CN111111676B - Coated nickel-based catalyst and preparation method thereof - Google Patents
Coated nickel-based catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a coated nickel-based catalyst and a preparation method thereof, belonging to the field of energy and environmental catalysis. The nickel core of the catalyst consists of aluminum oxide and active component nickel, and the shell component is cerium oxide. Wherein, the content of the active component nickel is 30 wt.%, the molar ratio of the aluminum to the nickel is 0.4-2.5, and the rest components are cerium oxide. The coated nickel-based catalyst prepared by the invention still has higher CO content under the conditions of normal pressure and medium temperature (325-2Methanation performance shows better hydrothermal stability, and can be suitable for high-temperature and high-humidity environments.
Description
Technical Field
The invention belongs to the field of energy and environmental catalysis, and particularly relates to a coated nickel-based catalyst and a preparation method thereof.
Background
CO2The amount of emissions, about 360 million tons produced by global annual combustion of fossil fuels, is enormous as a greenhouse gas, and its emissions have a serious influence on the living environment of human beings and global climate, so that CO is reduced2The discharge amount is extremely urgent. At present, the CO produced is treated2Mainly CO2Capture and Conversion Utilization (CCUS) technology. CO 22As an important member of C1 chemistry, carbon resources can be developed and utilized, and the CCUS technology can capture CO2And the carbon is converted into products with additional value, such as methanol, methane, dimethyl ether and the like, so that carbon cycle is realized. CO 22The methane generated by methanation reaction is an important component of natural gas, can be transported to all parts of the country through the existing pipelines, and relieves the energy of ChinaThe problem of unbalance of supply and demand is a better CO2And (4) converting the path.
At present, CO2The methanation catalyst is mainly a Ni-based catalyst, and is usually supported on Al2O3，CeO2，SiO2，TiO2，ZrO2Etc. on a reducing or inert support. Although the carrier is beneficial to the dispersion and stabilization of the active component Ni, the supported nickel-based catalyst still has the problems of easy sintering, poor hydrothermal stability and the like. One of the methods for alleviating the above problems is to wrap Ni nanoparticles on an inorganic shell layer to form a wrapping structure. In the wrapping type nickel-based catalyst, Ni particles are isolated by a shell layer material and are not easy to agglomerate and sinter, so that the stability of the catalyst is improved.
The shell material of the wrapped nickel-based catalyst is mostly SiO2，Al2O3，CeO2。SiO2The catalyst has a high specific surface area and a mature synthesis method, and is generally applied to a coated catalyst. But SiO2The interaction with Ni is weaker, and the catalyst activity and hydrothermal stability are easily poor. Al (Al)2O3Although the catalyst has better hydrothermal stability, Al2O3The precursor is easy to react with other ions in the synthesis process, and the preparation of Ni @ Al is increased2O3The difficulty of the catalyst. CeO (CeO)2Can adsorb more CO as an alkaline shell material2And its rich oxygen vacancies help to activate CO2Can obviously improve CO2Methanation low temperature activity, which is a better shell material. But CeO2The high-temperature sintering resistance is weak, crystal grains are easy to grow at high temperature, the specific surface area is reduced remarkably, and the stability of the catalyst is poor. And Al2O3Has excellent heat resistance, and Al is added into Ni2O3Not only can reduce the grain size of Ni, but also can strengthen Ni and CeO2Inhibit the interaction of Ni and CeO2And (4) sintering. Thus, the present invention adds Al to the nickel core2O3To improve Ni @ CeO2The hydrothermal stability of the catalyst is poor.
Disclosure of Invention
The invention provides a coated nickel-based catalyst and a preparation method thereof, aiming at the problem of insufficient hydrothermal stability of a Ni-based catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a coated Ni-base catalyst contains Ni core made of Al2O3And active component Ni, and shell component CeO2(ii) a Wherein the mass percentage of the active component Ni is 30 percent, the molar ratio of Al to Ni is 2.5-0.4 (preferably 2), and the balance is a shell component CeO2。
The coated nickel-based catalyst is prepared by a surfactant-assisted hydrothermal method and a sol-gel method, and the specific preparation method comprises the following steps:
(1) firstly, a certain amount of nickel nitrate, aluminum nitrate and PEG (20,000) are stirred and dissolved in deionized water, NaOH aqueous solution is dripped, stirring is carried out for 1 h after the dripping is finished, and the mixture is poured into a hydrothermal kettle to be hydrothermally carried out for 24 h at the temperature of 60 ℃. Centrifugally washing, vacuum drying, and roasting at 450 deg.C for 4 hr to obtain oxidized nickel core NiAlxO, 0.4 of<x<2.5。
(2) Nickel core NiAl in oxidation statexDispersing O in ethanol water by ultrasonic wave, adding Ce (NO)3)3·6H2O, stirred overnight. At room temperature, NiAl is dispersed inxSlowly dripping the L-arginine aqueous solution into the ethanol aqueous solution of the O nucleus, and after finishing dripping, heating to 75 ℃ and refluxing for 3 h. Cooling to room temperature, vacuum drying the precipitate at 60 deg.C for 12 h, and calcining at 1 deg.C/min to 600 deg.C for 4 h in a muffle furnace to obtain NiAl catalyst precursorxO@CeO2；NiAlxO@CeO2Identified as NiAl after reductionxO@CeO2Then the catalyst (marked as NiAl) is obtained after hydrothermal aging treatmentx@CeO2-HT）。
Further, the volume ratio of the ethanol aqueous solution in the step (2) is 1:1, and NiAl in the ethanol aqueous solutionxThe concentration of O nucleus is 1.0-3.0 mg/mL, L-arginine and Ce (NO)3)3·6H2The molar ratio of O is 4:1-1: 1.
Further, the reduction conditions in the step (2) are as follows: the reducing atmosphere was 75 vol% H2-N2The reduction temperature of the mixed gas is 400-800 ℃, and the reduction time is 90 min; the hydrothermal aging conditions are as follows: firstly, H is2O(g)/H2Treating at 800 deg.C for 800 min in hydrothermal atmosphere with molar ratio of 2, and switching to N2The atmosphere was cooled to room temperature.
The coated nickel-based catalyst can be applied to the reaction of preparing methane by catalyzing the hydrogenation of carbon dioxide.
The invention has the following remarkable advantages:
1. the invention synthesizes the wrapped nickel-based catalyst by adopting a step-by-step method, and compared with an in-situ wrapping method, the method has the advantages that the introduced impurities are reduced, and the synthesis process is more controllable.
2. The invention introduces Al into Ni2O3Ni is uniformly dispersed in Al2O3In the above, the Ni crystal grain size is smaller.
3. Al2O3The addition of the (C) is beneficial to enhancing the interaction of Ni and Ce and improving the active component Ni and the shell component CeO2The sintering resistance of the catalyst enables the catalyst to keep better catalytic activity under the atmosphere of high-temperature steam, embodies better hydrothermal stability and has industrial application value.
Drawings
FIG. 1 is an XRD spectrum of oxidized nickel nuclei obtained during the preparation of examples 1-3 and comparative example 1;
FIG. 2 is a graph showing H of the catalyst precursors prepared in examples 1 to 3 and comparative examples 1 to 22-a TPR map;
FIG. 3 is a TEM image of the corresponding catalysts of example 3 and comparative example 1;
FIG. 4 shows CO of corresponding catalysts of examples 1 to 3 and comparative examples 1 to 22FIG. C shows the evaluation of methanation activity.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Preparation of oxidized nickel-core NiAl0.5O: weigh 1.32 g PEG (M)W=20,000)、7.76 g Ni(NO3)2·6H2O and 5.00 g Al (NO)3)3·9H2O was dissolved in 160 mL of deionized water. 3.74 g of NaOH was weighed out and dissolved in 400mL of deionized water. And (3) dropping the NaOH aqueous solution into the aqueous solution of the mixed nitrate, continuing stirring for 1 h after the dropping is finished, and placing the mixture in a 60 ℃ oven for hydrothermal reaction for 24 h. The obtained precipitate is centrifuged, washed by deionized water and ethanol, dried in vacuum at 50 ℃ for 24 h, and roasted at 450 ℃ for 4 h at the heating rate of 1 ℃/min.
Preparation of NiAl0.5@CeO2-HT catalyst: 0.51 g of nickel nuclei in the oxidized state NiAl are weighed out0.5O and 1.44 g Ce (NO)3)3·6H2O is dispersed in 320 mL of 50% ethanol water solution by ultrasonic dispersion for 1 h and stirred overnight. 1.08 g L-arginine was weighed into 30 mL of deionized water. Dripping L-arginine aqueous solution into NiAl dispersed in the aqueous solution at room temperature0.5After the dropwise addition of the O nucleus in the ethanol water solvent, the temperature is raised to 75 ℃ for reflux reaction for 3 hours. Cooling to room temperature, centrifuging to obtain precipitate, drying in 60 deg.C vacuum drying oven for 12 h, and roasting at 600 deg.C at 1 deg.C/min for 4 h to obtain NiAl0.5O@CeO2A catalyst precursor. NiAl0. 5O@CeO2At 75 vol% H2-N2Reducing at 700 deg.C for 90 min, and hydrothermal atmosphere (H) at 800 deg.C2O(g)/H2The molar ratio is equal to 2, the space velocity is 24,000 mL/(g.h)), the mixture is aged for 800 min and then switched to N2Reducing the atmosphere to room temperature to obtain NiAl0.5@CeO2-a HT catalyst.
Example 2 preparation of nickel nuclei in oxidation state NiAlO: weigh 1.32 g PEG (M)W=20,000)、5.82 g Ni(NO3)2·6H2O and 7.50 g Al (NO)3)3·9H2O was dissolved in 160 mL of deionized water. 4 g of NaOH was weighed out and dissolved in 400mL of deionized water. And (3) dropping the NaOH aqueous solution into the aqueous solution of the mixed nitrate, continuing stirring for 1 h after the dropping is finished, and placing the mixture in a 60 ℃ oven for hydrothermal reaction for 24 h. The obtained precipitate was centrifuged, washed with deionized water and ethanolAfter washing, vacuum drying is carried out for 24 h at 50 ℃, and roasting is carried out for 4 h at 450 ℃ at the heating rate of 1 ℃/min.
Preparation of NiAl @ CeO2-HT catalyst: 0.64 g of nickel nuclei in the oxidized state NiAlO and 1.11 g of Ce (NO) are weighed out3)3·6H2O is dispersed in 320 mL of 50% ethanol water solution by ultrasonic dispersion for 1 h and stirred overnight. 0.83 g L-arginine was weighed out and dissolved in 30 mL of deionized water. Dripping the L-arginine aqueous solution into an ethanol aqueous solvent in which NiAlO nuclei are dispersed at room temperature, and heating to 75 ℃ for reflux reaction for 3 hours after finishing dripping. Cooling to room temperature, centrifuging to obtain precipitate, drying in 60 deg.C vacuum drying oven for 12 h, and roasting at 600 deg.C at 1 deg.C/min for 4 h to obtain NiAlO @ CeO2A catalyst precursor. NiAlO @ CeO2At 75 vol% H2-N2Reducing at 700 deg.C for 90 min, and hydrothermal atmosphere (H) at 800 deg.C2O(g)/H2The molar ratio is equal to 2, the space velocity is 24,000 mL/(g.h)), the mixture is aged for 800 min and then switched to N2The atmosphere is cooled to room temperature to obtain NiAl @ CeO2-a HT catalyst.
Example 3
Preparation of oxidized nickel-core NiAl2O: weigh 1.32 g PEG (M)W=20,000)、3.88 g Ni(NO3)2·6H2O and 10.00 g Al (NO)3)3·9H2O was dissolved in 160 mL of deionized water. 4.27 g of NaOH was weighed out and dissolved in 400mL of deionized water. And (3) dropping the NaOH aqueous solution into the aqueous solution of the mixed nitrate, continuing stirring for 1 h after the dropping is finished, and placing the mixture in a 60 ℃ oven for hydrothermal reaction for 24 h. The obtained precipitate is centrifuged, washed by deionized water and ethanol, dried in vacuum at 50 ℃ for 24 h, and roasted at 450 ℃ for 4 h at the heating rate of 1 ℃/min.
Preparation of NiAl2@CeO2-HT catalyst: 0.90 g of nickel nuclei in the oxidized state NiAl are weighed out2O and 0.45 g Ce (NO)3)3·6H2O is dispersed in 320 mL of 50% ethanol water solution by ultrasonic dispersion for 1 h and stirred overnight. 0.34 g L-arginine was weighed out and dissolved in 30 mL of deionized water. Dripping L-arginine aqueous solution into NiAl dispersed in the aqueous solution at room temperature2Adding O nucleus ethanol water solvent, heating to 75 deg.C after drippingAnd reacting for 3 h. Cooling to room temperature, centrifuging to obtain precipitate, drying in 60 deg.C vacuum drying oven for 12 h, and roasting at 600 deg.C at 1 deg.C/min for 4 h to obtain NiAl2O@CeO2A catalyst precursor. NiAl2O@CeO2At 75 vol% H2-N2Reducing at 700 deg.C for 90 min, and hydrothermal atmosphere (H) at 800 deg.C2O(g)/H2The molar ratio is equal to 2, the space velocity is 24,000 mL/(g.h)), the mixture is aged for 800 min and then switched to N2Reducing the atmosphere to room temperature to obtain NiAl2@CeO2-a HT catalyst.
Comparative example 1
Preparing an oxidation state nickel core NiO: weigh 1.32 g PEG (M)W=20,000) and 11.63 g Ni (NO)3)2·6H2O was dissolved in 160 mL of deionized water. 3.2 g of NaOH was weighed out and dissolved in 400mL of deionized water. And (3) dropping the NaOH aqueous solution into the aqueous solution of the nitrate, continuing stirring for 1 h after the dropping is finished, and placing the mixture in a 60 ℃ oven for hydrothermal reaction for 24 h. The obtained precipitate is centrifuged, washed by deionized water and ethanol, dried in vacuum at 50 ℃ for 24 h, and roasted at 350 ℃ for 4 h at the heating rate of 1 ℃/min.
Preparation of Ni @ CeO2-HT catalyst: 0.38 g of NiO core and 1.77 g of Ce (NO) were weighed out3)3·6H2O is dispersed in 320 mL of 50% ethanol water solution by ultrasonic dispersion for 1 h and stirred overnight. 1.31 g L-arginine was weighed into 30 mL of deionized water. And (3) dripping the L-arginine aqueous solution into the ethanol aqueous solvent in which the NiO nucleus is dispersed at room temperature, and heating to 75 ℃ for reflux reaction for 3 hours after finishing dripping. Cooling to room temperature, centrifuging to obtain precipitate, drying in a vacuum drying oven at 60 deg.C for 12 h, and roasting at 600 deg.C at a temperature rise rate of 1 deg.C/min for 4 h to obtain NiO @ CeO2A catalyst precursor. NiO @ CeO2At 75 vol% H2-N2Reducing at 400 deg.C for 90 min, and hydrothermal at 800 deg.C (H)2O(g)/H2The molar ratio is equal to 2, the space velocity is 24,000 mL/(g.h)), the mixture is aged for 800 min and then switched to N2The atmosphere is cooled to room temperature to obtain Ni @ CeO2-a HT catalyst.
Comparative example 2
Preparation of Ni/Al2O3-HT catalyst: 2.97 g of Ni (NO) are weighed3)2·6H2O、10.30 g Al(NO3)3·9H2O and 0.4 g PEG (4,000) were dissolved in 200 mL deionized water. Mixing the nitrate solution with 1M Na2CO3The solution is simultaneously dripped into a beaker filled with 100 mL of deionized water, and the temperature of the system is controlled at 60 ℃ and the pH value is controlled at 8.0 +/-0.2 in the reaction process. After the dropwise addition, the mixture is continuously stirred for 1 hour, and is aged for 16 hours at the constant temperature of 60 ℃. The obtained precipitate is dried for 12 hours at 90 ℃ in a vacuum drying oven after being filtered and washed, and then is roasted for 4 hours at 600 ℃ in a muffle furnace to obtain NiO/Al2O3A catalyst precursor. Finally at 75 vol% H2-N2Reducing at 700 deg.C for 90 min, and hydrothermal atmosphere (H) at 800 deg.C2O(g)/H2The molar ratio is equal to 2, the space velocity is 24,000 mL/(g.h)), the mixture is aged for 800 min and then switched to N2The atmosphere is cooled to room temperature to obtain Ni/Al2O3-a HT catalyst.
FIG. 1 is an XRD spectrum of oxidized nickel nuclei obtained in examples 1 to 3 and comparative example 1. Doped Al2O3Post-oxidation state nickel-core NiAlxNiO diffraction peak of O is lower than that of undoped Al2O3The oxidation state of the nickel core NiO is more dispersed and broadened, and Al2O3The larger the doping amount, the more the NiO diffraction peak is dispersed. FIG. 2 is H of the catalyst precursors of examples 1-3 and comparative examples 1-22-a TPR map. As can be seen from the figure, Al is doped2O3NiAl of (5)xO@CeO2The hydrogen reduction peak of the catalyst precursor (examples 1-3) was shifted to a higher temperature than that of undoped comparative example 1, indicating that Al was doped2O3Ni in the catalyst precursor and shell layer material CeO2The interaction is enhanced. Notably, NiAl2O@CeO2The catalyst has a reduction peak near 848 ℃ and can be classified as NiAl-like2O4And (4) reducing spinel. FIG. 3 is a TEM image of the catalysts of example 3 and comparative example 1 after hydrothermal aging treatment, comparing and finding that NiAlx@CeO2HT catalyst vs Ni @ CeO2The sintering degree of Ni particles in the HT catalyst is relieved, and the particle size is smaller.
Evaluation of catalyst Performance
CO of examples 1-3 and comparative examples 1-22The methanation reaction activity test is carried out in a normal-pressure continuous flow fixed bed reactor under the specific conditions that: weighing 50 mg of catalyst with the particle mesh number of 60-80, uniformly mixing with 250 mg of quartz sand with the same mesh number until the mixture is 75 vol% H2-N2Reducing for 30 min in mixed atmosphere, cooling to reaction temperature, and performing activity test. The mass space velocity of the reaction gas is 60,000 mL/(g.h), and the composition of the reaction gas is H2/CO2/N2=72/18/10(v/v/v, N2As an internal standard), the gas product was analyzed on-line by gas chromatography (Shimadzu GC-2014C), CO2、N2And the CO component is analyzed by a TCD detector, and the main product component CH4Analyzed by FID detector.
FIG. 4 is CO of examples 1 to 3 and comparative examples 1 to 22Evaluation of methanation Activity. As can be seen from the figure, Al is doped2O3The methanation activity of the examples 1 to 3 is obviously higher than that of undoped Al2O3Comparative example 1 and Al2O3Comparative example 2 as a support. In particular, in example 3 in which the molar ratio of Al to Ni was 2, NiAlO-like compound was formed4The sintering resistance of spinel and Ni under high-temperature steam atmosphere is greatly enhanced, and 45 percent of CO is still maintained at 375 DEG C2And (4) conversion rate.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A coated nickel-based catalyst, characterized by: the nickel core of the catalyst consists of Al2O3And active component Ni, the shell layer component is CeO2(ii) a Wherein the mass percentage of the active component Ni is 30 percent, the molar ratio of Al to Ni is 2, and the balance is a shell component CeO2；
The preparation method of the coated nickel-based catalyst comprises the following steps:
(1) preparing an oxidized nickel core: stirring and dissolving nickel salt, aluminum salt and surfactantDripping a precipitator into deionized water, stirring for 1 h, carrying out hydrothermal reaction, centrifugally washing, vacuum drying and roasting a product after the reaction to obtain oxidized nickel-core NiAlxO，x=2；
(2) Coating type nickel-based catalyst: the oxidized nickel nucleus NiAl obtained in the step (1) is usedxDispersing O in ethanol water by ultrasonic wave, adding Ce (NO)3)3·6H2Stirring O overnight, dripping an L-arginine aqueous solution at room temperature, heating to 75 ℃, reacting for 3 hours, and finally performing centrifugation, drying, roasting, reduction and hydrothermal aging treatment to obtain the coated nickel-based catalyst;
the hydrothermal reaction temperature of the step (1) is 60 ℃, the time is 24 hours, the roasting temperature is 450 ℃, and the time is 4 hours;
the reduction conditions in the step (2) are as follows: the reducing atmosphere was 75 vol% H2-N2The reduction temperature of the mixed gas is 400-800 ℃, and the reduction time is 90 min; the hydrothermal aging conditions are as follows: firstly, H is2O/H2Treating at 800 deg.C for 800 min in hydrothermal atmosphere with molar ratio of 2, and switching to N2The atmosphere was cooled to room temperature.
2. The wrapped nickel-based catalyst according to claim 1, characterized in that: the surfactant in the step (1) is PEG20000, the precipitator is NaOH, and the nickel salt and the aluminum salt are respectively Ni (NO)3)2·6H2O and Al (NO)3)3·9H2O。
3. The wrapped nickel-based catalyst according to claim 1, characterized in that: the volume ratio of the ethanol aqueous solution in the step (2) is 1:1, and the oxidation state NiAl in the ethanol aqueous solutionxThe concentration of the O nucleus is 1.0-3.0 mg/mL, and the molar ratio of the L-arginine to the cerium nitrate is 4:1-1: 1.
4. The wrapped nickel-based catalyst according to claim 1, characterized in that: the roasting temperature in the step (2) is 600 ℃, and the time is 4 hours.
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| CN107321354A (en) * | 2017-07-21 | 2017-11-07 | 中国华能集团公司 | A kind of high temperature high selectivity carbon dioxide methanation catalyst and preparation method thereof |
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