CN114749182A - Nickel-lanthanum oxide catalyst for dry reforming of methane and preparation method thereof - Google Patents

Nickel-lanthanum oxide catalyst for dry reforming of methane and preparation method thereof Download PDF

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CN114749182A
CN114749182A CN202210317980.2A CN202210317980A CN114749182A CN 114749182 A CN114749182 A CN 114749182A CN 202210317980 A CN202210317980 A CN 202210317980A CN 114749182 A CN114749182 A CN 114749182A
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nickel
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lanthanum oxide
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赵华华
丑凌军
宋焕玲
赵军
杨建�
闫亮
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention relates to a nickel-lanthanum oxide catalyst for dry reforming of methane, wherein the active component of the catalyst is metal Ni, and the carrier is La2O3An obvious Ni-La interface is formed between the active component and the carrier; the active component Ni accounts for 1.0-5.0 wt%, and the Ni nano-particles have the size of about 20 nm; carrier La2O3Weight (D)The percentage is 95.0-99.0%. Meanwhile, the invention also discloses a preparation method of the catalyst. The invention shows very high catalytic stability, thereby effectively solving the problems of high-temperature sintering and carbon deposition of active components.

Description

Nickel-lanthanum oxide catalyst for dry reforming of methane and preparation method thereof
Technical Field
The invention relates to the technical field of heterogeneous catalysis, in particular to a nickel-lanthanum oxide catalyst for dry reforming of methane and a preparation method thereof.
Background
The dry reforming of methane is to convert two kinds of carbon-molecule CH with very high stability simultaneously4And CO2As synthesis gas (CO and H)2) The process of (1). Therefore, theoretically, this reaction is a very challenging subject of research in carbon-one chemistry. From a practical point of view, the process is not only an important process for natural gas conversion, but also the large-scale chemical utilization of CO 2The method has the most promising approach of industrial application, thereby having important practical significance for relieving energy crisis and improving human living environment.
At present, the catalysts used for the reaction comprise two main types of noble metals and non-noble metals, wherein the non-noble metal Ni-based catalyst is most widely researched due to the higher methane activation capacity. Despite the environmental and economic advantages, Ni-based catalysts continue to be subject to industrial application due to their severe carbon deposition and sintering. Aiming at the stability problem of the Ni-based catalyst, the current literature reports strategies including changing the preparation method of the catalyst, the types of the auxiliary agent and the carrier and the like, so as to regulate the interaction between Ni and the carrier and further regulate the surface interface state of an active component Ni species. Commonly used supports are acidic metal oxides such as Al2O3、ZrO2Etc., inert metal oxides such as SiO2Etc. and basic metal oxides MgO and La2O3And the like.
Wherein the rare earth metal La2O3Ni-loaded catalyst capable of activating CO2To produce lanthanum oxycarbonate intermediate (La)2O3 + CO2 = La2O2CO3) Thereby playing a role of carbon elimination (La)2O2CO3 + C = La2O3+ CO) (Journal of Catalysis, 343, 2016, 208-214). Nickel-lanthanum oxide catalysts are typically prepared by impregnation (201080012085.5) or precipitation (20) 2110262555.3) loading Ni on La2O3Prepared on a carrier, but still faces active components Ni and carrier La in the reaction process2O3The interaction is not strong, and the carrier cannot eliminate carbon in time, so that the active components are subjected to carbon deposition and are separated from the surface of the carrier or particles grow up, and the catalyst is inactivated.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nickel-lanthanum oxide catalyst for methane dry reforming, which effectively solves the problems of high-temperature sintering and carbon deposition of active components, and a preparation method thereof.
In order to solve the problems, the invention provides a nickel-lanthanum oxide catalyst for dry reforming of methane, which is characterized in that: the active component of the catalyst is metal Ni, and the carrier is La2O3An obvious Ni-La interface is formed between the active component and the carrier; the active component Ni accounts for 1.0-5.0 wt%, and the Ni nano-particles have the size of about 20 nm; carrier La2O3The weight percentage is 95.0-99.0%.
The preparation method of the nickel-lanthanum oxide catalyst for dry reforming of methane is characterized by comprising the following steps: dropwise adding an alkaline precipitator solution into the La salt solution at room temperature, adjusting the pH value to 7.0-1.0, filtering and washing the obtained reactant until the pH value of the filtrate is neutral, drying overnight and then roasting to obtain lanthanum oxycarbonate (La) 2O2CO3) A carrier; then the Ni salt solution was impregnated into lanthanum oxycarbonate (La)2O2CO3) And (3) drying, roasting and reducing the carrier overnight in sequence to obtain the nickel-lanthanum oxide catalyst.
The La salt solution is prepared by dissolving La salt in deionized water to obtain the La salt solution with the concentration of 0.15-0.30 mol.L-1The mixed solution of (1); the La salt is any one or a combination of more than two of lanthanum nitrate, lanthanum acetate and lanthanum chloride.
The alkaline precipitant solution is obtained by dissolving an alkaline precipitant in deionized water to obtain a solution with a concentration of 0.5-2.0 mol.L-1The mixed solution of (1); the alkaline precipitator is NH4HCO3、(NH4)2CO3And NH3·H2O, or a combination of two or more thereof.
The Ni salt solution is prepared by dissolving Ni salt in deionized water to obtain the Ni salt solution with the concentration of 0.07-0.38 mol.L-1The mixed solution of (1); the Ni salt is any one or the combination of more than two of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate.
Ni salt in the Ni salt solution and the lanthanum carbonate oxide (La)2O2CO3) The mass ratio of the carrier is 0.04-0.24: 1.
the temperature for the overnight drying was 120 ℃.
The roasting condition of the carrier is that the temperature is 600 ℃ and the time is 2.0-4.0 h.
The roasting condition of the catalyst is that the temperature is 600-800 ℃ and the time is 2.0 h.
The reduction conditions refer to the volume ratio of 1: 2H2/N2Reducing for 2.0 h at 650-900 ℃ under the atmosphere.
The use of a nickel-lanthanum oxide catalyst for dry reforming of methane as described above in dry reforming of methane, characterized in that: under normal pressure, adding CH4And CO2Continuously introducing the mixture into a reaction furnace filled with the nickel-lanthanum oxide catalyst, and keeping the temperature at 650-850 ℃ and the space velocity at 15000-60000 h-1Under the conditions of (1) to produce CO and H2。
Compared with the prior art, the invention has the following advantages:
1. usually, Ni is supported directly on La2O3The nickel-lanthanum oxide catalyst is prepared on a carrier, and the active component Ni and the carrier La2O3Weaker interaction, showing reduced CH after prolonged methane dry reforming reaction4And CO2Conversion, gradual deactivation occurred. In the invention, Ni is loaded on La by the nickel-lanthanum oxide catalyst2O2CO3On a carrier, the reaction 2La can occur during the calcination of the catalyst2O2CO3(s)+ NiO(s) = La2O3(s) + La2NiO4(s) + 2CO2(g) Further byThe reduction can generate Ni-La interface with strong interaction in situ, and the generated CO2The gas can play a hole expanding role and increase the specific surface of the catalyst.
2. The Ni-based catalyst has high content of active components (Ni content is more than 5%), while the weight percentage of the Ni active components of the nickel-lanthanum oxide catalyst is 1.0-5.0%. Higher reaction activity can be obtained by controlling lower Ni content, and the preparation method has the advantages of simplicity and low production cost.
3. La is used for the invention2O2CO3The nickel-lanthanum oxide catalyst prepared for the carrier precursor has an obvious Ni-La interface, is used in the reaction of preparing the synthesis gas by dry reforming of methane, has the service life of 300 h without inactivation under the condition of no diluent gas and at the reaction temperature of 750 ℃, and shows very high catalytic stability, thereby effectively solving the problems of high-temperature sintering and carbon deposition of active components.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a TEM (a) and HRTEM (b) image of a nickel-lanthanum oxide catalyst prepared in example 1 of the present invention.
FIG. 2 is a TEM image (a) and an HRTEM image (b) of a nickel-lanthanum oxide catalyst prepared in example 2 of the present invention.
Detailed Description
A nickel-lanthanum oxide catalyst for dry reforming of methane contains Ni as active component and La as carrier2O3An obvious Ni-La interface is formed between the active component and the carrier; the active component Ni accounts for 1.0-5.0 wt%, and the Ni nano-particles have the size of about 20 nm; carrier La2O3The weight percentage is 95.0-99.0%.
The preparation method comprises the following steps: dropwise adding an alkaline precipitator solution into the La salt solution at room temperature, adjusting the pH value to 7.0-1.0, filtering and washing the obtained reactant until the pH value of the filtrate is neutral, drying the filtrate overnight at 120 ℃, roasting the filtrate at 600 ℃ in a muffle furnace for 2.0-4.0 hours to obtain lanthanum carbonate oxide (La) 2O2CO3) A carrier; then the Ni salt solution was impregnated into lanthanum oxycarbonate (La)2O2CO3) Drying the carrier at 120 ℃ overnight, roasting the carrier in a muffle furnace at 600-800 ℃ for 2.0H, and roasting the carrier in a tubular furnace H2/N2Reducing for 2.0 h at 650-900 ℃ in the atmosphere (volume ratio 1: 2) to obtain the nickel-lanthanum oxide catalyst.
Wherein: the La salt solution is prepared by dissolving La salt in deionized water to obtain the solution with the concentration of 0.15-0.30 mol.L-1The mixed solution of (1); the La salt is any one or the combination of more than two of lanthanum nitrate, lanthanum acetate and lanthanum chloride.
The alkaline precipitant solution is obtained by dissolving an alkaline precipitant in deionized water to obtain a solution with a concentration of 0.5-2.0 mol.L-1The mixed solution of (1); the alkaline precipitant is NH4HCO3、(NH4)2CO3And NH3·H2O, or a combination of two or more thereof.
The Ni salt solution is obtained by dissolving Ni salt in deionized water to obtain a concentration of 0.07-0.38 mol.L-1The mixed solution of (1); the Ni salt is any one or combination of more than two of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate.
Ni salt and lanthanum carbonate oxide (La) in Ni salt solution2O2CO3) The mass ratio (g/g) of the carrier is 0.04-0.24: 1.
the application of the nickel-lanthanum oxide catalyst in dry reforming of methane comprises the following steps: under normal pressure, adding CH4And CO2Continuously introducing the mixture into a reaction furnace filled with the nickel-lanthanum oxide catalyst, and keeping the temperature at 650-850 ℃ and the space velocity at 15000-60000 h -1Under the conditions of (1) to produce CO and H2。
Example 1
Preparing a carrier: 13 g of La (NO) was added in a 1L beaker at room temperature (around 25 ℃ C.)3)3·6H2O is dissolved in 200 mL of water with stirring, and then 1.0 mol. L is added dropwise-1 NH4HCO3The precipitant adjusts the pH of the mixed slurry to 8.0. After stirring for 0.5 h, the reaction was filtered and washed to a filtrate pH of 7.0 and dried in an oven at 120 ℃ overnightFinally, roasting the catalyst in a muffle furnace at the temperature of 600 ℃ for 2.0 h to obtain a catalyst carrier La2O2CO3；
Preparing a catalyst: 3.0 g of the La was added to a 50 mL crucible under irradiation of an infrared lamp2O2CO3Carrier, 0.30 g Ni (NO) was weighed3)2·6H2Dissolving O in 7 mL of water to obtain a precursor solution, adding the precursor solution into a crucible, stirring and dipping, drying the solvent by distillation, putting the solvent into an oven at 120 ℃ for overnight drying, roasting the solvent in a muffle furnace at 750 ℃ for 2.0H, and putting the product in a tube furnace H2/N2(volume ratio 1: 2) reduction at 750 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 2.0%. Ni-La obtained in example2O3The TEM and HRTEM images of the catalyst are shown in figure 1, and it can be seen from figure 1 that the Ni nano-particle size is about 20 nm, the particle size distribution is uniform, and the catalyst has obvious Ni-La2O3And (6) an interface.
Example 2
Preparing a carrier: in a 1L beaker, 24 g of La (CH) was added at room temperature (around 25 ℃ C.) 3COO)3·5H2O is dissolved in 200 mL of water with stirring, and then 0.5 mol. L is added dropwise-1 NH3·H2The O precipitant adjusts the pH of the mixed slurry to 8.0. Stirring for 0.5 h, filtering and washing the reactant until the pH value of the filtrate is 7.0, drying in an oven at 120 ℃ overnight, and finally roasting in a muffle furnace at 600 ℃ for 3.0 h to obtain the catalyst carrier La2O2CO3；
Preparing a catalyst: 3.0 g of the La was added to a 50 mL crucible under irradiation of an infrared lamp2O2CO3Carrier, 0.40 g Ni (CH) is weighed3COO)2·4H2Dissolving O in 7 mL of water to obtain a precursor solution, adding the precursor solution into a crucible, stirring and dipping, drying the solvent by distillation, putting the solvent into an oven at 120 ℃ for overnight drying, roasting the solvent in a muffle furnace at 800 ℃ for 2.0H, and putting the product in a tube furnace H2/N2(volume ratio 1: 2) reduction at 650 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 3.0%. Ni-La obtained in example2O3The TEM and HRTEM images of the catalyst are shown in figure 2, and it can be seen from figure 2 that the Ni nano-particle size is about 20 nm, the particle size distribution is uniform, and the catalyst has obvious Ni-La2O3And (6) an interface.
Example 3
Preparing a carrier: in a 1L beaker, 10 g of LaCl were added at room temperature (around 25 ℃ C.)3Stirred and dissolved in 200 mL of water, and then 2.0 mol. L of the solution was added dropwise-1 (NH4)2CO3The precipitant adjusts the pH of the mixed slurry to 9.0. Stirring for 0.5 h, filtering and washing the reactant until the pH value of the filtrate is 7.0, drying in an oven at 120 ℃ overnight, and finally roasting in a muffle furnace at 600 ℃ for 4.0 h to obtain the catalyst carrier La 2O2CO3；
Preparing a catalyst: 3.0 g of the La was added to a 50 mL crucible under irradiation of an infrared lamp2O2CO3Carrier, 0.43 g NiCl was weighed2·6H2Dissolving O in 7 mL of water to obtain a precursor solution, adding the precursor solution into a crucible, stirring and dipping, drying the solvent by distillation at 120 ℃ in an oven overnight, roasting at 600 ℃ in a muffle furnace for 2.0H, and putting the product in a tube furnace H2/N2(volume ratio 1: 2) reduction at 800 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 4.0%.
Example 4
Preparing a carrier: 13 g of La (NO) was added in a 1L beaker at room temperature (around 25 ℃ C.)3)3·6H2O is dissolved in 200 mL of water with stirring, and then 1.0 mol. L is added dropwise-1 NH4HCO3The precipitant adjusts the pH of the mixed slurry to 7.0. Stirring for 0.5 h, filtering and washing the reactant until the pH value of the filtrate is 7.0, drying in an oven at 120 ℃ overnight, and finally roasting in a muffle furnace at 600 ℃ for 2.0 h to obtain the catalyst carrier La2O2CO3；
Preparing a catalyst: 3.0 g of the La was added to a 50 mL crucible under irradiation of an infrared lamp2O2CO3Carrier, 0.70 g NiSO is weighed4·6H2Dissolving O in 7 mL of water to obtain a precursor solution, and dissolving the precursor solutionAdding the precursor solution into a crucible, stirring while dipping, drying the solvent by distillation, drying in an oven at 120 ℃ overnight, roasting in a muffle furnace at 650 ℃ for 2.0H, and putting in a tube furnace H 2/N2(volume ratio 1: 2) reduction at 700 ℃ for 2.0 h to obtain Ni-La2O3The catalyst, wherein the weight percentage of Ni is 5.0%.
Example 5
Preparing a carrier: 13 g of La (NO) was added in a 1L beaker at room temperature (around 25 ℃ C.)3)3·6H2O is dissolved in 200 mL of water with stirring, and then 1.0 mol. L is added dropwise-1 NH4HCO3The precipitant adjusts the pH of the mixed slurry to 10.0. Stirring for 0.5 h, filtering and washing the reactant until the pH value of the filtrate is 7.0, drying in an oven at 120 ℃ overnight, and finally roasting in a muffle furnace at 600 ℃ for 3.0 h to obtain the catalyst carrier La2O2CO3；
Preparing a catalyst: 3.0 g of the above La was charged into a 50 mL crucible under irradiation of an infrared lamp2O2CO3Carrier, 0.40 g Ni (NO) was weighed3)2·6H2Dissolving O in 7 mL of water to obtain a precursor solution, adding the precursor solution into a crucible, stirring and dipping, drying the solvent by distillation at 120 ℃ in an oven overnight, roasting at 700 ℃ in a muffle furnace for 2.0H, and performing H-tube furnace2/N2(volume ratio 1: 2) reduction at 900 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 2.5%.
Example 6
Preparing a carrier: 13 g of La (NO) was added in a 1L beaker at room temperature (around 25 ℃ C.)3)3·6H2O is dissolved in 200 mL of water with stirring, and then 1.0 mol. L is added dropwise-1 NH4HCO3The precipitant adjusts the pH of the mixed slurry to 8.0. Stirring for 0.5 h, filtering and washing the reactant until the pH value of the filtrate is 7.0, drying in an oven at 120 ℃ overnight, and finally roasting in a muffle furnace at 600 ℃ for 3.0 h to obtain the catalyst carrier La 2O2CO3；
Preparing a catalyst: 3 was added to a 50 mL crucible under infrared lamp irradiation.0 g of the above La2O2CO3Carrier, 0.12 g Ni (CH) is weighed3COO)2·4H2Dissolving O in 7 mL of water to obtain a precursor solution, adding the precursor solution into a crucible, stirring and dipping, drying the solvent by distillation, putting the solvent into an oven at 120 ℃ for overnight drying, roasting the solvent in a muffle furnace at 750 ℃ for 2.0H, and putting the product in a tube furnace H2/N2(volume ratio 1: 2) reduction at 850 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 1.0%.
Comparative example 1
Preparing a carrier: 13 g of La (NO) was added in a 1L beaker at room temperature (around 25 ℃ C.)3)3·6H2O is dissolved in 200 mL of water with stirring, and then 1.0 mol. L is added dropwise-1 NH4HCO3The precipitant adjusts the pH of the mixed slurry to 8.0. Stirring for 0.5 h, filtering and washing the reactant until the pH value of the filtrate is 7.0, drying in an oven at 120 ℃ overnight, and finally roasting in a muffle furnace at 800 ℃ for 3.0 h to obtain the catalyst carrier La2O3。
Preparing a catalyst: 3.0 g of the La was added to a 50 mL crucible under irradiation of an infrared lamp2O3Carrier, 0.24 g Ni (NO) was weighed3)2·6H2Dissolving O in 7 mL of water to obtain a precursor solution, adding the precursor solution into a crucible, stirring and dipping, drying the solvent by distillation, putting the solvent into an oven at 120 ℃ for overnight drying, roasting the solvent in a muffle furnace at 800 ℃ for 2.0H, and putting the product in a tube furnace H 2/N2(volume ratio 1: 2) reduction at 750 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 2.0%.
Comparative example 2 (this example is a catalyst prepared by comparative coprecipitation)
15 g of La (NO) was added in a 1L beaker at room temperature (around 25 ℃ C.)3)3·6H2O and 1.10 g Ni (NO)3)2·6H2O is dissolved in 200 mL of water with stirring, and then 1.0 mol. L is added dropwise-1 NH4HCO3The precipitant adjusts the pH of the mixed slurry to 8.0. After stirring for 0.5 h, the reaction was filtered and washed until the pH of the filtrate was7.0, drying in an oven at 120 ℃ overnight, calcining in a muffle furnace at 600 ℃ for 2.0H, and calcining in a tube furnace H2/N2(volume ratio 1: 2) reduction at 750 ℃ for 2.0 h to obtain Ni-La2O3Catalyst, wherein the weight percentage of Ni is 2.0%.
Application example 1
The nickel-lanthanum oxide catalysts prepared in examples 1-6 and comparative examples 1-2 were used in dry reforming reaction of methane, and the specific reaction conditions were: a fixed bed quartz tube reactor at atmospheric pressure was charged with 0.1 g of the calcined catalyst and diluted with 0.35 g of quartz sand. The catalyst was first subjected to a reduction treatment, the specific operation of which is shown in the above examples and comparative examples. After the reduction process is finished, the reaction temperature is adjusted and the gas is switched to N2Purging for 0.5 h, then introducing CH4With CO2(volume ratio is 1: 1) and the product is analyzed on line by gas chromatography. The results of the test when the reaction was carried out for 1.0 h are shown in Table 1.
TABLE 1 methane Dry reforming Performance results for the nickel-lanthanum oxide catalysts prepared in examples 1-6 and comparative examples 1-2
Figure 446830DEST_PATH_IMAGE001
As can be seen from Table 1, the nickel-lanthanum oxide catalyst prepared using the process of the present invention exhibits higher CH than the nickel-lanthanum oxide catalyst directly supported on lanthanum oxide4Conversion, CO2Conversion and H2The ratio of/CO is higher, and the dry reforming activity of methane is higher; compared with the nickel-lanthanum oxide catalyst prepared by a precipitation method, the nickel-lanthanum oxide catalyst prepared by the method has higher activity.
Application example 2
The nickel-lanthanum oxide catalysts prepared in example 1 and comparative example 1 were used for dry reforming of methane under the following specific reaction conditions: a fixed bed quartz tube reactor at atmospheric pressure was charged with 0.1 g of the calcined catalyst and diluted with 0.35 g of quartz sand. The catalyst was first subjected to a reduction treatment, the specific operation of which is shown in the above examples and comparative examples. After the reduction process is finished, the reaction is adjustedThe temperature is up to 750 ℃ and the gas is switched to N simultaneously2Purging for 0.5 h, then introducing CH4With CO2(volume ratio is 1: 1) and the space velocity of the raw material is 30000 mL g-1·h-1The product was analyzed on-line by gas chromatography. The catalyst stability test results are shown in table 2.
Table 2 results of methane dry reforming stability test of nickel-lanthanum oxide catalysts prepared in example 1 and comparative example 1
Figure 288884DEST_PATH_IMAGE002
As can be seen from Table 2, the catalyst prepared using the process of the present invention has CH after 300 h of reaction4Conversion and CO2The conversion rate is not obviously reduced, and the carbon deposition amount is greatly reduced, so that the catalyst prepared by the method has good methane dry reforming catalytic stability.
In addition, the inventor also refers to the mode of examples 1-6, and tests are carried out by using other raw materials and conditions listed in the specification, and the nickel-lanthanum oxide catalyst with higher methane dry reforming activity and good stability is prepared. Meanwhile, with reference to application examples 1-2, the catalyst is also used for preparing synthesis gas.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A nickel-lanthanum oxide catalyst for dry reforming of methane, characterized by: the active component of the catalyst is metal Ni, and the carrier is La2O3An obvious Ni-La interface is formed between the active component and the carrier; the active component Ni accounts for 1.0-5.0 wt%, and the Ni nano-particles have the size of about 20 nm; carrier La2O3The weight percentage is 95.0-99.0%.
2. The method of claim 1 for preparing a nickel-lanthanum oxide catalyst for dry reforming of methane, wherein: dropwise adding an alkaline precipitator solution into the La salt solution at room temperature, adjusting the pH value to 7.0-1.0, filtering and washing the obtained reactant until the pH value of the filtrate is neutral, drying overnight, and then roasting to obtain a lanthanum carbonate oxide carrier; then soaking Ni salt solution on lanthanum carbonate oxide carrier, drying overnight, roasting, reducing to obtain the nickel-lanthanum oxide catalyst.
3. The method of claim 2, wherein the nickel-lanthanum oxide catalyst is prepared by a method comprising: the La salt solution is prepared by dissolving La salt in deionized water to obtain the solution with the concentration of 0.15-0.30 mol.L-1The mixed solution of (1); the La salt is any one or the combination of more than two of lanthanum nitrate, lanthanum acetate and lanthanum chloride.
4. The method of claim 2 for preparing a nickel-lanthanum oxide catalyst for dry reforming of methane, comprising: the alkaline precipitant solution is prepared by dissolving an alkaline precipitant in deionized water to obtain a solution with a concentration of 0.5-2.0 mol.L-1The mixed solution of (1); the alkaline precipitator is NH4HCO3、(NH4)2CO3And NH3·H2O, or a combination of two or more thereof.
5. The method of claim 2, wherein the nickel-lanthanum oxide catalyst is prepared by a dry reforming methodThe method comprises the following steps: the Ni salt solution is prepared by dissolving Ni salt in deionized water to obtain the Ni salt solution with the concentration of 0.07-0.38 mol.L-1The mixed solution of (1); the Ni salt is any one or the combination of more than two of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate.
6. The method of claim 2, wherein the nickel-lanthanum oxide catalyst is prepared by a method comprising: the mass ratio of the Ni salt in the Ni salt solution to the lanthanum oxycarbonate carrier is 0.04-0.24: 1.
7. the method of claim 2, wherein the nickel-lanthanum oxide catalyst is prepared by a method comprising: the roasting condition of the carrier is that the temperature is 600 ℃ and the time is 2.0-4.0 h.
8. The method of claim 2, wherein the nickel-lanthanum oxide catalyst is prepared by a method comprising: the roasting condition of the catalyst is that the temperature is 600-800 ℃ and the time is 2.0 h.
9. The method of claim 2 for preparing a nickel-lanthanum oxide catalyst for dry reforming of methane, comprising: the reduction conditions refer to the volume ratio of 1: 2H2/N2Reducing for 2.0 h at 650-900 ℃ under the atmosphere.
10. The use of a nickel-lanthanum oxide catalyst for dry reforming of methane as claimed in claim 1 in dry reforming of methane, wherein: under normal pressure, adding CH4And CO2Continuously introducing the mixture into a reaction furnace filled with the nickel-lanthanum oxide catalyst, and keeping the temperature at 650-850 ℃ and the space velocity at 15000-60000 h-1Under the conditions of (1) to produce CO and H2。
CN202210317980.2A 2022-03-29 2022-03-29 Nickel-lanthanum oxide catalyst for dry reforming of methane and preparation method thereof Pending CN114749182A (en)

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