WO2025129712A1 - High-density fast fluidized bed reactor, and methanol to olefins device and method - Google Patents

Abstract

A high-density fast fluidized bed reactor, and a methanol to olefins device and method. The device comprises a high-density fast fluidized bed reactor and a fluidized bed regenerator. In the high-density fast fluidized bed reactor, the circulation intensity of a catalyst flowing to a reaction zone through a catalyst residence zone is as high as 500-1,000 kg/(m²·s), thereby increasing the bed density of the reaction zone, and achieving high bed density under a high superficial linear velocity condition. In the method, methanol or dimethyl ether or a mixture of methanol and dimethyl ether is used as a raw material to produce ethylene, propylene and butene, the production of propylene and butene can be increased by recycling ethylene, and the production of butene can be increased by recycling propylene, thereby achieving flexible adjustment of the distribution of ethylene, propylene and butene. The sum of the contents of ethylene, propylene and butene in the product is greater than or equal to 90%wt, and the potential content of α-butene in the product can reach up to 57%wt.

Description

A high-density fast fluidized bed reactor, methanol to olefins device and method Technical Field

The present application relates to the field of chemical technology, and in particular to a high-density fast fluidized bed reactor, a methanol to olefins device and a method.

Background Art

Olefins are important basic organic chemical raw materials and the cornerstone of the modern chemical industry. Traditional production technology is highly dependent on petroleum resources. Therefore, it is of great strategic significance to use my country's relatively abundant coal resources to replace petroleum resources.

The main technical routes for olefin production include naphtha cracking to olefins, methanol to olefins, propane dehydrogenation to propylene, alkane cracking to olefins, etc. Low-carbon olefins are very active and are prone to polymerization, alkylation, aromatization and other reactions to generate by-products, reducing the yield of low-carbon olefins.

Methanol to olefins (MTO) technology uses ethylene and propylene as target products. Methanol is converted into a mixture of ethylene, propylene, butene, pentene and alkanes under the action of molecular sieve catalysts. In 2010, the Shenhua Baotou Methanol to Olefins Plant, which uses the DMTO technology developed by the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences, was completed and put into production. This is the world's first industrial application of MTO technology. As of 2023, 16 DMTO industrial units have been put into production, with a total low-carbon olefin production capacity of approximately 9.3 million tons/year. Taking DMTO technology as an example, the carbon-based selectivity of ethylene and propylene is about 80%wt, and the selectivity of butene and pentene is about 15%wt.

In recent years, with the development of high-end polyolefin industry, the demand for α-butene has increased rapidly year by year. Flexible regulation of the product distribution of methanol to olefins technology and increased production of α-butene have become new market demands.

Summary of the invention

In view of this, the present application provides a high-density fast fluidized bed reactor, a methanol to olefins device and a method, the main purpose of which is to solve the technical problem of low α-butene production in methanol to olefins.

Methanol to olefins technology uses SAPO molecular sieve catalysts. The hydrocarbon pool mechanism believes that methanol is converted into ethylene, propylene and other products through aromatics cycle or olefin cycle in the molecular sieve catalyst. The main reactions include:
CH ₃ OH→C ₂ H ₄ +C ₃ H ₆ (1)
C ₂ H ₄ +CH ₃ OH→C ₃ H ₆ (2)
C ₃ H ₆ +CH ₃ OH→C ₄ H ₈ (3)
C ₄ H ₈ +CH ₃ OH→C ₅ H ₁₀ (4)

Reactions (1) and (2) produce ethylene and propylene. Reactions (2), (3) and (4) show that small olefins are more active and can be further converted into olefin molecules with larger carbon atoms by alkylation reactions to increase the number of carbon atoms in the olefin molecules.

SAPO molecular sieve catalyst is a selective catalyst. The olefin molecules in the methanol to olefins product are mainly linear olefin molecules. Among them, the content of 1-butene (α-butene) and 2-butene in butene is greater than 95%. 2-butene can be converted into 1-butene through isomerization technology. Therefore, the potential content of α-butene (1-butene and 2-butene) in the butene product of methanol to olefins technology is as high as 95%.

Methanol to olefins technology uses fluidized bed reactors, and increasing the capacity of a single reactor is one of the core goals of developing methanol to olefins reactors. An effective way to increase the capacity of a single reactor is to increase the superficial linear velocity of the fluidized bed reactor to achieve the purpose of increasing the feed amount of raw materials. However, when the superficial linear velocity is increased, the bed density of the reaction zone of the fluidized bed reactor usually decreases significantly, and the catalyst storage also decreases significantly, which leads to a decrease in methanol conversion rate. That is, there is a negative correlation between the feed amount of raw materials and the bed density of the fluidized bed reaction zone.

In order to increase the production of α-butene, the present application provides a high-density fast fluidized bed reactor on one hand; the high-density fast fluidized bed reactor comprises a reactor outer shell, a reactor inner shell and a conveying pipe;

The high-density fast fluidized bed reactor comprises a reactor outer shell, a reactor inner shell, a conveying pipe and a reactor heat collector;

The reactor outer shell is provided with at least a raw material inlet, a catalyst inlet, a gas phase product outlet and a catalyst outlet;

The reactor outer shell encloses an internal area;

The reactor inner shell is located at the lower part of the inner region. The enclosed area is the reaction zone;

The delivery pipe is located in the upper middle part of the inner area, and the bottom of the delivery pipe is connected to the reaction zone;

The area enclosed by the reactor shell and the delivery pipe is a gas-solid separation area;

The delivery pipe is provided with an outlet, and the delivery pipe is connected with the gas-solid separation zone;

The annular area enclosed by the reactor outer shell and the reactor inner shell is the catalyst retention area;

The bottom of the reaction zone is connected to the bottom of the catalyst retention zone;

The catalyst retention zone is connected to the gas-solid separation zone and is located below the gas-solid separation zone;

The reactor heat extractor is located in the catalyst retention zone.

Optionally, the high-density fast fluidized bed reactor comprises a catalyst distribution pipe, a fluidizing steam distributor, and a raw material distributor;

The catalyst distribution pipe passes through the inner shell of the reactor to connect the catalyst retention zone and the reaction zone;

The fluidizing steam distributor is arranged at the bottom of the catalyst retention zone;

The raw material distributor is arranged at the bottom of the reaction zone.

Optionally, a through hole is opened on the lower surface of the catalyst distribution tube.

Optionally, the high-density fast fluidized bed reactor includes a first gas-solid separation device and a second gas-solid separation device;

The first gas-solid separation device and the second gas-solid separation device are located in the gas-solid separation zone;

The inlet of the first gas-solid separation device is connected to the outlet of the conveying pipe;

The catalyst outlet of the first gas-solid separation device is located at the lower part of the gas-solid separation zone, and the gas outlet of the first gas-solid separation device is located at the upper part of the gas-solid separation zone.

Optionally, the inlet of the second gas-solid separation device is located at the upper part of the gas-solid separation zone.

The catalyst outlet of the second gas-solid separation device is located at the lower part of the gas-solid separation zone.

Optionally, the first gas-solid separation equipment is an inertial separator.

Optionally, the second gas-solid separation equipment is selected from one or more groups of gas-solid cyclone separators, and each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator.

Optionally, the high-density fast fluidized bed reactor includes a reactor gas collecting chamber and a product gas conveying pipe;

The reactor gas collection chamber is located at the top of the high-density fast fluidized bed reactor;

The product gas delivery pipe is connected to the top of the reactor gas collecting chamber;

The gas outlet of the second gas-solid separation device is communicated with the reactor gas collecting chamber.

The high-density fast fluidized bed reactor of the present application mainly comprises a reaction zone, a catalyst retention zone and a gas-solid separation zone. The catalyst circulation intensity flowing from the catalyst retention zone to the reaction zone is as high as 500-1000kg/( ^m2 ·s), thereby increasing the bed density of the reaction zone, achieving high bed density under high superficial linear velocity conditions, and overcoming the negative correlation between the feed rate of raw materials and the bed density of the fluidized bed reaction zone.

In a second aspect, the present application provides a methanol to olefins device, the device comprising the above-mentioned high-density fast fluidized bed reactor and a fluidized bed regenerator;

The catalyst extraction pipe passes through the reactor outer shell and is located at the lower part of the catalyst retention zone, and the catalyst extraction pipe is connected to the reactor stripper;

The inlet of the slide valve to be regenerated is connected to the bottom of the reactor stripper, the outlet of the slide valve to be regenerated is connected to the inlet of the spent agent delivery pipe, and the outlet of the spent agent delivery pipe is connected to the fluidized bed regenerator;

The regenerator stripper is located at the bottom of the fluidized bed regenerator, and a regenerator heat collector is arranged in the regenerator stripper; the inlet of the regeneration slide valve is connected to the bottom of the regenerator stripper, and the outlet of the regeneration slide valve is connected to the inlet of the regeneration agent delivery pipe, and the outlet of the regeneration agent delivery pipe is connected to the lower part of the gas-solid separation zone of the high-density fast fluidized bed reactor (i.e., the catalyst inlet where the regenerated catalyst returns to the reactor).

Optionally, the fluidized bed regenerator comprises a regenerator housing, a regenerator distributor, a third gas-solid separation device, a regenerator gas collecting chamber, and a flue gas conveying pipe;

The regenerator distributor is located at the bottom of the fluidized bed regenerator;

The third gas-solid separation device is located at the upper part of the fluidized bed regenerator. The inlet of the gas-solid separation device is located at the upper part of the fluidized bed regenerator, the gas outlet of the third gas-solid separation device is connected to the regenerator gas collecting chamber, the catalyst outlet of the third gas-solid separation device is located at the lower part of the fluidized bed regenerator, the regenerator gas collecting chamber is located at the top of the fluidized bed regenerator, and the flue gas conveying pipe is connected to the top of the regenerator gas collecting chamber.

Optionally, the inlet pipe of the regenerator stripper penetrates the regenerator shell and opens above the regenerator distributor.

Optionally, the third gas-solid separation equipment adopts one or more groups of gas-solid cyclone separators, and each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator.

In a third aspect, the present application provides a method for flexibly controlling the distribution of olefin products, which is carried out using the above-mentioned device.

Optionally, the method comprises the following steps:

Passing the vaporized raw material including methanol and/or dimethyl ether into the reaction zone, contacting with the catalyst, reacting, and generating a stream I containing product gas and the catalyst;

The logistics I passes through the delivery pipe, and the catalyst after gas-solid separation enters the catalyst retention area, and the product gas after gas-solid separation enters the downstream section;

A portion of the catalyst in the catalyst retention zone enters the reaction zone, and another portion of the catalyst is sent to the fluidized bed regenerator for regeneration. The regenerated catalyst enters the high-density fast fluidized bed reactor.

Optionally, the logistics I enters the first gas-solid separation equipment through a conveying pipe, and the catalyst after the first gas-solid separation enters the catalyst retention area.

Optionally, steam enters the catalyst retention zone from the fluidized steam distributor, and the steam carries a portion of the catalyst in the catalyst retention zone into the gas-solid separation zone; the product gas in the gas-solid separation zone and a portion of the catalyst carried by the steam enter the second gas-solid separation equipment, and the gas after the second gas-solid separation enters the reactor gas collecting chamber, and the separated catalyst returns to the catalyst retention zone.

Optionally, the product gas and steam after the second gas-solid separation enter the downstream section through the product gas delivery pipe; a portion of the catalyst in the catalyst retention zone enters the reaction zone through the catalyst distribution pipe; a portion of the catalyst in the catalyst retention zone enters the reaction zone through the bottom of the catalyst retention zone. The bottom of the reaction zone; a portion of the catalyst in the catalyst retention zone enters the reactor stripper through the catalyst extraction pipe.

Optionally, the raw materials include methanol and crude ethylene separated from product gas, the mass content of ethylene in the crude ethylene is greater than 90%, and the remaining components include at least one of methane, ethane, propane and propylene.

Optionally, the raw materials include methanol and crude propylene separated from product gas, the mass content of propylene in the crude propylene is greater than 90%, and the remaining components include at least one of ethane, ethylene, propane, butane and butene.

The present invention can increase the production of propylene and butene by recycling ethylene, and increase the production of butene by recycling propylene, thereby realizing flexible adjustment of the distribution of ethylene, propylene and butene; the potential content of α-butene in the product can reach up to 57%wt.

Optionally, the catalyst is selected from SAPO molecular sieve catalysts.

Optionally, the process operating conditions of the reaction zone of the high-density fast fluidized bed reactor include:

The gas superficial velocity is 1.5-7.0 m/s, the temperature is 350-500° C., the pressure is 50-500 kPa, and the bed density is 100-500 kg/m ³ .

Optionally, the gas superficial velocity in the reaction zone is selected from any value among 1.5m/s, 2m/s, 2.5m/s, 3m/s, 3.5m/s, 4m/s, 4.5m/s, 5m/s, 5.5m/s, 6m/s, 6.5m/s, 7m/s or any range between two of them.

Optionally, the temperature of the reaction zone is selected from any value of 350°C, 380°C, 400°C, 420°C, 450°C, 480°C, 500°C or any range therebetween.

Optionally, the pressure of the reaction zone is selected from any value of 50 kPa, 100 kPa, 150 kPa, 200 kPa, 250 kPa, 300 kPa, 350 kPa, 400 kPa, 450 kPa, 500 kPa, or any range therebetween.

Optionally, the bed density of the reaction zone is selected from any value of 100kg/ ^m3 , 150kg/ ^m3 , 200kg/ ^m3 , 250kg/ ^m3 , 300kg/ ^m3 , 350kg/ ^m3 , 400kg/ ^m3 , 450kg/ ^m3 , 500kg/ ^m3 or any range therebetween.

Optionally, the process operating conditions of the catalyst retention zone include:

The gas superficial velocity is 0.02-0.2 m/s, the temperature is 350-500°C, and the bed density is 500-800 kg/m ³ .

Optionally, the gas superficial velocity in the catalyst residence zone is selected from any value among 0.02 m/s, 0.05 m/s, 0.08 m/s, 0.1 m/s, 0.12 m/s, 0.15 m/s, 0.18 m/s, 0.20 m/s or any range between two values.

Optionally, the temperature of the catalyst retention zone is selected from any value of 350°C, 380°C, 400°C, 420°C, 450°C, 480°C, 500°C or any range therebetween.

Optionally, the bed density of the catalyst retention zone is any value of 500 kg/m ³ , 550 kg/m ³ , 600 kg/m ³ , 650 kg/m ³ , 700 kg/m ³ , 750 kg/m ³ , 800 kg/m ³ , or any range therebetween.

Optionally, the catalyst circulation intensity flowing from the catalyst retention zone to the reaction zone is 500-1000 kg/(m ² ·s).

Optionally, the catalyst circulation intensity is selected from any value of 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000 or any range between two values, and the unit is kg/(m ² ·s).

Optionally, the regeneration gas is air or a mixture of air and water vapor.

The present application provides a specific methanol to olefins device, comprising: a reactor outer shell, a reactor inner shell, a delivery pipe, a raw material distributor, a first gas-solid separation device, a fluidized steam distributor, a catalyst distribution pipe, a reactor heat collector, a second gas-solid separation device, a reactor gas collecting chamber, a product gas delivery pipe, a catalyst extraction pipe, a reactor stripper, a slide valve to be generated and a delivery pipe for a catalyst to be generated;

The area enclosed by the inner shell of the reactor is the reaction zone, the annular area enclosed by the outer shell of the reactor and the inner shell of the reactor is the catalyst retention zone, the bottom of the reaction zone is connected to the bottom of the catalyst retention zone, the area enclosed by the outer shell of the reactor and the conveying pipe is the gas-solid separation zone, the catalyst retention zone is connected to the gas-solid separation zone and is located below the gas-solid separation zone; the raw material distributor is located at the bottom of the reaction zone, the conveying pipe is located in the central area of the middle and upper part of the high-density fast fluidized bed reactor, the bottom end of the conveying pipe is connected to the top of the reaction zone, and the outlet of the conveying pipe is connected to the inlet of the first gas-solid separation device; the first gas-solid separation device is located in the gas-solid separation zone, the catalyst outlet of the first gas-solid separation device is located at the lower part of the gas-solid separation zone, and the gas outlet of the first gas-solid separation device is located at the upper part of the gas-solid separation zone; the fluidized steam distributor is located at the bottom of the catalyst retention zone; the catalyst distributor The pipe passes through the inner shell of the reactor to connect the catalyst retention zone and the reaction zone, and the lower surface of the catalyst distribution pipe has a hole; the reactor heat collector is located in the catalyst retention zone; the second gas-solid separation device is located in the gas-solid separation zone, the inlet of the second gas-solid separation device is located in the gas-solid separation zone, the gas outlet of the second gas-solid separation device is connected to the reactor gas collecting chamber, and the catalyst outlet of the second gas-solid separation device is located at the lower part of the gas-solid separation zone; the reactor gas collecting chamber is located at the top of the high-density fast fluidized bed reactor, and the product gas conveying pipe is connected to the top of the reactor gas collecting chamber;

The catalyst extraction pipe passes through the reactor shell and is located at the lower part of the catalyst retention zone; the reactor stripper is connected to the catalyst extraction pipe, the inlet of the slide valve to be regenerated is connected to the bottom of the reactor stripper, the outlet of the slide valve to be regenerated is connected to the inlet of the raw catalyst delivery pipe, and the outlet of the raw catalyst delivery pipe is connected to the fluidized bed regenerator;

The first gas-solid separation device adopts an inertial separator to achieve rapid separation of product gas and catalyst; the second gas-solid separation device adopts one or more groups of gas-solid cyclone separators, each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator;

The fluidized bed regenerator for regenerating the catalyst comprises: a regenerator shell, a regenerator distributor, a third gas-solid separation device, a regenerator gas collecting chamber, a flue gas conveying pipe, a regenerator stripper, a regenerator heat extractor, a regeneration slide valve and a regeneration agent conveying pipe;

The regenerator distributor is located at the bottom of the fluidized bed regenerator, the third gas-solid separation device is located at the upper part of the fluidized bed regenerator, the inlet of the third gas-solid separation device is located at the upper part of the fluidized bed regenerator, the gas outlet of the third gas-solid separation device is connected to the regenerator gas collecting chamber, the catalyst outlet of the third gas-solid separation device is located at the lower part of the fluidized bed regenerator, the regenerator gas collecting chamber is located at the top of the fluidized bed regenerator, and the flue gas conveying pipe is connected to the top of the regenerator gas collecting chamber;

The regenerator stripper is located outside the regenerator shell, and the inlet pipe of the regenerator stripper penetrates the regenerator shell and opens above the regenerator distributor; the regenerator heat collector is located in the regenerator stripper, the inlet of the regeneration slide valve is connected to the bottom of the regenerator stripper, the outlet of the regeneration slide valve is connected to the inlet of the regeneration agent delivery pipe, and the outlet of the regeneration agent delivery pipe is connected to the lower part of the gas-solid separation zone of the high-density fast fluidized bed reactor;

The third gas-solid separation equipment adopts one or more groups of gas-solid cyclone separators, each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator. Wind separator.

The present application provides a specific method for flexibly regulating the distribution of olefin products, comprising:

a. The catalyst from the regeneration agent delivery pipe enters the gas-solid separation zone of the high-density fast fluidized bed reactor, and then enters the catalyst retention zone; the gasified raw material enters the reaction zone from the raw material distributor, contacts with the catalyst, and generates product gas containing olefins. The product gas carries the catalyst through the delivery pipe and enters the first gas-solid separation device. After gas-solid separation, the catalyst enters the catalyst retention zone; steam enters the catalyst retention zone from the fluidized steam distributor, and the steam carries a small amount of catalyst from the catalyst retention zone into the gas-solid separation zone; the product gas and steam in the gas-solid separation zone carry the catalyst and enter the second gas-solid separation device. After gas-solid separation, the gas enters the reactor gas collection chamber, and the catalyst returns to the catalyst retention zone; the product gas and steam enter the downstream section through the product gas delivery pipe; the catalyst in the catalyst retention zone enters the reaction zone through the catalyst distribution pipe; the catalyst in the catalyst retention zone enters the bottom of the reaction zone through the bottom of the catalyst retention zone; the catalyst in the catalyst retention zone enters the reactor stripper through the catalyst extraction pipe, and after stripping, the catalyst enters the middle of the fluidized bed regenerator through the waiting slide valve and the waiting agent delivery pipe; the heat released by the reaction is taken out by the reactor heat extractor;

b. The regeneration gas enters the bottom of the fluidized bed regenerator from the regenerator distributor. In the fluidized bed regenerator, the regeneration gas contacts the catalyst, and part of the carbon deposits in the catalyst are burned and eliminated. The flue gas formed by the combustion carries the catalyst into the third gas-solid separation device. After gas-solid separation, the flue gas enters the regenerator gas collection chamber, and then enters the downstream flue gas treatment system through the flue gas conveying pipe. The catalyst returns to the bottom of the fluidized bed regenerator. The catalyst in the fluidized bed regenerator enters the regenerator stripper. After stripping and heat extraction, it enters the high-density fast fluidized bed reactor through the regeneration slide valve and the regeneration agent conveying pipe;

The raw material is one of methanol or dimethyl ether or a mixture of methanol and dimethyl ether; the raw material is methanol and crude ethylene separated from product gas, the mass content of ethylene in the crude ethylene is greater than 90%, and other components include methane, ethane, propane, and propylene; the raw material is methanol and crude propylene separated from product gas, the mass content of propylene in the crude propylene is greater than 90%, and other components include ethane, ethylene, propane, butane, and butene; the catalyst is a SAPO molecular sieve catalyst;

The process operating conditions of the reaction zone of the high-density fast fluidized bed reactor are: gas The superficial velocity is 1.5-7.0 m/s, the temperature is 350-500°C, the pressure is 50-500 kPa, and the bed density is 100-500 kg/m ³ ;

The process operating conditions of the catalyst retention zone are: gas superficial velocity of 0.02-0.2 m/s, temperature of 350-500°C, bed density of 500-800 kg/m ³ ; the catalyst circulation intensity flowing from the catalyst retention zone to the reaction zone is 500-1000 kg/(m ² ·s);

The regeneration gas is air or a mixture of air and water vapor;

The process operating conditions of the fluidized bed regenerator are: gas superficial linear velocity of 0.5-2.0 m/s, regeneration temperature of 600-750° C., regeneration pressure of 100-500 kPa, and bed density of 150-700 kg/m ³ .

In the method described in the present application, the composition of the product does not contain water generated from methanol or dimethyl ether.

The C ₅ + hydrocarbons mentioned in the present application refer to hydrocarbons having 5 or more carbon atoms in the molecule.

In the method described in the present application, the potential content of α-butene in the butene product is ≥95%wt; the potential content of α-butene in the product can be up to 57%wt.

In the method described in the present application, the latent content of α-butene in the butene product refers to the content of 1-butene and 2-butene in the butene product, and the latent content of α-butene in the product refers to the content of 1-butene and 2-butene in the product.

Compared with the prior art, this application has the following beneficial effects:

(1) The present application discloses a high-density fast fluidized bed reactor, which mainly comprises a reaction zone, a catalyst retention zone and a gas-solid separation zone. The catalyst circulation intensity flowing from the catalyst retention zone to the reaction zone is as high as 500-1000 kg/(m ² ·s), thereby increasing the bed density of the reaction zone, achieving high bed density under high superficial linear velocity conditions, and overcoming the negative correlation between the feed rate of raw materials and the bed density of the fluidized bed reaction zone.

(2) The first gas-solid separation device in the high-density fast fluidized bed reactor of the present application adopts an inertial separator to achieve rapid separation of product gas and catalyst, greatly shorten the gas-solid contact time, and reduce alkanes and C ₅ + hydrocarbons in the product.

(3) The methanol-to-olefins method of the present application can increase the production of propylene and butene by recycling ethylene, and can increase the production of butene by recycling propylene, thus achieving a flexible distribution of ethylene, propylene and butene. Active adjustment.

(4) In the method of producing olefins from methanol of the present application, the potential content of α-butene in the product can reach up to 57%wt.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a schematic diagram of a device according to an embodiment of the present application.

The reference numerals in FIG1 are described as follows:
1-High density fast fluidized bed reactor;
1-1 reactor outer shell, 1-2 reactor inner shell, 1-3 conveying pipe, 1-4 raw material distributor, 1-5 first gas-solid separation equipment, 1-6 fluidized steam distributor, 1-7 catalyst distribution pipe, 1-8 reactor heat collector, 1-9 second gas-solid separation equipment, 1-10 reactor gas collecting chamber, 1-11 product gas conveying pipe, 1-12 catalyst extraction pipe, 1-13 reactor stripper, 1-14 slide valve to be generated, 1-15 conveying pipe for catalyst to be generated;
2- Fluidized bed regenerator;
2-1 regenerator shell, 2-2 regenerator distributor, 2-3 third gas-solid separation equipment, 2-
4 regenerator gas collecting chamber, 2-5 flue gas conveying pipe, 2-6 regenerator stripper, 2-7 regenerator heat collector, 2-8 regeneration slide valve, 2-9 regeneration agent conveying pipe.

DETAILED DESCRIPTION

The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

Unless otherwise specified, the raw materials and catalysts in the examples of this application were purchased through commercial channels.

In a specific embodiment, the present application provides an apparatus of an embodiment, the structural schematic diagram of which is shown in FIG1 , and the apparatus comprises a high-density fast fluidized bed reactor (1) and a fluidized bed regenerator (2).

a. The high-density fast fluidized bed reactor (1) comprises: a reactor outer shell (1-1), a reactor inner shell (1-2), a conveying pipe (1-3), a raw material distributor (1-4), a first gas-solid separation device (1-5), a fluidizing steam distributor (1-6), a catalyst distribution pipe (1-7), a reactor heat collector (1-8), a second gas-solid separation device (1-9), a reactor gas collecting chamber (1-10), a product gas conveying pipe (1-11), a catalyst extraction pipe (1-12), and a reactor stripper (1-13). The reactor comprises a slide valve (1-14) and a conveying pipe (1-15) for the catalyst to be regenerated; the area enclosed by the reactor inner shell (1-2) is the reaction zone (A); the annular area enclosed by the reactor outer shell (1-1) and the reactor inner shell (1-2) is the catalyst retention zone (B); the bottom of the reaction zone (A) is connected to the bottom of the catalyst retention zone (B); the area enclosed by the reactor outer shell (1-1) and the conveying pipe (1-3) is the gas-solid separation zone (C); the catalyst retention zone (B) is connected to the gas-solid separation zone (C) and is located below the gas-solid separation zone (C); the raw material distributor (1-4) is located at the reaction zone (A); The bottom of the high-density fast fluidized bed reactor is characterized in that the conveying pipe (1-3) is located in the central area of the middle and upper part, the bottom end of the conveying pipe (1-3) is connected to the top of the reaction zone (A), and the outlet of the conveying pipe (1-3) is connected to the inlet of the first gas-solid separation device (1-5); the first gas-solid separation device (1-5) is located in the gas-solid separation zone (C), the catalyst outlet of the first gas-solid separation device (1-5) is located in the lower part of the gas-solid separation zone (C), and the gas outlet of the first gas-solid separation device (1-5) is located in the upper part of the gas-solid separation zone (C); the fluidized steam distributor (1-6) is located at the bottom of the catalyst retention zone (B); the catalyst distributor The pipe (1-7) passes through the inner shell (1-2) of the reactor to connect the catalyst retention zone (B) and the reaction zone (A); the lower surface of the catalyst distribution pipe (1-7) is opened; the reactor heat collector (1-8) is located in the catalyst retention zone (B); the second gas-solid separation device (1-9) is located in the gas-solid separation zone (C); the inlet of the second gas-solid separation device (1-9) is located in the gas-solid separation zone (C); the gas outlet of the second gas-solid separation device (1-9) is connected to the reactor gas collecting chamber (1-10); the catalyst outlet of the second gas-solid separation device (1-9) is located in the lower part of the gas-solid separation zone (C); the reactor gas collecting chamber (1-10) Located at the top of a high-density fast fluidized bed reactor, a product gas delivery pipe (1-11) is connected to the top of a reactor gas collecting chamber (1-10); a catalyst extraction pipe (1-12) passes through an outer shell of the reactor (1-1) and is located at the lower part of a catalyst retention zone (B); a reactor stripper (1-13) is connected to the catalyst extraction pipe (1-12), an inlet of a slide valve (1-14) to be regenerated is connected to the bottom of the reactor stripper (1-13), an outlet of the slide valve (1-14) to be regenerated is connected to an inlet of a catalyst delivery pipe (1-15), and an outlet of the catalyst delivery pipe (1-15) to be regenerated is connected to a fluidized bed regenerator (2).

b. The fluidized bed regenerator (2) comprises: a regenerator shell (2-1), a regenerator distributor (2-2), a third gas-solid separation device (2-3), a regenerator gas collecting chamber (2-4), a flue gas conveying pipe (2-5), a regenerator stripper (2-6), a regenerator heat collector (2-7), a regeneration slide valve (2-8) and a regeneration agent conveying pipe (2-9); the regenerator distributor (2-2) is located in the fluidized bed regenerator (2) The third gas-solid separation device (2-3) is located at the top of the fluidized bed regenerator (2), the inlet of the third gas-solid separation device (2-3) is located at the top of the fluidized bed regenerator (2), the gas outlet of the third gas-solid separation device (2-3) is connected to the regenerator gas collecting chamber (2-4), the catalyst outlet of the third gas-solid separation device (2-3) is located at the bottom of the fluidized bed regenerator (2), the regenerator gas collecting chamber (2-4) is located at the top of the fluidized bed regenerator (2), and the flue gas conveying pipe (2-5) is connected to the top of the regenerator gas collecting chamber (2-4); the regenerator stripper (2- 6) is located outside the regenerator shell (2-1), the inlet pipe of the regenerator stripper (2-6) penetrates the regenerator shell (2-1) and opens above the regenerator distributor (2-2), the regenerator heat collector (2-7) is located in the regenerator stripper (2-6), the inlet of the regeneration slide valve (2-8) is connected to the bottom of the regenerator stripper (2-6), the outlet of the regeneration slide valve (2-8) is connected to the inlet of the regeneration agent delivery pipe (2-9), and the outlet of the regeneration agent delivery pipe (2-9) is connected to the lower part of the gas-solid separation zone (C) of the high-density fast fluidized bed reactor (1).

As a preferred embodiment of the above embodiment, the first gas-solid separation device (1-5) adopts an inertial separator to achieve rapid separation of the product gas and the catalyst.

As a preferred embodiment of the above embodiment, the second gas-solid separation equipment (1-9) adopts one or more groups of gas-solid cyclone separators, and each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator.

As a preferred embodiment of the above embodiment, the third gas-solid separation equipment (2-3) adopts one or more groups of gas-solid cyclone separators, and each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator.

In a specific embodiment, the present application provides a method for flexibly regulating the distribution of olefin products, comprising the following steps:

a. The catalyst from the regeneration agent delivery pipe (2-9) enters the gas-solid separation zone (C) of the high-density fast fluidized bed reactor (1), and then enters the catalyst retention zone (B); the gasified raw material enters the reaction zone (A) from the raw material distributor (1-4), contacts with the catalyst, and generates a product gas containing olefins. The product gas carries the catalyst through the delivery pipe (1-3) and enters the first gas-solid separation device (1-5). After gas-solid separation, the catalyst enters the catalyst retention zone (B); steam enters the catalyst retention zone (B) from the fluidized steam distributor (1-6), and the steam carries a small amount of catalyst from the catalyst retention zone (B) into the gas-solid separation zone (C); the product gas and steam in the gas-solid separation zone (C) carry the catalyst and enter the second gas-solid separation device (1-9). After separation, the gas enters the reactor gas collecting chamber (1-10), and the catalyst returns to the catalyst retention zone (B); the product gas and steam enter the downstream section through the product gas delivery pipe (1-11); the catalyst in the catalyst retention zone (B) enters the reaction zone (A) through the catalyst distribution pipe (1-7); the catalyst in the catalyst retention zone (B) enters the bottom of the reaction zone (A) through the bottom of the catalyst retention zone (B); the catalyst in the catalyst retention zone (B) enters the reactor stripper (1-13) through the catalyst extraction pipe (1-12), and after stripping, the catalyst enters the middle part of the fluidized bed regenerator (2) through the regenerated slide valve (1-14) and the regenerated agent delivery pipe (1-15); the heat released by the reaction is taken out by the reactor heat extractor (1-8);

b. The regeneration gas enters the bottom of the fluidized bed regenerator (2) from the regenerator distributor (2-2). In the fluidized bed regenerator (2), the regeneration gas contacts the catalyst, and part of the carbon deposits in the catalyst are burned and eliminated. The flue gas formed by the combustion carries the catalyst into the third gas-solid separation device (2-3). After gas-solid separation, the flue gas enters the regenerator gas collecting chamber (2-4), and then enters the downstream flue gas treatment system through the flue gas conveying pipe (2-5). The catalyst returns to the bottom of the fluidized bed regenerator (2). The catalyst in the fluidized bed regenerator (2) enters the regenerator stripper (2-6). After stripping and heat extraction, it enters the high-density fast fluidized bed reactor (1) through the regeneration slide valve (2-8) and the regeneration agent conveying pipe (2-9).

Example 1

This embodiment 1 adopts the device shown in Figure 1.

In this Example 1, the raw material is methanol; the catalyst is a SAPO molecular sieve catalyst.

The process operating conditions of the reaction zone (A) of the high-density fast fluidized bed reactor (1) are: gas superficial linear velocity of 1.5 m/s, temperature of 450°C, pressure of 500 kPa, and bed density of 500 kg/ ^m3 .

The process operating conditions of the catalyst retention zone (B) are: gas superficial linear velocity of 0.12 m/s, temperature of 450°C, bed density of 630 kg/m ³ ; and the catalyst circulation intensity flowing from the catalyst retention zone (B) to the reaction zone (A) is 500 kg/(m ² ·s).

The regeneration gas is air. The process operating conditions of the fluidized bed regenerator (2) are: gas superficial linear velocity of 0.5 m/s, regeneration temperature of 600°C, regeneration pressure of 500 kPa, and bed density of 700 kg/m ³ .

In this embodiment 1, the composition of the product is 28%wt ethylene, 42%wt propylene, and 22%wt Butene and 8%wt of other components, the other components are methane, ethane, propane, butane, _C5 + hydrocarbons, hydrogen, CO, _CO2 and coke, etc. The sum of the contents of ethylene, propylene and butene in the product is 92%wt, and the potential content of α-butene in the product is 21%wt.

Example 2

This embodiment 2 adopts the device shown in Figure 1.

In this Example 2, the raw material is dimethyl ether; the catalyst is a SAPO molecular sieve catalyst.

The process operating conditions of the reaction zone (A) of the high-density fast fluidized bed reactor (1) are: gas superficial linear velocity of 3.0 m/s, temperature of 350°C, pressure of 270 kPa, and bed density of 290 kg/ ^m3 .

The process operating conditions of the catalyst retention zone (B) are: gas superficial linear velocity of 0.2 m/s, temperature of 350°C, bed density of 500 kg/m ³ . The catalyst circulation intensity flowing from the catalyst retention zone (B) to the reaction zone (A) is 760 kg/(m ² ·s).

The regeneration gas is a mixture of air and water vapor. The process operating conditions of the fluidized bed regenerator (2) are: gas superficial linear velocity of 2.0 m/s, regeneration temperature of 650°C, regeneration pressure of 270 kPa, and bed density of 150 kg/m ³ .

In this Example 2, the composition of the product is 21%wt ethylene, 46%wt propylene, 26%wt butene and 7%wt other components, the other components are methane, ethane, propane, butane, _C5 + hydrocarbons, hydrogen, CO, _CO2 and coke, etc. The sum of the contents of ethylene, propylene and butene in the product is 93%wt, and the potential content of α-butene in the product is 25%wt.

Example 3

This embodiment 3 adopts the device shown in Figure 1.

In this embodiment 3, the raw materials are methanol and crude ethylene separated from the product gas, the mass content of ethylene in the crude ethylene is greater than 90%, and other components include methane, ethane, propane, and propylene.

The catalyst is a SAPO molecular sieve catalyst.

The process operating conditions of the reaction zone (A) of the high-density fast fluidized bed reactor (1) are: gas superficial linear velocity of 5.0 m/s, temperature of 400°C, pressure of 100 kPa, and bed density of 180 kg/ ^m3 .

The process operating conditions of the catalyst retention zone (B) are: gas superficial linear velocity of 0.09 m/s, temperature of 400°C, bed density of 730 kg/m ³ . The catalyst circulation intensity flowing from the catalyst retention zone (B) to the reaction zone (A) is 1000 kg/(m ² ·s).

The regeneration gas is air. The process operating conditions of the fluidized bed regenerator (2) are: gas superficial linear velocity of 1.4 m/s, regeneration temperature of 690°C, regeneration pressure of 100 kPa, and bed density of 330 kg/m ³ .

In this Example 3, the composition of the product is 5%wt ethylene, 50%wt propylene, 36%wt butene and 9%wt other components, the other components are methane, ethane, propane, butane, _C5 + hydrocarbons, hydrogen, CO, _CO2 and coke, etc. The sum of the contents of ethylene, propylene and butene in the product is 91%wt, and the potential content of α-butene in the product is 34%wt.

Example 4

This embodiment 4 adopts the device shown in Figure 1.

In this embodiment 4, the raw materials are methanol and crude propylene separated from the product gas, the mass content of propylene in the crude propylene is greater than 90%, and other components include ethane, ethylene, propane, butane, and butene.

The catalyst is a SAPO molecular sieve catalyst.

The process operating conditions of the reaction zone (A) of the high-density fast fluidized bed reactor (1) are: gas superficial linear velocity of 7.0 m/s, temperature of 500°C, pressure of 50 kPa, and bed density of 100 kg/ ^m3 .

The process operating conditions of the catalyst retention zone (B) are: gas superficial linear velocity of 0.02 m/s, temperature of 500°C, bed density of 800 kg/m ³ . The catalyst circulation intensity flowing from the catalyst retention zone (B) to the reaction zone (A) is 850 kg/(m ² ·s).

The regeneration gas is air. The process operating conditions of the fluidized bed regenerator (2) are: gas superficial linear velocity of 0.9 m/s, regeneration temperature of 750°C, regeneration pressure of 50 kPa, and bed density of 480 kg/m ³ .

In this Example 4, the composition of the product is 22%wt of ethylene, 8%wt of propylene, 60%wt of butene and 10%wt of other components, and the other components are methane, ethane, propane, butane, _C5 + hydrocarbons, hydrogen, CO, _CO2 and coke, etc. The sum of the contents of ethylene, propylene and butene in the product is 90%wt, and the potential content of α-butene in the product is 57%wt.

The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims (23)

A high-density fast fluidized bed reactor, characterized in that the high-density fast fluidized bed reactor comprises a reactor outer shell, a reactor inner shell, a conveying pipe and a reactor heat collector; The reactor outer shell is provided with at least a raw material inlet, a catalyst inlet, a gas phase product outlet and a catalyst outlet; The reactor outer shell encloses an internal area; The reactor inner shell is located at the lower part of the internal area, and the area enclosed by the reactor inner shell is the reaction area; The delivery pipe is located in the upper middle part of the inner area, and the bottom of the delivery pipe is connected to the reaction zone; The area enclosed by the reactor shell and the delivery pipe is a gas-solid separation area; The delivery pipe is provided with an outlet, and the delivery pipe is connected with the gas-solid separation zone; The annular area enclosed by the reactor outer shell and the reactor inner shell is the catalyst retention area; The bottom of the reaction zone is connected to the bottom of the catalyst retention zone; The catalyst retention zone is connected to the gas-solid separation zone and is located below the gas-solid separation zone; The reactor heat extractor is located in the catalyst retention zone. The high-density fast fluidized bed reactor according to claim 1, characterized in that the high-density fast fluidized bed reactor comprises a catalyst distribution pipe, a fluidizing steam distributor, and a raw material distributor; The catalyst distribution pipe passes through the inner shell of the reactor to connect the catalyst retention zone and the reaction zone; The fluidizing steam distributor is arranged at the bottom of the catalyst retention zone; The raw material distributor is arranged at the bottom of the reaction zone. The high-density fast fluidized bed reactor according to claim 2 is characterized in that a through hole is opened on the lower surface of the catalyst distribution tube. The high-density fast fluidized bed reactor according to any one of claims 1 to 3 is characterized in that the high-density fast fluidized bed reactor comprises a first gas-solid separation device and a second gas-solid separation device; the first gas-solid separation device and the second gas-solid separation device are located in the gas-solid separation zone; the inlet of the first gas-solid separation device is connected to the outlet of the conveying pipe; the catalyst outlet of the first gas-solid separation device is located in the lower part of the gas-solid separation zone, and the gas outlet of the first gas-solid separation device is located in the upper part of the gas-solid separation zone. The high-density fast fluidized bed reactor according to claim 4, characterized in that the inlet of the second gas-solid separation device is located at the upper part of the gas-solid separation zone; The catalyst outlet of the second gas-solid separation device is located at the lower part of the gas-solid separation zone. The high-density fast fluidized bed reactor according to claim 4 or 5, characterized in that the first gas-solid separation device is an inertial separator; The second gas-solid separation equipment is selected from one or more groups of gas-solid cyclone separators, and each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator. The high-density fast fluidized bed reactor according to any one of claims 1 to 6, characterized in that the high-density fast fluidized bed reactor comprises a reactor gas collecting chamber and a product gas conveying pipe; The reactor gas collection chamber is located at the top of the high-density fast fluidized bed reactor; The product gas delivery pipe is connected to the top of the reactor gas collecting chamber; The gas outlet of the second gas-solid separation device is communicated with the reactor gas collecting chamber. A methanol to olefins device, characterized in that the device comprises the high-density fast fluidized bed reactor and the fluidized bed regenerator according to any one of claims 1 to 7; The catalyst extraction pipe passes through the reactor outer shell and is located at the lower part of the catalyst retention zone, and the catalyst extraction pipe is connected to the reactor stripper; The inlet of the slide valve to be regenerated is connected to the bottom of the reactor stripper, the outlet of the slide valve to be regenerated is connected to the inlet of the spent agent delivery pipe, and the outlet of the spent agent delivery pipe is connected to the fluidized bed regenerator; The regenerator stripper is located at the bottom of the fluidized bed regenerator, and a regenerator heat collector is arranged in the regenerator stripper; the inlet of the regeneration slide valve is connected to the bottom of the regenerator stripper, and the outlet of the regeneration slide valve is connected to the inlet of the regeneration agent delivery pipe, and the outlet of the regeneration agent delivery pipe is connected to the lower part of the gas-solid separation zone of the high-density fast fluidized bed reactor. The methanol to olefins device according to claim 8, characterized in that the fluidized bed regenerator comprises a regenerator shell, a regenerator distributor, a third gas-solid separation device, a regenerator gas collecting chamber, and a flue gas conveying pipe; The regenerator distributor is located at the bottom of the fluidized bed regenerator; The third gas-solid separation equipment is located at the upper part of the fluidized bed regenerator, the inlet of the third gas-solid separation equipment is located at the upper part of the fluidized bed regenerator, the gas outlet of the third gas-solid separation equipment is connected with the regenerator gas collecting chamber, the catalyst outlet of the third gas-solid separation equipment is located at the lower part of the fluidized bed regenerator, the regenerator gas collecting chamber is located at the top of the fluidized bed regenerator, and the flue gas conveying pipe is connected to the top of the regenerator gas collecting chamber. The methanol to olefins device according to claim 8 or 9 is characterized in that the inlet pipe of the regenerator stripper penetrates the regenerator shell and opens above the regenerator distributor. The methanol to olefins apparatus according to claim 9 or 10 is characterized in that the third gas-solid separation equipment adopts one or more groups of gas-solid cyclone separators, and each group of gas-solid cyclone separators includes a first-stage gas-solid cyclone separator and a second-stage gas-solid cyclone separator. A method for flexibly regulating the distribution of olefin products, characterized in that it is carried out using the device described in any one of claims 8 to 11. The method for flexibly controlling the distribution of olefin products according to claim 12, characterized in that it comprises the following steps: Passing the vaporized raw material including methanol and/or dimethyl ether into the reaction zone, contacting with the catalyst, reacting, and generating a stream I containing product gas and the catalyst; The logistics I passes through the delivery pipe, and the catalyst after gas-solid separation enters the catalyst retention area, and the product gas after gas-solid separation enters the downstream section; A portion of the catalyst in the catalyst retention zone enters the reaction zone, and another portion of the catalyst is sent to the fluidized bed regenerator for regeneration. The regenerated catalyst enters the high-density fast fluidized bed reactor. The method for flexibly controlling the distribution of olefin products according to claim 13 is characterized in that the logistics I enters the first gas-solid separation equipment through a conveying pipe, and the catalyst after the first gas-solid separation enters the catalyst retention area. A method for flexibly controlling the distribution of olefin products according to any one of claims 12 to 14, characterized in that steam enters the catalyst retention zone from a fluidized steam distributor, and the steam carries a portion of the catalyst in the catalyst retention zone into the gas-solid separation zone; the product gas in the gas-solid separation zone and a portion of the catalyst carried by the steam enter the second gas-solid separation equipment, the gas after the second gas-solid separation enters the reactor gas collection chamber, and the separated catalyst returns to the catalyst retention zone. According to a method for flexibly controlling the distribution of olefin products as described in claim 15, it is characterized in that the product gas and steam after the second gas-solid separation enter the downstream section via the product gas conveying pipe; a portion of the catalyst in the catalyst retention zone enters the reaction zone via the catalyst distribution pipe; a portion of the catalyst in the catalyst retention zone enters the bottom of the reaction zone via the bottom of the catalyst retention zone; a portion of the catalyst in the catalyst retention zone enters the reactor stripper via the catalyst extraction pipe. A method for flexibly controlling the distribution of olefin products according to any one of claims 13 to 16, characterized in that the raw materials include methanol and crude ethylene separated from the product gas, the mass content of ethylene in the crude ethylene is greater than 90%, and the remaining components include at least one of methane, ethane, propane and propylene. A method for flexibly controlling the distribution of olefin products according to any one of claims 13 to 16, characterized in that the raw materials include methanol and crude propylene separated from the product gas, the mass content of propylene in the crude propylene is greater than 90%, and the remaining components include at least one of ethane, ethylene, propane, butane and butene. The method for flexibly controlling the distribution of olefin products according to any one of claims 13 to 18, characterized in that the catalyst is selected from a SAPO molecular sieve catalyst. The method for flexibly controlling the distribution of olefin products according to any one of claims 13 to 19 is characterized in that the process operating conditions of the reaction zone of the high-density fast fluidized bed reactor include: gas superficial linear velocity of 1.5 to 7.0 m/s, temperature of 350 to 500° C., pressure of 50 to 500 kPa, and bed density of 100 to 500 kg/m ³ . The method for flexibly controlling olefin product distribution according to any one of claims 13 to 20 is characterized in that the process operating conditions of the catalyst retention zone include: gas superficial velocity of 0.02 to 0.2 m/s, temperature of 350 to 500° C., and bed density of 500 to 800 kg/m ³ . The method for flexibly controlling olefin product distribution according to any one of claims 13 to 21 is characterized in that the catalyst circulation intensity flowing from the catalyst retention zone to the reaction zone is 500 to 1000 kg/(m ² ·s). A method for flexibly controlling olefin product distribution according to any one of claims 13 to 22, characterized in that the regeneration gas is air or a mixture of air and water vapor. things.