromatization product (18).
10. The process according to any one of claims 5 to 9, characterized in that the regenerated catalyst has a carbon content of less than 0.1% by mass, based on the total mass of the catalyst.
CN202010608744.7A 2020-06-29 2020-06-29 Reaction device and method for preparing aromatic hydrocarbon through catalytic conversion of methanol Pending CN113926395A (en)

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