CN112934215B - Catalyst for converting methane and preparation method and application thereof - Google Patents
Catalyst for converting methane and preparation method and application thereof Download PDFInfo
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- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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Abstract
The invention relates to the field of ethylene preparation, and discloses a catalyst for converting methane, a preparation method and application thereof. The catalyst for converting methane comprises a carrier and an active component loaded on the carrier; the carrier is cristobalite, and the active component comprises oxides of indium oxide, sodium tungstate and manganese; and the content of indium oxide is 0.1-10 wt%, the content of sodium tungstate is 1-10 wt%, and the content of manganese oxide is 0.5-7.5 wt% calculated as manganese element based on the weight of the cristobalite in the catalyst. The catalyst provided by the invention is used in methane coupling oxidation reaction, has stability under high temperature condition, and can promote methane to generate ethylene, ethane and other hydrocarbon with two or more carbon atoms.
Description
Technical Field
The invention relates to the field of ethylene preparation, in particular to a catalyst for converting methane, a preparation method and application thereof.
Background
As the most important basic organic chemical raw material, the production of ethylene depends on petroleum cracking routes for a long time, and the problems of environmental pollution and the like are becoming serious. In addition, the price of crude oil is continuously rising in recent years, and the price of ethylene cracking raw materials is rising, so that the phenomenon of supply shortage of ethylene cracking raw materials is very prominent. In view of this current situation, energy utilization structures are being regulated in various countries of the world, and new ethylene production routes are being continuously sought.
Natural gas is an important energy source with abundant reserves, and is one of important research directions for replacing petroleum to synthesize olefin in order to meet the requirements of global energy and petrochemical raw material structure transformation. Currently, methods for producing ethylene from natural gas include direct methods (oxidative coupling, chloridizing coupling, direct dehydrogenation) and indirect methods. The indirect method is to convert natural gas into synthetic gas and then prepare olefin from the synthetic gas, including improved F-T method, and olefin preparation by methanol cracking. When natural gas is used as an initial raw material, a three-step method (POM/GTM/MTO) for preparing synthesis gas/methanol/olefin by partial oxidation is adopted to prepare ethylene, so that the reaction process steps are numerous, oxygen atoms are firstly inserted and then taken out, the non-atomic economic reaction is realized, and the multi-step method is not an economic and reasonable choice from the aspects of resource utilization, technology, environmental protection and the like. The oxidative coupling of natural gas, methane, to ethylene (OCM) is the most straightforward process and has been the focus of research by scientists worldwide for decades.
The first report on OCM was published in 1982 from UCC corporation in the United states, and up to thousands of catalysts have been studied to date. At present, the catalytic system with better reaction performance mainly focuses on basic compounds, oxide-supported alkali metals and alkaline earth metals, single-phase oxides, transition metal oxides supported by alkali metal ions, halogen ion-modified oxides and solid superacid. In the report of the preparation of the existing catalyst, a supported catalyst with silicon dioxide as a carrier and sodium tungstate and manganese as active components is one of the systems with the best performance (Li, S. (2003), "Reaction Chemistry of W-Mn/SiO 2 Catalyst for the Oxidative Coupling of Methane. "Journal of Natural Gas Chemistry (01): 1-9.). In addition, CN1067831A adoptsImpregnation and slurry processes for preparing catalysts for conversion of methane to higher hydrocarbons (ethylene and ethane) in the form of SiO 2 Or Al 2 O 3 The pellets are carriers. CN101385982a provides a method of assembling the active components of the catalyst into the mesoporous molecular sieve SBA-15 to improve the activity and stability of the catalyst.
The reaction temperature for preparing ethylene by oxidative coupling of methane is usually more than 750 ℃, the reaction is exothermic, the catalyst is required to have stability under the high-temperature condition, and the low catalytic activity and the low product selectivity of the catalyst at the high temperature at present are still important factors for restricting the industrialization of the method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a catalyst for converting methane, and a preparation method and application thereof. The catalyst provided by the invention is used in methane coupling oxidation reaction, has stability under high temperature condition, and can promote methane to generate ethylene, ethane and other hydrocarbons (C) 2+ Hydrocarbons).
According to a first aspect of the present invention there is provided a catalyst for converting methane, the catalyst comprising a support and an active component supported on the support; wherein the carrier is cristobalite, and the active component comprises oxides of indium oxide, sodium tungstate and manganese; in the catalyst, based on the weight of the cristobalite, the content of indium oxide is 0.1-10 wt%, the content of sodium tungstate is 1-10 wt%, and the content of manganese oxide is 0.5-7.5 wt% in terms of manganese.
According to a second aspect of the present invention there is provided a method of preparing a catalyst for converting methane, the method comprising: in the presence of water, the soluble salts of indium, sodium tungstate and manganese are contacted with cristobalite, and the soluble salts are dried and roasted to enable oxides of indium oxide, sodium tungstate and manganese to be loaded on the cristobalite; the soluble salts of cristobalite, indium, sodium tungstate and manganese are used in such amounts that the catalyst is prepared with indium oxide in an amount of 0.1 to 10 wt.%, sodium tungstate in an amount of 1 to 10 wt.%, and manganese oxide in an amount of 0.5 to 7.5 wt.%, calculated as manganese, based on the weight of cristobalite.
According to a third aspect of the present invention there is provided a catalyst for converting methane produced by the production process.
According to a fourth aspect of the present invention there is provided the use of the catalyst for converting methane in a methane oxidative coupling reaction.
The catalyst for converting methane adopts oxides of indium oxide, sodium tungstate and manganese as active components and combines cristobalite with stable high-temperature structure and performance as a carrier, so that the occurrence of methane oxidative coupling reaction can be effectively promoted. As can be seen from the examples, the methane conversion catalyst of the present invention has high catalytic activity and C 2+ Hydrocarbon selectivity and still meet high methane conversion and C during long-term operation of the reaction 2+ Hydrocarbon yield and high stability of the catalyst.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention there is provided a catalyst for converting methane, the catalyst comprising a support and an active component supported on the support.
In the catalyst of the present invention, the carrier is cristobalite, and the active component includes indium oxide (In 2 O 3 ) Sodium tungstate (Na) 2 WO 4 ) And manganese oxide, and in the catalyst, indium oxide is contained in an amount of 0.1 to 10 wt%, sodium tungstate is contained in an amount of 1 to 10 wt%, and manganese oxide is contained in an amount of 0.5 to 7.5 wt% in terms of manganese (Mn), based on the weight of the cristobalite. The content of each component in the catalyst is calculated according to the feeding amount.
Preferred caseIn the catalyst, the content of indium oxide is 0.5 to 8 wt%, more preferably 2 to 7 wt%, based on the weight of the cristobalite; sodium tungstate in an amount of 1 to 8 wt%; the manganese oxide content is 1-6wt% based on manganese, more preferably 1-5wt%, so as to further exert synergistic effect between active components and cristobalite, and improve methane conversion rate and C 2+ Hydrocarbon yield and high temperature stability of the catalyst.
According to a second aspect of the present invention there is provided a method of preparing a catalyst for converting methane, the method comprising: the soluble salts of indium, sodium tungstate and manganese are brought into contact with cristobalite in the presence of water, and dried and calcined so that oxides of indium oxide, sodium tungstate and manganese are supported on the cristobalite.
In the preparation method of the invention, the cristobalite serving as a carrier has the characteristics of high-temperature structure and stable performance. The cristobalite may be obtained commercially or by calcining amorphous silica.
In the preparation method of the invention, the soluble salt of indium, sodium tungstate, soluble salt of manganese and cristobalite are used in amounts such that the content of indium oxide is 0.1 to 10 wt%, the content of sodium tungstate is 1 to 10 wt% and the content of manganese oxide is 0.5 to 7.5 wt% based on the weight of cristobalite in the prepared catalyst.
Preferably, the soluble salts of indium, sodium tungstate, soluble salts of manganese and cristobalite are used in amounts such that the catalyst prepared has an indium oxide content of 0.5 to 8% by weight, more preferably 2 to 7% by weight, based on the weight of cristobalite; sodium tungstate in an amount of 1 to 8 wt%; the content of the oxides of manganese is 1 to 6% by weight, more preferably 1 to 5% by weight, based on manganese.
In the production method of the present invention, the soluble salts of indium and manganese may be various water-soluble active ingredient precursors as long as indium oxide (In 2 O 3 ) And various oxides of manganese. For the purposes of the present invention, the soluble salt of indium is preferably indium nitrate, the nitric acid of manganeseThe salt is preferably manganese nitrate. Commercially available indium nitrate is typically present in its hydrate form and may be, for example, indium nitrate 4.5 hydrate, sodium tungstate is typically sodium tungstate hydrate, for example sodium tungstate dihydrate.
In the preparation method of the invention, the roasting temperature can be 500-850 ℃ and the roasting time can be 2-10 hours. Preferably, the roasting process comprises: the dried product is warmed to 700-850 ℃ at a constant rate of 1-15 ℃/min, (more preferably 5-10 ℃/min) and incubated for 2-8 hours.
The preparation method of the invention is to load each active component on cristobalite by impregnation to form the catalyst. The cristobalite may be impregnated stepwise with soluble salts of sodium tungstate, manganese, and soluble salts of indium to support the active ingredient on the cristobalite (the stepwise impregnation may be impregnation of the cristobalite with one or both salts thereof first), or the active ingredient may be supported on the carrier by simultaneous impregnation. It will be appreciated that in the sequential impregnation of the cristobalite with the aqueous solutions containing the precursors of the respective active ingredients, each impregnation process involves a contact and drying operation, the final impregnation including the calcination. The simultaneous impregnation means that the cristobalite is simultaneously impregnated with an aqueous solution containing the precursors of each active ingredient, and then dried and calcined.
In the preparation method of the invention, each drying process is preferably carried out in a two-stage method: the first stage: rotary evaporating the contact product at 70-90 deg.c for 0.5-4 hr; and a second stage: the product obtained by evaporation is dried at 110-180 ℃ for 1-6 hours.
In the preparation method of the invention, each contact is usually carried out under stirring, the temperature of stirring can be 20-80 ℃, and the stirring time can be 1-2 hours.
According to a specific embodiment, the method for preparing the catalyst comprises the following steps: and respectively contacting an aqueous solution of sodium tungstate, an aqueous solution of soluble salt of manganese and an aqueous solution of soluble salt of indium with the cristobalite, and drying the product obtained after each contact. In this embodiment, the order of contacting the three aqueous solutions with cristobalite is not particularly limited, and for example, the aqueous solution of the soluble salt of indium may be contacted with cristobalite first, or the cristobalite may be contacted with the other two salt solutions first and then contacted with the aqueous solution of the soluble salt containing indium; the drying step is included after each contact.
According to another specific embodiment, the method for preparing the catalyst comprises the following steps:
1) Contacting an aqueous solution of a soluble salt containing manganese and sodium tungstate with the cristobalite in the presence of water, and then drying to obtain cristobalite impregnated with manganese and sodium tungstate;
2) And (3) contacting the cristobalite impregnated with manganese and sodium tungstate with a soluble salt water solution of indium, and then drying and roasting.
In step 1), cristobalite may be impregnated with an aqueous solution of a soluble salt of manganese and an aqueous solution of sodium tungstate, or cristobalite may be impregnated with an aqueous solution of a soluble salt of manganese and an aqueous solution of sodium tungstate at the same time. The contacting is carried out with stirring, preferably at room temperature (20-45 ℃) for a period of 1-2 hours.
In step 2), the contacting is carried out with stirring, preferably at a temperature of 40-80℃for a period of 1-2 hours.
In the preparation method of the present invention, in each of the brine solutions used for impregnating the carrier, the concentration of the soluble salt of indium (for example, indium nitrate hydrate) may be, for example, 0.01 to 15 wt%, the concentration of sodium tungstate (for example, sodium tungstate dihydrate) may be, for example, 1 to 10 wt%, and the concentration of the soluble salt of manganese (for example, manganese nitrate) may be, for example, 1 to 15 wt%.
In the preparation method of the present invention, in order to obtain a catalyst product of a certain particle size distribution, the preparation method further comprises: tabletting, crushing and sieving the roasted product.
The preparation method of the catalyst for converting methane provided by the invention has simple steps, so that the catalyst has a higher industrial application prospect.
According to a third aspect of the present invention there is provided a catalyst for converting methane produced by the production process.
According to a fourth aspect of the present invention there is provided the use of the catalyst for converting methane in a methane oxidative coupling reaction. The application comprises: and (3) in the presence of the catalyst for converting methane, subjecting methane and oxygen to methane oxidative coupling reaction.
In the application of the invention, methane and an oxygen source can be directly introduced for reaction, or natural gas and the oxygen source can be reacted. The oxygen source may be oxygen or a mixed gas containing oxygen, such as air.
In the application of the invention, the catalyst for converting methane can be used in various types of reactors, such as fluidized bed reactors, fixed bed reactors (e.g., fixed bed quartz tube reactors), and the like.
In the application of the invention, in the oxidative coupling reaction of methane, the reaction temperature can be 750-850 ℃, and the molar ratio of methane to oxygen is (1-10) to 1, preferably (2-5) to 1; the reaction space velocity is 15000-50000 mL/(g.h). The catalyst for converting methane can improve the conversion rate of methane and can obtain higher C such as ethylene 2+ Hydrocarbon selectivity, and high temperature stability.
The present invention will be described in detail by examples.
In the following examples and comparative examples,
amorphous silica was purchased from Qingdao ocean chemical Co., ltd;
cristobalite is purchased from national pharmaceutical group chemical company, inc;
manganese nitrate solution (50 wt% aqueous solution), sodium tungstate hydrate (Na 2 WO 4 ·2H 2 O) are all purchased from national pharmaceutical group chemicals limited;
indium nitrate hydrate (In (NO) 3 ) 3 ·4.5H 2 O) was purchased from national pharmaceutical chemicals limited.
The percentage content of active components in the catalyst refers to the mass percentage content and is based on the weight of the carrier.
Example 1
5.86g of manganese nitrate solution was dissolved in 32mL of water, 15g of cristobalite carrier was added, stirred at room temperature for 1 hour, and rotated at 80 ℃After evaporation for 4h, drying at 120℃for 2h, a manganese impregnated cristobalite was obtained. Dissolving 0.34g of sodium tungstate hydrate in 30mL of water, adding the cristobalite impregnated with manganese, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 130 ℃ for 2h to obtain the cristobalite impregnated with manganese and sodium tungstate. 0.206g of indium nitrate hydrate is dissolved in 30mL of water, cristobalite impregnated with manganese and sodium tungstate is added, stirred at 50 ℃ for 1h, rotary evaporated at 80 ℃ for 3h, dried at 120 ℃ for 3h, and then heated to 800 ℃ in air at a rate of 5 ℃/min for 5h for roasting. Cooled to room temperature to give catalyst A1 (Na 2 WO 4 -Mn-In 2 O 3 Cristobalite), wherein In 2 O 3 0.5％，Na 2 WO 4 2.0% of Mn oxide, 6.0% of Mn.
Comparative example 1
5.86g of manganese nitrate solution was dissolved in 32mL of water, 15g of amorphous silica carrier was added, stirred at room temperature for 1 hour, rotary evaporated at 80℃for 4 hours, and dried at 120℃for 3 hours to obtain a manganese impregnated carrier. Sodium tungstate hydrate 0.34g is dissolved in 30mL of water, a carrier impregnated with manganese is added, the mixture is stirred at room temperature for 1h, after rotary evaporation for 2h at 80 ℃, the mixture is dried at 130 ℃ for 2h, and then the mixture is heated to 800 ℃ in air at a speed of 5 ℃/min for 5h for roasting. Cooling to room temperature to obtain catalyst D1, wherein Na 2 WO 4 2.0% of Mn oxide, 6.0% of Mn.
Comparative example 2
5.86g of manganese nitrate solution was dissolved in 32mL of water, 15g of amorphous silica carrier was added, stirred at room temperature for 1 hour, rotary evaporated at 80℃for 4 hours, and dried at 120℃for 2 hours to obtain a manganese impregnated carrier. Dissolving 0.34g of sodium tungstate hydrate in 30mL of water, adding the cristobalite impregnated with manganese, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 130 ℃ for 2h to obtain the cristobalite impregnated with manganese and sodium tungstate. 0.206g of indium nitrate hydrate is dissolved in 30mL of water, cristobalite impregnated with manganese and sodium tungstate is added, stirred at 50 ℃ for 1h, rotary evaporated at 80 ℃ for 3h, dried at 120 ℃ for 3h, and then heated to 800 ℃ in air at a rate of 5 ℃/min for 5h for roasting. Cooling to room temperature to obtain catalyst D2, wherein In 2 O 3 0.5％，Na 2 WO 4 2.0% of Mn oxide, 6.0% of Mn.
Example 2
0.98g of manganese nitrate solution was dissolved in 30mL of water, 15g of cristobalite carrier was added, stirred at room temperature for 1 hour, rotary evaporated at 80℃for 3 hours, and dried at 120℃for 2 hours to obtain manganese-impregnated cristobalite. 1.35g of sodium tungstate hydrate is dissolved in 30mL of water, and the cristobalite impregnated with manganese is added, stirred at room temperature for 1h, and dried at 140 ℃ for 2h after rotary evaporation at 80 ℃ to obtain the cristobalite impregnated with manganese and sodium tungstate. 0.825g of indium nitrate hydrate is dissolved in 30mL of water, cristobalite impregnated with manganese and sodium tungstate is added, stirred at 40 ℃ for 1h, rotary evaporated at 80 ℃ for 3h, dried at 120 ℃ for 2h, and then heated to 850 ℃ in air at a rate of 10 ℃/min for 5h. After cooling to room temperature, catalyst A2 (Na 2 WO 4 -Mn-In 2 O 3 Cristobalite), wherein In 2 O 3 2.0％，Na 2 WO 4 8.0% of Mn oxide, 1.0% of Mn.
Example 3
4.88g of manganese nitrate solution was dissolved in 31mL of water, 15g of cristobalite carrier was added, stirred at room temperature for 1 hour, rotary evaporated at 80℃for 2 hours, and dried at 120℃for 2 hours to obtain manganese-impregnated cristobalite. 1.179g of sodium tungstate hydrate is dissolved in 30mL of water, and the cristobalite impregnated with manganese is added, stirred at room temperature for 1h, rotary evaporated at 80 ℃ for 3h, and dried at 180 ℃ for 1h to obtain the cristobalite impregnated with manganese and sodium tungstate. 2.06g of indium nitrate hydrate is dissolved in 30mL of water, cristobalite impregnated with manganese and sodium tungstate is added, stirred at 60 ℃ for 1h, rotary evaporated at 80 ℃ for 2h, dried at 150 ℃ for 2h, and then heated to 850 ℃ in air at a rate of 5 ℃/min for 5h for roasting. After cooling to room temperature, catalyst A3 (Na 2 WO 4 -Mn-In 2 O 3 Cristobalite), wherein In 2 O 3 5.0％，Na 2 WO 4 7.0% of Mn oxide, 5.0% of Mn.
Example 4
0.168g of sodium tungstate hydrate is dissolved in 15mL of water, 1.48g of manganese nitrate solution is dissolved in 15mL of water, the mixture is added into 15g of cristobalite, and after rotary evaporation for 2h at 90 ℃, the mixture is subjected to rotary evaporation at 120 DEG CDrying for 2 hours to obtain the cristobalite impregnated with manganese and sodium tungstate. 2.89g of indium nitrate hydrate is dissolved in 40mL of water, cristobalite impregnated with manganese and sodium tungstate is added, stirred at 40 ℃ for 1h, rotary evaporated at 80 ℃ for 4h, dried at 120 ℃ for 2h, and then heated to 850 ℃ in air at a rate of 10 ℃/min for 5h for calcination. After cooling to room temperature, catalyst A4 (Na 2 WO 4 -Mn-In 2 O 3 Cristobalite), wherein In 2 O 3 7.0％，Na 2 WO 4 1.0% of Mn oxide 1.5% in terms of Mn.
Comparative example 3
0.168g of sodium tungstate hydrate is dissolved in 15mL of water, 1.48g of manganese nitrate solution is dissolved in 15mL of water, the mixture is added into 15g of cristobalite, the mixture is subjected to rotary evaporation at 90 ℃ for 2h, then is dried at 120 ℃ for 2h, and is heated to 850 ℃ in air at a speed of 10 ℃/min for 5h for roasting. After cooling to room temperature, catalyst D3 was obtained, wherein Na 2 WO 4 1.0% of Mn oxide 1.5% in terms of Mn.
Example 5
3.87g of manganese nitrate solution was dissolved in 35mL of water, 15g of cristobalite carrier was added, stirred at room temperature for 1 hour, rotary evaporated at 80℃for 2 hours, and dried at 120℃for 2 hours to obtain manganese-impregnated cristobalite. Sodium tungstate hydrate 0.84g is dissolved in 30mL of water, and manganese-impregnated cristobalite is added, stirred at room temperature for 1h, rotary evaporated at 80 ℃ for 2h, and dried at 160 ℃ for 1h to obtain manganese-and sodium tungstate-impregnated cristobalite. 3.3g of indium nitrate hydrate is dissolved in 50mL of water, cristobalite impregnated with manganese and sodium tungstate is added, stirred at 60 ℃ for 1h, rotary evaporated at 90 ℃ for 2h, dried at 150 ℃ for 3h, and then heated to 750 ℃ in air at a rate of 5 ℃/min for 5h for roasting. After cooling to room temperature, catalyst A5 (Na 2 WO 4 -Mn-In 2 O 3 Cristobalite), wherein In 2 O 3 8.0％，Na 2 WO 4 5.0% of Mn oxide, calculated as Mn, 4.0%.
Test case
And respectively tabletting, crushing and sieving the catalysts A1-A5 and the catalysts D1-D3, and taking a part between 40 meshes and 60 meshes for the following methane oxidative coupling reaction.
A fixed bed quartz tube reactor (inner diameter: 8 mm) was charged with 0.2g of the above catalyst, and the catalyst was filled with quartz sand (20-40 mesh) up and down. Methane and oxygen are then injected therein to effect the oxidative coupling reaction of methane under set operating conditions. The reaction results were analyzed by Agilent 7890A gas chromatography, wherein hydrocarbons were detected using a FID detector, an alumina capillary column, and methane, carbon monoxide, and carbon dioxide using a TCD detector. During operation, the evaluation was carried out at 800℃and 22000 mL/(g.h), CH 4 /O 2 =2.2 catalytic performance at initial reaction and after 500h of continuous operation, in CH 4 Conversion, C 2+ Selectivity and C 2+ The yields were shown in Table 1.
TABLE 1
Note that: "CH 4 /O 2 "means the molar ratio of methane to oxygen.
As can be seen from a comparison of comparative examples 1 to 3, the converted methane catalysts prepared in examples 1 to 5 can improve methane conversion and C in the oxidative coupling reaction of methane, in combination with the results of Table 1 2+ The hydrocarbon yield has higher high-temperature stability and higher application value.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A method of preparing a catalyst for converting methane, the method comprising: in the presence of water, the soluble salts of indium, sodium tungstate and manganese are contacted with cristobalite, and the soluble salts are dried and roasted to enable oxides of indium oxide, sodium tungstate and manganese to be loaded on the cristobalite; wherein the soluble salts of indium, sodium tungstate, soluble salts of manganese and cristobalite are used in amounts such that the content of indium oxide in the prepared catalyst is 5-7% by weight based on the weight of cristobalite; the content of sodium tungstate is 7-8 wt%, and the content of manganese oxide is 1-5 wt% based on manganese.
2. The method of manufacturing according to claim 1, wherein the firing process comprises: heating the dried product to 700-850 ℃ at a constant rate of 1-15 ℃/min, and preserving the heat for 2-8 hours.
3. The preparation method according to claim 1, wherein the soluble salt of indium is indium nitrate and the soluble salt of manganese is manganese nitrate.
4. A production method according to any one of claims 1 to 3, wherein the method comprises: and respectively contacting an aqueous solution of sodium tungstate, an aqueous solution of soluble salt of manganese and an aqueous solution of soluble salt of indium with the cristobalite.
5. A method of preparation according to any one of claims 1-3, wherein the method comprises the steps of:
1) Contacting an aqueous solution of a soluble salt containing manganese and sodium tungstate with the cristobalite in the presence of water, and then drying to obtain cristobalite impregnated with manganese and sodium tungstate;
2) And (3) contacting the cristobalite impregnated with manganese and sodium tungstate with a soluble salt water solution of indium, and then drying and roasting.
6. The process according to claim 4, wherein the contacting is carried out under stirring at a temperature of 20 to 80℃for a period of 1 to 2 hours.
7. The process according to claim 5, wherein the contacting is carried out under stirring at a temperature of 20 to 80℃for a period of 1 to 2 hours.
8. A method according to any one of claims 1-3, wherein the method further comprises: and tabletting, crushing and sieving the roasted product.
9. A catalyst for converting methane produced by the production process according to any one of claims 1 to 8.
10. Use of the catalyst for converting methane according to claim 9 in a methane oxidative coupling reaction.
11. The application of claim 10, wherein the application comprises: in the presence of the catalyst for converting methane, methane and oxygen are subjected to methane oxidative coupling reaction; the conditions for the oxidative coupling reaction of methane include: the reaction temperature is 750-850 ℃, the molar ratio of methane to oxygen is (1-10) to 1, and the reaction space velocity is 15000-50000 mL/(g.h).
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