CN105170138A - Methane oxidative coupling reaction catalyst and preparation method thereof - Google Patents
Methane oxidative coupling reaction catalyst and preparation method thereof Download PDFInfo
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- CN105170138A CN105170138A CN201410409044.XA CN201410409044A CN105170138A CN 105170138 A CN105170138 A CN 105170138A CN 201410409044 A CN201410409044 A CN 201410409044A CN 105170138 A CN105170138 A CN 105170138A
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Abstract
The invention discloses a methane oxidative coupling catalyst and a preparation method thereof. The method comprises: under an ultrasonic condition, subjecting a carrier to first dipping in a metal compound aqueous solution, and conducting drying, then carrying out second dipping in a metal compound aqueous solution under the ultrasonic condition, and performing drying and roasting. The preparation method of the methane oxidative coupling reaction catalyst is simple and easy to operate, and the methane oxidation coupling reaction catalyst prepared by the method has uniformly distributed active components with small particle size. By applying the methane oxidative coupling catalyst prepared by the method to methane oxidative coupling reaction, the conversion rate of methane and the selectivity of C2 hydrocarbons can be increased simultaneously.
Description
Technical field
The present invention relates to field of catalyst preparation, particularly, the preparation method relating to a kind of oxidative coupling of methane catalyst and the oxidative coupling of methane catalyst prepared by the method.
Background technology
Ethene is as most important basic organic chemical raw material, and for a long time, its production depends on petroleum cracking route always, and the problems such as consequent environmental pollution are on the rise.In recent years, crude oil price continues soaring, causes the rise of ethylene cracking material price, simultaneously supply falls short of demand that phenomenon is also very outstanding for ethylene cracking material, in the face of this present situation, new ethylene production route all in adjustment using energy source structure, and is constantly found in countries in the world.Natural gas is as a kind of important energy source, and abundant reserves are that its utilization in chemical industry provides good guarantee.Meanwhile, in the world for adapting to 21 century global energy and the demand of petrochemical materials Structure Transformation, be one of important research direction by substitute gas oil synthesis alkene.
At present, direct method and indirect method is had from the method for natural gas preparing ethylene.Direct method has oxidative coupling, chlorination coupling, direct dehydrogenation method; Indirect method is first synthesis gas by conversion of natural gas, then by synthesis gas alkene, comprise the methods such as improvement F-T method, methanol decomposition alkene.
From natural gas; according to portion oxidation synthesis gas/synthesising gas systeming carbinol/methanol-to-olefins three-step approach (POM/GTM/MTO) preparing ethylene; not only course of reaction step is various; and want first oxygen atom to be inserted to take out again; it is non-atomic economy reaction; from the viewpoint of technology, the utilization of resources, environmental protection etc.; multistep processes is not the selection of economical rationality; and natural gas namely for methane oxidative coupling ethene (OCM) is the most direct method; therefore in decades, OCM is the emphasis of countries in the world scientist research always.
Nineteen eighty-two, Keller and Bhasin of UCC company of the U.S. has delivered first section of research report about OCM, and so far, the catalyst studied reaches more than 2000 kinds, and the element used includes the whole elements except group 0 element.At present, on the basis of generally screening, the good catalyst system and catalyzing of reactivity worth mainly concentrates on alkali compounds, the alkali and alkaline earth metal ions of oxide supported, single-phase oxide, transition metal oxide that alkali metal containing ion supports, the oxide of halide ion modification, this few class caltalyst of solid super-strong acid are fastened.(Li, S. (2003). " ReactionChemistryofW-Mn/SiO2CatalystfortheOxidativeCoupl ingofMethane. " JournalofNaturalGasChemistry (01): 1-9.) bibliographical information take silica as carrier, one of system that sodium tungstate and manganese to be the loaded catalyst of active component be performance is best.
In the report of the preparation of existing methane oxidative coupling catalyst, usually adopt infusion process or Slurry mixing preparation.But the active component granularity of the catalyst adopting these methods to prepare is comparatively large, skewness, and the methane conversion shown when being applied in oxidative coupling of methane and C 2 hydrocarbon selective all lower.
Summary of the invention
The active component granularity that the object of the invention is to overcome existing methane oxidative coupling catalyst is large, skewness, and in oxidative coupling of methane, methane conversion is low, the selective low defect of C 2 hydrocarbon, the preparation method providing a kind of oxidative coupling of methane catalyst and the oxidative coupling of methane catalyst prepared by the method.
To achieve these goals, the invention provides a kind of preparation method of oxidative coupling of methane catalyst, the method comprises: under ultrasound condition, carrier is carried out the first dipping in the metallic compound aqueous solution, drying, then carries out the second dipping under ultrasound condition in the metallic compound aqueous solution, dry also roasting, wherein, the metallic compound in the described metallic compound aqueous solution and the mass ratio of described carrier are 1:0.001-200; The mass ratio of the water in described carrier and the described metallic compound aqueous solution is 1:1-20;
Present invention also offers a kind of oxidative coupling of methane catalyst, wherein, described oxidative coupling of methane catalyst is prepared by method provided by the invention.
The preparation method of described oxidative coupling of methane catalyst provided by the invention is simple to operation, and the oxidative coupling of methane catalyst activity component particle size prepared by the method little, be evenly distributed; And, by the oxidative coupling of methane catalyst application prepared by the method in oxidative coupling of methane, the conversion ratio of methane and the selective of C 2 hydrocarbon can be improved simultaneously.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the stereoscan photograph of the oxidative coupling of methane catalyst according to embodiment 1 preparation.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of described oxidative coupling of methane catalyst provided by the invention comprises: under ultrasound condition, carrier is carried out the first dipping in the metallic compound aqueous solution, dry, then under ultrasound condition, in the metallic compound aqueous solution, the second dipping is carried out, dry also roasting, wherein, the metallic compound in the described metallic compound aqueous solution and the mass ratio of described carrier are 1:0.001-200; The mass ratio of the water in described carrier and the described metallic compound aqueous solution is 1:1-20.
Preferably, the metallic compound in the described metallic compound aqueous solution and the mass ratio of described carrier are 1:0.003-100; The mass ratio of the water in described carrier and the described metallic compound aqueous solution is 1:1-15.
Further preferably, the metallic compound in the described metallic compound aqueous solution and the mass ratio of described carrier are 1:0.005-50; The mass ratio of the water in described carrier and the described metallic compound aqueous solution is 1:1-10.
Metallic compound in the aqueous solution of metallic compound described in the present invention can be one or more in IA race metallic compound, group vib metallic compound and VIIB race metallic compound.Described IA race metallic compound can be such as one or more in compounds containing sodium and potassium-containing compound.Described compounds containing sodium can be such as sodium carbonate (Na
2cO
3), sodium acetate (CH
3cOONaH
2and sodium tungstate (Na O)
2wO
42H
2o) one or more in.Described potassium-containing compound can be such as potash (K
2cO
3) and potassium nitrate (KNO
3) in one or more.Described group vib metallic compound can be such as Tungstenic compound.Described Tungstenic compound can be such as ammonium tungstate ((NH
4)
10w
12o
41~ xH
2o).Described VIIB race metallic compound such as can for containing manganese compound.Described can be such as manganese nitrate (Mn (NO containing manganese compound
3)
24H
2o), the described manganese compound that contains can use with the form of manganese nitrate solution (as 50% manganese nitrate solution).
Described in the present invention, the metallic compound of the first dipping is different from the metallic compound that second floods.
The kind of the present invention to described carrier is not particularly limited, such as, can be titanium oxide (TiO
2), carborundum (SiC), silica (SiO
2), aluminium oxide (Al
2o
3) and barium titanate (BaTiO
3) in one or more, wherein, be preferably in silica, aluminium oxide and barium titanate one or more.
The ultrasound condition of the first dipping process described in the present invention and the second dipping process can identical also can not be identical, the first dipping process of the present invention is preferably identical with the ultrasound condition of the second dipping process.
In the present invention, particular/special requirement be there is no to the ultrasound condition of described first dipping process and the second dipping process, as long as in the first dipping process and the second dipping process, can be loaded on carrier by metallic compound respectively.Such as, described ultrasound condition generally comprises: supersonic frequency can be 10-200KHz, and ultrasonic temperature can be 5-80 DEG C, and ultrasonic time can be 0.1-48h.Under preferable case, can load on carrier better to make described metallic compound in the first dipping process and the second dipping process, make the active component granularity of the oxidative coupling of methane catalyst obtained little, be evenly distributed, described ultrasound condition comprises: supersonic frequency is 45-100KHz, ultrasonic temperature is 10-60 DEG C, and ultrasonic time is 0.5-24h.
Described in the present invention first dipping after drying condition flood with second after drying condition can identical also can not be identical, the present invention first dipping after drying condition flood with second after drying condition preferably identical.
Do not have particular/special requirement to described drying condition in the present invention, concrete implementation condition can be determined according to the drying condition of this area routine.Such as, it can be 80-150 DEG C that described drying condition generally comprises dry temperature, is preferably 100-130 DEG C; The dry time can be 1-48h, is preferably 10-25h.
Do not have particular/special requirement to described roasting condition in the present invention, concrete implementation condition can be determined according to the roasting condition of this area routine.Such as, the temperature that described roasting condition generally comprises roasting can be 200-950 DEG C, and be preferably 500-900 DEG C, the time of described roasting can be 1-24h, is preferably 5-15h.
Water in the aqueous solution of metallic compound described in the present invention can be selected from running water, deionized water or distilled water, wherein, is preferably distilled water.
The oxidative coupling of methane catalyst prepared by preparation method of the present invention may be used for any type of reactor, such as fixed bed reactors, fluidized-bed reactor etc.
Below will be described the present invention by embodiment.
Embodiment 1
Take 0.28g sodium tungstate, join in the beaker of 25g distilled water, dissolve completely, in beaker, add 5g silica, beaker is put into ultrasonic cleaner, supersonic frequency is set as 45KHz, ultrasonic temperature is 30 DEG C, ultrasonic process 4h, puts into 120 DEG C of freeze-day with constant temperature baking ovens, and dry 24h obtains the silica that load has sodium tungstate; Take 0.65g manganese nitrate (50% aqueous solution), join in the beaker of 25g distilled water, dissolve completely, the silica that above-mentioned load has sodium tungstate is added in beaker, beaker is put into ultrasonic cleaner, supersonic frequency is set as 45KHz, ultrasonic temperature is 30 DEG C, ultrasonic process 4h, put into 100 DEG C of dry 24h of freeze-day with constant temperature baking oven, move to roasting in Muffle furnace, be warming up to 550 DEG C and keep within 5 hours, then continuing to be warming up to 850 DEG C of maintenances 5 hours, obtain oxidative coupling of methane Na-W-Mn/SiO
2catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane Na-W-Mn/SiO
2the performance test results of catalyst is as shown in table 2.
Embodiment 2
Take 3.02g manganese nitrate (50% aqueous solution), join in the beaker of 10g distilled water, dissolve completely, 5g barium titanate is added in beaker, beaker is put into ultrasonic cleaner, and supersonic frequency is set as 80KHz, and ultrasonic temperature is 30 DEG C, ultrasonic process 2.5h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the barium titanate that load has manganese nitrate; Take 1.02g sodium carbonate, join in the beaker of 10g distilled water, dissolve completely, the barium titanate that above-mentioned load has manganese nitrate is added in beaker, beaker is put into ultrasonic cleaner, and supersonic frequency is set as 80KHz, and ultrasonic temperature is 30 DEG C, ultrasonic process 2.5h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the barium titanate that load has sodium carbonate and manganese nitrate; Take 3.05g ammonium tungstate, join in the beaker of 10g distilled water, dissolve completely, in beaker, add the barium titanate that above-mentioned load has sodium carbonate and manganese nitrate, beaker is put into ultrasonic cleaner, supersonic frequency is set as 80KHz, ultrasonic temperature is 30 DEG C, and ultrasonic process 2.5h, moves to roasting in Muffle furnace, be warming up to 550 DEG C to keep within 5 hours, then continuing to be warming up to 850 DEG C of maintenances 5 hours, obtain oxidative coupling of methane Na-W-Mn/BaTiO
3catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane Na-W-Mn/BaTiO
3the performance test results of catalyst is as shown in table 2.
Embodiment 3
Take 1.64g sodium acetate, join in the beaker of 30g distilled water, dissolve completely, 5g aluminium oxide is added in beaker, beaker is put into ultrasonic cleaner, and supersonic frequency is set as 100KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 8h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the aluminium oxide that load has sodium acetate; Take 3.82g manganese nitrate (50% aqueous solution), join in the beaker of 30g distilled water, dissolve completely, the aluminium oxide that above-mentioned load has leaching sodium acetate is added in beaker, put into ultrasonic cleaner, supersonic frequency is set as 100KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 8h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the aluminium oxide that load has sodium acetate and manganese nitrate; Take 3.45g ammonium tungstate, join in the beaker of 30g distilled water, dissolve completely, in beaker, add the aluminium oxide that above-mentioned load has sodium acetate and manganese nitrate, put into ultrasonic cleaner, supersonic frequency is set as 100KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 8h, put into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven, move to roasting in Muffle furnace, be warming up to 850 DEG C and keep 8 hours, obtain oxidative coupling of methane Na-W-Mn/Al
2o
3catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane Na-W-Mn/Al
2o
3the performance test results of catalyst is as shown in table 2.
Embodiment 4
Take 2.69g potash, join in the beaker of 30g distilled water, dissolve completely, 5g silica is added in beaker, beaker is put into ultrasonic cleaner, and supersonic frequency is set as 45KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 8h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the silica that load has potash; Take 4.3g manganese nitrate (50% aqueous solution), join in the beaker of 30g distilled water, the silica that above-mentioned load has potash is added in beaker, beaker is put into ultrasonic cleaning machine, supersonic frequency is set as 45KHz, ultrasonic temperature is 40 DEG C, ultrasonic process 8h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the silica that load has potash and manganese nitrate; Take 6.08g ammonium tungstate, join in the beaker of 30g distilled water, in beaker, add the silica that above-mentioned load has potash and manganese nitrate, beaker is put into ultrasonic cleaning machine, and supersonic frequency is set as 45KHz, ultrasonic temperature is 40 DEG C, ultrasonic process 8h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven, moves to roasting in Muffle furnace, be warming up to 850 DEG C to keep 8 hours, obtain oxidative coupling of methane K-W-Mn/SiO
2catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane K-W-Mn/SiO
2the performance test results of catalyst is as shown in table 2.
Embodiment 5
Take 4.03g potassium nitrate, join in the beaker of 8g distilled water, dissolve completely, 5g silica is added in beaker, beaker is put into ultrasonic cleaning machine, and supersonic frequency is set as 80KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 2h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the silica that load has potassium nitrate; Take 4.12g manganese nitrate (50% aqueous solution), join in the beaker of 8g distilled water, the silica that above-mentioned load has potassium nitrate is added in beaker, beaker is put into ultrasonic cleaning machine, supersonic frequency is set as 80KHz, ultrasonic temperature is 40 DEG C, ultrasonic process 2h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the silica that load has potassium nitrate and manganese nitrate; Take 2.08g ammonium tungstate, join in the beaker of 8g distilled water, dissolve completely, in beaker, add the silica that above-mentioned load has potassium nitrate and manganese nitrate, beaker is put into ultrasonic cleaning machine, supersonic frequency is set as 80KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 2h, put into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven, move to roasting in Muffle furnace, be warming up to 850 DEG C and keep 8 hours, obtain oxidative coupling of methane K-W-Mn/SiO
2catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane K-W-Mn/SiO
2the performance test results of catalyst is as shown in table 2.
Embodiment 6
Take 0.31g ammonium tungstate, join in the beaker of 35g distilled water, 5g silica is added in beaker, beaker is put into ultrasonic cleaning machine, supersonic frequency is set as 100KHz, ultrasonic temperature is 40 DEG C, ultrasonic process 24h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the silica that load has ammonium tungstate; Take 0.66g manganese nitrate (50% aqueous solution), join in the beaker of 35g distilled water, add in beaker above-mentioned enter load have the silica of ammonium tungstate, beaker is put into ultrasonic cleaning machine, supersonic frequency is set as 100KHz, ultrasonic temperature is 40 DEG C, ultrasonic process 24h, puts into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven and obtains the silica that load has ammonium tungstate and manganese nitrate; Take 0.11g potassium nitrate, join in the beaker of 35g distilled water, dissolve completely, add in beaker above-mentioned enter load have the silica of ammonium tungstate and manganese nitrate, beaker is put into ultrasonic cleaning machine, supersonic frequency is set as 100KHz, and ultrasonic temperature is 40 DEG C, ultrasonic process 24h, put into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven, move to roasting in Muffle furnace, be warming up to 850 DEG C and keep 8 hours, obtain oxidative coupling of methane K-W-Mn/SiO
2catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane K-W-Mn/SiO
2the performance test results of catalyst is as shown in table 2.
Embodiment 7
Take 0.6g sodium tungstate, join in the beaker of 12g distilled water, dissolve completely, 5g silica is added in beaker, beaker is put into ultrasonic cleaning machine, and supersonic frequency is set as 45KHz, and ultrasonic temperature is 50 DEG C, ultrasonic process 8h, puts into the silica that 120 DEG C of dry 12h of freeze-day with constant temperature baking oven obtain sodium tungstate; Take 0.69g manganese nitrate (50% aqueous solution), join in the beaker of 12g distilled water, the silica that above-mentioned load has sodium tungstate is added in beaker, put into ultrasonic cleaning machine, supersonic frequency is set as 45KHz, ultrasonic temperature is 50 DEG C, ultrasonic process 8h, put into 120 DEG C of dry 12h of freeze-day with constant temperature baking oven, move to roasting in Muffle furnace, be warming up to 850 DEG C keep 8 hours, obtain oxidative coupling of methane Na-W-Mn/SiO2 catalyst, the preparation condition in preparation process and each amounts of components as shown in table 1.This Na-W-Mn/SiO
2the performance test results of catalyst is as shown in table 2.
Comparative example 1
Oxidative coupling of methane Na-W-Mn/SiO is prepared according to the method for embodiment 1
2catalyst, replaces with at 80 DEG C of stirred in water bath 2h unlike by ultrasonic in dipping process.This oxidative coupling of methane Na-W-Mn/SiO
2preparation condition in catalyst preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane Na-W-Mn/SiO
2the performance test results of catalyst is as shown in table 2.
Comparative example 2
Oxidative coupling of methane Na-W-Mn/Al is prepared according to the method for embodiment 3
2o
3catalyst, replaces with at 100 DEG C of stirred in water bath 2.5h unlike by ultrasonic in dipping process.This oxidative coupling of methane Na-W-Mn/Al
2o
3preparation condition in catalyst preparation process and each amounts of components as shown in table 1.This oxidative coupling of methane Na-W-Mn/Al
2o
3the performance test results of catalyst is as shown in table 2.
Table 1
Test case
Catalyst prepared by above-described embodiment and comparative example is taken 0.4g respectively, and to be respectively charged into internal diameter be in the fixed bed quartz tube reactor of 8mm, then methane and oxygen are injected and wherein carry out oxidative coupling of methane, wherein, total air speed of methane and oxygen is 10000ml/ (g.h), CH
4/ O
2volume ratio 4.
Table 2
As can be seen from the data of table 2, by oxidative coupling of methane to prepare in the process of C 2 hydrocarbon, adopt the oxidative coupling of methane catalyst that method of the present invention is obtained, substantially increase the conversion ratio of methane and the selective of C 2 hydrocarbon.
In addition, can find out by embodiment 1-2 and 4-7 and embodiment 3 are carried out contrast, the oxidative coupling of methane catalyst adopting aluminium oxide to prepare as carrier has relatively low catalytic activity, particularly, and the conversion ratio of the methane shown and the selective relatively low of C 2 hydrocarbon.But, can find out by embodiment 3 and comparative example 2 are carried out contrast, even if the oxidative coupling of methane catalyst adopting aluminium oxide to prepare as carrier has relatively low catalytic activity, but still can significantly improve the catalytic activity of the catalyst prepared as carrier by aluminium oxide according to method of the present invention.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. the preparation method of an oxidative coupling of methane catalyst, the method comprises: under ultrasound condition, carrier is carried out the first dipping in the metallic compound aqueous solution, dry, then under ultrasound condition, in the metallic compound aqueous solution, the second dipping is carried out, dry also roasting, wherein, the metallic compound in the described metallic compound aqueous solution and the mass ratio of described carrier are 1:0.001-200; The mass ratio of the water in described carrier and the described metallic compound aqueous solution is 1:1-20.
2. method according to claim 1, wherein, the metallic compound in the described metallic compound aqueous solution and the mass ratio of described carrier are 1:0.005-50; The mass ratio of the water in described carrier and the described metallic compound aqueous solution is 1:1-10.
3. method according to claim 1 and 2, wherein, the metallic compound in the described metallic compound aqueous solution is one or more in IA race metallic compound, group vib metallic compound and VIIB race metallic compound; Preferably, IA race metal is sodium and/or potassium, and group vib metal is tungsten, and VIIB race metal is manganese; Preferably, described metallic compound is one or more in sodium carbonate, sodium acetate, sodium tungstate, potash, manganese nitrate, potassium nitrate and ammonium tungstate.
4. according to the method in claim 1-3 described in any one, wherein, the metallic compound of described first dipping is different from the metallic compound that second floods.
5. method according to claim 1 and 2, wherein, described carrier is one or more in titanium oxide, carborundum, silica, aluminium oxide and barium titanate, is preferably one or more in silica, aluminium oxide and barium titanate.
6. method according to claim 1 and 2, wherein, described ultrasound condition comprises: supersonic frequency is 10-200KHz, and ultrasonic temperature is 5-80 DEG C, and ultrasonic time is 0.1-48h.
7. method according to claim 1 and 2, wherein, the temperature of described drying is 80-150 DEG C, and the dry time is 1-48h; The temperature of described roasting is 200-950 DEG C, and the time of described roasting is 1-24h.
8. oxidative coupling of methane catalyst prepared by the method according to any one in claim 1-7.
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| CN115254087A (en) * | 2021-04-30 | 2022-11-01 | 中国石油天然气股份有限公司 | Supported catalyst and preparation method and application thereof |
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