CN113122336B - Method and system for preparing hydrogen by thermal conversion of biomass - Google Patents

Method and system for preparing hydrogen by thermal conversion of biomass Download PDF

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CN113122336B
CN113122336B CN201911417736.8A CN201911417736A CN113122336B CN 113122336 B CN113122336 B CN 113122336B CN 201911417736 A CN201911417736 A CN 201911417736A CN 113122336 B CN113122336 B CN 113122336B
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calcium
gas
regeneration
hydrogen
thermal conversion
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CN113122336A (en
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王鑫
张彪
赵丽萍
吴斯侃
王博
宋永一
张长安
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/0014—Physical processing by adsorption in solids
    • C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves

Abstract

The invention discloses a method and a system for preparing hydrogen by biomass thermal conversion, wherein biomass raw materials enter a microwave pyrolysis reactor for reaction, and materials obtained after the reaction enter a gasification reactor for gasification reaction to obtain crude synthesis gas and solid-phase residues; the obtained crude synthesis gas contacts with a calcium-based adsorbent to react to obtain high-purity hydrogen and carbonated calcium-based adsorbent; and regenerating the carbonated calcium-based adsorbent and the solid-phase residue to obtain a regenerated calcium-based adsorbent, and returning the regenerated calcium-based adsorbent to the gasification reactor for recycling. The method can obtain high-purity hydrogen, simultaneously realize the maximization of hydrogen yield and the simplification of the process flow, the obtained hydrogen can meet the requirement of industrial hydrogen, solve the problems of poor hydrogen quality, complex process flow, high energy consumption and the like in the process for preparing the hydrogen by taking biomass as a raw material in the prior art, obviously improve the process economy and have good application prospect.

Description

Method and system for preparing hydrogen by thermal conversion of biomass
Technical Field
The invention belongs to the technical field of biomass utilization, and relates to a method and a system for preparing hydrogen by biomass thermal conversion.
Background
Hydrogen is an important clean energy source and is recognized as the most promising energy carrier to partially replace traditional fossil fuels. The global hydrogen market size in 2017 was about $ 1292.5 billion, and international hydrogen energy council projected that the annual demand for hydrogen might increase by 10-fold by 2050. At present, 96% of hydrogen comes from natural gas and coal, which aggravates energy crisis and environmental pollution, and the overall cost for preparing hydrogen by using biomass is about 25 yuan/kg, which is higher than 13-18 yuan/kg of hydrogen preparation by using methane, but lower than 40 yuan/kg of hydrogen preparation by using electrolyzed water, so that the method has strong market competitiveness. At present, the foreign biomass hydrogen production technology enters a commercialization stage from pilot plant, and the biomass with the hydrogen concentration of 40-60% and the yield of 60-80g/kg can be obtained on the mature serial bubbling fluidized bed and circulating fluidized bed technology, and compared with the prior art, the domestic research in the field is still in the stage from pilot plant to pilot plant. In specific practical application, the common problems of low hydrogen production concentration, difficult removal of entrained tar, complex process and the like still exist.
Aiming at the problem of low hydrogen production concentration, CN107142128A provides a biomass furnace internal calcium-spraying circulating fluidized bed combustion gasification H2The hydrogen producing process with in-situ adsorption and reinforced water-steam conversion includes gasifying biomass in the furnace under the action of air and water vapor, spraying calcium lime for catalytic synergism, and feeding the produced synthetic gas into the moving bed reactor for H2Hydrogen is produced by in-situ adsorption enhanced water-vapor shift reaction, the produced hydrogen is adsorbed and stored in a hydrogen absorbing material, and the hydrogen absorbing material is separated and regenerated to release to obtain a high-purity hydrogen product. However, the method for producing hydrogen by adopting the fluidized bed has the problem that gas carries tar, the subsequent hydrogen-rich separation process is influenced, and H2The hydrogen production process by the in-situ adsorption enhanced water-vapor shift reaction is carried out at 250-350 ℃, the water-vapor conversion rate is extremely low, the hydrogen concentration in the product gas only accounts for about 5%, and the water-vapor consumption is large; in addition, the whole process involves frequent temperature-changing heat exchange operation, and the process is complex and has high energy loss.
In order to further solve the problem that the tar is difficult to remove and purify in the hydrogen-carrying process, CN104129754A discloses a device for coupling a pyrolysis gasification device and a rotary chemical-link membrane hydrogen production device, wherein a rotary oxygen carrier rotor with a honeycomb pore channel structure is used for replacing the traditional bed material circulation, on one hand, the catalytic cracking effect of the oxygen carrier on pyrolysis gas and tar at high temperature is utilized to reduce the oxygen carrier and reduce the tar content in the product, on the other hand, the rotary oxygen carrier rotor with the honeycomb pore channel structure realizes the oxidation regeneration of the oxygen carrier by rotating around a central axis to generate hydrogen-rich gas, and the hydrogen prepared by the method has high purity and does not contain tar. However, the invention neglects the fine particles carried in the gas product, and the fine particles not only block the pores of the chemical chain membrane, but also react with the oxygen carrier, so that the chemical chain reaction activity is obviously reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method and a system for preparing hydrogen by biomass thermal conversion, which can realize the maximization of hydrogen yield and the simplification of the process flow while obtaining high-purity hydrogen, the obtained hydrogen can meet the requirement of industrial hydrogen, the problems of poor hydrogen quality, complex process flow, high energy consumption and the like in the process for preparing hydrogen by taking biomass as a raw material in the prior art are solved, the process economy is obviously improved, and the method and the system have good application prospects.
The invention provides a method for preparing hydrogen by biomass thermal conversion, which comprises the following steps:
(1) the biomass raw material enters a microwave pyrolysis reactor for reaction to obtain a hydrogen-containing pyrolysis volatile component and a pyrolysis solid-phase material;
(2) allowing the hydrogen-containing pyrolysis volatile component and the pyrolysis solid-phase material obtained in the step (1) to enter a gasification reactor to contact with steam for gasification reaction to obtain crude synthesis gas and solid-phase residue;
(3) contacting the crude synthesis gas obtained in the step (2) with an activated calcium-based adsorbent to perform cracking, reforming, water-gas shift and carbonation reactions, and performing gas-solid separation to obtain high-purity hydrogen and carbonated calcium-based adsorbent;
(4) and (3) feeding the carbonated calcium-based adsorbent in the step (3) and the solid-phase residue in the step (2) into an adsorbent regenerator for regeneration treatment, and returning the obtained regenerated calcium-based adsorbent to the gasification reactor for recycling.
In the method for preparing hydrogen by thermal conversion of biomass, the calcium-based adsorbent in the step (3) comprises an active component A, an auxiliary agent B and a component C; based on the total weight of the calcium-based adsorbent, the content of the active component A is 50-80%, the content of the auxiliary agent B is 5-10%, and the content of the component C is 10-40%; the active component A is one or more of calcium oxide, calcium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxalate, calcium acetate, dolomite and shell, and preferably calcium carbonate; the auxiliary agent B is one or more of calcium sulfate, calcium sulfite, calcium hydrogen sulfate, calcium hydrogen sulfite and calcium sulfide, and preferably calcium sulfate; the component C comprises CA and CB, wherein the CA is selected from mullite, alumina, ZSM molecular sieve (the ZSM molecular sieve can be one or more of ZSM-5, ZSM-8, ZSM-11, ZSM-21, ZSM-35 and ZSM-38 molecular sieves), beta-molecular sieve, titanium silicalite TS-1, zirconium silicalite molecular sieve, cordierite and silicon carbide; the CB is selected from one or more of tricalcium silicate, dicalcium silicate, monocalcium aluminate, tricalcium aluminate, monocalcium dialuminate and heptaaluminic acid, tetracalcium aluminoferrite, barium zirconium aluminate, calcium fluoroaluminate, gehlenite and ettringite, preferably silicon carbide and monocalcium dialuminate, and the mass ratio of the silicon carbide to the monocalcium dialuminate is 1: 0.1-1.
In the above method for producing hydrogen by thermal conversion of biomass, the method for preparing the calcium-based adsorbent in step (3) is as follows: mixing the active component A, the auxiliary agent B, the component C and the pore-forming agent, grinding, adding a proper amount of water, stirring to form a uniform wet material, and carrying out forming, curing and high-temperature treatment to obtain the calcium-based adsorbent.
In the preparation method of the calcium-based adsorbent, the pore-forming agent is a carbonized material selected from carbonized materials of organic substances such as biomass and wastes thereof, industrial organic wastes, and town organic wastes, including but not limited to one or more of biocoke, plastic product coke, rubber product coke, kitchen waste coke, and fiber product coke, and preferably biocoke.
In the preparation method of the calcium-based adsorbent, the molar ratio of carbon in the pore-forming agent to calcium in the auxiliary agent B is 2-10: 1.
in the preparation method of the calcium-based adsorbent, the forming comprises but is not limited to any one of an extrusion forming method, a rotation forming method and an extrusion spheronization method, preferably the extrusion spheronization method is adopted, wherein the extrusion spheronization method has the extrusion temperature of 15-60 ℃, the pressure of 0.5-5 MPa, the extrusion time of 5-30 minutes and the rotation speed of a spheronization disc of 150-500 revolutions per minute, and spherical particles with the diameter of 0.5-5 mm can be obtained.
In the preparation method of the calcium-based adsorbent, the curing is performed for 1-10 days at a temperature of 15-60 ℃ and a humidity of not less than 90%.
In the preparation method of the calcium-based adsorbent, the high-temperature treatment comprises anaerobic reduction treatment and aerobic roasting treatment, wherein the temperature of the anaerobic reduction treatment is 850-1000 ℃, the treatment time is 0.5-5 h, the temperature of the aerobic roasting treatment is 900-1100 ℃, and the treatment time is 0.5-5 h.
In the method for preparing hydrogen by thermal conversion of biomass, the biomass raw material in the step (1) can be derived from any substance containing lignocellulose, such as corn straws, rice husks, wheat straws, wood blocks, leaves or branches, and the granularity of the raw material is 1-10 mm.
In the above method for producing hydrogen by thermal conversion of biomass, the reaction conditions in the microwave pyrolysis reactor in step (1) are as follows: the pyrolysis temperature is 400-600 ℃, the pyrolysis time is 10-60 minutes, and the microwave power density is 0.5 multiplied by 105～5×105W/m3. Through the working procedure, the pyrolysis product of the biomass is prepared by pyrolyzing volatile components and pyrolyzing solid-phase materials, wherein the pyrolysis solid-phase materials are biological semicoke, the pyrolysis volatile components account for 65-85 wt%, and the biological semicoke accounts for 15-35 wt%; the content of non-condensable gas in the pyrolysis volatile components reaches more than 80 percent.
In the above method for producing hydrogen by thermal conversion of biomass, the reaction conditions in the gasification reactor in steps (2) and (3) are as follows: the gasification temperature is 600-800 ℃, the reaction time is 10-30 minutes, and the water vapor flow is 0.2-2 m3/h。
In the method for preparing hydrogen by thermal conversion of biomass, the gasification reactor in the step (2) is heated by microwave with the microwave power density of 0.1 multiplied by 105～1×105W/m3The method mainly comprises the steps of cracking tar in pyrolysis volatile components by using the biological semicoke, gasifying water vapor of the biological semicoke, carrying out water vapor shift reaction and the like to obtain the crude synthesis gas with higher carbon-hydrogen ratio.
In the above method for producing hydrogen by thermal conversion of biomass, in step (3), the gasification reactor maintains the gasification temperature by using the self-heat of the high-temperature calcium-based adsorbent, and mainly generates the calcium-based adsorbent to enhance the hydrogen production reaction of the crude synthesis gas, so as to obtain a hydrogen product with a purity close to 95%, wherein the mass ratio of the biomass to the calcium-based adsorbent is 1:1 to 10.
In the above method for producing hydrogen by thermal conversion of biomass, the regeneration in step (4) includes a first stage pre-regeneration treatment and a second stage regeneration treatment, the first stage pre-regeneration treatment is a treatment in the presence of a pre-regeneration gas, and the treatment conditions are as follows: the reaction temperature is 850-1000 ℃, the reaction time is 2-10 seconds, and the flow of pre-regeneration gas is 2-5 m3H; the pre-regeneration gas is one of air and flue gas mixed gas, air and nitrogen mixed gas, air, nitrogen and flue gas mixed gas, wherein the flue gas can be flue gas generated in the regeneration process of the calcium-based adsorbent; the second stage regeneration treatment is carried out in an air atmosphere, and the treatment conditions are as follows: the reaction temperature is 900-1100 ℃, the reaction time is 1-5 seconds, and the air flow is 1-5 m3/h。
In the above method for producing hydrogen by thermal conversion of biomass, the gas-solid separation is based on gravity settling, centrifugal separation, filter screen separation, electrostatic separation, adsorption separation and other means, but is not limited to the above means, and specifically includes one or more of cyclone separation, cloth bag filtration, electrostatic dust removal and adsorption separation.
In a second aspect, the present invention provides a system for producing hydrogen by thermal conversion of biomass, the system comprising:
the microwave pyrolysis reactor is used for receiving the biomass raw material and obtaining pyrolysis volatile components and pyrolysis solid-phase materials after reaction;
the gasification reactor is used for receiving pyrolysis volatile components and pyrolysis solid-phase materials from the microwave pyrolysis reactor and water vapor from a water vapor feeding pipeline, and obtaining gas-phase materials and gasification residues containing calcium-based adsorbents after contact reaction in the presence of calcium-based adsorbents;
the first gas-solid separator is used for receiving the gas-phase material from the gasification reactor and obtaining a hydrogen product and dust after separation;
the adsorbent regeneration device is used for receiving the gasification residue containing the calcium-based adsorbent from the gasification reactor and performing regeneration treatment under the action of air and flue gas;
the second gas-solid separator is used for receiving the reacted materials from the adsorbent regeneration device, separating the materials to obtain a regenerated adsorbent and gas-phase materials, and returning the regenerated adsorbent to the gasification reactor for recycling;
and the third gas-solid separator is used for receiving the separated gas-phase material from the second gas-solid separator, separating to obtain flue gas and dust, wherein part or all of the flue gas is communicated with the inlet of the adsorbent regeneration device through a pipeline and is used for conveying the gasification residues of the calcium-based adsorbent from the gasification reactor.
In the biomass thermal conversion hydrogen production system, a sleeve structure is arranged at the lower part of the gasification reactor, the sleeve structure is composed of a conical nonporous sleeve and a cylindrical porous sleeve which are closed downwards, an obtuse angle b between the inclined plane of the conical nonporous sleeve and the vertical plane of the cylindrical porous sleeve is 120-170 ℃, the opening size of the cylindrical porous sleeve is phi 0.5-phi 5mm, and the opening distance is 2-20 mm; the outer diameter of the cylindrical porous sleeve accounts for 1/8-1/2 of the inner diameter of the gasification reactor, and an obtuse angle c between the opening direction of the cylindrical porous sleeve and the vertical surface of the cylindrical porous sleeve is 100-160 degrees.
In the system for preparing hydrogen by thermal conversion of biomass, a cylindrical sleeve structure is further preferably arranged at the upper part of the gasification reactor, a hole is formed in the lower part of the cylinder wall of the cylindrical sleeve, the length of the cylinder wall with the hole is 1/2-5/6 of the length of the cylinder wall of the whole sleeve, the hole size phi 1-phi 10mm, and the hole distance is 2-20 mm; an acute angle a between the opening direction and the vertical surface of the cylinder body is 15-75 ℃, and a gap between the outer wall of the cylindrical sleeve and the inner wall of the gasification reactor is 2-20 mm.
In the biomass thermal conversion hydrogen production system, the distance d between the lower end of the cylindrical sleeve structure arranged on the upper part of the gasification reactor and the upper end of the inclined plane of the sleeve structure on the lower part of the reactor in the vertical direction is 5-50 mm.
In the biomass thermal conversion hydrogen production system, the microwave pyrolysis reactor is a horizontal moving bed reactor, a spiral part is arranged in the reactor, the spiral part not only plays roles of pushing and extruding materials, but also has dispersing and mixing functions, and the type of the spiral part can be one or more of solid spiral, belt spiral, blade spiral and the like; the horizontal moving bed reactor with the spiral component arranged inside ensures the continuous and stable movement of the materials and avoids the phenomena of wall sticking and material blockage.
In the biomass thermal conversion hydrogen production system, the microwave pyrolysis reactor and the gasification reactor are made of microwave-dedicated ceramic materials, the outer sleeve is made of stainless steel materials capable of shielding microwave leakage, the wall of the stainless steel is provided with corresponding microwave transmission windows, each window corresponds to one microwave generator, the power of each microwave generator is 1000-2000W, the specific number of the windows is set according to the volume and other conditions of the reactor, the number of the microwave generators of the microwave pyrolysis reactor and the microwave part of the gasification reactor is generally 4-40, and the power density in the reactor is ensured to be 0.1 multiplied by 105～5×105W/m3。
In the biomass thermal conversion hydrogen production system, the adsorbent regeneration device comprises a pre-regeneration region and a regeneration region, wherein the pre-regeneration region and the regeneration region can be of an integrated structure; or can be respectively and independently arranged and communicated with each other through pipelines; preferably, the structure is an integral structure, when the structure is an integral structure, the pre-regeneration area is communicated with the regeneration area through the reducing unit, the outer diameter of the regeneration area is 1/3-4/5 of the outer diameter of the pre-regeneration area, and the height ratio of the pre-regeneration area to the regeneration area is 1: 1-5; an obtuse angle e between the inclined plane of the reducing unit and the vertical plane of the pre-regeneration area is 100-160 degrees.
In the above system for producing hydrogen by thermal conversion of biomass, the first gas-solid separator, the second gas-solid separator and the third gas-solid separator are based on one or more of gravity settling, centrifugal separation, filter screen separation, static electricity, adsorption and the like, but are not limited to the above manner, and the gas-solid separator may be specifically one or more of a cyclone separator, a cloth bag filter, an electrostatic dust collector and an adsorption separator.
Compared with the prior art, the method and the system for preparing hydrogen by thermally converting biomass have the following advantages:
1. in the method and the system for preparing hydrogen by biomass thermal conversion, a biomass dual-reactor hydrogen preparation technical method and a biomass dual-reactor hydrogen preparation technical system are initiated, firstly, the biomass is pyrolyzed by microwave to obtain hydrogen-rich gas, then the hydrogen-rich gas passes through a high-temperature carbon layer formed by byproduct biological semicoke to obtain the hydrogen-rich gas with less tar and low carbon hydrocarbon, and the hydrogen-rich gas with less tar and low carbon hydrocarbon and a calcium-based adsorbent are subjected to gas reforming, water-vapor conversion and carbon dioxide adsorption reaction to obtain high-quality hydrogen.
2. In the method and the system for preparing hydrogen by biomass thermal conversion, the calcium-based adsorbent comprises the active component A, the auxiliary agent B and the component C, and particularly the auxiliary agent B plays a role in maintaining the activity of the calcium-based adsorbent to be stable, prevents the active component A from being aggregated and ensures that the calcium-based adsorbent can be recycled for many times. Calcium sulfide and (sulfite) sulfate are used as the auxiliary agent B, and the ratio of the calcium sulfide and (sulfite) sulfate to calcium oxide (rho =3.35 g/cm) is mainly used3) And calcium carbonate (ρ =2.93 g/cm)3) Has the characteristic of lower density, particularly the volume of the calcium-based adsorbent is sharply expanded when the calcium-based adsorbent is subjected to carbonation reaction in the biomass thermal conversion process (see reaction 1), and the lower density calcium sulfate (rho =2.32 g/cm)3) The expansion of the calcium-based adsorbent can be partially counteracted due to the high free space, so that the cracking and the crushing of the calcium-based adsorbent are effectively slowed down; when the carbonated calcium-based adsorbent is regenerated, the adsorbent is obviously aggregated to form a densified structure (see reaction 2), so that the effect of the adsorbent is reduced, and after the calcium sulfate is introduced, the lower-density calcium sulfate can partially form higher-density calcium sulfide (see reaction 3) in the early stage of regeneration (pre-regeneration), but the density of the calcium sulfide (rho =2.6 g/cm)3) The calcium sulfide is lower than calcium oxide, still can play a role in slowing down the aggregation and densification of the calcium oxide, and the generated calcium sulfide can be converted into calcium sulfate again in the middle and later regeneration stages (see reaction 4), so that the inhibition effect on the aggregation and densification of the calcium oxide is enhanced, and the guarantee is provided for the structural stability, activity maintenance and mechanical performance of the calcium-based adsorbent.
Volume sharp expansion reaction: CaO + CO2→CaCO3(reaction 1, temperature lower than 825 ℃ C.)
Volume sharply shrinking reaction: CaCO3→CaO+CO2(reaction 2, temperature higher than 825 ℃ C.)
Moderate volume shrinkageThe following steps are required: CaSO4+C→CaS+CO2(reaction 3, temperature higher than 850 ℃ C.)
Volume moderate swelling reaction: CaS + O2→CaSO4(reaction 4, temperature lower than 1200 ℃ C.)
3. According to the method and the system for preparing hydrogen by thermal conversion of biomass, a particle moving bed is formed in a gasification reactor by utilizing the gravity action of the granular calcium-based adsorbent, and the radial movement of hydrogen-rich pyrolysis gas is enhanced through the design of the embedded porous cylinder, so that the removal efficiency of hydrogen-rich gas impurities and carried dust is further improved. In addition, dust enriched by the particle moving bed is discharged through a multi-stage gas-solid separation device, so that multi-stage and layered recovery and utilization of products are realized.
Drawings
FIG. 1 is a schematic diagram of a biomass thermal conversion hydrogen production system of the present invention.
Fig. 2 is a schematic view of a biomass gasification reactor of the present invention.
Fig. 3 is a schematic diagram of a calcium-based sorbent regenerator of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples and comparative examples, all the raw materials used were commercially available unless otherwise specified.
As shown in fig. 1-3, the present invention provides a system for producing hydrogen by thermal conversion of biomass, which comprises a microwave pyrolysis reactor 1, a gasification reactor 2, a first gas-solid separator 3, a second gas-solid separator 4, an adsorbent regeneration device (including a pre-regeneration zone 5 and a regeneration zone 6), and a third gas-solid separator 7; wherein the biomass raw material 8 is conveyed into the microwave pyrolysis reactor 1 through the feeding device 9, the pyrolysis volatile component and the pyrolysis solid phase material obtained after the reaction directly enter the gasification reactor 2, under the action of the water vapor 10, the pyrolysis volatile components react with the pyrolysis solid-phase material and the calcium-based adsorbent from the outlet 11 at the bottom of the first gas-solid separator 3 in turn, wherein the pyrolysis solid phase material and the tar cracking, the fuel gas reforming and the biological coke steam gasification reaction are carried out, and the generated hydrogen-rich material 13 enters the second gas-solid separator 4 through a gas outlet 12 at the top of the gasification reactor 2, a high-quality hydrogen product is obtained from a gas outlet of the second gas-solid separator 4 after gas-solid separation, and the discharged dust 15 is collected through an outlet at the bottom of the second gas-solid separator 4. The residue (containing carbonated calcium-based adsorbent) 16 of the gasification reaction is discharged from the bottom of the gasification reactor 2 and is sent to the pre-regeneration zone 5 through the flue gas 17, under the action of a proper amount of air 18, the carbonated calcium-based adsorbent is pre-regenerated, the pre-regenerated calcium-based adsorbent further enters the regeneration zone 6 and completely reacts under the action of sufficient air 19, the obtained regenerated calcium-based adsorbent 20 and the first flue gas 21 enter the first gas-solid separator 3 for gas-solid separation, the obtained regenerated calcium-based adsorbent 20 enters the gasification reactor 2 for recycling, the second flue gas 22 enters the third gas-solid separator 7 for re-separation to obtain the flue gas 17 and the dust 24, and part of the flue gas in the flue gas 17 is used as carrier gas for adsorbent regeneration.
The gasification reactors employed in examples 1 to 9 of the present invention and comparative example 1 were provided with a sleeve structure at the middle-lower part and a cylindrical sleeve structure at the upper part. The gasification reactor employed in example 10 was provided with a sleeve structure only at the lower portion.
Example 1
According to the mass fraction, 60% of calcium carbonate, 6% of calcium sulfate, 24% of silicon carbide and 10% of monocalcium dialuminate are mixed with a proper amount of biological coke and then ball-milled, wherein the molar ratio of carbon in the biological coke to calcium in the calcium sulfate is 6:1, a proper amount of water is added after ball-milling, the mixture is stirred to form a uniform wet material, and the wet material is molded by adopting an extrusion spheronization method, wherein the extrusion temperature is 60 ℃, the pressure is 2MPa, the extrusion time is 10 minutes, and the rotating speed of a spheronization disc is 300 revolutions per minute, so that 3mm spherical particles are obtained. And taking out the molding material, putting the molding material into a container for curing, keeping the humidity not lower than 90% at the temperature of 15 ℃, putting the molding material into a muffle furnace for high-temperature treatment after 10 days of curing, firstly carrying out anaerobic treatment at the temperature of 950 ℃ for 5 hours, and then carrying out aerobic roasting treatment at the temperature of 1000 ℃ for 5 hours to obtain the calcium-based adsorbent CA 1.
Example 2
Mixing 50% of calcium oxide, 10% of calcium sulfite, 26% of molecular sieve ZSM-5 and 14% of calcium fluoroaluminate with a proper amount of biological coke according to the mass fraction, and then carrying out ball milling, wherein the molar ratio of carbon in the biological coke to calcium in the calcium sulfite is 10:1, adding a proper amount of water after ball milling, stirring to form a uniform wet material, and carrying out molding treatment by adopting an extrusion rounding method, wherein the extrusion temperature is 15 ℃, the pressure is 0.5MPa, the extrusion time is 30 minutes, and the rotating speed of a rounding plate is 150 r/min, so as to obtain 5mm spherical particles. And taking out the molding material, putting the molding material into a container for maintenance, keeping the humidity not lower than 90% at the temperature of 60 ℃, putting the molding material into a muffle furnace for high-temperature treatment after 1 day of maintenance, firstly carrying out anaerobic treatment for 5 hours at the temperature of 850 ℃, and then carrying out aerobic roasting treatment for 5 hours at the temperature of 900 ℃ to obtain the calcium-based adsorbent CA 2.
Example 3
According to the mass fraction, 70% of calcium oxalate, 10% of calcium sulfide, 10% of titanium silicalite TS-1 and 10% of dicalcium heptaluminate are mixed with a proper amount of biological coke and then ball-milled, wherein the molar ratio of carbon in the biological coke to calcium in the calcium sulfide is 2:1, a proper amount of water is added after ball-milling, the mixture is stirred to form a uniform wet material, and an extrusion rounding method is adopted for molding treatment, wherein the extrusion temperature is 60 ℃, the pressure is 5MPa, the extrusion time is 5 minutes, and the rotating speed of a rounding plate is 300 revolutions per minute, so that 0.5mm spherical particles are obtained. And taking out the molding material, putting the molding material into a container for curing, keeping the humidity not lower than 90 percent at the temperature of 15 ℃, putting the molding material into a muffle furnace for high-temperature treatment after 10 days of curing, firstly carrying out anaerobic treatment at the temperature of 1000 ℃ for 0.5h, and then carrying out aerobic roasting treatment at the temperature of 1100 ℃ for 0.5h to obtain the calcium-based adsorbent CA 3.
Example 4
According to the mass fraction, 65% of dolomite, 5% of calcium bisulfate, 10% of mullite and 20% of tetracalcium aluminoferrite are mixed with a proper amount of biological coke and then ball-milled, wherein the molar ratio of carbon in the biological coke to calcium in the calcium bisulfate is 6:1, a proper amount of water is added after ball-milling, the mixture is stirred to form a uniform wet material, and the uniform wet material is molded by adopting an extrusion rolling method, wherein the extrusion temperature is 60 ℃, the pressure is 2MPa, the extrusion time is 10 minutes, and the rotating speed of a rolling disc is 300 revolutions per minute, so that 3mm spherical particles are obtained. And taking out the molding material, putting the molding material into a container for curing, keeping the humidity not lower than 90% at the temperature of 15 ℃, putting the molding material into a muffle furnace for high-temperature treatment after 10 days of curing, firstly carrying out anaerobic treatment at the temperature of 950 ℃ for 5 hours, and then carrying out aerobic roasting treatment at the temperature of 1000 ℃ for 5 hours to obtain the calcium-based adsorbent CA 4.
Example 5
Mixing 64% of calcium carbonate, 25.5% of silicon carbide, 10.5% of monocalcium dialuminate and a proper amount of biological coke according to mass fraction, performing ball milling, adding a proper amount of water after ball milling, stirring to form a uniform wet material, and performing molding treatment by adopting an extrusion rounding method, wherein the extrusion temperature is 60 ℃, the pressure is 2MPa, the extrusion time is 10 minutes, and the rotating speed of a rounding plate is 300 revolutions per minute, so that 3mm spherical particles are obtained. Taking out the molding material, placing the molding material into a container for curing, keeping the humidity not lower than 90% and the temperature at 15 ℃, placing the molding material into a muffle furnace for high-temperature treatment after 10 days of curing, firstly carrying out anaerobic treatment for 5 hours at the temperature of 950 ℃, and then carrying out aerobic roasting treatment for 5 hours at the temperature of 1000 ℃ to obtain the calcium-based adsorbent CA-5.
Example 6
Taking a biomass raw material and a calcium-based adsorbent CA1 according to the mass ratio of 1:10, wherein the calcium-based adsorbent CA1 is fed from a gasification reactor, the biomass raw material is treated to 5mm and enters a microwave pyrolysis reactor, the pyrolysis temperature is 600 ℃, the pyrolysis time is 10 minutes, and the microwave power density is 2 multiplied by 105W/m3Under the condition, obtaining gaseous pyrolysis volatile components and pyrolysis solid-phase materials, wherein the pyrolysis volatile components account for 85%, and the biological semicoke accounts for 15%; directly feeding the gaseous pyrolysis volatile component and the pyrolysis solid-phase material into a gasification reactor, and reacting at 800 deg.C for 10 min and water vapor flow of 2m3The power density of the microwave is 1 multiplied by 105W/m3Under the conditions, the solid phase material and the calcium-based adsorbent CA1 react in sequence, the generated gas-phase product is subjected to gas-solid separation to obtain a hydrogen product with the purity of 94%, and the gas-phase residue is sent from the gasification reactor to the adsorbent pre-regenerator and the regenerator in sequence, wherein the pre-regeneration conditions are as follows: the reaction temperature is 900 ℃, the reaction time is 6 seconds, and the flue gas flow is 3.6m3Flow rate of air/h, 0.4m3H, regeneration conditions: the reaction temperature is 1000 ℃, the reaction time is 3 seconds,Air flow 3m3And h, recycling the regenerated calcium-based adsorbent CA1 to a gasification reactor through gas-solid separation, and partially recycling the flue gas after two-stage gas-solid separation and performing a pre-regeneration process of the calcium-based adsorbent CA 1.
Example 7
Taking a biomass raw material and a calcium-based adsorbent CA2 according to the mass ratio of 1:1, wherein the calcium-based adsorbent CA2 is fed from a gasification reactor, the biomass raw material is treated to 10mm and enters a microwave pyrolysis reactor, the pyrolysis temperature is 600 ℃, the pyrolysis time is 10 minutes, and the microwave power density is 5 multiplied by 105W/m3Under the condition, obtaining gaseous pyrolysis volatile components and pyrolysis solid-phase materials, wherein the pyrolysis volatile components account for 80%, and the biological semicoke accounts for 20%; directly feeding the gaseous pyrolysis volatile component and the pyrolysis solid-phase material into a gasification reactor, and reacting at 600 deg.C for 30 min and with water vapor flow of 0.2m3The microwave power density is 0.1 multiplied by 105W/m3Under the conditions, the solid phase material and the calcium-based adsorbent CA2 react in sequence, the generated gas-phase product is subjected to gas-solid separation to obtain a hydrogen product with the purity of 75%, and the gas-phase residue is sent from the gasification reactor to the adsorbent pre-regenerator and the regenerator in sequence, wherein the pre-regeneration conditions are as follows: the reaction temperature is 850 ℃, the reaction time is 10 seconds, and the flue gas flow is 1.9 m3Flow rate of air/h, 0.1m3H, regeneration conditions: the reaction temperature is 900 ℃, the reaction time is 5 seconds, and the air flow is 1m3And h, recycling the regenerated calcium-based adsorbent CA2 to a gasification reactor through gas-solid separation, and partially recycling the flue gas after two-stage gas-solid separation and performing a pre-regeneration process of the calcium-based adsorbent CA 2.
Example 8
Taking a biomass raw material and a calcium-based adsorbent CA3 according to the mass ratio of 1:10, wherein the calcium-based adsorbent CA3 is fed from a gasification reactor, the biomass raw material is treated to 1mm and enters a microwave pyrolysis reactor, the pyrolysis temperature is 400 ℃, the pyrolysis time is 60 minutes, and the microwave power density is 0.5 multiplied by 105W/m3Under the condition, obtaining gaseous pyrolysis volatile components and pyrolysis solid-phase materials, wherein the pyrolysis volatile components account for 65 percent, and the biological semicoke accounts for 35 percent; subjecting the gaseous pyrolysis volatile matter and pyrolysisDirectly feeding the solid phase material into a gasification reactor, reacting at 800 deg.C for 10 min, and steam flow of 2m3The power density of the microwave is 1 multiplied by 105W/m3Under the conditions, the solid phase material and the calcium-based adsorbent CA3 react in sequence, the generated gas-phase product is subjected to gas-solid separation to obtain a hydrogen product with the purity of 88%, and the gas-phase residue is sent from the gasification reactor to the adsorbent pre-regenerator and the regenerator in sequence, wherein the pre-regeneration conditions are as follows: the reaction temperature is 1000 ℃, the reaction time is 2 seconds, and the flue gas flow is 4m3Flow rate of air/h 1m3H, regeneration conditions: the reaction temperature is 1100 ℃, the reaction time is 1 second, and the air flow is 5m3And h, recycling the regenerated calcium-based adsorbent CA3 to a gasification reactor through gas-solid separation, and partially recycling the flue gas after two-stage gas-solid separation and performing a pre-regeneration process of the calcium-based adsorbent CA 3. Wherein the reaction conditions of the pre-regeneration zone are as follows: the reaction temperature is 850-1000 ℃, the reaction time is 2-10 seconds, and the flow of pre-regeneration gas is 2-5 m3The pre-regeneration gas can be one of air and nitrogen, air and flue gas, air and nitrogen and flue gas, the volume content of the air in the pre-regeneration gas is 5-20%, and the combination of the air and the flue gas is optimized; the reaction conditions in the regeneration zone are as follows: the reaction temperature is 900-1100 ℃, the reaction time is 1-5 seconds, and the air flow is 1-5 m3/h。
Example 9
Taking a biomass raw material and a calcium-based adsorbent CA4 according to the mass ratio of 1:5, wherein the calcium-based adsorbent CA4 is fed from a gasification reactor, the biomass raw material is treated to 5mm and enters a microwave pyrolysis reactor, the pyrolysis temperature is 600 ℃, the pyrolysis time is 10 minutes, and the microwave power density is 2 multiplied by 105W/m3Under the condition, obtaining gaseous pyrolysis volatile components and pyrolysis solid-phase materials, wherein the pyrolysis volatile components account for 83 percent, and the biological semicoke accounts for 17 percent; directly feeding the gaseous pyrolysis volatile component and the pyrolysis solid-phase material into a gasification reactor, and reacting at 800 deg.C for 10 min and water vapor flow of 2m3The power density of the microwave is 1 multiplied by 105W/m3Under the condition, the reaction is sequentially carried out with pyrolysis solid phase materials and a calcium-based adsorbent CA4, and the purity of the generated gas phase product is obtained by gas-solid separationThe gas phase residue is sent from the gasification reactor to an adsorbent pre-regenerator and a regenerator in sequence, wherein the pre-regeneration conditions are as follows: the reaction temperature is 900 ℃, the reaction time is 6 seconds, and the flue gas flow is 3.6m3Flow rate of air/h, 0.4m3H, regeneration conditions: the reaction temperature is 1000 ℃, the reaction time is 3 seconds, and the air flow is 3m3And h, recycling the regenerated calcium-based adsorbent CA4 to a gasification reactor through gas-solid separation, and partially recycling the flue gas after two-stage gas-solid separation and performing a pre-regeneration process of the calcium-based adsorbent CA 4.
Example 10
Taking a biomass raw material and a calcium-based adsorbent CA1 according to a mass ratio of 1:10, wherein the calcium-based adsorbent CA1 is fed from a gasification reactor, the biomass raw material is processed to 5mm and enters a microwave pyrolysis reactor, and a gaseous pyrolysis volatile component and a pyrolysis solid-phase material are obtained under the conditions that the pyrolysis temperature is 600 ℃, the pyrolysis time is 10 minutes and the microwave power density is 2 multiplied by 105W/m3, wherein the pyrolysis volatile component accounts for 85 percent, and the biological semicoke accounts for 15 percent; directly feeding the gaseous pyrolysis volatile component and the pyrolysis solid-phase material into a gasification reactor, sequentially reacting with the pyrolysis solid-phase material and a calcium-based adsorbent CA1 under the conditions that the gasification temperature is 800 ℃, the reaction time is 10 minutes, the water vapor flow is 2m3/h and the microwave power density is 1 multiplied by 105W/m3, carrying out gas-solid separation on the generated gas-phase product to obtain a hydrogen product with the purity of 92%, and sequentially feeding the gas-phase residue into an adsorbent pre-regenerator and a regenerator from the gasification reactor, wherein the pre-regeneration conditions are as follows: the reaction temperature is 900 ℃, the reaction time is 6 seconds, the flue gas flow is 3.6m3/h, the air flow is 0.4m3/h, and the regeneration conditions are as follows: the reaction temperature is 1000 ℃, the reaction time is 3 seconds, the air flow is 3m3/h, the regenerated calcium-based adsorbent CA1 is recycled to the gasification reactor through gas-solid separation, and the flue gas is partially recycled after two-stage gas-solid separation and is pre-regenerated with the calcium-based adsorbent CA 1.
Comparative example 1
Taking a biomass raw material and a calcium-based adsorbent CA5 according to the mass ratio of 1:10, wherein the calcium-based adsorbent CA5 is fed from a gasification reactor, the biomass raw material is treated to be 5mm and enters a microwave pyrolysis reactor, the pyrolysis time is 10 minutes at the pyrolysis temperature of 600 ℃, and the microwave power is denseDegree of 2X 105W/m3Under the condition, obtaining gaseous pyrolysis volatile components and pyrolysis solid-phase materials, wherein the pyrolysis volatile components account for 86%, and the biological semicoke accounts for 14%; directly feeding the gaseous pyrolysis volatile component and the pyrolysis solid-phase material into a gasification reactor, and reacting at 800 deg.C for 10 min and water vapor flow of 2m3The power density of the microwave is 1 multiplied by 105W/m3Under the conditions, the solid phase material and the calcium-based adsorbent CA5 react in sequence, the generated gas-phase product is subjected to gas-solid separation to obtain a hydrogen product with the purity of 86%, and the gas-phase residue is sent from the gasification reactor to the adsorbent pre-regenerator and the regenerator in sequence, wherein the pre-regeneration conditions are as follows: the reaction temperature is 900 ℃, the reaction time is 6 seconds, and the flue gas flow is 3.6m3Flow rate of air/h, 0.4m3H, regeneration conditions: the reaction temperature is 1000 ℃, the reaction time is 3 seconds, and the air flow is 3m3And h, recycling the regenerated calcium-based adsorbent CA5 to a gasification reactor through gas-solid separation, and partially recycling the flue gas after two-stage gas-solid separation and performing a pre-regeneration process of the calcium-based adsorbent CA 5.

Claims (20)

1. A method for producing hydrogen by thermal conversion of biomass, comprising:
(1) the biomass raw material enters a microwave pyrolysis reactor for reaction to obtain a hydrogen-containing pyrolysis volatile component and a pyrolysis solid-phase material;
(2) allowing the hydrogen-containing pyrolysis volatile component and the pyrolysis solid-phase material obtained in the step (1) to enter a gasification reactor to contact with steam for gasification reaction to obtain crude synthesis gas and solid-phase residue;
(3) contacting the crude synthesis gas obtained in the step (2) with an activated calcium-based adsorbent to perform cracking, reforming, water-gas shift and carbonation reactions, and performing gas-solid separation to obtain high-purity hydrogen and carbonated calcium-based adsorbent;
(4) the calcium-based adsorbent carbonized in the step (3) and the solid phase residue in the step (2) enter an adsorbent regenerator for regeneration treatment, and the obtained regenerated calcium-based adsorbent is returned to the gasification reactor for recycling;
the calcium-based adsorbent in the step (3) comprises an active component A, an auxiliary agent B and a component C, wherein the active component A is calcium carbonate; the auxiliary agent B is calcium sulfate; the component C comprises CA and CB, wherein CA is silicon carbide; CB is monocalcium dialuminate.
2. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: based on the total weight of the calcium-based adsorbent, the content of the active component A is 50-80%, the content of the auxiliary agent B is 5-10%, and the content of the component C is 10-40%.
3. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: the preparation method of the calcium-based adsorbent in the step (3) comprises the following steps: mixing the active component A, the auxiliary agent B, the component C and the pore-forming agent, grinding, adding a proper amount of water, stirring to form a uniform wet material, and carrying out forming, curing and high-temperature treatment to obtain a calcium-based adsorbent;
the high-temperature treatment comprises anaerobic reduction treatment and aerobic roasting treatment, wherein the temperature of the anaerobic reduction treatment is 850-1000 ℃, the treatment time is 0.5-5 h, the temperature of the aerobic roasting treatment is 900-1100 ℃, and the treatment time is 0.5-5 h.
4. The method for producing hydrogen by thermal conversion of biomass according to claim 3, characterized in that: the pore-forming agent is a carbonized material and is selected from one or more of biological coke, plastic product coke, rubber product coke, kitchen waste coke and fiber product coke.
5. The method for producing hydrogen by thermal conversion of biomass according to claim 4, characterized in that: the carbonized material is biological coke.
6. The method for producing hydrogen by thermal conversion of biomass according to claim 3, characterized in that: the molar ratio of carbon in the pore-forming agent to calcium in the auxiliary B is 2-10: 1.
7. the method for producing hydrogen by thermal conversion of biomass according to claim 3, characterized in that: and the maintenance is carried out for 1-10 days at the humidity of not less than 90% and the temperature of 15-60 ℃.
8. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: the biomass raw material in the step (1) is derived from corn straws, rice hulls, wheat straws, wood blocks, leaves or branches.
9. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: the reaction conditions in the microwave pyrolysis reactor in the step (1) are as follows: the pyrolysis temperature is 400-600 ℃, the pyrolysis time is 10-60 minutes, and the microwave power density is 0.5 multiplied by 105～5×105W/m3。
10. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: the reaction conditions in the gasification reactor in steps (2) and (3) are as follows: the gasification temperature is 600-800 ℃, and the water vapor flow is 0.2-2 m3/h。
11. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: in the step (2), the gasification reactor is heated by microwaves, and the microwave power density is 0.1 multiplied by 105～1×105W/m3。
12. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: the mass ratio of the biomass to the calcium-based adsorbent in the step (3) is 1:1 to 10.
13. The method for producing hydrogen by thermal conversion of biomass according to claim 1, characterized in that: the regeneration in the step (4) comprises a first-stage pre-regeneration treatment and a second-stage regeneration treatment, wherein the first-stage pre-regeneration treatment is carried out in the presence of pre-regeneration gas, and the treatment conditions are as follows: the reaction temperature is 850-1000 ℃, the reaction time is 2-10 seconds, and the pre-regeneration airflowThe amount of the particles is 2-5 m3H; the pre-regeneration gas is one of air and flue gas mixed gas, air and nitrogen mixed gas, air, nitrogen and flue gas mixed gas; the second stage regeneration treatment is carried out in an air atmosphere, and the treatment conditions are as follows: the reaction temperature is 900-1100 ℃, the reaction time is 1-5 seconds, and the air flow is 1-5 m3/h。
14. A system for producing hydrogen by thermal conversion of biomass using the method of any one of claims 1 to 13, the system comprising:
the microwave pyrolysis reactor is used for receiving the biomass raw material and obtaining pyrolysis volatile components and pyrolysis solid-phase materials after reaction;
the gasification reactor is used for receiving pyrolysis volatile components and pyrolysis solid-phase materials from the microwave pyrolysis reactor and water vapor from a water vapor feeding pipeline, and obtaining gas-phase materials and gasification residues containing calcium-based adsorbents after contact reaction in the presence of calcium-based adsorbents;
the first gas-solid separator is used for receiving the gas-phase material from the gasification reactor and obtaining a hydrogen product and dust after separation;
the adsorbent regeneration device is used for receiving the gasification residue containing the calcium-based adsorbent from the gasification reactor and performing regeneration treatment under the action of air and flue gas;
the second gas-solid separator is used for receiving the reacted materials from the adsorbent regeneration device, separating the materials to obtain a regenerated adsorbent and gas-phase materials, and returning the regenerated adsorbent to the gasification reactor for recycling;
and the third gas-solid separator is used for receiving the separated gas-phase material from the second gas-solid separator, separating to obtain flue gas and dust, wherein part or all of the flue gas is communicated with the inlet of the adsorbent regeneration device through a pipeline and is used for conveying the gasification residues of the calcium-based adsorbent from the gasification reactor.
15. The system for producing hydrogen by thermal conversion of biomass according to claim 14, wherein: a sleeve structure is arranged at the lower part of the gasification reactor, the sleeve structure is composed of a conical nonporous sleeve and a cylindrical porous sleeve which are closed downwards, an obtuse angle b between the inclined plane of the conical nonporous sleeve and the vertical plane of the cylindrical porous sleeve is 120-170 ℃, the opening size of the cylindrical porous sleeve is phi 0.5-phi 5mm, and the opening distance is 2-20 mm; the outer diameter of the cylindrical porous sleeve accounts for 1/8-1/2 of the inner diameter of the gasification reactor, and an obtuse angle c between the opening direction of the cylindrical porous sleeve and the vertical surface of the cylindrical porous sleeve is 100-160 degrees.
16. The system for producing hydrogen by thermal conversion of biomass according to claim 14 or 15, wherein: a cylindrical sleeve structure is arranged at the upper part of the gasification reactor, a hole is formed in the lower part of the cylinder wall of the cylindrical sleeve, the length of the cylinder wall with the hole is 1/2-5/6 of the length of the cylinder wall of the whole sleeve, the hole size phi 1-phi 10mm, and the hole distance is 2-20 mm; an acute angle a between the opening direction and the vertical surface of the cylinder body is 15-75 ℃, and a gap between the outer wall of the cylindrical sleeve and the inner wall of the gasification reactor is 2-20 mm.
17. The system for producing hydrogen by thermal conversion of biomass according to claim 16, wherein: the distance d between the lower end of the cylindrical sleeve structure arranged on the upper part of the gasification reactor and the upper end of the inclined plane of the sleeve structure on the lower part of the reactor in the vertical direction is 5-50 mm.
18. The system for producing hydrogen by thermal conversion of biomass according to claim 14, wherein: the microwave pyrolysis reactor is a horizontal moving bed reactor, and a spiral part is arranged in the reactor.
19. The system for producing hydrogen by thermal conversion of biomass according to claim 14, wherein: the adsorbent regeneration device comprises a pre-regeneration zone and a regeneration zone, wherein the pre-regeneration zone and the regeneration zone can be of an integrated structure; or can be respectively and independently arranged and communicated with each other through pipelines.
20. The system for producing hydrogen by thermal conversion of biomass according to claim 19, wherein: the pre-regeneration zone and the regeneration zone are of an integrated structure; the pre-regeneration zone is communicated with the regeneration zone through a diameter-changing unit, the outer diameter of the regeneration zone is 1/3-4/5 of the outer diameter of the pre-regeneration zone, and the height ratio of the pre-regeneration zone to the regeneration zone is 1: 1-5; an obtuse angle e between the inclined plane of the reducing unit and the vertical plane of the pre-regeneration area is 100-160 degrees.
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