CN212894505U - Catalytic conversion device for producing low-carbon olefin and aromatic hydrocarbon - Google Patents
Catalytic conversion device for producing low-carbon olefin and aromatic hydrocarbon Download PDFInfo
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A catalytic conversion device for producing low-carbon olefin and aromatic hydrocarbon comprises a catalytic cracking reactor, a regenerator, an aromatization reactor, an alkane dehydrogenation reactor, a first oil-gas separation system and a second oil-gas separation system; the regenerator is communicated with the bottom of the catalytic cracking reactor, a spent catalyst outlet of the catalytic cracking reactor is communicated with the regenerator, an oil-gas outlet of the catalytic cracking reactor is communicated with the first oil-gas separation system, a C4 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, a C4 outlet of the second oil-gas separation system is communicated with the alkane dehydrogenation reactor, and a product outlet of the alkane dehydrogenation reactor is communicated with the catalytic cracking reactor. The device provided by the utility model is used for hydrocarbon oil catalytic conversion production low carbon olefin and arene, can reduce the energy consumption and the operating cost of carbon four-cycle by a wide margin, increases ethylene, propylene and arene productivity simultaneously.
Description
Technical Field
The utility model relates to a device of petroleum feedstock production industrial chemicals, more specifically say, relate to a device of four component production ethylene of carbon, propylene and arene.
Background
Ethylene, propylene and BTX aromatics are growing in demand each year as a large group of basic chemical feedstocks. The catalytic cracking is used as a device for processing heavy oil to produce gasoline, and a large amount of propylene is also produced as a byproduct, so that the catalytic cracking is a main supplement source of the propylene market. Wherein, the deep catalytic cracking (such as DCC process) using more selective molecular sieve (ZSM-5) as an active center can produce propylene in large quantity and produce certain propylene and BTX aromatic hydrocarbon as byproducts. 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 mixed as a raw material.
The technology for preparing propylene from liquefied gas rich in olefin takes liquefied gas with lower added value as raw material, and the carbon tetraolefin in the liquefied gas is cracked under the action of catalyst to generate propylene and ethylene with high added value and aromatic hydrocarbon-rich gasoline component with high octane value, for example, in the DCC family technology, C4 olefin is returned to a catalytic cracking device for cyclic cracking to generate ethylene and propylene. Meanwhile, ethanol gasoline is popularized nationwide in 2020, so that etherified C4 or etherified light gasoline products are limited to be added into finished gasoline, a large number of C4 etherifying devices are idle, and reprocessing and utilization of C4 olefins are concerned.
CN1034586A discloses a method for producing low-carbon olefin by catalytic cracking, which adopts gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and a mixture as raw materials, and adopts a Y-shaped molecular sieve and a phosphorus-containing ZSM-5 molecular sieve as active centers; a fluidized bed or a riser reactor is adopted; the operation conditions are that the pressure is 120 kPa-400 kPa, the reaction temperature is 480 ℃ and 680 ℃, the residence time is 0.1-6 seconds, the agent-oil ratio is 4-20, and the atomized water vapor accounts for 1-50 percent of the weight of the raw materials. This method, despite modifying the catalyst, has similar problems to CN104878, i.e. high reaction temperature, more methane by-product, and generation of large amount of unusable carbon four and diesel.
CN1056595A discloses a method for producing low carbon olefin by using multi-stage feeding. The method adopts ethane to residual oil as raw materials, and uses an alkaline earth metal-containing molecular sieve as an active center; a riser reactor is adopted; the operation conditions are that the pressure is 130 kPa-400 kPa, the reaction temperature is 600-900 ℃, the residence time is 0.1-6 seconds and the catalyst-oil ratio is 5-100, and the multi-stage feeding cracking is carried out from high to low according to different cracking difficulties. Although the method solves the problem of byproducts such as carbon four, the method also has the problem of more byproducts such as methane and coke for raw materials with poor processing property,
CN1065963A publicA method for producing low-carbon olefin by multi-stage feeding is provided, the method takes gasoline, vacuum wax oil and residual oil as raw materials, and takes a Y-shaped molecular sieve and a ZSM-5 molecular sieve as active centers; adopting a riser reactor and a fluidized bed reactor; the operating conditions are that the pressure is 130 kPa-400 kPa, the reaction temperature is 500-600 ℃, the riser residence time is 1-5 seconds, and the space velocity of the fluidized bed is 0.2-20hr-1And the agent-oil ratio is 6-15, the atomized water vapor accounts for 1-60% of the weight of the raw material, 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 that the by-products of methane, carbon four and diesel oil are more.
CN102337148A discloses a method for producing low-carbon olefins by using gasoline rich in four to eight carbon atoms as a raw material. The method uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; adopting a riser reactor and a fluidized bed reactor; the operating conditions are that the pressure is 150 kPa-300 kPa, the reaction temperature is 480--1And the agent-oil ratio is 8-40. The method cannot solve the accumulation of alkane components despite the recycling of four to eight carbon olefins.
CN101362961A discloses a method for producing low-carbon olefin and aromatic hydrocarbon by using hydrocarbons with the temperature of 160-270 ℃ as raw materials, and the method uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; a riser reactor or a fluidized bed reactor is adopted; the operating conditions are that the pressure is 100 kPa-1000 kPa, the reaction temperature is 450 ℃ and 750 ℃, and the space velocity is 1-150hr-1And the agent-oil ratio is 1-150. The method solves the problem of the export of part of diesel oil.
CN101747928A discloses a method for producing low-carbon olefins and aromatics from vacuum wax oil and residual oil. The method uses a Y-type molecular sieve and a ZSM-5 molecular sieve as active centers; a riser reactor or a fluidized bed reactor is adopted; the feed reactor and the recycle reactor for the C4 olefin-250 ℃ product share a single regenerator. The method solves the problem of the output of part of diesel oil at will, but cannot solve the problem of the accumulation of alkane components and polycyclic aromatic hydrocarbon components.
CN 1667089a discloses a method for producing low-carbon olefins, which uses gasoline, kerosene, diesel oil, vacuum wax oil, residual oil and mixture as raw materials, first performs hydrotreating on the raw materials and recycle streams, and then enters the streams into a catalytic cracking reactor. Wherein the gas recycle is ethane, propane and C4. The liquid circulation feed is C5-C6, heavy gasoline aromatic raffinate oil, LCO, HCO and oil slurry. Although the method solves the problem of the output of most by-products, the method cannot solve the problem of the accumulation of alkane components and polycyclic aromatic hydrocarbon components.
CN101747928A discloses a method for producing low carbon olefins and aromatics, which uses vacuum wax oil and residual oil as raw materials and combines catalytic cracking and steam cracking. The method comprises the steps of separating c 2-gasoline alkane from a catalytic cracking product, feeding the separated product into a steam cracking reactor, and feeding butylene, recycle oil and oil slurry back to the catalytic cracking reactor. Aromatic hydrocarbons are produced by an aromatic extraction process. The method solves the problem of accumulation of alkane components and polycyclic aromatic hydrocarbon components. However, the separation of olefins and paraffins from components above C4 is very energy intensive and is not reimburseable.
The reaction speed of the tetracarbon is obviously slower than that of the tetracarbon, so that the conversion rate of the tetracarbon is higher and the conversion rate of the tetracarbon is extremely low in the mixed tetracarbon reaction process in the riser reactor. In the prior art, in the carbon four-component cycle reaction process, unreacted carbon tetralkyl hydrocarbon is retained in the carbon four-component, and alkane generated by raw oil is continuously accumulated in a cycle material flow. There is caused a problem that if the carbon four cycle ratio is not increased, the propylene yield is lowered due to the decrease in the olefin content in carbon four. If the carbon four cycle ratio is increased, the energy consumption is greatly increased.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is to solve the problem of the alkane component accumulation of hydrocarbon oil preparation low carbon olefin in-process among the prior art, provide a hydrocarbon oil production low carbon olefin and aromatic's catalytic conversion device who reduces alkane component accumulation, high yield.
The utility model provides a catalytic conversion device of production low carbon olefin and arene, include: the system comprises a catalytic cracking reactor, a regenerator, an aromatization reactor, an alkane dehydrogenation reactor, a first oil-gas separation system and a second oil-gas separation system; the regenerator has a regenerant outlet communicated with the bottom of the catalytic cracking reactor, the upper part of the catalytic cracking reactor is provided with a settler and a gas-solid separation device, a spent 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 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, a C4 outlet of the second oil-gas separation system is communicated with an alkane dehydrogenation reactor, and a product outlet of the alkane dehydrogenation reactor is communicated with the catalytic cracking reactor.
The utility model provides an application method of catalytic conversion device, include:
(1) introducing four components of raw material carbon into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from a regenerator, allowing a mixture of oil gas and the catalyst obtained by the reaction to enter a settler for gas-solid separation, separating the separated reaction oil gas into dry gas, liquefied gas, gasoline, diesel oil and oil slurry through a separation system, and further separating propylene, propane and a first four-component carbon from the liquefied gas;
(2) the separated first four carbon components enter an aromatization reactor to contact and react with an aromatization catalyst, dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, propylene, propane and a second four carbon components are further separated from the liquefied gas, and the aromatic hydrocarbon is further separated from the gasoline rich in aromatic hydrocarbon;
(3) and the second carbon four components enter an alkane dehydrogenation reactor, contact with a dehydrogenation catalyst to perform dehydrogenation reaction, and return the reaction product to the catalytic cracking reactor.
The utility model provides a catalytic conversion device of production low carbon olefin and arene's beneficial effect:
the utility model provides a catalytic conversion device of production low carbon olefin and arene is used for hydrocarbon oil catalytic conversion production ethylene, propylene and arene, is particularly useful for carbon four components raw materials catalytic conversion production ethylene, propylene and arene. The device provided by the utility model solves the problem of alkane accumulation in the carbon four-component circulation material flow, and can greatly reduce the energy consumption and the operation cost of the carbon four-circulation; meanwhile, the yields of ethylene, propylene and aromatic hydrocarbon are greatly increased; the device provided by the utility model can also reduce the heat load of the aromatization device and reduce the energy consumption of the aromatization device; more high quality cracking raw materials of ethane, propane and n-butane can be provided for steam cracking, so that the yield of ethylene and propylene is greatly increased.
Drawings
Fig. 1 is a schematic diagram of a catalytic conversion apparatus for producing low-carbon olefins and aromatic hydrocarbons according to the present invention.
FIG. 2 is a schematic diagram of an apparatus for producing ethylene and propylene from the carbon four components in comparative examples 1 and 2.
Wherein:
1-a catalytic cracking reactor; 2-an aromatization reactor; 3-alkane dehydrogenation reactor; 4-a regenerator; 5-a first oil-gas separation system; 6-a second oil-gas separation system; 8-regenerated catalyst inclined tube; 9-spent catalyst inclined tube; 10-a stripping section; 11-a settler; a 32-propane cracking furnace; a 33-ethane cracking furnace; 35-a gas separation device; 31. 34-dry gas line, 37-ethane line; 7-feed line; 12. 13, 14, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 36, 38-lines.
Detailed Description
The following specifically describes embodiments of the present invention:
the utility model provides a catalytic conversion device of production low carbon olefin and arene, include: the system comprises a catalytic cracking reactor, a regenerator, an aromatization reactor, an alkane dehydrogenation reactor, a first oil-gas separation system and a second oil-gas separation system; the regenerator has a regenerant outlet communicated with the bottom of the catalytic cracking reactor, the upper part of the catalytic cracking reactor is provided with a settler and a gas-solid separation device, a spent 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 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, a C4 outlet of the second oil-gas separation system is communicated with an alkane dehydrogenation reactor, and a product outlet of the alkane dehydrogenation reactor is communicated with the catalytic cracking reactor.
In the device provided by the utility model, the catalytic cracking reactor is provided with a carbon four-raw material inlet; the bottom of the regenerator is provided with a regeneration gas inlet, and the top of the regenerator is provided with a regeneration gas outlet.
Preferably, the dry gas outlets of the first oil-gas separation system and the second oil-gas separation system are communicated with a gas separation device, and the gas separation device can adopt the same set of gas separation device and can also be respectively introduced into different gas separation devices. The gas separation device comprises a plurality of rectifying towers and accessory equipment.
Preferably, the ethane and propane outlets of the gas separation device are communicated with the steam cracking furnace. More preferably, the propane outlets of the first oil-gas separation system and the second oil-gas separation system are communicated with a propane steam cracking furnace; the ethane outlet of the gas separation device is communicated with an ethane steam cracking furnace.
In the device provided by the utility model, the catalytic cracking reactor is a reactor combined by one or more of a riser reactor, a turbulent bed reactor and a fast bed reactor, and is preferably a riser reactor; the aromatization reactor is a fixed bed reactor, and the alkane dehydrogenation reactor is a fixed bed reactor.
The regenerator is a regenerator of various forms in the art, which uses air or air mixed oxygen-rich gas to react with coke on the spent catalyst, burns off the coke on the spent catalyst to restore the activity of the spent catalyst (called regenerated catalyst), and raises the catalyst temperature to 600 ℃ to 760 ℃ in order to return to the reactor to bring heat and catalytic media to the reaction.
The device provided by the utility model, first, second oil-gas separation system adopt one or more combinations in fractionating tower, rectifying column, absorption tower, the desorber. And (4) the same gas separation device is adopted for dry gas separation in the step (4), and the gas separation device comprises a rectifying tower and accessory equipment.
Preferably, the steam cracking furnace is an ethane steam cracking furnace and a propane steam cracking furnace, the ethane pipeline of the gas separation device is communicated with the ethane steam cracking furnace, and the propane pipeline of the gas separation device is communicated with the propane steam cracking furnace.
Preferably, the product outlet of the alkane dehydrogenation reactor is also communicated with a four-carbon product pipeline leading-out device.
Preferably, the C4 outlet of the first oil-gas separation system is respectively communicated with the aromatization reactor, the catalytic cracking reactor and the carbon four product pipeline leading-out device.
Preferably, the C4 outlet of the second oil-gas separation system is respectively communicated with the alkane dehydrogenation reactor and the four-carbon product pipeline leading-out device.
The utility model provides an application method of catalytic conversion device, include:
(1) introducing four components of raw material carbon into a catalytic cracking reactor, carrying out contact reaction with a regenerated catalyst from a regenerator, allowing a mixture of oil gas and the catalyst obtained by the reaction to enter a settler for gas-solid separation, separating the separated reaction oil gas into dry gas, liquefied gas and gasoline through a separation system, and further separating propylene, propane and a first four-component carbon from the liquefied gas;
(2) the separated first four carbon components enter an aromatization reactor to contact and react with an aromatization catalyst, dry gas, liquefied gas and gasoline rich in aromatic hydrocarbon are separated from reaction products through a separation system, propylene, propane and a second four carbon components are further separated from the liquefied gas, and the aromatic hydrocarbon is further separated from the gasoline rich in aromatic hydrocarbon;
(3) and the second carbon four components enter an alkane dehydrogenation reactor, contact with a dehydrogenation catalyst to perform dehydrogenation reaction, and return the reaction product to the catalytic cracking reactor.
Wherein, still include step (4): and (3) separating propane from dry gas in the steps (1) and (2) to obtain ethane, and introducing the ethane into a steam cracking furnace for steam cracking to generate ethylene and propylene.
Wherein the raw material carbon four components come from a catalytic cracking unit and contain carbon four-olefin and carbon four-alkane, and the olefin content in the raw material carbon four components is more than 20 wt%. Preferably, the olefin content in the feed carbon four components is 40 wt% to 80 wt%.
The catalyst in the step (1) is a catalytic cracking catalyst, and contains an MFI structure molecular sieve, a Y-type molecular sieve, clay and a binder, wherein based on the total weight of the catalyst, 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%.
Wherein, the operation conditions of the catalytic cracking reactor are as follows: 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。
Wherein, 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 subjected to steam stripping in a steam stripper. The separated reaction oil gas enters a catalytic cracking fractionating tower, products below the gasoline obtained from the top of the fractionating tower enter an absorption stabilizing system, the products of the gasoline, dry gas and liquefied gas separated by the stabilizing system enter a gas separation device, and the four components of propylene, propane and carbon are separated from the liquefied gas. The dry gas enters a split separation device to separate ethylene, ethane and other gases.
And carrying out aromatization reaction on the first four-carbon component in an aromatization reactor to generate dry gas, liquefied gas and a gasoline fraction rich in aromatic hydrocarbon, wherein the aromatic hydrocarbon is C6-C10 monocyclic aromatic hydrocarbon.
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。
The aromatization reactor adopts an aromatization catalyst and 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, VIB, VIII, IIB and VIIB elements, and the heat-resistant inorganic oxide is preferably silicon oxide and aluminum oxide.
The operation conditions of the alkane dehydrogenation reactor are as follows: the reaction temperature is 550-650 ℃, the reaction pressure is 0.10-0.5 MPa, and the reaction space velocity is 0.2-2 h-1。
The alkane dehydrogenation reactor adopts an alkane dehydrogenation catalyst, the alkane dehydrogenation catalyst contains a molecular sieve and one or more metal active components, the metal active components are selected from one or more of rare earth elements, IA, IIA, VIB, VIII, IB and VIIB elements, and can contain silicon oxide and aluminum oxide.
Adopting a propane steam cracking furnace and an ethane steam cracking furnace or adopting an ethane-propane cracking furnace in the step (4); it is preferable to use a propane steam cracking furnace and an ethane steam cracking furnace. The steam cracking furnace is a cracking furnace which can be used in the field of steam cracking, and the operating conditions are as follows: the reaction temperature is 780-850 ℃, and the retention time is 0.01-3 seconds.
The lower olefins described herein are ethylene and propylene.
The following describes the catalytic converter for producing light olefins and aromatics provided by the present invention with reference to the accompanying drawings, but the present invention is not limited thereto.
Fig. 1 is a schematic diagram of a catalytic conversion apparatus for producing low-carbon olefins and aromatic hydrocarbons according to the present invention. As shown in the attached figure 1, the catalytic conversion device for producing the low-carbon olefin and the aromatic hydrocarbon comprises: the system comprises a catalytic cracking reactor 1, a regenerator 4, an aromatization reactor 2, an alkane dehydrogenation reactor 3, a first oil-gas separation system 5 and a second oil-gas separation system 6; the device is characterized in that a regenerator 4 is communicated with the bottom of a catalytic cracking reactor 1 through a regenerated catalyst inclined tube 8, a settler 11 and a gas-solid separation device are arranged at the upper part of the catalytic cracking reactor 1, the gas-solid separation device is communicated with the regenerator 4 through a spent catalyst inclined tube 9, an oil-gas outlet of the gas-solid separation device is communicated with a first oil-gas separation system 5 through a pipeline 12, a C4 outlet of the first oil-gas separation system 5 is communicated with an aromatization reactor 2 through a pipeline 14, an outlet of the aromatization reactor 2 is communicated with a second oil-gas separation system 6, a C4 outlet of the second oil-gas separation system 6 is communicated with an alkane dehydrogenation reactor 3 through a pipeline 19, and a product outlet of the alkane dehydrogenation reactor 3 is communicated with the catalytic cracking reactor 1 through a pipeline 24. The dry gas outlets of the first oil-gas separation system and the second oil-gas separation system are communicated with a gas separation device 35 through pipelines 31 and 34, the ethane outlet of the gas separation device 35 is communicated with an ethane steam cracking furnace 33, and the propane outlets of the first oil-gas separation system and the second oil-gas separation system are communicated with a propane steam cracking furnace 32.
The utility model provides an application method of a catalytic conversion device for producing low-carbon olefin and aromatic hydrocarbon, and a flow schematic diagram of the method is shown in figure 1, as shown in the attached figure 1, the carbon four raw material enters a catalytic cracking reactor 1 through a pipeline 7 after being preheated to contact and react with the hot regenerated catalyst from a regenerator 4 through a regenerated catalyst inclined pipe 8, the catalytic cracking reactor 1 is a riser reactor, the generated oil gas and catalyst enter a settler 11, a gas-solid separation device is arranged in the settler 11, oil gas and catalyst are separated in a settler 11, the separated spent catalyst with carbon enters a stripping section 10 for stripping and then enters a regenerator 4 through a spent catalyst inclined pipe 9, the air from the regenerator 4 through the line 25 burns off coke on the spent catalyst to restore activity, and then enters the bottom of the catalytic cracking reactor 1 through the regenerated catalyst inclined tube 8 for recycling. The separated oil and gas enters the first oil and gas separation system 5 through a pipeline 12. Gasoline of the first oil-gas separation system is led out through a pipeline 15, diesel oil is led out through a pipeline 16, oil slurry is led out through a pipeline 26, propylene is led out through a pipeline 27, propane is led out through a pipeline 13 and enters a propane cracking furnace 32; the dry gas enters a gas separation device 35 through a pipeline 31, the gas separation device consists of a plurality of rectifying towers, H2-CH4 is led out through a pipeline 28 after separation, 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 first carbon four components separated by the first oil-gas separation system are led out through a pipeline 14 and enter the aromatization reactor 2, and a part of the first carbon four components are recycled to the catalytic cracking reactor through a pipeline 40.
The aromatization reactor is a fixed bed reactor, the second carbon four components and an aromatization catalyst are in contact reaction in the aromatization reactor, the reaction product enters a second oil-gas separation system through a pipeline 17, after separation, gasoline rich in aromatic hydrocarbon is obtained and is led out through a pipeline 20, propylene is led out through a pipeline 18, propane is led out through a pipeline 21 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 second carbon four components are led out through a pipeline 19 and enter an alkane dehydrogenation and dehydrogenation reactor 3.
In the alkane dehydrogenation-dehydrogenation reactor 3, the four carbon components are in contact reaction with an alkane dehydrogenation catalyst, wherein the tetracarbon is dehydrogenated to generate tetracarbon olefin, and the reaction product is returned to the catalytic cracking reactor for reaction through a pipeline 24.
Propane separated by the first oil-gas separation system 5 enters the propane steam cracking furnace 32 through a pipeline 13, and propane separated by the second oil-gas separation system 6 enters the propane steam cracking furnace 32 through a pipeline 21 to generate propylene and ethylene. The ethane separated by the gas separation unit 35 is fed to the ethane cracking furnace 33 through a line 37 to produce ethylene and propylene.
The effect of the process for producing ethylene, propylene and aromatic hydrocarbons from heavy oil provided by the present invention is illustrated below by examples and comparative examples, but the present invention is not limited thereby.
Comparative examples and examples, the C4 component used was a catalytic cracking separation column from Shijiazhuang, a division of petrochemical Co., Ltd., China, and the properties are shown in Table 1. The catalyst used is DMMC-1 catalyst produced by catalyst division of China petrochemical company Limited. The properties are shown in Table 2. The aromatization catalyst used is sold under the trademark DLP-XA and is produced by Shandong Daqi chemical technology Co. The dehydrogenation catalyst used was a commercial product number BDH-5, manufactured by Dalian Mittac.
Comparative examples 1 to 2
Comparative examples 1-2 the apparatus and method for producing ethylene and propylene by using C4 recycle catalytic cracking shown in fig. 2 is shown in fig. 2, the raw material carbon four components are preheated and then enter a catalytic cracking riser reactor through a line 7 to contact with the thermal regenerated catalyst from a regenerator 4 through a regenerated catalyst inclined tube 8, catalytic cracking reaction is carried out, the generated oil gas and catalyst flow upward and enter a settler 11, a gas-solid separation device is arranged in the settler 11, the reaction oil gas and catalyst are separated in the settler 11, the separated spent catalyst with carbon is stripped by a stripping section 10 and then enters a regenerator 4 through a spent catalyst inclined tube 9, the coke on the spent catalyst is burned by air from a line 25 in the regenerator 4 to restore the activity, and then the air enters the bottom of the riser reactor through the spent catalyst inclined tube 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, oil slurry 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 passed to a gas separation unit 35, separated ethylene 28, other gases 36 and ethane 37, which is withdrawn via line 37 and passed to an ethane cracking furnace 33 to produce ethylene and propylene. The four carbon components are withdrawn via line 14, a portion of the four carbon components are returned to the catalytic cracking reactor via line 28, and the remaining four carbon components are withdrawn from the unit via line 20 as product.
The reaction conditions of comparative examples 1-2 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) four components of raw material carbon are introduced into a catalytic cracking reactor and contact with a regenerated catalyst from a regenerator for reaction, an oil gas and catalyst mixture obtained by the reaction enters a settler for gas-solid separation, the separated reaction oil gas is separated into dry gas, liquefied gas, gasoline, diesel oil and oil slurry through a separation system, and further ethylene, propylene, aromatic hydrocarbon products and a first four components of carbon are separated; (2) the first four carbon 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, so that ethylene, propylene, a second four carbon components and aromatic hydrocarbon products are further separated; (3) the second carbon four components enter an alkane dehydrogenation reactor, contact with a dehydrogenation catalyst to perform dehydrogenation reaction, and the reaction product returns to the catalytic cracking reactor; (4) and (2) separating the dry gas and the liquefied gas in the step (1) and (2) to obtain ethane and propane, and respectively introducing the ethane and the propane into an ethane steam cracking furnace and a propane steam cracking furnace for steam cracking to generate ethylene and propylene.
The reaction conditions of 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 cycle ratios (carbon four feed/feedstock) of the examples of the carbon four feedstock a and the carbon four feedstock B are reduced by 0.2 and 0.3, respectively, compared to the comparative examples, and energy consumption is saved. In the product distribution, ethylene is respectively increased by 0.76 percent and 1.49 percent, propylene is respectively increased by 2.10 percent and 2.16 percent, and aromatic hydrocarbon (BTX) is respectively increased by 10.47 percent and 17.11 percent.
TABLE 1 composition of C4 components
| Raw materials | C4 component A | C4 component B |
| Isobutane | 26.18 | 38.75 |
| N-butane | 6.35 | 9.97 |
| Butene-1 | 10.01 | 11.18 |
| Isobutene | 28.90 | 12.92 |
| Cis-butenediol | 16.52 | 14.06 |
| Butene of trans-butene | 12.03 | 13.12 |
TABLE 2 catalyst composition and Properties
| RE2O3 | 0.56 |
| Al2O3 | 54 |
| Physical Properties | |
| Specific surface area, m2/g | 100 |
| Pore volume, cm3/g | 0.176 |
| Micropore volume, cm3/g | 0.026 |
| Apparent density, g/cm3 | 0.91 |
| Sieving, according to | |
| 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 |
| Slightly reactive, wt% (520 ℃ C.) | 55 |
TABLE 3
| Item | Comparative example 1 | Example 1 | Comparative example 2 | Example 2 |
| Catalytic cracking reactor | ||||
| C4 raw material | C4 component A | C4 component A | C4 component B | C4 component B |
| Reaction pressure/MPa | 0.2 | 0.2 | 0.28 | 0.28 |
| Reaction temperature/. degree.C | 620 | 620 | 650 | 650 |
| Regenerator temperature/. degree.C | 690 | 690 | 710 | 710 |
| Ratio of agent to |
15 | 15 | 20 | 20 |
| Reaction space velocity/ |
10 | 10 | 50 | 50 |
| Atomized steam/%) | 25 | 25 | 15 | 15 |
| Carbon to 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 |
| Alkane dehydrogenation reactor | ||||
| Reaction pressure/MPa | / | 0.3 | / | 0.3 |
| Reaction temperature/. degree.C | / | 600 | / | 620 |
| Reaction space velocity/h-1 | / | 0.5 | / | 1.1 |
| Ethane cracking reactor | ||||
| Temperature/. degree.C | 830 | 830 | 830 | 830 |
| pressure/MPa | 0.13 | 0.13 | 0.13 | 0.13 |
| Atomized steam/%) | 60 | 60 | 60 | 60 |
| Propane cracking reactor | ||||
| Temperature/. degree.C | 815 | 815 | 815 | 815 |
| pressure/MPa | 0.13 | 0.13 | 0.13 | 0.13 |
| Atomized steam/%) | 60 | 60 | 60 | 60 |
TABLE 4
| Example numbering | Comparative example 1 | Example 1 | Comparative example 2 | Example 2 |
| Product yield | ||||
| H2-C2 | 5.77 | 8.12 | 7.94 | 9.38 |
| C3-C4 | 76.38 | 54.51 | 86.26 | 72.73 |
| C5+ gasoline | 13.51 | 31.61 | 3.04 | 14.27 |
| Diesel oil | 0.77 | 1.31 | 0.42 | 0.75 |
| Heavy oil | 0.02 | 0.30 | 0.12 | 0.29 |
| Coke | 3.36 | 3.64 | 2.02 | 2.19 |
| Ethylene | 3.47 | 4.96 | 3.99 | 4.75 |
| Propylene (PA) | 16.59 | 18.75 | 8.58 | 10.68 |
| BTX | 1.26 | 18.37 | 1.34 | 11.81 |
Claims (11)
1. A catalytic converter for producing lower olefins and aromatics, comprising: the system comprises a catalytic cracking reactor, a regenerator, an aromatization reactor, an alkane dehydrogenation reactor, a first oil-gas separation system and a second oil-gas separation system; the regenerator has a regenerant outlet communicated with the bottom of the catalytic cracking reactor, the upper part of the catalytic cracking reactor is provided with a settler and a gas-solid separation device, a spent 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 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, a C4 outlet of the second oil-gas separation system is communicated with an alkane dehydrogenation reactor, and a product outlet of the alkane dehydrogenation reactor is communicated with the catalytic cracking reactor.
2. The catalytic conversion apparatus for producing light olefins and aromatic hydrocarbons according to claim 1, wherein the bottom of the catalytic cracking reactor is provided with a carbon four-material inlet; the bottom of the regenerator is provided with a regeneration gas inlet, and the top of the regenerator is provided with a regeneration gas outlet.
3. The catalytic conversion apparatus for producing lower olefins and aromatic hydrocarbons according to claim 2, wherein the dry gas outlets of the first and second oil-gas separation systems are communicated with the gas separation apparatus.
4. The catalytic conversion apparatus for producing lower olefins and aromatic hydrocarbons according to claim 3, wherein the propane outlets of the first and second oil-gas separation systems are communicated with a propane steam cracking furnace; the ethane outlet of the gas separation device is communicated with an ethane steam cracking furnace.
5. The catalytic conversion apparatus for producing light olefins and aromatic hydrocarbons according to claim 2, wherein the catalytic cracking reactor is one or a combination of several of a riser reactor, a turbulent bed reactor and a fast bed reactor, the aromatization reactor is a fixed bed reactor, and the alkane dehydrogenation reactor is a fixed bed reactor.
6. The catalytic converter apparatus for producing light olefins and aromatic hydrocarbons according to claim 5, wherein the catalytic cracking reactor is a riser reactor.
7. The catalytic conversion apparatus for producing light olefins and aromatic hydrocarbons according to any one of claims 1 to 5, wherein the first and second oil-gas separation systems are one or more of a fractionating tower, a rectifying tower, an absorption tower and a desorption tower.
8. The catalytic converter for producing lower olefins and aromatic hydrocarbons according to claim 3 or 4, wherein the gas separation unit is a combination of a plurality of rectifying towers.
9. The catalytic conversion device for producing the light olefins and the aromatic hydrocarbons according to any one of claims 1 to 5, wherein a product outlet of the alkane dehydrogenation reactor is further communicated with a four-carbon product pipeline leading-out device.
10. The catalytic conversion apparatus for producing lower olefins and aromatic hydrocarbons according to any of claims 1 to 5, wherein the C4 outlet of the first oil-gas separation system is respectively communicated with the aromatization reactor, the catalytic cracking reactor and the carbon four product pipeline leading-out apparatus.
11. The catalytic conversion device for producing the light olefins and the aromatic hydrocarbons according to any one of claims 1 to 5, wherein the C4 outlet of the second oil-gas separation system is respectively communicated with the alkane dehydrogenation reactor and the four-carbon product pipeline leading-out device.
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