CN112452328A - NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst - Google Patents

NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst Download PDF

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CN112452328A
CN112452328A CN202011229366.8A CN202011229366A CN112452328A CN 112452328 A CN112452328 A CN 112452328A CN 202011229366 A CN202011229366 A CN 202011229366A CN 112452328 A CN112452328 A CN 112452328A
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孙予罕
王慧
张磊
马春辉
杜洋
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
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Abstract

The invention discloses NiO @ SiO2The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that a nickel source and polyvinylpyrrolidone are dissolved in an alcohol solution to react to obtain NiO nano-particles; adding the mixture into a mixed solution of ethanol, deionized water, ammonia water and hexadecyl trimethyl ammonium bromide, and adding tetraethoxysilane to obtain NiO@SiO2Dispersing the alumina sol in the alumina sol, repeating for many times to obtain NiO @ SiO with different alumina sol coating thicknesses2@ AlOOH; mixing a cobalt source with NH4F is dissolved in deionized water, NiO @ SiO is added2@ AlOOH, reaction; drying, roasting and reducing to obtain Ni @ SiO2@Co‑Al2O3A multi-stage core-shell catalyst. The catalyst has a multi-stage core-shell structure, can improve the carbon deposition resistance and sintering resistance of Ni to a greater extent, and greatly improves the stability and service life of the catalyst.

Description

NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst
Technical Field
The invention belongs to the technical field of energy utilization and environment, and relates to NiO @ SiO2A preparation method of a @ CoAl-LDH multistage core-shell catalyst and application thereof in methane carbon dioxide reforming reaction.
Background
To solve the problem of greenhouse gas (CH)4、CO2) Global warming problem caused by rising concentration, CH4And CO2Have been the focus of research. Methane carbon dioxide Dry Reforming (DRM) is not only capable of converting these two major greenhouse gases into a synthesis gas (V) of industrial valueH2/VCO1) and the synthesis gas can be used for the synthesis of long-chain hydrocarbons or oxygenates. Ni-based catalysts are considered to be the most promising catalysts for industrialization due to their low economic cost and high activity. However, under severe reforming conditions, Ni-based catalysts are susceptible to deactivation by sintering and carbon deposition. Therefore, the development of a highly stable and anti-carbon deposition, anti-sintering Ni catalyst is the main objective of the study herein.
The improved approach mainly comprises the following aspects: the method has the advantages of reducing the size of Ni particles, improving the dispersibility of the Ni particles, controlling the acidity and alkalinity of the catalyst, selectively passivating active metal Ni, designing and regulating the structure of the catalyst and the like. In recent years, novel multifunctional core-shell composite materials are widely applied to the research in the field of catalysis due to unique structure and properties, and the core-shell catalyst plays a certain protection role because the nano metal active particles are coated by the outer layer, so that the growth of the active metal nano particles can be effectively inhibited in the process of catalytic reaction, particularly in high-temperature reaction. Therefore, the design and synthesis of the nano Ni-based catalyst with the core-shell structure can hopefully solve the key problems that the carbon deposition and sintering of the catalyst greatly limit the application of the Ni-based catalyst in the methane carbon dioxide reaction.
The patent CN107262097A discloses a NiCo/SiO2A preparation method of a core-shell catalyst. Firstly, preparing NiCo alloy nano particles, then adding a silicon source, stirring for reaction, settling a solid product by using methanol, centrifugally washing, drying a washed sample, and roasting at high temperature to obtain NiCo/SiO2A core-shell catalyst. The reactivity is high, but the reaction life is not long enough, the Ni particle size is not controllable, and the synergy of NiCo alloy needs a certain distance to exert the function to the maximum extent.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to improve the sintering resistance and the carbon deposition resistance of the existing Ni active center.
In order to solve the technical problem, the invention provides NiO @ SiO2The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized by comprising the following steps of:
step 1): dissolving a nickel source and polyvinylpyrrolidone in an alcohol solution, stirring until the nickel source and the polyvinylpyrrolidone are dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, filtering after the reaction is finished, washing and drying to obtain NiO nano-particles;
step 2): preparing a mixed solution of ethanol, deionized water, ammonia water and hexadecyl trimethyl ammonium bromide, then adding the NiO nano-particles obtained in the step 1) into the mixed solution, ultrasonically dispersing for 10-60min, and continuously stirring for 0.5-3h at room temperature to uniformly disperse the NiO nano-particles in the solution; slowly adding tetraethoxysilane into the NiO solution under vigorous stirring, reacting at room temperature, washing the obtained product with ethanol, drying and roasting to obtain NiO @ SiO2；
Step 3): NiO @ SiO obtained in step 2)2Dispersing in aluminum sol, stirring vigorously, filtering, washing with anhydrous ethanol, and drying at room temperature to obtain NiO @ SiO2@ AlOOH; the obtained NiO @ SiO2Dispersing in aluminum sol at a constant temperature, and repeating the above operation as required for several times to obtainNiO @ SiO with different alumina sol coating thicknesses2@AlOOH；
Step 4): mixing a cobalt source with NH4F is dissolved in deionized water to prepare a solution, and then NiO @ SiO obtained in the step 3) is added2Adding @ AlOOH into the solution, transferring the obtained solution into a hydrothermal kettle with a polytetrafluoroethylene lining, and reacting in an oven; then centrifugally washing the obtained product to be neutral, and drying the product in an oven to obtain NiO @ SiO2@CoAl-LDH；
Step 5): NiO @ SiO obtained in the step 4)2Baking @ CoAl-LDH in muffle furnace to obtain oxide catalyst, and reacting in reactor via H2After gas reduction, Ni @ SiO is prepared2@Co-Al2O3A multi-stage core-shell catalyst.
Preferably, the nickel source in step 1) is nickel acetate; the alcohol solution is at least one aqueous solution of methanol, ethanol, propanol and glycol, and the volume ratio of the alcohol to the water is 1 (0.1-1); the ratio of nickel acetate to polyvinylpyrrolidone was 1 mmol: (1-8 g); the ratio of nickel to alcoholic solution is 1 mmol: (50-400) mL; the molecular weight of polyvinylpyrrolidone is 54,000.
Preferably, the temperature of the hydrothermal reaction in the step 1) is 100-180 ℃, and the time is 6-16 h.
Preferably, the ratio of nickel to the sum of the volumes of ethanol and deionized water in the step 2) is 1 mmol: (50-300) mL; the volume ratio of ethanol, deionized water and ammonia water in the mixed solution is 50: 50: (1-8); the molar ratio of hexadecyl trimethyl ammonium bromide to Ni is (1-10): 1; the usage amount of the tetraethoxysilane is as follows according to the molar ratio of Si to Ni (0.5-4): 1 is the standard.
Preferably, the reaction time in the step 2) is 12-36 hours, and the roasting temperature is 400-700 ℃.
Preferably, the alumina sol in the step 3) is AlOOH, NiO @ SiO2The ratio to AlOOH is 1 mmol: 10-50 mL; the number of repetition is 2-20.
Preferably, the time for vigorous stirring in the step 3) is 1 h; the drying time was 1 h.
Preferably, said step4) The medium cobalt source is cobalt nitrate; NiO @ SiO2@ AlOOH, cobalt, NH4The molar ratio of F is (0.3-1.5): 1: 1.5; the ratio of cobalt to deionized water was 1 mmol: 20-60 mL.
Preferably, the reaction temperature in the step 4) is 80-150 ℃ and the reaction time is 12-60 h.
Preferably, the roasting temperature in the step 5) is 400-800 ℃, and the roasting time is 4-12 h.
Compared with the prior art, the invention has the following advantages:
(1) the hydrothermal method can easily control the size of Ni by controlling conditions such as reaction temperature, reaction time and the like, and ensures that Ni has smaller particle size, thereby having better catalytic performance and stability.
(2) The catalyst has a multi-stage core-shell structure, can improve the carbon deposition resistance and sintering resistance of Ni to a greater extent, and greatly improves the stability and service life of the catalyst.
(3) The preparation method of the catalyst can realize industrial amplification in each step, has high yield of the prepared catalyst, and can not cause resource waste.
(4) The catalyst contains magnetic metal Co, so that the magnet can be used for recovering the catalyst, and the problem of industrial catalyst recovery is more conveniently realized.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the catalyst provided by the present invention.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
NiO @ SiO prepared in example2@ CoAl-LDH catalyst and NiO, Co prepared in comparative examples3O4And Al2O3Loaded on SiO2The evaluation of the use of the supported catalyst for the carbon dioxide reforming reaction of methane was as follows:
0.1g (80-100 meshes) of catalyst and 0.9g (80-100 meshes) of quartz sand are weighed and mixed evenly in H2/N2Atmosphere (50% each by volume, flow rate)120mL/min), and pre-reducing for 2h at 700 ℃. After the reduction is finished, the reaction temperature is 850 ℃, the ratio of methane to carbon dioxide in the raw material gas is 1.2, and N2As an internal standard, 3%. The flow rate of the raw material gas is 141.7mL/min, the space velocity is 85000mL/(gh), and the raw material gas directly passes through the catalyst bed layer. CH can be obtained by gas chromatography TCD and calculation with internal standard method4，CO2Conversion and products CO and H2The ratio of (a) to (b). The evaluation data shown in all the examples are evaluation data after 500h of the evaluation reaction.
Example 1
First, 1.25g of nickel acetate tetrahydrate and 10g of polyvinylpyrrolidone are dissolved in a propanol solution, the volume ratio of alcohol to water being 1: 1. stirring until the solution is dissolved, transferring the solution into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the propanol solution is 1500mL, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 16 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on the NiO nano-particles for 60min, uniformly dispersing the NiO nano-particles in a solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of ethanol, deionized water and ammonia water are respectively 250mL, 250mL and 10 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 7.29 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 3.12 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 700 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of the AlOOH is 250 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 10 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate hexahydrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F was added in an amount of 2.43g and 0.46g, respectively. Deionized waterThe volume is 200 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 12 h. And centrifugally washing, drying and roasting the product at 400 ℃ for 4 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 13.6nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 78.56%, CH4Conversion 81.73%, H2The ratio of/CO was 0.80.
Example 2
Firstly, 1.25g of nickel acetate tetrahydrate and 5g of polyvinylpyrrolidone are dissolved in a methanol solution, the volume ratio of alcohol to water being 1: 0.3. stirring until the solution is dissolved, transferring the solution into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the methanol solution is 2000mL, the hydrothermal reaction temperature is 100 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on the NiO nano-particles for 60min, uniformly dispersing the NiO nano-particles in a solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are respectively 750mL, 750mL and 15 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 3.65 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 2.60 g. Then reacting for 12h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting for 6h at 500 ℃ to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 5 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added to 1.46g and 0.28g, respectively. The volume of the deionized water is 150 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 150 ℃, and the reaction time is 12 h. And centrifugally washing, drying and roasting the product at 400 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 12.1nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion 80.12%, CH4Conversion 84.37%, H2The ratio of/CO was 0.81.
Example 3
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.5. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the ethanol solution is 500mL, the hydrothermal reaction temperature is 140 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on the NiO nano-particles for 60min, uniformly dispersing the NiO nano-particles in a solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of ethanol, deionized water and ammonia water are respectively 250mL, 250mL and 20 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 9.11 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 2.08 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 500 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 10 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added to 1.46g and 0.28g, respectively. The volume of the deionized water is 250 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 700 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
As a result of characterization by XRD, TEM and the like, it was found that the Ni particles were small in size and had an average particle diameter of 7.4 nm. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 90.36%, CH4Conversion 94.51%, H2the/CO is 0.89, and the catalyst has no inactivation within 1000h of evaluation and very good catalytic performance.
Example 4
Firstly, 1.25g of nickel acetate tetrahydrate and 40g of polyvinylpyrrolidone are dissolved in a glycol solution, and the volume ratio of alcohol to water is 1: 0.1. stirring until the solution is dissolved, transferring the solution into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the ethanol solution is 250mL, the hydrothermal reaction temperature is 180 ℃, and the hydrothermal reaction time is 6 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on the NiO nano-particles for 60min, uniformly dispersing the NiO nano-particles in a solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are respectively 125mL, 125mL and 20 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 18.22 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 0.52 g. Then reacting for 36h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 400 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 50 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 20 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added in an amount of 0.97g and 0.19g, respectively. The volume of the deionized water is 300 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 80 ℃, and the reaction time is 60 h. And centrifugally washing, drying and roasting the product at 800 ℃ for 12 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 15.4nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion 75.12%, CH4Conversion was 78.51%, H2The ratio of/CO was 0.80.
Example 5
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.7. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the proportion of an ethanol solution is 500mL, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on NiO nano particles for 60min, uniformly dispersing the NiO nano particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are 500mL, 500mL and 40mL respectively; the addition amount of hexadecyl trimethyl ammonium bromide is 12.75 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Ethyl orthosilicate was then slowly added thereto in an amount of 4.16 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 500 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in air to complete the first aluminum dissolvingWrapping with glue; repeating the above operation for 2 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F was added in an amount of 2.43g and 0.46g, respectively. The volume of the deionized water is 250 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 120 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 600 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 9.7nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 82.11%, CH4Conversion was 85.86%, H2The ratio/CO was 0.82.
Example 6
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.9. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the proportion of ethanol solution is 1000mL, the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on NiO nano particles for 60min, uniformly dispersing the NiO nano particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are 250mL, 250mL and 30mL respectively; the adding amount of hexadecyl trimethyl ammonium bromide is 16.40 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 1.04 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 600 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then using anhydrous ethyl acetateWashing with alcohol, and drying in air to finish the first alumina sol coating; repeating the above operation for 2 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added to 1.46g and 0.28g, respectively. The volume of the deionized water is 100 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 700 ℃ for 6 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 8.3nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 84.24%, CH4Conversion was 86.68, H2The ratio/CO was 0.82.
Example 7
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.5. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the proportion of an ethanol solution is 500mL, the hydrothermal reaction temperature is 140 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on NiO nano particles for 60min, uniformly dispersing the NiO nano particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the volumes of the ethanol, deionized water and ammonia water mixed solution are 250mL, 250mL and 35mL respectively; the addition amount of hexadecyl trimethyl ammonium bromide is 9.11 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 2.08 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 700 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersed in AlOOH sol and vigorously placed in a beakerStirring for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 10 times to obtain NiO @ SiO2@AlOOH。。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added to 4.85g and 0.93g, respectively. The volume of the deionized water is 250 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 700 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 7.9nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 86.51%, CH4Conversion was 88.97, H2The ratio/CO was 0.84.
Comparative example 1
Nickel nitrate, cobalt nitrate and aluminum nitrate are mixed according to the proportion of Ni: co: the molar ratio of Al is 1: 1: 1 in 50mL of deionized water, and then impregnating the solution into commercial SiO by an equal volume impregnation method2On a carrier, SiO2The molar ratio to Ni was 1: 1. the operation can load three elements of Ni, Co and Al on SiO uniformly2On a carrier. Then roasting the mixture for 4 hours at 700 ℃ in a muffle furnace under static air to obtain NiO and Co3O4And Al2O3Loaded on SiO2A supported catalyst.
As a result of characterization by XRD, TEM, etc., it was found that the Ni particles were very non-uniform in size and that agglomeration phenomenon was present, the average particle size of which was 25 nm. Then the catalyst is loaded into a methane reforming evaluation device, and the evaluation result shows that the catalyst has CO2Conversion was only 50.48%, CH4Conversion 55.89%, H2the/CO is 0.73, the activity of the catalyst is continuously reduced within 50h of evaluation, and finally the reaction tube is blocked due to serious carbon deposition, which indicates that the catalytic performance and the stability of the catalyst are poor.

Claims (10)

1. NiO @ SiO2The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized by comprising the following steps of:
step 1): dissolving a nickel source and polyvinylpyrrolidone in an alcohol solution, stirring until the nickel source and the polyvinylpyrrolidone are dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, filtering after the reaction is finished, washing and drying to obtain NiO nano-particles;
step 2): preparing a mixed solution of ethanol, deionized water, ammonia water and hexadecyl trimethyl ammonium bromide, then adding the NiO nano-particles obtained in the step 1) into the mixed solution, ultrasonically dispersing for 10-60min, and continuously stirring for 0.5-3h at room temperature to uniformly disperse the NiO nano-particles in the solution; slowly adding tetraethoxysilane into the NiO solution under vigorous stirring, reacting at room temperature, washing the obtained product with ethanol, drying and roasting to obtain NiO @ SiO2；
Step 3): NiO @ SiO obtained in step 2)2Dispersing in aluminum sol, stirring vigorously, filtering, washing with anhydrous ethanol, and drying at room temperature to obtain NiO @ SiO2@ AlOOH; the obtained NiO @ SiO2The @ AlOOH is dispersed in the alumina sol again, and the operation is repeated for a plurality of times as required to obtain NiO @ SiO with different alumina sol coating thicknesses2@AlOOH；
Step 4): mixing a cobalt source with NH4F is dissolved in deionized water to prepare a solution, and then NiO @ SiO obtained in the step 3) is added2Adding @ AlOOH into the solution, transferring the obtained solution into a hydrothermal kettle with a polytetrafluoroethylene lining, and reacting in an oven; then centrifugally washing the obtained product to be neutral, and drying the product in an oven to obtain NiO @ SiO2@CoAl-LDH；
Step 5): NiO @ SiO obtained in the step 4)2Baking @ CoAl-LDH in muffle furnace to obtain oxide catalyst, and reacting in reactor via H2After gas reduction, Ni @ SiO is prepared2@Co-Al2O3A multi-stage core-shell catalyst.
2. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the nickel source in the step 1) is nickel acetate; the alcohol solution is at least one aqueous solution of methanol, ethanol, propanol and glycol, and the volume ratio of the alcohol to the water is 1 (0.1-1); the ratio of nickel acetate to polyvinylpyrrolidone was 1 mmol: (1-8 g); the ratio of nickel to alcoholic solution is 1 mmol: (50-400) mL; the molecular weight of polyvinylpyrrolidone is 54,000.
3. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the temperature of hydrothermal reaction in the step 1) is 100-180 ℃, and the time is 6-16 h.
4. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the ratio of nickel to the sum of the volumes of ethanol and deionized water in the step 2) is 1 mmol: (50-300) mL; the volume ratio of ethanol, deionized water and ammonia water in the mixed solution is 50: 50: (1-8); the molar ratio of hexadecyl trimethyl ammonium bromide to Ni is (1-10): 1; the usage amount of the tetraethoxysilane is as follows according to the molar ratio of Si to Ni (0.5-4): 1 is the standard.
5. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the reaction time in the step 2) is 12-36 hours, and the roasting temperature is 400-700 ℃.
6. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multi-stage core-shell catalyst is characterized in that the alumina sol in the step 3) is AlOOH, NiO @ SiO2The ratio to AlOOH is 1 mmol: 10-50 mL; the number of repetition is 2-20.
7. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in thatThe time for vigorous stirring in the step 3) is 1 h; the drying time was 1 h.
8. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the cobalt source in the step 4) is cobalt nitrate; NiO @ SiO2@ AlOOH, cobalt, NH4The molar ratio of F is (0.3-1.5): 1: 1.5; the ratio of cobalt to deionized water was 1 mmol: 20-60 mL.
9. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the reaction temperature in the step 4) is 80-150 ℃, and the reaction time is 12-60 hours.
10. The NiO @ SiO of claim 12The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that the roasting temperature in the step 5) is 400-800 ℃, and the roasting time is 4-12 hours.
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