CN107754780A - A kind of preparation method and application of alkali metals modified tin ash catalyst for methane oxidation coupling - Google Patents

A kind of preparation method and application of alkali metals modified tin ash catalyst for methane oxidation coupling Download PDF

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CN107754780A
CN107754780A CN201711055417.8A CN201711055417A CN107754780A CN 107754780 A CN107754780 A CN 107754780A CN 201711055417 A CN201711055417 A CN 201711055417A CN 107754780 A CN107754780 A CN 107754780A
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methane
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王翔
彭亮
方修忠
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Nanchang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A kind of preparation method and application of alkali metals modified tin ash catalyst for methane oxidation coupling.Adjusting stannic chloride pentahydrate pH value of water solution with the ammoniacal liquor of mass fraction 25 28% makes Sn to 74+Ion precipitation is complete.Filtered, and be washed with deionized to TDS afterwards<10.Then SnO is made through drying, roasting2Carrier.By this SnO2Carrier is added in appropriate alkali nitrates solution by drying, roasting, and it is n (M) that a mole composition, which is made,:n(Sn)=x:The catalyst of (10 x), wherein M are Li, Na, K or Cs.The catalyst of gained of the invention shows good cryogenic property and stability in the reaction of simulation methane oxidation coupling ethane and ethene.The present invention prepares associated catalysts using cheap metal salt as raw material using equi-volume impregnating.Catalyst has the advantages that production cost is low, and synthesis technique is simple, and building-up process is easily controlled.

Description

A kind of preparation of alkali metals modified tin ash catalyst for methane oxidation coupling Method and application
Technical field
The invention belongs to energy catalysis technical field, is related to one kind and is used for oxidative coupling of methane, directly by cheap first Alkane changes into the preparation of the alkali metals modified tin ash catalyst of ethene and ethane product with high economy and industrial value Method.
Background technology
Global Oil resource worsening shortages, the unclean environmental pollution for causing getting worse using the energy of the mankind.In face of more next The severeer energy and environmental crisis, exploitation green novel energy source are extremely urgent.Methane is the main component of natural gas, relative to coal For other fossil energies such as oil, it is more cleaned and reserves are relatively abundant.Utilize methane as raw material, synthesis high level chemistry Product, such as methanol, ethene, it is always the study hotspot of World Science man.Effective utilization of methane, can be divided into direct method and indirectly Method.Direct method has oxidative coupling, chlorination coupling, direct dehydrogenation method etc.；Indirect method is primarily referred to as that methane first is converted into synthesis gas, Again by synthesis gas alkene, including methane steam reforming, methane portion oxidation, methane dry gas are reformed, improvement Fischer- The methods of Tropsch methods, methanol decomposition alkene.Step complexity, high energy consumption, high water consume, high CO be present in indirect method2Discharge etc. is asked Topic, and use direct method to reduce CO from source efficiently using methane synthesis high level chemicals2Discharge, improvement atmospheric environment, Optimize using energy source structure, the adjustment to chemicals industrial chain is significant.Methane oxidation coupling (OCM) technique is either Consider there is its realistic meaning from thermodynamics of reactions or economic benefit, and the technique is natural gas ethene so far One of most simple and direct technique, one step of reaction are completed.
The catalyst applied to oxidative coupling of methane mainly includes following four classes at present：Mn/Na2WO4/SiO2Class is urged Agent；ABO3Perovskite composite oxide class catalyst；Li/MgO classes catalyst and RexO yClass catalyst.Urged for these There is problems with for agent：Reaction temperature is high, must be carried out at 700-900 DEG C,；Methane conversion per pass and C2Yield compared with It is low.Researcher is directed to the research of oxidative coupling of methane always, but due to one way C2Yield do not reach 30% it is minimum will Ask and be difficult to industrialize.Exploitation is a kind of good, cheap easy in cryogenic conditions oxidative coupling of methane superior performance, stability The catalyst obtained is current domestic and international researcher focus of attention.
Chinese patent CN105170138A discloses a kind of modified Mn/Na2WO4/SiO2Catalyst, the catalyst activity Component particle size is small, is evenly distributed, for that in oxidative coupling of methane, can improve the conversion ratio and C2 products of methane simultaneously Selectivity.Chinese patent CN104759291A discloses a kind of titaniferous or not manganese-sodium-tungsten of titaniferous-Si composite oxide catalysis Agent, the catalyst are used for oxidative coupling of methane, have excellent catalytic activity and generation ethylene/propene selective and anti- Answer stability.But such modified Mn/Na2WO4/SiO2The reaction temperature of catalyst is higher, need to can be only achieved maximum at 800 DEG C Methane conversion and C2Selectivity of product.Chinese patent CN1061730A discloses a kind of thorium oxide, lanthana, barium carbonate group Into catalyst, but the C when 780-900 DEG C of high temperature reaches higher methane conversion2Selectivity is relatively low.Chinese patent CN1145824A discloses a kind of Sm-Li/MgO catalyst, and in 800 DEG C of high temperature, methane conversion and stability are preferable, but C2 Selectivity of product and C2Product yield is relatively low.Chinese patent CN101138720A discloses a kind of metal base monolithic catalyst, In 820 DEG C of high temperature, methane conversion is preferable, but catalyst component is complicated, and synthesis technique is cumbersome and C2Selectivity of product and C2Production Thing yield is relatively low.
SnO2Belong to cubic Rutile structure, be a kind of typical n-type semiconductor, because its high high-temp stability is good, Had a wide range of applications in gas sensitive, gas sensor and detector, semiconductor and battery etc..SnO2Surface, which has, lives The advantages that bold and vigorous vacant oxygen and reducible lattice surface oxygen and excellent water-resistance, its application in terms of catalysis is also increasingly Cause the extensive concern of people.Worldwide generally acknowledging the methane oxidative coupling catalyst of most industrialization prospect at present is Mn/Na2WO4/SiO2Class catalyst.The catalyst methane oxidative coupling activity of the type is high and stability is good, but reaction temperature is very It is high（725-950℃）, it is basic without activity below 700 DEG C.The type catalyst reported at present can reach more than 800 DEG C Maximum C2Yield is 20-26%.Up to the present due to the C of all catalyst2Yield does not reach more than 30%, it is difficult to realizes Industrialization.The catalyst of gained of the invention shows good low temperature active and stably in oxidative coupling of methane is simulated Property, optimize be expected to obtain the low temperature methane oxidative coupling catalyst with industrial prospect on this basis.
The content of the invention
The purpose of the present invention is to propose to a kind of system of the alkali metals modified tin ash catalyst for methane oxidation coupling Preparation Method, and application of the alkali metals modified tin ash catalyst in methane-oxidizing and-coupling reaction, can pass through first Cheap methane is directly changed into the ethane with high economy and industrial value, ethene alkali metals modified two by alkoxide coupling reaction Tin oxide catalysts.
The catalyst series are prepared using equi-volume impregnating.At ambient pressure, reaction gas composition is 10%O2+40%CH4, 50% Ar Balance Airs, under the conditions of gas flow rate is 30~60mL/min, the catalyst has high catalytic activity.
A kind of preparation method of alkali metals modified tin ash catalyst for methane oxidation coupling of the present invention, It is characterized in that comprise the following steps：
（1）Stannic chloride pentahydrate precursor salt is weighed, distilled water is dissolved in and is made into the aqueous solution, Sn in the solution4+Ion concentration For 0.4~0. 6mol/L.
（2）Step is added dropwise in mass fraction 25-28% ammoniacal liquor（1）In the butter of tin aqueous solution of preparation, pH is adjusted Make Sn to 74+Ion precipitation is complete, is filtered afterwards, and sediment is washed with deionized to TDS<10, products therefrom is 110 12h is dried at DEG C.
（3）By step（2）Products therefrom is ground, and is then heated in Muffle furnace with 2 DEG C/min heating rate 600 DEG C of roasting 4h, are made SnO2Carrier.
（4）By alkali nitrates（MNO3）It is dissolved in distilled water and is configured to M+Ion concentration is 0.3~2mol/L solution, Wherein M is Li, Na, K or Cs.
（5）By step（3）Obtained SnO2Carrier is added to step（4）In the alkali metal aqueous solution of preparation, wherein alkali is golden Category and SnO2Mol ratio be 1:9~7:3.Gained mixture is evaporated in 80 DEG C of water-bath, is continued afterwards dry at 110-120 DEG C Dry aging 12h.
（6）By step（5）Products therefrom is ground, and is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, it is n (M) to obtain mol ratio:n(Sn)=x:The final catalyst of (10-x), wherein M are Li, Na, K or Cs.
Compared with prior art, the catalyst that prepared by the present invention has the following advantages that：Low cost of raw materials, prepare Technique is simple, and preparation process is easily controlled, and equipment requirement is low, nontoxic solvent is harmless, to environment non-secondary pollution.Prepared Catalyst alkali metal molar fraction is 10~70%, and excellent cryogenic property and stably is shown in oxidative coupling of methane Property.
Brief description of the drawings
Fig. 1 is the XRD material phase analysis results of different alkali metals modified tin ash catalyst prepared by the inventive method.
Fig. 2 is the CH of different alkali metals modified tin ash catalyst prepared by the inventive method4Conversion results.
Fig. 3 is the C of different alkali metals modified tin ash catalyst prepared by the inventive method2Yield result.
Fig. 4 is Li prepared by the inventive method:Sn mol ratios are 5:5 catalyst reaction stability test result.
Fig. 5 is Li prepared by the inventive method:Sn mol ratios are 5:Before 5 catalyst and at present generally acknowledged most commercial Application The Mn/Na of scape2WO4/SiO2Class catalyst is used for the low temperature CH of oxidative coupling of methane4Conversion ratio comparing result.
Fig. 6 is Li prepared by the inventive method:Sn mol ratios are 5:Before 5 catalyst and at present generally acknowledged most commercial Application The Mn/Na of scape2WO4/SiO2Class catalyst is used for the low temperature C of oxidative coupling of methane2Yield comparing result.
Embodiment
For the clearer explanation present invention, following examples are enumerated, but it is without any restrictions to the scope of the present invention.
Embodiment 1.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier.
Embodiment 2.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；Weigh 0.0670g LiNO3Add in 2mL deionized water solutions, added after salt is completely dissolved 1.3590g obtained SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C aging 12h is dried, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (Li):n (Sn)=1:9。
Embodiment 3.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；Weigh 0.0849g NaNO3Add in 2mL deionized water solutions, added after salt is completely dissolved 1.3590g obtained SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C aging 12h is dried, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (Na):n (Sn)=1:9。
Embodiment 4.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；Weigh 0.1011g KNO3Add in 2mL deionized water solutions, added after salt is completely dissolved 1.3590g obtained SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C aging 12h is dried, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (K):n (Sn)=1:9。
Embodiment 5.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；Weigh 0.1949 g CsNO3Add in 2mL deionized water solutions, added after salt is completely dissolved 1.3590g obtained SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C aging 12h is dried, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (Cs):n (Sn)=1:9。
Embodiment 6.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；Weigh 0.2069g LiNO3Add in 2mL deionized water solutions, added after salt is completely dissolved 1.3590g obtained SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C aging 12h is dried, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (Li):n (Sn)=3:7。
Embodiment 7.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；Weigh 0.5171 g LiNO3Add in 2mL deionized water solutions, added after salt is completely dissolved 1.3590g obtained SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C aging 12h is dried, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (Li):n (Sn)=5:5。
Embodiment 8.
Weigh 15gSnCl4•5H2Quality point is added dropwise after adding 200mL deionized water stirring and dissolvings in 500mL beakers in O dropwise Number 25-28% ammoniacal liquor regulation pH to 7 makes Sn4+Ion precipitation is complete.Filtered afterwards, sediment is washed with deionized extremely TDS<10, products therefrom dries 12h at 110 DEG C, is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier, with 2 DEG C/min heating rate in Muffle furnace, 4h is calcined under the conditions of 600 DEG C, is made and urges Agent SnO2；Weigh 0.7240g LiNO3Add in 2mL deionized water solutions, 1.3590g is added after salt is completely dissolved and is made SnO2Carrier, stirs 5-6h, and gained mixture is evaporated in 80 DEG C of water-bath, continued afterwards in 110-120 DEG C of dry aging 12h, 600 DEG C of roasting 4h are then heated to 2 DEG C/min heating rate in Muffle furnace, are designated as n (Li):n(Sn)=7:3.
Test result indicates that Li is modified, tin ash catalyst methane oxidative coupling performance is best, and the amount of the material as Li Activity is best when fraction is 50%.Fig. 1 represents different alkali metals modified tin ash catalyst XRD material phase analysis in case study on implementation As a result.The characteristic diffraction peak of tin ash is only observed in figure, shows that alkali metal is highly dispersed in catalyst surface.Fig. 2 tables Show different alkali metals modified tin ash catalyst performance results in case study on implementation.As a result the tin ash catalysis that Li is modified is shown Agent shows best Performance for Oxidative Coupling of Methane Over.Fig. 3 represents that the Li that the amount fraction of material in case study on implementation is 50% is modified dioxy Change tin catalyst stability test result.As a result show to remain good reactivity in 100h stability test Can, and highest C2Product yield is 18.4%.Fig. 4 represents that the Li that the amount fraction of material in case study on implementation is 50% is modified tin ash Catalyst and the Mn/Na of universally acknowledged better performances2WO4/SiO 2Class catalyst methane oxidative coupling reaction cryogenic property contrasts As a result.As a result show in the present invention that catalyst shows superior reactivity worth in the range of 650-700 DEG C of low temperature.

Claims (2)

  1. A kind of 1. preparation method of alkali metals modified tin ash catalyst for methane oxidation coupling, it is characterised in that including Following steps：
    （1）Stannic chloride pentahydrate precursor salt is weighed, distilled water is dissolved in and is made into the aqueous solution, Sn in the solution4+Ion concentration For 0.4~0. 6mol/L；
    （2）Step is added dropwise in the ammoniacal liquor that mass fraction is 25-28%（1）In the butter of tin aqueous solution of preparation, regulation pH to 7 make Sn4+Ion precipitation is complete, is filtered afterwards, and sediment is washed with deionized to TDS<10, products therefrom is at 110 DEG C Lower dry 12h；
    （3）By step（2）Products therefrom is ground, and is then heated to 600 DEG C in Muffle furnace with 2 DEG C/min heating rate 4h is calcined, SnO is made2Carrier；
    （4）Alkali nitrates are dissolved in distilled water and are configured to the solution that alkali metal ion concentration is 0.3~2mol/L, wherein alkali Metal is Li, Na, K or Cs；
    （5）By step（3）Obtained SnO2Carrier is added to step（4）In the alkali metal aqueous solution of preparation, wherein alkali metal with SnO2Mol ratio be 1:9~7:3；Gained mixture is evaporated in 80 DEG C of water-bath, continues to dry always at 110-120 DEG C afterwards Change 12h；
    （6）By step（5）Products therefrom is ground, and is then heated to 600 DEG C of roastings in Muffle furnace with 2 DEG C/min heating rate 4h, it is n (M) to obtain mol ratio:n(Sn)=x:The final catalyst of (10-x), wherein M are Li, Na, K or Cs.
  2. 2. application of the alkali metals modified tin ash catalyst in methane-oxidizing and-coupling reaction described in claim 1, It is characterized in that catalytic condition is：At ambient pressure, reaction gas 10%O2+40%CH4, 50%Ar Balance Airs, gas velocity is 30~60mL/ min。
CN201711055417.8A 2017-11-01 2017-11-01 A kind of preparation method and application of alkali metals modified tin ash catalyst for methane oxidation coupling Pending CN107754780A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111151287A (en) * 2020-01-17 2020-05-15 厦门大学 Alkaline oxide modified boron nitride catalyst and preparation method and application thereof
CN112473703A (en) * 2020-11-28 2021-03-12 南昌大学 Preparation method and application of high-ethylene-selectivity methane oxidation coupling catalyst
CN115591563A (en) * 2022-10-08 2023-01-13 华东师范大学（Cn） Catalyst suitable for fluidized bed to perform methane oxidation coupling reaction and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
K.KAVIYARASU ET AL.,: "One pot synthesis and characterization of cesium doped SnO2 nanocrystals via a hydrothermal process", 《J.MATER.SCI.TECHNOL.》 *
王仲权等: "甲烷氧化偶联制乙烯的研究I.SnO2催化剂的活性考察", 《C1化学与化工》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111151287A (en) * 2020-01-17 2020-05-15 厦门大学 Alkaline oxide modified boron nitride catalyst and preparation method and application thereof
CN111151287B (en) * 2020-01-17 2021-12-03 厦门大学 Alkaline oxide modified boron nitride catalyst and preparation method and application thereof
CN112473703A (en) * 2020-11-28 2021-03-12 南昌大学 Preparation method and application of high-ethylene-selectivity methane oxidation coupling catalyst
CN115591563A (en) * 2022-10-08 2023-01-13 华东师范大学（Cn） Catalyst suitable for fluidized bed to perform methane oxidation coupling reaction and preparation method and application thereof
CN115591563B (en) * 2022-10-08 2024-04-23 华东师范大学 Catalyst suitable for fluidized bed methane oxidative coupling reaction and preparation method and application thereof

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