CN114272950A - CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof - Google Patents
CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of catalysts, and discloses CH4、CO2The catalyst is prepared by taking a clay-based ordered mesoporous molecular sieve as a carrier to load nickel, manganese and zirconium as active metals, wherein the carrier is synthesized by taking attapulgite acidified by inorganic acid as a silicon source and a template agent through hydrothermal crystallization under an alkaline condition, and the loading amounts of the active metals are respectively as follows: 1-15 wt% of nickel, 1-5 wt% of manganese and 1-5 wt% of zirconium. The invention utilizes the compounding of three metals of nickel, manganese and zirconium to improve the sintering resistance of the catalyst and the carbon deposit removing capability of the catalyst, reduces the production cost of the catalyst compared with other nickel-based catalysts, is applied to the reaction of preparing the synthesis gas by catalytic reforming of low-concentration coal mine gas/carbon dioxide,can obviously improve the carbon deposit resistance and sintering resistance of the catalyst, prolong the service life of the catalyst and have wide application prospect.
Description
Technical Field
The invention relates to the field of catalysts, in particular to CH4、CO2A catalyst for reforming and preparing synthesis gas, a preparation method and application thereof.
Background
Synthesis gas (mainly H)2And CO) is an important feed gas for the production of premium fuels and platform chemicals. They are generally synthesized by natural gas partial oxidation or steam reforming, petroleum (heavy oil) partial oxidation, petroleum (light oil) steam reforming, and coal gasification processes. In the process, the problems of high operating condition requirement, high cost of raw materials of a process route and the like exist.
Coal mine gas is a natural gas resource which is produced in a coal seam and takes methane as a main component along with coal. However, in the coal mine gas mining process in China, the problems that the utilization rate of coal mine gas (mainly low-concentration coal mine gas with the methane concentration lower than 30%) is not high, the coal mine gas is directly emptied and the like generally exist. This results in a large waste of resources and at the same time aggravates the greenhouse effect and environmental stress. By utilizing the reforming principle and adopting the low-concentration coal mine gas/carbon dioxide catalytic reforming to prepare the synthetic gas, the problems that the raw material of the synthetic gas is expensive and the low-concentration coal mine gas is directly exhausted can be effectively solved, and the value-added utilization of the synthetic gas and the carbon dioxide is realized.
The design, development and utilization of the metal-supported catalyst are effective means for further improving the yield of the synthesis gas prepared by reforming the low-concentration coal mine gas/carbon dioxide. At present, research at home and abroad mainly focuses on development of nickel-based catalysts, but the nickel-based catalysts show high carbon-hydrogen bond breaking capacity in the process of preparing synthesis gas by catalyzing low-concentration coal mine gas/carbon dioxide reforming, and meanwhile, the service life of the nickel-based catalysts is still limited by key scientific problems of sintering and carbon deposit inactivation.
Disclosure of Invention
To solve the above-mentioned problems in the background art, the present invention provides a CH4、CO2The catalyst has high activity and high stability of resisting active component sintering and carbon deposit.
The purpose of the invention can be realized by the following technical scheme:
CH (physical channel)4、CO2The catalyst for preparing the synthesis gas by reforming is prepared by taking a clay-based ordered mesoporous molecular sieve as a carrier to load nickel, manganese and zirconium as active metals, taking attapulgite acidified by inorganic acid as a silicon source as the carrier to synthesize the carrier by hydrothermal crystallization with a template agent under an alkaline condition, wherein the loading amounts of the active metals are respectively as follows: 1-15 wt% of nickel, 1-5 wt% of manganese and 1-5 wt% of zirconium.
CH (physical channel)4、CO2The preparation method of the catalyst for preparing the synthesis gas by reforming comprises the following steps:
s1, acidifying the attapulgite for 10-15 hours at the temperature of 150-200 ℃ and the concentration of inorganic acid of 3.5-6 mol/L, and filtering, washing and drying to obtain an attapulgite-based silicon source;
s2, fully stirring the obtained silicon source, a template agent and sodium hydroxide, regulating and controlling the pH value by an acid titration method in the process to enable the pH value to be stable within the range of 10-12, then sealing and carrying out hydrothermal treatment on the suspension for a period of time, and obtaining the attapulgite-based ordered mesoporous molecular sieve carrier through centrifugation, washing, drying and calcination;
s3, mixing the nickel, manganese and zirconium-containing metal precursor salt solution with citric acid for a period of time, adding the mixture into the attapulgite-based silicon source suspension, stirring the mixture fully until gel is formed, evaporating, drying, grinding, sieving and calcining the gel to obtain the catalyst.
Further preferably, in step S1, the inorganic acid is selected from one or two of hydrochloric acid and sulfuric acid.
Further preferably, in the step S2, the template agent is cetyl trimethyl ammonium bromide, the mass ratio of the attapulgite silicon source to the template agent is 1: 1.58-1.94, the stirring temperature is 30-40 ℃, and the stirring time is 6-12 hours.
Further preferably, the hydrothermal treatment temperature in step S2 is 100-180 ℃, the time is 24-96 h, the drying temperature is 100 ℃, the time is 8-12 h, and the calcination treatment condition is that the temperature is increased to 550-650 ℃ in a gradient of 2-4 ℃/min under the flowing air atmosphere and is kept for 6-8 h.
Further preferably, in the step S3, the nickel, manganese and zirconium metal precursor salts are respectively nickel nitrate hexahydrate, manganese nitrate hexahydrate and zirconium nitrate pentahydrate, the molar ratio of metal ions to citric acid in the precursor salt solution is 1: 1-2, the evaporation temperature is 70-90 ℃, the drying temperature is 100 ℃, the time is 8-12 h, and the calcination treatment condition is that the temperature is increased to 500-700 ℃ at a temperature gradient of 2-4 ℃/min under the flowing air atmosphere and is kept for 3-5 h.
CH (physical channel)4、CO2The application of the catalyst for preparing the synthesis gas by reforming comprises the steps of firstly reducing the catalyst in a hydrogen/nitrogen atmosphere, and then carrying out performance test on the synthesis gas prepared by reforming low-concentration coal mine gas with carbon dioxide in a miniature fixed bed reactor.
More preferably, the reduction condition is 10-15 vol% H at 100-150 mL/min2/N2Treating the gas flow for 1-3 h at 600-800 ℃, wherein the reaction conditions for preparing the synthesis gas by catalytically reforming the low-concentration coal mine gas (methane) carbon dioxide are as follows: the catalyst dosage is 0.1-0.5 g, the molar ratio of methane to carbon dioxide in the feeding is 1-1.2, the gas feeding airspeed is 10000-60000 mL-h-1-gcat-1, and the reaction temperature is 400-700 ℃.
The invention has the beneficial effects that:
according to the invention, three metals of nickel, manganese and zirconium are compounded, and manganese, zirconium and nickel can form a metal alloy or spinel structure in the calcining and reducing processes, so that the anchoring capability on active metals can be enhanced, and the sintering resistance of the catalyst is improved; meanwhile, the manganese and zirconium multi-valence metal can form oxygen defects on the surface of the catalyst to enhance the adsorption and activation capacity of the catalyst on carbon dioxide, so that the carbon deposition removing capacity of the catalyst is improved; compared with other nickel-based catalysts, the invention utilizes attapulgite with high thermal stability as a silicon source to synthesize the ordered mesoporous molecular sieve as a carrier, thereby reducing the production cost of the catalyst.
When the catalyst is applied to catalyzing low-concentration coal mine gas to reform carbon dioxide to prepare synthesis gas, the conversion rate of methane and carbon dioxide can exceed 80%, and H in the synthesis gas2The ratio of/CO is 0.8-1, the catalyst does not lose activity after 500h of reaction, has the advantages of high activity, high stability and low cost, and meets the requirement of low-concentration coal mine gas carbon dioxideThe industrial requirement of preparing synthesis gas by catalytic reforming; the invention is applied to the reaction of preparing synthesis gas by catalytic reforming of low-concentration coal mine gas/carbon dioxide, can obviously improve the carbon deposit resistance and sintering resistance of the catalyst, prolongs the service life of the catalyst and has wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The various starting materials used in the following examples are all commercially available products known in the art unless otherwise specified.
Example 1
In the catalyst for preparing synthesis gas by reforming low-concentration coal mine gas/carbon dioxide prepared in the embodiment, the active component nickel (Ni) content is 1 wt%, the manganese (Mn) content is 1 wt%, the zirconium (Zr) content is 1 wt%, and the rest components are attapulgite-based ordered mesoporous molecular sieve carriers, and the preparation method is as follows: weighing 20g of attapulgite clay, uniformly dispersing in 120mL3.5mol/L hydrochloric acid solution by ultrasonic oscillation to form a suspension I, transferring the suspension I into a 200mL polytetrafluoroethylene-lined hydrothermal kettle, treating at 150 ℃ for 10h, cooling to room temperature, filtering and washing with deionized water to neutrality, filtering and washing with absolute ethyl alcohol for three times, drying in a 100 ℃ oven for 8h, and grinding with a mortar to obtain the attapulgite-based silicon source. Weighing 2.00g of attapulgite-based silicon source, and uniformly dispersing in 20mL of deionized water to form a suspension II; 3.16g of cetyltrimethylammonium bromide and 0.55g of sodium hydroxide were weighed out and dissolved in 20mL of deionized water at 35 ℃ to form a solution S-1. And dropwise adding the suspension II into the solution S-1, stirring for 6 hours, and then dropwise adding a 0.1mol/L hydrochloric acid solution to adjust the pH to 11 to form a suspension III. Transferring the suspension III into a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization at 120 ℃ for 96h, cooling to room temperature, centrifuging, washing with water, and washing with ethanol to obtain a suspensionAnd (3) neutralizing, drying in an oven at 100 ℃ for 8h, grinding, calcining in a flowing air atmosphere at 550 ℃ for 6h, and removing the template agent to obtain the attapulgite-derived ordered mesoporous molecular sieve. 0.10g of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O), 0.11g of manganese nitrate hexahydrate (Mn (NO)3)2·6H2O) and 0.10g of zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O) is completely dissolved in 25mL of deionized water to form a suspension IV; weighing 0.18g of citric acid, completely dissolving in 25mL of deionized water to form a solution S-2, slowly pouring the solution S-2 into the suspension IV, continuously stirring to form sol, adding 2g of attapulgite-based ordered mesoporous molecular sieve, uniformly stirring, evaporating to dryness at 70 ℃, washing, filtering, drying, grinding and screening to obtain white powder. And putting the obtained white powder in a tubular furnace, introducing air atmosphere, raising the temperature from room temperature to 600 ℃ at the heating rate of 4 ℃/min, calcining at constant temperature for 4h, and cooling to room temperature to obtain the catalyst, wherein the number is 1 #.
Example 2
In the catalyst for preparing synthesis gas by reforming low-concentration coal mine gas/carbon dioxide prepared in the embodiment, the active component nickel (Ni) content is 15 wt%, the manganese (Mn) content is 5 wt%, the zirconium (Zr) content is 5 wt%, and the rest components are attapulgite-based ordered mesoporous molecular sieve carriers, and the preparation method is as follows: weighing 20g of attapulgite clay, uniformly dispersing in 120mL of 4mol/L sulfuric acid solution by ultrasonic oscillation to form a suspension I, transferring the suspension I into a 200mL of a polytetrafluoroethylene-lined hydrothermal kettle, treating at 160 ℃ for 12h, cooling to room temperature, filtering and washing with deionized water to be neutral, filtering and washing with absolute ethyl alcohol for three times, drying in a 100 ℃ oven for 12h, and grinding with a mortar to obtain the attapulgite-based silicon source. Weighing 2.00g of attapulgite-based silicon source, and uniformly dispersing in 20mL of deionized water to form a suspension II; 3.88g of cetyltrimethylammonium bromide and 0.55g of sodium hydroxide were weighed out and dissolved in 20mL of deionized water at 40 ℃ to form a solution S-1. And dropwise adding the suspension II into the solution S-1, stirring for 8 hours, and then dropwise adding a 0.1mol/L hydrochloric acid solution to adjust the pH to 11.5 to form a suspension III. Transferring the suspension III into a 50mL hydrothermal kettle with a polytetrafluoroethylene liningCarrying out hydrothermal crystallization at 100 ℃ for 24h, cooling to room temperature, centrifuging, washing with water, washing with ethanol to neutrality, drying in an oven at 100 ℃ for 12h, grinding, calcining in a flowing air atmosphere at 600 ℃ for 8h, and removing the template agent to obtain the attapulgite-derived ordered mesoporous molecular sieve. 1.98g of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O), 0.70g manganese nitrate hexahydrate (Mn (NO)3)2·6H2O) and 0.63g of zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O) is completely dissolved in 25mL of deionized water to form a suspension IV; weighing 0.36g of citric acid, completely dissolving in 25mL of deionized water to form a solution S-2, slowly pouring the solution S-2 into the suspension IV, continuously stirring to form sol, adding 2g of attapulgite-based ordered mesoporous molecular sieve, uniformly stirring, evaporating at 75 ℃, washing, filtering, drying, grinding and screening to obtain white powder. And putting the obtained white powder in a tubular furnace, introducing air atmosphere, raising the temperature from room temperature to 700 ℃ at the heating rate of 2 ℃/min, calcining at constant temperature for 3h, and cooling to room temperature to obtain the catalyst, wherein the number is 2 #.
Example 3
In the catalyst for preparing synthesis gas by reforming low-concentration coal mine gas/carbon dioxide prepared in the embodiment, the active component nickel (Ni) content is 10 wt%, the manganese (Mn) content is 5 wt%, the zirconium (Zr) content is 5 wt%, and the rest components are attapulgite-based ordered mesoporous molecular sieve carriers, and the preparation method is as follows: weighing 20g of attapulgite clay, uniformly dispersing in 120mL of 6mol/L hydrochloric acid solution by ultrasonic oscillation to form a suspension I, transferring the suspension I into a 200mL of polytetrafluoroethylene-lined hydrothermal kettle, treating at 200 ℃ for 12h, cooling to room temperature, filtering and washing with deionized water to be neutral, filtering and washing with absolute ethyl alcohol for three times, drying in a 100 ℃ oven for 12h, and grinding with a mortar to obtain the attapulgite-based silicon source. Weighing 2.00g of attapulgite-based silicon source, and uniformly dispersing in 20mL of deionized water to form a suspension II; 3.88g of cetyltrimethylammonium bromide and 0.55g of sodium hydroxide were weighed out and dissolved in 20mL of deionized water at 40 ℃ to form a solution S-1. Dropwise adding the suspension II into the solution S-1, stirring for 8h, and dropwise adding 0.1mol/L hydrochloric acid solution to adjust the pH to 11.5 to form suspensionAnd III. And (3) transferring the suspension III into a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization at 100 ℃ for 24h, cooling to room temperature, centrifuging, washing with water, washing with ethanol to neutrality, drying in a 100 ℃ oven for 12h, grinding, calcining in a 600 ℃ flowing air atmosphere for 6h, and removing the template agent to obtain the attapulgite-derived ordered mesoporous molecular sieve. 1.24g of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O), 0.65g of manganese nitrate hexahydrate (Mn (NO)3)2·6H2O) and 0.59g of zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O) is completely dissolved in 25mL of deionized water to form a suspension IV; weighing 0.43g of citric acid, completely dissolving in 25mL of deionized water to form a solution S-2, slowly pouring the solution S-2 into the suspension IV, continuously stirring to form sol, adding 2g of attapulgite-based ordered mesoporous molecular sieve, uniformly stirring, evaporating at 80 ℃, washing, filtering, drying, grinding and screening to obtain white powder. And putting the obtained white powder in a tubular furnace, introducing air atmosphere, raising the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, calcining at constant temperature for 5h, and cooling to room temperature to obtain the catalyst, wherein the number is 3 #.
Example 4
In the catalyst for preparing synthesis gas by reforming low-concentration coal mine gas/carbon dioxide prepared in the embodiment, the active component nickel (Ni) content is 10 wt%, the manganese (Mn) content is 2.5 wt%, the zirconium (Zr) content is 2.5 wt%, and the rest components are attapulgite-based ordered mesoporous molecular sieve carriers, and the preparation method is as follows: weighing 20g of attapulgite clay, uniformly dispersing in 120mL of 6mol/L sulfuric acid solution by ultrasonic oscillation to form a suspension I, transferring the suspension I into a 200mL of polytetrafluoroethylene-lined hydrothermal kettle, treating at 180 ℃ for 15h, cooling to room temperature, filtering and washing with deionized water to be neutral, filtering and washing with absolute ethyl alcohol for three times, drying in a 100 ℃ oven for 10h, and grinding with a mortar to obtain the attapulgite-based silicon source. Weighing 2.00g of attapulgite-based silicon source, and uniformly dispersing in 20mL of deionized water to form a suspension II; 3.76g of cetyltrimethylammonium bromide and 0.55g of sodium hydroxide were weighed out and dissolved in 20mL of deionized water at 40 ℃ to form a solution S-1. The suspension II is gradually dropped into the solution S-1,after stirring for 8h, 0.1mol/L hydrochloric acid solution was added dropwise to adjust the pH to 12 to form a suspension III. And (3) transferring the suspension III into a 50mL hydrothermal kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization at 180 ℃ for 36h, cooling to room temperature, centrifuging, washing with water, washing with ethanol to neutrality, drying in a 100 ℃ oven for 12h, grinding, calcining at 650 ℃ in a flowing air atmosphere for 7h, and removing the template agent to obtain the attapulgite-derived ordered mesoporous molecular sieve. 1.16g of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O), 0.31g manganese nitrate hexahydrate (Mn (NO)3)2·6H2O) and 0.28g of zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O) is completely dissolved in 25mL of deionized water to form a suspension IV; weighing 0.43g of citric acid, completely dissolving in 25mL of deionized water to form a solution S-2, slowly pouring the solution S-2 into the suspension IV, continuously stirring to form sol, adding 2g of attapulgite-based ordered mesoporous molecular sieve, uniformly stirring, evaporating at 80 ℃, washing, filtering, drying, grinding and screening to obtain white powder. And putting the obtained white powder in a tubular furnace, introducing air atmosphere, raising the temperature from room temperature to 500 ℃ at the heating rate of 4 ℃/min, calcining at constant temperature for 3h, and cooling to room temperature to obtain the catalyst, wherein the number is 4 #.
A catalyst performance test for preparing synthesis gas by reforming low-concentration coal mine gas/carbon dioxide is carried out by diluting laboratory pure methane with nitrogen gas as follows: taking 0.1-0.5 g of the No. 1-4 catalyst in a micro fixed bed reactor, and passing through 10 vol% H at 100mL/min2/N2Performing performance test after reduction treatment for 2h at 600-800 ℃ in the flow, wherein the molar ratio of methane to carbon dioxide in the feed is 1, and the air speed of gas feeding is 10000-60000 mL.h-1·gcat -1The reaction temperature is 400-700 ℃. The specific reaction conditions and results are shown in Table 1.
TABLE 1 catalyst Performance testing of synthesis gas prepared by reforming low-concentration coal mine gas/carbon dioxide in laboratory
A catalyst performance test for preparing synthetic gas by reforming low-concentration coal mine gas/carbon dioxide is disclosed, wherein the low-concentration coal mine gas is respectively derived from medium petroleum coal bed gas, Shanxi coal bed gas, middle-linked coal bed gas and Oriran coal bed gas: taking 0.1-0.5 g of the No. 1-4 catalyst in a micro fixed bed reactor, passing through 10 vol% H at 100mL/min2/N2Performing performance test after reduction treatment for 2h at 800 ℃ in the flow, wherein the molar ratio of methane to carbon dioxide in the feed is 1, and the air speed of gas feed is 10000-60000 mL.h-1·gcat-1The reaction temperature is 400-700 ℃. The specific reaction conditions and results are shown in Table 2.
TABLE 2 catalyst Performance testing of a syngas prepared by gas/carbon dioxide reforming of a mined low-concentration coal mine
From the above results, it can be seen that the catalyst for preparing synthesis gas by low-concentration coal mine gas/carbon dioxide reforming can realize the conversion rate of methane and carbon dioxide of over 80 percent, and the H content in the synthesis gas2The ratio of/CO is 0.8-1, and the catalyst does not lose activity after 500 hours of reaction.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (8)
1. CH (physical channel)4、CO2The catalyst for preparing the synthesis gas by reforming is characterized in that the catalyst takes a clay-based ordered mesoporous molecular sieve as a carrier to load nickel, manganese and zirconium as active metals, the carrier is synthesized by taking attapulgite acidified by inorganic acid as a silicon source and a template agent through hydrothermal crystallization under an alkaline condition, and the loading amounts of the active metals are respectively as follows: 1-15 wt% of nickel, 1-5 wt% of manganese and 1-5 wt% of zirconium.
2. CH (physical channel)4、CO2The preparation method of the catalyst for preparing the synthesis gas by reforming is characterized by comprising the following steps of:
s1, acidifying the attapulgite for 10-15 hours at the temperature of 150-200 ℃ and the concentration of inorganic acid of 3.5-6 mol/L, and filtering, washing and drying to obtain an attapulgite-based silicon source;
s2, fully stirring the obtained silicon source, a template agent and sodium hydroxide, regulating and controlling the pH value by an acid titration method in the process to enable the pH value to be stable within the range of 10-12, then sealing and carrying out hydrothermal treatment on the suspension for a period of time, and obtaining the attapulgite-based ordered mesoporous molecular sieve carrier through centrifugation, washing, drying and calcination;
s3, mixing the nickel, manganese and zirconium-containing metal precursor salt solution with citric acid for a period of time, adding the mixture into the attapulgite-based silicon source suspension, stirring the mixture fully until gel is formed, and evaporating, drying, grinding, sieving and calcining the gel to obtain the catalyst.
3. The CH of claim 24、CO2The preparation method of the catalyst for preparing the synthesis gas by reforming is characterized in that in the step S1, one or two of hydrochloric acid and sulfuric acid is selected as the inorganic acid.
4. The CH of claim 24、CO2ReformingThe preparation method for preparing the synthesis gas catalyst is characterized in that in the step S2, the template agent is cetyl trimethyl ammonium bromide, the mass ratio of the attapulgite silicon source to the template agent is 1: 1.58-1.94, the stirring temperature is 30-40 ℃, and the stirring time is 6-12 hours.
5. The CH of claim 24、CO2The preparation method of the catalyst for reforming and preparing the synthesis gas is characterized in that in the step S2, the hydrothermal treatment temperature is 100-180 ℃, the time is 24-96 hours, the drying temperature is 100 ℃, the time is 8-12 hours, and the calcining treatment condition is that the temperature is increased to 550-650 ℃ in a gradient manner at a speed of 2-4 ℃/min under the flowing air atmosphere and is kept for 6-8 hours.
6. The CH of claim 14、CO2The preparation method of the catalyst for preparing the synthesis gas through reforming is characterized in that in the step S3, nickel, manganese and zirconium metal precursor salts are respectively nickel nitrate hexahydrate, manganese nitrate hexahydrate and zirconium nitrate pentahydrate, the molar ratio of metal ions to citric acid in the precursor salt solution is 1: 1-2, the evaporation temperature is 70-90 ℃, the drying temperature is 100 ℃, the time is 8-12 h, and the calcining treatment condition is that the temperature is increased to 500-700 ℃ in a gradient manner at a speed of 2-4 ℃/min under the flowing air atmosphere and is kept for 3-5 h.
7. CH (physical channel)4、CO2The application of the catalyst for preparing the synthesis gas by reforming is characterized in that the catalyst is firstly reduced in a hydrogen/nitrogen atmosphere, and then the synthesis gas is prepared by catalyzing coal mine gas-carbon dioxide reforming in a miniature fixed bed reactor.
8. The CH of claim 74、CO2The application of the catalyst for preparing the synthesis gas by reforming is characterized in that the reduction condition is 10-15 vol% H at 100-150 mL/min2/N2Treating the gas flow for 1-3 h at 600-800 ℃, wherein the reaction conditions for preparing the synthesis gas by catalytically reforming the coal mine gas-carbon dioxide are as follows: the dosage of the catalyst is 0.1-0.5 g, and the molar ratio of methane to carbon dioxide in the feed is 1-1.2. The air speed of gas feeding is 10000-60000 mL-h-1·gcat-1The reaction temperature is 400-700 ℃.
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| CN114832820A (en) * | 2022-05-31 | 2022-08-02 | 南京工业大学 | Modified montmorillonite-loaded ruthenium-based catalyst and preparation method and application thereof |
| CN114950440A (en) * | 2022-06-30 | 2022-08-30 | 淮安中顺环保科技有限公司 | Macro room temperature preparation method of attapulgite-nano nickel powder compound |
| CN115518652A (en) * | 2022-06-13 | 2022-12-27 | 安徽理工大学 | Silicon-cerium composite microporous material packaged metal catalyst and preparation method and application thereof |
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| CN114950440A (en) * | 2022-06-30 | 2022-08-30 | 淮安中顺环保科技有限公司 | Macro room temperature preparation method of attapulgite-nano nickel powder compound |
| CN114950440B (en) * | 2022-06-30 | 2023-11-07 | 淮安中顺环保科技有限公司 | Macroscopic room temperature preparation method of attapulgite-nano nickel powder compound |
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