CN107321351B - Preparation method of efficient catalyst for methane/carbon dioxide reforming reaction - Google Patents
Preparation method of efficient catalyst for methane/carbon dioxide reforming reaction Download PDFInfo
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Abstract
A preparation method of a high-efficiency catalyst for methane/carbon dioxide reforming reaction relates to a preparation method of the catalyst, wherein the catalyst takes nickel nitrate and nickel chloride as nickel sources, and takes alkoxy silane, high-purity silicon powder, high-purity fumed silica and silica sol as silicon sources. With N, N-dimethylformamideAbsolute ethyl alcohol is used as a solvent, alkyl ammonium halide is used as a surfactant, a high molecular microsphere template agent is added, and a sol-gel method, a hydrothermal method and a solvothermal method are adopted to prepare the hierarchical porous Ni/SiO2The catalyst is used for reaction at the temperature of 700 ℃ and under the normal pressure, and the contact time is 1 gh & mol－1Under the reaction condition, the conversion rate of methane can reach 83%, the conversion rate of carbon dioxide can reach 89%, the carbon deposition rate is reduced by 30% compared with the traditional catalyst under the same reaction time, and the service life of the catalyst is greatly prolonged. The catalyst is easy to prepare, has low cost and good industrial application prospect.
Description
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of a high-efficiency catalyst for methane/carbon dioxide reforming reaction.
Background
Currently, methane reforming is mainly methane steam reforming (SMR) and methane partial oxidation reforming (POM) and methane-carbon dioxide reforming (DM). Steam reforming of methane, which is now industrialized, is a strongly endothermic process that must be carried out at high temperatures>Reaction at 800 deg.C, and high water-carbon ratio operation (H) is required to prevent carbon deposition2O/CH4= 2.5-3), so the process has high energy consumption (large amount of water vapor), large investment and low production capacity, and can not economically meet the future large-scale requirements; partial oxidation of methane presents a significant safety hazard, and there is the potential for explosion once the combined volume of methane and oxygen is within the explosive limits. The reaction is a mild exothermic reaction, the reaction speed is very high, hot spots exist on the surface of the catalyst, the loss of active components can seriously affect the stability of the catalyst, and in addition, the carbon deposition of the catalyst is also an important factor influencing the reaction stability. And CO2/CH4Reforming can eliminate CH simultaneously4、CO2Two major greenhouse gases are of interest. CO 22/CH4The reforming reaction is a strongly endothermic reaction, and the reaction needs to be carried out at a high temperature (>700 deg.c) and how to improve the high-temperature stability and the reactivity of the reforming catalyst is the key of technical research.
Foreign scholars study the reforming reaction time in laboratory by using noble metal as catalystNow, Ru and Rn are CO-coupled2Sensitive to decomposition, and carrying out CO at 600-900 deg.C2/CH4The reforming reaction does not generate carbon deposit basically, and is the most suitable active component for reforming catalyst. Although noble metals have high catalytic activity, good carbon deposition resistance and sintering resistance, noble metal catalysts are very expensive and are not suitable for large-scale industrial production. Domestic research mainly focuses on non-noble metal catalysts, and the research finds that the active sequence is Ni>Co>Cu>Fe, wherein the activity of Ni and Co based catalysts can be compared with that of noble metals, but non-noble metal catalysts have poor high-temperature stability and are inactivated too fast due to carbon deposition. Most researchers believe that CO is present2/CH4The deactivation of reforming catalyst is mainly formed by carbon deposition and CH in CO disproportionation reaction4Sintering of the active metal, caused by the cracked carbon deposits, may also be a factor in deactivation. The particle size and dispersity of the active metal of the supported catalyst are closely related to the catalytic activity and stability of the supported catalyst. The literature results show that when the Ni crystallite size is small, the carbon deposition rate on the catalyst is comparable to the carbon elimination rate, so that the catalyst maintains stable activity. To prepare highly dispersed, small crystallite catalysts, large surface area supports are typically employed. For general oxide carriers, the specific surface area and the pore diameter are in inverse proportion, so that the pore diameter of the carrier with large surface area is small, which is not beneficial to the diffusion of reaction and products in the pore channels of the catalyst and further influences the reaction rate. Meanwhile, the aperture of the catalyst is small, and the reduction of the catalyst is not facilitated due to the excessively strong acting force between the metal and the carrier. However, the catalyst is easy to reduce, and the product and the reactant diffuse fast in the catalyst pores, however, the catalyst has low dispersity, small metal active surface area, insufficient utilization of active metal and low reaction activity. Therefore, how to solve the mutual restriction relationship among the metal dispersion degree, the reduction degree and the diffusion efficiency is one of the key factors for preparing the high-activity metal catalyst. Due to the existence of the double-pore structure, the specific surface area of the carrier is improved, and high dispersion of active metal is facilitated; secondly, the existence of the double-pore structure is also beneficial to the diffusion of reactants and products in the pore channel of the catalyst; finally, introducedThe heteroatomic oxide also acts as a catalyst promoter for the reaction.
Inui et al prepare double-channel Ni/SiO by using strong acid corrosivity of aqua regia2The catalyst greatly improves the methanation reaction activity of the catalyst on carbon dioxide. Tsubaki et al prepared a bimodal SiO by introducing nanoparticles into the macropores of the macroporous silica by impregnation2The catalyst is used for investigating the reaction performance of the catalyst in Fischer-Tropsch synthesis, and the result shows that the double-pore catalyst has high active metal dispersity and high CO conversion rate, and simultaneously, the double-pore structure is favorable for compressing CH4And (4) selectivity. A series of Pt-based SiO are prepared by pottery Kai and the like2The dual pore carrier is used for methane carbon dioxide reforming reaction and compared with single large pore and single small pore catalyst. It was found that the dual pore catalyst is superior to the single pore catalyst. The catalytic performance increases with the difference in the support in the following order: Pt/SiO2-SiO2<Pt/ZrO2-SiO2<Pt/Al2O3-SiO2. Although Pt-based SiO2The dual pore catalyst shows superior catalytic performance, but the noble metal catalyst is expensive and not suitable for large-scale industrial application. In addition, a large number of research results show that the surface properties, acidity and alkalinity of the carrier, the interaction between the carrier and the active component and the dispersion degree of the active metal caused by the interaction, and the change of the grain size have important influences on the reaction activity and the deactivation resistance of the catalyst. The reforming catalyst carrier reported in the literature at present is Al2O3、SiO2、TiO2、ZrO2And composite oxide Al2O3-MgO、ZrO2-CeO2And molecular sieves, and the like. Therefore, the catalyst carrier with proper pore size, pore channel distribution (double pore channels) and large specific surface area can improve the dispersion degree of the active metal (Ni), accelerate the diffusion of reactants and products and introduce an auxiliary agent to promote the reaction, is an effective means for improving the efficiency and stability of the catalyst and greatly reduces the cost of producing the synthesis gas on a large scale by catalytic reforming. Disclosure of Invention
The invention aims to provide a method for preparing a high-efficiency catalyst for methane/carbon dioxide reforming reactionThe method adopts a sol-gel method, a hydrothermal method and a solvothermal method to prepare the graded porous Ni/SiO2The catalyst is used for reaction at the temperature of 700 ℃ and under the normal pressure, and the contact time is 1 gh & mol－1Under the reaction condition, the conversion rate of methane can reach 83%, the conversion rate of carbon dioxide can reach 89%, and the service life of the catalyst is greatly prolonged.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a high efficiency catalyst for methane/carbon dioxide reforming reaction, the method comprising the steps of:
the active center of the catalyst is nano non-noble metal nickel and 10-30% of its oxide, the catalyst takes Ni as main active component, the carrier is silicon dioxide with hierarchical porous structure; the reaction suitable for the catalyst is a reforming reaction of methane and carbon dioxide to synthesize high-grade hydrogen energy and synthesis gas; nano non-noble metal nickel is taken as a main active component, and a carrier is graded porous to silicon dioxide with a micropore-mesopore-macropore structure; the preparation method of the catalyst adopts a hydrothermal-sol method, and a graded porous nickel-based catalyst is prepared by drying with a normal pressure blower; n, N-dimethylformamide and ethanol are taken as solvents, and alkyl ammonium halide is added as a surfactant, wherein the dosage proportion is 0.002-2%. Adding a polymer microsphere template agent with the addition amount of 1-30%; the prepared solution forms sol after hydrothermal reaction at the temperature of 120-180 ℃, and then the sol is dried and granulated to obtain the catalyst.
According to the preparation method of the high-efficiency catalyst for the methane/carbon dioxide reforming reaction, the active component nickel takes nickel nitrate hexahydrate and nickel chloride hexahydrate as nickel sources, and the loading amount is 10-30% (by weight).
According to the preparation method of the high-efficiency catalyst for the methane/carbon dioxide reforming reaction, the carrier takes alkoxy silane, high-purity silicon powder, high-purity fumed silica and silica sol as silicon sources.
The preparation method of the high-efficiency catalyst for the methane/carbon dioxide reforming reaction has the reaction temperature of 600-800 ℃.
The invention has the advantages and effects that:
the present invention is directed toThe performance of the catalyst for the existing methane/carbon dioxide catalytic reforming reaction is insufficient, and a new catalyst is provided, so that the reaction effect is improved; preparing hierarchical porous Ni/SiO by sol-gel method, hydrothermal method and solvothermal method2The catalyst is used for reaction at the temperature of 700 ℃ and under the normal pressure, and the contact time is 1 gh & mol－1Under the reaction condition, the conversion rate of methane can reach 83%, the conversion rate of carbon dioxide can reach 89%, the carbon deposition rate is reduced by 30% compared with the traditional catalyst under the same reaction time, and the service life of the catalyst is greatly prolonged.
Drawings
FIG. 1 is a scanning electron microscope image of DMF as solvent catalyst;
FIG. 2 is a scanning electron microscope image of a catalyst with ethanol as a solvent.
Detailed Description
The present invention will be described in detail with reference to examples.
The preparation method of the hierarchical porous catalyst for catalyzing the catalytic reforming reaction of methane/carbon dioxide comprises the following concrete implementation steps:
the active center of the catalyst is nano non-noble metal nickel and 10-30% of its oxide, the catalyst takes Ni as main active component, and the carrier is silicon dioxide with hierarchical porous structure. The catalyst methane and carbon dioxide carry out reforming reaction to synthesize high-grade hydrogen energy and synthesis gas. The catalyst takes nano-scale non-noble metal nickel as a main active component. The catalyst support is a hierarchical porous to silica with a microporous-mesoporous-macroporous structure. The preparation method of the catalyst adopts a hydrothermal-sol method, and a graded porous nickel-based catalyst is prepared by drying with a normal pressure blower. Wherein the active component nickel takes nickel nitrate hexahydrate and nickel chloride hexahydrate as nickel sources, and the loading amount is 10-30 percent (weight). The carrier takes alkoxy silane, high-purity silicon powder, high-purity fumed silica and silica sol as silicon sources. N, N-dimethylformamide and ethanol are taken as solvents, alkyl ammonium halide is added as a surfactant, the dosage proportion is 0.002-2%, and a polymer microsphere template is added, and the addition amount is 1-30%. The prepared solution forms sol after hydrothermal reaction at the temperature of 120-180 ℃, and then the sol is dried and granulated to obtain the catalyst; the reforming reaction of methane and carbon dioxide is carried out, and the reaction temperature is 600-800 ℃.
Example 1
The method comprises the following steps: 0.918g of nickel nitrate hexahydrate, 60ml of DMF and 2.8ml of tetraethyl orthosilicate are weighed into a beaker and stirred at room temperature for 5-10 minutes until a clear, particle-free green solution is obtained.
Step two: 0.02g of cetyltrimethylammonium bromide was weighed into the above solution, and sufficiently stirred uniformly.
Step three: the solution was poured into a hydrothermal kettle and heated at 180 ℃ for 720 minutes. And cooling to obtain the product. The sol was dried at 70 ℃ for 900 minutes to give a brownish solid cake.
Step four: grinding, calcining, setting the temperature at 400 ℃ in the calcining stage (setting the temperature at 5 ℃/min in the heating stage), and setting the time at 240 minutes. The calcined product was a black powder. Tabletting, granulating and screening out 20-40 mesh samples.
Step five: 0.1g of the catalyst was weighed out and subjected to activity evaluation on a continuous flow fixed bed reactor. The conversion rate of methane is 76%, the conversion rate of carbon dioxide is 82%, the selectivity of carbon monoxide is 92%, and the catalyst is not obviously deactivated after running for 300 hours. The morphology of the catalyst is shown in figure 1, and DMF is a scanning electron microscope picture of the solvent catalyst.
Example 2
The method comprises the following steps: 0.918g of nickel nitrate hexahydrate, 65ml of absolute ethyl alcohol and 2.8ml of tetraethyl orthosilicate are weighed and stirred for 5-10 minutes to obtain a clear green solution without particles. The other steps are the same as in example 1.
The second, third and fourth steps are the same as in example 1.
Step five: 0.1g of the catalyst was weighed out and subjected to activity evaluation on a continuous flow fixed bed reactor. The conversion rate of methane is 83%, the conversion rate of carbon dioxide is 91%, the selectivity of carbon monoxide is 93%, and the catalyst is not obviously deactivated after running for 300 hours. The morphology of the catalyst is shown in figure 2, wherein ethanol is a scanning electron microscope picture of the solvent catalyst.
Example 3
The first and second steps are the same as in example 1.
Step three: the solution was poured into a hydrothermal kettle and heated at 180 ℃ for 240 minutes. And cooling to obtain the product. The sol was dried at 70 ℃ for 900 minutes.
Step four and step five are the same as in example 1
0.1g of the catalyst was weighed out and subjected to activity evaluation on a continuous flow fixed bed reactor. The methane conversion was 65%, the carbon dioxide conversion was 78%, and the carbon monoxide selectivity was 90%. The catalyst is deactivated after 120 hours of operation, the carbon deposition is obvious in thermogravimetric analysis, and the morphology of the catalyst is in a random state.
Example 4
2ml of polystyrene microsphere aqueous solution, 60ml of DMF, 2.8ml of tetraethyl orthosilicate and 0.918g of nickel nitrate hexahydrate are taken. Pouring the substances into a beaker, and mixing for 20 minutes; pouring the mixture into a hydrothermal kettle for hydrothermal reaction, wherein the temperature is set to be 180 ℃, and the time is set to be 720 minutes. Then taking out the sample, wherein the sample is green sol, and drying the sample for 12 hours at the temperature of 80 ℃. Taking out the dried sample, grinding, loading into a crucible, calcining at 400 ℃ (temperature rise stage 5 ℃/min) for 240 minutes. And (5) taking out the sample, tabletting and granulating.
0.1g of the catalyst was weighed out and subjected to activity evaluation on a continuous flow fixed bed reactor. The methane conversion was 79%, the carbon dioxide conversion was 87%, and the carbon monoxide selectivity was 92%. The catalyst was run for 300 hours with some catalyst deactivation.
Example 6
2ml of polymethyl methacrylate microsphere aqueous solution, 60ml of DMF, 2.8ml of tetraethyl orthosilicate and 0.918g of nickel nitrate hexahydrate are taken. Pouring the substances into a beaker, and mixing for 15 minutes; pouring the mixture into a hydrothermal kettle for hydrothermal reaction, wherein the temperature is set to be 180 ℃, and the time is set to be 720 minutes. Then taking out the sample, wherein the sample is green sol, and drying the sample for 12 hours at the temperature of 80 ℃. Taking out the dried sample, grinding, loading into a crucible, calcining at 400 ℃ (temperature rise stage 5 ℃/min) for 240 minutes. And (5) taking out the sample, tabletting and granulating.
0.1g of the catalyst was weighed out and subjected to activity evaluation on a continuous flow fixed bed reactor. The methane conversion was 81%, the carbon dioxide conversion was 90%, and the carbon monoxide selectivity was 93%. The catalyst was run for 300 hours with some catalyst deactivation.
Example 7
0.918g of nickel nitrate hexahydrate, 2.06ml of silica sol and 20ml of deionized water are taken. And pouring the solution into a beaker, mixing, and stirring at a constant temperature of 50 ℃ for 120 minutes by using a constant-temperature water bath kettle. Drying and aging are carried out, and finally, a viscous light green precipitate is obtained. And finally, the final product is formed into blocks, the blocks are ground into fine particles by a mortar, and the fine particles are loaded into a crucible for calcination at the calcination temperature of 400 ℃ (the temperature rise stage is 5 ℃/min) for 240 minutes. And (5) taking out the sample, tabletting and granulating. 0.1g of the catalyst was weighed out for activity evaluation. The methane conversion was 54%, the carbon dioxide conversion was 68%, and the carbon monoxide selectivity was 89%. The catalyst is obviously deactivated after 120 hours of operation, and the carbon deposition is serious in thermogravimetric analysis of the catalyst.
Claims (1)
1. A method for preparing a high-efficiency catalyst for methane/carbon dioxide reforming reaction is characterized by comprising the following processes:
the method comprises the following steps: weighing 0.918g of nickel nitrate hexahydrate, 65ml of absolute ethyl alcohol and 2.8ml of tetraethyl orthosilicate, and stirring for 5-10 minutes to obtain a clear green solution without particles;
step two: 0.02g of hexadecyl trimethyl ammonium bromide is weighed and added into the solution, and the mixture is fully and uniformly stirred;
step three: pouring the solution into a hydrothermal kettle, and heating for 720 minutes at 180 ℃; drying the sol at 70 ℃ for 900 minutes to obtain a brown solid block;
step four: grinding and calcining, wherein the temperature is set to be 400 ℃ in the calcining stage, 5 ℃/min is set in the temperature rising stage, and the set time is 240 minutes; the calcined product is black powder; tabletting, granulating and screening out 20-40 mesh samples.
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| CN108371952A (en) * | 2018-02-28 | 2018-08-07 | 西京学院 | A kind of method that coordination-infusion process prepares methane-CO 2 reformation nickel-base catalyst |
| CN109499578A (en) * | 2019-01-23 | 2019-03-22 | 华东师范大学 | A kind of Ni base catalyst and preparation method thereof and the application in methyl methanol syngas is being prepared using coke-stove gas as raw material |
| CN110252385A (en) * | 2019-06-17 | 2019-09-20 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking catalyst |
| CN111370663B (en) * | 2020-03-18 | 2021-05-25 | 浙江锂宸新材料科技有限公司 | Porous silicon @ amorphous carbon/carbon nanotube composite material and preparation method and application thereof |
| CN114804023A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method and application of metal-molten salt for hydrogen production from natural gas and carbon black |
| CN115069260B (en) * | 2022-07-29 | 2023-05-05 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
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| CN101708853B (en) * | 2009-07-08 | 2013-03-27 | 济南大学 | Hollow silicon dioxide microsphere with different surface configurations and preparation method thereof |
| CN102698789B (en) * | 2012-05-18 | 2014-07-23 | 清华大学 | Preparation method of catalyst for preparing synthetic gas by reforming methane with carbon dioxide |
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