A catalyst for promoting hydrogen production from mixed biomass pyrolysis or gasification, and a preparation method and application thereof

Abstract

The application discloses a catalyst for promoting hydrogen production by mixed biomass pyrolysis or gasification, and a preparation method and application thereof. According to the catalyst disclosed by the application, the particle size is small, the metal is uniformly distributed, and the original porous channel structure of the CaO carrier is reserved. When the catalyst is applied to a process of preparing hydrogen-rich fuel gas by catalytic pyrolysis of paper materials and plastic mixtures, the catalyst has the advantages of high reaction activity, high hydrogen selectivity and good stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen-rich fuel gas production process and catalyst, and particularly relates to a catalyst for promoting hydrogen production by mixed biomass pyrolysis or gasification and a preparation method and application thereof. BACKGROUND

[0002] Organic solid waste is a kind of generalized biomass resource, and paper materials and plastic products are main categories in municipal solid waste. For example, paper printed matter can be regarded as a composite material of biomass and thermoplastic plastic, and has the characteristics of fixed proportion and stable properties. Compared with wood-plastic materials prepared by general melting mixing, the paper material does not contain moisture and does not need complicated pretreatment, and can be effectively collected and utilized as resources. The mixed biomass can be understood as containing at least one biomass, and the biomass refers to a substance produced by organisms in nature or a living substance or its primary processed product produced by human production activities (including agricultural, animal husbandry and industrial production activities), such as grains, wood, meat, fur, cells and the like. It can also refer to biological raw materials or waste available in nature.

[0003] The hydrogen-rich fuel gas is a kind of synthetic gas rich in hydrogen energy. The hydrogen energy is a kind of energy with the most development potential in the 21st century. Nowadays, the application of hydrogen energy has penetrated into various industries, and its uses include: 1) as a high-energy fuel; 2) for power generation, such as hydrogen fuel cells and the like; 3) for industrial fields and the like. The hydrogen-rich fuel gas developed from various biomasses is a typical "green energy", and can be directly combusted by a Fischer-Tropsch process or further converted into other chemical substances. For example, it can be converted into liquid hydrocarbons, mainly diesel and kerosene, and can also be converted into dimethyl ether (DME), in addition to which bio-synthetic natural gas (Bio-SNG) and bio-dimethyl ether (Bio-DME) can be used as fuels for gasoline or diesel vehicles, respectively.

[0004] Among numerous thermochemical conversion methods for producing hydrogen, pyrolysis is a practical method because pyrolysis can produce synthesis gas, liquid oil and char at a temperature of 300 to 1000 degrees Celsius from solid raw materials, and the synthesis gas is mainly non-condensable gas such as H2, CO, CO2 and CH4. Therefore, catalytic pyrolysis is considered as an effective strategy for converting low-value solid waste into high-value fuel.

[0005] In the field of catalytic pyrolysis for producing hydrogen-rich fuel gas, the main problem faced by pyrolysis for hydrogen production is the large amount of by-products produced in the pyrolysis process, especially the production of tar which can block the reactor, reduce the heat transfer efficiency and affect the normal progress of the reaction. The catalyst with single performance is not ideal in improving the yield of hydrogen-rich components in the fuel gas and the stability of the catalyst in the use process, and therefore it is necessary to prepare a composite catalyst with good performance, high catalytic efficiency and high stability. SUMMARY

[0006] The present application aims to provide a green catalyst for promoting hydrogen production from mixed biomass pyrolysis or gasification, and a preparation method and application thereof, so as to solve the above technical problems.

[0007] According to an aspect of the present application, a catalyst for promoting hydrogen production from mixed biomass pyrolysis or gasification is provided, which comprises nickel (Ni), iron (Fe) and calcium oxide (CaO).

[0008] Preferably, the catalyst comprises NiO, CaO, Fe2O3 and Ca2Fe2O5 tetraphase.

[0009] Preferably, in the XRD pattern of the catalyst, the diffraction angle position of the first strong peak is 43.29°, the diffraction angle position of the second strong peak is 33.16°, and the diffraction angle position of the third strong peak is 37.25°.

[0010] Preferably, the catalyst comprises 30wt% of Ni, 20wt% of Fe and 50wt% of CaO.

[0011] Preferably, the CaO in the catalyst has a multi-channel structure, and the particle size of the catalyst is 0.1mm-0.25mm.

[0012] According to another aspect of the present application, a method for preparing the catalyst is provided, which comprises: calcining a shell or an eggshell to obtain a carrier of the catalyst; loading active metals Ni and Fe on the carrier to obtain a precursor of the catalyst; and heat-treating the precursor to obtain the catalyst.

[0013] Preferably, the shell or the eggshell is calcined at a temperature of 900℃ for 3 hours to obtain the carrier of the catalyst.

[0014] Preferably, the loading of active metals Ni and Fe on the carrier to obtain the precursor of the catalyst comprises: after dispersing the carrier into a solution containing Fe(NO3)3 and Ni(NO3)2, evaporating the solution to obtain the precursor of the catalyst, wherein the molar ratio of Ca:Ni:Fe in the solution is 5:3:2.

[0015] Preferably, after dispersing 2.8059 g of the carrier into 20 mL of the solution containing Fe(NO3)3 and Ni(NO3)2, stirring at a speed of 240-300 rpm / min for 10-12 h at a temperature of 20-28 ℃, and continuously stirring at a temperature of 50-70 ℃ until the water content is less than 20%, the solutes in the solution contain 8.7273 g of Ni(NO3)2·6H2O and 8.0801 g of Fe(NO3)3·9H2O.

[0016] Preferably, the heat treatment of the precursor to obtain the catalyst comprises: grinding the dried precursor uniformly and then calcining to obtain the catalyst, wherein the drying condition is: a temperature of 120 ℃ and a time of 12 h; and the calcining condition is: a heating rate of 10-20 ℃ / min, a calcining temperature of 900 ℃, and a calcining time of 4 h.

[0017] According to still another aspect of the present application, there is provided an application of the above-mentioned catalyst in the preparation of hydrogen-rich fuel gas by activated mixed biomass pyrolysis or gasification.

[0018] Preferably, the activation condition of the catalyst is: placing the catalyst in a tube furnace, passing in a carrier gas with a hydrogen flow rate of 80-100 mL / min and a nitrogen flow rate of 200-220 mL / min, increasing the temperature to 700-900 ℃ at a heating rate of 10-20 ℃ / min, and reducing for 2-4 h; and the mixed biomass pyrolysis or gasification condition is: using a fixed bed reactor for reaction, a mass ratio of the mixed biomass feed to the catalyst of 2:1, a reaction temperature of 700-900 ℃, and a nitrogen flow rate of 200 mL / min.

[0019] The catalyst provided by the present application has a small particle size, a uniform metal distribution, and retains the original porous channel structure of the CaO carrier, and has the advantages of high reaction activity, high hydrogen selectivity, and good stability when applied to the process of preparing hydrogen-rich fuel gas by catalytic pyrolysis of paper materials and plastic mixtures. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings, which are included to provide a further understanding of the present application and are incorporated in and constitute a part of this application, illustrate embodiments of the present application and together with the description serve to explain the present application. In the drawings:

[0021] Figure 1 FIG. 1 shows a SEM characterization spectrum of a catalyst C1 according to an embodiment of the present application;

[0022] Figure 2 FIG. 2 shows an XRD characterization spectrum of a catalyst C1 according to an embodiment of the present application; and

[0023] Figure 3 An apparatus diagram is shown according to an embodiment of the present application. DETAILED DESCRIPTION

[0024] The following examples are provided to enable those skilled in the art to more clearly understand and to practice the present application. It is intended to cover any and all modifications of the application within the scope of the claims. The materials, reagents and devices mentioned in the following examples are commercially available or are prepared by known methods, unless otherwise indicated.

[0025] The present application provides a method for synthesizing a Ni-Fe bimetallic supported catalyst with CaO as a carrier prepared from a biomass green organic calcium source, comprising the following steps:

[0026] 1) Selecting common biomass organic calcium sources such as eggshells and oyster shells as raw materials, taking eggshells as an example, washing with distilled water several times to remove dust and impurities on the surface, including some sticky organic matter. The washed eggshells are dried in an oven, and then calcined at 900℃ in a muffle furnace for 3 hours to obtain a CaO carrier.

[0027] 2) Add 8.72g of Ni(NO3)2·6H2O and 8.08g of Fe(NO3)3·9H2O to 20mL of distilled water, and then add 2.8g of dry CaO carrier to the mixed solution. It should be noted that the same results can be obtained by conducting experiments with the same proportions, and the solution is stirred thoroughly (first at 20-28℃ with a speed of 240-300rpm / min for 10-12h, and then continuously stirred at a temperature of 50-70℃ until the water content is less than 20%).

[0028] 3) Dry the sample obtained in step 2) in an oven at 120℃ for 12h.

[0029] 4) Grind the compound obtained in step 3) uniformly.

[0030] 5) Calcine the uniformly ground compound of step 4) in a muffle furnace, with a heating rate of 10-20℃ / min, a calcination temperature of 900℃, and a calcination time of 4h.

[0031] 6) After the catalyst calcined in step 5) is cooled, it is taken out and ground again to uniformly crush all the catalyst into particles of 0.10-0.25mm to obtain a supported bimetallic catalyst NiFeCaO.

[0032] The application further provides application of the metal supported catalyst, which is used to prepare hydrogen-rich fuel gas by using mixed biomass as catalytic raw material and fixed bed catalytic pyrolysis, and is activated before catalytic pyrolysis, and the activation condition is as follows: the catalyst particles are placed in a tube furnace, the carrier gas with a hydrogen flow rate of 80-100 mL / min and a nitrogen flow rate of 200-220 mL / min is introduced, the temperature is increased to 700-900 DEG C at a heating rate of 5-100 DEG C / min, and reduction is performed for 2-4 h.

[0033] The reaction condition for preparing hydrogen-rich fuel gas by using the fixed bed paper material and plastic mixture catalytic pyrolysis is as follows: the paper material and plastic mixture is 1 g, the catalyst is 0.5 g, the reaction temperature is 700-900 DEG C, and the nitrogen flow rate of the protective gas is 180-200 mL / min.

[0034] The application further discloses a supported catalyst prepared by using CaO prepared by calcining eggshells as a carrier and loading Ni and Fe active metals, and containing NiO, CaO, Fe2O3 and Ca2Fe2O5 four phases.

[0035] The component ratio is 30wt.% Ni-20wt.% Fe-50wt.% CaO. The NiFeCaO catalyst presents uniform nanoscale particles, the particles are superimposed to form nanoscale pore channels, and the nanoscale pore channels are beneficial to providing a higher specific surface area to enhance the adsorption capacity of the catalyst to CO2.

[0036] The XRD pattern is obtained by using a D8 Advance X-ray diffractometer of a German Bruker AXS company to perform X-ray powder diffraction experiments on the sample, and the test condition is as follows: a Cu target, an incident wavelength of 0.15406 nm, a tube voltage and a tube current of 40 KV and 30 mA, a scanning range of 10 DEG to 80 DEG, a scanning step of 0.02 DEG, and a scanning speed of 10 DEG / min. According to the characteristic peak position appearing in the XRD spectrum, and by referring to the standard XRD data (JCPDS, Joint Committee on Powder Diffraction Standards) of the International Powder Diffraction Standard Joint Committee, the Fe, Ni and Ca phases loaded on the catalyst are confirmed.

[0037] XRD pattern results show that CaO phase appears at 2θ = 32.20°, 37.36°, 53.86° and 64.16°, which belong to (111), (200), (220) and (311) crystal faces respectively. In the NiFeCaO catalyst, the active metal Ni is observed as NiO phase at 2θ = 37.25° (111), 43.29° (200), 62.88° (220), 75.41° (311) and 76.41° (222). Among them, (111) and (200) are the main crystal forms. Fe2O3 phase is at 2θ = 24.15° (012), 33.16° (104) and 62.43° (214). At the same time, it can be observed that when Fe combines with Ni and Ca species, Ca2Fe2O5 spinel phase will be formed. The peaks of Ca2Fe2O5 phase at 2θ = 22.81°, 29.22°, 33.57°, 43.49°, 48.29° and 57.88° are (101), (131), (210), (161), (222) and (143) respectively. Under high temperature conditions, these species have certain effect on improving the anti-sintering performance and carbon deposition performance of the catalyst. The Ca2Fe2O5 spinel peak values at 22.81° and 43.49° in the characterization results are weak and are mainly submerged by Fe2O3 and NiO peaks, indicating that Ca2Fe2O5 particles are small or highly dispersed on the surface of the catalyst, and the oxygen carrier formed has a promoting effect on the generation of hydrogen.

[0038] Biomass green organic calcium source is one of the main components of food waste, including various poultry eggshells, shellfish shells and the like. Taking chicken eggshell as an example, it is actually a kind of natural porous bioceramics material, and the specific structure is composed of a layer of foamy cutin layer, a layer of calcite or calcium carbonate layer and two layers of shell membranes. The eggshell surface is unevenly distributed with 7000-17000 funnel-shaped pores, which can be used for water and gas exchange reactions. At the same time, 97% of the composition is calcium carbonate, which can be prepared into high-purity calcium oxide after calcination. In the present application, the chicken eggshell is used to prepare calcium-based catalyst, which not only has high production efficiency, but also can promote the resource utilization of organic solid waste.

[0039] CaO is a widely used carrier, adsorbent and catalyst. The CaO-based catalyst is characterized by wide source, low cost, and strong CO2 adsorption capacity, which can effectively reduce the content of CO2 in the hydrogen production process, thereby changing the movement of chemical reaction equilibrium and effectively improving the yield of hydrogen. However, the adsorption-desorption cycle stability of the CaO-based catalyst is poor, and the cycle life is low, which is mainly because the CaO particles will sinter under the adsorption-desorption reaction at high temperature, resulting in smaller pore size or even blockage, affecting the specific surface area, thereby resulting in fewer adsorption sites and lower adsorption capacity. The NiFeCaO catalyst provided in the application solves the problem of easy sintering of the CaO-based catalyst, and the sintering phenomenon is greatly improved compared with before loading. Research shows that the CaO-based catalyst is suitable for pyrolysis systems with higher pyrolysis temperature and larger amount.

[0040] The NiO, CaO, Fe2O3 and Ca2Fe2O metal oxides in the application are used as promoters and active components of various heterogeneous catalytic reactions to change the distribution of product components by their different acid-base positions, thereby promoting or inhibiting the formation of certain products. The application solves the technical problems in the field of catalytic pyrolysis for preparing hydrogen-rich fuel gas, such as the large amount of by-products produced in the pyrolysis process, especially the production of tar which can block the reactor, reduce the heat transfer efficiency and affect the normal progress of the reaction.

[0041] The catalyst obtained in the application has small particle size, uniform metal distribution and maintains the porous structure of CaO. By incorporating Ni and Fe into the CaO catalyst and applying it to the catalytic pyrolysis of paper materials and plastic mixtures, the results show that the catalyst has good deoxygenation effect, can effectively promote the ring-opening and dehydration reaction of sugars, promote the formation of various light organic matters, and can also effectively inhibit the generation of CO2, induce the water-gas shift reaction, thereby promoting the generation of high-calorific-value components such as hydrogen.

[0042] Example 1

[0043] Catalyst preparation: 2.8059 g of dry CaO support was added to a mixed solution of 8.7273 g of Ni(NO3)2*6H2O and 8.0801 g of Fe(NO3)3*9H2O (molar ratio of Ca:Ni:Fe in the solution was 5:3:2) in 20 mL. The solution was then stirred at room temperature for 12 h at 280 rpm / min, and then continuously stirred at 60 °C to slowly evaporate the solution to a water content of less than 20%. The sample was dried in an oven at 120 °C for 12 h, and then the composite was ground uniformly and calcined in a muffle furnace. The temperature was raised to 900 °C at a rate of 10 °C / min and calcined for 4 h, and then removed after cooling and ground again. Finally, the calcined catalyst was reduced in a tube furnace (hydrogen flow rate in carrier gas was 100 mL / min, nitrogen flow rate was 200 mL / min) at a temperature of 900 °C at a rate of 10 °C / min for 2 h to obtain a supported bimetallic catalyst NiFeCaO, denoted as C1.

[0044] Figure 1 SEM image of the catalyst in Example 1. The sample morphology was observed using a field emission scanning electron microscope of the SU8100 type produced by Hitachi, Ltd., Japan, and a field emission scanning electron microscope of the Sigma 300 type produced by Carl Zeiss AG, Germany. It can be seen from the image that the NiFeCaO catalyst presents uniform nanoscale particles, which are superimposed on each other to form nanoscale pore channels, which are conducive to providing a higher specific surface area to enhance the adsorption capacity of the catalyst for CO2.

[0045] Figure 2XRD pattern of the catalyst in Example 1. The XRD pattern results show that CaO phase appears at 2q = 32.20°, 37.36°, 53.86° and 64.16°, which belong to (111), (200), (220) and (311) crystal planes, respectively. The active metal Ni in the NiFeCaO catalyst is observed as NiO phase at 2q = 37.25° (111), 43.29° (200), 62.88° (220), 75.41° (311) and 76.41° (222). Among them, (111) and (200) are the main crystal forms. Fe2O3 phase is at 2q = 24.15° (012), 33.16° (104) and 62.43° (214). At the same time, it can be observed that when Fe combines with Ni and Ca species, Ca2Fe2O5 spinel phase will be formed. The Ca2Fe2O5 phase has peaks at 2q = 22.81°, 29.22°, 33.57°, 43.49°, 48.29° and 57.88°, which are (101), (131), (210), (161), (222) and (143), respectively. Under high temperature conditions, these species have a certain effect on improving the sintering resistance and carbon deposition performance of the catalyst. The Ca2Fe2O5 spinel peak values at 22.81° and 43.49° in the characterization results are weak and are mainly submerged by Fe2O3 and NiO peaks, indicating that Ca2Fe2O5 particles are small or highly dispersed on the surface of the catalyst, and the oxygen carrier formed has a promoting effect on the generation of hydrogen.

[0046] Table 1 is the BET characterization results of the catalyst in Example 1. The specific surface area, pore volume and pore size distribution of the prepared sample were tested by using the American Micromeritics ASAP 2020 series full-automatic gas adsorption system specific surface and porosity analyzer and JW-BK132F type specific surface and porosity analyzer produced by Beijing Jingwei Gaobo Science and Technology Co., Ltd. The test conditions are as follows: the sample is degassed pretreatment at 300°C for 12h. The specific surface area (SBET) of the sample is calculated by Brunauer-Emmett-Teller (BET) theoretical model, and the total pore analysis of the sample is obtained by NLDFT model statistics.

[0047] Table 1 BET characterization parameters of catalyst C1

[0048]

[0049]

Example 2

[0050] Pyrolysis application of catalyst: 0.5g of the prepared sample C1 was filled into the middle of the pyrolysis quartz tube (fixed catalyst sample), and then the pyrolysis furnace was heated to 900℃, the quartz tube was placed in the pyrolysis furnace B, the gas pipeline was connected, N2 with a flow rate of 200 mL / min and H2 with a flow rate of 100 mL / min were introduced, and reduction was performed for 2h.

[0051] The pyrolysis furnace A was heated to 900℃, the quartz tube to be used containing 1g of playing card prints was placed in the pyrolysis furnace, N2 with a flow rate of 200 mL / min was introduced, and after the playing card started to be pyrolyzed, the timing was started. The reaction results are shown in Table 2, and the catalyst stability evaluation is shown in Table 3. From the data, it can be seen that the hydrogen yield after using the catalyst for catalytic pyrolysis to produce hydrogen is increased by 53.4% compared with before use, and the catalytic performance is still stable after 20min.

[0052] Figure 3 The schematic diagram of the application device of the catalyst in Example 1 is shown. It mainly consists of three parts of gas device, pyrolysis furnace and gas collection and analysis device. The pyrolysis gas produced in the pyrolysis furnace A is catalyzed by the catalyst in the pyrolysis furnace B, and then the generated gas is collected and analyzed.

[0053]

Example 3

[0054] Gasification application of catalyst: 0.5g of the prepared sample C1 was filled into the middle of the pyrolysis quartz tube (fixed catalyst sample), and then the pyrolysis furnace was heated to 800℃, the quartz tube was placed in the pyrolysis furnace B, the gas pipeline was connected, N2 with a flow rate of 200 mL / min and H2 with a flow rate of 100 mL / min were introduced, and reduction was performed for 2h.

[0055] The pyrolysis furnace A was heated to 800℃, the quartz tube to be used containing 1g of playing card prints was placed in the pyrolysis furnace, distilled water with a flow rate of 50μL / min and N2 with a flow rate of 200 mL / min were introduced, and after the playing card started to be gasified, the timing was started. The reaction results are shown in Table 2, and the catalyst stability evaluation is shown in Table 3. From the data, it can be seen that the hydrogen yield after using the catalyst for catalytic pyrolysis to produce hydrogen is increased by 139.8% compared with before use, and the catalytic performance is still maintained at a high level after 20min.

[0056] Table 2. Reaction results of the catalyst C1 prepared in Example 1 (yield unit: μmol / g cat .min)

[0057] Catalyst H2 yield CO2 yield CO yield CH4yield C X H Y yield <!-- 5 -->]]> Not used 373.8 74.8 157.5 46.6 27.3 Pyrolysis 573.4 57.8 124.9 32.8 12.0 Gasification 896.4 135.5 337.4 80.7 9.7

[0058] Table 3. Catalyst stability evaluation of the catalyst C1 in Examples 2 and 3 (yield unit: μmol / g cat .min)

[0059] Time Pyrolysis hydrogen yield Gasification hydrogen yield 2 min 286.5 659.6 5 min 573.4 896.4 10 min 468.6 687.8 20 min 443.5 376.6 30 min 235.4 75.4

[0060] The above description is merely that of the preferred embodiments of the application and is not intended to limit the application. One skilled in the art can make various modifications and variations without departing from the spirit and scope of the application. Any modifications, equivalent replacements, improvements, etc. made within the principles and technical scope of the application shall be included in the protection scope of the application.

Claims

1. A catalyst for promoting hydrogen production from mixed biomass pyrolysis or gasification, characterized in that, The catalyst comprises nickel (Ni), iron (Fe) and calcium oxide (CaO), the catalyst comprises NiO, CaO, Fe2O3 and Ca2Fe2O5 tetraphase, the catalyst comprises 30wt% of Ni, 20wt% of Fe and 50wt% of CaO, Ca2Fe2O5 spinel peaks at 22.81° and 43.49° are weak and are mainly submerged by Fe2O3 and NiO peaks.

2. The catalyst according to claim 1, characterized in that, In the XRD pattern of the catalyst, the diffraction angle position of the first strong peak is 43.29°, the diffraction angle position of the second strong peak is 33.16°, and the diffraction angle position of the third strong peak is 37.25°.

3. The catalyst of claim 1, wherein The CaO in the catalyst has a multi-channel structure, and the particle size of the catalyst is 0.1mm-0.25mm.

4. A method for preparing the catalyst according to any one of claims 1 to 3, comprising: calcining a shell or an eggshell to obtain a carrier of the catalyst; loading active metals Ni and Fe on the carrier to obtain a precursor of the catalyst, wherein after dispersing the carrier into a solution containing Fe(NO3)3 and Ni(NO3)2, the solution is evaporated to obtain the precursor of the catalyst, and the molar ratio of Ca:Ni:Fe in the solution is 5:3:2; heat-treating the precursor to obtain the catalyst.

5. The method of claim 4, wherein, The shell or the eggshell is calcined at a temperature of 900℃ for 3 hours to obtain the carrier of the catalyst.

6. The method of claim 4, wherein, After dispersing 2.8059g of the carrier into 20mL of the solution containing Fe(NO3)3 and Ni(NO3)2, stirring at a speed of 240-300rpm / min for 10-12h at a temperature of 20-28℃, and continuously stirring at a temperature of 50-70℃ until the water content is less than 20%, the solutes in the solution comprise 8.7273g of Ni(NO3)2·6H2O and 8.0801g of Fe(NO3)3·9H2O.

7. The method of claim 4, wherein, Heat-treating the precursor to obtain the catalyst, comprising: grinding the dried precursor uniformly and then performing calcination treatment to obtain the catalyst, wherein the drying conditions are a temperature of 120℃ and a time of 12h, and the calcination conditions are a heating rate of 10-20℃ / min, a calcination temperature of 900℃ and a calcination time of 4h.

8. Use of the catalyst according to any one of claims 1 to 3 in activated mixed biomass pyrolysis or gasification for preparing hydrogen-rich fuel gas.

9. Use according to claim 8, characterized in that, The activation conditions of the catalyst are as follows: the catalyst is placed in a tube furnace, a carrier gas with a hydrogen flow rate of 80-100mL / min and a nitrogen flow rate of 200-220mL / min is introduced, the temperature is raised to 700-900℃ at a heating rate of 10-20℃ / min, and reduction is performed for 2-4h; The mixed biomass pyrolysis or gasification conditions are as follows: a fixed bed reactor is used for reaction, the mass ratio of the mixed biomass feed to the catalyst is 2:1, the reaction temperature is 700-900℃, and the flow rate of the protective gas nitrogen is 200mL / min.

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