Preparation method and application of high-stability CH4 / CO2 dry reforming catalyst
The preparation of the integrated catalyst Ni-M-Si-Al-O with metal additives by a one-pot method solves the problem of sintering traditional catalysts at high temperatures, significantly improving the conversion rate of methane and carbon dioxide and the stability of the catalyst.
Patent Information
- Application Number
- CN202510080165.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-19
- Publication Date
- 2025-05-30
AI Technical Summary
Traditional methane dry reforming catalysts are prone to sintering under high temperature reaction conditions, resulting in a decrease in reaction stability. The existing overall catalysts have poor activity and are difficult to maintain stability.
The integrated catalyst Ni-M-Si-Al-O is prepared by a one-pot method. By doping metal additives such as Cu, Co, Ca, Fe, Mn, and K, the particle size of Ni particles and the interaction force between the active metal-support is regulated to improve the stability and activity of the catalyst.
At 700°C, the methane conversion of the catalyst was increased by 5% and the carbon dioxide conversion was increased by 8%. The 20-hour stability evaluation showed that the CH4 and CO2 conversion of the catalyst was almost not reduced, which significantly improved the stability and activity of the catalyst.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to a preparation method and application of a highly stable CH 4 / CO 2 dry reforming catalyst. Specifically, it is a catalyst used to convert two main greenhouse gases, CO 2 and CH 4 into syngas (CO and H 2 ) through a reforming reaction, and belongs to the fields of waste gas treatment technology and environmental protection catalysis environment. Background Art
[0002] As an efficient, green and low-carbon energy technology, methane conversion technology is of great significance under the current situation. Especially the methane dry reforming technology, which can effectively convert greenhouse gases CO 2 and CH 4 into syngas. According to the ratio of H 2 and CO in the syngas, it can be used either as a power generation fuel or as a raw material for various production processes.
[0003] Compared with traditional steam reforming and partial oxidation syngas production processes, methane dry reforming has several significant advantages. First, methane dry reforming uses carbon dioxide (a major greenhouse gas) instead of water in steam reforming as a reactant, thus providing a valuable opportunity for carbon dioxide capture and utilization, and further providing a potential solution for reducing greenhouse gas emissions. In addition, with the discovery of shale gas reserves and the progress of hydraulic fracturing technology, the supply of methane resources has increased significantly. In addition to shale gas, biogas and landfill gas (both produced by anaerobic decomposition) are also important sources of carbon dioxide and methane and can be used in the methane dry reforming process.
[0004] The methane dry reforming technology needs to be carried out at a relatively high reaction temperature. Nickel metal is the only inexpensive transition metal with catalytic performance comparable to that of precious metals. In methane dry reforming catalysts, the interaction between the active metal and the support of the supported Ni catalyst is weak. Under high-temperature reaction conditions, Ni particles are prone to sintering, resulting in a high reaction deactivation rate. The sintering of Ni under methane dry reforming conditions leads to a decrease in the reaction stability.
[0005] The design idea of this patent is to prepare a green monolithic catalyst with high stability, anti-sintering, and strong interaction between the active metal and the support through a simple preparation method and low-cost raw materials. Literature reports that the impregnation method is more convenient for preparing supported catalysts. The Ni / Al 2 O 3 prepared by the impregnation method has poor stability. Literature reports that the promoter Si can stabilize Al 2 O 3structure, while a small amount of Si reduces the Lewis acidity of alumina, improving the stability and activity of the reaction. Introducing metal promoters can enhance the stability. Literature also reports that ZSM-5 zeolites with different Si / Al ratios are used as supports to load Ni, and promoter metals are added simultaneously to prepare supported catalysts Ni-M / ZSM-5 (M is a general term for metal promoters). It is also difficult to maintain the stability of reforming catalysts. Literature reports that the one-pot method can significantly improve the activity and stability of catalysts. Therefore, the monolithic catalyst Ni-Si-Al-O was synthesized by the one-pot method, but its activity was poor. Summary of the Invention
[0006] The object of the present invention is to provide a preparation method and application of a highly stable CH 4 / CO 2 dry reforming catalyst. This method has the advantages of simple process, easy operation, and low cost. Using Ni as the active component and aluminum isopropoxide as the framework raw material, the monolithic catalyst Ni-M-Si-Al-O is prepared by the one-pot method, where M (Cu, Co, Ca, Fe, Mn, K). By doping metal promoters and modulating different metal promoters, the particle size of Ni particles and the interaction force between the active metal and the support are regulated to improve the stability of the catalyst. All components are mixed simultaneously in the same reaction environment, and the active components are highly uniformly distributed. At the same time, there is a strong interaction between the active components and the support. The more uniform active components enhance the adsorption capacity of the catalyst for CH 4 and CO 2 , thereby improving the catalytic activity and stability of the catalyst. The stronger interaction force can inhibit the sintering of active components under high-temperature reaction conditions and extend the service life of the catalyst. The application of the one-pot method to prepare the monolithic catalyst Ni-M-Si-Al-O containing promoter M (Cu, Co, Ca, Fe, Mn, K) in methane dry reforming catalysis has rarely been reported. In particular, the interaction between Fe and Ni can optimize the active sites of the catalyst, improving stability and activity. The first problem solved by the present invention is to develop a catalyst with strong stability and high activity with independent intellectual property rights; the second problem solved by the present invention is to regulate the particle size of Ni particles and the interaction force between the metal and the support, having high activity and stability at 700 °C; compared with unmodified Ni-Si-Al-O, the methane conversion rate of Ni-Fe-Si-Al-O is 81% (an increase of 5%) at 700 °C, and the carbon dioxide conversion rate is 80% (an increase of 8%). The 20-hour stability evaluation shows that the CH 4 and CO 2 conversion rates of the catalyst hardly decrease.
[0007] To achieve the above object, the technical solution adopted by the present invention is:
[0008] A preparation method and application of a highly stable catalyst for methane dry reforming to syngas, comprising the following steps:
[0009] (1) Weigh the active components in a stoichiometric ratio (the total mass without promoter metals is 100%, the mass percentage of active component Ni in the catalyst is 10%, Si accounts for 5% of the total mass, and Al accounts for 85% of the total mass). Nickel nitrate hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) is the source of active component Ni, tetraethyl orthosilicate (C 8 H 20 O 4 Si) is the source of promoter Si, and aluminum isopropoxide (C 9 H 21 AlO 3 ) is the source of main framework material Al. Metal promoters copper nitrate (Cu(NO 3 ) 2 ), cobalt nitrate hexahydrate (Co(NO 3 ) 2 ·6H 2 O), iron nitrate nonahydrate (Fe(NO 3 ) 3 ·9H 2 O), potassium chloride (Kcl), calcium nitrate tetrahydrate (Ca(NO 3 ) 2 ·4H 2 O), and manganese nitrate tetrahydrate (Mn(NO 3 ) 2 ·4H 2 O). The metal promoters are used as additional promoters and do not affect the content of the main catalyst, and the addition amount is 3% of the catalyst mass.
[0010] (2) Add the Ni(NO 3 ) 2 ·6H 2 O weighed in (1) and the metal promoters to deionized water, and stir until completely dissolved to obtain a transparent solution. Add the metal promoters to deionized water respectively, and stir until completely dissolved to obtain a transparent solution.
[0011] (3) Add the C 9 H 21 AlO 3 measured in step (1) to anhydrous ethanol, seal and stir with a constant temperature magnetic stirrer for 20 min to obtain a white solution;
[0012] (4) The C 8 H 20 O 4 weighed in step (1)Add it to the white slurry obtained in step (3); seal the constant temperature magnetic stirrer and stir for 20 min to obtain a mixed solution;
[0013] (5) Add the transparent solution obtained in step (2) to the mixed solution obtained in step (4), seal the constant temperature magnetic stirrer and stir for 20 min to obtain a mixed solution;
[0014] (6) Uncover the seal of the mixed slurry obtained in step (5), rotate and stir in a constant temperature heating magnetic stirrer until it is evaporated to dryness to form a powder;
[0015] (7) Place the powder obtained in step (6) in an oven and dry it overnight to obtain a powder;
[0016] (8) Place the powder obtained in step (7) in a muffle furnace, calcine it, naturally cool it to room temperature, press it into tablets, and grind it into a catalyst with a mesh size of 20-40, thus obtaining a catalyst for dry reforming of methane to syngas.
[0017] According to the above scheme, the activation method is calcination.
[0018] According to the above scheme, keeping the mass of the catalyst unchanged at 100%, the metal promoter is an additional promoter, and the addition amount is 3% of the mass of the catalyst.
[0019] According to the above scheme, the temperature of sealing the constant temperature magnetic stirrer for 20 min is 20 °C.
[0020] According to the above scheme, the temperature of rotating and stirring in a constant temperature heating magnetic stirrer until it is evaporated to dryness to form a powder is 80 °C;
[0021] Preferably, the drying temperature is 110 °C;
[0022] The drying time is 11-13 h;
[0023] The calcination temperature is 700 °C;
[0024] The calcination time is 5 h.
[0025] The present invention also provides the application of the catalyst for dry reforming of methane to syngas prepared by the preparation method described in any one of the above technical schemes in carbon dioxide conversion.
[0026] Compared with the prior art, the beneficial technical effects brought by the technical scheme of the present invention application are:
[0027] 1. The one-pot method of the present invention is used to prepare a Ni-based catalyst Ni-Fe-Si-Al-O doped with a metal promoter Fe for CH 4 / CO 2The reforming reaction has a significantly improved catalytic activity compared to the Ni-Si-Al-O catalyst prepared by the one-pot method. At 700 °C, the initial conversion rates of methane and carbon dioxide reach 81% and 80% respectively. The 20-hour stability evaluation shows that the CH 4 and CO 2 conversion rates of the catalyst hardly decrease.
[0028] 2. The Ni-Fe-Si-Al-O catalyst was prepared by the one-pot method. This preparation method has a simple process and low cost, and has high catalytic activity and strong stability for the dry reforming of methane, making it suitable for industrial production.
[0029] Figure 1 It is a test chart of the catalytic performance of the catalysts prepared in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.
[0030] Figure 2 It is the XRD spectrum of the catalysts prepared in Examples 1, 2, 3, 4, 5, 6 and 7.
[0031] Figure 3 It is the H 2 -TPR spectrum of the catalysts prepared in Examples 1, 2, 3, 4, 5, 6 and 7. Detailed implementation mode
[0032] The present invention will be further described below through some examples, but the present invention is not limited thereby.
[0033] Example 1
[0034] For the preparation of the dry reforming catalyst for methane, the steps are as follows:
[0035] Weigh 0.991 g of Ni(NO 3 ) 2 ·6H 2 O into a beaker, add 30 ml of deionized water to dissolve it, then add 1.8 g of γ-Al 2 O 3 , impregnate for 45 min, dry it in a water bath with a constant temperature heating magnetic stirrer at 80 °C, then take it out and place it in an oven at 110 °C for 12 h of drying; place it in a muffle furnace and calcine it at 700 °C in an air atmosphere for 5 h. Press the calcined powder into tablets with a tablet press at a pressure of 8 Mp and crush it to 20-40 mesh to obtain the Ni / Al 2 O 3 catalyst. The composition of the catalyst in Example 1 is shown in Table 1.
[0036] Evaluation of the catalyst
[0037] The stability evaluation of the catalyst was carried out in a self-made continuous flow fixed-bed reactor. The reaction tube was a quartz tube with an inner diameter of 6 mm and a length of 33 cm. The reaction temperature was measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature was controlled using a programmed temperature controller. The gas flow rate was controlled by a mass flow meter, and the space velocity was Reaction feed gas: 24.2 ml / min CH 4 , 26.4 ml / min CO 2 . In the experiment, the catalyst dosage was 0.1 g, the reaction temperature was 700 °C, and samples were taken every 0.5 h. The gas compositions of the reactants and products were analyzed using a gas chromatograph (SC3000B) to calculate the conversion rates of CH4 and CO 2 . The conversion curves of the catalyst for CH 4 and CO 2 are shown in Figure 1 . The initial conversion rates of CH 4 and CO 2 are shown in Table 1.
[0038] Example 2
[0039] 7.211 g of aluminum isopropoxide (mass fraction of component Al is 90%) was dissolved in 120 ml of absolute ethanol and stirred for 20 min. 0.991 g of nickel nitrate hexahydrate (mass fraction of active component Ni is 10%) dissolved in 20 ml of deionized water was added to the aluminum isopropoxide solution and stirred for 40 min. It was dried in a water bath using a constant temperature heating magnetic stirrer at 80 °C, then taken out and placed in an oven at 110 °C for 12 h of drying; it was calcined in a muffle furnace in an air atmosphere at 700 °C for 5 h. The calcined powder was pressed into tablets using a tablet press at a pressure of 8 MPa and crushed to 20 - 40 mesh to obtain the Ni-Al-O catalyst. The catalyst composition of Example 2 is shown in Table 1.
[0040] Evaluation of the catalyst
[0041] According to the evaluation method of Example 1, specifically as follows: The catalytic performance evaluation of the catalyst was carried out in a self-made continuous flow fixed-bed reactor. The reaction tube was a quartz tube with an inner diameter of 6 mm and a length of 33 cm. The reaction temperature was measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature was controlled using a programmed temperature controller. The gas flow rate was controlled by a mass flow meter, and the space velocity was Reaction feed gas: 24.2 ml / min CH 4 , 26.4 ml / min CO 2 . In the experiment, the catalyst dosage was 0.1 g, the reaction temperature was 700 °C, and samples were taken every 0.5 h. The gas compositions of the reactants and products were analyzed using a gas chromatograph (SC3000B) to calculate the conversion rates of CH 4 and CO 2Conversion rate. The catalyst's conversion of CH 4 and CO 2 is shown in the conversion curve graph as Figure 2 shown. The initial conversion rates of CH 4 and CO 2 are shown in Table 1.
[0042] Example 3
[0043] Dissolve 7.211 g of aluminum isopropoxide (mass fraction of component Al is 85%) in 120 ml of absolute ethanol and stir for 20 min. Then add 0.1 g of tetraethyl orthosilicate (mass fraction of component Si is 5%) dropwise and stir for another 20 min. After that, place the beaker in a constant-temperature magnetic water bath at 80 °C and stir until the liquid evaporates to a powder, then dry it in an oven at 110 °C for 12 h to obtain the support Si-Al-O. Put the obtained support into a muffle furnace and calcine it step by step, and finally keep it at 700 °C for 5 h to obtain the support Si-Al-O. Weigh 0.991 g of nickel nitrate hexahydrate (mass fraction of active component Ni is 10%) and add it to an appropriate amount of deionized water and stir to completely dissolve it. Then add 1.85 g of Si-Al-O, stir and mix evenly, and impregnate at room temperature for 45 min. Dry it in a water bath with a constant-temperature heating magnetic stirrer at 80 °C, then take it out and place it in an oven at 110 °C and dry for 12 h; place it in a muffle furnace and calcine it at 700 °C for 5 h in an air atmosphere. Press the calcined powder into tablets with a tablet press under a pressure of 8 Mp and crush it to 20 - 40 mesh, then the Ni / Si-Al-O catalyst is obtained. The catalyst composition of Example 3 is shown in Table 1.
[0044] Evaluation of the catalyst
[0045] According to the evaluation method of Example 1, specifically as follows: The catalytic performance evaluation of the catalyst is carried out in a self-made continuous flow fixed-bed reactor. The reaction tube is a quartz tube with an inner diameter of 6 mm and a length of 33 cm. The reaction temperature is measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature is controlled by a programmed temperature controller. The gas flow rate is controlled by a mass flow meter, and the space velocity is Reaction feed gas: 24.2 ml / min CH 4 , 26.4 ml / min CO 2 . In the experiment, the catalyst dosage is 0.1 g, the reaction temperature is 700 °C, and samples are taken every 0.5 h. Analyze the gas composition of the reactants and products with a gas chromatograph (SC3000B) to calculate the conversion rates of CH 4 and CO 2 . The conversion curve graphs of the catalyst for CH 4 and CO 2 at different time points are as Figure 2 shown. The CH 4 and CO 2The initial conversion rate is shown in Table 1.
[0046] Example 4
[0047] Dissolve 7.211 g of aluminum isopropoxide (mass fraction of component Al is 85%) in 120 ml of absolute ethanol and stir for 20 min. Then add 0.1 g of tetraethyl orthosilicate (mass fraction of component Si is 5%) dropwise and stir for another 20 min. Add 0.991 g of nickel nitrate hexahydrate (mass fraction of active component Ni is 10%) dissolved in 20 ml of deionized water to the aluminum isopropoxide solution and stir for 20 min. Dry it in a water bath with a constant temperature heating magnetic stirrer at 80 °C, then take it out and place it in an oven at 110 °C for 12 h of drying; calcine it in a muffle furnace at 700 °C in an air atmosphere for 5 h. Press the calcined powder into tablets with a tablet press at a pressure of 8 Mp and crush it to 20 - 40 mesh, then the Ni-Si-Al-O catalyst is obtained. The catalyst composition of Example 4 is shown in Table 1.
[0048] Evaluation of the catalyst
[0049] According to the evaluation method of Example 1, specifically as follows: The catalytic performance evaluation of the catalyst is carried out in a self-made continuous flow fixed-bed reactor. The reaction tube is a quartz tube with an inner diameter of 6 mm and a length of 33 cm. The reaction temperature is measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature is controlled by a programmable temperature controller. The gas flow rate is controlled by a mass flow meter, and the space velocity is Reaction raw material gas: 24.2 ml / min CH 4 , 26.4 ml / min CO 2 . In the experiment, the catalyst dosage is 0.1 g, the reaction temperature is 700 °C, and samples are taken every 0.5 h. Analyze the gas composition of the reactants and products with a gas chromatograph (SC3000B) to calculate the conversion rates of CH 4 and CO 2 . The conversion curves of the catalyst for CH 4 and CO 2 at different time points are as shown in Figure 2 . The initial conversion rates of CH 4 and CO 2 are shown in Table 1.
[0050] Example 5
[0051] Dissolve 7.211 g of aluminum isopropoxide (mass fraction of component Al is 85%) in 120 ml of absolute ethanol and stir for 20 min. Then add 0.1 g of tetraethyl orthosilicate (mass fraction of component Si is 5%) dropwise and stir for another 20 min. Mix 0.991 g of nickel nitrate hexahydrate (mass fraction of active component Ni is 10%) dissolved in 20 ml of deionized water with 0.088 g of Cu(NO 3 ) 2(Based on 3% of the catalyst's heavy mass), add it to the aluminum isopropoxide solution and stir for 20 min. Dry it in a water bath using a constant temperature heating magnetic stirrer at 80 °C, then take it out and place it in an oven at 110 °C for 12 h of drying; calcine it in a muffle furnace under an air atmosphere at 700 °C for 5 h. Press the calcined powder into tablets with a tablet press under a pressure of 8 MPa and crush it to 20 - 40 mesh to obtain the Ni-Cu-Si-Al-O catalyst. The catalyst composition of Example 5 is shown in Table 1.
[0052] Evaluation of the catalyst
[0053] According to the evaluation method of Example 1, specifically as follows: The catalytic performance evaluation of the catalyst is carried out in a self-made continuous flow fixed bed reactor. The reaction tube is a quartz tube with an inner diameter of 6 mm and a length of 33 cm. The reaction temperature is measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature is controlled using a programmed temperature controller. The gas flow rate is controlled by a mass flow meter, and the space velocity is Reaction feed gas: 24.2 ml / min CH 4 , 26.4 ml / min CO 2 . During the experiment, the catalyst dosage is 0.1 g, the reaction temperature is 700 °C, and samples are taken every 0.5 h. Analyze the gas composition of the reactants and products using a gas chromatograph (SC3000B) to calculate the conversion rates of CH 4 and CO 2 . The conversion curves of the catalyst for CH 4 and CO 2 at different time points are as shown in Figure 2 . The initial conversion rates of CH 4 and CO 2 are shown in Table 1.
[0054] Examples 6 - 10
[0055] Compared with Example 5, only the metal promoter in the catalyst is different (keeping the original N-Si-Al-O catalyst unchanged, and the addition amount of the metal promoter is 3% of the catalyst mass), that is, the mass of the metal promoter (Co(NO 3 ) 2 ·6H 2 O) is 0.148 g, ferric nitrate nonahydrate (Fe(NO 3 ) 3 ·9H 2 O) is 0.216 g, potassium chloride (Kcl) is 0.057 g, calcium nitrate tetrahydrate (Ca(NO 3 ) 2 ·4H 2 O) is 0.1767 g, manganese nitrate tetrahydrate (Mn(NO 3 ) 2 ·4H 2O) was 0.137 g, and the remaining steps were exactly the same as those in Example 5.
[0056] Evaluation of the catalyst
[0057] According to the evaluation method of Example 1, the details are as follows: The catalytic performance evaluation of the catalyst was carried out in a self-made continuous flow fixed bed reactor. The reaction tube was a quartz tube with an inner diameter of 6 mm and a length of 33 cm. The reaction temperature was measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature was controlled using a programmed temperature controller. The gas flow rate was controlled by a mass flow meter, and the space velocity was Reaction feed gas: 24.2 ml / min CH 4 、26.4 ml / min CO 2 , in the experiment, the catalyst dosage was 0.1 g, the reaction temperature was 700 °C, and samples were taken every 0.5 h. The gas composition of the reactants and products was analyzed by a gas chromatograph (SC3000B) to calculate the conversion rates of CH 4 and CO 2 . The conversion curves of the catalyst for CH 4 and CO 2 at different time points are as shown in Figure 1 , and the initial conversion rates of CH 4 and CO 2 are shown in Table 1.
[0058] Table 1 Composition of molecular sieve catalysts in specific examples and conversion rates of CH 4 、CO 2 and CO yield:
[0059] Table 2 Deactivation rates of CH 4 after the reaction of the catalysts in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10: Example Name of catalyst Reaction time Deactivation rate (%) 1 <![CDATA[Ni / Al 2 O 3 > 20h 1.51 2 Ni-Al-O 20h 1.69 3 Ni / Si-Al-O 20h 4.22 4 Ni-Si-Al-O 20h 0.72 5 Ni-Cu-Si-Al-O 20h 14.89 6 Ni-Co-Si-Al-O 20h 6.64 7 Ni-Fe-Si-Al-O 20h 0.057 8 Ni-K-Si-Al-O 20h 4.25 9 Ni-Ca-Si-Al-O 20h 2.40 10 Ni-Mn-Si-Al-O 20h 8.25
[0060] XRD characterization
[0061] The XRD patterns of Examples 1, 2, 3, 4, 5, 6, and 7 are as shown in Figure 2 . Characteristic diffraction peaks of NiO appeared at 2θ = 37.2°, 43.3°, 62.9°, 75.4° and 79.4° [PDF#47-1049]. Compared with the conventional Ni / Al 2 O 3 catalyst, the intensities of the characteristic diffraction peaks of the Ni-based catalyst doped with the metal promoter Fe were significantly reduced, indicating that the doping of the metal promoter could improve the dispersion of Ni particles in the catalyst to a certain extent.
[0062] Using BSD-Chem200 with H 2 -TPR, the reducibility of the fresh catalyst was studied. 0.06 g of the catalyst was weighed and placed in a tube, which was stuffed with cotton at both ends. Initially, it was treated at 300 °C for about 30 min under argon, and then the TPR measurement temperature was raised to 1000 °C at a heating rate of 10 °C·min 2 in 10% H -1 / Ar and treated for 30 min.
[0063] The H 2 -TPR spectra of the catalysts prepared in Example 1, Example 2, Example 3, Example 4, Example 5, Example 7, Example 8 and Example 9 are as Figure 3 shown. Comparing with Ni / Al 2 O 3 and Ni-Si-Al-O catalysts, the addition of metal promoters makes the peaks of H 2 -TPR appear at higher temperatures, indicating a stronger interaction between the active metal and the support in the catalyst.
Claims
1. A preparation method and application of a high-stability CH4 / CO2 dry reforming catalyst, characterized in that: The method comprises the following steps: (1) Weigh the active components in the stoichiometric ratio (the total mass without the additive metal is 100%, the mass percentage of the active component Ni in the catalyst is 10%, Si accounts for 5% of the total mass, and Al accounts for 85% of the total mass) nickel nitrate hexahydrate (Ni(NO3)2·6H2O) as the active component Ni source, tetraethyl orthosilicate (C8H 20 O4Si) as Si source, aluminum isopropoxide (C9H 21 AlO3) is the Al source of the main framework material. Metal additives include copper nitrate (Cu(NO3)2), cobalt nitrate hexahydrate (Co(NO3)2·6H2O), iron nitrate nonahydrate (Fe(NO3)3·9H2O), potassium chloride (Kcl), calcium nitrate tetrahydrate (Ca(NO3)2·4H2O), and manganese nitrate tetrahydrate (Mn(NO3)2·4H2O). Metal additives are additional additives and do not affect the content of the main catalyst. The addition amount is 3% of the catalyst mass. (2) Add the weighed Ni(NO3)2·6H2O and metal additives in (1) to deionized water and stir until they are completely dissolved to obtain a transparent solution. Add the metal additives to deionized water separately and stir until they are completely dissolved to obtain a transparent solution. (3) The C9H measured in step (1) 21 AlO3 was added to anhydrous ethanol and a constant temperature magnetic stirrer was closed for 20 min to obtain a white solution; (4) The weighed C8H 20 O4Si is added to the white slurry obtained in step (3); The thermostatic magnetic stirrer was closed for 20 min to obtain a mixed solution; (5) adding the active metal and auxiliary metal transparent solution obtained in step (2) to the mixed solution obtained in step (4), and stirring in a closed constant temperature magnetic stirrer for 20 minutes to obtain a mixed solution; (6) opening the sealed mold of the mixed slurry obtained in step (5), and rotating and stirring in a constant temperature heated magnetic stirrer until evaporated to dryness to form a powder; (7) placing the powder obtained in step (6) in an oven and drying overnight to obtain a powder; (8) The powder obtained in step (7) is placed in a muffle furnace, calcined, naturally cooled to room temperature, pressed into tablets, and ground into 20-40 mesh catalysts to obtain a methane dry reforming catalyst for producing synthesis gas.
2. The method for preparing a catalyst for producing synthesis gas by dry reforming of methane according to claim 1, characterized in that: The activation method is calcination.
3. The method for preparing a catalyst for producing synthesis gas by dry reforming of methane according to claim 1-2, characterized in that: The total mass of the carrier is 90%, the Si source accounts for 5%, and the main frame Al accounts for 85%.
4. The method for preparing a catalyst for producing synthesis gas by dry reforming of methane according to any one of claims 1 to 3, characterized in that: The carrier is aluminum isopropoxide (C9H 21 AlO3) as raw material.
5. The method for preparing the catalyst for producing synthesis gas by dry reforming of methane according to any one of claims 1 to 4, characterized in that: The catalyst without promoter metal is 100%, and the mass percentage of active component Ni is 10%.
6. The method for preparing the catalyst for producing synthesis gas by dry reforming of methane according to any one of claims 1 to 5, characterized in that: The metal additive is an additional additive and does not affect the content of the main catalyst. The added amount is 3% of the catalyst mass.
7. The method for preparing the catalyst for producing synthesis gas by dry reforming of methane according to any one of claims 1 to 6, characterized in that: All were prepared by one-pot method.
8. The method for preparing the catalyst for producing synthesis gas by dry reforming of methane according to any one of claims 1 to 7, characterized in that: The stirring temperature is 80°C; the drying temperature is 110°C; and the drying time is 11-13h.
9. The method for preparing the catalyst for producing synthesis gas by dry reforming of methane according to any one of claims 1 to 8, characterized in that: The calcination temperature is 700°C and the calcination time is 5 hours.
10. Use of the catalyst for producing synthesis gas through dry reforming of methane according to any one of claims 1 to 9 in the conversion of carbon dioxide.