CN114797857B - Nanometer flower-like copper-based material, and preparation method and application thereof - Google Patents
Nanometer flower-like copper-based material, and preparation method and application thereof Download PDFInfo
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- CN114797857B CN114797857B CN202210550385.3A CN202210550385A CN114797857B CN 114797857 B CN114797857 B CN 114797857B CN 202210550385 A CN202210550385 A CN 202210550385A CN 114797857 B CN114797857 B CN 114797857B
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- 239000010949 copper Substances 0.000 title claims abstract description 91
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229920001661 Chitosan Polymers 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002407 reforming Methods 0.000 claims abstract description 19
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 239000002057 nanoflower Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 27
- 229960000583 acetic acid Drugs 0.000 claims description 15
- 239000012362 glacial acetic acid Substances 0.000 claims description 15
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- -1 copper zinc aluminum Chemical compound 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- B01J23/72—Copper
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/399—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
Abstract
The utility model discloses a nanometer flower-like copper-based material, a preparation method and application thereof. The preparation method of the nano flower-shaped copper-based material comprises the steps of preparing active metal copper and carrier alumina into uniform solution, preparing chitosan into uniform solution by adding a solvent, mixing the two solutions, evaporating the two solutions to dryness, and carrying out reduction reaction after heat treatment for 1-2 h at 200-300 ℃. The obtained copper-based material takes chitosan as a carbon source to be introduced and takes a nano flower needle-shaped structure, which can effectively provide attachment points for the attachment of active metals, increase the attachment area of Cu of the active metals and increase the attachment area of Cu and Al 2 O 3 The synergistic effect of (2) enables Cu to be uniformly distributed in the nano flower-like copper-based material. The nano flower-like copper-based material is used as a catalyst in the field of hydrogen production by alcohol liquid phase reforming, solves the problem of active metal agglomeration on the copper-based catalyst in the prior art, ensures that the catalyst has higher catalytic activity, improves the hydrogen production rate and simultaneously increases the hydrogen selectivity.
Description
Technical Field
The utility model relates to the technical field of catalysts, in particular to a nano flower-shaped copper-based material, a preparation method and application thereof.
Background
With the development of global energy situation, energy safety and environmental pollution become important problems facing human beings, and the development of green energy and the search of clean and pollution-free fossil fuel substitutes are the problems to be solved in the development of modern energy. The hydrogen energy is used as a well-known clean secondary energy source, the combustion product of the hydrogen energy is only water, and the hydrogen energy does not pollute the environment, so the hydrogen energy is an ideal alternative energy source. At present, 30% of hydrogen in industrialized hydrogen production is synthesized from refinery/chemical waste gas, 48% is obtained from steam methane reforming, 18% is obtained from coal gasification, 3.9% is obtained from water electrolysis and 0.1% is obtained from other approaches, but the methods cannot conform to the current environmental protection concept due to the fact that harmful gases are discharged in large quantities, carbon emission is increased.
The alcohol reforming hydrogen production 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 firstly researched and applied to industry, has mature technology, can realize high-capacity hydrogen production and is one of important sources of the current industrial hydrogen. 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 in the liquid phase reforming technology is used, under the pressure range, macromolecule in the reaction product of preparing hydrogen by alcohol liquid weight relative to impurity components of hydrogen can be selectively adsorbed by utilizing a pressure swing adsorption technology or a membrane separation technology, and the hydrogen with small molecules is not easy to adsorb and passes through an adsorption bed layer, so that the hydrogen and the 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 And reduces the selectivity of CO, but high temperature sintering, carbon deposition can lead to deactivation of the catalyst. Therefore, on the basis of the traditional catalyst, the catalyst with high selectivity and strong stability can be prepared by metal doping, using different carriers and the like.
The catalyst for preparing hydrogen by alcohol liquid phase reforming widely used in industry at present is a supported catalyst with a carbon coating layer, 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 a catalyst for preparing hydrogen by alcohol liquid phase reforming and a preparation method thereof, wherein 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 alcohol liquid phase reforming hydrogen production process, and the hydrogen selectivity reaches 85%. The existing supported catalyst applied to a carbon coating layer of an alcohol liquid phase reforming hydrogen production reaction has the technical problems of active metal agglomeration on a carrier, low hydrogen production rate, high later gas purification cost caused by insufficient hydrogen selectivity and the like, and needs further improvement and optimization.
Disclosure of Invention
The utility model provides a preparation method of a nanometer flower-shaped copper-based catalyst, which aims to overcome the defects of active metal agglomeration, low hydrogen production rate and insufficient hydrogen selectivity of the alcohol liquid hydrogen preparation catalyst in the prior art.
Another object of the present utility model is to provide the nanoflower-like copper-based material.
Another object of the present utility model is to provide the use of the nanoflower-like copper-based material.
In order to solve the technical problems, the utility model adopts the following technical scheme:
the preparation process of nanometer flower-like copper base material includes 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), and heating, evaporating and drying the obtained mixed solution A to obtain a solid B;
s2, carrying out heat treatment and reduction on the solid B obtained in the S1 at 200-300 ℃ to finally obtain the required nano flower-shaped copper-based material.
In the utility model, the copper-based material introduces chitosan as a carbon source, al 2 O 3 As a carrier, the carbon-coated nanometer flower-shaped structure is provided, petals are nanometer flower-shaped, al 2 O 3 Forming a metal framework in the catalyst due to the active metals Cu and Al 2 O 3 So that the metal Cu is inlaid in Al 2 O 3 Effectively solves the problem of active metal aggregation of Cu-based catalyst in the metal framework. Compared with other carbon sources, the active adsorption center of the chitosan is surface free amino, cu can be well adsorbed on Al by carbon generated by the chitosan 2 O 3 On the carrier, other carbon sources are simply coated, and copper particles cannot be well exposed while adsorption is stable. The nano flower-shaped copper-based material is applied to the catalytic field of hydrogen production by methanol liquid phase reforming, has almost no side reaction, and compared with other carbon source introduction modes, the chitosan is used as a carbon source, so that the nano flower-shaped copper-based material can have high-load copper elements, and can better improve the hydrogen selectivity and the hydrogen production rate.
Preferably, the mass ratio of the copper nitrate, the alumina and the chitosan of the mixed solution A in the step S1 is 1:
(0.6～0.8):(0.6～0.8)。
more preferably, the mass ratio of the copper nitrate, the aluminum oxide and the chitosan of the mixed solution A in the step S1 is 1:0.7:0.7.
Preferably, the method for obtaining the solid B in S1 includes magnetically stirring the mixed solution a, heating and evaporating, evaporating the mixed solution a until the mixed solution a is sticky, and drying.
The temperature rise of the magnetic stirring evaporation crystallization in the S1 is 30-80 ℃, and the rotating speed is 300-800 rpm.
The drying condition temperature in the S1 is 60-120 ℃ and the drying time is 6-24 h.
Preferably, the drying temperature in S1 is 80 ℃.
Preferably, the temperature of the heat treatment condition in the S2 is 200-300 ℃ and the time is 1-2 h.
The carrier gas for heat treatment in the S2 is inert gas, and is one or more of nitrogen, helium and argon.
The solvent of the chitosan solution in the 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.
The reduction temperature in the S2 is 260-300 ℃ and the time is 1-3 h.
In the utility model, the reducing carrier gas in S2 is hydrogen or the combination of hydrogen and other inert gases, the concentration of hydrogen is more than 5 percent, and the inert gases are one or more of nitrogen, helium and argon.
The utility model also provides a nanometer flower-shaped copper-based material, which is prepared by the preparation method.
The nanometer flower-like copper-based material consists of carbon and a 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-shaped copper-based material.
The utility model protects the application of the nano flower-shaped copper-based material in hydrogen production by alcohol liquid phase reforming.
The alcohol is one or more of methanol, ethanol, propanol or glycerol.
The utility model also protects a catalyst applied to the alcohol liquid phase reforming hydrogen production reaction, and the catalyst comprises the nano flower-shaped copper-based material prepared by the preparation method.
Compared with the prior art, the utility model has the beneficial effects that:
(1) The active metal Cu is uniformly distributed on the carbon carrier. The Cu-based material prepared by the utility model is in a nano flower-shaped structure, can provide a larger attachment area for active metal Cu, and simultaneously, cu and Al 2 O 3 Has good synergistic effect, so that metal Cu can be inlaid in Al 2 O 3 In the metal framework of the catalyst, the problem of active metal aggregation of the Cu-based catalyst is effectively solved.
(2) The catalytic activity is high. The nano flower-shaped copper-based material prepared by the method has a spherical structure with carbon wrapped nano flowers, the particle size of Cu metal is 13nm through electron microscope analysis, and under the condition of the same quality, the method can provide a larger contact area between active metal and reaction liquid, so that 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 produced gas of the nano flower-like copper-based catalyst is not less than 99% under the condition of 210 ℃, so that the difficulty and cost expenditure of the later gas purification can be effectively reduced.
Drawings
Fig. 1 is a structural diagram of a nanoflower-shaped copper-based material in example 1, wherein fig. (a) shows a transmission electron microscope image of the nanoflower-shaped copper-based material, fig. (B) shows a statistical graph of particle size of the material, and wherein fig. (C) and (D) show partial enlarged views of (a).
FIG. 2 is a graph showing the hydrogen production rate statistics of the catalytic methanol liquid phase reforming hydrogen production reaction of the examples and the comparative examples.
FIG. 3 is a graph showing hydrogen production selectivity of the catalytic methanol liquid phase reforming hydrogen production reaction of the examples and comparative examples.
Detailed Description
The utility model will be further described with reference to the following specific embodiments, but the examples are not intended to limit the utility model in any way. Alterations, substitutions, and modifications will remain within the scope of the utility model for those skilled in the art upon understanding the utility model. Raw materials reagents used in the examples of the present utility model are conventionally purchased raw materials reagents unless otherwise specified.
The raw material sources are as follows: all chemicals were purchased from ala Ding Shiji limited except that the copper zinc aluminum commercial catalyst of comparative example 1 was purchased from sikawa high tech co.
Example 1
The preparation method of the nanometer flower-like copper-based catalyst comprises the following steps:
s1. an amount of copper nitrate trihydrate (Cu (NO 3 ) 2 ·3H 2 O) completely dissolving in deionized water, adding a certain amount of ground alumina powder, and uniformly mixing to obtain a solution (1); dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution (2), wherein the volume ratio of water to glacial acetic acid is 1:9; uniformly mixing the solutions (1) and (2) 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 1:0.7:0.7; the solution A is heated to 80 ℃ for evaporation until the solution is sticky, and then the solution is dried: 100 ℃ for 12 hours until the moisture is completely separated, thus obtaining blocky solid B;
s2, grinding the massive solid B, and performing heat treatment: the temperature programming is carried out at 300 ℃ and 5 ℃/min for 2 hours,introducing nitrogen as carrier gas to obtain powder C; powder C was reduced at 260℃for 2h at a hydrogen flow rate of 50 mL/min. Finally, black brown nano flower-like copper-based material is obtained and recorded as Cu/Al 2 O 3 And @ C. Through detection, cu accounts for 40% of the total mass of the nano flower-shaped copper-based material.
Example 2
Unlike example 1, S1 an amount of copper nitrate trihydrate (Cu (NO 3 ) 2 ·3H 2 O) completely dissolving in deionized water, adding a certain amount of ground alumina powder, and uniformly mixing to obtain a solution (1); dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution (2), wherein the volume ratio of water to glacial acetic acid is 1:9; uniformly mixing the solution (1) and the solution (2) to obtain a solution A, wherein the mass ratio of copper nitrate to alumina to 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
Unlike example 1, S1 an amount of copper nitrate trihydrate (Cu (NO 3 ) 2 ·3H 2 O) completely dissolving in deionized water, adding a certain amount of ground alumina powder, and uniformly mixing to obtain a solution (1); dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution (2), wherein the volume ratio of water to glacial acetic acid is 1:9; and (3) uniformly mixing the solution (1) and the solution (2) to obtain a solution A, wherein the mass ratio of the copper nitrate to the aluminum oxide to the 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
Unlike example 1, S1 an amount of copper nitrate trihydrate (Cu (NO 3 ) 2 ·3H 2 O) completely dissolving in deionized water, adding a certain amount of ground alumina powder, and uniformly mixing to obtain a solution (1); dissolving a certain amount of chitosan in a mixed solution of glacial acetic acid and deionized water to obtain a solution (2), wherein the volume ratio of water to glacial acetic acid is 1:9; and (3) uniformly mixing the solution (1) and the solution (2) to obtain a solution A, wherein the mass ratio of the copper nitrate to the aluminum oxide to the 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 heat treated: and (3) heating at 200 ℃ at 5 ℃/min for 1h, and introducing nitrogen as carrier gas to obtain powder C.
Comparative example 1
After grinding and crushing the copper zinc aluminum commercial catalyst (Cu/Zn/Al), the catalyst was reduced at 260 ℃ for 2 hours at a hydrogen flow rate of 50 mL/min.
Comparative example 2
The difference from example 1 is that in S1, solution A was subjected to hydrothermal reaction at 80℃for 3 hours to obtain a solid-liquid mixture;
and (3) 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 placing the viscous solid-liquid mixture in an oven to dry the viscous solid-liquid mixture for 12 hours at the temperature of 100 ℃ to obtain a massive solid B.
Comparative example 3
Unlike example 1, polyethylene glycol (molecular weight 5000) was dissolved in a mixed solution of glacial acetic acid and deionized water in S1 to form solution (2).
Comparative example 4
Unlike example 1, lignin was dissolved in a mixed solution of glacial acetic acid and deionized water in S1 to form solution (2).
Comparative example 5
The difference from example 1 is that the carbon nanotubes were dissolved in a mixed solution of glacial acetic acid and deionized water in S1 to form a solution (2).
Performance testing
The prepared nano flower-like copper-based material is applied to an alcohol liquid phase reforming hydrogen production reaction to test the hydrogen production catalytic performance:
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 in a molar ratio of 3:1 (mass ratio: 1.75:1) was added. Taking 2MPa nitrogen as a protective gas, carrying out hydrogen production performance test in a batch reactor, reacting for 2 hours at 210 ℃, and quantitatively analyzing a gas phase product by using gas chromatography after cooling to room temperature.
Fig. 1 is a block diagram of a nano flower-shaped copper-based material in example 4, wherein (a) shows that the nano flower-shaped catalyst of the utility model has a carbon-coated nano flower-shaped structure, petals of the catalyst are in a nano flower-shaped structure, and (C) and (D) show that active metal Cu can be dispersed to a greater extent as partial enlarged views of (a), so that the technical problem of uneven distribution of active metal of the conventional copper-based catalyst is solved. (B) The graph is a particle size distribution statistical graph of the material, and the graph (B) shows that the particle size of the metal Cu of the prepared nano flower-shaped copper-based catalyst is 13nm, and the contact area of the active metal and the reaction liquid can be provided higher under the condition of the same quality, so that the hydrogen production rate and the hydrogen selectivity are improved.
Fig. 2 is a statistical graph of hydrogen production rate of the catalytic methanol liquid phase reforming hydrogen production reaction of the example and the comparative example, and it can be seen from fig. 2: under the above reaction conditions, the nano flower-like copper-based catalyst of the present utility model produced hydrogen at a rate of not less than 13.21. Mu. Mol H in examples 1 to 5 at 210℃under the reaction conditions 2 Per g cat/s (example 5), wherein the optimum hydrogen production rate is 23.02. Mu. Mol H 2 Per g cat/s (example 1), the performance was better than that of a commercial Cu-Zn-Al catalyst (15.98. Mu. Mol H) 2 /g cat/s). As can be seen from fig. 3: from the viewpoint of purity of hydrogen production, the hydrogen selectivity of the nano flower-like copper-based catalyst of the utility model in examples 1 to 5 is not less than 99.7%, wherein the optimal hydrogen selectivity is 99.95%, and the selectivity to hydrogen is superior to that of the copper-zinc-aluminum commercial catalyst (99.89%).
Experiments on the addition amount of copper nitrate and the catalytic hydrogen production activity of the catalyst in examples 1-4 finally find that when the mass ratio of copper nitrate to aluminum oxide to chitosan is 1:0.7:0.7 (example 1), the hydrogen production rate reaches the maximum 23.02 mu mol H 2 Per g cat/s (example 1), when the mass ratio of copper nitrate, alumina, chitosan is 1:0.6:0.6 (example 2), it is possible that aggregation of copper particles occurs due to too high copper content, reducing the relative surface area of copper, resulting in a slight decrease in hydrogen production rate of 19.39. Mu. Mol H 2 The hydrogen selectivity per g cat/s (example 2) was 99.94% and 99.92%, respectively, and remained essentially unchanged. In examples 1 to 5 and comparative examples 1 to 5, methanol was reformed by liquid phaseThe catalytic activity of the nano flower-like copper-based catalyst prepared by the utility model is higher than that of a copper zinc aluminum commercial catalyst (Cu/Zn/Al) as the catalytic result of the hydrogen production reaction.
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, and compared with other carbon sources, the active adsorption center of the chitosan is surface free amino groups, 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 utility model 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 simply coated, so that the Cu particles can not be well exposed while adsorption is stable, and the loss or inactivation of the Cu element is greatly increased. Therefore, the active metal Cu can be dispersed to a greater extent by using chitosan as a carbon source, and Cu and Al are simultaneously dispersed 2 O 3 Has good synergistic effect, al 2 O 3 Forming a metal frame in the catalyst so that metal Cu can be inlaid in Al 2 O 3 In the metal framework of the catalyst, the problem of active metal aggregation of the Cu-based catalyst is effectively solved. The material is applied to the catalytic field of hydrogen production by methanol liquid phase reforming, has few side reactions, 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 a copper-based catalyst by using polyethylene glycol, lignin and carbon nanotubes as introduced carbon sources in comparative examples 3, 4 and 5 under the same condition.
It is to be understood that the above examples of the present utility model are provided by way of illustration only and not by way of limitation of the embodiments of the present utility model. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the utility model are desired to be protected by the following claims.
Claims (9)
1. The preparation method of the nano flower-shaped copper-based material is characterized by comprising the following steps of:
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), and heating, evaporating and drying the obtained mixed solution A to obtain a solid B;
s2, carrying out heat treatment and reduction on the solid obtained in the S1 at the temperature of 200-300 ℃ for 1-2 hours, and finally obtaining the required nano flower-shaped copper-based material;
the metal Cu in the nano flower-shaped copper-based material is inlaid in Al 2 O 3 Is arranged in the metal frame of the frame.
2. The preparation method of the nano flower-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).
3. The method for preparing the nano flower-like copper-based material according to claim 1, wherein the method for obtaining the solid B in S1 is to magnetically stir the mixed solution A, raise the temperature and evaporate the mixed solution A, evaporate the mixed solution A until the mixed solution A is sticky, and dry the mixed solution A.
4. The method for preparing a nano flower-like copper-based material according to claim 1, wherein the chitosan solution in S1 is a chitosan glacial acetic acid solution.
5. A nanoflower-shaped copper-based material, characterized in that it is prepared by the method for preparing a nanoflower-shaped copper-based material according to any one of claims 1 to 4.
6. The nano flower-like copper-based material according to claim 5, wherein the nano flower-like copper-based material is composed of carbon, carrier Al 2 O 3 And the active metal Cu accounts for 30-45% of the total mass of the nano flower-shaped copper-based material.
7. Use of the nanoflower-like copper-based material according to claim 5 or 6 for catalytic alcohol liquid phase reforming hydrogen production.
8. The use according to claim 7, wherein the alcohol is one or more of methanol, ethanol, propanol or glycerol.
9. A catalyst for liquid phase reforming of alcohols to produce hydrogen, comprising the nanoflower copper-based material of claim 5 or 6.
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