CN116099538A - Preparation method of biomass internal and external metal synergistic catalyst - Google Patents

Preparation method of biomass internal and external metal synergistic catalyst Download PDF

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Publication number
CN116099538A
CN116099538A CN202310040383.4A CN202310040383A CN116099538A CN 116099538 A CN116099538 A CN 116099538A CN 202310040383 A CN202310040383 A CN 202310040383A CN 116099538 A CN116099538 A CN 116099538A
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straw powder
biomass
loaded
nickel
external metal
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冯冬冬
尚琦
张宇
赵义军
孙绍增
张文达
张林瑶
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • 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
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen

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Abstract

The invention discloses a preparation method of a biomass internal and external metal synergistic catalyst, which comprises the following steps: s1, crushing and screening corn straw biomass to obtain straw powder, and pickling to obtain pickled straw powder; s2, soaking the pickled straw powder in a potassium carbonate solution, and then, sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic metal elements; s3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel element; s4, placing the straw powder loaded with the potassium element and the nickel element into a furnace body, and carbonizing at high temperature in a nitrogen atmosphere to obtain the nickel-biochar catalyst. According to the preparation method of the biomass internal and external metal synergistic catalyst, the AAEMs in biomass and volatile matters in the pyrolysis process are utilized, so that the transition metal oxidation state can be reduced to the simple substance state efficiently, and the catalytic performance is improved.

Description

Preparation method of biomass internal and external metal synergistic catalyst
Technical Field
The invention relates to the technical field of biochar catalysts, in particular to a preparation method of a biomass internal and external metal synergistic catalyst.
Background
Biomass energy is clean renewable energy which can be fully utilized, and has the characteristics of wide source, zero carbon and short cycle period. Biomass thermochemical conversion processes include combustion, pyrolysis, gasification, and hydrothermal liquefaction, where pyrolysis is considered a clean and efficient thermal conversion technology with high potential to develop. Biomass pyrolysis is the conversion of organic components of biomass into combustible gases (CO, H) in an oxygen-free, high temperature environment 2 、CO 2 、CH 4 ) Tar and biomass coke, wherein the biomass tar is formed by condensing volatile matters after pyrolysis, and the problems of blocking experimental pipelines, meters and the like exist. The means currently in common use are the use of gasifier downstream cleaning techniques (secondary removal methods) and gasifier internal treatment techniques (in situ removal methods). The secondary removal method mainly comprises a physical purification method and a chemical conversion method, and can convert tar into substances such as micromolecular synthesis gas by catalytic pyrolysis, wherein the transition metal (nickel, iron and cobalt) based catalyst has the characteristics of low cost, easy acquisition, excellent catalytic performance and the like, plays an important role in aspects such as tar reforming and methane pyrolysis, and is the most widely used catalyst at present. The transition metal-based catalyst mainly reduces the activation energy of the reaction through elemental metal in tar reforming, and the efficient synthesis of the transition metal elemental is beneficial to further improving the reforming efficiency of the catalyst.
Biomass itself volatiles and CO, H 2 Has reducibility and can play a role in the preparation process of the catalystThe important function is that the volatile matters in the pyrolysis process can be utilized to prepare the simple substance transition metal catalyst with high catalytic performance and taking the biochar as the carrier. The biomass contains rich AAEMs, the effect on the biomass pyrolysis process is remarkable, the AAEMs are widely applied to transition metal catalyst auxiliaries, and the catalytic performance characteristics of the transition metal catalyst are enhanced by utilizing the AAEMs contained in the biomass, so that the preparation method for preparing the high-efficiency transition metal catalyst can be provided.
Disclosure of Invention
The invention aims to provide a preparation method of a biomass internal and external metal synergistic catalyst, which utilizes AAEMs in biomass and volatile matters in a pyrolysis process to complete efficient reduction of oxidized metal into an elemental state and improve catalytic performance.
In order to achieve the aim, the invention provides a preparation method of a biomass internal and external metal synergistic catalyst, which comprises the following steps:
s1, crushing and screening corn straw biomass to obtain straw powder, and pickling to obtain pickled straw powder;
s2, soaking the pickled straw powder in a potassium carbonate solution, and then, sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic potassium elements;
s3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel element;
s4, placing the straw powder loaded with the potassium element and the nickel element into a furnace body, and carbonizing at high temperature in a nitrogen atmosphere to obtain the nickel-biochar catalyst.
Preferably, in the step S1, the particle size of the straw powder is 150-250 μm.
Preferably, in the step S1, the straw powder and the 0.2mol/L sulfuric acid solution are stirred and mixed uniformly in a nitrogen atmosphere for 24 hours, and then the mixture is rinsed to be neutral by deionized water.
Preferably, in the step S2, the concentration of the potassium carbonate solution is 0.8mol/L, and the potassium element loaded on the straw powder is 1-5% of the mass of the straw powder.
Preferably, in the step S3, the nickel element loaded on the straw powder is 10-20% of the mass of the straw powder.
Preferably, in the step S4, the carbonization temperature is 600-700 ℃, and the heat preservation time is 20-40min.
The preparation method of the biomass internal and external metal synergistic catalyst has the advantages and positive effects that:
1. the invention adopts corn straw to load transition metal elements, thereby preparing the transition metal simple substance-biochar catalyst, and the raw materials have wide sources and low price.
2. According to the invention, the straw powder is immersed in the potassium carbonate solution and the nickel nitrate solution, so that the straw powder is loaded with potassium element and nickel element, and the potassium element can increase the relative proportion of oxygen with defects on the surface of the catalyst in the pyrolysis process, so that the fluidity of oxygen is increased, the electron transfer is promoted, and the catalytic activity of the nickel-biochar is enhanced.
3. The nickel nitrate loaded by straw powder is completely reduced into elemental nickel by a large amount of reducing substances generated in the biomass pyrolysis process, and the yield of the nickel-biomass catalyst is high.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a flow chart of an embodiment of a method for preparing a biomass internal and external metal synergistic catalyst according to the present invention;
FIG. 2 is an XRD pattern of a first embodiment of a method for preparing a biomass internal and external metal synergistic catalyst according to the invention;
FIG. 3 is a transmission electron microscope image of a first embodiment of a method for preparing a biomass internal and external metal synergistic catalyst according to the present invention;
fig. 4 is an XPS diagram of a preparation method of a biomass internal and external metal synergistic catalyst according to an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Example 1
The preparation method of the biomass internal and external metal synergistic catalyst comprises the following steps:
s1, crushing and screening corn straw biomass to obtain straw powder, wherein the particle size of the straw powder is 200 mu m; and (5) acid washing to obtain acid washed straw powder. The pickling process is to stir and mix straw powder and 0.2mol/L sulfuric acid solution uniformly in nitrogen atmosphere for 24 hours, and then rinse the mixture to neutrality with deionized water.
S2, soaking the pickled straw powder with 0.8mol/L potassium carbonate solution, and then sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic potassium elements; the potassium element loaded on the straw powder is 2% of the mass of the straw powder.
S3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel element; the nickel element loaded on the straw powder is 15% of the mass of the straw powder.
S4, placing the straw powder loaded with the potassium element and the nickel element into a furnace body, and carbonizing at high temperature in a nitrogen atmosphere to obtain the nickel-biochar catalyst. The carbonization temperature is 650 ℃, and the heat preservation time is 30min.
Example 2
The preparation method of the biomass internal and external metal synergistic catalyst comprises the following steps:
s1, crushing and screening corn straw biomass to obtain straw powder, wherein the particle size of the straw powder is 150 mu m; and (5) acid washing to obtain acid washed straw powder. The pickling process is to stir and mix straw powder and 0.2mol/L sulfuric acid solution uniformly in nitrogen atmosphere for 24 hours, and then rinse the mixture to neutrality with deionized water.
S2, soaking the pickled straw powder with 0.8mol/L potassium carbonate solution, and then sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic potassium elements; the potassium element loaded on the straw powder is 5% of the mass of the straw powder.
S3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel element; the nickel element loaded on the straw powder is 10% of the mass of the straw powder.
S4, placing the straw powder loaded with the potassium element and the nickel element into a furnace body, and carbonizing at high temperature in a nitrogen atmosphere to obtain the nickel-biochar catalyst. The carbonization temperature is 600 ℃, and the heat preservation time is 40min.
Example 3
The preparation method of the biomass internal and external metal synergistic catalyst comprises the following steps:
s1, crushing and screening corn straw biomass to obtain straw powder, wherein the particle size of the straw powder is 250 mu m; and (5) acid washing to obtain acid washed straw powder. The pickling process is to stir and mix straw powder and 0.2mol/L sulfuric acid solution uniformly in nitrogen atmosphere for 24 hours, and then rinse the mixture to neutrality with deionized water.
S2, soaking the pickled straw powder with 0.8mol/L potassium carbonate solution, and then sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic potassium elements; the potassium element loaded on the straw powder is 1% of the mass of the straw powder.
S3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel element; the nickel element loaded on the straw powder is 20% of the mass of the straw powder.
S4, placing the straw powder loaded with the potassium element and the nickel element into a furnace body, and carbonizing at high temperature in a nitrogen atmosphere to obtain the nickel-biochar catalyst. The carbonization temperature is 700 ℃, and the heat preservation time is 20min.
The performance of the nickel-biomass catalyst obtained in example 1 was investigated. FIG. 2 is an XRD pattern of an embodiment of a method for preparing a biomass internal and external metal synergistic catalyst according to the present invention. As shown in the figure, XRD patterns showed characteristic diffraction peaks at 44.5 °, 51.7 ° and 76.3 °, corresponding to Ni (111), ni (200) and Ni (220), respectively, during biomass pyrolysis stage, a large amount of reducing substances (CO, H) are generated due to biomass devolatilization 2 Etc.), supported Ni (NO 3 ) 2 Is reduced to metallic Ni 0 No NiO crystallites were detected in all samples, indicating that the reducing atmosphere formed during the thermal devolatilization process allowed complete reduction of NiO.
Fig. 3 is a transmission electron microscope image of a preparation method embodiment of a biomass internal and external metal synergistic catalyst. As shown in the figure, it was observed by HRTEM treatment of the sample that the regions with interplanar spacings of 0.213nm and 0.181nm correspond to the (111) and (200) planes of Ni, respectively.
Fig. 4 is an XPS diagram of a preparation method of a biomass internal and external metal synergistic catalyst according to an embodiment of the present invention. As shown in the figure, in the nickel-biochar catalyst, the interaction between nickel and biochar is mainly carried out by taking oxygen-containing functional groups as media, and peak separation of the oxygen-containing functional groups of XPS shows that potassium can increase the relative proportion of oxygen with surface defects of the catalyst, the oxygen with the surface defects obviously increases the electronic charge near the oxygen atoms of the surface lattice, the fluidity of oxygen is increased, the electron transfer is promoted, O-H is easier to break, and the catalytic activity is enhanced. K directly influences lattice oxygen electronic characteristics of transition metal Ni by taking O as a medium.
Therefore, the preparation method of the biomass internal and external metal synergistic catalyst can be used for efficiently reducing the oxidation state of the transition metal into the simple substance state by utilizing AAEMs in biomass and volatile matters in the pyrolysis process, and the catalytic performance is improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.

Claims (6)

1. The preparation method of the biomass internal and external metal synergistic catalyst is characterized by comprising the following steps of:
s1, crushing and screening corn straw biomass to obtain straw powder, and pickling to obtain pickled straw powder;
s2, soaking the pickled straw powder in a potassium carbonate solution, and then, sufficiently filtering and washing with deionized water to enable the straw powder to be loaded with organic potassium elements;
s3, soaking the straw powder treated in the S2 with a nickel nitrate solution to enable the straw powder to be loaded with nickel element;
s4, placing the straw powder loaded with the potassium element and the nickel element into a furnace body, and carbonizing at high temperature in a nitrogen atmosphere to obtain the nickel-biochar catalyst.
2. The method for preparing the biomass internal and external metal synergistic catalyst according to claim 1, which is characterized in that: in the step S1, the grain diameter of the straw powder is 150-250 mu m.
3. The method for preparing the biomass internal and external metal synergistic catalyst according to claim 1, which is characterized in that: in the step S1, the straw powder and the sulfuric acid solution with the concentration of 0.2mol/L are stirred and mixed uniformly in the nitrogen atmosphere, the stirring time is 24 hours, and then deionized water is used for washing until the mixture is neutral.
4. The method for preparing the biomass internal and external metal synergistic catalyst according to claim 1, which is characterized in that: in the step S2, the concentration of the potassium carbonate solution is 0.8mol/L, and the potassium element loaded on the straw powder is 1-5% of the mass of the straw powder.
5. The method for preparing the biomass internal and external metal synergistic catalyst according to claim 1, which is characterized in that: in the step S3, nickel element loaded on the straw powder is 10-20% of the mass of the straw powder.
6. The method for preparing the biomass internal and external metal synergistic catalyst according to claim 1, which is characterized in that: in the step S4, the carbonization temperature is 600-700 ℃, and the heat preservation time is 20-40min.
CN202310040383.4A 2023-01-13 2023-01-13 Preparation method of biomass internal and external metal synergistic catalyst Pending CN116099538A (en)

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