阅读说明：本技术 组合式流化床煤催化气化制氢的装置及方法 (Device and method for producing hydrogen by catalytic coal gasification of combined fluidized bed ) 是由 金渭龙 钟思青 徐俊 高攀 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种组合式流化床煤催化气化制氢的装置及方法,采用流化床气化炉和再生炉组合,于原料进口位于流化床气化炉上层空间,流化床气化炉下层空间的返料出口通过返料装置与再生炉的返料进口相连接,再生炉上方出口通过返料装置与流化床气化炉上层空间的返料进口相连接技术方案,主要解决氢气含量低、碳转化率低、能耗高等问题。本发明的装置及方法,较好地解决了上述问题,可应用于煤制氢领域。(The invention discloses a combined fluidized bed coal catalytic gasification hydrogen production device and a method, wherein a fluidized bed gasification furnace and a regeneration furnace are combined, a raw material inlet is positioned in the upper space of the fluidized bed gasification furnace, a return material outlet of the lower space of the fluidized bed gasification furnace is connected with a return material inlet of the regeneration furnace through a return material device, and an upper outlet of the regeneration furnace is connected with the return material inlet of the upper space of the fluidized bed gasification furnace through the return material device. The device and the method of the invention better solve the problems and can be applied to the field of hydrogen production from coal.)

1. A combined fluidized bed coal catalytic gasification hydrogen production device comprises a fluidized bed gasification furnace (1), a raw material inlet (2), a gasification furnace lower layer gas distributor (3), a gasification furnace upper layer gas distributor (4), a gasification furnace outlet (5), a gasification furnace slag discharge port (6), a gasification furnace return outlet (7), a return device (8), a regeneration furnace return inlet (9), a regeneration furnace (10), a carrier feed port (11), a regeneration furnace gas distributor (12), a regeneration furnace gas outlet (13), a regeneration furnace slag discharge port (14), a first cyclone separator (15), an ash hopper (16), a return straight pipe (17), a U-shaped return device (18), a gasification furnace return inlet (19), a gasification furnace heat recovery unit (20), a separation purification unit (21), a second cyclone separator (22) and a regeneration furnace cooling purification unit (23),

the device is characterized in that the raw material inlet (2) is connected with the fluidized bed gasification furnace (1), the fluidized bed gasification furnace (1) is connected with the material returning device (8) through the gasification furnace material returning outlet (7), the material returning device (8) is connected with the regeneration furnace (10) through the regeneration furnace material returning inlet (9), the carrier charging opening (11) is connected with the regeneration furnace (10), the regeneration furnace gas outlet (13) is connected with the first cyclone separator (15), the bottom of the first cyclone separator (15) is connected with the ash hopper (16) and the material returning straight pipe (17), the U-shaped material returning device (18) is connected with the fluidized bed gasification furnace (1) through the gasification furnace material returning inlet (19), the outlet of the first cyclone separator (15) is connected with the second cyclone separator (22), the second cyclone separator (22) is connected with the regeneration furnace cooling and purifying unit (23), and the gasification furnace outlet (5) is connected with the gasification furnace heat recovery unit (20) and the separation and purification unit (21).

2. The apparatus according to claim 1, wherein the fluidized-bed gasification furnace (1) is composed of an upper space and a lower space; the inner diameter of the upper layer space is larger than that of the lower layer space, preferably 1.2-5.0 times of that of the lower layer space; and/or the height of the upper layer space is greater than or equal to the height of the lower layer space, preferably 1.0-3.0 times of the height of the lower layer space.

3. The apparatus according to claim 1 or 2, wherein the gasifier lower gas distributor (3) is located at the bottom of the lower space of the fluidized bed gasifier (1) and forms an included angle of less than or equal to 60 degrees, preferably 15-45 degrees, with the horizontal axis, and the conical surface of the gasifier lower gas distributor (3) is provided with gas holes; preferably, the air holes are uniformly arranged along the circumference; further preferably, 5-50 ring air holes are arranged, and the opening rate is 1-5%;

and/or the gasifier upper gas distributor (4) is positioned at the bottom of the upper space of the fluidized bed gasifier (1) and forms an included angle of less than or equal to 60 degrees with the horizontal axis, preferably 15-45 degrees, and the conical surface of the gasifier upper gas distributor (4) is provided with gas holes; preferably, the air holes are uniformly arranged along the circumference; more preferably, 10-100 ring air holes are arranged, and the opening rate is 1-5%.

4. The apparatus according to any one of claims 1 to 3, wherein the raw material inlet (2) is located in the upper space of the fluidized-bed gasification furnace (1) at a position lower than 2/3, preferably between 1/5 and 3/5, the height of the upper space;

and/or the gasifier return outlet (7) is positioned in the lower space of the fluidized bed gasifier (1), preferably between 1/5 and 4/5 of the height of the lower space;

and/or the gasifier feed back inlet (19) is positioned in the upper space of the fluidized bed gasifier (1), preferably between 1/3 and 2/3 of the height of the upper space.

5. The apparatus according to any of claims 1 to 4, wherein the regenerator feed back inlet (9) is located below the regenerator (10) at a position 1/2 below the height of the regenerator (10), preferably between 1/5 and 1/2 of the height of the regenerator (10);

and/or the regenerating furnace (10) is provided with 1-5 carrier feeding ports (11), and the carrier feeding ports (11) are positioned in the middle of the regenerating furnace (10), preferably between 1/3-2/3 of the height of the regenerating furnace (10).

6. A method for producing hydrogen by catalytic coal gasification according to the device of any one of claims 1 to 5, comprising the following main steps:

s1, raw material coal (A) enters from the raw material inlet (2) into the upper space of the fluidized bed gasification furnace (1), is mixed with water vapor from the gasification furnace lower layer gas distributor (3) and the gasification furnace upper layer gas distributor (4) and the oxidation state high-temperature heat carrier (G) of the gasification furnace return inlet (19) to perform catalytic pyrolysis, gasification and shift reaction, and generates H-containing gas₂、CO、CO₂、CH₄The synthesis gas of (2); the oxidation state high-temperature heat carrier (G) and the CO in the synthesis gas₂Carrying out carbonation reaction to absorb CO in the synthesis gas₂And generating a carbonate carrier;

s2, the synthesis gas after the carbonation reaction passes through the gasifier heat recovery unit (20) and the separation purification unit (21) to obtain hydrogen-rich synthesis gas (K);

s3, the carbonate carriers and the gasified semicoke (C) obtained in the S1 enter the regeneration furnace (10) from the material returning device (8), the gasified semicoke and the oxygen-containing gas from the regeneration furnace gas distributor (12) perform high-temperature combustion reaction to decompose the carbonate carriers, so that the carbonate carriers are regenerated to obtain an oxidized state high-temperature heat carrier (G), the oxidized state high-temperature heat carrier (G) and fine ash (H) are discharged from the top regeneration furnace gas outlet (13), the oxidized state high-temperature heat carrier (G) is separated in the first cyclone separator (15), the oxidized state high-temperature heat carrier (G) is circulated back to the upper space of the fluidized bed gasification furnace (1) through the gasification furnace material returning inlet (19) by the U-shaped material returning device (18), and the fine ash (H) is separated in the second cyclone separator (22), and the residual flue gas (I) is discharged after passing through the regeneration furnace cooling and purifying unit (23).

7. The method as claimed in claim 6, wherein the reaction temperature in the fluidized-bed gasification furnace (1) is 600-900 ℃, and the linear velocity of the gas phase is 0.1-1.0 m/s; the reaction temperature in the regeneration furnace (10) is 800-1200 ℃, and the linear velocity of the gas phase is 1-10 m/s; the reaction pressure ranges of the fluidized bed gasification furnace (1) and the regeneration furnace (10) are both 0-2.0 MPa.

8. The method as claimed in claim 6 or 7, characterized in that the gasifier lower layer gas distributor (3) and the gasifier upper layer gas distributor (4) are filled with water vapor, the temperature of the water vapor is 200 ℃ and 800 ℃, preferably, the proportion of the water vapor filled in the gasifier upper layer gas distributor (4) accounts for 10% -50% of the sum of the water vapor amount in the gasifier upper layer gas distributor (4) and the gasifier lower layer gas distributor (3); preferably, the molar ratio of the steam to the carbon in the raw coal, i.e., the water-carbon ratio, is 1.0 to 5.0 mol/mol.

9. The method according to any one of claims 6 to 8, wherein the oxygen-containing gas introduced into the regenerator gas distributor (12) is selected from one or more of oxygen, air and oxygen-enriched air, and preferably the molar ratio of oxygen in the oxygen-containing gas to carbon in the circulating semicoke, i.e. the oxygen-carbon ratio, is 1.5mol/mol or more.

10. Process according to any one of claims 6 to 9, characterized in that the heat carrier is chosen from natural ores; or mixtures of alkali metals, transition metals and natural minerals, or alkaliOne or more of a mixture of a metal, a transition metal and an alkaline earth metal Ca; preferably, the natural ore is limestone, dolomite or olivine; preferably, the alkali metal, the transition metal or the alkaline earth metal Ca accounts for 0.1 to 30 percent of the weight of the catalyst according to the active component, and is loaded on the Al in an impregnation method, a dry mixing method or an ion exchange method₂O₃、ZrO₂、TiO₂Or SiO₂On a carrier.

Technical Field

The invention belongs to the technical field of coal hydrogen production, relates to a device and a method for producing hydrogen by combined fluidized bed coal catalytic gasification, and particularly relates to a device and a method for producing hydrogen by catalytic gasification combined by a fluidized bed gasification furnace and a fluidized bed regeneration furnace of a layered reaction.

Background

The hydrogen energy is used as a clean energy, the final product is water in the energy conversion process, zero emission can be really realized, and the hydrogen energy is widely applied to the aspects of space power, vehicle-mounted fuel, fuel cells, combustion power generation, chemical production and the like and plays an increasingly important role in energy structures. The main methods for preparing hydrogen energy at present comprise partial oxidation reforming hydrogen production of heavy oil, hydrogen production by water electrolysis, coal gasification hydrogen production and the like, wherein the coal gasification hydrogen production conforms to the energy structure characteristics and the basic national conditions of China and is a mainstream hydrogen production technology. The traditional coal hydrogen production mainly comprises the processes of coal gasification, coal gas purification, CO conversion, purification and the like, and has the defects of more related equipment, difficult temperature and pressure matching among the equipment, high energy consumption, long flow and low system energy conversion rate. The coal gasification device is key equipment for preparing hydrogen from coal, the coal gasification device in the prior art mainly adopts an entrained flow bed and a fluidized bed gasification furnace, the content of hydrogen in the synthesis gas at the outlet of the coal gasification device is generally low, and the load of subsequent purification, transformation and purification processes is increased.

Patent CN 101372312a proposes a method for preparing hydrogen by coal gasification, which adopts a two-stage gasification method, wherein in the first step, coal is thermally cracked under the condition of isolating air and not higher than 900 ℃, coal pyrolysis gasification, tar and coal tar are mainly obtained, coal pyrolysis gasification and tar are separated, the obtained coal tar enters the second step, gasification reaction is performed by using a gasification agent under the condition of not higher than 800 ℃, and the obtained coal tar is purified to obtain a target product hydrogen. The method has problems in that it is difficult to maintain the reaction temperature without external heat supply, superheated steam needs to be heated to a temperature required for gasification reaction, energy consumption is high, particle residence time is long, carbon conversion rate is low, and economical efficiency for industrial application is poor.

Patent CN 102585911a proposes a coal gasification hydrogen production apparatus and method, in which a reactor couples three processes of coal gasification, carbon dioxide capture by calcium-based adsorbent and calcium carbonate calcination, and carbon dioxide in coal gasification syngas is captured by calcium-based adsorbent to increase hydrogen content. However, the synthesis gas at the outlet of the gasification reactor of the device needs to enter the adsorption reactor after being cooled by the external heat exchanger, the temperature matching between the two reactors is poor, and the coal ash carried in the synthesis gas is easy to cause pipeline blockage. The calcium-based adsorbent generated by the combustion reactor is divided into two parts which respectively enter the gasification reactor and the adsorption reactor, the pressure balance is difficult to control, the calcium-based adsorbent cannot enter the proportion of each section of reactor, the effect of each reaction is not easy to control, and the technical index of the outlet is influenced.

Disclosure of Invention

In the technology, the promotion effect of the catalyst or the carrier on the reaction process in the gasification furnace is considered, and the promotion effect has a little effect on the promotion of the hydrogen content in the outlet synthesis gas, but a reasonable and effective method is not formed from the aspect of reaction process enhancement, and the adopted catalyst or the carrier cannot meet the requirements of technical indexes and economy. Therefore, the intensified transformation and CO2 absorption reaction can be considered, and the hydrogen production process by coal catalytic gasification can be improved by adopting a carrier with high-efficiency catalytic performance, so that high-quality hydrogen-rich synthetic gas is generated. Based on the consideration, the conversion and carbonation reaction can be enhanced in the gasification furnace, and a coal catalytic gasification hydrogen production technology which is high in gasification reaction rate, conversion reaction degree and catalytic reaction performance, simple in process, stable in operation and efficient is researched.

The invention mainly solves the technical problems of low carbon conversion rate and gasification intensity, low hydrogen yield, high energy consumption and poor operation stability in the prior art, and provides a combined fluidized bed coal catalytic gasification hydrogen production device which comprises a fluidized bed gasification furnace and a fluidized bed regeneration furnace, wherein raw material coal A, an oxidation state high-temperature heat carrier G, an upper layer gas distributor gasification agent and a lower layer gas distributor gasification agent are introduced into the fluidized bed gasification furnace for pyrolysis, gasification, transformation and carbonation reaction to generate hydrogen-rich synthesis gas, gasified semicoke and a carbonate carrier, and the carbonate carrier and the gasified semicoke enter a regeneration furnace to perform high-temperature combustion reaction with oxygen-containing gas to decompose the carbonate carrier and generate the oxidation state high-temperature heat carrier again. Realizes the cyclic regeneration of the high-temperature heat carrier, balances heat flow and material flow, and improves gasification strength, carbon conversion rate and hydrogen yield.

The second technical problem to be solved by the invention is to provide a catalytic gasification reaction method corresponding to the first technical problem.

The invention provides a combined fluidized bed coal catalytic gasification hydrogen production device, which comprises a fluidized bed gasification furnace, a raw material inlet, a gasification furnace lower layer gas distributor, a gasification furnace upper layer gas distributor, a gasification furnace outlet, a gasification furnace slag discharge port, a gasification furnace return outlet, a return device, a regeneration furnace return inlet, a regeneration furnace, a carrier feed inlet, a regeneration furnace gas distributor, a regeneration furnace gas outlet, a regeneration furnace slag discharge port, a first cyclone separator, an ash hopper, a return straight pipe, a U-shaped return device, a gasification furnace return inlet, a gasification furnace heat recovery unit, a separation and purification unit, a second cyclone separator and a regeneration furnace cooling and purification unit, wherein the raw material inlet is connected with the fluidized bed gasification furnace, the fluidized bed gasification furnace is connected with the return device through the gasification furnace return outlet, the return device is connected with the regeneration furnace through the regeneration furnace return inlet, the carrier charging opening is connected with the regenerating furnace, a gas outlet of the regenerating furnace is connected with the first cyclone separator, the bottom of the first cyclone separator is connected with the ash hopper and the return straight pipe, the U-shaped return device is connected with the fluidized bed gasification furnace through a return inlet of the gasification furnace, an outlet of the first cyclone separator is connected with the second cyclone separator, the second cyclone separator is connected with the cooling and purifying unit of the regenerating furnace, and an outlet of the gasification furnace is connected with the heat recovery unit of the gasification furnace and the separation and purification unit.

Researches show that the fluidized bed gasification furnace has obvious advantages in the aspects of strengthening the reaction process, material mass transfer and heat transfer by optimizing the structure and the process of the fluidized bed gasification furnace.

According to some embodiments of the present invention, the fluidized-bed gasification furnace is composed of an upper space and a lower space; the inner diameter of the upper layer space is larger than that of the lower layer space; and/or the height of the upper layer space is greater than or equal to the height of the lower layer space,

according to some embodiments of the invention, the inner diameter of the upper space is 1.2 to 5.0 times the inner diameter of the lower space; and/or the height of the upper layer space is 1.0-3.0 times of the height of the lower layer space.

According to some embodiments of the present invention, the gasifier lower gas distributor is located at the bottom of the lower space of the fluidized bed gasifier) and forms an included angle of less than or equal to 60 ° with the horizontal axis, and the conical surface of the gasifier lower gas distributor is provided with gas holes;

and/or the gasifier upper gas distributor is positioned at the bottom of the upper space of the fluidized bed gasifier and forms an included angle of less than or equal to 60 degrees with the horizontal axis, and the conical surface of the gasifier upper gas distributor is provided with gas holes.

According to some embodiments of the invention, the gasifier lower layer gas distributor is positioned at the bottom of the lower layer space of the fluidized bed gasifier and forms an included angle of 15-45 degrees with a horizontal axis, and the conical surface of the gasifier lower layer gas distributor is provided with gas holes which are uniformly distributed along the circumference;

and/or the gasifier upper gas distributor is positioned at the bottom of the upper space of the fluidized bed gasifier and forms an included angle of 15-45 degrees with the horizontal axis, and the conical surface of the gasifier upper gas distributor is provided with gas holes; the air holes are uniformly arranged along the circumference.

According to some embodiments of the invention, the gasifier lower layer gas distributor is provided with 5-50 ring air holes, and the opening rate is 1-5%;

and/or the upper layer gas distributor of the gasification furnace is provided with 10-100 ring air holes with the aperture ratio of 1-5%.

According to some embodiments of the present invention, the raw material inlet is located in an upper space of the fluidized-bed gasification furnace at a position 2/3 lower than the height of the upper space;

and/or the gasifier return outlet is positioned in the lower layer space of the fluidized bed gasifier;

and/or the gasifier feed back inlet is positioned in the upper space of the fluidized bed gasifier.

According to some embodiments of the invention, the feedstock inlet is located between 1/5-3/5 of the height of the upper space;

and/or the gasifier return outlet is positioned between 1/5 and 4/5 of the height of the lower space;

and/or the gasifier feed back inlet is positioned between 1/3 and 2/3 of the height of the upper space.

According to some embodiments of the invention, the regenerator return inlet is located below the regenerator at 1/2 below the height of the regenerator;

and/or the regeneration furnace is provided with 1-5 carrier charging openings, and the carrier charging openings are positioned in the middle of the regeneration furnace.

According to some embodiments of the invention, the regenerator return inlet is located between 1/5-1/2 of the regenerator height;

and/or the regenerating furnace is provided with 1-5 carrier feeding ports, and the carrier feeding ports are positioned between 1/3-2/3 of the height of the regenerating furnace.

The second aspect of the invention provides a method for preparing hydrogen by coal catalytic gasification according to the device of the first aspect, which comprises the following main steps:

s1, the raw material coal enters the upper space of the fluidized bed gasification furnace from the raw material inlet, is mixed with the water vapor from the lower gas distributor of the gasification furnace and the upper gas distributor of the gasification furnace and the oxidation state high-temperature heat carrier at the material return inlet of the gasification furnace, and is subjected to catalytic pyrolysis, gasification and shift reaction to generate a mixture containing H₂、CO、CO₂、CH₄The synthesis gas of (2); the oxidation state high-temperature heat carrier is then mixed with CO in the synthesis gas₂To carry outCarbonation reaction absorbing CO from the syngas₂And generating a carbonate carrier;

s2, the synthesis gas after the carbonation reaction passes through the gasifier heat recovery unit and the separation purification unit (21) to obtain hydrogen-rich synthesis gas;

s3, the carbonate carrier and the gasified semicoke obtained in the step S1 enter the regenerating furnace from the material returning device, the gasified semicoke and oxygen-containing gas from the gas distributor of the regenerating furnace perform high-temperature combustion reaction to decompose the carbonate carrier, so that the carbonate carrier is regenerated to obtain an oxidized high-temperature heat carrier, the oxidized high-temperature heat carrier and fine ash are discharged from a gas outlet of the top regenerating furnace, the oxidized high-temperature heat carrier is separated out in the first cyclone separator, the oxidized high-temperature heat carrier circulates back to the upper space of the fluidized bed gasification furnace through the gasification furnace material returning inlet by the U-shaped material returning device, the fine ash is separated out in the second cyclone separator, and the residual flue gas is discharged after passing through the cooling and purifying unit of the regenerating furnace.

The reaction temperature in the fluidized bed gasification furnace is 600-900 ℃, and the linear velocity of the gas phase is 0.1-1.0 m/s; the reaction temperature in the regeneration furnace is 800-1200 ℃, and the gas phase linear velocity is 1-10 m/s; the reaction pressure ranges of the fluidized bed gasification furnace and the regeneration furnace are both 0-2.0 MPa.

According to some embodiments of the present invention, the gasifier lower gas distributor and the gasifier upper gas distributor are filled with water vapor, and the temperature of the water vapor is 200-800 ℃.

According to some embodiments of the present invention, the gasifier lower layer gas distributor and the gasifier upper layer gas distributor are filled with water vapor, and the proportion of the water vapor filled in the gasifier upper layer gas distributor accounts for 10% -50% of the sum of the water vapor amount in the gasifier upper layer gas distributor and the gasifier lower layer gas distributor.

According to some embodiments of the invention, the molar ratio of steam to carbon in the raw coal, i.e. the water to carbon ratio, is 1.0 to 5.0 mol/mol.

According to some embodiments of the invention, the oxygen-containing gas introduced into the regenerator gas distributor is selected from one or more of oxygen, air and oxygen-enriched air.

According to some embodiments of the invention, the molar ratio of oxygen in the oxygen-containing gas to carbon in the circulating semicoke, i.e. the oxygen to carbon ratio, is 1.5mol/mol or more.

According to some embodiments of the invention, the heat carrier is selected from natural ores; or a mixture of alkali metal, transition metal and natural ore, or one or more of alkali metal, transition metal and alkaline earth metal Ca.

According to some embodiments of the invention, the natural ore is limestone, dolomite or olivine.

According to some embodiments of the invention, the alkali metal, transition metal or alkaline earth metal Ca is supported on the Al in an impregnation method, a dry mixing method or an ion exchange method, wherein the active component accounts for 0.1-30% of the weight of the catalyst₂O₃、ZrO₂、TiO₂Or SiO₂On a carrier.

The technological process adopted by the equipment of the invention is briefly described as follows:

the raw material coal enters a fluidized bed gasification furnace to be mixed and contacted with a gasification agent from an upper layer gas distributor and a lower layer gas distributor of the gasification furnace for carrying out pyrolysis, gasification and shift reaction, the operation temperature is 600-₂、CO₂、CH₄The generated synthesis gas and the steam from the gasifying agent in the upper layer gas distributor of the gasification furnace further generate enhanced shift reaction, thereby improving the CO in the synthesis gas₂And H₂Content of (A), CO in the syngas after the shift reaction₂Carrying out carbonation reaction with an oxidation state high-temperature heat carrier from a gasification furnace return material inlet to generate a carbonate carrier and absorb CO in the synthesis gas₂And the hydrogen-rich synthetic gas is discharged from the outlet of the fluidized bed gasification furnace. The carbonate carrier and the gasified semicoke enter the regenerating furnace from a return outlet of the lower gasification furnace through a return device. Gasification semicoke in regenerator with oxygen-containing gas from regenerator gas distributorBurning at 800-1200 deg.c and 0-2.0MPa to decompose carbonate carrier and to produce oxidized high temperature heat carrier and CO₂And the fine ash after the entrained combustion is discharged from the outlet of the regeneration furnace and enters a first cyclone separator, the oxidation state high-temperature heat carrier is separated and circulated back to the fluidized bed gasification furnace through a return straight pipe and a U-shaped return device, and the fine ash and the flue gas enter a second cyclone separator and a regeneration furnace cooling and purifying unit.

The invention has the beneficial effects that:

1) the catalytic gasification hydrogen production device combining the fluidized bed gasification furnace and the regeneration furnace is adopted to carry out pyrolysis, gasification, transformation and carbonation reactions in the fluidized bed gasification furnace, and the gasified semicoke and the carbonate carrier enter the regeneration furnace to carry out high-temperature combustion reaction, so that the carbon conversion rate and the reaction strength are improved. The fluidized bed gasification furnace and the regeneration furnace are relatively independent, the synthetic gas at the outlet of the fluidized bed gasification furnace and the flue gas at the outlet of the regeneration furnace are respectively discharged from respective pipelines, the synthetic gas at the outlet of the fluidized bed gasification furnace hardly contains nitrogen, and CO is₂And SO₂The content of (a) is low, and the aims of high gasification efficiency and methane yield are achieved.

2) Oxidized high-temperature heat carrier generated by combustion of regenerative furnace and heat required by pyrolysis and gasification reactions in fluidized bed gasification furnace and CO₂The heat released by the reaction is provided, and the heat of the oxidation state high-temperature heat carrier is released by the combustion of the carbon residue in the gasified semicoke, so that the stable heat balance is realized, and the process heat efficiency and the heat utilization rate are more efficient than those of the traditional gasification process.

3) The fluidized bed gasification furnace is divided into an upper layer space and a lower layer space, water vapor is additionally introduced into the upper layer space, the shift reaction process in the furnace is strengthened, the temperature of the upper layer space is slightly lower than that of the lower layer space, the balance of shift reaction in the upper layer space can be promoted, and the hydrogen content is improved. In addition, the upper space has a larger inner diameter than the lower space, which prolongs the residence time of gas between coal particles and promotes the gasification and shift reaction.

4) The gasification furnace return inlet is positioned in the upper space of the fluidized bed gasification furnace and is a middle area of the upper space height, after the oxidation state high-temperature heat carrier enters the fluidized bed gasification furnace, the oxidation state high-temperature heat carrier is fluidized and moves to the lower space of the fluidized bed gasification furnace from top to bottom, the mixing contact time of the oxidation state high-temperature heat carrier with the gasified semicoke and the gasified synthesis gas is long, the material mixing effect is good, the uniform heat transfer is facilitated, and the pyrolysis, gasification and carbonation reaction are effectively promoted to be carried out.

5) The heat carrier can be selected from limestone, dolomite, olivine and other cheap natural ores; or alkali metal, transition metal and natural ore, or mixture of alkali metal, transition metal and alkaline earth metal Ca, wherein the active component accounts for 0.1-30% of the catalyst, and is loaded on Al by immersion method, dry mixing method or ion exchange method₂O₃，ZrO₂，TiO₂，SiO₂And the like. The physical difference between the carrier and the coal ash is large, the carrier and the coal ash can complete the separation process in a regeneration furnace through combustion and simple separation equipment, and the problem of difficult separation is solved.

According to the technical scheme, catalytic pyrolysis, gasification, transformation and carbonation reactions are carried out in the fluidized bed gasification furnace through the combination of the fluidized bed gasification furnace and the regeneration furnace, the gasified semicoke and the carbonate carrier are introduced into the regeneration furnace to carry out high-temperature combustion reaction, and an oxidation state high-temperature heat carrier, coal ash and flue gas are generated, wherein the oxidation state high-temperature heat carrier is circulated and returned to the fluidized bed gasification furnace through the U-shaped material returning device, so that the circulation of heat flow and material flow is realized, and the purpose of full utilization is achieved. The conversion rate of carbon at the outlet of the device can reach 95%, the content of hydrogen in the outlet synthesis gas is 80%, and the device has the characteristics of high reaction strength, high energy utilization rate and simple and compact structure, greatly reduces equipment investment and production cost, and has good application prospect.

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 principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a schematic flow diagram of a combined fluidized bed coal catalytic gasification hydrogen production plant;

FIG. 2 is a schematic structural view of a lower gas distributor of a gasification furnace, wherein a is a top view and b is a side view; b, the included angle is 45 degrees;

FIG. 3 is a schematic structural diagram of an upper gas distributor of a gasification furnace, wherein a is a top view and b is a side view; and the included angle in the b is 35 degrees.

Detailed Description

The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the examples.

In fig. 1, 1 is a fluidized bed gasification furnace; 2 is a raw material inlet; 3 is a gasifier lower gas distributor; 4 is a gasifier upper gas distributor; 5 is the outlet of the gasification furnace; 6 is a slag discharge port of the gasification furnace; 7 is a return outlet of the gasification furnace; 8 is a material returning device; 9 is a material return inlet of the regeneration furnace; 10 is a regeneration furnace; 11 is a carrier charging port; 12 is a gas distributor of a regenerating furnace; 13 is a regeneration furnace outlet; 14 is a regenerative furnace slag discharging port; 15 is a first cyclone separator; 16 is an ash bucket; 17 is a return straight pipe; 18 is a U-shaped material returning device; 19 is a return inlet of the gasification furnace; 20 is a gasifier heat recovery unit; 21 is a separation and purification unit; 22 is a second cyclone separator; and 23, a cooling and purifying unit of the regenerating furnace. A is raw material coal; b is carbonate carrier and gasified ash; c is carbonate carrier and gasified semicoke; d is return gas; e is a supplementary vector; f is combustion ash; g is an oxidation state regeneration heat carrier; h is fine ash; i is flue gas; j is tar; k is hydrogen-rich synthesis gas.

Raw material coal A enters a fluidized bed gasification furnace 1 through a raw material inlet 2, is mixed and contacted with a gasifying agent (water vapor) from an upper layer gas distributor 4 and a lower layer gas distributor 3 of the gasification furnace, and is subjected to pyrolysis, gasification and shift reaction to generate CO and H₂、CO₂、CH₄The generated synthesis gas and the steam in the upper layer gas distributor 4 of the gasification furnace further generate enhanced shift reaction to improve the CO in the synthesis gas₂And H₂Content of (A), CO in the syngas after the shift reaction₂Carrying out carbonation reaction with an oxidation state high-temperature heat carrier from a gasification furnace material returning inlet 19 to absorb CO in the synthesis gas₂The hydrogen-rich synthetic gas is discharged from the outlet 5 of the fluidized bed gasification furnace, enters the gasification furnace heat recovery unit 20 and is separated and purifiedAnd a unit 21. The carbonate carrier and the gasified semicoke C leave the fluidized-bed gasification furnace 1 from a gasification furnace return outlet 7 at the lower part of the fluidized-bed gasification furnace 1 and enter a regeneration furnace 10 through a return device 8. The gasified semicoke in the regenerator 10 is combusted with the oxygen-containing gas from the regenerator gas distributor 12 to decompose the carbonate carriers to produce an oxidized high temperature heat carrier and CO₂The fine ash with the burnt fine ash is discharged from the outlet 13 of the regenerator and enters a first cyclone separator 15, the oxidation state high-temperature heat carrier G is separated and circulated back to the fluidized bed gasification furnace 1 through a return straight pipe 17 and a U-shaped return device 18, and the fine ash and the flue gas enter a second cyclone separator 22 and a regenerator cooling and purifying unit 23.

[ example 1 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, raw materials import height is located the 1/2 of fluidized bed gasifier height, regenerator return charge import is located the 2/3 of fluidized bed gasifier height, gasifier return charge export is located the 1/4 of fluidized bed gasifier height, gasifier return charge import is located the 3/5 regenerator internal diameter 1.2m of fluidized bed gasifier height, height 15mm, regenerator return charge import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 3.0 mol/mol. CaO high-temperature heat carrier enters a fluidized bed gasifier from a return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 80 percent. The carbonate carrier and the partially gasified semicoke enter the regenerating furnace through a material returning device to be combusted with air from a gas distributor of the regenerating furnacePerforming a burning reaction at an operating temperature of 1000 ℃, an operating pressure of normal pressure and an oxygen-carbon ratio of 2.0mol/mol, and decomposing the carbonate carrier into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 95%.

[ example 2 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 3m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 3.0 mol/mol. CaO high-temperature heat carrier enters a fluidized bed gasifier from a return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 620 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 82%. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier passes through a first cyclone separator, a descending straight pipe andthe U-shaped material returning device is separated, collected and circularly introduced into the fluidized bed gasification furnace to provide sensible heat and oxygen carrier for pyrolysis and gasification reaction in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 95%.

[ example 3 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 50% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 3.0 mol/mol. CaO high-temperature heat carrier enters a fluidized bed gasifier from a return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 85 percent. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 95%.

[ example 4 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 3.0 mol/mol. CaO high-temperature heat carrier enters a fluidized bed gasifier from a return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 80 percent. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1100 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.5mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 99%.

[ example 5 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 2.0 mol/mol. CaO high-temperature heat carrier enters a fluidized bed gasifier from a return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 73%. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1100 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.5mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 96%.

[ example 6 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 3.0 mol/mol. Load K₂CO₃The CaO high-temperature heat carrier enters a fluidized bed gasifier from a material return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 90 percent. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 99%.

[ example 7 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 1/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, high-temperature water vapor with the temperature of 500 ℃ is introduced into an upper layer gas distributor and a lower layer gas distributor of the fluidized bed, the water vapor introduced into the upper layer gas distributor of the gasification furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the gasification furnace and the lower layer gas distributor of the gasification furnace, and the water-carbon ratio is 3.0 mol/mol. CaO high-temperature heat carrier enters a fluidized bed gasifier from a return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, the position of the return inlet of the gasifier is low, the material mixing and contact time is short, the mixing effect is poor, and H in the synthesis gas at an outlet is₂The content is 70%. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 95%.

[ example 8 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

Selecting inner Mongolia lignite as a raw material, adding the inner Mongolia lignite into a fluidized bed gasification furnace from a raw material inlet, and introducing bottom gas of a lower-layer space of the fluidized bed gasification furnaceHigh-temperature steam with the temperature of 500 ℃ is introduced into the body distributor, and the water-carbon ratio is 3.0 mol/mol. Load K₂CO₃The CaO high-temperature heat carrier enters a fluidized bed gasifier from a material return inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, carbonate carriers, semicoke and synthesis gas rich in hydrogen are generated, wherein H in the synthesis gas at an outlet₂The content is 70%. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 92%.

[ example 9 ]

Adopt the device that a modular fluidized bed coal catalytic gasification hydrogen manufacturing that fig. 1 shows, fluidized bed gasifier lower floor space internal diameter 1.0m, lower floor space height 3m, fluidized bed gasifier upper strata space internal diameter 2m, upper strata space height 6m, the raw materials import height is located the 1/2 of fluidized bed gasifier height, the regenerator feed back import is located the 2/3 of fluidized bed gasifier height, the gasifier feed back export is located the 1/4 of fluidized bed gasifier height, the gasifier feed back import is located the 3/5 of fluidized bed gasifier height, regenerator internal diameter 1.2m, height 15mm, the regenerator feed back import is located 1/10 of regenerator height.

The inner Mongolia lignite is selected as a raw material and is added into a fluidized bed gasification furnace from a raw material inlet, 500 ℃ high-temperature steam is introduced into a gas distributor at the bottom of the upper space of the fluidized bed gasification furnace, and the water-carbon ratio is 3.0 mol/mol. Load K₂CO₃The CaO high-temperature heat carrier enters a fluidized bed gasifier from a return material inlet of the gasifier, a plurality of materials are mixed and contacted to carry out pyrolysis, gasification, change and carbonation reactions, the operating temperature of the fluidized bed gasifier is 600 ℃, the operating pressure is normal pressure, and carbonate carriers are generatedSemicoke and a hydrogen-rich synthesis gas, wherein H is contained in the synthesis gas at the outlet₂The content is 50%. The carbonate carrier and the gasified semicoke enter a regeneration furnace through a material returning device, and are subjected to combustion reaction with air from a gas distributor of the regeneration furnace, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, and the carbonate carrier is decomposed into an oxidation state high-temperature heat carrier and CO₂The oxidation state high-temperature heat carrier is separated, collected and circularly introduced into the fluidized bed gasification furnace through the first cyclone separator, the descending straight pipe and the U-shaped material returning device, sensible heat and oxygen carriers are provided for pyrolysis and gasification reactions in the fluidized bed gasification furnace, and the carbon conversion rate at the outlet of the regeneration furnace reaches 70%.

[ COMPARATIVE EXAMPLE 1 ]

A coal gasification reaction device in the traditional coal hydrogen production process takes a shell entrained-flow bed gasification furnace as an example, coal is selected as lignite, the operating pressure is 3.0MPa, the average operating temperature is 1800 ℃, and H in an outlet gas component obtained is H₂The content is 30 percent, and the carbon conversion rate is 98 percent.

[ COMPARATIVE EXAMPLE 2 ]

A coal gasification reaction device in the traditional coal hydrogen production process takes a winkler fluidized bed gasification furnace as an example, coal is selected as brown coal, the operating pressure is 3.0MPa, the average operating temperature is 1000 ℃, and H in an outlet gas component is obtained₂The content is 33 percent, and the carbon conversion rate is 90 percent.

[ COMPARATIVE EXAMPLE 3 ]

A gasification reaction device in a multi-layer fluidized bed catalytic gasification process proposed by Xinao group is adopted, inner Mongolia lignite is selected as a raw material, 15% of potassium carbonate catalyst is loaded, the operating pressure is 2.5MPa, and the operating temperature is 700 ℃. The hydrogen content in the obtained outlet gas component was 43%, and the carbon conversion rate was 50%.

A comparison of the parameters of the examples and comparative examples is shown in Table 1.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.