CN109908885A - A kind of rhombohedron cerium oxide and its preparation method and application - Google Patents
A kind of rhombohedron cerium oxide and its preparation method and application Download PDFInfo
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- CN109908885A CN109908885A CN201910302103.6A CN201910302103A CN109908885A CN 109908885 A CN109908885 A CN 109908885A CN 201910302103 A CN201910302103 A CN 201910302103A CN 109908885 A CN109908885 A CN 109908885A
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Abstract
The invention belongs to the synthesis of special appearance metal oxide and atmosphere Treatment process fields, and in particular to a kind of rhombohedron cerium oxide and preparation method thereof and in gaseous elemental mercury (Hg0) application in removing.For the present invention using cerous nitrate as raw material, polyvinylpyrrolidone passes through ultrasonic wave added raw material homogeneous reaction in aqueous solution as surfactant.PH is adjusted using urea as alkali source, and through microwave, rhombohedron cerium oxide is obtained after calcining.The present invention prepares cerium oxide by microwave method, does not need transformation modification, reaction process rapid cleaning, process is simple, energy saving.Special rhombohedron structure provides angular edge abundant for material, makes it have more faults of construction and reactivity site, and low temperature active and oxygen storage capacity are sufficiently promoted, and catalytic performance is superior.Material significant effect in atmosphere demercuration under the conditions of pure nitrogen gas, is 100-300 DEG C in temperature, handles mercury fume (concentration~240 μ g m‑3) demercuration rate up to 98%.
Description
Technical field
The invention belongs to the synthesis of the metal oxide of special appearance and atmospheric treatment technical field, and in particular to a kind of diamond shape
Hexahedron cerium oxide and preparation method, and its Hg in flue gas0Application in removing.
Background technique
Gaseous elemental mercury (Hg0) because of its strong toxicity, not soluble in water and intractable characteristic becomes in current atmosphere pollution
Outstanding problem.In existing demercuration method, it is excellent that catalytic oxidation has that efficiency is higher, equipment is simple, loss is small etc.
Gesture becomes the research hotspot in demercuration field in recent years.Hg is taken off in catalysis oxidation0Research in, the design and synthesis of catalyst
Most important, current research is concentrated mainly on noble metal catalyst and catalyst of transition metal oxide, but precious metal catalyst
Agent cost is high, is not suitable for large-scale promotion, and transition metal oxide efficiency is lower and easy poisoning.With these two types of catalyst
It compares, cerium oxide is because of its good redox ability (Ce3+/Ce4+Conversion) and superior Oxygen storage capacity be considered as
The catalyst of the great application prospect in demercuration field.
But for cerium oxide there are still (1) catalytic activity is poor in carrying out demercuration application, active oxygen is dense at present
Degree is not high, generally requires to can be only achieved preferable demercuration effect by certain density oxygen or hydrogen chloride gas；(2) activity temperature
Spend it is higher, need to just can Hg with higher in 300-400 DEG C of range of reaction temperature0Oxidation efficiency.And practical flue gas condition
It is big often to there is oxygen content fluctuation, after flue-gas temperature especially dedusting the case where temperature lower (100-200 DEG C), will limit
Practical application of the cerium oxide in flue gas demercuration.Synthetic method rapid cleaning, excellent low temperature active and storage oxygen are developed as a result,
The cerium oxide catalyst material of ability has certain realistic meaning.
Research shows that the appearance structure of regulation cerium oxide is the effective ways for promoting its performance, construction has abundant rib
The material of corner edge can be such that its surface defect concentration increases, and have more active sites in catalytic reaction process, be conducive to mention
Rise the low temperature active and Oxygen storage capacity of pure zirconia cerium material.
Summary of the invention
To solve the above-mentioned problems of the prior art.The purpose of the present invention is to provide one kind to have rhombohedron special
The cerium oxide of different pattern, and its simple, quick, the good preparation method of repeatability, it is de- in flue gas to additionally provide the material
Application in mercury.Cerium oxide pattern prepared by the present invention is unique, has high oxygen storage capacity, catalytic performance is excellent, demercuration effect
Good, preparation method is simple, easy to use.
The purpose of the present invention is what is be accomplished by the following way.
A kind of rhombohedron cerium oxide, particle size range are 800nm-2.5 μm.
A kind of preparation method of rhombohedron cerium oxide includes the following steps: soluble cerium salt and surface is living
Property agent be added in deionized water, ultrasonic treatment is uniformly sufficiently mixed reaction to soluble cerium salt and surfactant-dispersed, then
Urea is added and adjusts solution ph, stirs lower hydrolysis, is stirred and is condensed back while microwave reaction later
To white precipitate, deposit washing is dry, calcines the rhombohedron cerium oxide for being 800nm-2.5 μm to get particle size range
Material.
The soluble cerium salt is Ce (NO3)3·6H2O, surfactant include for polyvinylpyrrolidone.
Concentration of the soluble cerium salt in hybrid reaction system is 0.03-0.06mol L-1, surfactant exists
Concentration in hybrid reaction system is 5-15g L-1。
The ultrasonic treatment temperature is 20-50 DEG C, power 300-1000W, time 15min or more, is needed ultrasonic to molten
Until the complete clear of liquid, soluble cerium salt and surfactant are mixed thoroughly.
Urea is added in the above method and adjusts pH value of solution to 3-5, hydrolysis 15-50min under magnetic agitation.
Microwave reaction temperature is 60-100 DEG C in the above method, and heating rate is 10 DEG C of min-1, power 300-600W, instead
0.5-1.5h between seasonable is needed to continue to carry out magnetic agitation in reaction process, while being condensed back using 400mm condenser pipe.
Successively respectively to be washed at least 3 times with deionized water and ethyl alcohol, calcining is existed using Muffle furnace for washing in the above method
Under the conditions of 400-600 DEG C, 4-6h is calcined, heating rate is controlled in 600-900 DEG C of h-1。
The rhombohedron cerium oxide of above-mentioned method preparation is for Hg in flue gas0Removing.
In demercuration application process, gaseous state Hg0Concentration be 240 μ g m-3, carrier gas N2, reaction temperature is 100 DEG C -300
DEG C, it is 150000-200000h that rhombohedron cerium oxide catalyst amount, which is superficial linear velocity in a column,-1。
The invention has the advantages that
(1) the present invention provides a kind of preparation methods of cerium oxide is greatly shortened using ultrasonic wave added microwave method
Preparation time, raw material cleaning is simple, and it is not necessary that modification is transformed, cost is relatively low, is conducive to practical application.Ultrasound and microwave of the invention
The actual conditions of method are very big for the pattern influence of product, especially flowed back and stirred while microwave etc., this
A little reaction conditions are indispensable, and the synergistic effect that they are generated ultimately forms special rhombohedron structure.The structure is material
Material provides angular edge abundant, easily formation defect sturcture, provides more reactivity sites for catalysis reaction.Material point simultaneously
It is good to dissipate property, it can be with gaseous state Hg0It comes into full contact with and reacts, promote the catalysis oxidation efficiency.
(3) cerium oxide provided by the invention, redox property is superior compared with commercial cerium oxide, oxygen storage capacity
Height can keep good activity within the scope of certain temperature window.All have under low temperature and hot conditions good de-
Mercury effect, concentration for the treatment of is up to 240 μ g m under the conditions of 100 DEG C and 300 DEG C-3Gaseous state Hg0When, demercuration efficiency can reach
98%.
Detailed description of the invention
Fig. 1 is the CeO of rhombohedron structure prepared by the method for the present invention2Material SEM figure；
Fig. 2 is CeO prepared by the method for the present invention2Material XRD diagram；
Fig. 3 is material prepared by the method for the present invention and commercial CeO2The hydrogen of material-temperature programmed reduction analyzes (H2-
TPR) phenogram；
Fig. 4 is CeO prepared by the method for the present invention2Demercuration effect picture under material condition of different temperatures.
(m=0.1g, 240 μ g m-3Hg0,N2, Q=600mL min-1)
Specific embodiment
Illustrate that the present invention is described further below with specific embodiment, but it is necessary to note that following embodiment is only used
In the further explanation to summary of the invention, limitation of the present invention not will form.
Embodiment 1
By 0.868g cerous nitrate, 0.5g polyvinylpyrrolidone is added in 60mL deionized water, under the conditions of 25 DEG C, power
500W ultrasound 20min is sufficiently mixed cerous nitrate and polyvinylpyrrolidone uniformly.3g urea is added in reaction solution will
PH is adjusted to 4.0, and magnetic agitation reacts 30min, adds mixture in 100mL high-boron-silicon glass three-necked flask.By high boron
Silica glass three-necked flask is put into microwave catalysis synthesis/abstraction instrument, is 300W in power, heating rate is 10 DEG C of min-1, reaction
1h is reacted under conditions of 100 DEG C of temperature, needs to continue to carry out magnetic agitation in reaction process, while carrying out using 400mm condenser pipe
It is condensed back.Then gained white precipitate is washed with deionized three times, ethyl alcohol is washed three times, the dry 10h in 60 DEG C of baking ovens.
With 500 DEG C of calcining 4h of Muffle furnace, 600 DEG C of h of heating rate-1To get arrive rhombohedron cerium oxide.
Embodiment 2
Use H2TPR table levies microwave method and synthesizes CeO2The redox property and oxygen storage capacity of material.That is difficult to understand using Beijing for instrument
The PCA-1200 full-automatic multi-purpose adsorption instrument of moral company first pre-processes the sample of 100mg under the conditions of 120 DEG C of argon gas
Atmosphere after being cooled to room temperature, is switched to 7%H by 30min2/ Ar, flow are maintained at 30mL min-1, journey is carried out under this atmosphere
To 900 DEG C, heating rate is 10 DEG C of min for sequence temperature reaction-1.The result of the embodiment is as shown in Figure 3.
Embodiment 3
Demercuration reaction carries out in fixed-bed quartz reactor.Material prepared by 100mg embodiment 1 is put into quartz ampoule
In, reaction temperature is controlled at 100 DEG C using temperature control zone formula furnace, carrier gas is N in reaction process2, gas flow 600mL
min-1, gaseous state Hg0About 240 μ g m of initial concentration-3, demercuration effect can reach 98% or more.
Embodiment 4
Demercuration reaction carries out in fixed-bed quartz reactor.Material prepared by 100mg embodiment 1 is put into quartz ampoule
In, reaction temperature is controlled at 300 DEG C using temperature control zone formula furnace, carrier gas is N in reaction process2, gas flow 600mL
min-1, gaseous state Hg0About 240 μ g m of initial concentration-3, demercuration effect can reach 99% or more.
Claims (10)
1. a kind of rhombohedron cerium oxide.
2. material according to claim 1, which is characterized in that particle size range is 800nm-1.5 μm.
3. a kind of preparation method of rhombohedron cerium oxide, which comprises the steps of: by soluble cerium salt
It is added in deionized water with surfactant, ultrasonic treatment to soluble cerium salt and surfactant-dispersed is uniformly sufficiently mixed instead
It answers, urea is then added and adjusts solution ph, stir lower hydrolysis, be stirred and condense while microwave reaction later
Reflux obtains white precipitate, and deposit washing is dry, calcines the rhombohedron for being 800nm-1.5 μm to get particle size range
Cerium oxide.
4. the preparation method of rhombohedron cerium oxide according to claim 3, which is characterized in that described is solvable
Property cerium salt be Ce (NO3)3·6H2O, surfactant include for polyvinylpyrrolidone.
5. the preparation method of rhombohedron cerium oxide according to claim 3, which is characterized in that described is solvable
Property concentration of the cerium salt in hybrid reaction system be 0.03-0.06mol L-1, surfactant is dense in hybrid reaction system
Degree is 5-15g L-1。
6. the preparation method of rhombohedron cerium oxide according to claim 3, which is characterized in that the ultrasound
Treatment temperature is 20-50 DEG C, power 300-1000W, time 15min or more, needs ultrasound to the complete clear of solution, solvable
Until property cerium salt and surfactant are mixed thoroughly.
7. the preparation method of rhombohedron cerium oxide according to claim 3, which is characterized in that urea tune is added
PH value of solution is saved to 3-5, hydrolysis 15-50min under magnetic agitation.
8. the preparation method of rhombohedron cerium oxide according to claim 3, which is characterized in that microwave reaction temperature
Degree is 60-100 DEG C, and heating rate is 10 DEG C of min-1, power 300-600W, reaction time 0.5-1.5h are needed in reaction process
Magnetic agitation is persistently carried out, while being condensed back using 400mm condenser pipe.
9. the preparation method of rhombohedron cerium oxide according to claim 3, which is characterized in that
Successively respectively to be washed at least 3 times with deionized water and ethyl alcohol, calcining uses Muffle furnace under the conditions of 400-600 DEG C for washing,
4-6h is calcined, heating rate is controlled in 600-900 DEG C of h-1。
10. the rhombohedron cerium oxide of the described in any item method preparations of claim 3-9 is for Hg in flue gas0Removing.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589870A (en) * | 2019-09-16 | 2019-12-20 | 桂林电子科技大学 | Method for preparing monodisperse spherical nano rare earth oxide by uniform precipitation process |
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| CN101264922A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Method for preparing cerium oxide rhombus nano sheet-shaped material |
| CN102951669A (en) * | 2012-11-20 | 2013-03-06 | 陕西科技大学 | Method for preparing CeO2 nano solid spheres by microwave-assisted urea hydrolysis |
| CN107497419A (en) * | 2017-09-21 | 2017-12-22 | 北京科技大学 | NO and Hg in coal-fired flue-gas is purified for low temperature simultaneously0Ce Zr MnO2Method for preparing catalyst |
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2019
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| CN101264922A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Method for preparing cerium oxide rhombus nano sheet-shaped material |
| CN102951669A (en) * | 2012-11-20 | 2013-03-06 | 陕西科技大学 | Method for preparing CeO2 nano solid spheres by microwave-assisted urea hydrolysis |
| CN107497419A (en) * | 2017-09-21 | 2017-12-22 | 北京科技大学 | NO and Hg in coal-fired flue-gas is purified for low temperature simultaneously0Ce Zr MnO2Method for preparing catalyst |
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| DONGLEI SHI ET AL.: "Removal of elemental mercury from simulated flue gas by cerium oxide modified attapulgite", 《KOREAN J. CHEM. ENG.》 * |
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| CN110589870A (en) * | 2019-09-16 | 2019-12-20 | 桂林电子科技大学 | Method for preparing monodisperse spherical nano rare earth oxide by uniform precipitation process |
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Application publication date: 20190621 |