CN113209976B - Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction - Google Patents

Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction Download PDF

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CN113209976B
CN113209976B CN202110556182.0A CN202110556182A CN113209976B CN 113209976 B CN113209976 B CN 113209976B CN 202110556182 A CN202110556182 A CN 202110556182A CN 113209976 B CN113209976 B CN 113209976B
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hydrogen production
catalyst
steam reforming
methanol steam
methanol
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CN113209976A (en
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袁友珠
黄乐乐
谢素原
叶林敏
穆亚文
梁雪莲
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Xiamen University
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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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol

Abstract

The invention belongs to the technical field of energy chemical industry, and provides a catalyst for hydrogen production by methanol steam reforming, a preparation method and application thereof, and a hydrogen production reaction by methanol steam reforming. The catalyst provided by the invention comprises an oxide carrier and copper oxide and fullerene C loaded on the oxide carrier60. Fullerene C60The catalyst has excellent electron acceptor property, can reversibly capture and release electrons, can effectively regulate the electrons on the surface of copper, and controls the balance distribution and stability of the valence state of copper, thereby ensuring the stability of the catalyst. The catalyst provided by the invention has the following characteristics that the temperature is 240 ℃, the pressure is 0.1MPa, and the molar ratio of water to methanol is 1.2: 1, the mass space velocity of the methanol is 4.5h-1Under the condition, the hydrogen production rate is 0.4mol/g/h, the CO selectivity is lower than 0.3 percent, the structure and the performance are kept stable after continuous reaction for 200 hours, and the inactivation phenomenon does not occur.

Description

Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction
Technical Field
The invention relates to an energy chemical technology
The field, in particular to a catalyst for hydrogen production by methanol steam reforming, a preparation method and application thereof, and a hydrogen production reaction by methanol steam reforming.
Background
Hydrogen energy is regarded as the most promising clean energy source in this century and is an important research object for energy storage and transformation. The methanol steam reforming hydrogen production technology has the advantages of safe and easily obtained raw materials, low reaction temperature, few byproducts and the like, and is widely concerned by people. The methanol and steam reforming technology can be used for on-site hydrogen production to provide a hydrogen source for a fuel cell, not only solves the problem of difficult hydrogen transportation, but also has certain advantages in the aspects of safety and economy.
The key of the methanol steam reforming hydrogen production technology is focused on efficient and stable catalyst preparation and reactor design. The catalyst for hydrogen production by methanol steam reforming needs to take into account a plurality of factors such as raw material cost, reaction space velocity and temperature, methanol conversion rate, byproduct CO selectivity and the like. At present, catalysts for methanol steam reforming hydrogen production mainly comprise noble metal platinum-palladium-based and copper-based catalysts. Wherein, the platinum palladium-based catalyst has better stability and high activity, but the cost is too high; meanwhile, the reforming temperature of the platinum-palladium based catalyst reaches 300-500 ℃, and better methanol activation and conversion can be realized. The copper-based catalyst has obvious low-temperature activity and is usually required to be reformed within the range of 260-300 ℃. Meanwhile, the most fatal problems of the copper-based catalyst are poor stability, especially rapid inactivation caused by surface valence state imbalance; the valence state of Cu is changeable, and Cu (Cu) with different valence states is also needed in the methanol steam reforming reaction0And Cu +) and synergistic effect, can maintain the high-efficiency stable activation of the substrate; the generation of CO and the high temperature reducing atmosphere are not favorable for the stability of the copper-based catalyst.
Therefore, modified copper-based catalysts are currently being studied more. The influence of rare earth (lanthanum, cerium, samarium, gadolinium and the like) element doping on the catalytic performance of the copper-zinc-aluminum hydrotalcite derived catalyst is researched by the Yang Shuqian and the like (journal of Fuel chemistry [ J ],2018,46,179-188), and the result shows that: the introduction of rare earth elements can improve the dispersion degree, specific surface area and reduction property of the active component copper, thereby improving the catalytic activity of the catalyst.
Although many modified copper-based catalysts have been improved over traditional copper-based catalysts, the problem of poor stability still remains.
Disclosure of Invention
The invention aims to provide a catalyst for hydrogen production by methanol steam reforming, a preparation method and application thereof, and a hydrogen production reaction by methanol steam reforming. The catalyst provided by the invention has excellent stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a catalyst for hydrogen production by methanol steam reforming, which comprises an oxide carrier and an active component loaded on the oxide carrier; the active ingredients comprise copper oxide and fullerene C60(ii) a The oxide support comprises one or more of zinc oxide, alumina, zirconia, ceria and silica.
Preferably, in the catalyst for hydrogen production by methanol steam reforming, the mass percentage of the copper oxide is 10-60%; fullerene C60The mass percentage of the oxide carrier is 1-30%, and the balance is the oxide carrier.
The invention also provides a preparation method of the catalyst for hydrogen production by methanol steam reforming, which comprises the following steps:
dissolving soluble copper salt, water-soluble salt corresponding to oxide carrier, and fullerene C60Carrying out first mixing with water to obtain a first mixed solution;
the first mixed solution and the precipitant aqueous solution are mixed in a parallel flow mode and aged to obtain a coprecipitate;
and calcining the coprecipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
The invention also provides another preparation method of the catalyst for hydrogen production by methanol steam reforming, which comprises the following steps:
dissolving soluble copper salt, oxide carrier, and fullerene C60Carrying out second mixing with water to obtain a second mixed solution;
adding a precipitant aqueous solution into the second mixed solution, and aging to obtain a precipitate;
and calcining the deposition precipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
Preferably, the precipitant aqueous solution is ammonia water or alkaline aqueous solution; the mass concentration of the ammonia water is 26-28%; the alkaline matter in the alkaline water solution is urea, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
Preferably, the aging temperature is 30-120 ℃, and the aging time is 6-24 hours; the aging is carried out under the condition of stirring, and the rotating speed of the stirring is 200-900 r/min.
Preferably, the calcining temperature is 250-350 ℃, and the time is 1-12 h; the atmosphere of the calcination is air.
The invention also provides the application of the catalyst for hydrogen production by methanol steam reforming or the catalyst for hydrogen production by methanol steam reforming obtained by the preparation method in the technical scheme in catalyzing the reaction of hydrogen production by methanol steam reforming.
The invention also provides a methanol steam reforming hydrogen production reaction, which comprises the following steps:
reducing the catalyst for hydrogen production by methanol steam reforming according to the above technical scheme or the catalyst for hydrogen production by methanol steam reforming obtained by the preparation method according to the above technical scheme to obtain a reduced catalyst;
under the condition of a reduction catalyst, methanol and water carry out hydrogen production reaction to obtain hydrogen;
the reducing atmosphere is hydrogen, the temperature is 250-350 ℃, and the time is 1-12 h.
Preferably, the conditions of the hydrogen production reaction include: the temperature is 220-260 ℃, the pressure is 0.1-1.0 MPa, and the molar ratio of water to methanol is 0.9-1.5: 1, the mass space velocity of the methanol is 3-6 h-1。
The invention provides a catalyst for hydrogen production by methanol steam reforming, which comprises an oxide carrier and an active component loaded on the oxide carrier; the active ingredients comprise copper oxide and fullerene C60(ii) a The oxide support comprises one or more of zinc oxide, alumina, zirconia, ceria and silica. In the present invention, fullerene C60As a carbon simple substance material with definite structure and unique property, the material has excellent electron acceptor property and can reversibly trapElectrons are obtained and released, the electrons on the surface of copper can be effectively regulated, the balanced distribution and stability of the copper valence state are controlled, and the stability of the catalyst is further ensured.
The invention also provides a preparation method of the catalyst for hydrogen production by methanol steam reforming, which adopts a coprecipitation method and a deposition precipitation method to prepare respectively; the preparation method provided by the invention has the advantages of wide raw material source, simple operation and lower cost.
The invention also provides the application of the catalyst for hydrogen production by methanol steam reforming or the catalyst for hydrogen production by methanol steam reforming obtained by the preparation method in the technical scheme in catalyzing the reaction for hydrogen production by methanol steam reforming.
The data of the examples show that: when the catalyst provided by the invention is used for catalyzing methanol steam reforming hydrogen production reaction, the reaction temperature is 240 ℃, the pressure is 0.1MPa, and the molar ratio of water to methanol is 1.2: 1, the mass space velocity of the methanol is 4.5h-1Under the condition, the hydrogen production rate is 0.4mol/g/h, the CO selectivity is lower than 0.3 percent, the structure and the performance are kept stable after continuous reaction for 200 hours, and the inactivation phenomenon does not occur.
Drawings
FIG. 1 is a graph showing the life of a catalyst obtained in example 1 of the present invention used in a methanol steam reforming hydrogen production reaction;
FIG. 2 is an X-ray powder diffraction pattern of the catalysts for hydrogen production by methanol steam reforming obtained in example 1 of the present invention and comparative example 1;
FIG. 3 is a TEM photograph of the catalyst for hydrogen production by methanol steam reforming, which is obtained in example 1 of the present invention.
Detailed Description
The invention provides a catalyst for hydrogen production by methanol steam reforming, which comprises an oxide carrier and an active component loaded on the oxide carrier; the active ingredients comprise copper oxide and fullerene C60(ii) a The oxide carrier comprises zinc oxide, aluminum oxide,One or more of zirconia, ceria and silica.
The catalyst for hydrogen production by methanol steam reforming provided by the invention comprises an oxide carrier. In the present invention, the oxide support includes one or more of zinc oxide, alumina, zirconia, ceria, and silica.
The catalyst for hydrogen production by methanol steam reforming provided by the invention comprises an active component loaded on the oxide carrier. In the present invention, the active ingredients include copper oxide and fullerene C60. In the present invention, the copper oxide and fullerene C60Supported on the oxide support in the form of nanoparticles and nanoclusters.
In the catalyst for hydrogen production by methanol steam reforming, the mass percentage of the copper oxide is preferably 10 to 60%, and more preferably 20 to 50%. In the present invention, the fullerene C is contained in the catalyst for hydrogen production by methanol steam reforming60The content of (b) is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass. In the invention, the catalyst for hydrogen production by methanol steam reforming comprises an oxide carrier in balance.
In the present invention, fullerene C60As a carbon simple substance material with definite structure and unique property, the material has excellent electron acceptor property, can reversibly capture and release electrons, can effectively regulate the electrons on the surface of copper, controls the balanced distribution and stability of the valence state of copper, and further ensures the stability of the catalyst.
The invention also provides a preparation method of the catalyst for hydrogen production by methanol steam reforming, which comprises the following steps:
dissolving soluble copper salt, water-soluble salt corresponding to oxide carrier, and fullerene C60Mixing with water to obtain a first mixed solution;
the first mixed solution and the precipitant aqueous solution are mixed in a parallel flow mode and aged to obtain a coprecipitate;
and calcining the coprecipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention uses soluble copper salt, water-soluble salt corresponding to oxide carrier and fullerene C60And water to obtain a first mixed solution.
In the present invention, the soluble copper salt is preferably one or more of copper nitrate, copper sulfate, copper acetate and copper chloride, more preferably copper nitrate or copper acetate, and still more preferably copper nitrate.
In the present invention, the corresponding water-soluble salts of the oxide support preferably include: when the oxide carrier is zinc oxide, the water-soluble salt corresponding to the zinc oxide preferably comprises one or more of zinc sulfate, zinc chloride, zinc nitrate and zinc acetate; when the oxide is aluminum oxide, the water-soluble salt corresponding to the aluminum oxide preferably comprises one or more of aluminum chloride, aluminum sulfate, aluminum nitrate and aluminum acetate; when the oxide carrier is zirconia, the metal salt corresponding to the zirconia preferably comprises one or more of zirconium chloride, zirconium nitrate, zirconium sulfate and zirconium acetate; when the oxide carrier is cerium oxide, the water-soluble salt corresponding to the cerium oxide preferably comprises one or more of cerium chloride, cerium nitrate, cerium sulfate and cerium acetate; when the oxide carrier is silicon dioxide, the water-soluble salt corresponding to the silicon dioxide preferably comprises one or more of silica sol, silicon tetrachloride, tetramethyl silicate and tetraethyl silicate.
In the present invention, the fullerene C60The particle size of (A) is preferably 0.7-20 nm; the fullerene C60The purity of (A) is preferably 95-99.99%, more preferably 98-99.99%, most preferably 99-99.99%; the fullerene C60Contains trace C70And other fullerenes. In the present invention, the fullerene C60Is a hollow spherical molecule consisting of 60 carbon atoms, is black or brown powder, and is mainly prepared and purified by a combustion method and an electric arc method.
In the present invention, the water is preferably deionized water.
In the present invention, the order of the first mixing preferably includes:
mixing water-soluble copper salt, water-soluble salt corresponding to the oxide carrier and water to obtain a salt solution;
reacting fullerene C60Ultrasonically stirring and mixing with water to obtain C60The dispersion solution of (4);
mixing the salt solution with C60The dispersion solution is ultrasonically stirred and mixed to obtain the first mixed solution.
In the invention, the concentration of the water-soluble copper salt in the salt solution is preferably 0.05-0.6 mol/L, and more preferably 0.1-0.3 mol/L; the concentration of the water-soluble salt corresponding to the oxide carrier is preferably 0.1 to 2mol/L, and more preferably 0.2 to 1 mol/L.
In the present invention, said C60The concentration of the dispersion solution (2) is preferably 10 to 15mg/mL, and more preferably 12 mg/mL.
In the present invention, the salt solution and C60The volume ratio of the dispersion solution of (4): 1.
in the invention, the power of ultrasound in the ultrasonic stirring is preferably 20-60W, and more preferably 40W; the rotation speed of stirring in the ultrasonic stirring is preferably 200-900 r/min, and more preferably 400-800 r/min. In the invention, the time of ultrasonic stirring is preferably 20-45 min, and more preferably 30 min. The invention has no special requirements on the equipment used for ultrasonic stirring, and the equipment well known by the technical personnel in the field can be used. The invention adopts an ultrasonic stirring mode, and can ensure the uniform dispersion and close contact of all components in the solution.
After the first mixed solution is obtained, the first mixed solution and the precipitant aqueous solution are mixed in a parallel flow mode and aged to obtain the coprecipitate.
In the present invention, the aqueous precipitant solution is preferably aqueous ammonia or an aqueous alkali solution; the mass concentration of the ammonia water is preferably 26-28%. In the present invention, the concentration of the aqueous alkali solution is preferably 0.1 to 3mol/L, and more preferably 0.2 to 1.5 mol/L. In the present invention, the alkali in the aqueous alkali solution is preferably urea, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide, more preferably sodium carbonate or potassium carbonate, and still more preferably sodium carbonate.
In the invention, the flow rate of the first mixed solution is preferably 3-12 mL/min, and more preferably 6-8 mL/min; the flow rate of the precipitant aqueous solution is preferably 3-12 mL/min, and more preferably 6-8 mL/min.
In the invention, the aging temperature is preferably 30-120 ℃, more preferably 50-90 ℃, and more preferably 60-70 ℃; the time is preferably 1 to 12 hours, more preferably 2 to 8 hours, and still more preferably 3 to 5 hours. In the invention, the aging is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 200-900 r/min, and more preferably 400-800 r/min.
After the aging, the invention preferably further comprises the steps of carrying out solid-liquid separation on the obtained aging system, and washing and drying the obtained solid in sequence.
In the present invention, the solid-liquid separation is preferably filtration, and the operation of the filtration is not particularly limited in the present invention, and a filtration means known to those skilled in the art may be used.
In the present invention, the temperature of the washing is preferably room temperature; the washing preferably comprises water washing and ethanol washing in this order. In the present invention, the number of washing times is preferably 2 to 3, and the amount of the reagent used for washing is not particularly limited as long as the solid can be washed cleanly. In the present invention, the number of the ethanol washing is preferably 1, and the amount of the ethanol washing reagent used is not particularly limited as long as the reagent can be washed cleanly.
In the invention, the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and more preferably 100 ℃; the time is preferably 6-24 h, more preferably 8-16 h, and even more preferably 10-14 h. In the present invention, the drying is preferably performed in an air atmosphere. The present invention has no special requirement on the equipment used for drying, and the equipment known to those skilled in the art can be used, and in the embodiment of the present invention, the equipment used for drying is specifically a drying oven.
After obtaining the coprecipitate, the invention calcines the coprecipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
In the invention, the calcining temperature is preferably 250-350 ℃, and more preferably 300 ℃; the time is preferably 1 to 12 hours, more preferably 2 to 8 hours, and still more preferably 3 to 6 hours. In the present invention, the atmosphere of the calcination is preferably air. The equipment used for carrying out the calcination in the present invention has no special requirements, and can be equipment well known to those skilled in the art, and in the embodiment of the present invention, the equipment used for the calcination is specifically a muffle furnace.
In the invention, the calcination can sufficiently remove water and organic matters in the coprecipitate, so that the metal salt precursor is decomposed to obtain metal oxide, and the interaction between the active metal and the fullerene and the oxide carrier is further enhanced.
The invention also provides another preparation method of the catalyst for hydrogen production by methanol steam reforming, which comprises the following steps:
dissolving soluble copper salt, oxide carrier, and fullerene C60Carrying out second mixing with water to obtain a second mixed solution;
adding a precipitant aqueous solution into the second mixed solution, and aging to obtain a precipitate;
and calcining the deposition precipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
The invention uses soluble copper salt, oxide carrier and fullerene C60And carrying out second mixing with water to obtain a second mixed solution.
In the present invention, the kind of the soluble copper salt is preferably consistent with the above technical scheme, and is not described herein again.
In the present invention, the oxide support includes one or more of zinc oxide, aluminum oxide, zirconium oxide, cerium oxide, and silicon dioxide, and more preferably one or two of zinc oxide, aluminum oxide, zirconium oxide, cerium oxide, and silicon dioxide. In the present invention, the particle diameter of the oxide carrier is preferably 5 to 200nm,further preferably 5 to 50 nm; the specific surface area is preferably 20-800 m2(ii) g, more preferably 100 to 800m2/g。
In the present invention, the fullerene C60The purity and the source of the compound are preferably consistent with the technical scheme, and are not described in detail herein.
In the present invention, the order of the second mixing preferably includes:
mixing water-soluble copper salt and water to obtain a water-soluble copper salt solution;
reacting fullerene C60Ultrasonic stirring and mixing with water to obtain C60Dispersing the solution;
ultrasonically stirring and mixing an oxide carrier and water to obtain a dispersion solution of the oxide carrier;
mixing the water-soluble copper salt solution and C60And ultrasonically stirring and mixing the dispersion solution and the dispersion solution of the oxide carrier to obtain a second mixed solution.
In the present invention, the concentration of the water-soluble copper salt solution is preferably 0.05 to 0.6mol/L, and more preferably 0.1 to 0.3 mol/L.
In the present invention, said C60The concentration of the dispersion solution is preferably in accordance with the above-mentioned technical solution and will not be described in detail herein.
In the present invention, the concentration of the dispersion solution of the oxide carrier is preferably 10 to 50 mg/mL.
In the present invention, the water-soluble copper salt solution, C60The volume ratio of the dispersion solution to the dispersion solution of the oxide support is preferably 2: 1: 2.
in the present invention, the operation of the ultrasonic stirring is consistent with the above technical scheme, and is not described herein again.
After the second mixed solution is obtained, the invention adds the precipitant aqueous solution into the second mixed solution, and carries out aging to obtain the sediment.
In the present invention, the kind and concentration of the precipitant aqueous solution are preferably consistent with the above technical scheme, and are not described herein again.
In the invention, the adding speed of the precipitant aqueous solution is preferably 3-12 mL/min, and more preferably 6-8 mL/min.
In the present invention, the aging operation is consistent with the above technical solution, and is not described herein again.
After the sediment is obtained, the sediment is calcined to obtain the catalyst for hydrogen production by methanol steam reforming.
In the present invention, the calcination operation is the same as the above technical scheme, and is not described herein again.
The invention also provides the application of the catalyst for hydrogen production by methanol steam reforming or the catalyst for hydrogen production by methanol steam reforming, which is obtained by the preparation method in the technical scheme, in catalyzing the reaction of hydrogen production by methanol steam reforming.
The invention also provides a methanol steam reforming hydrogen production reaction, which comprises the following steps:
reducing the catalyst for hydrogen production by methanol steam reforming according to the above technical scheme or the catalyst for hydrogen production by methanol steam reforming obtained by the preparation method according to the above technical scheme to obtain a reduced catalyst;
under the condition of a reduction catalyst, methanol and water carry out hydrogen production reaction to obtain hydrogen.
The catalyst for hydrogen production by methanol steam reforming, which is obtained by the preparation method of the technical scheme, or the catalyst for hydrogen production by methanol steam reforming, which is obtained by the preparation method of the technical scheme, is reduced to obtain a reduced catalyst.
In the invention, the particle size of the catalyst for hydrogen production by methanol steam reforming is preferably 20-40 meshes.
In the invention, the reduction temperature is 250-350 ℃, and preferably 300 ℃; the time is 1-12 h, preferably 2-8 h, and more preferably 3-6 h. In the present invention, the reducing atmosphere is hydrogen; the flow rate of the hydrogen is preferably 10 to 200mL/min, more preferably 30 to 100mL/min, and even more preferably 40 to 50 mL/min. In the present invention, the apparatus for reduction is preferably a tube furnace, and the present invention has no particular requirement on the equipment used for the tube furnace, and the equipment known to those skilled in the art can be used.
In the invention, the reduction can fully activate the catalyst, and the reduction of the copper oxide particles to univalent or zero valence enables the reduced catalyst to have higher catalytic reaction activity.
After the reduced catalyst is obtained, the invention performs hydrogen production reaction on methanol and water under the condition of the reduced catalyst to obtain hydrogen.
In the present invention, the conditions of the hydrogen production reaction preferably include: the temperature is 220-260 ℃, and the preferable temperature is 230-250 ℃; the pressure is 0.1 to 1.0MPa, more preferably 0.1 to 0.3MPa, and still more preferably 0.1 MPa; the molar ratio of water to methanol is 0.9-1.5: 1, more preferably 1.0 to 1.3: 1, more preferably 1.2: 1; the mass space velocity of the methanol is 3-6 h-1More preferably 4.5 hours-1。
In the present invention, the hydrogen production reaction is preferably performed in a fixed bed reactor, and when the hydrogen production reaction is preferably performed in a fixed bed reactor, the hydrogen production process is preferably: introducing a mixed solution of methanol and water into a catalytic reaction tube through a sample injection pump; the loading amount of the reduced catalyst is preferably 0.5 to 5g, and more preferably 1 to 3 g.
In the present invention, the reaction off-gas is analyzed by on-line chromatography, and the analysis conditions preferably include: the chromatographic column is TDX-01, the column temperature is 100 ℃, the carrier gas is argon, the flow rate is 30mL/min, and the current is 80 mA. And calculating the conversion rate of the methanol and the selectivity of various products according to the proportion of each component in the reaction tail gas.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
4.56g of copper nitrate trihydrate, 3.83g of zinc nitrate hexahydrate and 3.31g of zinc nitrateg of aluminum nitrate nonahydrate was dissolved in 100mL of deionized water to give a salt solution. 0.3g of fullerene C60Ultrasonically stirring in 25mL of deionized water to obtain C60And (4) dispersing the solution. And mixing the two solutions, and performing ultrasonic stirring to obtain a first mixed solution. The power of the ultrasonic is 40W, the rotating speed of the stirring is 600r/min, and the time of the ultrasonic stirring is 30 min. Preparing 125mL of 0.45mol/L sodium carbonate solution, adding the sodium carbonate solution (6mL/min) and the first mixed solution (6mL/min) into a reactor in a cocurrent manner, stirring and aging for 4h under the heating condition of 60 ℃, filtering an aging system at room temperature, washing a solid obtained by filtering, washing with deionized water for 2 times, then washing with absolute ethyl alcohol for 1 time, washing to neutrality, and drying for 12h under the condition of 100 ℃ to obtain a coprecipitate. Then calcining the coprecipitate in air for 4h at 300 ℃ to obtain the catalyst for hydrogen production by methanol steam reforming, which is marked as C60-CuO/ZnO/Al2O3Wherein the theoretical mass percentage content of the copper oxide is 45 percent; fullerene C60The theoretical mass percentage content of (1) is 9.1%, and the rest is oxide carrier.
Example 2
4.56g of copper nitrate trihydrate, 3.66g of zirconium nitrate pentahydrate and 3.31g of aluminum nitrate nonahydrate were dissolved in 100mL of deionized water to obtain a salt solution. 0.3g of fullerene C60Ultrasonically stirring in 25mL of deionized water to obtain C60And (4) dispersing the solution. And mixing the two solutions, and performing ultrasonic stirring to obtain a first mixed solution. The power of the ultrasonic is 40W, the rotating speed of the stirring is 600r/min, and the time of the ultrasonic stirring is 30 min. Preparing 125mL of 0.45mol/L sodium carbonate solution, adding the sodium carbonate solution (6mL/min) and the first mixed solution (6mL/min) into a reactor in a cocurrent manner, stirring and aging for 4h under the heating condition of 60 ℃, filtering an aging system at room temperature, washing a solid obtained by filtering, washing with deionized water for 2 times, then washing with absolute ethyl alcohol for 1 time, washing to neutrality, and drying for 12h under the condition of 100 ℃ to obtain a coprecipitate. Then calcining the coprecipitate in air for 4h at 300 ℃ to obtain the catalyst for hydrogen production by methanol steam reforming, which is marked as C60-CuO/ZrO2/Al2O3Wherein the theoretical mass percentage content of the copper oxide is 45 percent; fullerene C60The content of the oxide carrier is 9.1 percent of the theoretical mass percentage, and the balance is the oxide carrier.
Example 3
4.56g of copper nitrate trihydrate, 3.66g of zirconium nitrate pentahydrate, and 0.85g of cerium nitrate hexahydrate were dissolved in 100mL of deionized water to obtain a salt solution. 0.3g of fullerene C60Ultrasonically stirring in 25mL of deionized water to obtain C60And (4) dispersing the solution. And mixing the two solutions, and performing ultrasonic stirring to obtain a first mixed solution. The power of the ultrasonic is 40W, the rotating speed of the stirring is 600r/min, and the time of the ultrasonic stirring is 30 min. Preparing 125mL of 0.45mol/L sodium carbonate solution, adding the sodium carbonate solution (6mL/min) and the first mixed solution (6mL/min) into a reactor in a cocurrent manner, stirring and aging for 4h under the heating condition of 60 ℃, filtering an aging system at room temperature, washing a solid obtained by filtering, washing with deionized water for 2 times, then washing with absolute ethyl alcohol for 1 time, washing to neutrality, and drying for 12h under the condition of 100 ℃ to obtain a coprecipitate. Then calcining the coprecipitate in air for 4h at 300 ℃ to obtain the catalyst for hydrogen production by methanol steam reforming, which is marked as C60-CuO/ZrO2/CeO2Wherein the theoretical mass percentage content of the copper oxide is 45 percent; fullerene C60The theoretical mass percentage content of (1) is 9.1%, and the rest is oxide carrier.
Example 4
4.56g of copper nitrate trihydrate was dissolved in 50mL of deionized water to obtain a copper nitrate solution. 0.3g of fullerene C60Ultrasonically stirring in 25mL of deionized water to obtain C60The solution is dispersed. 1.5g of silica carrier was dispersed in 50mL of deionized water with ultrasonic stirring to obtain a silica carrier dispersion solution. And mixing the three solutions, and performing ultrasonic stirring to obtain a second mixed solution. The power of the ultrasonic is 40W, the rotating speed of the stirring is 600r/min, and the time of the ultrasonic stirring is 30 min. 125mL of 0.3mol/L sodium carbonate solution is prepared, the sodium carbonate solution is added into the second mixed solution at the dropping speed of 6mL/min, the mixture is stirred at the heating temperature of 60 ℃ at the speed of 600r/min and aged for 4h,filtering the aging system at room temperature, washing the solid obtained by filtering, washing with deionized water for 2 times, then washing with absolute ethyl alcohol for 1 time, drying at 100 ℃ for 12 hours after washing to neutrality, and depositing a precipitate; then calcining the mixture for 4 hours in air at the temperature of 300 ℃ to obtain the catalyst for hydrogen production by methanol steam reforming, which is marked as C60-CuO/SiO2Wherein the theoretical mass percentage content of the copper oxide is 45 percent; fullerene C60The theoretical mass percentage content of (1) is 9.1%, and the rest is oxide carrier.
Comparative example 1
4.56g of copper nitrate trihydrate, 4.6g of zinc nitrate hexahydrate and 3.97g of aluminum nitrate nonahydrate were dissolved in 100mL of deionized water to give a salt solution. Preparing 125mL of 0.45mol/L sodium carbonate solution, adding the sodium carbonate solution (6mL/min) and the salt solution (6mL/min) into a reactor in a parallel flow manner, stirring and aging for 4h under the heating condition of 60 ℃, filtering an aging system at room temperature, washing a solid obtained by filtering, washing 2 times with deionized water, washing 1 time with absolute ethyl alcohol, drying for 12h under the condition of 100 ℃ after washing to be neutral, and obtaining a coprecipitate; then, calcining the coprecipitate for 4 hours in air at 300 ℃ to obtain the catalyst for hydrogen production by methanol steam reforming, which is recorded as CuO/ZnO/Al2O3Wherein the theoretical mass percentage content of the copper oxide is 45 percent, and the rest is an oxide carrier.
Comparative example 2
4.56g of copper nitrate trihydrate was dissolved in 50mL of deionized water to obtain a copper nitrate solution. 1.5g of silica carrier was dispersed in 50mL of deionized water with ultrasonic stirring to obtain a silica carrier dispersion solution. And mixing the two solutions, and performing ultrasonic stirring to obtain a second mixed solution. The power of the ultrasonic is 40W, the rotating speed of the stirring is 600r/min, and the time of the ultrasonic stirring is 30 min. Preparing 125mL of 0.3mol/L sodium carbonate solution, adding the sodium carbonate solution into the second mixed solution at the dropping speed of 6mL/min, stirring at 600r/min under the heating condition of 60 ℃, aging for 4h, filtering the aging system at room temperature, washing the solid obtained by filtering, washing with deionized water for 2 times, then washing with absolute ethyl alcohol for 1 timeWashing to be neutral, and drying for 12h at 100 ℃ to obtain a deposition precipitate; then, calcining the deposit sediment in air at 300 ℃ for 4h to obtain the catalyst for hydrogen production by methanol steam reforming, which is recorded as CuO/SiO2Wherein the theoretical mass percentage content of the copper oxide is 45 percent, and the rest is an oxide carrier.
Application examples 1 to 6
Tabletting and forming the catalyst for hydrogen production by methanol steam reforming prepared in the examples 1-4 and the comparative examples 1-2, and then screening to obtain 20-40 mesh catalyst particles; and further carrying out reduction treatment on the catalyst particles in 50mL/min hydrogen gas flow for 4h at the temperature of 300 ℃ to obtain the reduced catalyst.
The reduced catalysts prepared in the examples 1 to 4 and the comparative examples 1 to 2 are respectively placed in a fixed bed continuous reactor filled with a methanol-water mixed raw material for reaction, the filling amount of the methanol-steam reforming hydrogen production catalyst is 1.5g, the temperature is 240 ℃, the pressure is 0.1MPa, and the molar ratio of water to methanol is 1.2: 1, the mass space velocity of the methanol is 4.5h-1。
The components of the reaction products obtained in the corresponding examples 1 to 6 were measured, and the obtained results are shown in table 1; wherein: including methanol (MeOH) conversion, product carbon dioxide (CO)2) Selective distribution of carbon monoxide (CO), and hydrogen production rate.
TABLE 1 catalytic performances of catalysts obtained in examples 1-4 and comparative examples 1-2 for hydrogen production by methanol steam reforming
Figure BDA0003077287870000131
Figure BDA0003077287870000141
As can be seen from table 1: the catalyst for hydrogen production by methanol reforming prepared by the invention adopts fullerene C60Promoting copper to be used for activating methanol and water vapor, efficiently producing hydrogen at lower temperature, inhibiting the generation of byproduct CO, and showing excellent performanceThe catalytic effect of (2). Wherein the fullerene C obtained in example 160Promoted Cu/ZnO/Al2O3The highest hydrogen production rate is obtained, compared with Cu/ZnO/Al without adding fullerene2O3The hydrogen production rate of the catalyst is improved by 40 percent. In examples 2 and 3, by adjusting the composition of the catalyst oxide support, the excellent effect of hydrogen production by methanol steam reforming at low temperature was also obtained. In addition, Cu/SiO in comparative example 22Although the hydrogen production rate of the series of catalysts is low, no by-product CO is generated. By introducing fullerene C60C in example 4 was found60-Cu/SiO2The hydrogen production rate is improved by nearly one time, and no CO is generated.
Tabletting and molding the catalyst for hydrogen production by methanol steam reforming prepared in the embodiment 1, and then screening to obtain 20-40 mesh catalyst particles; further reducing the catalyst particles in 50mL/min hydrogen gas flow for 4h at 300 ℃ to obtain a reduced catalyst; and (3) testing the service life of the catalyst on a fixed bed reaction system, wherein the pressure of the reforming hydrogen production reaction is controlled to be 0.1MPa, the temperature is controlled to be 240 ℃, and the molar ratio of the raw material water to the methanol is 1.2: 1, the mass space velocity of the methanol is 4.5h-1And sampling every 4h on line to analyze the reaction result, and the obtained result is shown in figure 1. As can be seen from fig. 1: the conversion rate of the raw material methanol, the selectivity of CO and the hydrogen production rate are maintained to be stable, and after continuous reaction for 200 hours, no inactivation phenomenon occurs, which indicates that the structure and the performance of the catalyst for hydrogen production by methanol steam reforming, which is prepared in example 1, are very stable.
The catalysts for hydrogen production by methanol steam reforming obtained in example 1 and comparative example 1 were tested by X-ray powder diffraction, and the results are shown in fig. 2. It can be seen that: fullerene C60The catalyst has good dispersion in the catalyst, and the catalyst structure is not greatly influenced after the catalyst is introduced.
The catalyst for hydrogen production by methanol steam reforming obtained in example 1 was characterized by a transmission electron microscope, and the results are shown in fig. 3. The left image in FIG. 3 is enlarged 105The transmission electron microscope photo after the doubling is obtained,the right drawing is enlarged 106And (4) transmission electron microscope photographs after doubling. As can be seen from fig. 3: the sizes of zinc oxide and alumina carriers are between 5 and 30nm, the size of copper oxide is between 2 and 15nm, and the fullerene C60The relative molecular weight is light and the dispersion is good, and no obvious agglomeration is found in a transmission electron microscope.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A catalyst for hydrogen production by methanol steam reforming is characterized by comprising an oxide carrier and an active component loaded on the oxide carrier; the active ingredients comprise copper oxide and fullerene C60(ii) a The oxide carrier comprises one or more of zinc oxide, aluminum oxide, zirconium oxide, cerium oxide and silicon dioxide;
the preparation method of the catalyst for hydrogen production by methanol steam reforming comprises the following steps:
dissolving soluble copper salt, water-soluble salt corresponding to oxide carrier, and fullerene C60Carrying out first mixing with water to obtain a first mixed solution;
the first mixed solution and the precipitant aqueous solution are mixed in a parallel flow mode and aged to obtain a coprecipitate;
calcining the coprecipitate to obtain the catalyst for hydrogen production by methanol steam reforming;
in the catalyst for hydrogen production by methanol steam reforming, the mass percentage of the copper oxide is 10-60%.
2. The catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein the catalyst for hydrogen production by methanol steam reforming contains 1 to 30% by mass of fullerene C60, and the balance is an oxide carrier.
3. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 1 or 2, comprising the steps of:
carrying out first mixing on a soluble copper salt, a water-soluble salt corresponding to an oxide carrier, fullerene C60 and water to obtain a first mixed solution;
the first mixed solution and the precipitant aqueous solution are mixed in a parallel flow mode and aged to obtain a coprecipitate;
and calcining the coprecipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
4. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 1 or 2, comprising the steps of:
carrying out second mixing on soluble copper salt, an oxide carrier, fullerene C60 and water to obtain a second mixed solution;
adding a precipitant aqueous solution into the second mixed solution, and aging to obtain a precipitate;
and calcining the deposition precipitate to obtain the catalyst for hydrogen production by methanol steam reforming.
5. The production method according to claim 3 or 4, wherein the aqueous precipitant solution is an aqueous ammonia solution or an aqueous alkali solution; the mass concentration of the ammonia water is 26-28%; the alkaline matter in the alkaline water solution is urea, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
6. The preparation method according to claim 3 or 4, wherein the aging temperature is 30-120 ℃ and the aging time is 6-24 h; the aging is carried out under the condition of stirring, and the rotating speed of the stirring is 200-900 r/min.
7. The preparation method according to claim 3 or 4, wherein the calcining temperature is 250-350 ℃ and the calcining time is 1-12 h; the atmosphere of the calcination is air.
8. Use of the catalyst for hydrogen production by methanol steam reforming according to claim 1 or 2 or the catalyst for hydrogen production by methanol steam reforming obtained by the production method according to any one of claims 3 to 7 in catalyzing a reaction for hydrogen production by methanol steam reforming.
9. A methanol steam reforming hydrogen production reaction comprises the following steps:
reducing the catalyst for hydrogen production by methanol steam reforming according to claim 1 or 2 or the catalyst for hydrogen production by methanol steam reforming obtained by the production method according to any one of claims 3 to 7 to obtain a reduced catalyst;
under the condition of a reduction catalyst, methanol and water carry out hydrogen production reaction to obtain hydrogen;
the reducing atmosphere is hydrogen, the temperature is 250-350 ℃, and the time is 1-12 h.
10. The methanol steam reforming hydrogen production reaction of claim 9, wherein the hydrogen production reaction conditions include: the temperature is 220-260 ℃, the pressure is 0.1-1.0 MPa, the molar ratio of water to methanol is 0.9-1.5: 1, and the mass space velocity of methanol is 3-6 h-1。
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