WO2015081484A1 - 一种含氧化合物制低碳烯烃的方法及其使用的设备 - Google Patents

一种含氧化合物制低碳烯烃的方法及其使用的设备 Download PDF

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Publication number
WO2015081484A1
WO2015081484A1 PCT/CN2013/088388 CN2013088388W WO2015081484A1 WO 2015081484 A1 WO2015081484 A1 WO 2015081484A1 CN 2013088388 W CN2013088388 W CN 2013088388W WO 2015081484 A1 WO2015081484 A1 WO 2015081484A1
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Prior art keywords
catalyst
zone
fluidized bed
regeneration
dense phase
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PCT/CN2013/088388
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English (en)
French (fr)
Inventor
刘中民
叶茂
张涛
何长青
王贤高
赵银峰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to PCT/CN2013/088388 priority Critical patent/WO2015081484A1/zh
Priority to BR112016012646-7A priority patent/BR112016012646B1/pt
Priority to EP13898826.6A priority patent/EP3078652B1/en
Priority to SG11201604424YA priority patent/SG11201604424YA/en
Priority to DK13898826.6T priority patent/DK3078652T3/en
Priority to RU2016125852A priority patent/RU2635553C1/ru
Priority to MYPI2016701971A priority patent/MY177806A/en
Priority to AU2013407175A priority patent/AU2013407175B2/en
Priority to KR1020167017518A priority patent/KR101864442B1/ko
Priority to US15/100,834 priority patent/US9718743B2/en
Priority to JP2016535728A priority patent/JP6199493B2/ja
Publication of WO2015081484A1 publication Critical patent/WO2015081484A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • 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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Abstract

本发明涉及含氧化合物制低碳烯烃的方法及其使用的设备。更具体地，本发明提供一种含氧化合物制低碳烯烃的方法，以甲醇和/或二甲醚为主要原料，采用多级（n≥2）密相流化床反应器和多级（m≥2）催化剂再生器，解决了现有技术中催化剂积碳量和碳含量均匀性难以控制以及低碳烯烃选择性较低的问题。

Description

一种含氧化合物制低碳烯烃的方法及其使用的设备 技术领域
本发明涉及一种含氧化合物制取低碳烯烃的工艺及其使用的设备。 背景技术
低碳烯烃， 即乙烯和丙烯， 是两种重要的基础化工原料， 其需求量在 不断增加。一般地， 乙烯、 丙烯是通过石油路线来生产， 但由于石油资源 有限的供应量及较高的价格，由石油资源生产乙烯、丙烯的成本不断增加。 近年来， 人们开始大力发展替代原料转化制乙烯、 丙烯的技术。 甲醇转化 制烯烃 (MTO)的工艺受到越来越多的重视， 已实现百万吨级的生产规模。 随着世界经济的发展， 低碳烯烃， 特别是丙烯， 需求量与日倶增， 析迈公 司 (CMAI)分析称， 在 2016年前， 乙烯需求量将以年均 4.3%的速度增长， 丙烯需求量将以年均 4.4%的速度增长。 由于我国经济的高速增长， 我国 乙烯和丙烯的需求量的年增长率均超过世界平均水平。
20世纪 80年代初， UCC公司成功开发出了 SAPO系列分子筛，其中 SAPO-34分子筛催化剂在用于 MTO反应时表现出优异的催化性能， 具有 很高的低碳烯烃选择性， 而且活性很高， 但催化剂在使用一段时间后由于 积碳而失去活性。 SAPO-34 分子筛催化剂在使用过程中存在明显的诱导 期， 在诱导期内， 烯烃的选择性较低， 垸烃的选择性较高， 随着反应时间 的增加， 低碳烯烃选择性逐渐上升， 诱导期过后， 催化剂在一定时间内保 持高的选择性和高的活性，随着时间的继续延长，催化剂的活性迅速下降。
US6166282中公布了一种甲醇转化为低碳烯烃的技术和反应器，采用 快速流化床反应器， 气相在气速较低的密相反应区反应完成后， 上升到内 径急速变小的快分区后，采用特殊的气固分离设备初歩分离出大部分的夹 带催化剂。 由于反应后产物气与催化剂快速分离， 有效的防止了二次反应 的发生。 经模拟计算， 与传统的鼓泡流化床反应器相比， 该快速流化床反 应器内径及催化剂所需藏量均大大减少。但该方法中低碳烯烃碳基收率一 般均在 77%左右， 存在低碳烯烃收率较低的问题。
CN101402538B公布了一种提高低碳烯烃收率的方法， 该方法采用在 甲醇转化为低碳烯烃的第一反应区上部设置一个第二反应区，且该第二反 应区直径大于第一反应区，以增加第一反应区出口的产品气体在第二反应 区内的停留时间， 使得未反应的甲醇、生成的二甲醚和碳四以上烃继续反 应， 达到提高低碳烯烃收率的目的， 该方法虽然可以在一定程度上提高低 碳烯烃的收率， 但是由于第一反应区出来的催化剂已经带有较多的积碳， 而碳四以上烃裂解需要较高的催化剂活性，因此该方法中第二反应区内的 碳四以上烃转化效率仍然偏低， 从而导致低碳烯烃收率偏低。
CN102276406 A公布了一种增产丙烯的生产方法。该技术设置三个反 应区， 第一快速床反应区用于甲醇转化至烯烃， 提升管反应区和第二快速 床反应区串联用于转化乙烯、碳四以上烃和未反应的甲醇或二甲醚。此专 利中碳四以上烃等物质在提升管反应区和第二快速床反应区中的停留时 间较短， 转化效率偏低， 从而导致丙烯收率偏低。
CN102875289A 公布了一种内部布置提升管反应器的流化床反应装 置， 用于提高低碳烯烃的产率。第一原料进入流化床反应区， 与催化剂接 触， 生成包括低碳烯烃的产品， 同时形成待生催化剂； 待生催化剂一部分 进入再生器再生， 形成再生催化剂，一部分进入出口端位于反应区内部的 提升管， 与第二原料接触， 将待生催化剂提升至反应区内； 再生催化剂返 回流化床反应器反应区。此专利所披露的反应装置无汽提部分， 待生催化 剂将会携带部分产品气体进入再生器， 与氧气发生燃烧， 降低低碳烯烃的
CN102875296A公布的甲醇制烯烃技术设置了快速床、下行床和提升 管三个反应区。 催化剂在再生器、 快速床、 提升管和下行床之间循环， 流 向十分复杂、 流量分配和控制十分困难， 催化剂的活性变化较大。
本领域所公知的， 低碳烯烃的选择性和催化剂上的积碳量密切相关， 要保证高的低碳烯烃选择性， SAPO-34催化剂上需要一定数量的积碳。 目 前 MTO工艺所采用的主要反应器为流化床， 而流化床接近于全混流反应 器， 催化剂积炭分布很宽， 不利于提高低碳烯烃的选择性。 MTO工艺的 剂醇比很小， 生焦率较低， 要实现较大的、 容易控制的催化剂循环量， 就 需要在再生区中将催化剂上的积碳量、碳含量均匀性控制在一定水平， 进 而达到控制反应区内催化剂上的积碳量、碳含量均匀性的目的。 因此， 控 制反应区内的催化剂积碳量和碳含量均匀性于某一水平是 MTO工艺中的 关键技术。
为解决上述问题， 一些研究者提出了在流化床内设置上下两个反应 区、 两个流化床串联、 流化床和提升管、 下行床串联等技术， 初歩揭示了 控制催化剂积碳量和碳含量均匀性的方法， 取得了一定的有益效果， 但也 同时增加 MTO工艺的复杂性、 控制难度增加。 本发明提出了通过在密相 流化床中设置内构件形成多个二级反应区 (再生区:)的方案来解决控制催 化剂积碳量和碳含量均匀性的问题， 进而提高低碳烯烃的选择性。 发明内容
本发明所要解决的技术问题是现有技术中存在的低碳烯烃选择性不 高的问题， 目的在于提供一种新的提高低碳烯烃选择性的方法。该方法用 于低碳烯烃的生产中， 具有催化剂积碳均匀性好、低碳烯烃收率较高、低 碳烯烃生产工艺经济性较好的优点。
为实现上述目的， 一方面， 本发明提供一种含氧化合物制低碳烯烃的 方法， 包括以下歩骤：
a)将含有含氧化合物的原料从 n个进料支线并行通入密相流化床反应 器中的第 1个至第 n个二级反应区， 与催化剂接触， 生成含有低碳烯烃产 品的物流和待生催化剂；其中所述催化剂依序串行通过第 1个至第 n个二 级反应区， 碳含量逐渐增加； 其中所述密相流化床反应器由物料流动控制 器分隔成 n个二级反应区；
b) 将由所述第 1个至第 n个二级反应区流出的含低碳烯烃产品的物流 与其携带的待生催化剂分离；所述含低碳烯烃产品的物流进入产品分离工 段， 经分离、 提纯得到低碳烯烃产品； 分离出的待生催化剂进入第 n个二 级反应区；
c) 由第 n个二级反应区流出的待生催化剂经过汽提、提升进入密相流 化床再生器再生； 所述待生催化剂依序串行通过第 1至 m个二级再生区； 再生介质从 m个再生区进料支线并行通入第 1个至第 m个二级再生区， 所述待生催化剂与所述再生介质接触， 碳含量逐渐下降， 完成再生后的催 化剂随后经汽提、提升返回第 1个二级反应区； 其中所述密相流化床再生 器由物料流动控制器分隔成 m个二级再生区； 其中， n 2并且 m 2， 更 优选 8 n 3并且 8 m 3。
在一个优选实施方式中， 在所述密相流化床反应器中， 所述物料流动 控制器中的气体表观线速度小于等于催化剂的最小流化速度。
在一个优选实施方式中， 在所述密相流化床再生器中， 所述物料流动 控制器中的气体表观线速度小于等于催化剂的最小流化速度。
在一个优选实施方式中， 所述催化剂含有 SAPO-34分子筛。
在一个优选实施方式中， 所述密相流化床反应区反应条件为： 气体表 观线速度为 0.1-1.5m/s， 反应温度为 400-550 °C， 床层密度为 200-1200kg/m
在一个优选实施方式中， 所述密相流化床的第 1个至第 n个二级反应 区内的催化剂平均积炭量依次递增，第 1个二级反应区内的催化剂平均积 炭量为 0.5-3wt%， 第 n个二级反应区内的催化剂平均积炭量为 7-10wt%。
在一个优选实施方式中， 所述密相流化床再生区反应条件为： 气体表 观线速度为 0.1-1.5m/s， 再生温度为 500-700 °C， 床层密度为 200-1200kg/m
在一个优选实施方式中， 所述密相流化床再生区第 1个至第 m个二级 再生区内催化剂平均积炭量依次递减，第 1个二级再生区内的催化剂平均 积炭量为 3-10wt%，第 m个二级再生区内的催化剂平均积炭量为 0-3wt%。
在一个优选实施方式中， 所述含氧化合物为甲醇和 /或二甲醚； 所述低 碳烯烃为乙烯、丙烯或丁烯中的任意一种或任意几种的混合物； 所述再生 介质为空气、 贫氧空气或水蒸气中的任意一种或任意几种的混合物。
在另一方面，本发明提供一种用于实施上述方法的密相流化床反应器， 所述密相流化床反应器包括反应区、 气固分离区、 汽提区， 其特征在于， 所述反应区经由物料流动控制器分隔为 n个二级反应区， 其中 n 2。
在另一方面，本发明提供一种用于实施上述方法的密相流化床再生器， 所述密相流化床再生器包括再生区、 气固分离区、 汽提区， 其特征在于， 所述再生区经由物料流动控制器分隔为 m个二级再生区， 其中 m 2。
本发明的有益效果包括但不限于以下方面： （1)密相流化床具有较高 的床层密度， 催化剂速度较低、 磨损低； （2)物料流动控制器中的物料下 行流动管中的气速小于等于催化剂的最小流化速度，催化剂处于密相堆积 状态， 形成了催化剂的单向密相输送流， 避免了相邻二级反应区（或相邻 二级再生区） 之间的催化剂返混， 停留时间分布窄； （3)物料流动控制器 中的取热部件具有控制反应区温度的作用； （4)物料流动控制器将反应区 分隔为 n个二级反应区， 催化剂依次串行通过第 1至第 n二级反应区， 停 留时间分布窄， 待生催化剂碳含量的均匀性大幅度提高； （5)物料流动控 制器将再生区分隔为 m个二级再生区， 催化剂依次串行通过第 1至第 m 二级再生区， 停留时间分布窄， 再生催化剂碳含量的均匀性大幅度提高； (6)实现了较为精确的控制再生催化剂和待生催化剂的碳含量， 并且碳含 量分布较为均匀， 提高了低碳烯烃的选择性， 并可根据需求调控碳含量来 优化丙烯 /乙烯的比率； （7)因催化剂的碳含量分布较为均匀， 反应区所需 的催化剂藏量降低； （8)多个二级反应区的结构便于实现反应器的大型化。 附图说明
图 1为本发明所述方法的流程示意图；
图 2为本发明所述包含 4个二级反应区的密相流化床的结构示意图， 其中 A-A剖面图中的箭头是二级反应区间的催化剂流动方向 ·'
图 3为本发明所述包含 4个二级再生区的密相流化床的结构示意图， 其中 B-B剖面图中的箭头是二级再生区间的催化剂流动方向；
图 4为本发明所述汽提器的结构示意图；
图 5为本发明所述物料流动控制器的结构示意图。
附图中的附图标记说明如下：
1-反应器进料管线； 1-1第 1个二级反应区进料支线； 1-2第 2二级反 应区进料支线； 1-3第 3二级反应区进料支线； 1-4第 4二级反应区进料 支线； 2-密相流化床反应器； 2-1第 1二级反应区； 2-2第 2二级反应区； 2-3第 3二级反应区； 2-4第 4二级反应区； 3-旋风分离器； 4-产品物料管 线； 5-汽提器； 6-水蒸气管线； 7-提升管； 8-提升气管线； 9-再生器进料 管线； 9-1第 1二级再生区进料支线； 9-2第 2二级再生区进料支线； 9-3 第 3二级再生区进料支线； 9-4第 4二级再生区进料支线； 10-密相流化床 再生器； 10-1第 1二级再生区； 10-2第 2二级再生区； 10-3第 3二级再 生区； 10-4第 4二级再生区； 11-旋风分离器； 12-废气管线； 13-汽提器； 14-水蒸气管线； 15-提升管； 16-提升气管线； 17-物料流动控制器； 18-物 料溢流口； 19-隔板； 20-孔口； 21-物料下行流动管； 22-底部挡板； 23-取 热部件。 具体实施方式
为了提高含氧化合物制取低碳烯烃的工艺中的低碳烯烃选择性，本发 明提供一种含氧化合物制低碳烯烃的方法， 包括以下歩骤：
a) 将含有含氧化合物的原料从 n个进料支线并行通入密相流化床反 应器中的第 1个至第 n个二级反应区， 与催化剂接触， 生成含有低 碳烯烃产品的物流和待生催化剂；其中所述催化剂依序串行通过第 1个至第 n个二级反应区， 碳含量逐渐增加； 其中所述密相流化床 反应器由物料流动控制器分隔成 n个二级反应区；
b) 将由所述第 1个至第 n个二级反应区流出的含低碳烯烃产品的物流 与其携带的待生催化剂分离；所述含低碳烯烃产品的物流进入产品 分离工段， 经分离、 提纯得到低碳烯烃产品； 分离出的待生催化剂 进入第 n个二级反应区；
c) 由第 n个二级反应区流出的待生催化剂经过汽提、提升进入密相流 化床再生器再生； 所述待生催化剂依序串行通过第 1至 m个二级 再生区； 再生介质从 m个再生区进料支线并行通入第 1个至第 m 个二级再生区， 所述待生催化剂与所述再生介质接触， 碳含量逐渐 下降， 完成再生后的催化剂随后经汽提、提升返回第 1个二级反应 区； 其中所述密相流化床再生器由物料流动控制器分隔成 m个二 级再生区。
其中， n 2， 优选 8 n 3 ; m^2 , 优选 8 m 3。
优选地， 密相流化床反应器中， 物料流动控制器中气体表观线速度小 于等于催化剂的最小流化速度。
优选地， 密相流化床再生器中， 物料流动控制器中气体表观线速度小 于等于催化剂的最小流化速度。
优选地， 所述催化剂含有 SAPO-34分子筛。 优选地， 所述密相流化床反应区反应条件为： 气体表观线速度为
0.1-1.5m/s， 反应温度为 400-550 °C , 床层密度为 200-1200kg/m3 ; 第 1个 二级反应区内的催化剂平均积炭量为 0.5-3wt%， 第 n个二级反应区内的 催化剂平均积炭量为 7-10wt%。
优选地， 所述密相流化床再生区反应条件为： 气体表观线速度为 0.1-1.5m/s， 再生温度为 500-700 °C， 床层密度为 200-1200kg/m3; 第 1个 至第 m个二级再生区内催化剂平均积炭量依次递减， 第 1个二级再生区 内的催化剂平均积炭量为 3-10wt%， 第 m个二级再生区内的催化剂平均 积炭量为 0-3wt%。
优选地， 所述含氧化合物为甲醇和 /或二甲醚； 所述低碳烯烃为乙烯、 丙烯或丁烯中的任意一种或任意几种的混合物； 所述再生介质为空气、贫 氧空气或水蒸气中的任意一种或任意几种的混合物。
本发明提供的技术方案还包括：
(l)提供一种密相流化床反应器， 包括反应区、 气固分离区、 汽提区， 反应区由物料流动控制器分隔为 n个二级反应区， n 2;
(2；)提供一种密相流化床再生器， 包括再生区、 气固分离区、 汽提区， 再生区由物料流动控制器分隔为 m个二级再生区， m 2;
优选地，含有含氧化合物的原料进入密相流化床反应器与再生催化剂 接触， 生成包括低碳烯烃的产品和含碳的待生催化剂， 同时再生催化剂依 序通过第 1至第 n个二级反应区， 碳含量逐渐增加；
优选地， 由第 n个二级反应区流出的待生催化剂经过汽提、提升进入 密相流化床再生器再生， 待生催化剂依序通过第 1个至第 m个二级再生 区， 与再生介质接触， 碳含量逐渐下降， 随后经汽提、 提升返回第 1个二 级反应区；
优选地， 所述低碳烯烃产品物流与待生催化剂分离后进入分离工段， 分离出的待生催化剂进入第 n个二级反应区。
在一个具体实施方案中，本发明所述的含氧化合物制低碳烯烃的流程 示意图如图 1所示。 将含有含氧化合物的原料从反应器进料管线 （1 ) 及 其支线 （1-1， ……， 1-n) 并行通入密相流化床反应器 （2 ) 中的二级反 应区 （2-1， ……， 2-n)， 与包括 SAPO-34分子筛的催化剂接触， 生成气 相产品物流和待生催化剂，气相产品物流和夹带的待生催化剂进入旋风分 离器 （3 )， 气相产品物流经旋风分离器的出口、 产品物料管线 （4 ) 进入 后续分离工段，夹带的待生催化剂经旋风分离器的料腿进入第 n个二级反 应区（2-n) ;来自密相流化床再生器（10 )的再生催化剂经过汽提器（13)、 提升管（15 )进入密相流化床反应器（2)， 其中汽提器（13 )底部连接水 蒸气管线 （14)， 提升管（15 )底部连接提升气管线 （16)， 再生催化剂在 密相流化床反应器 （2 ) 中依序串行经过第 1 个至第 n 个二级反应区 (2-1， ……， 2-n) , 积碳后形成待生催化剂； 将再生介质从再生器进料 管线 （9)及其支线 （9-1， ……， 9-m) 并行通入密相流化床再生器（10) 中的二级再生区 （10-1， ……， 10-m)， 与待生催化剂接触， 烧炭后生成 尾气和再生催化剂， 尾气和夹带的再生催化剂进入旋风分离器 （11 )， 尾 气经旋风分离器的出口、废气管线（12)进入尾气处理工段， 处理后排放， 夹带的再生催化剂经旋风分离器的料腿进入第 m个二级再生区 （10-m); 来自密相流化床反应器 （2) 的待生催化剂经过汽提器 （5 )、 提升管 （7 ) 进入密相流化床再生器（10)， 其中汽提器（5 )底部连接水蒸气管线（6)， 提升管 （7 ) 底部连接提升气管线 （8)， 待生催化剂在密相流化床再生器 ( 10)中依序串行经过第 1个至第 m个二级再生区（10-1， ……， 10-m) , 烧炭后形成再生催化剂。
在一个更具体的实施方案中，本发明的包含 4个二级反应区的密相流 化床反应器的结构示意图如图 2所示。 3个物料流动控制器 （17 ) 和一个 挡板竖直设置， 将反应区分隔为 4个二级反应区， 催化剂依序通过第 1个 至第 4个二级反应区， 然后进入汽提器。
在一个更具体的实施方案中，本发明的包含 4个二级再生区的密相流 化床再生器的结构示意图如图 3所示。 3个物料流动控制器 （17 ) 和一个 挡板竖直设置， 将再生区分隔为 4个二级再生区， 催化剂依序通过第 1个 至第 4个二级再生区， 然后进入汽提器。
在一个更具体的实施方案中，本发明所述的汽提器的结构示意图如图 4所示。 汽提器上部管壁上开口作为第 n个二级反应区 (或第 m个二级再 生区：)与汽提器之间的物料溢流口 （18)。
在一个更具体的实施方案中，本发明所述的物料流动控制器的结构示 意图如图 5所示。 物料流动控制器（17 ) 由隔板 （19)、 孔口 （20)、 物料 下行流动管 （21 )、 底部挡板 （22) 和取热部件 （23 ) 组成。 催化剂由下 行流动管上方进入物料下行流动管，其中气体表观线速度小于等于最小流 化速度， 物料下行流动管内的催化剂处于密相堆积状态， 形成物料流动推 动力， 推动催化剂经过孔口流入其后的二级反应区 (或再生区：)。 取热部件 可采用盘管结构， 固定于隔板之上。
优选地， 上述技术方案中， 所述密相流化床反应区内气体表观线速度 为 0.1-1.5m/s;所述密相流化床再生区内气体表观线速度为 0.1-1.5m/s;所 述物料流动控制器内气体表观线速度小于等于催化剂的最小流化速度；所 述催化剂包括 SAPO-34分子筛； 所述反应区底部设有进料口， 进料包括 甲醇、 二甲醚等； 所述汽提器的汽提介质包含水蒸气； 所述再生区底部设 有再生介质入口， 再生介质包括空气、 贫氧空气、 水蒸气等； 所述反应区 的反应温度为 400-550°C，床层密度为 200-1200kg/m3，第 1个至第 n个二 级反应区内催化剂平均积炭量依次递增，第 1个二级反应区的平均积炭量 为 0.5-3wt%，第 n个二级反应区的平均积炭量为 7-10wt%；所述再生区的 反应温度为 500-700 °C， 床层密度为 200-1200kg/m3， 第 1个至第 m个二 级再生区内催化剂平均积炭量依次递减，第 1个二级再生区的平均积炭量 为 3-10wt%， 第 m个二级再生区的平均积炭量为 0-3wt%。 采用本发明的 方法， 可以达到控制催化剂积碳量、改善碳含量均匀性以及提高低碳烯烃 选择性的目的， 具有较大的技术优势， 可用于低碳烯烃的工业生产中。
为更好地说明本发明， 便于理解本发明的技术方案， 本发明的典型但 非限制性的实施例如下： 实施例 1
密相流化床反应器内设置 4个二级反应区，密相流化床再生器内设置 4个二级再生区， 含有含氧化合物的原料进入密相流化床反应器， 与包括 SAPO-34分子筛的催化剂接触，生成的气相产品物流和待生催化剂，气相 物料和夹带的待生催化剂进入旋风分离器，气相产品物流经旋风分离器的 出口进入后续分离工段， 夹带的待生催化剂经旋风分离器的料腿进入第 4 个二级反应区。 再生催化剂经过汽提器、 提升管进入密相流化床反应器， 并依序经过第 1个至第 4个二级反应区， 积碳后形成待生催化剂， 待生催 化剂再经过汽提器、提升管进入密相流化床再生器， 并依序经过第 1个至 第 4个二级再生区， 烧炭后形成再生催化剂。密相流化床反应器反应条件 为： 反应温度为 400°C， 气相线速度为 0.3m/s， 床层密度为 1000kg/m3， 第 1个二级反应区的平均积炭量为 2wt%， 第 2个二级反应区的平均积炭 量为 6wt%， 第 3个二级反应区的平均积炭量为 8wt%， 第 4个二级反应 区的平均积炭量为 10wt%； 密相流化床再生器反应条件为： 反应温度为 500 °C , 气相线速度为 0.3m/s， 床层密度为 1000kg/m3， 第 1个二级再生区 的平均积炭量为 7wt%， 第 2个二级再生区的平均积炭量为 4wt%， 第 3 个二级再生区的平均积炭量为 2wt%， 第 4个二级再生区的平均积炭量为 lwt%。 反应产品采用在线气相色谱分析， 低碳烯烃碳基收率为 91.1wt%。 实施例 2
密相流化床反应器内设置 3个二级反应区，密相流化床再生器内设置 2个二级再生区， 含有含氧化合物的原料进入密相流化床反应器， 与包括 SAPO-34分子筛的催化剂接触，生成的气相产品物流和待生催化剂，气相 物料和夹带的待生催化剂进入旋风分离器，气相产品物流经旋风分离器的 出口进入后续分离工段， 夹带的待生催化剂经旋风分离器的料腿进入第 3 个二级反应区。 再生催化剂经过汽提器、 提升管进入密相流化床反应器， 并依序经过第 1个至第 3个二级反应区， 积碳后形成待生催化剂， 待生催 化剂再经过汽提器、提升管进入密相流化床再生器， 并依序经过第 1个至 第 2个二级再生区， 烧炭后形成再生催化剂。密相流化床反应器反应条件 为： 反应温度为 450°C， 气相线速度为 0.5m/s， 床层密度为 900kg/m3， 第 1个二级反应区的平均积炭量为 3wt%， 第 2个二级反应区的平均积炭量 为 7wt%， 第 3二级反应区的平均积炭量为 9wt%； 密相流化床再生器反 应条件为：反应温度为 600 °C，气相线速度为 0.7m/s，床层密度为 700kg/m3， 第 1二级再生区的平均积炭量为 4wt%， 第 2个二级再生区的平均积炭量 为 2wt%。 反应产品采用在线气相色谱分析， 低碳烯烃碳基收率为 90.5wt%。 实施例 3
密相流化床反应器内设置 6个二级反应区，密相流化床再生器内设置 5个二级再生区， 含有含氧化合物的原料进入密相流化床反应器， 与包括 SAPO-34分子筛的催化剂接触，生成的气相产品物流和待生催化剂，气相 物料和夹带的待生催化剂进入旋风分离器，气相产品物流经旋风分离器的 出口进入后续分离工段， 夹带的待生催化剂经旋风分离器的料腿进入第 6 个二级反应区。 再生催化剂经过汽提器、 提升管进入密相流化床反应器， 并依序经过第 1个至第 6个二级反应区， 积碳后形成待生催化剂， 待生催 化剂再经过汽提器、提升管进入密相流化床再生器， 并依序经过第 1个至 第 5个二级再生区， 烧炭后形成再生催化剂。密相流化床反应器反应条件 为： 反应温度为 480°C， 气相线速度为 0.7m/s， 床层密度为 700kg/m3， 第 1个二级反应区的平均积炭量为 lwt%， 第 2个二级反应区的平均积炭量 为 3wt%， 第 3个二级反应区的平均积炭量为 4wt%， 第 4个二级反应区 的平均积炭量为 5wt%， 第 5个二级反应区的平均积炭量为 6wt%， 第 6 个二级反应区的平均积炭量为 7wt%； 密相流化床再生器反应条件为： 反 应温度为 650°C， 气相线速度为 1.0m/s， 床层密度为 500kg/m3， 第 1个二 级再生区的平均积炭量为 5wt%， 第 2 个二级再生区的平均积炭量为 3wt%, 第 3个二级再生区的平均积炭量为 2wt%， 第 4个二级再生区的平 均积炭量为 lwt%， 第 5个二级再生区的平均积炭量为 0.01wt%。 反应产 品采用在线气相色谱分析， 低碳烯烃碳基收率为 91.4wt%。 以上已对本发明进行了详细描述，但本发明并不局限于本文所描述具 体实施方式。本领域技术人员理解， 在不背离本发明范围的情况下， 可以 作出其他更改和变形。 本发明的范围由所附权利要求限定。

Claims

权 利 要 求
1. 一种含氧化合物制低碳烯烃的方法， 包括以下歩骤：
a)将含有含氧化合物的原料从 n个进料支线并行通入密相流化床反应 器中的第 1个至第 n个二级反应区， 与催化剂接触， 生成含有低碳烯烃产 品的物流和待生催化剂；其中所述催化剂依序串行通过第 1个至第 n个二 级反应区， 碳含量逐渐增加； 其中所述密相流化床反应器由物料流动控制 器分隔成 n个二级反应区；
b) 将由所述第 1个至第 n个二级反应区流出的含低碳烯烃产品的物流 与其所携带的待生催化剂分离；所述含低碳烯烃产品的物流进入产品分离 工段， 经分离、提纯得到低碳烯烃产品； 分离出的待生催化剂进入第 n个 二级反应区；
c) 由第 n个二级反应区流出的待生催化剂经过汽提、提升进入密相流 化床再生器再生； 所述待生催化剂依序串行通过第 1至 m个二级再生区； 再生介质从 m个再生区进料支线并行通入第 1个至第 m个二级再生区， 所述待生催化剂与所述再生介质接触， 碳含量逐渐下降， 完成再生后的催 化剂随后经汽提、提升返回第 1个二级反应区； 其中所述密相流化床再生 器由物料流动控制器分隔成 m个二级再生区；
其中， n 2并且 m 2。
2. 根据权利要求 1所述的方法， 其特征在于， 8 n≥3并且 8 m≥3。
3. 根据权利要求 1所述的方法， 其特征在于， 在所述密相流化床反应 器中，所述物料流动控制器中的气体表观线速度小于等于催化剂的最小流 化速度。
4. 根据权利要求 1所述的方法， 其特征在于， 在所述密相流化床再生 器中，所述物料流动控制器中的气体表观线速度小于等于催化剂的最小流 化速度。
5. 根据权利要求 1所述的方法，其特征在于，所述催化剂含有 SAPO-34 分子筛。
6. 根据权利要求 1所述的方法， 其特征在于， 所述密相流化床反应区 反应条件为： 气体表观线速度为 0.1-1.5m/s， 反应温度为 400-550 °C， 床层 密度为 200-1200kg/m3。
7. 根据权利要求 1所述的方法， 其特征在于， 所述密相流化床的第 1 个至第 n个二级反应区内的催化剂平均积炭量依次递增，第 1个二级反应 区内的催化剂平均积炭量为 0.5-3wt%， 第 n个二级反应区内的催化剂平 均积炭量为 7-10wt%。
8. 根据权利要求 1所述的方法， 其特征在于， 所述密相流化床再生区 反应条件为： 气体表观线速度为 0.1-1.5m/s， 再生温度为 500-700 °C， 床层 密度为 200-1200kg/m3。
9. 根据权利要求 1所述的方法， 其特征在于， 所述密相流化床再生区 第 1个至第 m个二级再生区内催化剂平均积炭量依次递减， 第 1个二级 再生区内的催化剂平均积炭量为 3-10wt%， 第 m个二级再生区内的催化 剂平均积炭量为 0-3wt%。
10. 根据权利要求 1 所述的方法， 其特征在于， 所述含氧化合物为甲 醇和 /或二甲醚； 所述低碳烯烃为乙烯、 丙烯或丁烯中的任意一种或任意 几种的混合物； 所述再生介质为空气、贫氧空气或水蒸气中的任意一种或 任意几种的混合物。
11. 一种用于实施根据权利要求 1-9 中任一项所述的方法的密相流化 床反应器， 所述密相流化床反应器包括反应区、 气固分离区、 汽提区， 其 特征在于， 所述反应区经由物料流动控制器分隔为 n个二级反应区， 其中 n^2 o
12. 一种用于实施根据权利要求 1-9中任一项所述的方法的密相流化 床再生器， 所述密相流化床再生器包括再生区、 气固分离区、 汽提区， 其 特征在于， 所述再生区经由物料流动控制器分隔为 m个二级再生区， 其 中 m 2。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020500100A (ja) * 2016-10-19 2020-01-09 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ 酸素含有化合物からプロピレン、ｃ４の炭化水素類を製造する高速流動床式反応器、装置及び方法
CN112705127A (zh) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 生产低碳烯烃的反应器及方法

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112016012633B1 (pt) * 2013-12-03 2021-07-20 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Método para preparar uma olefina leve com um composto que contém oxigênio
AU2016427080B2 (en) * 2016-10-19 2020-04-02 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method and device for manufacturing propene and C4 hydrocarbon
BR112019008014A2 (pt) * 2016-10-19 2019-07-09 Dalian Inst Chem & Physics Cas reator de camada fluidizada turbulante, dispositivo e método usando composto contendo oxigênio para propeno de fabricação e hidrocarboneto c4
US11712675B2 (en) 2017-11-30 2023-08-01 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Molecular sieve-based catalyst modification apparatus, and method
CN109865530B (zh) * 2017-12-05 2021-12-21 中国科学院大连化学物理研究所 部分再生甲醇制烯烃催化剂的方法和甲醇制烯烃方法
US11504703B2 (en) 2017-12-05 2022-11-22 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for partially regenerating methanol to olefin catalyst and methanol to olefin process
CN111054281B (zh) * 2018-10-17 2022-03-11 中国石油化工股份有限公司 催化剂流化床反应器、反应系统及应用该系统的方法
AU2021233959B2 (en) * 2020-03-13 2025-12-18 China Petroleum & Chemical Corporation Method for producing light olefin from oxygen-containing compound
WO2022077454A1 (zh) 2020-10-16 2022-04-21 中国科学院大连化学物理研究所 一种流化床反应器、装置以及应用
WO2022077457A1 (zh) * 2020-10-16 2022-04-21 中国科学院大连化学物理研究所 焦调控反应器、装置及含氧化合物制备低碳烯烃的方法
US12296324B2 (en) * 2020-10-16 2025-05-13 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Regeneration device, device for preparing low-carbon olefins, and use thereof
CN112851455A (zh) * 2021-01-18 2021-05-28 中国神华煤制油化工有限公司 甲醇制烯烃的方法
CN117019014A (zh) * 2023-08-02 2023-11-10 中国华能集团清洁能源技术研究院有限公司 二氧化碳加氢制烯烃反应器及其工作方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166282A (en) 1999-08-20 2000-12-26 Uop Llc Fast-fluidized bed reactor for MTO process
CN101239870A (zh) * 2007-02-07 2008-08-13 中国石油化工股份有限公司 甲醇和乙醇转化制低碳烯烃的方法
CN102276406A (zh) 2010-06-11 2011-12-14 中国石油化工股份有限公司 增产丙烯生产方法
CN102464535A (zh) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 甲醇或二甲醚生产低碳烯烃的方法
CN101402538B (zh) 2008-11-21 2013-01-09 中国石油化工股份有限公司 提高低碳烯烃收率的方法
CN102875296A (zh) 2011-07-12 2013-01-16 中国石油化工股份有限公司 甲醇制低碳烯烃的反应装置
CN102875289A (zh) 2011-07-12 2013-01-16 中国石油化工股份有限公司 制备低碳烯烃的方法
CN103193574A (zh) * 2012-01-10 2013-07-10 中国石油化工股份有限公司 甲醇制低碳烯烃反应－再生装置的开车方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2919241A (en) * 1955-06-17 1959-12-29 Kellogg M W Co Conversion process and apparatus with plural adjacent stages and central stripping zone
FR2417336A1 (fr) * 1978-02-16 1979-09-14 Melik Akhnazarov Talyat Procede de regeneration par oxydation du catalyseur vieilli du craking des matieres premieres hydrocarbonees et appareil pour sa mise en oeuvre
US6023005A (en) * 1997-07-03 2000-02-08 Exxon Chemicals Patents Inc. Process for converting oxygenates to olefins using molecular sieve catalysts comprising desirable carbonaceous deposits
US7057083B2 (en) 2003-11-12 2006-06-06 Exxonmobil Chemical Patents Inc. Catalyst pretreatment with C4-C7 olefins in an oxygenate to olefins reaction system
US7465845B2 (en) * 2004-12-22 2008-12-16 Exxonmobil Chemical Patents Inc. Increasing ethylene and/or propylene production in an oxygenate to olefins reaction systems
US7763765B2 (en) 2006-03-31 2010-07-27 Exxonmobil Chemical Patents Inc. Method of high pressure and high capacity oxygenate conversion with catalyst exposure cycle
CN101164687B (zh) * 2006-10-20 2010-05-12 中国石油化工股份有限公司 多反应区组合式反应器
CN101348404B (zh) 2007-07-18 2011-11-30 中国石油化工股份有限公司 甲醇或二甲醚转化过程中提高乙烯、丙烯收率的方法
CN101327445B (zh) 2008-06-12 2010-06-09 中国石油化工股份有限公司 含氧化合物制备低碳烯烃催化剂的高效再生方法
WO2009156434A2 (en) 2008-06-25 2009-12-30 Total Petrochemicals Research Feluy Process to make olefins from organics
CN101367700B (zh) 2008-09-18 2011-08-03 浙江大学 用于以含氧化合物为原料生产丙烯的径向移动床反应器
CN101367694B (zh) 2008-09-18 2012-06-13 浙江大学 用于以含氧化合物为原料生产丙烯的卧式移动床反应器
JP2014517766A (ja) 2011-05-12 2014-07-24 グラット インジェニェーアテヒニク ゲゼルシャフト ミット ベシュレンクテル ハフツング 流動床装置内で固体を連続処理するための設備
CN102875291B (zh) 2011-07-12 2014-11-26 中国石油化工股份有限公司 由甲醇生产低碳烯烃的方法
BR112016012633B1 (pt) * 2013-12-03 2021-07-20 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Método para preparar uma olefina leve com um composto que contém oxigênio

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166282A (en) 1999-08-20 2000-12-26 Uop Llc Fast-fluidized bed reactor for MTO process
CN101239870A (zh) * 2007-02-07 2008-08-13 中国石油化工股份有限公司 甲醇和乙醇转化制低碳烯烃的方法
CN101402538B (zh) 2008-11-21 2013-01-09 中国石油化工股份有限公司 提高低碳烯烃收率的方法
CN102276406A (zh) 2010-06-11 2011-12-14 中国石油化工股份有限公司 增产丙烯生产方法
CN102464535A (zh) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 甲醇或二甲醚生产低碳烯烃的方法
CN102875296A (zh) 2011-07-12 2013-01-16 中国石油化工股份有限公司 甲醇制低碳烯烃的反应装置
CN102875289A (zh) 2011-07-12 2013-01-16 中国石油化工股份有限公司 制备低碳烯烃的方法
CN103193574A (zh) * 2012-01-10 2013-07-10 中国石油化工股份有限公司 甲醇制低碳烯烃反应－再生装置的开车方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020500100A (ja) * 2016-10-19 2020-01-09 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ 酸素含有化合物からプロピレン、ｃ４の炭化水素類を製造する高速流動床式反応器、装置及び方法
CN112705127A (zh) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 生产低碳烯烃的反应器及方法
CN112705127B (zh) * 2019-10-24 2022-11-01 中国石油化工股份有限公司 生产低碳烯烃的反应器及方法

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