CN105148934A - Preparation and catalytic application of PtMnO2/Co3O4/CeO2 - Google Patents

Preparation and catalytic application of PtMnO2/Co3O4/CeO2 Download PDF

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CN105148934A
CN105148934A CN201410246804.XA CN201410246804A CN105148934A CN 105148934 A CN105148934 A CN 105148934A CN 201410246804 A CN201410246804 A CN 201410246804A CN 105148934 A CN105148934 A CN 105148934A
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catalyst
ptmno
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邵建军
焦安龙
鞠晓春
李家波
侯代文
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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

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Abstract

Disclosed are preparation of a catalyst of PtMnO2/Co3O4/CeO2 and a catalytic application of the catalyst to low-temperature oxidation of carbon monoxide and formaldehyde. The atomic ratio of Co to Mn to Ce in a composite oxide of MnO2/Co3O4/CeO2 is 38/1/1. The catalyst of PtMnO2/Co3O4/CeO2 related in the invention has preferable catalytic activity and has a conversion rate of CO oxidation of 99% at a relatively low temperature of 196K, wherein the conversion rate can continuously maintain for more than 480 min. Complete oxidation of formaldehyde can be realized at a room temperature.

Description

PtMnO 2/ Co 3o 4/ CeO 2preparation and catalytic applications
Technical field
The present invention relates to a kind of PtMnO 2/ Co 3o 4/ CeO 2the technology of preparing of composite oxides and the catalytic applications of this oxide in carbon monoxide and formaldehyde 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 environment such as spaceship, submarine.Research finds, section transitions metal oxide also can realize the low-temperature oxidation to carbon monoxide.Cunningham etc. [Catal.Lett.25 (1994) 257] report Co 3o 4in dry conditions can in the completely conversion of low temperature realization to carbon monoxide of 197K.Thorm hlen etc. [J.Catal.188 (1999) 300] report is by Co 3o 4support in Al 2o 3on the conversion ratio of carbon monoxide can be made to reach 50% in the temperature of 210K.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.B48 (2004) 267, ApplCatal, A251 (2003) 143] of catalyst.Cerium oxide is as second component, add in cobalt oxide catalyst, the ability of the resistance to steam of catalyst can be improved, likely improve the ability of the storage/release oxygen of catalyst, the carrying out of accelerating oxidation reaction, meanwhile, having of cerium oxide may enable cobalt oxide disperse better [Appl.Catal.A251 (2003) 143].M.Kang, waits [Appl.Catal.A251 (2003) 143-156] to have studied period 4 transition metal oxide and supports in CeO 2the research of upper CO reaction, finds CoO x/ CeO 2present optimum activity to CO, steam may be because vapour molecule and the reaction gas molecule competitive Adsorption mechanism on adsorption activity position causes 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 the Co of 1:2, formation 2+/ Co 3+the catalytic action of redox cycle can be there is in the oxidizing process of CO.By studying discovery further, the sintering temperature in catalyst preparation process affects it consumingly and resists moisture capacity, and the sintering temperature of thinking fit can obtain better crystalline form.F.Grillo etc. [Appl.Catal.B48 (2004) 267] are found by XPS research, and with the increase of cobalt content, acromion is than reducing, and in meaning cerium oxide, part oxygen enters in cobalt/cobalt oxide, and form the cobalt of high-valence state, this may be and CeO 2oxygen memory action relevant.Result shows, cerium is that cobalt provides oxygen, makes cobalt remain the state of high-valence state, and has higher activity.Preparation method is on the catalytic activity impact comparatively large [Appl.Catal.B97 (2010) 28 – 35, Appl.Catal.B119 – 120 (2012) 62 – 73] of catalyst.Shao Jianjun etc. [catalysis journal, 28 (2007) 163-169] have synthesized and have presented the cobalt of superior low temperature oxidation activity, ce composite oxidation catalyst reporting to carbon monoxide.Because cobalt cerium comparison catalyst is at comparatively large [AppliedCatalysisB66 (2006) 217 – 227 of catalytic activity impact, Appl.Catal.B128 (2012) 21 – 30], the low-temperature oxidation of cobalt and cerium compound oxide catalyst to carbon monoxide of research optimum proportioning is still a challenging problem.Formaldehyde is the gas that toxicity is higher, and research shows that short term contact formaldehyde can stimulate eyes, nasal cavity and respiratory tract to cause allergic reaction, and Long Term Contact then can increase the possibility suffering from cancer.At present absorption method is mainly to the administering method of formaldehyde in indoor air.There is the saturated shortcoming of absorption in this method.The formaldehyde that catalytic oxidation is removed in room air is a kind of long-acting method, and it can utilize the oxygen in air that formaldehyde is completely oxidized to carbon dioxide and water, and catalyst can Long-Time Service.After deliberation, in the catalytic performance of a series of catalyst of transition metal oxide PARA FORMALDEHYDE PRILLS(91,95) complete oxidation, MnO 2be good catalyst, at room temperature just can release carbon dioxide with formolite reaction, but conversion ratio be not high.
Summary of the invention
The object of the present invention is to provide a kind of PtMnO 2/ Co 3o 4/ CeO 2the complete oxidation to PARA FORMALDEHYDE PRILLS(91,95) under the Quick Oxidation of carbon monoxide and room temperature condition is realized under the preparation method of the composite oxides of carried metal and this catalyst low-temp reaction condition.
A kind of PtMnO 2/ Co 3o 4/ CeO 2the composite oxides of carried metal, is characterized in that: in composite oxides, the atomic ratio of Co and Mn, Ce is the content of 19/1/1, Pt is the 2wt.% of carrier, can further improve the oxidation activity of composite oxide catalysts.
PtMnO of the present invention 2/ Co 3o 4/ CeO 2its preparation method of composite oxides, is characterized in that: the cobalt nitrate of metering ratio, manganese nitrate and cerous nitrate mixed solution are slowly instilled 0.2mol/LNa in proportion 2cO 3in the aqueous solution, by 0.2mol/LNaOH adjust ph to 10.0, and at this temperature after aging 4h, diafiltration.Then, the sediment obtained mixed by deionized water again and stirs, and slowly instilling appropriate H 2o 2(30%).Again use deionized water diafiltration after aging 1h, the dry 12h of 383K, at 538K roasting temperature 4h.The method is characterized in that can make ceria, manganese dioxide and cobaltosic oxide mixing more evenly and obtain the Co of high-valence state 3+.
The MnO obtained by said method 2/ Co 3o 4/ CeO 2powder suspension, in the aqueous solution, adds dinitroso diammonia platinum under stirring, is then evaporated to dry at 323K, and the dry 12h of 383K, 533 roasting 4h, obtain PtMnO 2/ Co 3o 4/ CeO 2catalyst.
PtMnO of the present invention 2/ Co 3o 4/ CeO 2composite oxide catalysts can be used for equally changing carbon and formaldehyde low-temperature oxidation, it is characterized in that: carry out in the miniature fixed bed quartz tube reactor of normal pressure, reactor outlet gas HP-6890 type gas chromatograph on-line analysis, and nickel converter is installed before fid detector, respectively by CO and CO in hydrogen atmosphere 2be converted into CH quantitatively 4.
Accompanying drawing explanation
Fig. 1 is catalyst variation diagram (GHSV=15000ml/gh) to the stability time of CO oxidation reaction under differential responses condition.Fig. 2 is the formaldehyde complete oxidation stability test (GHSV=12000ml/gh) under catalyst room temperature condition.
Detailed description of the invention
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation.
Embodiment 1
Cobalt is the MnO of 19 to 1 to 1 with the atomic ratio of manganese, cerium 2/ Co 3o 4/ CeO 2the preparation of composite oxides.Adopting settlement-oxidation method to prepare cobalt with the atomic ratio of manganese, cerium is the MnO of 38 to 1 to 1 2/ Co 3o 4/ CeO 2composite oxide catalysts.Under 333K and stirring condition, by the Co (NO of 1mol/L 3) 26H 2mn (the NO of O, 1mol/L 3) 26H 2ce (the NO of O and 1mol/L 3) 36H 2the O aqueous solution slowly instills in the aqueous sodium carbonate of 0.2mol/L in proportion, by 0.2mol/LNaOH adjust ph to 10.0, and at this temperature after aging 4h, uses deionized water diafiltration.Then, the sediment obtained mixed by deionized water again and stirs, and slowly instilling appropriate H 2o 2(30%).Again use deionized water diafiltration after aging 1h, the dry 12h of 383K, at 538K roasting temperature 4h.
Embodiment 2
PtMnO 2/ Co 3o 4/ CeO 2the preparation of catalyst.The MnO obtained by said method 2/ Co 3o 4/ CeO 2powder suspension, in the aqueous solution, adds dinitroso diammonia platinum under stirring, is then evaporated to dry at 323K, and the dry 12h of 383K, 533 roasting 4h, obtain PtMnO 2/ Co 3o 4/ CeO 2catalyst.
Embodiment 3
The test of catalyst catalyzing carbon monoxide oxidation reaction performance.The active testing of catalyst carries 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 200mg is contained in the crystal reaction tube of Ф=6mm.Low-temp reaction immerses in liquid nitrogen container by U-shaped reactor, controls reaction temperature by regulating the distance of catalyst and liquid nitrogen liquid level.Moist conditions is that reaction gas is realized (moisture content is 3.1vol%) by 298K constant water bath box bubbling.Before reaction, catalyst is air pretreatment 1h under 538K first.Reactor outlet gas HP-6890 type gas chromatograph on-line analysis, and nickel converter is installed before fid detector, respectively by CO and CO in hydrogen atmosphere 2be converted into CH quantitatively 4.

Claims (3)

1. a PtMnO 2/ Co 3o 4/ CeO 2catalyst, has good catalytic activity.It is characterized in that: MnO 2/ Co 3o 4/ CeO 2in composite oxides, the atomic ratio of Co and Mn, Ce is 19/1/1.
2. a PtMnO according to claim 1 2/ Co 3o 4/ CeO 2the preparation method of composite oxides, is characterized in that: the cobalt nitrate of metering ratio, manganese nitrate and cerous nitrate mixed solution are slowly instilled 0.2mol/LNa in proportion 2cO 3in the aqueous solution, by 0.2mol/LNaOH adjust ph to 10.0, and at this temperature after aging 4h, diafiltration; Then, the sediment obtained mixed by deionized water again and stirs, and slowly instilling appropriate H 2o 2(30%), again use deionized water diafiltration after aging 1h, the dry 12h of 383K, at 538K roasting temperature 4h; The method is characterized in that can make ceria and manganese dioxide, cobaltosic oxide mixing more even.The MnO obtained by said method 2/ Co 3o 4/ CeO 2powder suspension, in the aqueous solution, adds dinitroso diammonia platinum under stirring, is then evaporated to dry at 323K, and the dry 12h of 383K, 533 roasting 4h, obtain PtMnO 2/ Co 3o 4/ CeO 2catalyst.
3. a PtMnO according to claim 1 2/ Co 3o 4/ CeO 2composite oxide catalysts can be used for carbon monoxide and formaldehyde low-temperature oxidation, it is characterized in that: carry out in the miniature fixed bed quartz tube reactor of normal pressure; Low-temp reaction immerses in liquid nitrogen container by U-shaped reactor, controls reaction temperature by regulating the distance of catalyst and liquid nitrogen liquid level; Moist conditions is that reaction gas is realized (moisture content is 3.1vol%) by 298K constant water bath box bubbling; Reactor outlet gas HP-6890 type gas chromatograph on-line analysis, and nickel converter is installed before fid detector, respectively by CO and CO in hydrogen atmosphere 2be converted into CH quantitatively 4.
CN201410246804.XA 2014-06-06 2014-06-06 Preparation and catalytic application of PtMnO2/Co3O4/CeO2 Pending CN105148934A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109603889A (en) * 2018-12-17 2019-04-12 上海应用技术大学 A kind of catalyst and preparation method thereof for formaldehyde low-temperature catalytic oxidation
CN110658186A (en) * 2019-10-22 2020-01-07 北京联合大学 Sensitive material for simultaneously measuring formaldehyde, benzene and carbon monoxide
CN112108147A (en) * 2020-09-13 2020-12-22 北京工业大学 Platinum-manganese-based bimetallic catalyst for catalyzing ethylene oxide at low temperature

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CN103752326A (en) * 2013-11-25 2014-04-30 邵建军 Preparation and catalysis application of Au/Co3O4 / CeO2 catalyst
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US4587231A (en) * 1983-11-21 1986-05-06 Nissan Motor Co., Ltd. Method of producing monolithic catalyst for purification of exhaust gas
CN103752326A (en) * 2013-11-25 2014-04-30 邵建军 Preparation and catalysis application of Au/Co3O4 / CeO2 catalyst
CN103752317A (en) * 2013-11-25 2014-04-30 邵建军 Preparation of Co3O4 / CeO2 composite oxide and catalytic application

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109603889A (en) * 2018-12-17 2019-04-12 上海应用技术大学 A kind of catalyst and preparation method thereof for formaldehyde low-temperature catalytic oxidation
CN109603889B (en) * 2018-12-17 2021-07-20 上海应用技术大学 Catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method thereof
CN110658186A (en) * 2019-10-22 2020-01-07 北京联合大学 Sensitive material for simultaneously measuring formaldehyde, benzene and carbon monoxide
CN110658186B (en) * 2019-10-22 2021-08-13 北京联合大学 Sensitive material for simultaneously measuring formaldehyde, benzene and carbon monoxide
CN112108147A (en) * 2020-09-13 2020-12-22 北京工业大学 Platinum-manganese-based bimetallic catalyst for catalyzing ethylene oxide at low temperature

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Application publication date: 20151216