CN114540069A - Method and device for preparing olefin by cracking petroleum hydrocarbon and application - Google Patents
Method and device for preparing olefin by cracking petroleum hydrocarbon and application Download PDFInfo
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- CN114540069A CN114540069A CN202210001905.5A CN202210001905A CN114540069A CN 114540069 A CN114540069 A CN 114540069A CN 202210001905 A CN202210001905 A CN 202210001905A CN 114540069 A CN114540069 A CN 114540069A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method, a device and application for preparing olefin by cracking petroleum hydrocarbon, wherein the method adopts a process flow combining thermal cracking reaction, coking reaction and regeneration reaction, wherein the thermal cracking reaction is to carry out the thermal cracking reaction on the petroleum hydrocarbon and a high-temperature solid heat carrier in a water vapor atmosphere, the reaction temperature is lower, and simultaneously low-carbon olefin with high yield can be obtained. The method has strong raw material adaptability and high energy utilization rate, and can be applied to the process for preparing the low-carbon olefin.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method and a device for preparing olefin by cracking petroleum hydrocarbon and application of the method and the device.
Background
The low-carbon olefin such as ethylene, propylene and the like is an important organic chemical raw material and has an irreplaceable position in industrial synthesis and production. At present, two methods for obtaining low-carbon olefins mainly include steam cracking and catalytic cracking, including two major types of synthetic routes using petroleum as a raw material and non-petroleum synthetic routes using natural gas, synthetic gas and low-carbon alcohol as raw materials. The technology for directly producing the low-carbon olefin chemical raw material by catalytic cracking by taking heavy oil or crude oil as a raw material meets the current market demand, and is a technology with great industrial prospect.
However, in the existing process of directly cracking crude oil, the reaction temperature is high, the coke formation amount is low, the temperature of the catalyst regenerated by directly burning cannot meet the heat requirement required by the cracking of the crude oil, and in order to meet the heat requirement required by the cracking of the crude oil, a certain amount of fuel oil is generally required to be sprayed into a regenerator to supplement the heat requirement of the whole process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method and a device for preparing olefin by cracking petroleum hydrocarbon and application.
The invention is realized by the following steps:
in one aspect, the invention provides a method for producing olefins by cracking petroleum hydrocarbons, comprising a thermal cracking reaction, a coking reaction and a regeneration reaction. The thermal cracking reaction comprises the steps that in a riser reactor, petroleum hydrocarbon and a high-temperature solid heat carrier are mixed under the steam atmosphere to generate the thermal cracking reaction, first gas-solid separation is carried out after the reaction is finished, the high-temperature solid heat carrier obtained through the first gas-solid separation and heavy oil are subjected to coking reaction in a fluidized bed reactor under the steam atmosphere, second gas-solid separation is carried out after the reaction is finished to obtain a coking solid heat carrier, the regeneration reaction comprises the steps of removing coke on the coking solid heat carrier and carrying out third gas-solid separation, and the obtained high-temperature solid heat carrier returns to the riser reactor to carry out the thermal cracking reaction.
In a second aspect, the invention provides a device for preparing olefin by cracking petroleum hydrocarbon, which comprises a riser reactor, a fluidized bed reactor and a fluidized bed regenerator, wherein the riser reactor and the fluidized bed reactor are connected through a conveying inclined pipe of a first gas-solid separator, the fluidized bed reactor and the fluidized bed regenerator are connected through a standby inclined pipe of a fluidized bed, and the fluidized bed regenerator and the riser reactor are connected through a regeneration inclined pipe of the riser.
In a third aspect, the invention provides an application of a method or a device for preparing olefin by cracking petroleum hydrocarbon in industrial preparation of olefin.
The invention has the following beneficial effects:
the method for preparing olefin by cracking petroleum hydrocarbon combines the thermal cracking reaction and the coking reaction, so that the raw material to be treated has strong adaptability, and not only can directly crack various light crude oils and heavy crude oils, but also can treat light hydrocarbon and heavy hydrocarbon, thereby widening the range of raw materials for producing low-carbon olefin to a greater extent. Meanwhile, the side chains of paraffin, cyclane and arene fed by the riser reactor in the thermal cracking reaction are almost completely cracked, so that the single-pass conversion rate is high, the coke production is low, the selectivity of olefin is improved, and the total yield of the obtained ethylene, propylene and butylene is higher. Heavy components such as polycyclic aromatic hydrocarbon fed into the fluidized bed reactor are easy to undergo condensation coking reaction and are converted into coke to be deposited on a heat carrier, the coking quantity of the solid heat carrier is improved, the generated coke is deposited on the solid heat carrier to carry out regeneration reaction, the coke on the solid heat carrier is combusted to meet the requirement of raw material cracking reaction heat in the riser reactor, heavy components such as polycyclic aromatic hydrocarbon which are difficult to process are converted, the problem of unbalanced heat of the whole process is solved, and the utilization rate of energy is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of an apparatus for producing olefins by cracking petroleum hydrocarbons according to example 1 of the present invention;
FIG. 2 is a schematic diagram of an apparatus for producing olefins by cracking petroleum hydrocarbons according to comparative example 1 of the present invention;
icon: FIG. 1 part: 100-device for preparing olefin by cracking petroleum hydrocarbon, 110-riser reactor, 111-first gas-solid separator, 112-riser steam feed inlet, 113-riser outlet, 114-feed section, 115-stripping section, 116-settling section, 117-riser oil gas feed inlet, 120-fluidized bed reactor, 121-second gas-solid separator, 122-fluidized bed second feed inlet, 123-fluidized bed first feed inlet, 124-fluidized bed outlet, 130-fluidized bed regenerator, 131-third gas-solid separator, 132-regenerator feed inlet, 133-regenerator outlet, 140-fractionating tower, 141-tower bottom outlet, 142-tower side outlet, 143-tower top outlet, 144-inferior high aromatic heavy oil feed inlet, 151-first gas-solid separator conveying inclined tube, 152-a fluidized bed to-be-regenerated inclined pipe and 153-a riser regeneration inclined pipe;
FIG. 2 is a partial view: the device comprises a device for preparing olefin by cracking petroleum hydrocarbon 1, a riser reactor 2, a vertical cyclone separator 3, a settler conveying inclined tube 4, a regenerator 5, a regenerator cyclone separator 6, a riser regenerating inclined tube 7, a riser feed inlet 9, a riser outlet 10, a regenerator outlet 11, a regenerator feed inlet 12, a regenerator feed inlet 13, a feed section 14, a stripping section 15 and a settling section 15.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The low-carbon olefin is an important organic chemical raw material, the existing preparation method of the low-carbon olefin mainly comprises steam cracking and catalytic cracking, but in the existing cracking process, the reaction temperature is high, the coke formation amount is low, the temperature of a catalyst regenerated by direct burning cannot meet the heat requirement required by crude oil cracking, and in order to meet the heat required by crude oil cracking, a certain amount of fuel oil is generally required to be sprayed into a regenerator to supplement the heat requirement of the whole process.
In a first aspect, the present invention provides a process for producing olefins by cracking petroleum hydrocarbons, comprising a thermal cracking reaction, a coking reaction and a regeneration reaction. The thermal cracking reaction comprises the steps that in a riser reactor, petroleum hydrocarbon and a high-temperature solid heat carrier are mixed under the steam atmosphere to generate the thermal cracking reaction, first gas-solid separation is carried out after the reaction is finished, the high-temperature solid heat carrier obtained through the first gas-solid separation and heavy oil are subjected to coking reaction in a fluidized bed reactor under the steam atmosphere, second gas-solid separation is carried out after the reaction is finished to obtain a coking solid heat carrier, the regeneration reaction comprises the steps of removing coke on the coking solid heat carrier and carrying out third gas-solid separation, and the obtained high-temperature solid heat carrier returns to the riser reactor to carry out the thermal cracking reaction.
The inventor finds out through research that the raw materials to be processed have strong adaptability by combining thermal cracking reaction and coking reaction, not only can directly crack various light crude oils and heavy crude oils, but also can process light hydrocarbons and heavy hydrocarbons, and widens the raw materials for producing the low-carbon olefins to a great extent. Meanwhile, the side chains of paraffin, cyclane and arene fed by the riser reactor in the thermal cracking reaction are almost completely cracked, so that the single-pass conversion rate is high, the coke production is low, the selectivity of olefin is improved, and the total yield of the obtained ethylene, propylene and butylene is higher.
In addition, the sintering temperature of the existing regenerator is low, so that the problem of unbalanced heat of the whole process is caused, the coking reaction is creatively combined into the preparation process of olefin, heavy components such as polycyclic aromatic hydrocarbon and the like fed into a fluidized bed reactor are subjected to condensation coking reaction and converted into coke which is deposited on a heat carrier, so that the coking quantity of the solid heat carrier is increased, the generated coke is deposited on the solid heat carrier for regeneration reaction, the coke on the solid heat carrier is combusted to meet the requirement of raw material cracking reaction heat in a riser reactor, heavy components such as polycyclic aromatic hydrocarbon and the like which are difficult to process are converted, the problem of unbalanced heat of the whole process is solved, and the utilization rate of energy is increased.
In some embodiments of the present invention, the high-temperature oil gas obtained by the first gas-solid separation and the coking reaction gas obtained by the second gas-solid separation enter a fractionating tower to be separated, and light components and heavy components are obtained by separation.
Optionally, in order to increase the yield of coke in the high-temperature solid heat carrier, the heavy oil used in the coking reaction comprises inferior high aromatic heavy oil and/or heavy components obtained by the above-mentioned fractionating tower reaction.
The inventor researches and discovers that heavy oil and a high-temperature solid heat carrier are subjected to coking reaction, the high-temperature solid heat carrier has high coke formation amount, the obtained coking solid heat carrier with high coke formation amount enters a regenerator to react, and the high-temperature solid heat carrier is heated by burning coke on the coking solid heat carrier so as to meet the requirement of raw material cracking reaction heat in a riser reactor. Because the coking reaction improves the raw coke amount of the high-temperature solid heat carrier, additional oil injection afterburning is not needed in the regeneration reaction process, heavy components such as polycyclic aromatic hydrocarbon and the like which are difficult to process are converted, and the problem of unbalanced heat of the whole process is solved.
Alternatively, the low-quality high aromatic heavy oil comprises one or more of vacuum gas oil, catalytic cracking slurry oil, atmospheric residue, vacuum residue and deoiled asphalt. The high aromatic hydrocarbon heavy oil can effectively improve the green coke amount of the high-temperature solid heat carrier, and solves the problem of unbalanced heat in the whole process.
In a preferred embodiment of the present invention, the heavy oil used in the coking reaction has a carbon residue value of 5.0% to 30%, preferably a carbon residue value of 15% to 25%.
In some embodiments of the invention, the fluidized bed reactor is a straight tube reactor with an expanded diameter dense phase section, and dense phase fluidization is achieved by expanding diameter and reducing velocity.
Specifically, heavy oil feed of coking reaction is sprayed above a dense phase section and flows downwards, and is in countercurrent contact with a fluidized high-temperature solid heat carrier in a fluidized bed reactor, so that heat exchange is carried out and coking reaction is carried out, and the high-temperature solid heat carrier adsorbs components with high boiling points, difficult cracking and easy coking, so that coking of the high-temperature solid heat carrier is promoted.
In a preferred embodiment of the present invention, the coking reaction temperature is 500-550 ℃, preferably 510-530 ℃. The coking reaction temperature is controlled within the range, so that the coke production amount of the high-temperature solid heat carrier is increased, the coking temperature of the regenerator is increased, and the expected technical effect of the invention is realized. For example, the coking reaction temperature may be 500 ℃, 510 ℃, 515 ℃, 520 ℃, 525 ℃, 530 ℃, 540 ℃, 550 ℃.
In some embodiments of the present invention, the thermal cracking reaction specifically includes injecting the heat-exchanged petroleum hydrocarbon into the riser reactor, allowing the high-temperature solid heat carrier to move upward along the riser reactor at a high speed under the action of steam, sufficiently mixing with the petroleum hydrocarbon, heating, vaporizing, and performing a thermal cracking reaction, and performing a first gas-solid separation after the reaction is completed.
In some embodiments of the invention, the petroleum hydrocarbons include a combination of one or more of light crude oil, heavy crude oil, straight run naphtha, catalytic gasoline, and coker gasoline. The coke formation amount of the raw materials is low when the raw materials are subjected to thermal cracking reaction, so that the selectivity of olefin is high, and the yield of the olefin is further improved.
In a preferred embodiment of the present invention, the thermal cracking temperature of the riser reactor is 650 to 750 ℃, preferably 680 to 720 ℃. Compared with steam cracking, the invention has lower temperature, less steam consumption and lower energy consumption. For example, the thermal cracking reaction temperature can be 650 ℃, 660 ℃, 670 ℃, 680 ℃, 685 ℃, 690 ℃, 695 ℃, 700 ℃, 705 ℃, 720 ℃, 715 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃.
In a preferred embodiment of the present invention, in order to improve the efficiency of the thermal cracking reaction, the reaction time of the riser reactor is 0.5 to 2s, the agent-oil ratio is 15 to 25, and the absolute pressure of the reaction is 0.10 to 0.30 MPa.
In a preferred embodiment of the present invention, the mass ratio of the steam to the petroleum hydrocarbon is 0.05:1 to 1:1, preferably 0.3:1 to 0.5:1, in order to increase the yield of the lower olefins. For example, the mass ratio of steam to petroleum hydrocarbon may be 0.05:1, 0.15:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1: 1.
In some embodiments of the present invention, removing coke from the coked solid heat carrier comprises introducing a regenerant into the bottom of the regenerator to char the coked solid heat carrier, and removing coke on the surface of the coked solid heat carrier to obtain a high-temperature solid heat carrier.
In a preferred embodiment of the present invention, the regenerant is at least one of air, an oxygen-containing gas, air or a mixture of an oxygen-containing gas and water vapor.
In a preferred embodiment of the present invention, the temperature of the regeneration reaction is 800-950 ℃, the pressure is 0.20-0.40 MPa, and the regeneration time is 5-20 min.
In some embodiments of the invention, the high temperature solid heat carrier comprises one or more of a combination of high temperature treated carbon microspheres, alumina particles, aluminum silicate porous microspheres. As the carbon microspheres, the alumina particles and the aluminum silicate porous microspheres have better high temperature resistance, the microsphere structure can not collapse due to overhigh reaction temperature in the process of preparing the olefin, and the smooth reaction is ensured.
In a preferred embodiment of the invention, the SiO content of the porous alumina silicate microspheres is calculated by mass percent210-50% of Al2O3The content is 50-90%.
In a preferred embodiment of the invention, in order to increase the contact area of the high-temperature solid heat carrier and the high-temperature oil gas, the average particle size of the high-temperature solid heat carrier is 10-300 microns, and preferably 30-200 microns.
In some embodiments of the present invention, in order to completely separate high-temperature oil gas and high-temperature solid heat carriers, the first gas-solid separation, the second gas-solid separation and the third gas-solid separation are separated by using cyclone separators.
In a second aspect, the invention also provides a device for preparing olefin by cracking petroleum hydrocarbon, which comprises a riser reactor, a fluidized bed reactor and a regenerator. The device comprises a riser reactor, a fluidized bed reactor, a regenerator and a first gas-solid separator, wherein the riser reactor is connected with the fluidized bed reactor through a first gas-solid separator conveying inclined pipe, the first gas-solid separator conveying inclined pipe is used for conveying a high-temperature solid heat carrier in the riser reactor to the fluidized bed reactor for coking reaction, the fluidized bed reactor is connected with the regenerator through a fluidized bed standby inclined pipe, the fluidized bed standby inclined pipe is used for conveying the coking solid heat carrier in the fluidized bed reactor to the regenerator for regeneration, the regenerator is connected with the riser reactor through a riser regeneration inclined pipe, and the riser regeneration inclined pipe is used for conveying the high-temperature solid heat carrier in the regenerator to the riser reactor to participate in the thermal cracking reaction again.
Specifically, the device for preparing olefin by cracking petroleum hydrocarbon and the treatment process are as follows:
in some embodiments of the present invention, the riser reactor includes a feeding section, a stripping section and a settling section, and the petroleum hydrocarbon, the high-temperature solid heat carrier and the steam enter the stripping section through the feeding section to undergo a thermal cracking reaction, and are settled and separated by the settling section to obtain the high-temperature oil gas and the high-temperature solid heat carrier.
Furthermore, a feeding section of the riser reactor is provided with a riser feeding hole and a riser regeneration inclined tube, the riser feeding hole is provided with an atomizing nozzle, the riser feeding hole comprises a riser steam feeding hole and a riser oil gas feeding hole, petroleum hydrocarbon raw materials are sprayed into the riser reactor through the atomizing nozzle of the riser oil gas feeding hole, a high-temperature solid heat carrier enters the riser reactor through the riser regeneration inclined tube, water steam is sprayed into the riser reactor through the atomizing nozzle of the riser steam feeding hole, the high-temperature solid heat carrier ascends at a high speed under the action of the water steam, is fully mixed, heated and vaporized with the atomized petroleum hydrocarbon raw materials in a stripping section, generates a pyrolysis reaction, continuously ascends to enter a settling section after the reaction is finished, the settling section is provided with a first gas-solid separator, and a gas-solid mixture obtained by the reaction in the stripping section is separated by the first gas-solid separator, obtaining high-temperature oil gas and a high-temperature solid heat carrier.
The high-temperature solid heat carrier obtained by separation of the riser reactor is conveyed from the first gas-solid separator to the inclined pipe to enter the fluidized bed reactor, the fluidized bed reactor comprises a fluidized bed feeding port and a second gas-solid separator, the fluidized bed feeding port is provided with an atomizing nozzle and comprises a first fluidized bed feeding port and a second fluidized bed feeding port, water vapor is sprayed into the fluidized bed reactor from the first fluidized bed feeding port to drive the high-temperature solid heat carrier to move upwards, and heavy oil is sprayed into the fluidized bed reactor from the second fluidized bed feeding port to be in counter-current contact with the high-temperature solid heat carrier and to be subjected to coking reaction. And separating the reacted gas-solid mixture by a second gas-solid separator to obtain coking reaction gas and a coking solid heat carrier.
In a preferred embodiment of the invention, the fluidized bed reactor is a straight tube reactor with an expanded diameter dense phase section. The reactor has the characteristics of strong raw material adaptability, low gas linear velocity, long reaction oil gas retention time, high coke rate of a solid heat carrier and the like.
In a preferred embodiment of the invention, the atomizing nozzles at the second feed port of the fluidized bed are arranged in multiple layers, so that the fed heavy oil is fully contacted with the fluidized high-temperature solid heat carrier section by section, and coke grows uniformly on the surface of the high-temperature solid heat carrier to obtain the coked solid heat carrier.
The water vapor injected into the first feeding port of the fluidized bed is used for increasing the stirring and friction between the high-temperature solid heat carrier and the coke and controlling the distribution condition and the shape of the coke on the high-temperature solid heat carrier.
And further, the coking solid heat carrier enters a fluidized bed regenerator from a fluidized bed inclined tube to be regenerated, the fluidized bed regenerator comprises a regenerator feed inlet, a regenerator outlet and a third gas-solid separator, wherein the regenerator outlet is arranged at one end of the fluidized bed regenerator close to the third gas-solid separator. And (3) spraying a regenerant into the fluidized bed regenerator from a feed inlet of the regenerator, burning the coked solid heat carrier, removing surface coke, and passing the obtained gas-solid mixture through a third gas-solid separator to obtain regenerated flue gas and a high-temperature solid heat carrier. The regenerated flue gas flows out through the outlet of the regenerator and enters a flue gas treatment system, and the high-temperature solid heat carrier returns to the riser reactor through a riser regeneration inclined tube and participates in the process flow of preparing olefin by cracking petroleum hydrocarbon again.
In some embodiments of the invention, the regenerator comprises a fluidized bed regenerator, preferably a straight tube reactor with an expanded dense phase section. The reactor has the characteristics of uniform regeneration temperature control, high regeneration efficiency, low coke content of the regenerated solid heat carrier, low solid particle content of the regenerated flue gas and the like.
In a preferred embodiment of the invention, in order to improve the gas-solid separation effect, the first gas-solid separator, the second gas-solid separator and the third gas-solid separator are cyclone separators.
In preferred embodiments of the invention, the cyclone separator comprises a horizontal cyclone separator and/or a vertical cyclone separator.
In some embodiments of the present invention, the apparatus further comprises a fractionating tower connected to the riser reactor and the fluidized bed reactor via pipes for fractionating the high-temperature oil gas separated by the first gas-solid separator and the coking reaction gas separated by the second gas-solid separator.
Specifically, the riser reactor is also provided with a riser outlet, and high-temperature oil gas obtained by separation of the first gas-solid separator is discharged from the riser outlet and flows into the fractionating tower along a pipeline; the fluidized bed reactor is also provided with a fluidized bed outlet, the coking reaction gas obtained by separating the second gas-solid separator is discharged from the fluidized bed outlet and flows into the fractionating tower along a pipeline, the high-temperature oil gas and the coking reaction gas react in the fractionating tower and are separated to obtain light components and heavy components, the light components flow into the next-stage reactor for treatment, and the heavy components return to the fluidized bed reactor to participate in the coking reaction.
In a third aspect, the invention provides an application of a method or a device for preparing olefin by cracking petroleum hydrocarbon in industrial preparation of olefin.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Referring to fig. 1, the present embodiment provides an apparatus 100 for cracking petroleum hydrocarbons to produce olefins, which includes a riser reactor 110, a fluidized bed reactor 120, and a fluidized bed regenerator 130.
The riser reactor 110 and the fluidized bed reactor 120 are connected through a first gas-solid separator conveying inclined pipe 151, the first gas-solid separator conveying inclined pipe 151 is used for conveying a high-temperature solid heat carrier in the riser reactor 110 to the fluidized bed reactor 120 for coking reaction, the fluidized bed reactor 120 and the fluidized bed regenerator 130 are connected through a fluidized bed standby inclined pipe 152, the fluidized bed standby inclined pipe 152 is used for conveying the coking solid heat carrier in the fluidized bed reactor 120 to the fluidized bed regenerator 130 for regeneration, the fluidized bed regenerator 130 and the riser reactor 110 are connected through a riser regeneration inclined pipe 153, and the riser regeneration inclined pipe 153 is used for conveying the high-temperature solid heat carrier in the fluidized bed regenerator 130 to the riser reactor 110 to participate in thermal cracking reaction again.
Specifically, the apparatus 100 for producing olefins by cracking petroleum hydrocarbons and the processing flow provided by this embodiment are as follows:
in this embodiment, the riser reactor 110 includes a feeding section 114, a stripping section 115, and a settling section 116, and the petroleum hydrocarbon, the high-temperature solid heat carrier, and the steam all enter the stripping section 115 through the feeding section 114 to undergo a thermal cracking reaction, and then undergo a settling separation through the settling section 116 to obtain the high-temperature oil gas and the high-temperature solid heat carrier. The riser reactor 110 has a throughput of 100 ten thousand tons/year.
Specifically, the feeding section of the riser reactor 110 is disposed at the lower part of the riser reactor 110, the bottom of the riser reactor 110 is provided with a riser feeding port, and the side wall of the feeding section 114 is connected with a riser regeneration inclined tube 153. The riser feed inlet is provided with an atomizing nozzle, which specifically comprises a riser oil gas feed inlet 117 on the side wall of the riser reactor 110 and a riser steam feed inlet 112 at the bottom of the riser reactor 110, petroleum hydrocarbon raw materials are injected into the riser reactor 110 through the atomizing nozzle of the riser oil gas feed inlet 117, water steam is injected into the riser reactor 110 through the atomizing nozzle of the riser steam feed inlet 112, a high-temperature solid heat carrier enters the riser reactor 110 through a riser regeneration inclined tube 153, the high-temperature solid heat carrier ascends at a high speed under the action of the water steam, is fully mixed, heated and vaporized with the atomized petroleum hydrocarbon raw materials in a stripping section 115, and carries out a thermal cracking reaction, and continuously ascends to enter a settling section 116 at the upper part of the riser reactor 110 after the reaction, the settling section 116 is provided with a first gas-solid separator 111, and a mixture obtained by the reaction in the stripping section 116 is separated by the first gas-solid separator 111, obtaining high-temperature oil gas and a high-temperature solid heat carrier.
The high-temperature solid heat carrier separated by the riser reactor 110 enters the fluidized bed reactor 120 from the inclined conveying pipe 151 of the first gas-solid separator, the processing capacity of the fluidized bed reactor 120 is 60 ten thousand tons per year, the fluidized bed reactor 120 is a straight pipe reactor with an expanded dense phase section and specifically comprises a fluidized bed feed port and a second gas-solid separator 121, the fluidized bed feed port is provided with an atomizing nozzle, the fluidized bed feed port comprises a first fluidized bed feed port 123 and a second fluidized bed feed port 122, water vapor is sprayed into the fluidized bed reactor 120 from the first fluidized bed feed port 123 to drive the high-temperature solid heat carrier to ascend, heavy oil is sprayed into the fluidized bed reactor 120 from the second fluidized bed feed port 122, the atomizing nozzle of the second fluidized bed feed port 122 is arranged in a multilayer mode, the heavy oil and the high-temperature solid heat carrier are in full countercurrent contact section by section and coking reaction is carried out, and coke is uniformly grown on the surface of the heat carrier. The reacted gas-solid mixture is separated by a second gas-solid separator 121 to obtain coking reaction gas and a coking solid heat carrier.
The coking solid heat carrier enters the fluidized bed regenerator 130 from the inclined tube 152 to be generated of the fluidized bed, the fluidized bed regenerator 130 is a straight tube reactor with an expanded diameter dense phase section, and specifically comprises a regenerator feed inlet 132, a regenerator outlet 133 and a third gas-solid separator 131, wherein the regenerator outlet 133 is arranged at one end of the top of the fluidized bed regenerator 130 close to the third gas-solid separator 131. And (3) injecting air into the fluidized bed regenerator 130 from a regenerator feed port 132 as a regenerant, burning the coked solid heat carrier in the fluidized bed regenerator 130, removing surface coke, and passing the obtained gas-solid mixture through a third gas-solid separator 131 to obtain regenerated flue gas and a high-temperature solid heat carrier. The regenerated flue gas flows out through the regenerator outlet 133 and enters the flue gas treatment system, and the high-temperature solid heat carrier returns to the riser reactor 110 through the riser regeneration inclined tube 153 and participates in the process flow of preparing olefin by cracking petroleum hydrocarbon again.
Specifically, the first gas-solid separator 111, the second gas-solid separator 121, and the third gas-solid separator 131 of the present embodiment are all vertical cyclone separators.
Further, the apparatus of this embodiment further includes a fractionating tower 140, and the fractionating tower 140 is connected to the riser reactor 110 and the fluidized bed reactor 120 through pipes, respectively, and is configured to fractionate the high-temperature oil gas separated by the first gas-solid separator and the coking reaction gas separated by the second gas-solid separator.
Specifically, a riser outlet 113 is arranged at the top of the riser reactor 110, and high-temperature oil gas separated by the first gas-solid separator 111 is discharged from the riser outlet 113 and flows into the fractionating tower 140 along a pipeline; the top of the fluidized bed reactor 120 is provided with a fluidized bed outlet 124, the coking reaction gas separated by the second gas-solid separator 121 is discharged from the fluidized bed outlet 124 and flows into the fractionating tower 140 along a pipeline, and the high-temperature oil gas and the coking reaction gas are separated in the fractionating tower 140 to obtain light components and heavy components. The fractionating tower is further provided with a tower top outlet 143, a tower side outlet 142 and a tower bottom outlet 141, light components flow into the next-stage reactor for processing along the tower top outlet 143 and the tower side outlet 142, heavy components flow out of the fractionating tower through the tower bottom outlet 141 and enter a pipeline, inferior high aromatic heavy oil flows into the pipeline from an inferior high aromatic heavy oil inlet 144, and after being mixed with the heavy components in the pipeline, the inferior high aromatic heavy oil returns to the fluidized bed reactor 120 to circularly participate in coking reaction.
Example 2
Based on the apparatus for preparing olefin by cracking petroleum hydrocarbon in example 1, this embodiment also provides a method for preparing olefin by cracking petroleum hydrocarbon, which includes:
the petroleum hydrocarbon used as the raw material for the thermal cracking reaction is crude oil, and the main properties are shown in table 1, wherein the high-temperature solid heat carrier is alumina particles, and the average particle size is 58.5 μm. The temperature of the thermal cracking reaction was 680 ℃ and the reaction time was 1.2 s. The absolute pressure of the thermal cracking reaction is 0.20MPa, and the agent-oil ratio is 20.
The heavy oil of the raw material of the coking reaction is a mixture of heavy components and vacuum residue obtained from a fractionating tower, the properties of the heavy oil are shown in Table 2, the coking reaction temperature is 510 ℃, the coking reaction pressure is 0.15MPa, and the agent-oil ratio is 20.
The regeneration reaction temperature is 850 ℃, the pressure is 0.25MPa, and the regeneration time is 10 min. The product distribution data obtained by reaction of the above parameters in the apparatus of example 1 are shown in Table 3.
TABLE 1 riser feed oil Properties
TABLE 2 fluidized bed feed oil Properties
Example 3
This example is the same as example 2 in the petroleum hydrocarbon component subjected to the thermal cracking reaction and the heavy oil component subjected to the coking reaction, and the reaction method is the same except that the thermal cracking reaction temperature is 700 ℃ and the regeneration reaction temperature is 870 ℃. The product distribution data obtained by reaction of the above parameters in the apparatus of example 1 are shown in Table 3.
Example 4
This example is the same as example 2 in the petroleum hydrocarbon component subjected to the thermal cracking reaction and the heavy oil component subjected to the coking reaction, and the reaction method is the same except that the thermal cracking reaction temperature is 720 ℃ and the regeneration reaction temperature is 890 ℃. The product distribution data obtained by reaction of the above parameters in the apparatus of example 1 are shown in Table 3.
Comparative example 1
This comparative example provides an apparatus 1000 for producing olefins by cracking petroleum hydrocarbons, which differs from example 1 only in that it does not include a fluidized bed reactor.
Referring specifically to fig. 2, the present comparative example provides an apparatus 1 for producing olefins by cracking petroleum hydrocarbons, comprising a riser reactor 2 and a regenerator 5. The riser reactor 2 comprises a feeding section 13, a stripping section 14 and a settling section 15, wherein the feeding section 13 is provided with a riser feeding port 9 and a riser regeneration inclined pipe 7, the stripping section 14 is provided with a settler conveying inclined pipe 4, the settling section 15 is provided with a settler and a riser outlet 10, and in the comparative example, the settler is specifically a vertical cyclone separator 3.
Petroleum hydrocarbon enters a riser reactor 2 through a riser feed inlet 9, and ascends at a high speed with a high-temperature solid heat carrier from a riser regeneration inclined tube 7 under the action of steam, the high-temperature solid heat carrier and the petroleum hydrocarbon in the riser reactor 2 are fully mixed, heated and thermally cracked to obtain a gas-solid mixture, the gas-solid mixture enters a settling section 15 and is subjected to gas-solid separation through a cyclone separator 3, and high-temperature oil gas obtained through separation enters a subsequent separation unit through a riser outlet 10; the separated high-temperature solid heat carrier enters a regenerator 5 through a settler conveying inclined pipe 4.
The regenerator 5 comprises a regenerator feed inlet 12, a regenerator outlet 11 and a regenerator cyclone separator 6, air enters the regenerator 5 from the regenerator feed inlet 12 to coke the coked solid heat carrier to remove coke on the coked solid heat carrier, and a gas-solid mixture obtained by reaction is separated by the regenerator cyclone separator 6 to obtain regenerated flue gas and a high-temperature solid heat carrier. The regenerated flue gas enters the flue gas treatment system through a regenerator outlet 11, the high-temperature solid heat carrier returns to a dense bed area of a regenerator 5, and returns to a feeding section 13 of the riser reactor 1 through a riser regeneration inclined tube 7 for cyclic reaction again.
Based on the device, the comparative example also provides a method for preparing olefin by cracking petroleum hydrocarbon. This comparative example, in which olefins were produced in the above-described apparatus, the petroleum hydrocarbon components for the thermal cracking reaction were the same as in example 2, and the reaction method was the same except that the coking reaction was not performed in this comparative example, and the temperature for the regeneration reaction was 830 ℃. The product distribution data obtained by reaction with the above parameters in the apparatus of comparative example 1 are shown in Table 3.
TABLE 3 comparison of operating conditions and product distribution
As can be seen from table 3, all examples of the present invention obtained higher yields of "ethylene + propylene + butene" than comparative example 1, wherein the yield of "ethylene + propylene + butene" of example 4 was the highest, reaching 40.08 wt%, significantly higher than 35.47 wt% of comparative example 1. Meanwhile, the coke loaded on the high-temperature solid heat carrier in the comparative example 1 is only 10.62%, the coke formation amount of the high-temperature solid heat carrier is low, the temperature for coke burning regeneration in the regenerator is low, and under the condition that the catalyst-to-oil ratio is not changed, the temperature for returning the high-temperature solid heat carrier to the riser reactor is low, and the reaction temperature in the riser reactor is reduced, so that the olefin yield of the comparative example 1 is reduced.
In summary, under the action of the high-temperature solid heat carrier, the embodiments 2 to 4 with the fluidized bed process of the present invention all achieve better low-carbon olefin yield and coke formation, and provide a new idea for the process technology for preparing olefin by cracking petroleum hydrocarbon.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing olefin by cracking petroleum hydrocarbon, which is characterized by comprising the following steps: thermal cracking reaction, coking reaction and regeneration reaction;
the thermal cracking reaction comprises the steps that in a riser reactor, petroleum hydrocarbon and a high-temperature solid heat carrier are mixed under the steam atmosphere to carry out thermal cracking reaction, and first gas-solid separation is carried out after the reaction is finished;
carrying out a coking reaction on the high-temperature solid heat carrier obtained by the first gas-solid separation and heavy oil in a fluidized bed reactor under a steam atmosphere, and carrying out second gas-solid separation after the reaction is finished to obtain a coking solid heat carrier;
and the regeneration reaction comprises removing coke on the coked solid heat carrier, performing third gas-solid separation, and returning the obtained high-temperature solid heat carrier to the riser reactor for thermal cracking reaction.
2. The method of claim 1, wherein the high-temperature oil gas obtained by the first gas-solid separation and the coking reaction gas obtained by the second gas-solid separation enter a fractionating tower to be separated to obtain a light component and a heavy component;
the heavy oil in the coking reaction comprises inferior high aromatic heavy oil and/or the heavy component;
preferably, the inferior high aromatic heavy oil comprises one or more of vacuum gas oil, catalytic cracking slurry oil, atmospheric residue, vacuum residue and deoiled asphalt;
preferably, the coking reaction temperature is 500-550 ℃, and more preferably 510-530 ℃;
preferably, the coking reaction pressure is 0.10-0.30 MPa, and the agent-oil ratio is 15-25.
3. The method of claim 1, wherein the petroleum hydrocarbons comprise a combination of one or more of light crude oil, heavy crude oil, straight run naphtha, catalytic gasoline, and coker gasoline;
preferably, the thermal cracking reaction temperature of the riser reactor is 650-750 ℃, and more preferably 680-720 ℃;
preferably, the reaction time of the riser reactor is 0.5-2 s, the agent-oil ratio is 15-25, and the absolute reaction pressure is 0.10-0.30 MPa;
preferably, the mass ratio of the steam to the petroleum hydrocarbon is 0.05:1 to 1:1, more preferably 0.3:1 to 0.5: 1.
4. The method of claim 1, wherein the removing coke from the coked solid heat carrier comprises introducing a regenerant into the bottom of the regenerator to char the coked solid heat carrier, and removing coke on the surface of the coked solid heat carrier to obtain a high-temperature solid heat carrier;
preferably, the regenerant is at least one of air, an oxygen-containing gas, air or a mixture of an oxygen-containing gas and water vapor;
preferably, the temperature of the regeneration reaction is 800-950 ℃, the pressure is 0.20-0.40 MPa, and the regeneration time is 5-20 min.
5. The method according to any one of claims 2-4, wherein the high temperature solid heat carrier comprises one or more of a combination of high temperature treated carbon microspheres, alumina particles, alumina silicate porous microspheres;
preferably, the SiO in the aluminum silicate porous microspheres is calculated by mass percentage210 to 50 percent of Al2O3The content is 50% -90%;
preferably, the average particle size of the high-temperature solid heat carrier is 10-300 microns, and more preferably 30-200 microns.
6. The method of claim 1, wherein the first gas-solid separation, the second gas-solid separation and the third gas-solid separation are separated by a cyclone separator.
7. The device for preparing olefin by cracking petroleum hydrocarbon is characterized by comprising a riser reactor, a fluidized bed reactor and a regenerator;
the riser reactor and the fluidized bed reactor are connected through a first gas-solid separator conveying inclined pipe, the fluidized bed reactor and the regenerator are connected through a fluidized bed inclined pipe to be regenerated, and the regenerator and the riser reactor are connected through a riser inclined pipe to be regenerated.
8. The apparatus of claim 7, wherein the regenerator comprises a fluidized bed regenerator;
preferably, the fluidized bed reactor and the fluidized bed regenerator are both straight tube reactors with expanding dense-phase sections;
preferably, the fluidized bed reactor is provided with a second fluidized bed feeding hole, the second fluidized bed feeding hole is provided with atomizing nozzles, and the atomizing nozzles are arranged in a multilayer manner;
preferably, a first gas-solid separator is arranged on the riser reactor, a second gas-solid separator is arranged on the fluidized bed reactor, a third gas-solid separator is arranged on the regenerator, and the first gas-solid separator, the second gas-solid separator and the third gas-solid separator are cyclone separators;
preferably, the cyclone separator comprises a horizontal cyclone separator and/or a vertical cyclone separator.
9. The apparatus of claim 8, further comprising a fractionating tower connected to the riser reactor and the fluidized bed reactor via pipes for fractionating the high temperature oil gas separated by the first gas-solid separator and the coking reaction gas separated by the second gas-solid separator.
10. Use of the method for producing olefins by cracking petroleum hydrocarbons according to any one of claims 1 to 6 or the apparatus for producing olefins by cracking petroleum hydrocarbons according to any one of claims 7 to 9 for the industrial production of olefins.
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| CN114989846A (en) * | 2022-06-16 | 2022-09-02 | 上海电气集团股份有限公司 | Plastic thermal cracking system and method |
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| CN102115675A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院过程工程研究所 | Heavy oil lightening method and device |
| CN110283609A (en) * | 2019-05-20 | 2019-09-27 | 宋佰盈 | A kind of pulverized coal pyrolysis prepares the pyrolysis-coking process integration and system of coal tar |
| CN113717740A (en) * | 2021-09-03 | 2021-11-30 | 中国石油化工股份有限公司 | Coupling method for cracking, coking and coke gasification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102115675A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院过程工程研究所 | Heavy oil lightening method and device |
| CN110283609A (en) * | 2019-05-20 | 2019-09-27 | 宋佰盈 | A kind of pulverized coal pyrolysis prepares the pyrolysis-coking process integration and system of coal tar |
| CN113717740A (en) * | 2021-09-03 | 2021-11-30 | 中国石油化工股份有限公司 | Coupling method for cracking, coking and coke gasification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114989846A (en) * | 2022-06-16 | 2022-09-02 | 上海电气集团股份有限公司 | Plastic thermal cracking system and method |
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