CN103657665A - High-activity lanthanum and cobalt composite oxide catalyst, preparation and application - Google Patents
High-activity lanthanum and cobalt composite oxide catalyst, preparation and application Download PDFInfo
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- CN103657665A CN103657665A CN201310617069.4A CN201310617069A CN103657665A CN 103657665 A CN103657665 A CN 103657665A CN 201310617069 A CN201310617069 A CN 201310617069A CN 103657665 A CN103657665 A CN 103657665A
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Abstract
A high-activity lanthanum and cobalt composite oxide catalyst is a composite oxide of lanthanum and cobalt and non-noble metal catalyst; and fluorine is doped in the composite oxide at different degrees. Lanthanum and cobalt soluble salt and citric acid are dissolved in absolute ethyl alcohol, and the molar ratio of citric acid and metal ions is 2-5; a hydrofluoric acid solution is added dropwise while stirred until the solution is turned into gel; drying is performed at the temperature of 100-160 DEG C, calcination is performed at the temperature of 200-500 DEG C for 2-6 hours, and the high-activity lanthanum and cobalt composite oxide catalyst is obtained. The composite oxide catalyst has the characteristics of economy, low price, simple preparation and the like. The catalyst has higher deep catalytic oxidation activity of propane, and propane with a concentration of 200 ppm (parts per million) can be fully converted at the temperature of 300 DEG C under the condition that the air speed is 100,000 mLg<-1>cath<-1>. Milder and more economic deep catalytic oxidation of propane is hopeful to realize by the aid of the catalyst.
Description
Technical field
The present invention relates to catalyst technical field, especially relate to a kind of high activity lanthanum cobalt composite oxide catalyst and preparation method and application.
Background technology
Along with national economy is fast-developing and urbanization paces accelerate, China's problem of environmental pollution goes from bad to worse, and serious threat is to ecological environment and human lives and health.Investigation shows, vehicle emission pollution has become the one of the main reasons of environmental pollution.Within 2012, < < China Motor Vehicle Pollution Prevention annual report > > points out, four gross contamination emissions of national motor vehicle are 4607.9 ten thousand tons, than 2010, increase by 3.5%.Wherein carbon monoxide (CO) is 3467.1 ten thousand tons, 441.3 ten thousand tons, hydrocarbon (HC), nitrogen oxide (NO
x) 637.5 ten thousand tons, 62.1 ten thousand tons of particles (PM).
For CO, NO in the hemi-closure spaces such as city tunnel or underground parking
ximprovement with PM etc., has caused people's concern, and has obtained good achievement.But rarely has report about the HC improvement aspect that in China's roads and tunnels, concentration is higher.Yet most HC are virose, some HC or even potential carcinogen.In addition, under sunburst irradiates, HC and NO
xthere is photochemical reaction, likely cause photochemical pollution, human health and ecological environment are caused to more serious impact.In fact in city atmosphere pollution the most serious be exactly the HC suspended material of a large amount of automotive emissions, not only severe contamination atmosphere, also causes tropical island effect to make extreme weather take place frequently.The improvement of HC has become current problem demanding prompt solution.
Low chain HC has the features such as nonpolar and chemical stability, and low temperature is difficult to remove.The activation of hydrocarbon key, the direct activation of the hydrocarbon key of especially low catenanes has significant challenge, is considered to " Holy grail " of chemistry.Therefore, developing efficient HC degree of depth catalyst for catalytic oxidation is a urgent and challenging problem of tool.Under laboratory simulation atmosphere, conventionally utilize C
3h
8and C
3h
6replace respectively alkane and olefin component in tail gas.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of high activity lanthanum cobalt composite oxide catalyst and preparation and application, reduce as far as possible motor-vehicle tail-gas processing cost and temperature.
A high activity lanthanum cobalt composite oxide catalyst, is characterized in that, described catalyst is the composite oxides of lanthanum and cobalt, and wherein lanthanum and cobalt mol ratio are 0.1 – 2.
In described composite oxide catalysts, there is fluorine doping in various degree.
When cobalt is manganese, iron, nickel, gained compound all has higher propane degree of depth catalytic oxidation activity.
A preparation method for high activity lanthanum cobalt composite oxide catalyst, is characterized in that, by lanthanum, cobalt soluble-salt, and citric acid is dissolved in absolute ethyl alcohol, and citric acid and metal ion mol ratio are 2 – 5; Under stirring condition, dropwise add hydrofluoric acid solution, change gel into solution; 100 160 ℃ of – are dry, and 200 500 ℃ of – roasting, 2 – 6 hours, obtain high activity lanthanum cobalt composite oxide catalyst.
Described cobalt source is solubility cobalt salt cobalt nitrate (Co (NO
3)
2), cobalt chloride (CoCl
2) in a kind of or its combination; Lanthanum is solubility lanthanum source lanthanum nitrate (La (NO
3)
3), lanthanum chloride (LaCl
3) in a kind of or its combination.
A high activity lanthanum cobalt composite oxide catalyst, it can be applicable to propane (C
3h
8), propylene (C
3h
6), methane (CH
4) deep oxidation reaction, there is good reactivity.
The present invention has relatively cheap, prepares the advantages such as simple.And gained catalyst has higher propane degree of depth catalytic oxidation activity, in air speed, is 100000 mLg
-1 cath
-1condition under, 300
oit is that the propane of 20 ppm transforms entirely that C can realize concentration.
Accompanying drawing explanation
The C3H8 degree of depth catalytic oxidation activity curve of the various composite oxides of Fig. 1.(C3H8 concentration is 20ppm, GHSV=100000 mLg-1cat h-1)
Fig. 1 shows that lanthanum cobalt composite oxide has very high C
3h
8degree of depth catalytic oxidation activity is 100000 mLg in air speed
-1 cath
-1condition under, 300
oit is that the propane of 20 ppm transforms entirely that C can realize concentration; Lanthanum manganese is compared with lanthanum cobalt composite oxide with lanthanum ni compound oxide catalytic activity slightly and is reduced; Lanthanum iron compound oxide activity is the poorest.
The specific embodiment
Embodiment 1:
Under room temperature, the La (NO that is 1 by mol ratio
3)
3, Co (NO
3)
2, and 3 times of citric acids to metal ion mole are dissolved in absolute ethyl alcohol.Under stirring condition, dropwise add HF solution, change gel into solution.120
oc is dry, and 300
oc roasting 3 h.
Embodiment 2:
Under room temperature, the La (NO that is 0.1 by mol ratio
3)
3, Co (NO
3)
2, and 3 times of citric acids to metal ion mole are dissolved in absolute ethyl alcohol.Under stirring condition, dropwise add HF solution, change gel into solution.120
oc is dry, and 300
oc roasting 3 h.
Embodiment 3:
Under room temperature, the La (NO that is 2 by mol ratio
3)
3, Co (NO
3)
2, and 3 times of citric acids to metal ion mole are dissolved in absolute ethyl alcohol.Under stirring condition, dropwise add HF solution, change gel into solution.120
oc is dry, and 300
oc roasting 3 h.
Embodiment 4:
Under room temperature, the La (NO that is 1 by mol ratio
3)
3, Mn (NO
3)
2, and 3 times of citric acids to metal ion mole are dissolved in absolute ethyl alcohol.Under stirring condition, dropwise add HF solution, change gel into solution.120
oc is dry, and 300
oc roasting 3 h.
Embodiment 5:
Under room temperature, the La (NO that is 1 by mol ratio
3)
3, Fe (NO
3)
3, and 3 times of citric acids to metal ion mole are dissolved in absolute ethyl alcohol.Under stirring condition, dropwise add HF solution, change gel into solution.120
oc is dry, and 300
oc roasting 3 h.
Embodiment 6:
Under room temperature, the La (NO that is 1 by mol ratio
3)
3, Ni (NO
3)
2, and 3 times of citric acids to metal ion mole are dissolved in absolute ethyl alcohol.Under stirring condition, dropwise add HF solution, change gel into solution.120
oc is dry, and 300
oc roasting 3 h.
Application examples 1:
The active testing of catalyst
Catalytic reaction condition: fixed-bed micro-reactor, tube inner diameter 8 mm; Unstripped gas propane concentration is 20 ppm, and unstripped gas air speed is 100000 mLg
-1 cath
-1.Active testing the results are shown in Figure 1.
Although the preparation of high activity lanthanum cobalt composite oxide catalyst and the application in propane degree of depth catalytic oxidation thereof have been carried out to detailed, concrete description in description, obviously this area researcher still can infer other apparent variation and content after having read the description of description above.Therefore, the invention is not restricted to specific embodiment in literary composition, all and spirit and scope of the invention does not want that the content of running counter to also should be included in the application.
Claims (6)
1. a lanthanum cobalt composite oxide catalyst, is characterized in that, described catalyst is the composite oxides of lanthanum and cobalt, and wherein lanthanum and cobalt mol ratio are 0.1 – 2.
2. a kind of high activity lanthanum cobalt composite oxide catalyst according to claim 1, is characterized in that, has fluorine doping in various degree in described composite oxide catalysts.
3. a kind of high activity lanthanum cobalt composite oxide catalyst according to claim 1, is characterized in that, when cobalt is manganese, iron, nickel, gained compound all has higher propane degree of depth catalytic oxidation activity.
4. according to claim 1, or a kind of preparation method of high activity lanthanum cobalt composite oxide catalyst described in 2, it is characterized in that, by lanthanum, cobalt soluble-salt, and citric acid is dissolved in absolute ethyl alcohol, and citric acid and metal ion mol ratio are 2 – 5; Under stirring condition, dropwise add hydrofluoric acid solution, change gel into solution; 100 160 ℃ of – are dry, and 200 500 ℃ of – roasting, 2 – 6 hours, obtain high activity lanthanum cobalt composite oxide catalyst.
5. a kind of preparation method of high activity lanthanum cobalt composite oxide catalyst according to claim 3, is characterized in that, described cobalt source is solubility cobalt salt cobalt nitrate (Co (NO
3)
2), cobalt chloride (CoCl
2) in a kind of or its combination; Lanthanum is solubility lanthanum source lanthanum nitrate (La (NO
3)
3), lanthanum chloride (LaCl
3) in a kind of or its combination.
6. according to a kind of high activity lanthanum cobalt composite oxide catalyst described in claim 1 – 3 any one, it can be applicable to propane (C
3h
8), propylene (C
3h
6), methane (CH
4) deep oxidation reaction, there is good reactivity.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383933A (en) * | 2014-11-05 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cerium oxide promoted cobaltosic oxide catalyst and preparation and application thereof |
| CN106540714A (en) * | 2016-11-07 | 2017-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of cerium cobalt complex oxides loaded palladium catalyst and preparation and application for propane catalysis oxidation |
| CN106563446A (en) * | 2016-11-10 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Light carrier catalyst for catalytically eliminating nitric oxide and preparation and application thereof |
| CN110120527A (en) * | 2019-04-15 | 2019-08-13 | 南京晓庄学院 | A kind of controlledly synthesis La doped cobalt/cobalt oxide nanometer sheet and its preparation method and application |
| CN115069259A (en) * | 2022-07-06 | 2022-09-20 | 四川大学 | Method for improving sintering resistance of cobalt oxide catalyst by doping lanthanum |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954289A (en) * | 2010-08-13 | 2011-01-26 | 华南理工大学 | Halogen doped perovskite composite oxide catalyst as well as preparation method and application thereof |
-
2013
- 2013-11-27 CN CN201310617069.4A patent/CN103657665B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954289A (en) * | 2010-08-13 | 2011-01-26 | 华南理工大学 | Halogen doped perovskite composite oxide catalyst as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| K. R. BARNARD ET AL: "Lanthanum Cobalt Oxide Oxidation Catalysts Derived from Mixed Hydroxide Precursors", 《JOURNAL OF CATALYSIS》, vol. 125, 31 December 1990 (1990-12-31) * |
| 张昕等: "Mo/La-Co-O催化剂上甲烷选择氧化制甲醇反应", 《催化学报》, vol. 24, no. 04, 30 April 2003 (2003-04-30), pages 305 - 311 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383933A (en) * | 2014-11-05 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cerium oxide promoted cobaltosic oxide catalyst and preparation and application thereof |
| CN104383933B (en) * | 2014-11-05 | 2016-04-27 | 上海纳米技术及应用国家工程研究中心有限公司 | The cobaltosic oxide catalyst that cerium oxide promotes and Synthesis and applications thereof |
| CN106540714A (en) * | 2016-11-07 | 2017-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of cerium cobalt complex oxides loaded palladium catalyst and preparation and application for propane catalysis oxidation |
| CN106563446A (en) * | 2016-11-10 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Light carrier catalyst for catalytically eliminating nitric oxide and preparation and application thereof |
| CN110120527A (en) * | 2019-04-15 | 2019-08-13 | 南京晓庄学院 | A kind of controlledly synthesis La doped cobalt/cobalt oxide nanometer sheet and its preparation method and application |
| CN110120527B (en) * | 2019-04-15 | 2021-03-16 | 南京晓庄学院 | Controllable synthesized lanthanum-doped cobalt oxide nanosheet and preparation method and application thereof |
| CN115069259A (en) * | 2022-07-06 | 2022-09-20 | 四川大学 | Method for improving sintering resistance of cobalt oxide catalyst by doping lanthanum |
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| CN103657665B (en) | 2016-02-03 |
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