CN114605218A - Method for oxidative coupling of methane - Google Patents
Method for oxidative coupling of methane Download PDFInfo
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- CN114605218A CN114605218A CN202011443896.2A CN202011443896A CN114605218A CN 114605218 A CN114605218 A CN 114605218A CN 202011443896 A CN202011443896 A CN 202011443896A CN 114605218 A CN114605218 A CN 114605218A
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Abstract
The invention relates to a method for oxidative coupling of methane. The method adopts methane as a reactant and water as an oxidant, and prepares ethylene through oxidative coupling reaction under the catalytic action of reducible metal oxides. The reaction conditions were as follows: the reaction is carried out in a fixed bed reactor, the reaction is carried out under normal pressure, the reaction temperature is 400-850 ℃, the feeding airspeed of methane is 10000-50000 mL/(g.h), CH4:H2O is 1:1 to 4: 1. The catalyst is simple to prepare and can catalyze the reaction with high efficiency, water is used as an oxygen source to replace oxygen in the prior art, excessive oxidation is avoided, the product selectivity is improved, and the selectivity of ethylene is 75%.
Description
Technical Field
The invention relates to a method for oxidative coupling of methane, in particular to a technology for preparing ethylene by oxidative coupling by taking methane and water as reactants.
Background
Ethylene is an important basic organic chemical raw material, and the production yield, the production technology and the application of the ethylene are marks for measuring the national chemical level. Currently, ethylene is produced industrially by naphtha cracking. China is short of oil gas resources, and ethylene sources mainly depend on imported and cracked naphtha. Therefore, the development of a process route for the non-petroleum route to ethylene is a major trend in the future. With the breakthrough of the exploitation technology of shale gas and combustible ice, natural gas with relatively abundant reserves, wide distribution and low price is used for replacing petroleum to produce basic organic chemical raw material ethylene, and has become a focus in recent years in the world. Methane is a major component of natural gas, combustible ice and shale gas, and is cleaner and more abundant than other petrochemical resources such as petroleum and coal. The methane is used as a raw material to synthesize the molecular ethylene of the high-value chemical platform, which increasingly draws attention in the industry. Among them, the oxidative coupling of methane to prepare ethylene is the main route, and the key point is the design and development of high-efficiency catalysts.
At present, catalytic systems for catalyzing methane oxidative coupling to prepare ethylene are mainly divided into three types: alkali metal-alkaline earth metal oxide catalysts, rare earth oxide catalysts, transition metal oxide catalysts; although the catalytic research of the current catalytic system is more, the method has some disadvantages: for example, the catalyst activity is relatively low, the conversion of methane is less than 50%, the selectivity of ethylene is less than 60%, i.e. the yield of ethylene is less than 30% (-25%); in addition, oxygen acts as an oxidizing agent, resulting in uncontrollable reaction and easy excessive oxidation to produce carbon-oxygen compounds. Therefore, the method has important significance for exploring a new methane oxidative coupling process and designing and preparing a high-efficiency catalytic system.
Disclosure of Invention
The invention has the significance of overcoming the defects existing in the process of preparing the ethylene by the oxidative coupling of the methane. The catalyst has high catalytic activity, high stability, simple reaction process, high ethylene yield and no side product.
The oxidative coupling of methane to produce ethylene according to the present invention is prepared according to the following scheme. A method for oxidative coupling of methane, characterized by: the process of oxidative coupling of methane is as follows: the method comprises the steps of taking methane and water as raw materials, reacting in a fixed bed reactor, filling a reducible oxide catalyst in a reaction tube, and placing the reaction tube in the fixed bed reactor, wherein the reaction temperature is 400-850 ℃. The reducible metal oxide catalyst is: one or two or more of indium oxide, titanium oxide, iron oxide, manganese oxide, cobalt oxide, tin oxide, tungsten oxide and copper oxide; the reducible metal oxide catalyst is preferably: one or two or more of indium oxide, titanium oxide, iron oxide and manganese oxide; the reducible metal oxide catalyst is most preferably: one or two or more of indium oxide and titanium oxide; the reducible metal oxide catalyst can be prepared by adopting a pyrolysis method, a precipitation method, a sol-gel method, a hydrothermal method, a solvothermal method and a template method; preferably adopting a precipitation method, a hydrothermal method, a solvothermal method and a template method for preparation; the reaction temperature is 400-850 ℃, the feeding airspeed of methane is 10000-50000 mL/(g.h), CH4:H2O is 1:1 to 4: 1; the reaction temperature is 400-600 ℃, and the feeding airspeed of methane is 10000-30000 mL/(g.h), CH4:H2O is 2:1 to 4: 1; the reaction temperature is 500-600 ℃, the feeding airspeed of methane is 20000-25000 mL/(g.h), CH4:H2O＝2:1～4:1。
The method for oxidative coupling of methane disclosed by the invention has the following characteristics: (1) water is used as an oxidant to replace oxygen in the traditional process as the oxidant, so that excessive oxidation of the oxygen is avoided, and the selectivity of ethylene is improved; (2) the catalyst adopts reducible metal oxide, and water molecules are activated by utilizing the dissociation of vacancy property. The adsorption and activation of water molecules by utilizing the oxygen vacancy property can be carried out at the temperature of more than 400 ℃, so that the reaction temperature of catalytic reaction can be obviously reduced, the energy consumption is reduced, and the problems of catalyst sintering and the like caused by high-temperature reaction are avoided.
The invention has the following advantages: (1) the reaction process is simple, and the catalyst activity and stability are high; (2) the reaction condition is relatively mild, and the energy consumption is low.
Detailed Description
Example 1
Weighing 5g of ferric trichloride, dissolving in 100mL of water, and stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into an aqueous solution of ferric trichloride under the stirring condition, continuously stirring for 4 hours, filtering, washing with water for three times, drying at 100 ℃, and roasting at 500 ℃ to obtain an iron oxide catalyst;
weighing 200mg of the iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 4:1 (molar ratio, the same applies below). After reacting at 550 ℃ for 400 minutes, the conversion of methane was 30% and the selectivity of ethylene was: 70 percent.
Example 2
Weighing 5g of indium chloride, dissolving the indium chloride in 100mL of water, adding a certain amount of citric acid, wherein the mass ratio of the citric acid to the indium chloride is 2:1, stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into an indium chloride water solution under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain an indium oxide catalyst;
weighing 200mg of the indium oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O-4: 1. Reacting at 550 deg.C for 400 min, performing on-line chromatographic analysis, and converting methaneThe conversion rate is 30%, and the selectivity of ethylene is as follows: 75 percent.
Example 3
Weighing 5g of ferric nitrate nonahydrate, dissolving in 100mL of water, adding a certain amount of citric acid, wherein the mass ratio of the citric acid to the ferric nitrate is 2:1, stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into an aqueous solution of ferric nitrate under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a cerium oxide catalyst;
weighing 200mg of the iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 2: 1. After reacting at 500 ℃ for 400 minutes, the conversion of methane was 25% and the selectivity to ethylene was: 70 percent.
Example 4
Weighing 5g of ferric nitrate nonahydrate, dissolving in 100mL of water, adding a certain amount of citric acid, wherein the mass ratio of the citric acid to the ferric nitrate is 2:1, stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into an aqueous solution of ferric nitrate under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a cerium oxide catalyst;
weighing 200mg of the iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 12000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample pump, and CH4:H2O is 2: 1. After reacting at 600 ℃ for 400 minutes, the conversion of methane was 35% and the selectivity of ethylene was: and 72 percent.
Example 5
Weighing 5g of indium chloride tetrahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into a cerium nitrate aqueous solution under the stirring condition, continuously stirring for 4 hours, filtering, washing with water for three times, drying at 100 ℃, and roasting at 500 ℃ to obtain an indium oxide catalyst;
weighing 200mg of the indium oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 12000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample pump, and CH4:H2O ═ 4: 1. The reaction was carried out at 680 ℃ for 400 minutes, after which the on-line chromatographic analysis showed a methane conversion of 38% and an ethylene selectivity of: 60 percent.
Example 6
Weighing 5g of indium chloride tetrahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into a cerium nitrate aqueous solution under the stirring condition, continuously stirring for 4 hours, filtering, washing with water for three times, drying at 100 ℃, and roasting at 500 ℃ to obtain an indium oxide catalyst;
weighing 200mg of the indium oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 12000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample pump, and CH4:H2O ═ 4: 1. Reaction at 680 deg.c for 400 min, and on-line chromatographic analysis, the conversion of methane was 38% and the selectivity of ethylene was: 60 percent.
Example 7
Weighing 5g of ferric nitrate nonahydrate, dissolving in 100mL of water, adding a certain amount of 10nm silicon oxide microspheres, wherein the adding amount is 1g/mol of Fe, and stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into an aqueous solution of ferric nitrate under the stirring condition, stirring the obtained precipitate at room temperature for 4 hours, filtering, washing with water for three times, and drying at 100 ℃ to obtain a precursor of the ferric oxide catalyst; and putting the catalyst precursor into hydrofluoric acid, and etching the silicon spheres to obtain the porous iron oxide catalyst.
Weighing 200mg of the iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 2: 1. After reacting at 500 ℃ for 400 minutes, the conversion of methane was 35% and the selectivity of ethylene was: 72 percent.
Example 8
Weighing 5g of manganese nitrate tetrahydrate, dissolving the manganese nitrate tetrahydrate in 100mL of water, adding a certain amount of sucrose, wherein the mass ratio of the sucrose to the manganese nitrate is 2:1, stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1 in an aqueous ammonia solution; dropwise adding the ammonia water solution into a manganese nitrate water solution under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a manganese oxide catalyst;
weighing 200mg of the manganese oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 2: 1. After reaction at 500 ℃ for 400 minutes, on-line chromatographic analysis showed 38% conversion of methane and selectivity to ethylene: 65 percent.
Example 9
Weighing 5g of manganese nitrate tetrahydrate and 5g of ferric nitrate, dissolving the manganese nitrate tetrahydrate and the ferric nitrate in 200mL of water, adding a certain amount of sucrose, wherein the mass ratio of the sucrose to metal ions (including Fe to Mn) is 2:1, stirring at room temperature; 100mL of ammonia water with the mass concentration of 28% is measured and dispersed in 100mL of water to prepare a mixture with the volume ratio of 1:1 in an aqueous ammonia solution; dropwise adding the ammonia water solution into the aqueous solution of metal salt under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a manganese oxide-iron oxide metal oxide catalyst;
weighing 200mg of the manganese oxide-iron oxide catalyst, filling the catalyst with 14-25 meshes by a forming sieve into a reaction tube, reacting at normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), pumping oxidant water into the reaction tube by a trace sample injection pump, and pumping CH4:H2O is 2: 1. After reacting at 500 ℃ for 400 minutes, the conversion of methane was 48% and the selectivity to ethylene was: 68 percent.
Example 10
Weighing 5g of manganese nitrate tetrahydrate and 5g of ferric nitrate, dissolving the manganese nitrate tetrahydrate and the ferric nitrate in 200mL of water, adding a certain amount of sucrose, wherein the mass ratio of the sucrose to metal ions (including Fe to Mn) is 2:1, stirring at room temperature; 100mL of ammonia water with the mass concentration of 28% is measured and dispersed in 100mL of water to prepare a mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into the aqueous solution of metal salt under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a manganese oxide-iron oxide metal oxide catalyst;
weighing 200mg of the manganese oxide-iron oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 1: 1. The reaction is carried out at 500 ℃, after 400 minutes, the conversion rate of methane is 40 percent and the selectivity of ethylene is as follows by on-line chromatographic analysis: 65 percent.
Example 11
Weighing 5g of manganese nitrate tetrahydrate and 5g of ferric nitrate, dissolving the manganese nitrate tetrahydrate and the ferric nitrate in 200mL of water, adding a certain amount of sucrose, wherein the mass ratio of the sucrose to metal ions (including Fe to Mn) is 2:1, stirring at room temperature; 100mL of ammonia water with the mass concentration of 28% is measured and dispersed in 100mL of water to prepare a mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into the aqueous solution of metal salt under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a manganese oxide-iron oxide metal oxide catalyst;
weighing 200mg of the above oxygenManganese-iron oxide catalyst, forming and sieving 14-25 mesh catalyst, filling into a reaction tube, reacting under normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample pump, and CH4:H2O is 2: 1. After reacting at 800 ℃ for 400 minutes, the conversion of methane was 58% and the selectivity of ethylene was: 58 percent.
Example 12
Weighing 5g of copper nitrate and 5g of ferric nitrate nonahydrate, and dissolving in 100mL of water; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into a copper nitrate water solution under the stirring condition, and adding a certain amount of sodium borohydride, wherein the mass ratio of the sodium borohydride to metal ions (including Cu and Fe) is 1:1, stirring for 4 hours at room temperature, filtering, washing for three times, and drying in vacuum at 100 ℃ to obtain a copper oxide-iron oxide catalyst;
weighing 200mg of the copper oxide-iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 48000 mL/(g.h), oxidant water is pumped into the reaction tube by a micro-sampling pump, and CH4:H2O is 1: 1. Reaction at 650 ℃ for 400 minutes, on-line chromatographic analysis, conversion of methane 40%, selectivity to ethylene: 70 percent.
Example 13
Weighing 5g of manganese nitrate hexahydrate and 5g of ferric nitrate nonahydrate, and dissolving in 100mL of water; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into a manganese nitrate water solution under the stirring condition, and adding a certain amount of sodium borohydride, wherein the mass ratio of the sodium borohydride to metal ions (including Mn and Fe) is 1:1, stirring for 4 hours at room temperature, filtering, washing for three times, and vacuum drying at 100 ℃ to obtain a manganese oxide-iron oxide catalyst;
weighing 200mg of the manganese oxide-iron oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 18000 mL/(g.h), and oxidant water is pumped by a trace sample injection pumpIs pumped into a reaction tube, CH4:H2O is 1: 1. At 750 ℃, after reacting for 400 minutes, the conversion of methane is 50% and the selectivity of ethylene is: 66 percent.
Example 14
Weighing 5g of stannic chloride and 5g of ferric nitrate nonahydrate, and dissolving in 100mL of water; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into a tin tetrachloride water solution under the stirring condition, and adding a certain amount of sodium borohydride, wherein the mass ratio of the sodium borohydride to metal ions (including Sn and Fe) is 1:1, stirring for 4 hours at room temperature, filtering, washing for three times, and vacuum drying at 100 ℃ to obtain a tin oxide-iron oxide catalyst;
weighing 200mg of the tin oxide-iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 18000 mL/(g.h), oxidant water is pumped into the reaction tube by a micro-sampling pump, and CH4:H2O is 1: 1. Reaction at 750 ℃ for 800 minutes, on-line chromatographic analysis, methane conversion 47%, ethylene selectivity: and 64 percent.
Example 15
Weighing 5g of manganese nitrate tetrahydrate and 5g of ferric nitrate, dissolving the manganese nitrate tetrahydrate and the ferric nitrate in 200mL of water, adding a certain amount of sucrose, wherein the mass ratio of the sucrose to metal ions (including Fe to Mn) is 2:1, stirring at room temperature; 100mL of ammonia water with the mass concentration of 28% is measured and dispersed in 100mL of water to prepare a mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into the aqueous solution of metal salt under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a manganese oxide-iron oxide metal oxide catalyst;
weighing 200mg of the manganese oxide-iron oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 2: 1. At 600 ℃ for 400 minutes, after whichLine chromatography analysis showed 51% conversion of methane and ethylene selectivity: 66 percent.
Example 16
Weighing 5g of manganese nitrate tetrahydrate and 5g of ferric nitrate, dissolving the manganese nitrate tetrahydrate and the ferric nitrate in 200mL of water, adding a certain amount of sucrose, wherein the mass ratio of the sucrose to metal ions (including Fe to Mn) is 2:1, stirring at room temperature; 100mL of ammonia water with the mass concentration of 28% is measured and dispersed in 100mL of water to prepare a mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into the aqueous solution of metal salt under the stirring condition, putting the obtained precipitate into a synthesis kettle, crystallizing for 24 hours at 100 ℃, cooling, filtering, washing with water for three times, and drying at 100 ℃ to obtain a manganese oxide-iron oxide metal oxide catalyst;
weighing 200mg of the manganese oxide-iron oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 2: 1. The reaction is carried out at 400 ℃, after 400 minutes, the conversion rate of methane is 45 percent and the selectivity of ethylene is as follows by on-line chromatographic analysis: and 69 percent.
Example 17
Weighing 5g of ammonium tungstate, and roasting for 4 hours at 500 ℃ in air to obtain tungsten oxide; dispersing the tungsten oxide material in 50mL of aqueous solution, adding sodium borohydride, wherein the molar ratio of sodium borohydride to ammonium tungstate is 2:1, stirring for 4 hours at room temperature, filtering, and drying in vacuum at 100 ℃ to obtain the tungsten oxide catalyst.
Weighing 200mg of the tungsten oxide catalyst, filling the tungsten oxide catalyst with 14-25 meshes in a forming sieve, reacting under normal pressure, wherein the space velocity of methane is 12000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample pump, and CH4:H2O is 2: 1. After reacting at 550 ℃ for 400 minutes, the conversion of methane was 35% and the selectivity to ethylene was: 66 percent.
Example 18
Weighing 5g of cobalt nitrate hexahydrate, dissolving in 100mL of water, and stirring at room temperature; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1, ammonia water solution; dropwise adding the ammonia water solution into a cobalt nitrate water solution under the stirring condition, continuously stirring for 4 hours, filtering, washing with water for three times, drying at 100 ℃, and roasting at 500 ℃ to obtain a cerium oxide catalyst;
weighing 200mg of the cobalt oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 18000 mL/(g.h), pumping oxidant water into the reaction tube by a trace sample injection pump, and pumping CH4:H2O ═ 4: 1. After reacting at 550 ℃ for 400 minutes, the conversion of methane was 24% and the selectivity to ethylene was: 70 percent.
Example 19
Weighing 5g of copper nitrate and 5g of ferric nitrate nonahydrate, and dissolving in 100mL of glycol aqueous solution; 50mL of ammonia water with the mass concentration of 28% is measured and dispersed in 50mL of water to prepare the mixture with the volume ratio of 1:1 in an aqueous ammonia solution; dropwise adding the ammonia water solution into a glycol solution of copper nitrate under the stirring condition, putting the precipitate into a synthesis kettle, crystallizing for 4 hours at 150 ℃, filtering, washing for three times, vacuum drying at 100 ℃, and performing heat treatment for 4 hours at 500 ℃ under nitrogen to obtain a copper oxide-iron oxide catalyst;
weighing 200mg of the cerium oxide-iron oxide catalyst, filling the catalyst with 14-25 meshes into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), pumping oxidant water into the reaction tube by a trace sample injection pump, and pumping CH4:H2O ═ 4: 1. Reacting at 450 ℃, and after reacting for 400 minutes, performing online chromatographic analysis, wherein the conversion rate of methane is 50%, and the selectivity of ethylene is as follows: 66 percent.
Example 20
Weighing 5g of ammonium tungstate and 5g of ferric nitrate nonahydrate, and dissolving in 100mL of glycol aqueous solution; 50mL of ammonia water with the mass concentration of 37% is measured and dispersed in 50mL of water to prepare a mixture with the volume ratio of 1:1 in an aqueous ammonia solution; dropwise adding the ammonia water solution into an ethylene glycol solution of ammonium tungstate under the stirring condition, putting the precipitate into a synthesis kettle, crystallizing for 4 hours at 150 ℃, filtering, washing for three times, vacuum drying at 100 ℃, and performing heat treatment for 4 hours at 500 ℃ under nitrogen to obtain a tungsten oxide-iron oxide catalyst;
weighing 200mg of the tungsten oxide-iron oxide catalyst, filling the 14-25 mesh catalyst into a reaction tube by a forming sieve, reacting at normal pressure, wherein the space velocity of methane is 10000 mL/(g.h), oxidant water is pumped into the reaction tube by a trace sample injection pump, and CH4:H2O is 1: 1. Reaction at 650 ℃ for 400 minutes, on-line chromatographic analysis, methane conversion 48%, ethylene selectivity: 66 percent.
Claims (6)
1. A method for oxidative coupling of methane, characterized by:
the process of oxidative coupling of methane is as follows: taking methane and water as raw materials, reacting in a fixed bed reactor, filling a reducible oxide catalyst in a reaction tube, and placing the reaction tube in the fixed bed reactor, wherein the reaction temperature is 400-850 ℃; the reducible metal oxide catalyst is: one or more of indium oxide, titanium oxide, iron oxide, manganese oxide, cobalt oxide, tin oxide, tungsten oxide, and copper oxide.
2. The method of claim 1, wherein:
the reducible metal oxide catalyst is preferably: one or more of indium oxide, titanium oxide, iron oxide and manganese oxide; the reducible metal oxide catalyst is most preferably: one or more of indium oxide and titanium oxide.
3. A method according to claim 1 or 2, characterized in that:
the reducible metal oxide catalyst can be prepared by one or more than two methods of pyrolysis, precipitation, sol-gel method, hydrothermal method, solvothermal method and template method; preferably prepared by one or more than two methods of a precipitation method, a hydrothermal method, a solvothermal method and a template method.
4. The method of claim 1, wherein:
the reaction temperature is 400-850 ℃, the feeding airspeed of methane is 10000-50000 mL/(g.h), CH4:H2O is 1:1 to 4:1 (molar ratio).
5. The method of claim 1 or 4, wherein:
the reaction temperature is 400-600 ℃, and the feeding airspeed of methane is 10000-30000 mL/(g.h), CH4:H2O is 2:1 to 4:1 (molar ratio).
6. The method of claim 1, 4 or 5, wherein:
the reaction temperature is 500-600 ℃, the feeding airspeed of methane is 20000-25000 mL/(g.h), and CH4:H2O is 2:1 to 4:1 (molar ratio).
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