CN109569565A - One kind being used for methane oxidation coupling non-stoichiometric defect fluorite method for preparing catalyst and application - Google Patents
One kind being used for methane oxidation coupling non-stoichiometric defect fluorite method for preparing catalyst and application Download PDFInfo
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- CN109569565A CN109569565A CN201811441666.5A CN201811441666A CN109569565A CN 109569565 A CN109569565 A CN 109569565A CN 201811441666 A CN201811441666 A CN 201811441666A CN 109569565 A CN109569565 A CN 109569565A
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- 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
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- 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
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Abstract
One kind being used for methane oxidation coupling non-stoichiometric defect fluorite method for preparing catalyst and application.According to stoichiometric ratio La3+:Ce4+=1:0.75 or La3+:Ce4+=0.75:1 weighs La3+And Ce4+Ion presoma, is made nitrate mixed solution, adds La3+And Ce4+The citric acid that 2 times of ion moles total number adjusts pH value to 2 with ammonium hydroxide, is placed on water-bath and is evaporated obtained gel, then aging 12 hours, roast obtained non-stoichiometric defect fluorite catalyst La again2Ce1.5O7Or La1.5Ce2O7Catalyst.The advantages that present invention is using cheap metal salt as raw material, and the catalyst prepared using Citrate Sol-gel Process is low with production cost, and synthesis technology is simple, and preparation process is easy to control.Excellent low-temp reaction performance and stability are shown in the reaction of simulation Catalyst for Oxidative Coupling of Methane and ethane.
Description
Technical field
The invention belongs to the energy and environment protection catalytic technical field, are related to one kind for oxidative coupling of methane, directly will
Cheap methane is converted to the ethylene with high economy and industrial value and the non-stoichiometric defect fluorite of ethane product is compound
The preparation method of oxide catalyst.
Background technique
Methane is the main component of natural gas, shale gas and combustible ice, more compared to other fossil resources such as coal and petroleum
Cleaning and abundance.Methane is also common greenhouse gases, utilizes methane as raw material, direct or indirect synthetic method synthesis
The high-valued product such as methanol, ethylene, ethane, reduce CH from source4Discharge, can both improve atmospheric environment or optimize the energy
Using structure, the adjustment of chemicals industrial chain is improved and is of great significance.Therefore, the effective ways of natural gas trans-utilization are explored
It is always the research hotspot of countries in the world scientist with process.The indirect reformer method of methane include aqueous vapor reform, dry gas reform and
The partial oxidation of methane, this kind of reaction converts synthesis gas for methane, further synthesizes high level chemical products, the disadvantage is that reaction
Step is more, and time-consuming, and energy consumption is big.And use the direct translation method of methane, can a step by methane convert high level chemical products.Second
The yield of alkene is to measure the mark of a national oil development of chemical industry level.Oxidative coupling of methane can be straight by single step reaction
It connects and prepares ethylene, either still economically consider there is its realistic meaning from thermodynamics of reactions.For current methane oxidation
There is following problems for coupling catalyst: the reaction is strong exothermal reaction, and reaction temperature is right generally at 700 DEG C -900 DEG C
Industrial equipment heat resistance requires very high;Existing reaction mechanism does not have epitaxy and universality.Researcher endeavours always
In the research of oxidative coupling of methane, but due to C2One-way yield is not achieved 30% or more and industrializes without realizing.Exploitation one
Kind is to grind both at home and abroad at present in cryogenic conditions oxidative coupling of methane superior performance, the catalyst that stability is good, cheap and easy to get
The person's of studying carefully focus of attention.
La2Ce2O7Belonging to the pyrochlore compounds of unordered defect fluorite crystal phase structure, the oxonium ion degree of disorder is high in structure,
Transfer ability is strong, and high thermal stability is good.For the reaction of many aerobic participations, the oxygen mobility enhancing of the catalyst obviously can be with
Promote its reactivity worth.Therefore, La2Ce2O7Composite oxides are the catalysis materials with potential using value.The world is public at present
Recognizing the best methane oxidative coupling catalyst of performance is Mn/Na2WO4/SiO2Class catalyst.The catalyst methane of the type aoxidizes
Coupling activity is high and stability is good, but reaction temperature is higher (750-950 DEG C), basic without activity at 700 DEG C or less.Report at present
The type catalyst in road is in 800 DEG C or more attainable maximum C2Yield is 20%-27%.Yield still be not up to 30% it is minimum
Industrial requirement and cannot achieve industrialization.The resulting catalyst of the present invention is shown in simulation oxidative coupling of methane
Excellent low-temp reaction performance and stability.
Summary of the invention
The purpose of the present invention is to propose to a kind of systems for methane oxidation coupling non-stoichiometric defect fluorite catalyst
Preparation Method and application.Such catalyst directly cheap methane can be converted to by oxidative coupling of methane have it is high economical and
The important chemical intermediate flat reaction raw material such as ethane, the ethylene of industrial value.
The catalyst is prepared using Citrate Sol-gel Process.Under normal pressure, reaction gas group becomes 10%O2+40%CH4,
50%Ar Balance Air, under the conditions of gas flow rate is 30mL/min~60mL/min, the catalyst have high low-temperature catalytic activity and
Stability.
One kind of the present invention is used for methane oxidation coupling non-stoichiometric defect fluorite method for preparing catalyst,
Be characterized in the following steps are included:
(1) according to stoichiometric ratio La3+:Ce4+=1:0.75 or La3+:Ce4+=0.75:1 weighs La respectively3+Ion presoma,
Ce4+Ion presoma, and nitrate homogeneous mixture solotion is made.
It (2) is La by mole3+And Ce4+The citric acid that 2 times of total ion concentration is added in mixed solution, is adjusted with ammonium hydroxide
PH to 2 is stirred 2-3 hours at room temperature.
(3) be evaporated in water-bath at 80-90 DEG C, gained gel 110-140 DEG C aging 12 hours.
(4) xerogel obtained by aging is ground, then with 5 DEG C/min heating rate in Muffle furnace, in 800 DEG C of item
Constant temperature calcining 4 hours under part, are made final catalyst.Stoichiometric ratio is La3+:Ce4+=1:0.75 catalyst is named as
La2Ce1.5O7, stoichiometric ratio La3+:Ce4+=0.75: 1 catalyst is named as La1.5Ce2O7。
La described in step (1) of the present invention3+Ion presoma can be La3+Nitrate, carbonate, the oxide of ion
Or one of hydroxide.For example La3+The nitrate of ion can be directly dissolved in distilled water and prepare solution;Its carbonate, oxygen
Compound or hydroxide first can prepare solution with dilute nitric acid solution dissolution.
Ce described in step (1) of the present invention4+Ion presoma can be Ce4+The nitrate of ion or in oxide one
Kind.For example Ce4+The nitrate of ion can be directly dissolved in distilled water and prepare solution;Its oxide can first be added with dilute nitric acid solution
Hydrogen peroxide dissolution prepares solution.
A kind of application for methane oxidation coupling non-stoichiometric defect fluorite catalyst of the present invention, it is special
Sign is that under normal pressure, reaction gas group becomes 10%O2+40%CH4, 50%Ar Balance Air, gas flow rate is 30mL/min~60mL/
min.Non-stoichiometric defect fluorite catalyst La2Ce1.5O7And La1.5Ce2O7It is anti-to be directly used in methane-oxidizing and-coupling
It answers.
Compared with prior art, catalyst prepared by the present invention has the advantages that
(1) the invention has the advantages of low raw material cost, preparation process is simple and easy, equipment requirement is lower, nontoxic solvent is harmless, to environment without
Secondary pollution.
(2) present invention prepares the catalysis of non-stoichiometric defect fluorite using traditional citric acid sol-gel method the preparation method
Agent, preparation process is simple, and preparation process is easy to control.
(3) the non-stoichiometric defect fluorite catalyst La prepared by the present invention prepared using this method2Ce1.5O7With
La1.5Ce2O7Excellent low-temperature reactivity and stability are shown in oxidative coupling of methane.
Detailed description of the invention
Fig. 1 is non-stoichiometric defect fluorite La prepared by the present invention1.5Ce2O7- A and La2Ce1.5O7C catalyst
XRD spectra.Synthesized catalyst compounds are illustrated as defect fluorite structure.
Fig. 2 is non-stoichiometric defect fluorite La prepared by the present invention2Ce1.5O7- A and La1.5Ce2O7C catalyst
With the current Mn/Na for generally acknowledging that performance is best2WO4/SiO 2Class catalyst methane oxidative coupling reaction performance comparison result.
Fig. 3 is La prepared by the present invention2Ce1.5O7- B defect fluorite catalyst stability test result.
Specific embodiment
Illustrate the present invention in order to clearer, enumerates following embodiment, but it is without any restrictions to the scope of the present invention.
Embodiment 1.
Presoma is the preparation process of nitrate: weighing 4.33g lanthanum nitrate (pentahydrate), 3.25g cerous nitrate (six water
Close object) in 200ml beaker, add 50ml deionized water dissolving;It adds 4.2g citric acid and stirs half an hour, ammonia is added dropwise dropwise
Water adjusts pH=2, continues stirring 1-2 hours.Beaker is placed on 80-90 DEG C of water bath method residual moisture in water-bath, is placed on
Aging 12 hours in 110-140 DEG C of baking oven.Later with the heating rate of 5 DEG C/min in Muffle furnace, constant temperature under the conditions of 800 DEG C
Catalyst La is made in roasting 4 hours2Ce1.5O7-A。
3.25g lanthanum nitrate (pentahydrate), 4.33g cerous nitrate (hexahydrate) are weighed in 200ml beaker, 50ml is added to go
Ionized water dissolution;It adds 4.2g citric acid and stirs half an hour, ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continues stirring 1-2 hours.
Beaker is placed on 80-90 DEG C of water bath method residual moisture in water-bath, is placed on aging 12 hours in 110-140 DEG C of baking oven.It
Afterwards with the heating rate of 5 DEG C/min in Muffle furnace, catalyst is made in the constant temperature calcining 4 hours under the conditions of 800 DEG C
La1.5Ce2.0O7-A。
Embodiment 2.
La3+Ion presoma is the preparation process of its hydroxide, oxide or carbonate: weighing 1.92g lanthanum hydroxide
Or 1.63g lanthana or 2.29g lanthanum carbonate, addition 50ml dust technology dissolve obtained clear solution in 200ml beaker.After be added
3.25g cerous nitrate (hexahydrate) and 4.2g citric acid simultaneously stir half an hour, and ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continue to stir 1-
2 hours.Beaker is placed on 80-90 DEG C of water bath method residual moisture in water-bath, it is small to be placed on aging 12 in 110-140 DEG C of baking oven
When.Later with the heating rate of 5 DEG C/min in Muffle furnace, catalyst is made in the constant temperature calcining 4 hours under the conditions of 800 DEG C
La2Ce1.5O7-B。
Weigh 1.44g lanthanum hydroxide or 1.22g lanthana or 1.69g lanthanum carbonate, and be added 50ml dilute nitric acid solution in
It is dissolved in 200ml beaker, adds 50ml deionized water obtained solution.4.33g cerous nitrate (hexahydrate) and 4.2g lemon is added
Lemon acid simultaneously stirs half an hour, and ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continues stirring 1-2 hours.Beaker is placed on 80-90 in water-bath
DEG C water bath method residual moisture, is placed on aging 12 hours in 110-140 DEG C of baking oven.Later with 5 DEG C/min's in Muffle furnace
Heating rate roasts 4 hours under the conditions of 800 DEG C, and catalyst La is made1.5Ce2.0O7-B。
Embodiment 3.
Ce4+Ion presoma is the preparation process of its oxide: weighing 1.29g cerium oxide, it is molten that suitable dust technology is added
Liquid and 30% hydrogen peroxide solution are dissolved in 200ml beaker, are placed in heat in 80 DEG C of water-bath clear solution is made.It is being formed
Ce4+Ion nitrate solution adds 4.33g lanthanum nitrate (pentahydrate) or dissolves 1.92g lanthanum hydroxide with dilute nitric acid solution
Or lanthanum solution made from 1.63g lanthana or 2.29g lanthanum carbonate and 4.2g citric acid and stir half an hour.Ammonium hydroxide tune is added dropwise dropwise
PH=2 are saved, stirring 1-2 hours is continued.Beaker is placed on 80-90 DEG C of water bath method residual moisture in water-bath, is placed on 110-
Aging 12 hours in 140 DEG C of baking ovens.Later with the heating rate of 5 DEG C/min in Muffle furnace, constant temperature calcining under the conditions of 800 DEG C
4 hours, catalyst La is made2Ce1.5O7-C。
1.72g cerium oxide is weighed, suitable dilute nitric acid solution is added and 30% hydrogen peroxide solution is dissolved in 200ml beaker
In, it is placed in 80 DEG C of heating water baths and clear solution is made.In the Ce of formation4+Ion salt solution adds 3.25g lanthanum nitrate (five water
Close object) or with dilute nitric acid solution to dissolve lanthanum nitrate made from 1.44g lanthanum hydroxide or 1.22g lanthana or 1.69g lanthanum carbonate molten
Liquid and 4.2g citric acid simultaneously stir half an hour.Ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continues stirring 1-2 hours.Beaker is placed on water
80-90 DEG C of water bath method residual moisture in bath is placed on aging 12 hours in 110-140 DEG C of baking oven.Later in Muffle furnace
With the heating rate of 5 DEG C/min, catalyst La is made in the constant temperature calcining 4 hours under the conditions of 800 DEG C1.5Ce2.0O7-C
The experimental results showed that the non-stoichiometric defect fluorite catalyst La that three above example is prepared2Ce1.5O7With
La1.5Ce2O7Catalyst shows excellent low-temp reaction performance for oxidative coupling of methane, and reactivity worth is without very big
Difference.Fig. 2 indicates La in case study on implementation2Ce1.5O7- A and La1.5Ce2.0CaO7- C pyrochlore catalyst and at present generally acknowledged performance are most
Good Mn/Na2WO4/SiO 2Class catalyst methane oxidative coupling reaction low temperature active comparing result.The result shows that being made in the present invention
Standby non-stoichiometric defect fluorite catalyst shows superior activity in 550-750 DEG C of low temperature range;Fig. 3 is indicated
La in case study on implementation2Ce1.5O7The stability test result of-B pyrochlore catalyst in 750 DEG C of lower temperatures.The result shows that 100
Well stable activity, C are remained in the stability test of hour2Product yield is 20.0%.
Claims (4)
1. one kind is used for methane oxidation coupling non-stoichiometric defect fluorite method for preparing catalyst, it is characterized in that including following
Step:
(1) according to stoichiometric ratio La3+:Ce4+=1:0.75 or La3+:Ce4+=0.75:1 weighs La respectively3+Ion presoma,
Ce4+Ion presoma, and nitrate mixed solution is made;
It (2) is La by mole3+And Ce4+The citric acid that 2 times of total ion concentration is added in mixed solution, adjusts pH to 2 with ammonium hydroxide,
It stirs 2-3 hours at room temperature;
(3) be evaporated in water-bath at 80-90 DEG C, gained gel 110-140 DEG C aging 12 hours;
(4) xerogel obtained by aging is ground, then with 5 DEG C/min heating rate in Muffle furnace, under conditions of 800 DEG C
Constant temperature calcining 4 hours;Stoichiometric ratio is La3+:Ce4+=1:0.75 catalyst is named as La2Ce1.5O7, stoichiometric ratio La3 +:Ce4+=0.75: 1 catalyst is named as La1.5Ce2O7。
2. according to claim 1 a kind of for methane oxidation coupling non-stoichiometric defect fluorite catalyst preparation side
Method, it is characterized in that La described in step (1)3+Ion presoma is La3+Nitrate, carbonate, oxide or the hydroxide of ion
One of object.
3. according to claim 1 a kind of for methane oxidation coupling non-stoichiometric defect fluorite catalyst preparation side
Method, it is characterized in that Ce described in step (1)4+Ion presoma is Ce4+The nitrate of ion or one kind of oxide.
4. non-stoichiometric defect fluorite catalyst described in claim 1 answering in methane-oxidizing and-coupling reaction
With it is characterized in that catalytic reaction condition are as follows: under normal pressure, reaction gas group becomes 10%O2+40%CH4, 50%Ar Balance Air, gas stream
Speed is 30mL/min~60mL/min.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109529804A (en) * | 2018-11-29 | 2019-03-29 | 南昌大学 | A kind of preparation method and application of the catalyst for low temperature methane oxidation coupling |
CN109876767A (en) * | 2019-04-19 | 2019-06-14 | 闽江学院 | A kind of preparation and application of diatomite/lanthanum cerate composite material |
CN113248255A (en) * | 2021-03-08 | 2021-08-13 | 东南大学 | High-temperature heat-insulation fluorite type intermediate entropy oxide and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107649114A (en) * | 2017-09-18 | 2018-02-02 | 南昌大学 | A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium |
-
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- 2018-11-29 CN CN201811441666.5A patent/CN109569565A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107649114A (en) * | 2017-09-18 | 2018-02-02 | 南昌大学 | A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium |
Non-Patent Citations (2)
Title |
---|
C.A.MIMS.: "Methane Oxidative Coupling over Nonstoichiometric Bismuth-Tin Pyrochlore Catalysts", 《JOURNAL OF CATALYSIS》 * |
JUNWEI XU,ET AL.: "Developing reactive catalysts for low temperature oxidative coupling of methane: On the factors deciding the reaction performance of Ln2Ce2O7 with different rare earth A sites", 《APPLIED CATALYSIS A, GENERAL》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109529804A (en) * | 2018-11-29 | 2019-03-29 | 南昌大学 | A kind of preparation method and application of the catalyst for low temperature methane oxidation coupling |
CN109876767A (en) * | 2019-04-19 | 2019-06-14 | 闽江学院 | A kind of preparation and application of diatomite/lanthanum cerate composite material |
CN113248255A (en) * | 2021-03-08 | 2021-08-13 | 东南大学 | High-temperature heat-insulation fluorite type intermediate entropy oxide and preparation method thereof |
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