CN115518664B - Nickel-carbide catalyst, preparation method and application of mesoporous alumina supported nickel-carbide catalyst - Google Patents

Nickel-carbide catalyst, preparation method and application of mesoporous alumina supported nickel-carbide catalyst Download PDF

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CN115518664B
CN115518664B CN202211223158.6A CN202211223158A CN115518664B CN 115518664 B CN115518664 B CN 115518664B CN 202211223158 A CN202211223158 A CN 202211223158A CN 115518664 B CN115518664 B CN 115518664B
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石川
刁亚南
张晓�
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Dalian University of Technology
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Abstract

The invention provides a method for preparing a high-dispersion nickel-carbide catalyst by plasma in situ, and the method is coupled with the plasma for low-temperature methane dry reforming reaction to improve the stability of the catalyst, remarkably improve the energy efficiency and reduce the energy consumption. The method comprises the following steps: in-situ preparation of mesoporous alumina supported nickel-carbide catalyst with high specific surface area by using methane and carbon dioxide as reaction gases and using plasma for preparing synthesis gas (H) with low hydrogen-carbon ratio 2 Co=1.07); the carbide is molybdenum carbide and tungsten carbide. The catalyst is prepared in situ, double active site metal Ni and carbide (molybdenum carbide and tungsten carbide) on the catalyst are utilized to the maximum extent in the reaction process, and the effective capacitance and energy efficiency of plasma are obviously improved by accurately adjusting the positions of the metal Ni and carbide on the catalyst, so that excellent plasma catalytic stability is obtained.

Description

Nickel-carbide catalyst, preparation method and application of mesoporous alumina supported nickel-carbide catalyst
Technical Field
The invention belongs to the field of synthesis gas preparation by a plasma-catalytic coupling methane dry reforming reaction, and particularly relates to a preparation method for synthesizing alumina loaded nickel-carbide (molybdenum carbide and tungsten carbide) with high specific surface area by using plasma in situ, which is applied to research on the dry reforming reaction performance of low-temperature plasma catalytic methane.
Background
The 2021 edition of "bp world energy statistics annual survey" indicates that global consumption of fossil fuels such as coal, petroleum and natural gas is increasing year by year and is used as a main energy resource, but the nature of the fossil fuels is not sustainable and renewable, which may cause exhaustion of fossil fuels, and limits future energy economic development. Methane, one of the largest reserves of energy on earth, can be converted to synthesis gas or lower carbon (C) by reforming, partial oxidation or oxidative coupling 2 、C 3 Etc.) hydrocarbon compounds. Due to CH 4 The dissociation energy of the C-H bond in the reaction mixture is high (434 kJ/mol), so that CH 4 The activation of (c) needs to be carried out under high temperature conditions, which means that high energy consumption is generated. Thus, under mild conditions, methane is converted into activated formA great challenge and research hotspot. On the other hand, the combustion of fossil fuels produces a large amount of carbon dioxide, resulting in an increase in greenhouse effects such as global warming. In recent years, CO 2 Emission reduction is also of increasing concern for CO 2 One method is to trap and seal carbon dioxide, and the other is to convert the carbon dioxide into high added value products.
Wherein the methane dry reforming reaction (dry reforming ofmethane, DRM) produces synthesis gas (H 2 And CO) are of great concern, the reaction CH 4 And CO 2 The two greenhouse gas micromolecules are used as carbon sources, a technical route for simultaneously converting and eliminating two main greenhouse gases is provided, and the method has multiple research values of economy, environmental protection, science and the like. Meanwhile, the low-hydrogen-carbon ratio synthesis gas generated by the dry reforming reaction of methane can be used as chemical raw materials to produce chemicals with high added value. The methane dry reforming reaction is a strong endothermic reaction, and requires a higher reaction temperature (above 700 ℃) to obtain a more ideal CH 4 And CO 2 Conversion rate. In recent years, there are three main types of catalysts for DRM reactions, namely, supported noble metal catalysts, carbide catalysts, and supported non-noble metal catalysts. The supported noble metal catalyst has excellent carbon deposition resistance and catalytic activity, but the high price of the supported noble metal catalyst leads to high economic cost of the catalyst, which is unfavorable for industrial application. Carbide catalysts (e.g. molybdenum carbide, tungsten carbide) have Pt-like properties and are relatively reactive in DRM reactions, but are prone to CO 2 And (5) oxidation deactivation. At present, a plurality of catalysts are supported non-noble metal catalysts, and particularly Ni-based catalysts are mainly used. The Ni-based catalyst has a good DRM reaction activity and low price, so that the Ni-based catalyst has a wide industrial application prospect. However, ni-based catalysts are susceptible to sintering and carbon deposition formation under high temperature conditions to deactivate them, limiting DRM reactions to date difficult to industrialize. Therefore, developing a catalyst which is efficient, highly resistant to carbon deposition, low in price and stable is of great significance for realizing industrial application of methane dry reforming reaction.
Al 2 O 3 As a catalyst carrier, it is cheap and easy to useThe obtained catalyst has good thermal stability and is often used as a carrier material for preparing Ni-based catalyst for methane dry reforming reaction. For Ni/Al prepared by traditional isovolumetric impregnation method 2 O 3 Catalyst, ni and Al on the one hand 2 O 3 The interaction between carriers is weak, the dispersion degree of the metal Ni is low, and the metal Ni is easy to agglomerate under the high-temperature reaction condition; ni/Al, on the other hand 2 O 3 The catalyst lacks an active component for activating carbon dioxide, so carbon deposition is easy to generate to deactivate the catalyst. Based on the above analysis, how to optimize the preparation method of the catalyst to maximize the utilization of the active sites becomes important for improving the catalytic performance of the catalyst.
Meanwhile, for the thermal catalytic methane dry reforming reaction, the reaction temperature is high, so that the energy consumption in the reaction process is high, and how to reduce the energy consumption in the reaction process is important for implementing energy conservation and emission reduction. Based on this, it is important to utilize an efficient catalytic process in addition to the innovative modification of the catalyst. The key to utilizing the novel process is to couple an advanced catalytic system to CH in a controllable reaction kinetics process 4 And CO 2 Effectively activates, and effectively converts heat energy, electric energy, light energy and the like into driving force for activating C-H bonds and C=O bonds by coupling external field action so as to realize the catalytic methane dry reforming reaction under mild conditions. Non-equilibrium plasma technology provides a means for low temperature activation of the converted reactive molecules, which serves as a means for promoting chemical reactions that can be accomplished in many ways that are difficult to perform under conventional conditions. However, the chemical reaction directly initiated by the simple plasma generally has the problems of poor directional conversion capability and low selectivity of reactants to target products. Therefore, there is a need to develop a Ni-based catalyst with high efficiency in anti-carbon and anti-sintering properties and coupled with a new plasma process for CH under mild conditions 4 And CO 2 High-efficiency transformation. For Ni-based catalysts, on the one hand, particle size control and stabilization of the active metal Ni is effective to enhance its methane activityThe chemical ability and high temperature sintering resistance are important; on the other hand, the Ni-based catalyst is improved in CO 2 The activation ability of the catalyst is also very important, effectively inhibits carbon deposition, and contributes to the improvement of the reactivity and the stability.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for preparing a highly dispersed nickel-carbide (molybdenum carbide, tungsten carbide) catalyst in situ by plasma, and precisely modulating the distance (proximity) of the bifunctional active sites to achieve maximum utilization of the active sites on the catalyst. In addition, the dual-function catalyst is coupled with a low-temperature plasma technology to catalyze the dry reforming reaction of methane, and shows high CH under the condition of no additional heating 4 And CO 2 The conversion rate, the excellent stability and the low energy consumption realize the activation conversion of reactant molecules under mild conditions, and make up for the high-temperature reaction conditions (usually>700 ℃ and deactivation of carbon on the surface of the catalyst. In one aspect, the mesoporous alumina supported nickel-oxide precursor is prepared by a one-step process, the particle size of the metallic Ni is small (about 1.9 nm), and the domain-limiting effect of the mesoporous channels can inhibit agglomeration of the metallic Ni. In addition, the precursor is carbonized into a high-dispersion Ni-carbide catalyst in situ under the mild condition of low-temperature plasma, and the adjacent effect of Ni and carbide is utilized to realize the oxidation-carbonization cycle of the catalyst in the reaction process, so that the catalytic performance of the catalyst is effectively improved. On the other hand, by the innovative design of the catalyst and the combination of the plasma technology, the energy efficiency of the plasma catalysis is obviously improved.
The invention is realized by the following technical scheme:
in one aspect, the invention provides a method for preparing a nickel-carbide catalyst, comprising the steps of:
by CH 4 And CO 2 The mesoporous alumina supported nickel-carbide catalyst is used as raw material gas for the dry reforming reaction of methane under the catalysis of plasma, and the reaction product is synthesis gas with low hydrogen-carbon ratio; the carbide is molybdenum carbide or tungsten carbide. In the method, a certain amount of mesoporous oxygen is addedThe aluminum-loaded nickel-oxide precursor is placed in low-temperature plasma reaction gas, and the aim of efficiently activating conversion reactant molecules under mild conditions is fulfilled by utilizing the synergistic effect between the plasma and the catalyst through optimizing discharge parameters. Meanwhile, the plasma catalytic coupling mode obviously improves the catalytic performance of the catalyst and the energy efficiency of a reaction system,
further, in the technical scheme, the mixed gas of methane, carbon dioxide and argon is introduced into the reactor according to a certain proportion, wherein the volume ratio of methane to carbon dioxide is adjusted to be 5/1-1/5, and the mass airspeed is 8,000-2,500,000 mL/g/h.
Further, in the above-described technical solution, the plasma discharge form is Dielectric Barrier Discharge (DBD).
Further, in the above technical scheme, no additional heat source is used for heating in the reaction process.
Further, in the technical scheme, the input power is 30-200W, the discharge power is 30-200W, the center frequency is 5-30kHz, and the input voltage is 10-200V.
Further, in the above technical scheme, the reaction is performed at normal pressure.
In another aspect, the invention provides a nickel-carbide catalyst prepared by the above preparation method.
Further, the nickel-carbide catalyst is coupled with plasma for low-temperature methane dry reforming reaction to improve catalyst stability, significantly improve energy efficiency and reduce energy consumption. Meanwhile, the energy consumption in the plasma catalysis process is reduced by an order of magnitude compared with that of thermal catalysis.
In still another aspect, the present invention provides a method for preparing the nickel-carbide catalyst supported by mesoporous alumina, which comprises the following steps:
(1) Preparing mesoporous alumina coated nickel-molybdenum oxide: dissolving a certain amount of P123 in ethanol, putting into a water bath kettle at 40-60 ℃, vigorously stirring for 1h until the P123 is completely dissolved, adding a certain amount of concentrated nitric acid and aluminum isopropoxide, vigorously stirring for 30min, then adding a certain amount of nickel salt and molybdate into the mixed solution, vigorously stirring for 6-24h, putting into an oven at 60-90 ℃ for drying for 24-48h, grinding the dried solid sample into powder, and roasting for 2-6h at 450-700 ℃ in air atmosphere to obtain a mesoporous alumina coated nickel-molybdenum oxide precursor;
(2) Preparing mesoporous alumina coated nickel-tungsten oxide: dissolving a certain amount of P123 in ethanol, putting into a water bath kettle at 40-60 ℃, vigorously stirring for 1h until the P123 is completely dissolved, adding a certain amount of concentrated nitric acid and aluminum isopropoxide, vigorously stirring for 30min, then adding a certain amount of nickel salt and tungstate into the mixed solution, vigorously stirring for 6-24h, putting into an oven at 60-90 ℃ for drying for 24-48h, grinding the dried solid sample into powder, and roasting for 2-6h at 450-700 ℃ in air atmosphere to obtain a mesoporous alumina coated nickel-tungsten oxide precursor;
(3) Preparing mesoporous alumina coated nickel-molybdenum carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out a certain CH treatment 4 /CO 2 In proportion, preparing a mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge for a certain time;
(4) Preparing mesoporous alumina coated nickel-tungsten carbide: tabletting and sieving mesoporous alumina coated nickel-tungsten oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out a certain CH treatment 4 /CO 2 In proportion, preparing a mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge for a certain time;
further, in the above technical scheme, the nickel salt is nickel acetate, nickel nitrate, nickel chloride; the molybdate is ammonium molybdate and sodium molybdate; the tungstate is sodium tungstate, ammonium meta-tungstate and ammonium tungstate.
Further, in the technical proposal, the plasma treatment device is characterized in that the input power of the plasma discharge is 30-200W, the center frequency of the power supply is 5-30kHz, the plasma treatment time is 0.5-10h, CH 4 /CO 2 The ratio is 5/1-1/5.
Further, in the above technical scheme, the reactor used in the process of plasma treatment of the catalyst is a quartz tube and a corundum tube, and the treatment temperature is 40-500 ℃.
Further, in the technical scheme, the method is characterized in that the molar ratio of nickel to molybdenum is 6/1-1/6, and the mass fraction of nickel is 5-40%.
Advantageous effects
1. The invention successfully prepares the mesoporous alumina loaded nickel-oxide precursor with high specific surface area by a one-step method, and then uses plasma in CO 2 /CH 4 And preparing the mesoporous alumina loaded nickel-carbide precursor in situ under the atmosphere. Compared with the catalyst prepared by the impregnation method, the catalyst prepared by the one-step method has smaller particle size of metal Ni, and improves the dispersion of Ni. Meanwhile, the specific surface area of the prepared mesoporous alumina supported nickel-oxide precursor is as high as 508cm 2 /g。
2. Compared with the traditional thermal carbonization (carbonization temperature is 700 ℃), the low-temperature plasma is in CO 2 /CH 4 The mesoporous alumina is carbonized in situ under the atmosphere to load the nickel-oxide precursor, so that the carbonization temperature is reduced, and agglomeration of metal Ni in the carbonization process is inhibited. Meanwhile, the limited area of the high-specific surface alumina pore canal is correspondingly beneficial to stabilizing the metal Ni, and the adjacent effect of the metal Ni and carbide enables the catalyst to form an oxidation-carbonization cycle in the reaction process, and the metal Ni and carbide are beneficial to improving the catalytic performance.
3. By the innovative design of the catalyst, the mesoporous alumina supported nickel-molybdenum carbide catalyst is coupled with plasma, and the catalyst shows excellent catalytic activity and stability under the condition of no additional heat source heating, namely CH in 325h reaction time 4 And CO 2 The conversion was kept at 95% and high energy efficiency was obtained.
4. Compared with the thermal catalytic methane dry reforming reaction, the energy consumption in the process of the plasma catalytic methane dry reforming reaction is reduced by one order of magnitude, and the method has a certain industrial application prospect.
Drawings
FIG. 1 shows N of mesoporous alumina supported catalysts prepared in example 1, example 3, and examples 7 to 8 2 Adsorption-desorption curves and pore size distribution plots;
FIG. 2 is a TEM image of the mesoporous alumina supported catalysts prepared in example 1, example 3, and examples 7-8;
FIG. 3 is a graph showing the comparison of the plasma catalytic activities of the mesoporous alumina supported catalysts prepared in examples 1, 3 and 7-8;
FIG. 4 is a graph of Mo 3dXPS after the reaction of the mesoporous alumina supported catalyst prepared in example 1;
FIG. 5 is a graph of the plasma catalyst stability of the 10Ni4MoAl-one pot catalyst prepared in example 1.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Example 1
And (3) preparing a catalyst:
(1) Preparing mesoporous alumina coated nickel-molybdenum oxide: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃, vigorously stirring for 1h until the P123 is completely dissolved, adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, adding 1.28g of nickel nitrate and 0.196g of ammonium molybdate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ for drying for 48h, grinding the dried solid sample into powder, and roasting for 4h at 550 ℃ in air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, and marking as 10Ni4MoAl-one pot;
(2) Preparing mesoporous alumina coated nickel-molybdenum carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out CH treatment 4 /CO 2 In proportion, preparing the mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the reaction tube was 8mm and the wall thickness was 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the reaction tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. Weighing scaleA certain amount of catalyst is put into a reaction tube, and the catalyst is put into H before the reaction 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, the CH on the 10Ni4MoAl-one pot catalyst 4 And CO 2 The conversion was 91.7% and 94.1%, respectively, the energy efficiency was 2.17mmol/kJ and the energy consumption was 0.24kWh/mol. Meanwhile, the catalyst has excellent reaction stability, namely CH in 325h reaction time when the mass space velocity is 100,000mL/g/h 4 And CO 2 The conversion rate is above 95%.
TABLE 1 specific surface area, pore size, pore volume comparison for different catalysts
Comparative example 1
And (3) preparing a catalyst:
preparation of an alumina nanoparticle supported nickel-molybdenum catalyst: the mass fraction of Ni is 10%, and the mass fraction of Mo is 4%. Firstly, measuring the water absorption rate (1.0 mL/g) of nano-sheet alumina, then weighing a certain amount of nickel nitrate and ammonium molybdate to be dissolved in 2.0mL of deionized water to obtain a nickel nitrate solution, and immersing the nickel nitrate solution in 1.0gAl in an equal volume manner 2 O 3 On particles (NP-Al) 2 O 3 ) Standing at room temperature for 24h, drying at 110deg.C for 24h, and calcining the dried precursor at 650deg.C for 4h in air atmosphere to obtain Ni-Mo/NP-Al 2 O 3 。
(2) Preparing mesoporous alumina coated nickel-molybdenum carbide: tabletting and sieving the alumina nanoparticle loaded nickel-molybdenum precursor to obtain precursor particles with 40-60 meshes, and then carrying out CH treatment 4 /CO 2 In proportion, preparing the mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge.
Evaluation of catalyst Performance
The dry reforming reaction performance of the methane catalyzed by the plasma is evaluated by adopting a common methodThe micro fixed bed quartz reactor is pressed. The inner diameter of the reaction tube was 8mm and the wall thickness was 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the reaction tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. Weighing a certain amount of catalyst, placing the catalyst in a reaction tube, and before the reaction, placing the catalyst in H 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. No external heating source, about 60W of input power under the room temperature discharge condition, and the mass airspeed of 800,000mL/g/h, ni-Mo/NP-Al 2 O 3 CH on catalyst 4 And CO 2 The conversion was 35% and 42%, respectively.
Example 2
And (3) preparing a catalyst:
(1) Preparing mesoporous alumina coated nickel-molybdenum oxide: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃, vigorously stirring for 1h until the P123 is completely dissolved, adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, adding 1.4g of nickel nitrate and 0.42g of ammonium molybdate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ for drying for 48h, grinding the dried solid sample into powder, and roasting for 4h at 550 ℃ in air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, and marking as 10Ni8MoAl-one pot;
(2) Preparing mesoporous alumina coated nickel-molybdenum carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out CH treatment 4 /CO 2 In proportion, preparing the mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the reaction tube was 8mm and the wall thickness was 2mm. The stainless steel mesh with the width of 10mm is wrapped on the outer wall of the reaction tube to be used as a ground electrode, and a stainless steel rod with the diameter of 3mm is fixed in the reaction tubeThe mandrel was used as a high voltage electrode with a discharge gap of 2.5mm and a center frequency of the plasma generator of 30kHz. Weighing a certain amount of catalyst, placing the catalyst in a reaction tube, and before the reaction, placing the catalyst in H 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, the CH on the 10Ni8MoAl-one pot catalyst 4 And CO 2 The conversion was 69.3% and 76.4%, respectively.
Example 3
And (3) preparing a catalyst:
preparing mesoporous alumina coated nickel: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃ and vigorously stirring for 1h until the P123 is completely dissolved, then adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, then adding 1.0g of nickel nitrate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ and drying for 48h, grinding the dried solid sample into powder, and roasting for 4h at 550 ℃ in an air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, and marking as 10NiAl-one pot.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the reaction tube was 8mm and the wall thickness was 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the reaction tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. Weighing a certain amount of catalyst, placing the catalyst in a reaction tube, and before the reaction, placing the catalyst in H 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, the CH on the 10NiAl-one pot catalyst 4 And CO 2 The conversion was 51% and 59%, respectively.
Example 4
And (3) preparing a catalyst:
(1) Preparing mesoporous alumina coated nickel-molybdenum oxide: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃ and vigorously stirring for 1h until the P123 is completely dissolved, then adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, then adding 1.0g of nickel nitrate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ and drying for 48h, grinding the dried solid sample into powder, and roasting for 2-6h at 500 ℃ in air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, which is marked as 10Ni4MoAl-one spot-500;
(2) Preparing mesoporous alumina coated nickel-molybdenum carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out CH treatment 4 /CO 2 In proportion, preparing the mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the reaction tube was 8mm and the wall thickness was 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the reaction tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. The specific surface area of the catalyst prepared under the roasting condition of 500 ℃ is as high as 508cm 2 And/g. Weighing a certain amount of catalyst, placing the catalyst in a reaction tube, and before the reaction, placing the catalyst in H 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, the catalyst is CH on a 10Ni4MoAl-one pot-500 catalyst 4 And CO 2 The conversion was 63.1% and 70%, respectively.
Example 5
And (3) preparing a catalyst:
(1) Preparing mesoporous alumina coated nickel-tungsten oxide: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃ and vigorously stirring for 1h until the P123 is completely dissolved, then adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, then adding 1.28g of nickel nitrate and 0.144g of ammonium tungstate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ and drying for 48h, grinding the dried solid sample into powder, and roasting at 550 ℃ for 2-6h under air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, and marking as 10Ni4WAl-one pot;
(2) Preparing mesoporous alumina coated nickel-tungsten carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out CH treatment 4 /CO 2 In proportion, preparing the mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the reaction tube was 8mm and the wall thickness was 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the reaction tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. Weighing a certain amount of catalyst, placing the catalyst in a reaction tube, and before the reaction, placing the catalyst in H 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, the CH on the 10Ni4WAl-one pot catalyst 4 And CO 2 The conversion was 65% and 71%, respectively.
Example 6
(1) Mesoporous alumina preparation: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃, vigorously stirring for 1h until P123 is completely dissolved, adding 8g of aluminum isopropoxide, vigorously stirring for 30min, then adding 1.28g of nickel nitrate and 0.196g of ammonium molybdate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ for drying for 48h, grinding the dried solid sample into powder, and roasting at 550 ℃ for 4h under an air atmosphere to obtain a mesoporous aluminum oxide coated nickel-molybdenum oxide precursor, and marking as Al-one spot;
(2) Preparing mesoporous alumina loaded nickel-molybdenum oxide: first, the mass fraction of Ni was 10% and the mass fraction of Mo was 4%. Measuring the water absorption rate (1.5 mL/g) of mesoporous alumina, weighing nickel nitrate, dissolving in ionized water to obtain nickel nitrate solution, and soaking in 1.0g S-Al with equal volume 2 O 3 And placing the support at room temperature for 24 hours, drying at 80 ℃ for 48 hours, and roasting the dried precursor for 4 hours at 550 ℃ in an air atmosphere to obtain mesoporous alumina-supported nickel-molybdenum oxide, which is marked as 10Ni4Mo/Al-IWI.
(3) Preparing mesoporous alumina loaded nickel-molybdenum carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out CH treatment 4 /CO 2 In proportion, preparing the mesoporous alumina coated nickel-molybdenum carbide catalyst in situ by plasma discharge.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the quartz reaction tube is 8mm, and the wall thickness is 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a quartz reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the quartz tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. Weighing a certain amount of catalyst, placing the catalyst in a quartz reaction tube, and placing the catalyst in H before reaction 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, the catalyst is CH on a 10Ni4Mo/Al-IWI catalyst 4 And CO 2 The conversion was 43% and 54%, respectively, and the energy efficiency was 1.5mmol/kJ.
Example 7
Preparing mesoporous alumina coated nickel: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃ and vigorously stirring for 1h until the P123 is completely dissolved, then adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, then adding 1.0g of nickel nitrate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ and drying for 48h, grinding the dried solid sample into powder, and roasting for 4h at 550 ℃ in an air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, and marking as 10NiAl-one pot.
(2)Mo 2 C-10NiAl preparation: 21mg Mo 2 Grinding C and 0.5g of 10NiAl-one pot for 1h in a mortar to obtain Mo 2 C-10NiAl catalyst.
Evaluation of catalyst Performance
The dry reforming reaction performance of the plasma catalytic methane is evaluated by adopting a micro fixed bed quartz reaction device at normal pressure. The inner diameter of the quartz reaction tube is 8mm, and the wall thickness is 2mm. A stainless steel mesh with the width of 10mm is wrapped on the outer wall of a quartz reaction tube to serve as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the quartz tube to serve as a high-voltage electrode, a discharge gap is 2.5mm, and the central frequency of a plasma generator is 30kHz. Weighing a certain amount of catalyst, placing the catalyst in a quartz reaction tube, and placing the catalyst in H before reaction 2 Pretreating at 650deg.C for 1 hr (100 mL/min), and introducing reaction gas (CH) 4 /CO 2 =1/1) was subjected to catalytic performance evaluation. The reaction product was detected on line using gas chromatography. Under the condition of no external heat source and room temperature discharge, the input power is about 60W, and when the mass airspeed is 800,000mL/g/h, mo 2 CH on C-10NiAl catalyst 4 And CO 2 The conversion was 68% and 77%, respectively, and the energy efficiency was 1.8 mmol/kJ.

Claims (1)

1. The application of nickel-carbide catalyst in dry reforming reaction of methane catalyzed by plasma is characterized in that methane and carbon dioxide are used as reaction gases, and mesoporous alumina loaded nickel-carbide catalyst with high specific surface area is prepared in situ by using plasma and is used for preparing synthesis gas H with low hydrogen-carbon ratio 2 Co=1.07, the carbide is molybdenum carbide, and the preparation of the catalyst comprises the following steps:
(1) Preparing mesoporous alumina coated nickel-molybdenum oxide: dissolving 4.2g of P123 in 80mL of ethanol solution, putting into a water bath kettle at 40 ℃, vigorously stirring for 1h until the P123 is completely dissolved, adding 6.4mL of concentrated nitric acid and 8g of aluminum isopropoxide, vigorously stirring for 30min, adding 1.28g of nickel nitrate and 0.196g of ammonium molybdate into the mixed solution, vigorously stirring for 10h, putting into a baking oven at 60 ℃ for drying for 48h, grinding the dried solid sample into powder, and roasting for 4h at 550 ℃ in air atmosphere to obtain a mesoporous alumina-coated nickel-molybdenum oxide precursor, and marking as 10Ni4MoAl-one pot;
(2) Preparing mesoporous alumina coated nickel-molybdenum carbide: tabletting and sieving mesoporous alumina coated nickel-molybdenum oxide precursor to obtain precursor particles of 40-60 meshes, and then carrying out CH treatment 4 And CO 2 Under the mixed gas of (1), the mesoporous alumina coated nickel-molybdenum carbide catalyst is prepared in situ by plasma discharge, and the catalytic reaction process is specifically as follows:
the dry reforming reaction performance evaluation of plasma catalyzed methane adopts a normal pressure micro fixed bed quartz reaction device, the inner diameter of a reaction tube is 8mm, the wall thickness is 2mm, a stainless steel mesh with the width of 10mm is wrapped on the outer wall of the reaction tube to be used as a ground electrode, a stainless steel rod with the diameter of 3mm is fixed at the central shaft of the reaction tube to be used as a high-voltage electrode, the discharge gap is 2.5mm, the central frequency of a plasma generator is 30kHz, a certain amount of catalyst is weighed and placed in the reaction tube, and the catalyst is firstly put in H with the flow rate of 100mL/min before the reaction 2 Pretreating at 650 ℃ for 1h, and then introducing CH 4 /CO 2= 1/1 of the reaction gas is subjected to catalytic performance evaluation, the reaction product is detected on line by adopting gas chromatography, no external heat source is adopted, the input power is 60W under the condition of room temperature discharge, and when the mass airspeed is 800,000mL/g/h, the CH on the 10Ni4MoAl-one pot catalyst is used 4 And CO 2 The conversion rates are 91.7% and 94.1%, the energy efficiency is 2.17mmol/kJ, the energy consumption is 0.24kWh/mol, the catalyst has excellent reaction stability, namely CH in 325h reaction time when the mass space velocity is 100,000mL/g/h 4 And CO 2 The conversion rate is above 95%;
wherein, the specific surface area of the 10Ni4MoAl-one pot catalyst is 348m 2 /g, pore size of 7.92nm and pore volume of 0.69cm 3 /g。
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