WO2020228488A1 - Method for comprehensive utilization of biomass material - Google Patents

Method for comprehensive utilization of biomass material Download PDF

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WO2020228488A1
WO2020228488A1 PCT/CN2020/085545 CN2020085545W WO2020228488A1 WO 2020228488 A1 WO2020228488 A1 WO 2020228488A1 CN 2020085545 W CN2020085545 W CN 2020085545W WO 2020228488 A1 WO2020228488 A1 WO 2020228488A1
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product
biomass
gas
tank
oil
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PCT/CN2020/085545
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French (fr)
Chinese (zh)
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马望京
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南京科津新材料研究院有限公司
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Publication of WO2020228488A1 publication Critical patent/WO2020228488A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/16—Features of high-temperature carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to a resource utilization method of biomass materials, in particular to a method for converting biomass materials into activated carbon, hydrogen-rich gas and liquid fuel under supercritical conditions using a composite metal catalyst microwave assist.
  • Biomass pyrolysis carbonization technology is a kind of biomass energy utilization technology. Biomass carbonization is the long-term cracking of biomass at a very low heating rate and a temperature of about 400°C to obtain coke to the maximum. The yield of coke is generally about 35%.
  • the traditional kiln-type carbonization furnace carbonization method uses hard logs to burn charcoal, which is not only a serious waste of resources, but also has high labor intensity, poor conditions, long production cycles, and serious pollution; it cannot treat a large amount of waste straw, straw and other biomass in rural areas. Pyrolysis of raw materials to make charcoal. Traditional biomass and organic waste are used to produce fuel gas, usually by gasification.
  • the object of the present invention is to provide a method for converting biomass materials into activated carbon, hydrogen-rich gas and liquid fuel by using a composite metal catalyst microwave assisted under supercritical conditions, which realizes efficient and comprehensive utilization of biomass materials.
  • the technical route adopted by the present invention is to cut the biomass raw materials into fragments and put them into the gas explosion tank, add a certain amount of water and raise the temperature to 100-150°C, and then pass in compressed air to increase the pressure to 7-10MPa, keep at constant temperature and pressure for 5-30min, then release the pressure, pass a 200-mesh sieve to obtain a biomass raw material meeting the particle size requirements; put the biomass raw material, dispersant, solvent, cosolvent, and water obtained in step a in the reactor Mix and stir uniformly in a certain ratio to prepare a biomass slurry, and preheat it to 120-350°C; add a transition metal composite catalyst to the slurry in step b, increase the pressure in the reactor to 17-40MPa, and Use microwave-assisted heating to continue heating to 400-650°C so that the reactant system in the reactor reaches a liquid supercritical state and react for 30-60 minutes to form a reaction product; after the reaction in step c, the reaction
  • the fiber structure damage rate of the biomass raw material treated in step a during the gas explosion process is less than 1%.
  • the biomass raw materials include one or more of wood chips, wild grasses, leaves, straws, livestock manure, and edible fungus residue.
  • the solvent of step b is dimethyl sulfoxide; the co-solvent is NaF.
  • the transition metal composite catalyst in step c is a composite catalyst in which Fe, Co, and Ni powders are composited on a porous alumina or mesoporous carbon substrate.
  • step d The solid product in step d is further carbonized by microwave-assisted heating to obtain activated carbon.
  • step d The gas product of step d is subjected to gas removal to obtain high-purity hydrogen-rich gas.
  • the oil product of step d is liquid fuel.
  • the method of the present invention performs gas explosion crushing of biomass materials under high pressure water vapor to ensure that the chemical structure of cellulose and hemicellulose is not destroyed as much as possible at a lower temperature, so that the cellulose and hemicellulose are maximized It can be better used for pyrolysis to prepare energy chemicals.
  • the present invention reuses waste biomass materials, which is beneficial to the development of sustainable ecological environment; while the gas explosion method is used to treat biomass materials, the fiber structure is maintained as much as possible.
  • the purity of the liquid fuel prepared by the gas explosion method can reach 95%, while the ordinary crushing method is only 60%; the solvent dimethyl
  • the addition of sulfoxide can make the prepared solid product activated carbon have a specific surface area of up to 320m2/g.
  • the prepared activated carbon has a specific surface area of only 200m2/g; the use of flux NaF can make the hydrogen-rich gas yield up to 95 %, and the yield of the flux is only 83%.
  • the composite metal catalyst adopts the transition metal to be supported on the alumina and silica matrix, which is particularly beneficial to the improvement of catalytic efficiency.
  • Microwave-assisted heating uses a specific frequency to catalyze and carbonize biomass materials, which is a favorable means to achieve efficient pyrolysis.
  • the biomass raw material is initially cut into fragments and put into the gas explosion tank. After adding 10% water, the temperature is raised to 120°C, and then compressed air is introduced to increase the pressure to 8MPa, and the pressure is released after keeping it under constant temperature and pressure for 10 minutes.
  • the biomass material is initially cut into fragments and put into the gas explosion tank. After adding a certain amount of water, the temperature is raised to 140°C, and then compressed air is introduced to increase the pressure to 9MPa, and the pressure is released after being maintained at a constant temperature and pressure for 20 minutes.

Abstract

The present invention relates to a method for the resource utilization of biomass material, and specifically relates to a method for converting biomass material into activated carbon, a hydrogen-rich gas and a liquid fuel under supercritical conditions using a composite metal catalyst and microwave assistance. In the method, gas explosion fragmentation is performed on the biomass material under high-pressure water vapor so that cellulose and hemicellulose are retained to the maximum extent; the described method may be better used for preparing energy chemicals by pyrolysis. The addition of a solvent dimethyl sulfoxide may increase the specific surface area of a prepared solid product of activated carbon; the use of fluxing agent NaF may increase the yield of the hydrogen-rich gas, and the composite metal catalyst employs a transition metal loaded on an aluminum oxide and silicon oxide matrix. The present invention is particularly conducive to the improvement of catalytic efficiency.

Description

一种生物质材料的综合利用方法A comprehensive utilization method of biomass materials 技术领域Technical field
本发明涉及一种生物质材料资源化利用方法，具体地说涉及一种在超临界条件下，利用复合金属催化剂微波辅助将生物质材料转化为活性炭、富氢气体和液体燃料的方法。The invention relates to a resource utilization method of biomass materials, in particular to a method for converting biomass materials into activated carbon, hydrogen-rich gas and liquid fuel under supercritical conditions using a composite metal catalyst microwave assist.
背景技术Background technique
资源短缺与环境污染的瓶颈性问题是当今世界的两大热点问题。将储量丰富的煤炭资源、可再生的生物质能源以及有机废物转化为清洁、高效的高热值气体燃料，是亟待解决的世界性问题。The bottleneck problems of resource shortage and environmental pollution are two major hot issues in the world today. The conversion of abundant coal resources, renewable biomass energy and organic waste into clean and efficient high-calorific value gas fuel is a worldwide problem that needs to be solved urgently.
生物质热解炭化技术是生物质能利用技术的一种。生物质炭化是生物质在极低的升温速率、温度约400℃下长时间裂解，以最大限度地得到焦炭，得炭率一般在35％左右。传统的窑式炭化炉炭化法多用硬质原木进行烧炭，不仅资源浪费严重，而且生产过程劳动强度大、条件差、生产周期长、污染严重；无法对农村大量的废弃秸秆、稻草等生物质原料热解制炭。传统的生物质和有机废物制取燃气，通常采用气化的方式。水蒸气气化只有水蒸气的温度达到700℃以上，气化效果才比较理想，这对蒸汽发生器性能提出了较高的要求。通常情况下，由于水蒸汽气化难以达到较高的温度，因此气体产率较低。同时，由于运行时焦炭和热载体都在较高温下循环，难以定量控制，较易引起炉温的起伏变化和不稳定，因此需要辅助的加热装置。美国General Atomics公司采用40％的有机废物浆料进行超临界水氧化或气化制氢，日本CCUJ公司以CaO为催化剂对煤进行超临界水气化，但两者都带来了固体废物处理问题，不适于工业化生产。Biomass pyrolysis carbonization technology is a kind of biomass energy utilization technology. Biomass carbonization is the long-term cracking of biomass at a very low heating rate and a temperature of about 400°C to obtain coke to the maximum. The yield of coke is generally about 35%. The traditional kiln-type carbonization furnace carbonization method uses hard logs to burn charcoal, which is not only a serious waste of resources, but also has high labor intensity, poor conditions, long production cycles, and serious pollution; it cannot treat a large amount of waste straw, straw and other biomass in rural areas. Pyrolysis of raw materials to make charcoal. Traditional biomass and organic waste are used to produce fuel gas, usually by gasification. Steam gasification only has an ideal gasification effect when the temperature of the steam reaches 700°C or more, which places higher requirements on the performance of the steam generator. Under normal circumstances, the gas yield is low because it is difficult to reach a higher temperature due to steam gasification. At the same time, because the coke and heat carrier circulate at a higher temperature during operation, it is difficult to quantitatively control, and it is easier to cause fluctuations and instability of the furnace temperature, so an auxiliary heating device is required. General Atomics of the United States uses 40% organic waste slurry for supercritical water oxidation or gasification to produce hydrogen, and Japan’s CCUJ uses CaO as a catalyst for supercritical water gasification of coal, but both have brought about solid waste treatment problems , Not suitable for industrial production.
发明内容Summary of the invention
本发明的目的是提供一种在超临界条件下，利用复合金属催化剂微波辅助将生物质材料转化为活性炭、富氢气体和液体燃料的方法，实现了高效综合利用生物质材料。The object of the present invention is to provide a method for converting biomass materials into activated carbon, hydrogen-rich gas and liquid fuel by using a composite metal catalyst microwave assisted under supercritical conditions, which realizes efficient and comprehensive utilization of biomass materials.
为了实现上述目的，本发明采用的技术路线是：将生物质原料初步切割为碎段后放入气爆罐内，加入一定量水之后升温至100-150℃，再通入压缩空气升压至7-10MPa，恒温恒压下保持5-30min后卸压，过200目筛获得满足粒度要求的生物质原料；将步骤a得到的生物质原料、分散剂、溶剂、助溶剂、水在反应器中以一定的比例混合搅拌均匀，制得生物质浆料，并预热至120～350℃；向步骤b的料浆中加入过渡金属复合催化剂，升高反应器内压力至17～40MPa，并以微波辅助加热方式继续升温至400～650℃使反应器内的反应物体系达到液态超临界状态进行反应30-60分钟，形成反应产物；步骤c的反应结束后将反应产物排出到固液气分离罐中，将分离出的固体产物由罐底排出到干品储罐，分离出的气体产物从罐顶排出，而留下的液态产物进入油水分离罐，油品由油水分离罐顶部取出，水则由油水分离罐底部排出。In order to achieve the above-mentioned purpose, the technical route adopted by the present invention is to cut the biomass raw materials into fragments and put them into the gas explosion tank, add a certain amount of water and raise the temperature to 100-150°C, and then pass in compressed air to increase the pressure to 7-10MPa, keep at constant temperature and pressure for 5-30min, then release the pressure, pass a 200-mesh sieve to obtain a biomass raw material meeting the particle size requirements; put the biomass raw material, dispersant, solvent, cosolvent, and water obtained in step a in the reactor Mix and stir uniformly in a certain ratio to prepare a biomass slurry, and preheat it to 120-350°C; add a transition metal composite catalyst to the slurry in step b, increase the pressure in the reactor to 17-40MPa, and Use microwave-assisted heating to continue heating to 400-650°C so that the reactant system in the reactor reaches a liquid supercritical state and react for 30-60 minutes to form a reaction product; after the reaction in step c, the reaction product is discharged to the solid-liquid gas In the separation tank, the separated solid product is discharged from the bottom of the tank to the dry product storage tank, the separated gas product is discharged from the top of the tank, and the remaining liquid product enters the oil-water separation tank, and the oil product is taken out from the top of the oil-water separation tank. Water is discharged from the bottom of the oil-water separation tank.
步骤a中处理后的所述生物质原料在气爆过程中对纤维结构破坏率低于1％。The fiber structure damage rate of the biomass raw material treated in step a during the gas explosion process is less than 1%.
所述生物质原料包括木屑、野草、树叶、秸秆、畜粪、食用菌渣中的一种或多种。The biomass raw materials include one or more of wood chips, wild grasses, leaves, straws, livestock manure, and edible fungus residue.
步骤b的溶剂为二甲基亚砜；助溶剂为NaF。The solvent of step b is dimethyl sulfoxide; the co-solvent is NaF.
步骤c的过渡金属复合催化剂为在多孔氧化铝或介孔碳基底上复合Fe、Co、Ni粉的复合催化剂。The transition metal composite catalyst in step c is a composite catalyst in which Fe, Co, and Ni powders are composited on a porous alumina or mesoporous carbon substrate.
步骤d的固体产物进一步利用微波辅助加热碳化制得活性炭。The solid product in step d is further carbonized by microwave-assisted heating to obtain activated carbon.
步骤d的气体产物经过气体除杂获得纯度高的富氢气体。The gas product of step d is subjected to gas removal to obtain high-purity hydrogen-rich gas.
步骤d的油品为液体燃料。The oil product of step d is liquid fuel.
本发明的方法在高压水蒸气下对生物质材料进行气爆碎化，以保证在较低温度下尽量不破坏纤维素和半纤维素的化学结构，使得纤维素和半纤维素得到最大程度的保留，能够更好地用于热解制备能源化学品。The method of the present invention performs gas explosion crushing of biomass materials under high pressure water vapor to ensure that the chemical structure of cellulose and hemicellulose is not destroyed as much as possible at a lower temperature, so that the cellulose and hemicellulose are maximized It can be better used for pyrolysis to prepare energy chemicals.
本发明与现有技术相比，将废弃的生物质材料再利用，有利于可持续生态环境发展；采用气爆法处理生物质原料，尽量保持了纤维结构的同时，研究人员发现，其与普通的破碎之后与其他辅助组分形成的混合体系所制备的液体燃料相比，气爆法处理的原料所制备的液体燃料纯度可达95％，而普通破碎法仅为60％；溶剂二甲基亚砜的添加可使制备的固体产物活性炭的比表面积高达320m2/g，不适用该溶剂时所制备的活 性炭比表面积仅200m2/g；助熔剂NaF的使用可使富氢气体的产率高达95％，而不适用该助熔剂产率仅83％。复合金属催化剂采用过渡金属负载于氧化铝、氧化硅基体上，特别有利于催化效率的提升。微波辅助加热借助特定的频率，对生物质材料催化及炭化，是实现高效热解的有利手段。Compared with the prior art, the present invention reuses waste biomass materials, which is beneficial to the development of sustainable ecological environment; while the gas explosion method is used to treat biomass materials, the fiber structure is maintained as much as possible. Compared with the liquid fuel prepared by the mixed system formed by other auxiliary components after the crushing, the purity of the liquid fuel prepared by the gas explosion method can reach 95%, while the ordinary crushing method is only 60%; the solvent dimethyl The addition of sulfoxide can make the prepared solid product activated carbon have a specific surface area of up to 320m2/g. When this solvent is not used, the prepared activated carbon has a specific surface area of only 200m2/g; the use of flux NaF can make the hydrogen-rich gas yield up to 95 %, and the yield of the flux is only 83%. The composite metal catalyst adopts the transition metal to be supported on the alumina and silica matrix, which is particularly beneficial to the improvement of catalytic efficiency. Microwave-assisted heating uses a specific frequency to catalyze and carbonize biomass materials, which is a favorable means to achieve efficient pyrolysis.
具体实施方式Detailed ways
实施例1：Example 1:
将生物质原料初步切割为碎段后放入气爆罐内，加入10％水之后升温至120℃，再通入压缩空气升压至8MPa，恒温恒压下保持10min后卸压，过200目筛获得满足粒度要求的生物质原料；将步骤a得到的生物质原料、分散剂、溶剂、助溶剂、水在反应器中以一定的比例混合搅拌均匀，制得生物质浆料，并预热至200℃；向步骤b的料浆中加入过渡金属复合催化剂，升高反应器内压力至30MPa，并以微波辅助加热方式继续升温至500℃使反应器内的反应物体系达到液态超临界状态进行反应40分钟，形成反应产物；步骤c的反应结束后将反应产物排出到固液气分离罐中，将分离出的固体产物由罐底排出到干品储罐，分离出的气体产物从罐顶排出，而留下的液态产物进入油水分离罐，油品由油水分离罐顶部取出，水则由油水分离罐底部排出。The biomass raw material is initially cut into fragments and put into the gas explosion tank. After adding 10% water, the temperature is raised to 120°C, and then compressed air is introduced to increase the pressure to 8MPa, and the pressure is released after keeping it under constant temperature and pressure for 10 minutes. Sieve to obtain biomass raw materials that meet the particle size requirements; mix the biomass raw materials, dispersant, solvent, co-solvent, and water obtained in step a in a reactor at a certain ratio and stir evenly to prepare a biomass slurry, and preheat To 200°C; add transition metal composite catalyst to the slurry of step b, increase the pressure in the reactor to 30MPa, and continue to heat up to 500°C by microwave-assisted heating to make the reactant system in the reactor reach a liquid supercritical state The reaction is carried out for 40 minutes to form a reaction product; after the reaction of step c, the reaction product is discharged into the solid-liquid gas separation tank, the separated solid product is discharged from the bottom of the tank to the dry product storage tank, and the separated gas product is discharged from the tank The top discharge, and the remaining liquid product enters the oil-water separation tank, the oil product is taken out from the top of the oil-water separation tank, and the water is discharged from the bottom of the oil-water separation tank.
实施例2：Example 2:
将生物质原料初步切割为碎段后放入气爆罐内，加入一定量水之后升温至140℃，再通入压缩空气升压至9MPa，恒温恒压下保持20min后卸压，过200目筛获得满足粒度要求的生物质原料；将步骤a得到的生物质原料、分散剂、溶剂、助溶剂、水在反应器中以一定的比例混合搅拌均匀，制得生物质浆料，并预热至300℃；向步骤b的料浆中加入过渡金属复合催化剂，升高反应器内压力至35MPa，并以微波辅助加热方式继续升温至550℃使反应器内的反应物体系达到液态超临界状态进行反应50分钟，形成反应产物；步骤c的反应结束后将反应产物排出到固液气分离罐中，将分离出的固体产物由罐底排出到干品储罐，分离出的气体产物从罐顶排出，而留下的液态产物进入油水分离罐，油品由油水分离罐顶部取出，水则由油水分离罐底部排出。The biomass material is initially cut into fragments and put into the gas explosion tank. After adding a certain amount of water, the temperature is raised to 140°C, and then compressed air is introduced to increase the pressure to 9MPa, and the pressure is released after being maintained at a constant temperature and pressure for 20 minutes. Sieve to obtain biomass raw materials that meet the particle size requirements; mix the biomass raw materials, dispersant, solvent, co-solvent, and water obtained in step a in a reactor at a certain ratio and stir evenly to prepare a biomass slurry, and preheat To 300°C; add the transition metal composite catalyst to the slurry of step b, increase the pressure in the reactor to 35MPa, and continue to heat up to 550°C by microwave assisted heating to make the reactant system in the reactor reach a liquid supercritical state The reaction is carried out for 50 minutes to form a reaction product; after the reaction in step c, the reaction product is discharged into the solid-liquid-gas separation tank, the separated solid product is discharged from the bottom of the tank to the dry product storage tank, and the separated gas product is discharged from the tank The top discharge, and the remaining liquid product enters the oil-water separation tank, the oil product is taken out from the top of the oil-water separation tank, and the water is discharged from the bottom of the oil-water separation tank.

Claims (10)

  1. 一种生物质材料的综合利用方法，其特征在于包括以下步骤：A method for comprehensive utilization of biomass materials, which is characterized by comprising the following steps:
    a.将生物质原料初步切割为碎段后放入气爆罐内，加入一定量水之后升温至100-150℃，再通入压缩空气升压至7-10MPa，恒温恒压下保持5-30min后卸压，过200目筛获得满足粒度要求的生物质原料；a. The biomass raw material is initially cut into fragments and put into the gas explosion tank, after adding a certain amount of water, the temperature is raised to 100-150℃, and then compressed air is introduced to increase the pressure to 7-10MPa, and the pressure is maintained at a constant temperature and pressure. After 30 minutes, the pressure is relieved, and the biomass raw material meeting the particle size requirements is obtained through a 200-mesh sieve;
    b.将步骤a得到的生物质原料、分散剂、溶剂、助溶剂、水在反应器中以一定的比例混合搅拌均匀，制得生物质浆料，并预热至120～350℃；b. The biomass raw materials, dispersant, solvent, cosolvent, and water obtained in step a are mixed and stirred uniformly in a certain ratio in a reactor to prepare a biomass slurry, and preheated to 120-350°C;
    c.向步骤b的料浆中加入过渡金属复合催化剂，升高反应器内压力至17～40MPa，并以微波辅助加热方式继续升温至400～650℃使反应器内的反应物体系达到液态超临界状态进行反应30-60分钟，形成反应产物；c. Add the transition metal composite catalyst to the slurry of step b, increase the pressure in the reactor to 17-40 MPa, and continue to raise the temperature to 400-650 ℃ by microwave-assisted heating to make the reactant system in the reactor reach a liquid super The reaction is carried out in a critical state for 30-60 minutes to form a reaction product;
    d.步骤c的反应结束后将反应产物排出到固液气分离罐中，将分离出的固体产物由罐底排出到干品储罐，分离出的气体产物从罐顶排出，而留下的液态产物进入油水分离罐，油品由油水分离罐顶部取出，水则由油水分离罐底部排出。d. After the reaction of step c, the reaction product is discharged into the solid-liquid-gas separation tank, the separated solid product is discharged from the bottom of the tank to the dry product storage tank, and the separated gas product is discharged from the top of the tank, leaving behind The liquid product enters the oil-water separation tank, the oil product is taken out from the top of the oil-water separation tank, and the water is discharged from the bottom of the oil-water separation tank.
  2. 根据权利要求1所述的方法，其特征在于：步骤a中处理后的所述生物质原料在气爆过程中对纤维结构破坏率低于1％。步骤b的溶剂为二甲基亚砜；助溶剂为NaF。The method according to claim 1, characterized in that the damage rate of the fiber structure to the fiber structure during the gas explosion process of the biomass raw material treated in step a is less than 1%. The solvent of step b is dimethyl sulfoxide; the co-solvent is NaF.
  3. 根据权利要求2所述的方法，其特征在于：所述生物质原料包括木屑、野草、树叶、秸秆、畜粪、食用菌渣中的一种或多种。The method according to claim 2, wherein the biomass raw material includes one or more of wood chips, weeds, leaves, straw, livestock manure, and edible fungus residue.
  4. 根据权利要求2所述的方法，其特征在于：步骤c的过渡金属复合催化剂为在多孔氧化铝或介孔碳基底上复合Fe、Co、Ni粉的复合催化剂。The method according to claim 2, wherein the transition metal composite catalyst in step c is a composite catalyst in which Fe, Co, and Ni powders are composited on a porous alumina or mesoporous carbon substrate.
  5. 根据权利要求2所述的方法，其特征在于：步骤d的固体产物进一步利用微波辅助加热碳化制得活性炭。The method according to claim 2, wherein the solid product in step d is further carbonized by microwave-assisted heating to obtain activated carbon.
  6. 根据权利要求2所述的方法，其特征在于：步骤d的气体产物经过气体除杂获得纯度高的富氢气体。The method according to claim 2, characterized in that: the gas product in step d is subjected to gas removal to obtain a high-purity hydrogen-rich gas.
  7. 根据权利要求2所述的方法，其特征在于：步骤d的油品为液体燃料。The method according to claim 2, wherein the oil product in step d is liquid fuel.
  8. 一种复合催化剂，该复合催化剂用于如权利要求1所述的生物质材料的综合利用方法中。A composite catalyst used in the comprehensive utilization method of biomass materials according to claim 1.
  9. 一种采用如权利要求1所述的生物质材料的综合利用方法获得的活性炭。An activated carbon obtained by adopting the method for comprehensive utilization of biomass materials according to claim 1.
  10. 一种富氢气体的制备方法，该富氢气体采用如权利要求1所述的生物质材料的综合利用方法制得。A method for preparing hydrogen-rich gas, which is prepared by the method for comprehensive utilization of biomass materials according to claim 1.
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