CN113509897A - Device of low carbon olefin of high efficiency oxygen compound production - Google Patents

Device of low carbon olefin of high efficiency oxygen compound production Download PDF

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Publication number
CN113509897A
CN113509897A CN202110275974.0A CN202110275974A CN113509897A CN 113509897 A CN113509897 A CN 113509897A CN 202110275974 A CN202110275974 A CN 202110275974A CN 113509897 A CN113509897 A CN 113509897A
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reactor
catalyst
reaction
main reactor
gas
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刘昱
乔立功
施磊
昌国平
张洁
要洁
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Sinopec Luoyang Guangzhou Engineering Co Ltd
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Sinopec Luoyang Petrochemical Engineering Corp
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    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J8/001—Controlling catalytic processes
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a device for producing low-carbon olefin by using an efficient oxygen-containing compound, which belongs to the technical field of petrochemical industry, and is suitable for the characteristics of quick reaction, strong heat release, lower alcohol-to-alcohol ratio, high product selectivity and the like of a process for preparing low-carbon olefin by using the oxygen-containing compound, so that the problem of low-carbon olefin selectivity in the prior art is solved, the advantages of the reaction can be exerted to the greatest extent, and the problem of low-carbon olefin selectivity is improved.

Description

Device of low carbon olefin of high efficiency oxygen compound production
Technical Field
The invention belongs to the technical field of olefin preparation, and particularly relates to a method and a device for producing low-carbon olefin by using an efficient oxygen-containing compound.
Background
Light olefins (ethylene, propylene, butadiene) and light aromatics (benzene, toluene, xylene) are basic feedstocks for petrochemical industry. The traditional preparation route of ethylene and propylene is produced by naphtha cracking, and the disadvantage is that the traditional preparation route is excessively dependent on petroleum. The preparation of low-carbon olefins (MTO for short) such as ethylene and propylene from Methanol is another process route for preparing olefins, and the development of the prior process technology tends To be mature. The industrialization of MTO technology opens up a new process route for producing petrochemical basic raw materials by gasifying coal or natural gas, is favorable for changing the product pattern of the traditional coal chemical industry, and is an effective way for realizing the extension development of the coal chemical industry to the petrochemical industry.
Oxygen-containing organic compounds represented by methanol or dimethyl ether are typical oxygen-containing organic compounds, and are mainly produced from coal-based or natural gas-based synthesis gas. The process for producing low-carbon olefins mainly comprising ethylene and propylene by using oxygen-containing organic compounds represented by methanol as raw materials mainly comprises MTO and MTP technologies at present.
The reaction features fast reaction, strong heat release, low alcohol-to-agent ratio, and reaction and regeneration in continuous reaction-regeneration dense-phase fluidized bed reactor. The high-temperature oil gas which is generated by the reaction and is rich in low-carbon olefins such as ethylene, propylene and the like needs to be quenched and washed by water, the catalyst in the oil gas is removed, the temperature of the oil gas is reduced, and then the oil gas is sent to an olefin separation system for separation. The existing on-stream device for preparing olefin from oxygen-containing compound has the following common problems: the selectivity of olefin is lower than that of the laboratory, and the unit consumption of methanol is increased.
In recent years, methods for improving the selectivity of lower olefins have become a focus and focus of research by those skilled in the art. People have conducted extensive research and exploration in the aspects of process flows, equipment structures and the like.
Chinese patent CN1102317238B discloses a process for converting an oxygenate feedstock to light olefins, and in particular, the invention relates to the conversion of an oxygenate feedstock to a product comprising light olefins in a reaction apparatus using a silicoaluminophosphate catalyst. More specifically, the present invention provides a means by which an optimum coke level can be determined and used to produce an optimum or near-optimum yield of light olefins, such as ethylene and propylene, in an oxygenate to olefin system.
Chinese patent CN1830926A discloses a catalyst cooler for an oxygenate conversion reactor. The invention comprises contacting an oxygenate feed stream with a catalyst in a reactor and converting the oxygenate feed stream to said light olefins. When reaction deposits block pores on the surface of the catalyst, the catalyst fails. A portion of the spent catalyst is regenerated in a regenerator and this portion is recycled back for contact with more oxygenate feed stream. A catalyst cooler coupled to the reactor is capable of cooling the spent catalyst circulated through the cooler before the spent catalyst is contacted with more of the oxygenate feed stream. In one embodiment, all of the spent catalyst entering the catalyst cooler is withdrawn from the bottom of the catalyst cooler.
Chinese patent CN102190548B discloses a method for increasing the yield of low-carbon olefins in a process for preparing olefins from methanol, which mainly comprises the following steps: (1) the method comprises the following steps that a raw material containing methanol enters a first fast fluidized bed reaction zone and contacts with a silicon-aluminum phosphate molecular sieve catalyst to generate a product material flow I containing low-carbon olefin and form an inactivated catalyst; (2) the deactivated catalyst enters a regenerator for regeneration, the regenerated catalyst enters a riser reaction zone and contacts with a raw material containing hydrocarbon with more than four carbon atoms, and the generated product and the catalyst enter a second fast fluidized bed reaction zone and contact with the raw material containing hydrocarbon with more than four carbon atoms and a second catalyst from the regenerator to generate a product material flow II containing low-carbon olefin and form a pre-carbon-deposited catalyst at the same time; (3) the product material flow II is mixed with the product material flow I after gas-solid separation and enters a separation section, and the catalyst of the pre-deposited carbon returns to the first fast bed reaction zone.
Chinese patent CN103073377B discloses a method for preparing low-carbon olefin by catalytic conversion of oxygen-containing compound, introducing oxygen-containing compound raw material into an internal circulation gas-solid fluidized bed reactor from the bottom, contacting with a cracking catalyst in a reaction zone and moving upwards, and carrying out alkylation and cracking reactions; after the reaction, the oil gas and the carbon deposition catalyst are subjected to gas-solid separation through a gas-solid separation zone at the upper part of the reaction zone, and the separated oil gas is further separated in a subsequent separation system; the separated carbon-deposited catalyst is settled in a stripping zone, oil gas adsorbed and carried in the catalyst is stripped, a part of the carbon-deposited catalyst in the stripping zone enters a catalyst descending zone to move downwards, and enters the bottom of a reaction zone through a gap at the bottom of the catalyst descending zone for recycling; the other part of the carbon-deposited catalyst is introduced into a catalyst regenerator through a catalyst inclined tube to be regenerated and burnt for regeneration, and the regenerated catalyst returns to the internal circulation gas-solid fluidized bed reactor for recycling. The reactor provided by the invention can be used for a method for preparing low-carbon olefin by using an oxygen-containing compound, and has the advantages of simple operation and high yield of the low-carbon olefin.
In summary, the reaction characteristics of the process for preparing low-carbon olefin from oxygen-containing compound (methanol is typically adopted at present) are rapid reaction, strong heat release and low alcohol content, and the reaction and the regeneration are carried out in a continuous reaction-regeneration dense-phase fluidized bed reactor. The high-temperature oil gas which is generated by the reaction and is rich in low-carbon olefins such as ethylene, propylene and the like needs to be quenched and washed by water, the catalyst in the high-temperature oil gas is removed, and the high-temperature oil gas is sent to a lower olefin separation system for separation after being cooled. The SAPO catalyst used in the process has high manufacturing cost, the price is 10-30 times that of a common catalytic cracking catalyst, and the abrasion and the running loss of the catalyst are reduced to the maximum extent during engineering design and equipment selection. Aiming at the reaction characteristics of the process, various types of device types are developed, and a representative reactor type comprises a fixed bed, a riser, a fast fluidized bed and the like.
In summary, in the prior art, the olefin selectivity is improved to a certain extent by optimizing the internal structure of the reactor, optimizing the process flow and optimizing the operating conditions, but the problem of low olefin selectivity still exists in the existing on-line device, and the invention specifically solves the problem.
Disclosure of Invention
The invention provides a high-efficiency device for producing low-carbon olefin by using an oxygen-containing compound, which is suitable for the characteristics of rapid reaction, strong heat release, low catalyst-alcohol ratio, high product selectivity and the like of a process for preparing low-carbon olefin by using the oxygen-containing compound, and aims to solve the problem of low-carbon olefin selectivity in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the utility model provides a device of high-efficient oxygen compound production low carbon olefin, mainly includes reactor, regenerator, waits to give birth to stripper and regeneration stripper, its characterized in that: the reactor comprises a main reactor and an auxiliary reactor, the auxiliary reactor and the main reactor are arranged in series, and the main reactor and the auxiliary reactor are communicated through an auxiliary reaction focusing catalyst circulating pipe; the main reactor comprises a reaction zone and a catalyst collecting zone, and the reaction zone of the main reactor is positioned below the catalyst collecting zone; the regenerator is connected with a regenerated catalyst conveying pipe through a regenerated stripper and a regenerated slide valve, and the regenerated catalyst conveying pipe extends into the auxiliary reactor; one end of the spent stripper is communicated with the catalyst collecting region of the main reactor, and the other end of the spent stripper is communicated with the bottom of the regenerator or respectively communicated with the bottom of the regenerator and the reaction region of the main reactor.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the inside of the main reactor is divided into a catalyst collecting region and a main reaction region from top to bottom, the catalyst collecting region and the reaction region of the main reactor are of an integral structure and are separated from the reaction region through a dilute phase pipe, a catalyst fast-separating device is arranged at the top of the dilute phase pipe, and an outlet of the catalyst fast-separating device is connected with an inlet of a gas-solid separation facility of the reactor.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further technically characterized in that: the auxiliary reaction focusing catalyst circulating pipe is a catalyst conveying pipe and is used for supplementing a focusing catalyst for the reaction zone of the main reactor, an inlet of the auxiliary reaction focusing catalyst circulating pipe is connected with the middle part or the lower part of the auxiliary reactor, and an outlet of the auxiliary reaction focusing catalyst circulating pipe is connected with the lower part of the reaction zone of the main reactor and can also be connected to different positions of the lower part of the reaction zone of the main reactor. A slide valve is arranged on the auxiliary reaction catalyst circulating pipe.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the catalyst circulating pipe is arranged between the catalyst collecting area and the main reactor reaction area, the catalyst circulating pipe is a catalyst conveying pipe and is used for controlling the airspeed of the main reactor reaction area so as to adjust the olefin selectivity of the main reactor, the inlet of the catalyst circulating pipe is connected with the lower part of the catalyst collecting area of the main reactor, the outlet of the catalyst circulating pipe is connected with the middle part and the lower part of the reaction area of the main reactor, and the catalyst circulating pipe is provided with a slide valve. The catalyst circulating pipe can also be an internal circulating pipe, the internal circulating pipe is arranged in the middle of the reaction zone of the main reactor and is coaxially arranged with the internal circulating pipe, the inlet is connected with the catalyst collecting zone of the main reactor, the outlet is connected with the bottom of the reaction zone of the main reactor, and the catalyst circulating pipe is provided with a plug valve and is positioned at the bottom of the reaction zone of the main reactor. The catalyst circulating pipe can be one or more.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: one end of the spent stripper is communicated with the lower part of the catalyst collecting region of the main reactor through a spent agent inlet pipe, and the other end of the spent stripper is communicated with the regenerator through a spent agent conveying pipe; or the other end is respectively communicated with the bottom of the reaction zone of the regenerator and the main reactor through a spent agent conveying pipe. A slide valve is arranged on the spent agent conveying pipe.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the spent stripper is internally provided with a stripping grating or a stripping baffle and a stripping medium distributor.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the catalyst collecting area of the main reactor is provided with a catalyst fast separation device and a reactor gas-solid separation facility, the top of the catalyst collecting area is provided with an oil-gas collecting chamber, and oil gas is introduced into the oil-gas collecting chamber. The catalyst quick separation device can be selected from one of an umbrella cap type, an inverted L type, a T type, a three-blade type and a coarse cyclone, and can also be connected with a primary cyclone separator of a reactor gas-solid separation facility. The reactor gas-solid separation facility is a one-stage or/and two-stage cyclone separator, and the one-stage or/and two-stage cyclone separator is introduced into the oil gas collection chamber.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the auxiliary reactor is internally provided with a gas-solid separation facility, the top of the auxiliary reactor is provided with an oil gas collection chamber, and oil gas is introduced into the oil gas collection chamber. The auxiliary reactor gas-solid separation facility is a one-stage or/and two-stage cyclone separator, and the one-stage or/and two-stage cyclone separator is introduced into the oil gas collection chamber.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the main reactor is provided with an internal and/or external heat-taking facility, and the internal heat-taking facility is arranged in a reaction zone of the high-efficiency main reactor and above a reaction zone feeding distributor. The internal heat taking and heat taking medium can be one or more of an oxygen-containing compound raw material, light hydrocarbon, water, an inert medium and heat conducting oil, preferably the light hydrocarbon and the oxygen-containing compound raw material are used as the heat taking medium, and the oxygen-containing compound raw material is preferably a liquid-phase raw material, wherein the temperature can be within the range of 25-200 ℃, preferably within the range of 25-150 ℃; the heat-taking medium of the external heat-taking facility is preferably deoxygenated water so as to generate steam with different grades.
The invention relates to a device for producing low-carbon olefin by using oxygen-containing compounds, which is further technically characterized in that: one or more feed distributors are arranged at the lower part of the reaction zone of the main reactor, and the raw materials of the main reactor can be injected into the lower part of the reaction zone of the main reactor in one or more strands. The reaction zone of the main reactor can be an oxygen-containing compound or a mixture of oxygen-containing compound and light hydrocarbon gas, preferably oxygen-containing compound.
The invention relates to a device for producing low-carbon olefin by using oxygen-containing compounds, which is further technically characterized in that: one or more feed distributors are arranged at the lower part of the auxiliary reactor, and the auxiliary reactor raw materials can be injected into the lower part of the auxiliary reactor in one or more strands. Light hydrocarbon gas (or a mixture of light hydrocarbon gas and an oxygen-containing compound, preferably light hydrocarbon gas) may be introduced into the auxiliary reactor.
The oxygen-containing compound is methanol or diThe oxygen-containing compound mainly comprises dimethyl ether, and the light hydrocarbon gas is C4～C10A gas.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the feeding distributor is positioned at the lower parts of the reaction zone of the main reactor and the auxiliary reactor and is a distribution pipe or a distribution plate, preferably a distribution pipe.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the regenerated catalyst transfer line may be used as a riser reactor. When light hydrocarbon gas (C) is recycled4～C10) In the process, the regenerated catalyst conveying pipe can be used as a riser reactor, and light hydrocarbon gas (C) is preferably fed into the riser reactor4～C10) Light hydrocarbon gas (C)4～C10) Can be injected into the upper, middle or lower part of the riser reactor in one or more portions. When light hydrocarbon gas (C) is not recycled4～C10) In this case, the regenerated catalyst transfer line may be used to transfer the regenerated catalyst, and the transfer medium is preferably steam.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the main reactor and the auxiliary reactor are both fluidized bed reactors. The secondary reactor is preferably a turbulent bed reactor, and the primary reactor may be a fast bed reactor or a turbulent bed reactor.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: a third cyclone is arranged outside or inside the main reactor, preferably outside. The reactor is coaxial with the main reactor when being arranged inside the main reactor; the reactor three-stage cyclone separator can be vertical or horizontal, and is preferably horizontal.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: a reactor fourth-stage cyclone separator is arranged outside the reactor, one end of the reactor fourth-stage cyclone separator is communicated with the reactor third-stage cyclone separator, and the other end of the reactor fourth-stage cyclone separator is communicated with a reactor third-stage recovery catalyst storage tank.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the regenerator is a fluidized bed regenerator. The regenerator is internally divided into a regenerator dilute phase section, a regenerator transition section and a regenerator coking section. The regenerator char section may be a turbulent bed or a fast bed or a combination of both.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the dilute phase section of the regenerator is provided with a gas-solid separation facility, the top of the dilute phase section is provided with a flue gas outlet, the regeneration and burning section is provided with a main air distributor, and the bottom of the regenerator is provided with a main air inlet. The main wind distributor can be a distribution pipe and/or a distribution plate, and is preferably a distribution pipe. Not only the main wind is evenly distributed and is wear-resistant, but also the service life is long.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the gas-solid separation device in the regenerator is preferably a cyclone separator, and the cyclone separator is 1-3 grade.
The regeneration mode of the catalyst in the regenerator can adopt incomplete regeneration or complete regeneration, and preferably adopts incomplete regeneration.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: an internal heat extraction facility and/or an external heat extraction facility are/is arranged in the regenerator.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the regenerated stripper has the double functions of stripping and cooling the regenerated catalyst, and is internally provided with a stripping grating or a stripping baffle, a stripping medium distributor and a heat extraction tube bundle.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: an external heat-taking device is arranged in the regenerator, and the external heat-taking device can be selected from one of an up-flow type, a down-flow type and a back-mixing type according to the flowing state and the flowing mode of the catalyst, and is preferably a back-mixing type external heat-taking device. The heat-taking medium is preferably deoxygenated water to generate different grades of steam.
The invention relates to a high-efficiency device for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized in that: the reactor is a multi-stage series reactor and comprises a main reactor and an auxiliary reactor, and the reactor can be a fast bed reactor or a turbulent bed. Raw materials are respectively fed into each reactor according to the reaction requirements, and light hydrocarbon gas (C) can be fed into auxiliary reactor4～C10) And oxygen-containing compounds such as methanol and dimethyl ether, or a mixture of both. Preference for light hydrocarbon gases (C)4～C10). The gas (C) can also be oxygen-containing compounds such as methanol, dimethyl ether and the like and light hydrocarbon gas4～C10) Or a mixture of both. Oxygen-containing compounds are preferred.
The invention relates to a high-efficiency device for producing low-carbon olefin by using an oxygen-containing compound, which better solves the problem of low selectivity of the low-carbon olefin in the prior art, exerts the advantages of each reactor to the greatest extent, improves the selectivity of the low-carbon olefin selectivity, and can be used in the industrial production of producing liquid products by using the oxygen-containing compound, such as: MTO technology (methanol to olefin technology), MTP technology (methanol to propylene technology), MTA technology (methanol to aromatics technology), MTG technology (methanol to gasoline technology) and the like. In addition, the equipment has the advantages of simple structure, easy realization, wide application range, low equipment investment and the like, and can be widely applied to devices for preparing low-carbon olefin products by converting oxygen-containing compounds.
Compared with the prior art, the invention has the advantages that:
1) the device provided by the invention can improve the linear speed of the reactor, reduce the diameter of the reactor and improve the treatment capacity of the device.
2) By adopting the device provided by the invention, the reactors are serial reactors, and the characteristics of different reactors can be utilized to efficiently improve the selectivity of target products, such as the selectivity and yield of low-carbon olefin products; by arranging the auxiliary reactor, the coke regulation and control technology of the catalyst is adopted to carry out coke regulation and control on the regenerated catalyst, the coke composition, the coke content and the coke distribution contained in the catalyst entering the main reactor are controlled, the selectivity of ethylene and propylene is improved, the side reaction is reduced, and the yield of ethylene and propylene is increased. And simultaneously, the temperature of the catalyst entering the main reactor is reduced. The cracking reaction of the auxiliary reactor is an endothermic reaction, so that the contact temperature of reaction oil gas and a high-temperature regenerated catalyst in the main reactor is reduced, the occurrence of non-target reactions is reduced, and the selectivity of low-carbon olefin is improved; the focusing catalyst continuously performs exothermic reaction with the oxygen-containing compound, reduces the influence of an induction period on the reaction, and is favorable for improving the selectivity of the low-carbon olefin. The yield of ethylene and propylene can be increased simultaneously through the cracking reaction of light hydrocarbon gas.
3) By adopting the device provided by the invention, the characteristics of strong heat release of the conversion of the oxygen-containing compound into the olefin and strong heat absorption of the conversion reaction of the light hydrocarbon gas are utilized, the light hydrocarbon gas reaction is carried out in a high-temperature area, the conversion requirement of the reaction is met, the heat coupling can be realized, and the mutual connection complete system is formed by coupling.
4) By adopting the device provided by the invention, the same catalyst is adopted in the reactions of strong heat release of the oxygen-containing compound converted olefin and light hydrocarbon gas conversion, and the mixing caused by using different catalysts is avoided; both the two are carried out in different reactors in a fluidized reaction mode, so that the advantages of respective reactions are exerted to the maximum extent, and the selectivity of target products is improved; the products are distributed similarly and can share a set of separation system.
The invention is further described with reference to the following figures and detailed description. But not to limit the scope of the invention.
Drawings
FIG. 1 is a schematic diagram of an efficient oxygenate to light olefins plant according to the present invention;
FIG. 2 is a schematic diagram of another efficient oxygenate to lower olefins plant of the present invention.
The reference symbols shown in the figures are: 1-regenerated catalyst conveying pipe, 2-light hydrocarbon gas, 3-oxygen-containing compound mainly containing methanol or dimethyl ether, 4-feeding distributor II, 5-spent slide valve I, 6-heat taking facility in main reactor, 7-reactor main reaction area, 8-auxiliary reaction focusing catalyst circulating pipe, 9-feeding distributor I, 10-auxiliary reactor, 11-auxiliary reactor gas-solid separation facility, 12-catalyst fast separation device, 13-main reactor catalyst collecting area, 14-reaction oil gas I, 15-waste catalyst, 16-reactor three-rotation recovery catalyst storage tank, 17-reactor four-stage cyclone separator, 18-reactor four-stage cyclone separator outlet gas, 19-reactor three-stage cyclone separator, 20-outlet gas of a reactor three-stage cyclone separator, 21-oil gas collection chamber (I), 22-main reactor gas-solid separation facility, 23-main reactor, 24-dilute phase tube, 25-spent agent inlet tube (I), 26-catalyst circulation tube, 27-inlet of main reactor external heat remover, 28-spent circulation slide valve/plug valve, 29-main reactor external heat remover, 30-spent slide valve (II), 31-spent agent delivery tube (I), 32-spent stripper, 33-regenerator internal heat removal facility, 34-regenerator scorching section, 35-flue gas, 36-flue gas collection chamber, 37-regenerator gas-solid separation facility, 38-regenerator, 39-regenerator dilute phase section, 40-regenerator transition section, 41-outlet of regenerator external heat remover, 42-external regenerator of regenerator, 43-main wind, 44-main wind distributor, 45-regenerative stripper, 46-regenerative slide valve, 47-conveying gas or raw material, 48-spent agent inlet pipe (II), 49-spent agent conveying pipe (II), 50-reaction external heat-extraction slide valve, 51-spent agent conveying pipe (III), 52-spent slide valve (III), 53-reaction oil gas (II) and 57-oil gas collection chamber (II).
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which do not limit the scope of the invention as claimed.
As shown in the attached figure 1, the device for producing the low-carbon olefin by the high-efficiency oxygen-containing compound comprises a reactor 23, an auxiliary reactor 10, a regenerator 38, a reactor three-stage cyclone separator 19, a reactor four-stage cyclone separator 17, a reactor three-cyclone recovered catalyst storage tank 16, a spent stripper 32, a regenerative stripper 45, a main reactor external heat remover 29 and a regenerator external heat remover 42. The primary reactor 23 comprises a reaction zone 7 and a catalyst collection zone 13, the primary reactor reaction zone 7 being located below the catalyst collection zone 13. The main reactor reaction zone 7 is connected with the catalyst collecting zone 13 through a dilute phase pipe 24, the top of the dilute phase pipe 24 is provided with a catalyst fast separation device 12, the outlet of the catalyst fast separation device 12 is connected with a reactor gas-solid separation facility 22. The catalyst collecting zone 13 is communicated with the main reactor reaction zone 7 through a catalyst circulating pipe 26; the main reactor reaction zone 7 is communicated with the lower part of the auxiliary reactor 10 through an auxiliary reaction catalyst circulating pipe 8; the main reactor 23 is communicated with a spent stripper 32, a main reactor external heat remover 29 and a reactor tertiary cyclone separator 19; the main reactor 23 is provided with a main reactor external heat extractor 29, is connected with the reactor catalyst collecting zone 13 through a spent agent inlet pipe (II) 48, and is connected with the main reactor reaction zone 7 through a spent agent conveying pipe (II) 49. The regenerator 38 is connected with a regenerative stripper 45, an external regenerator 42 and a spent agent conveying pipe (I) 31. The regenerator 38 is provided with an external regenerator heater 42, and is connected to the regenerator 38 through an external regenerator heat inlet 41.
The bottom of the auxiliary reactor 10 is provided with a first feeding distributor 9, the bottom of the main reactor reaction zone 7 is provided with a second feeding distributor 4, and raw material feeding is introduced into the first feeding distributor 9 or the second feeding distributor 4 for distribution.
One end of the spent stripper 32 is communicated with the bottom of the catalyst collecting zone 13 of the reactor through a spent agent inlet pipe (I) 25, and the other end is communicated with the regenerator 38 through a spent agent conveying pipe (I) 31; the catalyst fast separation device 12 and the main reactor gas-solid separation facility 22 are arranged in the main reactor 23. A regenerator gas-solid separation facility 37 is disposed within the regenerator 38. The regenerator 38 is provided with a regenerator inner heat-taking facility 33 and a regenerator outer heat-taking facility 42; the main reactor 23 is provided with internal and external heat extraction means, preferably internal heat extraction means 6 in the main reactor reaction zone 7.
An auxiliary reaction catalyst circulating pipe 8 is arranged between the main reactor reaction zone 7 and the lower part of the auxiliary reactor 10, the inlet of the auxiliary reaction catalyst circulating pipe 8 is connected with the middle and lower parts of the auxiliary reactor 10, the outlet is connected with the lower part of the main reactor reaction zone 7, and the auxiliary reaction catalyst circulating pipe can also be connected to different positions of the main reactor reaction zone 7. A spent slide valve (I) 5 is arranged on the auxiliary reaction focusing catalyst circulating pipe 8.
A catalyst circulation pipe 26 is provided between the main reactor reaction zone 7 and the catalyst collection zone 13. When the catalyst circulation pipe 26 is an external circulation pipe, the inlet of the external circulation pipe is connected to the middle and lower portions of the reactor catalyst collecting zone 13, and the outlet thereof is connected to the main reactor reaction zone 7. A spent cycle slide/plug valve 28 is provided on the catalyst circulation pipe 26. When the catalyst circulation pipe 26 is an internal circulation pipe, the internal circulation pipe is arranged in the middle of the main reactor 23 and is coaxially arranged with the internal circulation pipe, the inlet is connected with the catalyst collection area 13 of the main reactor, and the outlet is connected with the bottom of the reaction area 7 of the main reactor. A spent cycle slide/plug valve 28 is provided on the catalyst recycle line 26 at the bottom of the main reactor reaction zone 7. The catalyst circulation pipe 26 may be one or more.
The interior of the main reactor 23 is divided into a catalyst collecting zone 13 and a reaction zone 7 from the top to the bottom. The top of the main reactor 23 is provided with an oil gas collection chamber (I) 21, the reaction oil gas (I) 14 and the catalyst are primarily separated at the outlet of the dilute phase pipe 24 through the catalyst fast separation device 12, and are further separated through a main reactor gas-solid separation facility 22 and then are introduced into the oil gas collection chamber (I) 21. The regenerator 38 is internally divided into a regenerator dilute phase section 39, a regenerator transition section 40, and a regenerator char section 34. The regenerator char section 34 may be a turbulent bed or a fast bed or a combination of both. The regenerator dilute phase section 39 is provided with a regenerator gas-solid separation facility 37, the top of the regenerator dilute phase section is provided with a flue gas 35 outlet, the regeneration burning section 34 is provided with a main air distributor 44, and the bottom of the regenerator is provided with a main air 43 inlet.
Light hydrocarbon gas (C4-C10) 2 reaction raw materials enter a first feeding distributor 9 at the bottom of an auxiliary reactor 10 after being preheated, the light hydrocarbon gas (C4-C10) 2 in the auxiliary reactor 10 directly contacts with a high-temperature catalyst from a regenerator 38, coking regulation and control reaction is rapidly carried out under the action of the catalyst, reaction products are separated from reaction oil gas (II) 53 through an auxiliary reactor gas-solid separation facility 11, the reaction products are discharged from the top of the auxiliary reactor 10 through an oil gas collection chamber (II) 57, and the reacted focusing catalyst is conveyed to a reaction zone 7 of a main reactor through an auxiliary reaction focusing catalyst circulation pipe 8. Preheating an oxygen-containing compound 3 mainly containing methanol or dimethyl ether, then entering a second feeding distributor 4 in a main reactor reaction zone 7, reacting the oxygen-containing compound in the main reactor reaction zone 7 with a spent catalyst from an auxiliary reactor 10, and rapidly reacting under the action of the catalyst; the reaction product is separated from the reaction oil gas by a catalyst fast separation device 12, most of the carried catalyst is removed by a gas-solid separation facility 22 of the main reactor, and then is combined with the reaction oil gas (II) 53 of the auxiliary reactor 10, and the entrained catalyst is removed by a reactor three-stage cyclone separator 19 and a reactor four-stage cyclone separator 17 and then is led out; the outlet gas 18 of the reactor fourth-stage cyclone separator and the outlet gas 20 of the reactor third-stage cyclone separator are combined together, and are sent to a rear quenching and water washing system after heat exchange. The primary reactor gas-solid separation means 22 is a cyclone. The catalyst recovered by the reactor three-stage cyclone separator 19 and the reactor four-stage cyclone separator 17 enters a reactor three-stage recovery waste catalyst storage tank 16, and the waste catalyst 15 enters a waste catalyst tank 16 through a discharging pipeline.
The spent catalyst which loses activity after reaction enters a spent stripper 32 for stripping, and a stripping grid or a stripping baffle plate and a stripping medium distributor are arranged in the spent stripper 32. The device is used for stripping reaction gas carried by spent catalyst, and the stripped spent catalyst enters a regenerator 38 through a spent agent conveying pipe (I) 31; the spent agent delivery pipe (I) 31 is provided with a spent sliding valve (II) 30, and the spent agent delivery pipe (III) 51 is provided with a spent sliding valve (III) 52 which are respectively used for controlling the circulation amount of the catalyst. After the spent catalyst is in countercurrent contact with the main air 43 in the regenerator 38 for burning, the regenerated catalyst is stripped by the regeneration stripper 45 for stripping the flue gas carried by the regenerated catalyst, and the stripped regenerated catalyst enters the reactor auxiliary reactor 10 through the regenerated catalyst conveying pipe 1 and enters the light hydrocarbon gas 2 distributed in the feeding distributor I9 for focusing reaction. The regenerated flue gas 35 is discharged from the top of the regenerator through a flue gas collection chamber 36 after most of the carried catalyst is removed by a regenerator gas-solid separation facility 37, and is sent to a waste heat boiler to recover heat after passing through a pressure reducing valve (if needed), a double-acting slide valve and a pressure reducing pore plate, and then is discharged to the atmosphere through a chimney.
According to the reaction requirement, the raw materials enter each reactor respectively, and the raw materials enter the auxiliary reactor 10 and can be light hydrocarbon gas (C4-C10), oxygen-containing compounds such as methanol, dimethyl ether and the like, or a mixture of the two. Light hydrocarbon gas (C4-C10) 2 is preferred. The gas entering the main reactor reaction zone 7 can also be oxygen-containing compounds such as methanol, dimethyl ether and the like, light hydrocarbon gas (C4-C10) or a mixture of the two. The oxygen-containing compound 3 is preferably recommended.
The regenerated catalyst conveying pipe 1 can also be used as a riser reactor, light hydrocarbon gas (C4-C10) 2 can enter the riser reactor, the injection position of the light hydrocarbon gas (C4-C10) 2 can be arranged on a raw material feeding pipe, and the light hydrocarbon gas and the oxygen-containing compound are mixed and then enter an auxiliary reactor 10 or a main reactor reaction zone 7 together; or can be arranged at the upper part, the middle part or/and the lower part of the riser reactor and can be divided into one or more strands of light hydrocarbon gas (C4-C10) 2. When the light hydrocarbon gas (C4-C10) 2 is not recycled in the regenerated catalyst conveying pipe 1, the regenerated catalyst conveying pipe is used for conveying the regenerated catalyst, and the conveying gas or medium 47 is preferably steam.
The difference between the attached drawings 2 and 1 is that one end of a spent stripper 32 is communicated with the bottom of a catalyst collecting zone 13 of the reactor through a spent agent inlet pipe (I) 25, the other end is divided into two parts, one part enters a regenerator 38 through a spent agent conveying pipe (I) 31, the other part enters a reaction zone 7 of the main reactor through a spent agent conveying pipe (III) 51, and the rest parts are the same.

Claims (19)

1. The utility model provides a device of high-efficient oxygen compound production low carbon olefin, mainly includes reactor, regenerator, waits to give birth to stripper and regeneration stripper, its characterized in that: the reactor comprises a main reactor and an auxiliary reactor, the auxiliary reactor and the main reactor are arranged in series, and the main reactor and the auxiliary reactor are communicated through an auxiliary reaction focusing catalyst circulating pipe; the main reactor comprises a reaction zone and a catalyst collecting zone, and the reaction zone of the main reactor is positioned below the catalyst collecting zone; the regenerator is connected with a regenerated catalyst conveying pipe through a regenerated stripper and a regenerated slide valve, and the regenerated catalyst conveying pipe extends into the auxiliary reactor; one end of the spent stripper is communicated with the catalyst collecting region of the main reactor, and the other end of the spent stripper is communicated with the bottom of the regenerator or respectively communicated with the bottom of the regenerator and the reaction region of the main reactor.
2. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the inside of the main reactor is divided into a catalyst collecting region and a main reaction region from top to bottom, the catalyst collecting region and the reaction region of the main reactor are of an integral structure and are separated from the reaction region through a dilute phase pipe, a catalyst fast-separating device is arranged at the top of the dilute phase pipe, and an outlet of the catalyst fast-separating device is connected with an inlet of a gas-solid separation facility of the reactor.
3. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the auxiliary reaction focusing catalyst circulating pipe is a catalyst conveying pipe and is used for supplementing a focusing catalyst for the reaction zone of the main reactor, an inlet of the auxiliary reaction focusing catalyst circulating pipe is connected with the middle part or the lower part of the auxiliary reactor, an outlet of the auxiliary reaction focusing catalyst circulating pipe is connected with the lower part of the reaction zone of the main reactor, and a slide valve is arranged on the auxiliary reaction focusing catalyst circulating pipe.
4. The apparatus for producing light olefins from high efficiency oxygenates according to claim 2, characterized in that: the catalyst circulating pipe is arranged between the catalyst collecting area and the main reactor reaction area, the catalyst circulating pipe is a catalyst conveying pipe and is used for controlling the airspeed of the main reactor reaction area so as to adjust the olefin selectivity of the main reactor, the inlet of the catalyst circulating pipe is connected with the lower part of the catalyst collecting area of the main reactor, the outlet of the catalyst circulating pipe is connected with the middle part and the lower part of the reaction area of the main reactor, and the catalyst circulating pipe is provided with a slide valve.
5. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: one end of the spent stripper is communicated with the lower part of the catalyst collecting region of the main reactor through a spent agent inlet pipe, and the other end of the spent stripper is communicated with the regenerator through a spent agent conveying pipe; or the other end is respectively communicated with the bottom of the reaction zone of the regenerator and the main reactor through a spent agent conveying pipe; a slide valve is arranged on the spent agent conveying pipe.
6. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: a stripping grating or a stripping baffle plate and a stripping medium distributor are arranged in the spent stripper.
7. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the catalyst collecting area of the main reactor is provided with a catalyst fast separation device and a reactor gas-solid separation facility, the top of the catalyst collecting area is provided with an oil-gas collecting chamber, and oil gas is introduced into the oil-gas collecting chamber; the reactor gas-solid separation facility is a one-stage or/and two-stage cyclone separator, and the one-stage or/and two-stage cyclone separator is introduced into the oil gas collection chamber.
8. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: a gas-solid separation facility is arranged in the auxiliary reactor, an oil-gas collection chamber is arranged at the top of the auxiliary reactor, and oil gas is introduced into the oil-gas collection chamber; the auxiliary reactor gas-solid separation facility is a one-stage or/and two-stage cyclone separator, and the one-stage or/and two-stage cyclone separator is introduced into the oil gas collection chamber.
9. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the main reactor is provided with an internal and/or external heat-taking facility, and the internal heat-taking facility is arranged in a reaction zone of the high-efficiency main reactor and above a reaction zone feeding distributor.
10. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: one or more feed distributors are arranged at the lower part of the reaction zone of the main reactor, and the raw materials of the main reactor can be injected into the lower part of the reaction zone of the main reactor in one or more strands.
11. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: one or more feed distributors are arranged at the lower part of the auxiliary reactor, and the auxiliary reactor raw materials can be injected into the lower part of the auxiliary reactor in one or more strands.
12. The apparatus for producing light olefins from high efficiency oxygenates according to claim 10 or 11, characterized in that: the feeding distributor is a distribution pipe or a distribution plate.
13. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the raw material entering the reaction zone of the main reactor is oxygen-containing compound or a mixture of oxygen-containing compound and light hydrocarbon gas; the raw material entering the auxiliary reactor is light hydrocarbon gas or a mixture of light hydrocarbon gas and oxygen-containing compounds.
14. The apparatus for producing light olefins from high efficiency oxygenates according to claim 13, characterized in that: the oxygen-containing compound is an oxygen-containing compound mainly comprising methanol or dimethyl ether, and the light hydrocarbon gas is C4～C10A gas.
15. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the main reactor and the auxiliary reactor are both fluidized bed reactors.
16. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: when light hydrocarbon gas (C) is recycled4～C10) When the regenerated catalyst conveying pipe is used as a riser reactor, the feeding of the riser reactor is light hydrocarbon gas (C)4～C10) Light hydrocarbon gas (C)4～C10) One or more streams are injected into the upper, middle or lower portion of the riser reactor.
17. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the regenerator is a fluidized bed regenerator. The regenerator is internally divided into a regenerator dilute phase section, a regenerator transition section and a regenerator coking section.
18. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: an internal heat extraction facility and/or an external heat extraction facility are/is arranged in the regenerator.
19. The apparatus for producing light olefins from high efficiency oxygenates according to claim 1, characterized in that: the regeneration stripper is internally provided with a stripping grating or a stripping baffle, a stripping medium distributor and a heat extraction tube bundle.
CN202110275974.0A 2021-03-15 2021-03-15 Device of low carbon olefin of high efficiency oxygen compound production Pending CN113509897A (en)

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EP2143700A1 (en) * 2008-06-25 2010-01-13 Total Petrochemicals Research Feluy Process to make olefins from oxygenates
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CN110117214A (en) * 2019-05-29 2019-08-13 正大能源材料(大连)有限公司 A kind of device and method of methanol Efficient Conversion producing light olefins
CN110818521A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin by using oxygen-containing compound
CN111807916A (en) * 2020-07-10 2020-10-23 中石化洛阳工程有限公司 Device of low carbon olefin of high efficiency oxygen compound production

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2143700A1 (en) * 2008-06-25 2010-01-13 Total Petrochemicals Research Feluy Process to make olefins from oxygenates
CN102076638A (en) * 2008-06-25 2011-05-25 道达尔石油化学产品研究弗吕公司 Process to make olefins from organics
CN104582842A (en) * 2012-07-03 2015-04-29 国际壳牌研究有限公司 Process for preparing ethylene and/or propylene
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CN110818521A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin by using oxygen-containing compound
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