CN112538373B

CN112538373B - Method and device for co-production of heavy oil deep lightening-synthesis gas

Info

Publication number: CN112538373B
Application number: CN201910900599.7A
Authority: CN
Inventors: 高金森; 李大鹏; 张玉明; 蓝兴英; 高亚男; 王宁波; 王汝成; 杨会民; 姚晓虹; 黄勇; 黄传峰; 石孝刚; 王成秀; 蒋中山; 任健; 刘巧霞
Original assignee: Nanjing Zhonghui Energy Technology Research And Development Center; China University of Petroleum Beijing
Current assignee: Nanjing Zhonghui Energy Technology Research And Development Center; China University of Petroleum Beijing
Priority date: 2019-09-23
Filing date: 2019-09-23
Publication date: 2022-02-25
Anticipated expiration: 2039-09-23
Also published as: CN112538373A

Abstract

The invention provides a method and a device for the deep lightening of heavy oil and the co-production of synthesis gas, wherein a coupling reactor with a coke burning section, a cracking section and a gasification section is adopted, the coke burning section is communicated with the cracking section through a material dropping system, and the cracking section is communicated with the gasification section, and the method comprises the following steps: the heavy oil raw material enters a cracking section to contact with fluidized coke powder to generate light oil gas and coke powder particles; discharging the coke powder particles out of the coupling reactor and conveying the coke powder particles to a coking section for coking treatment, wherein one part of incompletely-coked coke powder particles descend and return to the cracking section, and the other part of incompletely-coked coke powder particles are conveyed to a gasification section to generate synthesis gas; the synthesis gas goes upward to the cracking section to be combined with the light oil gas, then separation treatment is carried out, oil gas fractionation is carried out on the output purified oil gas product, and light oil and synthesis gas products are obtained. 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

Method and device for co-production of heavy oil deep lightening-synthesis gas

Technical Field

The invention relates to a method and a device for the deep lightening of heavy oil and the co-production of synthesis gas, 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, and the generated coke is attached to the surface of the coke powder and is conveyed to a gasification/combustion reactor to be removed, so that the coke materials in the reaction need to be returned among the reactors for coking, combustion, gasification and the like, the operation difficulty of returning the coke materials among a plurality of reactors is increased, and the energy consumption of the cracking reaction is increased.

Disclosure of Invention

The invention provides a method for deep lightening of heavy oil and co-production of synthesis gas, 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 the light oil, and reduces the difficulty of process operation.

The invention also provides a device for realizing the method.

In order to achieve the above object, in one aspect, the present invention provides a method for deep heavy oil lightening-syngas co-production, which employs a coupled reactor having a char section, a pyrolysis section and a gasification section that are communicated with each other inside, wherein the bottom of the char section is communicated with the top of the pyrolysis section through a material descending system, and the top of the gasification section is communicated with the bottom of the pyrolysis section in a single direction, the method comprising:

heavy oil raw materials enter a cracking section in the middle of the coupling reactor and contact fluidized coke powder to carry out cracking reaction to generate light oil gas and coke powder particles;

discharging the coke powder particles out of the coupling reactor through the cracking section and conveying the coke powder particles to a coking section at the upper part of the coupling reactor for coking treatment, wherein the coke powder particles which are not completely coked in the coking section are divided into two parts, one part of the coke powder particles descend through the material descending system and return to the cracking section to participate in cracking of the heavy oil raw material, and the other part of the coke powder particles are discharged out of the coupling reactor and conveyed to a gasification section at the lower part of the coupling reactor to generate a gasification reaction so as to generate synthesis gas;

and the synthesis gas ascends to the top of the cracking section and is combined with the light oil gas to carry out oil gas-gas solid separation treatment, and oil gas fractionation is carried out on a purified oil gas product output by the oil gas-gas solid separation treatment to collect light oil and synthesis gas products.

Further, flue gas-solid separation treatment is carried out on the flue gas generated by the burning treatment, heat recovery is carried out on the purified flue gas output by the flue gas-solid separation treatment, and the coke powder particles output by the flue gas-solid separation treatment are returned to the burning section.

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 conditions of the scorch treatment are as follows: the scorching temperature is 600-.

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, before the coke powder particles in the cracking section are introduced into the coking section, 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 oil gas-solid separation treatment, the combined material flow of the synthesis gas and the light oil gas is subjected to cooling washing treatment.

In another aspect, the present invention also provides an apparatus for deep heavy oil upgrading-syngas co-production for carrying out any one of the above methods, the apparatus comprising a coupled reactor having a char section, a pyrolysis section, and a gasification section therein, wherein:

the bottom of the coke burning section of the coupling reactor is communicated with the top of the cracking section through a material descending system, and the top of the gasification section is communicated with the bottom of the cracking section in a one-way mode; the cracking section is provided with a heavy oil raw material inlet and a particle outlet to be burnt, and the upper part of the cracking section is provided with an oil gas outlet; the coking section is provided with a flue gas outlet, a to-be-coked particle inlet and an unfired-coked particle outlet, and the to-be-coked particle inlet is communicated with the to-be-coked particle outlet through an external first conveying pipeline; the gasification section is provided with a to-be-gasified particle inlet, and the to-be-gasified particle inlet is communicated with the unburned particle outlet through an external second conveying pipeline;

the oil gas-solid separation section is arranged between the material falling system and the cracking section and is used for carrying out oil gas-solid separation treatment on the combined material flow of the light oil gas and the synthesis gas in the cracking section.

Further, the top of the coking section is also provided with a flue gas-solid separation section for carrying out flue gas-solid separation treatment on the flue gas generated in the coking section.

The implementation of the invention has at least the following advantages:

1. the invention fully exerts the synergistic effect among three reactions of heavy oil cracking, coke burning and coke gasification. On one hand, coke generated in the cracking process is used as a reaction raw material of the gasification reactor to generate high-quality synthesis gas after being partially combusted and heated, so that petroleum coke is prevented from being generated, and the hydrogen source of a refinery is enriched; on the other hand, the synthesis gas generated by gasification enters the bottom of the cracking section, provides heat for cracking the heavy raw oil in the cracking section, and provides a hydrogen atmosphere for cracking reaction. Therefore, the invention realizes the technical advantages of mutual material supply, energy complementation, synergistic reaction, oil-gas co-production and the like among the three reactions.

2. According to the processing device for the deep lightening of the heavy oil and the co-production of the synthesis gas, the heavy oil cracking section, the coking section and the 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 an apparatus for deep heavy oil lightening and synthesis gas 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 method for deep lightening of heavy oil and co-production of synthesis gas, which adopts a coupling reactor internally provided with a burning section, a cracking section and a gasification section, wherein the bottom of the burning section is communicated with the top of the cracking section through a material dropping system, and the top of the gasification section is communicated with the bottom of the cracking section in a one-way mode, and the method comprises the following steps: heavy oil raw materials enter a cracking section in the middle of the coupling reactor and contact fluidized coke powder to carry out cracking reaction to generate light oil gas and coke powder particles; discharging the coke powder particles out of the coupling reactor through the cracking section and conveying the coke powder particles to a coking section at the upper part of the coupling reactor for coking treatment, wherein the coke powder particles which are not completely coked in the coking section are divided into two parts, one part of the coke powder particles descend through the material descending system and return to the cracking section to participate in cracking of the heavy oil raw material, and the other part of the coke powder particles are discharged out of the coupling reactor and conveyed to a gasification section at the lower part of the coupling reactor to generate a gasification reaction so as to generate synthesis gas; and the synthesis gas ascends to the top of the cracking section and is combined with the light oil gas to carry out oil gas-gas solid separation treatment, and oil gas fractionation is carried out on a purified oil gas product output by the oil gas-gas solid separation treatment to collect light oil and synthesis gas products.

The coupling reactor of the invention is an integrated coupling reactor which can simultaneously carry out cracking reaction, charring treatment and gasification reaction, and the interior of the coupling reactor sequentially comprises a charring section, a cracking section and a gasification section from top to bottom. The upper coke burning section is coupled with the middle cracking section through a material lowering system, and the middle cracking section is coupled with the lower gasification section. Specifically, the bottom of the upper coking section is communicated with an inlet of a material descending system, and an outlet of the material descending system is communicated with the top of the middle cracking section; the middle cracking section is in one-way conduction with the bottom gasification section, and the one-way conduction means that the material flow direction is transmitted from the bottom gasification section to the middle cracking section.

Wherein, the material system that falls between section of burning and the schizolysis section not only can make the fine coke granule in the section of burning fall into the schizolysis section down, more can realize the effective isolation of schizolysis and two reactions of burning, guarantees independent reaction environment separately, avoids the adhesion and the reunion between the fine coke granule to improve the security and the stability of whole technology. The material descending system can be a high-temperature-resistant material descending pipe, coke powder particles which are not completely burnt in the coking section can descend to enter the cracking section, a one-way plug valve can be arranged at the lower end of the material descending pipe, and the one-way plug valve can be opened after the coke powder particles entering the material descending pipe reach a certain number, so that one-way transmission of the coke powder particles from the coking section to the cracking section is ensured.

And the unidirectional conduction from the gasification section to the cracking section can be realized by arranging a gas distribution plate between the cracking section and the gasification section. The gas distribution plate enables the stream (syngas) in the gasification section to go directly up into the cracking section and prevents the stream in the cracking section from going directly down into the gasification section.

In the method, the heavy oil raw material enters a cracking section through a raw material inlet in a coupling reactor, and contacts with fluidized coke powder in the cracking section to perform cracking reaction to generate light oil gas and coke powder particles, wherein the coke powder particles are particles formed by coke aggregation and adhesion on the surface of the coke powder. 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 coupling reactor, the coke powder particles are lifted to a coking section at the upper part of the cracking section through the outside of the coupling reactor, the coking treatment is carried out in the coking section to generate high-temperature flue gas, the flue gas-solid separation treatment can be carried out on the high-temperature flue gas, the flue gas after the gas-solid separation is collected to recover heat, and the coke powder particles obtained by the gas-solid separation can return to the coking section; and the coke powder particles which are not fully combusted in the coke burning section can be divided into two parts to enter subsequent different reactions.

Specifically, a part of coke breeze particles which are not fully combusted in the coking section carry heat to descend to the cracking section through a material descending system, serve as a reaction bed material and a heat donor for the cracking section and continuously participate in the cracking of the heavy oil raw material; the other part of the coke powder particles which are not fully combusted in the coke burning section carry heat to be input into the gasification section through a conveying pipeline outside the coupling reactor, and are subjected to gasification reaction with a gasification agent in the gasification section to generate synthesis gas containing active micromolecules such as hydrogen, carbon monoxide and the like, and the carried heat can also be used as energy compensation of the gasification reaction.

Along with the continuous generation of the synthesis gas in the gasification section, the synthesis gas can move upwards from the gasification section to the cracking section, on one hand, the heat required by the cracking reaction can be provided, so that the heat of the cracking-gasification two reaction sections can be utilized in a matching way, the overall energy efficiency is improved, on the other hand, the hydrogen in the synthesis gas can inhibit the coking reaction causing the heavy oil cracking reaction to a certain extent, the product distribution of the heavy oil cracking is improved, and the quality and the yield of oil gas are improved. And the synthesis gas also fully fluidizes the coke breeze particles in the cracking section.

The synthesis gas can be combined with the light oil gas at the top of the cracking section along with the continuous ascending of the synthesis gas in the cracking section, in order to avoid the entrainment of coke powder particles in the collected light oil gas and the synthesis gas, the combined material flow of the light oil gas and the synthesis gas can be subjected to oil-gas-solid separation treatment, the purified oil gas product output after the oil-gas-solid separation is collected, and the purified oil gas product is subjected to oil-gas fractionation and other means to obtain the synthesis gas product, the gas products such as dry gas, liquefied gas and the like, and the light oil, and possibly the heavy oil product. 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; the coke powder particles output after gas-solid separation can be recycled and recycled, for example, the coke powder particles are returned to the cracking section to participate in the cracking reaction again, so that the use efficiency of the coke powder particles is further increased, and the processing cost of heavy oil weight conversion is reduced.

The invention utilizes the coupling reactor of upper burning-middle cracking-lower gasification to carry out cracking treatment on the heavy oil raw material, provides a more convenient path for the reciprocating cyclic utilization of coke powder particles, not only leads the coke powder particles of a cracking section to be burned in a burning section to directly decompose the heat supply for a heat exchange network, but also leads the incompletely burned coke powder particles 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 also 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.

The invention can form mutual supply and heat complementation of raw materials among cracking, charring and gasification in one system, and realizes the technical advantages of reaction cooperative 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.

And further, before the coke powder particles in the cracking section enter the coke burning section through the outside of the coupling reactor, the coke powder particles in the cracking section descend in the cracking section and are sequentially subjected to steam stripping treatment and particle size refining treatment.

Specifically, a steam stripping section and a particle size refining section can be arranged at the lower part of the cracking 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 bottom of the cracking section of the coupling reactor and are lifted into a coking section for coking treatment.

The steam stripping section and the particle size refining section can realize effective isolation of the gasification section and the cracking section, ensure various relatively independent reaction areas, and also can avoid agglomeration of coke powder particles, thereby improving the safety and the operation stability of deep lightening of the heavy oil raw material.

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.

In the method, the cracking section is positioned at the lower part of the coking section, so that the coke powder particles in the cracking section can be efficiently returned to the coking section, and the coke powder particles at the bottom of the cracking section can be lifted to the coking section through the coupling reactor in a lifting gas driving mode. Wherein, air can be adopted as the lifting gas, and the gas velocity of the lifting gas is controlled to be 0.2-3.0 m/s.

Further, before the combined material flow of the light oil gas and the synthesis gas is subjected to oil gas-gas solid separation treatment, the combined material flow can be subjected to cooling washing treatment, so that the combined material flow is subjected to low-temperature liquid medium treatment and then subjected to gas-solid separation treatment. 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.

Meanwhile, in order to improve the utilization rate of the coke powder particles, the coke powder particles in the cracking section can enter the coking section after being subjected to bulk separation, so that the coke powder particles can be uniformly distributed in the coking section, and the efficiency of coking treatment 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 0.1-20s, 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. Wherein the superficial gas velocity refers to the superficial gas velocity of the synthesis gas and the collection of fluidizing gas for fluidizing the coke powder particles, and the reaction time is the residence time of the coke powder particles in the cracking zone.

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 and schizolysis section, thereby help going on of gasification reaction and schizolysis 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.

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 conditions can ensure the smooth proceeding of the gasification reaction, thereby ensuring the stability of the whole process. 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.

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.

Example 1

Fig. 1 is a schematic diagram of an apparatus for heavy oil deep upgrading-syngas co-production according to an embodiment of the present invention, in which the apparatus shown in fig. 1 is used in the method for heavy oil deep upgrading-syngas co-production, and the apparatus at least includes:

the device comprises a coupling reactor 100, a coking section 1, a cracking section 2 and a gasification section 3 are arranged in the coupling reactor 100, the bottom of the coking section 1 of the coupling reactor 100 is communicated with the top of the cracking section 2 through a material descending system 4, the bottom of the cracking section 2 is communicated with the top of the gasification section 3 in a one-way mode (a gas distribution plate 5 is arranged between the cracking section 1 and the gasification section 2 and used for enabling synthesis gas in the gasification section 3 to directly ascend into the cracking section 1 and preventing material flow in the cracking section 2 from directly descending to carry out the gasification section 3); the cracking section 2 is provided with a heavy oil raw material inlet and a particle outlet to be burnt, and the upper part of the cracking section is provided with an oil gas outlet; the coking section 1 is provided with a flue gas outlet, a particle inlet to be coked and a particle outlet not to be coked, and the particle inlet to be coked is communicated with the particle outlet to be coked through an external first conveying pipeline; the gasification section 3 is provided with a to-be-gasified particle inlet, and the to-be-gasified particle inlet is communicated with the unburned particle outlet through an external second conveying pipeline;

specifically, the coupling reactor 100 may be obtained by appropriately modifying and assembling a cracking reactor, a char-combusting reactor and a gasification reactor, which are commonly used in the art, the cracking reactor may be, for example, a fluidized bed reactor, the top end of the cracking reactor is communicated with the bottom end of the char-combusting reactor through a material descending system 4, the gasification reactor may be, for example, a fluidized bed reactor, and the top end of the gasification reactor is in one-way communication with the bottom of the cracking reactor through a gas distribution plate 5; the cracking reactor, the coke burning 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 2, so that the coke powder and the particles are in a fluidized state through the action of the fluidized bed and serve as carriers of the cracking reaction;

the coking section 1 can comprise a coking reactor;

the gasification section 3 can comprise a fluidized bed, coke breeze 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.

An oil gas-solid separation section (not shown) arranged between the material falling system 4 and the cracking section 2 and used for carrying out oil gas-solid separation treatment on the combined material flow of the light oil gas and the synthesis gas in the cracking section 2;

the oil gas-solid separation section is used for receiving the combined flow of the light oil gas and the synthesis gas from the cracking section 2, the oil gas-solid separation solid phase outlet is communicated with the cracking section 2, and the gas-solid separation oil gas outlet is communicated with the oil gas outlet;

the gas-solids separation section may comprise a gas-solids separator, such as a cyclone separator, as is common in the art. The oil-gas-solid separator comprises an inlet of the oil-gas-solid separator, a solid phase outlet of the oil-gas-solid separator and an oil-gas outlet of the oil-gas-solid separator.

On the basis of the above, the coupling reactor 100 in fig. 1 further includes:

the flue gas-solid separation section 6 is positioned at the upper part of the coking section 1 and can comprise a flue gas-solid separator 61, such as a cyclone separator commonly used in the field, and is used for carrying out gas-solid separation on the flue gas generated by the coking section 1; the flue gas-solid separator 61 comprises a flue gas inlet, a purified flue gas outlet and a flue gas coke powder particle outlet, wherein the flue gas inlet is used for receiving flue gas of the coking section 1, the purified flue gas outlet is communicated with the flue gas outlet, and the flue gas coke powder particle outlet is communicated with the coking section 1 and is used for returning separated coke powder particles to the coking section 1;

a steam stripping section 7, the steam stripping section 7 may comprise steam stripping baffles to remove oil and gas from the surface of the coke breeze particles in the downward travel by injecting steam, and the steam stripping section 7 has an inlet for injecting steam;

a particle size refining section (not shown), which may include a steam jet mill, for refining and milling the stripped coke powder particles by injecting steam, and which has an inlet for injecting milling steam;

an atomization device (not shown) disposed in the cracking section 2, which is communicated with the heavy oil feedstock inlet and is used for atomizing the heavy oil feedstock, and may be an atomizer;

a dispersing device (not shown) which is arranged in the coking section 1, is communicated with the inlet of the coke particles to be coked and is used for dispersing the coke powder particles entering the coking section 1 from the cracking section 2 through an external first conveying pipeline;

a cooling washing section 8, wherein the cooling washing section 8 is arranged between the cracking section 2 and the oil gas-gas solid separation section and is communicated with the cracking section 2, and is used for cooling and washing a combined stream (a mixture of light oil gas and synthesis gas) entering the oil gas-gas solid separator;

the method for carrying out deep heavy oil lightening and 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 2 of the coupling reactor 100 through a heavy oil raw material inlet, the heavy oil raw material is atomized by an atomization device and then directly contacts with fluidized coke powder (including coke powder particles with coke attached to the outside) to generate cracking reaction, 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 7, and then the coke powder particles are cut and refined through a particle size refining section. And finally, the coke powder particles enter an external first conveying pipeline from the outlet of the particles to be coked of the cracking section 2 and enter the coking section 1 through the inlet of the particles to be coked of the coking section 1.

In the coking section 1, the coke powder particles and air introduced into the coking section through a coking gas inlet are combusted at high temperature to generate flue gas, the flue gas enters the flue gas-solid separation section 6 and enters the flue gas-solid separator 61 through a flue gas inlet for gas-solid separation, purified flue gas output by the flue gas-solid separator 61 is output from a purified flue gas outlet, and can enter a subsequent heat exchange network for flue gas waste heat recovery after being output from the flue gas outlet of the coking section 1, and the coke powder particles output by the flue gas-solid separator 61 are output from a flue gas coke powder particle outlet and enter the coking section 1; the coke powder particles which are not completely combusted in the coking section 1 are divided into two parts, one part of the coke powder particles goes down to enter the cracking section 2 through the material descending system 4, the other part of the coke powder particles enters an external second conveying pipeline through an outlet of the coke powder particles which are not completely combusted, and enters the gasification section 3 through an inlet of the coke powder particles to be gasified, wherein the coke powder particles entering the cracking section 2 are primary coke powder particles, and the coke powder particles entering the gasification section 3 are secondary coke powder particles.

The coke powder particles which are not completely combusted in the coking section 1 enter the cracking section 2 through the material descending system 4 to form first-grade coke powder particles, the first-grade coke powder particles can be used as reaction bed materials and continue to contact with heavy oil raw materials to generate cracking reaction, heat carried by the first-grade 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 which are not completely combusted in the coke burning section 1 are output from the coupling reactor 100 through an unfired coke particle outlet and enter the gasification section 3 through a particle inlet to be gasified to form secondary coke powder particles, the secondary coke powder particles can be used as reaction raw materials and generate synthesis gas through gasification reaction with a gasification agent in the gasification section 3, 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 ascends to enter the cracking section 2, and reaction heat and reaction atmosphere are provided for the cracking reaction of the heavy oil raw material.

And the synthesis gas can be mixed with the light oil gas, then enters an oil gas-solid separation section after being cooled and washed by a cooling washing section 7, enters an oil gas-solid separator through an inlet of the oil gas-solid separator for gas-solid separation treatment, 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 after passing through an oil gas outlet output coupling reactor 100 to respectively obtain the synthesis gas, the dry gas, the liquefied gas and other gas products and the light oil product. 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 coke powder particles obtained by the oil gas-gas solid separation treatment can be output from a solid phase outlet of the oil gas-gas solid separator and return to the cracking section 2.

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.

To verify the effectiveness of the present invention, the Liaohe vacuum residue was tested using the apparatus and process 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

Sample name	Liaohe vacuum residuum
		Density (20 ℃ C.)/g-cm^-3	1.0271
Kinematic viscosity (100 ℃ C.)/mm²·s^-1	3380
		Conradson carbon residue/wt%	20.04
C/wt％	86.05
		H/wt％	10.09
S/wt％	0.48
		N/wt％	1.55
n(H)/n(C)	1.41
		Saturated fraction/wt%	16.36
The fragrance is divided by weight%	36.91
		Colloid/wt%	41.12
Asphaltenes/wt%	5.61
		Ni/ppm	175
V/ppm	3.6
		Initial boiling point	412
10％	456
		30％	498
50％	547
		70％	611
90％	672
		End point of distillation	775
VGO proportion (350-	30.98％
		Heavy oil fraction ratio (>500℃)	69.02％

As can be seen from Table 1: the Liaohe vacuum residue has high carbon residue value and density, and the carbon residue value 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

Sample name/wt%	Liaohe vacuum residuum
		Yield of dry gas	4.95
Yield of liquefied gas	1.46
		Gasoline fraction	2.57
Diesel oil fraction	6.61
		Vacuum distillate	32.22
Heavy oil fraction	35.21
		Coke yield	16.98

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%)	39.9	39.7	18.7	1.7

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

1. A method for the deep lightening of heavy oil and the co-production of synthesis gas is characterized in that a coupling reactor with a coke burning section, a cracking section and a gasification section inside is adopted, the bottom of the coke burning section is communicated with the top of the cracking section through a material dropping system, and the top of the gasification section is communicated with the bottom of the cracking section in a one-way mode, and the method comprises the following steps:

the synthesis gas ascends to the top of the cracking section and is combined with the light oil gas to carry out oil gas-gas solid separation treatment, and oil gas fractionation is carried out on a purified oil gas product output by the oil gas-gas solid separation treatment to collect light oil and synthesis gas products;

before the coke powder particles in the cracking section are introduced into the coking section, 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;

before the oil gas-solid separation treatment, the combined material flow of the synthesis gas and the light oil gas is subjected to cooling washing treatment.

2. The method as claimed in claim 1, wherein the flue gas generated by the burning treatment is subjected to flue gas-solid separation treatment, the purified flue gas output by the flue gas-solid separation treatment is subjected to heat recovery, and the coke powder particles output by the flue gas-solid separation treatment are returned to the burning section.

3. The method according to claim 1, characterized in that the conditions of the cleavage reaction 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 method according to claim 1, wherein the conditions of the scorch treatment are: the scorching temperature is 600-.

5. The method 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.

6. The method according to claim 5, 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. An apparatus for the deep heavy oil lightening-synthesis gas co-production for carrying out the method of any one of claims 1 to 6, wherein the apparatus comprises a coupled reactor with a coke burning section, a cracking section, a gasification section, a steam stripping section, a particle size refining section and a cooling washing section, wherein:

the steam stripping section and the particle size refining section are arranged at the lower part of the cracking section, and the top of the steam stripping section is communicated with the bottom of the cracking section;

the steam stripping section is positioned at the upper part of the grain size refining section;

the cooling washing section is positioned between the cracking section and the gasification section and is used for cooling and washing the light oil gas in the cracking section;

8. The device as claimed in claim 7, wherein a flue gas-solid separation section is further arranged at the top of the coking section and is used for carrying out flue gas-solid separation treatment on the flue gas generated in the coking section.