CN112138654B - Catalyst for hydromethanation of carbon dioxide and application thereof - Google Patents
Catalyst for hydromethanation of carbon dioxide and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for hydromethanation of carbon dioxide and application thereof, wherein a catalyst carrier contains TiO 2 、ZrO 2 MgO and metal powder, wherein TiO 2 、ZrO 2 The mass ratio of MgO to metal powder is 50-80:5-30:1-10:1-10, and the metal powder is one or more of zinc powder, aluminum powder or tin powder. Dripping liquid-phase titanium salt into deionized water under ice water bath to form transparent solution, mixing the transparent solution with zirconium and magnesium metal salt solution to obtain uniform solution, adding alkali liquor to precipitate completely, filtering and washing the obtained suspension, collecting titanium-zirconium-magnesium compound, adding metal powder, mixing uniformly, compacting, and drying to obtain a catalyst carrier; and loading active components and auxiliary agents to the obtained carrier, drying and roasting, and then treating with a dilute NaOH solution to obtain the carbon dioxide methanation catalyst, wherein the active component elements are one or more of Pt, ru, ni, co, and the auxiliary agent elements are one of Re, ir, B or P. The catalyst is applied to the carbon dioxide hydromethanation reaction of the gas regeneration technology in the cabin of the underwater vehicle, the enriched carbon dioxide hydromethanation reaction in the biogas purification process and the carbon dioxide hydromethanation reaction in the purification of the synthesis ammonia feed gas.
Description
Technical Field
The invention belongs to the field of catalysts, and a preparation method and application thereof, and particularly relates to a carbon dioxide hydromethanation catalyst, and a preparation method and application thereof.
Background
It is widely accepted in the scientific community today that the greenhouse gas CO formed by the combustion of fossil fuels 2 The global climate change problem caused by emissions is becoming increasingly more serious and presents a great threat to the human and global ecosystem. This reduces the reserves of this non-renewable energy source and faces the exhaustion crisis on the one hand, and on the other hand, also generates a large amount of carbon dioxide emissions. Against the global warming problem caused by the greenhouse effect, various national governments and united nations worldwide have adopted a number of related international programs and actions in the past decades. Wherein, one potential solution is to electrolyze the hydrogen produced by water with renewable energy sources such as photovoltaic, wind power and the like, and simultaneously capture the carbon dioxide generated in production and life as a carbon source and then pass through CO 2 To produce useful chemicals or fuels. This solution can help to solve the CO in the atmosphere 2 The environmental problems caused by the increase of the concentration can be relieved, and the problems of excessive dependence on fossil fuel and storage of renewable energy sources can be relieved.
The most typical example of carbon dioxide hydromethanation is research for syngas conversion processes. The process belongs to a high-temperature high-pressure reaction process, and the catalytic system is used for solving the problems of industrial scale hydromethanation reaction after purifying and changing and adjusting the hydrocarbon ratio of gases containing carbon oxides and hydrogen such as synthesis gas, pyrolysis gas, coke oven gas and the like. There have been a great deal of research reports on catalysts and methods of preparation in this field, with emphasis on Ni-based methanation catalysts for synthesis gas conversion processes. The catalyst has good activity at high temperature, but is easy to sinter and deactivate, and has low-temperature activity.
In the biomass field, the components of the biogas mainly comprise methane (50% -60%) and carbon dioxide (40% -50%), and in the process of purifying and converting the biogas into natural gas, the content of methane and the energy density in the biogas can be improved mainly by removing the carbon dioxide, nitrogen, sulfur and other small molecular impurity gas components in the biogas, so that the high-quality biological natural gas is prepared. The refined biological natural gas can be used as automobile and train fuel after being pressurized and modulated. The method for removing carbon dioxide in the biogas can be realized by various methods, such as an absorption method, a pressure swing adsorption method and the like. The carbon dioxide after being removed and absorbed can realize the enrichment of methane gas through catalytic conversion, and further utilizes carbon resources in the methane gas.
In the special closed environment of an underwater vehicle and the like, the gas regeneration technology of the environmental control life-saving system is to collect and concentrate carbon dioxide generated by personnel in a cabin, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, the carbon dioxide and hydrogen can be reacted and reduced to generate methane and water, and the water is supplied to an electrolysis system for electrolysis to generate oxygen. As electrolyzed water, the oxygen supply system generated by electrolysis is used as the consumption of system personnel in the cabin, and the generated hydrogen can be supplied to the heterogeneous catalytic reaction system for reduction reaction. The use of such a closed system will greatly reduce the supply of consumable materials, and the water, oxygen and carbon dioxide absorbent will essentially form a closed loop.
From the above analysis, it was found that carbon dioxide hydromethanation is a core technology in the above application fields. Because carbon dioxide has high thermodynamic stability and strong chemical inertness, to realize activation of carbon dioxide, a catalyst is a key element, and the reaction process is as follows:
the methanation reaction of carbon dioxide is a violently exothermic chemical reaction, but the chemical inertness of carbon dioxide leads to a relatively high activation energy of the corresponding reaction, so that the activation is promoted by both increasing the reaction temperature and reducing the activation energy by adopting a high-activity catalyst.
In the prior art, the carbon dioxide hydromethanation catalyst needs an additional hydrogen source, and the reduction activation step is carried out under the heating condition; the activity of the carbon dioxide methanation catalyst at a low temperature (200-350 ℃) is not high, and the carbon dioxide conversion rate is generally below 50% at the reaction temperature; meanwhile, the methanation catalytic reaction temperature is higher and is generally higher than 400 ℃ (CN 106268858), and the methanation catalyst has poor stability under the high-temperature condition and is easy to cause aggregation and growth of crystal grains, so that the catalyst is sintered and deactivated; in the application of hydromethanation of carbon dioxide, the reaction selectivity is difficult to reach 100 percent, and the process of purifying and converting methane into natural gas is difficult to realize grid connection with a natural gas pipeline; the application of the existing catalyst in the gas regeneration technology of the environmental-control life-saving system is difficult to realize by adopting a small amount of carbon monoxide in the hydromethanation process of carbon dioxide.
Disclosure of Invention
In order to further improve the activity of the carbon dioxide hydromethanation reaction catalyst, the technical problem to be solved by the invention is to provide an in-situ pore-forming reduction method, a carbon dioxide hydromethanation catalyst with high-low temperature activity and high-temperature stability and application thereof.
To this end, the present invention provides a carbon dioxide hydromethanation catalyst, the catalyst preparation method comprising:
a. preparing a mixed aqueous solution containing a liquid-phase titanium salt precursor, zirconium metal salt and magnesium metal salt, and adding alkali liquor into the prepared mixed solution to mix to obtain a suspension;
b. c, centrifugally collecting the suspension obtained in the step a, adding metal powder into the precipitate, uniformly mixing, forming, drying and roasting to obtain a catalyst carrier; the metal powder is one or more of zinc powder, aluminum powder or tin powder, and the obtained catalyst carrier contains TiO 2 ,ZrO 2 MgO and metal powder, the TiO 2 ,ZrO 2 The mass ratio of MgO to metal powder is 50-80:5-30:1-10:1-10;
c. b, loading active component metal elements and auxiliary agent elements on the carrier obtained in the step B, and drying and roasting to obtain a catalyst precursor, wherein the active component is one or more of Pt, ru, ni, co, and the auxiliary agent elements are one of Re, ir, B or P;
d. and c, treating the catalyst precursor obtained in the step c by adopting a NaOH solution to obtain the carbon dioxide methanation catalyst.
Further, the step a includes: firstly, dropwise adding deionized water into a liquid-phase titanium salt precursor under the condition of ice water bath to form a transparent solution; then dissolving zirconium-containing metal salt and magnesium-containing metal salt in the transparent solution to obtain a mixed aqueous solution.
Optionally, the liquid phase titanium salt precursor is TiCl 4 Tetrabutyl titanate, tetraethyl titanate, or tetraisopropyl titanate. TiCl may be preferred 4 Or tetraethyl titanate.
Optionally, the zirconium metal salt is ZrOCl 2 Or ZrOCl 2 A hydrate.
Alternatively, the magnesium metal salt is Mg (NO 3 ) 2 Or MgCl 2 。
Optionally, the alkali solution is one of NaOH aqueous solution, KOH aqueous solution or ammonia solution, and the alkali solution is added to precipitate until ph=12-14, preferably ammonia solution.
Optionally, the mass concentration of the NaOH solution in the step d is 8% -20%.
Preferably, the calcination temperature in step b is 200-600 ℃, and may preferably be 300-450 ℃.
Preferably, the loading of the active component metal element is 0.5 to 10.0wt.% of the catalyst support, and may preferably be 1.0 to 5.0wt.%; the total loading of the adjunct elements is 0.5 to 5.0wt.% of the catalyst support, and may preferably be 1.0 to 3.0wt.%.
Optionally, in the step c, an isovolumetric impregnation method, an excessive impregnation method or an alkali precipitation method is adopted to load the active component metal element and the auxiliary metal element onto the solid solution carrier obtained in the step b.
Alternatively, the catalyst precursor is treated with a NaOH solution having a mass concentration of 8% to 20%, preferably 10% to 15%.
The present invention provides for the use of the carbon dioxide hydromethanation catalyst for carbon dioxide hydromethanation in the purification of a synthetic ammonia feed gas, for enriching carbon dioxide hydromethanation in a biogas purification process, in particular for use in an underwater vehicle cabin gas regeneration technology.
According to the carbon dioxide hydromethanation reaction, a carbon source obtained by separating and purifying methane can be utilized as a carbon dioxide raw material, and in the methane separation and purification process, the purpose of removing carbon dioxide in methane is achieved by utilizing the characteristic of selective adsorption of carbon dioxide by an adsorbent (such as a molecular sieve and the like), namely, the carbon dioxide on the adsorbent has a higher separation coefficient than other gaseous components. In the adsorption process, carbon dioxide in the raw material gas is adsorbed in an adsorption tower under the condition of pressurization, other weak adsorption gases such as methane and the like are discharged as purified gas, and the adsorption column is depressurized or even vacuumized after adsorption is saturated so as to release the adsorbed carbon dioxide.
The carbon dioxide hydromethanation reaction disclosed by the invention has the advantages that carbon dioxide raw materials can be carbon dioxide generated by human metabolism in an underwater vehicle for collection and concentration, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, the carbon dioxide and hydrogen can be subjected to reaction, hydrogenation reduction and methane generation and water generation, and the water is supplied to an electrolysis system for electrolysis and oxygen generation; as electrolyzed water, the oxygen supply system generated by electrolysis is used as the consumption of system personnel in the cabin, and the generated hydrogen can be supplied to the heterogeneous catalytic reaction system for reduction reaction. The use of such a closed system will greatly reduce the supply of consumable materials, and the water, oxygen and carbon dioxide absorbent will essentially form a closed loop.
The invention uses the high-efficiency composite oxide catalyst carrier, adopts the solid solution form to lead the titanium dioxide of the catalyst carrier to generate surface defects, and promotes the formation of intermediate species with stronger reaction activity such as excited state molecules, free radical ions and the like in a reaction system; active components and catalyst auxiliary agents are added, and the surface energy level structure of the catalyst and the free radical reaction process in the reaction system are changed by the influence of the active components and the catalyst auxiliary agents on electron spin, so that the catalyst is more beneficial to CO 2 Polarization and ionization of molecules to achieve CO under mild reaction conditions and low energy consumption 2 Is improved. CO of the invention 2 The improvement of the hydromethanation reaction technology level, on the one hand, can use a high-efficiency catalyst,on the other hand, the limitation of the traditional thermocatalytic process can be broken through; for example, while the catalytic reaction is controlled by utilizing conventional parameters such as temperature, pressure, airspeed and the like, an auxiliary external field such as a magnetic field, illumination and the like can be applied to a reaction system, so that the catalytic reaction path can be optimized and CO can be promoted 2 Efficient conversion provides more development space. Specifically, the present invention relates to a method for manufacturing a semiconductor device.
(1) The metal powder is Al powder, zn powder or Sn powder in the design of the carbon dioxide hydromethanation catalyst, when the metal powder is treated with NaOH solution, the metal powder and NaOH undergo oxidation-reduction reaction, a new pore area is generated after the metal powder is reacted, effective pores are provided for diffusion of methanation catalytic reactants and products, the hydromethanation reaction rate of the inner surface and the outer surface of the catalyst is improved, and further, the methanation selectivity is improved, and the selectivity reaches 100%;
(2) Al powder, zn powder or Sn powder reacts with NaOH dilute solution to generate a large amount of active hydrogen, and metal active components such as Pt, ru, ni, co and the like can be reduced under the action of active hydrogen atoms in a hydrogen atmosphere, so that the reaction product is directly used for the hydromethanation reaction of carbon dioxide, an additional hydrogen source is not needed, and a reduction and activation step is omitted;
(3) The carbon dioxide methanation catalyst has high activity at low temperature (200-350 ℃), and the carbon dioxide conversion rate is generally over 80 percent at the reaction temperature;
(4) In the application of hydromethanation of carbon dioxide, the reaction selectivity is difficult to reach 100 percent, and the process of purifying and converting methane into natural gas is difficult to realize grid connection with a natural gas pipeline;
(5) Carbon monoxide is not generated in the hydromethanation process of carbon dioxide, and the application of the gas regeneration technology carbon dioxide hydromethanation reaction of the environmental control life-saving system in the underwater vehicle can be realized.
Detailed Description
According to the design of the carbon dioxide hydromethanation catalyst, the metal powder is Al powder, zn powder or Sn powder, when the metal powder is treated with the NaOH solution, the metal powder and the NaOH undergo oxidation-reduction reaction, a new pore area is generated after the metal powder is reacted, effective pores are provided for diffusion of methanation catalytic reactants and products, the hydromethanation reaction rate of the inner surface and the outer surface of the catalyst is improved, and the methanation selectivity is improved; meanwhile, al powder, zn powder or Sn powder reacts with NaOH dilute solution to generate a large amount of active hydrogen, and metal active components such as Pt, ru, ni, co and the like can be reduced under the action of active hydrogen atoms in a hydrogen atmosphere, so that the reaction product is directly used for carbon dioxide hydromethanation reaction, no extra hydrogen source is needed, and a reduction and activation step is omitted, wherein the reaction principle of the Al powder, zn powder or Sn powder and the NaOH dilute solution is as follows:
2Al+2NaOH+2H 2 O→2NaAlO 2 +3H 2 ↑；
Zn+2NaOH→2NaZnO 2 +H 2 ↑；
Sn+2NaOH→2NaSnO 2 +H 2 ↑。
the present invention is further illustrated by the following examples, but the present invention is not limited by the following examples.
Example 1:
TiCl is added to the mixture 4 (0.876 mol,166.2 g) was dropped into 180.0ml deionized water under ice-water bath, vigorously mixed, and ZrOCl was added thereto 2 (0.122mol,21.7g)、MgCl 2 (0.122 mol,11.8 g) is dissolved in the solution to obtain a uniformly mixed solution, the uniformly mixed solution is fully stirred to obtain a uniform solution, then NaOH aqueous solution with the mass concentration of 26.0% is dropwise added at room temperature, the dropwise adding amount per minute is controlled to be 1.0ml, the stirring is continuously carried out until the pH value of the suspension is 14, the formed slurry is filtered, the solution is fully washed to be neutral by deionized water, the titanium-zirconium-magnesium compound is prepared, aluminum powder is added, and TiO is added according to the mass parts 2 :ZrO 2 MgO and Al are respectively added in a ratio of 70:15:5:5, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and molded, and then the mixture is dried at 120 ℃ for 12 hours and baked at 400 ℃ for 8 hours to prepare a catalyst carrier;
RuCl is to be processed 3 ·3H 2 O (0.061 mol,15.9 g) and NaBO 2 ·4H 2 O (0.189 mol,26.1 g) was dissolved in 200mL of 50% volume fraction aqueous ethanol; then adding 205g of the catalyst carrier, and strongly stirring and dipping for 16h; evaporating the solvent from the obtained material, drying at 60deg.C for 8 hr, androasting at 380 deg.c for 8 hr. And taking out the calcined catalyst precursor, and then treating the catalyst precursor for 3 hours at 90 ℃ by using 15% NaOH solution to obtain the carbon dioxide methanation catalyst A.
Example 2:
the titanium zirconium magnesium composite carrier preparation method is different from example 1: tiCl is added to the mixture 4 (1.064 mol,201.7 g) was dropped into 180.0ml deionized water under ice water bath, vigorously mixed, and ZrOCl was added thereto 2 (0.162mol,28.9g)、MgCl 2 (0.07 mol,7.08 g) is dissolved in the solution, and is precipitated by adopting 26.0 percent ammonia water solution to prepare a titanium-zirconium-magnesium compound, and zinc powder is added into the titanium-zirconium-magnesium compound, and TiO is added according to the mass parts 2 :ZrO 2 MgO and Zn are respectively added in a proportion of 85:20:3:8, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and molded, and the mixture is roasted for 5 hours at 350 ℃ to prepare a catalyst carrier;
then through the dipping method, ruCl is added 3 ·3H 2 O (0.122 mol,31.8 g) and NaBO 2 ·4H 2 O (0.114 mol,15.7 g) to 245.7g of catalyst carrier, drying and roasting, and then treating for 6 hours at 85 ℃ by 10% NaOH solution to obtain the carbon dioxide methanation catalyst B.
Example 3:
the titanium zirconium magnesium composite carrier preparation method is different from example 1: tiCl is added to the mixture 4 (0.751 mol,142.4 g) dropwise adding 180.0ml deionized water under ice water bath, mixing vigorously, and then ZrOCl 2 (0.202mol,36.1g)、MgCl 2 (0.124 mol,11.8 g) is dissolved in the solution, and is precipitated by 15.0 percent KOH aqueous solution to prepare a titanium zirconium magnesium compound, and tin powder is added into the compound, and TiO is added according to the mass part 2 :ZrO 2 MgO and Sn are respectively added in a ratio of 60:25:5:3, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and molded, and the mixture is roasted for 5 hours at 350 ℃ to prepare a catalyst carrier;
then through the dipping method, ruCl is added 3 ·3H 2 O (0.05 mol,12.9 g) and NaBO 2 ·4H 2 O (0.0.463mol, 63.7 g) to 250g of catalyst carrier, drying, roasting, and treating with 10% NaOH solution at 85 ℃ for 6 hours to obtain the carbon dioxide methanation catalyst C.
Example 4:
titanium zirconium magnesium compositeThe procedure for the preparation of the support is different from example 1 in that: tiCl is added to the mixture 4 (0.688 mol,130.6 g) was dropped into 180.0ml deionized water under ice-water bath, vigorously mixed, and ZrOCl was added thereto 2 (0.243mol,43.4g)、MgCl 2 (0.248 mol,23.6 g) was dissolved in the solution, and precipitated with 15.0% KOH aqueous solution to obtain a titanium zirconium magnesium composite, and tin powder was added thereto in parts by mass of TiO 2 :ZrO 2 MgO and Sn are respectively added in a proportion of 55:30:10:5, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and molded, and the mixture is roasted for 5 hours at 350 ℃ to prepare a catalyst carrier;
then through the dipping method, ruCl is added 3 ·3H 2 O (0.146 mol,38.4 g) and NaBO 2 ·4H 2 O (0.274 mol,37.8 g) to 296g of catalyst carrier, drying and roasting, and then treating the catalyst carrier with 10% NaOH solution at 85 ℃ for 6 hours to obtain the carbon dioxide methanation catalyst D.
Example 5:
the titanium zirconium magnesium composite carrier preparation method is different from example 1: tiCl is added to the mixture 4 (1.12 mol,213.6 g) was dropped into 180.0ml deionized water under an ice water bath, vigorously mixed, and ZrOCl was added thereto 2 (0.081mol,14.4g)、MgCl 2 (0.198 mol,18.9 g) was dissolved in the solution, and precipitated with 15.0% KOH aqueous solution to obtain a titanium zirconium magnesium composite, which was added with aluminum powder, tiO in parts by mass 2 :ZrO 2 MgO and Al are respectively added in a ratio of 90:10:8:5, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and molded, and the mixture is roasted for 5 hours at 350 ℃ to prepare a catalyst carrier; then through the dipping method, ruCl is added 3 ·3H 2 O (0.099 mol,26.1 g) and NaBO 2 ·4H 2 O (0.233 mol,32.1 g) to 252g of the catalyst carrier, and then treating the catalyst carrier with 15% NaOH solution at 85 ℃ for 6 hours to obtain the carbon dioxide methanation catalyst E.
Example 6:
the titanium zirconium magnesium composite carrier preparation method is different from example 5 in that: pt (NO) 3 ) 2 (0.063 mol,20.1 g) and NaBO 2 (0.114 mol,15.7 g) into 23.5mL of 50% ethanol aqueous solution by volume fraction; then 245.7g of catalyst carrier is added, and the mixture is strongly stirred and immersed for 16 hours; evaporating the obtained material to drynessThen dried at 50℃for 8 hours and calcined at 400℃for 8 hours. And taking out the calcined catalyst precursor, and then treating the catalyst precursor for 6 hours at 85 ℃ by using 8% NaOH solution to obtain the carbon dioxide methanation catalyst F.
Example 7:
the titanium zirconium magnesium composite carrier preparation method is different from example 5 in that: niCl is added 2 ·6H 2 O (0.416 mol,99.1 g) and NH 4 ReO 7 (0.013 mol,3.54 g) was dissolved in 23.5mL of 50% volume fraction aqueous ethanol; then 245.7g of catalyst carrier is added, and the mixture is strongly stirred and immersed for 16 hours; the resulting material was then evaporated to dryness, dried at 70℃for 6h and calcined at 360℃for 12h. And taking out the calcined catalyst precursor, and then treating the catalyst precursor for 5 hours at 60 ℃ by using a 20% NaOH solution to obtain the carbon dioxide methanation catalyst G.
Example 8:
the titanium zirconium magnesium composite carrier preparation method is different from example 5 in that: coCl is to be processed 2 ·6H 2 O (0.416 mol,99.1 g) and (NH) 4 ) 2 IrCl 6 (0.026 mol,11.3 g) into 23.5mL of 50% ethanol aqueous solution; then 245.7g of catalyst carrier is added, and the mixture is strongly stirred and immersed for 16 hours; the resulting material was then evaporated to dryness, dried at 70℃for 6h and calcined at 360℃for 12h. And taking out the calcined catalyst precursor, and then treating the catalyst precursor for 5 hours at 60 ℃ by using 15% NaOH solution to obtain the carbon dioxide methanation catalyst H.
Example 9:
the titanium zirconium magnesium composite carrier preparation method is different from example 5 in that: ruCl is to be processed 3 ·3H 2 O (0.122 mol,31.8 g) and (NH) 4 ) 2 HPO 4 (0.079 mol,10.5 g) was dissolved in 23.5mL of 50% volume fraction aqueous ethanol; then 245.7g of catalyst carrier is added, and the mixture is strongly stirred and immersed for 16 hours; the resulting material was then evaporated to dryness, dried at 60℃for 8h and calcined at 380℃for 8h. And taking out the calcined catalyst precursor, and then treating the catalyst precursor for 3 hours at 90 ℃ by using 15% NaOH solution to obtain the carbon dioxide methanation catalyst I.
Example 10:
the titanium zirconium magnesium composite carrier preparation method is different from example 5 in that: ruCl is to be processed 3 ·3H 2 O (0.073 mol,19.1 g) and NH 4 ReO 7 (0.04 mol,10.6 g) was dissolved in 23.5mL of 50% volume fraction aqueous ethanol; then 245.7g of catalyst carrier is added, and the mixture is strongly stirred and immersed for 16 hours; the resulting material was then evaporated to dryness, dried at 70℃for 6h and calcined at 360℃for 12h. And taking out the calcined catalyst precursor, and then treating the catalyst precursor for 5 hours at 60 ℃ by using a 20% NaOH solution to obtain the carbon dioxide methanation catalyst J.
Example 11:
in the process of purifying and converting methane into natural gas, the carbon dioxide in the methane is removed by utilizing the characteristic of selective adsorption of the adsorbent (such as molecular sieve and the like) on the carbon dioxide, namely, the carbon dioxide on the adsorbent has a higher separation coefficient than other gaseous components. In the adsorption process, carbon dioxide in the raw material gas is adsorbed in an adsorption tower under the condition of pressurization, other weak adsorption gases such as methane and the like are discharged as purified gas, and the adsorption column is depressurized or even vacuumized after adsorption is saturated so as to release the adsorbed carbon dioxide.
Separating and purifying biogas, and resolving the obtained CO 2 95.4% by volume and the balance of nitrogen-containing and sulfur-containing micromolecular gas, and CO in the volume flow 2 /H 2 /N 2 1/4/4 of the total airspeed 18000-24000 L.kg -1 ·h -1 Next, the reactor is warmed to 200-350℃to conduct a carbon dioxide hydromethanation reaction.
The catalyst was evaluated using a fixed bed reactor with dimensions 400 mm. Phi. 10 mm. Times.1 mm. The reaction is carried out under 0.1MPa, the catalyst is filled with 0.25g, the particle size of the catalyst is 0.25-0.4mm, the reactor is heated to the specified temperature for carrying out the carbon dioxide hydromethanation reaction, the composition of the product gas is analyzed by gas chromatography, and the obtained catalyst performance data is the result after the reaction is stable. The results are shown in Table 1 below.
TABLE 1
Example 12:
under the special closed environment such as an underwater simulated vehicle, carbon dioxide generated by human metabolism in the underwater vehicle is collected and concentrated, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, and CO is produced at the volume flow rate 2 /H 2 /N 2 At 1/4/5, total airspeed 22000-44000 L.kg -1 ·h -1 Next, the reactor was warmed to 200-300℃to conduct a carbon dioxide hydromethanation reaction, the composition of the product gas was analyzed by gas chromatography, and the catalyst was evaluated in the same manner as in example 11, and the results are shown in Table 2 below.
TABLE 2
Example 13:
under the special closed environment such as an underwater simulated vehicle, carbon dioxide generated by metabolism of personnel in the underwater vehicle is collected and concentrated, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, the reaction conditions are the same as those of example 12, the composition of product gas is analyzed through gas chromatography, the catalyst evaluation mode is the same as that of example 11, and the results are shown in the following table 3.
TABLE 3 Table 3
Claims (9)
1. A carbon dioxide hydromethanation catalyst, wherein the catalyst preparation process comprises:
a. preparing a mixed aqueous solution containing a liquid-phase titanium salt precursor, zirconium metal salt and magnesium metal salt, and adding alkali liquor into the prepared mixed solution to mix to obtain a suspension;
b. c, centrifugally collecting the suspension obtained in the step a, adding metal powder into the precipitate, uniformly mixing, forming, drying and roasting to obtain a catalyst carrier; the metal powder is one or more of zinc powder, aluminum powder or tin powder, and the obtained catalyst carrier contains TiO 2 ,ZrO 2 MgO and metal powder, the TiO 2 ,ZrO 2 The mass ratio of MgO to metal powder is 50-80:5-30:1-10:1-10;
c. b, loading active component metal elements and auxiliary agent elements on the carrier obtained in the step B, and drying and roasting to obtain a catalyst precursor, wherein the active component is one or more of Pt and Ru, and the auxiliary agent elements are one of Re, ir, B or P;
d. and c, treating the catalyst precursor obtained in the step c by adopting a NaOH solution to obtain the carbon dioxide methanation catalyst.
2. The carbon dioxide hydromethanation catalyst according to claim 1, wherein step a comprises: firstly, dropwise adding deionized water into a liquid-phase titanium salt precursor under the condition of ice water bath to form a transparent solution; then dissolving zirconium-containing metal salt and magnesium-containing metal salt in the transparent solution to obtain a mixed aqueous solution.
3. The carbon dioxide hydromethanation catalyst of claim 1, wherein the liquid phase titanium salt precursor is TiCl 4 Tetrabutyl titanate, tetraethyl titanate, or tetraisopropyl titanate; the zirconium metal salt is ZrOCl 2 Or ZrOCl 2 A hydrate; the magnesium metal salt is Mg (NO) 3 ) 2 Or MgCl 2 。
4. The carbon dioxide hydromethanation catalyst according to claim 1, wherein the lye is one of an aqueous NaOH solution, an aqueous KOH solution or an aqueous ammonia solution, and the lye is added for precipitation until pH = 12-14.
5. The carbon dioxide hydromethanation catalyst according to claim 1, wherein the NaOH solution in step d has a mass concentration of 8% -20%.
6. The carbon dioxide hydromethanation catalyst according to claim 1, wherein the calcination temperature in step b is in the range of 200 to 600 ℃.
7. The carbon dioxide hydromethanation catalyst according to claim 1, wherein the loading of the active component metal element is 0.5 to 10.0wt.% of the catalyst support; the total loading of the auxiliary elements is 0.5-5.0wt.% of the catalyst carrier.
8. The carbon dioxide hydromethanation catalyst according to claim 1, wherein the active component metallic element and the auxiliary metallic element are supported on the solid solution carrier obtained in step b in step c by an isovolumetric impregnation method or an overimpregnation method or an alkali precipitation method.
9. Use of the catalyst of any one of claims 1-8 as a catalyst for a carbon dioxide hydromethanation reaction, the carbon dioxide hydromethanation reaction comprising: a gas regeneration reaction in a closed space of the underwater vehicle, a gas regeneration reaction of an environmental control life-saving system, a carbon dioxide hydromethanation reaction in purification of a synthesis ammonia feed gas or a carbon dioxide hydromethanation reaction enriched in a biogas purification process.
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| CN103191749A (en) * | 2013-04-08 | 2013-07-10 | 西北化工研究院 | Methanation catalyst for synthesizing substitute natural gas and preparation method thereof |
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