CN112538375B - Processing method and device for heavy oil lightening/synthesis gas co-production - Google Patents
Processing method and device for heavy oil lightening/synthesis gas co-production Download PDFInfo
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- CN112538375B CN112538375B CN201910900612.9A CN201910900612A CN112538375B CN 112538375 B CN112538375 B CN 112538375B CN 201910900612 A CN201910900612 A CN 201910900612A CN 112538375 B CN112538375 B CN 112538375B
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
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Abstract
The invention provides a processing method and a device for heavy oil lightening/synthesis gas co-production, wherein a cracking/gasification coupling reactor with a cracking section and a gasification section which are communicated in a one-way mode inside is used as a reactor, and the method comprises the following steps: the heavy oil raw material is put into a cracking section to contact with fluidized coke powder to carry out cracking reaction, so as to generate light oil gas and coke powder particles; introducing the coke powder particles into a coke burning device for partial coke burning treatment, and respectively introducing the residual coke powder particles in the coke burning device into a cracking section and a gasification section; part of coke powder particles in the gasification section are subjected to gasification reaction to generate synthesis gas; the synthetic gas goes upward to enter a cracking section, and is combined with the light oil gas to carry out gas-solid separation treatment to carry out oil gas fractionation on the purified oil gas product, and the light oil and the synthetic gas product are collected; returning the coke breeze particles remaining in the gasification section to the pyrolysis section. The method optimizes the circulation path of coke generated in the cracking reaction of the heavy oil raw material, reduces the energy consumption of the cracking reaction, and improves the quality and yield of the light oil.
Description
Technical Field
The invention relates to a processing method and a device for heavy oil lightening/synthesis gas co-production, belonging to the technical field of petroleum processing.
Background
With the heavy and inferior crude oil, the yield of inferior heavy oil (heavy oil, super heavy oil, oil sand asphalt, vacuum residue oil, oil slurry, deoiled asphalt, etc.) is increased dramatically. The inferior heavy oil generally has the characteristics of low H/C ratio, high contents of sulfur, nitrogen and heavy metals, large carbon residue value and the like, and the coking tendency of the heavy oil in the processing process is serious due to the carbon residue and asphaltene components enriched inside. Due to the problems of catalyst deactivation, high hydrogen consumption, long-period operation and the like, the direct processing and treatment requirements of a large amount of inferior heavy oil are difficult to meet by directly adopting means such as catalytic cracking or catalytic hydrogenation. The inferior heavy oil is processed by adopting the combination of technologies such as solvent deasphalting, visbreaking, catalytic cracking, hydrotreating and delayed coking, and the like, and compared with a one-step heavy oil processing technology, the method has the advantages of longer overall process flow and higher investment cost.
The delayed coking process is used as an inferior heavy oil processing technology widely applied at present, and has the problems of furnace tube coking, large environmental protection pressure in a decoking process, low liquid yield and the like. In addition, a large amount of solid coke is produced as a byproduct in the delayed coking process, particularly high-sulfur coke has low value, and the latest environment-friendly requirement is to take factory-limiting measures on the high-sulfur coke with the sulfur content of more than 3%. In some domestic refineries, petroleum coke generated by delayed coking is used for a circulating fluidized bed combustion power generation or gasification poly-generation process, so that the conversion and utilization of coke are realized. Heavy oil is firstly converted into low-activity petroleum coke, and then the petroleum coke is converted by cooling, grinding and reheating, but the overall process flow is complex and the efficiency is low.
In addition, because the poor heavy oil raw material has a low H/C atomic ratio, the light oil product can be produced to the maximum extent only through the hydrogenation process, and the quality requirement of clean oil products is met, so that the problem of hydrogen source shortage in the process of processing the poor heavy oil in a refinery is more prominent, and hydrogen generated in the technical processes of catalytic reforming and the like is not enough to meet the hydrogen requirement of clean oil product production. Although the direct gasification of inferior heavy oil can directly convert heavy oil into small molecules such as synthesis gas, the oil gas molecules and hydrogen elements existing in the heavy oil are not fully utilized, and the resource waste of the heavy oil is also caused to a certain extent.
In response to the above problems, many researchers have proposed a corresponding short-flow technical solution for conversion of inferior heavy oil processing. One of the processes developed by Exxon is the flexicoking series using fluidized coke powder as the bed material for heavy oil cracking reaction.
The flexible coking process takes coke powder as a heat carrier for heavy oil cracking reaction, the generated coke is attached to the surface of the coke powder and is conveyed to a gasification/combustion reactor for removal, so that the coke material in the reaction needs to be returned among reactors such as coking, combustion and gasification, the difficulty in returning the coke powder material among a plurality of reactors is increased, direct material flow or heat exchange between coke gasification and heavy oil coking reaction is difficult to realize, and the energy consumption of the cracking reaction is increased.
Disclosure of Invention
The invention provides a processing method for heavy oil lightening/synthesis gas co-production, which optimizes a circulation path of coke generated in a cracking reaction of a heavy oil raw material, improves the utilization value of the coke, reduces the energy consumption of the cracking reaction, improves the quality and yield of light oil, and reduces the process operation difficulty.
The invention also provides a device for realizing the method.
In order to achieve the above objects, in one aspect, the present invention provides a heavy oil lightening/syngas co-production processing method, using a cracking/gasification coupled reactor having a cracking section and a gasification section which are in one-way communication as a reactor, the method comprising the steps of:
the heavy oil raw material enters a cracking section at the upper part of the cracking/gasification coupling reactor and contacts with fluidized coke powder to carry out cracking reaction, so as to generate light oil gas and coke powder particles; the coke powder particles are introduced into a coke burning device outside the cracking/gasification coupling reactor to carry out partial coke burning treatment, and the residual coke powder particles in the coke burning device are respectively introduced into the cracking section and a gasification section at the lower part of the cracking section;
the coke powder particles introduced into the gasification section are subjected to gasification reaction, the generated synthesis gas ascends to enter the cracking section to be combined with the light oil gas for gas-solid separation, and the purified oil gas product output by the gas-solid separation treatment is subjected to oil gas fractionation to obtain light oil and synthesis gas products;
coke breeze particles which are not completely gasified in the gasification section are discharged out of the cracking/gasification coupling reactor and conveyed back to the cracking section to participate in cracking the heavy oil raw material.
Further, the Conradson carbon residue value of the heavy oil raw material is more than or equal to 8 wt%.
Further, the cracking reaction conditions are as follows: the reaction temperature is 450 ℃ and 700 ℃, the reaction pressure is 0.1-6.0Mpa, the reaction time is 1-20s, the apparent gas velocity is 1-20m/s, and the catalyst-oil ratio is 4-20.
Further, the gasification reaction conditions are as follows: the reaction temperature is 850 ℃ and 1200 ℃, the reaction pressure is 0.1-6.0Mpa, the apparent gas velocity is 0.1-5.0m/s, and the retention time of coke powder particles is 1-20 min.
Further, the conditions of the scorch treatment are as follows: the scorching temperature is 600-.
Further, before the coke powder particles in the cracking section are introduced into the coke burner, the coke powder particles in the cracking section descend in the cracking section and are subjected to steam stripping treatment and particle size refining treatment in sequence.
Further, the steam stripping treatment conditions are as follows: the mass ratio of the water vapor to the heavy oil raw material is 0.1-0.3, the temperature of the water vapor is 200-400 ℃, and the apparent gas velocity of the water vapor is 0.5-5.0 m/s.
And further, before the synthesis gas and the light oil gas are combined for gas-solid separation treatment, the synthesis gas and the light oil gas are subjected to cooling washing treatment.
In another aspect, the present invention also provides a process plant for heavy oil upgrading/syngas co-production for carrying out any of the above methods, the plant comprising:
the cracking/gasification coupled reactor comprises a cracking section and a gasification section, wherein the cracking section and the gasification section are communicated in a one-way mode, and the cracking section is positioned at the upper part of the gasification section; the cracking section is provided with a particle outlet to be burnt, a first inlet of unburnt particles and an inlet of unburnt particles, the gasification section is provided with a particle outlet to be cracked and a second inlet of unburnt particles, and the top of the cracking/gasification coupling reactor is provided with an oil gas outlet;
the cracking/gasification coupling reactor is characterized by further comprising a gas-solid separation section positioned at the upper part of the cracking section, wherein the gas-solid separation section comprises a gas-solid separation inlet, a gas-solid separation solid phase outlet and a gas-solid separation oil gas outlet, the gas-solid separation inlet is used for receiving light oil gas and synthetic gas from the cracking section, and the gas-solid separation oil gas outlet is communicated with the oil gas outlet;
the coke burning device is positioned outside the cracking/gasification coupling reactor and comprises a coke burning device inlet, a coke burning device solid phase outlet and a coke burning device gas phase outlet;
the outlet of the particles to be coked is communicated with the inlet of the coke burner, the solid-phase outlet of the coke burner is respectively communicated with the first inlet of the particles which are not coked and the second inlet of the particles which are not coked, and the outlet of the particles to be cracked is communicated with the inlet of the particles which are not gasified.
Further, a gas distribution plate is arranged between the cracking section and the gasification section, and the gas distribution plate is used for realizing one-way conduction from the gasification section to the cracking section.
The implementation of the invention has at least the following advantages:
1. the invention fully exerts the synergistic effect between the heavy oil cracking reaction and the coke gasification reaction. On one hand, after part of coke breeze particles obtained by cracking and coke formation are combusted and heated, the rest coke breeze particles are respectively used as reaction raw materials of a gasification section and reaction bed materials of a cracking section, wherein the coke breeze particles entering the gasification section react with a gasifying agent to generate high-quality synthesis gas, and the synthesis gas directly goes upwards to enter the cracking section to provide a hydrogen atmosphere for cracking reaction, thereby effectively reducing coke generation, improving the yield of light oil and enriching the hydrogen source of a refinery; on the other hand, coke powder particles which are not completely gasified in the gasification section can return to the cracking section after being heated by the gasification section, and are contacted with heavy raw oil to provide heat for cracking. Therefore, the method of the invention adopts the coupling reactor integrating the cracking section and the gasification section, thereby realizing the technical advantages of mutual material supply, heat complementation, synergistic reaction, oil-gas co-production and the like in the two reaction processes of heavy oil cracking and coke gasification.
2. According to the processing device for the co-production of the light inferior heavy oil and the synthesis gas, the upper heavy oil cracking section and the lower coke gasification section are coupled in the same reaction system, so that the problems of difficult cyclic operation, complex process, large occupied area, high investment and the like among a plurality of reactors in the process of flexible coking and the like are solved, the energy efficiency is further improved, and the technical economy of the method is improved.
Drawings
Fig. 1 is a schematic diagram of a processing apparatus for heavy oil lightening/syngas co-production according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a processing method for heavy oil lightening/synthesis gas co-production, which adopts a cracking/gasification coupling reactor with a cracking section and a gasification section which are internally provided with one-way conduction as a reactor, and comprises the following steps:
the heavy oil raw material enters a cracking section at the upper part of the cracking/gasification coupling reactor and contacts with fluidized coke powder to carry out cracking reaction, so as to generate light oil gas and coke powder particles; the coke powder particles are introduced into a coke burning device outside the cracking/gasification coupling reactor to carry out partial coke burning treatment, and the residual coke powder particles in the coke burning device are respectively introduced into the cracking section and a gasification section at the lower part of the cracking section; the coke powder particles introduced into the gasification section are subjected to gasification reaction, the generated synthesis gas ascends to enter the cracking section to be combined with the light oil gas for gas-solid separation, and the purified oil gas product output by the gas-solid separation treatment is subjected to oil gas fractionation to obtain light oil and synthesis gas products; coke breeze particles which are not completely gasified in the gasification section are discharged out of the cracking/gasification coupling reactor and conveyed back to the cracking section to participate in cracking the heavy oil raw material.
The cracking/gasification coupled reactor of the present invention refers to an integrated coupled reactor capable of simultaneously performing a cracking reaction and a gasification reaction, and the cracking section is located at the upper part of the gasification section. The direction from the gasification section to the cracking section is in one-way conduction, namely, material flow in the gasification section can directly go upwards to the cracking section, and material flow in the cracking section cannot directly go downwards to enter the gasification section.
In the method, the heavy oil raw material enters a cracking section through a raw material inlet in a cracking/gasification coupling reactor, and contacts with fluidized coke powder in the cracking section to generate cracking reaction to generate light oil gas and coke, wherein the coke is attached to the surface of coke powder particles to form coke powder particles. In order to increase the contact area between the heavy oil raw material and the fluidized coke powder, an atomization device can be arranged at the raw material inlet to atomize the heavy oil raw material and then contact the heavy oil raw material with the fluidized coke powder to generate cracking reaction.
Coke powder particles with serious coking and larger particle size in the cracking section descend in the cracking section and are output from the cracking/gasification coupling reactor to enter a coke burner outside the cracking/gasification coupling reactor. In the coke burning device, part of coke powder particles can be fully burned (coke burning treatment) to generate high-temperature flue gas, the high-temperature flue gas can be collected to recover heat, and the coke powder particles which are not fully burned carry the heat to be divided into two paths under the driving of gas (such as air) in the coke burning device to respectively enter a cracking section and a gasification section, wherein the coke powder particles entering the cracking section can be continuously used as bed materials of cracking reaction, the heat carried by the coke powder particles can also provide heat for the cracking reaction, and the energy consumption of the cracking reaction is reduced; the coke powder particles entering the gasification section can generate gasification reaction with a gasification agent to generate synthesis gas of active micromolecules such as hydrogen, carbon monoxide and the like, and the heat carried by the synthesis gas can also be used as energy compensation of the gasification reaction.
Along with the continuous generation of the synthesis gas, the synthesis gas can move upwards to enter a cracking section, the synthesis gas can provide heat required by cracking reaction on one hand, so that the heat of two reaction zones of cracking and gasification can be utilized in a matching way, the overall energy efficiency is improved, on the other hand, hydrogen in the synthesis gas can inhibit a coking reaction causing heavy oil cracking reaction to a certain extent, the product distribution of heavy oil cracking is improved, and the quality and the yield of oil gas are improved. And the upward syngas can also sufficiently fluidize the coke breeze particles in the cracking section.
In addition, the light oil gas in the cracking section can be combined with the upward synthesis gas, so that in order to avoid the entrainment of coke powder particles in the collected light oil gas and the synthesis gas, the light oil gas and the synthesis gas can be subjected to gas-solid separation treatment, purified oil gas products output after the gas-solid separation are collected, and the purified oil gas products are subjected to means such as oil gas fractionation and the like to obtain gas products such as synthesis gas products, dry gas, liquefied gas and the like, light oil and possibly heavy oil products. Wherein the light oil can be further cut to obtain liquid products with different distillation ranges, and the heavy oil product can be returned to the cracking section for recycling processing; collecting coke powder particles output after gas-solid separation, returning the coke powder particles to the cracking section, and continuously taking the coke powder particles as bed materials to participate in cracking reaction.
In the gasification section, part of coke powder particles which are not completely gasified can be remained, and the part of coke powder particles can be returned to the cracking section through a conveying pipeline outside the cracking/gasification coupling reactor, so that the coke powder particles can be used as cracking reaction bed materials to continue to participate in the cracking reaction, and heat can be provided for the cracking reaction, thereby further reducing the energy consumption of the cracking reaction. Meanwhile, the effective utilization rate of coke powder particles is further improved, and the cost for processing heavy oil is reduced.
The invention utilizes the coupling reactor of upper cracking-lower gasification to carry out cracking treatment of heavy oil raw materials, provides a more convenient path for the reciprocating cyclic utilization of coke breeze particles, not only leads the coke breeze particles at the cracking section to be burnt in the coker to directly decompose the heat supply for a heat exchange network, but also leads the coke breeze particles which are not completely burnt to carry heat to respectively return to the cracking section and the gasification section to be used as bed materials of cracking reaction and raw materials of gasification reaction; meanwhile, the synthesis gas carrying heat in the gasification section can directly go upwards to enter the cracking section, so that reaction heat is provided for cracking reaction, hydrogen atmosphere is provided for cracking reaction, coke formation of cracking reaction is inhibited, and the quality and yield of oil gas are improved.
In addition, the coke powder particles which do not participate in the gasification reaction in the gasification section can be circulated to the cracking section to be used as a reaction bed material and heat supply party to continue to participate in the cracking reaction, so that the overall energy consumption is reduced, the process flow is simplified, and the heat loss of the coke powder particles caused by a complex path is avoided.
The invention can form mutual supply and heat complementation of raw materials between cracking reaction and gasification reaction in one reactor, and realizes the technical advantages of reaction synergistic coupling, oil-gas co-production and the like. The entire coupled reactor can be operated at high pressure, thereby greatly increasing processing capacity and achieving upgrading of high quality syngas to heavy oil cracking processes at high pressure.
Further, before the coke powder particles in the cracking section are introduced into the coke burner, the coke powder particles in the cracking section descend in the cracking section and are subjected to steam stripping treatment and particle size refining treatment in sequence.
Specifically, a steam stripping section and a particle size refining section can be arranged between the cracking section and the gasification section of the coupling reactor and are used for sequentially carrying out steam stripping and particle size refining on coke breeze particles descending from the cracking section. The steam stripping can clear oil gas on the surfaces of descending coke powder particles, and the particle size refinement can cut and refine the particle size of the coke powder particles subjected to steam stripping, so that the coke powder particles are prevented from being bonded and agglomerated. Generally, the particle size of the coke powder particles after steam stripping is 10-500 μm. After the coke powder particles are subjected to steam stripping treatment and particle size refining treatment in sequence, the coke powder particles are output from the coupling reactor and enter a coke burner for coke burning treatment.
In addition, a steam stripping section and a grain size refining section are arranged between the cracking section and the gasification section, so that relatively independent reaction environments of the cracking section and the gasification section can be ensured, and the safety and the operation stability of the cracking-gasification coupling reaction are ensured.
In particular implementations, the steam stripping section may include a multi-layer stripping configuration to remove light oil and gas from the surface of the coke particles by the action of stripping steam entering through a stripping steam inlet. In detail, the multi-layer stripping structure can adopt one or more combinations of herringbone baffles, annular baffles, conical baffles, grid baffles, bulk packing or structured packing and the like.
The particle size refines the section and can include the jet mill, and the jet mill is used for utilizing the vapor that gets into from grinding the vapor entry to carry out crushing and screening to the coke granule after the steam strip section is handled to guarantee that the coke granule that gets into the gasification section can have bigger area of contact with the gasification agent, guarantee that gasification reaction's high efficiency goes on.
It will be appreciated that the steam stripping section is provided with a stripping steam inlet and the particle size refining section is provided with a grinding steam inlet.
Further, before the gas-solid separation treatment is carried out on the combined material flow of the light oil gas and the synthesis gas, the combined material flow can be subjected to cooling washing treatment, so that the combined material flow is subjected to the gas-solid separation treatment after being treated by the low-temperature liquid medium. The cooling washing treatment can clear away some fine coke particles in the combined material flow on the one hand, and the fine coke particles that make clear away fall back to the schizolysis section and continue to act as the schizolysis carrier, and on the other hand can cool down combined material flow, avoids light oil gas wherein to continue to produce coke with high temperature state in gas-solid separation processing to further improve the quality of light oil, also avoided producing coke too much and caused the jam to gas-solid separation system.
In particular, the reduced temperature washing may be performed in a reduced temperature washing section. The cooling washing section can adopt a built-in filler type structure to strengthen the contact between the mixed material flow and the low-temperature liquid, and can also adopt a tower plate type structure to strengthen the contact between the mixed material flow and the low-temperature liquid.
The built-in packing structure can comprise loose packing such as Raschig rings, pall rings, step rings, arc saddle packing, intalox saddle packing, metal ring intalox saddle, spherical packing and the like, or a combination of more than one of regular packing such as grid packing, corrugated packing, pulse packing and the like.
The tower plate structure comprises one or more of bubble cap tower plate, sieve pore tower plate, floating valve tower plate, jet tower plate and flow-through tower plate.
The cryogenic liquid may be a heavy oil feedstock. In the actual operation process, the heavy oil raw material enters the cracking section in two paths, one path of heavy oil raw material directly contacts with the coke powder to perform cracking reaction, the other path of heavy oil raw material is used as low-temperature liquid and firstly passes through the washing section to perform heat exchange, and then goes downwards to perform cracking reaction with the coke powder, so that the energy consumption required by the cracking reaction is effectively reduced. In the present invention, the heavy oil feedstock as the low-temperature liquid is 5 to 10% by mass of the total mass of the heavy oil feedstock.
In the method, because the gasification section is positioned at the lower part of the cracking section, in order to ensure that coke powder particles which do not generate gasification reaction in the gasification section can be efficiently returned to the cracking section, the coke powder particles which are completely gasified at the bottom of the gasification section can be lifted to the cracking section through the outside of the coupling reactor in a lifting gas driving mode. Wherein the gas velocity of the lifting gas is 0.2-3.0 m/s.
Meanwhile, in order to improve the utilization rate of the coke powder particles, the coke powder particles which are not completely gasified in the gasification section can enter the cracking section after being dispersed, so that the coke powder particles can be uniformly distributed in the cracking section, and the reaction efficiency of the cracking reaction is improved.
The invention also limits the process parameters in the coupling reactor as follows, thereby further realizing the matching of material flow and energy flow in the heavy oil processing process, ensuring the stability in the whole heavy oil processing process and improving the overall energy efficiency.
The cracking reaction conditions are as follows: the reaction temperature is 450 ℃ and 700 ℃, the reaction pressure is 0.1-6.0Mpa, the reaction time is 1-20s, the apparent gas velocity is 1-20m/s, and the catalyst-oil ratio is 4-20. In general, heavy oil is preheated to the temperature of 220 ℃ and 300 ℃ and then enters a cracking section for reaction. Where superficial gas velocity refers to the superficial gas velocity of the synthesis gas entering the pyrolysis section and the collection of fluidizing gas used to fluidize the coke breeze particles.
The gasification reaction conditions are as follows: the reaction temperature is 850 ℃ and 1200 ℃, the reaction pressure is 0.1-6.0Mpa, the apparent gas velocity is 0.1-5.0m/s, and the retention time of coke powder particles is 1-20 min. The reaction condition can ensure the smooth proceeding of the gasification reaction, and is helpful for reasonably distributing the coke powder particles in the gasification section, thereby ensuring the stability of the whole flow. Wherein the superficial gas velocity is the superficial gas velocity of the combination of the gasifying agent and the fluidizing gas used to fluidize the coke breeze particles, and the residence time of the coke breeze particles is the residence time of the coke breeze particles in the gasification zone.
The gasification agent can be introduced into the gasification section from the outside of the coupling reactor, and specifically, the gasification agent can be one or more of oxygen, water vapor, oxygen-enriched air and air.
The conditions of the scorch treatment were: the scorching temperature is 600-. This reaction condition can guarantee that coking treatment goes on smoothly to can carry out rational distribution to the fine coke granule that gets into in the coker, make partial fine coke granule can not take place complete combustion and can get into gasification section or pyrolysis section, thereby help going on of gasification reaction, guarantee the stability of whole flow. Wherein, the air velocity refers to the air velocity of the air entering the coking device and participating in the coke burning treatment.
Further, in the steam stripping treatment, the mass ratio of the steam to the heavy oil is 0.1-0.3, the temperature of the steam is 200-400 ℃, and the superficial gas velocity of the steam is 0.5-5.0 m/s.
The Conradson carbon residue value of the heavy oil raw material is more than or equal to 8 percent, and the Conradson carbon residue raw material can be a mixture of one or more of heavy oil, super heavy oil, oil sand asphalt, normal pressure heavy oil, vacuum residual oil, catalytic cracking oil slurry and solvent deoiling asphalt in any proportion, and can also be a mixture of one or more of heavy tar and residual oil in the coal pyrolysis or liquefaction process, heavy oil generated by dry distillation of oil shale, low-temperature pyrolysis liquid products in biomass and other derived heavy oils in any proportion.
The coke powder of the present invention may be in the form of microspherical coke powder with excellent fluidizing performance. Generally, the particle size of the coke powder is 10 to 500. mu.m, and further 20 to 200. mu.m.
The invention is explained in detail below with reference to specific embodiments and the accompanying drawings.
Fig. 1 is a schematic diagram of a processing apparatus for heavy oil upgrading/synthesis gas co-production according to an embodiment of the present invention, in which the processing method for heavy oil upgrading/synthesis gas co-production uses the apparatus shown in fig. 1, the apparatus at least includes:
the cracking/gasification coupling reactor 100 comprises a cracking section 1 and a gasification section 2 which are internally communicated in a one-way mode, wherein the cracking section 1 is positioned at the upper part of the gasification section 2; the cracking section 1 is provided with a particle outlet to be burnt, a first inlet of unburnt particles and an inlet of unburnt particles, the gasification section 2 is provided with a particle outlet to be cracked and a second inlet of unburnt particles, and the top of the cracking/gasification coupling reactor 100 is provided with an oil gas outlet;
the cracking/gasification coupling reactor 100 further comprises a gas-solid separation section 3 positioned at the upper part of the cracking section 1, the gas-solid separation section 3 comprises a gas-solid separation inlet, a gas-solid separation solid phase outlet and a gas-solid separation oil gas outlet, the gas-solid separation inlet is used for receiving light oil gas and synthetic gas from the cracking section 1, and the gas-solid separation oil gas outlet is communicated with the oil gas outlet;
specifically, the cracking/gasification coupled reactor 100 may be obtained by appropriately modifying and assembling a cracking reactor and a gasification reactor commonly used in the art, and the cracking reactor may be, for example, a fluidized bed reactor, and the bottom end of the cracking reactor is communicated with the top end of the gasification reactor. The cracking reactor and the gasification reactor are preferably coaxially arranged so as to facilitate the transportation and circulation of materials;
wherein, a fluidized bed can be included in the cracking section 1, so that the coke powder and the particles are in a fluidized state by the action of the fluidized bed and serve as a carrier of the cracking reaction;
the gasification section 2 can comprise a fluidized bed, coke powder particles are in a fluidized state under the action of the fluidized bed and are in contact with a gasification agent to carry out gasification reaction, and the gasification section is also provided with a gasification agent inlet for injecting the gasification agent and a slag discharge port for outputting impurities which cannot be reacted and converted, such as solid ash and the like;
the gas-solid separation section may comprise a gas-solid separator 31, such as a cyclone separator as is commonly used in the art. Wherein, the gas-solid separation inlet is an inlet of the gas-solid separator, the gas-solid separation solid phase outlet is a solid phase outlet of the gas-solid separator, and the gas-solid separation oil gas outlet is an oil gas outlet of the gas-solid separator.
A coke burner 200, wherein the coke burner 200 is located outside the cracking/gasification coupling reactor 100 and comprises a coke burner inlet, a coke burner solid phase outlet and a coke burner gas phase outlet;
the outlet of the particles to be coked is communicated with the inlet of the coke burner, the solid-phase outlet of the coke burner is respectively communicated with the first inlet of the particles which are not coked and the second inlet of the particles which are not coked, and the outlet of the particles to be cracked is communicated with the inlet of the particles which are not gasified.
On the basis of the above, the cracking/gasification coupled reactor 100 in fig. 1 further includes:
the gas distribution plate 4 is arranged between the cracking section 1 and the gasification section 2 and is used for realizing that material flow (synthesis gas) in the gasification section 2 directly goes upwards into the cracking section 1 and preventing the material flow in the cracking section 1 from directly going downwards to carry out the gasification section 2;
a steam stripping section 5, which is arranged in the steam stripping section 5 and can comprise steam stripping baffles so as to remove oil gas on the surface of coke powder particles in the descending process by spraying steam, and is provided with an inlet for injecting stripping steam;
a particle size refining section (not shown) disposed between the steam stripping section 5 and the gas distribution plate 4, the particle size refining section may include a steam jet mill for refining and milling the stripped coke breeze particles by injecting steam, and the particle size refining section has an inlet for injecting milling steam;
an atomization device (not shown) disposed in the cracking section 1, which is communicated with the raw material inlet, and is used for atomizing the heavy oil raw material, and specifically may be an atomizer;
a dispersing device (not shown) which is arranged in the cracking section 1, is communicated with the non-gasified particle inlet and is used for dispersing the coke powder particles entering the cracking section 1 through the gasification section 2;
and the cooling washing section 6 is arranged between the cracking section 1 and the gas-solid separation section 3, and is used for cooling and washing the combined material flow of the light oil gas and the synthesis gas which are about to enter the gas-solid separation section 3.
The processing method for heavy oil lightening/synthesis gas co-production by using the device provided by the embodiment is briefly described as follows:
the fully preheated heavy oil raw material is input into the cracking section 1 in the cracking/gasification coupling reactor 100 through a raw material inlet, and after the heavy oil raw material is atomized by an atomization device, the heavy oil raw material is directly contacted with fluidized coke powder (including coke powder particles externally attached with coke) in the cracking section 2 to perform cracking reaction, so that light oil gas and coke are respectively obtained, and the coke can be attached to the surface of the coke powder to form coke powder particles.
Coke powder particles with serious coking and larger particle size can descend under the action of gravity, and in the descending process, light oil gas remained on the surfaces of the coke powder particles is removed through a steam stripping section 5, and then the coke powder particles are cut and refined through a particle size refining section. Finally, the coke breeze particles are output from the outlet of the to-be-coked particles of the cracking section 1 to the cracking/gasification coupling reactor 100 and enter the coke burner 200 through the inlet of the coke burner.
In the coke burning device 200, part of coke powder particles and air introduced into the coke burning device 200 are burnt at high temperature to generate flue gas, and the flue gas is output from a gas phase outlet of the coke burning device and then can enter a subsequent heat exchange network for flue gas waste heat recovery; the coke powder particles which are not completely combusted in the coke burner 200 enter the cracking section 1 and the gasification section 2 respectively, wherein the coke powder particles entering the cracking section 1 are first-grade coke powder particles, and the coke powder particles entering the gasification section 2 are second-grade coke powder particles.
The first-grade coke powder particles can be used as reaction bed materials and continuously contacted with a heavy oil raw material to generate a cracking reaction, and heat carried by the first-grade coke powder particles can also provide heat for the cracking reaction, so that the energy consumption of the cracking reaction is reduced.
The secondary coke powder particles can be used as reaction raw materials and generate gasification reaction with a gasification agent in the gasification section 2 to produce synthesis gas, and heat carried by the secondary coke powder particles can also provide heat for the gasification reaction, so that the energy consumption of the gasification reaction is reduced. Along with the generation of the synthesis gas, the synthesis gas will move upwards under the driving of the gasifying agent and enter the cracking section 1, so as to provide reaction heat and reaction atmosphere for the cracking reaction of the heavy oil raw material (the gas amount of the synthesis gas moving upwards can be controlled by regulating and controlling the type of the gasifying agent, the gas speed and the like, so as to ensure the matching of the material flow and the energy flow inside the cracking/gasifying coupling reactor 100).
And the synthesis gas and the light oil gas are mixed into a combined material flow, the combined material flow enters a gas-solid separator 31 from a gas-solid separation inlet for gas-solid separation treatment after being subjected to temperature reduction and washing by a temperature reduction washing section 6, and the obtained purified oil gas product can further pass through a gas-liquid fractionating tower, an oil gas absorption stabilizing tower and other systems to respectively obtain gas products such as synthesis gas, dry gas, liquefied gas and the like and light oil products. Of course, the oil product can be further cut and separated to obtain liquid products with different distillation range components, wherein heavy oil (possibly including part of contact agent solid particles) can be mixed with heavy oil raw materials for recycling processing; the resulting coke breeze particles can be returned to the pyrolysis section 1.
The coke powder particles which are not completely reacted in the gasification section 2 can be driven by the lifting gas to be output to the cracking/gasification coupling reactor 100 through the particle outlet to be cracked and enter the cracking section 1 through the particle inlet which is not gasified, so that the coke powder particles serve as bed materials for cracking reaction and provide certain heat.
The conditions of the cracking reaction are as follows: the reaction temperature is 450 ℃ and 700 ℃, the reaction pressure is 0.1-6.0Mpa, the reaction time is 1-20s, the apparent gas velocity is 1-20m/s, and the agent-oil ratio is 4-20;
the conditions of the above gasification reaction are: the reaction temperature is 850 ℃ and 1200 ℃, the reaction pressure is 0.1-6.0Mpa, the apparent gas velocity is 0.1-5.0m/s, and the retention time of coke powder particles is 1-20 min.
The conditions of the above-mentioned scorch treatment are: the scorching temperature is 600-.
The conditions of the steam stripping treatment are as follows: the mass ratio of the water vapor to the heavy oil is 0.1-0.3, the temperature of the water vapor is 200-400 ℃, and the apparent gas velocity of the water vapor is 0.5-5.0 m/s.
In order to verify the effect of the invention, the Liaohe reduced pressure heavy oil was tested by using the apparatus and the process flow shown in FIG. 1.
Table 1 shows the properties of the heavy oil feedstock. Table 2 shows specific reaction parameters, and compared with the conventional heavy oil cracking process, the method of this embodiment can improve the yield of light oil, improve the yield of liquid, significantly reduce the yields of dry gas and coke, and show detailed product distribution in tables 3 and 4.
TABLE 1
As can be seen from Table 1: the density and carbon residue value of the heavy oil raw material are both high, and the carbon residue value of the Liaohe vacuum residue is more than 20%. In addition, the high asphaltene content and the high heavy component content of greater than 500 ℃ in the heavy oil feedstock means that the heavy oil feedstock has a severe propensity to coke during cracking.
TABLE 2
TABLE 3
As can be seen from Table 3:
1. the method and the device of the embodiment can obviously improve the yield of the light oil and inhibit the generation of coke;
2. the coke yield to carbon residue ratio is about 0.8 to 0.9, much less than the coke/carbon residue ratio of 1.4 to 1.6 in delayed coking, compared to the initial carbon residue value of the feedstock. The liquid quality yield is kept between 70 and 80 percent, and the heavy oil fraction with the temperature of more than 500 ℃ is contained in the liquid, and can be processed in a recycling mode.
TABLE 4
| Synthesis gas Components | H2 | CO | CO2 | CH4Etc. other components |
| Volume content (vol%) | 40.4 | 39.5 | 18.7 | 1.4 |
As can be seen from Table 4: the synthesis gas obtained in this example was H2The sum of the volume fraction of the carbon dioxide and the CO is about 80 percent, and the carbon dioxide can be used as high-quality synthesis gas for subsequent processes of hydrogen production by reforming or F-T synthesis of oil products and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A processing method for heavy oil lightening/synthesis gas co-production is characterized in that a cracking/gasification coupling reactor with a cracking section and a gasification section which are communicated in a one-way mode inside is used as a reactor, a particle size refining section and a steam stripping section are sequentially arranged on the lower portion in the cracking section, and a cooling washing section is arranged on the upper portion in the cracking section, and the method comprises the following steps:
the heavy oil raw material enters a cracking section at the upper part of the cracking/gasification coupling reactor and contacts with fluidized coke powder to carry out cracking reaction, so as to generate light oil gas and coke powder particles; descending the coke powder particles in the cracking section, sequentially carrying out steam stripping treatment and particle size refining treatment, introducing the coke powder particles into a coke burning device outside the cracking/gasification coupling reactor for partial coke burning treatment, and introducing the residual coke powder particles in the coke burning device into the cracking section and a gasification section at the lower part of the cracking section respectively;
carrying out gasification reaction on coke powder particles introduced into a gasification section, enabling the generated synthesis gas to go upwards to enter a cracking section to be combined with the light oil gas, carrying out cooling washing treatment on the synthesis gas and the light oil gas, carrying out gas-solid separation, carrying out oil-gas fractionation on a purified oil gas product output by the gas-solid separation treatment, and collecting light oil and a synthesis gas product;
coke breeze particles which are not completely gasified in the gasification section are discharged out of the cracking/gasification coupling reactor and conveyed back to the cracking section to participate in cracking the heavy oil raw material.
2. The process of claim 1, wherein the heavy oil feedstock has a conradson carbon residue value of 8 wt.% or more.
3. The process of claim 1, wherein the cleavage reaction conditions are: the reaction temperature is 450 ℃ and 700 ℃, the reaction pressure is 0.1-6.0Mpa, the reaction time is 1-20s, the apparent gas velocity is 1-20m/s, and the catalyst-oil ratio is 4-20.
4. The process of claim 1, wherein the gasification reaction conditions are: the reaction temperature is 850 ℃ and 1200 ℃, the reaction pressure is 0.1-6.0Mpa, the apparent gas velocity is 0.1-5.0m/s, and the retention time of coke powder particles is 1-20 min.
5. The process according to claim 1, characterized in that the conditions of said scorch treatment are: the scorching temperature is 600-.
6. The process according to claim 1, characterized in that the conditions of the steam stripping treatment are: the mass ratio of the water vapor to the heavy oil raw material is 0.1-0.3, the temperature of the water vapor is 200-400 ℃, and the apparent gas velocity of the water vapor is 0.5-5.0 m/s.
7. A process plant for the heavy oil lightening/syngas co-production for carrying out the process according to any one of claims 1-6, characterized in that it comprises:
the cracking/gasification coupled reactor comprises a cracking section and a gasification section, wherein the cracking section and the gasification section are communicated in a one-way mode, and the cracking section is positioned at the upper part of the gasification section; the cracking section is provided with a particle outlet to be burnt, a first inlet of unburnt particles and an inlet of unburnt particles, the gasification section is provided with a particle outlet to be cracked and a second inlet of unburnt particles, and the top of the cracking/gasification coupling reactor is provided with an oil gas outlet; the lower part in the cracking section is sequentially provided with a particle size refining section and a steam stripping section, and the upper part in the cracking section is provided with a cooling washing section;
the cracking/gasification coupling reactor is characterized by further comprising a gas-solid separation section positioned at the upper part of the cracking section, wherein the gas-solid separation section comprises a gas-solid separation inlet, a gas-solid separation solid phase outlet and a gas-solid separation oil gas outlet, the gas-solid separation inlet is used for receiving light oil gas and synthetic gas from the cracking section, and the gas-solid separation oil gas outlet is communicated with the oil gas outlet;
the coke burning device is positioned outside the cracking/gasification coupling reactor and comprises a coke burning device inlet, a coke burning device solid phase outlet and a coke burning device gas phase outlet;
the outlet of the particles to be coked is communicated with the inlet of the coke burner, the solid-phase outlet of the coke burner is respectively communicated with the first inlet of the particles which are not coked and the second inlet of the particles which are not coked, and the outlet of the particles to be cracked is communicated with the inlet of the particles which are not gasified.
8. The processing apparatus as claimed in claim 7, wherein a gas distribution plate is disposed between the pyrolysis section and the gasification section, and the gas distribution plate is used for realizing one-way conduction from the gasification section to the pyrolysis section.
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| CN101451073A (en) * | 2007-12-06 | 2009-06-10 | 中国石油化工股份有限公司 | Method for combination processing heavy oil by pyrolysis and gasification |
| CN102234535A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Method for processing low-quality heavy oil and simultaneously producing synthetic gas |
| CN107099328A (en) * | 2017-07-05 | 2017-08-29 | 洛阳德正废弃资源再利用有限公司 | The recovery processing technique that waste mineral oil is discharged without danger |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451073A (en) * | 2007-12-06 | 2009-06-10 | 中国石油化工股份有限公司 | Method for combination processing heavy oil by pyrolysis and gasification |
| CN102234535A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Method for processing low-quality heavy oil and simultaneously producing synthetic gas |
| CN107099328A (en) * | 2017-07-05 | 2017-08-29 | 洛阳德正废弃资源再利用有限公司 | The recovery processing technique that waste mineral oil is discharged without danger |
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