CN105344359A - Preparation method and use of CuO/Ce-Mn-O catalyst - Google Patents
Preparation method and use of CuO/Ce-Mn-O catalyst Download PDFInfo
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- CN105344359A CN105344359A CN201510735617.2A CN201510735617A CN105344359A CN 105344359 A CN105344359 A CN 105344359A CN 201510735617 A CN201510735617 A CN 201510735617A CN 105344359 A CN105344359 A CN 105344359A
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Abstract
The invention discloses a preparation method of a CuO/Ce-Mn-O catalyst. The preparation method comprises 1, mixing a Ce(NO3)3 solution and a Mn(NO3)2 solution according to a certain mole ratio, adjusting pH, carrying out stirring, carrying out standing, carrying out separation, washing precipitates until pH is 7, drying the precipitates and carrying out calcination to obtain a carrier, and 2, weighing 1g of the carriers, adding a Cu(NO3)2 solution into the carriers, carrying out stirring, carrying out oil bath treatment until water is evaporated, and carrying out drying, grinding and calcination to obtain the CuO/Ce-Mn-O catalyst. The CuO/Ce-Mn-O catalyst can be used for a CO catalytic oxidation reaction. Mn-doped CeO2 as a carrier carries a CuO composite oxide to form the CuO/Ce-Mn-O catalyst. The CuO/Ce-Mn-O catalyst has very high catalytic activity, has a CO conversion rate of 100% in a catalytic oxidation reaction, has a low reaction temperature and has high feasibility. The preparation method has simple processes, can be operated easily and has a low cost.
Description
Technical field
The invention belongs to environmental protection technical field, relate to the preparation method of CuO/Ce-Mn-O catalyst and the application of this catalyst.
Background technology
Containing a large amount of CO gas in vehicle exhaust, CO is a kind of to blood and the very strong pollutant of nervous system toxicity, can cause great injury to the healthy of the mankind and living environment.CO oxidation is one of key reaction of process vehicle exhaust, prepares the important topic that good CO oxidation catalyst becomes current environmental protection research.
CeO
2that in rare earth oxide, activity is the highest, the catalyst of most study.It has unique crystal structure, and the higher ability storing oxygen, therefore has stronger redox property.CeO
2as the metal oxide of the effective spread loads of carrier, increase catalyst thermal stability.But CeO
2time separately as catalyst carrier, catalytic activity is not high.At present, in order to improve catalytic activity, adopt different technology to CeO
2carry out modification or load, improve catalytic activity.
Now, most research is all carry out modification CeO by some rare earth elements that adulterate, transition metal
2, or some noble metals of load or transition metal oxide, by increasing its lattice defect, increasing Lacking oxygen, increasing specific surface, change crystallite size, thus improve catalytic activity.Transition metal oxide has good low temperature active as active component, and wherein the oxide of manganese is particularly outstanding, and this is mainly due to MnO
xkind and corresponding element valence more, the MnO of different crystal forms and valence state
xmutually can transform in the reaction, be conducive to the carrying out of redox reaction.Xing etc. [Ceram.Int.41 (2015) 4675 – 4682] report adopts water heat transfer Ce-Mn-O
xcompound, CO oxidation catalytic activity is improved.But when CO conversion ratio reaches 100%, required catalytic temperature is 260-280 DEG C.The purer CeO of Ce-Mn composite oxides CO oxidation catalytic activity of Chen etc. [Adv.Funct.Mater.2012,22,3914 – 3920] report synthesis
2, MnO
2with the CeO of mechanical mixture
2-MnO
2mixture wants high a lot.But catalytic activity temperature is still higher.Because CuO also shows high activity in redox reaction, even can match in excellence or beauty with noble metal.CO catalytic oxidation activity can be improved by load or composite Cu O.[J.Rare.EarthVol.33, No.6, Jun.2015, P.604] report adopts the method synthesis Ce-Mn-O of nitrate and the rear calcining of urea mixing to ZHAO etc.
xcompound, then by infusion process Supported CuO, obtain CuO/Ce-Mn-O
xcompound.Catalytic activity is greatly improved, but when CO conversion ratio is 100%, even if utilize best proportioning, during CO catalytic oxidation, temperature is still 175 DEG C.In sum, along with more deep research, although can further be promoted catalytic activity in CO catalytic reaction process, it is when utilizing catalyst described above to carry out catalytic reaction, and reaction temperature is all higher.Reaction temperature is high makes catalytic reaction on the one hand compared with difficultly carrying out, operation easier is large, and on the other hand required consersion unit is required higher, add reaction cost, high temperature power consumption is simultaneously large.Therefore, need that a kind of catalytic activity is high, catalytic performance good badly, the catalyst that catalytic reaction process temperature more easily realizes carries out catalytic reaction to CO.
The information being disclosed in this background technology part is only intended to increase the understanding to general background of the present invention, and should not be regarded as admitting or imply in any form that this information structure has been prior art that persons skilled in the art are known.
Summary of the invention
The object of the present invention is to provide a kind of employing cerous nitrate solution (Ce (NO
3)
3solution), manganese nitrate solution (Mn (NO
3)
2solution) be raw material, ammoniacal liquor is precipitating reagent, prepares Ce-Mn-O carrier with coprecipitation, then by infusion process Supported CuO, obtains the method for CuO/Ce-Mn-O catalyst, and is oxidized in CO by gained catalyst application.Due to Mn
x+the polytropy of valence state, doped with Mn
x+in CeO
2supported CuO again after carrier, significantly improves CO catalytic oxidation activity.
For achieving the above object, technical scheme provided by the invention is as follows:
The preparation method of CuO/Ce-Mn-O catalyst, comprises following operating procedure:
(1) preparation of Ce-Mn-O carrier: by Ce (NO
3)
3solution and Mn (NO
3)
2solution is the ratio mixing of 10:0.5 ~ 10:10 in Ce:Mn mol ratio, obtain mixed liquor, stir, then mixed liquor pH value is adjusted to 10 ~ 12, Keep agitation, after leaving standstill 12 ~ 18h, centrifugation, taking precipitate, washing precipitate is to neutral, calcining after gained drying precipitate, grinding, obtains Ce-Mn-O carrier;
(2) preparation of CuO/Ce-Mn-O catalyst: take gained Ce-Mn-O carrier in 1g step (1), add Cu (NO
3)
2solution, stirs, carries out drying, grinding, then calcine, obtain CuO/Ce-Mn-O catalyst after oil bath to water evaporate to dryness.
Preferably, the Ce (NO described in step (1)
3)
3solution molar concentration is 0.08mol/L, Mn (NO
3)
2solution molar concentration is 0.8mol/L.
Preferably, in step (1) under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, be adjusted to pH=10 ~ 12, Keep agitation 3h, leave standstill 12 ~ 18h.
Preferably, in step (1), centrifugal gained sediment keeps temperature to be grind after 60 DEG C of dry 24h, and calcines 3h at putting into 500 DEG C, obtains Ce-Mn-O carrier.
Preferably, the Cu (NO described in step (2)
3)
2solution molar concentration is 0.1mol/L, and consumption is 15.1mL, and namely the load capacity of CuO is 12%.
Preferably, stir 1h in step (2), oil bath temperature is 110 DEG C.
Preferably, in step (2), baking temperature is 60 DEG C, grinds after dry 24h.
Preferably, in step (2), calcining heat is 450 DEG C, calcining 4h.
Preferably, above-mentioned gained CuO/Ce-Mn-O catalyst application of preparing is in CO catalytic oxidation.
One utilizes above-mentioned gained CuO/Ce-Mn-O catalyst application of preparing in CO catalytic oxidation, and CO catalytic oxidation temperature is 85 ~ 100 DEG C.
Compared with prior art, the present invention has following beneficial effect:
The present invention prepares the CuO/Ce-Mn-O catalyst of gained, is with Mn doped Ce O
2for carrier, then the composite oxides gained of Supported CuO; Catalyst of the present invention is very high in CO catalytic oxidation catalytic activity, CO conversion ratio can be made to reach 100%, and during catalytic oxidation, temperature is low, easily realizes during catalytic oxidation; Preparation method of the present invention is simple and direct, easy to operate simultaneously, cost is low.
Accompanying drawing explanation
fig. 1the XRD according to a series of CuO/Ce-Mn-O catalyst of the present invention
figurespectrum.
fig. 2it is the CO conversion ratio tested according to the CO oxidation activity of a series of CuO/Ce-Mn-O catalyst of the present invention
figure.
Detailed description of the invention
Be described in detail below in conjunction with detailed description of the invention, but be to be understood that protection scope of the present invention not by the restriction of detailed description of the invention.Ce (NO
3)
36H
2o, 50% Mn (NO
3)
2solution all commercially buys gained.
Ce (NO
3)
3solution, Mn (NO
3)
2solution preparation process:
With Ce (NO
3)
36H
2o and distilled water prepare the Ce (NO of 0.08mol/L
3)
3solution, for subsequent use; With the Mn (NO that mass fraction is 50%
3)
2solution preparation becomes the Mn (NO of 0.8mol/L
3)
2solution, for subsequent use.
Embodiment 1
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:0.5 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 18h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 2
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:1 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 12h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 3
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:2 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 15h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 4
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:4 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 12h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 5
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:6 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 13h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 6
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:8 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 12h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 7
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:10 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 11, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 12h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 8
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:6 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 10, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 12h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
Embodiment 9
(1) preparation of Ce-Mn-O carrier: be 0.08mol/LCe (NO by above-mentioned preparation gained molar concentration
3)
3solution and molar concentration are 0.8mol/LMn (NO
3)
2solution, the ratio being 10:4 in Ce:Mn mol ratio is put into beaker and is mixed, obtain mixed liquor, under agitation, be that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor by molar concentration, regulate mixed liquor pH value to 12, beaker is placed on normal temperature Keep agitation 3h on magnetic stirring apparatus, after leaving standstill 12h, centrifuge is separated, taking precipitate, with deionized water washing sediment to neutral, use centrifuge again, gained sediment grinds after putting into 60 DEG C of dry 24h of baking oven, grinding gained material is put into Muffle furnace and is kept temperature to be 500 DEG C of calcining 3h, obtain Ce-Mn-O carrier,
(2) preparation of CuO/Ce-Mn-O catalyst: take in 1g step (1) and prepare gained Ce-Mn-O carrier and put into beaker, add the Cu (NO that molar concentration is 0.1mol/L
3)
2solution 15.1mL, namely the load capacity of CuO is 12%, stir 1h, then beaker being put into temperature is the water evaporate to dryness that 110 DEG C of oil baths are heated to beaker material, gained material puts into 60 DEG C of oven drying 24h, take out grinding, then put into Muffle furnace control temperature be 450 DEG C calcining 4h, obtain CuO/Ce-Mn-O catalyst.
CO catalytic oxidation
Utilize the above-mentioned gained CuO/Ce-Mn-O catalyst oxidation CO for preparing to react, reaction temperature is 85 ~ 100 DEG C.
Above-described embodiment is prepared gained catalyst and is detected
1, CuO/Ce-Mn-O catalyst XRD characterizes:
On X-ray diffractometer, material phase analysis is carried out, CuK α radiation, 40Kv, 40mA, graphite monochromatic ware, sweep limits angle 20 ° ~ 80 °, result by preparing gained CuO/Ce-Mn-O catalyst in the various embodiments described above
as Fig. 1shown in.
Interpretation of result: XRD result shows Mn
x+mix CeO
2form Ce-Mn-O carrier, and form CuO crystalline phase.Meanwhile, along with the amount of mixing manganese is on the increase, diffraction maximum offsets more to the right, and diffraction maximum all broadens, and illustrates that manganese mixes CeO
2crystalline phase, the crystal defect of formation is more.
2, the test of CuO/Ce-Mn-O Catalyst for CO catalytic oxidation performance:
The active testing that above-described embodiment 1 ~ 7 prepares gained CuO/Ce-Mn-O catalyst carries out in the miniature fixed bed quartz tube reactor of normal pressure.Gained CuO/Ce-Mn-O catalyst fines compression molding prepared by above-described embodiment 1 ~ 7, and fragmentation is screened to 40-60 order, get 50mg sieve after gained CuO/Ce-Mn-O catalyst be contained in quartz ampoule.Reaction gas by volume percentage is CO:O
2: N
2=1.6vol.%:20.8vol.%:77.6vol.%, air speed is 30000mLg
-1h
-1.Catalyst before reaction in quartz ampoule first passes into N at 100 DEG C
2pretreatment 1h, then normal temperature is down to, pass into CO and air reaction again, according to heating rate be 5 DEG C/min start heating, when temperature is raised to 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, respectively the quartz tube reactor exit gas of above-mentioned each temperature stage is detected, each temperature stage detects three times, average, the GC-7890II type gas chromatograph on-line analysis of quartz tube reactor exit gas, acquired results
as Fig. 2shown in: 12Cu/20Ce1Mn is that embodiment 1 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve, 12Cu/10Ce1Mn is that embodiment 2 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve, 12Cu/10Ce2Mn is that embodiment 3 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve, 12Cu/10Ce4Mn is that embodiment 4 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve, 12Cu/10Ce6Mn is that embodiment 5 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve, 12Cu/10Ce8Mn is that embodiment 6 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve, 12Cu/10Ce10Mn is that embodiment 7 prepares gained Catalyst for CO catalytic oxidation detection acquired results curve.
Active testing result shows: CuO/Mn-Ce-O catalyst catalytic activity when catalytic reaction temperature is relatively low is high.When using the present invention to prepare gained catalyst oxidation CO reaction, temperature is 85 DEG C ~ 100 DEG C the bests, and in this temperature range, CO conversion ratio can reach 60% ~ 100%, and conversion ratio is high, and reaction temperature is low, less energy consumption.
The present invention prepares gained catalyst higher CO catalytic oxidation activity at low temperatures.The source metal of mixing different amount has larger impact to carrier loaded CuO and its CO oxidation activity.Due to Mn
x+the radius ratio Ce of ion
4+and Ce
3+little, within the specific limits, the Mn mixed
x+the Ce-Mn-O carrier of rear formation has more crystal defect, forms more Lacking oxygen simultaneously, improves catalysis CO oxidation activity.Have impact on the valence state of CuO load on carrier simultaneously, make it there is more Cu
+, be conducive to the absorption of CO, and produce more Lacking oxygen, further increase catalysis CO oxidation activity.
The aforementioned description to concrete exemplary of the present invention is to illustrate and the object of illustration.These descriptions not want the present invention to be defined as disclosed precise forms, and obviously, according to above-mentioned instruction, can much change and change.The object selected exemplary embodiment and describe is to explain certain principles of the present invention and practical application thereof, thus those skilled in the art can be realized and utilize various different exemplary of the present invention and various different selection and change.Scope of the present invention is intended to limited by claims and equivalents thereof.
Claims (10)
- The preparation method of 1.CuO/Ce-Mn-O catalyst, is characterized in that, comprises following operating procedure:(1) preparation of Ce-Mn-O carrier: by Ce (NO 3) 3solution and Mn (NO 3) 2solution is the ratio mixing of 10:0.5 ~ 10:10 in Ce:Mn mol ratio, obtain mixed liquor, stir, then mixed liquor pH value is adjusted to 10 ~ 12, Keep agitation, after leaving standstill 12 ~ 18h, centrifugation, taking precipitate, washing precipitate is to neutral, calcining after gained drying precipitate, grinding, obtains Ce-Mn-O carrier;(2) preparation of CuO/Ce-Mn-O catalyst: take gained Ce-Mn-O carrier in 1g step (1), add Cu (NO 3) 2solution, stirs, carries out drying, grinding, then calcine, obtain CuO/Ce-Mn-O catalyst after oil bath to water evaporate to dryness.
- 2. preparation method according to claim 1, is characterized in that: the Ce (NO described in step (1) 3) 3solution molar concentration is 0.08mol/L, Mn (NO 3) 2solution molar concentration is 0.8mol/L.
- 3. preparation method according to claim 1, is characterized in that: in step (1) under agitation, is that the ammoniacal liquor of 1mol/L dropwise adds in mixed liquor, is adjusted to pH=10 ~ 12, Keep agitation 3h by molar concentration, leaves standstill 12 ~ 18h.
- 4. preparation method according to claim 1, is characterized in that: in step (1), centrifugal gained sediment keeps temperature to be grind after 60 DEG C of dry 24h, and calcines 3h at putting into 500 DEG C, obtains Ce-Mn-O carrier.
- 5. preparation method according to claim 1, is characterized in that: the Cu (NO described in step (2) 3) 2solution molar concentration is 0.1mol/L, and consumption is 15.1mL, and namely the load capacity of CuO is 12%.
- 6. preparation method according to claim 1, is characterized in that: stir 1h in step (2), oil bath temperature is 110 DEG C.
- 7. preparation method according to claim 1, is characterized in that: in step (2), baking temperature is 60 DEG C, grinds after dry 24h.
- 8. preparation method according to claim 1, is characterized in that: in step (2), calcining heat is 450 DEG C, calcining 4h.
- 9. preparation method according to claim 1, is characterized in that: above-mentioned gained CuO/Ce-Mn-O catalyst application of preparing is in CO catalytic oxidation.
- 10. utilize claim 1 to prepare gained CuO/Ce-Mn-O catalyst application in a CO catalytic oxidation, it is characterized in that: CO catalytic oxidation temperature is 85 ~ 100 DEG C.
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| CN201510735617.2A CN105344359A (en) | 2015-11-03 | 2015-11-03 | Preparation method and use of CuO/Ce-Mn-O catalyst |
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| CN110092983A (en) * | 2018-01-29 | 2019-08-06 | 中国石油化工股份有限公司 | Synergistic halogen-free flame retardants and its application and EPDM/PP thermoplastic elastomer (TPE) and its preparation method and application |
| CN113663667A (en) * | 2021-07-16 | 2021-11-19 | 华南理工大学 | Manganese-based composite catalyst based on transition metal modification and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732644A (en) * | 2016-11-22 | 2017-05-31 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of supported by cobalt oxide cerium manganese composite oxides and preparation and application |
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| CN110092983A (en) * | 2018-01-29 | 2019-08-06 | 中国石油化工股份有限公司 | Synergistic halogen-free flame retardants and its application and EPDM/PP thermoplastic elastomer (TPE) and its preparation method and application |
| CN110092983B (en) * | 2018-01-29 | 2021-12-21 | 中国石油化工股份有限公司 | Synergistic halogen-free flame retardant and application thereof, EPDM/PP thermoplastic elastomer and preparation method and application thereof |
| CN113663667A (en) * | 2021-07-16 | 2021-11-19 | 华南理工大学 | Manganese-based composite catalyst based on transition metal modification and preparation method and application thereof |
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