Preparation method of metal modified C-RBP composite catalyst material and application thereof

Abstract

The application discloses a preparation method of a metal modified C-RBP composite catalyst material for catalyzing biomass and by-products to realize high-value utilization, and particularly relates to a preparation method of a solid acid catalyst based on RBP and biomass carbon-based double carriers for directional conversion of biomass and by-products into hydrogen-rich fuel gas. After activation, the waste RBP is used as a carrier together with green, cheap and easily obtained biomass after carbonization, so that active sites are provided for loading of active metals, the contact area of the biomass and the catalyst is increased, and a new preparation method of a catalyst for high-value utilization of biomass and by-products is provided.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalytic materials, and particularly relates to a preparation method of a metal-modified C-RBP composite catalyst material and application thereof. BACKGROUND

[0002] Biomass thermo-chemical conversion is an effective way for biomass energy production, mainly including combustion, gasification and pyrolysis, and biomass gasification refers to decomposition of materials at high temperature under oxygen-free or oxygen-deficient conditions to produce CO, H2, CH4 and other flammable gases, organic liquids and solid residues; the biomass pyrolysis process is extremely complex, including molecular bond breaking, isomerization and small molecule polymerization and other reactions, and the process is equivalent to the gasification process, which also produces gas, liquid and solid three-phase products; among them, the gas products mainly include synthesis gas such as H2 and CH4, and the liquid products mainly include oxygen-containing functional group compounds such as aldehydes, ketones, sugars, phenols and aromatics, i.e. biomass tar; the residual solid has increasing carbon content as the temperature increases. However, in the process of biomass gasification / pyrolysis, in addition to the production of useful flammable gases, some by-products (such as fly ash, NO X , SO2 and tar, etc.) are also produced, especially a large amount of biomass tar. The tar contains a large amount of hazardous chemicals, which can condense on the pipe wall, filter or downstream equipment, causing equipment failure; in addition, biomass tar can cause catalyst deterioration in the refining process, which seriously limits the development of biomass thermo-chemical conversion technology. Therefore, tar, as the main pollutant in the process of biomass thermal utilization, its removal is still an important problem that has not been completely solved.

[0003] Waste red brick powder (RBP) is a material with pozzolanic properties, and its annual production in China is huge, which has the performance as a catalyst support material. If it is used as a catalyst during biomass pyrolysis, it will promote the catalytic cracking of tar, and further produce high-value combustible gases, etc., which not only can solve the problems of corrosion and pollution of tar, but also can bring significant economic and social benefits. SUMMARY

[0004] This section is intended to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of the specification of the present application to avoid obscuring the purpose of this section, abstract and title, and such simplifications or omissions cannot be used to limit the scope of the present application.

[0005] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0006] Therefore, the present application aims at overcoming the deficiencies in the prior art and providing a preparation method of a metal-modified C-RBP composite catalyst material.

[0007] To solve the above technical problems, the present application provides a preparation method of a metal-modified C-RBP composite catalyst material, comprising,

[0008] activating the surface of the RBP to obtain pretreated RBP;

[0009] crushing the waste biomass to obtain pretreated biomass;

[0010] mixing the pretreated RBP and the pretreated biomass, adding a dispersing agent, high-temperature stirring, filtering, drying, and calcining to obtain a C-RBP composite material carrier;

[0011] using the C-RBP composite material as the carrier, and using a directional selection metal and a modification method, to obtain the metal-modified C-RBP composite catalyst material.

[0012] As a preferred scheme of the preparation method, the surface of the RBP is activated, wherein the activation method is one of acid treatment, alkali treatment, and hydrothermal treatment; the acid treatment is that the RBP is added to a weak acid for ultrasonic stirring for 20-60 min, and then is placed in a muffle furnace for calcination at 400-600 DEG C for 3-5 h.

[0013] As a preferred scheme of the preparation method, the waste biomass is crushed, wherein the waste biomass is at least one of corn straw, rice husk, and elm sawdust, and the crushing is to be put into a crusher for crushing to 40-80 mesh.

[0014] As a preferred scheme of the preparation method, the pretreated RBP is mixed with the pretreated biomass, wherein the mass ratio of the pretreated RBP to the pretreated biomass is 1-5:1.

[0015] As a preferred scheme of the preparation method, the dispersing agent is added, wherein the dispersing agent is water or ethanol.

[0016] As a preferred scheme of the preparation method, the high-temperature stirring, filtering, drying, and calcining are performed, wherein the stirring temperature is 140-160 DEG C, the stirring time is 3-6 h; the drying temperature is 105-120 DEG C, the drying time is 10-24 h; and the calcination temperature is 300-600 DEG C, and the calcination time is 3-5 h.

[0017] As a preferred scheme of the preparation method, the application discloses a directional selection metal and a modification method, wherein the directional selection metal is different active metals selected according to the use of the structural catalyst and the target product of the directional catalytic biomass conversion, and the active metal is one of alkali metal, rare earth metal and transition metal; and the modification method is one of a coprecipitation method and an impregnation method.

[0018] Another object of the application is to provide a metal-modified C-RBP composite catalyst material to overcome the defects in the prior art.

[0019] Another object of the application is to provide an application of the metal-modified C-RBP composite catalyst material in catalyzing biomass and by-products to overcome the defects in the prior art.

[0020] As a preferred scheme of the preparation method, the application discloses an application, including,

[0021] The metal-modified C-RBP composite catalyst material applied in catalyzing biomass and by-products can improve the yield by more than 80%.

[0022] The application has the following beneficial effects:

[0023] The raw materials used in the experiment are agricultural and forestry wastes and construction wastes, which are cheap and easy to obtain, and the active components are rich, thereby saving the economic cost of the catalyst; and the catalyst manufacturing method is simple.

[0024] The application provides a metal-modified C-RBP composite catalyst material for catalyzing biomass and by-products and high-value utilization, and particularly relates to a solid acid catalyst preparation method based on RBP and biomass carbon-based double carriers for directional conversion of biomass and by-products into hydrogen-rich fuel gas.

[0025] The metal-modified C-RBP composite catalyst material prepared by the application can improve the yield by more than 80% when applied in catalyzing biomass and by-products. DETAILED DESCRIPTION

[0026] In order to make the above objects, features and advantages of the application more apparent and understandable, the specific embodiments of the application are described in detail below with reference to the description and examples.

[0027] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, it will be apparent to one skilled in the art that the present application can be practiced without the specific details set forth in this description. In other instances, well-known methods have not been described in detail in order not to unnecessarily obscure aspects of the present application.

[0028] Second, the "one embodiment" or "an embodiment" as used herein means a specific implementation that can include features, structures, or characteristics that are not included in other implementations. The various embodiments described throughout this specification are not necessarily mutually exclusive, as some embodiments can be combined with one or more other embodiments to form new embodiments.

[0029] The RBP used in the embodiments of the present application is red brick powder from Jilin Brothers Brick Factory, which is crushed to 40-80 mesh in a crusher. The surface properties and relative mineral element content of the RBP are shown in Table 1.

[0030] Table 1 Surface properties and relative mineral element content of RBP

[0031]

[0032] Example 1

[0033] A method for preparing a metal-modified C-RBP composite catalyst material, comprising the following steps:

[0034] (1) RBP is added to hydrochloric acid and stirred and ultrasonicated for 25 min, and then calcined in a muffle furnace at 600°C for 4 h to obtain pretreated RBP;

[0035] (2) Corn straw is crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0036] (3) The pretreated RBP and pretreated corn straw are mixed at a ratio of 1:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 150°C for 4 h. The product obtained after treatment is collected by filtration and dried in a blast drying oven for 12 h. Then it is calcined in a nitrogen-protected constant-temperature tube furnace at 600°C for 4 h to obtain a C-RBP composite material.

[0037] (4) Co metal is selected as the active component, and the C-RBP composite material is selected as the carrier. A co-precipitation method is used, with ethanol as the dispersant, and the reaction temperature is 80°C and the reaction time is 3 h, to obtain a metal-modified C-RBP composite catalyst material.

[0038] (5) The metal modified C-RBP composite catalyst material is mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate is 20 ℃ / min from room temperature to 900 ℃, and pyrolysis gas is obtained. The pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 6%, 90% and 4% respectively. The hydrogen yield is 224 ml / g, the carbon monoxide yield is 90 ml / g, the methane yield is 72 ml / g, and the carbon dioxide yield is 99 ml / g.

[0039] Example 2

[0040] (1) The RBP is added to hydrochloric acid and stirred under ultrasonic for 25 min, and then calcined in a muffle furnace at 600 ℃ for 4 h to obtain pretreated RBP;

[0041] (2) The corn straw is crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0042] (3) The pretreated RBP and the pretreated corn straw are mixed at a ratio of 2:1, and then placed in a magnetic hydrothermal stirrer with ethanol as a dispersant and stirred at 150 ℃ for 4 h. The obtained product is filtered to collect the solid, which is dried in a blast drying oven for 12 h. Then the product is placed in a nitrogen-protected constant temperature tube furnace and calcined at 600 ℃ for 4 h to obtain a C-RBP composite material.

[0043] (4) The Co metal is selected as the active component, and the C-RBP composite material is selected as the carrier. The metal modified C-RBP composite catalyst material is obtained by co-precipitation method, with ethanol as the dispersant, at a reaction temperature of 80 ℃ and a reaction time of 3 h.

[0044] (5) The metal modified C-RBP composite catalyst material is mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate is 20 ℃ / min from room temperature to 900 ℃, and pyrolysis gas is obtained. The pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 6%, 90% and 4% respectively. The hydrogen yield is 224 ml / g, the carbon monoxide yield is 90 ml / g, the methane yield is 72 ml / g, and the carbon dioxide yield is 99 ml / g.

[0045] Example 3

[0046] (1) The RBP is added to hydrochloric acid and stirred under ultrasonic for 25 min, and then calcined in a muffle furnace at 600 ℃ for 4 h to obtain pretreated RBP;

[0047] (2) The corn straw is crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0048] (3) The pretreated RBP and the pretreated corn stalks were mixed at a ratio of 1:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 150°C for 4h. The product obtained by the treatment was collected by filtration and dried in a blast drying oven for 12h. Then it was placed in a constant temperature tube furnace under nitrogen protection and calcined at 600°C for 4h to obtain a C-RBP composite material.

[0049] (4) The Ni metal was selected as an active component, and the C-RBP composite material was selected as a carrier. A metal-modified C-RBP composite catalyst material was obtained by a coprecipitation method with ethanol as a dispersant at a reaction temperature of 80°C for 3h.

[0050] (5) The metal-modified C-RBP composite catalyst material was mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed-bed pyrolysis system under N2 atmosphere. The heating rate was 20°C / min from room temperature to 900°C to obtain pyrolysis gas. The pyrolysis gas was subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 5%, 83% and 12%, respectively. The hydrogen yield was 176ml / g, the carbon monoxide yield was 69ml / g, the methane yield was 54ml / g, and the carbon dioxide yield was 60ml / g.

[0051] Example 4

[0052] (1) The RBP was added to hydrochloric acid and stirred under ultrasonic for 25min, and then placed in a muffle furnace for calcination at 600°C for 4h to obtain pretreated RBP;

[0053] (2) The corn stalks were crushed to 80 mesh in a crusher to obtain pretreated corn stalks;

[0054] (3) The pretreated RBP and the pretreated corn stalks were mixed at a ratio of 2:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 160°C for 4h. The product obtained by the treatment was collected by filtration and dried in a blast drying oven for 12h. Then it was placed in a constant temperature tube furnace under nitrogen protection and calcined at 600°C for 4h to obtain a C-RBP composite material.

[0055] (4) The Ni metal was selected as an active component, and the C-RBP composite material was selected as a carrier. A metal-modified C-RBP composite catalyst material was obtained by a coprecipitation method with ethanol as a dispersant at a reaction temperature of 80°C for 3h.

[0056] (5) The metal modified C-RBP composite catalyst material is mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate is 20°C / min from room temperature to 900°C, and pyrolysis gas is obtained. The pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 6%, 87% and 7% respectively. The hydrogen yield is 218 ml / g, the carbon monoxide yield is 75 ml / g, the methane yield is 65 ml / g, and the carbon dioxide yield is 106 ml / g.

[0057] Example 5

[0058] (1) The RBP is added to hydrochloric acid and stirred under ultrasonic for 25 min, and then calcined in a muffle furnace at 600°C for 4 h to obtain pretreated RBP;

[0059] (2) The corn straw is crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0060] (3) The pretreated RBP and the pretreated corn straw are mixed at a ratio of 3:1, and then placed in a magnetic hydrothermal stirrer with ethanol as a dispersant and stirred at 150°C for 4 h. The obtained product is filtered to collect the solid, which is then dried in a blast drying oven for 12 h. Then the solid is calcined in a nitrogen-protected constant temperature tube furnace at 600°C for 4 h to obtain a C-RBP composite material.

[0061] (4) The Co metal is selected as the active component, and the C-RBP composite material is selected as the carrier. The metal modified C-RBP composite catalyst material is obtained by co-precipitation method, with ethanol as the dispersant, at a reaction temperature of 80°C and a reaction time of 3 h.

[0062] (5) The metal modified C-RBP composite catalyst material is mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate is 20°C / min from room temperature to 900°C, and pyrolysis gas is obtained. The pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 6%, 87% and 7% respectively. The hydrogen yield is 218 ml / g, the carbon monoxide yield is 75 ml / g, the methane yield is 65 ml / g, and the carbon dioxide yield is 106 ml / g.

[0063] Example 6

[0064] (1) The RBP is added to hydrochloric acid and stirred under ultrasonic for 25 min, and then calcined in a muffle furnace at 600°C for 4 h to obtain pretreated RBP;

[0065] (2) The corn straw is crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0066] (3) The pretreated RBP and the pretreated corn stalks are mixed at a ratio of 5:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 150°C for 4h. The product obtained by the treatment is filtered to collect the solid, which is then dried in a blast drying oven for 12h. Then, the solid is placed in a constant temperature tube furnace under nitrogen protection and calcined at 600°C for 4h to obtain a C-RBP composite material.

[0067] (4) The Co metal is selected as an active component, and the C-RBP composite material is selected as a carrier. A metal-modified C-RBP composite catalyst material is obtained by a coprecipitation method with ethanol as a dispersant at a reaction temperature of 80°C and a reaction time of 3h.

[0068] (5) The metal-modified C-RBP composite catalyst material is mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed-bed pyrolysis system under N2 atmosphere. The heating rate is 20°C / min from room temperature to 900°C to obtain pyrolysis gas. The pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 6%, 85% and 9%, respectively. The hydrogen yield is 205ml / g, the carbon monoxide yield is 86ml / g, the methane yield is 79ml / g, and the carbon dioxide yield is 91ml / g.

[0069] Example 7

[0070] (1) The RBP is added to hydrochloric acid and stirred under ultrasonic for 25min, and then placed in a muffle furnace for calcination at 600°C for 4h to obtain pretreated RBP;

[0071] (2) The corn stalks are crushed to 80 mesh in a crusher to obtain pretreated corn stalks;

[0072] (3) The pretreated RBP and the pretreated corn stalks are mixed at a ratio of 2:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 150°C for 4h. The product obtained by the treatment is filtered to collect the solid, which is then dried in a blast drying oven for 12h. Then, the solid is placed in a constant temperature tube furnace under nitrogen protection and calcined at 600°C for 4h to obtain a C-RBP composite material.

[0073] (4) The Ce metal is selected as an active component, and the C-RBP composite material is selected as a carrier. A metal-modified C-RBP composite catalyst material is obtained by a coprecipitation method with ethanol as a dispersant at a reaction temperature of 80°C and a reaction time of 3h.

[0074] (5) The metal-modified C-RBP composite catalyst material was mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate was 20 ℃ / min from room temperature to 900 ℃, and the pyrolysis gas was obtained. The liquid product, pyrolysis gas and semi-coke were obtained by gas reforming and component adjustment, and the yield was 12%, 83%, 5% respectively. The hydrogen yield was 203 ml / g, the carbon monoxide yield was 64 ml / g, the methane yield was 47 ml / g, and the carbon dioxide yield was 65 ml / g.

[0075] Comparative Example 1

[0076] (1) The RBP was added to hydrochloric acid and stirred for 25 min under ultrasonic, and then calcined in a muffle furnace at 600 ℃ for 4 h to obtain pretreated RBP;

[0077] (2) The corn straw was crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0078] (3) The pretreated RBP and pretreated corn straw were mixed at a ratio of 1:1, and ethanol was used as a dispersant. The mixture was placed in a magnetic hydrothermal stirrer and stirred at 150 ℃ for 4 h. The solid product obtained after filtration was dried in a blast drying oven for 12 h. Then it was placed in a nitrogen-protected constant temperature tube furnace and calcined at 600 ℃ for 4 h to obtain C-RBP composite material.

[0079] (4) The C-RBP composite catalyst material without metal modification was mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate was 20 ℃ / min from room temperature to 900 ℃, and the pyrolysis gas was obtained. The liquid product, pyrolysis gas and semi-coke were obtained by gas reforming and component adjustment, and the yield was 26%, 60%, 14% respectively. The hydrogen yield was 124 ml / g, the carbon monoxide yield was 32 ml / g, the methane yield was 19 ml / g, and the carbon dioxide yield was 40 ml / g.

[0080] Comparative Example 2

[0081] (1) The RBP was added to hydrochloric acid and stirred for 25 min under ultrasonic, and then calcined in a muffle furnace at 600 ℃ for 4 h to obtain pretreated RBP;

[0082] (2) The corn straw was crushed to 80 mesh in a crusher to obtain pretreated corn straw;

[0083] (3) The pretreated RBP and pretreated corn stalks were mixed at a ratio of 1:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 160°C for 4h. The product obtained by the treatment was collected by filtration and dried in a blast drying oven for 12h. Then it was placed in a constant temperature tube furnace under nitrogen protection and calcined at 600°C for 4h to obtain C-RBP composite material.

[0084] (4) The unmodified C-RBP composite material catalyst was mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate was 20°C / min from room temperature to 900°C to obtain pyrolysis gas. The pyrolysis gas was subjected to gas reforming and component adjustment to obtain liquid product, pyrolysis gas and semi-coke, with yields of 22%, 65%, and 13%, respectively. The hydrogen yield was 123ml / g, the carbon monoxide yield was 35ml / g, the methane yield was 21ml / g, and the carbon dioxide yield was 39ml / g.

[0085] Comparative Example 3

[0086] (1) The RBP was not pretreated;

[0087] (2) The corn stalks were crushed to 80 mesh in a crusher to obtain pretreated corn stalks;

[0088] (3) The unpretreated RBP and pretreated corn stalks were mixed at a ratio of 1:1, and then placed in magnetic hydrothermal stirring with ethanol as a dispersant at 150°C for 4h. The product obtained by the treatment was collected by filtration and dried in a blast drying oven for 12h. Then it was placed in a constant temperature tube furnace under nitrogen protection and calcined at 600°C for 4h to obtain C-RBP composite material.

[0089] (4) The Co metal was selected as the active component, and the C-RBP composite material was used as the carrier. The metal-modified C-RBP composite catalyst material was obtained by co-precipitation method with ethanol as the dispersant at a reaction temperature of 80°C and a reaction time of 3h.

[0090] (5) The metal-modified C-RBP composite catalyst material was mixed with biomass (pulverized poplar to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed bed pyrolysis system under N2 atmosphere. The heating rate was 20°C / min from room temperature to 900°C to obtain pyrolysis gas. The pyrolysis gas was subjected to gas reforming and component adjustment to obtain liquid product, pyrolysis gas and semi-coke, with yields of 30%, 53%, and 17%, respectively. The hydrogen yield was 103ml / g, the carbon monoxide yield was 29ml / g, the methane yield was 32ml / g, and the carbon dioxide yield was 40ml / g.

[0091] Comparative Example 4

[0092] (1) RBP without pretreatment;

[0093] (2) Put corn stalks into a crusher to be crushed to 80 mesh to obtain pretreated corn stalks;

[0094] (3) Mix the untreated RBP and the pretreated corn stalks at a ratio of 1:1, use ethanol as a dispersant, and place them in a magnetic hydrothermal stirring at 150°C for 4h; collect the solid after filtering the obtained product and dry it in a blast drying oven for 12h; then place it in a nitrogen-protected constant-temperature tube furnace and calcine it at 600°C for 4h to obtain a C-RBP composite material.

[0095] (4) Select Co metal as the active component, use the C-RBP composite material as the carrier, use the coprecipitation method, select ethanol as the dispersant, and the reaction temperature is 80°C and the reaction time is 3h to obtain a metal-modified C-RBP composite catalyst material.

[0096] (5) Mix the metal-modified C-RBP composite catalyst material and biomass (pulverized poplar to 200 mesh) uniformly at a mass ratio of 1:1, add them to a two-stage fixed-bed pyrolysis system under N2 atmosphere, heat from room temperature to 900°C at a heating rate of 20°C / min to obtain pyrolysis gas; the pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, with yields of 32%, 52%, and 16% respectively, hydrogen yield of 105ml / g, carbon monoxide of 26ml / g, methane of 33ml / g, and carbon dioxide of 38ml / g.

[0097] Comparative Example 5

[0098] Prepare a catalyst that can be used for catalytic biomass pyrolysis to prepare combustible gas according to CN115739085A Example 4.

[0099] Mix the prepared catalyst and biomass (pulverized poplar to 200 mesh) uniformly at a mass ratio of 1:1, add them to a two-stage fixed-bed pyrolysis system under N2 atmosphere, heat from room temperature to 900°C at a heating rate of 20°C / min to obtain pyrolysis gas; the pyrolysis gas is subjected to gas reforming and component adjustment to obtain a hydrogen yield of up to 64ml / g, and a gas conversion rate of 44%.

[0100] Comparative Example 6

[0101] (1) Add RBP to hydrochloric acid and stir for 25min under ultrasonic, then place it in a muffle furnace and calcine it at 600°C for 4h to obtain pretreated RBP;

[0102] (2) Put corn stalks into a crusher to be crushed to 80 mesh to obtain pretreated corn stalks;

[0103] (3) The pretreated RBP and pretreated corn stalks are mixed at a ratio of 1:1, and then stirred in a magnetic hydrothermal stirring device at 150 DEG C for 4h with ethanol as a dispersant; the product obtained by the treatment is filtered to collect the solid, which is dried in a blast drying oven for 12h; then the solid is calcined in a nitrogen-protected constant-temperature tube furnace at 600 DEG C for 4h to obtain a C-RBP composite material.

[0104] (4) The Mg metal is selected as an active component, the C-RBP composite material is selected as a carrier, and a metal-modified C-RBP composite catalyst material is obtained by using a coprecipitation method with ethanol as a dispersant and at a reaction temperature of 80 DEG C and a reaction time of 3h.

[0105] (5) The metal-modified C-RBP composite catalyst material is mixed with biomass (pulverized poplar wood to 200 mesh) at a mass ratio of 1:1, and then added to a two-stage fixed-bed pyrolysis system under a N2 atmosphere, heated from room temperature to 900 DEG C at a heating rate of 20 DEG C / min to obtain pyrolysis gas; the pyrolysis gas is subjected to gas reforming and component adjustment to obtain liquid products, pyrolysis gas and semi-coke, and the yield rates are 26%, 56% and 18% respectively, the hydrogen yield rate is 106ml / g, the carbon monoxide yield rate is 46ml / g, the methane yield rate is 35%, and the carbon dioxide yield rate is 32%.

[0106] The pyrolysis gas yield rates and hydrogen yield rates of Examples 1-7 and Comparative Examples 1-6 are shown in Table 2.

[0107] Table 2

[0108]

[0109]

[0110] It can be seen that the metal-modified C-RBP composite catalyst material prepared by the method has an application in catalyzing biomass and by-products, and can increase the yield rate by more than 80%; when the ratio of the pretreated RBP and pretreated corn stalks is 1:1, the pyrolysis gas yield rate and hydrogen yield rate are the highest.

[0111] The application provides a preparation method of a metal-modified C-RBP composite catalyst material for catalyzing biomass and by-products and high-value utilization, and particularly relates to a preparation method of a solid acid catalyst based on RBP and biomass carbon double carriers for directional conversion of biomass and by-products into hydrogen-rich fuel gas, which provides active sites for loading of active metals by activating waste RBP and carbonizing green and cheap biomass together as carriers, is beneficial to increasing the contact area of biomass and the catalyst, and provides a new preparation method of a catalyst for high-value utilization of biomass and by-products.

[0112] It should be noted that the above examples are only used to illustrate the technical solutions of the present application but not limit the present application. Although the present application is described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced, without departing from the spirit and scope of the present application, which should be covered in the scope of the present application.

Claims

1. A method for preparing a metal-modified C-RBP composite catalyst material, characterized in that: include, The RBP surface is activated to obtain pretreated RBP; Waste biomass is crushed to obtain pre-treated biomass; Pretreated RBP was mixed with pretreated biomass, a dispersant was added, the mixture was stirred at high temperature, filtered, dried, and calcined to obtain a C-RBP composite material carrier. Using C-RBP composite material as a carrier, metals and modification methods are selected in a directional manner to obtain metal-modified C-RBP composite catalyst materials. The activation of the RBP surface is carried out by one of acid treatment, alkali treatment, or hydrothermal treatment. The acid treatment involves adding RBP to a weak acid and ultrasonically stirring for 20-60 minutes, then placing it in a muffle furnace and calcining it at 400-600°C for 3-5 hours. The high-temperature stirring, filtering, drying, and calcining processes are as follows: the stirring temperature is 140–160℃, and the stirring time is 3–6 h; the drying temperature is 105–120℃, and the drying time is 10–24 h; the calcining temperature is 300–600℃, and the calcining time is 3–5 h.

2. The preparation method according to claim 1, characterized in that: The process of crushing waste biomass involves placing the waste biomass into a crusher and crushing it to a mesh size of 40-80.

3. The preparation method according to claim 1, characterized in that: The process involves mixing pretreated RBP with pretreated biomass, wherein the mass ratio of pretreated RBP to pretreated biomass is 1 to 5:

1.

4. The preparation method according to claim 1, characterized in that: The dispersant is added, wherein the dispersant is water or ethanol.

5. The preparation method according to claim 1, characterized in that: The directional selection of metals and modification method, wherein the directional selection of metals involves selecting different active metals based on the application of the structural catalyst and the target product of the directional catalytic biomass conversion, and the active metal is one of alkali metals, rare earth metals, and transition metals; the modification method is one of co-precipitation method and impregnation method.

6. The metal-modified C-RBP composite catalyst material prepared by any one of the preparation methods described in claims 1 to 5.

7. The application of the metal-modified C-RBP composite catalyst material as described in claim 6 in the catalysis of biomass and by-products.

8. The application as described in claim 7, characterized in that: The metal-modified C-RBP composite catalyst material can increase the yield of biomass and by-products by more than 80% when applied to catalyze them.

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