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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/82—Phosphates
  • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
  • B01J29/85—Silicoaluminophosphates [SAPO compounds]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/90—Regeneration or reactivation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
  • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
  • B01J38/12—Treating with free oxygen-containing gas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1818—Feeding of the fluidising gas
  • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1836—Heating and cooling the reactor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1872—Details of the fluidised bed reactor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
  • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
  • B01J8/34—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
  • B01J8/36—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed through which there is an essentially horizontal flow of particles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00106—Controlling the temperature by indirect heat exchange
  • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
  • B01J2208/00141—Coils
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00796—Details of the reactor or of the particulate material
  • B01J2208/00893—Feeding means for the reactants
  • B01J2208/00902—Nozzle-type feeding elements
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/82—Phosphates
  • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
  • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/584—Recycling of catalysts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/40—Ethylene production

Definitions

• the present invention relates to a process for producing low carbon olefins from oxygenates and apparatus therefor. Background technique
• Low-carbon olefins namely ethylene and propylene
• ethylene and propylene are two important basic chemical materials, and their demand is increasing.
• ethylene and propylene are produced through petroleum routes, but the cost of producing ethylene and propylene from petroleum resources is increasing due to the limited supply of petroleum resources and higher prices.
• people have begun to vigorously develop technologies for converting raw materials into ethylene and propylene.
• MTO methanol conversion to olefins
• the process of methanol conversion to olefins (MTO) has received increasing attention and has achieved a production scale of millions of tons.
• MTO methanol conversion to olefins
• the CMAI analysis said that by 2016, ethylene demand will grow at an average annual rate of 4.3%, propylene. Demand will grow at an average annual rate of 4.4%. Due to the rapid growth of China's economy, the annual growth rate of ethylene and propylene demand in China exceeds the world average.
• SAPO-34 molecular sieve catalyst showed excellent catalytic performance when used in MTO reaction, with high low-carbon olefin selectivity and high activity. However, the catalyst loses its activity due to carbon deposition after a period of use.
• the SAPO-34 molecular sieve catalyst has a significant induction period during use. During the induction period, the selectivity of olefins is lower, and the selectivity of hydrazines is higher. As the reaction time increases, the selectivity of low olefins gradually increases. After the induction period, the catalyst maintains high selectivity and high activity for a certain period of time, and the activity of the catalyst rapidly decreases as time continues to increase.
• U.S. Patent 6,166,282 discloses a technique and a reactor for the conversion of methanol to lower olefins using a fast fluidized bed reactor. After the reaction of the gas phase in the dense phase reaction zone where the gas velocity is low, the gas phase rises to a fast zone where the inner diameter rapidly decreases. Afterwards, most of the entrained catalyst was separated by a special gas-solid separation device. Since the product gas is quickly separated from the catalyst after the reaction, the occurrence of the secondary reaction is effectively prevented. According to the simulation calculation, the inner diameter of the fast fluidized bed reactor and the required reserves of the catalyst are greatly reduced as compared with the conventional bubbling fluidized bed reactor. However, the yield of low carbon olefins in the process is generally about 77%, and there is a problem that the yield of low carbon olefins is low.
• CN101402538B discloses a method for increasing the yield of low carbon olefins, which is used in a second reaction zone is disposed on the upper portion of the first reaction zone where methanol is converted to a lower olefin, and the second reaction zone has a larger diameter than the first reaction zone to increase the retention of the product gas at the outlet of the first reaction zone in the second reaction zone. Time, the unreacted methanol, the produced dimethyl ether and the carbon four or more hydrocarbons continue to react to achieve the purpose of increasing the yield of the low-carbon olefin.
• the method can improve the yield of the low-carbon olefin to a certain extent,
• CN102276406 A discloses a process for producing propylene.
• the technology provides three reaction zones, a first fast bed reaction zone for methanol conversion to olefins, a riser reaction zone and a second fast bed reaction zone for series conversion of ethylene, carbon tetrahydrocarbons and unreacted methanol or dimethyl ether.
• substances such as carbon and more hydrocarbons have a shorter residence time in the riser reaction zone and the second fast-bed reaction zone, and the conversion efficiency is lower, resulting in a lower propylene yield.
• a fluidized bed reactor for internally arranging a riser reactor for increasing the yield of light olefins is disclosed.
• the first raw material enters the fluidized bed reaction zone, contacts with the catalyst to form a product including a low-carbon olefin, and simultaneously forms a catalyst to be produced; a part of the catalyst to be produced enters the regenerator to be regenerated, forms a regenerated catalyst, and a part enters the outlet end and is located inside the reaction zone.
• the riser is in contact with the second raw material to raise the catalyst to be reacted into the reaction zone; the regenerated catalyst is returned to the reaction zone of the fluidized bed reactor.
• the reaction device disclosed in this patent has no stripping part, and the raw catalyst will carry some product gas into the regenerator, burning with oxygen, and reducing low-carbon olefins.
• the methanol to olefins technology disclosed in CN102875296A provides three reaction zones of a fast bed, a down bed and a riser.
• the catalyst circulates between the regenerator, the fast bed, the riser and the descending bed.
• the flow is very complicated, the flow distribution and control are very difficult, and the activity of the catalyst changes greatly.
• the selectivity of the low olefins is closely related to the amount of carbon deposited on the catalyst.
• a certain amount of carbon is required on the SAPO-34 catalyst.
• the main reactor used in the MTO process is a fluidized bed, and the fluidized bed is close to the full mixed-flow reactor.
• the distribution of catalyst coke is wide, which is not conducive to improving the selectivity of low-carbon olefins.
• the MTO process has a small ratio of solvent to alcohol and a low coke yield.
• the purpose of controlling the carbon deposition amount and the carbon content uniformity on the catalyst in the reaction zone is achieved. Therefore, control The uniformity of carbon deposition and carbon content in the reaction zone is a key technology in the MTO process.
• the invention proposes to solve the problem of controlling the carbon deposition amount and the carbon content uniformity of the catalyst by forming an internal member to form a plurality of secondary reaction zones (regeneration zone:) in the dense phase fluidized bed, thereby improving the low carbon olefins. Selectivity. Summary of the invention
• the technical problem to be solved by the present invention is the problem of low selectivity of low carbon olefins existing in the prior art, and aims to provide a new method for improving the selectivity of low carbon olefins.
• the method is used in the production of low-carbon olefins, and has the advantages of good catalyst carbon uniformity, high yield of low-carbon olefins, and good economical production process of low-carbon olefins.
• the present invention provides a method for producing a low carbon olefin from an oxygen compound, comprising the following steps:
• the spent catalyst flowing out from the nth secondary reaction zone is stripped and upgraded into a dense phase fluidized bed regenerator for regeneration; the spent catalyst is serially passed through the first to m secondary regeneration zones;
• the regeneration medium is fed into the first to mth secondary regeneration zones from the m feed zone of the regeneration zone in parallel, and the carbon dioxide content is gradually decreased when the catalyst is contacted with the regeneration medium, and the catalyst after completion of regeneration is subsequently steamed.
• the separator is divided into m secondary regeneration zones by a material flow controller; wherein, n 2 and m 2 , more preferably 8 n 3 and 8 m 3 .
• the apparent linear velocity of the gas in the material flow controller is less than or equal to the minimum fluidization velocity of the catalyst.
• the apparent line velocity of the gas in the material flow controller is less than or equal to the minimum fluidization velocity of the catalyst.
• the catalyst contains SAPO-34 molecular sieves.
• the reaction conditions of the dense phase fluidized bed reaction zone are: an apparent linear velocity of gas of 0.1-1.5 m/s, a reaction temperature of 400-550 ° C, and a bed density of 200-1200 kg/ m
• the average carbon deposition amount of the catalyst in the first to nth secondary reaction zones of the dense phase fluidized bed is sequentially increased, and the average carbon deposition amount of the catalyst in the first secondary reaction zone is increased.
• the catalyst has an average carbon deposition amount of 7 to 10% by weight in the n-th secondary reaction zone of 0.5 to 3 wt%.
• reaction conditions of the dense phase fluidized bed regeneration zone are: an apparent gas velocity of 0.1-1.5 m/s, a regeneration temperature of 500-700 ° C, and a bed density of 200-1200 kg/ m
• the average carbon deposition amount of the catalyst in the first to mth secondary regeneration zone of the dense phase fluidized bed regeneration zone is successively decreased, and the average carbon deposition amount of the catalyst in the first secondary regeneration zone is The catalyst has an average carbon deposition amount of 0 to 3 wt% in the m-th secondary regeneration zone of 3 to 10 wt%.
• the oxygen-containing compound is methanol and/or dimethyl ether;
• the low-carbon olefin is any one or a mixture of any of ethylene, propylene or butene; Any one or a mixture of any of air, oxygen-depleted air or water vapor.
• the present invention provides a dense phase fluidized bed reactor for carrying out the above method, the dense phase fluidized bed reactor comprising a reaction zone, a gas-solid separation zone, and a stripping zone, wherein The reaction zone is separated into n secondary reaction zones via a material flow controller, wherein n 2 .
• the present invention provides a dense phase fluidized bed regenerator for carrying out the above method, the dense phase fluidized bed regenerator comprising a regeneration zone, a gas-solid separation zone, and a stripping zone, wherein The regeneration zone is separated into m secondary regeneration zones via a material flow controller, where m 2 .
• Advantageous effects of the present invention include, but are not limited to, the following aspects: (1) dense phase fluidized bed has a higher bed density, lower catalyst speed and low wear; (2) material under the material flow controller The gas velocity in the flow tube is less than or equal to the minimum fluidization velocity of the catalyst, and the catalyst is in a dense phase accumulation state, forming a unidirectional dense phase transport flow of the catalyst, avoiding adjacent secondary reaction zones (or adjacent secondary regeneration zones) Between the catalyst back mixing, the residence time distribution is narrow; (3) the heat taking part in the material flow controller has the function of controlling the temperature of the reaction zone; (4) The material flow controller separates the reaction zone into n secondary reactions In the zone, the catalyst passes through the first to the nth secondary reaction zones in series, the residence time distribution is narrow, and the uniformity of the carbon content of the catalyst to be produced is greatly improved; (5) the material flow controller separates the regeneration zone into m secondary stages.
• the catalyst passes through the first to mth secondary regeneration zones in series, the residence time distribution is narrow, and the uniformity of the carbon content of the regenerated catalyst is greatly improved; (6) the precise control of the regenerated catalyst and the catalyst to be produced is realized. Carbon content, and carbon content distribution is more uniform, improve the selectivity of low-carbon olefins, and can adjust the carbon content according to demand to optimize the ratio of propylene / ethylene; (7) due to Carbon content agent is more evenly distributed, reducing the storage amount of the catalyst required for the reaction zone; (8) a plurality of second reaction zone structure facilitates upsizing of the reactor.
• FIG. 2 is a schematic structural view of a dense phase fluidized bed comprising four secondary reaction zones according to the present invention, wherein the arrow in the A-A cross-sectional view is the catalyst flow direction in the secondary reaction zone.
• FIG. 3 is a schematic structural view of a dense phase fluidized bed comprising four secondary regeneration zones according to the present invention, wherein the arrow in the B-B cross-sectional view is the flow direction of the catalyst in the secondary regeneration zone;
• FIG. 4 is a schematic structural view of a stripper according to the present invention.
• Figure 5 is a schematic view showing the structure of the material flow controller of the present invention.
• the present invention provides a process for the preparation of lower olefins from oxygenates, comprising the following steps:
• the spent catalyst flowing out from the nth secondary reaction zone is stripped and upgraded into a dense phase fluidized bed regenerator for regeneration;
• the spent catalyst is serially passed through the first to m secondary regeneration zones;
• the regeneration medium is fed into the first to mth secondary regeneration zones from the feeding branches of the m regeneration zones in parallel, and the carbon dioxide content is gradually decreased in contact with the regeneration medium, and the catalyst after completion of regeneration is subsequently steamed. Lifting and lifting back to the first secondary reaction zone; wherein the dense phase fluidized bed regenerator is divided into m secondary regeneration zones by a material flow controller.
• n 2 is preferably 8 n 3 ; m ⁇ 2 , preferably 8 m 3 .
• the apparent line velocity of the gas in the material flow controller is less than or equal to the minimum fluidization velocity of the catalyst.
• the apparent line velocity of the gas in the material flow controller is less than or equal to the minimum fluidization velocity of the catalyst.
• the catalyst contains a SAPO-34 molecular sieve.
• the reaction condition of the dense phase fluidized bed reaction zone is: the apparent apparent linear velocity of the gas is
• the reaction temperature is 400-550 ° C
• the bed density is 200-1200 kg / m 3
• the average carbon deposition of the catalyst in the first secondary reaction zone is 0.5-3 wt%
• the nth The catalyst in the secondary reaction zone has an average carbon deposition amount of 7 to 10% by weight.
• the reaction conditions of the dense phase fluidized bed regeneration zone are: an apparent apparent linear velocity of gas of 0.1-1.5 m/s, a regeneration temperature of 500-700 ° C, and a bed density of 200-1200 kg/m 3 ;
• the average carbon deposition amount of the catalyst in the 1st to mth secondary regeneration zone is successively decreased, and the average carbon deposition amount of the catalyst in the first secondary regeneration zone is 3-10wt%, and the average catalyst in the mth secondary regeneration zone is averaged.
• the amount of carbon deposited is 0-3 wt%.
• the oxygen-containing compound is methanol and/or dimethyl ether
• the low-carbon olefin is any one of ethylene, propylene or butene or a mixture of any of the following
• the regeneration medium is air, oxygen-poor Any one or a mixture of any of air or water vapor.
• a dense phase fluidized bed reactor comprising a reaction zone, a gas-solid separation zone, a stripping zone, and the reaction zone is separated by the material flow controller into n secondary reaction zones, n 2;
• a dense phase fluidized bed regenerator comprising a regeneration zone, a gas-solid separation zone, a stripping zone, and the regeneration zone is divided by the material flow controller into m secondary regeneration zones, m 2;
• the oxygenate-containing feedstock is contacted with the regenerated catalyst in a dense phase fluidized bed reactor to produce a product comprising a lower olefin and a carbon-containing catalyst, while the regenerated catalyst sequentially passes through the first to the nth Grade reaction zone, carbon content gradually increases;
• the catalyst to be produced flowing out from the nth second-stage reaction zone is stripped and upgraded into a dense-phase fluidized bed regenerator, and the catalyst to be passed sequentially passes through the first to mth secondary regeneration zones, and When the regenerated medium contacts, the carbon content gradually decreases, and then is stripped and lifted back to the first secondary reaction zone;
• the low-carbon olefin product stream is separated from the catalyst to be produced and then enters a separation section, and the separated catalyst is introduced into the n-th second-stage reaction zone.
• FIG. 1 a schematic diagram of the process for preparing a lower olefin from an oxygenate according to the present invention is shown in FIG.
• the catalyst enters the nth secondary reaction zone (2-n) via the feed leg of the cyclone; the regenerated catalyst from the dense phase fluidized bed regenerator (10) passes through the stripper (13) and the riser (15).
• a dense phase fluidized bed reactor (2) wherein the bottom of the stripper (13) is connected to the water vapor line (14), the bottom of the riser (15) is connected to the lift gas line (16), and the regenerated catalyst is reacted in a dense phase fluidized bed (2) sequentially passes through the first to nth secondary reaction zones (2-1, ..., 2-n), and forms a catalyst to be produced after carbon deposition; feeding the regeneration medium from the regenerator
• the line (9) and its branch lines (9-1, ..., 9-m) are fed in parallel to the secondary regeneration zone (10-1, ..., 10-m) in the dense phase fluidized bed regenerator (10)
• Contact with the catalyst to be produced generate exhaust gas and regenerate catalyst after burning charcoal, and exhaust gas and entrained regenerated catalyst enter the cyclone
• the air separator (11) the exhaust gas enters the tail gas treatment section through the outlet of the cyclone separator and the exhaust gas line (12), and is discharged after treatment, and the entrained regenerated catalyst enters the mth second-
• FIG. 1 a schematic structural view of a dense phase fluidized bed reactor comprising four secondary reaction zones of the present invention is shown in FIG.
• Three material flow controllers (17) and one baffle are vertically arranged to divide the reaction zone into four secondary reaction zones.
• the catalyst passes through the first to fourth secondary reaction zones in sequence, and then enters the stripper. .
• FIG. 1 a schematic structural view of a dense phase fluidized bed regenerator comprising four secondary regeneration zones of the present invention is shown in FIG.
• Three material flow controllers (17) and one baffle are vertically arranged to divide the regeneration zone into four secondary regeneration zones.
• the catalyst passes through the first to fourth secondary regeneration zones in sequence, and then enters the stripper. .
• the structural schematic of the stripper of the present invention is shown in FIG.
• the opening in the upper tube wall of the stripper serves as the material overflow port (18) between the nth secondary reaction zone (or the mth secondary regeneration zone:) and the stripper.
• the material flow controller (17) is composed of a partition (19), an orifice (20), a material downstream flow tube (21), a bottom baffle (22) and a heat take-up component (23).
• the catalyst enters the material downstream flow tube from above the downstream flow tube, wherein the apparent line velocity of the gas is less than or equal to the minimum fluidization speed, and the catalyst in the downstream flow tube of the material is in a dense phase accumulation state, forming a material flow driving force, pushing the catalyst into the orifice through the orifice.
• the heat taking part can be fixed on the partition by a coil structure.
• the apparent apparent linear velocity of the gas in the dense phase fluidized bed reaction zone is 0.1-1.5 m/s; and the apparent apparent linear velocity of the gas in the dense phase fluidized bed regeneration zone is 0.1-1.5 m/s;
• the apparent flow velocity of the gas in the material flow controller is less than or equal to the minimum fluidization velocity of the catalyst;
• the catalyst comprises SAPO-34 molecular sieve;
• the bottom of the reaction zone is provided with a feed port, and the feed includes methanol, Dimethyl ether or the like;
• the stripping medium of the stripper comprises water vapor;
• the bottom of the regeneration zone is provided with a regeneration medium inlet, the regeneration medium includes air, oxygen-poor air, water vapor, etc.;
• the reaction temperature of the reaction zone is 400-550 ° C, the bed density is 200-1200 kg / m 3 , the average carbon deposition of the catalyst in the first to the nth secondary reaction zone increases in turn, and the average carbon deposition in the first secondary reaction zone is 0.5-3
• the purpose of controlling the carbon deposition amount of the catalyst, improving the uniformity of the carbon content and improving the selectivity of the low-carbon olefin can be achieved, and the technical advantage is large, and it can be used in the industrial production of the low-carbon olefin.
• Example 1 In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and a typical but non-limiting embodiment of the present invention is as follows: Example 1
• the catalyst of -34 molecular sieve is contacted, the formed gas phase product stream and the catalyst to be produced, the gas phase material and the entrained catalyst to enter the cyclone separator, and the gas phase product stream passes through the outlet of the cyclone separator into the subsequent separation section, and the entrained catalyst is entrained.
• the leg of the cyclone separator enters the fourth secondary reaction zone.
• the regenerated catalyst enters the dense phase fluidized bed reactor through a stripper and a riser.
• the reaction conditions of the dense phase fluidized bed reactor are as follows: the reaction temperature is 400 ° C, the gas phase linear velocity is 0.3 m / s, the bed density is 1000 k g / m 3 , and the average carbon deposition amount in the first secondary reaction zone is 2wt%, the average carbon deposition in the second secondary reaction zone is 6wt%, the average carbon deposition in the third secondary reaction zone is 8wt%, and the average carbon deposition in the fourth secondary reaction zone is 10wt%.
• reaction conditions of the dense phase fluidized bed regenerator are: reaction temperature 500 °C, gas phase linear velocity 0.3 m/s, bed density 1000 kg / m 3 , average carbon deposition amount of the first secondary regeneration zone 7wt%, the average carbon deposition in the second secondary regeneration zone is 4wt%, the average carbon deposition in the third secondary regeneration zone is 2wt%, and the average carbon deposition in the fourth secondary regeneration zone is lwt %.
• the reaction product was analyzed by on-line gas chromatography, and the yield of the low carbon olefin carbon group was 91.1% by weight.
• Three secondary reaction zones are arranged in the dense phase fluidized bed reactor, and two secondary regeneration zones are arranged in the dense phase fluidized bed regenerator, and the oxygenate-containing raw materials are introduced into the dense phase fluidized bed reactor, including SAPO.
• the catalyst of -34 molecular sieve is contacted, the formed gas phase product stream and the catalyst to be produced, the gas phase material and the entrained catalyst to enter the cyclone separator, and the gas phase product stream passes through the outlet of the cyclone separator into the subsequent separation section, and the entrained catalyst is entrained.
• the leg of the cyclone separator enters the third secondary reaction zone.
• the regenerated catalyst enters the dense phase fluidized bed reactor through the stripper and the riser, and sequentially passes through the first to third secondary reaction zones, and forms a catalyst to be produced after carbon deposition, and the catalyst is further passed through the stripper.
• the riser enters the dense phase fluidized bed regenerator and sequentially passes through the first to second secondary regeneration zones to form a regenerated catalyst after charring.
• the reaction conditions of the dense phase fluidized bed reactor are: reaction temperature is 450 ° C, gas phase linear velocity is 0.5 m / s, bed density is 900 kg / m 3 , and average carbon deposition in the first secondary reaction zone is 3 wt.
• the average carbon deposition in the second secondary reaction zone is 7wt%
• the average carbon deposition in the third secondary reaction zone is 9wt%
• the dense phase fluidized bed regenerator reaction conditions are: the reaction temperature is 600 °C
• the gas phase linear velocity was 0.7 m/s
• the bed density was 700 kg/m 3
• the average carbon deposition amount of the first secondary regeneration zone was 4 wt%
• the average secondary carbon deposition amount of the second secondary regeneration zone was 2 wt%.
• the reaction product was analyzed by on-line gas chromatography, and the yield of the low carbon olefin carbon group was 90.5 wt%.
• the oxygen-containing raw materials enter the dense-phase fluidized bed reactor, including SAPO.
• the catalyst of -34 molecular sieve is contacted, the formed gas phase product stream and the catalyst to be produced, the gas phase material and the entrained catalyst to enter the cyclone separator, and the gas phase product stream passes through the outlet of the cyclone separator into the subsequent separation section, and the entrained catalyst is entrained.
• the leg of the cyclone separator enters the sixth secondary reaction zone.
• the regenerated catalyst enters the dense phase fluidized bed reactor through the stripper and the riser, and sequentially passes through the first to sixth secondary reaction zones, and forms a catalyst to be produced after carbon deposition, and the catalyst is then passed through the stripper.
• the riser enters the dense phase fluidized bed regenerator and sequentially passes through the first to fifth secondary regeneration zones to form a regenerated catalyst after charring.
• reaction temperature is 480 ° C
• gas phase linear velocity is 0.7 m / s
• bed density 700 kg / m 3
• the average carbon deposition amount of the first secondary reaction zone is lwt %
• the average carbon deposition in the second secondary reaction zone is 3 wt%
• the average carbon deposition in the third secondary reaction zone is 4 wt%
• the average carbon deposition in the fourth secondary reaction zone is 5 wt%.
• the average carbon deposition in the fifth secondary reaction zone is 6 wt%, and the average carbon deposition in the sixth secondary reaction zone is 7 wt%;
• the reaction condition of the dense phase fluidized bed regenerator is: reaction temperature is 650 ° C,
• the gas phase linear velocity is 1.0 m/s, the bed density is 500 kg/m 3 , the average carbon deposition in the first secondary regeneration zone is 5 wt%, and the average carbon deposition in the second secondary regeneration zone is 3 wt%.
• the average carbon deposition of the third secondary regeneration zone is 2 wt%, the average carbon deposition of the fourth secondary regeneration zone is 1 wt%, and the average carbon deposition of the fifth secondary regeneration zone is 0.01 wt%.

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