A method and system for producing hydrogen from biomass

Abstract

The present invention discloses a method and system for producing hydrogen from biomass, wherein the method firstly pre-treats a biomass raw material to obtain a first stream; then the obtained first stream enters a carbonization reactor for carbonization reaction, and after the reaction, a solid second stream and a gaseous third stream are obtained; the solid second stream obtained by the carbonization reactor enters a gasification reactor, and is contacted with water vapor for reaction, and after the reaction, a gaseous fourth stream is obtained; the gaseous fourth stream is further subjected to a water vapor shift reaction and pressure swing adsorption treatment to obtain a hydrogen product. The present invention converts biomass into a hydrogen product through a combined process, and has the advantages of simple process, high hydrogen yield, and high energy utilization.

Description

Technical Field

[0001] The present invention relates to the technical field of biomass utilization, and in particular to a method and system for producing hydrogen from biomass. Background Art

[0002] Hydrogen is non-toxic, lightweight, and has good combustion properties. It has the highest calorific value among traditional fuels and is recognized as a clean energy source. Its efficient development and utilization will help solve energy crises and environmental pollution problems. In the traditional petrochemical industry, hydrogen is an important raw material for the production of methanol and ammonia. In addition, hydrogen is also used to hydrocracking and hydrorefining of petroleum products to increase the yield of light oil and improve the quality of oil products. A large amount of hydrogen is also used in the gasification and liquefaction of coal. In the face of today's environmental and energy problems, hydrogen has shown new ways of use in more fields. For example, fuel cells have pushed the use of hydrogen to a new level, especially hydrogen fuel cell vehicles.

[0003] At present, hydrogen production basically relies entirely on fossil energy, which makes hydrogen energy unable to achieve the whole process of renewable and clean. Traditional hydrogen production processes such as water electrolysis and coal conversion have the disadvantages of high energy consumption and large carbon dioxide release. Biomass has the characteristics of zero carbon dioxide emissions and renewable resources, and hydrogen production technology using it as raw material has attracted attention. According to statistics, the annual biomass output in the world is about 30 billion tons, but only 4wt% is used as energy, and there is huge potential for hydrogen production. Biomass hydrogen production mainly includes biological method and thermochemical conversion method. From the application point of view, biological hydrogen production technology is not mature enough, the reaction rate is low, and it is not easy to scale up. The technical route of hydrogen production by catalytic reforming of biomass liquid products is complicated, while thermochemical hydrogen production is easier to achieve large-scale production and therefore attracts more attention.

[0004] Patent CN1435369A discloses a method for producing hydrogen by catalytic cracking of biomass, using air or / water vapor as the working gas, using animal and plant materials of a certain particle size as the biomass raw material, and the fluidized bed reactor includes a combustion zone, a catalytic gasification zone and a tar catalytic cracking zone. The generated hydrogen-rich gas contains more than 70% hydrogen. The hydrogen-rich gas is purified by a fixed bed tar cracker after dust removal by a cyclone separator. However, this process has the disadvantages of high gasification temperature, high energy consumption, high equipment requirements, expensive alkali metal catalysts and nickel-based catalysts, and harsh use conditions. Patent CN105692551A continuously feeds biomass and water vapor into a fluidized bed reactor for rapid cracking at 600°C. The generated cracking gas and biochar enter the fluidized bed reactor together with water vapor for synchronous gasification of cracking gas and biochar. The gas from the fluidized bed reactor undergoes catalytic reforming reaction to generate hydrogen-rich gas. The catalytic reforming uses Co and Cu-based modified catalysts, which have the disadvantages of harsh biomass water vapor gasification reaction conditions and expensive reforming catalysts. Patent CN 104194834 A provides a biomass chemical chain hydrogen production device, which uses NiFe2O4 oxygen carrier for chemical chain hydrogen production, but has problems such as expensive oxygen carrier, cycle life and reaction activity.

[0005] In summary, in order to further improve the utilization rate of biomass and hydrogen yield and obtain higher economic benefits, it is necessary to innovate on the basis of existing technologies and improve the rate and efficiency of hydrogen production. The development of new thermochemical conversion hydrogen production processes, cheap catalysts and energy consumption reduction of hydrogen production processes are still the focus and difficulty of research. Summary of the invention

[0006] In view of the common problems in the prior art, the purpose of the present invention is to provide a method and system for producing hydrogen from biomass, which converts biomass into hydrogen products through a combined process, and has the advantages of simple process, high hydrogen yield and high energy utilization rate.

[0007] The first aspect of the present invention provides a method for producing hydrogen from biomass according to a first embodiment, comprising the following steps:

[0008] (1) mixing the biomass raw material, the crude wood vinegar, and the iron-containing compound under contact conditions, mixing them uniformly and drying them to obtain a first material stream;

[0009] (2) The first material stream obtained in step (1) enters a carbonization reactor for a carbonization reaction, and after the reaction, a solid second material stream and a gaseous third material stream are obtained;

[0010] (3) The solid second stream obtained in the carbonization reactor of step (2) is mixed with the alkali metal sulfate, and after being evenly mixed, enters the gasification reactor, contacts with water vapor for reaction, and obtains the gaseous fourth stream after the reaction;

[0011] (4) The gas phase fourth stream obtained in step (3) is further subjected to water gas shift reaction and pressure swing adsorption treatment to obtain a hydrogen product.

[0012] The second aspect of the present invention provides a method for producing hydrogen from biomass according to a second embodiment, comprising the following steps:

[0013] (1) mixing the biomass raw material, the crude wood vinegar, the iron-containing compound, and the activated carbon under contact conditions, mixing them uniformly and drying them to obtain a first material stream;

[0014] (2) The first material stream obtained in step (1) enters a carbonization reactor for a carbonization reaction, and after the reaction, a solid second material stream and a gaseous third material stream are obtained;

[0015] (3) The solid second stream obtained in the carbonization reactor of step (2) is mixed with the alkali metal sulfate, and after being evenly mixed, enters the gasification reactor for activation, and then contacts with water vapor for reaction, and obtains the gaseous fourth stream after the reaction;

[0016] (4) The gas phase fourth stream obtained in the gasification reactor in step (3) is further subjected to water gas shift reaction and pressure swing adsorption treatment to obtain a hydrogen product.

[0017] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the biomass raw material can be derived from any material containing lignocellulose, such as forestry residues or agricultural residues, and more specifically can be any material containing lignocellulose such as straw, rice husk, wheat straw, wood block, leaves, branches, etc. The shape of the biomass raw material can be any shape such as sheet, round, cylindrical, conical, square, irregular, etc., and the largest dimension of the raw material in a direction does not exceed 30 mm, preferably 1 to 25 mm.

[0018] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the iron-containing compound is an iron salt and / or a ferrous salt, which can be selected from one or more of inorganic iron salts, inorganic ferrous salts, organic iron salts, and organic ferrous salts. Furthermore, the iron-containing compound can be specifically selected from one or more of ferric nitrate, ferric chloride, ferric sulfate, ferric carbonate, ferric acetate, ferric oxalate, ferric citrate, ferrous nitrate, ferrous chloride, and ferrous sulfate, preferably one or more of ferric nitrate, ferric chloride, ferrous sulfate, ferric acetate, ferric citrate, ferrous nitrate, ferrous chloride, and ferrous sulfate, and more preferably one or more of ferrous chloride, ferrous sulfate, and ferrous nitrate.

[0019] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the crude wood vinegar includes wood vinegar and wood tar. Furthermore, in general, the content of wood vinegar in the crude wood vinegar is 60-70wt%.

[0020] Furthermore, in the above-mentioned method for preparing synthesis gas by carbonization-gasification of biomass, the crude wood vinegar is obtained from the biomass pyrolysis or dry distillation system and is directly used without any separation and purification process. The plant organic composite substances such as acids, alcohols, ketones, aldehydes, etc. in the crude wood vinegar contain a certain amount of organic functional groups. On the one hand, through the mixing process, the water absorption and swelling of cellulose, hemicellulose and lignin in the biomass can be achieved, and the complete infiltration of aqueous substances can be achieved, which weakens the interaction between different components of the biomass and is more conducive to the carbonization process. On the other hand, the wood tar in the crude wood vinegar can be evenly dispersed on the surface of the biomass raw material through the mixing process.

[0021] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the weight ratio of the biomass raw material to the crude wood vinegar is 1:3 to 1:6.

[0022] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the activated carbon is one or more of biomass-based activated carbon, asphalt-based activated carbon, and petroleum coke-based activated carbon, preferably asphalt-based activated carbon and / or petroleum coke-based activated carbon with dense structure. Petroleum coke-based activated carbon refers to activated carbon with rich pore structure obtained by physical and / or chemical activation process using petroleum coke as raw material. Further preferably, the petroleum coke-based activated carbon is an activated carbon product obtained by activating petroleum coke produced in the coking process, and has a specific surface area of ​​1200 to 3000 m 2 / g, the pore size is generally 0.5-8nm, and the mesoporosity is 10%-30%. For those skilled in the art, the petroleum coke physics and / or activation process is well known and can be selected from existing methods as needed.

[0023] Furthermore, in the above method for producing hydrogen from biomass, the weight ratio of the biomass raw material to the activated carbon is 1:0.3 to 1:2.

[0024] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the rich pore structure and large pore volume of the activated carbon can achieve in-situ capture of the tar components produced by pyrolysis, especially the heavy tar components rich in polycyclic aromatic hydrocarbons, during the biomass pyrolysis carbonization process, which not only reduces the tar content in the pyrolysis gas, but also provides sufficient condensation reaction space for the heavy tar components, deposits amorphous coke on the inner surface of the activated carbon, increases the carbonization yield, and provides sufficient space for the amorphous biocoke on the inner surface of the activated carbon to react with water vapor during the biocoke gasification stage in the gasification reactor, thereby improving the gasification reaction conversion rate of the biocoke and the synthesis gas yield. The activated carbon basically does not participate in the reaction during the biomass pyrolysis process, and a small amount of reaction will occur during the biocoke gasification stage, but it has no effect on the properties of the synthesis gas product.

[0025] Furthermore, in the above method for producing hydrogen from biomass, the specific conditions for drying in step (1) are: the drying temperature is 40 to 100° C., and the drying is preferably carried out under vacuum conditions.

[0026] Furthermore, in the above method for producing hydrogen from biomass, the weight ratio of the biomass raw material to the iron-containing compound is 60:1 to 10:1, preferably 50:1 to 10:1.

[0027] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the carbonization reaction temperature in step (2) is 120-550°C, preferably 200-500°C; further preferably, the carbonization reaction is carried out in two stages, the carbonization reaction temperature of the first stage is 120-300°C, and the carbonization reaction temperature of the second stage is 350-550°C.

[0028] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the carbonization reaction is carried out in two stages, wherein the carbonization temperature of the first stage is relatively low, and the reaction is mainly based on the interaction between the biomass and wood vinegar. The lower carbonization temperature deepens the interaction process between the wood vinegar and the cellulose, lignin and hemicellulose in the biomass. The acids, alcohols, ketones, aldehydes and other plant organic complex substances in the wood vinegar further interact with the cellulose, hemicellulose and lignin in the biomass with the participation of activated carbon to achieve the initial carbonization of the biomass. In this process, the amount of gas and tar produced is relatively small, and more carbon precursors are retained for the second stage of carbonization. The second carbonization reaction is carried out at a relatively high reaction temperature. The carbonization process of biomass proceeds rapidly, and a certain amount of gas and tar are produced. Tar encounters activated carbon with rich pore structure during the escape process of gas. The rich pore structure of activated carbon reduces the escape rate of tar molecules. On the one hand, it can provide space for secondary cracking of light tar components produced in the process of wood vinegar and biomass carbonization. On the other hand, it increases the residence time of heavier tar macromolecules. Tar molecules and carbon deposit precursors deep inside the activated carbon particles are difficult to diffuse and transform in time, and coke and carbonize directly in the micropores, thereby increasing the yield of biomass charcoal. At the same time, the amorphous biochar generated inside the activated carbon has high reactivity, and is easy to undergo gasification reaction in the subsequent steam gasification process to increase the yield and selectivity of synthesis gas.

[0029] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the solid second material flow obtained after the carbonization reaction includes biochar, ash, elemental iron, ferroferric oxide, ferrous oxide, ferrous oxide, and iron salts.

[0030] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the alkali metal sulfate can be selected from one or more of lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, and francium sulfate.

[0031] Furthermore, in the above method for producing hydrogen from biomass, the weight ratio of the alkali metal sulfate to the biomass raw material is 1:50 to 1:10.

[0032] Furthermore, in the above-mentioned method for producing hydrogen from biomass, when the alkali metal sulfate is mixed with the solid second material flow from the carbonization reactor, a dry mixing method can be used for mixing. Specifically, before entering the gasification reactor, the solid second material flow from the carbonization reactor is propelled in a screw propeller, flipped up and down, etc. with the alkali metal sulfate to achieve uniform mixing, and the two are used as feed for the gasification reactor.

[0033] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the activation temperature in step (3) is 450-750°C, preferably 500-700°C; the activation is carried out in the presence of a reducing atmosphere, the reducing atmosphere can be a hydrogen-containing gas, specifically hydrogen, or a mixture of hydrogen and a carrier gas, the carrier gas is one or more of helium and nitrogen, and the volume fraction of hydrogen in the mixture is 5%-50%.

[0034] Furthermore, in the above method for producing hydrogen from biomass, the gasification reaction conditions in step (3) are: reaction temperature 700-950°C, preferably 750-900°C, and the water vapor flow rate is 0.05-0.8 mL / min.

[0035] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the water vapor shift reaction in step (4) can adopt the existing water vapor shift process in the art, such as the copper-based low-temperature shift catalyst B208, which is composed of CuO / ZnO / Al2O3 (CuO mass fraction 38%, ZnO mass fraction 40%, Al2O3 mass fraction 8%), and the catalyst particle size is 20-40 mesh. The gaseous fourth stream obtained in the gasification reactor in step (3) enters the water vapor shift device and reacts with the water vapor simultaneously entering the device. In general, the water vapor shift reaction conditions are: reaction temperature 250-300°C, volume flow ratio of water vapor to gaseous fourth stream 0.5-0.9, gasification gas volume space velocity 1500-2500h -1 .

[0036] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the pressure swing adsorption in step (4) is carried out by using an existing pressure swing adsorption device in the art, and the outlet gas of the water vapor conversion device is sent to the adsorbent bed of the pressure swing adsorption device. The adsorbent can be a graded adsorbent composed of activated carbon, molecular sieve, silica gel, and activated alumina in a certain proportion. Through pressure change, high-purity hydrogen flows out from the outlet through the adsorption layer, and the pressure swing adsorption system is depressurized, desorbed, replaced, and evacuated to -0.08MPa. After desorption, the pressure is increased to regenerate the pressure swing adsorption system, and the process is cyclically processed in sequence. The pressure swing adsorption operating conditions are: pressure of 1.5-4MPa and temperature of 20-30°C.

[0037] Furthermore, in the above-mentioned method for producing hydrogen from biomass, the gaseous third stream obtained from the carbonization reaction in the carbonization reactor in step (2) is a volatile gas, including combustible gases generated during biomass pyrolysis and carbonization, volatile tar components, and other gases escaping from the carbonization reactor in gaseous form. Furthermore, the gaseous third stream from the carbonization reactor can enter the burner for full combustion (meaning that the combustion products are only carbon dioxide and water), and the heat generated by the combustion is supplied to the steam generator, the carbonization reactor, and the gasification reactor, with priority given to the steam generator, and the excess heat is used to assist the carbonization reactor and the gasification reactor.

[0038] The third aspect of the present invention provides a system for producing hydrogen from biomass, comprising the following contents:

[0039] A mixer for receiving and mixing the biomass feedstock, the crude wood vinegar, the iron-containing compound and optionally the activated carbon;

[0040] A dryer, which is used to receive and dry the material after being evenly mixed from the mixer, and obtain a first material flow after drying;

[0041] A carbonization reactor is used to receive the first material flow obtained from the dryer. The first material flow enters the carbonization reactor for carbonization reaction to obtain a solid second material flow and a gaseous third material flow after the reaction.

[0042] A gasification reactor is used to receive the solid second material flow and the alkali metal sulfate obtained from the carbonization reactor. After the solid second material flow and the alkali metal sulfate are evenly mixed, they enter the gasification reactor for activation and then contact with water vapor for reaction to obtain a gaseous fourth material flow;

[0043] A water gas shift reactor, which is used to receive a fourth gaseous material stream obtained after a reaction in a gasification reactor and obtain a fifth gaseous material stream after treatment;

[0044] The pressure swing adsorption reactor is used to receive the gas phase fifth material flow obtained after treatment in the water gas shift reactor, and obtain hydrogen after treatment.

[0045] Furthermore, in the above-mentioned biomass hydrogen production system, the dryer can adopt any one of the existing devices in the art that can achieve the drying function, specifically any one or more of a blast drying oven, a vacuum drying oven, a hot air circulation oven, etc.

[0046] Furthermore, in the above-mentioned biomass system for producing hydrogen, the carbonization reactor can adopt any one of the existing carbonization reactors in the art, specifically any one of the biomass microwave vertical fixed bed reactor, the biomass spiral propeller carbonization reactor, the biomass rotary furnace carbonization reactor, etc.

[0047] Furthermore, in the above biomass hydrogen production system, the gasification reactor can be any one of a microwave vertical fixed bed gasification reactor, a microwave fluidized bed gasification reactor, an electric heating vertical fixed bed reactor, and the like.

[0048] Furthermore, the above-mentioned system for producing hydrogen from biomass includes a steam generator for generating water vapor.

[0049] Furthermore, the above-mentioned biomass hydrogen production system includes a burner, and the gaseous third material flow from the carbonization reactor enters the burner for complete combustion (the complete combustion generally refers to the combustion products being only carbon dioxide and water), and the heat generated by the gas combustion can be supplied to the steam generator, the carbonization reactor and the gasification reactor for use. Preferably, the steam generator is first supplied for use, and the excess heat is used to assist the carbonization reactor and the gasification reactor.

[0050] Furthermore, in the above-mentioned biomass hydrogen production system, the water vapor shift reactor and the pressure swing adsorption reactor adopt any one of the existing devices in the field, and those skilled in the art can select a water vapor shift reactor and a pressure swing adsorption reactor suitable for the technical solution of the present application from the existing devices according to actual needs.

[0051] Compared with the prior art, the method and system for producing hydrogen from biomass of the present invention have the following technical effects:

[0052] 1. In the biomass hydrogen production method of the present invention, in the gasification reactor, the biocoke gasification process uses alkali metal sulfate and iron-containing compounds as gasification catalysts, and produces a metastable active component group in the biocoke water vapor gasification system through in-situ ion exchange, hydrolysis, reduction and other reactions, which greatly improves the hydrogen production reaction activity of biocoke and overcomes the problem of low catalytic activity when cheap alkali metal sulfate is used as a catalytic material. In addition, the catalytic materials used are widely available, alkali metal sulfate can be obtained from natural ores and seawater, and iron-based catalysts are inexpensive compared to precious metal catalysts, which greatly reduces the catalytic cost of biocoke water vapor gasification, and can also be recycled and reused through a water-soluble method.

[0053] 2. In the biomass hydrogen production method of the present invention, the biomass raw material is converted into a hydrogen product through a carbonization-gasification combined treatment process, which has the advantages of simple process, high hydrogen yield and high energy utilization rate.

[0054] 3. In the biomass hydrogen production method of the present invention, the crude wood vinegar derived from the biomass pyrolysis or dry distillation process is reused in the method of the present invention, which not only finds a suitable utilization path for the low-value-added crude wood vinegar, but also effectively promotes the biomass carbonization process without affecting the product properties. In addition, the use of crude wood vinegar can effectively enhance the dispersibility of iron-containing compounds on the inner and outer surfaces of biomass raw materials and improve the catalytic effect.

[0055] 4. In the biomass hydrogen production method of the present invention, the two-stage carbonization process is adjusted to effectively cooperate with wood vinegar and activated carbon to achieve in-situ capture and conversion of tar components, significantly improve the coke yield, and at the same time, in the biocoke gasification stage, provide sufficient space for the amorphous biocoke on the inner surface of the activated carbon to react with water vapor, thereby maximizing the gasification reaction conversion rate of the biocoke and the synthesis gas yield.

[0056] 5. In the biomass hydrogen production method of the present invention, the volatile components generated in the carbonization reactor are sent to the burner in a high-temperature state for combustion, and the tar components are burned together with the combustible gas in a gaseous state to avoid environmental pollution caused by tar emissions and gas purification, prevent the pipeline blockage caused by tar condensation, and solve the oil and gas separation problem, greatly simplifying the reaction steps. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, providing heat and reaction temperature for the hydrogen production reaction, assisting the energy supply of the entire process, and ensuring the smooth operation of the reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a schematic flow chart of the method for producing hydrogen from biomass of the present invention. DETAILED DESCRIPTION

[0058] The present invention is described in detail below with reference to the embodiments, but the protection scope of the present invention is not limited by the embodiments.

[0059] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0060] In this document, for the convenience of description, spatial relative terms such as "below", "below", "down", "above", "above", "upper", etc. may be used to describe the relationship between one element or feature and another element or feature in the accompanying drawings. It should be understood that the spatial relative terms are intended to include different directions of objects in use or operation in addition to the directions drawn in the drawings. For example, if the object in the figure is turned over, the elements described as being "below" or "below" other elements or features will be oriented "above" the elements or features. Therefore, the exemplary term "below" can include both below and above directions. Objects may also have other orientations (rotated 90 degrees or other orientations) and the spatial relative terms used in this document should be interpreted accordingly.

[0061] In this document, the terms "first", "second", etc. are used to distinguish two different elements or parts, and are not used to limit a specific position or relative relationship. In other words, in some embodiments, the terms "first", "second", etc. can also be interchangeable.

[0062]

[0043] All numerical values ​​for parameters (eg, amounts or conditions) herein are to be understood as being modified in all instances by the term "about", whether or not "about" actually appears before the numerical value.

[0063] In this paper, the specific surface area and pore size distribution curves of the samples were obtained by nitrogen adsorption-desorption curves on a Micromeritics ASAP 2020 adsorption instrument. The operating temperature was -196 °C (liquid nitrogen temperature). The samples were pretreated with dehydration at 300 °C under nitrogen protection before testing. The specific surface area and pore size distribution were calculated by the BET method and the DFT method, respectively.

[0064] Example 1

[0065] Weigh 100g of petroleum coke, mix the petroleum coke with 280g of potassium hydroxide, activate it at 800℃ for 40min in a nitrogen atmosphere, cool it to room temperature, wash the product with dilute hydrochloric acid and deionized water to neutrality, dry it in a blast drying oven at 105℃ for 10h, and obtain petroleum coke-based activated carbon. The specific surface area is 1896m 2 / g, mesoporosity 18%, pore size range 0.5 ~ 8nm.

[0066] Example 2

[0067] Weigh 100g of high softening point asphalt, mix petroleum coke with 280g of potassium hydroxide, activate at 850℃ for 60min in nitrogen atmosphere, cool to room temperature, wash the product with dilute hydrochloric acid and deionized water to neutrality, dry it at 105℃ in a blast drying oven for 10h to obtain asphalt-based activated carbon. The specific surface area is 2014m 2 / g, mesoporosity 14%, pore size range 0.5 ~ 15nm.

[0068] Example 3

[0069] Weigh 100 g of coconut shell carbonized material, activate the coconut shell at 800 °C in a nitrogen-water vapor atmosphere with a water vapor flux of 0.1 mL / min for 5 h, cool to room temperature, and dry at 105 °C in a forced air drying oven for 4 h to obtain bio-based activated carbon. The specific surface area was determined by a physical adsorption instrument to be 1056 m 2 / g, mesoporosity 19%, pore size range 0.8~50nm.

[0070] Example 4

[0071] Add 0.55g of iron nitrate Fe(NO3)3 into 98.4g of crude wood vinegar and stir to dissolve, weigh 32.8g of three-year-old bamboo and willow crushed material and 9.84g of bio-based activated carbon, stir and mix evenly, let it stand and soak for 6h, and dry it at 40℃ in vacuum for 24h to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 120°C for 60 min, and the second carbonization reaction temperature was 550°C for 50 min. The solid second stream obtained after the carbonization reaction was evenly mixed with 3.28 g K2SO4 in a screw feeder and entered the gasification reactor. It was activated at 750°C under a nitrogen-hydrogen mixed atmosphere (hydrogen gas volume fraction was 20%) for 20 min. After the activation, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 700°C, normal pressure, water vapor flux of 0.8 mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction of 50.2%. The gasification gas was further increased by the water vapor shift reactor to increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 61.8%, and the hydrogen concentration could be increased to 98% by pressure swing adsorption. The biomass hydrogen production rate of the entire process was 124.8 g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0072] Example 5

[0073] 3.06 g of ferrous sulfate FeSO4·7H2O was added to 183.6 g of crude wood vinegar and stirred to dissolve. 30.6 g of chopped fish-scale spruce and 61.2 g of petroleum coke-based activated carbon were weighed and stirred to mix evenly. The mixture was allowed to stand and soak for 6 h, and dried at 100°C in vacuum for 20 h to obtain a first material stream. The first stream was added to the carbonization reactor for reaction. The temperature of the first carbonization reaction was 300°C for 40 minutes. The second carbonization reaction was 350°C for 60 minutes. The solid second stream of the carbonization reaction was evenly mixed with 0.61g K2SO4 in a screw feeder and entered the gasification reactor. The catalyst was activated at 450°C under a hydrogen atmosphere for 40 minutes. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 950°C, normal pressure, water vapor flux 0.05mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 53.9%. The gasification gas passed through the water vapor shift reactor to further increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 62.3%. The hydrogen concentration can be increased to 97% by pressure swing adsorption. The biomass hydrogen production rate of the entire process is 67.2g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0074] Example 6

[0075] Add 1.78 g of ferrous chloride FeCl2 into 135.6 g of crude wood vinegar and stir to dissolve, weigh 33.9 g of ground Larix gmelinii and 30.5 g of asphalt-based activated carbon and stir to mix evenly, let stand and soak for 6 hours, and dry at 80°C in vacuum for 15 hours to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 300°C for 40 minutes. The second carbonization reaction temperature was 350°C for 60 minutes. The solid second stream of the carbonization reaction was evenly mixed with 2.32gK2SO4 in a screw feeder and entered the gasification reactor. It was activated at 550°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 50%) for 40 minutes. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 950°C, normal pressure, water vapor flux 0.05mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 51.3%. The gasification gas was further increased by the water vapor shift reactor to increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 62.9%. The hydrogen concentration can be increased to 99% by pressure swing adsorption. The biomass hydrogen production rate of the entire process is 137.2g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0076] Example 7

[0077] 2.53 g of ferric chloride FeCl3▪6H2O was added to 119.6 g of crude wood vinegar and stirred to dissolve. 31.5 g of larch crushed material and 22.5 g of asphalt-based activated carbon were weighed and stirred to mix evenly. The mixture was allowed to stand and soak for 6 h, and dried at 80°C in vacuum for 15 h to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 280°C for 60 min, the second carbonization reaction temperature was 450°C for 40 min, the solid second stream of the carbonization reaction was mixed evenly with 2.51 g Na2SO4 in a screw feeder and entered the gasification reactor, and activated at 500°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 30%) for 50 min. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 800°C, normal pressure, water vapor flux 0.25 mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 54.2%. The gasification gas was further increased through the water vapor shift reactor to increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 61.8%, and the hydrogen concentration could be increased to 98% through pressure swing adsorption. The biomass hydrogen production rate of the entire process was 109.4 g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0078] Example 8

[0079] 1.71 g of ferric acetate Fe(COOCH3)2 was added to 167.0 g of crude wood vinegar and stirred to dissolve. 33.4 g of red spruce crushed material and 33.4 g of petroleum coke-based activated carbon were weighed and stirred to mix evenly. The mixture was allowed to stand and soak for 6 h, and dried at 80°C in vacuum for 15 h to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 270°C for 60 min, and the second carbonization reaction temperature was 440°C for 40 min. The solid second stream of the carbonization reaction was evenly mixed with 2.08 g K2SO4 in a screw feeder and entered the gasification reactor. It was activated at 500°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 20%) for 60 min. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 790°C, normal pressure, water vapor flux 0.40 mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 50.8%. The gasification gas passed through the water vapor shift reactor to further increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 65.7%, and the hydrogen concentration could be increased to 99% by pressure swing adsorption. The biomass hydrogen production rate of the entire process was 167.2 g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0080] Example 9

[0081] 3.06 g of ferrous sulfate FeSO4·7H2O was added to 183.6 g of crude wood vinegar and stirred to dissolve, 30.6 g of chopped fish-scale spruce was weighed, stirred and mixed evenly, allowed to stand and soak for 6 h, and dried at 100° C. in vacuum for 20 h to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The temperature of the first carbonization reaction was 300°C for 40 minutes. The second carbonization reaction was 350°C for 60 minutes. The solid second stream of the carbonization reaction was evenly mixed with 0.61g K2SO4 in a screw feeder and entered the gasification reactor. The catalyst was activated at 450°C under a hydrogen atmosphere for 40 minutes. After the activation, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 950°C, normal pressure, water vapor flux 0.05mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 51.8%. The gasification gas passed through the water vapor shift reactor to further increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 61.8%, and the hydrogen concentration could be increased to 97% by pressure swing adsorption. The biomass hydrogen production rate of the entire process was 48.7g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0082] Example 10

[0083] 1.71 g of ferric acetate Fe(COOCH3)2 was added to 167.0 g of crude wood vinegar and stirred to dissolve. 33.4 g of red spruce crushed material and 33.4 g of petroleum coke-based activated carbon were weighed and stirred to mix evenly. The mixture was allowed to stand and soak for 6 h, and dried at 80°C in vacuum for 15 h to obtain the first material stream. The first material stream was added to the carbonization reactor for reaction at a carbonization reaction temperature of 440°C for 40 minutes. The solid second material stream of the carbonization reaction was evenly mixed with 2.08gK2SO4 in a screw feeder and entered the gasification reactor for activation at 500°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 20%) for 60 minutes. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 790°C, normal pressure, water vapor flux of 0.40mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction of 52.7%. The gasification gas was further increased through a water vapor shift reactor to increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 63.1%, and the hydrogen concentration could be increased to 97% through pressure swing adsorption. The biomass hydrogen production rate of the entire process was 152.4g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0084] Comparative Example 1

[0085] 1.78 g of ferrous chloride FeCl2·4H2O was added to 135.6 g of water and stirred to dissolve. 33.9 g of ground Larix gmelinii and 30.5 g of asphalt-based activated carbon were weighed and stirred to mix evenly. The mixture was allowed to stand and soak for 6 h, and dried at 80°C in vacuum for 15 h to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 300°C for 40 min, and the second carbonization reaction temperature was 350°C for 60 min. The solid second stream of the carbonization reaction was evenly mixed with 2.32 g K2SO4 in a screw feeder and entered the gasification reactor. It was activated at 550°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 50%) for 40 min. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 950°C, normal pressure, water vapor flux 0.05 mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 52.7%. The gasification gas passed through the water vapor shift reactor to further increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 61.2%, and the hydrogen concentration could be increased to 98% by pressure swing adsorption. The biomass hydrogen production rate of the entire process was 118.5 g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0086] Comparative Example 2

[0087] 31.5 g of larch crushed material and 22.5 g of asphalt-based activated carbon were weighed and added into 119.6 g of crude wood vinegar, stirred and mixed evenly, allowed to stand and soak for 6 h, and dried at 80° C. in vacuum for 15 h to obtain a first material stream. The first material stream is added to the carbonization reactor for reaction. The temperature of the first carbonization reaction is 280°C, and the reaction time is 60 minutes. The second carbonization reaction temperature is 450°C, and the reaction time is 40 minutes. The solid phase second material stream of the carbonization reaction is evenly mixed with 2.51gNa2SO4 in a screw feeder and enters the gasification reactor. Water vapor is introduced for water vapor gasification reaction. The reaction conditions are: temperature 800°C, normal pressure, water vapor flux 0.25mL / min, and the gas composition at the outlet of the gasification reactor is H2 volume fraction 54.2%. The gasification gas passes through the water vapor shift reactor to further increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reaches 62.5%. The hydrogen concentration can be increased to 97% by pressure swing adsorption. The biomass hydrogen production rate of the entire process is 102.6g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0088] Comparative Example 3

[0089] 1.71 g of ferric acetate Fe(COOCH3)2 was added to 167.0 g of crude wood vinegar and stirred to dissolve. 33.4 g of red spruce crushed material and 33.4 g of petroleum coke-based activated carbon were weighed and stirred to mix evenly. The mixture was allowed to stand and soak for 6 h, and dried at 80°C in vacuum for 15 h to obtain the first material stream. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 270°C for 60 min, and the second carbonization reaction temperature was 440°C for 40 min. The solid second stream of the carbonization reaction was pushed into the gasification reactor in a screw feeder and activated at 500°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 20%) for 60 min. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 790°C, normal pressure, water vapor flux 0.40 mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 58.7%. The gasification gas was further increased through the water vapor shift reactor to increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 61.8%, and the hydrogen concentration could be increased to 98% through pressure swing adsorption. The biomass hydrogen production rate of the entire process was 121.7 g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0090] Comparative Example 4

[0091] 1.78g of ferrous chloride FeCl2·4H2O was added to 135.6g of crude wood vinegar and stirred to dissolve. 33.9g of Scotch pine crushed material and 30.5g of asphalt-based activated carbon (specific surface area 1244m 2 / g, mesoporosity 2%, pore size mainly micropores below 1 nm) were stirred and mixed evenly, allowed to stand and impregnate for 6 hours, and dried at 80°C in vacuum for 15 hours to obtain the first material flow. The first stream was added to the carbonization reactor for reaction. The first carbonization reaction temperature was 300°C for 40 min, and the second carbonization reaction temperature was 350°C for 60 min. The solid second stream of the carbonization reaction was evenly mixed with 2.32 g K2SO4 in a screw feeder and entered the gasification reactor. It was activated at 550°C under a helium-hydrogen mixed atmosphere (hydrogen gas volume fraction was 50%) for 40 min. After the activation was completed, water vapor was introduced for water vapor gasification reaction. The reaction conditions were: temperature 950°C, normal pressure, water vapor flux 0.05 mL / min, and the gas composition at the outlet of the gasification reactor was H2 volume fraction 53.8%. The gasification gas was further increased by the water vapor shift reactor to increase the hydrogen concentration in the gas. The H2 volume fraction in the gas from the outlet of the water vapor shift reactor reached 62.1%, and the hydrogen concentration could be increased to 98% by pressure swing adsorption. The biomass hydrogen production rate of the entire process was 119.8 g hydrogen / kg biomass. At the same time, the volatile components produced in the carbonization reactor are sent to the combustion furnace at high temperature for combustion. Through the regenerative heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor, thus providing guarantee for the energy supply of the entire process, greatly reducing the energy consumption of the process itself, and only a small amount of auxiliary heating is needed to ensure the smooth operation of the reaction.

[0092] It can be seen from the data of Examples 1-10 that in the biomass carbonization process of the present invention, the yield of biocoke is maximized by impregnating crude wood vinegar, adding petroleum coke-based activated carbon, adjusting the temperature, etc., and the iron salt and the alkali metal sulfate are effectively coupled, and a strong interaction occurs during the catalyst activation process to form an intermediate substance that can improve the reaction activity of potassium salt and fix potassium at the same time, which can significantly improve the water vapor gasification reaction activity and reduce the gasification reaction temperature. At the same time, it also plays a good role in fixing the alkali metal and greatly reduces the volatilization amount of the alkali metal.

[0093] In the present invention, the volatile components generated in the carbonization reactor are sent to the combustion furnace in a high-temperature state for combustion, and the tar components are burned together with the combustible gas in a gaseous state to avoid environmental pollution caused by tar emissions and gas purification, prevent the problem of pipeline blockage caused by tar condensation, and avoid the complicated solution of oil and gas separation problems, greatly simplifying the reaction steps. Through the heat storage heat exchanger, the huge heat generated by the combustion of the volatile components is supplied to the steam generator, the carbonization reactor, and the gasification reactor to provide heat and reaction temperature for the hydrogen production reaction, provide most of the energy supply for the entire process, ensure the smooth operation of the reaction, and greatly reduce the energy consumption of the reaction. Therefore, the method and system for producing hydrogen from biomass disclosed in the present invention have the advantages of simple process, high hydrogen yield, and high energy utilization rate, and have broad promotion value.

Claims

1. A method for producing hydrogen from biomass, comprising the following steps: (1) mixing a biomass raw material, a crude wood vinegar, and an iron-containing compound under contact conditions, mixing them uniformly and drying them to obtain a first material stream; after the crude wood vinegar is obtained from the biomass pyrolysis system, it is directly used without any separation and purification process; (2) The first material stream obtained in step (1) enters a carbonization reactor for a carbonization reaction, and after the reaction, a solid second material stream and a gaseous third material stream are obtained; (3) The solid second stream obtained in the carbonization reactor of step (2) is mixed with the alkali metal sulfate, and after being evenly mixed, enters the gasification reactor for activation, and then contacts with water vapor for reaction, and after the reaction, obtains the gaseous fourth stream; (4) The gas phase fourth stream obtained in step (3) is further subjected to water gas shift reaction and pressure swing adsorption treatment to obtain a hydrogen product.

2. A method for producing hydrogen from biomass, comprising the following steps: (1) under contact conditions, mixing a biomass raw material, crude wood vinegar, an iron-containing compound, and activated carbon, mixing them uniformly and drying them to obtain a first material stream; after the crude wood vinegar is obtained from the biomass pyrolysis system, it is directly used without any separation and purification process; (2) The first material stream obtained in step (1) enters a carbonization reactor for a carbonization reaction, and after the reaction, a solid second material stream and a gaseous third material stream are obtained; (3) The solid second stream obtained in the carbonization reactor of step (2) is mixed with the alkali metal sulfate, and after being evenly mixed, enters the gasification reactor for activation, and then contacts with water vapor for reaction, and after the reaction, obtains the gaseous fourth stream; (4) The gas phase fourth stream obtained in the gasification reactor in step (3) is further subjected to water gas shift reaction and pressure swing adsorption treatment to obtain a hydrogen product.

3. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: Biomass raw materials are any materials containing lignocellulose, such as forestry residues or agricultural residues.

4. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The iron-containing compound is a ferric salt and / or a ferrous salt, which is selected from one or more of inorganic ferric salts, inorganic ferrous salts, organic ferric salts and organic ferrous salts.

5. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The iron-containing compound is selected from one or more of ferric nitrate, ferric chloride, ferric sulfate, ferric carbonate, ferric acetate, ferric oxalate, ferric citrate, ferrous nitrate, ferrous chloride and ferrous sulfate.

6. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The iron-containing compound is one or more of ferric nitrate, ferric chloride, ferric sulfate, ferric acetate, ferric citrate, ferrous nitrate, ferrous chloride and ferrous sulfate.

7. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The iron-containing compound is one or more of ferrous chloride, ferrous sulfate and ferrous nitrate.

8. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The crude wood vinegar comprises wood vinegar and wood tar, and the content of wood vinegar in the crude wood vinegar is 60-70wt%.

9. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The weight ratio of the biomass raw material to the crude wood vinegar is 1:3 to 1:

6.

10. The method for producing hydrogen from biomass according to claim 2, wherein: The activated carbon is one or more of biomass-based activated carbon, asphalt-based activated carbon, and petroleum coke-based activated carbon.

11. The method for producing hydrogen from biomass according to claim 10, wherein: Petroleum coke-based activated carbon refers to activated carbon with rich pore structure obtained by physical and / or chemical activation process using petroleum coke as raw material, with a specific surface area of ​​1200-3000m 2 / g, the pore size is 0.5~8nm, and the mesoporosity is 10%~30%.

12. The method for producing hydrogen from biomass according to claim 2, wherein: The weight ratio of biomass raw material to activated carbon is 1:0.3 to 1:

2.

13. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The drying conditions in step (1) are: the drying temperature is 40 to 100°C.

14. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The drying in step (1) is carried out under vacuum conditions.

15. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The weight ratio of the biomass raw material to the iron-containing compound is 60:1 to 10:

1.

16. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The weight ratio of the biomass raw material to the iron-containing compound is 50:1 to 10:

1.

17. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The carbonization reaction in step (2) is carried out in two stages. The carbonization reaction temperature in the first stage is 120-300°C, and the carbonization reaction temperature in the second stage is 350-550°C.

18. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The alkali metal sulfate is selected from one or more of lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate and francium sulfate.

19. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The weight ratio of alkali metal sulfate to biomass raw material is 1:50 to 1:

10.

20. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The activation temperature in step (3) is 450-750° C. The activation is carried out in the presence of a reducing atmosphere, wherein the reducing atmosphere is a hydrogen-containing gas, which is a mixture of hydrogen and a carrier gas, wherein the carrier gas is one or more of helium and nitrogen, and the volume fraction of hydrogen in the mixture is 5%-50%.

21. The method for producing hydrogen from biomass according to claim 20, wherein: The activation temperature in step (3) is 500-700°C.

22. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The gasification reaction conditions in step (3) are: reaction temperature 700-950°C, water vapor flow rate 0.05-0.8 mL / min.

23. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The gasification reaction conditions in step (3) are: reaction temperature 750-900°C, water vapor flow rate 0.05-0.8 mL / min.

24. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The gas phase fourth material flow obtained in the gasification reactor in step (3) enters the water vapor shift device and reacts with the water vapor simultaneously entering the device. The water vapor shift reaction conditions are: reaction temperature 250-300°C, volume flow ratio of water vapor to gas phase fourth material flow 0.5-0.9, gasification gas volume space velocity 1500-2500h -1 .

25. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The pressure swing adsorption operating conditions in step (4) are: pressure of 1.5-4 MPa and temperature of 20-30°C.

26. The method for producing hydrogen from biomass according to claim 1 or 2, wherein: The gas phase third material flow from the carbonization reactor enters the burner for full combustion, and the heat generated by the combustion is supplied to the steam generator, the carbonization reactor and the gasification reactor.

27. A system for producing hydrogen from biomass, comprising the following contents: A mixer, which is used to receive and mix the biomass raw material, the crude wood vinegar, and the iron-containing compound. After the crude wood vinegar is obtained from the biomass pyrolysis system, it is directly used without any separation and purification process; A dryer, which is used to receive and dry the material after being evenly mixed from the mixer, and obtain a first material flow after drying; A carbonization reactor is used to receive the first material flow obtained from the dryer. The first material flow enters the carbonization reactor for carbonization reaction to obtain a solid second material flow and a gaseous third material flow after the reaction. A gasification reactor is used to receive the solid second material flow and the alkali metal sulfate obtained from the carbonization reactor. After the solid second material flow and the alkali metal sulfate are evenly mixed, they enter the gasification reactor for activation and then contact with water vapor for reaction to obtain a gaseous fourth material flow; A water gas shift reactor, which is used to receive a fourth gaseous material stream obtained after a reaction in a gasification reactor and obtain a fifth gaseous material stream after treatment; The pressure swing adsorption reactor is used to receive the gas phase fifth material flow obtained after treatment in the water gas shift reactor, and obtain hydrogen after treatment.

28. A system for producing hydrogen from biomass, comprising the following contents: A mixer, which is used to receive and mix the biomass raw material, crude wood vinegar, iron-containing compounds and activated carbon. After the crude wood vinegar is obtained from the biomass pyrolysis system, it is directly used without any separation and purification process; A dryer, which is used to receive and dry the material after being evenly mixed from the mixer, and obtain a first material flow after drying; A carbonization reactor is used to receive the first material flow obtained from the dryer. The first material flow enters the carbonization reactor for carbonization reaction to obtain a solid second material flow and a gaseous third material flow after the reaction. A gasification reactor is used to receive the solid second material flow and the alkali metal sulfate obtained from the carbonization reactor. After the solid second material flow and the alkali metal sulfate are evenly mixed, they enter the gasification reactor for activation and then contact with water vapor for reaction to obtain a gaseous fourth material flow; A water gas shift reactor, which is used to receive a fourth gaseous material stream obtained after a reaction in a gasification reactor and obtain a fifth gaseous material stream after treatment; The pressure swing adsorption reactor is used to receive the gas phase fifth material flow obtained after treatment in the water gas shift reactor, and obtain hydrogen after treatment.

29. The system for producing hydrogen from biomass according to claim 27 or 28, wherein: A water vapor generator is included for generating water vapor.

30. The system for producing hydrogen from biomass according to claim 27 or 28, wherein: The invention comprises a burner. The gas phase third material flow from the carbonization reactor enters the burner for full combustion. The heat generated by the combustion is supplied to the steam generator, the carbonization reactor and the gasification reactor.

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