CN117772192A - For normal temperature CO 2 Preparation method and application of trapping-low-temperature in-situ conversion integrated bifunctional catalyst - Google Patents
For normal temperature CO 2 Preparation method and application of trapping-low-temperature in-situ conversion integrated bifunctional catalyst Download PDFInfo
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 19
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
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Abstract
The invention relates to a method for preparing CO at normal temperature 2 A preparation method and application of a dual-function catalyst integrating trapping and low-temperature in-situ conversion. First, NO is prepared 3 ‑ Intercalation LDHs precursorBody containing CO 2 CO is realized by adding metal salt solution under gas atmosphere 2 In the form of CO 3 2‑ The trapping process stored between the alkali carbonate LDHs layers reduces the metal to obtain the catalyst. The catalyst is applied to a reaction device of an integrated technology, and interlayer CO 3 2‑ At H 2 The atmosphere is converted into a high added value product in situ. Cooling by a cooling device after the reaction, and continuously and selectively capturing CO in the raw material gas by the catalyst 2 Realize CO 2 The trapping and in-situ conversion are integrated. The process CO 2 The method has the advantages of high selectivity, mild reaction conditions, low energy consumption, high efficiency, reusable catalyst and suitability for CO in industrial waste gas such as flue gas 2 Capturing and utilizing; in addition, the device is simple, the occupied area is small, the process flow that heat is transferred to condensed water vapor can be realized in the cooling stage, and different industrial requirements are met.
Description
Technical Field
The invention relates to a method for preparing CO at normal temperature 2 A preparation method and application of a dual-function catalyst integrating trapping and low-temperature in-situ conversion.
Background
As is well known, numerous industrial processes such as boiler combustion, industrial kiln and stack exhaust gas emit a large amount of carbon dioxide so that the atmospheric concentration is continuously increased, and reduction of carbon dioxide emissions has become a problem that is in urgent need of various technical and policy solutions. The key point of carbon dioxide emission reduction is carbon dioxide capture, utilization and sequestration (CCUS). In order to improve the efficiency of the whole process and reduce the cost, the capture of the carbon dioxide and the hydrogenation can be combined to prepare the CO 2 The capturing-in-situ conversion integrated double-function catalyst converts carbon dioxide into other value-added products, and realizes the process of industrial gas emission and reutilization.
The bifunctional catalyst with more use at present uses a calcium-based adsorbent as CO 2 The carrier captures CO at 600 DEG C 2 Product CaCO 3 Pyrolysis releases gas at 900 ℃ with a large temperature difference, so thatThe process flow is complicated and more energy is required to change the temperature. Document 1 in Integrated CO 2 capture and conversion as an efficient process for fuels from greenhouse acs catalyst, 2018,8:2815-2823 Ni/MgO-Al is used 2 O 3 Catalyst and CaO adsorbent, direct CO conversion 2 By integration into CO 2 In capture, CO is allowed to be captured 2 Complete conversion. But the temperature in the capture experiment is still up to 800 ℃, and the synthesis of materials is divided into the synthesis of dry reforming catalyst and the synthesis of catalyst and CO 2 The mixing of the trapping adsorbent in two separate steps is relatively complex.
On the basis, develop the proper CO 2 The preparation method and the application of the trapping-low temperature in-situ conversion integrated bifunctional catalyst have very important effects on simplifying the process flow and reducing the energy input.
Hydrotalcite is layered double hydroxide (Layered double Hydroxides, abbreviated LDHs), is a novel inorganic functional material, and is used for preparing CO 3 2- The ion shows stronger affinity and has excellent CO in a solution environment 2 The capturing and enriching capacity is a basic carbonate. By utilizing the characteristic of LDHs basic carbonate and the interlayer CO thereof 3 2- Can be used as carbon source to solve the problem of CO in catalytic reaction 2 Is a problem of in situ capture and conversion. CO by LDHs 2 The catalyst can directly stir in the air to selectively absorb CO in the air 2 Interlayer CO is carried out 3 2- The energy consumption is reduced, and the aim of repeated use can be fulfilled.
The bifunctional catalyst of the invention has higher CO at normal temperature 2 The capturing capacity, while most flue gas discharged by industrial combustion has a certain temperature, the technology can be further combined with a cooling device to realize technology continuity in order to avoid consuming more energy. And (3) introducing condensed water, and transferring heat in the flue gas to the condensed water based on high-temperature heat energy contained in the flue gas, so that the temperature of the flue gas is rapidly reduced, and the condensed water is gradually heated and converted into water vapor to realize a cooling process.
Therefore, the hydrotalcite is selected as a precursor, and the metal-loaded dual-functional catalyst for preparing the basic carbonate finishes the normal-temperature CO in a flowing reaction system 2 The trapping-low temperature in-situ conversion integrated reaction ensures CO 2 Is converted into other chemical products (methane, methanol, CO and other gases) with high added value. Firstly, the dual-function catalyst is utilized to perform in-situ conversion aiming at the emission of flue gas, the reacted catalyst enters a cooling process to generate water vapor, and the cooled catalyst enters an adsorption capturing process to be recycled, so that the reutilization of industrial emission and the efficient utilization of resources are realized. The whole method and the device have simple design and CO 2 Provides a new idea and direction for capturing, utilizing and sealing (CCUS) industrial carbon dioxide; and simultaneously, the conversion process of condensed water to water vapor is combined, so that more possibilities are provided for energy utilization and recovery.
Disclosure of Invention
The invention aims to provide a method for preparing CO at normal temperature 2 A preparation method and application of a dual-function catalyst integrating trapping and low-temperature in-situ conversion.
The chemical formula of the catalyst prepared by the invention is N/CO 3 2- -M 2+ M 3+ LDHs, wherein N represents noble metals Pt, pd, ru; m is M 2+ Is Mg 2+ 、Zn 2+ 、Co 2+ 、Cu 2+ One or two of the following components; m is M 3+ Is Al 3+ 、Fe 3+ 、Ga 3+ One of the following; m is M 2+ ：M 3+ The molar ratio of (2) to (4) to (1); compared with the prior art, the catalyst is used for selectively capturing CO in industrial waste gas such as lime kiln gas, ammonia production hydrogen production byproduct gas, flue gas and the like 2 And under the temperature condition of 100-300 ℃ under H 2 Conversion in situ in atmosphere to high value added product CH 4 Wherein the bifunctional catalyst of the present invention is used for CO under normal temperature conditions 2 The capture capacity of the catalyst reaches 1.023-1.543 mmol/g; in the reaction process, the carbonate radical between LDHs nano-sheets is continuously consumed and converted into a reduction product CH at low temperature 4 Can selectively absorb CO in the mixed atmosphere after the reaction 2 Conversion to interlaminar CO 3 2- Recovering, and repeating for multiple times to realize CO 2 The trapping and in-situ conversion are integrated.
The invention provides a method for preparing CO at normal temperature 2 The preparation method of the trapping-low temperature in-situ conversion integrated bifunctional catalyst comprises the following specific preparation steps:
A. will be soluble M 2+ 、M 3+ Dissolving nitrate in CO 2 Preparing mixed solution A, M in deionized water 2+ ：M 3+ The molar ratio of (2) to (4) to (1), M 2+ And M 3+ The total ion concentration is 0.45mol/L to 0.75mol/L;
said M 2+ Is Mg 2+ 、Zn 2+ 、Co 2+ 、Cu 2+ One or two of the following components; m is M 3+ Is Al 3+ 、Fe 3+ 、Ga 3+ One of the following;
B. CO removal by alkali dissolution 2 Preparing a precipitant solution B in deionized water, wherein the alkali is NaOH or KOH and is alkali-soluble
The concentration of the liquid is 0.375 mol/L-1.25 mol/L;
C. adding not more than 1/3 of the volume of the container to the reactor to remove CO 2 Deionized water of N 2 Dripping the solution A and the solution B with equal volumes into a reactor under the atmosphere, and keeping the pH of the solution between 9 and 11 in the titration process to obtain the hydrotalcite precursor
A body, denoted NO 3 - -M 2+ M 3+ -LDHs；
D. Placing the hydrotalcite precursor solution obtained in the step C under an air atmosphere, dropwise adding another metal N salt solution into the solution, wherein the addition amount of the metal N salt solution is such that the mass ratio of the metal N to the LDHs in the final catalyst is 1-5%, and stirring for 1-2 h; adding NaBH 4 Liquid phase reduction of metal N, naBH 4 The molar quantity of the added solution is 5 times of that of the added metal N salt, the solution is stirred for 1 to 2 hours, the obtained solution is filtered, the solution is washed to be neutral by deionized water, and the solid is placed in a freeze dryer for vacuum drying for 24 hours to obtain CO loaded with the metal N 3 2- Intercalated hydrotalcite, denoted N/CO 3 2- -M 2+ M 3+ -LDHs；
The metal N salt is H 2 PtCl 4 、Na 2 PdCl 4 、RuCl 3 ·3H 2 And one of the O, wherein the metal N salt load is the mass percentage of N salt in the catalyst.
The invention provides a method for preparing CO at normal temperature 2 The double-function catalyst integrating trapping and low-temperature in-situ conversion can continuously complete the carbon dioxide trapping and converting process and the cooling process in industrial waste gas such as lime kiln gas, ammonia production hydrogen production byproduct gas, flue gas and the like in a reactor. The catalyst application specific process comprises three stages; (1) adsorption capture stage: the dual-function catalyst is used for preparing CO in raw material gas 2 Selective capture of CO 2 In the form of CO 3 2- Form storage between LDHs layers; (2) gasification reaction stage: interlaminar CO 3 2- At H 2 In-situ conversion to high value-added product CH by consumption in atmosphere 4 The method comprises the steps of carrying out a first treatment on the surface of the (3) cooling stage: after the temperature is reduced by the cooling device, the catalyst can continuously selectively capture CO in the raw material gas in the reactor 2 Conversion to CO 3 2- Realize CO 2 The trapping-in-situ conversion is integrated, and heat transfer to condensed water is realized to generate steam.
The invention also provides a double-function catalyst for normal temperature CO 2 The device is characterized in that the device is an integrated reactor device for trapping and low-temperature in-situ conversion, an exhaust port is arranged at the upper part of the reactor, a reaction medium and a condensate water reflux device are filled in the reactor, and a raw material gas inlet, a hydrogen device and a gas purging port are arranged at the bottom of the reactor.
CO in the flue gas 2 Before adsorption and capture, cooling the flue gas, introducing condensed water to cool down to complete the capture process, and then opening a hydrogen device and feeding raw gas into a reactor at the same time to generate CO 2 In situ conversion reaction process. The catalyst after reaction can enter a cooling process again, and the cooled catalyst enters an adsorption capturing process for recycling.
Normal temperature CO 2 The application process of the trapping-low temperature in-situ conversion integrated bifunctional catalyst is characterized by comprising the following steps ofThe application under flue gas atmosphere was simulated according to the following steps:
(1) N/CO 3 2- -M 2+ M 3+ The LDHs catalyst alkali carbonate and quartz sand are uniformly mixed and are filled into a steel tube reactor as a reaction medium;
(2) The air in the reactor was purged with an inert gas stream, followed by 0.1MPa 15% CO in the reactor 2 +85％N 2 Simulation of flue gas and H 2 Sealing the mixed gas, circulating the gas flow by using a peristaltic pump, wherein the temperature of the flue gas is the reaction temperature, and reacting at constant temperature for 2-2.5 h;
(3) After the reaction, a cooling device is opened to be filled with condensed water for cooling, and CO in the raw material gas is cooled under the condition of the existence of water vapor 2 Selective capture of CO 2 In the form of CO 3 2- Is stored between the alkali carbonate LDHs layers and used in the next reaction.
The product obtained in the above steps is characterized as follows:
FIG. 1 is an XRD spectrum of a sample obtained in the above step, and a synthesized catalyst having characteristic peaks of LDHs shows successful synthesis of CO 3 2- The diffraction peak positions of (003), (006) and (009) of the MgAl-LDHs are not changed after the metal Pt is loaded, and obvious characteristic diffraction peaks of obvious Pt particles are not observed, which indicates that the crystal structure type and interlayer spacing of the LDHs are not changed obviously after the metal Pt is loaded.
Fig. 2 is a diagram showing that after analyzing the morphology of a sample and loading Pt on a laminate by a liquid phase reduction method, the LDHs laminate structure is still maintained, which lays a foundation for carbon dioxide capturing and conversion.
FIG. 3 is a graph showing the variation of catalyst performance with temperature, showing that in pure H 2 The LDHs-based dual-function material under the atmosphere can realize the in-situ reduction of the interlaminar carbonate radical at the low temperature of 100-300 ℃, and the main hydrogenation product is CH 4 It is noted that the yield of the hydrogenation product of the catalyst in the reaction temperature interval exhibits a volcanic-type curve, wherein the hydrogenation performance is optimal at 180-280 ℃.
FIG. 4 is a catalyst addition CO 2 Mixture gas (15% CO) 2 +85％N 2 、15％CO 2 +85％N 2 +200ppm NO 2 、15％CO 2 +85％N 2 +200ppm SO 2 ) CO in the presence of steam 2 The capturing reaction shows that under the mixed gas containing nitrogen oxide or sulfur oxide, the catalyst can still selectively capture CO at the reaction temperature 2 The selectivity is more than 97 percent, and NO 2 Atmosphere for CO 2 The selectivity of capture has little effect.
FIG. 5 is Pt/CO 3 2- The MgAl-LDHs catalyst has 5 repeated use performances, and the result shows that the catalyst still has better stability after five repeated use.
The invention has the beneficial effects that:
1. the invention is normal temperature CO 2 The trapping-low temperature in-situ conversion integrated bifunctional catalyst utilizes the characteristics of LDHs basic carbonate and NO among LDHs 3 - Capable of adsorbing CO in air 2 The catalyst can be supplemented with carbon source from air, can be recovered in air, achieves the aim of repeated use for multiple times, has high selectivity, reduces carbon emission, and realizes CO 2 And (5) recycling.
2. The invention provides a normal temperature CO 2 Method and application of trapping-low temperature in-situ conversion integrated bifunctional catalyst, and can be applied to selectively trapping CO in industrial waste gases such as lime kiln gas, ammonia production hydrogen production byproduct gas, flue gas and the like 2 And under the temperature condition of 100-300 ℃ under H 2 Conversion in situ in atmosphere to high value added product CH 4 Not only can realize CO with high efficiency 2 The trapping and the utilization of the catalyst, the temperature in the reaction process is greatly reduced, and the energy consumption is lower than that of the traditional CO 2 The trapping technology is beneficial to reducing the cost and investment.
3. The integrated design of the invention has small occupied area, simple working procedure and small loss, and converts the waste gas generated in the industrial production process, wherein the cooling process can realize the process flow that heat is transferred to condensed water vapor, thereby improving the energy utilization efficiency and meeting the manufacturing requirements of different industries.
Drawings
Fig. 1 is an XRD spectrum of the sample in example 1.
Fig. 2 is a HRTEM photograph of the catalyst prepared in example 1.
FIG. 3 shows the catalyst prepared in example 1 under the conditions of application example in pure H 2 Catalytic properties obtained at different temperatures under an atmosphere.
FIG. 4 shows the catalyst prepared in example 1 under the conditions of the application example in CO 2 CO obtained under mixed gas 2 Selectivity of capture. .
FIG. 5 shows the reusability of the catalyst prepared in example 1 according to the conditions of the application example
FIG. 6 is a graph of ambient CO 2 And (3) an application device diagram of the trapping-low-temperature in-situ conversion integrated technology.
Detailed Description
Example 1
A, 0.0135mol of Mg (NO 3 ) 2 ·6H 2 O solid and 0.0045mol of Al (NO) 3 ) 3 ·9H 2 O solid, three salts were dissolved in a beaker containing 100mL of deionized water to prepare a mixed solution A.
And B, weighing 0.045mol of NaOH solid, and dissolving the solid in a beaker containing 100ml of deionized water to prepare a mixed solution B.
Synthesizing MgAl-LDHs by coprecipitation method, adding 100mL deionized water into a three-neck flask, adding N into the mixture 2 The two solutions of step A, B were dropped into a 500mL flask under an atmosphere to give a hydrotalcite precursor, denoted as NO 3 - -MgAl-LDHs；
D, placing the hydrotalcite precursor obtained in the step C under an air atmosphere, and dropwise adding 1.44mL, 50mmol/L H into the solution 2 PtCl 4 Stirring for 1 h; weigh 5 times mole of NaBH 4 Liquid phase reduction stirring of metal for 1h, filtering the obtained solution, washing with deionized water until the supernatant becomes neutral, vacuum drying the solid in a freeze dryer for 24h to obtain Pt-loaded materialCO 3 2- Intercalated hydrotalcite, denoted Pt/CO 3 2- -MgAl-LDHs。
Example 2
A, 0.027mol of Zn (NO) is weighed 3 ) 2 ·6H 2 O solid and 0.009mol Ga (NO) 3 ) 3 ·9H 2 O solid, three salts were dissolved in a beaker containing 100mL of deionized water to prepare a mixed solution A.
And B, weighing 0.045mol of NaOH solid, and dissolving the solid in a beaker containing 100ml of deionized water to prepare a mixed solution B.
Synthesizing ZnGa-LDHs by coprecipitation method, adding 100mL deionized water into a three-neck flask, adding N into the mixture 2 The two solutions of step A, B were dropped into a 500mL flask under an atmosphere to give a hydrotalcite precursor, denoted as NO 3 - -ZnGa-LDHs；
D, placing the hydrotalcite precursor obtained in the step C under an air atmosphere, and dropwise adding 1.13mL, 50mmol/L RuCl into the solution 3 ·3H 2 O, stirring for 1 h; weigh 5 times mole of NaBH 4 Liquid phase reduction stirring of metal for 1h, filtering the obtained solution, washing with deionized water until the supernatant is neutral, vacuum drying the solid in a freeze dryer for 24h to obtain Ru-loaded CO 3 2- Intercalated hydrotalcite, denoted Ru/CO 3 2- -ZnGa-LDHs。
Example 3
A, 0.001mol of Co (NO) 3 ) 2 ·6H 2 O solid, 0.001mol of Mg (NO 3 ) 2 ·6H 2 O solid and 0.001mol of Al (NO) 3 ) 3 ·9H 2 O solid. Three salts were dissolved in a beaker containing 100mL of deionized water to prepare a mixed solution a.
And B, weighing 0.064mol of NaOH solid, and dissolving the solid in a beaker containing 100ml of deionized water to prepare a mixed solution B.
C, synthesizing CoMgAl-LDHs by a coprecipitation method, adding 100mL of deionized water into a three-neck flask, and adding N into the three-neck flask 2 Dropping the two solutions in the step A, B into a 500mL flask under the atmosphere to obtain a hydrotalcite precursorRepresented by NO 3 - -CoMgAl-LDHs；
D, placing the hydrotalcite precursor obtained in the step C under an air atmosphere, and dropwise adding 1.13mL, 50mmol/L Na into the solution 2 PdCl 4 Stirring for 1 h; weigh 5 times mole of NaBH 4 Liquid phase reduction stirring of metal for 1h, filtering the obtained solution, washing with deionized water until the supernatant is neutral, vacuum drying the solid in a freeze dryer for 24h to obtain Pd-loaded CO 3 2- Intercalated hydrotalcite, denoted Pd/CO 3 2- -CoMgAl-LDHs。
Example 4
A, 0.01mol of Cu (NO) is weighed 3 ) 2 ·6H 2 O solid, 0.005mol of Mg (NO 3 ) 2 ·6H 2 O solid and 0.005mol of Fe (NO) 3 ) 3 ·9H 2 O solid. Three salts were dissolved in a beaker containing 100mL of deionized water to prepare a mixed solution a.
And B, weighing 1.8NaOH solid, and dissolving the solid in a beaker containing 100ml of deionized water to prepare a mixed solution B.
C, synthesizing CuMgFe-LDHs by using a coprecipitation method, adding 100mL of deionized water into a three-neck flask, and adding N into the three-neck flask 2 The two solutions in step A, B were dropped into a 500mL flask under an atmosphere to obtain NO 3 - The CuMgAl-LDHs precursor is placed in air atmosphere, and is stirred for 1 hour, and the CO is obtained through centrifugation, washing, drying and grinding 3 2- -CuMgFe-LDHs。
D, weighing 0.300g of the catalyst obtained in the step C, dissolving in a beaker containing 30.0mL of deionized water, and adding 1.13mL of 50mmol/L Na 2 PdCl 4 Is reduced for 30min under the light intensity condition of 300W after being stirred for 1h, the obtained solution is filtered, the supernatant is washed by deionized water to be neutral, and the solid is put into a freeze dryer for hollow drying for 24h to obtain Pd-loaded CO 3 2- Intercalated hydrotalcite, denoted Pd/CO 3 2- -CuMgFe-LDHs。
Application example 1
The catalysts prepared in examples 1 to 4 were used separatelyAmbient temperature CO 2 In the trapping-low temperature in-situ conversion integrated reaction:
the reaction conditions are as follows: mixing 0.2000g of catalyst powder with 1.8000g of quartz sand with particle size of 40-70 meshes, filling the mixture into the middle section of a reactor, introducing inert gas to replace air in a device, and then introducing H with 0.1MPa into the reactor 2 The mixed gas is sealed, the temperature is raised to the reaction temperature (100-300 ℃) at the heating rate of 10 ℃/min, and the peristaltic pump is utilized to circulate the air flow. After the reaction was started, 1mL of gas was injected into the gas chromatograph with a stainless steel airtight needle every 1 hour, and the concentration of the product in the gas was measured to evaluate the catalyst reactivity.
After completion of the reaction, N is used 2 Purifying the reaction system, and introducing CO of 0.1MPa 2 Mixture gas (15% CO) 2 +85％N 2 、15％CO 2 +85％N 2 +200ppm NO 2 、15％CO 2 +85％N 2 +200ppm SO 2 ) CO in the presence of steam 2 The capture reaction was continued for 10h. Repeating the steps to perform in-situ conversion reaction after capturing.
The bifunctional materials obtained in accordance with examples 1 to 4 were used for ambient temperature CO 2 In the trapping-low temperature in-situ conversion integrated reaction, the result is shown in table 1, and as can be seen from table 1, the dual-function catalyst basic carbonate of the invention is used for converting CO 2 The capture capacity of the catalyst is 1.023-1.543 mmol/g, and the catalyst is pure H at low temperature 2 For CH under atmosphere 4 Has higher selectivity and captures CO 2 Can be efficiently converted into CH 4 Further achieving carbon dioxide capture, utilization and sequestration (CCUS) reactions under mild conditions.
TABLE 1
Claims (4)
1. For normal temperature CO 2 The preparation method of the trapping-low temperature in-situ conversion integrated bifunctional catalyst is characterized by comprising the following steps:
a, dissolving the soluble metal salt M 2+ And M 3+ Dissolving in the CO to remove 2 Preparing a mixed solution A in deionized water, wherein the soluble metal salt refers to M 2+ 、M 3+ Nitrate salt, M 2+ Is Mg 2+ 、Zn 2+ 、Co 2+ 、Cu 2+ One or two of the following components; m is M 3+ Is Al 3+ 、Fe 3+ 、Ga 3+ One of the following; m is M 2+ ：M 3+ The molar ratio of (2) to (4) to (1); m is M 2+ And M 3+ The total ion concentration is 0.45mol/L to 0.75mol/L;
b, dissolving with alkali to remove CO 2 Preparing a precipitant solution B in deionized water, wherein the alkali is NaOH or KOH, and the concentration of the alkali solution is 0.375 mol/L-1.25 mol/L;
adding not more than 1/3 of the volume of the container into the reactor to remove CO 2 Deionized water of N 2 Dropping the solution A and the solution B with equal volumes into a reactor under the atmosphere, and keeping the pH of the solution between 9 and 11 in the titration process to obtain hydrotalcite precursor expressed as NO 3 - -M 2+ M 3+ -LDHs；
D, placing the hydrotalcite precursor solution obtained in the step C in an air atmosphere, dropwise adding another metal N salt solution into the hydrotalcite precursor solution, wherein the addition amount of the metal N salt solution is such that the mass ratio of the metal N to the LDHs in the final catalyst is 1-5%, and stirring for 1-2 h; adding NaBH 4 Liquid phase reduction of metal N, naBH 4 The molar quantity of the added solution is 5 times of that of the added metal N salt, the solution is stirred for 1 to 2 hours, the obtained solution is filtered, the solution is washed to be neutral by deionized water, and the solid is placed in a freeze dryer for vacuum drying for 24 hours to obtain CO loaded with the metal N 3 2- Intercalated hydrotalcite, denoted N/CO 3 2- -M 2+ M 3+ -LDHs；
The metal N salt is H 2 PtCl 4 、Na 2 PdCl 4 、RuCl 3 ·3H 2 One of O.
2. A bifunctional catalyst prepared by the process of claim 1, whereinThe catalyst is used for selectively capturing CO in industrial waste gas such as lime kiln gas, ammonia production hydrogen production byproduct gas, flue gas and the like 2 And under the temperature condition of 100-300 ℃ under H 2 Conversion in situ in atmosphere to high value added product CH 4 Wherein the bifunctional catalyst of the present invention is used for CO under normal temperature conditions 2 The capture capacity of the catalyst reaches 1.023-1.543 mmol/g.
3. Use of a bifunctional catalyst according to claim 2, characterized in that the catalyst application process comprises three stages; (1) adsorption capture stage: the dual-function catalyst is used for preparing CO in raw material gas 2 Selective capture of CO 2 In the form of CO 3 2- Form storage between LDHs layers; (2) gasification reaction stage: interlaminar CO 3 2- At H 2 In-situ conversion to high value-added product CH by consumption in atmosphere 4 The method comprises the steps of carrying out a first treatment on the surface of the (3) cooling stage: after the temperature is reduced by the cooling device, the catalyst can continuously selectively capture CO in the raw material gas in the reactor 2 Conversion to CO 3 2- Realize CO 2 The trapping-in-situ conversion is integrated, and meanwhile, heat transfer to condensed water is realized to generate steam;
provides a double-function catalyst for normal temperature CO 2 The device comprises a trapping-low-temperature in-situ conversion integrated reactor device, wherein an exhaust port is arranged at the upper part of the reactor, a reaction medium and a condensate water reflux device are filled in the reactor, and a raw material gas inlet, a hydrogen device and a gas purging port are arranged at the bottom of the reactor;
CO in the flue gas 2 Before adsorption and capture, cooling the flue gas, introducing condensed water to cool down to complete the capture process, and then opening a hydrogen device and feeding raw gas into a reactor at the same time to generate CO 2 An in-situ conversion reaction process; the catalyst after reaction enters a cooling process again, and the cooled catalyst enters an adsorption capturing process for recycling.
4. Use according to claim 3, characterized in that it is applied under simulated flue gas atmosphere according to the following steps:
(1) N/CO 3 2- -M 2+ M 3+ The LDHs catalyst alkali carbonate and quartz sand are uniformly mixed and are filled into a reactor as a reaction medium;
(2) The air in the reactor was purged with an inert gas stream, followed by 0.1MPa 15% CO in the reactor 2 +85％N 2 Simulation of flue gas and H 2 Sealing the mixed gas, circulating the gas flow by using a peristaltic pump, wherein the temperature of the flue gas is the reaction temperature, and reacting at constant temperature for 2-2.5 h;
(3) After the reaction, a cooling device is opened to be filled with condensed water for cooling, and CO in the raw material gas is cooled under the condition of the existence of water vapor 2 Selective capture of CO 2 In the form of CO 3 2- Is stored between the alkali carbonate LDHs layers and used in the next reaction.
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