CN108017487B - Two-stage reaction method for preparing aromatic hydrocarbon from oxygen-containing compound-containing raw material - Google Patents

Two-stage reaction method for preparing aromatic hydrocarbon from oxygen-containing compound-containing raw material Download PDF

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CN108017487B
CN108017487B CN201610973691.2A CN201610973691A CN108017487B CN 108017487 B CN108017487 B CN 108017487B CN 201610973691 A CN201610973691 A CN 201610973691A CN 108017487 B CN108017487 B CN 108017487B
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fluidized bed
bed reactor
raw material
oxygen
catalyst
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CN108017487A (en
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李晓红
齐国祯
徐俊
王菊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • B01J8/28Chemical 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 the one above the other
    • 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
    • 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 two-stage reaction method for preparing aromatic hydrocarbon from an oxygen-containing compound-containing raw material, which mainly solves the problem of low aromatic hydrocarbon selectivity in the prior art. The two fluidized bed reactors with different diameters are arranged in an overlapping mode and are sequentially a first-stage fluidized bed reactor and a second-stage fluidized bed reactor from top to bottom, and the two reactors are connected together through a low-pressure-drop distribution plate; the mixed hydrocarbon raw material enters a first-stage fluidized bed reactor with the temperature range of 530-600 ℃ to be in contact reaction with a regenerant, and the raw material containing oxygen-containing compounds enters a second-stage fluidized bed reactor with the temperature range of 450-530 ℃ to be in contact reaction with a semi-spent catalyst.

Description

Two-stage reaction method for preparing aromatic hydrocarbon from oxygen-containing compound-containing raw material
Technical Field
The invention relates to a two-stage reaction method for preparing aromatic hydrocarbon from oxygen-containing compound raw materials.
Background
Aromatic hydrocarbons (especially triphenyl, Benzene, Toluene, Xylene, i.e., BTX) are important basic organic synthesis feedstocks. Driven by the demand for downstream derivatives, the market demand for aromatics continues to increase.
The steam cracking process using liquid hydrocarbons (such as naphtha, diesel oil, secondary processing oil) as raw materials is the main production process of aromatic hydrocarbons. The process belongs to the production technology of petroleum routes, and in recent years, the cost of raw materials is continuously increased due to the limited supply and higher price of petroleum resources. Due to the factors, the technology for preparing aromatic hydrocarbon by replacing raw materials draws more and more extensive attention. China has relatively rich coal resources. With the successful development of high-efficiency and long-period methanol catalyst and methanol device large-scale technology in recent years, the production cost of coal-based methanol and/or dimethyl ether is greatly reduced, and a cheap raw material source is provided for the production of downstream products (olefin, aromatic hydrocarbon and the like) of methanol and/or dimethyl ether. Therefore, the production of aromatic hydrocarbons from methanol and/or dimethyl ether as a raw material is considered.
This technology was first reported in 1977 by Chang et al (Journal of Catalysis, 1977, 47, 249) by Mobil corporation to prepare hydrocarbons such as aromatic hydrocarbons by conversion of methanol and its oxygenates over a ZSM-5 molecular sieve catalyst. In 1985, Mobil corporation in the applied US1590321 thereof, 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 airspeed of methanol and dimethyl ether is 1.3h < -1 >.
Chinese patents 201010111821.4, 200910090002.3, 200810102684.0, 200910135643.6 and 200910089699.2 adopt a reactor, the reactor only has a reaction zone, and a single reaction temperature is adopted. Liquefied gas and ethylene in light hydrocarbon generated by methanol aromatization reaction in the system proposed by the Chinese patent 201410447321.6 are returned to the methanol aromatization reactor for further conversion. The oil phase hydrocarbons with the carbon number of less than 7 obtained by separating the product of the alcohol/ether aromatization reaction device in the system proposed by Chinese patent 201410106062.0 enter the alcohol/ether aromatization reaction device for further reaction. 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.
Chinese patents 200610012703.1 (using different catalysts), 200910089698.8 (using different fixed beds and different catalysts), 201210254472.0 (using different catalysts), 20100108008.1 (fixed bed reactor), 201010146915.5 propose using two reactors, and part or all of the gas phase product obtained by the reaction in the first reactor enters the second reactor for further reaction. Wherein the two reactors of the 200610012703.1, 200910089698.8, 201210254472.0 patents each employ a different type of catalyst; both 200910089698.8, 20100108008.1 patents employ two fixed bed reactors; 201010146915.5 patent aromatization reactor, the C2+ low carbon hydrocarbon mixture separated from the product of aromatization reactor enters into the low carbon hydrocarbon reactor for aromatization, the process flow is complex and the energy consumption is high.
Chinese patent 201310346922.3 proposes a multi-stage fluidized bed device and method for preparing aromatic hydrocarbon by alcohol/ether catalytic conversion, which is divided into multiple catalyst filling stages by a transverse porous distribution plate. 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.
The above patent technologies all have the problem of low selectivity of aromatic hydrocarbon. The invention provides a technical scheme pertinently and solves the problems.
Disclosure of Invention
The invention aims to solve the technical problem of low aromatic selectivity in the prior art, and provides a two-stage reaction method for preparing aromatic hydrocarbon from an oxygen-containing compound-containing raw material. The method has the advantages of simple process and high selectivity of aromatic hydrocarbon.
The technical scheme adopted by the invention is as follows: providing a catalyst comprising an aluminosilicate molecular sieve, and two superposed fluidized bed reactors with different diameters, namely a first fluidized bed reactor 1 and a second fluidized bed reactor 2 from top to bottom, wherein the two reactors are connected together by a low-pressure-drop distribution plate 11; the mixed hydrocarbon raw material 7 enters a first-stage fluidized bed reactor 1 with the temperature range of 530-600 ℃, and is in contact reaction with a regenerant 9 entering the first-stage fluidized bed reactor 1 through a regeneration inclined tube 4, an obtained product 10 rich in aromatic hydrocarbon enters a subsequent separation system, and an obtained semi-spent catalyst 12 enters a second-stage fluidized bed reactor 2 through a semi-spent inclined tube 3; the method comprises the following steps that a raw material 6 containing oxygen compounds enters a second-stage fluidized bed reactor 2 with the temperature range of 450-530 ℃, contacts and reacts with a semi-spent catalyst 12, the obtained product enters a first-stage fluidized bed reactor 1 through a low-pressure-drop distribution plate 11, and the obtained spent catalyst 8 returns to a regenerator for regeneration through a spent inclined tube 5; the ratio of the mass flow of the catalyst entering the first-stage fluidized bed reactor 1 through the low-pressure-drop distribution plate 11 in the second-stage fluidized bed reactor 2 to the mass flow of the semi-spent catalyst 12 in the semi-spent inclined tube 3 is (0.1-0.9): 1.
In the above technical scheme, preferably, the diameter ratio of the main reaction zone of the first-stage fluidized bed reactor 1 to the diameter ratio of the second-stage fluidized bed reactor 2 is 3-1.01: 1.
In the technical scheme, preferably, the mixed hydrocarbon raw material 7 enters a first-stage fluidized bed reactor 1 with the temperature range of 550-590 ℃; the raw material 6 containing the oxygen-containing compound enters a two-stage fluidized bed reactor 2 with the temperature range of 470-520 ℃.
In the above technical solution, preferably, the conversion rate of the oxygen-containing compound at the inlet of the low pressure drop distribution plate 11 is greater than 80%.
In the above technical solution, preferably, the total mass percentage of the olefin in the gas phase stream is greater than 20%.
In the above technical solution, preferably, the content of carbon on the spent catalyst 12 is 0.05 to 1.2% by mass of the catalyst.
In the above technical solution, preferably, the weight space velocity of the raw material 6 containing the oxygen-containing compound is 0.2 to 5 hours-1The weight space velocity of the mixed hydrocarbon raw material 7 is 0.5-4 hours-1
In the above technical scheme, preferably, the reaction gauge pressure of the fluidized bed reactor is 0 to 0.6 mpa.
In the above technical solution, preferably, the mixed hydrocarbon feedstock 7 is a hydrocarbon or a mixture of hydrocarbons having a distillation range above carbon two of less than 350 ℃.
In the above technical solution, preferably, the second-stage fluidized-bed reactor 2 is provided with at least one set of internal and/or external heat collectors.
In the technical scheme, preferably, the density of the catalyst bed layer in the first-stage fluidized bed reactor 1 is 200-480 kg/cubic meter, and the density of the catalyst bed layer in the second-stage fluidized bed reactor 2 is 150-400 kg/cubic meter.
In the above technical solution, the mass ratio of the feed amount of the oxygenate-containing feedstock 6 to the feed amount of the mixed hydrocarbon feedstock 7 is preferably 19 to 1.2: 1.
In the above technical solution, preferably, the raw material 6 containing the oxygen-containing compound includes at least one selected from methanol, ethanol, n-propanol, isopropanol, and C4~C20Compounds of alcohols, methyl ethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, acetone, acetic acid; the oxygenate-containing feedstock (6) has an oxygenate content of at least 10% by weight.
In the above technical solution, preferably, the catalyst is at least one of ZSM-5 and ZSM-11 modified by a modifying element, the modifying element is at least one of Zn, L a, P, In, and Ga, and the content of the modifying element is 0.01 to 15% by weight of the catalyst.
In the above technical solution, preferably, the modifying element is preferably at least one selected from Zn, Ga, and In.
In the above technical solution, preferably, the modifying element is preferably selected from Zn, Ga and In; more preferably, the weight ratio of Ga to In is 1:1 to 5: 1.
Research results show that in the temperature range of 450-530 ℃, the conversion rate of the reaction of dehydrating the oxygen-containing compound to generate the low-carbon hydrocarbon is more than 99 weight percent, when the temperature exceeds 530 ℃, the thermal decomposition reaction of the oxygen-containing compound is accelerated, and CO in the product2The content is increased. The low-carbon hydrocarbon aromatization reaction is obviously influenced by the reaction temperature, the temperature is lower than 530 ℃, and the aromatic selectivity is lower. Therefore, the oxygen-containing compound and the low-carbon hydrocarbon can respectively carry out dehydration and aromatization reactions under different temperature conditions, the oxygen-containing compound carries out dehydration reaction at the temperature of 450-530 ℃ to generate the low-carbon hydrocarbon, and the low-carbon hydrocarbon is aromatized into aromatic hydrocarbon with high selectivity at the temperature of 530-600 ℃. In addition, the dehydration reaction of the oxygen-containing compound is easy to occur, the aromatization reaction of the low-carbon hydrocarbon is difficult,the required catalyst activity is high. Therefore, the low-carbon hydrocarbon can contact with the high-activity regenerated catalyst, the high-selectivity aromatization can be carried out to the aromatic hydrocarbon, and meanwhile, the semi-spent catalyst with a certain carbon deposition amount is obtained, and the carbon content is 0.1-1.5% in terms of the mass percentage of the catalyst. The activity of the semi-spent catalyst can still meet the requirement of the dehydration reaction of the oxygen-containing compound. The technical scheme of the invention is obtained according to the research result. By adopting the technical scheme of the invention, the yield of the aromatic hydrocarbon carbon base is 75.5 wt%, and a better technical effect is obtained.
Drawings
FIG. 1 is a schematic view of a reaction apparatus of the present invention.
In FIG. 1, 1 is a one-stage fluidized bed reactor; 2 is a two-stage fluidized bed reactor; 3 is a semi-standby inclined tube; 4 is a regeneration inclined tube; 5 is a to-be-grown inclined tube; 6 is a feedstock containing an oxygenate; 7 is a mixed hydrocarbon raw material; 8 is a spent agent; 9 is a regenerant; 10 is an aromatic-rich product; 11 is a low pressure drop distribution plate; 12 is a semi-spent catalyst.
In the figure 1, a mixed hydrocarbon raw material 7 enters a first-stage fluidized bed reactor 1 and contacts and reacts with a regenerant 9 entering the first-stage fluidized bed reactor 1 through a regeneration inclined tube 4, an obtained aromatic-rich product 10 enters a subsequent separation system, and an obtained semi-spent catalyst 12 enters a second-stage fluidized bed reactor 2 through a semi-spent inclined tube 3; the raw material 6 containing oxygen-containing compounds enters a second-stage fluidized bed reactor 2, contacts and reacts with a semi-spent catalyst 12, the obtained product enters the first-stage fluidized bed reactor 1 through a low-pressure-drop distribution plate 11, and the obtained spent catalyst 8 returns to a regenerator for regeneration through a spent inclined tube 5.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
Two fluidized bed reactors with different diameters which are arranged in an overlapping way are a first-stage fluidized bed reactor 1 and a second-stage fluidized bed reactor 2 from top to bottom, and the two reactors are connected together by a low-pressure-drop distribution plate 11. The mixed hydrocarbon raw material 7 enters the first-stage fluidized bed reactor 1, and contacts and reacts with the regenerant 9 entering the first-stage fluidized bed reactor 1 through the regeneration inclined tube 4, the obtained product 10 rich in aromatic hydrocarbon enters a subsequent separation system, and the obtained semi-spent catalyst 12 enters the second-stage fluidized bed reactor 2 through the semi-spent inclined tube 3. The raw material 6 containing oxygen-containing compounds enters a second-stage fluidized bed reactor 2, contacts and reacts with a semi-spent catalyst 12, the obtained product enters the first-stage fluidized bed reactor 1 through a low-pressure-drop distribution plate 11, and the obtained spent catalyst 8 returns to a regenerator for regeneration through a spent inclined tube 5.
The mixed hydrocarbon feedstock 7 is C3~C7Mixed chain hydrocarbon, the mass percentage of propane is 30 percent. The oxygenate-containing feedstock 6 is dimethyl ether. The mass ratio of the feed amount of the oxygenate-containing feedstock 6 to the feed amount of the mixed hydrocarbon feedstock 7 was 19: 1.
The diameter ratio of the main reaction zone of the first-stage fluidized bed reactor 1 to the diameter ratio of the second-stage fluidized bed reactor 2 is 3: 1; the ratio of the mass flow of the catalyst entering the first-stage fluidized bed reactor 1 through the low-pressure-drop distribution plate 11 in the second-stage fluidized bed reactor 2 to the mass flow of the semi-spent catalyst 12 in the semi-spent inclined tube 3 is 0.1: 1; the oxygenate conversion at the inlet of the low pressure drop distribution plate 11 was 80.1% and the total mass percentage of olefins in the gas phase stream was 20.1%. The second-stage fluidized bed reactor 2 is provided with a group of built-in heat collectors.
The temperature of the catalyst bed layer of the first-stage fluidized bed reactor 1 is 530 ℃, and the density of the catalyst bed layer is 200 kg/cubic meter. The temperature of the catalyst bed layer of the two-stage fluidized bed reactor 2 is 450 ℃, the density of the catalyst bed layer is 150 kg/cubic meter, and the weight space velocity of the raw material 6 containing the oxygen-containing compound is 5 hours-1The weight space velocity of the mixed hydrocarbon feedstock 7 was 4 hours-1The reaction gauge pressure was 0.3 MPa.
The content of carbon on the spent catalyst 12 was 1.2% by mass of the catalyst.
A Zn-L a-P-ZSM-5 catalyst is adopted, and the mass percentage of the catalyst is that the Zn element content is 7%, the L a element content is 5%, and the P element content is 3%.
The results showed a carbon-based yield of 68.7 wt% of aromatic hydrocarbons.
[ example 2 ]
Following the conditions and procedures described in example 1, the mixed hydrocarbon feedstock 7 is C2~C7Mixed chain hydrocarbon, the mass percentage of propane is 70 percent. The raw material 6 containing the oxygen-containing compound is a mixture of methanol and ethanol, and the mass ratio of the methanol to the ethanol is 8: 2. The mass ratio of the feed amount of the oxygenate-containing feedstock 6 to the feed amount of the mixed hydrocarbon feedstock 7 was 1.2: 1.
The diameter ratio of the main reaction zone of the first-stage fluidized bed reactor 1 to the diameter ratio of the second-stage fluidized bed reactor 2 is 1.01: 1; the ratio of the mass flow of the catalyst entering the first-stage fluidized bed reactor 1 through the low-pressure-drop distribution plate 11 in the second-stage fluidized bed reactor 2 to the mass flow of the semi-spent catalyst 12 in the semi-spent inclined tube 3 is 0.9: 1; the oxygenate conversion at the inlet of the low pressure drop distribution plate 11 is 90% and the total mass percentage of olefins in the gas phase stream is 40%. The second-stage fluidized bed reactor 2 is provided with a group of external heat collectors.
The temperature of the catalyst bed layer of the first-stage fluidized bed reactor 1 is 600 ℃, and the density of the catalyst bed layer is 480 kg/cubic meter. The temperature of the catalyst bed layer of the two-stage fluidized bed reactor 2 is 530 ℃, the density of the catalyst bed layer is 400 kg/cubic meter, and the weight space velocity of the raw material 6 containing the oxygen-containing compound is 0.2 hour-1The weight space velocity of the mixed hydrocarbon feedstock 7 was 0.5 hours-1The reaction pressure is normal pressure.
The content of carbon on the spent catalyst 12 was 0.05% by mass of the catalyst.
Adopts Zn-ZSM-5 catalyst, and the Zn element content is 0.01 percent by mass percent of the catalyst.
The results showed a carbon-based yield of 68.4 wt% of aromatic hydrocarbons.
[ example 3 ]
Following the conditions and procedures described in example 1, the mixed hydrocarbon feedstock 7 is C3~C7Mixed chain hydrocarbon, the mass percentage of the propane is 40 percent. The raw material 6 containing the oxygen-containing compound is methanol, and the mass percentage of the methanol is 98 percent. The mass ratio of the feed amount of the oxygenate-containing feedstock 6 to the feed amount of the mixed hydrocarbon feedstock 7 was 8: 1.
The diameter ratio of the main reaction zone of the first-stage fluidized bed reactor 1 to the diameter ratio of the second-stage fluidized bed reactor 2 is 1.5: 1; the ratio of the mass flow of the catalyst entering the first-stage fluidized bed reactor 1 through the low-pressure-drop distribution plate 11 in the second-stage fluidized bed reactor 2 to the mass flow of the semi-spent catalyst 12 in the semi-spent inclined tube 3 is 0.7: 1; the oxygenate conversion at the inlet of the low pressure drop distribution plate 11 was 95% and the total mass percentage of olefins in the gas phase stream was 60%. The second-stage fluidized bed reactor 2 is provided with a group of external heat collectors.
The temperature of the catalyst bed layer of the first-stage fluidized bed reactor 1 is 570 ℃, and the density of the catalyst bed layer is 380 kg/cubic meter. The temperature of the catalyst bed layer of the two-stage fluidized bed reactor 2 is 500 ℃, the density of the catalyst bed layer is 300 kg/cubic meter, and the weight space velocity of the raw material 6 containing the oxygen-containing compound is 1 hour-1The weight space velocity of the mixed hydrocarbon feedstock 7 was 0.8 hours-1The reaction gauge pressure was 0.2 MPa.
The content of carbon on the spent catalyst 12 was 0.1% by mass of the catalyst.
A Zn-P-ZSM-5 catalyst is adopted, and the content of Zn element is 3.5 percent and the content of P element is 2.1 percent in percentage by mass of the catalyst.
The results showed a yield of 74.8 wt% based on aromatic carbon.
[ example 4 ]
The starting materials, conditions and procedures described in example 3 were followed. A Zn-Ga-In-ZSM-5 catalyst is adopted, and the mass percentage of the catalyst is that the Zn element content is 3.5%, the Ga element content is 1.2%, and the In element content is 1.2%.
The results showed that the yield of aromatic hydrocarbon based on carbon was 75.5% by weight.
[ example 5 ]
The starting materials, conditions and procedures described in example 3 were followed. A Zn-Ga-In-ZSM-5 catalyst is adopted, and the mass percentage of the catalyst is that the Zn element content is 3.5%, the Ga element content is 2% and the In element content is 0.4%.
The results showed that the yield of aromatic hydrocarbon based on carbon was 76.0 wt%.
[ example 6 ]
The catalyst, feed and procedure described in example 3 were followed with a first stage fluidized bed reactor 1 having a catalyst bed temperature of 540 ℃. The catalyst bed temperature of the two-stage fluidized bed reactor 2 was 460 ℃.
The results showed that the yield of aromatic hydrocarbon based on carbon was 70.1 wt%.
[ example 7 ]
The catalyst, feed and procedure described in example 3 were followed with a catalyst bed temperature of 598 ℃ in the first stage fluidized bed reactor 1. The temperature of the catalyst bed layer of the two-stage fluidized bed reactor 2 is 525 ℃.
The results showed that the yield of aromatic hydrocarbon based on carbon was 72.5 wt%.
Comparative example 1
The procedure, catalyst and reaction conditions of example 3 were used. The catalyst bed temperature of the first-stage fluidized bed reactor 1 is 520 ℃. The catalyst bed temperature of the two-stage fluidized bed reactor 2 was 440 ℃. The total mass percentage of olefin in the gas phase stream was 10%. The results showed that the yield of aromatic hydrocarbon based on carbon was 58.3 wt%.
Comparative example 2
The procedure, catalyst and reaction conditions of example 3 were used. The diameter of the main reaction zone of the first fluidized bed reactor 1 and the diameter ratio of the second fluidized bed reactor 2 are 1: 1. The results showed that the yield of aromatic hydrocarbon based on carbon was 67.8 wt%.
Comparative example 3
The procedure and reaction conditions of example 3 were used. A Zn-P-ZSM-5 catalyst is adopted, and the content of Zn element is 8.5 percent and the content of P element is 7.1 percent in percentage by mass of the catalyst. The results showed a yield of 69.1 wt% based on aromatic carbon.
Comparative example 4
The procedure and reaction conditions of example 3 were used. ZSM-5 catalyst is adopted. The results showed that the yield of aromatic hydrocarbon based on carbon was 65.3 wt%.

Claims (11)

1. A method for preparing aromatic hydrocarbon by using an oxygen-containing compound raw material through two-stage reaction comprises the following steps:
providing a catalyst comprising an aluminosilicate molecular sieve, and two superposed fluidized bed reactors with different diameters, namely a first-stage fluidized bed reactor (1) and a second-stage fluidized bed reactor (2) from top to bottom in sequence, wherein the two reactors are connected together by a low-pressure-drop distribution plate (11);
the mixed hydrocarbon raw material (7) enters a first-stage fluidized bed reactor (1) with the temperature range of 550-590 ℃, and is in contact reaction with a regenerant (9) entering the first-stage fluidized bed reactor (1) through a regeneration inclined tube (4), an obtained aromatic hydrocarbon-rich product (10) enters a subsequent separation system, and an obtained semi-spent catalyst (12) enters a second-stage fluidized bed reactor (2) through a semi-spent inclined tube (3);
the method comprises the following steps that a raw material (6) containing oxygen-containing compounds enters a two-stage fluidized bed reactor (2) with the temperature range of 470-520 ℃ to be in contact reaction with a semi-spent catalyst (12), an obtained product enters a one-stage fluidized bed reactor (1) through a low-pressure-drop distribution plate (11), and an obtained spent catalyst (8) returns to a regenerator for regeneration through a spent inclined tube (5);
the ratio of the mass flow of the catalyst entering the first-stage fluidized bed reactor (1) through the low-pressure drop distribution plate (11) in the second-stage fluidized bed reactor (2) to the mass flow of the semi-spent catalyst (12) in the semi-spent inclined tube (3) is (0.1-0.9): 1;
the conversion rate of the oxygen-containing compound at the inlet of the low-pressure-drop distribution plate (11) is more than 80 percent;
the content of carbon on the semi-spent catalyst (12) is 0.05-1.2% by mass of the catalyst.
2. The process of claim 1, wherein the total mass percent of olefins in the gas phase stream is greater than 20%.
3. The method for the two-stage reaction for preparing the aromatic hydrocarbon from the oxygen-containing compound raw material according to claim 1, wherein the ratio of the diameter of the main reaction zone of the first-stage fluidized bed reactor (1) to the diameter of the second-stage fluidized bed reactor (2) is 3-1.01: 1.
4. The method for the two-stage reaction for preparing the aromatic hydrocarbon from the raw material containing the oxygen-containing compound according to claim 1, wherein the weight space velocity of the raw material (6) containing the oxygen-containing compound is 0.2 to 5 hoursTime of flight-1The weight space velocity of the mixed hydrocarbon raw material (7) is 0.5-4 hours-1
5. The method for the two-stage reaction for preparing the aromatic hydrocarbon from the oxygen-containing compound raw material according to claim 1, wherein the reaction gauge pressure of the fluidized bed reactor is 0-0.6 MPa.
6. The method for the two-stage reaction for preparing the aromatic hydrocarbon from the oxygen-containing compound raw material according to claim 1, wherein the density of the catalyst bed in the first-stage fluidized bed reactor (1) is 200-480 kg/m, and the density of the catalyst bed in the second-stage fluidized bed reactor (2) is 150-400 kg/m.
7. The method for preparing aromatic hydrocarbon by two-stage reaction of the raw material containing the oxygen-containing compound according to claim 1, characterized in that the mixed hydrocarbon raw material (7) is hydrocarbon or a mixture of hydrocarbons with a distillation range above carbon two lower than 350 ℃.
8. The process according to claim 1, wherein the oxygenate-containing feedstock (6) comprises at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, C4~C20Compounds of alcohols, methyl ethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, acetone, acetic acid; the oxygenate-containing feedstock (6) has an oxygenate content of at least 10% by weight.
9. The method for preparing aromatic hydrocarbons by two-stage reaction of the raw material containing the oxygen-containing compounds according to claim 1, characterized in that the mass ratio of the feeding amount of the raw material (6) containing the oxygen-containing compounds to the feeding amount of the mixed hydrocarbon raw material (7) is 19-1.2: 1.
10. The method for preparing aromatic hydrocarbon through two-stage reaction of the oxygen-containing compound raw material according to claim 1, wherein the catalyst is at least one of ZSM-5 and ZSM-11 modified by a modifying element, the modifying element is at least one of Zn, L a, P, In and Ga, and the content of the modifying element is 0.01-15% by weight of the catalyst.
11. The method for the two-stage reaction of preparing the aromatic hydrocarbon from the raw material containing the oxygen-containing compound according to claim 1, wherein the two-stage fluidized bed reactor (2) is provided with at least one set of internal and/or external heat collectors.
CN201610973691.2A 2016-11-04 2016-11-04 Two-stage reaction method for preparing aromatic hydrocarbon from oxygen-containing compound-containing raw material Active CN108017487B (en)

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CN110818521B (en) * 2018-08-07 2022-06-07 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin by using oxygen-containing compound
CN110819373B (en) * 2018-08-07 2021-12-14 中石化广州工程有限公司 Device and method for preparing gasoline by using oxygen-containing compound
CN110819375B (en) * 2018-08-07 2021-12-14 中石化广州工程有限公司 Device and method for preparing gasoline from oxygen-containing compound
CN111097337B (en) * 2018-10-25 2022-04-05 中国石油化工股份有限公司 Zoned fluidized bed reaction-regeneration device and process for preparing aromatic hydrocarbon through methanol conversion
CN111099947B (en) * 2018-10-25 2022-08-12 中国石油化工股份有限公司 Method for preparing aromatic hydrocarbon by efficiently converting methanol
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CN114130313A (en) * 2021-11-08 2022-03-04 清华大学 C is to be3-C9Fluidized bed continuous reaction regeneration system and method for converting alkane into aromatic hydrocarbon
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