System and method for preparing hydrogen-rich synthesis gas based on adsorption enhancement of high-pressure bubbling bed

Abstract

The invention provides a system and a method for preparing hydrogen-rich synthesis gas based on adsorption enhancement of a high-pressure bubbling bed, and belongs to the field of adsorption enhancement hydrogen production. The method comprises the following steps: introducing raw materials into a high-pressure bubbling bed, introducing high-temperature steam, carrying out pyrolysis and gasification reactions, and releasing carbon dioxide and hydrogen; introducing an oxygen carrier into the air reactor, introducing air, and carrying out oxidation reaction to release heat; the oxidized oxygen carrier is separated and then enters a calcination reactor to be heated to the temperature above the calcium carbonate decomposition temperature; calcium carbonate is introduced into the calcination reactor to be heated and decomposed into calcium oxide and carbon dioxide; the generated calcium oxide and oxygen carrier are separated and then enter a high-pressure bubbling bed, the calcium oxide adsorbs carbon dioxide to obtain hydrogen-rich synthesis gas, and generated calcium carbonate is returned to the calcination reactor; the oxygen carrier is reduced in the high-pressure bubbling bed and returns to the air reactor through the calcining reactor; carbon dioxide is introduced into the calcination reactor to serve as fluidizing gas. The preparation efficiency of the hydrogen-rich synthesis gas is improved, and the energy consumption is reduced.

Description

Technical Field

[0001] The present invention belongs to the field of adsorption-enhanced hydrogen production, and in particular relates to a system and method for preparing hydrogen-rich synthesis gas by adsorption-enhanced production based on a high-pressure bubbling bed. Background Art

[0002] Hydrogen energy, as a secondary clean energy source that releases energy through the chemical reaction of hydrogen and oxygen, not only has high combustion efficiency but also can achieve zero pollution. Energy conversion is generally carried out in the form of hydrogen fuel cells, which convert the chemical energy of hydrogen into electrical energy. However, hydrogen, as a secondary fuel, must be produced from primary energy sources such as fossil fuels, which will result in large amounts of carbon dioxide emissions. Currently, 96% of the world's hydrogen is produced through processes such as steam reforming, cracking or partial oxidation of fossil fuels. However, the hydrogen production process also produces a large amount of greenhouse gases, as well as pollutants such as nitrogen, sulfur, and particulate matter. Therefore, in order to meet the needs of the future of sustainable energy, it is necessary to develop a low-cost hydrogen production method with low carbon emissions.

[0003] In the existing technology, hydrogen synthesis gas can be prepared by adsorption enhancement. Adsorption-enhanced hydrogen production generally includes material drying, pyrolysis and gasification. Among them, gasification is to partially oxidize carbon-containing materials by high temperature in an atmosphere in the presence of a gasifying agent, thereby converting them into carbon monoxide, carbon dioxide, hydrogen, methane and water vapor, etc., while producing pollutants such as coke particles, tar and ash. The pollutants produced will affect the hydrogen production reaction and be toxic to the catalysts therein. The current adsorption-enhanced hydrogen production generally has the following problems: the output of tar and coke is high, and the yield of synthesis gas is low; the output of hydrogen in the synthesis gas is low, and the output of carbon dioxide is high; the heat transfer effect of the reactor is poor and the gasification reaction temperature is low, and the self-heating balance cannot be achieved between the reactors, the energy consumption is large, and the cracking of coke and tar is insufficient; the preparation process is complex and the cost is high. For example, Chinese patent publication number CN112624041A discloses a method for producing hydrogen from waste biomass carbon, in which waste materials such as wood chips and bamboo chips are isolated from air and subjected to thermal cracking. The gaseous and liquid products obtained by the cracking are utilized separately, and the solid product carbon obtained is used as a raw material for hydrogen production, or biomass carbon obtained by other methods is used as a raw material; the carbon undergoes a gasification reforming reaction with water vapor at 800-1500°C in a gasifier to convert it into H2, CO, CO2, and CH4. The high-temperature gas after the reaction is cooled by heat exchange and waste heat is utilized to reduce the temperature to less than 300°C, and a desulfurization conversion reaction is performed to convert the CO therein into H2 and CO2 by reacting with H2O. Finally, impurities such as carbon dioxide and methane are purified to obtain high-quality hydrogen; however, the output of tar and coke is high, pollution is serious, and the synthesis gas yield is low. Summary of the Invention

[0004] In view of the above-mentioned defects or deficiencies in the prior art, the embodiments of the present invention aim to provide a system and method for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed. By using calcium oxide as an adsorbent, carbon dioxide is effectively adsorbed and the water-gas shift reaction is promoted; a high-pressure bubbling bed, a calcination reactor, and an air reactor are used in combination, and an oxygen carrier is introduced to cause an oxidation reaction, releasing a large amount of heat to provide reaction enthalpy for driving endothermic calcination; a fluidized bed reactor is used to improve heat transfer and reduce energy consumption; and at the same time, high-pressure conditions are provided to fully crack tar and coke, thereby improving the overall efficiency and hydrogen content of preparing hydrogen-rich synthesis gas.

[0005] In order to achieve the above objectives, the embodiments of the present invention adopt the following technical solutions:

[0006] In a first aspect, an embodiment of the present invention provides a system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, the system comprising a high-pressure bubbling bed 1, a calcination reactor 2, a first cyclone separator 3 and a steam pump 6; wherein,

[0007] A steam inlet 10 is provided in the middle of the bottom of the bubbling bed body 101, and the steam inlet 10 is connected to the steam pump 6; the steam pump 6 is used to send high-temperature steam into the high-pressure bubbling bed body 101; a bubbling bed air distribution plate 13 is provided at the bottom of the bubbling bed body 101 and above the steam inlet 10; a raw material inlet 9 is provided at the lower part of one side of the bubbling bed body 101 and is higher than the air distribution plate 13, and a material outlet 12 is provided at the upper part of the other side; an adsorbent inlet 8 is provided on one side of the top of the bubbling bed body 101, and a hydrogen-rich synthesis gas outlet 11 is provided on the other side, the adsorbent inlet 8 extends to the interior of the bubbling bed body 101 to the upper side of the bubbling bed air distribution plate 13 and is lower than the raw material inlet 9; the adsorbent inlet 8 is connected to the material outlet of the first cyclone separator 3; the material outlet 12 is connected to the material inlet 15 of the calcination reactor 2 through a screw feeder;

[0008] A fluidizing gas inlet 17 is provided in the middle of the bottom of the calcination reactor body 201, and the fluidizing gas inlet 17 is connected to the gas outlet of the first cyclone separator 3; a calcination reactor air distribution plate 16 is provided at the bottom of the calcination reactor body 201 and above the fluidizing gas inlet 17; a material inlet 15 is provided at the lower part of one side of the calcination reactor body 201 and is higher than the air distribution plate 16, an adsorbent outlet 18 is provided at the upper part, and a calcium carbonate inlet 14 is provided in the middle of the top; the adsorbent outlet 18 is connected to the material inlet of the first cyclone separator 3.

[0009] As a preferred embodiment of the present invention, the calcination reactor 2 is a fluidized bed reactor; and a plurality of micropores are provided on the bubbling bed air distribution plate 13 and the calcination reactor air distribution plate 16 .

[0010] As a preferred embodiment of the present invention, the temperature in the high-pressure bubbling bed 1 is 1000-1500° C. and the pressure is 5-10 MPa; the temperature in the calcination reactor 2 is 1000-1500° C. and the pressure is 0.1 MPa.

[0011] As a preferred embodiment of the present invention, the raw materials used include biomass, municipal solid waste, coal, bio-oil and / or methane.

[0012] In a second aspect, an embodiment of the present invention further provides a method for preparing hydrogen-rich synthesis gas using the above-described system, characterized in that the method comprises:

[0013] Step S11: The crushed raw material is fed into the high-pressure bubbling bed body 101 through the raw material inlet 9 using a screw feeder. Simultaneously, high-temperature steam is introduced into the bottom of the high-pressure bubbling bed body 101 through the steam pump 6. The raw material in the high-pressure bubbling bed body 101 is mixed with the high-temperature steam and undergoes pyrolysis and gasification reactions, releasing carbon dioxide and hydrogen.

[0014] In step S13, the calcining reactor 2 is heated to a temperature above the decomposition temperature of calcium carbonate; the sieved calcium carbonate particles are introduced into the calcium carbonate inlet 14 at the top of the calcining reactor 2, and the calcium carbonate particles are decomposed into calcium oxide particles and carbon dioxide by the heat in the calcining reactor 2; the generated calcium oxide particles and carbon dioxide enter the first cyclone separator 3 through the adsorbent outlet 18 on one side of the upper portion of the calcining reactor 2 for gas-solid separation;

[0015] Step S15: gas-solid separation is performed in the first cyclone separator 3, and the separated calcium oxide particles are used as an adsorbent and enter the high-pressure bubbling bed 1 through the adsorbent inlet 8, and the separated carbon dioxide is introduced into the calcining reactor 2 as the fluidizing gas of the calcining reactor;

[0016] Step S17: In the high-pressure bubbling bed body 101, the calcium oxide adsorbent adsorbs the carbon dioxide generated by the reaction and simultaneously generates calcium carbonate particles; the calcium carbonate particles return to the calcination reactor through the material outlet 12, and step S13 is continued;

[0017] In step S19, the gas generated in the high-pressure bubbling bed body 101 becomes hydrogen-rich synthesis gas after carbon dioxide is adsorbed, and is discharged through the hydrogen-rich synthesis gas outlet 11 for back-end energy application.

[0018] In a third aspect, an embodiment of the present invention provides a system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, the system comprising a high-pressure bubbling bed 1, a calcination reactor 2, a first cyclone separator 3, a steam pump 6, an air reactor 4, a second cyclone separator 5 and an air pump 7; wherein,

[0019] A steam inlet 10 is provided in the middle of the bottom of the bubbling bed body 101, and the steam inlet 10 is connected to the steam pump 6; the steam pump 6 is used to send high-temperature steam into the high-pressure bubbling bed body 101; a bubbling bed air distribution plate 13 is provided at the bottom of the bubbling bed body 101 and above the steam inlet 10; a raw material inlet 9 is provided at the lower part of one side of the bubbling bed body 101 and is higher than the air distribution plate 13, and a material outlet 12 is provided at the upper part of the other side; an adsorbent inlet 8 is provided on one side of the top of the bubbling bed body 101, and a hydrogen-rich synthesis gas outlet 11 is provided on the other side, the adsorbent inlet 8 extends to the interior of the bubbling bed body 101 to the upper side of the bubbling bed air distribution plate 13 and is lower than the raw material inlet 9; the adsorbent inlet 8 is connected to the material outlet of the first cyclone separator 3; the material outlet 12 is connected to the material inlet 15 of the calcination reactor 2 through a screw feeder;

[0020] A fluidizing gas inlet 17 is provided in the middle of the bottom of the calcining reactor body 201, and the fluidizing gas inlet 17 is connected to the gas outlet of the first cyclone separator 3; a calcining reactor air distribution plate 16 is provided at the bottom of the calcining reactor body 201, above the fluidizing gas inlet 17; a material inlet 15 is provided at the lower part of one side of the calcining reactor body 201, which is higher than the calcining reactor air distribution plate 16, and an adsorbent outlet 18 is provided at the upper part; and a calcium carbonate inlet 14 is provided at the middle of the top; the adsorbent outlet 18 is connected to the material inlet of the first cyclone separator 3; a calcining reactor solid inlet 19 is provided at the lower part of the side opposite to the material inlet 15, which is higher than the calcining reactor air distribution plate 16, and a calcining reactor solid outlet 20 is provided at the upper part; the solid inlet 19 is connected to the material outlet of the second cyclone separator 5;

[0021] An air inlet 25 is provided in the middle of the bottom of the air reactor body 401, and the air inlet 25 is connected to the air pump 7; an air reactor air distribution plate 23 is provided at the bottom of the air reactor body 401 and above the air inlet 25; an air reactor solid inlet 24 is provided at the lower part of one side of the air reactor body 401 and is higher than the air distribution plate 23, and an oxygen carrier outlet 22 is provided at the upper part, and an oxygen carrier inlet 21 is provided at the lower part of the other side and is higher than the air reactor solid inlet 24; the air reactor solid inlet 24 is connected to the calcination reactor solid outlet 20 of the calcination reactor 2; the oxygen carrier outlet 22 is connected to the material inlet of the second cyclone separator 5.

[0022] As a preferred embodiment of the present invention, the calcination reactor 2 and the air reactor 4 are both fluidized bed reactors; and a plurality of micropores are provided on the bubbling bed air distribution plate 13, the calcination reactor air distribution plate 16 and the air reactor air distribution plate 23.

[0023] As a preferred embodiment of the present invention, the temperature in the high-pressure bubbling bed 1 is 1000-1500°C and the pressure is 5-10 MPa; the temperature in the calcination reactor 2 is 1000-1500°C and the pressure is 0.1 MPa; the temperature in the air reactor 4 is 600-1000°C and the pressure is 0.1 MPa.

[0024] In a fourth aspect, an embodiment of the present invention further provides a method for preparing hydrogen-rich synthesis gas using the above-described system, the method comprising:

[0025] In step S21, the crushed raw material is fed into the high-pressure bubbling bed body 101 through the raw material inlet 9 using a screw feeder. At the same time, high-temperature steam is introduced into the bottom of the high-pressure bubbling bed body 101 through the steam pump 6. The raw material in the high-pressure bubbling bed body 101 is mixed with the high-temperature steam and undergoes pyrolysis and gasification reactions, releasing carbon dioxide and hydrogen.

[0026] In step S22, a granular oxygen carrier is introduced into the air reactor 4 through the oxygen carrier inlet 21, and air is simultaneously introduced into the bottom through the air pump 7. The oxygen carrier and air in the air reactor 4 are mixed and an oxidation reaction occurs, while releasing heat. The oxidized oxygen carrier enters the second cyclone separator 6 through the oxygen carrier outlet 22 for gas-solid separation. The separated nitrogen is discharged into the air, and the separated oxygen carrier carrying heat enters the calcination reactor body 201 through the solid inlet 19 of the calcination reactor, providing a large amount of heat to the calcination reactor 2, heating the calcination reactor 2 to above the decomposition temperature of calcium carbonate.

[0027] In step S23, the sieved calcium carbonate particles are introduced into the calcium carbonate inlet 14 at the top of the calcination reactor 2. The calcium carbonate particles are decomposed into calcium oxide particles and carbon dioxide by heat in the calcination reactor 2. The generated calcium oxide particles, oxygen carrier particles, and carbon dioxide enter the first cyclone separator 3 through the adsorbent outlet 18 on one side of the upper portion of the calcination reactor 2 for gas-solid separation.

[0028] Step S25: Gas-solid separation is performed in the first cyclone separator 3. The separated calcium oxide particles and oxygen carrier particles enter the high-pressure bubbling bed 1 through the adsorbent inlet 8. The separated carbon dioxide is introduced into the calcining reactor 2 as the fluidizing gas of the calcining reactor; wherein the calcium oxide particles serve as the adsorbent.

[0029] In step S27, in the high-pressure bubbling bed body 101, the calcium oxide adsorbent adsorbs the carbon dioxide generated by the reaction to form calcium carbonate particles, which promotes the water-gas shift reaction, causing the reaction to proceed in the direction of generating hydrogen; the oxygen carrier particles undergo a reduction reaction in the high-pressure bubbling bed 1 and are reduced to oxygen carrier particles again; the calcium carbonate particles and the oxygen carrier particles return to the calcination reactor through the material outlet 12;

[0030] Step S28, in the calcination reactor, the returned calcium carbonate particles are separated from the reduced oxygen carrier particles; wherein the calcium carbonate particles are subjected to step S23; the reduced oxygen carrier particles are returned to the air reactor body 401 from the solid outlet 20 of the calcination reactor and are subjected to step S22;

[0031] In step S29 , the gas generated in the high-pressure bubbling bed body 101 becomes hydrogen-rich synthesis gas after carbon dioxide is adsorbed, and is discharged through the hydrogen-rich synthesis gas outlet 11 for back-end energy application.

[0032] As a preferred embodiment of the present invention, in step S21, when the raw material is crushed, the raw material is crushed to a particle size of less than 10 mm.

[0033] The technical solution provided by the embodiment of the present invention has the following beneficial effects:

[0034] The present invention provides a system and method for producing hydrogen-rich syngas by adsorption enhancement based on a high-pressure bubbling bed. The system has the following beneficial effects:

[0035] The present invention adopts a high-pressure bubbling bed, which can reduce the tar yield and the total amount of alkanes and oxygen-containing compounds. At the same time, high pressure can reduce the activation energy of carbon-containing materials, make tar easier to crack, and increase the synthesis gas content. The present invention adopts calcium oxide as an adsorbent to adsorb carbon dioxide, promote the water-gas shift reaction, and greatly improve the overall efficiency when preparing hydrogen-rich synthesis gas. At the same time, the purity of hydrogen in the hydrogen-rich synthesis gas is improved. The present invention adopts a calcination reactor and an air reactor, which are both fluidized beds, so that the heat transfer effect of the system as a whole is improved, which is conducive to the reaction and reduces energy consumption. Under high pressure conditions, the present invention can adopt a higher gasification temperature, so that the tar and coke produced by the reaction are cracked more fully, greatly improving the quality of hydrogen. The present invention adopts a high-pressure bubbling bed, a calcination reactor, and an air reactor in combination, and introduces an oxygen carrier to cause an oxidation reaction, releasing a large amount of heat to provide reaction enthalpy for driving endothermic calcination, achieving self-heating balance, reducing energy consumption, and achieving energy conservation and emission reduction.

[0036] Of course, it is not necessary to achieve all of the advantages described above simultaneously in order to implement any product or method of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0038] Figure 1 Schematic diagram of the system structure for preparing hydrogen-rich synthesis gas based on adsorption enhancement of a bubbling bed according to the first embodiment of the present invention;

[0039] Figure 2 2. It is a schematic diagram of the system structure for preparing hydrogen-rich synthesis gas based on adsorption enhancement of a bubbling bed according to the second embodiment of the present invention;

[0040] Figure 3 2 is a front cross-sectional schematic diagram of a high-pressure bubbling bed in an embodiment of the present invention;

[0041] Figure 4 1 is a schematic front cross-sectional view of a calcination reactor according to an embodiment of the present invention;

[0042] Figure 5 1 is a front cross-sectional schematic diagram of an air reactor in an embodiment of the present invention.

[0043] Description of reference numerals:

[0044] 1. High-pressure bubbling bed; 2. calcining reactor; 3. First cyclone separator; 4. Air reactor; 5. Second cyclone separator; 6. Steam pump; 7. Air pump; 8. Adsorbent inlet; 9. Raw material inlet; 11. Hydrogen-rich synthesis gas outlet; 12. Material outlet; 13. Bubbling bed air distribution plate; 14. Calcium carbonate inlet; 15. Material inlet; 16. Calcination reactor air distribution plate; 17. Fluidizing gas inlet; 18. Adsorbent outlet; 19. Calcination reactor solid inlet; 20. Calcination reactor solid outlet; 21. Including oxygen carrier inlet; 22. Oxygen carrier outlet; 23. Air reactor air distribution plate; 24. Air reactor solid inlet; 25. Air inlet. DETAILED DESCRIPTION

[0045] After discovering the above problems, the inventors of this application conducted a detailed study on the existing adsorption-enhanced hydrogen production method. The study found that in the three stages of adsorption-enhanced hydrogen production, the first step is the rapid drying stage. In this stage, the material mass loss is relatively small, mainly due to the volatilization of the water inside the material, which is generally completed within the temperature range of 20-150°C; the second step is rapid pyrolysis at 300-500°C, which produces biochar, condensable hydrocarbons, tar and gas; finally, when the temperature is higher than 500°C, the reaction enters the gasification reaction stage. A part of the carbon-containing material is not directly converted into synthesis gas, but is first converted into biochar and tar, and then further converted into synthesis gas through redox reaction. In the gasification stage of biomass, as the pressure increases, the tar yield can be reduced, the total amount of alkanes and oxygen-containing compounds also decreases, and the synthesis gas content increases. At the same time, high pressure reduces the activation energy of the carbon-containing material, making the tar easier to crack.

[0046] It should be noted that the defects existing in the solutions in the above-mentioned prior art are the results obtained by the inventors after practice and careful research. Therefore, the discovery process of the above-mentioned problems and the solutions proposed in the embodiments of the present invention below for the above-mentioned problems should all be the contributions made by the inventors to the present invention in the process of the invention.

[0047] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings herein can be arranged and designed in various different configurations. It should be noted that the embodiments of the present invention and the features in the embodiments can also be combined with each other in the absence of conflict.

[0048] It should be noted that similar reference numerals and letters represent similar items in the following figures. Therefore, once an item is defined in one figure, it does not need to be further defined or explained in subsequent figures. In the description of the present invention, the terms "first," "second," "third," "fourth," etc. are used only to distinguish the description and are not to be understood as indicating or implying relative importance.

[0049] Based on the above analysis of the adsorption-enhanced hydrogen production process, embodiments of the present invention provide a system and method for producing hydrogen-rich syngas by adsorption-enhanced gas production using a high-pressure bubbling bed, aiming to improve hydrogen purity and overall hydrogen production efficiency. The system comprises a high-pressure bubbling bed, a calcining reactor, and an air reactor. The high-pressure bubbling bed is equipped with an adsorbent inlet, a feedstock inlet, a steam inlet, a hydrogen-rich syngas outlet, a material outlet, and a bubbling bed air distribution plate. The calcining reactor includes a calcium carbonate inlet, a material inlet, a fluidized bed air distribution plate, a fluidizing gas inlet, and an adsorbent outlet. The air reactor includes an oxygen carrier inlet, an oxygen carrier outlet, an air reactor air distribution plate, an air reactor solids inlet, and an air inlet. The present invention uses calcium oxide as an adsorbent to effectively adsorb carbon dioxide and promote the water-gas shift reaction, thereby significantly improving the overall efficiency of producing hydrogen-rich syngas. In addition, the use of a fluidized bed reactor improves the heat transfer effect of the system, facilitates the smooth progress of the reaction, and reduces energy consumption. Under high pressure conditions, a higher gasification temperature can be used, resulting in more complete cracking of the tar and coke produced by the reaction, greatly improving the quality of the hydrogen. Three reactors are used in combination to form a complete process circulation system. By introducing oxygen carriers to carry out redox reactions, the heat released during the oxidation process of the oxygen carriers drives the endothermic calcination reaction in the system, so that the entire reaction system achieves self-thermal balance, reduces energy consumption, and effectively achieves energy conservation and emission reduction.

[0050] First embodiment

[0051] like Figure 1As shown, this embodiment provides a system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, comprising: a high-pressure bubbling bed 1, a calcining reactor 2, a first cyclone separator 3, and a steam pump 6. The system for preparing hydrogen-rich synthesis gas provided in this embodiment, comprising a high-pressure bubbling bed and a calcining reactor, is a dual-reactor system.

[0052] Among them, Figure 3 As shown, the high-pressure bubbling bed 1 includes a bubbling bed body 101, an adsorbent inlet 8, a raw material inlet 9, a steam inlet 10, a hydrogen-rich synthesis gas outlet 11, a material outlet 12, and a bubbling bed air distribution plate 13. The calcining reactor 2 includes a calcining reactor body 201, a calcium carbonate inlet 14, a material inlet 15, a calcining reactor air distribution plate 16, a fluidizing gas inlet 17, and an adsorbent outlet 18. The material outlet 12 is used to discharge calcium carbonate particles and send them to the calcining reactor 2.

[0053] A steam inlet 10 is provided in the middle of the bottom of the bubbling bed body 101, and the steam inlet 10 is connected to the steam pump 6; the steam pump 6 is used to send high-temperature steam into the high-pressure bubbling bed body 101; a bubbling bed air distribution plate 13 is provided at the bottom of the bubbling bed body 101 and above the steam inlet 10; a raw material inlet 9 is provided at the lower part of one side of the bubbling bed body 101 and is higher than the air distribution plate 13, and a material outlet 12 is provided at the upper part of the other side; an adsorbent inlet 8 is provided on one side of the top of the bubbling bed body 101, and a hydrogen-rich synthesis gas outlet 11 is provided on the other side, the adsorbent inlet 8 extends to the interior of the bubbling bed body 101 to the upper side of the bubbling bed air distribution plate 13 and is lower than the raw material inlet 9; the adsorbent inlet 8 is connected to the material outlet of the first cyclone separator 3; the material outlet 12 is connected to the material inlet 15 of the calcination reactor 2 through a screw feeder. The use of a high-pressure bubbling bed in the pyrolysis and gasification of raw materials can reduce the tar yield and the total amount of alkanes and oxygen-containing compounds. At the same time, high pressure can reduce the activation energy of carbon-containing materials, making tar easier to crack and increasing the synthesis gas content.

[0054] A fluidizing gas inlet 17 is provided in the middle of the bottom of the calcination reactor body 201, and the fluidizing gas inlet 17 is connected to the gas outlet of the first cyclone separator 3; a calcination reactor air distribution plate 16 is provided at the bottom of the calcination reactor body 201 and above the fluidizing gas inlet 17; a material inlet 15 is provided at the lower part of one side of the calcination reactor body 201 and is higher than the air distribution plate 16, an adsorbent outlet 18 is provided at the upper part, and a calcium carbonate inlet 14 is provided in the middle of the top; the adsorbent outlet 18 is connected to the material inlet of the first cyclone separator 3.

[0055] The calcination reactor 2 is a fluidized bed reactor, which improves the heat transfer effect of the entire system, facilitates the reaction, and reduces energy consumption.

[0056] The bubbling bed air distribution plate 13 and the calcining reactor air distribution plate 16 are both provided with a plurality of micropores.

[0057] The temperature in the high-pressure bubbling bed 1 is 1000-1500° C., and the pressure is 5-10 MPa; the temperature in the calcination reactor 2 is 1000-1500° C., and the pressure is 0.1 MPa.

[0058] The adsorbent used is for adsorbing carbon dioxide, the material used is calcium oxide, and the fluidizing gas involved is carbon dioxide.

[0059] The raw materials used include but are not limited to biomass, municipal solid waste, coal, bio-oil, methane, etc.

[0060] Based on the above-mentioned system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, an embodiment of the present invention further provides a method for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, the method comprising the following steps:

[0061] In step S11, the crushed raw materials are fed into the high-pressure bubbling bed body 101 through the raw material inlet 9 using a screw feeder. At the same time, high-temperature steam is introduced into the bottom of the high-pressure bubbling bed body 101 through the steam pump 6. The raw materials in the high-pressure bubbling bed body 101 are mixed with the high-temperature steam and undergo pyrolysis and gasification reactions, resulting in a water-gas shift reaction of CO+H2O=CO2+H2, releasing a large amount of carbon dioxide and hydrogen.

[0062] In this step, the raw material (such as biomass) reacts with steam in a high-pressure bubbling bed to generate synthesis gas, and the generated CO2 is immediately adsorbed by the circulating CaO; the adsorbed CO2 drives the water-gas shift reaction forward, and "hydrogen production + carbon capture" are simultaneously achieved during the reaction process, forming a reaction-adsorption synergistic mechanism.

[0063] In step S13, the calcining reactor 2 is heated to a temperature above the decomposition temperature of calcium carbonate; the sieved calcium carbonate particles are introduced into the calcium carbonate inlet 14 at the top of the calcining reactor 2, and the calcium carbonate particles are decomposed into calcium oxide particles and carbon dioxide by heat in the calcining reactor 2. The decomposition reaction of calcium carbonate is CaCO3=CaO+CO2; the generated calcium oxide particles and carbon dioxide enter the first cyclone separator 3 from the adsorbent outlet 18 on one side of the upper part of the calcining reactor 2 for gas-solid separation.

[0064] In this step, CaCO3 is decomposed at high temperature in a calcination reactor to generate CaO and CO2. CO2 is introduced into the lower part of the calcination bed as a fluidizing gas. At the same time, the generated CaO particles are separated into gas and solid and then returned to the bubbling bed, thereby integrating adsorbent regeneration and carrier gas utilization, saving energy and avoiding material waste.

[0065] Step S15: gas-solid separation is performed in the first cyclone separator 3, and the separated calcium oxide particles are used as an adsorbent and enter the high-pressure bubbling bed 1 through the adsorbent inlet 8, and the separated carbon dioxide is introduced into the calcining reactor 2 as the fluidizing gas of the calcining reactor;

[0066] In step S17, in the high-pressure bubbling bed body 101, the calcium oxide adsorbent adsorbs the carbon dioxide generated by the reaction to form calcium carbonate particles, which promotes the water-gas shift reaction, causing the reaction to proceed toward hydrogen generation; the calcium carbonate particles return to the calcination reactor through the material outlet 12, and step S13 is continued;

[0067] In step S19, the gas generated in the high-pressure bubbling bed body 101 becomes hydrogen-rich synthesis gas after carbon dioxide is adsorbed and discharged through the hydrogen-rich synthesis gas outlet 11. After being discharged, the hydrogen-rich synthesis gas is dried, dust-removed, and filtered before being used for back-end energy applications.

[0068] Second embodiment

[0069] like Figure 2 As shown, this embodiment also provides a system for preparing hydrogen-rich syngas by adsorption enhancement based on a high-pressure bubbling bed. This system is similar to the system described in the first embodiment, except that, based on the system described in the first embodiment, the system of this embodiment further includes: an air reactor 4, a second cyclone separator 5, and an air pump 7. The system for preparing hydrogen-rich syngas provided in this embodiment includes a high-pressure bubbling bed, a calcination reactor, and an air reactor, forming a three-reactor system. Compared to the first embodiment, the air reactor is added, further optimizing the structure.

[0070] Among them, Figure 3 As shown, the high-pressure bubbling bed 1 includes a bubbling bed body 101, an adsorbent inlet 8, a raw material inlet 9, a steam inlet 10, a hydrogen-rich synthesis gas outlet 11, a material outlet 12 and a bubbling bed air distribution plate 13; Figure 4 As shown, the calcination reactor 2 includes a calcination reactor body 201, a calcium carbonate inlet 14, a material inlet 15, a calcination reactor air distribution plate 16, a fluidizing gas inlet 17, an adsorbent outlet 18, a calcination reactor solid inlet 19 and a calcination reactor solid outlet 20; Figure 5 As shown, the air reactor 4 includes an air reactor body 401 , an oxygen carrier inlet 21 , an oxygen carrier outlet 22 , an air reactor air distribution plate 23 , an air reactor solid inlet 24 , and an air inlet 25 .

[0071] The structure and configuration of the high-pressure bubbling bed 2 in this embodiment are exactly the same as those in the first embodiment, and will not be described again here.

[0072] The calcining reactor 2 also includes a calcining reactor solids inlet 19 and a calcining reactor solids outlet 20. On the side opposite the material inlet 15, the calcining reactor solids inlet 19 is provided below and above the air distribution plate 16, and the calcining reactor solids outlet 20 is provided above; the solids inlet 19 is connected to the material outlet of the second cyclone separator 5.

[0073] An air inlet 25 is provided in the middle of the bottom of the air reactor body 401, and the air inlet 25 is connected to the air pump 7; an air reactor air distribution plate 23 is provided at the bottom of the air reactor body 401 and above the air inlet 25; an air reactor solid inlet 24 is provided at the lower part of one side of the air reactor body 401 and is higher than the air distribution plate 23, and an oxygen carrier outlet 22 is provided at the upper part, and an oxygen carrier inlet 21 is provided at the lower part of the other side and is higher than the air reactor solid inlet 24; the air reactor solid inlet 24 is connected to the calcination reactor solid outlet 20 of the calcination reactor 2; the oxygen carrier outlet 22 is connected to the material inlet of the second cyclone separator 5.

[0074] The calcination reactor 2 and the air reactor 4 are both fluidized bed reactors.

[0075] The bubbling bed air distribution plate 13, the calcining reactor air distribution plate 16 and the air reactor air distribution plate 23 are all provided with a plurality of micropores.

[0076] The temperature in the high-pressure bubbling bed 1 is 1000-1500°C and the pressure is 5-10 MPa; the temperature in the calcination reactor 2 is 1000-1500°C and the pressure is 0.1 MPa; the temperature in the air reactor 4 is 600-1000°C and the pressure is 0.1 MPa.

[0077] The adsorbent used is used to adsorb carbon dioxide, the material used is calcium oxide, and the fluidizing gas involved is carbon dioxide; the oxygen carrier is an iron-based oxygen carrier or a nickel-based oxygen carrier.

[0078] The raw materials used include but are not limited to biomass, municipal solid waste, coal, bio-oil, methane, etc.

[0079] Based on the above-mentioned system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, this embodiment further provides a method for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, the method comprising the following steps:

[0080] In step S21, the crushed raw material is fed into the high-pressure bubbling bed body 101 through the raw material inlet 9 using a screw feeder. At the same time, high-temperature steam is introduced into the bottom of the high-pressure bubbling bed body 101 through the steam pump 6. The raw material in the high-pressure bubbling bed body 101 is mixed with the high-temperature steam and undergoes pyrolysis and gasification reactions, resulting in a water-gas shift reaction of CO + H2O = CO2 + H2, releasing a large amount of carbon dioxide and hydrogen.

[0081] In step S22, a granular oxygen carrier is introduced into the air reactor 4 through the oxygen carrier inlet 21, and air is introduced into the bottom through the air pump 7. The oxygen carrier and air in the air reactor 4 are mixed and an oxidation reaction occurs, while releasing heat. Taking an iron-based oxygen carrier as an example, the reaction equation is 4FeO+O2→Fe2O3; the oxidized oxygen carrier enters the second cyclone separator 6 through the oxygen carrier outlet 22 for gas-solid separation; the separated nitrogen is discharged into the air, and the separated oxygen carrier carrying heat enters the calcination reactor body 201 through the calcination reactor solid inlet 19, and provides heat to the calcination reactor 2, heating the calcination reactor 2 to above the decomposition temperature of calcium carbonate;

[0082] In step S23, the screened calcium carbonate particles are introduced into the calcium carbonate inlet 14 at the top of the calcination reactor 2. The calcium carbonate particles are decomposed into calcium oxide particles and carbon dioxide by heat in the calcination reactor 2. The decomposition reaction of calcium carbonate is CaCO3=CaO+CO2. The generated calcium oxide particles, oxygen carrier particles and carbon dioxide enter the first cyclone separator 3 through the adsorbent outlet 18 on one side of the upper portion of the calcination reactor 2 for gas-solid separation.

[0083] Step S25: Gas-solid separation is performed in the first cyclone separator 3. The separated calcium oxide particles and oxygen carrier particles enter the high-pressure bubbling bed 1 through the adsorbent inlet 8. The separated carbon dioxide is introduced into the calcining reactor 2 as the fluidizing gas of the calcining reactor; wherein the calcium oxide particles serve as the adsorbent.

[0084] In step S27, in the high-pressure bubbling bed body 101, the calcium oxide adsorbent absorbs the carbon dioxide generated by the reaction to form calcium carbonate particles, which promotes the water-gas shift reaction, causing the reaction to proceed toward hydrogen production. The oxygen carrier particles undergo a reduction reaction in the high-pressure bubbling bed 1, returning to oxygen carrier particles. The oxygen carrier redox reaction equation is 3Fe + [2O]2 = Fe3O4. The calcium carbonate particles and oxygen carrier particles return to the calcination reactor through the material outlet 12.

[0085] Step S28, in the calcination reactor, the returned calcium carbonate particles are separated from the reduced oxygen carrier particles; wherein the calcium carbonate particles are subjected to step S23; the reduced oxygen carrier particles are returned to the air reactor body 401 from the solid outlet 20 of the calcination reactor and are subjected to step S22;

[0086] In step S29, the gas generated in the high-pressure bubbling bed body 101 becomes hydrogen-rich synthesis gas after carbon dioxide is adsorbed and discharged through the hydrogen-rich synthesis gas outlet 11. After being discharged, the hydrogen-rich synthesis gas is dried, dust-removed, and filtered before being used for back-end energy applications.

[0087] Preferably, in step S11 and step S21, when the raw material is crushed, the raw material is crushed to a particle size of less than 10 mm.

[0088] In the three-reactor system of this embodiment, the reaction in the air reactor releases a large amount of heat, providing heat to the system. Therefore, the calcination reactor, which decomposes calcium carbonate, does not require additional heat to be heated to the calcium carbonate decomposition temperature. Heat from the air reactor is then directed to the calcination reactor. An oxygen carrier is introduced through the air reactor to carry out a redox reaction. The heat released during the oxidation of the oxygen carrier drives the endothermic calcination reaction within the system, achieving self-heating equilibrium for the entire reaction system, reducing energy consumption and effectively achieving energy conservation and emission reduction.

[0089] It can be seen from the above technical solutions that the system and method for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed provided in the embodiment of the present invention adopts calcium oxide as an adsorbent to effectively adsorb carbon dioxide and promote the water-gas shift reaction, thereby significantly improving the overall efficiency of preparing hydrogen-rich synthesis gas; the use of a fluidized bed reactor improves the heat transfer effect of the system, is conducive to the smooth progress of the reaction, and reduces energy consumption; under high-pressure conditions, a higher gasification temperature can be used to make the tar and coke produced by the reaction more fully cracked, greatly improving the quality of hydrogen, not only achieving hydrogen enrichment, but also embedding CO2 capture in the process flow design, which is highly integrated; at the same time, three reactors are used in combination to form a complete process cycle system, and by introducing an oxygen carrier for redox reaction, the heat released during the oxidation process of the oxygen carrier drives the endothermic calcination reaction in the system, so that the entire reaction system achieves self-thermal balance, reduces energy consumption, and effectively achieves energy conservation and emission reduction.

[0090] The above description is only a preferred embodiment of the present invention and an explanation of the technical principles used. It is not intended to limit the scope of the invention to be protected, but merely represents a preferred embodiment of the present invention. Those skilled in the art should understand that the scope of the invention involved in the present invention is not limited to the technical solutions formed by a specific combination of the above-mentioned technical features, but should also cover other technical solutions formed by any combination of the above-mentioned technical features or their equivalent features without departing from the inventive concept. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative work shall fall within the scope of protection of the present invention.

Claims

1. A system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, characterized in that: The system includes a high-pressure bubbling bed, a calcining reactor, a first cyclone separator and a steam pump; wherein, A steam inlet is provided in the middle of the bottom of the bubbling bed body, and the steam inlet is connected to a steam pump; the steam pump is used to send high-temperature steam into the high-pressure bubbling bed body; a bubbling bed air distribution plate is provided at the bottom of the bubbling bed body and above the steam inlet; a raw material inlet is provided at the lower part of one side of the bubbling bed body and is higher than the air distribution plate, and a material outlet is provided at the upper part of the other side; an adsorbent inlet is provided on one side of the top of the bubbling bed body, and a hydrogen-rich synthesis gas outlet is provided on the other side, the adsorbent inlet extends to the interior of the bubbling bed body to the upper side of the bubbling bed air distribution plate and is lower than the raw material inlet; the adsorbent inlet is connected to the material outlet of the first cyclone separator; the material outlet is connected to the material inlet of the calcination reactor through a screw feeder; A fluidizing gas inlet is provided in the middle of the bottom of the calcination reactor body, and the fluidizing gas inlet is connected to the gas outlet of the first cyclone separator; a calcination reactor air distribution plate is provided at the bottom of the calcination reactor body and above the fluidizing gas inlet; a material inlet is provided at the lower part of one side of the calcination reactor body and is higher than the air distribution plate, an adsorbent outlet is provided at the upper part, and a calcium carbonate inlet is provided in the middle of the top; the adsorbent outlet is connected to the material inlet of the first cyclone separator.

2. The system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed according to claim 1, characterized in that: The calcination reactor is a fluidized bed reactor; and a plurality of micropores are provided on the bubbling bed air distribution plate and the calcination reactor air distribution plate.

3. The system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed according to claim 1, characterized in that: The temperature in the high-pressure bubbling bed is 1000-1500° C. and the pressure is 5-10 MPa; the temperature in the calcination reactor is 1000-1500° C. and the pressure is 0.1 MPa.

4. The system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed according to claim 1, characterized in that: Feedstocks used include biomass, municipal solid waste, coal, bio-oil and / or methane.

5. A method for preparing hydrogen-rich synthesis gas using the system according to any one of claims 1 to 4, characterized in that: The method comprises: Step S11: The crushed raw materials are fed into the high-pressure bubbling bed body through the raw material inlet using a screw feeder. Simultaneously, high-temperature steam is introduced into the bottom of the high-pressure bubbling bed body through a steam pump. The raw materials in the high-pressure bubbling bed body are mixed with the high-temperature steam and undergo pyrolysis and gasification reactions, releasing carbon dioxide and hydrogen. Step S13: heating the calcining reactor to a temperature above the decomposition temperature of calcium carbonate; introducing the screened calcium carbonate particles into the calcium carbonate inlet at the top of the calcining reactor; the calcium carbonate particles are decomposed into calcium oxide particles and carbon dioxide by the heat in the calcining reactor; the generated calcium oxide particles and carbon dioxide enter the first cyclone separator from the adsorbent outlet on one side of the upper portion of the calcining reactor for gas-solid separation; Step S15: gas-solid separation is performed in the first cyclone separator, the separated calcium oxide particles are used as an adsorbent and enter the high-pressure bubbling bed through the adsorbent inlet, and the separated carbon dioxide is introduced into the calcining reactor as the fluidizing gas of the calcining reactor; Step S17: In the high-pressure bubbling bed, the calcium oxide adsorbent adsorbs the carbon dioxide generated by the reaction and simultaneously generates calcium carbonate particles; the calcium carbonate particles return to the calcination reactor through the material outlet, and step S13 is continued; In step S19, the gas generated in the high-pressure bubbling bed body becomes hydrogen-rich synthesis gas after carbon dioxide is adsorbed, and is discharged through the hydrogen-rich synthesis gas outlet for back-end energy applications.

6. A system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed, characterized in that: The system includes a high-pressure bubbling bed, a calcining reactor, a first cyclone separator, a steam pump, an air reactor, a second cyclone separator and an air pump; wherein, A steam inlet is provided in the middle of the bottom of the bubbling bed body, and the steam inlet is connected to a steam pump; the steam pump is used to send high-temperature steam into the high-pressure bubbling bed body; a bubbling bed air distribution plate is provided at the bottom of the bubbling bed body and above the steam inlet; a raw material inlet is provided at the lower part of one side of the bubbling bed body and is higher than the air distribution plate, and a material outlet is provided at the upper part of the other side; an adsorbent inlet is provided on one side of the top of the bubbling bed body, and a hydrogen-rich synthesis gas outlet is provided on the other side, the adsorbent inlet extends to the interior of the bubbling bed body to the upper side of the bubbling bed air distribution plate and is lower than the raw material inlet; the adsorbent inlet is connected to the material outlet of the first cyclone separator; the material outlet is connected to the material inlet of the calcination reactor through a screw feeder; A fluidizing gas inlet is provided in the middle of the bottom of the calcining reactor body, and the fluidizing gas inlet is connected to the gas outlet of the first cyclone separator; an air distribution plate for the calcining reactor is provided at the bottom of the calcining reactor body, above the fluidizing gas inlet; a material inlet is provided at the lower part of one side of the calcining reactor body and is higher than the air distribution plate, an adsorbent outlet is provided at the upper part, and a calcium carbonate inlet is provided at the middle of the top; the adsorbent outlet is connected to the material inlet of the first cyclone separator; a solid inlet for the calcining reactor is provided at the lower part on the side opposite to the material inlet, and is higher than the air distribution plate, and a solid outlet for the calcining reactor is provided at the upper part; the solid inlet is connected to the material outlet of the second cyclone separator; An air inlet is provided in the middle of the bottom of the air reactor body, and the air inlet is connected to an air pump; an air reactor air distribution plate is provided at the bottom of the air reactor body and above the air inlet; an air reactor solid inlet is provided at the lower part of one side of the air reactor body and is higher than the air distribution plate, and an oxygen carrier outlet is provided at the upper part, and an oxygen carrier inlet is provided at the lower part of the other side and is higher than the air reactor solid inlet; the air reactor solid inlet is connected to the calcination reactor solid outlet of the calcination reactor; the oxygen carrier outlet is connected to the material inlet of the second cyclone separator.

7. The system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed according to claim 6, characterized in that: The calcination reactor and the air reactor are both fluidized bed reactors; and a plurality of micropores are provided on the bubbling bed air distribution plate, the calcination reactor air distribution plate and the air reactor air distribution plate.

8. The system for preparing hydrogen-rich synthesis gas by adsorption enhancement based on a high-pressure bubbling bed according to claim 6, characterized in that: The temperature in the high-pressure bubbling bed is 1000-1500°C and the pressure is 5-10Mpa; the temperature in the calcination reactor is 1000-1500°C and the pressure is 0.1Mpa; the temperature in the air reactor is 600-1000°C and the pressure is 0.1Mpa.

9. A method for preparing hydrogen-rich synthesis gas using the system according to any one of claims 6 to 8, characterized in that: The method comprises: Step S21: The crushed raw material is fed into the high-pressure bubbling bed body through the raw material inlet using a screw feeder. Simultaneously, high-temperature steam is introduced into the bottom of the high-pressure bubbling bed body through a steam pump. The raw material in the high-pressure bubbling bed body is mixed with the high-temperature steam and undergoes pyrolysis and gasification reactions, releasing carbon dioxide and hydrogen. In step S22, a granular oxygen carrier is introduced into the air reactor through the oxygen carrier inlet, and air is simultaneously introduced into the bottom through an air pump. In the air reactor, the oxygen carrier and air are mixed and an oxidation reaction occurs, while releasing heat. The oxidized oxygen carrier enters the second cyclone separator through the oxygen carrier outlet for gas-solid separation. The separated nitrogen is discharged into the air, and the separated oxygen carrier carrying heat enters the calcination reactor body through the solid inlet of the calcination reactor, providing heat to the calcination reactor, and heating the calcination reactor to above the decomposition temperature of calcium carbonate. In step S23, the screened calcium carbonate particles are introduced into the calcium carbonate inlet at the top of the calcination reactor. The calcium carbonate particles are decomposed into calcium oxide particles and carbon dioxide by heat in the calcination reactor. The generated calcium oxide particles, oxygen carrier particles, and carbon dioxide enter the first cyclone separator from the adsorbent outlet on one side of the upper portion of the calcination reactor for gas-solid separation. Step S25: gas-solid separation is performed in the first cyclone separator, and the separated calcium oxide particles and oxygen carrier particles enter the high-pressure bubbling bed through the adsorbent inlet, and the separated carbon dioxide is introduced into the calcination reactor as the fluidizing gas of the calcination reactor; wherein the calcium oxide particles serve as the adsorbent; In step S27, in the high-pressure bubbling bed body, the calcium oxide adsorbent adsorbs the carbon dioxide generated by the reaction to form calcium carbonate particles, which promotes the water-gas shift reaction, causing the reaction to proceed in the direction of generating hydrogen; the oxygen carrier particles undergo a reduction reaction in the high-pressure bubbling bed and are reduced to oxygen carrier particles again; the calcium carbonate particles and the oxygen carrier particles return to the calcination reactor through the material outlet; Step S28, in the calcination reactor, the returned calcium carbonate particles are separated from the reduced oxygen carrier particles; wherein the calcium carbonate particles are subjected to step S23; the reduced oxygen carrier particles are returned to the air reactor body from the solid outlet of the calcination reactor and are subjected to step S22; In step S29, the gas generated in the high-pressure bubbling bed body becomes hydrogen-rich synthesis gas after carbon dioxide is adsorbed, and is discharged through the hydrogen-rich synthesis gas outlet for back-end energy applications.

10. The method according to claim 9, characterized in that In step S21, when the raw material is crushed, the raw material is crushed to a particle size of less than 10 mm.

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