CN106590712B

CN106590712B - A kind of coal hydrogenation catalysis gasification method and device

Info

Publication number: CN106590712B
Application number: CN201611270349.2A
Authority: CN
Inventors: 刘雷; 毛燕东; 李克忠
Original assignee: ENN Science and Technology Development Co Ltd
Current assignee: ENN Science and Technology Development Co Ltd
Priority date: 2016-12-30
Filing date: 2016-12-30
Publication date: 2019-08-02
Anticipated expiration: 2036-12-30
Also published as: CN106590712A

Abstract

The present invention provides a kind of coal hydrogenation catalysis gasification method and devices, are related to Coal Gasification Technology field, solve gasification furnace gas outlet CH in existing catalytic coal gasifaction technology₄The problem of content is low, complex process.Include the following steps: the coal dust that coal dust and catalyst are generated to supported catalyst；Under the effect of the catalyst, so that the coal dust and H of supported catalyst₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, containing catalyst it is residual coke with CO₂With H₂Reaction generates CH₄；Under the effect of the catalyst, so that residual burnt and water vapour, O containing catalyst₂Mixed gas carry out the reaction of residual coke gasification and generate H₂、CO₂；The coal dust of supported catalyst and the H of generation₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, residual coke containing catalyst, the CO of generation₂With H₂It reacts and generates CH₄；Repeat hydrogenation catalyst gasification reaction and the reaction of residual coke gasification and obtains CH until the residual coke containing catalyst is converted into the residue containing catalyst₄.The coal hydrogenation catalysis gasification method is applied to coal gasification field.

Description

Coal hydrogenation catalytic gasification method and device

Technical Field

The invention relates to the technical field of coal gasification, in particular to a coal hydrogenation catalytic gasification method and a coal hydrogenation catalytic gasification device.

Background

At present, the energy resource status of China has the characteristics of rich coal, less oil and gas shortage, and the technology for preparing the gas from the coal is a shortcut which is suitable for the national conditions of China, solves the energy crisis and ensures the energy safety by converting the coal into natural gas which is the best fuel in fossil energy.

The coal catalytic gasification technology is one of the most effective process approaches in the coal gas making technology. The existing coal catalytic gasification technology adopts alkali metal catalyst to make coal react with water vapor at relatively low temperature to generate H₂CO, H produced₂The CO further undergoes shift reaction and methanation reaction under the action of an alkali metal catalyst to finally generate CH₄. The addition of the alkali metal catalyst enables a plurality of reactions in the coal catalytic gasification technology to occur in one device at the same time, thereby improving the energy thermal efficiency. However, CH in the outlet of the gasification furnace of this coal catalytic gasification technology₄The volume content is low (only about 20 percent), and unreacted H in the gas needs to be removed subsequently₂CO and CH₄Separating and then removing unreacted H₂CO conveying gasification furnace or methanation device for further resynthesis of CH₄The above-mentioned separation and re-synthesis steps inevitably lead to a complicated process.

Disclosure of Invention

The invention aims to provide a coal hydrogenation catalytic gasification method and a coal hydrogenation catalytic gasification device, which solve the problem that a gasification furnace gas outlet CH in the existing coal catalytic gasification technology₄Low content and complex process.

In order to achieve the purpose, the invention provides the following technical scheme:

in a first aspect, the present invention provides a coal hydrogenation catalytic gasification method, which comprises the following steps:

s1: carrying out a coal powder catalyst loading process on coal powder and a catalyst to generate catalyst-loaded coal powder;

s2: the coal powder loaded with the catalyst enters the hydrogenation catalytic gasification part, and under the action of the catalyst, the coal powder loaded with the catalyst and H existing in the hydrogenation catalytic gasification part₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-containing residual coke and aromatic oil compound, and CO present in the hydrogenation catalytic gasification section₂And H₂Reaction to form CH₄；

S3: the residual coke containing the catalyst enters a residual coke gasification part, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part, and under the action of a catalyst, residual coke containing the catalyst, water vapor and O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂；

S4: generation of H₂、CO₂The coal powder is conveyed to the hydrogen-added catalytic gasification part to load the catalyst and the generated H₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-containing residual coke and aromatic oil compound, and CO produced₂And H₂React to form CH₄；

S5: repeating the steps S3-S4 until the catalyst-containing residual coke is converted into catalyst-containing residue to obtain entrained H₂、CO₂Dust and aromatic oil compound CH₄。

He-ShiCompared with the prior art, the coal hydrogenation catalytic gasification method provided by the invention comprises the following steps of firstly, carrying out a coal powder catalyst loading process on coal powder and a catalyst to generate catalyst-loaded coal powder; then, conveying the coal powder loaded with the catalyst to a hydrogenation catalytic gasification part, and under the action of the catalyst, loading the coal powder loaded with the catalyst and H₂Can be directly converted into CH at lower gasification temperature₄Simultaneously generating catalyst-rich residual coke and aromatic oil compounds, and allowing the catalyst-rich residual coke generated in the hydrogenation catalytic gasification part to enter the residual coke gasification part and water vapor and O₂Reaction to form H₂And CO₂H produced in the gasification part of residual coke₂And CO₂Can be circulated into a hydrogenation catalytic gasification part to further generate CH together with coal powder₄The residual coke rich in catalyst and aromatic oil compounds, the hydrogenation catalytic gasification part and the residual coke gasification part form a circulating system, and the above steps are repeated in such a way, so that when the reaction in the coal hydrogenation catalytic gasification device reaches or approaches the thermodynamic equilibrium limit, a large amount of CH can be generated₄Improve CH₄Production rate, carbon conversion rate and CH of gas outlet of hydrocatalytic gasification section₄The content and carbon conversion rate are more than 95 percent, and CH at the gas outlet of the hydrogenation catalytic gasification part₄The content can reach 80 percent, and CO are reduced₂The generation of byproducts effectively solves the problem of the prior catalytic gasification process that the gas outlet CH of the gasification furnace is generated₄Low content, need to separate and re-CH₄The conversion rate of conversion and the existing hydropyrolysis carbon is low. At the same time, in the presence of coal dust and H₂Hydrogenation catalytic gasification reaction to generate CH₄Meanwhile, the coal powder can be mixed with H₂The reaction generates high added value aromatic oil compounds such as benzene-toluene-xylene mixture (BTX), phenol-cresol-xylenol mixture (PCX), naphthalene and the like with high economic value.

In a second aspect, the present invention provides a coal hydrogenation catalytic gasification apparatus for use in the above coal hydrogenation catalytic gasification method, the coal hydrogenation catalytic gasification apparatus comprising: a catalyst loading unit and a hydrogenation catalytic gasification reaction unit; the hydrogenation catalytic gasification reaction unit comprises a catalyst and a catalyst which are connected with each otherA hydrogen catalytic gasification unit and a residual coke gasification unit; the coal powder inlet of the catalyst loading unit is connected with a coal powder conveying pipeline, and the coal powder outlet of the catalyst loading unit is connected with the coal powder inlet of the hydrogenation catalytic gasification part; the catalyst inlet of the catalyst loading unit is connected with a catalyst conveying pipeline; the mixed gas inlet of the residual coke gasification part is used for conveying water vapor and O₂The gas inlet pipeline is connected, and a gas outlet of the hydrogenation catalytic gasification part is connected with a methane collection device.

Compared with the prior art, the coal hydrogenation catalytic gasification device provided by the invention has the advantages that the coal powder inlet of the catalyst loading unit is connected with the coal powder conveying pipeline, the catalyst inlet of the catalyst loading unit is connected with the catalyst conveying pipeline, coal powder and a catalyst are respectively conveyed to the catalyst loading unit through the coal powder conveying pipeline and the catalyst conveying pipeline, and in the catalyst loading unit, the coal powder and the catalyst are subjected to a process of loading the catalyst by the coal powder to generate coal powder loaded with the catalyst; conveying the coal powder loaded with the catalyst to a hydrogenation catalytic gasification reaction unit, wherein the hydrogenation catalytic gasification reaction unit is divided into a hydrogenation catalytic gasification part and a residual coke gasification part, the hydrogenation catalytic gasification part and the residual coke gasification part form a circulation system, and under the action of the catalyst, the coal powder loaded with the catalyst and H₂Can be directly converted into CH at lower gasification temperature₄Simultaneously generating catalyst-rich residual coke and aromatic oil compounds, and allowing the catalyst-rich residual coke generated in the hydrogenation catalytic gasification part to enter the residual coke gasification part and water vapor and O₂Reaction to form H₂And CO₂H produced in the gasification part of residual coke₂And CO₂Can be circulated into a hydrogenation catalytic gasification part to further generate CH together with coal powder₄Residual coke rich in catalyst and aromatic oil compounds, and the steps are repeated in a circulating way, so that when the reaction in the coal hydrogenation catalytic gasification device reaches or approaches the thermodynamic equilibrium limit, a large amount of CH can be generated₄Improve CH₄Production rate, carbon conversion rate and CH of gas outlet of hydrocatalytic gasification section₄The content and carbon conversion rate are more than 95 percent, and CH at the gas outlet of the hydrogenation catalytic gasification part₄Content (wt.)Can reach 80 percent, and reduces CO and CO₂The generation of byproducts effectively solves the problem of the prior catalytic gasification process that the gas outlet CH of the gasification furnace is generated₄Low content, need to separate and re-CH₄The conversion rate of conversion and the existing hydropyrolysis carbon is low. At the same time, in the presence of coal dust and H₂Hydrogenation catalytic gasification reaction to generate CH₄Meanwhile, the coal powder can be mixed with H₂The reaction generates high added value aromatic oil compounds such as benzene-toluene-xylene mixture (BTX), phenol-cresol-xylenol mixture (PCX), naphthalene and the like with high economic value.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 is a schematic structural diagram of a coal hydrogenation catalytic gasification device provided by the present invention, wherein a hydrogenation catalytic gasification part and a residual coke gasification part are integrated devices;

FIG. 2 is another schematic structural diagram of a coal hydrogenation catalytic gasification device provided by the present invention, wherein a hydrogenation catalytic gasification part and a residual coke gasification part are split devices;

FIG. 3 is a flow chart of a coal hydrocatalytic gasification process provided by the present invention.

Reference numerals:

1-a catalyst support unit; 2-a hydrogenation catalytic gasification reaction unit;

201-a hydrocatalytic gasification part; 202-residual coke gasification part;

3, a slag discharging unit; 4-a catalyst recovery unit;

5-a gas-solid separation unit; 6-an indirect condensation unit;

7-a gas purification unit; 8-hydrogen separation unit.

Detailed Description

The purpose, features and advantages of the present invention will become more apparent. It is obvious that the described embodiments are only some, not all embodiments of the proposed solution. 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.

Referring to fig. 1-2, the invention provides a coal hydrogenation catalytic gasification device, which comprises a catalyst loading unit 1 and a hydrogenation catalytic gasification reaction unit 2, wherein the hydrogenation catalytic gasification reaction unit 2 comprises a hydrogenation catalytic gasification part 201 and a residual coke gasification part 202 which are connected with each other, a coal powder inlet of the catalyst loading unit 1 is connected with a coal powder conveying pipeline, and a coal powder outlet of the catalyst loading unit 1 is connected with a coal powder inlet of the hydrogenation catalytic gasification part 201; the catalyst inlet of the catalyst loading unit 1 is connected with a catalyst conveying pipeline; mixed gas inlet of residual coke gasification part 202 and method for conveying water vapor and O₂Is connected with the gas inlet pipeline of the hydrogenation catalytic gasification part 201, and the gas outlet of the hydrogenation catalytic gasification part is connected with the methane collection device.

The catalyst loading unit 1 is used for the process of loading a catalyst on coal dust, and the hydrogenation catalytic gasification part 201 is used for coal dust and H₂Performing hydrogenation catalytic gasification reaction, and using the residual coke gasification part 202 for residual coke, water vapor and O₂And carrying out gasification reaction of residual coke.

The working process of the coal hydrogenation catalytic gasification device provided by the invention is as follows by combining the attached drawings:

s1: the coal dust and the catalyst are carried out the process of loading the catalyst on the coal dust in the catalyst loading unit 1 to generate the coal dust loading the catalyst.

S2: the coal powder loaded with the catalyst enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the coal powder loaded with the catalyst and H existing in the hydrogen catalytic gasification part 202₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-rich residual coke and aromatic oil compounds, and CO present in hydrogen catalytic gasification unit 202₂And H₂Reaction to form CH₄。

Specifically, as the raw material charged into the hydrogenation catalytic gasification part 201 is the coal powder loaded with the catalyst, the C-C bond of the carbon particles in the coal powder is broken under the action of the catalyst to generate C atoms with reaction activity, and meanwhile, H exists in the hydrogenation catalytic gasification part 201₂The presence of a catalyst excites H₂Dissociating to generate reactive H atoms, and overflowing the reactive H atoms to the surface of the reactive C atoms to generate CH through hydrogenation catalytic gasification reaction under the action of a catalyst₄。

S3: the residual coke rich in catalyst enters a residual coke gasification part 202, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part 202 through the gas inlet pipeline, and under the action of the catalyst, the residual coke rich in the catalyst, the water vapor and the O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂。

S4: generation of H₂、CO₂The coal powder and the generated H are conveyed to a hydrogenation catalytic gasification part 201 to load the catalyst₂Hydrogenation catalytic gasification reaction to generate CH₄Residual coke rich in catalyst and aromatic oil compound, and CO generated₂And H₂React to form CH₄。

S5: repeating the steps S3-S4 until the catalyst-rich residual coke is converted into catalyst-rich residue (the carbon content of the residue is less than 10 percent), and obtaining entrained H₂、CO₂Dust and aromatic oil compound CH₄。

Compared with the prior art, the method has the advantages that,according to the coal hydrogenation catalytic gasification device provided by the invention, a coal powder inlet of a catalyst loading unit 1 is connected with a coal powder conveying pipeline, a catalyst inlet of the catalyst loading unit 1 is connected with a catalyst conveying pipeline, coal powder and a catalyst are respectively conveyed to the catalyst loading unit 1 through the coal powder conveying pipeline and the catalyst conveying pipeline, and in the catalyst loading unit 1, the coal powder and the catalyst are subjected to a process of loading the catalyst by the coal powder to generate coal powder loaded with the catalyst; conveying the coal powder loaded with the catalyst to a hydrogenation catalytic gasification reaction unit 2, wherein the hydrogenation catalytic gasification reaction unit 2 is divided into a hydrogenation catalytic gasification part 201 and a residual coke gasification part 202 which form a circulation system, and under the action of the catalyst, the coal powder loaded with the catalyst and H₂Can be directly converted into CH at lower gasification temperature₄Simultaneously generates catalyst-rich residual coke and aromatic oil compounds, and the catalyst-rich residual coke generated by the hydrogenation catalytic gasification part 201 enters the residual coke gasification part 202 and water vapor and O₂Reaction to form H₂And CO₂H produced in the residual coke gasification part 202₂And CO₂Can be recycled to the hydrogenation catalytic gasification part 201 and further generates CH with the coal powder₄Residual coke rich in catalyst and aromatic oil compounds, and the steps are repeated in a circulating way, so that a large amount of CH can be generated when the reaction in the coal hydrogenation catalytic gasification device reaches or approaches a thermodynamic equilibrium limit state₄Improve CH₄The production rate, the carbon conversion rate, and the CH at the gas outlet of the hydrocatalytic gasification part 201₄The content and the carbon conversion rate reach more than 95 percent, and CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content can reach 80 percent, and CO are reduced₂The generation of byproducts effectively solves the problem of the prior catalytic gasification process that the gas outlet CH of the gasification furnace is generated₄Low content, need to separate and re-CH₄The conversion rate of conversion and the existing hydropyrolysis carbon is low. At the same time, in the presence of coal dust and H₂Hydrogenation catalytic gasification reaction to generate CH₄Meanwhile, the coal powder can be mixed with H₂The reaction generates high added value aromatic oil compounds such as benzene-toluene-xylene mixture (BTX), phenol-cresol-xylenol mixture (PCX), naphthalene and the like with high economic value。

Here, it should be noted that, although, at the initial stage of the reaction, H is present in the air₂And CO₂Has a low content of (A), and generates CH₄The hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 of the coal hydrogenation catalytic gasification device provided by the invention are a circulation system, so that a large amount of H can be generated when the circulation system reaches dynamic balance₂And CO₂Thereby generating a large amount of CH₄。

Preferably, the position of the hydrogenation catalytic gasification part 201 in the gravity direction is higher than the position of the residual coke gasification part 202 in the gravity direction; CH produced in the hydrocatalytic gasification section 201 thus positioned above₄Discharged from the top of the hydrocatalytic gasification part 201, and the produced catalyst-rich residual coke falls into the residual coke gasification part 202 and the steam and O under the action of gravity₂Reaction to form H₂And CO₂High temperature H generated in the residual coke gasification part 202₂And CO₂And rises into the hydrocatalytic gasification part 201 positioned above to further participate in the reaction. Therefore, the residual coke rich in the catalyst and the movement or flow of various gases are realized by utilizing the action of gravity or airflow without an additional power device, and the automatic circulation of the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 is realized.

Specifically, the hydrogenation catalyst gasification unit 201 and the residual coke gasification unit 202 in the hydrogenation catalyst gasification reaction unit 2 may be an integrated device or a separate device.

When the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 are an integrated device, the hydrogenation catalytic gasification reaction unit 2 is a gasification furnace, the gasification furnace is divided into the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 along the gravity direction, and the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 have no definite limit; the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 are integrated into one device, and the coal powder and H in the hydrogenation catalytic gasification part 201₂Residual coke rich in catalyst and generated after hydrogenation catalytic gasification reaction directly falls into the reactor under the action of gravityGasification part 202 of residual coke and steam and O₂Reaction to form H₂And CO₂High temperature H generated in the residual coke gasification part 202₂And CO₂Directly rise and get into hydrogenation catalytic gasification portion 201, the circulation between hydrogenation catalytic gasification portion 201 and the incomplete burnt gasification portion 202 need not through the pipe-line transportation for the reaction is more abundant, and can simplify the inner structure of device, is favorable to the maintenance in later stage.

When the hydrogenation catalytic gasification unit 201 and the residual coke gasification unit 202 are separate devices, both the hydrogenation catalytic gasification unit 201 and the residual coke gasification unit 202 are gasification furnaces, that is, the hydrogenation catalytic gasification unit 201 is a hydrogenation catalytic gasification furnace, and the residual coke gasification unit 202 is a residual coke gasification furnace.

The hydrogenation catalytic gasification unit 201 may be a fluidized bed, and the residual coke gasification unit 202 may be a fluidized bed or a moving bed. The specific reasons that the hydrogenation catalytic gasification part 201 adopts a fluidized bed and the residual coke gasification part 202 adopts a fluidized bed or a moving bed are as follows: the reaction in the hydrocatalytic gasification part 201 is coal dust and H₂The operation form of the fluidized bed is selected to ensure that the coal powder and the H₂The contact is full, and the running speed of the fluidized bed is more matched with the reaction speed of the hydrogenation catalytic gasification; in the residual coke gasification part 202, the reaction in the residual coke gasification part 202 is the catalyst-rich residual coke, water vapor and O₂The gasification reaction of the residual coke is carried out in a mode of operating a fluidized bed or a moving bed to ensure that the residual coke rich in the catalyst is mixed with water vapor and O₂And the operation rate of the fluidized bed or the moving bed is more matched with the reaction rate of the gasification reaction of the residual coke. By using a fluidized bed for the hydrocatalytic gasification part 201 and a fluidized bed or moving bed for the residual coke gasification part 202, CH can be further increased₄The production rate, the carbon conversion rate, and the CH at the gas outlet of the hydrocatalytic gasification part 201₄And (4) content.

Generally, the coal hydrogenation catalytic gasification device also comprises a post-treatment unit, wherein the post-treatment unit comprises a gas-solid separation unit 5, an indirect condensation unit 6, a coal gas purification unit 7 and hydrogen which are connected in sequenceA separation unit 8, a methane outlet of the hydrogenation catalytic gasification part 201 passes through the gas-solid separation unit 5, the indirect condensation unit 6 and the gas purification unit 7 in sequence for separating H₂And CH₄The hydrogen separation unit 8 of (a) is connected to a methane collection device.

In practice, first, the carrier tape H is₂、CO₂Dust and aromatic oil compound CH₄Entering a gas-solid separation unit 5 to separate CH₄、H₂、CO₂Gas-solid separation is carried out on the aromatic oil compound and the dust to obtain the dust and the entrained H after the dust is removed₂、CO₂And CH of aromatic oil compound₄。

Then, will entrain H₂、CO₂And CH of aromatic oil compound₄Cooling in an indirect condensing unit 6, recovering heat to generate steam, and delivering the steam to the residual coke gasification part 202₂And residual coke rich in catalyst is subjected to residual coke gasification reaction to generate H₂And CO₂Of course, the steam can also be directly conveyed to a steam turbine to generate electricity; meanwhile, according to different distillation ranges, high value-added aromatic oil compounds such as benzene-toluene-xylene mixture (BTX), phenol-cresol-xylenol mixture (PCX), naphthalene and the like can be obtained, and entrained H of water vapor and the aromatic oil compounds can be obtained₂And CO₂CH (A) of₄。

Secondly, will entrain H₂And CO₂CH (A) of₄Deacidifying by a coal gas purification unit 7 to remove CO in the gas₂To obtain an entrainment H₂CH (A) of₄。

Finally, entrain H₂CH (A) of₄Passing through a hydrogen separation unit 8, H is separated₂And CH₄Separating to obtain CH₄。

In the above post-treatment unit, the gas-solid separation unit 5 can be a multi-stage cyclone separatorThe multi-stage cyclone separator is used as the gas-solid separation unit 5, so that CH can be more effectively separated₄、H₂、CO₂Separating aromatic oil compounds from the dust to obtain CH with less solid dust content₄、H₂、CO₂Aromatic oil compounds; the indirect condensation unit 6 can be a multi-stage indirect heat exchanger, and can generate water vapor with different qualities by recovering different heat; the hydrogen separation unit 8 can be preferably a pressure swing adsorption hydrogen separation device which has the characteristics of low energy consumption, thorough separation, simple process flow, high automation degree, good environmental benefit and the like, and the pressure swing adsorption hydrogen separation device is adopted for H₂And CH₄Can obtain purer CH₄And is more beneficial to realizing the automation and environmental protection of the coal hydrogenation catalytic gasification device provided by the invention.

Preferably, the dust outlet of the gas-solid separation unit 5 is connected with the dust inlet of the residual coke gasification part 202, and the gas outlet of the gas-solid separation unit 5 is connected with the gas inlet of the indirect condensation unit 6, so that the dust separated in the gas-solid separation unit 5 is conveyed to the residual coke gasification part 202 and is mixed with the water vapor and O₂Reaction to form H₂And CO₂Further increase CH₄The production rate, the carbon conversion rate, and the CH at the gas outlet of the hydrocatalytic gasification part 201₄And (4) content.

The hydrogen outlet of the hydrogen separation unit 8 is connected with the hydrogen inlet of the hydrogenation catalytic gasification part 201, and the separated H₂Is conveyed to a hydrogenation catalytic gasification part 201 to perform hydrogenation catalytic gasification reaction with coal powder to generate CH₄。

The coal hydrogenation catalytic gasification device further comprises a slag discharging unit 3 and a catalyst recovery unit 4, wherein a residue outlet of the residual coke gasification part 202 is connected with the catalyst loading unit 1 sequentially through the slag discharging unit 3 and the catalyst recovery unit 4.

In specific implementation, when the reaction in the coal hydrogenation catalytic gasification device reaches a limit state, the residue rich in catalyst and having a C content of less than 10% obtained after deep cracking of the coal powder is conveyed from the residual coke gasification part 202 to the slag discharge system 3 and the catalyst recovery unit 4 for catalyst recovery, and the recovered catalyst is conveyed to the catalyst loading unit 1 for recycling, so that the utilization rate of the catalyst is improved.

The invention also provides a coal hydrogenation catalytic gasification method, which comprises the following steps:

s1: the coal powder with the particle size of less than 6mm and the water content of less than 5 percent and the catalyst are subjected to a coal powder catalyst loading process in the catalyst loading unit 1 to generate the catalyst-loaded coal powder.

S2: the coal powder loaded with the catalyst enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the coal powder loaded with the catalyst and H existing in the hydrogen catalytic gasification part 202₂Hydrogenation catalytic gasification reaction to generate CH₄(shown in formula I), catalyst-rich residual coke and aromatic oil compounds, and CO existing in hydrogen catalytic gasification part 202₂And H₂Reaction to form CH₄(as shown in formula II);

C+2H₂→CH₄——(I)

4H₂+CO₂→CH₄+2H₂O——(II)

s3: the residual coke rich in catalyst enters a residual coke gasification part 202, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part 202 through the gas inlet pipeline, and under the action of the catalyst, the residual coke rich in the catalyst, the water vapor and the O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂(as shown in formulas III-VI).

2C+2H₂O→2H₂+2CO——(III)

CO+H₂O→CO₂+H₂——(IV)

2C+O₂→2CO——(V)

C+O₂→CO₂——(VI)

Compared with the prior art, the coal hydrogenation catalytic gasification method provided by the invention comprises the following steps of firstly, carrying out a coal powder catalyst loading process on coal powder and a catalyst to generate catalyst-loaded coal powder; then, the catalyst-loaded pulverized coal is transported to the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal and H are carried₂Can be directly converted into CH at lower gasification temperature₄Simultaneously generates catalyst-rich residual coke and aromatic oil compounds, and the catalyst-rich residual coke generated by the hydrogenation catalytic gasification part 201 enters the residual coke gasification part 202 and water vapor and O₂Reaction to form H₂And CO₂H produced in the residual coke gasification part 202₂And CO₂Can be recycled to the hydrogenation catalytic gasification part 201 and further generates CH with the coal powder₄Residual coke rich in catalyst and aromatic oil compounds, and the steps are repeated in a circulating way, so that when the reaction in the coal hydrogenation catalytic gasification device reaches or approaches the thermodynamic equilibrium limit, a large amount of CH can be generated₄Improve CH₄The production rate, the carbon conversion rate, and the CH at the gas outlet of the hydrocatalytic gasification part 201₄The content and the carbon conversion rate reach more than 95 percent, and CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content can reach 80 percent, and CO are reduced₂The generation of by-products effectively solves the problem of the prior catalytic gasGasification process gasifier gas outlet CH₄Low content, need to separate and re-CH₄The conversion rate of conversion and the existing hydropyrolysis carbon is low. At the same time, in the presence of coal dust and H₂Hydrogenation catalytic gasification reaction to generate CH₄Meanwhile, the coal powder can be mixed with H₂The reaction generates high added value aromatic oil compounds such as benzene-toluene-xylene mixture (BTX), phenol-cresol-xylenol mixture (PCX), naphthalene and the like with high economic value.

In the coal hydrogenation catalytic gasification method of the present invention, the pulverized coal may be one or more of pulverized lignite, pulverized bituminous coal, sub-pulverized bituminous coal or pulverized anthracite, and preferably one or more of pulverized bituminous coal, sub-pulverized bituminous coal or pulverized bituminous coal with a volatile component mass percentage higher than 30%. This is because the pulverized lignite, the pulverized hypo-bituminous coal or the pulverized bituminous coal with the mass percentage of the volatile components higher than 30% have the characteristics of low ash, low sulfur, high volatile components, strong activity and the like, and can obtain more oil products and CH₄。

In addition, the mode of loading the catalyst on the coal dust can be one of dry mixing, impregnation, partial dry mixing and partial impregnation mixing methods.

With respect to the choice of catalyst, the catalyst may be a single catalyst or a composite catalyst.

When the catalyst is a single catalyst, the single catalyst is a transition metal salt, preferably one or more of Fe salt, Co salt and Ni salt mixed in any proportion.

In the coal hydrogenation catalytic gasification method provided by the invention, the catalyst is preferably a composite catalyst, when the catalyst is a composite catalyst, the main catalyst in the composite catalyst is preferably one or more of Fe salt, Co salt and Ni salt mixed at any proportion, and the auxiliary catalyst is preferably one or more of Ca salt, Ca oxide, Mg salt or Mg oxide mixed at any proportion.

For the composite catalyst, the main catalyst catalyzes C and H, respectively₂、CO₂And H₂Generating CH₄The cocatalyst is mainly used for increasing the dispersibility and catalytic activity of the main catalyst, improving the adsorption capacity of the main catalyst on an active site, forming more active centers, inhibiting inactivation, reducing inactivation probability and improving catalytic performance; meanwhile, when the residual coke rich in the catalyst after the hydrogenation catalytic gasification reaction is further gasified, the cocatalyst, namely the alkaline earth metal catalyst is favorable for the gasification reaction of the residual coke to generate H₂And CO₂The direction is carried out.

Furthermore, in the coal powder loaded with the catalyst, the mass of the main catalyst in the composite catalyst accounts for 3-8% of the mass of the coal powder, and the mass of the cocatalyst accounts for 0.2-2% of the mass of the coal powder; preferably: in the coal powder loaded with the catalyst, the mass of the main catalyst in the composite catalyst accounts for 4-6% of the mass of the coal powder, and the mass of the cocatalyst accounts for 0.4-0.8% of the mass of the cocatalyst. The number of active sites on the particles of the pulverized coal is limited, the addition amount of the main catalyst is too high, the redundant main catalyst cannot play a role in catalysis after the active sites are saturated, and the economic cost is increased due to excessive addition; however, if the addition amount of the main catalyst is too low, the catalyst cannot completely catalyze the active sites on the pulverized coal particles, and cannot achieve the expected catalytic effect, so that the gas outlet CH of the hydrogenation catalytic gasification furnace is caused₄The content and carbon conversion rate decrease; when the addition amount of the cocatalyst is too high, the cocatalyst competes with the main catalyst for active sites on the particles of the coal dust, so that the active sites are covered by the cocatalyst, and further the contact probability of the main catalyst and the active sites is reduced, so that the activity is reduced, and when the addition amount of the cocatalyst is too low, the dispersibility and catalytic activity of the main catalyst cannot be effectively increased, and the inactivation of the main catalyst cannot be effectively inhibited, therefore, when the catalyst is preferably a composite catalyst, the addition amounts of the main catalyst and the cocatalyst are limited by catalytic performance and technical economy, in the coal dust loaded with the catalyst, the mass of the main catalyst in the composite catalyst is limited to be 3-8% of the mass of the coal dust, and the mass of the cocatalyst is limited to be 0.2-2% of the mass of the coal dust; preferably: in the coal powder loaded with the catalyst, the mass of the main catalyst in the composite catalyst accounts for 4-6% of the mass of the coal powder, and the mass of the cocatalystThe mass of the catalyst is 0.4-0.8% of the mass of the coal dust.

Preferably, the operating pressure of the hydrogenation catalytic gasification reaction is 0.5MPa to 8MPa, preferably 1MPa to 7MPa, and the reaction temperature of the hydrogenation catalytic gasification reaction is 650 ℃ to 900 ℃, preferably 700 ℃ to 800 ℃. For the selection of the operation pressure of the hydrogenation catalytic gasification reaction, according to the thermodynamic equilibrium, the operation pressure of the hydrogenation catalytic gasification reaction is in the range of 0.5MPa-8MPa, which is more favorable for the hydrogenation catalytic gasification reaction to generate CH₄The method can improve the reaction rate of the hydrogenation catalytic gasification, increase the treatment capacity in unit time, increase the operating pressure of the hydrogenation catalytic gasification reaction to be higher than 8MPa, and increase the operation danger due to uncontrollable reaction caused by too high reaction rate of the hydrogenation catalytic gasification reaction, and increase the equipment investment due to high pressure requirement on equipment, while the operating pressure of the hydrogenation catalytic gasification reaction to be lower than 0.5MPa is not favorable for the hydrogenation catalytic gasification reaction to generate CH₄The reaction rate is too slow, and the treatment capacity per unit time is reduced; with the selection of the reaction temperature of the hydrogenation catalytic gasification reaction, the catalyst can more stimulate the C-C bond fracture in the coal and promote H in the range of 650-900 DEG C₂The H atom overflows to the surface of the C with reactivity to generate CH₄The reaction temperature of the hydrogenation catalytic gasification reaction higher than 900 ℃ leads to sintering deactivation of the catalyst, while the reaction temperature lower than 650 ℃ leads to poor catalytic effect and slow reaction rate.

Preferably, the operating pressure of the gasification reaction of the residual coke is 0.5MPa to 8MPa, preferably 1MPa to 7MPa, and the reaction temperature of the gasification reaction of the residual coke is 800 ℃ to 1000 ℃. The selection of the operating pressure of the gasification reaction of the residual coke is more beneficial to the gasification reaction of the residual coke to generate H according to the thermodynamic equilibrium and the operating pressure of the gasification reaction of the residual coke is in the range of 0.5MPa to 8MPa₂、CO₂The operation pressure of the gasification reaction of the residual coke is higher than 8MPa, the gasification reaction rate of the residual coke is too high, the reaction is uncontrollable, the operation danger is increased, the high pressure requirement on equipment is high, the equipment investment is increased, and the operation pressure of the gasification reaction of the residual coke is lower than 0.5MPa, so that the operation speed is not increasedIs beneficial to the gasification reaction of residual coke to generate CH₄The reaction speed is too slow, the treatment capacity in unit time is reduced, further, the operating pressure of the gasification reaction of the residual coke is equal to the operating pressure of the hydrogenation catalytic gasification reaction, and the system pressure of the whole hydrogenation catalytic gasification reaction unit 2 is kept balanced, so that the operation is more facilitated; the reaction temperature of the gasification reaction of the residual coke is selected, and the catalyst can promote the gasification reaction of the residual coke to generate H at 800-1000 DEG C₂、CO₂In the direction of (2) to generate more H₂、CO₂For generating CH₄。

After the step S5, the coal hydrogenation catalytic gasification method provided by the invention further comprises a post-treatment stage, wherein the post-treatment stage comprises a gas-solid separation stage, an indirect condensation stage, a coal gas purification stage and a hydrogen separation stage.

Specifically, the gas-solid separation stage comprises: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Entering a gas-solid separation unit 5 to separate CH₄、H₂、CO₂Gas-solid separation is carried out on the aromatic oil compound and the dust to obtain the dust and the entrained H after the dust is removed₂、CO₂And CH of aromatic oil compound₄。

The indirect condensation stage comprises: will entrain H₂、CO₂And CH of aromatic oil compound₄Cooling in indirect condensation unit 6, recovering heat, distilling to obtain benzene-toluene-xylene mixture (BTX), phenol-cresol-xylenol mixture (PCX), and high value-added aromatic oil compounds such as naphthalene, and removing water vapor and entrained H of aromatic oil compounds₂And CO₂CH (A) of₄。

The gas purification stage comprises: will entrain H₂And CO₂CH (A) of₄Deacidifying by a coal gas purification unit 7 to remove CO in the gas₂To obtain an entrainment H₂CH (A) of₄。

Hydrogen separation stage packageComprises the following steps: is entrained with H₂CH (A) of₄Passing through a hydrogen separation unit 8, H is separated₂And CH₄Separating to obtain the final product CH₄。

Further, the dust obtained in the gas-solid separation stage is conveyed to the residual coke gasification part 202 to be further mixed with water vapor and O₂Reaction to form H₂And CO₂Further increase CH₄The production rate, the carbon conversion rate, and the CH at the gas outlet of the hydrocatalytic gasification part 201₄And (4) content.

Further, H obtained in the hydrogen separation stage₂Is conveyed to a hydrogenation catalytic gasification part 201 to further generate hydrogenation catalytic gasification reaction with coal powder to generate CH₄。

After step S5, the coal hydrogenation catalytic gasification method further includes: a catalyst recovery stage.

In the catalyst recovery stage, the residue rich in the catalyst and with the content of C less than 10% is subjected to catalyst recovery through the deslagging system 3 and the catalyst recovery unit 4, and the recovered catalyst is conveyed to the catalyst loading unit 1 for recycling, so that the utilization rate of the catalyst is improved.

It should be noted that: the catalyst recovery stage is one or more of water washing, acid washing, alkali washing and ammonia leaching, and can be selected according to actual conditions.

Several alternative embodiments of the coal hydrogenation catalytic gasification method provided by the present invention are given below with reference to the accompanying drawings, which are only for illustration and are not intended to limit the scope of the present invention.

Example one

The embodiment provides a coal hydrogenation catalytic gasification method, which comprises the following steps:

s1: the anthracite powder with the particle size of less than 6mm and the water content of less than 5 percent and the catalyst are dry-mixed in the catalyst loading unit 1 to generate the anthracite powder loaded with Fe salt, wherein the catalyst is Fe salt.

S2: the anthracite powder loaded with the catalyst enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the anthracite powder loaded with the catalyst and H existing in the hydrogen catalytic gasification part 202₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-rich residual coke and aromatic oil compounds, and CO present in hydrogen catalytic gasification unit 202₂And H₂Reaction to form CH₄Wherein the operation pressure of the hydrogenation catalytic gasification reaction is 0.5MPa, and the reaction temperature of the hydrogenation catalytic gasification reaction is 900 ℃.

S3: the residual coke rich in catalyst enters a residual coke gasification part 202, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part 202 through the gas inlet pipeline, and under the action of the catalyst, the residual coke rich in the catalyst, the water vapor and the O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂Wherein the operating pressure of the gasification reaction of the residual coke is 0.5MPa, and the reaction temperature of the gasification reaction of the residual coke is 1000 ℃.

S4: generation of H₂、CO₂The anthracite powder and the generated H are conveyed to a hydrogenation catalytic gasification part 201 to load the catalyst₂Hydrogenation catalytic gasification reaction to generate CH₄Residual coke rich in catalyst and aromatic oil compound, and CO generated₂And H₂React to form CH₄；

S6: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Carrying out gas-solid separation stage, indirect condensation stage, gas purification stage and hydrogen separation stage in sequence to obtain the final product CH₄(ii) a Gas-solid separation stageThe dust is conveyed to the residual coke gasification part 202 and further mixed with steam and O₂Reaction to form H₂And CO₂(ii) a H obtained in the hydrogen separation stage₂Is conveyed to a hydrogenation catalytic gasification part 201 to further generate hydrogenation catalytic gasification reaction with the anthracite powder to generate CH₄(ii) a The residue rich in the catalyst and with the C content less than 10 percent is washed by water through a slag discharging system 3 and a catalyst recovery unit 4, and the recovered catalyst is conveyed to a catalyst loading unit 1 for recycling.

Through tests, the carbon conversion rate of the coal hydrogenation catalytic gasification method provided by the embodiment is more than 95%, and the CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content of (b) is 80% by volume.

Example two

s1: the method comprises the steps of dipping and partially dry-mixing the sub-bituminous coal powder with the particle size of less than 6mm and the water content of less than 5% and a catalyst in a catalyst loading unit 1 to generate the catalyst-loaded sub-bituminous coal powder, wherein the catalyst is a mixture of Co salt and Ni salt.

S2: the sub-bituminous coal powder of the mixture loaded with the catalyst enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the sub-bituminous coal powder loaded with the catalyst and H existing in the hydrogen catalytic gasification part 202₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-rich residual coke and aromatic oil compounds, and CO present in hydrogen catalytic gasification unit 202₂And H₂Reaction to form CH₄Wherein the operation pressure of the hydrogenation catalytic gasification reaction is 8MPa, and the reaction temperature of the hydrogenation catalytic gasification reaction is 650 ℃.

S3: the residual coke rich in catalyst enters a residual coke gasification part 202, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part 202 through the gas inlet pipeline, and under the action of the catalyst, the residual coke rich in the catalyst and the catalyst are mixedWater vapor, O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂Wherein the operating pressure of the gasification reaction of the residual coke is 8MPa, and the reaction temperature of the gasification reaction of the residual coke is 800 ℃.

S4: generation of H₂、CO₂The coal powder is conveyed to a hydrogenation catalytic gasification part 201, and the catalyst-loaded secondary bituminous coal powder and the generated H₂Hydrogenation catalytic gasification reaction to generate CH₄Residual coke rich in catalyst and aromatic oil compound, and CO generated₂And H₂React to form CH₄；

S5: repeating the steps S3-S4 until the residual coke rich in the catalyst is converted into residue rich in the mixture of Co salt and Ni salt (the carbon content of the residue is less than 10 percent), and obtaining the entrained H₂、CO₂Dust and aromatic oil compound CH₄。

S6: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Carrying out gas-solid separation stage, indirect condensation stage, gas purification stage and hydrogen separation stage in sequence to obtain the final product CH₄(ii) a The dust obtained in the gas-solid separation stage is conveyed to the residual coke gasification part 202 to be further mixed with water vapor and O₂Reaction to form H₂And CO₂(ii) a H obtained in the hydrogen separation stage₂Is conveyed to a hydrogenation catalytic gasification part 201 to further generate hydrogenation catalytic gasification reaction with the sub-bituminous coal powder to generate CH₄(ii) a The residue rich in the catalyst and with the C content less than 10 percent is subjected to acid washing through a slag discharging system 3 and a catalyst recovery unit 4, and the recovered catalyst is conveyed to a catalyst loading unit 1 for recycling.

Through tests, the carbon conversion rate of the coal hydrogenation catalytic gasification method provided by the embodiment is more than 96%, and the CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content of (b) was 82% by volume.

EXAMPLE III

s1: the method comprises the steps of impregnating and partially dry-mixing a coal powder mixture with the particle size of less than 6mm and the water content of less than 5% and a catalyst in a catalyst loading unit 1 to generate the coal powder mixture loading the catalyst, wherein the coal powder mixture is a mixture of secondary bituminous coal powder and bituminous coal powder with the mass percentage of volatile components higher than 30%, the catalyst is a composite catalyst, a main catalyst of the composite catalyst is Fe salt, an auxiliary catalyst of the composite catalyst is Mg salt, the mass of the Fe salt accounts for 3% of the mass of the coal powder, and the mass of the Mg salt accounts for 0.2% of the mass of the coal powder.

S2: the coal powder mixture loaded with the catalyst enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the coal powder mixture loaded with the catalyst and H existing in the hydrogen catalytic gasification part 202₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-rich residual coke and aromatic oil compounds, and CO present in hydrogen catalytic gasification unit 202₂And H₂Reaction to form CH₄Wherein the operation pressure of the hydrogenation catalytic gasification reaction is 1MPa, and the reaction temperature of the hydrogenation catalytic gasification reaction is 800 ℃.

S3: the residual coke rich in catalyst enters a residual coke gasification part 202, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part 202 through the gas inlet pipeline, and under the action of the catalyst, the residual coke rich in the catalyst, the water vapor and the O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂Wherein the operating pressure of the gasification reaction of the residual coke is 1MPa, and the reaction temperature of the gasification reaction of the residual coke is 1000 ℃.

S4: generation of H₂、CO₂The coal powder mixture is conveyed to a hydrogenation catalytic gasification part 201, and the coal powder mixture carrying the catalyst and the generated H₂Hydrogenation catalytic gasification reaction to generate CH₄Residual coke rich in catalyst and aromatic oil compound, and CO generated₂And H₂React to form CH₄；

S6: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Carrying out gas-solid separation stage, indirect condensation stage, gas purification stage and hydrogen separation stage in sequence to obtain the final product CH₄(ii) a The dust obtained in the gas-solid separation stage is conveyed to the residual coke gasification part 202 to be further mixed with water vapor and O₂Reaction to form H₂And CO₂(ii) a H obtained in the hydrogen separation stage₂Is conveyed to a hydrogenation catalytic gasification part 201 to further generate hydrogenation catalytic gasification reaction with the sub-bituminous coal powder to generate CH₄(ii) a And (3) carrying out alkaline washing on the residue of the mixture rich in Co salt and Ni salt and containing less than 10% of C through a slag discharge system 3 and a catalyst recovery unit 4, and conveying the recovered catalyst to a catalyst loading unit 1 for recycling.

Through tests, the carbon conversion rate of the coal hydrogenation catalytic gasification method provided by the embodiment is more than 97%, and the CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content of (b) was 85% by volume.

Example four

s1: the method comprises the steps of carrying out partial impregnation mixing on a coal powder mixture with the particle size of less than 6mm and the water content of less than 5% and a catalyst in a catalyst loading unit 1 to generate the coal powder mixture loading the catalyst, wherein the coal powder mixture is a mixture of secondary bituminous coal powder and bituminous coal powder with the mass percentage of volatile components higher than 30%, the catalyst is a composite catalyst, a main catalyst of the composite catalyst is Co salt, a cocatalyst is a mixture of Ca salt and Mg oxide, the mass of the Co salt accounts for 8% of the mass of the coal powder, and the mass of the mixture of the Ca salt and the Mg oxide accounts for 2% of the mass of the coal powder.

S2: the coal powder mixture loaded with the catalyst enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the coal powder mixture loaded with the catalyst and H existing in the hydrogen catalytic gasification part 202₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-rich residual coke and aromatic oil compounds, and CO present in hydrogen catalytic gasification unit 202₂And H₂Reaction to form CH₄Wherein the operation pressure of the hydrogenation catalytic gasification reaction is 7MPa, and the reaction temperature of the hydrogenation catalytic gasification reaction is 700 ℃.

S3: the residual coke rich in catalyst enters a residual coke gasification part 202, and water vapor and O₂The mixed gas is introduced into the residual coke gasification part 202 through the gas inlet pipeline, and under the action of the catalyst, the residual coke rich in the catalyst, the water vapor and the O₂The mixed gas is subjected to gasification reaction of residual coke to generate H₂、CO₂Wherein the operating pressure of the gasification reaction of the residual coke is 7MPa, and the reaction temperature of the gasification reaction of the residual coke is 800 ℃.

S6: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Carrying out gas-solid separation stage, indirect condensation stage, gas purification stage and hydrogen separation stage in sequence to obtain the final product CH₄(ii) a Dust transfer from gas-solid separation stageTo the residual coke gasification part 202, and further with steam and O₂Reaction to form H₂And CO₂(ii) a H obtained in the hydrogen separation stage₂Is conveyed to a hydrogenation catalytic gasification part 201 to further generate hydrogenation catalytic gasification reaction with the sub-bituminous coal powder to generate CH₄(ii) a The residue of the mixture rich in Co salt and Ni salt with C content less than 10% is subjected to ammonia leaching through a slag discharging system 3 and a catalyst recovery unit 4, and the recovered catalyst is conveyed to a catalyst loading unit 1 for recycling.

Through tests, the carbon conversion rate of the coal hydrogenation catalytic gasification method provided by the embodiment is more than 97%, and the CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content of (b) was 88% by volume.

EXAMPLE five

s1: the method comprises the steps of carrying out partial impregnation mixing on a coal powder mixture with the particle size of less than 6mm and the water content of less than 5% and a catalyst in a catalyst loading unit 1 to generate the coal powder mixture loaded with the catalyst, wherein the coal powder mixture comprises brown coal powder and secondary bituminous coal powder, the catalyst is a composite catalyst, a main catalyst of the composite catalyst is Ni salt, a cocatalyst of the composite catalyst is a mixture of Ca salt and Ca oxide, the mass of the Ni salt accounts for 4% of that of the coal powder, and the mass of the mixture of the Ca salt and the Ca oxide accounts for 0.4% of that of the coal powder.

S6: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Carrying out gas-solid separation stage, indirect condensation stage, gas purification stage and hydrogen separation stage in sequence to obtain the final product CH₄(ii) a The dust obtained in the gas-solid separation stage is conveyed to the residual coke gasification part 202 to be further mixed with water vapor and O₂Reaction to form H₂And CO₂(ii) a H obtained in the hydrogen separation stage₂Is conveyed to a hydrogenation catalytic gasification part 201 to further generate hydrogenation catalytic gasification reaction with the sub-bituminous coal powder to generate CH₄(ii) a The residue of the mixture rich in Co salt and Ni salt with C content less than 10% is subjected to ammonia leaching through a slag discharging system 3 and a catalyst recovery unit 4, and the recovered catalyst is conveyed to a catalyst loading unit 1 for recycling.

Tests show that the carbon conversion rate of the coal hydrogenation catalytic gasification method provided by the embodiment is more than 97%, and the carbon conversion rate of the hydrogenation catalytic gasification part 201CH of gas outlet₄The content of (b) is 90% by volume.

EXAMPLE six

s1: the method comprises the steps of carrying out partial impregnation mixing on a coal powder mixture with the particle size of less than 6mm and the water content of less than 5% and a catalyst in a catalyst loading unit 1 to generate the coal powder mixture loaded with the catalyst, wherein the coal powder mixture comprises brown coal powder and secondary bituminous coal powder, the catalyst is a composite catalyst, a main catalyst of the composite catalyst is Ni salt, a cocatalyst of the composite catalyst is a mixture of Ca salt and Ca oxide, the mass of the Ni salt accounts for 6% of the mass of the coal powder, and the mass of the mixture of the Ca salt and the Ca oxide accounts for 0.8% of the mass of the coal powder.

S4: generation of H₂、CO₂The coal powder mixture is conveyed to a hydrogenation catalytic gasification part 201, and the coal powder mixture carrying the catalyst and the generated coal powder mixtureH₂Hydrogenation catalytic gasification reaction to generate CH₄Residual coke rich in catalyst and aromatic oil compound, and CO generated₂And H₂React to form CH₄；

Through tests, the carbon conversion rate of the coal hydrogenation catalytic gasification method provided by the embodiment is more than 97%, and the CH at the gas outlet of the hydrogenation catalytic gasification part 201₄The content of (b) was 94% by volume.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims

1. A coal hydrogenation catalytic gasification method is characterized by comprising the following steps:

s1: carrying out a coal powder catalyst loading process on coal powder and a catalyst to generate catalyst-loaded coal powder; wherein the catalyst is a single catalyst or a composite catalyst; the single catalyst is a transition metal salt; the composite catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is transition metal salt;

s2: the coal powder loaded with the catalyst enters a hydrogenation catalytic gasification part and is subjected to catalytic hydrogenation reaction under the action of the catalyst,so that the coal powder of the loaded catalyst and H existing in the hydrogenation catalytic gasification part₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-containing residual coke and aromatic oil compound, and CO present in the hydrogenation catalytic gasification section₂And H₂Reaction to form CH₄；

S4: generation of H₂、CO₂The coal powder and the generated H are conveyed to the hydrogenation catalytic gasification part to load the catalyst₂Hydrogenation catalytic gasification reaction to generate CH₄Catalyst-containing residual coke and aromatic oil compound, and CO produced₂And H₂React to form CH₄；

2. The coal hydrogenation catalytic gasification method according to claim 1, wherein the pulverized coal is one or more of pulverized lignite, pulverized bituminous coal, sub-pulverized bituminous coal or pulverized anthracite which are mixed in any proportion.

3. The coal hydrogenation catalytic gasification method according to claim 2, wherein in the S1, the particle size of the pulverized coal is less than 6mm, and the water content of the pulverized coal is less than 5%.

4. The coal hydrogenation catalytic gasification method according to claim 1, wherein when the catalyst is a single catalyst, the single catalyst is one or more of Fe salt, Co salt and Ni salt mixed in any proportion.

5. The coal hydrogenation catalytic gasification method according to claim 1, wherein when the catalyst is a composite catalyst, the main catalyst in the composite catalyst is one or more of Fe salt, Co salt and Ni salt, and the promoter in the composite catalyst is one or more of Ca salt, Ca oxide, Mg salt or Mg oxide mixed in any proportion.

6. The coal hydrogenation catalytic gasification method according to claim 5, wherein in the coal dust loaded with the catalyst, the mass of the main catalyst in the composite catalyst accounts for 3-8% of the mass of the coal dust; the mass of the cocatalyst accounts for 0.2-2% of the mass of the coal powder.

7. The coal hydrogenation catalytic gasification method according to claim 1, wherein the operating pressure of the hydrogenation catalytic gasification reaction is 0.5MPa-8MPa, and the reaction temperature of the hydrogenation catalytic gasification reaction is 650 ℃ to 900 ℃;

the operating pressure of the gasification reaction of the residual coke is 0.5MPa to 8MPa, and the reaction temperature of the gasification reaction of the residual coke is 800 ℃ to 1000 ℃.

8. The coal hydrogenation catalytic gasification method according to claim 1, further comprising a gas-solid separation stage, an indirect condensation stage, a gas purification stage and a hydrogen separation stage after S5, wherein,

the gas-solid separation stage comprises: will entrain H₂、CO₂Dust and aromatic oil compound CH₄Gas-solid separation is carried out to obtain dust and entrained H after dust removal₂、CO₂And CH of aromatic oil compound₄；

The indirect condensation stage comprises: will entrain H₂、CO₂And CH of aromatic oil compound₄Cooling, recovering heat to obtain aromatic oil compounds, and removing water vapor and aromatic oil compoundsEntrainment of matter H₂And CO₂CH (A) of₄；

The gas purification stage comprises: will entrain H₂And CO₂CH (A) of₄Deacidifying to remove CO in gas₂To obtain an entrainment H₂CH (A) of₄；

The hydrogen separation stage comprises: will entrain H₂CH (A) of₄Separating to obtain CH₄。

9. The coal hydrocatalytic gasification process of claim 8 wherein said gas-solid separation stage further comprises: conveying the dust to the residual coke gasification part and water vapor and O₂Reaction to form H₂And CO₂；

The hydrogen separation stage further comprises: h is to be₂Is conveyed to a hydrogenation catalytic gasification part to generate CH with coal powder through hydrogenation catalytic gasification reaction₄。

10. The coal hydrocatalytic gasification process of claim 1, comprising a catalyst recovery stage after said S5;

the catalyst recovery stage comprises: and recovering the catalyst from the catalyst-containing residue, and conveying the recovered catalyst to a catalyst loading unit for recycling.

11. A coal hydrogenation catalytic gasification apparatus used in the coal hydrogenation catalytic gasification method according to any one of claims 1 to 10, comprising: a catalyst loading unit and a hydrogenation catalytic gasification reaction unit; the hydrogenation catalytic gasification reaction unit comprises a hydrogenation catalytic gasification part and a residual coke gasification part which are connected with each other; wherein,

the coal dust inlet of the catalyst loading unit is connected with a coal dust conveying pipeline, and the coal dust outlet of the catalyst loading unit is connected with the coal dust inlet of the hydrogenation catalytic gasification part; the catalyst inlet of the catalyst loading unit is connected with a catalyst conveying pipeline;

the mixed gas inlet of the residual coke gasification part is used for conveying water vapor and O₂The gas inlet pipeline is connected, and a gas outlet of the hydrogenation catalytic gasification part is connected with a methane collection device.

12. The coal hydrocatalytic gasification device of claim 11, wherein said hydrocatalytic gasification section is at a higher position in the direction of gravity than said residual coke gasification section.

13. The coal hydrocatalytic gasification device of claim 11 wherein said hydrocatalytic gasification reaction unit is a gasifier divided into a hydrocatalytic gasification section and said char gasification section in the direction of gravity;

or the hydrogenation catalytic gasification part and the residual coke gasification part are both gasification furnaces.

14. The coal hydrogenation catalytic gasification device according to any one of claims 11 to 13, wherein a gas outlet of the hydrogenation catalytic gasification unit is used for separating H sequentially through a gas-solid separation unit, an indirect condensation unit, a gas purification unit₂And CH₄The hydrogen separation unit is connected with a methane collection device.

15. The coal hydrogenation catalytic gasification device according to claim 14, wherein the dust outlet of the gas-solid separation unit is connected with the dust inlet of the residual coke gasification part, and the gas outlet of the gas-solid separation unit is connected with the gas inlet of the indirect condensation unit; and a hydrogen outlet of the hydrogen separation unit is connected with a hydrogen inlet of the hydrogenation catalytic gasification part.

16. The coal hydrogenation catalytic gasification apparatus according to any one of claims 11 to 13, wherein a residue outlet of the residual coke gasification section is connected to the catalyst supporting unit sequentially through a slag discharge unit and a catalyst recovery unit.