WO2011054205A1 - Device for preparing lower alkenes with methanol or dimethyl ether - Google Patents

Device for preparing lower alkenes with methanol or dimethyl ether Download PDF

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Publication number
WO2011054205A1
WO2011054205A1 PCT/CN2010/074459 CN2010074459W WO2011054205A1 WO 2011054205 A1 WO2011054205 A1 WO 2011054205A1 CN 2010074459 W CN2010074459 W CN 2010074459W WO 2011054205 A1 WO2011054205 A1 WO 2011054205A1
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Prior art keywords
catalyst
reactor
pretreatment
methanol
regenerator
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PCT/CN2010/074459
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French (fr)
Chinese (zh)
Inventor
魏小波
梅岭
刘伟伟
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兆威兴业有限公司
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Publication of WO2011054205A1 publication Critical patent/WO2011054205A1/en

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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
    • 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
    • B01J8/38—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 containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/384—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 containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
    • B01J8/388—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 containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only externally, i.e. the particles leaving the vessel and subsequently re-entering it
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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
    • 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 invention relates to a device for preparing low-carbon olefins, in particular to a device for preparing low-carbon olefins by using methanol or dimethyl ether, and belongs to the technical field of chemical equipment.
  • Low-carbon olefins such as ethylene and propylene are important chemical raw materials.
  • an important way to produce low-carbon olefins such as ethylene and propylene is to obtain light oils such as naphtha and light diesel oil, while naphtha and light diesel oil are mainly used. From oil.
  • the use of abundant raw materials such as coal and natural gas to produce ethylene and propylene has become more and more important at home and abroad.
  • CN116478A discloses a process for preparing low-carbon olefins such as ethylene and propylene from methanol or dimethyl ether.
  • the catalyst is used and regenerated in an upstream dense-phase bed circulating fluidization reactor, and the coke accumulated on the surface after regeneration of the catalyst. After being burned off, the activity is recovered, thereby realizing the recycling of the catalyst in the reactor and the regenerator, and continuously producing low-carbon olefins such as ethylene and propylene, and the selectivity of ethylene and propylene obtained by the method and apparatus described in the invention.
  • the sum is 81.01%.
  • 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 alkanes is higher. As the reaction time increases, the selectivity of low-carbon olefins gradually increases. After the 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.
  • WO 01/66497 A1 discloses a methanol to olefin plant, in which two reaction zones are provided in the reactor, a first reaction zone is arranged in the lower part of the reactor, and the reaction is mainly carried out in the first reactor to complete the reaction of methanol to olefin.
  • a second reaction zone is arranged in the upper part of the reactor, and the heavier components such as C4 olefins contained in the gas coming out of the first reactor continue to react in the second reaction zone to increase the yield of the olefin and form coke on the catalyst.
  • the catalyst with coke enters the first reaction zone to increase the selectivity of the lower olefins during methanol conversion.
  • Methanol or dimethyl ether to olefins process there are reactors and regenerators in the pilot plant that have been built, most of which use dense-phase fluidized bed reactors in order to obtain higher low-carbon olefin selectivity. It is of great significance to develop new reaction devices in the process of making olefins from methanol or dimethyl ether.
  • the catalyst pretreatment the by-product gas returned by the product gas separation process may be used, or a part of the raw material gas or a catalyst which can be fresh or regenerated by other gases may be used for pretreatment, so that the catalyst is preliminarily contained with a certain amount of coke to eliminate or Reduce the induction period of the catalyst, reduce the formation of alkanes and higher olefins, thereby increasing the selectivity of ethylene and propylene; since the pretreated catalyst in the reactor is in optimal operation, higher ethylene and propylene can be obtained.
  • the present invention provides an apparatus for preparing a low-carbon olefin using methanol or dimethyl ether, and the specific technical scheme is as follows:
  • a device for preparing a low-carbon olefin using methanol or dimethyl ether comprising a reactor body, a gas distributor disposed at the bottom of the reactor, a cyclone separator disposed at the top of the reactor, a catalyst regenerator body, and a catalyst a gas distributor at the bottom of the regenerator, a cyclone separator disposed at the top of the catalyst regenerator, the reactor body and the catalyst regenerator body being juxtaposed, the reactor body and the bottom of the catalyst regenerator body being connected by a pipe
  • the apparatus also includes a catalyst pre-processor having a gas inlet and a gas distributor at the bottom of the catalyst pre-processor, the upper portion of the catalyst pre-processor being coupled to the reactor body.
  • the apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether wherein the catalyst pre-processor adopts a riser pre-processor, the riser pre-processor is arranged side by side with the reactor main body and the regenerator, and the riser pre-processor The upper portion is connected to the upper middle or lower portion of the reactor body.
  • the apparatus for preparing a low carbon olefin by using methanol or dimethyl ether wherein a catalyst rapid separation device, a cyclone separator and a gas outlet are arranged at the top of the riser pretreatment device, and the outlet of the catalyst rapid separation device is provided. It is connected to the upper part of the reactor.
  • the apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether wherein the catalyst pre-processor adopts a riser pre-processor, the riser pre-processor is arranged coaxially with the reactor main body, and the riser pretreatment The top of the unit is connected to the lower portion of the reactor body.
  • the apparatus for preparing a low-carbon olefin using methanol or dimethyl ether the upper portion of the riser pre-processor is passed through the dense bed of the reactor, and the catalyst rapid separation device is disposed at the top of the riser pre-processor.
  • the apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether characterized in that: a cyclone for a pretreatment device is further provided at the top of the reactor main body, a gas outlet of the catalyst rapid separation device and the The cyclone separator for the preconditioner is connected.
  • the apparatus for preparing a low carbon olefin by using methanol or dimethyl ether wherein the catalyst pretreatment device adopts a dense phase fluidized bed pretreatment device, and a cyclone separation is arranged on the top of the dense phase fluidized bed pretreatment device.
  • the dense phase fluidized bed pretreatment unit is arranged side by side with the reactor body and the regenerator, and the middle and lower portions of the dense phase fluidized bed pretreatment unit are connected to the upper middle or lower portion of the reactor main body.
  • the apparatus for preparing a low carbon olefin by using methanol or dimethyl ether wherein the catalyst pretreatment device adopts a moving bed pretreatment device, and a cyclone separator is arranged on the top of the moving bed pretreatment device, and the moving bed pretreatment
  • the reactor is arranged side by side with the reactor body and the regenerator, and the lower portion of the moving bed preconditioner is connected to the upper middle or lower portion of the reactor body.
  • the apparatus for preparing a low-carbon olefin using methanol or dimethyl ether adopts a fixed bed pre-processor, the fixed-bed pre-processor is arranged side by side with the reactor main body and the regenerator, and the fixed bed pre-processor The lower portion is connected to the upper middle or lower portion of the reactor body.
  • the apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether adopting a fluidized bed, a moving bed or a fixed bed reactor, and the reactor preferably adopts a fluidized bed;
  • the catalyst regenerator adopts a fluidized bed, a moving bed or
  • the regenerator preferably uses a fluidized bed;
  • the reactor, the catalyst regenerator, and the catalyst pretreatment each use a different reactor, or two or more of them use the same reactor.
  • the apparatus for preparing a low-carbon olefin using methanol or dimethyl ether a stripper between the reactor and the regenerator, a gas distributor at the bottom of the stripper, and a top portion
  • the cyclone is connected to the bottom of the reactor and the regenerator via a line.
  • the invention has the following advantages and outstanding effects: a pretreatment device is added between the regenerator and the reactor, and the regenerated catalyst is first pretreated to make the catalyst skip the lower selectivity induction.
  • the catalyst can be directly involved in the reaction of methanol or dimethyl ether to produce low-carbon olefins in a highly selective operation zone, thereby enabling the process to obtain higher ethylene and propylene yields.
  • Figure 1 is a schematic view showing the structure of an apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein a catalyst pre-processor adopts a riser, a riser outlet is connected to an upper part of the reactor, a catalyst pretreatment unit and a reaction The devices are arranged side by side.
  • FIG. 2 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the outlet of the riser is connected to the lower part of the reactor, the catalyst pre-processor and the reaction
  • the devices are arranged side by side.
  • FIG. 3 is a schematic structural view of another apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser tube, and the top of the catalyst pre-processor has a catalyst rapid separation device and a cyclone separator.
  • the catalyst preconditioner is arranged side by side with the reactor.
  • FIG. 4 is a schematic view showing the structure of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, and the catalyst pre-processor is arranged coaxially with the reactor.
  • FIG. 5 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast.
  • the separation device, the catalyst preprocessor is arranged coaxially with the reactor.
  • FIG. 6 is a schematic structural view of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast.
  • the separation device is further provided with a cyclone for the catalyst pretreatment at the top of the reactor, and the catalyst pretreatment is arranged coaxially with the reactor.
  • FIG. 7 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a dense-phase fluidized bed, and the top of the dense-phase fluidized bed is provided with a cyclone separator.
  • the catalyst preconditioner is arranged coaxially with the reactor.
  • Figure 8 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a moving bed, a cyclone separator is arranged on the top of the moving bed, and the catalyst pre-processor and reaction The device is coaxially arranged.
  • Figure 9 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a fixed bed, a cyclone separator is arranged at the top of the fixed bed, and the catalyst pre-processor and reaction The device is coaxially arranged.
  • the present invention provides an apparatus for preparing a low carbon olefin using methanol or dimethyl ether, the apparatus comprising a reactor body, a gas distributor disposed at the bottom of the reactor, a cyclone disposed at the top of the reactor, and a catalyst regenerator body a gas distributor disposed at the bottom of the catalyst regenerator, a cyclone separator disposed at the top of the catalyst regenerator, the reactor body and the catalyst regenerator body being juxtaposed, the reactor body and the bottom of the catalyst regenerator body
  • the apparatus further includes a catalyst pre-processor through which a gas inlet and a gas distributor are disposed at the bottom of the catalyst pre-processor, and an outlet of the catalyst pre-processor is coupled to the reactor body.
  • the reactor and catalyst regenerator are intended to provide a vessel in which the feed gas or regeneration gas is contacted with the catalyst, and a reactor which provides a gas in contact with the catalyst can function as a reactor and a regenerator in the apparatus.
  • both the reactor and the regenerator of the present invention may be conventional fixed bed, fluidized bed or moving bed.
  • the preferred reactor and regenerator of the present invention is a fluidized bed.
  • the catalyst pretreatment device is for providing a container for contacting a raw material gas or a regeneration gas with a catalyst, and a reactor for providing a gas in contact with the catalyst can realize the function of pretreatment of the catalyst in the device, and therefore, the catalyst of the invention
  • the preprocessor can be a conventional fixed bed, fluidized bed or moving bed.
  • the preferred preconditioner of the present invention is a riser fluidized bed reactor or a dense phase fluidized bed reactor.
  • the reactor, the catalyst regenerator and the catalyst pretreatment device may respectively adopt different reactors according to different operation modes, or two or more of the same reactors may be used; that is, different reactors may be used.
  • the cycle operation is carried out in series, and the same reactor can also be used for batch operation.
  • the catalyst and the reaction tail gas are discharged from the pretreatment device, and the catalyst and the pretreatment tail gas may enter the reactor without separation, or may be separated, and the separation device may be selected according to requirements.
  • the preferred separation apparatus of the present invention is a catalyst rapid separation apparatus or/and a cyclone separation apparatus, and the separated catalyst enters the reactor, and the separated pretreatment tail gas may enter the reactor or may not enter the reactor.
  • the processor gas outlet is exhausted.
  • the catalyst and the pretreatment tail gas are discharged into the pretreatment unit, and the catalyst and the pretreatment tail gas can enter the dense phase region of the reactor, so that the pretreatment tail gas continues to react with the catalyst, and It is possible to enter the dilute phase zone of the reactor and discharge the reactor together with the product gas.
  • FIG. 1 is a schematic view showing the structure of an apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein a catalyst pre-processor adopts a riser, a riser outlet is connected to an upper part of the reactor, a catalyst pretreatment unit and a reaction
  • the devices are arranged side by side.
  • the catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process.
  • the feed gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1;
  • the device 1 is sent to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the regenerated catalyst is from the catalyst regenerator 2 Enter the riser preconditioner 3 for circulation.
  • FIG. 2 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the outlet of the riser is connected to the lower part of the reactor, the catalyst pre-processor and the reaction
  • the devices are arranged side by side.
  • the catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process.
  • the gas and the catalyst enter the dense phase region of the reactor 1; the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1;
  • the reactor 1 is sent to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is regenerated by the catalyst.
  • the device 2 enters the riser preconditioner 3 for circulation.
  • FIG. 3 is a schematic structural view of another apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser tube, and the top of the catalyst pre-processor has a catalyst rapid separation device and a cyclone separator.
  • the catalyst preconditioner is arranged side by side with the reactor.
  • the catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process.
  • the gas flows through the cyclone 10 and exits the pretreatment unit 3, and the catalyst enters the dilute phase region of the reactor 1; the raw material gas enters through the gas distributor 4
  • the reactor 1 is reacted with the catalyst and then flows out of the reactor 1 through the cyclone separator 5; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to be burned off.
  • the coke in the catalyst it flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is introduced into the riser preconditioner 3 by the catalyst regenerator 2 for circulation.
  • FIG. 4 is a schematic view showing the structure of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, and the catalyst pre-processor is arranged coaxially with the reactor.
  • the catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process.
  • the gas and the catalyst enter the dense phase region of the reactor 1; the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1;
  • the reactor 1 is sent to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is regenerated by the catalyst.
  • the device 2 enters the riser preconditioner 3 for circulation.
  • FIG. 5 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast.
  • the separation device, the catalyst preprocessor is arranged coaxially with the reactor.
  • the catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process.
  • the catalyst After the gas and catalyst are separated from the catalyst by the catalyst rapid separation device 9 at the top of the pretreatment unit 3, the catalyst enters the dense phase region of the reactor 1, and the gas is mixed with the gas in the reactor; the raw material gas enters the reactor 1 through the gas distributor 4.
  • the reaction with the exhaust gas of the preconditioner passes through the cyclone 5 and then flows out of the reactor 1; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and the catalyst After contact with the coke in the catalyst, it is passed through the cyclone 7 and then exits the reactor 2; the catalyst to be treated is passed from the catalyst regenerator 2 into the riser preconditioner 3 for circulation.
  • FIG. 6 is a schematic structural view of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast.
  • the separation device is further provided with a cyclone for the catalyst pretreatment at the top of the reactor, and the catalyst pretreatment is arranged coaxially with the reactor.
  • the catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process.
  • the gas flows out of the pretreatment unit 3 through the cyclone 10, and the catalyst enters the dense phase region of the reactor 1; the raw material gas enters through the gas distributor 4
  • the reactor 1 is reacted with the catalyst and then flows out of the reactor 1 through the cyclone separator 5; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to be burned off.
  • the coke in the catalyst it flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is introduced into the riser preconditioner 3 by the catalyst regenerator 2 for circulation.
  • FIG. 7 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a dense-phase fluidized bed, and the top of the dense-phase fluidized bed is provided with a cyclone separator.
  • the catalyst preconditioner is arranged coaxially with the reactor.
  • the catalyst to be treated enters the dense phase fluidized bed pretreatment unit 3 from the catalyst regenerator 2, and the pretreatment gas enters the dense phase fluidized bed pretreatment unit 3 through the gas distributor 8 to pretreat the treated catalyst, and then through the cyclone.
  • the separator 10 flows out of the pretreatment unit 3; the treated catalyst enters the reactor 1 from the dense phase fluidized bed pretreatment unit 3, and the raw material gas enters the reactor 1 through the gas distributor 4, and is reacted with the catalyst to pass through the cyclone separator 5.
  • the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out through the cyclone 7
  • the catalyst to be treated is circulated by the catalyst regenerator 2 into the dense phase fluidized bed pretreatment unit 11.
  • Figure 8 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a moving bed, a cyclone separator is arranged on the top of the moving bed, and the catalyst pre-processor and reaction The device is coaxially arranged.
  • the catalyst to be treated enters the moving bed preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the moving bed pretreatment unit 3 through the gas distributor 8, the catalyst to be treated is pretreated, and then pretreated through the cyclone 10
  • the treated catalyst is introduced into the reactor 1 by the moving bed preconditioner 3, and the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; From the reactor 1 to the catalyst regenerator 2, the regeneration gas enters the regenerator through the gas distributor 6, contacts the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is composed of the catalyst
  • the regenerator 2 enters the moving bed preconditioner 14 for circulation.
  • Figure 9 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a fixed bed, a cyclone separator is arranged at the top of the fixed bed, and the catalyst pre-processor and reaction The device is coaxially arranged.
  • the catalyst to be treated enters the fixed bed pretreatment unit 3 from the catalyst regenerator 2, the pretreatment gas is passed to the fixed bed pretreatment unit 3, the catalyst to be treated is pretreated, and then flows out of the pretreatment unit 3;
  • the pre-processor 3 enters the reactor 1, and the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2
  • the regeneration gas enters the regenerator through the gas distributor 6, is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7;
  • the fixed bed preconditioner 3 may be composed of two or more fixed beds. The alternating use of individual fixed beds allows the entire process to be cycled.
  • Catalyst pretreatment 100 g of regenerated SAPO-34 catalyst was added to an internal diameter of 50 In a fluidized bed reactor of mm, the initial carbon content of the catalyst is 0.1-0.3% based on the weight of the catalyst, the pretreatment temperature is 450 °C, the absolute pressure is 0.15 MPa, and the high purity N2 is first purged 30. Min, the nitrogen flow rate is 60 L / h, and then the pretreatment gas is added from the bottom of the reactor, the composition of the pretreatment gas is methanol, the mass space velocity is 1 / h, the access time lasts 10 min, and then the high purity N2 Purge 30 Min, the treated catalyst has a carbon content of 3.1-3.7% based on the weight of the catalyst.
  • MTO reaction the reactor used in the catalyst pretreatment was maintained at a reaction temperature of 500 ° C and an absolute pressure of 0.15. MPa, the raw material methanol is vaporized by the preheater and then introduced into the reactor. The mass space velocity of methanol relative to the catalyst is 3/h, the outlet product of the reactor is condensed by a condenser tube, and the condensed reaction gas is carried out with a gas collecting bottle. The liquid is collected for online methanol concentration analysis, and the reaction is stopped until the mass concentration of the liquid phase methanol reaches 4%. The gas in the gas cylinder is analyzed by gas chromatography for gas content, and the selectivity of ethylene and propylene in the gas phase product is selected. The sum is 81.7-82.8%, and the coke content in the catalyst after use is 7.2-7.6% based on the weight of the catalyst.
  • Catalyst regeneration The reactor used in the catalyst pretreatment unit was maintained at a regeneration temperature of 600 ° C and an absolute pressure of 0.15. MPa, air is used as the regeneration gas, the air flow rate is 60 L/h, and the introduction time is 1 h.
  • the regenerated catalyst contains 0.1-0.3% of coke on average based on the weight of the catalyst.
  • Example 2 Using the reaction apparatus of Example 5, the pretreatment gas in the catalyst pretreatment apparatus is 1-butene, the pretreatment temperature is controlled at 580-600 ° C, and the absolute pressure is 0.14-0.16. MPa, the pretreatment gas mass space velocity is 1.5/h, based on the weight of the catalyst, the average coke content in the riser outlet catalyst is 2.1-2.5%; the reaction gas in the reactor is methanol, and the reaction temperature is controlled at 470-480.
  • the pretreatment gas in the catalyst pretreatment apparatus is 1-butene
  • the pretreatment temperature is controlled at 580-600 ° C
  • the absolute pressure is 0.14-0.16. MPa
  • the pretreatment gas mass space velocity is 1.5/h, based on the weight of the catalyst, the average coke content in the riser outlet catalyst is 2.1-2.5%
  • the reaction gas in the reactor is methanol, and the reaction temperature is controlled at 470-480.
  • Example 3 Using the reaction apparatus of Example 6, the pretreatment gas in the catalyst pretreatment apparatus is a mixed gas of propylene and propane having a volume content of 50% and 50%, and the pretreatment temperature is controlled at 540-560 ° C, and the absolute pressure is 0.14-0.16 MPa, the pretreatment gas mass space velocity is 2 / h, based on the weight of the catalyst, the average coke content in the catalyst is 3-3.5%; the reaction gas in the reactor is methanol, the reaction temperature is controlled at 500-510 ° C, absolutely The pressure is 0.14-0.16 MPa, methanol mass space velocity is 2 / h, based on the weight of the catalyst, the average coke content in the catalyst is 7.1-7.6%; the regeneration gas in the catalyst regenerator uses air, the regeneration temperature is controlled at 650-660 ° C, absolute pressure Is 0.14-0.16 MPa, the average coke content in the catalyst is from 0.1 to 0.3% based on the weight of the catalyst. Under the above operating conditions, the selectivity of ethylene and prop
  • the process for preparing low-carbon olefins from methanol or dimethyl ether can be realized by using the apparatus.
  • the reaction result is superior to the existing apparatus such as CN1166478A by the addition of the catalyst pre-processor, and the purpose of increasing the selectivity of ethylene and propylene is achieved.

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Abstract

Disclosed is a device for preparing lower alkenes with methanol or dimethyl ether, which comprises a catalyst pre-treater besides a reactor and a catalyst regenerator. A gas inlet and a gas distributor are arranged in the bottom of the said catalyst pre-treater, and the upper portion of the catalyst pre-treater is connected to the main body of the reactor. The catalyst pre-treater is a riser pre-treater, a dense-phase fluidized bed pre-treater, a moving bed pre-treater or a fixed bed pre-treater. The catalyst is used in the device in a circulation way, recycled in turn from the reactor to the regenerator, then to the catalyst pre-treater, and finally to the reactor. The catalyst pre-treater is arranged between the regenerator and the reactor, and the regenerated catalyst is firstly pre-treated. Hence, higher yields of ethylene and propylene can be obtained by the process.

Description

一种采用甲醇或二甲醚制备低碳烯烃的装置  Device for preparing low carbon olefins by using methanol or dimethyl ether
本发明涉及一种制备低碳烯烃的装置，特别涉及一种采用甲醇或二甲醚制备低碳烯烃的装置，属于化工设备技术领域。 The invention relates to a device for preparing low-carbon olefins, in particular to a device for preparing low-carbon olefins by using methanol or dimethyl ether, and belongs to the technical field of chemical equipment.
乙烯、丙烯等低碳烯烃是重要的化工原料，目前制取乙烯、丙烯等低碳烯烃的重要途径是通过裂解石脑油、轻柴油等轻质油来获取，而石脑油、轻柴油主要来源于石油。随着石油资源的逐渐匮乏，采用丰富的煤、天然气等原料制取乙烯、丙烯的技术路线，愈来愈受到国内外的重视。Low-carbon olefins such as ethylene and propylene are important chemical raw materials. Currently, an important way to produce low-carbon olefins such as ethylene and propylene is to obtain light oils such as naphtha and light diesel oil, while naphtha and light diesel oil are mainly used. From oil. With the gradual shortage of petroleum resources, the use of abundant raw materials such as coal and natural gas to produce ethylene and propylene has become more and more important at home and abroad.
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甲醇制烯烃（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催化剂表面积有焦炭而失去活性。In the early 1980s, UCC successfully developed the SAPO series of molecular sieves, in which the SAPO-34 molecular sieve catalyst exhibited excellent catalytic performance in the methanol to olefin (MTO) reaction and had high low carbon olefin selectivity. Moreover, the activity is high, but the catalyst loses activity after a period of use due to coke on the surface area of the catalyst.
CN116478A公开了一种由甲醇或二甲醚制取乙烯、丙烯等低碳烯烃的方法，催化剂在上行式密相床循环流化反应装置进行使用和再生，催化剂在再生后，表面上积的焦炭被烧除，活性得以回复，从而实现催化剂在反应器和再生器中循环使用，能连续的制取乙烯、丙烯等低碳烯烃，利用发明中所述的方法和装置得到的乙烯和丙烯选择性之和为81.01%。CN116478A discloses a process for preparing low-carbon olefins such as ethylene and propylene from methanol or dimethyl ether. The catalyst is used and regenerated in an upstream dense-phase bed circulating fluidization reactor, and the coke accumulated on the surface after regeneration of the catalyst. After being burned off, the activity is recovered, thereby realizing the recycling of the catalyst in the reactor and the regenerator, and continuously producing low-carbon olefins such as ethylene and propylene, and the selectivity of ethylene and propylene obtained by the method and apparatus described in the invention. The sum is 81.01%.
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，烷烃的选择性较高，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，随时间的继续延长，催化剂的活性迅速下降。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 alkanes is higher. As the reaction time increases, the selectivity of low-carbon olefins gradually increases. After the 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.
WO01/66497A1公开了一种甲醇制烯烃的装置，在反应器中设有两个反应区，在反应器下部设有第一反应区，反应主要在第一反应器，完成甲醇到烯烃的反应，在反应器上部设有第二反应区，从第一反应器出来的气体中含有的C4烯烃等较重组分在第二反应区继续反应，以增大烯烃的产率，同时在催化剂上形成焦炭，带有焦炭的催化剂进入第一反应区，可提高甲醇转化时低碳烯烃的选择性。WO 01/66497 A1 discloses a methanol to olefin plant, in which two reaction zones are provided in the reactor, a first reaction zone is arranged in the lower part of the reactor, and the reaction is mainly carried out in the first reactor to complete the reaction of methanol to olefin. A second reaction zone is arranged in the upper part of the reactor, and the heavier components such as C4 olefins contained in the gas coming out of the first reactor continue to react in the second reaction zone to increase the yield of the olefin and form coke on the catalyst. The catalyst with coke enters the first reaction zone to increase the selectivity of the lower olefins during methanol conversion.
甲醇或二甲醚制烯烃过程，目前已建成的中试装置中都有反应器和再生器的部分，绝大部分是采用密相流化床反应器，为了获得更高的低碳烯烃选择性，在甲醇或二甲醚制烯烃的过程中开发新的反应装置，有非常重要的意义。Methanol or dimethyl ether to olefins process, there are reactors and regenerators in the pilot plant that have been built, most of which use dense-phase fluidized bed reactors in order to obtain higher low-carbon olefin selectivity. It is of great significance to develop new reaction devices in the process of making olefins from methanol or dimethyl ether.
本发明的目的是提出了一种采用甲醇或二甲醚制备低碳烯烃的装置，装置除包括反应器和催化剂再生器外，还包括催化剂预处理器。在催化剂预处理器中可以采用产品气分离工艺返回的副产气体、或采用部分原料气、或采用其它气体能新鲜或再生的催化剂进行预处理，使催化剂预先含上一定的焦炭，以消除或减小催化剂的诱导期，减少烷烃和高碳烯烃的生成，从而增加乙烯和丙烯的选择性；由于反应器中预处理后的催化剂处于最佳的操作状态，因此可获得更高的乙烯和丙烯的收率； It is an object of the present invention to provide an apparatus for the preparation of lower olefins using methanol or dimethyl ether, the apparatus including a catalyst preconditioner in addition to the reactor and catalyst regenerator. In the catalyst pretreatment, the by-product gas returned by the product gas separation process may be used, or a part of the raw material gas or a catalyst which can be fresh or regenerated by other gases may be used for pretreatment, so that the catalyst is preliminarily contained with a certain amount of coke to eliminate or Reduce the induction period of the catalyst, reduce the formation of alkanes and higher olefins, thereby increasing the selectivity of ethylene and propylene; since the pretreated catalyst in the reactor is in optimal operation, higher ethylene and propylene can be obtained. Yield
技术解决方案Technical solution
为了实现上述目的，本发明提供了一种采用甲醇或二甲醚制备低碳烯烃的装置，具体技术方案如下：In order to achieve the above object, the present invention provides an apparatus for preparing a low-carbon olefin using methanol or dimethyl ether, and the specific technical scheme is as follows:
一种采用甲醇或二甲醚制备低碳烯烃的装置，该装置包括反应器主体，设置在反应器底部的气体分布器，设置在反应器顶部的旋风分离器，催化剂再生器主体，设置在催化剂再生器底部的气体分布器，设置在催化剂再生器顶部的旋风分离器，所述的反应器主体和催化剂再生器主体并列布置，所述的反应器主体和催化剂再生器主体的底部通过管道连接，该装置还包括催化剂预处理器，在所述的催化剂预处理器的底部设有气体进口和气体分布器，催化剂预处理器的上部与反应器主体相连接。 A device for preparing a low-carbon olefin using methanol or dimethyl ether, the device comprising a reactor body, a gas distributor disposed at the bottom of the reactor, a cyclone separator disposed at the top of the reactor, a catalyst regenerator body, and a catalyst a gas distributor at the bottom of the regenerator, a cyclone separator disposed at the top of the catalyst regenerator, the reactor body and the catalyst regenerator body being juxtaposed, the reactor body and the bottom of the catalyst regenerator body being connected by a pipe, The apparatus also includes a catalyst pre-processor having a gas inlet and a gas distributor at the bottom of the catalyst pre-processor, the upper portion of the catalyst pre-processor being coupled to the reactor body.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，所述的催化剂预处理器采用提升管预处理器，提升管预处理器与反应器主体和再生器并列布置，提升管预处理器的上部与反应器主体的中上部或下部连接。The apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether, wherein the catalyst pre-processor adopts a riser pre-processor, the riser pre-processor is arranged side by side with the reactor main body and the regenerator, and the riser pre-processor The upper portion is connected to the upper middle or lower portion of the reactor body.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，在所述的提升管预处理器的顶部设有催化剂快速分离装置、旋风分离器和气体出口，所述的催化剂快速分离装置的出口与反应器中上部相连接。The apparatus for preparing a low carbon olefin by using methanol or dimethyl ether, wherein a catalyst rapid separation device, a cyclone separator and a gas outlet are arranged at the top of the riser pretreatment device, and the outlet of the catalyst rapid separation device is provided. It is connected to the upper part of the reactor.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，所述的催化剂预处理器采用提升管预处理器，所述的提升管预处理器与反应器主体同轴布置，提升管预处理器的顶部与反应器主体的下部连接。The apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether, wherein the catalyst pre-processor adopts a riser pre-processor, the riser pre-processor is arranged coaxially with the reactor main body, and the riser pretreatment The top of the unit is connected to the lower portion of the reactor body.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，提升管预处理器的上部穿过反应器的密相床层，在提升管预处理器的顶部设有催化剂快速分离装置。The apparatus for preparing a low-carbon olefin using methanol or dimethyl ether, the upper portion of the riser pre-processor is passed through the dense bed of the reactor, and the catalyst rapid separation device is disposed at the top of the riser pre-processor.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述反应器主体的顶部还设有供预处理器用的旋风分离器，该催化剂快速分离装置的气体出口与所述的供预处理器用的旋风分离器相连接。The apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether, characterized in that: a cyclone for a pretreatment device is further provided at the top of the reactor main body, a gas outlet of the catalyst rapid separation device and the The cyclone separator for the preconditioner is connected.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，所述的催化剂预处理器采用密相流化床预处理器，在所述的密相流化床预处理器顶部设有旋风分离器，密相流化床预处理器与反应器主体和再生器并列布置，密相流化床预处理器的中下部与反应器主体的中上部或下部连接。The apparatus for preparing a low carbon olefin by using methanol or dimethyl ether, wherein the catalyst pretreatment device adopts a dense phase fluidized bed pretreatment device, and a cyclone separation is arranged on the top of the dense phase fluidized bed pretreatment device. The dense phase fluidized bed pretreatment unit is arranged side by side with the reactor body and the regenerator, and the middle and lower portions of the dense phase fluidized bed pretreatment unit are connected to the upper middle or lower portion of the reactor main body.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，所述的催化剂预处理器采用移动床预处理器，在所述的移动床预处理器顶部设有旋风分离器，移动床预处理器与反应器主体和再生器并列布置，移动床预处理器的下部与反应器主体的中上部或下部连接。The apparatus for preparing a low carbon olefin by using methanol or dimethyl ether, wherein the catalyst pretreatment device adopts a moving bed pretreatment device, and a cyclone separator is arranged on the top of the moving bed pretreatment device, and the moving bed pretreatment The reactor is arranged side by side with the reactor body and the regenerator, and the lower portion of the moving bed preconditioner is connected to the upper middle or lower portion of the reactor body.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，所述的催化剂预处理器采用固定床预处理器，固定床预处理器与反应器主体和再生器并列布置，固定床预处理器的下部与反应器主体的中上部或下部连接。The apparatus for preparing a low-carbon olefin using methanol or dimethyl ether, the catalyst pre-processor adopts a fixed bed pre-processor, the fixed-bed pre-processor is arranged side by side with the reactor main body and the regenerator, and the fixed bed pre-processor The lower portion is connected to the upper middle or lower portion of the reactor body.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，反应器采用流化床、移动床或固定床反应器，反应器优选采用流化床；催化剂再生器采用流化床、移动床或固定床再生器，再生器优选采用流化床；反应器、催化剂再生器、催化剂预处理器各自采用不同的反应器，或是其中两个或多个采用同一反应器。The apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether, the reactor adopting a fluidized bed, a moving bed or a fixed bed reactor, and the reactor preferably adopts a fluidized bed; the catalyst regenerator adopts a fluidized bed, a moving bed or For the fixed bed regenerator, the regenerator preferably uses a fluidized bed; the reactor, the catalyst regenerator, and the catalyst pretreatment each use a different reactor, or two or more of them use the same reactor.
所述的采用甲醇或二甲醚制备低碳烯烃的装置，在所述的反应器与再生器之间还有汽提器，在所述的汽提器底部设有气体分布器，顶部设有旋风分离器，汽提器与反应器和再生器的底部通过管路相连接。The apparatus for preparing a low-carbon olefin using methanol or dimethyl ether, a stripper between the reactor and the regenerator, a gas distributor at the bottom of the stripper, and a top portion The cyclone is connected to the bottom of the reactor and the regenerator via a line.
有益效果Beneficial effect
本发明与现有技术相比，具有以下优点及突出性效果：在再生器和反应器中间加上预处理器，对再生后的催化剂先进行预处理，使催化剂跳过选择性较低的诱导期前期，使催化剂刚参与甲醇或二甲醚制低碳烯烃的反应就能处于高选择性操作区域，因此可使工艺获得更高的乙烯和丙烯收率。 Compared with the prior art, the invention has the following advantages and outstanding effects: a pretreatment device is added between the regenerator and the reactor, and the regenerated catalyst is first pretreated to make the catalyst skip the lower selectivity induction. In the early stage, the catalyst can be directly involved in the reaction of methanol or dimethyl ether to produce low-carbon olefins in a highly selective operation zone, thereby enabling the process to obtain higher ethylene and propylene yields.
附图说明DRAWINGS
图1是本发明提供的一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管出口与反应器中上部相连，催化剂预处理器与反应器并列布置。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of an apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein a catalyst pre-processor adopts a riser, a riser outlet is connected to an upper part of the reactor, a catalyst pretreatment unit and a reaction The devices are arranged side by side.
图2是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管出口与反应器下部相连，催化剂预处理器与反应器并列布置。2 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the outlet of the riser is connected to the lower part of the reactor, the catalyst pre-processor and the reaction The devices are arranged side by side.
图3是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，催化剂预处理器顶部有催化剂快速分离装置和旋风分离器，催化剂预处理器与反应器并列布置。3 is a schematic structural view of another apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser tube, and the top of the catalyst pre-processor has a catalyst rapid separation device and a cyclone separator. The catalyst preconditioner is arranged side by side with the reactor.
图4是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，催化剂预处理器与反应器同轴布置。4 is a schematic view showing the structure of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, and the catalyst pre-processor is arranged coaxially with the reactor.
图5是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管穿过催化剂床层，提升管顶部设有催化剂快速分离装置，催化剂预处理器与反应器同轴布置。5 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast. The separation device, the catalyst preprocessor is arranged coaxially with the reactor.
图6是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管穿过催化剂床层，提升管顶部设有催化剂快速分离装置，反应器顶部还设有供催化剂预处理器用的旋风分离器，催化剂预处理器与反应器同轴布置。6 is a schematic structural view of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast. The separation device is further provided with a cyclone for the catalyst pretreatment at the top of the reactor, and the catalyst pretreatment is arranged coaxially with the reactor.
图7是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用密相流化床，密相流化床顶部设有旋风分离器，催化剂预处理器与反应器同轴布置。7 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a dense-phase fluidized bed, and the top of the dense-phase fluidized bed is provided with a cyclone separator. The catalyst preconditioner is arranged coaxially with the reactor.
图8是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用移动床，移动床顶部设有旋风分离器，催化剂预处理器与反应器同轴布置。Figure 8 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a moving bed, a cyclone separator is arranged on the top of the moving bed, and the catalyst pre-processor and reaction The device is coaxially arranged.
图9是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用固定床，固定床顶部设有旋风分离器，催化剂预处理器与反应器同轴布置。Figure 9 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a fixed bed, a cyclone separator is arranged at the top of the fixed bed, and the catalyst pre-processor and reaction The device is coaxially arranged.
图中：1－反应器；2-催化剂再生器；3-催化剂预处理器；4-第一气体分布器；5-第一旋风分离器；6-第二气体分布器；7-第二旋风分离器b；8-第三气体分布器；9-催化剂快速分离装置10-第三旋风分离器；In the figure: 1-reactor; 2-catalyst regenerator; 3-catalyst preprocessor; 4-first gas distributor; 5-first cyclone separator; 6-second gas distributor; 7-second cyclone Separator b; 8 - third gas distributor; 9 - catalyst rapid separation device 10 - third cyclone separator;
本发明的实施方式Embodiments of the invention
本发明提供了一种采用甲醇或二甲醚制备低碳烯烃的装置，该装置包括反应器主体，设置在反应器底部的气体分布器，设置在反应器顶部的旋风分离器，催化剂再生器主体，设置在催化剂再生器底部的气体分布器，设置在催化剂再生器顶部的旋风分离器，所述的反应器主体和催化剂再生器主体并列布置，所述的反应器主体和催化剂再生器主体的底部通过管道连接，该装置还包括催化剂预处理器，在所述的催化剂预处理器的底部设有气体进口和气体分布器，催化剂预处理器的出口与反应器主体相连接。The present invention provides an apparatus for preparing a low carbon olefin using methanol or dimethyl ether, the apparatus comprising a reactor body, a gas distributor disposed at the bottom of the reactor, a cyclone disposed at the top of the reactor, and a catalyst regenerator body a gas distributor disposed at the bottom of the catalyst regenerator, a cyclone separator disposed at the top of the catalyst regenerator, the reactor body and the catalyst regenerator body being juxtaposed, the reactor body and the bottom of the catalyst regenerator body The apparatus further includes a catalyst pre-processor through which a gas inlet and a gas distributor are disposed at the bottom of the catalyst pre-processor, and an outlet of the catalyst pre-processor is coupled to the reactor body.
所述的反应器和催化剂再生器，目的是提供原料气或再生气与催化剂接触的容器，可提供气体与催化剂接触的反应器均可实现本装置中的反应器和再生器的作用。因此，本发明中的反应器和再生器均可选用常规的固定床、流化床或移动床，本发明优选的反应器和再生器是流化床。The reactor and catalyst regenerator are intended to provide a vessel in which the feed gas or regeneration gas is contacted with the catalyst, and a reactor which provides a gas in contact with the catalyst can function as a reactor and a regenerator in the apparatus. Thus, both the reactor and the regenerator of the present invention may be conventional fixed bed, fluidized bed or moving bed. The preferred reactor and regenerator of the present invention is a fluidized bed.
所述的催化剂预处理器，目的是提供原料气或再生气与催化剂接触的容器，可提供气体与催化剂接触的反应器均可实现本装置中催化剂预处理的作用，因此，本发明中的催化剂预处理器可选用常规的固定床、流化床或移动床，本发明优选的预处理器是提升管流化床反应器或密相流化床反应器。The catalyst pretreatment device is for providing a container for contacting a raw material gas or a regeneration gas with a catalyst, and a reactor for providing a gas in contact with the catalyst can realize the function of pretreatment of the catalyst in the device, and therefore, the catalyst of the invention The preprocessor can be a conventional fixed bed, fluidized bed or moving bed. The preferred preconditioner of the present invention is a riser fluidized bed reactor or a dense phase fluidized bed reactor.
所述的反应器、催化剂再生器和催化剂预处理器，根据操作方式的不同，即可分别采用不同的反应器，也可以其中两个或多个采用同一反应器；即可以采用不同的反应器串联进行循环操作，也可以采用同一反应器进行间歇操作。The reactor, the catalyst regenerator and the catalyst pretreatment device may respectively adopt different reactors according to different operation modes, or two or more of the same reactors may be used; that is, different reactors may be used. The cycle operation is carried out in series, and the same reactor can also be used for batch operation.
对于所述的预处理反应器，在预处理过程完成后催化剂和反应尾气要排出预处理器，催化剂和预处理尾气可以不经分离一起进入反应器，也可以经过分离，分离装置可根据需要选用不同的装置，本发明优选的分离装置是催化剂快速分离装置或/和旋风分离装置，分离后的催化剂进入反应器，分离后的预处理尾气可以进入反应器，也可以不进入反应器，由预处理器气体出口排出。For the pretreatment reactor, after the pretreatment process is completed, the catalyst and the reaction tail gas are discharged from the pretreatment device, and the catalyst and the pretreatment tail gas may enter the reactor without separation, or may be separated, and the separation device may be selected according to requirements. Different apparatus, the preferred separation apparatus of the present invention is a catalyst rapid separation apparatus or/and a cyclone separation apparatus, and the separated catalyst enters the reactor, and the separated pretreatment tail gas may enter the reactor or may not enter the reactor. The processor gas outlet is exhausted.
所述的预处理反应器，在预处理过程完成后催化剂和预处理尾气要排出预处理器，催化剂和预处理尾气可以进入反应器的密相区，使预处理尾气继续与催化剂接触反应，也可以进入反应器的稀相区，同产品气一同排出反应器。In the pretreatment reactor, after the pretreatment process is completed, the catalyst and the pretreatment tail gas are discharged into the pretreatment unit, and the catalyst and the pretreatment tail gas can enter the dense phase region of the reactor, so that the pretreatment tail gas continues to react with the catalyst, and It is possible to enter the dilute phase zone of the reactor and discharge the reactor together with the product gas.
为了更好的说明本发明的技术方案和技术效果，下面接合附图说明本发明的具体实施方式：In order to better explain the technical solutions and technical effects of the present invention, the specific embodiments of the present invention will be described below with reference to the accompanying drawings:
图1是本发明提供的一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管出口与反应器中上部相连，催化剂预处理器与反应器并列布置。待处理的催化剂由催化剂再生器2进入提升管预处理器3，预处理气体经气体分布器8进入提升管预处理器3，携带待处理的催化剂上升，在上升过程中对催化剂进行预处理，在预处理器3顶部和催化剂一起进入反应器1稀相区；原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；再生后的催化剂由催化剂再生器2进入提升管预处理器3进行循环。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of an apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein a catalyst pre-processor adopts a riser, a riser outlet is connected to an upper part of the reactor, a catalyst pretreatment unit and a reaction The devices are arranged side by side. The catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process. At the top of the pretreatment unit 3 together with the catalyst enters the dilute phase zone of the reactor 1; the feed gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; The device 1 is sent to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the regenerated catalyst is from the catalyst regenerator 2 Enter the riser preconditioner 3 for circulation.
图2是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管出口与反应器下部相连，催化剂预处理器与反应器并列布置。待处理的催化剂由催化剂再生器2进入提升管预处理器3，预处理气体经气体分布器8进入提升管预处理器3，携带待处理的催化剂上升，在上升过程中对催化剂进行预处理，在预处理器3顶部气体和催化剂进入反应器1的密相区；原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入提升管预处理器3进行循环。2 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the outlet of the riser is connected to the lower part of the reactor, the catalyst pre-processor and the reaction The devices are arranged side by side. The catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process. At the top of the pretreatment unit 3, the gas and the catalyst enter the dense phase region of the reactor 1; the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; The reactor 1 is sent to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is regenerated by the catalyst. The device 2 enters the riser preconditioner 3 for circulation.
图3是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，催化剂预处理器顶部有催化剂快速分离装置和旋风分离器，催化剂预处理器与反应器并列布置。待处理的催化剂由催化剂再生器2进入提升管预处理器3，预处理气体经气体分布器8进入提升管预处理器3，携带待处理的催化剂上升，在上升过程中对催化剂进行预处理，在预处理器3顶部气体和催化剂经催化剂快速分离装置9与催化剂分离后，气体经旋风分离器10后流出预处理器3，催化剂进入反应器1稀相区；原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入提升管预处理器3进行循环。3 is a schematic structural view of another apparatus for preparing a low-carbon olefin by using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser tube, and the top of the catalyst pre-processor has a catalyst rapid separation device and a cyclone separator. The catalyst preconditioner is arranged side by side with the reactor. The catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process. After the gas and catalyst are separated from the catalyst by the catalyst rapid separation device 9 at the top of the pretreatment unit 3, the gas flows through the cyclone 10 and exits the pretreatment unit 3, and the catalyst enters the dilute phase region of the reactor 1; the raw material gas enters through the gas distributor 4 The reactor 1 is reacted with the catalyst and then flows out of the reactor 1 through the cyclone separator 5; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to be burned off. After the coke in the catalyst, it flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is introduced into the riser preconditioner 3 by the catalyst regenerator 2 for circulation.
图4是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，催化剂预处理器与反应器同轴布置。待处理的催化剂由催化剂再生器2进入提升管预处理器3，预处理气体经气体分布器8进入提升管预处理器3，携带待处理的催化剂上升，在上升过程中对催化剂进行预处理，在预处理器3顶部气体和催化剂进入反应器1的密相区；原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入提升管预处理器3进行循环。4 is a schematic view showing the structure of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, and the catalyst pre-processor is arranged coaxially with the reactor. The catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process. At the top of the pretreatment unit 3, the gas and the catalyst enter the dense phase region of the reactor 1; the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; The reactor 1 is sent to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is regenerated by the catalyst. The device 2 enters the riser preconditioner 3 for circulation.
图5是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管穿过催化剂床层，提升管顶部设有催化剂快速分离装置，催化剂预处理器与反应器同轴布置。待处理的催化剂由催化剂再生器2进入提升管预处理器3，预处理气体经气体分布器8进入提升管预处理器3，携带待处理的催化剂上升，在上升过程中对催化剂进行预处理，在预处理器3顶部气体和催化剂经催化剂快速分离装置9与催化剂分离后，催化剂进入反应器1的密相区，气体与反应器中气体混合；原料气经气体分布器4进入反应器1，与催化剂接触反应后与预处理器的尾气一起经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入提升管预处理器3进行循环。5 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast. The separation device, the catalyst preprocessor is arranged coaxially with the reactor. The catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process. After the gas and catalyst are separated from the catalyst by the catalyst rapid separation device 9 at the top of the pretreatment unit 3, the catalyst enters the dense phase region of the reactor 1, and the gas is mixed with the gas in the reactor; the raw material gas enters the reactor 1 through the gas distributor 4. After contacting with the catalyst, the reaction with the exhaust gas of the preconditioner passes through the cyclone 5 and then flows out of the reactor 1; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and the catalyst After contact with the coke in the catalyst, it is passed through the cyclone 7 and then exits the reactor 2; the catalyst to be treated is passed from the catalyst regenerator 2 into the riser preconditioner 3 for circulation.
图6是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用提升管，提升管穿过催化剂床层，提升管顶部设有催化剂快速分离装置，反应器顶部还设有供催化剂预处理器用的旋风分离器，催化剂预处理器与反应器同轴布置。待处理的催化剂由催化剂再生器2进入提升管预处理器3，预处理气体经气体分布器8进入提升管预处理器3，携带待处理的催化剂上升，在上升过程中对催化剂进行预处理，在预处理器3顶部气体和催化剂经催化剂快速分离装置9与催化剂分离后，气体经旋风分离器10后流出预处理器3，催化剂进入反应器1密相区；原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入提升管预处理器3进行循环。6 is a schematic structural view of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a riser, the riser passes through the catalyst bed, and the top of the riser is provided with a catalyst fast. The separation device is further provided with a cyclone for the catalyst pretreatment at the top of the reactor, and the catalyst pretreatment is arranged coaxially with the reactor. The catalyst to be treated enters the riser preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the riser preconditioner 3 through the gas distributor 8, carries the catalyst to be treated up, and pretreats the catalyst during the ascending process. After the gas and catalyst are separated from the catalyst by the catalyst rapid separation device 9 at the top of the pretreatment unit 3, the gas flows out of the pretreatment unit 3 through the cyclone 10, and the catalyst enters the dense phase region of the reactor 1; the raw material gas enters through the gas distributor 4 The reactor 1 is reacted with the catalyst and then flows out of the reactor 1 through the cyclone separator 5; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to be burned off. After the coke in the catalyst, it flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is introduced into the riser preconditioner 3 by the catalyst regenerator 2 for circulation.
图7是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用密相流化床，密相流化床顶部设有旋风分离器，催化剂预处理器与反应器同轴布置。待处理的催化剂由催化剂再生器2进入密相流化床预处理器3，预处理气体经气体分布器8进入密相流化床预处理器3，对待处理的催化剂进行预处理，然后经旋风分离器10流出预处理器3；处理后的催化剂由密相流化床预处理器3进入反应器1，原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入密相流化床预处理器11进行循环。7 is a schematic structural view of another apparatus for preparing a low-carbon olefin using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a dense-phase fluidized bed, and the top of the dense-phase fluidized bed is provided with a cyclone separator. The catalyst preconditioner is arranged coaxially with the reactor. The catalyst to be treated enters the dense phase fluidized bed pretreatment unit 3 from the catalyst regenerator 2, and the pretreatment gas enters the dense phase fluidized bed pretreatment unit 3 through the gas distributor 8 to pretreat the treated catalyst, and then through the cyclone. The separator 10 flows out of the pretreatment unit 3; the treated catalyst enters the reactor 1 from the dense phase fluidized bed pretreatment unit 3, and the raw material gas enters the reactor 1 through the gas distributor 4, and is reacted with the catalyst to pass through the cyclone separator 5. After flowing out of the reactor 1; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2, and the regeneration gas enters the regenerator through the gas distributor 6, and is contacted with the catalyst to burn off the coke in the catalyst, and then flows out through the cyclone 7 The catalyst to be treated is circulated by the catalyst regenerator 2 into the dense phase fluidized bed pretreatment unit 11.
图8是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用移动床，移动床顶部设有旋风分离器，催化剂预处理器与反应器同轴布置。待处理的催化剂由催化剂再生器2进入移动床预处理器3，预处理气体经气体分布器8进入移动床预处理器3，对待处理的催化剂进行预处理，然后经旋风分离器10流出预处理器3；处理后的催化剂由移动床预处理器3进入反应器1，原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；待处理的催化剂由催化剂再生器2进入移动床预处理器14进行循环。Figure 8 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a moving bed, a cyclone separator is arranged on the top of the moving bed, and the catalyst pre-processor and reaction The device is coaxially arranged. The catalyst to be treated enters the moving bed preconditioner 3 from the catalyst regenerator 2, and the pretreatment gas enters the moving bed pretreatment unit 3 through the gas distributor 8, the catalyst to be treated is pretreated, and then pretreated through the cyclone 10 The treated catalyst is introduced into the reactor 1 by the moving bed preconditioner 3, and the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; From the reactor 1 to the catalyst regenerator 2, the regeneration gas enters the regenerator through the gas distributor 6, contacts the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the catalyst to be treated is composed of the catalyst The regenerator 2 enters the moving bed preconditioner 14 for circulation.
图9是本发明提供的又一种采用甲醇或二甲醚制备低碳烯烃的装置的结构示意图，其中催化剂预处理器采用固定床，固定床顶部设有旋风分离器，催化剂预处理器与反应器同轴布置。待处理的催化剂由催化剂再生器2进入固定床预处理器3，将预处理气体通入固定床预处理器3，对待处理的催化剂进行预处理，然后流出预处理器3；处理后的催化剂由预处理器3进入反应器1，原料气经气体分布器4进入反应器1，与催化剂接触反应后经旋风分离器5后流出反应器1；待生催化剂从反应器1送至催化剂再生器2，再生气体经气体分布器6进入再生器，与催化剂接触烧除催化剂中的焦炭后，经旋风分离器7后流出反应器2；固定床预处理器3可由两个或多个固定床组成，各个固定床交替使用可使整个过程循环操作。Figure 9 is a schematic view showing the structure of another apparatus for preparing low-carbon olefins using methanol or dimethyl ether provided by the present invention, wherein the catalyst pre-processor adopts a fixed bed, a cyclone separator is arranged at the top of the fixed bed, and the catalyst pre-processor and reaction The device is coaxially arranged. The catalyst to be treated enters the fixed bed pretreatment unit 3 from the catalyst regenerator 2, the pretreatment gas is passed to the fixed bed pretreatment unit 3, the catalyst to be treated is pretreated, and then flows out of the pretreatment unit 3; The pre-processor 3 enters the reactor 1, and the raw material gas enters the reactor 1 through the gas distributor 4, reacts with the catalyst, passes through the cyclone separator 5, and then flows out of the reactor 1; the catalyst to be produced is sent from the reactor 1 to the catalyst regenerator 2 The regeneration gas enters the regenerator through the gas distributor 6, is contacted with the catalyst to burn off the coke in the catalyst, and then flows out of the reactor 2 through the cyclone 7; the fixed bed preconditioner 3 may be composed of two or more fixed beds. The alternating use of individual fixed beds allows the entire process to be cycled.
实施例1：Example 1:
催化剂预处理：将100 g再生后的SAPO-34催化剂加入内径为50 mm的流化床反应器中，以催化剂的重量为基准计,催化剂初始含碳量为0.1-0.3%，预处理温度为450 ℃，绝对压力为0.15 MPa，先用高纯N2吹扫30 min，氮气流量为60 L/h，再将预处理气从反应器底部加入，预处理气的成分是甲醇，其质量空速为1/h，通入时间持续10 min，再用高纯N2吹扫30 min，以催化剂的重量为基准计,处理后的催化剂含炭量为3.1-3.7%。Catalyst pretreatment: 100 g of regenerated SAPO-34 catalyst was added to an internal diameter of 50 In a fluidized bed reactor of mm, the initial carbon content of the catalyst is 0.1-0.3% based on the weight of the catalyst, the pretreatment temperature is 450 °C, the absolute pressure is 0.15 MPa, and the high purity N2 is first purged 30. Min, the nitrogen flow rate is 60 L / h, and then the pretreatment gas is added from the bottom of the reactor, the composition of the pretreatment gas is methanol, the mass space velocity is 1 / h, the access time lasts 10 min, and then the high purity N2 Purge 30 Min, the treated catalyst has a carbon content of 3.1-3.7% based on the weight of the catalyst.
MTO反应：使用催化剂预处理器所使用的反应器，维持反应温度为500 ℃，绝对压力为0.15 MPa，原料甲醇经预热器气化后通入反应器中，甲醇相对于催化剂的质量空速为3/h，反应器出口产品用冷凝管冷凝，经冷凝后的反应气体用集气瓶进行收集，液体进行在线甲醇浓度分析，反应直至出口液相甲醇质量浓度达到4%时停止反应，取集气瓶中气体用气相色谱进行烃类含量的分析，气相产品中乙烯和丙烯的选择性之和为81.7-82.8%，以催化剂的重量为基准计,使用后的催化剂中焦炭含量为7.2-7.6%。MTO reaction: the reactor used in the catalyst pretreatment was maintained at a reaction temperature of 500 ° C and an absolute pressure of 0.15. MPa, the raw material methanol is vaporized by the preheater and then introduced into the reactor. The mass space velocity of methanol relative to the catalyst is 3/h, the outlet product of the reactor is condensed by a condenser tube, and the condensed reaction gas is carried out with a gas collecting bottle. The liquid is collected for online methanol concentration analysis, and the reaction is stopped until the mass concentration of the liquid phase methanol reaches 4%. The gas in the gas cylinder is analyzed by gas chromatography for gas content, and the selectivity of ethylene and propylene in the gas phase product is selected. The sum is 81.7-82.8%, and the coke content in the catalyst after use is 7.2-7.6% based on the weight of the catalyst.
催化剂再生：使用催化剂预处理器所使用的反应器，维持再生温度为600 ℃，绝对压力为0.15 MPa，使用空气作为再生气体，空气流量为60L/h，通入时间为1h，以催化剂的重量为基准计,再生后的催化剂平均含有0.1-0.3%的焦炭。Catalyst regeneration: The reactor used in the catalyst pretreatment unit was maintained at a regeneration temperature of 600 ° C and an absolute pressure of 0.15. MPa, air is used as the regeneration gas, the air flow rate is 60 L/h, and the introduction time is 1 h. The regenerated catalyst contains 0.1-0.3% of coke on average based on the weight of the catalyst.
实施例2：采用实施例5中的反应装置，催化剂预处理器中预处理气体采用1-丁烯，预处理温度控制在580-600℃，绝对压力为0.14-0.16 MPa，预处理气体质量空速为1.5/h，以催化剂的重量为基准计,提升管出口催化剂中平均焦炭含量为2.1-2.5%；反应器中反应气体采用甲醇，反应温度控制在470-480℃，绝对压力为0.14-0.16 MPa，甲醇质量空速为4/h，以催化剂的重量为基准计,催化剂中平均焦炭含量为7.3-7.8%；催化剂再生器中再生气体采用空气，再生温度控制在650-660℃，绝对压力为0.14-0.16 MPa，以催化剂的重量为基准计,催化剂中平均焦炭含量为0.1-0.3%。在上述操作条件下，反应器出口气相烃类中乙烯与丙烯的选择性之和可达83.2-83.7%。Example 2: Using the reaction apparatus of Example 5, the pretreatment gas in the catalyst pretreatment apparatus is 1-butene, the pretreatment temperature is controlled at 580-600 ° C, and the absolute pressure is 0.14-0.16. MPa, the pretreatment gas mass space velocity is 1.5/h, based on the weight of the catalyst, the average coke content in the riser outlet catalyst is 2.1-2.5%; the reaction gas in the reactor is methanol, and the reaction temperature is controlled at 470-480. °C, absolute pressure is 0.14-0.16 MPa, methanol mass space velocity is 4 / h, based on the weight of the catalyst, the average coke content in the catalyst is 7.3-7.8%; the regeneration gas in the catalyst regenerator uses air, the regeneration temperature is controlled at 650-660 ° C, absolute pressure Is 0.14-0.16 MPa, the average coke content in the catalyst is from 0.1 to 0.3% based on the weight of the catalyst. Under the above operating conditions, the selectivity of ethylene and propylene in the gas phase hydrocarbons at the outlet of the reactor can reach 83.2-83.7%.
实施例3：采用实施例6中的反应装置，催化剂预处理器中预处理气体采用体积含量为50%、50%的丙烯和丙烷混合气体，预处理温度控制在540-560℃，绝对压力为0.14-0.16 MPa，预处理气体质量空速为2/h，以催化剂的重量为基准计,催化剂中平均焦炭含量为3-3.5%；反应器中反应气体采用甲醇，反应温度控制在500-510℃，绝对压力为0.14-0.16 MPa，甲醇质量空速为2/h，以催化剂的重量为基准计,催化剂中平均焦炭含量为7.1-7.6%；催化剂再生器中再生气体采用空气，再生温度控制在650-660℃，绝对压力为0.14-0.16 MPa，以催化剂的重量为基准计,催化剂中平均焦炭含量为0.1-0.3%。在上述操作条件下，反应器出口气相烃类中乙烯与丙烯的选择性之和可达82.3-83.3%。Example 3: Using the reaction apparatus of Example 6, the pretreatment gas in the catalyst pretreatment apparatus is a mixed gas of propylene and propane having a volume content of 50% and 50%, and the pretreatment temperature is controlled at 540-560 ° C, and the absolute pressure is 0.14-0.16 MPa, the pretreatment gas mass space velocity is 2 / h, based on the weight of the catalyst, the average coke content in the catalyst is 3-3.5%; the reaction gas in the reactor is methanol, the reaction temperature is controlled at 500-510 ° C, absolutely The pressure is 0.14-0.16 MPa, methanol mass space velocity is 2 / h, based on the weight of the catalyst, the average coke content in the catalyst is 7.1-7.6%; the regeneration gas in the catalyst regenerator uses air, the regeneration temperature is controlled at 650-660 ° C, absolute pressure Is 0.14-0.16 MPa, the average coke content in the catalyst is from 0.1 to 0.3% based on the weight of the catalyst. Under the above operating conditions, the selectivity of ethylene and propylene in the gas phase hydrocarbons at the outlet of the reactor can reach 82.3-83.3%.
利用本装置可实现甲醇或二甲醚制备低碳烯烃的过程，由于加入催化剂预处理器，反应结果优于现有如CN1166478A所述装置的结果，达到增加乙烯和丙烯的选择性的目的。The process for preparing low-carbon olefins from methanol or dimethyl ether can be realized by using the apparatus. The reaction result is superior to the existing apparatus such as CN1166478A by the addition of the catalyst pre-processor, and the purpose of increasing the selectivity of ethylene and propylene is achieved.

Claims (1)

  1. 1. 一种采用甲醇或二甲醚制备低碳烯烃的装置，该装置包括反应器主体（1），设置在反应器底部的气体分布器（4），设置在反应器顶部的旋风分离器（5），催化剂再生器主体（2），设置在催化剂再生器底部的气体分布器（6），设置在催化剂再生器顶部的旋风分离器（7），所述的反应器主体和催化剂再生器主体并列布置，所述的反应器主体和催化剂再生器主体的底部通过管道连接，其特征在于：该装置还包括催化剂预处理器（3），在所述的催化剂预处理器的底部设有气体进口和气体分布器（8），催化剂预处理器的上部与反应器主体相连接。 1. A device for preparing a low-carbon olefin using methanol or dimethyl ether, the device comprising a reactor body (1), a gas distributor (4) disposed at the bottom of the reactor, and a cyclone separator (5) disposed at the top of the reactor a catalyst regenerator body (2), a gas distributor (6) disposed at the bottom of the catalyst regenerator, a cyclone separator (7) disposed at the top of the catalyst regenerator, the reactor body and the catalyst regenerator body being juxtaposed The reactor body and the bottom of the catalyst regenerator body are connected by a pipe, characterized in that the device further comprises a catalyst pre-processor (3), and a gas inlet and a gas are provided at the bottom of the catalyst pre-processor The distributor (8), the upper portion of the catalyst preconditioner, is connected to the reactor body.
    2. 按照权利要求1所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述的催化剂预处理器采用提升管预处理器，提升管预处理器与反应器主体和再生器并列布置，提升管预处理器的上部与反应器主体的中上部或下部连接。2. The apparatus for preparing a low carbon olefin using methanol or dimethyl ether according to claim 1, wherein said catalyst pretreatment device comprises a riser preconditioner, a riser preconditioner and a reactor main body and a regenerator In a side-by-side arrangement, the upper portion of the riser preconditioner is connected to the upper or lower portion of the reactor body.
    3. 按照权利要求2所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：在所述的提升管预处理器的顶部设有催化剂快速分离装置（9）、旋风分离器（10）和气体出口，所述的催化剂快速分离装置的出口与反应器中上部相连接。3. The apparatus for preparing a low-carbon olefin using methanol or dimethyl ether according to claim 2, characterized in that a catalyst rapid separation device (9) and a cyclone separator are provided on the top of the riser pretreatment device. And a gas outlet, the outlet of the catalyst rapid separation device is connected to the upper portion of the reactor.
    4. 按照权利要求1所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述的催化剂预处理器采用提升管预处理器，所述的提升管预处理器与反应器主体同轴布置，提升管预处理器的顶部与反应器主体的下部连接。4. The apparatus for preparing a low-carbon olefin using methanol or dimethyl ether according to claim 1, wherein said catalyst pretreatment device comprises a riser preprocessor, said riser preprocessor and a reactor main body In a coaxial arrangement, the top of the riser preconditioner is connected to the lower portion of the reactor body.
    5. 按照权利要求4所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：提升管预处理器的上部穿过反应器的密相床层，在提升管预处理器的顶部设有催化剂快速分离装置（9）。5. The apparatus for preparing a low carbon olefin using methanol or dimethyl ether according to claim 4, wherein the upper portion of the riser pretreatment unit passes through the dense phase bed of the reactor, and is disposed on the top of the riser pretreatment unit. There is a catalyst rapid separation device (9).
    6. 按照权利要求5所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述反应器主体的顶部还设有供预处理器用的旋风分离器（10），该催化剂快速分离装置的气体出口与所述的供预处理器用的旋风分离器相连接。6. The apparatus for preparing a low-carbon olefin using methanol or dimethyl ether according to claim 5, characterized in that a cyclone (10) for a pretreatment unit is further provided at the top of the reactor main body, and the catalyst is rapidly separated. The gas outlet of the apparatus is connected to the cyclone for the preconditioner.
    7. 按照权利要求1所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述的催化剂预处理器采用密相流化床预处理器，在所述的密相流化床预处理器顶部设有旋风分离器（10），密相流化床预处理器与反应器主体和催化剂再生器并列布置，密相流化床预处理器的中下部与反应器主体的中上部或下部连接。7. The apparatus for preparing a low carbon olefin using methanol or dimethyl ether according to claim 1, wherein said catalyst pretreatment apparatus employs a dense phase fluidized bed pretreatment apparatus in said dense phase fluidized bed The top of the preprocessor is provided with a cyclone separator (10), and the dense phase fluidized bed pretreatment device is arranged side by side with the reactor main body and the catalyst regenerator, and the middle and lower parts of the dense phase fluidized bed pretreatment unit and the upper middle part of the reactor main body Or the lower part is connected.
    8. 按照权利要求1所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述的催化剂预处理器采用移动床预处理器，在所述的移动床预处理器顶部设有旋风分离器（10），移动床预处理器与反应器主体和催化剂再生器并列布置，移动床预处理器的下部与反应器主体的中上部或下部连接。8. The apparatus for preparing a low carbon olefin using methanol or dimethyl ether according to claim 1, wherein said catalyst pretreatment device is provided with a moving bed pretreatment device at the top of said moving bed pretreatment device. The cyclone separator (10), the moving bed preconditioner is arranged side by side with the reactor body and the catalyst regenerator, and the lower portion of the moving bed preconditioner is connected to the upper middle or lower portion of the reactor body.
    9. 按照权利要求1所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：所述的催化剂预处理器采用固定床预处理器，所述固定床预处理器与反应器主体和催化剂再生器并列布置，固定床预处理器的下部与反应器主体的中上部或下部连接。9. The apparatus for preparing a low carbon olefin using methanol or dimethyl ether according to claim 1, wherein said catalyst pretreatment apparatus employs a fixed bed pretreatment apparatus, said fixed bed pretreatment apparatus and said reactor main body and The catalyst regenerators are arranged side by side, and the lower portion of the fixed bed preconditioner is connected to the upper middle or lower portion of the reactor body.
    10. 按照权利要求1-9任一所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：反应器采用流化床、移动床或固定床反应器，反应器优选采用流化床；催化剂再生器采用流化床、移动床或固定床再生器，再生器优选采用流化床；反应器、催化剂再生器、催化剂预处理器各自采用不同的反应器，或是其中两个或多个采用同一反应器。10. The apparatus for producing a low-carbon olefin using methanol or dimethyl ether according to any one of claims 1 to 9, characterized in that the reactor is a fluidized bed, a moving bed or a fixed bed reactor, and the reactor is preferably a fluidized bed. The catalyst regenerator uses a fluidized bed, a moving bed or a fixed bed regenerator, and the regenerator preferably uses a fluidized bed; the reactor, the catalyst regenerator, and the catalyst pretreatment each use a different reactor, or two or more of them One using the same reactor.
    11．按照权利要求1-9任一所述的采用甲醇或二甲醚制备低碳烯烃的装置，其特征在于：在所述的反应器与催化剂再生器之间还设有汽提器，在所述的汽提器底部设有气体分布器，顶部设有旋风分离器，汽提器与反应器和催化剂再生器的底部通过管路相连接。11. An apparatus for producing a low carbon olefin using methanol or dimethyl ether according to any one of claims 1 to 9, wherein a stripper is further disposed between said reactor and said catalyst regenerator, The bottom of the stripper is provided with a gas distributor, and the top is provided with a cyclone separator, and the stripper is connected to the bottom of the reactor and the catalyst regenerator through a pipeline.
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