CN116060035A - Solid reverse phase catalyst, preparation method thereof and application of solid reverse phase catalyst in catalyzing methanation of low-temperature carbon dioxide - Google Patents

Solid reverse phase catalyst, preparation method thereof and application of solid reverse phase catalyst in catalyzing methanation of low-temperature carbon dioxide Download PDF

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CN116060035A
CN116060035A CN202310129152.0A CN202310129152A CN116060035A CN 116060035 A CN116060035 A CN 116060035A CN 202310129152 A CN202310129152 A CN 202310129152A CN 116060035 A CN116060035 A CN 116060035A
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reverse phase
oxide
solid
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林丽利
唐鑫
武艺超
宋楚乔
卢晗锋
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Zhejiang University of Technology ZJUT
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    • B01J23/74—Iron group metals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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Abstract

The invention discloses a solid reverse phase catalyst, a preparation method thereof and application of catalyzing methanation of low-temperature carbon dioxide, wherein the catalyst takes a single metal or alloy component with hydrogen dissociation capability as a carrier phase, and metal oxide nano particles for generating adsorption activated carbon dioxide as a carrier phase, and the prepared catalyst interface is that the oxide nano particles are loaded on the surface of the metal, which is different from the traditional metal loaded on the surface of the oxide carrier, and is a new typeA solid reverse phase catalyst; under certain reaction conditions, the reverse phase catalyst prepared by the invention is applied to the methanation reaction of carbon dioxide, and the reverse phase catalyst is prepared under the low temperature condition of 200 ℃ and high reaction space velocity (127,000 h) ‑1 ) Has excellent performance over most reported catalysts, wherein the methane selectivity can reach more than 99 percent and the methane generation rate can reach 50g CH4 /g cat And exhibits excellent stability over a long period of 1500 hours.

Description

Solid reverse phase catalyst, preparation method thereof and application of solid reverse phase catalyst in catalyzing methanation of low-temperature carbon dioxide
Technical Field
The invention relates to a solid reverse phase catalyst, a preparation method thereof and application thereof in a heterogeneous catalytic carbon dioxide hydromethanation reaction.
Background
Human over-exploitation and use of fossil energy sources results in large amounts of CO 2 Emissions, which cause a series of serious environmental problems such as climate abnormality, sea level elevation, glacier retraction, frozen soil thawing, reduced animal and plant diversity, and the like. CO in plant exhaust gas 2 Capturing and converting it to methane, methanol or other high value chemicals is a two-way strategy to address environmental pollution and energy shortages. Wherein CO is 2 Methanation is used in energy conversion and H 2 Can be used for storage and has wide prospect.
Figure BDA0004083162240000011
ΔH 298 K ＝-165.1 kJ mol -1 (1)
Figure BDA0004083162240000012
ΔH 298 K ＝41.2 kJ mol -1 (2)
CO 2 The thermodynamic enthalpy of the methanation reaction (equation 1) becomes-165.1 kJ mol -1 Is a strongly exothermic reaction, so that the low temperature thermodynamic properties of the reaction process are advantageous. But CO 2 Reduction to CH 4 Involving the transfer of eight electrons, there is a very high kinetic barrier during hydrogenation, usually requiring @ higher operating temperatures>300 ℃ to obtain satisfactory CH 4 Space-time yield. However, too high a reaction temperature not only inhibits CO 2 Methanation is facilitated, and side reaction and inverse water vapor change reaction (equation 2) are facilitated, and generated by-product CO can lead CH to 4 Additional separation and purification steps are needed in the subsequent energy utilization, and CH is improved 4 Utilization as fuelCost, CO weakening 2 Application advantages of methanation. Therefore, the cost is low, the temperature is high and the CO is high 2 The design and development of methanation catalyst can effectively promote CO 2 The practical application of methanation improves the competitiveness.
Traditional low temperature CO 2 The design of the hydrogenation methane catalyst mainly expands around the metal/oxide supported catalyst formed by the metal nano-particles and the oxide substrate. On the interface of the traditional metal/oxide catalyst, partial oxygen-containing intermediate adsorbed on oxide sites generally has extremely high thermodynamic stability, has high hydroconversion energy barrier and is easy to occupy active centers, so that the low-temperature activity of the catalyst is greatly reduced. The reversed phase oxide/metal catalyst formed by the oxide clusters supported by the metal carrier has an interface space structure different from the traditional metal/oxide, and has the potential of improving the conversion rate of the oxygen-containing intermediate, even changing the reaction path and improving the performance of the catalyst. Furthermore, in practical applications, the cost of some metals (e.g., iron, cobalt, nickel, copper, etc.) is substantially even lower than that of oxides. The design of the reversed phase oxide/metal structure can be a high efficiency CO 2 The creation of hydrogenation catalysts provides new opportunities.
The invention provides a solid reverse phase catalyst with oxide nano particles supported on a metal carrier and a preparation method thereof, wherein the reverse phase catalyst has a low temperature of 200 ℃ and below and a high reaction space velocity (127,000 h) -1 ) CO with more than most of the reported catalysts 2 Methanation activity, methane selectivity is more than 99%, and methane generation rate can reach 50g CH4 /g cat And the reverse phase catalyst was confirmed to have excellent stability in a long-term operation of 1500 hours.
Disclosure of Invention
The invention aims to provide a solid reverse phase catalyst and a preparation method thereof, and the catalyst can realize high-conversion, high-selectivity and high-stability CO under the low-temperature condition 2 Methanation process.
The technical scheme of the invention is as follows:
the solid reverse phase catalyst takes metal dissociated with hydrogen as a carrier, nano oxide which generates oxygen vacancies to adsorb activated carbon dioxide as a load phase, the nano oxide is uniformly dispersed on the surface of the metal carrier, and the catalyst has a nano oxide/metal reverse phase interface structure;
wherein, the liquid crystal display device comprises a liquid crystal display device,
the carrier metal is selected from one or more of cobalt, nickel, aluminum, copper and ruthenium;
the supported phase nano oxide is selected from one or more of titanium oxide, aluminum oxide, manganese oxide, cerium oxide, zirconium oxide, silicon oxide and tungsten oxide;
the mole fraction of metal in the support phase is in the range of 0.01 to 30% based on the total molar amount of metal in the support and support phase.
The preparation method of the solid reverse phase catalyst provided by the invention comprises the following steps: preparing a carrier precursor under the conditions of a proper precipitator and a solvent by a hydrothermal method and a coprecipitation method; preparing nano oxide dispersion liquid under the conditions of a proper precipitator, a solvent and a protective agent by a sol method; the nano oxide is deposited and precipitated or impregnated on the carrier precursor in situ by means of in-situ precipitation, over-volume impregnation and the like, and the obtained powdery solid is subjected to roasting and reduction steps, so that the nano oxide accounting for less nano oxide is uniformly dispersed on the surface of the metal carrier, and the solid reverse phase catalyst is obtained.
Preferably, the preparation method of the solid reverse phase catalyst comprises the following steps:
(1) Synthesis of nano-oxides
Dissolving precursor salt of a load phase in a solvent, and adding the obtained solution (with the concentration of 0.01-5 mol/L) into a precipitant solution (with the concentration of 0.01-5 mol/L) to obtain hydroxide sol; adding the obtained hydroxide sol into ethanol to obtain hydroxide-ethanol sol; dispersing hydroxide-ethanol sol into a mixed solution of oleic acid/oleylamine/ethanol, stirring uniformly, transferring into an autoclave, sealing, performing solvothermal treatment at 80-220 ℃ for 1-24h, collecting a solid product, washing with deionized water until the pH of a washing solution is neutral, and freeze-drying to obtain nano oxide, and dispersing in ethanol to obtain nano oxide dispersion for later use;
in step (1), the precursor salt of the support phase is selected from titanium tetrachloride, tetrabutyl titanate; aluminum nitrate, aluminum nitrate hydrate, and aluminum chloride; manganese nitrate, manganese nitrate hydrate and manganese chloride; cerium nitrate, hydrated cerium nitrate, and cerium chloride; zirconium nitrate, zirconium nitrate hydrate, zirconium chloride; ethyl orthosilicate; one or more of ammonium metatungstate, sodium tungstate and tungsten chloride;
the solvent is selected from one or more of water, methanol, ethanol, butanol, tetrahydrofuran and methyl tertiary butyl ether;
the precipitant is one or more of ammonium carbonate, ammonia water, urea, sodium hydroxide, sodium bicarbonate, ammonium oxalate and oxalic acid;
(2) Synthesis of solid reverse phase catalyst (in situ precipitation method)
Dissolving a precursor salt of a carrier in a solvent, dropwise adding the nano oxide dispersion liquid prepared in the step (1) into the obtained solution (with the concentration of 0.01-5 mol/L), then dropwise adding a precipitant solution (with the concentration of 0.01-5 mol/L) under stirring, controlling the pH to be=9, aging at room temperature, filtering, washing, drying, calcining in static air, and reducing in a hydrogen atmosphere after the calcining is finished to prepare a solid reverse phase catalyst;
in the step (2), the precursor salt of the carrier is selected from one or more of cobalt nitrate, cobalt nitrate hydrate, cobalt chloride, nickel nitrate hydrate, nickel chloride, copper nitrate hydrate, copper chloride and ruthenium chloride;
the solvent is selected from one or more of water, methanol, ethanol, butanol, tetrahydrofuran and methyl tertiary butyl ether;
the precipitant is one or more of ammonium carbonate, ammonia water, urea, sodium hydroxide, sodium bicarbonate, ammonium oxalate and oxalic acid;
preferably, the aging time is 1 to 24 hours;
preferably, the drying temperature is 40-200 ℃ and the drying time is 1-24 hours;
preferably, the calcination temperature is 200-600 ℃ and the calcination time is 1-12 h;
preferably, the temperature of the reduction is 200-700 ℃ and the time is 1-6 h; preferably, the concentration range of hydrogen in the reducing atmosphere is 5-100%, and the total flow range is 5-100 ml/min;
the granularity of the prepared solid reverse phase catalyst is 10-200 meshes.
The solid reverse phase catalyst disclosed by the invention can be applied to carbon dioxide methanation reaction. The specific application method comprises the following steps:
placing a solid reverse phase catalyst in a fixed bed reactor, and introducing carbon dioxide and hydrogen in a molar ratio of 1:4, the volume space velocity of the reaction gas is 9000-127000 h -1 The reaction pressure ranges from normal pressure to 6Mpa, and the reaction temperature ranges from 25 ℃ to 450 ℃;
the experimental result of the stability of the catalyst is that the catalyst runs stably for 1500 hours, the conversion rate of carbon dioxide is maintained at about 90%, the methane selectivity is more than 99%, the reaction temperature is preferably 200 ℃, and the pressure is normal pressure.
The invention has the advantages that:
the prepared oxide/metal reverse phase catalyst can catalyze the methanation reaction of carbon dioxide with high conversion rate, high selectivity and high stability at the low temperature of not more than 200 ℃ and normal pressure, the conversion rate of carbon dioxide is more than 80% at the high space velocity, and the methane selectivity is more than 99%. The activity of the same phase conventional metal/oxide catalyst is achieved under the condition of 250 ℃ or higher temperature and pressure. In addition, the solid reverse phase catalyst prepared by the method has good stability in a reaction system of carbon dioxide hydrogenation, and can be used for a long time or recycled for multiple times.
Drawings
FIG. 1 shows CO 2 Thermodynamic diagram of methanation reaction and side reaction reverse steam change reaction along with temperature change.
FIG. 2 is a graph showing the reaction results of a catalyst at different temperatures in one embodiment.
FIG. 3 is a graph showing the reaction results for catalysts at different volumetric space velocities in one embodiment.
FIG. 4 is a graph of CO in one embodiment over a catalyst 1500h 2 Conversion of (C) to CH 4 And (5) selectively testing the result.
FIG. 5 is a graph showing the results of an investigation of the effect of different precipitants on methanation activity of a shift catalyst in one embodiment.
FIG. 6 is a comparison of methanation activity of different metal support supported metal oxide cluster catalysts in one embodiment.
FIG. 7 is a comparison of methanation activity of a binary two-way catalyst with a conventional forward catalyst in one embodiment.
FIG. 8 is a HAADF-STEM photograph of the catalyst prepared in example 1.
Detailed Description
For the purposes of making the objects, technical solutions, and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other technical solutions obtained by a person skilled in the art based on the examples in the present application fall within the scope of protection of the present application.
The traditional methanation catalyst is generally prepared by adopting a dipping method, a liquid phase reduction method and the like, and after the catalyst prepared by adopting the method is subjected to a roasting and reduction step, less metal components are dispersed on an oxide carrier in a nano particle form so as to form a metal/oxide interface structure. Conventional carbon dioxide methanation catalysts typically use oxides of cerium oxide, zirconium oxide, aluminum oxide, silicon oxide, titanium oxide, and the like as the bulk phase to provide oxygen vacancy dissociated carbon dioxide in an amount of about 50% to 99.9% by mole of the catalyst. The metal iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, platinum and the like are used as catalyst loading phases for dissociating hydrogen, and the catalyst loading phases account for about 0.01 to 30 percent of the mole fraction of the catalyst. The traditional forward catalyst usually needs a temperature of more than 250 ℃ to catalyze methanation reaction, the active center of the loaded nano particles is easy to agglomerate and deactivate in a strongly exothermic reaction system, and in addition, the catalyst is easy to accumulate and deactivate due to high unsaturated coordination of the nano particles.
The invention takes one or more of metals dissociated from hydrogen as a bulk phase, takes oxide generating oxygen vacancy to adsorb and activate carbon dioxide as a load phase, and the obtained reverse phase catalyst can realize the methanation of carbon dioxide with high activity and high selectivity under high airspeed at the temperature of below 200 DEG CThe catalyst has 450-DEG C high-temperature cycle stability, the surface coordination unsaturation degree of the metal center existing in the form of bulk phase is reduced, and the generation of carbon deposit is inhibited. In a specific embodiment, the volume space velocity is 9000 to 127000h -1 Conversion rate of carbon dioxide is more than 80%, methane selectivity>99%, stability exceeding 1500h. The specific synthesis method is as follows:
1. synthesis of nano-oxides
Dissolving one or more corresponding precursor salts or hydrates of metals generating oxygen vacancies to adsorb and activate carbon dioxide in a solvent in a certain concentration (between 0.01mol/L and 5 mol/L), stirring until the precursor salts or hydrates are completely dissolved, adding the solution into a precipitator solution to obtain hydroxide sol, and adding the obtained sol into ethanol to obtain hydroxide-ethanol sol. Dispersing a quantity of hydroxide sol in oleic acid: oleylamine: the ethanol mixed solution was neutralized and stirred uniformly, and transferred to a 100ml polytetrafluoroethylene-lined autoclave. Subsequently, the autoclave was sealed and solvothermal treated at a temperature (80 ℃ -220 ℃) for a period of time (1-24 h), the precursor obtained was washed several times with deionized water until the washing solution had a neutral pH, lyophilized overnight to give the nano-oxide, which was then dissolved in ethanol to give a transparent dispersion of nano-oxide.
The above method is applicable to the synthesis of the following nano-oxides or mixed oxides (titanium oxide, aluminum oxide, manganese oxide, cerium oxide, zirconium oxide, silicon oxide, tungsten oxide, etc.).
2. Preparation of support oxides
2.1 hydrothermal Process
One or more corresponding precursor salts or hydrates of metals (cobalt, nickel, aluminum, copper, ruthenium) dissociated with hydrogen are dissolved in a solvent in a certain concentration (between 0.01mol/L and 5 mol/L), stirred until completely dissolved, and transferred to a 100ml polytetrafluoroethylene lining autoclave. A certain amount of precipitant was dissolved in 50ml of solvent and added to the above suspension to form a stock solution. The autoclave is sealed and hydrothermally treated for a period of time (1-24 h) at a certain temperature (80-220 ℃), the obtained precursor is washed with deionized water for several times until the pH of the washing solution is neutral, and the washing solution is freeze-dried overnight, so that the metal carrier oxide is obtained.
2.2 Co-precipitation method
One or more corresponding precursor salts or hydrates of metals (cobalt, nickel, aluminum, copper and ruthenium) dissociated with hydrogen are dissolved in a solvent in a certain concentration (between 0.01mol/L and 5 mol/L), and the solution is stirred by ultrasonic until the precursor salts or hydrates are completely dissolved. And (3) dropwise adding a proper amount of precipitant solution into the precursor salt solution under vigorous stirring, continuously stirring for 4 hours after the dropwise adding, centrifugally washing with absolute ethyl alcohol for three times, drying in a drying oven, grinding and calcining in a muffle furnace to obtain the metal carrier oxide.
3. Synthesis of reverse phase catalyst
3.1 in situ deposition of precipitated metal precursors in nanoparticle solutions
One or more corresponding precursor salts or hydrates of metals (cobalt, nickel, aluminum, copper and ruthenium) dissociated with hydrogen are dissolved in a solvent in a certain concentration (between 0.01mol/L and 5 mol/L), and the solution is stirred by ultrasonic until the precursor salts or hydrates are completely dissolved. Then a certain amount of nano oxide suspension prepared in the step 1 is dripped into the solution according to a certain molar ratio. The precipitant solution of a certain concentration was added dropwise to the suspension under vigorous stirring, and the pH was controlled at about 9. The resulting precipitate was further aged at room temperature for 1 hour and then filtered, and then washed with deionized water at room temperature. The resulting material was dried in air overnight and then calcined in static air. And (3) reducing in a hydrogen atmosphere after the calcination is finished, and loading the nano oxide obtained by the reduction on a metal solid to obtain the prepared reverse phase catalyst.
3.2 impregnation by volume
The metal support oxide powder prepared in step 2 (or the metal support after reduction passivation in step 2) was dispersed in 100mL of absolute ethanol. Then a certain amount of nano oxide suspension prepared in the step 1 is dripped into the solution according to a certain molar ratio. Then stirred for 0.5h and sonicated for a further 1h to achieve good dispersion of the slurry. The slurry was then condensed at 70 ℃ under reflux for 2h. And then spin-drying the solution, freeze-drying the obtained precipitate overnight, and reducing the precipitate in a hydrogen (residual nitrogen) atmosphere after freeze-drying is finished, wherein the nano oxide obtained by reduction is loaded on a metal solid to obtain the prepared catalyst.
3.3 monolithic catalyst
One of the nickel foam, copper foam or cobalt foam in the form of a sheet having a length of 3cm, a width of 2cm and a thickness of 2mm was sonicated with diluted hydrochloric acid (2 mol/L), ethanol and deionized water, respectively, for 30min. The treated sheet-shaped carrier is immersed into hydroxide ethanol sol in the step 1, stirred uniformly and then transferred into a polytetrafluoroethylene lining autoclave with 100 mL. Subsequently, the autoclave was sealed and heat treated at a temperature (80-200 ℃) for a period of time (1-12 hours), the resulting sheet metal foam was washed several times with deionized water, the resulting material was dried in air overnight, and then calcined in static air. And (3) reducing in a hydrogen atmosphere after the calcination is finished, wherein the sheet material of the nano oxide loaded on the metal foam carrier obtained by the reduction is the prepared reverse phase catalyst.
In the invention, the load refers to the percentage content of substances carrying phase metals on the carrier to the total substances of the catalyst, and the calculation formula of the load is as follows: load = amount of supported phase metal species/amount of catalyst total species x 100%.
In the invention, the granularity of the solid catalytic carrier is 10-200 meshes (20 meshes, 30 meshes, 60 meshes, 80 meshes, 100 meshes and 150 meshes); and (3) placing the mixture in a gas-solid phase to carry out carbon dioxide methanation reaction.
The molar ratio of carbon dioxide to hydrogen is 1:4, the volume space velocity of the reaction gas is 9000 to 127000h -1 The reaction pressure ranges from normal pressure to 6Mpa, and the reaction temperature ranges from 25 ℃ to 450 ℃.
In a specific embodiment, the catalyst stability test results show that the catalyst is stable in 1500h operation, the carbon dioxide conversion is maintained at about 90%, the methane selectivity is >99%, the reaction temperature is 200 ℃, and the pressure is normal pressure.
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples.
Example 1
Dissolving zirconium chloride and manganese chloride in 50mL of water at a concentration of 0.075mol/L, stirring until the zirconium chloride and the manganese chloride are completely dissolved, adding the zirconium chloride and the manganese chloride into 50mL of 2.5% ammonia water solution, stirring for 2h to obtain zirconium hydroxide and manganese hydroxide sol, and finally adding the zirconium hydroxide and manganese hydroxide sol into 20mL of absolute ethyl alcohol to obtain zirconium ethoxide and manganese ethoxide sol. 5g of zirconium ethoxide, manganese ethoxide sol were added to oleic acid: oleylamine: ethanol was 40mL:5mL:5mL of the mixed solution was neutralized and stirred well, and then transferred to a 100mL polytetrafluoroethylene-lined autoclave. Subsequently, the autoclave was sealed and heated at 200 ℃ for 12 hours, the obtained precipitate was washed several times with deionized water until the pH of the washing solution was neutral, lyophilized overnight to obtain nano-zirconium manganese oxide, and then dispersed in ethanol to obtain a nano-zirconium manganese oxide transparent dispersion.
0.01mol of Ni (NO) 3 )·6H 2 O was dissolved in 100mL of absolute ethanol. Then a certain amount of the prepared nano zirconium manganese oxide mixed oxide suspension is dripped into a nickel nitrate solution according to the mol ratio of Ni to Mn to Zr=40 to 3. An appropriate amount of 0.50mol L was added with vigorous stirring (500 r) -1 Na 2 CO 3 The solution (0.5 mol/L,50 ml) was injected with the precursor salt solution by a syringe pump (1 ml/min) and the pH of the solution was controlled at about 9. The resulting precipitate was further aged at room temperature for 1 hour and then filtered, and then washed with deionized water at room temperature. The resulting material was dried overnight in air at 75 ℃ and then calcined in static air at 400 ℃ for 3 hours. Reducing for 3h at 450 ℃ in hydrogen atmosphere after the calcination is finished, wherein the solid powder obtained by the reduction is the prepared reverse phase catalyst which is marked as ZrMnO 4 /Ni。
Granulating the granularity of the solid catalyst to 60-80 meshes, and placing the solid catalyst in a gas-solid phase reactor for carbon dioxide methanation reaction. The molar ratio of carbon dioxide to hydrogen is 1:4, the airspeed of the reaction gas is 21000 to 127000h -1 The reaction pressure is normal pressure, and the reaction temperature is 130-320 ℃.
Example 2
Dissolving zirconium chloride and titanium tetrachloride in 50mL of water at a concentration of 0.075mol/L, stirring until the zirconium chloride and titanium tetrachloride are completely dissolved, adding the zirconium chloride and titanium tetrachloride solution into 50mL of 2.5% ammonia water solution, stirring for 2h to obtain zirconium hydroxide and titanium hydroxide sol, and finally adding the zirconium hydroxide and titanium hydroxide sol into 20mL of absolute ethyl alcohol to obtain zirconium ethoxide and titanium ethoxide sol. 5g of zirconium ethoxide, titanium ethoxide sol was added to oleic acid: oleylamine: ethanol was 40mL:5mL:5mL of the mixed solution was neutralized and stirred well, and then transferred to a 100mL polytetrafluoroethylene-lined autoclave. Subsequently, the autoclave was sealed and heated at 200 ℃ for 12 hours, the obtained precipitate was washed with deionized water several times until the pH of the washing solution was neutral, lyophilized overnight to obtain nano zirconium titanium oxide, and then dispersed in ethanol to obtain a nano zirconium titanium oxide solid solution transparent dispersion.
0.01mol of Ni (NO) 3 )6H 2 O was dissolved in 100mL of absolute ethanol. Then a certain amount of the prepared nano zirconium titanium oxide mixed oxide suspension is dripped into a nickel nitrate solution according to the mol ratio of Ni to Ti to Zr=40 to 3. An appropriate amount of 0.50mol L was added with vigorous stirring (500 r) -1 Na 2 CO 3 The solution (0.5 mol/L50 ml) was injected with the precursor salt solution by a syringe pump (1 ml/min) and the pH of the solution was controlled at about 9. The resulting precipitate was further aged at room temperature for 1 hour and then filtered, and then washed with deionized water at room temperature. The resulting material was dried overnight in air at 75 ℃ and then calcined in static air at 400 ℃ for 3 hours. Reducing for 3h at 450 ℃ in hydrogen atmosphere after the calcination is finished, wherein the solid powder obtained by the reduction is the prepared reverse phase catalyst which is marked as ZrTiO 4 /Ni。
Granulating the granularity of the solid catalyst to 60-80 meshes, and placing the solid catalyst in a gas-solid phase to carry out carbon dioxide methanation reaction. The molar ratio of carbon dioxide to hydrogen is 1:4, the space velocity of the reaction gas is 21000h -1 The reaction pressure is normal pressure, and the reaction temperature is 130-320 ℃.
Example 3
The procedure of example 2 was followed except that the precursor salt was nickel nitrate hexahydrate, titanium tetrachloride and cerium chloride.
Example 4
The procedure of example 1 was followed except that the precursor salt was nickel nitrate hexahydrate, aluminum chloride and zirconium chloride.
Example 5
The procedure of example 1 was followed except that the support precursor salt was nickel nitrate hexahydrate and aluminum nitrate nonahydrate, and the supported oxide precursor salt was zirconium chloride and manganese chloride, wherein the molar ratio of Ni/Al/Zr/Mn was 30/10/3/3.
Example 6
The procedure of example 1 was followed except that the carrier precursor salt was cobalt nitrate hexahydrate.
Example 7
The procedure of example 1 was followed except that the support precursor salt was nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the supported oxide precursor salt was zirconium chloride and manganese chloride, wherein the molar ratio of Ni/Co/Zr/Mn was 30/10/3/3.
Example 8
Dissolving zirconium chloride and manganese chloride in 50mL of water at a concentration of 0.075mol/L, stirring until the zirconium chloride and the manganese chloride are completely dissolved, adding the zirconium chloride and the manganese chloride into 50mL of 2.5% ammonia water solution, stirring for 2h to obtain zirconium hydroxide and manganese hydroxide sol, and finally adding the zirconium hydroxide and manganese hydroxide sol into 20mL of absolute ethyl alcohol to obtain zirconium ethoxide and manganese ethoxide sol. 5g of zirconium ethoxide, manganese ethoxide sol were added to oleic acid: oleylamine: ethanol was 40mL:5mL:5mL of the mixed solution was neutralized and stirred well, and then transferred to a 100mL polytetrafluoroethylene-lined autoclave. Subsequently, the autoclave was sealed and heated at 200 ℃ for 12 hours, the obtained precipitate was washed with deionized water several times until the pH of the washing solution was neutral, lyophilized overnight to obtain nano-zirconia manganese, and then dispersed in ethanol to obtain a nano-zirconia manganese mixed oxide transparent dispersion.
0.01mol of Ni (NO) 3 )·6H 2 O was dissolved in 100mL of absolute ethanol. Then the prepared nano zirconium manganese oxide mixed oxide suspension is added into nickel nitrate solution according to the mole ratio of Ni to Mn to Zr=40 to 3. An appropriate amount of 0.50mol.L was stirred vigorously (500 r) -1 Na 2 CO 3 The solution (0.5 mol/L50 ml) was injected with the precursor salt solution by a syringe pump (1 ml/min) and the pH of the solution was controlled at about 9. The resulting precipitate was further aged at room temperature for 1 hour and then filtered, and then washed with deionized water at room temperature. The resulting precipitate was dried overnight in air at 75 ℃.
Diluting 0.32mL of ruthenium trichloride solution (13.89 mg/mL) to 15mL with deionized water, then vigorously stirring, adding 1.0g of the above-mentioned oven-driedAnd (5) post-precipitation. The suspension was then evaporated to dryness in a 60 ℃ water bath and then dried at 110 ℃. The resulting solid was expressed as ZrMnO x Ni-Ru, calcined in air at 400℃for 3h. Reducing for 3h at 450 ℃ in hydrogen atmosphere after the calcination is finished, wherein the solid powder obtained by the reduction is the prepared reverse phase catalyst which is marked as ZrMnO 4 /Ni-Ru。
Example 9
The procedure of example 1 was followed except that the support precursor salt was nickel nitrate hexahydrate and the supported metal oxide precursor salt was zirconium chloride, wherein the Ni/Zr molar ratio was 40/6.
Example 10
The procedure of example 1 was followed except that the support precursor salt was nickel nitrate hexahydrate and the supported metal oxide precursor salt was manganese nitrate hexahydrate, wherein the Ni/Mn molar ratio was 40/6.
Example 11
The procedure of example 2 was followed except that the support precursor salt was nickel nitrate hexahydrate and the supported oxide precursor salt was titanium tetrachloride, with a Ni/Ti molar ratio of 40/6.
Example 12
The procedure of example 1 was followed except that the support precursor salt was nickel nitrate hexahydrate and the supported metal oxide precursor salt was aluminum chloride, with a Ni/Al molar ratio of 40/6.
Example 13
Dissolving zirconium chloride and manganese chloride in 50mL of water at a concentration of 0.075mol/L, stirring until the zirconium chloride and the manganese chloride are completely dissolved, adding the zirconium chloride and the manganese chloride into 50mL of 2.5% ammonia water solution, stirring for 2h to obtain zirconium hydroxide and manganese hydroxide sol, and finally adding the zirconium hydroxide and manganese hydroxide sol into 20mL of absolute ethyl alcohol to obtain zirconium ethoxide and manganese ethoxide sol. 5g of zirconium ethoxide, manganese ethoxide sol were added to oleic acid: oleylamine: ethanol was 40mL:5mL:5mL of the mixed solution is neutralized and stirred uniformly.
A sheet-like foam nickel (0.47 g) having a length of 3cm, a width of 2cm and a thickness of 2mm was sonicated with diluted hydrochloric acid (2 mol/L), ethanol and deionized water, respectively, for 30min. The foam nickel after treatment is immersed into the sol of zirconium ethoxide (0.0006 mol) and manganese ethoxide (0.0006 mol) (Zr: M)n=1:1) in a 100mL polytetrafluoroethylene lined autoclave. Subsequently, the autoclave was sealed and heated at 200 ℃ for 12 hours, the resulting nickel foam was washed several times with deionized water, the resulting material was dried overnight in air at 75 ℃, and then calcined in static air at 400 ℃ for 3 hours. Reducing for 3h at 450 ℃ in hydrogen atmosphere after the calcination is finished, wherein the sheet material obtained by the reduction is the prepared reverse phase catalyst which is marked as ZrMnO 4 /NF。
The granularity of the solid catalyst is 60-80 meshes, and the solid catalyst is placed in a gas-solid phase reactor for carbon dioxide methanation reaction. The molar ratio of carbon dioxide to hydrogen is 1:4, the airspeed of the reaction gas is 21000 to 127000h -1 The reaction pressure is normal pressure, and the reaction temperature is 180-320 ℃.
Comparative example 1
The procedure of example 1 was repeated except that the Ni/Zr/Mn ratio was 40/1/9.
Comparative example 2
The procedure of example 1 was repeated except that the Ni/Zr/Mn ratio was 40/9/1.
Comparative example 3
The procedure of example 1 was repeated except that the Ni/Zr/Mn ratio was changed to 6/20/20.
Comparative example 4
The procedure of example 1 was repeated except that the Ni/Mn molar ratio was 6/40.
Comparative example 5
The procedure of example 1 was repeated except that the Ni/Zr molar ratio was 6/40.
Comparative example 6
The procedure of example 1 was followed except that the precipitating agent was ammonium carbonate.
Comparative example 7
The procedure of example 1 was repeated except that the precipitating agent was ammonium oxalate.
Comparative example 8
The procedure of example 1 was repeated except that the precipitating agent was aqueous ammonia.
Comparative example 9
The procedure of example 1 was followed except that the precipitant was sodium hydroxide.
Comparative example 10
Dissolving zirconium chloride and manganese chloride in 50mL of water at a concentration of 0.075mol/L, stirring until the zirconium chloride and the manganese chloride are completely dissolved, adding the zirconium chloride and the manganese chloride into 50mL of 2.5% ammonia water solution, stirring for 2h to obtain zirconium hydroxide and manganese hydroxide sol, and finally adding the zirconium hydroxide and manganese hydroxide sol into 20mL of absolute ethyl alcohol to obtain zirconium ethoxide and manganese ethoxide sol. 5g of zirconium ethoxide, manganese ethoxide sol were added to oleic acid: oleylamine: ethanol was 40mL:5mL:5mL of the mixed solution was neutralized and stirred well, and then transferred to a 100mL polytetrafluoroethylene-lined autoclave. Subsequently, the autoclave was sealed and heated at 200 ℃ for 12 hours, the obtained precipitate was washed with deionized water several times until the pH of the washing solution was neutral, and lyophilized overnight to obtain a nano zirconium manganese dioxide mixed oxide, and then dispersed in ethanol to obtain a nano zirconium manganese oxide mixed oxide transparent dispersion.
1g of P123 was dissolved in 50ml of deionized water and transferred to a 50ml polytetrafluoroethylene-lined autoclave. Then, 0.9g of nickel nitrate hexahydrate, 0.9g of urea and 25mL of deionized water were added to the above suspension to form a stock solution. Subsequently, the autoclave was sealed and heated at 140 ℃ for 12h, the precipitate was collected by centrifugation, washed with deionized water and ethanol, and lyophilized overnight. The solid obtained was heated in a tube furnace at 400℃for 3h to give NiO powder.
0.01mol of nickel oxide powder was dispersed in 100mL of absolute ethanol and added to a round bottom flask. Then a certain amount of the prepared nano zirconium manganese oxide mixed oxide suspension is dripped into a round bottom flask according to the mole ratio of Ni to Mn to Zr=40 to 3. Then stirred for 0.5h and sonicated for a further 1h to achieve good dispersion of the slurry. The slurry was then condensed at 70 ℃ under reflux for 2h. The flask was transferred to a rotary evaporator, warmed to 60 ℃, the rotational speed was controlled at 200r/min, the solution was spun dry, and the resulting precipitate was lyophilized overnight.
Reducing at 400deg.C in hydrogen atmosphere for 2 hr after freeze-drying, and reducing the obtained solid powder (ZrMnO 4 Ni) is the prepared catalyst. The granularity of the solid catalyst is 60-80 meshes, and the solid catalyst is placed in a gas-solid phase to carry out carbon dioxide methanation reaction. The molar ratio of carbon dioxide to hydrogen is 1:4, space velocity of the reaction gas is21000h -1 The reaction pressure is normal pressure, and the reaction temperature is 150-300 ℃.
Comparative example 11
The procedure of comparative example 10 was repeated except that the precursor salt for the support was nickel nitrate hexahydrate and the precursor salt for the supported metal oxide was manganese chloride, in which the Ni/Mn molar ratio was 40/6.
Comparative example 12
The procedure of comparative example 10 was repeated except that the precursor salt for the support was nickel nitrate hexahydrate and the precursor salt for the supported metal oxide was zirconium chloride, in which the molar ratio of Ni/Zr was 40/6.
Comparative example 13
The procedure of example 1 was followed except that the precursor salt for the support was cobalt nitrate hexahydrate, and the precursor salt for the supported metal oxide was zirconium chloride and manganese chloride, in which the molar ratio of Co/Zr/Mn was 6/20/20.
Comparative example 14
The procedure of example 2 was followed except that the precursor salt for the support was nickel nitrate hexahydrate and the precursor salt for the supported metal oxide was tetrabutyl titanate, in which the Ni/Ti molar ratio was 6/40.
Comparative example 15
The procedure of example 1 was followed except that the precursor salt for the support was nickel nitrate hexahydrate and the precursor salt for the supported metal oxide was aluminum chloride, with a Ni/Al molar ratio of 6/40.
Comparative example 16
The procedure of example 1 was followed except that the precursor salt for the support was nickel nitrate hexahydrate and the precursor salt for the supported metal oxide was magnesium chloride, wherein the Ni/Mg molar ratio was 6/40.
Comparative example 17
Glucose (0.01 mol) and acrylamide (0.015 mol) were stirred and dissolved in deionized water (80 mL), and cerium nitrate hexahydrate (0.0045 mol) and lanthanum nitrate hexahydrate (0.0005 mol) were added to form a clear solution. Then 3.2mL of 25wt% ammonia solution was added dropwise with stirring, and the pH was kept at around 10. After stirring for 5h, it was then transferred to a 100mL Teflon lined autoclave. The autoclave was hydrothermally heated at 180℃for 72h, cooled to room temperature and the solid precipitate was collected by filtrationThe material was washed with deionized water and absolute ethanol multiple times. Drying at 100deg.C for 10 hr, calcining at 600deg.C for 2 hr, and heating at 5deg.C for min -1 Is marked as La-CeO 2 -600。
Nickel nitrate hexahydrate (0.165 g) was dissolved in a certain amount of ethylene glycol (0.2 mL), and then the above solution was dropped into the above-mentioned preparation carrier (0.3 g), sealed at 40℃for 24 hours, dried at 100℃for 12 hours, and then air was taken at 5℃for min -1 Is calcined at 400 c for 2 hours. Reducing for 2h at 400 ℃ in hydrogen atmosphere after the calcination is finished, and reducing the obtained Ni/La-CeO 2 Namely the prepared catalyst [1] 。
Comparative example 18
An amount of nickel nitrate hexahydrate and ruthenium nitrosylnitrate solution were mixed in 40mL deionized water, and then an amount of Ce was added 0.5 Zr 0.5 O 2 In (commercial) the suspension was then evaporated to dryness in a 50 ℃ water bath and then dried at 110 ℃. The resulting solid was expressed as Ni-Ru/CeZrO x Calcining in air at 400 ℃ for 3h, reducing in hydrogen atmosphere at 400 ℃ for 2h after calcining, and reducing the obtained Ni-Ru/Ce 0.5 Zr 0.5 O 2 Namely the prepared catalyst [2] 。
Comparative example 19
An amount of nickel nitrate hexahydrate and ruthenium nitrosylnitrate solution were mixed in 40mL deionized water, and then an amount of Ce was added 0.5 Al 0.5 O 2 In (commercial) the suspension was then evaporated to dryness in a 50 ℃ water bath and then dried at 110 ℃. The resulting solid was calcined in air at 400 ℃ for 3h. Reducing for 2h at 400 ℃ in hydrogen atmosphere after the calcination is finished, and reducing the obtained Ni-Ru/Ce 0.5 Al 0.5 O 2 Namely the prepared catalyst [2] 。
Comparative example 20
Nickel nitrate hexahydrate (0.297 g) and manganese acetate tetrahydrate (0.501 g) were dissolved in 6mL deionized water. The appropriate amount of TiO was stirred at room temperature 2 (about 2 g) was slowly added to the aqueous solution. The suspension was left for 3 hours and then heated to 80℃to remove excess H 2 O. Finally, the obtained solid is dried in a static air oven at 110 ℃ overnight to obtain Ni-Mn/TiO 2 Namely the prepared catalyst [3] 。
Comparative example 21
Nickel nitrate hexahydrate (0.44 g,1.50 mmol), aluminum nitrate nonahydrate (0.19 g,0.50 mmoL), zirconium nitrate pentahydrate (0.02 g,0.005 mmoL) and urea (0.60 g,10.00 mmoL) were dissolved in deionized water (70 mL). Subsequently, the mixed solution was placed in a teflon-lined autoclave, and a hydrothermal reaction was performed at 120 ℃ for 12 hours. Centrifuging to obtain solid product, washing with deionized water and ethanol until the pH of the solution is close to 7, drying at 80deg.C for 15 hr, and designated Ni 0.73 Zr 0.03 Al 0.24 -LDH. The Ni obtained 0.73 Zr 0.03 Al 0.24 H of LDH at 600 DEG C 2 Reducing for 2h in gas (heating rate of 5 ℃/min) -1 ，H 2 The flow rate is 50mL min -1 ) The catalyst prepared is [4] 。
Comparative example 22
A cylindrical foam nickel treated to a length of 5cm and a diameter of 2cm was immersed in a solution containing nickel nitrate hexahydrate (0.009 mol), aluminum nitrate nonahydrate (0.0015 mol), iron nitrate (0.0015 mol) and urea (0.04 mol), stirred for 30 minutes, and transferred to a 100mL polytetrafluoro-lined autoclave. Subsequently, the autoclave was sealed and heated at 110 ℃ for 8 hours, and the resulting precursor was washed several times with deionized water and dried in air at 65 ℃ for 12 hours. Finally, flowing H through the precursor in a tube furnace at 500℃at a heating rate of 2℃per minute 2 /N 2 The Ni-Fe-Al/NF obtained by in-situ reduction in atmosphere (1/10, V/V) is the prepared catalyst [5] 。
Comparative example 23
Cerium nitrate hexahydrate and chromium nitrate nonahydrate are dissolved in 30mL of deionized water, and the Cr/Ce molar ratio is 1:9. the aqueous ammonia solution was added dropwise to the precursor salt solution while stirring continuously until complete precipitation at ph=10. The mixture was filtered to collect precipitate, which was repeatedly rinsed with deionized water. The solid was dried at 110℃overnight and calcined at 500℃for 4h to give Cr-CeO 2 A carrier.
Cr-CeO 2 Impregnated into RuCl 3 ·3H 2 O in aqueous solution. The mixture was evaporated with vigorous stirring in a water bath at 70 ℃ for 4h and then further dried overnight at 110 ℃. The resulting solid was designated RuO 2 /Cr-CeO 2 Calcining in 500 ℃ air for 4 hours, and reducing in hydrogen atmosphere at 400 ℃ for 2 hours after calcining, thus obtaining Ru/Cr-CeO 2 Namely the prepared catalyst [6] 。
Comparative example 24
Ru-TiO 2 0.6g of ruthenium trichloride hydrate was diluted to 50mL with deionized water, then vigorously stirred, and 2.0g of anatase titanium dioxide was added. The suspension was then evaporated to dryness in a 50 ℃ water bath and then dried at 110 ℃. The resulting solid was expressed as Ru/TiO 2 Calcining in air at 400 ℃ for 3h. Then, the sample was repeatedly washed with a dilute ammonia solution to remove residual chloride, and the sample was dried at 60℃overnight to obtain Ru/TiO 2 Namely the prepared catalyst. Ru/TiO 2 The loading of Ru in the catalyst was 10wt%.
Comparative example 25
Commercial Ru/Al 2 O 3
Except Ru-TiO 2 And commercial Ru-Al 2 O 3 The procedure of example 1 was repeated except that the reduction temperature was 200 ℃.
The use of each catalyst for CO is given in Table 1 2 CO in methanation reactions 2 Conversion rate.
Table 1 catalysts for CO 2 CO in methanation reactions 2 Conversion rate
Figure BDA0004083162240000091
Figure BDA0004083162240000101
a: the material was not detected, the content was negligible
Examples 1 to 13 in Table 1 show higher low temperature CO than the comparative example 2 Methanation activity shows that the reversed-phase oxide/metal catalyst catalyzes CO at low temperature compared with the traditional forward metal/oxide catalyst 2 Advantages of methanation.
FIG. 1 shows CO 2 The thermodynamic diagram of methanation reaction and side reaction reverse steam change reaction along with the change of temperature, the methanation reaction is a strong exothermic reaction, and the reaction is facilitated at low temperature. The reverse water gas shift reaction is an endothermic reaction, and the high temperature is favorable for the generation of CO.
FIG. 2 shows a comparison of the reaction results of examples 1, 9, 10 with comparative examples 1, 2, 3, 24, 25 at 130-320℃in the reverse phase ZrMnO x The Ni catalyst shows excellent performance at 170-180 ℃ and 21000h -1 CO at airspeed that can reach near equilibrium conversion 2 Conversion performance, and target product methane selectivity of more than 99.9%, far exceeding commercial Ru/Al 2 O 3 Catalyst and Ru/TiO 2 Catalyst performance. While Ni is supported on ZrMnO x Forward catalyst of oxide solid solution can reach more than 50% CO at more than 260 DEG C 2 Conversion rate.
FIG. 3 shows that example 1 was run at 190℃for 21000-127000h -1 Methanation activity results in the space velocity range, it can be seen that the reverse phase ZrMnO is present at high space velocity x the/Ni catalyst still maintains high CO 2 Conversion and methane selectivity approaching 100%.
FIG. 4 shows the stability test results for example 1 at 180℃over a 1500h range, without significant changes in catalyst activity after 1500h of operation.
FIG. 5 shows the results of the reactions of example 1 with comparative examples 6, 7, 8, 9, in which sodium carbonate works best as a precipitant to produce high performance low temperature methanation catalyst with respect to various precipitated sodium carbonate, ammonia, ammonium carbonate, ammonium oxalate, sodium hydroxide.
FIG. 6 shows the reaction results of examples 1, 6 and 7 and comparative example 13 at 130-220℃compared to the reverse ZrMnO x Ni catalyst, cobalt doping causes activity to be reduced to a certain extent, co is loaded on ZrMnO x The forward catalyst activity of the oxide solid solution is significantly reduced compared to the reverse phase.
Table 1 comparative examples 1, 9, 10, 13 and comparative examples 10, 11, 12, the bulk impregnation, the precipitation by deposition and the preparation of porous monolithic catalyst impregnated oxide nanoparticle precursor salts all allowed the synthesis of the inverse methanation catalyst with excellent performance.
FIG. 7 shows the reaction results of examples 9-10 and comparative examples 4-5, and it can be seen that consistent with the three-way reverse catalyst trend, the two-way reverse catalyst also has superior reaction performance to conventional forward catalysis.
FIG. 8 is a HAADF-STEM photograph of the catalyst prepared in example 1, and it can be seen that the catalyst prepared in the present invention has a metal carrier particle size of about 10nm and oxides are uniformly dispersed on the metal carrier.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, alternatives, and alternatives falling within the spirit and scope of the invention.
Reference to the literature
[1]Zhang T,Wang W,Gu F,et al.Enhancing the low-temperature CO 2 methanation over Ni/La-CeO 2 catalyst:The effects of surface oxygen vacancy and basic site on the catalytic performance[J].Applied Catalysis B:Environmental,2022,312:121385.
[2]Merkouri L P,Le SachéE,Pastor-Pérez L,et al.Versatile Ni-Ru catalysts for gas phase CO 2 conversion:Bringing closer dry reforming,reverse water gas shift and methanation to enable end-products flexibility[J].Fuel,2022,315:123097.
[3]Vrijburg W L,Moioli E,Chen W,et al.Efficient base-metal NiMn/TiO 2 catalyst for CO 2 methanation[J].Acs Catalysis,2019,9(9):7823-7839.
[4]He F,Zhuang J,Lu B,et al.Ni-based catalysts derived from Ni-Zr-Al ternary hydrotalcites show outstanding catalytic properties for low-temperature CO 2 methanation[J].Applied Catalysis B:Environmental,2021,293:120218.
[5]Gao Y,Dou L,Zhang S,et al.Coupling bimetallic Ni-Fe catalysts and nanosecond pulsed plasma for synergistic low-temperature CO 2 methanation[J].Chemical Engineering Journal,2021,420:127693.
[6]Xu X,Liu L,Tong Y,et al.Facile Cr 3+ -doping strategy dramatically promoting Ru/CeO 2 for low-temperature CO 2 methanation:Unraveling the roles of surface oxygen vacancies and hydroxyl groups[J].ACS Catalysis,2021,11(9):5762-5775.

Claims (9)

1. The solid reverse phase catalyst is characterized in that the solid reverse phase catalyst takes metal dissociated from hydrogen as a carrier, nano oxide which generates oxygen vacancies to adsorb activated carbon dioxide is taken as a load phase, the nano oxide is uniformly dispersed on the surface of the metal carrier, and the solid reverse phase catalyst has a nano oxide/metal reverse phase interface structure;
wherein, the liquid crystal display device comprises a liquid crystal display device,
the carrier metal is selected from one or more of cobalt, nickel, aluminum, copper and ruthenium;
the supported phase nano oxide is selected from one or more of titanium oxide, aluminum oxide, manganese oxide, cerium oxide, zirconium oxide, silicon oxide and tungsten oxide;
the mole fraction of metal in the support phase is in the range of 0.01 to 30% based on the total molar amount of metal in the support and support phase.
2. The method for preparing a solid reverse phase catalyst according to claim 1, wherein the method comprises:
preparing a carrier precursor under the conditions of a precipitator and a solvent by a hydrothermal method or a coprecipitation method;
preparing nano oxide dispersion liquid under the conditions of a precipitator, a solvent and a protective agent by a sol method;
the nano oxide is deposited in situ or impregnated on the precursor of the carrier by means of in-situ deposition or over-volume impregnation, and the obtained powdery solid is subjected to roasting and reduction steps, and the nano oxide is uniformly dispersed on the surface of the metal carrier, so that the solid reverse phase catalyst is obtained.
3. The method for preparing the solid reverse phase catalyst according to claim 2, comprising the steps of:
(1) Synthesis of nano-oxides
Dissolving precursor salt of a load phase in a solvent, and adding the obtained solution into a precipitant solution to obtain hydroxide sol; adding the obtained hydroxide sol into ethanol to obtain hydroxide-ethanol sol; dispersing hydroxide-ethanol sol into a mixed solution of oleic acid/oleylamine/ethanol, stirring uniformly, transferring into an autoclave, sealing, performing solvothermal treatment at 80-220 ℃ for 1-24h, collecting a solid product, washing with deionized water until the pH of a washing solution is neutral, and freeze-drying to obtain nano oxide, and dispersing in ethanol to obtain nano oxide dispersion for later use;
wherein the precursor salt of the support phase is selected from titanium tetrachloride, tetrabutyl titanate; aluminum nitrate, aluminum nitrate hydrate, and aluminum chloride; manganese nitrate, manganese nitrate hydrate and manganese chloride; cerium nitrate, hydrated cerium nitrate, and cerium chloride; zirconium nitrate, zirconium nitrate hydrate, zirconium chloride; ethyl orthosilicate; one or more of ammonium metatungstate, sodium tungstate and tungsten chloride;
(2) Synthesis of solid reverse phase catalyst
Dissolving a precursor salt of a carrier in a solvent, dropwise adding the nano oxide dispersion liquid prepared in the step (1) into the obtained solution, then dropwise adding a precipitant solution under stirring, controlling the pH to be 9, aging at room temperature, filtering, washing, drying, calcining in static air, and reducing in a hydrogen atmosphere after the calcining is finished to prepare a solid reverse phase catalyst;
wherein the precursor salt of the carrier is selected from one or more of cobalt nitrate, cobalt nitrate hydrate, cobalt chloride, nickel nitrate hydrate, nickel chloride, copper nitrate hydrate, copper chloride and ruthenium chloride;
4. the method for preparing a solid reverse phase catalyst according to claim 3, wherein in the step (1) or the step (2), the solvent is one or more selected from the group consisting of water, methanol, ethanol, butanol, tetrahydrofuran and methyl tert-butyl ether.
5. The method for preparing a solid reverse phase catalyst according to claim 3, wherein in the step (1) or the step (2), the precipitant is one or more selected from the group consisting of ammonium carbonate, ammonia water, urea, sodium hydroxide, sodium bicarbonate, ammonium oxalate and oxalic acid.
6. The method for preparing a solid reverse phase catalyst according to claim 3, wherein in the step (2), the calcination temperature is 200 to 600 ℃ and the time is 1 to 12 hours.
7. The method for preparing a solid reverse phase catalyst according to claim 3, wherein in the step (2), the reduction temperature is 200 to 700 ℃ and the time is 1 to 6 hours; the concentration of hydrogen in the reducing atmosphere ranges from 5 to 100 percent, and the total flow ranges from 5 to 100ml/min.
8. Use of the solid reverse phase catalyst of claim 1 in a methanation reaction of carbon dioxide.
9. The application according to claim 8, wherein the method of application is:
placing a solid reverse phase catalyst in a fixed bed reactor, and introducing carbon dioxide and hydrogen in a molar ratio of 1:4, the volume space velocity of the reaction gas is 9000-127000 h -1 The reaction pressure ranges from normal pressure to 6Mpa, and the reaction temperature ranges from 25 ℃ to 450 ℃.
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