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

Abstract

The invention provides a coal hydrogenation catalytic gasification method and device, relates to the technical field of coal gasification, and solves the problems of low _CH4 content and complicated process in the gas outlet of the gasifier in the existing coal catalytic gasification technology. The method includes the following steps: forming the coal powder and the catalyst to generate the catalyst-loaded coal powder; under the action of the catalyst, the catalyst-loaded coal powder and H ₂ are subjected to a hydrogenation catalytic gasification reaction to generate CH ₄ , the catalyst-containing residual coke, and CO ₂ reacts with H ₂ to generate CH ₄ ; under the action of the catalyst, the residual coke containing the catalyst and the mixed gas of steam and O ₂ are gasified to generate H ₂ and CO ₂ ; The hydrogenated H ₂ undergoes a hydrocatalytic gasification reaction to generate CH ₄ and residual coke containing the catalyst, and the generated CO ₂ reacts with H ₂ to generate CH ₄ ; repeat the hydrocatalytic gasification reaction and the residual coke gasification reaction until the residual coke contains The residual coke of the catalyst is converted to a catalyst-containing residue to give _CH4 . The coal hydrogenation catalytic gasification method is applied to the field of coal gasification.

Description

A kind of coal hydrogenation catalytic gasification method and device

technical field

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

Background technique

At present, my country's energy resources are characterized by "rich coal, less oil, and lack of gas". Converting coal into natural gas, the highest quality fuel in fossil energy, is the coal-to-gas technology, which is suitable for my country's national conditions, resolves the energy crisis, guarantees Shortcuts to energy security.

Coal catalytic gasification technology is one of the most effective processes in coal-to-gas technology. The existing coal catalytic gasification technology uses an alkali metal catalyst to make coal react with steam at a relatively low temperature to generate H ₂ and CO, and the generated H ₂ and CO further undergo a shift reaction under the action of the alkali metal catalyst. , the methanation reaction finally produces CH ₄ . The addition of alkali metal catalysts enables multiple reactions in the coal catalytic gasification technology to occur simultaneously in one device, improving the thermal efficiency of energy. However, the volume content of CH ₄ in the gasifier outlet of this coal catalytic gasification technology is low (only about 20%), and the unreacted H ₂ , CO and CH ₄ in the gas need to be separated subsequently, and then the The unreacted H ₂ and CO are transported to the gasifier or the methanation unit to further synthesize CH ₄ , and the above-mentioned separation, re-synthesis and other procedures will inevitably lead to complicated processes.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a coal hydrogenation catalytic gasification method and device to solve the problems of low _CH4 content and complex process in the gas outlet of the gasifier in the existing coal catalytic gasification technology.

In order to achieve the above object, the present invention provides the following technical solutions:

In a first aspect, the present invention provides a coal hydrocatalytic gasification method, which comprises the following steps:

S1: subject the pulverized coal and the catalyst to the process of loading the catalyst with the pulverized coal to generate the pulverized coal loaded with the catalyst;

S2: The catalyst-loaded pulverized coal enters the hydrocatalytic gasification section, and under the action of the catalyst, the catalyst-loaded pulverized coal and the H ₂ existing in the hydrocatalytic gasification section undergo a hydrocatalytic gasification reaction to generate CH ₄ , Residual coke containing catalyst and aromatic oil compounds, CO ₂ existing in the hydrogenation catalytic gasification part reacts with H ₂ to generate CH ₄ ;

S3: _The residual coke containing the catalyst enters the residual coke gasification part, and the mixed gas of steam and O ₂ is passed into the residual coke gasification part. The mixed gas is subjected to residual coke gasification reaction to generate H ₂ and CO ₂ ;

S4: The generated H ₂ and CO ₂ are sent to the hydrogen catalytic gasification unit, and the catalyst-loaded coal powder and the generated H ₂ undergo a hydro catalytic gasification reaction to generate CH ₄ , catalyst-containing residual coke and aromatic oil Compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Steps S3 to S4 are repeated until the catalyst-containing residual coke is converted into a catalyst-containing residue to obtain CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds.

Compared with the prior art, in the coal hydrogenation catalytic gasification method provided by the present invention, firstly, the coal powder and the catalyst are subjected to the process of loading the catalyst with the coal powder to generate the catalyst-loaded coal powder; then, the catalyst-loaded coal powder is transported To the hydrocatalytic gasification part, under the action of the catalyst, the catalyst-loaded pulverized coal and H ₂ can be directly converted into CH ₄ at a lower gasification temperature, and at the same time, catalyst-rich residual coke and aromatic oils are generated. The compound, the catalyst-rich residual coke generated in the hydrogenation catalytic gasification part enters the residual coke gasification part and reacts with steam and O ₂ to generate H ₂ and CO ₂ , and the H ₂ and CO ₂ generated in the residual coke gasification part can be used again. It is circulated into the hydrocatalytic gasification part, and further generates CH ₄ , catalyst-rich residual coke and aromatic oil compounds with pulverized coal. The hydrocatalytic gasification part and the residual coke gasification part form a circulating system, so The cycle is repeated, when the reaction in the coal hydrocatalytic gasification unit reaches or approaches the thermodynamic equilibrium limit, a large amount of CH ₄ can be produced, which improves the CH ₄ generation rate, carbon conversion rate and gas in the hydrocatalytic gasification section. The CH ₄ content of the outlet, the carbon conversion rate is over 95%, the CH ₄ content of the gas outlet of the hydrogenation catalytic gasification unit can reach 80%, and the generation of by-products such as CO and CO ₂ is reduced, effectively solving the current situation. There are problems that the content of _CH4 in the gas outlet of the gasifier in the catalytic gasification process is not high, the CH4 needs to be separated and then converted into _CH4 , and the conversion rate of carbon in the existing hydropyrolysis is low. At the same time, when the pulverized coal and H ₂ undergo hydrogenation catalytic gasification reaction to generate CH ₄ , the pulverized coal can also react with H ₂ to generate high economic value benzene-toluene-xylene mixture (BTX), phenol-cresol- High value-added aromatic oil compounds such as xylenol mixture (PCX) and naphthalene.

In a second aspect, the present invention provides a coal hydrocatalytic gasification device for use in the above coal hydrocatalytic gasification method, the coal hydrocatalytic gasification device comprising: a catalyst loading unit and a hydrocatalytic gasification reaction unit The hydrocatalytic gasification reaction unit comprises a hydrocatalytic gasification part and a residual coke gasification part which are connected to each other; wherein, the pulverized coal inlet of the catalyst loading unit is connected with the pulverized coal conveying pipeline, and the catalyst loading unit The pulverized coal outlet is connected with the pulverized coal inlet of the hydrocatalytic gasification part; the catalyst inlet of the catalyst loading unit is connected with the catalyst conveying pipeline; the mixed gas inlet of the residual coke gasification part is connected with the inlet for conveying water vapor and O ₂ are connected to the inlet pipes, and the gas outlet of the hydrogenation catalytic gasification part is connected to the methane collection device.

Compared with the prior art, in the coal hydrogenation catalytic gasification device provided by the present invention, the coal powder inlet of the catalyst loading unit is connected with the coal powder transportation pipeline, the catalyst inlet of the catalyst loading unit is connected with the catalyst transportation pipeline, and the coal powder and The catalyst is transported to the catalyst loading unit through the pulverized coal transportation pipeline and the catalyst transportation pipeline respectively. In the catalyst loading unit, the pulverized coal and the catalyst carry out the process of loading the catalyst with the pulverized coal to generate the pulverized coal loaded with the catalyst; the pulverized coal loaded with the catalyst is transported to the Hydrocatalytic gasification reaction unit, the hydrocatalytic gasification reaction unit is divided into a hydrocatalytic gasification part and a residual coke gasification part, which form a circulation system. Under the action of the catalyst, the catalyst-loaded coal powder and H ₂ It can be directly converted into CH ₄ at a lower gasification temperature, and at the same time, catalyst-rich residual coke and aromatic oil compounds are generated. The catalyst-rich residual coke generated in the hydrocatalytic gasification part enters the residual coke gasification. The H ₂ and _{CO 2 generated} in the residual coke gasification part can be recycled into the _{hydrocatalytic} gasification part to further generate _{CH 4} with pulverized coal, which is rich in catalysts. Residual coke and aromatic oil compounds, in this cycle, when the reaction in the coal hydrocatalytic gasification unit reaches or approaches the thermodynamic equilibrium limit, a large amount of CH ₄ can be produced, which improves the formation rate of CH ₄ and carbon conversion. The carbon conversion rate can reach more than 95%, the _CH4 content of the gas outlet of the _{hydrocatalytic} gasification part can reach 80%, and the reduction of CO, _CO , etc. The generation of by-products effectively solves the problems of low CH ₄ content in the gas outlet of the gasifier in the existing catalytic gasification process, the need for separation and re-CH ₄ conversion, and the low conversion rate of the existing hydropyrolysis carbon. At the same time, when the pulverized coal and H ₂ undergo hydrogenation catalytic gasification reaction to generate CH ₄ , the pulverized coal can also react with H ₂ to generate high economic value benzene-toluene-xylene mixture (BTX), phenol-cresol- High value-added aromatic oil compounds such as xylenol mixture (PCX) and naphthalene.

Description of drawings

The accompanying drawings described herein are used to provide further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the attached image:

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

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

Fig. 3 is a flow chart of the coal hydrocatalytic gasification method provided by the present invention.

Reference number:

1-catalyst loading unit; 2-hydrocatalytic gasification reaction unit;

201-hydrogenation catalytic gasification part; 202-residual coke gasification part;

3-slagging unit; 4-catalyst recovery unit;

5-Gas-solid separation unit; 6-Indirect condensation unit;

7-Gas purification unit; 8-Hydrogen separation unit.

Detailed ways

In order to make the objectives, features and advantages of the technical solutions proposed by the present invention more obvious and easy to understand, the description is made. Obviously, the described embodiments are only some embodiments of the proposed technical solution, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

Referring to Figures 1-2, the present invention provides a coal hydrogenation catalytic gasification device, comprising a catalyst loading unit 1 and a hydrogenation catalytic gasification reaction unit 2, wherein the hydrogenation catalytic gasification reaction unit 2 includes interconnected hydrogenation The catalytic gasification part 201 and the residual coke gasification part 202, wherein the pulverized coal inlet of the catalyst loading unit 1 is connected with the pulverized coal conveying pipeline, and the pulverized coal outlet of the catalyst loading unit 1 is connected with the pulverized coal inlet of the hydrogenation catalytic gasification part 201 The catalyst inlet of the catalyst loading unit 1 is connected with the catalyst conveying pipeline; the mixed gas inlet of the residual coke gasification part 202 is connected with the intake pipeline for conveying water vapor and O ₂ , and the gas outlet of the hydrogenation catalytic gasification part 201 Connected to a methane collector.

The catalyst loading unit 1 is used for the pulverized coal loading catalyst process, the hydrocatalytic gasification part 201 is used for the hydrocatalytic gasification reaction of pulverized coal and _H2 , and the residual coke gasification part 202 is used for the residual coke and steam and _O2 Carry out residual coke gasification reaction.

Below in conjunction with accompanying drawing, the working process of the coal hydrogenation catalytic gasification device provided by the present invention is as follows:

S1: The process of loading the catalyst with the pulverized coal and the catalyst is carried out in the catalyst loading unit 1 to generate the pulverized coal loaded with the catalyst.

S2: The catalyst-loaded pulverized coal enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal and the _H2 existing in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction to generate CH _4. The residual coke and aromatic oil compounds rich in catalyst, CO ₂ existing in the hydrogen catalytic gasification part 202 react with H ₂ to generate CH ₄ .

Specifically, since the feedstock in the hydrogenation catalytic gasification part 201 is the catalyst-loaded pulverized coal, under the action of the catalyst, the CC bonds of the carbon particles in the pulverized coal are broken to generate reactive C atoms. At the same time, the hydrogenation catalytic gasification part There is H ₂ in 201, and the presence of the catalyst stimulates the dissociation of H ₂ to generate reactive H atoms. Under the action of the catalyst, the generated reactive H atoms overflow to the surface of the reactive C atoms and undergo hydrogenation. The catalytic gasification reaction produces CH ₄ .

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the intake pipe, and under the action of the catalyst, the residual coke rich in catalyst is made Residual coke gasification reaction is carried out with the mixed gas of steam and O ₂ to generate H ₂ and CO ₂ .

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded coal powder and the generated H ₂ undergo hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatic oil Compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ .

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

Compared with the prior art, in the coal hydrogenation catalytic gasification device provided by the present invention, the coal powder inlet of the catalyst loading unit 1 is connected with the coal powder transportation pipeline, and the catalyst inlet of the catalyst loading unit 1 is connected with the catalyst transportation pipeline. The pulverized coal and the catalyst are transported to the catalyst loading unit 1 through the pulverized coal conveying pipeline and the catalyst conveying pipeline respectively. The pulverized coal is transported to the hydrogenation catalytic gasification reaction unit 2. The hydrogenation catalytic gasification reaction unit 2 is divided into a hydrogenation catalytic gasification part 201 and a residual coke gasification part 202. The two form a circulation system. Under the action of the catalyst , the catalyst-loaded pulverized coal and H ₂ can be directly converted into CH ₄ at a lower gasification temperature, and at the same time, catalyst-rich residual coke and aromatic oil compounds are generated. The residual coke of the catalyst enters the residual coke gasification part 202 and reacts with steam and O ₂ to generate H ₂ and CO ₂ , and the H ₂ and CO ₂ generated in the residual coke gasification part 202 can be recycled into the hydrocatalytic gasification part 201, It is further combined with pulverized coal to generate CH ₄ , catalyst-rich residual coke and aromatic oil compounds. This cycle is repeated. When the reaction in the coal hydrocatalytic gasification unit reaches or approaches the thermodynamic equilibrium limit state, a large amount of carbon dioxide can be produced. CH ₄ , the generation rate of CH ₄ , the carbon conversion rate and the CH ₄ content at the gas outlet of the hydrocatalytic gasification part 201 are improved, and the carbon conversion rate is over 95%. The content of ₄ can reach 80%, and the generation of by-products such as CO and CO ₂ is reduced, effectively solving the problem that the content of CH ₄ in the gas outlet of the gasifier in the existing catalytic gasification process is not high, the need to separate and re-CH ₄ and the existing problems. The problem of low carbon conversion in hydropyrolysis. At the same time, when the pulverized coal and H ₂ undergo hydrogenation catalytic gasification reaction to generate CH ₄ , the pulverized coal can also react with H ₂ to generate high economic value benzene-toluene-xylene mixture (BTX), phenol-cresol- High value-added aromatic oil compounds such as xylenol mixture (PCX) and naphthalene.

Here, it should be noted that, although the content of H ₂ and CO ₂ in the air is relatively low at the initial stage of the reaction, and the generated CH ₄ and residual coke rich in catalytic aggregates are relatively small, however, due to the coal provided by the present invention The hydrocatalytic gasification part 201 and the residual coke gasification part 202 of the hydrocatalytic gasification device are a circulation system. When the circulation system reaches a dynamic equilibrium, a large amount of H ₂ and CO ₂ can be generated, thereby generating a large amount of CH ₄ .

Preferably, the position of the hydrocatalytic gasification part 201 in the direction of gravity is higher than the position of the residual coke gasification part 202 in the direction of gravity; in this way, the _CH4 generated in the hydrocatalytic gasification part 201 located above is removed from the hydrocatalytic gas The top of the gasification part 201 is discharged, and the generated catalyst-rich residual coke falls into the residual coke gasification part 202 located below under the action of gravity and reacts with steam and O ₂ to generate H ₂ and CO ₂ , and the residual coke gasification part 202 The high-temperature H ₂ and CO ₂ generated in the upper part rise into the hydrocatalytic gasification part 201 located above to further participate in the reaction. It can be seen that the movement or flow of the above-mentioned catalyst-rich residual coke and various gases is based on the action of gravity or airflow, without additional power devices, and the automatic circulation of the hydrocatalytic gasification part 201 and the residual coke gasification part 202 is realized. .

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

When the hydrocatalytic gasification part 201 and the residual coke gasification part 202 are integrated devices, the hydrocatalytic gasification reaction unit 2 is a gasifier, and the gasifier is divided into a hydrocatalytic gasification part 201 and a gasification furnace along the gravity direction. The residual coke gasification part 202, the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 have no clear boundaries; The catalyst-rich residual coke generated after the hydrocatalytic gasification reaction of pulverized coal and H ₂ in the gasification part 201 directly falls into the residual coke gasification part 202 under the action of gravity and reacts with steam and O ₂ to generate H ₂ and CO ₂ , high temperature H ₂ and CO ₂ generated in the residual coke gasification part 202 rise directly into the hydrocatalytic gasification part 201 , and the circulation between the hydrocatalytic gasification part 201 and the residual coke gasification part 202 does not need to go through a pipeline Conveying makes the reaction more sufficient, and can simplify the internal structure of the device, which is beneficial to the later maintenance.

When the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 are separate devices, the hydrogenation catalytic gasification part 201 and the residual coke gasification part 202 are both gasifiers, that is, the hydrogenation catalytic gasification part 201 is a gasifier. Hydrocatalytic gasifier, residual coke gasification part 202 is a residual coke gasifier.

It should be noted that the hydrocatalytic gasification part 201 can be a fluidized bed, and the residual coke gasification part 202 can be a fluidized bed or a moving bed. The specific reason why the hydrocatalytic gasification part 201 uses a fluidized bed and the residual coke gasification part 202 uses a fluidized bed or a moving bed is: the reaction that occurs in the hydrocatalytic gasification part 201 is between pulverized coal and H ₂ In the hydrocatalytic gasification reaction, the operation form of the fluidized bed is selected to make the pulverized coal and _H2 fully contact, and the operating rate of the fluidized bed is more matched with the reaction rate of the hydrocatalytic gasification; and for the residual coke gasification part 202, the residual coke The reaction that takes place in the gasification part 202 is the residual coke gasification reaction between the catalyst-rich residual coke and water vapor and O ₂ , and the operation form of a fluidized bed or a moving bed is used to make the catalyst-rich residual coke and water vapor. There is sufficient contact with _O2 , and the operating rate of the fluidized bed or moving bed is more matched with the reaction rate of the residual coke gasification reaction. By adopting a fluidized bed in the hydrocatalytic gasification part 201 and a fluidized bed or a moving bed in the residual coke gasification part 202, the generation rate of _CH4 , the carbon conversion rate and the gas outlet of the hydrocatalytic gasification part 201 can be further improved. _CH4 content.

Generally, the coal hydrocatalytic gasification device of the present invention further comprises a post-processing unit, and the post-processing unit comprises a gas-solid separation unit 5, an indirect condensation unit 6, a gas purification unit 7 and a hydrogen separation unit 8 which are connected in sequence. The methane outlet of the gasification part 201 is connected to the methane collection device through the gas-solid separation unit 5, the indirect condensation unit 6, the gas purification unit 7, and the hydrogen separation unit 8 for separating _H2 and _CH4 in sequence.

In specific implementation, firstly, CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds enters the gas-solid separation unit 5 , and CH ₄ , H ₂ , CO ₂ , aromatic oil compounds and dust are separated into gas The solid is separated to obtain dust and CH ₄ containing H ₂ , CO ₂ and aromatic oil compounds after removing the dust.

Next, the CH ₄ entrained with H ₂ , CO ₂ and aromatic oil compounds enters the indirect condensation unit 6 to cool down, recovers heat to generate water vapor, and transports the water vapor to the residual coke gasification part 202 to mix with O ₂ and rich The residual coke containing the catalyst undergoes a residual coke gasification reaction to generate H ₂ and CO ₂ , of course, the water vapor can also be directly transported to the steam turbine to generate electricity; at the same time, benzene-toluene-xylene mixture can be obtained according to different distillation ranges ( BTX), phenol-cresol-xylenol mixture (PCX), naphthalene and other high value-added aromatic oil compounds, and can obtain CH ₄ entrained with H ₂ and CO ₂ that removes water vapor and aromatic oil compounds.

Next, the CH ₄ entrained with H ₂ and CO ₂ is subjected to deacidification treatment through the gas purification unit 7 to remove CO ₂ in the gas to obtain CH ₄ entrained with H ₂ .

Finally, the CH ₄ entrained with H ₂ passes through the hydrogen separation unit 8 to separate H ₂ and CH ₄ to obtain CH ₄ .

In the above post-processing unit, the gas-solid separation unit 5 can be a multi-stage cyclone separator, and the multi-stage cyclone separator is used as the gas-solid separation unit 5, which can more effectively separate CH ₄ , H ₂ , CO ₂ , and aromatic oils. The compound and dust are separated to obtain CH ₄ , H ₂ , CO ₂ and aromatic oil compounds with less solid dust content; the indirect condensing unit 6 can be a multi-stage indirect heat exchanger, which can generate different heat by recovering different heat. The hydrogen separation unit 8 can preferably be a pressure swing adsorption hydrogen separation device. The pressure swing adsorption hydrogen separation device has the characteristics of low energy consumption, complete separation, simple process flow, high degree of automation, and good environmental benefits. The adsorption hydrogen separation device separates H ₂ and CH ₄ , which can obtain purer CH ₄ , and is more conducive to realizing the automation and environmental protection of the coal hydrogenation catalytic gasification device provided by the present invention.

Preferably, the dust outlet of the gas-solid separation unit 5 is connected to the dust inlet of the residual coke gasification part 202, and the gas outlet of the gas-solid separation unit 5 is connected to the gas inlet of the indirect condensation unit 6, so that the gas-solid separation unit 5 separates out The dust is transported to the residual coke gasification part 202 to react with steam and O ₂ to generate H ₂ and CO ₂ , which further improves the generation rate of CH ₄ , the carbon conversion rate and the CH ₄ content of the gas outlet of the hydrocatalytic gasification part 201 .

The hydrogen outlet of the hydrogen separation unit 8 is connected to the hydrogen inlet of the hydrogenation catalytic gasification part 201 , and the separated H ₂ is transported to the hydrogenation catalytic gasification part 201 to undergo a hydrogenation catalytic gasification reaction with pulverized coal to generate CH ₄ .

The coal hydrocatalytic gasification device of the present invention also includes a slag discharge unit 3 and a catalyst recovery unit 4. The residue outlet of the residual coke gasification part 202 is connected to the catalyst load unit 1 through the slag discharge unit 3 and the catalyst recovery unit 4 in sequence.

In specific implementation, when the reaction in the coal hydrocatalytic gasification device reaches the limit state, the catalyst-rich residue with C content <10% obtained after the deep cracking of pulverized coal will be transported from the residual coke gasification unit 202 to the slag discharge The system 3 and the catalyst recovery unit 4 perform catalyst recovery, and the recovered catalyst is transported to the catalyst loading unit 1 for recycling, thereby improving the utilization rate of the catalyst.

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

S1: The process of loading the catalyst with the pulverized coal with the particle size of 6 mm or less and the water content <5% and the catalyst is carried out in the catalyst loading unit 1 to generate the pulverized coal with the catalyst loaded.

S2: The catalyst-loaded pulverized coal enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal and the _H2 existing in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction to generate CH ₄ (as shown in formula I), catalyst-rich residual coke and aromatic oil compounds, CO ₂ present in the hydrogen catalytic gasification part 202 reacts with H ₂ to generate CH ₄ (as shown in formula II);

C+2H ₂ →CH ₄ ——(I)

4H ₂ +CO ₂ →CH ₄ +2H ₂ O——(II)

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the intake pipe, and under the action of the catalyst, the residual coke rich in catalyst is made Residual coke gasification reaction is carried out with the mixed gas of steam and O ₂ to generate H ₂ and CO ₂ (as shown in formulas III to VI).

2C+2H ₂ O→2H ₂ +2CO——(III)

CO+H ₂ O→CO ₂ +H ₂ ——(IV)

2C+O ₂ →2CO——(V)

C+O ₂ →CO ₂ ——(VI)

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded coal powder and the generated H ₂ undergo hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatic oil Compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ .

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

Compared with the prior art, in the coal hydrogenation catalytic gasification method provided by the present invention, firstly, the coal powder and the catalyst are subjected to the process of loading the catalyst with the coal powder to generate the catalyst-loaded coal powder; then, the catalyst-loaded coal powder is transported To the hydrocatalytic gasification part 201, under the action of the catalyst, the catalyst-loaded coal powder and H ₂ can be directly converted into CH ₄ at a lower gasification temperature, and at the same time, catalyst-rich residual coke and aromatic oil are generated. The catalyst-rich residual coke generated in the hydrogenation catalytic gasification part 201 enters the residual coke gasification part 202 to react with steam and O ₂ to generate H ₂ and CO ₂ , and the H ₂ and CO 2 generated in the residual coke gasification part 202 CO ₂ can be recycled into the hydrocatalytic gasification part 201, and further generates CH ₄ , catalyst-rich residual coke and aromatic oil compounds with pulverized coal, and so on. When the thermodynamic equilibrium limit is reached or approached, a large amount of CH ₄ can be produced, which improves the CH ₄ generation rate, the carbon conversion rate and the CH ₄ content at the gas outlet of the hydrocatalytic gasification unit 201, and the carbon conversion rate reaches more than 95%. , the _CH4 content of the gas outlet of the hydrogenation catalytic gasification part 201 can reach 80%, and the generation of by-products such as CO and _CO2 is reduced, effectively solving the problem of _CH4 at the gas outlet of the gasifier in the existing catalytic gasification process. The content is not high, it needs to be separated and then _CH4 is converted, and the existing hydropyrolysis carbon conversion rate is low. At the same time, when the pulverized coal and H ₂ undergo hydrogenation catalytic gasification reaction to generate CH ₄ , the pulverized coal can also react with H ₂ to generate high economic value benzene-toluene-xylene mixture (BTX), phenol-cresol- High value-added aromatic oil compounds such as xylenol mixture (PCX) and naphthalene.

It should be noted that, in the coal hydrogenation catalytic gasification method of the present invention, the coal powder can be selected from one or more of lignite powder, bituminous coal powder, sub-bituminous coal powder or anthracite powder mixed in any proportion, preferably lignite One or more kinds of powder, sub-bituminous coal powder or bituminous coal powder whose mass percentage is higher than 30% are mixed in any proportion. This is because lignite powder, sub-bituminous coal powder or bituminous coal powder with a mass percentage of volatile matter higher than 30% has the characteristics of low ash, low sulfur, high volatile matter, strong activity, etc., and can obtain more oil and CH ₄ .

In addition, the manner of the pulverized coal-supported catalyst can be selected from one of dry mixing, impregnation, and partial dry mixing and partial impregnation mixing.

For the choice of catalyst, the catalyst can 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 present 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 in any proportion. , the promoter is preferably one or more of Ca salt, Ca oxide, Mg salt or Mg oxide mixed in any proportion.

For the composite catalyst, the main catalyst catalyzes the reaction of C and H ₂ , CO ₂ and H ₂ to generate CH ₄ respectively, and the co-catalyst is mainly to increase the dispersibility and catalytic activity of the main catalyst, and improve the adsorption capacity of the main catalyst on the active site. , forming more active centers, inhibiting deactivation, reducing the probability of deactivation, and improving catalytic performance; at the same time, when the residual coke rich in catalyst after the hydrogenation catalytic gasification reaction is further subjected to residual coke gasification, the cocatalyst, that is, the alkaline earth metal catalyst, It is favorable for the residual coke gasification reaction to proceed in the direction of generating H ₂ and CO ₂ .

Further, in the catalyst-loaded pulverized coal, the mass of the main catalyst in the composite catalyst accounts for 3% to 8% of the mass of the pulverized coal, and the mass of the co-catalyst accounts for 0.2% to 2% of the mass of the pulverized coal; In the powder, the mass of the main catalyst in the composite catalyst accounts for 4% to 6% of the mass of the pulverized coal, and the mass of the cocatalyst accounts for 0.4% to 0.8% of the mass of the cocatalyst of the mass of the pulverized coal. Among them, due to the limited number of active sites on the particles of pulverized coal, the addition amount of the main catalyst is too high, and the excess main catalyst after the active sites are saturated cannot play a catalytic role, and excessive addition will increase the economic cost; If the addition amount is too low, the active sites on the particles of pulverized coal cannot be completely catalyzed, and the expected catalytic effect cannot be achieved, resulting in the reduction of the CH ₄ content and the carbon conversion rate at the outlet of the hydrocatalytic gasifier; the addition amount of the co-catalyst is too high It will compete with the main catalyst for the active sites on the pulverized coal particles, causing the active sites to be covered by the co-catalyst, thereby reducing the contact probability between the main catalyst and the active site, reducing the activity, and the addition of the co-catalyst is too low. The dispersibility and catalytic activity of the catalyst cannot effectively suppress the deactivation of the main catalyst. Therefore, when the catalyst is preferably a composite catalyst, the addition amount of the main catalyst and co-catalyst is limited by the catalytic performance and technical economy. In the pulverized coal, the mass of the main catalyst in the composite catalyst is limited to 3% to 8% of the mass of the pulverized coal, and the mass of the auxiliary catalyst is limited to 0.2% to 2% of the mass of the pulverized coal; In the composite catalyst, the mass of the main catalyst accounts for 4% to 6% of the mass of the pulverized coal, and the mass of the cocatalyst accounts for 0.4% to 0.8% of the mass of the cocatalyst of the mass of the pulverized coal.

Preferably, the operating pressure of the hydrocatalytic gasification reaction is 0.5MPa-8MPa, preferably 1MPa-7MPa, and the reaction temperature of the hydrocatalytic gasification reaction is 650°C-900°C, preferably 700°C-800°C. For the selection of the operating pressure of the hydrocatalytic gasification reaction, according to the thermodynamic equilibrium, the operating pressure of the hydrocatalytic gasification reaction in the range of 0.5MPa-8MPa is more favorable for the hydrocatalytic gasification reaction to proceed in the direction of generating _CH4 , It can improve the reaction rate of hydrogenation catalytic gasification and increase the processing capacity per unit time. The operating pressure of hydrogenation catalytic gasification reaction is higher than 8MPa, and the reaction rate of hydrogenation catalytic gasification is too fast, which will cause the reaction to be uncontrollable and increase the risk of operation. , and the high pressure requires high equipment, increasing equipment investment, and the operating pressure of the hydrogenation catalytic gasification reaction is lower than 0.5MPa, it is not conducive to the hydrogenation catalytic gasification reaction to the direction of generating _CH4 , the reaction rate is too slow, unit The amount of time processing is reduced; for the selection of the reaction temperature of the hydrogenation catalytic gasification reaction, the catalyst in the range of 650℃-900℃ is more able to stimulate the CC bond in the coal to break and promote the dissociation of _H2 , and the H atom overflows to have reactive activity A reaction occurs on the surface of the C of the hydrocatalytic gasification to generate CH ₄ . The reaction temperature of the hydrogenation catalytic gasification reaction is higher than 900 °C, which will lead to the deactivation of catalyst sintering, while the reaction temperature is lower than 650 °C, which will lead to poor catalytic effect and slow reaction rate.

Preferably, the operating pressure of the residual coke gasification reaction is 0.5MPa-8MPa, preferably 1MPa-7MPa, and the reaction temperature of the residual coke gasification reaction is 800°C-1000°C. For the selection of the operating pressure of the residual coke gasification reaction, according to the thermodynamic equilibrium, the operating pressure of the residual coke gasification reaction in the range of 0.5MPa-8MPa is more conducive to the residual coke gasification reaction in the direction of generating H ₂ and CO ₂ . It can improve the reaction rate of residual coke gasification. The operating pressure of residual coke gasification reaction is higher than 8MPa. If the residual coke gasification reaction rate is too fast, the reaction will be uncontrollable and the operation risk will be increased. In addition, high pressure requires high equipment and increases equipment investment. , and the operating pressure of the residual coke gasification reaction is lower than 0.5MPa, which is not conducive to the residual coke gasification reaction in the direction of generating _CH4 , the reaction rate is too slow, and the processing capacity per unit time is reduced. The operating pressure is equal to the operating pressure of the hydrocatalytic gasification reaction, and the system pressure of the entire hydrocatalytic gasification reaction unit 2 is kept in balance, which is more conducive to operation; for the selection of the reaction temperature of the residual coke gasification reaction, the catalyst is at 800 ℃ -1000°C will promote the residual coke gasification reaction in the direction of generating H ₂ and CO ₂ , and generate more H ₂ and CO ₂ for generating CH ₄ .

After step S5, the coal hydrocatalytic gasification method provided by the present invention further includes a post-processing stage, and the post-processing stage includes a gas-solid separation stage, an indirect condensation stage, a gas purification stage and a hydrogen separation stage.

Specifically, the gas-solid separation stage includes: entering CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds into the gas-solid separation unit 5 , and separating CH ₄ , H ₂ , CO ₂ , aromatic oil compounds with The dust is subjected to gas-solid separation to obtain dust and CH ₄ containing H ₂ , CO ₂ and aromatic oil compounds after the dust has been removed.

The indirect condensation stage includes: the CH ₄ entrained with H ₂ , CO ₂ and aromatic oil compounds enters the indirect condensation unit 6 for cooling, recovers heat, and obtains benzene-toluene-xylene mixture (BTX), phenol-cresol according to the distillation range -Xylenol mixture (PCX), naphthalene and other high value-added aromatic oil compounds, and obtain CH ₄ with H ₂ and CO ₂ entrained by removing water vapor and aromatic oil compounds.

The gas purification stage includes: deacidification of CH ₄ entrained with H ₂ and CO ₂ through the gas purification unit 7 to remove CO ₂ in the gas to obtain CH ₄ entrained with H ₂ .

The hydrogen separation stage includes: the CH ₄ entrained with H ₂ passes through the hydrogen separation unit 8 to separate H ₂ and CH ₄ to obtain the final product CH ₄ .

Further, the dust obtained in the gas-solid separation stage is transported to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ , which further improves the generation rate of CH ₄ , the carbon conversion rate and the hydrogenation catalytic gasification. _CH4 content at the gas outlet of section 201.

Further, the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further hydrogenation catalytic gasification reaction with the pulverized coal to generate CH ₄ .

After step S5, the coal hydrocatalytic gasification method provided by the present invention further includes: a catalyst recovery stage.

Specifically, in the catalyst recovery stage, the catalyst-rich residue with a C content of less than 10% passes through the slag discharge system 3 and the catalyst recovery unit 4 for catalyst recovery, and the recovered catalyst is transported to the catalyst loading unit 1 for recycling, improving the utilization rate of the catalyst. .

It should be noted that the method of the catalyst recovery stage is one or more of water washing, acid washing, alkali washing, and ammonia dipping, which can be selected according to the actual situation.

Several optional embodiments of the coal hydrocatalytic gasification method provided by the present invention are given below in conjunction with the accompanying drawings, which are only for illustration and are not intended to limit the protection scope of the present invention.

Example 1

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

S1: dry-mix anthracite pulverized coal with a particle size of 6 mm or less and a water content of less than 5% and a catalyst in the catalyst loading unit 1 to generate Fe salt-loaded anthracite pulverized coal, and the catalyst is Fe salt.

S2: The catalyst-loaded anthracite pulverized coal enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded anthracite pulverized coal and _H2 existing in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction to generate CH _4. The residual coke and aromatic oil compounds rich in catalyst, CO ₂ and H ₂ present in the hydrogen catalytic gasification part 202 react with H 2 to generate CH ₄ , wherein the operating pressure of the hydrogen catalytic gasification reaction is 0.5 MPa, The reaction temperature of the hydrocatalytic gasification reaction was 900°C.

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the intake pipe, and under the action of the catalyst, the residual coke rich in catalyst is made The residual coke gasification reaction is carried out with the mixed gas of steam and O ₂ to generate H ₂ and CO ₂ . The operating pressure of the residual coke gasification reaction is 0.5MPa, and the reaction temperature of the residual coke gasification reaction is 1000°C.

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded anthracite pulverized coal and the generated H ₂ undergo hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatic oil Compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

S6: carry out the gas-solid separation stage, the indirect condensation stage, the gas purification stage and the hydrogen separation stage with the CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds in sequence to obtain the final product CH ₄ ; the gas-solid separation stage The obtained dust is sent to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ ; the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further hydrogenation and catalysis with anthracite pulverized coal. The gasification reaction generates CH ₄ ; the catalyst-rich residue with a C content of less than 10% is washed with water through the slag discharge system 3 and the catalyst recovery unit 4 , and the recovered catalyst is sent to the catalyst loading unit 1 for recycling.

According to the test, the carbon conversion rate of the coal hydrocatalytic gasification method provided in this embodiment is over 95%, and the volume content of _CH4 at the gas outlet of the hydrocatalytic gasification part 201 is 80%.

Embodiment 2

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

S1: The sub-bituminous coal powder with a particle size of 6 mm or less and a water content of less than 5% and a catalyst are impregnated and partially dry-mixed in the catalyst loading unit 1 to generate a sub-bituminous coal powder with a supported catalyst. The catalyst is a mixture of Co salt and Ni salt. mixture.

S2: The sub-bituminous coal powder of the catalyst-loaded mixture enters the hydrogenation catalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded sub-bituminous coal powder and the H existing in the _hydrogen catalytic gasification part 202 are hydrogenated The catalytic gasification reaction generates CH ₄ , catalyst-rich residual coke and aromatic oil compounds, and the CO ₂ present in the hydrogen catalytic gasification part 202 reacts with H ₂ to generate CH ₄ . The operating pressure was 8MPa, and the reaction temperature of the hydrocatalytic gasification reaction was 650°C.

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the intake pipe, and under the action of the catalyst, the residual coke rich in catalyst is made The residual coke gasification reaction is carried out with the mixed gas of steam and O ₂ to generate H ₂ and CO ₂ . The operating pressure of the residual coke gasification reaction is 8MPa, and the reaction temperature of the residual coke gasification reaction is 800°C.

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded sub-bituminous coal powder and the generated H ₂ undergo a hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatics Group of oil compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Repeat steps S3 to S4 until the catalyst-rich residual coke is converted into a residue rich in a mixture of Co salts and Ni salts (the carbon content of the residue is less than 10%) to obtain entrained H ₂ , CO ₂ , dust and aroma CH ₄ of family oils.

S6: carry out the gas-solid separation stage, the indirect condensation stage, the gas purification stage and the hydrogen separation stage with the CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds in sequence to obtain the final product CH ₄ ; the gas-solid separation stage The obtained dust is sent to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ ; the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further reaction with sub-bituminous coal powder. The hydrogen catalytic gasification reaction generates CH ₄ ; the catalyst-rich residue with C content less than 10% is pickled by the slag discharge system 3 and the catalyst recovery unit 4 , and the recovered catalyst is sent to the catalyst loading unit 1 for recycling.

According to the test, the carbon conversion rate of the coal hydrocatalytic gasification method provided in this embodiment is over 96%, and the volume content of CH ₄ at the gas outlet of the hydrocatalytic gasification part 201 is 82%.

Embodiment 3

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

S1: Impregnate and partially dry-mix the pulverized coal mixture with a particle size of 6 mm or less and a moisture content of less than 5% in the catalyst loading unit 1 to generate a pulverized coal mixture loaded with catalyst. The pulverized coal mixture is sub-bituminous pulverized coal and volatile coal The mixture of bituminous coal powder whose mass percentage is higher than 30%, the catalyst is a composite catalyst, the main catalyst of the composite catalyst is Fe salt, the co-catalyst is Mg salt, the mass of Fe salt accounts for 3% of the mass of coal powder, and the Mg salt The mass of pulverized coal accounts for 0.2% of the mass of pulverized coal.

S2: The catalyst-loaded pulverized coal mixture enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal mixture and the _H2 present in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction CH ₄ , catalyst-rich residual coke and aromatic oil compounds are generated, and CO ₂ and H ₂ present in the hydrogen catalytic gasification part 202 react to generate CH ₄ , wherein the operating pressure of the hydrogen catalytic gasification reaction is 1 MPa , the reaction temperature of the hydrogenation catalytic gasification reaction is 800 ℃.

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the air inlet pipe. Under the action of the catalyst, the residual coke rich in catalyst is made to be The mixed gas of steam and O ₂ undergoes residual coke gasification reaction to generate H ₂ and CO ₂ . The operating pressure of residual coke gasification reaction is 1 MPa, and the reaction temperature of residual coke gasification reaction is 1000°C.

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded pulverized coal mixture and the generated H ₂ undergo a hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatics Oil compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

S6: carry out the gas-solid separation stage, the indirect condensation stage, the gas purification stage and the hydrogen separation stage with the CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds in sequence to obtain the final product CH ₄ ; the gas-solid separation stage The obtained dust is sent to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ ; the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further reaction with sub-bituminous coal powder. The hydrogen catalytic gasification reaction generates CH ₄ ; the residue of the mixture rich in Co salt and Ni salt with a C content of less than 10% is alkali-washed by the slag discharge system 3 and the catalyst recovery unit 4, and the recovered catalyst is sent to the catalyst loading unit 1 for circulation use.

According to the test, the carbon conversion rate of the coal hydrocatalytic gasification method provided in this embodiment is over 97%, and the volume content of _CH4 at the gas outlet of the hydrocatalytic gasification part 201 is 85%.

Embodiment 4

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

S1: Partially impregnating a pulverized coal mixture with a particle size of 6 mm or less and a water content of less than 5% and a catalyst in the catalyst loading unit 1 to generate a pulverized coal mixture that supports the catalyst. The pulverized coal mixture is sub-bituminous pulverized coal and volatile matter The mass percentage of bituminous coal powder is higher than 30%, the catalyst is a composite catalyst, the main catalyst of the composite catalyst is Co salt, and the co-catalyst is a mixture of Ca salt and Mg oxide, and the mass of Co salt accounts for the mass of coal powder. 8%, the mass of the mixture of Ca salts and Mg oxides accounts for 2% of the mass of the pulverized coal.

S2: The catalyst-loaded pulverized coal mixture enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal mixture and the _H2 present in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction CH ₄ , catalyst-rich residual coke and aromatic oil compounds are generated, and CO ₂ and H ₂ present in the hydrogen catalytic gasification part 202 react to generate CH ₄ , wherein the operating pressure of the hydrogen catalytic gasification reaction is 7MPa , the reaction temperature of the hydrogenation catalytic gasification reaction is 700 ℃.

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the air inlet pipe. Under the action of the catalyst, the residual coke rich in catalyst is made to be The mixed gas of steam and O ₂ is subjected to residual coke gasification reaction to generate H ₂ and CO ₂ . The operating pressure of residual coke gasification reaction is 7MPa, and the reaction temperature of residual coke gasification reaction is 800°C.

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded pulverized coal mixture and the generated H ₂ undergo a hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatics Oil compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

S6: carry out the gas-solid separation stage, the indirect condensation stage, the gas purification stage and the hydrogen separation stage with the CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds in sequence to obtain the final product CH ₄ ; the gas-solid separation stage The obtained dust is sent to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ ; the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further reaction with sub-bituminous coal powder. The hydrogen catalytic gasification reaction generates CH ₄ ; the residue of the mixture rich in Co salt and Ni salt with a C content of less than 10% is subjected to ammonia leaching through the slag discharge system 3 and the catalyst recovery unit 4, and the recovered catalyst is sent to the catalyst loading unit 1 for circulation use.

According to the test, the carbon conversion rate of the coal hydrocatalytic gasification method provided in this embodiment is over 97%, and the volume content of CH ₄ at the gas outlet of the hydrocatalytic gasification part 201 is 88%.

Embodiment 5

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

S1: Partially impregnating a pulverized coal mixture with a particle size of 6 mm or less and a water content of less than 5% and a catalyst in the catalyst loading unit 1 to generate a pulverized coal mixture loaded with catalyst, the pulverized coal mixture is lignite pulverized coal and sub-bituminous coal pulverized coal. , the catalyst is a composite catalyst, the main catalyst of the composite catalyst is Ni salt, the co-catalyst is a mixture of Ca salt and Ca oxide, the mass of Ni salt accounts for 4% of the mass of pulverized coal, and the mixture of Ca salt and Ca oxide The mass of pulverized coal accounts for 0.4% of the mass of pulverized coal.

S2: The catalyst-loaded pulverized coal mixture enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal mixture and the _H2 present in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction CH ₄ , catalyst-rich residual coke and aromatic oil compounds are generated, and CO ₂ and H ₂ present in the hydrogen catalytic gasification part 202 react to generate CH ₄ , wherein the operating pressure of the hydrogen catalytic gasification reaction is 7MPa , the reaction temperature of the hydrogenation catalytic gasification reaction is 700 ℃.

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the air inlet pipe. Under the action of the catalyst, the residual coke rich in catalyst is made to be The mixed gas of steam and O ₂ is subjected to residual coke gasification reaction to generate H ₂ and CO ₂ . The operating pressure of residual coke gasification reaction is 7MPa, and the reaction temperature of residual coke gasification reaction is 800°C.

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded pulverized coal mixture and the generated H ₂ undergo a hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatics Oil compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

S6: carry out the gas-solid separation stage, the indirect condensation stage, the gas purification stage and the hydrogen separation stage with the CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds in sequence to obtain the final product CH ₄ ; the gas-solid separation stage The obtained dust is sent to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ ; the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further reaction with sub-bituminous coal powder. The hydrogen catalytic gasification reaction generates CH ₄ ; the residue of the mixture rich in Co salt and Ni salt with a C content of less than 10% is subjected to ammonia leaching through the slag discharge system 3 and the catalyst recovery unit 4, and the recovered catalyst is sent to the catalyst loading unit 1 for circulation use.

Through testing, it can be seen that the carbon conversion rate of the coal hydrocatalytic gasification method provided in this embodiment is more than 97%, and the volume content of CH ₄ at the gas outlet of the hydrocatalytic gasification part 201 is 90%.

Embodiment 6

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

S1: Partially impregnating a pulverized coal mixture with a particle size of 6 mm or less and a water content of less than 5% and a catalyst in the catalyst loading unit 1 to generate a pulverized coal mixture loaded with catalyst, the pulverized coal mixture is lignite pulverized coal and sub-bituminous coal pulverized coal. , the catalyst is a composite catalyst, the main catalyst of the composite catalyst is Ni salt, the co-catalyst is a mixture of Ca salt and Ca oxide, the mass of Ni salt accounts for 6% of the mass of pulverized coal, and the mixture of Ca salt and Ca oxide The mass of pulverized coal accounts for 0.8% of the mass of pulverized coal.

S2: The catalyst-loaded pulverized coal mixture enters the hydrocatalytic gasification part 201, and under the action of the catalyst, the catalyst-loaded pulverized coal mixture and the _H2 present in the hydrogen catalytic gasification part 202 undergo a hydrocatalytic gasification reaction CH ₄ , catalyst-rich residual coke and aromatic oil compounds are generated, and CO ₂ and H ₂ present in the hydrogen catalytic gasification part 202 react to generate CH ₄ , wherein the operating pressure of the hydrogen catalytic gasification reaction is 7MPa , the reaction temperature of the hydrogenation catalytic gasification reaction is 700 ℃.

S3: The residual coke rich in catalyst enters the residual coke gasification part 202, and the mixed gas of water vapor and O ₂ is passed into the residual coke gasification part 202 through the air inlet pipe. Under the action of the catalyst, the residual coke rich in catalyst is made to be The mixed gas of steam and O ₂ is subjected to residual coke gasification reaction to generate H ₂ and CO ₂ . The operating pressure of residual coke gasification reaction is 7MPa, and the reaction temperature of residual coke gasification reaction is 800°C.

S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part 201 , and the catalyst-loaded pulverized coal mixture and the generated H ₂ undergo a hydrocatalytic gasification reaction to generate CH ₄ , catalyst-rich residual coke and aromatics Oil compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ;

S5: Steps S3 to S4 are repeated until the catalyst-rich residual coke is converted into a catalyst-rich residue (the carbon content of the residue is less than 10%) to obtain CH with entrained H ₂ , CO ₂ , dust and aromatic oil compounds ₄ .

S6: carry out the gas-solid separation stage, the indirect condensation stage, the gas purification stage and the hydrogen separation stage with the CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds in sequence to obtain the final product CH ₄ ; the gas-solid separation stage The obtained dust is sent to the residual coke gasification part 202 and further reacts with water vapor and O ₂ to generate H ₂ and CO ₂ ; the H ₂ obtained in the hydrogen separation stage is sent to the hydrogenation catalytic gasification part 201 for further reaction with sub-bituminous coal powder. The hydrogen catalytic gasification reaction generates CH ₄ ; the residue of the mixture rich in Co salt and Ni salt with a C content of less than 10% is subjected to ammonia leaching through the slag discharge system 3 and the catalyst recovery unit 4, and the recovered catalyst is sent to the catalyst loading unit 1 for circulation use.

According to the test, the carbon conversion rate of the coal hydrocatalytic gasification method provided in this embodiment is over 97%, and the volume content of CH ₄ at the gas outlet of the hydrocatalytic gasification part 201 is 94%.

The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention. should be included within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims (16)

1. a coal hydrogenation catalytic gasification method, is characterized in that, this method comprises the steps: S1: The process of carrying the pulverized coal and the catalyst into the pulverized coal catalyst to generate the pulverized coal carrying the catalyst; wherein, the catalyst is a single catalyst or a composite catalyst; the single catalyst is a transition metal salt; the composite catalyst includes a main catalyst and a promoter a catalyst, the main catalyst is a transition metal salt; S2: The catalyst-loaded pulverized coal enters the hydrocatalytic gasification section, and under the action of the catalyst, the catalyst-loaded pulverized coal and the H ₂ existing in the hydrocatalytic gasification section undergo a hydrocatalytic gasification reaction to generate CH ₄ , Residual coke containing catalyst and aromatic oil compounds, CO ₂ existing in the hydrogenation catalytic gasification part reacts with H ₂ to generate CH ₄ ; S3: _The residual coke containing the catalyst enters the residual coke gasification part, and the mixed gas of steam and O ₂ is passed into the residual coke gasification part. The mixed gas is subjected to residual coke gasification reaction to generate H ₂ and CO ₂ ; S4: The generated H ₂ and CO ₂ are sent to the hydrocatalytic gasification part, and the catalyst-loaded coal powder and the generated H ₂ undergo hydrocatalytic gasification reaction to generate CH ₄ , catalyst-containing residual coke and aromatic oil Compounds, the generated CO ₂ reacts with H ₂ to generate CH ₄ ; S5: Steps S3 to S4 are repeated until the catalyst-containing residual coke is converted into a catalyst-containing residue to obtain CH ₄ entrained with H ₂ , CO ₂ , dust and aromatic oil compounds. 2. The coal hydrogenation catalytic gasification method according to claim 1, wherein the coal powder is one or more of lignite powder, bituminous coal powder, sub-bituminous coal powder or anthracite powder mixed in any proportion . 3 . The coal hydrocatalytic gasification method according to claim 2 , wherein, in the S1 , the particle size of the pulverized coal is less than 6 mm, and the moisture content of the pulverized coal is less than 5%. 4 . 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, 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 of Fe salt, Co salt, and Ni salt Or more, the cocatalyst 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 hydrocatalytic gasification method according to claim 5 , wherein, in the catalyst-loaded coal powder, the mass of the main catalyst in the composite catalyst accounts for 3% to 8% of the mass of the coal powder; The quality of pulverized coal accounts for 0.2% to 2% of the quality of pulverized coal. 7. The coal hydrocatalytic gasification method according to claim 1, wherein the operating pressure of the hydrocatalytic gasification reaction is 0.5MPa-8MPa, and the reaction temperature of the hydrocatalytic gasification reaction is 650℃-900℃; The operating pressure of the residual coke gasification reaction is 0.5MPa-8MPa, and the reaction temperature of the residual coke gasification reaction is 800°C-1000°C. 8. The coal hydrocatalytic gasification method according to claim 1, characterized in that, after said S5, it further comprises a gas-solid separation stage, an indirect condensation stage, a gas purification stage and a hydrogen separation stage, wherein, The gas-solid separation stage includes: gas-solid separation of _CH4 entrained with H ₂ , CO ₂ , dust and aromatic oil compounds to obtain dust and entrained H ₂ , CO ₂ and aromatic oil compounds after removing the dust CH ₄ ; The indirect condensation stage includes: cooling the CH ₄ entrained with H ₂ , CO ₂ and aromatic oil compounds, recovering heat to obtain aromatic oil compounds, and removing the entrained H ₂ of water vapor and aromatic oil compounds and CH ₄ of CO ₂ ; The gas purification stage includes: carrying out deacidification treatment of CH ₄ entrained with H ₂ and CO ₂ to remove CO ₂ in the gas to obtain CH ₄ entrained with H ₂ ; The hydrogen separation stage includes: separating CH ₄ entrained with H ₂ to obtain CH ₄ . 9 . The coal hydrocatalytic gasification method according to claim 8 , wherein the gas-solid separation stage further comprises: transporting dust to the residual coke gasification part to react with water vapor and O ₂ to generate H 9 . ₂ and CO ₂ ; The hydrogen separation stage further includes: transporting H ₂ to the hydrocatalytic gasification part to undergo hydrocatalytic gasification reaction with pulverized coal to generate CH ₄ . 10. The coal hydrocatalytic gasification method according to claim 1, characterized in that, after the S5, a catalyst recovery stage is included; The catalyst recovery stage includes: recovering the catalyst from the residue containing the catalyst, and transporting the recovered catalyst to the catalyst loading unit for recycling. 11. A coal hydrocatalytic gasification device, characterized in that it is used in the coal hydrocatalytic gasification method according to any one of claims 1 to 10, and the coal hydrocatalytic gasification device comprises: a catalyst A load unit and a hydrocatalytic gasification reaction unit; the hydrocatalytic gasification reaction unit includes a hydrocatalytic gasification part and a residual coke gasification part which are connected to each other; wherein, The pulverized coal inlet of the catalyst loading unit is connected with the pulverized coal transportation pipeline, the pulverized coal outlet of the catalyst loading unit is connected with the pulverized coal inlet of the hydrogenation catalytic gasification part; the catalyst inlet of the catalyst loading unit is connected with the catalyst transportation pipeline connected; The mixed gas inlet of the residual coke gasification part is connected with the inlet pipeline for conveying water vapor and O ₂ , and the gas outlet of the hydrogenation catalytic gasification part is connected with the methane collection device. 12 . The coal hydrocatalytic gasification device according to claim 11 , wherein the position of the hydrocatalytic gasification part in the direction of gravity is higher than the position of the residual coke gasification part in the direction of gravity. 13 . 13 . The coal hydrocatalytic gasification device according to claim 11 , wherein the hydrocatalytic gasification reaction unit is a gasifier, and the gasifier is divided into hydrocatalytic gasification along the direction of gravity. 14 . part and the residual coke gasification part; Or, both the hydrogenation catalytic gasification part and the residual coke gasification part are gasifiers. 14. The coal hydrocatalytic gasification device according to any one of claims 11 to 13, wherein the gas outlet of the hydrocatalytic gasification section passes through a gas-solid separation unit, an indirect condensation unit, and a gas purification unit in sequence. The unit, the hydrogen separation unit for separation of _H2 and _CH4 , is connected to the methane collection unit. 15. The coal hydrocatalytic gasification device according to claim 14, wherein the dust outlet of the gas-solid separation unit is connected to the dust inlet of the residual coke gasification part, and the gas-solid separation unit has a dust outlet. The gas outlet is connected with the gas inlet of the indirect condensation unit; the hydrogen outlet of the hydrogen separation unit is connected with the hydrogen inlet of the hydrocatalytic gasification part. 16. The coal hydrocatalytic gasification device according to any one of claims 11 to 13, wherein the residue outlet of the residual coke gasification part passes through a slag discharge unit and a catalyst recovery unit in sequence with the catalyst load units are connected.