CN111450832A - Microwave-assisted coprecipitation preparation of CaO modified Ni-Al2O3Method and application of catalyst - Google Patents

Microwave-assisted coprecipitation preparation of CaO modified Ni-Al2O3Method and application of catalyst Download PDF

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CN111450832A
CN111450832A CN202010402381.1A CN202010402381A CN111450832A CN 111450832 A CN111450832 A CN 111450832A CN 202010402381 A CN202010402381 A CN 202010402381A CN 111450832 A CN111450832 A CN 111450832A
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宋夫交
许琦
岳仁亮
吴傲立
齐丛亮
曹燕
杨百忍
严金龙
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Yancheng Institute of Technology
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Abstract

The invention discloses a microwave-assisted coprecipitation method for preparing CaO modified Ni-Al2O3A method for preparing the catalyst and application thereof. The method comprises the following steps of adding CaCl2、Ni(NO3)2·6H2O、NaOH、Al2O3Mixing with PVP, adding deionized water, stirring, transferring toA 100 m L reaction kettle, placing the kettle in a microwave reactor, setting the microwave power at 400-600W and the temperature at 80-120 ℃, carrying out constant temperature reaction for 10-30 min under the autogenous pressure of the kettle, and after the kettle is cooled, carrying out centrifugation, drying, calcination and H2Reduction and the like to obtain Ni/CaO-Al2O3A catalyst; the invention solves the problem of longer reaction time when the catalyst is prepared by a common coprecipitation method, improves the problem of uneven dispersion of the active component Ni and the adsorption auxiliary agent CaO, and can effectively improve the CO content of the catalyst2Selective adsorption and its activity in catalytic hydrogenation reactions.

Description

Microwave-assisted coprecipitation preparation of CaO modified Ni-Al2O3Method and application of catalyst
Technical Field
The invention belongs to CO2The technical field of catalytic hydrogenation, in particular to a microwave-assisted coprecipitation method for preparing CaO modified Ni-Al2O3A method for preparing the catalyst and application thereof.
Background
In recent years, various techniques have been used to study the reduction of CO produced by the combustion of fossil fuels2And (5) discharging. Considering that hydrogen is an energy source that can be produced by renewable energy sources such as solar energy, CO is added2The catalytic hydrogenation after the capture becomes a research hotspot, and the development of a catalyst with higher activity, stability and low price is the key for realizing the industrialization of the catalyst. Among the numerous non-noble metal catalysts, Ni-Al2O3Catalysts are commonly used for CO2In the reaction of preparing methane by hydrogenation, Ni is used as an active center and has the advantages of higher activity, carbon deposition resistance, low price and the like, and Al2O3As a catalyst carrier, the catalyst carrier has the advantages of high mechanical strength, good thermal stability and the like, but the catalytic performance of the catalyst carrier cannot meet the industrial application.
In CO2In the reaction of preparing methane by hydrogenation, whether the catalyst can react with CO or not2Is effectively identified and fixed as oneA very critical issue. Metal pair CO of Ni and the like2All show certain adsorption performance, however, the adsorption performance to CO2Has a limited adsorption capacity by strengthening CO2Adsorption to promote CO2The effect of hydrogenation is greatly limited. If a suitable adsorbent can be found for CO2Selective identification and adsorption fixation are carried out, a catalyst with adsorption, activation and catalytic hydroconversion is constructed, and CO is developed2A novel series reaction of adsorption and catalytic conversion is then CO2The catalytic hydrogenation methane preparation method brings a new idea. Research finds that the alkaline earth metal absorbent CaO has high CO2Adsorption capacity, CaCO, the carbonated reaction product thereof3The decomposition temperature of (C) is influenced by the particle size thereof, if CaO can be loaded to Ni-Al2O3In the catalyst, the selective regulation and control of the particle sizes of the active component Ni and the adsorption additive CaO are realized, and the catalyst with high CO content can be prepared2The catalyst with adsorption capacity and methanation performance is a key problem to find a method for preparing an active component Ni and an adsorption additive CaO with controllable particle size.
The coprecipitation method is a method of preparing a solid product by simultaneously precipitating by using a precipitant and two or more metal salt solutions, is commonly used for preparing a multi-component catalyst, and can also be used for loading one or more active components. The better dispersibility and uniformity are the most advantages compared with other methods such as an immersion method, and the addition of the precipitating agent can cause the local concentration of the solution to be too high, generate agglomeration and influence the dispersibility and uniformity. The early researches show that the high-frequency transformation energy field generated by the microwave can change the molecule from the non-motion state to the ordered high-frequency motion state, and can effectively improve the uniform distribution of the metal salt on the surface of the carrier when the active component is loaded, thereby obtaining the catalyst with high dispersibility. Meanwhile, the microwave technology converts molecular kinetic energy into heat energy to achieve the purpose of heating, and the unique heating mode can greatly shorten the time of coprecipitation reaction.
Application number CN201911051174.X discloses a method for rapidly synthesizing Ni-based catalyst Ni/CaO-CeO by directly heating wet gel through microwave calcination method2Or Ni/CaO-L a2O3The preparation method comprises the following steps: s1, adding cerium nitrate or lanthanum nitrate, calcium nitrate and nickel nitrate into deionized water, stirring until the cerium nitrate or the lanthanum nitrate, the calcium nitrate and the nickel nitrate are completely dissolved, then adding citric acid into the mixed solution, and stirring until the citric acid is completely dissolved; s2, placing the solution obtained in the step (1) in a water bath at the temperature of 75-85 ℃ and heating for 4-5h to obtain wet gel; s3, calcining the wet gel obtained in the step (2) in a microwave muffle furnace at the temperature of 850 ℃ under the microwave condition of 800-2Or Ni/CaO-L a2O3Wherein the content of Ni is 8-20%, CeO2Or L a2O3The content is 5-15%, and the content of CaO is 87-65%; the catalyst prepared by the invention has better catalytic activity and stability for reforming ethanol to prepare hydrogen at medium and low temperature, and compared with the catalyst prepared by the traditional muffle furnace calcination method, the catalyst prepared by the method has short synthesis time and low energy consumption, thereby greatly reducing the production cost and opening up a new way for the industrial process of the alcohol reforming hydrogen preparation catalyst.
Application number CN201510406209.2 discloses a preparation method of a microwave heating synthesis catalyst and a method for synthesizing cyclohexylamine by a one-step method based on the catalyst prepared by the preparation method, and the preparation method of the catalyst is characterized by comprising the following steps: a. putting the carrier into a nickel salt solution, uniformly mixing, and stirring and reacting for 0.5-2 hours by adopting microwave heating; b. heating and evaporating the water in the carrier and the nickel salt solution system to dryness, grinding, drying by microwave, and roasting for 3-5 h at 350-400 ℃; c. and reducing the roasted powder for 2-4 h at 300-450 ℃ in a hydrogen atmosphere to obtain a supported nickel-based hydrogenation catalyst, and then using the supported nickel-based hydrogenation catalyst for catalytic synthesis of cyclohexylamine. The invention selects cheap nickel as the active component, and has the advantages of simple preparation method, low cost, simple and convenient catalyst recycling and long catalyst service life.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing CaO modified Ni-Al by microwave-assisted coprecipitation2O3The method and application of the catalyst solve the problems of long reaction time, no dispersion of the active component Ni and the adsorption auxiliary agent CaO existing in the prior coprecipitation methodThe uniformity problem is an efficient preparation method, and the CO content of the catalyst can be effectively improved2Selective adsorption and its activity in catalytic hydrogenation reactions.
In order to achieve the purpose, the invention adopts the technical scheme that:
microwave-assisted coprecipitation preparation of CaO modified Ni-Al2O3A process for the preparation of a catalyst comprising the steps of:
step 1, adding CaCl2、Ni(NO3)2·6H2O、NaOH、γ-Al2O3Mixing with PVP, adding deionized water, stirring uniformly, ensuring that all groups of materials are fully dissolved, transferring to a 100 m L polytetrafluoroethylene lining, and spin-sealing a cover;
step 2, transferring the reaction kettle in the step 1 into a microwave reactor, setting the microwave power to be 400-600W and the temperature to be 80-120 ℃, and carrying out constant-temperature reaction for 10-30 min under the autogenous pressure of the reaction kettle;
step 3, cooling the product in the step 2 to room temperature, centrifuging and drying the product, and calcining the product at the temperature of 400-2O3；
Step 4, the precursor obtained in the step 3 is put in H2/N2Reducing in mixed atmosphere at 400 ℃ to obtain Ni/CaO-Al2O3A catalyst.
As a modification, Ni (NO) in the step 13)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O310 to 30 weight percent of CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing 5-15 wt%, pouring into a polytetrafluoroethylene reaction kettle with a pressure sensor inside, adding a solution with the concentration of PVP being 0.1 mol/L and the concentration of 50 m L NaOH being 2 mol/L, and then stirring for 10 min by magnetic force to fully dissolve.
The improvement is that the pressure in the kettle is controlled to be less than or equal to 10 MPa in the microwave reaction process in the step 2.
The improvement is that the reduction time in the step 4 is 40-60 min, and the mixture is mixedH in the gas2And N2Is 2: 3.
CaO modified Ni-Al prepared by the method2O3Catalyst for adsorbing and catalyzing CO2The application of (1).
As an improvement, when the loading amounts of Ni and CaO are 0.2 and 0.15 respectively, CO is catalyzed2When the conversion rate in the hydrogenation reaction reaches 50%, the corresponding temperature is 218 ℃.
Has the advantages that:
compared with the prior art, the CaO modified Ni-Al prepared by microwave-assisted coprecipitation2O3The catalyst is prepared by adopting a coprecipitation method assisted by a microwave reactor and adding a PVP dispersing agent, and the load time of Ni and CaO in the coprecipitation method is reduced through the synergistic effect of the two. The surface active agent polyvinylpyrrolidone (PVP) is adopted to improve the dispersibility of the active component Ni and the adsorption additive CaO on the surface of the carrier, and deionized water with higher dielectric loss factor () is selected as a reaction solvent, thereby being beneficial to microwave heating. Compared with a coprecipitation method, the method shortens the reaction time and effectively improves the Ni/CaO-Al2O3Catalyst pair CO2Selective adsorption and its activity in catalytic hydrogenation reactions.
Drawings
FIG. 1 shows Ni/CaO-Al prepared by different methods2O3SEM topography of catalyst, wherein (a) is Ni0.2/CaO0.10/Al2O3-MC, (b) is Ni0.2/CaO0.10/Al2O3-CP。
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
Microwave-assisted coprecipitation preparation of CaO modified Ni-Al2O3A process for the preparation of a catalyst comprising the steps of:
(1) mixing Ni (NO)3)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O3= 20 wt% mixing, CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing the components by weight percentage of 5 percent, adding a solution with the concentration of PVP being 0.1 mol/L and the concentration of NaOH being 2 mol/L and 50 m of L, then magnetically stirring the solution for 10 min to fully dissolve the solution, transferring the solution to a polytetrafluoroethylene lining with a pressure sensor arranged inside, and spin tightly and seal a cover;
(2) checking whether a gasket in the reaction kettle is complete before the reaction kettle in the step (1) is transferred to a microwave reactor, setting the microwave power to be 500W and the temperature to be 100 ℃, carrying out constant-temperature reaction for 20min under the autogenous pressure, and controlling the pressure in the reaction kettle to be less than or equal to 10 MPa in the microwave reaction process;
(3) after the reaction in the step (2) is finished, after the temperature in the reaction kettle is cooled to room temperature, taking out the product from the reaction kettle, centrifuging the product for 3 times by using deionized water, drying the product, and calcining the product for 4 hours at 500 ℃ to obtain a precursor NiO/CaO-Al of the catalyst2O3；
(4) NiO/CaO-Al serving as the catalyst precursor obtained in the step (3)2O3At H2/N2(2/3, v/v) reducing for 50 min at 400 ℃ in mixed atmosphere to obtain Ni/CaO-Al2O3Catalyst, labelled Ni0.2/CaO0.05/Al2O3-MC, where "0.2" and "0.05" represent the loading of Ni and CaO, respectively, and "MC" represents the preparation by microwave-assisted co-precipitation.
Example 2
(1) Mixing Ni (NO)3)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O3= 20 wt% mixing, CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing the components by weight percent of the mixture, adding a solution with the concentration of PVP being 0.1 mol/L and the concentration of NaOH being 2 mol/L and 50 m of L, then magnetically stirring the mixture for 10 min to fully dissolve the mixture, transferring the mixture to a polytetrafluoroethylene lining with a pressure sensor arranged inside, and spin-sealing the cover;
(2) checking whether a gasket in the reaction kettle is complete before the reaction kettle in the step (1) is transferred to a microwave reactor, setting the microwave power to be 500W and the temperature to be 100 ℃, carrying out constant-temperature reaction for 20min under the autogenous pressure, and controlling the pressure in the reaction kettle to be less than or equal to 10 MPa in the microwave reaction process;
(3) after the reaction in the step (2) is finished, after the temperature in the reaction kettle is cooled to room temperature, taking out the product from the reaction kettle, centrifuging the product for 3 times by using deionized water, drying the product, and calcining the product for 4 hours at 500 ℃ to obtain a precursor NiO/CaO-Al of the catalyst2O3；
(4) NiO/CaO-Al serving as the catalyst precursor obtained in the step (3)2O3At H2/N2(2/3, v/v) reducing for 50 min at 400 ℃ in mixed atmosphere to obtain Ni/CaO-Al2O3Catalyst, labelled Ni0.2/CaO0.10/Al2O3-MC, where "0.2" and "0.10" represent the loading of Ni and CaO, respectively, and "MC" represents the preparation by microwave-assisted co-precipitation.
Example 3
(1) Mixing Ni (NO)3)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O3= 20 wt% mixing, CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing the components in an amount of not less than 15 wt%, adding a solution of 50 m L NaOH of 2 mol/L and PVP concentration of 0.1 mol/L, magnetically stirring for 10 min to dissolve the components completely, transferring the solution to a polytetrafluoroethylene lining with a pressure sensor inside, and spin-sealing the lid tightly;
(2) checking whether a gasket in the reaction kettle is complete before the reaction kettle in the step (1) is transferred to a microwave reactor, setting the microwave power to be 500W and the temperature to be 100 ℃, carrying out constant-temperature reaction for 20min under the autogenous pressure, and controlling the pressure in the reaction kettle to be less than or equal to 10 MPa in the microwave reaction process;
(3) after the reaction in the step (2) is finished, after the temperature in the reaction kettle is cooled to room temperature, taking out the product from the reaction kettle, centrifuging the product for 3 times by using deionized water, drying the product, and calcining the product for 4 hours at 500 ℃ to obtain a precursor NiO/CaO-Al of the catalyst2O3；
(4) NiO/CaO-Al serving as the catalyst precursor obtained in the step (3)2O3At H2/N2(2/3, v/v) reducing for 50 min at 400 ℃ in mixed atmosphere to obtain Ni/CaO-Al2O3Catalyst, labelled Ni0.2/CaO0.05/Al2O3-MC, where "0.2" and "0.15" represent the loading of Ni and CaO, respectively, and "MC" represents the preparation by microwave-assisted co-precipitation.
Comparative example 1
(1) Mixing Ni (NO)3)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O3= 20 wt% mixing, CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing the components by weight percent of the mixture, adding a solution with the concentration of PVP being 0.1 mol/L and the concentration of NaOH being 2 mol/L and 50 m of L, then stirring the mixture by magnetic force for 10 min to fully dissolve the mixture, and transferring the mixture into a crucible;
(2) transferring the crucible in the step (1) into a constant-temperature water bath kettle, and continuously performing magnetic stirring for 8 hours at the temperature of 60 ℃;
(3) after the reaction in the step (2) is finished, centrifuging the sample in the crucible for 3 times by using deionized water, drying, and calcining at 500 ℃ for 4 hours to obtain a precursor NiO/CaO-Al of the catalyst2O；
(4) NiO/CaO-Al serving as the catalyst precursor obtained in the step (3)2O3At H2/N2(2/3, v/v) reducing for 50 min at 400 ℃ in mixed atmosphere to obtain Ni/CaO-Al2O3Catalyst, labelled Ni0.2/CaO0.05/Al2O3-CP, wherein "0.2" and "0.05" represent the loading of Ni and CaO, respectively, and "CP" represents the preparation by coprecipitation.
Comparative example 2
(1) Mixing Ni (NO)3)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O3= 20 wt% mixing, CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing the components by weight percent of = 10%, adding a solution with the concentration of PVP being 0.1 mol/L and 50 m of L NaOH being 2 mol/L, then stirring the solution by magnetic force for 10 min to fully dissolve the solution, and transferring the solution into a crucible;
(2) transferring the crucible in the step (1) into a constant-temperature water bath kettle, and continuously performing magnetic stirring for 8 hours at the temperature of 60 ℃;
(3) after the reaction in the step (2) is finished, centrifuging the sample in the crucible for 3 times by using deionized water, drying, and calcining at 500 ℃ for 4 hours to obtain a precursor NiO/CaO-Al of the catalyst2O；
(4) NiO/CaO-Al serving as the catalyst precursor obtained in the step (3)2O3At H2/N2(2/3, v/v) reducing for 50 min at 400 ℃ in mixed atmosphere to obtain Ni/CaO-Al2O3Catalyst, labelled Ni0.2/CaO0.05/Al2O3-CP, wherein "0.2" and "0.10" represent the loading of Ni and CaO, respectively, and "CP" represents the preparation by coprecipitation.
Comparative example 3
(1) Mixing Ni (NO)3)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O3= 20 wt% mixing, CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing the components by weight percent of = 15%, adding a solution with the concentration of PVP being 0.1 mol/L and 50 m of L NaOH being 2 mol/L, then stirring the solution by magnetic force for 10 min to fully dissolve the solution, and transferring the solution into a crucible;
(2) transferring the crucible in the step (1) into a constant-temperature water bath kettle, and continuously performing magnetic stirring for 8 hours at the temperature of 60 ℃;
(3) after the reaction in the step (2) is finished, centrifuging the sample in the crucible for 3 times by using deionized water, drying, and calcining at 500 ℃ for 4 hours to obtain a precursor NiO/CaO-Al of the catalyst2O；
(4) NiO/CaO-Al serving as the catalyst precursor obtained in the step (3)2O3At H2/N2(2/3, v/v) mixed atmosphere and reduction at 400 ℃ for 50 min to obtain Ni/CaO-Al2O3Catalyst, labelled Ni0.2/CaO0.05/Al2O3-CP, wherein "0.2" and "0.15" represent the loading of Ni and CaO, respectively, and "CP" represents the preparation by coprecipitation.
The catalyst is selected from Ni0.2/CaO0.10/Al2O3-MC and Ni0.2/CaO0.10/Al2O3-CP testing. Testing the apparent morphology of the catalyst by using a Field Emission Scanning Electron Microscope (FESEM); the average particle size of the Ni particles is obtained by performing particle size distribution statistics on Ni particles in a high power transmission electron microscope (HRTEM) picture; the dispersibility of the active component Ni is H as measured by Temperature Programmed Desorption (TPD)2Adsorption capacity, Ni mass percent and temperature programmed reduction (H)2-TPR) test, the reduction degree of the Ni component, etc; CO of catalyst2The performance of the hydrogenation methane preparation is tested on a fixed bed reactor, the inner diameter of the reactor is 5 mm, the loading amount of the catalyst is 1.0 g, and the reaction gas is H2: CO2: N290 m L/min mixed gas with the speed of 4: 1: 4 and the space velocity (GHSV) of 4200 m L/h gcat。
Average particle size and dispersity of Ni particles of catalyst prepared in above examples and application thereof in CO2The temperatures at which the conversion reached 50% in the hydrogenation reaction are shown in table 1:
TABLE 1 average particle size and dispersibility of Ni particles in catalyst and their use in CO2The temperature corresponding to the conversion rate of 50% in the hydrogenation reaction
Figure 651211DEST_PATH_IMAGE001
aTemperature corresponding to 50% conversion
As can be seen from Table 1, the average particle size of Ni particles of both catalysts increases with the CaO loading, the Ni dispersibility increases and then decreases with the CaO loading, and CO2When the conversion rate in the hydrogenation reaction reaches 50 percent, the corresponding temperature is firstly reduced and then increased along with the increase of the CaO loading amount. Two areThe optimum CaO loading of the seed catalyst was 0.10, Ni0.2/CaO0.10/Al2O3-MC and Ni0.2/CaO0.10/Al2O3The average particle diameters of Ni particles of the-CP are respectively 8.9 nm and 13.7 nm, and the dispersivity of the catalyst active component Ni is respectively 28.6 percent and 16.3 percent. Therefore, compared with the common coprecipitation method, the Ni/CaO-Al prepared by the microwave-assisted coprecipitation method2O3The catalyst has smaller Ni particles and higher Ni dispersibility. Thus, both catalysts are in CO2The temperatures corresponding to the conversion rate of 50% in the hydrogenation reaction are 218 ℃ and 259 ℃ respectively, and the catalytic performance of the catalyst at low temperature is superior.

Claims (6)

1. Microwave-assisted coprecipitation preparation of CaO modified Ni-Al2O3A method of catalyzing, comprising the steps of:
step 1, adding CaCl2、Ni(NO3)2·6H2O、NaOH、γ-Al2O3Mixing with PVP, adding deionized water, stirring uniformly, ensuring that all groups of materials are fully dissolved, transferring to a 100 m L polytetrafluoroethylene lining, and spin-sealing a cover;
step 2, transferring the reaction kettle in the step 1 into a microwave reactor, setting the microwave power to be 400-600W and the temperature to be 80-120 ℃, and carrying out constant-temperature reaction for 10-30 min under the autogenous pressure of the reaction kettle;
step 3, cooling the product in the step 2 to room temperature, centrifuging and drying the product, and calcining the product at the temperature of 400-2O3；
Step 4, the precursor obtained in the step 3 is put in H2/N2Reducing in mixed atmosphere at 400 ℃ to obtain Ni/CaO-Al2O3A catalyst.
2. The microwave-assisted co-precipitation preparation of CaO modified Ni-Al according to claim 12O3A process for the preparation of a catalyst, characterized by: ni (NO) in said step 13)2·6H2O、γ-Al2O3According to Ni: gamma-Al2O310 to 30 weight percent of CaCl2、γ-Al2O3According to Ca: gamma-Al2O3Mixing 5-15 wt%, pouring into a polytetrafluoroethylene reaction kettle with a pressure sensor inside, adding a solution with the concentration of PVP being 0.1 mol/L and the concentration of 50 m L NaOH being 2 mol/L, and then stirring for 10 min by magnetic force to fully dissolve.
3. The microwave-assisted co-precipitation preparation of CaO modified Ni-Al according to claim 12O3A process for the preparation of a catalyst, characterized by: and (3) controlling the pressure in the kettle to be less than or equal to 10 MPa in the microwave reaction process in the step (2).
4. The microwave-assisted co-precipitation preparation of CaO modified Ni-Al according to claim 12O3A process for the preparation of a catalyst, characterized by: in step 4, the reduction time is 40-60 min, and H in the mixed gas2And N2Is 2: 3.
5. CaO modified Ni-Al prepared based on the method of any one of claims 1 to 42O3Catalyst for adsorbing and catalyzing CO2The application of (1).
6. Use according to claim 5, wherein the CO is catalysed when the Ni and CaO loadings are 0.2 and 0.15 respectively2When the conversion rate in the hydrogenation reaction reaches 50%, the corresponding temperature is 218 ℃.
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