CN113509893A - Method for producing low-carbon olefin by using efficient oxygen-containing compound - Google Patents

Method for producing low-carbon olefin by using efficient oxygen-containing compound Download PDF

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CN113509893A
CN113509893A CN202110274830.3A CN202110274830A CN113509893A CN 113509893 A CN113509893 A CN 113509893A CN 202110274830 A CN202110274830 A CN 202110274830A CN 113509893 A CN113509893 A CN 113509893A
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catalyst
reactor
reaction
containing compound
main reactor
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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
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • 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
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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

Abstract

The invention discloses a method for producing low-carbon olefin by high-efficiency oxygen-containing compounds in the technical field of petrochemical industry, wherein reaction raw materials are preheated by an auxiliary reactor which is arranged in series with a main reactor, and then directly contact with a high-temperature catalyst from a regenerator through the auxiliary reactor to rapidly react under the action of the catalyst; the method 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 the low-carbon olefin from the oxygen-containing compound, and aims to solve the problems of low-carbon olefin selectivity, furthest exert the advantages of the reaction and improve the low-carbon olefin selectivity in the prior art.

Description

Method for producing low-carbon olefin by using efficient oxygen-containing compound
Technical Field
The invention belongs to the technical field of olefin preparation, and particularly relates to a high-efficiency method for producing low-carbon olefin by using an 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 relates to a process for converting a feedstock comprising oxygenates to a product comprising light olefins. 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.
The invention discloses a method for improving the yield of low-carbon olefin in a process for preparing olefin from methanol, which relates to a method for improving the yield of low-carbon olefin in a process for preparing olefin from methanol, and mainly solves the problem of low yield of low-carbon olefin in the prior art. The invention adopts a method for improving the yield of low-carbon olefin in a process for preparing olefin 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, a method for generating 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 reaction; 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 method for producing low-carbon olefin by using an oxygen-containing compound, which is suitable for the characteristics of rapid reaction, strong heat release, low alcohol-solvent 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 method for producing the low-carbon olefin by the high-efficiency oxygen-containing compound is characterized by comprising the following steps of:
1) the reaction raw material of the auxiliary reactor is preheated by the main reactor which is arranged in series with the auxiliary reactor, enters the bottom of the auxiliary reactor to directly contact with the high-temperature catalyst from the regenerator, and quickly carries out coking regulation and control reaction under the action of the catalyst, the reaction product is led out from the top of the auxiliary reactor after the catalyst and reaction oil gas are separated by a gas-solid separation facility, and the focusing catalyst after the reaction is sent to the main reactor through an auxiliary reaction catalyst circulating pipe;
2) preheating reaction raw materials of the main reactor, then entering the main reactor to react with a focusing catalyst from the auxiliary reactor, leading out a reaction product of the main reactor from the top of the main reactor, and combining the reaction product with the reaction product led out from the top of the auxiliary reactor in the step 1);
3) the spent catalyst after the reaction of the main reactor is collected in the catalyst collecting area, and the catalyst is supplemented for the reaction area of the main reactor through a catalyst circulating pipe, so that the space velocity of the reaction area of the main reactor is controlled, and the aim of adjusting the olefin selectivity of the main reactor is fulfilled;
4) the spent catalyst which loses activity after reaction enters a spent stripper from a catalyst collecting region for steam stripping and then enters a regenerator through a spent conveying pipe; or one part enters the regenerator through the spent conveying pipe, and the other part enters the reaction zone of the main reactor;
5) after the catalyst to be regenerated is burnt in the regenerator, the regenerated catalyst is stripped by the regenerated stripper, and the stripped regenerated catalyst enters the auxiliary reactor through the regenerated catalyst conveying pipe.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the auxiliary reactor is connected with the main reactor in series, and the main reactor is communicated with the auxiliary reactor through an auxiliary reaction catalyst circulating pipe; catalyst circulating pipes are arranged between the reaction zone and the catalyst collecting zone of the main reactor, and a slide valve or a plug valve is arranged on each circulating pipe to control the circulating amount of the catalyst.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the catalyst collecting region and the reaction region of the main reactor are of an integral structure, the reaction region is arranged below the catalyst collecting region and separated from the catalyst collecting 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 method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: and 2) leading out a reaction product of the main reactor from the top of the main reactor after removing most of carried catalyst by a catalyst quick separation device and a 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 method for producing low-carbon olefin by using oxygen-containing compounds, which is further characterized by comprising the following steps: and 2) removing the entrained catalyst from the reaction product in the step 2) through a reactor three-stage cyclone separator and a reactor four-stage cyclone separator, leading out, and sending to a rear quenching and water washing system after heat exchange. The catalyst recovered by the reactor three-stage cyclone separator and the reactor four-stage cyclone separator enters a waste reactor three-cyclone recovery catalyst storage tank, and the waste catalyst is sent to a waste catalyst tank through a discharging agent pipeline.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: raw materials are adopted to respectively enter each reactor according to reaction requirements, and light hydrocarbon gas or a mixture of the light hydrocarbon gas and an oxygen-containing compound can enter the auxiliary reactor, preferably the light hydrocarbon gas. The main reactor may also be an oxygenate or a mixture of oxygenates and light hydrocarbon gases, preferably oxygenates.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the oxygen-containing compound is an oxygen-containing compound mainly comprising methanol or dimethyl ether, and the light hydrocarbon gas is C4～C10A gas.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the main reactor and the auxiliary reactor are both fluidized bed reactors. The auxiliary reactor is preferably a turbulent bed reactor, and the main reactor can be a fast bed reactor or a turbulent bed reactor;
the invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: focusing catalyst of the auxiliary reactor enters the reaction zone of the main reactor through an auxiliary reaction focusing catalyst circulating pipe to provide catalyst required by the reaction for the reaction zone of the main reactor; the spent catalyst in the catalyst collecting area of the main reactor enters the reaction area of the main reactor through a catalyst circulating pipe and is used for controlling the airspeed of the reaction area of the main reactor so as to adjust the olefin selectivity of the main reactor
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the regenerated catalyst conveying pipe can also be used as a riser reactor, and light hydrocarbon gas can be injected when the regenerated catalyst conveying pipe is used as the riser reactor, and the light hydrocarbon gas can be injected into the upper part, the middle part or the lower part of the riser reactor in one or more strands (2-5 strands).
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the raw material feeding pipe line is provided with a light hydrocarbon gas injection port, and light hydrocarbon gas enters the main reactor and the auxiliary reactor through the raw material feeding pipe independently or after being mixed with oxygen-containing compounds.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: and 4) a stripping grating or a stripping baffle plate and a stripping medium distributor are arranged in the spent stripper.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: a stripping grating or a stripping baffle and/or a heat extraction facility and a stripping medium distributor are arranged in the regeneration stripper of the step 5).
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: and 5) removing most of carried catalyst from the flue gas generated after the catalyst and main air are contacted and burned in a countercurrent mode through a two-stage cyclone separator, discharging the flue gas, sending the flue gas to a waste heat boiler through a pressure reducing valve (if needed), a double-acting slide valve and a pressure reducing pore plate to recover heat, and exhausting the flue gas to atmosphere through a chimney.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the main reactor is provided with an inner heat remover and/or an outer heat remover, the inner heat remover is positioned in the reaction zone of the main reactor, the outer heat remover is respectively communicated with the catalyst collecting zone and the reaction zone of the main reactor, and the spent catalyst in the catalyst collecting zone of the main reactor enters the outer heat remover through an outer heat-removing inlet pipe to be heated and then returns to the reaction zone of the main reactor.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the regenerator is provided with an internal heat collector and/or an external heat collector.
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 method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the reaction temperature of the auxiliary reactor is in the range of 350-700 ℃, preferably 450-650 ℃; the reaction temperature of the main reactor is within the range of 250-650 ℃, preferably within the range of 350-600 ℃; the linear speed of the reactor is in the range of 0.1-5 m/s, the main reactor is preferably in the range of 0.6-3 m/s, and the auxiliary reactor is preferably in the range of 0.1-1 m/s.
The regeneration temperature is within the range of 400-700 ℃, preferably within the range of 450-650 ℃; the reaction pressure is in the range of 0.05-3.0 MPaG, preferably in the range of 0.1-2.0 MPaG; the regeneration pressure is in the range of 0.1-3.0 MPaG, preferably in the range of 0.1-2.0 MPaG.
The invention relates to a method for producing low-carbon olefin by using high-efficiency oxygen-containing compounds, which is further characterized by comprising the following steps: the temperature of the reactor three-stage cyclone separator is within the range of 300-650 ℃, preferably within the range of 400-550 ℃; the pressure is in the range of 0.01 to 3.0MPaG, preferably in the range of 0.04 to 2.0 MPaG.
The invention relates to a method for producing low-carbon olefin by using an efficient 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 reaction zone to the maximum extent, improves the selectivity of the low-carbon olefin selectivity, and can be used in the industrial production of liquid products produced 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 method provided by the invention can improve the linear speed of the reactor, reduce the diameter of the reactor and improve the handling capacity of the device.
2) By adopting the method 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) The method provided by the invention utilizes the characteristics of strong heat release of oxygen-containing compound converted olefin and strong heat absorption of light hydrocarbon gas conversion reaction to carry out light hydrocarbon gas reaction in a high-temperature region, thereby not only meeting the conversion requirement of the reaction, but also realizing the coupling of heat and forming an interconnected complete system by coupling.
4) By adopting the method 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 flow chart of a process for producing lower olefins from an oxygenate according to the present invention;
FIG. 2 is a schematic flow chart of another process for producing lower olefins from oxygenates 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-main reactor reaction zone, 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 zone, 14-reaction oil gas I, 15-waste catalyst, 16-reactor three-rotation recovered 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.
The difference between the attached drawing 2 and the attached drawing 1 is that one end of the spent stripper is communicated with the lower part of the catalyst collecting area of the main reactor through a spent agent inlet pipe, and the other end of the spent stripper is respectively communicated with the bottom of the reaction area of the regenerator and the main reactor through a spent agent conveying pipe.
As shown in fig. 1, a schematic flow chart of a method for producing low-carbon olefins from an efficient oxygen-containing compound includes a reactor 23, an auxiliary reactor 10, a regenerator 38, a reactor third-stage cyclone 19, a reactor fourth-stage cyclone 17, a reactor third-cycle 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, and the other part enters a reaction zone 7 of the main reactor through a spent agent conveying pipe (III) 51. The rest is the same.

Claims (16)

1. The method for producing the low-carbon olefin by the high-efficiency oxygen-containing compound is characterized by comprising the following steps of:
1) the reaction raw material of the auxiliary reactor is preheated by the main reactor which is arranged in series with the auxiliary reactor, enters the bottom of the auxiliary reactor to directly contact with the high-temperature catalyst from the regenerator, and quickly carries out coking regulation and control reaction under the action of the catalyst, the reaction product is led out from the top of the auxiliary reactor after the catalyst and reaction oil gas are separated by a gas-solid separation facility, and the focusing catalyst after the reaction is sent to the main reactor through an auxiliary reaction catalyst circulating pipe;
2) preheating reaction raw materials of the main reactor, then entering the main reactor to react with a focusing catalyst from the auxiliary reactor, leading out a reaction product of the main reactor from the top of the main reactor, and combining the reaction product with the reaction product led out from the top of the auxiliary reactor in the step 1);
3) the spent catalyst after the reaction of the main reactor is collected in the catalyst collecting area, and the catalyst is supplemented for the reaction area of the main reactor through a catalyst circulating pipe, so that the space velocity of the reaction area of the main reactor is controlled, and the aim of adjusting the olefin selectivity of the main reactor is fulfilled;
4) the spent catalyst which loses activity after reaction enters a spent stripper from a catalyst collecting region for steam stripping and then enters a regenerator through a spent conveying pipe; or one part enters the regenerator through the spent conveying pipe, and the other part enters the reaction zone of the main reactor;
5) after the catalyst to be regenerated is burnt in the regenerator, the regenerated catalyst is stripped by the regenerated stripper, and the stripped regenerated catalyst enters the auxiliary reactor through the regenerated catalyst conveying pipe.
2. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the auxiliary reactor is connected with the main reactor in series, and the main reactor is communicated with the auxiliary reactor through an auxiliary reaction focusing catalyst circulating pipe; catalyst circulating pipes are arranged between the reaction zone and the catalyst collecting zone of the main reactor, and a slide valve or a plug valve is arranged on each circulating pipe to control the circulating amount of the catalyst.
3. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the catalyst collecting region and the reaction region of the main reactor are of an integral structure, the reaction region is arranged below the catalyst collecting region and separated from the catalyst collecting 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.
4. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: step 2) leading out a reaction product of the main reactor from the top of the main reactor after removing most of carried catalyst by a catalyst quick separation device and a 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.
5. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 4, characterized in that: and 2) removing the entrained catalyst from the reaction product in the step 2) through a reactor three-stage cyclone separator and a reactor four-stage cyclone separator, leading out, and sending to a rear quenching and water washing system after heat exchange. The catalyst recovered by the reactor three-stage cyclone separator and the reactor four-stage cyclone separator enters a waste reactor three-cyclone recovery catalyst storage tank, and the waste catalyst is sent to a waste catalyst tank through a discharging agent pipeline.
6. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the reaction raw material entering the main reactor is oxygen-containing compound or a mixture of oxygen-containing compound and light hydrocarbon gas; the reaction raw material entering the auxiliary reactor is light hydrocarbon gas or a mixture of the light hydrocarbon gas and oxygen-containing compounds.
7. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 6, 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.
8. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the main reactor and the auxiliary reactor are both fluidized bed reactors.
9. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the regenerated catalyst conveying pipe is used as a riser reactor, light hydrocarbon gas is injected when the regenerated catalyst conveying pipe is used as the riser reactor, and the light hydrocarbon gas is injected into the upper part, the middle part or the lower part of the riser reactor in one or more strands.
10. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: and 4) a stripping grating or a stripping baffle plate and a stripping medium distributor are arranged in the spent stripper. .
11. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: a stripping grating or a stripping baffle and/or a heat extraction facility and a stripping medium distributor are arranged in the regeneration stripper of the step 5).
12. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: and 5) removing most of carried catalyst from the flue gas generated after the catalyst and main air are contacted and burned in a countercurrent mode through a two-stage cyclone separator, discharging the flue gas, sending the flue gas to a waste heat boiler through a pressure reducing valve, a double-acting slide valve and a pressure reducing pore plate to recover heat, and exhausting the flue gas to atmosphere through a chimney.
13. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the main reactor is provided with an inner heat remover and/or an outer heat remover, the inner heat remover is positioned in the reaction zone of the main reactor, the outer heat remover is respectively communicated with the catalyst collecting zone and the reaction zone of the main reactor, and the spent catalyst in the catalyst collecting zone of the main reactor enters the outer heat remover through an outer heat-removing inlet pipe to be heated and then returns to the reaction zone of the main reactor.
14. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the reaction temperature of the auxiliary reactor is within the range of 350-700 ℃; the reaction temperature of the main reactor is within the range of 250-650 ℃.
15. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the linear speed of the main reactor is within the range of 0.6-3 m/s, and the linear speed of the auxiliary reactor is within the range of 0.1-1 m/s.
16. The method for producing low-carbon olefin by using high-efficiency oxygen-containing compound according to claim 1, characterized in that: the regeneration temperature is within the range of 400-700 ℃; the regeneration pressure is in the range of 0.1-3.0 MPaG; the reaction pressure is in the range of 0.05-3.0 MPaG.
CN202110274830.3A 2021-03-15 2021-03-15 Method for producing low-carbon olefin by using efficient oxygen-containing compound Pending CN113509893A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

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