CN109967081B - High-activity and carbon deposition-resistant methane dry gas reforming catalyst and preparation method thereof - Google Patents

High-activity and carbon deposition-resistant methane dry gas reforming catalyst and preparation method thereof Download PDF

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CN109967081B
CN109967081B CN201910257000.2A CN201910257000A CN109967081B CN 109967081 B CN109967081 B CN 109967081B CN 201910257000 A CN201910257000 A CN 201910257000A CN 109967081 B CN109967081 B CN 109967081B
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carbon deposition
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陆安慧
贺雷
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Dalian University of Technology
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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Abstract

The invention discloses a high-activity and anti-carbon deposition methane dry gas reforming catalyst and a preparation method thereof, and particularly relates to a catalyst with a nano flaky coating structure, which is obtained by preparing stable sol with a nano flaky structure by a precipitation method, coating a second component in situ, drying, roasting, reducing and activating, and shows high-activity and anti-carbon deposition performance in a methane dry gas reforming reaction, and has no obvious inactivation when continuously running at the temperature of 400-plus 900 ℃. The method has the advantages of easily obtained raw materials and simple process, and can be widely applied to methane steam reforming, carbon dioxide-assisted dehydrogenation of ethane propane and water vapor shift reaction.

Description

High-activity and carbon deposition-resistant methane dry gas reforming catalyst and preparation method thereof
Technical Field
The invention belongs to the field of methane dry gas reforming, and particularly relates to a high-activity and carbon deposition-resistant methane dry gas reforming catalyst and a preparation method thereof.
Background
Methane dry gas reforming to synthesis gas (CH)4+CO2＝CO+H2) Is an important process for utilizing natural gas, and the process can simultaneously realize the conversion and utilization of two main greenhouse gases to obtain CO/H in the synthesis gas2The ratio is close to 1, which is beneficial to synthesizing oxygen-containing compounds or obtaining high value-added products such as hydrocarbons through a Fischer-Tropsch process, and has important environmental protection significance and economic value. The catalyst is the key to realize the reforming of the methane dry gas, and the VIII group transition metal catalyst is the main active component. Among them, the supported noble metals Ru and Rh have excellent reactivity, but their industrial applications are greatly limited due to the high price and limited reserves of the noble metals. Among non-noble metal catalysts, the supported Ni-based catalyst shows initial activity similar to that of noble metals, and is the most promising catalytic system for industrial application. But because Ni has a low Taeman temperature, it is dried at high temperatureIn the gas reforming reaction (>800 deg.c), small Ni particles are easy to aggregate and grow, resulting in the decrease of active site number and deactivation of the catalyst. In the dry gas reforming process at a lower temperature (600 ℃), the surfaces of Ni particles are easy to deposit carbon, and the catalyst is inactivated due to the fact that a large amount of carbon deposits are generated to cover active sites, and meanwhile the problems of catalyst particle pulverization, reactor pipe blockage and the like are caused. Therefore, how to improve the activity and the anti-carbon deposition performance of the Ni-based catalyst is a key and difficult point for realizing the industrial application of the Ni-based catalyst.
In order to improve the dry gas reforming activity and the anti-carbon deposition performance of the supported Ni-based catalyst, researchers at home and abroad perform a great deal of exploration including the exploration of carrier types, the addition of auxiliary agents, the addition of second metal components and the like. However, the traditional supported Ni-based catalyst is usually prepared by an impregnation method, and the obtained catalyst has the problems of non-uniform Ni particle size distribution, easy sintering and deactivation, influence of the interaction of the metal-carrier-auxiliary agent on the exposure of active components, and the like, and is difficult to realize high activity and anti-carbon deposition performance of the catalyst at the same time. Therefore, in order to simultaneously consider the high activity and the anti-carbon deposition performance of the catalyst, the design of a supported Ni-based catalyst with a novel microstructure through the innovation of a synthesis method is urgently needed.
The catalytic material with the nano-sheet structure has better activity, selectivity and stability in catalytic reaction than the traditional massive or granular catalytic material due to good mass transfer and heat transfer performance and a specific surface exposed structure. For example, a lamellar alumina material (ACS Nano,2013,7, 4902; Angew. chem. int. Ed.2015,54,13994) is prepared by improvement of the synthesis method, can be used as a carrier of a catalyst, and shows excellent catalytic performance in alkane dehydrogenation. Layered hydroxides, such as magnesium hydroxide, nickel hydroxide, magnesium aluminum hydrotalcite and the like, have nanosheet layered structure units, are adjustable in element composition, and can be used as precursors for preparing high-dispersion metal catalytic materials (patent: 201410670739.3). However, for the reforming reaction of the methane dry gas, the operation condition is often carried out at a higher temperature (>600 ℃), and after high-temperature treatment, the sheet-shaped hydroxide material is easy to agglomerate and stack, and loses the original lamellar structure, and in the process, the specific surface area of the material is reduced, the utilization rate of active metal is reduced, and the catalyst is inactivated.
Disclosure of Invention
Aiming at the problems, the invention provides a high-activity and carbon deposition-resistant methane reforming catalyst and a preparation method thereof. Obtaining a precursor nanosheet containing an active metal component by utilizing a coprecipitation-hydrothermal two-step method, then realizing in-situ coating of the nanosheet by utilizing hydrolysis of the precursor nanosheet, and obtaining the catalyst after activation. On one hand, the coating layer plays a role in stabilizing a lamellar structure and improving the exposure degree of active metal, and high activity of the catalyst is realized; on the other hand, the catalyst plays roles in isolating active metal, avoiding sintering and weakening carbon deposition generation, and improves the carbon deposition resistance of the catalyst. The preparation process of the catalyst adopts cheap inorganic salt, precipitator and water as raw materials, the process is simple, the coated catalyst with the nano flaky structure can be obtained without adding a template, the product is easy to separate, the production cost is low, and the large-scale production is facilitated.
The invention adopts the following technical scheme:
a preparation method of a high-activity and anti-carbon deposition methane dry gas reforming catalyst comprises the following steps:
s1, mixing divalent inorganic metal salt and trivalent inorganic metal salt to obtain mixed salt, dissolving the mixed salt in water to form mixed salt solution, adding the mixed salt solution into a precipitant aqueous solution, stirring and reacting for 0.5-6 hours, and separating and washing to obtain precipitate; the mixed salt is composed of active metal precursor salt and metal oxide precursor salt;
s2, re-dispersing the precipitate in water, and carrying out hydrothermal treatment to obtain stable sol (precursor nanosheet) with a nano flaky structure;
s3, mixing the coating layer precursor, the hydrolysis accelerant and the stable sol obtained in S2, stirring and reacting for 8-24 hours at the reaction temperature of 20-50 ℃, and then separating, washing and drying to obtain the composite material with the sheet coating structure;
s4, roasting, reducing and activating the composite material with the sheet-shaped coating structure obtained in the S3 to obtain the high-activity carbon deposition resistant catalyst.
Preferably, the cation of the divalent inorganic metal salt is Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Mg2+And Ca2+The cation of the trivalent inorganic metal salt is Fe3+、Co3+、Ti3+、Al3+One or more of (a); the total concentration of the cations in the mixed salt solution is 0.05-0.20mol/L, wherein the molar ratio of the divalent ions to the trivalent ions is 1: 1-6: 1.
The divalent and trivalent inorganic metal salts are one or more of nitrate, acetate, sulfate and chloride, the lamellar structure is composed of cations, and anions are arranged between layers.
Preferably, in the step S1, the precipitant is one or two of sodium hydroxide, sodium bicarbonate, ammonia water and ammonium carbonate, and the concentration of the precipitant is 0.10-0.33 mol/L; the solid content of the stable sol in the step S2 is 1-7 mg/mL; furthermore, the concentration of the precipitator is 0.13-0.33 mol/L; the solid content of the stable sol in the step S2 is 4-7mg/mL, when other conditions are the same, the solid content of the stable sol is increased by increasing the concentration of the precipitating agent, and meanwhile, the solid content of the stable sol can reach 4-7mg/mL, so that compared with the prior art (less than 3mg/mL), the separation energy consumption is reduced, and the yield of the final catalyst is effectively improved.
The coating layer precursor in the step S3 is aluminum isopropoxide, aluminum potassium sulfate, tetraethyl orthosilicate or tetrabutyl titanate; the mass ratio of the coating layer precursor to the stable sol is 3:1-0.5: 1.
In the step S4, the roasting temperature is 300-900 ℃, and the roasting time is 2-8 hours; the reduction activation conditions are as follows: introduction of H2/N2Mixed gas of H2The content is 5-100%, the flow rate is 10-100mL/min, the temperature is 300-900 ℃, and the activation time is 0.5-3 hours.
In step S2, the hydrothermal time is 10-20 hours, and the hydrothermal temperature is 80-180 ℃.
In step S3, the hydrolysis accelerator is oxalic acid, acetic acid, glutamic acid, ammonium bicarbonate, ammonia water or urea.
The separation mode in the steps S1 and S3 is suction filtration or centrifugation.
The drying mode in the steps S1 and S3 is freeze drying or oven drying, the drying temperature of the oven is 50-120 ℃, and the drying time is 24-48 hours.
The invention also provides a high-activity and carbon deposition-resistant methane dry gas reforming catalyst, which comprises a nano flaky structure and a coating layer (coating structure), wherein the thickness of a central flaky layer of the nano flaky structure is 1-10nm, the diameter of the central flaky layer is 50-200nm, and the thickness of the coating layer is 1-14 nm; the nano-sheet structure is composed of an active metal and a metal oxide support.
The active metal is one or more of Zn, Fe, Co, Ni and Cu; the metal oxide carrier is Al2O3、MgO、SiO2、TiO2And one or more of CaO.
The invention also provides application of the catalyst in the methane dry gas reforming reaction, which is characterized in that the reaction temperature is 400--1h-1。
The invention has the beneficial effects that:
the catalytic material provided by the invention has a nanosheet layer coating structure, the thickness of a precursor nanosheet is 1-10nm, the diameter of the precursor nanosheet is 30-200nm, the composition, thickness and diameter of the nanosheet can be adjusted through cation type, cation concentration and precipitant concentration, the precursor nanosheet can be dispersed in water, and a stable colloid with the solid content of 1-7mg/mL can be obtained without a surfactant. The surfactant has the functions of forming stable micelles, promoting the enrichment of TEOS and other coating precursors on the surface of an object to be coated by utilizing positive and negative electron matching and the like, and the surfactant (such as CTAB) is usually required to be added in the conventional coating process so as to realize the directional assembly of the coating on the surface of the object to be coated and prevent the self-assembly of the coating precursors from causing phase splitting. The invention can be realized without adding a surfactant in the coating process. By utilizing the interaction of positive and negative charges, the coating layer precursor and the precursor nanosheet can be directionally assembled, so that the composite material with the flaky coating structure can be obtained without the assistance of a surfactant. The use of a surfactant is reduced, the utilization rate of raw materials and the yield of the composite material are improved, the operation steps are simplified, and the waste generated in the post-treatment process is reduced. In addition, the existence of the coating layer limits the aggregation growth of Ni particles in the dry gas reforming reaction and blocks carbon deposition sites, so that the carbon deposition rate is obviously reduced.
The nano flaky structure is beneficial to the exposure of active centers and mass transfer and diffusion of reactants, so that the catalyst has high activity. The catalyst can still keep a sheet structure after being activated at high temperature, so that the catalyst can efficiently catalyze the methane dry gas reforming reaction at the temperature of 400-900 ℃. Meanwhile, the coating layer effectively prevents the active metal from sintering at high temperature and promotes the elimination of carbon deposition, thereby improving the stability of the catalyst and having no obvious inactivation when the catalyst is continuously operated at the temperature of 400-900 ℃ in the methane dry gas reforming reaction. In addition, the catalyst with different active components can be prepared by changing the species and the proportion of the precursor cations, and can be widely applied to methane steam reforming, carbon dioxide-assisted dehydrogenation of ethane propane and steam shift reaction, and the catalyst shows excellent performance.
Drawings
Fig. 1 is an X-ray diffraction pattern of NMA prepared in example 1.
Figure 2 is an X-ray diffraction pattern of NMAS-1 prepared in example 1.
Figure 3 is a transmission electron microscope image of NMAS-1 prepared in example 1.
FIG. 4 is a transmission electron micrograph of NMAS-1-R prepared in example 1.
FIG. 5 shows the results of the long-term stability test of NMAS-1-R prepared in example 1.
Fig. 6 is a transmission electron microscope photograph of NMAS-5 prepared in comparative example 2.
Detailed Description
Example 1
Preparing a Ni-Mg-Al nanosheet: 5.0mmol of Ni (NO) was respectively taken3)2·6H2O, 40.0mmol of Mg (NO)3)2·6H2O and 15.0mmol of Al (NO)3)3·9H2O, dissolving in 50mL of deionized water,to prepare a solution A. 200mL of NaOH solution having a concentration of 0.13mol/L was prepared and referred to as solution B. And (3) placing the solution B in a water bath kettle at 30 ℃, adding the solution A into the solution B under the condition of vigorous stirring, and continuing to stir for reaction for 60 minutes. And after filtering and washing, re-dispersing the precipitate into 200mL of deionized water, putting the deionized water into a hydrothermal kettle, and carrying out hydrothermal treatment at 100 ℃ for 16 hours to obtain the nanosheet sol with the solid content of 4.0 mg/mL. The XRD results confirmed (fig. 1) that the material had a nano-platelet structure, denoted NMA.
Preparation of coated Ni-Mg-Al @ SiO2The composite material comprises the following components: measuring 90mL of nanosheet sol, adding 7mL of ammonia water and 1.30mL of tetraethyl orthosilicate (TEOS), and stirring and reacting in a water bath kettle at 30 ℃ for 16 h. And centrifuging and washing the product, and drying to obtain the composite material with the lamellar coating structure. XRD result shows that the material still maintains the original nano flaky structure (figure 2), the inner layer of the material is Ni-Mg-Al nano sheet, and transmission electron microscope result (figure 3) shows that the thickness of the sheet is about 1nm, and the coating layer is SiO2About 4nm thick, about 9nm thick throughout and 50-100nm in diameter, and is designated NMAS-1.
Roasting, reduction and activation: weighing NMAS-10.2 g, roasting for 2H at 800 ℃ by using a muffle furnace, and then using a tube furnace and 10% H2/N2Reducing for 1h in the atmosphere at 800 ℃ to obtain the high-activity and anti-carbon deposition methane dry gas reforming catalyst NMAS-1-R, wherein the result of a transmission electron microscope is shown in figure 4, the catalyst still keeps a sheet-shaped coating structure, and the size of Ni particles is 5-13 nm.
Example 2
Example 1 was repeated, but the amount of TEOS added was 0.65mL, yielding composite NMAS-2 with a lamellar coating structure, with a coating thickness of 2 nm. The high-activity and anti-carbon deposition methane dry gas reforming catalyst NMAS-2-R is obtained after reduction and activation.
Example 3
Example 1 was repeated, but the amount of TEOS added was 2.60mL, to give composite NMAS-3 of a sheet-coated structure, with a coating thickness of 7 nm. The high-activity and anti-carbon deposition methane dry gas reforming catalyst NMAS-3-R is obtained after reduction and activation.
Example 4
Preparation of Cu-Zn-Al NaRice flake: respectively taking 18.0mmol of Cu (NO)3)2·6H2O, 22.0mmol ZnCl2·6H2O and 15.0mmol of Al (NO)3)3·9H2O, dissolved in 50mL of deionized water to prepare solution A. 200mL of NaOH solution having a concentration of 0.33mol/L was prepared and referred to as solution B. And (3) placing the solution B in a water bath kettle at 30 ℃, adding the solution A into the solution B under the condition of vigorous stirring, and continuing to stir for reaction for 60 minutes. And after filtering and washing, re-dispersing the precipitate into 300mL of deionized water, putting the deionized water into a hydrothermal kettle, and carrying out hydrothermal treatment at 100 ℃ for 16 hours to obtain the nanosheet sol with the solid content of 7 mg/mL.
Preparation of coated Cu-Zn-Al @ Al2O3The composite material comprises the following components: and taking 30mL of the sol, adding 7mL of ammonia water, adding 70mL of aluminum isopropoxide/isopropanol solution (containing 1.2mmol of aluminum isopropoxide), and stirring in a water bath kettle at the temperature of 30 ℃ for reaction for 16 hours. Separating and drying to obtain the composite material with a lamellar coating structure, wherein the inner layer of the material is a Cu-Zn-Al nanosheet, and the coating layer is Al2O3。
Roasting, reduction and activation: weighing Cu-Zn-Al @ Al2O30.2g of composite material, roasting for 2 hours at 300 ℃ by using a muffle furnace, and then using a tube furnace and 10% H2/N2Reducing for 1h in atmosphere at 300 deg.C to obtain catalyst for water-gas shift reaction.
Example 5
Preparing Co-Al nanosheets: respectively taking 45.0mmol of Co (CH)3COO)2And 15.0mmol of Al (NO)3)3·9H2O, dissolved in 50mL of deionized water to prepare solution A. 200mL of NaOH and Na are prepared2CO3Mixing the solution, NaOH concentration is 0.15mol/L, Na2CO3The concentration was 0.10mol/L and was referred to as solution B. And (3) placing the solution B in a water bath kettle at 30 ℃, adding the solution A into the solution B under the condition of vigorous stirring, and continuing to stir for reaction for 30 minutes. And after filtering and washing, re-dispersing the precipitate into 300mL of deionized water, putting the deionized water into a hydrothermal kettle, and carrying out hydrothermal treatment at 100 ℃ for 16 hours to obtain nanosheet sol, wherein the solid content is 5.8mg/mL, so that Co-Al nanosheets are obtained and recorded as Co-Al.
Preparation of coated Co-Al @ TiO2The composite material comprises the following components: 50mL of nanosheet sol is measured, and 40mL of ethanol and 7mL of ammonia water are added to obtain a mixed solution A. Dissolving 0.82mL of tetrabutyl titanate in 10mL of ethanol, slowly dripping the solution into the solution A in a water bath kettle at the temperature of 30 ℃, and stirring for reacting for 4 hours. Centrifuging and washing the product, and drying to obtain the composite material with a lamellar coating structure, wherein the inner layer of the material is Co-Al nanosheet, and the coating layer is TiO2。
Roasting, reduction and activation: weighing Co-Al @ TiO20.2g of composite material, roasting for 2 hours at 600 ℃ by using a muffle furnace, and then using a tube furnace and 10% H2/N2Reducing for 1h in atmosphere at 600 ℃ to obtain the Co-based catalyst.
Example 6
Preparing a bimetallic coated catalyst: example 1 was repeated, but in the precursor salt solution for the preparation of Ni-Mg-Al nanoplates, FeCl was added2And the molar ratio of Fe to Ni is 1:1, and the high-activity and carbon deposition-resistant methane dry gas reforming catalyst NFMAS-R is obtained after reduction activation.
Example 7
Preparing a bimetallic coated catalyst: example 1 was repeated, but in the precursor salt solution for the preparation of Ni-Mg-Al nanoplates, Co (CH) was added3COO)2And the molar ratio of Co to Ni is 1:1, and the high-activity and carbon deposition-resistant methane dry gas reforming catalyst NCMAS-R is obtained after reduction activation.
Example 8
Preparing a bimetallic coated catalyst: example 1 was repeated, but in the precursor salt solution for the preparation of Ni-Mg-Al nanosheets, ZnSO was added4And the molar ratio of Zn to Ni is 1:1, and the high-activity and carbon deposition-resistant methane dry gas reforming catalyst NZMAS-R is obtained after reduction and activation. Comparative example 1 (not according to the invention)
Adding surfactant to prepare Ni-Mg-Al @ SiO2The composite material comprises the following components: 73mL of the Ni-Mg-Al sol prepared in example 1 was weighed, diluted to 100mL, 1.0g of CTAB, 7mL of ammonia water and 1.30mL of tetraethyl orthosilicate were added, and the mixture was stirred in a 30 ℃ water bath and reacted for 16 hours. And centrifuging and washing the product, and drying to obtain the composite material with a lamellar coating structure, wherein the thickness of the coating layer is about 2nm and is recorded as NMAS-4.
Taking NMAS-40.2 g, roasting for 2H at 800 ℃ by using a muffle furnace, and then using a tubular furnace and 10% H2/N2Reducing for 1h in the atmosphere at the reduction temperature of 800 ℃ to obtain the catalyst NMAS-4-R. Comparative example 2 (not according to the invention)
Preparation of Ni-Mg-Al @ SiO by traditional coprecipitation method2The composite material comprises the following components: 5.0mmol of Ni (NO) was respectively taken3)2·6H2O, 40.0mmol of Mg (NO)3)2·6H2O and 15.0mmol of Al (NO)3)3·9H2Dissolving 0.6mol of O and urea in 250mL of deionized water to prepare a mixed solution, placing the mixed solution in a water bath kettle at 90 ℃, and reacting for 18h under the stirring condition to obtain a precipitate. 30mg of the precipitate is redispersed in 200mL of water, 7mL of ammonia water and 1.30mL of tetraethyl orthosilicate, and the mixture is stirred in a water bath kettle at the temperature of 30 ℃ to react for 16 hours. And centrifuging and washing the product, and drying to obtain the composite material with a lamellar coating structure, wherein the thickness of the coating layer is about 4nm and is recorded as NMAS-5.
Taking NMAS-50.2 g, roasting for 2H at 800 ℃ by using a muffle furnace, and then using a tubular furnace and 10% H2/N2Reducing for 1h in the atmosphere at the reduction temperature of 800 ℃ to obtain the catalyst NMAS-5-R. COMPARATIVE EXAMPLE 3 (not in accordance with the invention)
Preparation of Ni/Al by traditional dipping method2O3: weigh 0.5g Ni (NO)3)2·6H2O was dissolved in 10mL of deionized water, and 0.9g of Al was separately weighed2O3Adding into the nickel nitrate solution while stirring, soaking, and drying the excessive water to obtain Ni-based catalyst, named Ni/Al, by soaking method2O3。
Taking Ni/Al2O30.2g, roasting for 2 hours at 800 ℃ by using a muffle furnace, and then using a tube furnace and 10% H2/N2Reducing for 1h in atmosphere at 800 ℃ to obtain the catalyst Ni/Al2O3-R。
Example 9 catalyst Activity test
The evaluation of the catalyst of the invention was carried out on a fixed bed reactor, taking methane reforming with carbon dioxide as an example, under the following experimental conditions: space velocity 60000mLg-1h-1100mg of catalyst and 100mLmin of total flow of raw material gas-1Wherein the volume ratio is V (CH)4:CO2:N2) The results of the activity tests for the different preparation methods were compared as 1:1:3, as in table 1. As can be seen from Table 1, Ni/Al prepared by the conventional impregnation method of comparative example 3 at the reaction temperature of 600 ℃ at which carbon deposition is most severe2O3Compared with the-R catalyst, the nano flaky catalytic material NMA in the embodiment 1 shows better reaction activity, and the composite material NMAS-1 with the nano flaky coating structure is subjected to reduction activation to obtain NMAS-1-R, so that the nano flaky catalytic material NMA shows more excellent catalytic performance, the reaction rate is nearly twice of that of the traditional catalyst at the same reaction temperature, and no obvious carbon deposition exists in the reaction interval of 300-900 ℃; when the coating thickness is changed to obtain NMAS-2 and NMAS-3, the reduction and activation are carried out to obtain the reaction activity and H of the catalyst2The ratio of/CO is changed, and the coating thickness can be selected according to the working condition requirement; in the comparative example 1, a surfactant CTAB is added in the coating process, the carbon deposition rate of the obtained catalyst is 5 times that of NMAS-1-R, and the stability is poor; the precursor sheet prepared by the conventional coprecipitation method in comparative example 2 has a diameter of about 1-2 μm, a thickness of 50-400nm (see fig. 6), a large size, a poor activity of the resulting catalyst, and a large carbon deposition rate.
The bimetal has excellent catalytic activity and carbon deposition resistance, especially the sintering resistance is further enhanced, Ni particles do not obviously aggregate after reaction, and H2the/CO ratio can be modulated as desired.
Example 10 catalyst stability Performance test
In order to test the service life of the catalyst in the dry methane reforming, the test is carried out in a carbon deposition area at 600 ℃, the conversion rate is controlled to be lower than the equilibrium conversion rate, and the specific experimental conditions are as follows: fixed bed reactor, NMAS-1-R catalyst 50mg, raw gas total flow 50mL min-1Space velocity of 60000mL g-1h-1In which CH4Flow rate 10mL min-1，CO2Flow rate 10mL min-1The dilution gas is N2As a result, as shown in FIG. 5, no catalyst deactivation was observed within the reaction time of 60 hours.
Table 1 comparative table of activity test results of catalysts
Figure BDA0002014049270000131

Claims (7)

1. The preparation method of the anti-carbon deposition methane dry gas reforming catalyst is characterized by comprising the following steps:
s1, mixing divalent inorganic metal salt and trivalent inorganic metal salt, dissolving the mixture in water to form mixed salt solution, adding the mixed salt solution into a precipitant aqueous solution, reacting for 0.5-6 hours, separating and washing to obtain precipitate; the mixed salt is composed of active metal precursor salt and metal oxide precursor salt;
s2, re-dispersing the precipitate in water, and carrying out hydrothermal treatment to obtain stable sol with a nano flaky structure;
s3, mixing the coating precursor, the hydrolysis promoter and the stable sol, and reacting at 20-50 deg.CoC, reacting for 4-24 hours, and then separating, washing and drying to obtain the composite material with the sheet-shaped coating structure;
s4, roasting, reducing and activating the composite material with the sheet-shaped coating structure to obtain the high-activity and anti-carbon deposition methane dry gas reforming catalyst;
the coating layer precursor in the step S3 is aluminum isopropoxide, aluminum potassium sulfate, tetraethyl orthosilicate or tetrabutyl titanate; the mass ratio of the coating layer precursor to the stable sol is 3:1-0.5: 1;
the catalyst comprises a nano flaky structure and a coating layer, wherein the thickness of a central flaky layer of the nano flaky structure is 1-10nm, the diameter of the central flaky structure is 50-200nm, and the thickness of the coating layer is 1-14 nm; the nano flaky structure is composed of active metal and a metal oxide carrier; the active metal is one or more of Zn, Fe, Co, Ni and Cu; the metal oxide carrier is Al2O3、MgO、SiO2、TiO2And one or more of CaO.
2. The anti-carbon deposition methane dry gas reforming catalyst as claimed in claim 1The preparation method of the agent is characterized in that: the cation of the divalent inorganic metal salt is Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Mg2+And Ca2+The cation of the trivalent inorganic metal salt is Fe3+、Co3+、Ti3+、Al3+One or more of (a); the total concentration of the cations in the mixed salt solution is 0.05-0.20mol/L, wherein the molar ratio of the divalent ions to the trivalent ions is 1: 1-6: 1.
3. The method for preparing the anti-carbon deposition methane dry gas reforming catalyst as claimed in claim 1 or 2, wherein the method comprises the following steps: in the step S1, the precipitant is one or two of sodium hydroxide, sodium bicarbonate, ammonia water and ammonium carbonate, and the concentration of the precipitant is 0.10-0.33 mol/L; the solid content of the stable sol in step S2 is 1-7 mg/mL.
4. The method for preparing the anti-carbon deposition methane dry gas reforming catalyst as claimed in claim 3, wherein the method comprises the following steps: the concentration of the precipitant is 0.13-0.33 mol/L; the solid content of the stable sol in step S2 was 4-7 mg/mL.
5. The method for preparing the anti-carbon deposition methane dry gas reforming catalyst as claimed in claim 1, wherein the method comprises the following steps: the reduction activation conditions in step S4 are: introduction of H2/N2Mixed gas of H2The content is 5-100%, the flow rate is 10-100mL/min, and the temperature is 300-oAnd C, activating for 0.5-3 hours.
6. The method for preparing the anti-carbon deposition methane dry gas reforming catalyst as claimed in claim 1, wherein the method comprises the following steps: step S2, the hydrothermal time is 10-20 hours, and the hydrothermal temperature is 80-180oC。
7. The use of the catalyst obtained by the preparation method according to claim 1 in the methane dry gas reforming reaction, wherein: the reaction temperature is 400-oC, the molar ratio of the methane to the carbon dioxide is 1:1-1:1.3, the volume concentration of the methane is 10-40%, and the volume space velocity is 20-180L g-1h-1。
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