CN108654527A - Synthesis gas prepares the two sections of recirculating fluidized bed reaction-regeneration systems and method of aromatic hydrocarbons - Google Patents

Abstract

A two-stage circulating fluidized bed reaction-regeneration system and method for preparing aromatics from synthesis gas, comprising an aromatization reactor and a catalyst regeneration reactor, the two are connected to each other through pipelines, and the aromatization reactor includes a first The catalyst loading area and the second catalyst loading area; the catalyst regeneration reactor includes the fourth catalyst loading area and the third catalyst loading area, and the hydrocarbon synthesis catalyst and the aromatization catalyst are filled in the aromatization reactor, and under the action of air flow, The hydrocarbon synthesis catalyst mainly stays in the lower area, and the aromatization catalyst mainly stays in the upper area, and it is announced that after the aromatization catalyst is deactivated, it first enters the low-temperature low-oxygen zone of the catalyst regeneration reactor, and then enters its high-temperature high-oxygen zone. The regeneration method of the zone, the invention realizes the control of different temperatures, and reduces the design difficulty of the catalyst.

Description

Two-stage circulating fluidized bed reaction-regeneration system and method for preparing aromatics from syngas

technical field

The invention relates to the technical field of chemical processes and equipment, in particular to a two-stage circulating fluidized bed reaction-regeneration system and method for preparing aromatics from synthesis gas.

Background technique

The synthesis gas aromatization technology is an emerging aromatics production process, one of which is to form hydrocarbon intermediates in the synthesis gas first, and then prepare aromatics through hydrocarbons. The obvious advantage of combining the two reactions in one reactor is that there is no need to separate the complex hydrocarbon components and prepare high-purity products, so that the separation units of the two processes that were originally carried out independently can be effectively merge. The technical challenge is that the original catalyst for hydrocarbon synthesis works at 300-380°C, and the catalyst for preparing aromatic hydrocarbons from hydrocarbons works at 350-500°C. At present, there are reports on the preparation of multifunctional composite catalysts, hoping to directly prepare aromatics without generating hydrocarbon products. However, at present, such catalysts are restricted by chemical balance, the conversion rate of synthesis gas is not high, and the selectivity of producing _CO2 is relatively high. At the same time, the catalyst for this process needs to be regenerated at high temperature, and there is no such technical report so far.

Contents of the invention

In order to overcome the deficiencies of the above-mentioned prior art, the object of the present invention is to provide a two-stage circulating fluidized bed reaction-regeneration system and method for preparing aromatics from syngas, and a method of introducing a transverse porous baffle in the axial direction of the reactor to realize " Hydrocarbons are first generated, aromatics are regenerated" fluidized bed reactor structure, and at the same time, a temperature difference and a concentration difference are established in the upper and lower sections of the catalyst regeneration two-stage fluidized bed reactor to restore and protect the activity of the catalyst, with raw material gas conversion High efficiency, mild pressure conditions, easy temperature control, continuous and easy control of the process, etc.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A two-stage circulating fluidized bed reaction-regeneration system for preparing aromatics from synthesis gas, including an aromatization reactor 1 and a catalyst regeneration reactor 13, which are connected to each other through pipelines, and the aromatization reactor 1 Divided into a fluidized bed with both ends, the bottom is the first catalyst loading area 1a, and the top is the second catalyst loading area 1b. The bottom of the first catalyst loading area 1a is provided with a first gas inlet 2. The first catalyst A first transverse porous distribution plate 3 is arranged between the loading area 1a and the second catalyst loading area 1b, and a first gas inlet 4 and a first catalyst outlet 5 are arranged at the lower part of the second catalyst loading area 1b. The top of the second catalyst loading area 1b is provided with a first gas outlet 7, and the upper part is provided with a first catalyst inlet 6;

The catalyst regeneration reactor 13 is divided into a fluidized bed at both ends, including the fourth catalyst loading area 13b above and the third catalyst loading area 13a below, and the bottom of the third catalyst loading area 13a is provided with a second gas Inlet 8, a second catalyst outlet 12 is provided below the third catalyst loading area 13a;

A second transverse porous distribution plate 9 is provided between the fourth catalyst loading area 13b and the third catalyst loading area 13a below, and the second catalyst inlet 11 and the top of the fourth catalyst loading area 13b are provided on the top. Second gas outlet 10;

The output end of the first catalyst outlet 5 is connected to the input end of the second catalyst inlet 11 , and the output end of the second catalyst outlet 12 is connected to the input end of the first catalyst inlet 6 .

The first catalyst loading area 1a is a hydrocarbon synthesis catalyst area, the second catalyst loading area 1b is a hydrocarbon aromatization catalyst area, and the first catalyst loading area 1a is low-carbon hydrocarbons produced from low-temperature syngas The second catalyst loading area 1b is a high temperature hydrocarbon aromatization area, the fourth catalyst loading area 13b is a low temperature low oxygen area, and the third catalyst loading area 13a is a high temperature high oxygen area.

The present invention also provides a method for preparing aromatics from synthesis gas by utilizing the above-mentioned device, comprising the steps of:

(1) Both the synthetic hydrocarbon catalyst and the aromatization catalyst are pre-installed in the first catalyst loading area 1a of the aromatization reactor 1, and the synthesis gas is preheated from the first gas inlet in the lower section of the aromatization reactor 1 2, the aromatization catalyst is blown to the second catalyst loading area 1b through the first transverse porous distribution plate 3, and the synthesis gas is mainly contacted with the catalyst for synthesizing hydrocarbons in the first catalyst loading area 1a to generate various hydrocarbons, Pass through the first transverse porous distribution plate 3 and enter the second catalyst loading area 1b;

(2) Hydrocarbon gas contacts with the aromatization catalyst in the second catalyst loading area 1b to generate aromatic hydrocarbons and other organic products, and exits the aromatization reactor 1 from the first gas outlet 7 of the reactor, and undergoes steps such as heat exchange and separation , recycle C ₃ -C ₈ non-aromatic hydrocarbons, enter the second catalyst loading zone 1b from the first gas inlet 4, and carry out back refining;

(3) Part of the catalyst is preloaded in the third catalyst loading area 13a in the catalyst regeneration reactor 13, and the second gas inlet 8 at the bottom is passed into an oxygen-containing gas (such as air, oxygen, or oxygen-containing CO ₂ , nitrogen or argon, etc., the volume content of oxygen is 2%-100%), the generated gas in the third catalyst loading area 13a passes through the second transverse porous distribution plate 9, and enters the fourth catalyst loading area 13b;

(4) After the carbon deposition of the catalyst in the second catalyst loading area 1b in the aromatization reactor 1, it is removed from the first catalyst outlet 5 of the aromatization reactor 1, transported through a pipeline, and enters catalyst regeneration through the second catalyst inlet 11 In the fourth catalyst loading area 13b of the reactor 13, the coke-containing catalyst that enters from the second catalyst inlet 11 passes through the second transverse porous distribution plate 9 after being burned off part of the coke in the fourth catalyst loading area 13b, and enters the first catalyst loading area 13b. Three catalyst loading areas 13a, the gas exits the catalyst regeneration reactor 13 through the second gas outlet 10;

(5) In the third catalyst loading area 13a, most of the coke on the catalyst is burned off, and is transported through the pipeline from the second catalyst outlet 12, and returns to the aromatization reactor 1 through the first catalyst inlet 6;

(6) Repeat the above steps to make the process continue.

The temperature of the first catalyst loading zone 1a is 250-380°C, the temperature of the second catalyst loading zone 1b is 450-550°C, and the pressure is 0.1-3.5MPa.

The temperature of the third catalyst packing area 13a is 550-650°C, the temperature of the fourth catalyst packing area 13b is 480-600°C, and the pressure is 0.1-3.5 MPa.

The main active components of the low-carbon hydrocarbon synthesis catalyst in the first catalyst loading zone 1a in the aromatization reactor 1 are Fe, Cr, Co, Mo, Ni, Mn and those in their carbonized state and nitrogenated state. One or more, the carrier is one or more of alumina, zirconia, silicon oxide, and molecular sieves, the active ingredient accounts for 1-50% of the total mass of the hydrocarbon synthesis catalyst, and the rest is the carrier; The average particle size of the catalyst is 200-350 microns.

The hydrocarbon aromatization catalyst in the second catalyst loading area 1b is a metal or metal oxide-molecular sieve+carrier trifunctional catalyst, and the metal or metal oxide is Cu, Zn, Cr, Fe, Co, Ni, ZnO, One or more of CeO2, La2O3, Ga ₂ O ₃ , Fe ₂ O ₃ and MoO ₃ , the molecular sieve is one or more of ZSM-5, ZSM-12, Y molecular type and β molecular sieve, and the carrier is One or more of aluminum oxide, kaolin and silicon oxide; wherein: the molecular sieve accounts for 20-40% of the total mass of the hydrocarbon aromatization catalyst, and the carrier accounts for 20-40% of the total mass of the hydrocarbon aromatization catalyst The fraction is 45-65%, the mass fraction of the metal or metal oxide in the total mass of the hydrocarbon aromatization catalyst is 1-15%, and the average particle diameter of the catalyst is 40-120 microns.

Beneficial effects of the present invention:

The reaction of synthesizing hydrocarbons and generating aromatics can realize different temperature control, and can use different types of catalysts, which reduces the difficulty of catalyst design. Through the setting of two reaction zones, the back-mixing of intermediate products can be reduced, and the amount of _CO2 generation can be reduced by 80%. 30% lower cost than other processes.

The catalyst regeneration reactor adopts a two-stage fluidized bed with variable temperature setting, which has heat controllability compared with single-stage fluidized bed regeneration, prolongs the life of the catalyst by 50-65%, and reduces catalyst pulverization by 5%. After the catalyst is regenerated, it is passed into the aromatization reaction area, and the temperature difference is small, and the powdering of the catalyst is reduced by 10-20% compared with the direct passage into the hydrocarbon synthesis area.

The cyclic conversion of C ₃ -C ₈ non-aromatics can increase the yield of aromatics by 10-20%.

Description of drawings

Figure 1 is a two-stage circulating fluidized bed reaction system for preparing aromatics from syngas.

Detailed ways

The present invention is described in further detail below in conjunction with embodiment.

As shown in Figure 1, a two-stage circulating fluidized bed reaction-regeneration system for preparing aromatics from synthesis gas of the present invention includes an aromatization reactor 1 and a catalyst regeneration reactor 13, which are connected to each other by pipelines, The aromatization reactor 1 is divided into a fluidized bed with both ends, the first catalyst loading area 1a is located below, and the second catalyst loading area 1b is located above, and the bottom of the first catalyst loading area 1a is provided with a first gas Inlet 2, a first transverse porous distribution plate 3 is provided between the first catalyst loading area 1a and the second catalyst loading area 1b, and a first gas inlet 4 and a second gas inlet 4 are provided at the lower part of the second catalyst loading area 1b. A catalyst outlet 5, the top of the second catalyst loading area 1b is provided with a first gas outlet 7, and the upper part is provided with a first catalyst inlet 6;

The catalyst regeneration reactor 13 is divided into a fluidized bed at both ends, including the fourth catalyst loading area 13b above and the third catalyst loading area 13a below, and the bottom of the third catalyst loading area 13a is provided with a second gas Inlet 8, a second catalyst outlet 12 is provided below the third catalyst loading area 13a;

A second transverse porous distribution plate 9 is provided between the fourth catalyst loading area 13b and the third catalyst loading area 13a below, and the second catalyst inlet 11 and the top of the fourth catalyst loading area 13b are provided on the top. Second gas outlet 10.

The first catalyst loading area 1a is a hydrocarbon synthesis catalyst area, the second catalyst loading area 1b is a hydrocarbon aromatization catalyst area, and the first catalyst loading area 1a is low-carbon hydrocarbons produced from low-temperature syngas The second catalyst loading area 1b is a high temperature hydrocarbon aromatization area, the fourth catalyst loading area 13b is a low temperature low oxygen area, and the third catalyst loading area 13a is a high temperature high oxygen area.

Example 1

The hydrocarbon synthesis catalyst (iron nitride/alumina, the mass fraction of iron nitride is 50%, the rest is alumina, the average particle size of the catalyst is 350 microns) and the aromatization catalyst (Ga ₂ O ₃ /Y molecular sieve/ Alumina type, wherein alumina, Y molecular sieve, Ga ₂ O ₃ mass fractions are 60%, 30%, 10% respectively, and the average particle diameter of the catalyst is 120 microns) is packed in the first catalyst packing of aromatization reactor 1 Zone 1a area. Preheat the lower area of the aromatization reactor 1 to 250°C, feed synthesis gas (CO and hydrogen), control the pressure at 3MPa, and blow the aromatization catalyst from the first catalyst loading area 1a to the second catalyst loading area In 1b, the temperature of the second catalyst loading zone 1b is controlled to be 550°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction in the hydrocarbon aromatization catalyst zone.

Part of the aromatization catalyst is pre-loaded in the third catalyst loading area 13a in the catalyst regeneration reactor 13, and air is introduced from the second gas inlet 8 at the bottom, and the generated gas in the third catalyst loading area 13a passes through the second horizontal The porous distribution plate 9 enters the fourth catalyst loading area 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 620°C and 530°C respectively.

When the catalyst in the second catalyst loading area 1b in the aromatization reactor is deactivated by carbon deposition, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters catalyst regeneration through the second catalyst inlet 11 In the fourth catalyst loading zone 13b of the reactor 13. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regenerator 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Example 2

Hydrocarbon synthesis catalyst (Fe/Cr/alumina catalyst, alumina, Fe, Cr mass fraction are respectively 5%, 20%, 75%, the average particle diameter of catalyst is 200 microns) and aromatization catalyst (ZnO/ Ga ₂ O ₃ /ZSM-5/alumina, in which alumina, ZSM-5 molecular sieve, Ga ₂ O ₃ , and ZnO mass fractions are 50%, 35%, 5%, and 10%, respectively, and the average particle size of the catalyst is 40 Micrometers) are loaded in the first catalyst loading zone 1a area of the reactor. The lower area of the reactor was preheated to 380°C, and the synthesis gas (CO and hydrogen) was introduced to control the pressure at 2MPa. The aromatization catalyst is blown from the first catalyst loading area 1a into the second catalyst loading area 1b, and the temperature of the second catalyst loading area 1b is controlled to be 450°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction.

Part of the aromatization catalyst is prepacked in the third catalyst loading zone 13a in the catalyst regeneration _two -stage fluidized bed reactor 13, and the CO containing 15% oxygen is introduced from the second gas inlet 8 at the bottom. The generated gas in the loading area 13a passes through the second transverse porous distribution plate 9 and enters the fourth catalyst loading area 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 580°C and 490°C respectively.

When the catalyst in the second catalyst loading area 1b in the aromatization reactor is deactivated by carbon deposition, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters the reactor through the second catalyst inlet 11 13 in the fourth catalyst loading area 13b. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regenerator 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Example 3

The hydrocarbon synthesis catalyst (Co/Mn/alumina/silicon oxide catalyst (Co, Mn, alumina, silica mass fraction is 0.6%, 0.4%, 70%, 29%, the average particle diameter of catalyst is 270- Micron) and aromatization catalyst (MoO ₃ /Fe/β molecular sieve/alumina, wherein the mass fractions of alumina, β molecular sieve, MoO ₃ and Fe are 58%, 36%, 3%, 3%, the average particle size of the catalyst diameter of 80 microns) is packed in the first catalyst loading area 1a area of the reactor. The lower area of the reactor is preheated to 280 ° C, and the synthesis gas (CO and hydrogen) is introduced, and the control pressure is 0.1 MPa. The aromatization The catalyst is blown from the first catalyst loading area 1a to the second catalyst loading area 1b, and the temperature of the second catalyst loading area 1b is controlled to be 480°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction.

Part of the aromatization catalyst is pre-packed in the third catalyst loading zone 13a in the catalyst regeneration two-stage fluidized bed reactor 13, and the second gas inlet 8 from the bottom is passed into the argon containing 8% oxygen, and the third catalyst The generated gas in the loading area 13a passes through the second transverse porous distribution plate 9 and enters the fourth catalyst loading area 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 620°C and 550°C respectively.

When the catalyst in the second catalyst loading area 1b in the aromatization reactor is deactivated by carbon deposition, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters the reactor through the second catalyst inlet 11 13 in the fourth catalyst loading area 13b. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regenerator 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Example 4

The hydrocarbon synthesis catalyst (molybdenum nitride/alumina, molybdenum nitride, alumina fractions are 10%, 90% respectively, the average particle size of the catalyst is 250 microns) and the aromatization catalyst (Fe ₂ O ₃ /ZnO/ ZSM-5/kaolin/silicon oxide, kaolin, silicon oxide, ZSM-5 molecular sieve, Fe ₂ O ₃ , ZnO mass fractions are 30%, 30%, 30%, 6%, 4%, respectively, and the average particle size of the catalyst is 75 microns) is loaded in the first catalyst loading zone 1a area of the reactor. Preheat the lower area of the reactor to 320°C, feed synthesis gas (CO and hydrogen), control the pressure at 3.5MPa, and blow the aromatization catalyst in the first catalyst loading area 1a to the second catalyst loading area 1b , controlling the temperature of the second catalyst loading zone 1b to be 400°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction.

Part of the aromatization catalyst is pre-packed in the third catalyst loading area 13a in the catalyst regeneration two-stage fluidized bed reactor 13, and oxygen is introduced from the second gas inlet 8 at the bottom, and the generated gas in the third catalyst loading area 13a , pass through the second transverse porous distribution plate 9, and enter the fourth catalyst packing area 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 550°C and 480°C respectively.

When the catalyst in the second catalyst loading area 1b in the aromatization reactor is deactivated by carbon deposition, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters the reactor through the second catalyst inlet 11 13 in the fourth catalyst loading area 13b. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regenerator 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Example 5

Synthetic hydrocarbon catalyst (molybdenum carbide/Ni/Cr/alumina, wherein molybdenum carbide, Ni, Cr mass fraction are respectively 10%, 15%, 18%, the rest is alumina, and the average particle diameter of catalyst is 280 microns) With aromatization catalyst (Bi/Ga ₂ O ₃ /ZSM-5/alumina type, wherein the mass fractions of Bi, Ga ₂ O ₃ , ZSM-5 and alumina are 6%, 5%, 35%, 54 %, the average particle diameter of the catalyst is 90 microns) is packed in the first catalyst packing area 1a area in the reactor. Preheat the lower area of the reactor to 280°C, feed synthesis gas (CO and hydrogen), and control the pressure at 2.5MPa. The aromatization catalyst in the first catalyst loading area 1a is blown into the second catalyst loading area 1b, and the temperature of the second catalyst loading area 1b is controlled to be 450°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction.

Part of the aromatization catalyst is pre-packed in the third catalyst loading area 13a in the catalyst regeneration two-stage fluidized bed reactor 13, and the second gas inlet 8 at the bottom is passed into nitrogen containing 50% oxygen, and the third catalyst is loaded The generated gas in zone 13a passes through the second transverse perforated distribution plate 9 and enters the fourth catalyst loading zone 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 600°C and 500°C respectively.

When the catalyst in the second catalyst loading area 1b in the aromatization reactor is deactivated by carbon deposition, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters the reactor through the second catalyst inlet 11 13 in the fourth catalyst loading area 13b. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regenerator 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Example 6

The hydrocarbon synthesis catalyst (iron carbide/chromium oxide/alumina/zirconia, wherein iron carbide, chromium oxide, aluminum oxide, and zirconia mass fractions are respectively 5%, 10%, 60%, 25%, the average particle size of the catalyst diameter is 300 microns) and aromatization catalyst (ZnO/Fe/CeO ₂ /ZSM-12/silica type, wherein the mass fractions of ZnO, Fe CeO ₂ , ZSM-12, and silicon oxide are 0.3%, 0.5%, respectively, 0.2%, 40%, 59%, the average particle size of the catalyst is 100 micrometers) are packed in the first catalyst loading zone 1a area in the reactor. Preheat the lower area of the reactor to 350°C, feed synthesis gas (CO and hydrogen), control the pressure to 3MPa, blow the aromatization catalyst from the first catalyst loading area 1a to the second catalyst loading area 1b, and control The temperature of the second catalyst packing zone 1b was 500°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction.

Part of the aromatization catalyst is pre-packed in the third catalyst loading area 13a in the catalyst regeneration two-stage fluidized bed reactor 13, and air is introduced from the second gas inlet 8 at the bottom, and the generated gas in the third catalyst loading area 13a , pass through the second transverse porous distribution plate 9, and enter the fourth catalyst packing area 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 650°C and 600°C respectively.

When the catalyst in the second catalyst loading area 1b in the aromatization reactor is deactivated by carbon deposition, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters the reactor through the second catalyst inlet 11 13 in the fourth catalyst loading area 13b. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regeneration reactor 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Example 7

The hydrocarbon synthesis catalyst (cobalt carbide/Cr/ZSM-5/Al ₂ O ₃ , wherein cobalt carbide, Cr, ZSM-5 molecular sieve, and Al ₂ O ₃ mass fractions are respectively 10%, 10%, 30%, 50% , the average particle size of the catalyst is 200 microns) and the aromatization catalyst (Fe2O3/MoO3/Cr/CeO ₂ /ZSM-5/kaolin/Al ₂ O ₃ type, Fe2O3, MoO3, Cr, La ₂ O ₃ , ZSM- 5. Kaolin, Al ₂ O ₃ mass fractions are 3%, 2%, 5%, 5%, 20%, 30%, 35%, the average particle diameter of the catalyst is 60 microns) the first catalyst is packed in the reactor Load zone 1a area. Preheat the lower area of the reactor to 300°C, feed synthesis gas (CO and hydrogen), control the pressure at 2.5MPa, blow the aromatization catalyst from the first catalyst loading area 1a to the second catalyst loading area 1b, The temperature of the second catalyst loading zone 1b was controlled to be 520°C.

The synthesis gas generates hydrocarbons in the first catalyst loading zone 1a, and the hydrocarbons further react in the second catalyst loading zone 1b to generate aromatic hydrocarbons. Aromatics, by-produced light hydrocarbons, water and unreacted synthesis gas exit the aromatization reactor 1 through the product first gas outlet 7. The gas exiting the aromatization reactor 1 is heat-exchanged, and after cooling, the water, aromatic hydrocarbons, light hydrocarbons and synthesis gas are separated sequentially, and the C ₃ -C ₈ components in the light hydrocarbons are recycled into the first gas inlet 4 light hydrocarbons The inlet is recycled to the second catalyst loading zone 1b of the aromatization reactor 1 to continue the reaction.

In the catalyst regenerating two-stage fluidized bed reactor 13, the third catalyst loading area 13a pre-packs part of the aromatization catalyst, and feeds nitrogen with 2% oxygen from the second gas inlet 8 at the bottom, in the third catalyst loading area The generated gas at 13a passes through the second transverse porous distribution plate 9 and enters the fourth catalyst loading area 13b. The temperatures of the third catalyst loading area 13a and the fourth catalyst loading area 13b are controlled to be 650°C and 480°C respectively.

When the catalyst carbon deposit in the second catalyst loading area 1b in the aromatization reactor 1 is deactivated, it is removed from the first catalyst outlet 5 in the upper section of the aromatization reactor 1, transported through a pipeline, and enters the reaction through the second catalyst inlet 11. In the fourth catalyst loading area 13b of the vessel 13. After burning part of the coke, it passes through the second transverse porous distribution plate 9 and enters the third catalyst loading area 13a. The gas exits the catalyst regeneration reactor 13 through the second gas outlet 10 . In the third catalyst loading zone 13a, most of the coke on the catalyst is burned off. And from the second catalyst outlet 12, through the pipeline, return to the aromatization reactor 1 through the first catalyst inlet 6.

Repeat the above steps to make the process continuous.

Claims (7)

1. a kind of synthesis gas prepares two sections of recirculating fluidized bed reaction-regeneration systems of aromatic hydrocarbons, which is characterized in that anti-including aromatisation Device (1) and catalyst regeneration reactor (13) are answered, is connected with each other between the two by pipeline, the aromatization reactor (1) It is divided into both ends fluid bed, lower section is the first catalyst filling zone (1a), and top is the second catalyst filling zone (1b), described the The bottom one catalyst filling zone (1a) is provided with first gas import (2), first catalyst filling zone (1a) and second The first lateral multihole distributor (3) is provided between catalyst filling zone (1b), under second catalyst filling zone (1b) Portion is provided with first gas import (4) and the first catalyst outlet (5), is arranged at the top of second catalyst filling zone (1b) There is first gas to export (7), top is provided with the first catalyst inlet (6)；

The catalyst regeneration reactor (13) is divided into both ends fluid bed, includes the 4th catalyst filling zone (13b) of top With the third catalyst filling zone (13a) of lower section, described bottom third catalyst filling zone (13a) be provided with second gas into Mouth (8) is provided with the second catalyst outlet (12) below third catalyst filling zone (13a)；4th Catalyst packing It is provided with the second lateral multihole distributor (9) between area (13b) and the third catalyst filling zone (13a) of lower section, described the The top four catalyst filling zones (13b) is provided with second gas outlet (10) of the second catalyst inlet (11) with top；

The output end of first catalyst outlet (5) connects the second catalyst inlet (11) input terminal, and the second catalyst goes out The output end of mouth (12) connects the first catalyst inlet (6) input terminal.

2. a kind of synthesis gas according to claim 1 prepares two sections of recirculating fluidized bed reaction-regeneration systems of aromatic hydrocarbons, special Sign is that first catalyst filling zone (1a) is hydrocarbon synthesis catalyst area, second catalyst filling zone (1b) is hydrocarbon aromatization catalyst area, and the first catalyst filling zone (1a) is the synthesis of gas produced low-carbon hydro carbons region of low temperature, the Two catalyst filling zones (1b) are the aromatization of hydrocarbons region of high temperature, and the 4th catalyst filling zone (13b) is that low temperature is low Oxygen area, third catalyst filling zone (13a) are high temperature hyperoxia area.

3. a kind of method that synthesis gas being prepared aromatic hydrocarbons using 1 device of above-mentioned power, which is characterized in that

(1) Synthin catalyst and aromatized catalyst are all mounted in the first Catalyst packing of aromatization reactor (1) in advance Area (1a) is passed through after preheating synthesis gas from the first gas import (2) of aromatization reactor (1) hypomere, by Aromatizatian catalytic Agent blows to the second catalyst filling zone (1b) by the first lateral multihole distributor (3), and synthesis gas is mainly filled in the first catalyst It fills out area (1a) and contacts the various hydro carbons of generation with the catalyst of Synthin, by the first lateral multihole distributor (3), into second Catalyst filling zone (1b)；

(2) hydrocarbon gas is contacted at the second catalyst filling zone (1b) with aromatized catalyst, generates aromatic hydrocarbons and other organic productions Object goes out aromatization reactor (1) from reactor first gas outlet (7), by heat exchange with detach, by C₃-C₈It is non-aromatic Hydrocarbon recycles, and enters the second catalyst filling zone (1b) from first gas import (4), carries out freshening；

(3) the prefilled partial catalyst in third catalyst filling zone (13a) in catalyst regeneration reactor (13), and the bottom of from Portion's second gas import (8) is passed through oxygen-containing gas, in the generation gas of third catalyst filling zone (13a), laterally by second Multihole distributor (9), into the 4th catalyst filling zone (13b)；

(4) in aromatization reactor (1) after the catalyst carbon deposition of the second catalyst filling zone (1b), from aromatization reactor (1) The first catalyst outlet (5) remove, by pipeline, enter catalyst regeneration reaction by the second catalyst inlet (11) 4th catalyst filling zone (13b) of device (13), the catalyst containing coke entered by the second catalyst inlet (11), the 4th After being burned off part of coke in catalyst filling zone (13b), by the second lateral multihole distributor (9), into third catalyst Filling area (13a), gas go out catalyst regeneration reactor (13) by second gas outlet (10)；

(5) in third catalyst filling zone (13a), the most regions coke on catalyst is burned off, and from the second catalyst It exports (12), by pipeline, aromatization reactor (1) is returned through the first catalyst inlet (6)；

(6) it repeats the above steps, process is made to be carried out continuously.

4. the method that synthesis gas according to claim 3 prepares aromatic hydrocarbons, which is characterized in that first Catalyst packing The temperature in area (1a) is 250-380 DEG C, and the temperature of the second catalyst filling zone (1b) is 450-550 DEG C, pressure 0.1- 3.5MPa。

5. the method that synthesis gas according to claim 3 prepares aromatic hydrocarbons, which is characterized in that the third Catalyst packing The temperature in area (13a) is 550-650 DEG C, and the temperature of the 4th catalyst filling zone (13b) is 480-600 DEG C, pressure 0.1- 3.5MPa。

6. the method that synthesis gas according to claim 3 prepares aromatic hydrocarbons, which is characterized in that the aromatization reactor (1) in the first catalyst filling zone (1a) in the main active of low-carbon hydrocarbon synthesis catalyst be Fe, Cr, Co, Mo, Ni, Mn and its carbonization state with nitrogenize one or more in state, carrier is alundum (Al2O3), zirconium oxide, silica, in molecular sieve It is one or more, active constituent account for hydrocarbon synthesis catalyst gross mass mass fraction be 1-50%, remaining is carrier；Catalysis The average grain diameter of agent is 200-350 microns.

7. the method that synthesis gas according to claim 3 prepares aromatic hydrocarbons, which is characterized in that second Catalyst packing Hydrocarbon aromatization catalyst is three function catalyst of metal or metal oxide-molecular sieve+carrier, metal or metal in area (1b) Oxide is Cu, Zn, Cr, Fe, Co, Ni, ZnO, CeO2, La2O3, Ga₂O₃、Fe₂O₃And MoO₃In one or more, molecular sieve One or more in Y molecule-types and beta-molecular sieve for ZSM-5, ZSM-12, carrier is alundum (Al2O3), kaolin and silica In it is one or more；Wherein：The mass fraction that molecular sieve accounts for hydrocarbon aromatization catalyst gross mass is 20-40%, and carrier accounts for The mass fraction of hydrocarbon aromatization catalyst gross mass is 45-65%, and metal or metal oxide account for hydrocarbon aromatization catalyst The mass fraction of gross mass is 1-15%, and the average grain diameter of catalyst is 40-120 microns.