CN113426450A - Biomass tar steam reforming monolithic catalyst and preparation method thereof - Google Patents

Biomass tar steam reforming monolithic catalyst and preparation method thereof Download PDF

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CN113426450A
CN113426450A CN202110678821.0A CN202110678821A CN113426450A CN 113426450 A CN113426450 A CN 113426450A CN 202110678821 A CN202110678821 A CN 202110678821A CN 113426450 A CN113426450 A CN 113426450A
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catalyst
steam reforming
nickel
monolithic catalyst
tar steam
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王燕刚
张思倩
许海洋
项侠安
沈张锋
李溪
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Jiaxing University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1252—Cyclic or aromatic hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical problem of catalyst preparation, and particularly relates to a biomass tar steam reforming monolithic catalyst and a preparation method thereof. The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the biomass tar steam reforming monolithic catalyst takes carbonized wood as a monolithic catalyst carrier and takes a nickel-based hydrotalcite derivative as the active component, and the nickel-based hydrotalcite derivative accounts for 0.5-2.5% of the total mass of the catalyst; the catalyst also contains one or two of metal promoter iron or cerium, and in the catalyst, the molar ratio of Ni to (Fe + Ce) is 1-3: 1. the preparation method takes urea as an alkali source and takes metal nitrate as precursors of Ni, Fe and Ce, and has the characteristics of simple and convenient operation, good process repeatability and the like.

Description

Biomass tar steam reforming monolithic catalyst and preparation method thereof
Technical Field
The invention belongs to the technical problem of catalyst preparation, and particularly relates to a biomass tar steam reforming monolithic catalyst and a preparation method thereof.
Background
At present, coal, petroleum and natural gas are still the main sources of global energy. However, the use of traditional fossil fuels in large quantities not only brings about increasingly serious environmental pollution (such as the emission of a large amount of greenhouse gas carbon dioxide), but also severely restricts the sustainable development of the economic society, and the reserves of coal, petroleum and natural gas are gradually reduced, so that the development of new energy resources is expected. The new energy is not only the key for adjusting the energy structure, but also the practical need for energy conservation and emission reduction in order to cope with climate change. Among the renewable energy sources, biomass energy is considered as a main potential substitute of future fossil fuel due to large resource quantity, wide distribution and renewability. Gasification of biomass, which can be pyrolyzed at high temperature and in the absence of oxygen to produce H-rich biomass, is considered a promising technology2And CO.
However, the gasification of biomass produces large quantities of tar, including various aromatics, with toluene being the major component and naphthalene and other aromatics being the next. The presence of tar mainly causes the following drawbacks: (1) resulting in energy waste and reduced biomass gasification efficiency. The energy of the tar products in the biomass gasification process generally accounts for 5-15% of the total energy of the biomass, and if the tar products cannot be converted into high-value-added products, the gasification efficiency of the biomass can be greatly reduced. (2) The tar can block and corrode gasification equipment. When the temperature of the gasified gas is reduced, the formed tar mist can corrode gasification equipment; the viscous liquid formed by the combination of tar with water, coke, dust, etc. can adhere to the pipeline of the gasification equipment, causing pipeline blockage. (3) Tar can be harmful to gas burning equipment. At a temperature of more than 200 ℃, the gas tar can be completely mixed with the gasified gas, and at a temperature of less than 200 ℃, the tar is fine liquid drops, and particles such as carbon black generated during combustion can seriously damage gasified gas combustion equipment (such as a gas turbine, an internal combustion engine and the like). (4) The toxic and harmful substances in the tar can cause pollution to the environment and harm the health of human bodies. Therefore, how to effectively remove tar is very important for developing biomass gasification technology.
The steam catalytic reforming technology is thatMore efficient tar removal process for converting tar to H at lower temperatures2Rich in synthesis gas. Because the nickel-based catalyst is low in cost and high in catalytic efficiency, the nickel-based catalyst is a commonly used catalytic biomass tar steam reforming catalyst at present. However, metallic nickel is very easily agglomerated at high temperature and carbon deposition is very easily formed on the surface of metallic nickel, thereby rapidly deactivating the nickel-based catalyst. The porous carrier can increase the specific surface area of the nickel-based catalyst and improve the dispersity of nickel metal particles, thereby improving the performance of the nickel-based catalyst. At present, ceramic materials, natural minerals and the like are more commonly used as porous carriers, but the carriers are usually granular (such as spheres, cylinders or other geometric figures) and have higher tortuosity and complex pore channel structures, which can cause higher gas flow resistance and influence the contact of reactants and active sites (metallic nickel). Therefore, the development of an economical and efficient biomass tar steam reforming catalyst is of great significance for efficient utilization of biomass energy.
Disclosure of Invention
The invention provides a biomass tar steam reforming monolithic catalyst which can prevent the formation of carbon deposit and the agglomeration of nickel metal in use and has higher catalytic activity and stability.
The invention also provides a preparation method of the biomass tar steam reforming monolithic catalyst, which is simple and easy to repeat.
In order to solve the problems, the invention adopts the following technical scheme:
the biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the biomass tar steam reforming monolithic catalyst takes carbonized wood as a monolithic catalyst carrier and takes a nickel-based hydrotalcite derivative as the active component, and the nickel-based hydrotalcite derivative accounts for 0.5-2.5% of the total mass of the catalyst;
the catalyst also contains one or two of metal promoter iron or cerium,
in the catalyst, the molar ratio of Ni to (Fe + Ce) is 1-3: 1.
the calcination temperature during the preparation of the catalyst is 500-900 ℃.
Preferably, the nickel-based hydrotalcite derivative is uniformly dispersed in the pores of the support carbonized wood (as shown in fig. 2 and 3).
Preferably, the molar ratio of Ni to (Fe + Ce) is 2: 1.
preferably, the molar ratio of Fe to Ce is 8-12: 1, the molar ratio of Fe to Ce is preferably 10: 1.
a preparation method of the biomass tar steam reforming monolithic catalyst comprises the following steps:
s1, preparation of a precursor mixed solution:
mixing urea, nickel nitrate, ferric nitrate and optionally added cerium nitrate with water, stirring to obtain a precursor mixed solution, stirring for 0.5-3 h, adding cut logs into the precursor mixed solution, and performing vacuum impregnation for 1-5 times;
s2, putting the precursor mixed solution obtained in the step S1 and the raw wood into a reaction kettle, heating for 12-36 hours at 80-200 ℃, cooling to room temperature, washing the raw wood for 3-4 times with water, and drying for 8-24 hours at 30-100 ℃;
and S3, calcining the log obtained in the step S2 in a tubular furnace at 500-900 ℃ in a nitrogen atmosphere for 2-8 h, and naturally cooling to obtain the catalyst.
Preferably, the ratio of urea: the ratio of nickel nitrate, ferric nitrate, cerous nitrate and water is 100-300 mmol, 0.5-10 mmol, 0-1 mmol, and 30-100 ml.
Action and Effect of the invention
The biomass tar steam reforming monolithic catalyst provided by the invention takes nickel-based hydrotalcite derivatives as active components and carbonized wood as a carrier, so that microscopic pore channels of wood can be well reserved. As shown in figure 1, the wood micro-channel is formed by arranging sparse large channels and dense small channels according to a certain rule, the distribution density is extremely high, meanwhile, small holes exist between pipe walls, transverse transmission of substances across the walls can be realized, and the open pore channels and the open pore structures can remarkably promote permeation of biomass tar and water vapor and shorten the diffusion distance. Meanwhile, carbon dioxide generated in the carbonization process has the function of pore forming, the specific surface area and the porosity of wood are further increased, more active sites are provided for the nickel-based catalyst, the catalyst is more uniformly loaded on the wood, and the active sites are prevented from sintering. In addition, the hydrotalcite-like compound is used as a precursor, and the chemical composition of the catalyst is optimized, so that the surface acidity and alkalinity of the nickel-based catalyst are adjusted, the dispersion degree of active components is improved, the interaction between metal and a carrier is enhanced, the electron cloud density of the metal is modulated, the carbon deposition effect can be effectively relieved in the biomass tar steam reforming catalytic reaction process, and the service life of the catalyst is further prolonged.
The preparation method takes urea as an alkali source and takes metal nitrate as precursors of Ni, Fe and Ce, and has the characteristics of simple and convenient operation, good process repeatability and the like.
Drawings
FIG. 1 is SEM image of micro-channel structure of natural wood,
FIG. 2 is an SEM picture of a biomass tar steam reforming monolithic catalyst according to the present invention;
FIG. 3 is a TEM image of a biomass tar steam reforming monolithic catalyst according to the present invention;
fig. 4 is a mapping of the corresponding nickel element of the monolithic biomass tar steam reforming catalyst of the present invention, and the white dots in b indicate that the Ni element is uniformly distributed in the selected region.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example one
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 8g of urea, 1g of nickel nitrate and 1.4g of ferric nitrate in 30ml of deionized water, stirring for 1h to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 2 times;
the amounts of urea, nickel nitrate, ferric nitrate and deionized water used were calculated according to the ratio of urea, nickel nitrate, ferric nitrate and deionized water, 133.3 mmol: 3.44 mmol: 3.44 mmol: 30 ml.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 12h at 100 ℃, cooling to room temperature, washing wood for 3 times by using water, and drying for 24h at 50 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 4 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming integral catalyst prepared by the method.
The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the active component is a nickel-based hydrotalcite derivative, and the carrier is carbonized wood. The mass fraction of the nickel-based hydrotalcite derivative accounts for 0.7 percent of the mass of the catalyst, and the molar ratio of Ni to Fe is 1: 1.
The biomass tar steam reforming monolithic catalyst prepared according to the embodiment can achieve 99% of tar conversion rate at 550 ℃, and can still achieve 88% of tar conversion rate after continuous 48-hour reaction.
Example two
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 10g of urea, 1.5g of nickel nitrate and 2.1g of ferric nitrate in 35ml of deionized water, stirring for 2 hours to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 3 times;
the amounts of urea, nickel nitrate, ferric nitrate and deionized water used were calculated according to the ratio of urea, nickel nitrate, ferric nitrate and deionized water being 166.7 mmol: 5.16 mmol: 5.16 mmol: 35 ml.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 12h at 100 ℃, cooling to room temperature, washing wood for 3 times by using water, and drying for 18h at 60 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 3 hours at 600 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming integral catalyst prepared by the method.
The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the active component is a nickel-based hydrotalcite derivative, and the carrier is carbonized wood. The mass fraction of the nickel-based hydrotalcite derivative accounts for 1 percent of the mass of the catalyst, and the molar ratio of Ni to Fe is 1: 1.
The biomass tar steam reforming monolithic catalyst prepared according to the embodiment can achieve a tar conversion rate of 98% at 550 ℃, and the conversion rate can still achieve 90% after continuous 48-hour reaction.
EXAMPLE III
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 10g of urea, 1.5g of nickel nitrate and 1.1g of ferric nitrate in 35ml of deionized water, stirring for 3 hours to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 4 times;
the amounts of urea, nickel nitrate, ferric nitrate and deionized water used were calculated according to the ratio of urea, nickel nitrate, ferric nitrate and deionized water, 133.3 mmol: 5.16 mmol: 2.58 mmol: 35 ml.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 24h at 150 ℃, cooling to room temperature, washing wood for 3 times by using water, and drying for 24h at 80 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 4 hours at 800 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming integral catalyst prepared by the method.
The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the active component is a nickel-based hydrotalcite derivative, and the carrier is carbonized wood. The mass fraction of the nickel-based hydrotalcite derivative accounts for 0.8 percent of the mass of the catalyst, and the molar ratio of Ni to Fe is 2: 1.
The biomass tar steam reforming monolithic catalyst prepared by the method of the embodiment can achieve 99% of tar conversion rate at 550 ℃, and can still achieve 92% of tar conversion rate after continuous 48-hour reaction.
Example four
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 15g of urea, 1.7g of nickel nitrate, 1g of ferric nitrate and 0.3 g of cerous nitrate in 35ml of deionized water, stirring for 2 hours to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 3 times;
the amounts of urea, nickel nitrate, ferric nitrate, cerium nitrate and deionized water used were calculated in a ratio of urea, nickel nitrate, ferric nitrate, cerium nitrate and deionized water of 250 mmol: 6 mmol: 2.4 mmol: 0.6 mmol: 35 ml.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 36h at 100 ℃, cooling to room temperature, washing wood for 4 times by using water, and drying for 20h at 60 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 6 hours at 600 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming integral catalyst prepared by the method.
The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the active component is a nickel-based hydrotalcite derivative, and the carrier is carbonized wood. The mass fraction of the nickel-based hydrotalcite derivative accounts for 1.5 percent of the mass of the catalyst, and the molar ratio of Ni to (Fe + Ce) is 2: 1.
The biomass tar steam reforming monolithic catalyst prepared by the method of the embodiment can achieve 99% of tar conversion rate at 550 ℃, and can still achieve 97% of tar conversion rate after continuous 48-hour reaction.
EXAMPLE five
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 15g of urea, 2.6g of nickel nitrate, 1g of ferric nitrate and 0.3 g of cerous nitrate in 100ml of deionized water, stirring for 3 hours to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 5 times;
the amounts of the urea, the nickel nitrate, the ferric nitrate, the cerium nitrate and the deionized water are calculated according to the proportion of 250 mmol of the urea, 9 mmol of the nickel nitrate, 2.4 mmol of the ferric nitrate, 0.6 mmol of the cerium nitrate and 100ml of the deionized water.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 24h at 180 ℃, cooling to room temperature, washing wood for 3 times by using water, and drying for 8h at 80 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 3h at 800 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming integral catalyst prepared by the method.
The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the active component is a nickel-based hydrotalcite derivative, and the carrier is carbonized wood. The mass fraction of the nickel-based hydrotalcite derivative accounts for 1.9 percent of the mass of the catalyst, and the molar ratio of Ni to (Fe + Ce) is 3: 1.
The biomass tar steam reforming monolithic catalyst prepared according to the embodiment can achieve 99% of tar conversion rate at 550 ℃, and the conversion rate can still achieve 98% after continuous 48-hour reaction.
EXAMPLE six
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 12g of urea, 2.6g of nickel nitrate, 3.4g of ferric nitrate and 0.5 g of cerous nitrate in 100ml of deionized water, stirring for 3 hours to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 5 times;
the amounts of the urea, the nickel nitrate and the ferric nitrate used were calculated according to the ratio of 200 mmol/9 mmol/8.1 mmol/0.9 mol/100 ml of urea/nickel nitrate/ferric nitrate/cerium nitrate/deionized water.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 36h at 100 ℃, cooling to room temperature, washing wood for 3 times by using water, and drying for 8h at 80 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 8 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming monolithic catalyst prepared by the method.
The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, wherein the active component is a nickel-based hydrotalcite derivative, and the carrier is carbonized wood. The mass fraction of the nickel-based hydrotalcite derivative accounts for 2.5 percent of the mass of the catalyst, and the molar ratio of Ni to (Fe + Ce) is 1: 1.
The biomass tar steam reforming monolithic catalyst prepared by the method of the embodiment can achieve 99% of tar conversion rate at 550 ℃, and the conversion rate can still achieve 98% after continuous 48-hour reaction.
EXAMPLE seven
A preparation method of a biomass tar steam reforming monolithic catalyst specifically comprises the following steps:
(1) dissolving 3.6g of urea, 1.74g of nickel nitrate, 0.97g of ferric nitrate and 0.26 g of cerium nitrate in 20ml of deionized water, stirring for 1h to obtain a precursor mixed solution, adding 12 pieces of wood (1 cm by 1.2 cm), and carrying out vacuum impregnation for 3 times;
the amounts of the urea, the nickel nitrate, the ferric nitrate, the cerous nitrate and the deionized water are calculated according to the proportion of 60 mmol of the urea, 6 mmol of the nickel nitrate, 2.4 mmol of the ferric nitrate, 0.6 mmol of the cerium nitrate and 20ml of the deionized water.
(2) Putting the mixture obtained in the step (1) into a reaction kettle, heating for 24h at 100 ℃, cooling to room temperature, washing wood for 3 times by using water, and drying for 24h at 50 ℃;
(3) and (3) placing the wood obtained in the step (2) into a tubular furnace, calcining for 4 hours at 800 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the biomass tar steam reforming monolithic catalyst.
The conversion rate of the monolithic catalyst prepared by the embodiment to tar is 99.5% at 550 ℃, and the conversion rate can still reach 97% after continuous 48-hour reaction.
SEM and TEM pictures of the monolithic catalyst prepared in this example are shown in FIGS. 2 and 3, and FIG. 2 demonstrates that at N2After calcining in the atmosphere, a large amount of hydroxyl groups are removed from the hydrotalcite, the structure is partially collapsed, and the lamellar structure gradually shrinks and is converted into snowflake-shaped spots. The spots are a mixture of metal simple substances and metal oxides of NiFeFe formed after hydroxyl of hydrotalcite is removed, wherein the metal simple substances come from carbothermic reduction reaction at high temperature, and the metal oxides are partially unreduced Fe or Ce oxides. Fig. 3 demonstrates that the catalyst metal nanoparticles are uniformly dispersed.
Fig. 4 is a corresponding nickel element map of the biomass tar steam reforming monolithic catalyst, and white dots in b indicate uniform distribution of Ni element in selected regions.
In order to overcome the traditional common powder catalyst (Ni/Al)2O3、Ni/active carbon、Ni/SiO2Etc.) the agglomeration and growth of metal particles in the synthesis process, bed layer blockage and rapid carbon deposition caused in the catalytic reaction process, etc. The invention expands the function of the wood microchannel, takes the wood microchannel as the place for synthesizing the powder catalyst in situ, realizes the in-situ growth of the nickel-based hydrotalcite in the wood microreactor and the control of the metal active site and the shape, and can be directly used for the tar steam reforming catalytic reaction through simple carbonization treatment.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The biomass tar steam reforming monolithic catalyst and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (8)

1. The biomass tar steam reforming monolithic catalyst comprises an active component and a carrier, and is characterized in that the biomass tar steam reforming monolithic catalyst takes carbonized wood as a monolithic catalyst carrier and takes a nickel-based hydrotalcite derivative as the active component, wherein the nickel-based hydrotalcite derivative accounts for 0.5-2.5% of the total mass of the catalyst;
the catalyst also contains one or two of metal promoter iron or cerium,
in the catalyst, the molar ratio of Ni to (Fe + Ce) is 1-3: 1.
2. the biomass tar steam reforming monolithic catalyst of claim 1, wherein: the calcination temperature during the preparation of the catalyst is 500-900 ℃.
3. The biomass tar steam reforming monolithic catalyst of claim 1, wherein: the nickel-based hydrotalcite derivative is uniformly dispersed in the pore channels of the carbonized wood carrier.
4. The biomass tar steam reforming monolithic catalyst of claim 1, wherein: the molar ratio of Ni to (Fe + Ce) is 2: 1.
5. the biomass tar steam reforming monolithic catalyst according to claim 1 or 4, characterized in that: the molar ratio of Fe to Ce is 8-12: 1.
6. the biomass tar steam reforming monolithic catalyst according to claim 1 or 4, characterized in that: the molar ratio of Fe to Ce is 10: 1.
7. the preparation method of the biomass tar steam reforming monolithic catalyst as recited in claim 1, characterized in that the method comprises the following steps:
s1, preparation of a precursor mixed solution:
mixing urea, nickel nitrate, ferric nitrate and optionally added cerium nitrate with water, stirring to obtain a precursor mixed solution, stirring for 0.5-3 h, adding cut logs into the precursor mixed solution, and performing vacuum impregnation for 1-5 times;
s2, putting the precursor mixed solution obtained in the step S1 and the raw wood into a reaction kettle, heating for 12-36 hours at 80-200 ℃, cooling to room temperature, washing the raw wood for 3-4 times with water, and drying for 8-24 hours at 30-100 ℃;
and S3, calcining the log obtained in the step S2 in a tubular furnace at 500-900 ℃ in a nitrogen atmosphere for 2-8 h, and naturally cooling to obtain the catalyst.
8. The method of claim 7, wherein: the urea: the ratio of nickel nitrate, ferric nitrate, cerous nitrate and water is 100-300 mmol, 0.5-10 mmol, 0-1 mmol, and 30-100 ml.
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