CN113620768B - Method for producing ethylene, propylene and aromatic hydrocarbon and catalytic reaction system - Google Patents

Method for producing ethylene, propylene and aromatic hydrocarbon and catalytic reaction system Download PDF

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Publication number
CN113620768B
CN113620768B CN202010383192.4A CN202010383192A CN113620768B CN 113620768 B CN113620768 B CN 113620768B CN 202010383192 A CN202010383192 A CN 202010383192A CN 113620768 B CN113620768 B CN 113620768B
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propylene
gas
oil
reaction
reactor
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CN113620768A (en
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张执刚
龚剑洪
李东
魏晓丽
张策
崔琰
刘宪龙
陈昀
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06Catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80Mixtures of different zeolites
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/182Regeneration
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084Y-type faujasite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

A method and catalytic reaction system for producing ethylene, propylene and aromatic hydrocarbons, comprising: (1) Introducing the carbon four components from the catalytic cracking fractionating tower into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from the regenerator, allowing the oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, and separating ethylene, propylene, aromatic hydrocarbon products and the carbon four components from the separated reaction oil gas by a separation system; (2) The separated carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, and the reaction product is separated into ethylene, propylene and aromatic hydrocarbon products through a separation system; (3) And (3) separating the dry gas and the liquefied gas in the steps (1) and (2) to obtain ethane and propane, and then feeding the ethane and propane into a steam cracking furnace for steam cracking to generate ethylene and propylene. The method provided by the invention has high yield of ethylene, propylene and aromatic hydrocarbon and low energy consumption.

Description

Method for producing ethylene, propylene and aromatic hydrocarbon and catalytic reaction system
Technical Field
The invention relates to a method and a system for producing chemical raw materials from petroleum raw materials, in particular to a method and a reaction system for producing ethylene, propylene and aromatic hydrocarbon from heavy oil.
Technical Field
Ethylene, propylene and BTX aromatics are growing in demand annually as a large number of basic chemical feedstocks. Catalytic cracking, which is used as a device for producing gasoline by processing heavy oil, also produces a large amount of propylene as a byproduct, and is a main supplementary source in the propylene market. Wherein deep catalytic cracking (such as DCC process) using more shape selective molecular sieve (ZSM-5) as active center can produce propylene in large quantity and by-produce certain propylene and BTX aromatic hydrocarbon. At present, wax oil or hydrogenated wax oil is generally adopted in the process, and a small amount of residual oil or paraffin-based atmospheric residual oil is doped as a raw material.
The technology for preparing propylene from liquefied gas rich in olefin uses liquefied gas with lower added value as raw material, and uses the cracking reaction of carbon tetraolefin in liquefied gas under the action of catalyst to produce propylene, ethylene and high-octane aromatic hydrocarbon-rich gasoline component with high added value, for example, in the DCC family technology, C4 olefin is returned into catalytic cracking device to make cyclic re-cracking so as to produce ethylene and propylene. Meanwhile, ethanol gasoline is promoted nationwide by 2020, etherified C4 or etherified light gasoline products are limited to be added into finished gasoline, a large number of C4 etherification devices are idle, and the reprocessing and the utilization of C4 olefins are paid attention to.
CN104878A discloses a process for producing low-carbon olefin, which uses gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materials, and uses Y-type molecular sieveAnd ZSM-5 molecular sieve as active center; a fluidized bed or moving bed reactor is adopted; the operation conditions are that the pressure is 150 kPa-300 kPa, the reaction temperature is 550-650 ℃, and the airspeed is 0.2-20hr -1 And the agent-oil ratio is 2-12. The method has high reaction temperature, more methane byproducts and generates a large amount of unusable carbon four and diesel oil.
CN1056595a discloses a process for low-carbon olefin production using multistage feed from ethane to resid as feedstock. The method uses an alkaline earth metal-containing molecular sieve as an active center; a riser reactor is adopted; the operation conditions are 130kPa to 400kPa of pressure, 600 ℃ to 900 ℃ of reaction temperature, 0.1 to 6 seconds of residence time and 5 to 100 of catalyst-oil ratio, and the cracking of the multi-stage feed is carried out from high to low according to different cracking difficulties. Although the method solves the problems of byproducts such as carbon four, the method also has the problems of more methane and coke byproducts for the raw materials with poor processing property,
CN1065963a discloses a method for producing low-carbon olefin by multi-stage feeding of hydrocarbon oil, which uses gasoline, vacuum wax oil and residual oil as raw materials and uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; a riser reactor and a fluidized bed reactor are adopted; the operation conditions are that the pressure is 130 kPa-400 kPa, the reaction temperature is 500-600 ℃, the retention time of the riser is 1-5 seconds, and the space velocity of the fluidized bed is 0.2-20hr -1 And the agent-oil ratio is 6-15, the atomized water vapor accounts for 1% -60% of the weight of the raw materials, wherein the mixture of the vacuum wax oil and the residual oil enters the bottom of the riser reactor, the gasoline component enters the fluidized bed reactor, and the riser reactor and the fluidized bed reactor are connected in series. The method can not solve the problem of more methane, carbon four and diesel byproducts.
CN102337148A discloses a method for producing low-carbon olefin by using gasoline rich in four to eight carbon atoms as raw material. The method uses Y-type molecular sieve and ZSM-5 molecular sieve as active centers; a riser reactor and a fluidized bed reactor are adopted; the operation conditions are that the pressure is 150 kPa-300 kPa, the reaction temperature is 480-680 ℃, the retention time of the riser is 1-5 seconds, and the space velocity of the fluidized bed is 0.2-30hr -1 The agent-oil ratio is 8-40. The method can not solve the accumulation of alkane components despite the cyclic utilization of the C four-to C eight-alkene.
CN101362961A discloses a method for producing low-carbon olefin and aromatic hydrocarbon by using hydrocarbon at 160-270 ℃ as raw material. The method uses Y-type molecular sieve and ZSM-5 molecular sieve as active centers; a riser reactor or a fluidized bed reactor is adopted; the operation conditions are that the pressure is 100 kPa-1000 kPa, the reaction temperature is 450-750 ℃, and the airspeed is 1-150hr -1 The agent-oil ratio is 1-150. The method solves the problem of partial diesel oil outlet.
CN 1667089a discloses a method for producing low-carbon olefin by using gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materials. The method comprises the steps of hydrotreating a raw material and a circulating material flow, and then feeding the material flows into a catalytic cracking reactor. Wherein the gas recycle is ethane, propane and carbon four. The liquid circulation feed is C5-C6, heavy gasoline aromatic raffinate oil, LCO, HCO and slurry oil. Although the method solves the outlet of most byproducts, the method can not solve the accumulation problem of alkane components and polycyclic aromatic hydrocarbon components.
In the method, the problems of high circulating ratio of the four carbon components, low propylene yield and high energy consumption exist.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problems of high circulation proportion of carbon four components, low propylene yield and high energy consumption in the prior art, and provide a method for producing ethylene, propylene and aromatic hydrocarbon with high product yield.
The second technical problem to be solved by the invention is to provide a catalytic conversion reaction system for producing ethylene, propylene and aromatic hydrocarbon.
The method for producing ethylene, propylene and aromatic hydrocarbon provided by the invention comprises the following steps:
(1) Introducing the carbon four components into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalytic cracking catalyst from a regenerator, allowing an oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, separating dry gas, liquefied gas and gasoline from the separated reaction oil gas by a first oil-gas separation system, and further separating propylene, propane and the carbon four components from the liquefied gas;
(2) The separated carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, and dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, and ethylene, ethane, propylene, propane and aromatic hydrocarbon products are further separated;
(3) And (3) in the steps (1) and (2), the propane and the ethane enter a steam cracking furnace for steam cracking to generate ethylene and propylene.
A catalytic conversion system for producing ethylene, propylene and aromatic hydrocarbons comprising a reaction unit, a catalyst and a reactant stream; the reaction device comprises a catalytic cracking reactor, a regenerator, a first oil-gas separation system, an aromatization reactor, a second oil-gas separation system and a gas separation device which are sequentially communicated, wherein a regenerant outlet of the regenerator is communicated with the bottom of the catalytic cracking reactor, a settler and gas-solid separation equipment are arranged at the upper part of the catalytic cracking reactor, a spent agent outlet of the gas-solid separation equipment is communicated with the regenerator, an oil-gas outlet of the gas-solid separation equipment is communicated with the first oil-gas separation system, a C4 component outlet of the first oil-gas separation system is communicated with the aromatization reactor, an outlet of the aromatization reactor is communicated with the second oil-gas separation system, and a dry gas outlet and a liquefied gas outlet of the second oil-gas separation system are connected with the gas separation device; the catalytic cracking catalyst circularly flows in the catalytic cracking reactor and the regenerator, the aromatization catalyst is filled in the aromatization reactor, and light hydrocarbon raw materials are introduced through a raw material inlet and react in a reaction device.
The method for producing ethylene, propylene and aromatic hydrocarbon and the catalytic conversion reaction system provided by the invention have the beneficial effects that:
in the method for producing the low-carbon olefin by further catalytically cracking the carbon four components in the catalytic cracking reactor in the prior art, the reaction speed of the carbon four alkane is obviously slower than that of the carbon four olefin, so the conversion rate of the carbon four olefin is higher in the reaction process, and the conversion rate of the carbon four alkane is extremely low. In the prior art, the carbon four components obtained from the catalytic cracking product are recycled to the catalytic cracking reactor, so that the recycle material flow of the carbon four alkanes is continuously accumulated. If the ratio of the four carbon cycles is not increased, the propylene yield is reduced due to the reduced content of olefins in the four carbon cycles. If the carbon four cycle ratio is increased, the energy consumption is greatly increased.
According to the method for producing ethylene, propylene and aromatic hydrocarbon, disclosed by the invention, the problem of accumulation of the carbon tetraalkylalkanes in the carbon tetraalkylalkane circulating material flow is solved by aromatizing the carbon tetraalkylalkane, and the energy consumption and the operation cost in the catalytic cracking of the carbon tetraalkylalkane are greatly reduced. And simultaneously, the yields of ethylene, propylene and aromatic hydrocarbon are greatly increased. The method for producing ethylene, propylene and aromatic hydrocarbon can also reduce the heat-taking load of the aromatization device and reduce the energy consumption of the aromatization device. The method for producing ethylene, propylene and aromatic hydrocarbon can provide more high-quality cracking raw materials of ethane and propane for steam cracking, thereby greatly increasing the yield of ethylene and propylene.
Drawings
FIG. 1 is a schematic flow chart of a process for producing ethylene, propylene and aromatic hydrocarbons according to the present invention.
FIG. 2 is a schematic flow chart of a method for producing ethylene and propylene from heavy oil in comparative examples 1 and 2.
Wherein:
1-a catalytic cracking reactor; a 2-aromatization reactor; 4-regenerator; 5-a first oil-gas separation system; 6-a second oil-gas separation system; 8-regenerating the catalyst chute; 9-a spent catalyst chute; 10-stripping section; 11-a settler; a 32-propane pyrolysis furnace; 33-ethane pyrolysis furnace; 35-a gas separation device; 31. 34-dry gas line, 37-ethane line; 7-a raw material pipeline; 12. 14, 18, 19, 20, 21, 22, 23, 29, 30-lines.
Detailed Description
The following describes specific embodiments of the present invention:
the method for producing ethylene, propylene and aromatic hydrocarbon provided by the invention comprises the following steps:
(1) Introducing the carbon four components into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalytic cracking catalyst from a regenerator, allowing an oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, separating dry gas, liquefied gas and gasoline from the separated reaction oil gas by a separation system, and further separating ethylene, ethane, propylene, propane and the carbon four components from the liquefied gas;
(2) The separated carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, and dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, and ethylene, ethane, propylene, propane and aromatic hydrocarbon products are further separated;
(3) And (3) in the steps (1) and (2), the propane and the ethane enter a steam cracking furnace for steam cracking to generate ethylene and propylene.
In the method provided by the invention, the carbon four component is obtained from a catalytic cracking device and contains C4 olefin and C4 alkane, wherein the olefin content is more than 20wt%. Preferably, the olefin content in the carbon four component is 40wt% to 80wt%.
In the method provided by the invention, the catalytic cracking catalyst in the step (1) contains an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, wherein the content of the MFI structure molecular sieve is 5-60 wt%, preferably 10-50 wt%, the content of the Y-type molecular sieve is 1-40 wt%, preferably 1-30 wt%, the content of the clay is 10-70 wt%, preferably 15-45 wt%, and the content of the binder is 5-40 wt%, preferably 5-30 wt%, based on the total weight of the catalyst.
In the method provided by the invention, the catalytic cracking reactor is one or a combination of a riser reactor, a turbulent bed reactor and a rapid bed reactor; the operating conditions of the catalytic cracking reactor were: the average temperature is 550-700 ℃, the reaction pressure is 0.15-0.5 MPa, and the reaction space velocity is 2-600 h -1
In the method provided by the invention, the gas-solid separation in the step (1) is carried out in a settler, a cyclone gas-solid separator is adopted to separate the catalyst and the reaction oil gas, and the separated catalyst is stripped in a stripper.
In the method provided by the invention, the aromatization reactor is a fixed bed reactor.
In the method provided by the invention, the aromatization catalyst contains a molecular sieve, a metal active component and a heat-resistant inorganic oxide carrier, wherein the metal active component is selected from one or more of rare earth elements and VIB, VIII, IIB, VIIB elements, and the heat-resistant inorganic oxide is preferably silicon oxide and aluminum oxide.
In the method provided by the invention, the operating conditions of the aromatization reactor are as follows: the reaction temperature is 350-450 ℃, the reaction pressure is 0.20-2.0 MPa, and the reaction space velocity is 0.2-2 h -1
In the method provided by the invention, propane in the step (3) enters a propane steam cracking furnace for reaction, and ethane enters an ethane steam cracking furnace for reaction to generate ethylene and propylene.
The steam cracking operation condition in the step (3) is that the reaction temperature is 780-850 ℃ and the residence time is 0.01-3 seconds.
In the method provided by the invention, preferably, in the steps (1) and (2), the dry gas enters the same gas separation device to separate ethylene, ethane, propylene and propane, and the gas separation device adopts a combination of a plurality of rectifying towers. The separation system comprises a fractionating tower, an absorption stabilizing system and a gas separation device. Specifically, the separated reaction oil gas enters a catalytic cracking fractionating tower, and the middle part of the fractionating tower is pumped out of the product gasoline. The gasoline and rich gas obtained from the top of the fractionating tower enter an absorption stabilizing system, and the product gasoline, dry gas and liquefied gas separated by the stabilizing system enter a gas separating device to separate propylene, propane and carbon four components. The dry gas enters a split separation device to separate ethylene, ethane and other gases.
The arene obtained in the step (2) is C6 to C10 monocyclic arene.
In the method provided by the invention, the C4 component from the catalytic cracking fractionating tower refers to the C4 component produced by a catalytic cracking device, the catalytic cracking device is used for contacting a heavy oil raw material with a catalytic cracking catalyst, and carrying out a cracking reaction under a catalytic cracking condition to obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil, wherein the liquefied gas is further separated to obtain the C4 component. The heavy oil raw material is selected from one or a mixture of more than one of wax oil and atmospheric residue vacuum residue, or other organic compounds or hydrocarbons with carbon number more than 16. The catalytic cracking catalyst comprises an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, wherein the content of the MFI structure molecular sieve is 5-60 wt%, preferably 10-50 wt%, the content of the Y-type molecular sieve is 1-40 wt%, preferably 1-30 wt%, the content of the clay is 10-70 wt%, preferably 15-45 wt%, and the content of the binder is 5-40 wt%, preferably 5-35 wt%, based on the total weight of the catalyst.
The operating conditions of the reactor in the catalytic cracking device are as follows: the average temperature is 500-700 ℃, the reaction pressure is 0.15-0.5 MPa, and the reaction space velocity is 2-600 h -1
A catalytic conversion system for producing ethylene, propylene and aromatics, comprising a reaction device, a catalyst and a reactant stream; the reaction device comprises a catalytic cracking reactor, a regenerator, a first oil-gas separation system, an aromatization reactor, a second oil-gas separation system and a gas separation device which are sequentially communicated, wherein a regenerant outlet of the regenerator is communicated with the bottom of the catalytic cracking reactor, a settler and gas-solid separation equipment are arranged at the upper part of the catalytic cracking reactor, a spent agent outlet of the gas-solid separation equipment is communicated with the regenerator, an oil-gas outlet of the gas-solid separation equipment is communicated with the first oil-gas separation system, a C4 component outlet of the first oil-gas separation system is communicated with the aromatization reactor, an outlet of the aromatization reactor is communicated with the second oil-gas separation system, and a dry gas outlet and a liquefied gas outlet of the second oil-gas separation system are connected with the gas separation device; the catalytic cracking catalyst circularly flows in a catalytic cracking reactor and a regenerator, the aromatization catalyst is filled in the aromatization reactor, and light hydrocarbon raw materials, preferably carbon four components, are introduced through a raw material inlet and react in a reaction device.
In the catalytic conversion system provided by the invention, the catalytic cracking reactor is selected from one or a combination of a plurality of riser reactors, turbulent bed reactors and rapid bed reactors; preferably a riser reactor, and the aromatization reactor is a fixed bed reactor.
The regenerator is a type of regenerator in the art that uses air or air-mixed oxygen-enriched gas to react with coke on the spent catalyst, burns the coke off the spent catalyst to restore the activity of the spent catalyst, known as regenerated catalyst, and raises the catalyst temperature to 600 to 760 ℃ in order to return the reactor to bring heat and catalytic media to the reaction.
In the method and the system provided by the invention, products of the catalytic cracking reactor and the aromatization reactor are separated by adopting an oil-gas separation system, and the oil-gas separation system can be one or a combination of more of a fractionating tower, a rectifying tower, an absorbing tower and a desorber.
The present method is described below with reference to the accompanying drawings, but the invention is not limited thereto.
FIG. 1 is a schematic flow chart of the method for producing ethylene, propylene and aromatic hydrocarbon according to the present invention, as shown in FIG. 1: the four components of raw materials are preheated and then enter a catalytic cracking reactor 1 through a pipeline 7 to contact and react with a thermal regenerated catalyst from a regenerator 4 through a regenerated catalyst inclined pipe 8, the catalytic cracking reactor 1 is a riser reactor, oil gas and catalyst after reaction enter a settler 11, gas-solid separation equipment is arranged in the settler 11, the oil gas and the catalyst are separated in the settler 11, the separated regenerated catalyst with carbon enters a stripping section 10 to be stripped, enters the regenerator 4 through a regenerated catalyst inclined pipe 9, the air from the pipeline 25 in the regenerator 4 burns coke on the regenerated catalyst to restore activity, and then enters the bottom of the catalytic cracking reactor 1 through the regenerated catalyst inclined pipe 8 to be recycled; the separated oil and gas enters the first oil and gas separation system 5 through a pipeline 12. The first oil-gas separation system 5 leads out gasoline through a pipeline 15, diesel oil through a pipeline 16, slurry oil through a pipeline 26, propylene through a pipeline 27, and propane through a pipeline 13, and then enters a propane cracking furnace 32; dry gas enters a gas separation device 35 through a pipeline 31, the gas separation device 35 consists of a plurality of rectifying towers, H2-CH4 is led out through a pipeline 28 after being separated by the rectifying towers, ethylene is led out through a pipeline 36, and ethane is led out through a pipeline 37 and enters an ethane cracking furnace 33; the second carbon-four component is withdrawn via line 14 and a portion of the second carbon-four component is recycled back to the catalytic cracking reactor 1 via line 28.
The other part of the second carbon four component enters an aromatization reactor 2 through a pipeline 14, wherein the aromatization reactor is a fixed bed reactor. In the aromatization reactor, the second carbon four components and the aromatization catalyst are in contact reaction, the reaction product enters the second oil-gas separation system 6 through a pipeline 17, aromatic hydrocarbon-rich gasoline is obtained after separation and is led out through a pipeline 21, propylene is led out through a pipeline 18, propane is led out through a pipeline 19 and enters a propane cracking furnace 32, dry gas is led out through a pipeline 34 and enters a gas separation device 35, and the separated carbon four components are led out through a pipeline 20.
The effects of the method for producing ethylene, propylene and aromatic hydrocarbon provided by the present invention are illustrated below by examples and comparative examples, but the present invention is not limited thereto.
In the comparative examples and examples, the C4 component of the raw material used was taken from a catalytic cracking separation tower of Shijia division of China petrochemical Co., ltd, and the properties are shown in Table 1. The catalytic cracking catalyst used was DMMC-1 catalyst manufactured by catalyst division of China petrochemical Co., ltd. And the properties thereof are shown in Table 2. The adopted aromatization catalyst has the commodity brand of DLP-XA and is produced by Shandong Dazier chemical technology Co.
Comparative examples 1 to 2
Comparative examples 1-2A process for producing ethylene and propylene by C4-back catalytic cracking shown in figure 2 is carried out, as shown in figure 2, four components of raw materials enter a catalytic cracking riser reactor through a pipeline 7 after being preheated, contact with a thermal regenerated catalyst from a regenerator 4 through a regenerated catalyst inclined pipe 8, catalytic cracking reaction is carried out, generated oil gas and catalyst flow upwards into a settler 11, gas-solid separation equipment is arranged in the settler 11, the reacted oil gas and catalyst are separated, the separated catalyst to be regenerated with carbon enters the regenerator 4 through a stripping section 10 after being stripped, coke on the catalyst to restore activity is burnt out through air from the pipeline 25 in the regenerator 4, and then the catalyst enters the bottom of the riser reactor through the inclined pipe 8 to circularly participate in the reaction. The separated oil and gas enters the first oil and gas separation system 5 through a pipeline 12. The first oil-gas separation system consists of a fractionating tower, a rectifying tower, an absorption tower and a desorption tower, gasoline obtained after separation is led out through a pipeline 15, diesel oil is led out through a pipeline 16, slurry oil is led out through a pipeline 26, propylene is led out through a pipeline 27, and propane is led out through a pipeline 13 and enters a propane cracking furnace 32 to generate propylene 23 and ethylene 22. The resulting dry gas is withdrawn via line 31 and enters a gas separation unit 35 where the separated ethylene 28, other gases 36 and ethane 37 are withdrawn via line 37 and enter an ethane cracker 33 to produce ethylene and propylene. The four carbon components are led out through a pipeline 14, a part of four carbon components are returned to the catalytic cracking reactor through a pipeline 28, and the rest of four carbon components are taken as a product outlet device through a pipeline 20.
The reaction operating conditions of comparative examples 1 to 2 are shown in Table 3, and the product yields are shown in Table 4.
Examples 1 to 2
The embodiment 1-2 adopts a reaction flow shown in the attached figure 1, specifically, (1) raw material carbon four components are introduced into a catalytic cracking reactor to contact and react with regenerated catalyst from the regenerator, oil gas and catalyst mixture obtained by the reaction enter a settler to carry out gas-solid separation, and separated reaction oil gas is separated into dry gas, liquefied gas and gasoline by a first oil-gas separation system to further separate ethylene, propylene, aromatic hydrocarbon products and carbon four components; (2) The separated carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, and the reaction product is separated into dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon by a second oil-gas separation system, and ethylene, propylene and aromatic hydrocarbon products are further separated; (3) And (3) separating the dry gas and the liquefied gas in the steps (1) and (2) to obtain ethane and propane, and feeding the ethane and propane into an ethane-propane steam cracking furnace and a propane steam cracking furnace for steam cracking to generate ethylene and propylene.
The reaction operating conditions for examples 1-2 are shown in Table 3 and the product yields are shown in Table 4.
As can be seen from table 4, the carbon four recycle ratio (carbon four feed/feedstock) of the examples with C4 component a and C4 component B as feedstock was reduced by 0.2 and 0.3, respectively, ethylene was increased by 0.36 and 1.05 percentage points, propylene was increased by 1.10 and 1.70 percentage points, respectively, and aromatic hydrocarbon (BTX) was increased by 7.86 and 16.38 percentage points, respectively, as compared to the comparative examples.
TABLE 1 carbon four component feed
Raw materials Carbon four component A Carbon four component B
Isobutane 26.18 38.75
N-butane 6.35 9.97
Butene-1 10.01 11.18
Isobutene (i-butene) 28.90 12.92
Maleic anhydride 16.52 14.06
Fumaric acid 12.03 13.12
TABLE 2 catalytic cracking catalyst compositions and Properties
RE 2 O 3 0.56
Al 2 O 3 54
Physical Properties
Specific surface, m 2 /g 100
Pore volume, cm 3 /g 0.176
Micropore volume, cm 3 /g 0.026
Apparent density, g/cm 3 0.91
Sieving,% of
0-20μm 0.8
0-40μm 10.4
0-80μm 70.8
0-110μm 88.5
0-149μm 97.8
>149μm 2.2
APS,μm 64.3
Micro-inverse Activity, w% (520 ℃ C.) 55
TABLE 3 Table 3
Project Comparative example 1 Example 1 Comparative example 2 Example 2
Catalytic cracking reactor
C4 raw material Carbon four component A Carbon four component A Carbon four component B Carbon four component B
Reaction pressure/MPa 0.2 0.2 0.28 0.28
Reaction temperature/. Degree.C 620 620 650 650
Regenerator temperature/°c 690 690 710 710
Ratio of agent to oil 15 15 20 20
Reaction space velocity/h -1 10 10 50 50
Atomizing steam/% 25 25 15 15
Carbon four cycle ratio 0.5 0.2 0.4 0.2
Aromatization reactor
Reaction pressure/MPa / 1.1 / 1.3
Reaction temperature/. Degree.C / 380 / 420
Reaction space velocity/h -1 / 1.0 / 1.3
Ethane steam cracking furnace
Temperature/. Degree.C / 830 / 830
pressure/MPa / 0.13 / 0.13
Atomizing steam/% / 60 / 60
Propane steam cracking furnace
Temperature/. Degree.C / 815 / 815
pressure/MPa / 0.13 / 0.13
Atomizing steam/% / 60 / 60
TABLE 4 Table 4
Example numbering Comparative example 1 Example 1 Comparative example 2 Example 2
Product yield
H2-C2 5.77 7.99 7.94 8.74
C3-C4 76.38 59.67 86.26 75.01
C5+ gasoline 13.51 27.03 3.04 13.19
Diesel oil 0.77 1.20 0.42 0.68
Slurry oil 0.02 0.25 0.12 0.26
Coke 3.36 3.58 2.02 2.11
Wherein:
ethylene 3.47 4.52 3.99 4.35
Propylene 16.59 17.69 8.58 10.28
BTX 1.26 17.64 1.34 9.20

Claims (14)

1. A process for producing ethylene, propylene and aromatics comprising:
(1) Introducing the carbon four components into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalytic cracking catalyst from a regenerator, allowing an oil gas and catalyst mixture obtained by the reaction to enter a settler for gas-solid separation, separating dry gas, liquefied gas, gasoline, diesel oil and slurry oil from the separated reaction oil gas by a first oil-gas separation system, and further separating propylene, propane and the carbon four components from the liquefied gas;
(2) The separated carbon four components enter an aromatization reactor to contact and react with an aromatization catalyst, the reaction temperature is 350-450 ℃, dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a second oil-gas separation system, and ethylene, ethane, propylene, propane and aromatic hydrocarbon products are further separated;
(3) And (3) in the steps (1) and (2), the propane and the ethane enter a steam cracking furnace for steam cracking to generate ethylene and propylene.
2. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 1, wherein the carbon four components introduced into the catalytic cracking reactor are derived from a catalytic cracker and comprise C4 olefins and C4 paraffins, wherein the olefins content is greater than 20wt%。
3. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 2, wherein the olefin content of the carbon four component introduced into the catalytic cracking reactor is 40wt%-80wt%。
4. A process for producing ethylene, propylene and aromatic hydrocarbons according to any one of claims 1 to 3, wherein the catalytic cracking catalyst in step (1) comprises an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, the MFI structure molecular sieve being present in an amount of 5 to 60% by weight, the Y-type molecular sieve being present in an amount of 1 to 40% by weight, the clay being present in an amount of 10 to 70% by weight, and the binder being present in an amount of 5 to 40% by weight, based on the total weight of the catalyst.
5. The method for producing ethylene, propylene and aromatic hydrocarbon according to claim 4, wherein the content of MFI structure molecular sieve is 10 to 50 wt%, the content of Y type molecular sieve is 1 to 30 wt%, the content of clay is 15 to 45 wt%, and the content of binder is 5 to 30 wt%, based on the total weight of the catalyst.
6. A process for producing ethylene, propylene and aromatics according to any one of claims 1-3, wherein said catalytic cracking reactor is one or a combination of a riser reactor, a turbulent bed reactor and a fast bed reactor; the operating conditions of the catalytic cracking reactor were: the average temperature is 550-700 ℃, the reaction pressure is 0.15-0.5 MPa, and the reaction space velocity is 2-600 h -1
7. A process for producing ethylene, propylene and aromatic hydrocarbons according to any one of claims 1 to 3, wherein said aromatization catalyst comprises a molecular sieve, a metal active component and a refractory inorganic oxide support, said metal active component being selected from one or more of rare earth elements, group VIB, VIII, IIB, VIIB elements.
8. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 7, wherein said refractory inorganic oxide is silica and/or alumina.
9. A process for producing ethylene, propylene and aromatic hydrocarbons according to any one of claims 1 to 3, wherein said aromatization reactor is a fixed bed reactor.
10. The process for producing ethylene, propylene and aromatic hydrocarbons according to claim 9, wherein the operating conditions of said aromatization reactor are: the reaction pressure is 0.20-2.0 MPa, and the reaction space velocity is 0.2-2 h -1
11. A process for producing ethylene, propylene and aromatic hydrocarbons according to any one of claims 1 to 3, wherein the steam cracking in step (3) is operated at a reaction temperature of 780 ℃ to 850 ℃ and a residence time of 0.01 to 3 seconds.
12. The process for producing ethylene, propylene and aromatics according to claim 11, wherein in step (3) propane is fed to a propane steam cracker for reaction, and ethane is fed to an ethane steam cracker for reaction to produce ethylene and propylene.
13. A process for producing ethylene, propylene and aromatic hydrocarbons according to any one of claims 1 to 3, wherein the dry gas and the liquefied gas in step (1) (2) are fed to the same gas separation unit to separate ethylene, ethane, propylene and propane, and the separation system employs a combination of a plurality of rectifying columns.
14. A method for producing ethylene, propylene and aromatic hydrocarbon according to any one of claims 1 to 3, wherein the reaction device is a catalytic cracking reactor, a regenerator, a first oil-gas separation system, an aromatization reactor, a second oil-gas separation system and a gas separation device which are communicated in sequence, wherein a regenerant outlet of the regenerator is communicated with the bottom of the catalytic cracking reactor, a settler and a gas-solid separation device are arranged at the upper part of the catalytic cracking reactor, a to-be-produced agent outlet of the gas-solid separation device is communicated with the regenerator, an oil-gas outlet of the gas-solid separation device is communicated with the first oil-gas separation system, a C4 component outlet of the first oil-gas separation system is communicated with the aromatization reactor, an outlet of the aromatization reactor is communicated with the second oil-gas separation system, and a dry gas outlet of the first oil-gas separation system and a dry gas outlet of the second oil-gas separation system are connected with the gas separation device.
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