CN114797857A - Nanometer flower-shaped copper-based material and preparation method and application thereof - Google Patents

Nanometer flower-shaped copper-based material and preparation method and application thereof Download PDF

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CN114797857A
CN114797857A CN202210550385.3A CN202210550385A CN114797857A CN 114797857 A CN114797857 A CN 114797857A CN 202210550385 A CN202210550385 A CN 202210550385A CN 114797857 A CN114797857 A CN 114797857A
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copper
based material
flower
chitosan
solution
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CN114797857B (en
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朱海枰
王铁军
胡昌淞
刘舒婷
林纯英
卢明磊
黄雪儿
黄海峰
陈子董
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Guangdong University of Technology
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    • 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
    • B01J23/72—Copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • 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
    • C01B2203/02—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
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials

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Abstract

The invention discloses a nanometer flower-shaped copper-based material and a preparation method and application thereof. The preparation method of the nano flower-like copper-based material comprises the steps of preparing a uniform solution from active metal copper and carrier alumina, preparing a uniform solution from chitosan and a solvent, mixing the two solutions, evaporating to dryness, carrying out heat treatment at 200-300 ℃ for 1-2 hours, and carrying out reduction reaction to obtain the nano flower-like copper-based material. The obtained copper-based material takes chitosan as a carbon source, is in a nanometer flower needle-shaped structure, can effectively provide attachment points for the attachment of active metal, increases the attachment area of the active metal Cu, and increases Cu and Al 2 O 3 The synergistic effect of (a) enables the Cu to be uniformly distributed in the nano flower-like copper-based material. The nanometer flower-shaped copper-based material is applied to the field of alcohol liquid phase reforming hydrogen production as a catalyst, solves the problem of active metal agglomeration on the copper-based catalyst in the prior art, enables the catalyst to have higher catalytic activity, improves the hydrogen production rate and increases hydrogenAnd (4) selectivity.

Description

Nanometer flower-shaped copper-based material and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a nanometer flower-shaped copper-based material and a preparation method and application thereof.
Background
With the development of energy situation in the global scope, energy safety and environmental pollution become great problems for human beings, and the development of green energy and the search of clean and pollution-free fossil fuel substitutes are urgent problems to be solved in the development of modern energy. Hydrogen energy is regarded as a recognized clean secondary energy source, and the combustion product of the hydrogen energy is only water, so that the hydrogen energy does not pollute the environment and is an ideal alternative energy source. At present, 30% of hydrogen in industrial hydrogen production is synthesized from refinery/chemical waste gas, 48% is from steam methane reforming, 18% is from coal gasification, 3.9% is from water electrolysis, and 0.1% is from other ways, but the methods are not in accordance with the current concept of environmental protection due to large amount of harmful gas emission and increase of carbon emission.
The hydrogen production by reforming alcohols has the advantages of wide raw material source, low conversion temperature, low energy consumption and the like, and has wide application prospect. The traditional methanol reforming hydrogen production is a technology which is researched at the earliest and applied to industry, is mature in technology, can realize high-capacity hydrogen production, and is one of important sources of industrial hydrogen at present. The temperature and pressure of the liquid phase reforming reaction are favorable for the water gas reaction, only a small amount of CO is generated while hydrogen is prepared in a single chemical reactor, and the pressure range (generally 1.5-4 MPa) used by the liquid phase reforming technology can selectively adsorb impurity component macromolecules relative to hydrogen in the reaction product of the alcohol liquid-phase heavy hydrogen production by using the pressure swing adsorption technology or the membrane separation technology in the pressure range,the micromolecular hydrogen is not easy to adsorb and passes through the adsorption bed layer, so that the hydrogen and impurity components are separated, the hydrogen selectivity is increased, and the hydrogen purification cost is reduced. The key core of the alcohol liquid phase reforming technology is the selection and use of a catalyst, and the catalyst with high catalytic performance can improve the conversion rate of methanol and H 2 The yield of the catalyst is low, the selectivity of CO is reduced, but the catalyst is deactivated due to high-temperature sintering and carbon deposition. Therefore, on the basis of the traditional catalyst, the catalyst with high selectivity and strong stability can be prepared by metal doping, different carriers and the like.
The catalyst for preparing hydrogen by alcohol liquid phase reforming, which is widely used in industry at present, is a carbon-coated supported catalyst, and the catalyst has relative advantages in the aspects of alcohol conversion activity, reaction selectivity, reaction temperature, raw material cost and the like. The prior art discloses an alcohol liquid phase reforming hydrogen production catalyst and a preparation method thereof, the catalyst is a supported catalyst with a carbon coating layer, active metal nickel is supported on a zirconia carrier, and the inner core is coated by the carbon coating layer. The method is applied to the process of hydrogen production by alcohol liquid phase reforming, and the hydrogen selectivity reaches 85 percent. The existing supported catalyst of the carbon coating layer applied to the alcohol liquid phase reforming hydrogen production reaction has the technical problems of active metal agglomeration on a carrier, low hydrogen production rate, high gas purification cost in the later period due to insufficient hydrogen selectivity and the like, and needs further improvement and optimization.
Disclosure of Invention
The invention provides a preparation method of a nano flower-shaped copper-based catalyst, aiming at overcoming the defects of active metal agglomeration, low hydrogen production rate and insufficient hydrogen selectivity of the alcohol liquid-heavy hydrogen production catalyst in the prior art.
The invention also aims to provide the nano flower-shaped copper-based material.
The invention also aims to provide application of the nano flower-like copper-based material.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for preparing a nanometer flower-shaped copper-based material comprises the following steps:
s1, mixing a solution of copper nitrate and aluminum oxide with a chitosan solution to obtain a mixed solution A, wherein the mass ratio of the copper nitrate to the aluminum oxide to the chitosan in the mixed solution A is 1 (0.6-1) to (0.6-1), and heating, evaporating and drying the mixed solution A to obtain a solid B;
s2, carrying out heat treatment and reduction on the solid B obtained in the step S1 at the temperature of 200-300 ℃, and finally preparing the required nano flower-shaped copper-based material.
In the invention, the copper-based material introduces chitosan as a carbon source, and Al 2 O 3 As carrier, carbon-coated nanoflower structure with nanoflower-shaped petals and Al 2 O 3 Forming a metal framework in the catalyst due to the active metals Cu and Al 2 O 3 The synergistic effect of the components enables the metal Cu to be embedded in Al 2 O 3 The problem of active metal aggregation of the Cu-based catalyst is effectively solved. Compared with other carbon sources, the active adsorption center of the chitosan is surface free amino, and Cu can be well adsorbed on Al by carbon generated by the chitosan 2 O 3 On the carrier, other carbon sources are only simply wrapped, and the copper particles cannot be well exposed while being stably adsorbed. The nano flower-like copper-based material is applied to the field of methanol liquid phase reforming hydrogen production catalysis, almost has no side reaction, and compared with other carbon source introduction modes, the nano flower-like copper-based material using chitosan as a carbon source can have high-load copper element, so that the selectivity of hydrogen and the hydrogen production rate can be better improved.
Preferably, the mass ratio of copper nitrate, alumina and chitosan in the mixed solution a in S1 is 1:
(0.6～0.8):(0.6～0.8)。
more preferably, the mass ratio of copper nitrate, alumina and chitosan in the mixed solution a in S1 is 1:0.7: 0.7.
Preferably, in S1, the solid B is obtained by magnetically stirring the mixture a, heating to evaporate, and drying after the mixture a is evaporated to a viscous state.
In the S1 process, the temperature of the magnetic stirring evaporation crystallization is raised to 30-80 ℃, and the rotating speed is 300-800 rpm.
The drying condition in S1 is 60-120 ℃ and the time is 6-24 h.
Preferably, the drying temperature in S1 is 80 ℃.
Preferably, the heat treatment in S2 is carried out at 200-300 ℃ for 1-2 h.
The heat treatment carrier gas in the S2 is inert gas, and is one or more of nitrogen, helium and argon.
The solvent of the chitosan solution in S1 is a mixed solution prepared from water and glacial acetic acid, and the volume ratio of the water to the glacial acetic acid is 1 (7-10). Further, the volume ratio of water to glacial acetic acid is 1: 9.
In the S2 process, the reduction temperature is 260-300 ℃, and the time is 1-3 h.
In the S2, the reduction carrier gas is hydrogen or the combination of hydrogen and other inert gases, the concentration of the hydrogen is more than 5%, and the inert gases are one or more of nitrogen, helium and argon.
The invention also discloses a nanometer flower-shaped copper-based material prepared by the preparation method.
The nano flower-like copper-based material consists of carbon and carrier Al 2 O 3 And active metal Cu, wherein the active metal Cu accounts for 30-45% of the total mass of the nano flower-like copper-based material.
The invention protects the application of the nanometer flower-like copper-based material in alcohol liquid phase reforming hydrogen production.
The alcohol is one or more of methanol, ethanol, propanol or glycerol.
The invention also discloses a catalyst applied to the alcohol liquid phase reforming hydrogen production reaction, and the catalyst comprises the nanometer flower-shaped copper-based material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the active metal Cu is uniformly distributed on the carbon support. The Cu-based material prepared by the invention is in a nano flower-shaped structure and can provide larger attachment for active metal CuIn terms of area, Cu and Al simultaneously 2 O 3 Has good synergistic effect, so that the metal Cu can be embedded in Al 2 O 3 The problem of active metal aggregation of the Cu-based catalyst is effectively solved.
(2) The catalytic activity is high. The nanometer flower-shaped copper-based material prepared by the invention has a spherical structure of carbon-coated nanometer flowers, and the particle size of Cu metal is 13nm through electron microscope analysis, so that under the condition of the same mass, the contact area between active metal and reaction liquid can be larger, the catalyst has higher catalytic activity, and the hydrogen production rate is improved.
(3) The hydrogen selectivity is high. The concentration of hydrogen in the gas produced by the reaction of the nano flower-shaped copper-based catalyst at 210 ℃ is not less than 99%, so that the difficulty and cost of later-stage gas purification can be effectively reduced.
Drawings
Fig. 1 is a structural view of the nano flower-like copper-based material in example 1, in which (a) shows a transmission electron microscope image of the nano flower-like copper-based material, and (B) shows a statistical view of the particle size of the material, in which (C) and (D) show partial enlarged views of (a).
FIG. 2 is a statistical chart of hydrogen production rates of catalytic methanol liquid phase reforming hydrogen production reactions of examples and comparative examples.
FIG. 3 is a statistical chart of hydrogen production selectivity of catalytic methanol liquid phase reforming hydrogen production reactions of examples and comparative examples.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. Those skilled in the art should understand the present invention and make various changes, substitutions and improvements on the invention while remaining within the scope of the invention. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The raw material sources are as follows: all chemical reagents were purchased from Aladdin reagents, Inc., except that the commercial Cu-Zn-Al catalyst of comparative example 1 was purchased from Sichuan Asian high tech Co.
Example 1
A preparation method of a nanometer flower-shaped copper-based catalyst comprises the following steps:
s1, adding a certain amount of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) is completely dissolved in deionized water, and a certain amount of ground alumina powder is added and uniformly mixed to obtain a solution I; dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution II, wherein the volume ratio of water to glacial acetic acid is 1: 9; uniformly mixing the first solution and the second solution to obtain a mixed solution A, wherein the mass ratio of copper nitrate, aluminum oxide and chitosan in the mixed solution A is 1:0.7: 0.7; heating the solution A to 80 ℃ for evaporation until the solution is viscous, and drying: at 100 ℃, for 12 hours until the water is completely separated to obtain a blocky solid B;
s2, grinding the blocky solid B, and performing heat treatment: carrying out temperature programming at 300 ℃ and 5 ℃/min for 2h, and introducing nitrogen as carrier gas to obtain powder C; the powder C was reduced at 260 ℃ for 2h at a hydrogen flow rate of 50 mL/min. Finally obtaining black brown nano flower-shaped copper-based material recorded as Cu/Al 2 O 3 @ C. Through detection, Cu accounts for 40% of the total mass of the nano flower-shaped copper-based material.
Example 2
The difference from example 1 is that S1. a certain amount of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) is completely dissolved in deionized water, and a certain amount of ground alumina powder is added and uniformly mixed to obtain a solution I; dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution II, wherein the volume ratio of water to glacial acetic acid is 1: 9; uniformly mixing the first solution and the second solution to obtain a solution A, wherein the mass ratio of copper nitrate, aluminum oxide and chitosan in the solution A is 1:0.6: 0.6; through detection, Cu accounts for 45% of the total mass of the nano flower-shaped copper-based material.
Example 3
The difference from example 1 is that S1. a certain amount of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) is completely dissolved in deionized water, and a certain amount of ground alumina powder is added and uniformly mixed to obtain a solution I;dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution II, wherein the volume ratio of water to glacial acetic acid is 1: 9; and uniformly mixing the solution I and the solution II to obtain a solution A, wherein the mass ratio of copper nitrate to aluminum oxide to chitosan in the solution A is 1:1: 1. Through detection, Cu accounts for 30% of the total mass of the nano flower-shaped copper-based material.
Example 4
The difference from example 1 is that S1. a certain amount of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) is completely dissolved in deionized water, and a certain amount of ground alumina powder is added and uniformly mixed to obtain a solution I; dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution II, wherein the volume ratio of water to glacial acetic acid is 1: 9; uniformly mixing the first solution and the second solution to obtain a solution A, wherein the mass ratio of copper nitrate, aluminum oxide and chitosan in the solution A is 1:0.8: 0.8.
Example 5
The difference from example 1 is that, s2, the bulk solid B is ground and subjected to a heat treatment: and (3) carrying out temperature programming at 200 ℃ and 5 ℃/min for 1h, and introducing nitrogen as a carrier gas to obtain powder C.
Comparative example 1
After the Cu-Zn-Al commercial catalyst (Cu/Zn/Al) was crushed by grinding, it was reduced at 260 ℃ for 2h under a hydrogen flow rate of 50 mL/min.
Comparative example 2
The difference from example 1 is that the solution A is hydrothermally reacted at 80 ℃ for 3 hours in S1 to obtain a solid-liquid mixture;
and filtering the solid-liquid mixture, centrifugally washing the solid-liquid mixture for 3 times by using absolute ethyl alcohol to obtain a viscous solid-liquid mixture, and drying the viscous solid-liquid mixture in an oven at the temperature of 100 ℃ for 12 hours to obtain a blocky solid B.
Comparative example 3
The difference from example 1 is that in S1, polyethylene glycol (molecular weight 5000) is dissolved in a mixed solution of glacial acetic acid and deionized water to form a solution (c).
Comparative example 4
The difference from example 1 is that in S1, lignin is dissolved in a mixed solution of glacial acetic acid and deionized water to form a solution (c).
Comparative example 5
The difference from example 1 is that in S1, carbon nanotubes are dissolved in a mixed solution of glacial acetic acid and deionized water to form a solution (c).
Performance testing
The prepared nanometer flower-shaped copper-based material is applied to alcohol liquid phase reforming hydrogen production reaction, and hydrogen production catalysis performance is tested:
30mg of the catalyst obtained in examples 1 to 5 and comparative examples 1 to 5 was weighed, and 20mL of a reaction solution of water and methanol at a molar ratio of 3:1 (mass ratio of 1.75:1) was added. And (3) taking 2MPa nitrogen as a protective gas, carrying out hydrogen production performance test in an intermittent reaction kettle, reacting for 2 hours at 210 ℃, and carrying out quantitative analysis on a gas product by using a gas chromatography after cooling to room temperature.
Fig. 1 is a structural diagram of a nanoflower-shaped copper-based material in example 4, wherein (a) shows that the nanoflower-shaped catalyst of the present invention has a carbon-coated nanoflower-shaped structure, whose petals are in a nanoflower needle-like structure, and (C) and (D) show a partial enlarged view of (a), showing that active metal Cu can be dispersed to a greater extent, thereby solving the technical problem of uneven distribution of active metal in the conventional copper-based catalyst. (B) The figure is a particle size distribution statistical diagram of the material, and the figure (B) shows that the particle size of metal Cu of the prepared nano flower-shaped copper-based catalyst is 13nm, and under the condition of the same mass, the contact area of active metal and reaction liquid can be higher, so that the hydrogen production rate and the hydrogen selectivity are improved.
Fig. 2 is a statistical chart of hydrogen production rates of catalytic methanol liquid phase reforming hydrogen production reactions of examples and comparative examples, and it can be known from fig. 2 that: under the reaction conditions, the hydrogen production rate of the nano flower-shaped copper-based catalyst is not lower than 13.21 mu molH in the examples 1-5 under the reaction condition of 210 DEG C 2 Cat/g/s (example 5), with an optimum hydrogen production rate of 23.02. mu. mol H 2 Per g cat/s (example 1), superior performance to a commercial Cu-Zn-Al catalyst (15.98. mu. mol H) under equivalent conditions 2 Cat/g/s). As can be seen from fig. 3: from the viewpoint of purity of hydrogen productionIn the embodiments 1-5, the hydrogen selectivity of the nano flower-shaped copper-based catalyst is not lower than 99.7%, wherein the optimal hydrogen selectivity is 99.95%, and the selectivity to hydrogen is better than that of a commercial copper-zinc-aluminum catalyst (99.89%).
In examples 1 to 4, experiments were carried out on the addition amount of copper nitrate and the catalytic hydrogen production activity of the catalyst, and finally, it was found that when the mass ratio of copper nitrate, alumina and chitosan was 1:0.7:0.7 (example 1), the maximum hydrogen production rate was 23.02. mu. mol H 2 (example 1) when the mass ratio of copper nitrate, aluminum oxide and chitosan is 1:0.6:0.6 (example 2), the gathering of copper particles can occur due to the excessive content of copper, the relative surface area of copper is reduced, and the hydrogen production rate is slightly reduced by 19.39 mu molH 2 The hydrogen selectivity was 99.94% and 99.92%, respectively, at/g cat/s (example 2), which remained essentially unchanged. In the examples 1-5 and the comparative examples 1-5, the catalytic activity of the nano flower-shaped copper-based catalyst for hydrogen production by methanol liquid phase reforming is higher than that of a commercial copper-zinc-aluminum catalyst (Cu/Zn/Al).
In general, the nano flower-shaped copper-based material takes chitosan as a carbon source, has a carbon-coated nano flower-shaped structure and is in a nano flower needle shape, compared with other carbon sources, the active adsorption center of the chitosan is surface free amino, and a plurality of inorganic salts, organic acids and even amphoteric compounds can be adsorbed and combined by the chitosan. The Cu ions in the invention can be well adsorbed on the surface of chitosan, while other carbon sources (polyethylene glycol, lignin and carbon nano tubes are used in comparative examples 3, 4 and 5) are only simply wrapped, so that copper particles cannot be well exposed while being stably adsorbed, and the loss or inactivation of copper elements is greatly increased. Therefore, the active metal Cu using chitosan as a carbon source can be dispersed to a greater extent, and simultaneously Cu and Al 2 O 3 Has good synergistic effect, Al 2 O 3 Forming a metal frame in the catalyst to enable the metal Cu to be embedded in Al 2 O 3 The problem of active metal aggregation of the Cu-based catalyst is effectively solved. The material is applied to the field of methanol liquid phase reforming hydrogen production catalysis, and almost does not existThe method has side reaction, reduces the emission of toxic and harmful gases, can ensure high selectivity to hydrogen under the condition of ensuring the hydrogen production rate, and is far superior to the hydrogen production performance of preparing the copper-based catalyst by using polyethylene glycol, lignin and carbon nano tubes as introduced carbon sources in comparative examples 3, 4 and 5 under the same condition.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a nanometer flower-shaped copper-based material is characterized by comprising the following steps:
s1, mixing a solution of copper nitrate and aluminum oxide with a chitosan solution to obtain a mixed solution A, wherein the mass ratio of the copper nitrate to the aluminum oxide to the chitosan in the mixed solution A is 1 (0.6-1) to (0.6-1), and heating, evaporating and drying the mixed solution A to obtain a solid B;
s2, carrying out heat treatment and reduction on the solid obtained in the step S1 at the temperature of 200-300 ℃, and finally preparing the required flower-like copper-based material.
2. The method for preparing a nanoflower-shaped copper-based material according to claim 1, wherein the mass ratio of copper nitrate, aluminum oxide and chitosan in the S1 mixed solution A is 1 (0.6-0.8) to (0.6-0.8).
3. The method for preparing a copper-based material with a nanometer flower shape according to claim 1, wherein the heat treatment in S3 is performed at 200-300 ℃ for 1-2 h.
4. The method for preparing the nanoflower-like copper-based material according to claim 1, wherein the step of obtaining the solid B in the step S1 is to magnetically stir the mixed solution A, raise the temperature for evaporation, evaporate the mixed solution A until the mixed solution A is viscous, and then dry the mixed solution A.
5. The method for preparing a copper-based material in the shape of a nanometer flower according to claim 1, wherein the chitosan solution in S1 is chitosan glacial acetic acid solution.
6. A nanoflower-shaped copper-based material prepared by the method according to any one of claims 1 to 5.
7. The nano flower-like copper-based material as claimed in claim 6, wherein the nano flower-like copper-based material is prepared from carbon and Al as a carrier 2 O 3 And active metal Cu, wherein the active metal Cu accounts for 30-45% of the total mass of the nano flower-like copper-based material.
8. The use of the nanoflower-like copper-based material according to claim 6 or 7 in catalyzing alcohol liquid phase reforming to produce hydrogen.
9. The use of claim 8, wherein the alcohol is one or more of methanol, ethanol, propanol, or glycerol.
10. A catalyst for hydrogen production by alcohol liquid-phase reforming, comprising the nanoflower-shaped copper-based material according to claim 6 or 7.
CN202210550385.3A 2022-05-20 2022-05-20 Nanometer flower-like copper-based material, and preparation method and application thereof Active CN114797857B (en)

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CN113398928A (en) * 2021-06-16 2021-09-17 广东工业大学 Copper-based composite material and preparation method and application thereof
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CN101444739A (en) * 2008-12-22 2009-06-03 长沙星纳气凝胶有限公司 Copper-based nano-catalyst for hydrogen production by ethanol steam reforming and preparation method thereof
CN103785856A (en) * 2014-02-26 2014-05-14 北京科技大学 Composite material in which carbon spheres are loaded with copper nanoparticles and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116037113A (en) * 2022-12-13 2023-05-02 广东工业大学 Copper-based supported catalyst and preparation method and application thereof

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