CN103752317A - Preparation of Co3O4 / CeO2 composite oxide and catalytic application - Google Patents

Preparation of Co3O4 / CeO2 composite oxide and catalytic application Download PDF

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CN103752317A
CN103752317A CN201310600448.2A CN201310600448A CN103752317A CN 103752317 A CN103752317 A CN 103752317A CN 201310600448 A CN201310600448 A CN 201310600448A CN 103752317 A CN103752317 A CN 103752317A
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ceo
composite oxide
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co3o4
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邵建军
鞠晓春
李家波
周学滨
张永坤
陈高杰
赵鹏远
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    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
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Abstract

The invention discloses preparation of Co3O4 / CeO2 composite oxide and catalytic application in low-temperature oxidation of carbon monoxide. The atomic ratio of Co to Ce in the Co3O4 / CeO2 composite oxide is 19 / 1. The Co3O4 / CeO2 composite oxide has a strong oxidation function, at a lower temperature (196K), the conversion rate of the catalyst for CO oxidation is 99%, and can be continuously maintained for more than 480min, and when a reaction gas contains 3.1vol.% of moisture, and the temperature is 383K, the CO conversion rate still maintains at 81% after 2580min of reaction.

Description

Co 3o 4/ CeO 2composite oxides preparation and catalytic applications
Technical field
The present invention relates to a kind of Co 3o 4/ CeO 2the technology of preparing of composite oxides and the catalytic applications of this oxide in CO low temperature oxidation.
Background technology
CO low temperature oxidation is widely used in weather monitoring, breathing mask and the removal to trace carbon monoxide in the enclosed environments such as spaceship, submarine.Research discovery, part transition metal oxide also can be realized the low-temperature oxidation to carbon monoxide.Cunningham etc. [Catal. Lett. 25 (1994) 257] report Co 3o 4under drying condition, can realize the conversion completely to carbon monoxide in the low temperature of 197 K.Thorm hlen etc. [J.Catal.188 (1999) 300] report is by Co 3o 4support in Al 2o 3the upper temperature at 210 K can make the conversion ratio of carbon monoxide reach 50%.In practical application and unstripped gas, the existence of water is inevitable, due to Co 3o 4there is strong absorptive, cause the rapid deactivation [Appl.Catal.B 48 (2004) 267, Appl Catal, A 251 (2003) 143] of catalyst.Cerium oxide is as second component, add in cobalt oxide catalyst, can improve the ability of the water-fast vapour of catalyst, likely improve the ability of the storage/release oxygen of catalyst, the carrying out of accelerating oxidation reaction, meanwhile, having of cerium oxide may make cobalt oxide can disperse better [Appl.Catal.A 251 (2003) 143].M. Kang, waits [Appl. Catal. A 251 (2003) 143-156] to study period 4 transition metal oxide and supports in CeO 2the research of upper CO reaction, finds CoO x/ CeO 2cO is presented to optimum activity, and steam may be that the competitive Adsorption mechanism on adsorption activity position causes due to vapour molecule and reaction gas molecule to the inhibitory action of oxidation reaction.Co 3o 4comprise two kinds of cations, i.e. tetrahedral Co 2+and octahedral Co 3+ion, the atomic ratio of the two is 1:2, the Co of formation 2+/ Co 3+in to the oxidizing process of CO, can there is the catalytic action of redox cycle.By further research, find, the sintering temperature in catalyst preparation process affects consumingly it and resists moisture capacity, and the sintering temperature of thinking fit can obtain better crystalline form.F. Grillo etc. [Appl. Catal. B 48 (2004) 267] finds by XPS research, and with the increase of cobalt content, acromion is than reducing, and in meaning cerium oxide, partial oxygen enters in cobalt/cobalt oxide, forms the cobalt of high valence state, and this may be and CeO 2oxygen memory action relevant.Result shows, cerium, for cobalt provides oxygen, makes cobalt keep the state of high valence state, and has higher activity.Preparation method affects large [Appl. Catal. B 97 (2010) 28 – 35, Appl. Catal. B 119 – 120 (2012) 62 – 73] to the catalytic activity of catalyst.Shao Jianjun etc. [catalysis journal, 28 (2007) 163-169] have synthesized carbon monoxide are presented cobalt, the ce composite oxidation catalyst of excellent low-temperature oxidation activity and reported.Because cobalt cerium comparison catalyst is at large [Applied Catalysis B 66 (2006) 217 – 227 of catalytic activity impact, Appl. Catal. B 128 (2012) 21 – 30], the cobalt and cerium compound oxide catalyst of studying best proportioning is still a challenging problem to the low-temperature oxidation of carbon monoxide.
Summary of the invention
The object of the present invention is to provide a kind of Co 3o 4/ CeO 2under the preparation method of composite oxides and this composite oxide catalytic low-temp reaction condition, realize the Quick Oxidation to carbon monoxide.
A kind of Co 3o 4/ CeO 2composite oxides, is characterized in that: in composite oxides, the atomic ratio of Co and Ce is 19/1, can further improve the oxidation activity of composite oxide catalysts.
Co of the present invention 3o 4/ CeO 2its preparation method of composite oxides, is characterized in that: cobalt nitrate and the cerous nitrate mixed solution of metering ratio are slowly splashed into 0.2 mol/L Na in proportion 2cO 3in the aqueous solution, with 0.2 mol/L NaOH, regulate pH value to 10.0, and at this temperature after aging 4 h, diafiltration.Then, the sediment obtaining is again mixed by deionized water and stirred, and slowly splash into appropriate H 2o 2(30%).After aging 1 h, again use deionized water diafiltration, 383 K are dried 12 h, at 538 K roasting temperature 4 h.The method is characterized in that can make ceria and cobaltosic oxide mixing more evenly and obtain the Co of high valence state 3+.
Co of the present invention 3o 4/ CeO 2composite oxide catalysts can be used for equally changing carbon low-temperature oxidation, it is characterized in that: in the miniature fixed bed quartz tube reactor of normal pressure, carry out, HP-6890 type gas chromatograph on-line analysis for reactor outlet gas, and nickel converter is installed before fid detector, in hydrogen atmosphere respectively by CO and CO 2be converted into quantitatively CH 4.
Accompanying drawing explanation
Fig. 1 be catalyst under differential responses condition to the variation diagram of the stability time of CO oxidation reaction (GHSV=15000 ml/gh).
The specific embodiment
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation.
Embodiment 1
The Co that the atomic ratio of cobalt and cerium is 19 to 1 3o 4/ CeO 2the preparation of composite oxides.The Co that the atomic ratio that adopts precipitation oxidizing process to prepare cobalt and cerium is 19 to 1 3o 4/ CeO 2composite oxide catalysts.Under 333K and stirring condition, by the Co (NO of 1 mol/L 3) 26H 2ce (the NO of O and 1 mol/L 3) 36H 2the O aqueous solution slowly splashes in the aqueous sodium carbonate of 0.2 mol/L in proportion, regulates pH value to 10.0, and after aging 4 h, use deionized water diafiltration with 0.2 mol/L NaOH at this temperature.Then, the sediment obtaining is again mixed by deionized water and stirred, and slowly splash into appropriate H 2o 2(30%).After aging 1 h, again use deionized water diafiltration, 383 K are dried 12 h, at 538 K roasting temperature 4 h.
Embodiment 2
The Co that the atomic ratio of cobalt and cerium is 19 to 1 3o 4/ CeO 2the test of composite oxide catalysts catalyzing carbon monoxide oxidation reaction performance.The active testing of catalyst is to carry out in the miniature fixed bed quartz tube reactor of normal pressure.By composite oxide power compression molding, and fragmentation is screened to 40-60 order, and 200 mg are contained in the crystal reaction tube of Ф=6 mm.Reaction gas CO/O 2/ He=1 %/21 %/He, gas overall flow rate is 50 ml/min.Low-temp reaction is that U-shaped reactor is immersed in liquid nitrogen container, by regulating the distance of catalyst and liquid nitrogen liquid level to control reaction temperature.Moisture condition is that reaction gas is realized to (moisture content is 3.1 vol%) by 298 K constant water bath box bubblings.Before reaction, catalyst is air pretreatment 1 h under 538 K first.HP-6890 type gas chromatograph on-line analysis for reactor outlet gas, and nickel converter is installed before fid detector, in hydrogen atmosphere respectively by CO and CO 2be converted into quantitatively CH 4.Fig. 1 is the stability test result of catalyst to CO low temperature oxidation reaction.At dried feed gas and 196 K temperature, catalyst surpasses 480 min to the reaction time of the conversion of 99 % of CO.In reaction gas, containing 3.1 % volume ratio steam, temperature, be to react after 2580 min under the condition of 383 K, catalyst maintains 81% to the conversion ratio of carbon monoxide.

Claims (3)

1. a Co 3o 4/ CeO 2composite oxides, have catalytic oxidation function, it is characterized in that: in composite oxides, the atomic ratio of Co and Ce is 19/1, shows good performance aspect catalytic oxidation of carbon monoxide under low temperature.
2. a Co claimed in claim 1 3o 4/ CeO 2the preparation method of composite oxides, is characterized in that: cobalt nitrate and the cerous nitrate mixed solution of metering ratio are slowly splashed into 0.2 mol/L Na in proportion 2cO 3in the aqueous solution, with 0.2 mol/L NaOH, regulate pH value to 10.0, and at this temperature after aging 4 h, diafiltration; Then, the sediment obtaining is again mixed by deionized water and stirred, and slowly splash into appropriate H 2o 2(30%), after aging 1 h, again use deionized water diafiltration, 383 K are dried 12 h, at 538 K roasting temperature 4 h; The method is characterized in that can make ceria and cobaltosic oxide mixing more evenly and obtain the Co of high valence state 3+.
3. a Co claimed in claim 1 3o 4/ CeO 2composite oxide catalysts can be used for CO low temperature oxidation, it is characterized in that: in the miniature fixed bed quartz tube reactor of normal pressure, carry out; Low-temp reaction is that U-shaped reactor is immersed in liquid nitrogen container, by regulating the distance of catalyst and liquid nitrogen liquid level to control reaction temperature; Moisture condition is that reaction gas is realized to (moisture content is 3.1 vol%) by 298 K constant water bath box bubblings; HP-6890 type gas chromatograph on-line analysis for reactor outlet gas, and nickel converter is installed before fid detector, in hydrogen atmosphere respectively by CO and CO 2be converted into quantitatively CH 4.
CN201310600448.2A 2013-11-25 2013-11-25 Preparation of Co3O4 / CeO2 composite oxide and catalytic application Pending CN103752317A (en)

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN104338533A (en) * 2014-09-09 2015-02-11 上海纳米技术及应用国家工程研究中心有限公司 Cobaltosic oxide catalyst subjected to hydrogen peroxide surface treatment and preparation and application of cobaltosic oxide catalyst
CN105148934A (en) * 2014-06-06 2015-12-16 邵建军 Preparation and catalytic application of PtMnO2/Co3O4/CeO2
CN105327706A (en) * 2015-09-23 2016-02-17 上海交通大学 Catalyst for low temperature catalytic removal of environment pollutants, and preparation method thereof
CN105854887A (en) * 2016-03-25 2016-08-17 武汉工程大学 Cobalt-cerium double-metal oxide nanosphere and preparation method thereof
CN106378142A (en) * 2016-08-30 2017-02-08 上海化工研究院 Catalyst for removing alkene material flow impurity through deep purification at room temperature, preparation method and application thereof
CN106807392A (en) * 2017-03-07 2017-06-09 北京工业大学 A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst
CN107362804A (en) * 2017-07-14 2017-11-21 重庆交通大学 Flower-shaped Co3O4‑CeO2The preparation method of composite oxide catalysts
CN109546001A (en) * 2018-11-22 2019-03-29 京东方科技集团股份有限公司 A kind of display panel and preparation method thereof, display device
CN109647403A (en) * 2018-12-13 2019-04-19 西北大学 A kind of controllable method for preparing of cobaltosic oxide catalyst and its application in CO methanation

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SHAO JIANJUN ET AL.: "A CoOx/CeO2 Catalyst for Low-Temperature CO Oxidation", 《催化学报》, vol. 27, no. 11, 30 November 2006 (2006-11-30), pages 937 - 939 *
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105148934A (en) * 2014-06-06 2015-12-16 邵建军 Preparation and catalytic application of PtMnO2/Co3O4/CeO2
CN104338533B (en) * 2014-09-09 2016-04-27 上海纳米技术及应用国家工程研究中心有限公司 Hydrogen peroxide surface-treated cobaltosic oxide catalyst and Synthesis and applications thereof
CN104338533A (en) * 2014-09-09 2015-02-11 上海纳米技术及应用国家工程研究中心有限公司 Cobaltosic oxide catalyst subjected to hydrogen peroxide surface treatment and preparation and application of cobaltosic oxide catalyst
CN105327706B (en) * 2015-09-23 2018-07-03 上海交通大学 A kind of catalyst of low-temperature catalyzed removal environmental contaminants and preparation method thereof
CN105327706A (en) * 2015-09-23 2016-02-17 上海交通大学 Catalyst for low temperature catalytic removal of environment pollutants, and preparation method thereof
CN105854887A (en) * 2016-03-25 2016-08-17 武汉工程大学 Cobalt-cerium double-metal oxide nanosphere and preparation method thereof
CN105854887B (en) * 2016-03-25 2018-06-08 武汉工程大学 A kind of cobalt cerium bimetallic oxide nanosphere and preparation method thereof
CN106378142A (en) * 2016-08-30 2017-02-08 上海化工研究院 Catalyst for removing alkene material flow impurity through deep purification at room temperature, preparation method and application thereof
CN106378142B (en) * 2016-08-30 2019-09-27 上海化工研究院有限公司 The catalyst of room temperature deep purifying removing olefin stream impurity and its preparation and application
CN106807392A (en) * 2017-03-07 2017-06-09 北京工业大学 A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst
CN107362804A (en) * 2017-07-14 2017-11-21 重庆交通大学 Flower-shaped Co3O4‑CeO2The preparation method of composite oxide catalysts
CN107362804B (en) * 2017-07-14 2020-04-28 重庆交通大学 Flower-like Co3O4-CeO2Process for producing composite oxide catalyst
CN109546001A (en) * 2018-11-22 2019-03-29 京东方科技集团股份有限公司 A kind of display panel and preparation method thereof, display device
CN109647403A (en) * 2018-12-13 2019-04-19 西北大学 A kind of controllable method for preparing of cobaltosic oxide catalyst and its application in CO methanation
CN109647403B (en) * 2018-12-13 2021-12-03 西北大学 Controllable preparation method of cobaltosic oxide catalyst and application of cobaltosic oxide catalyst in CO methanation

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Application publication date: 20140430