CN101734707A - High-stability nano cerium oxide material for catalyzing and oxidizing ortho-xylene at low temperature and application thereof - Google Patents
High-stability nano cerium oxide material for catalyzing and oxidizing ortho-xylene at low temperature and application thereof Download PDFInfo
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- CN101734707A CN101734707A CN200910243061A CN200910243061A CN101734707A CN 101734707 A CN101734707 A CN 101734707A CN 200910243061 A CN200910243061 A CN 200910243061A CN 200910243061 A CN200910243061 A CN 200910243061A CN 101734707 A CN101734707 A CN 101734707A
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Abstract
The invention provides a cerium oxide nano cubical material which has excellent thermal stability and can catalyze and oxidize ortho-xylene into harmless CO2 and H2O with high efficiency under a condition of low temperature and a preparation method thereof. The preparation method of the material comprises the following steps of: taking soluble cerium salt as a precursor, adding excessive sodium hydroxide as a precipitator, then transferring the excessive sodium hydroxide into a reaction kettle, keeping the temperature constant within a range of 80-120 DEG C for 8-12h, washing the obtained precipitate with deionized water, drying over night and calcining at the temperature of 350-750 DEG C in a muffle furnace to obtain a nano cerium oxide cube. The method has the advantages of simple preparation method, low price and easy acquirement of raw materials, controllable appearance of the obtained material and the like; and the prepared nano material presents favorable uniformity, monodispersity and thermal stability and can be used as a catalyst and a carrier of the catalyst. Nano cerium oxide in the invention is used as the catalyst, can directly oxidize the ortho-xylene into the CO2 and the H2O within a temperature range of 140-260 DEG C, does not generate a by-product, represents favorable low-temperature catalytic activity and has higher practical value.
Description
Technical field
The present invention relates to a kind of thermal stability excellence, can the efficiently catalyzing and oxidizing o-Xylol be harmless CO under cold condition
2And H
2Cerium oxide nano cubes material of O and preparation method thereof.
Background technology
O-Xylol is a kind of volatile organic contaminant (VOCs) of wide material sources, is one of principal pollutant of indoor-outdoor air.Outdoor source mainly comes from the production of industrial chemicals such as paint, coating, lubricated wet goods, the burning of industrial waste, the discharging of motor-vehicle tail-gas etc.Indoor mainly is to produce by house decoration, house life.
O-Xylol can enter into human body by breathing, absorption and skin contact, and the histoorgan of human body is caused in various degree injury, and is especially bigger to women and children's influence.Discover that the short period of time is exposed to the mucous membrane that the skin that can make the people in the dimethylbenzene gas, eyes, nose, throat etc. locate and is upset, and also can cause expiratory dyspnea, damage lung, liver, kidney and heart.Simultaneously, be for a long time or the short period of time be exposed in the dimethylbenzene and all can work the mischief central nervous system.
At present, the means such as gas adsorption, biodegradation technique, plasma technique, membrane separation technique and catalyzed oxidation technology that adopt are carried out o-Xylol removal in the indoor environment more, industrial then many dischargings of subduing this pollutent with methods such as tail gas absorption, waste-gas burnings.The present invention utilizes the cerium oxide nano cubes of high stability to be catalyzer, is free of contamination CO with the o-Xylol catalyzed oxidation of lower concentration
2And H
2O realizes o-Xylol low temperature, the efficient purification.
Catalyzer such as precious metals pd, Pt, Au, Ag have that combustion initiation temperature is low, perfect combustion temperature and combustion initiation temperature differ very little, long service life, characteristics such as applied widely, so people start to walk early to the research of noble metal catalyst, that also studies simultaneously is more deep, but because of its price height, resource-constrained, so metal oxide catalyst more and more is subjected to various countries research worker's favor.The rare earth resources of China is very abundant, and industrial reserves is the first in the world, for China's rare-earth industry development provides advantageous condition.Among this, the compound of cerium accounts for about 50% of proven reserve.Nano material is because characteristic and potential high-tech application prospects such as its unique light, sound, electricity, magnetic, heat, catalysis mechanics have caused people's common concern.Cerium dioxide is a kind of cheapness and broad-spectrum material, and CeO
2The dimensional effect of nano material makes it have some special physics and chemical property, therefore, and CeO
2The preparation of nano material and research have been subjected to people's extensive concern.
Chinese patent CN1426963 has proposed at normal temperatures and pressures a kind of, the method for cerium ion solution and basic solution prepared in reaction nano cerium oxide powder under the condition of introducing tensio-active agent.
Chinese patent CN1840480 has proposed a kind ofly to exist under the situation at water, organic solvent or mixed solvent, the urea soln of 100-200 ℃ of hydrothermal treatment consists solubility cerium salt, through washing, dry, 450 ℃ of roastings, prepare the method for cerium oxide nano particle, nanometer rod, nanofiber, nanoprisms.
Chinese patent CN101407330 has proposed under a kind of 10-40 ℃ mild conditions, with aging 1 hour-9 days of the mixed solution of solubility cerium salt and concentrated base, through washing, drying, prepares the method for cerium oxide nano-rod.
Chinese patent CN1556039 proposed a kind of in 200-250 ℃ of temperature range the hydrogen peroxide solution of hydrothermal treatment consists cerous nitrate, through washing and the dry method for preparing cerium oxide nano cubes and nano wire.Chinese patent CN101224903 proposed a kind of in 180-240 ℃ of temperature range hydrothermal treatment consists solubility cerium salt and excessive sodium hydrate reaction product, through the preparation method who separates, washing, drying obtain cerium dioxide nano cubic block.
When being used as catalyzer or support of the catalyst as the nano-cerium oxide with above-mentioned several method preparation, aforesaid method also exists following shortcoming: (1) introduces tensio-active agent or organic solvent in reaction system; (2) made sample is many without roasting.The introducing of tensio-active agent or organic solvent has reduced degree of purity of production, thereby has influenced its catalytic activity.Sample has influenced purity, structure and the stability of prepared material without roasting.Fujihara etc. discover that the sample after the calcination process can be removed residual OH and water molecules makes sample purer, and nanometer rod is assembled (Yasuha Higashine easily after the calcination process, ShinobuFujihara, Journal of the Ceramic Society of Japan, 2007,115,916-919).Satisfactory stability is one of key factor whether the decision catalyzer can practical application, when being catalyzer or support of the catalyst with material without calcination process, when the hot environment that the experience catalyzed reaction may occur, its stability can not ensure, influences its practical application.
Still show single dispersion, the good cerium oxide method for preparing Nano cube of homogeneity, the carrier of useful as catalysts and catalyzer after the invention provides 350-750 ℃ of roasting of a kind of process; This material has possessed the excellent specific property of excellent catalyzing and oxidizing ortho-xylene at low temperature.
Summary of the invention
The present invention relates to the cubical preparation method of a kind of high stability cerium oxide nano.
It is harmless CO that the present invention also provides a kind of efficient cryogenic catalyzing and oxidizing ortho-xylene
2And H
2The cerium oxide nano cubes catalyzer of O.
Nano-cerium oxide provided by the invention is characterized in that:
Described cerium oxide is a nanocubes;
Described cerium oxide nano cubes presents favorable uniformity, monodispersity and thermostability through 350-750 ℃ of temperature roasting;
Described nanocubes specific surface area is 19-83m
2/ g;
The size of described nanocubes is 7-50nm.
The preparation method of cerium oxide nano materials provided by the invention, its key step is:
Getting solubility cerium salt and sodium hydroxide is dissolved in respectively in an amount of water, sodium hydroxide solution is added drop-wise in the solubility cerium solution, dropwise the back and continue to stir 10-30min, then it is transferred in the reactor, with being placed on constant temperature 8-12h in the thermostat container, the throw out that obtains is through deionized water wash, 60 ℃ of dried overnight, and roasting 4h obtains cerium oxide nano materials in retort furnace;
Described preparation method is characterized in that:
Solubility cerium salt is a kind of in cerous nitrate or Cerium II Chloride or the cerous acetate, and its concentration is 0.1～1mol/L;
Described preparation method, concentration of sodium hydroxide solution is at 0.1～15mol/L;
Described preparation method, its hydro-thermal synthesis temperature is 80～120 ℃;
Described preparation method, maturing temperature is 350～750 ℃.
The catalyzer of the present invention's preparation is in air atmosphere, and air speed is 10,000h
-1, o-Xylol carries out the catalyzed oxidation experiment on the fixed-bed reactor.The result shows that the cerium oxide nano materials of roasting under the differing temps just can be that the o-Xylol gas direct oxidation of 500ppm is CO with concentration in 140 ℃～260 ℃ temperature range
2And H
2O, and no coupling product generation show good low-temperature catalytic activity.
The characteristics of cerium oxide nano catalyzer of the present invention are:
(1) by control solubility cerium salt and concentration sodium hydroxide, realize the morphology control of cerium oxide nano particle under lower hydrothermal temperature 80-120 ℃ condition, starting material are cheap and easy to get, and preparation is simple, with low cost, the cerium oxide nano materials homogeneity that makes is good.
(2) prepared nano-cerium oxide cubes possesses excellent thermostability, 350-750 ℃ of temperature roasting, presents favorable uniformity and monodispersity.
(3) have the low temperature active of excellent catalyzing and oxidizing ortho-xylene, and no coupling product generates, have a good application prospect.
Description of drawings
Fig. 1 is the cerium oxide nano materials XRD figure spectrum of the embodiment of the invention 1 preparation;
Fig. 2 is cerium oxide nano materials transmission electron microscope (TEM) the pattern photo of the embodiment of the invention 1 preparation;
Fig. 3 is cerium oxide nano materials transmission electron microscope (TEM) the pattern photo of the embodiment of the invention 2 preparations;
Fig. 4 is cerium oxide nano materials transmission electron microscope (TEM) the pattern photo of the embodiment of the invention 3 preparations;
Fig. 5 is cerium oxide nano materials transmission electron microscope (TEM) the pattern photo of the embodiment of the invention 4 preparations;
Fig. 6 is cerium oxide nano materials transmission electron microscope (TEM) the pattern photo of the embodiment of the invention 5 preparations;
Embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to scope of the present invention.
The Preparation of Catalyst example
Embodiment 1: claim Ce (NO
3)
36H
2O 3g is dissolved in the 60ml deionized water, obtains solution 1.Weighing sodium hydroxide 0.84g is dissolved in the 21ml deionized water in addition, obtains solution 2.Solution 2 is added drop-wise in the solution 1, dropwises the back and continue to stir 20min, then it is transferred in the reactor, be put in 100 ℃ of thermostat containers and heat 10h, the throw out that obtains with washed with de-ionized water after 60 ℃ of dried overnight, 350 ℃ of roasting 4h of retort furnace.Fig. 1 is the X-ray powder diffraction figure of product.Fig. 2 is the transmission electron microscope results of product, shows that this roasting sample is a nanocubes.BET test shows specific surface area is 78m
2/ g.
Embodiment 2: difference from Example 1 is, 450 ℃ of maturing temperatures.It is nanocubes that transmission electron microscope (Fig. 3) records this roasting sample, and size is 7-20nm.BET test shows specific surface area is 83m
2/ g.
Embodiment 3: difference from Example 1 is, 550 ℃ of maturing temperatures.It is nanocubes that transmission electron microscope (Fig. 4) records this roasting sample, and size is 7-20nm.BET test shows specific surface area is 59m
2/ g.
Embodiment 4: difference from Example 1 is, 650 ℃ of maturing temperatures.It is nanocubes that transmission electron microscope (Fig. 5) records this roasting sample, and size is 10-25nm.BET test shows specific surface area is 43m
2/ g.
Embodiment 5: difference from Example 1 is, 750 ℃ of maturing temperatures.It is nanocubes that transmission electron microscope (Fig. 6) records this roasting sample, and size is 15-30nm.BET test shows specific surface area is 19m
2/ g.
The catalyzing and oxidizing ortho-xylene example
Embodiment 6: it is the quartz tube reactor of 6mm that the catalyzer of getting a certain amount of 40～60 order embodiment 1 places internal diameter, feeds O
220mlmin
-1, N
280mlmin
-1With the reactant gases of 500ppm o-Xylol, reaction velocity (GHSV) is 10,000h
-1Down, the temperature of reaction interval is from 160 ℃～210 ℃.O-Xylol concentration utilizes GC-MS to measure, and product utilization GC measures.
Reaction result shows, in the time of 160 ℃, behind catalyst system, is 5% to the transformation efficiency of o-Xylol.In the time of 210 ℃, the transformation efficiency of o-Xylol is reached 100%.
Table one CeO
2Nanocubes catalyst activity evaluation result
Embodiment 7: it is the quartz tube reactor of 6mm that the catalyzer of getting a certain amount of 40～60 order embodiment 2 places internal diameter, feeds O
220mlmin
-1, N
280mlmin
-1With the reactant gases of 500ppm o-Xylol, reaction velocity (GHSV) is 10,000h
-1Down, the temperature of reaction interval is from 160 ℃～220 ℃.O-Xylol concentration utilizes GC-MS to measure, and product utilization GC measures.
Reaction result shows, in the time of 160 ℃, behind catalyst system, is 8.6% to the transformation efficiency of o-Xylol.In the time of 210 ℃, the transformation efficiency of o-Xylol is reached 97%.
Table two CeO
2Nanocubes catalyst activity evaluation result
Embodiment 8: it is the quartz tube reactor of 6mm that the catalyzer of getting a certain amount of 40～60 order embodiment 3 places internal diameter, feeds O
220mlmin
-1, N
280mlmin
-1With the reactant gases of 500ppm o-Xylol, reaction velocity (GHSV) is 10,000h
-1Down, the temperature of reaction interval is from 160 ℃～210 ℃.O-Xylol concentration utilizes GC-MS to measure, and product utilization GC measures.
Reaction result shows, in the time of 160 ℃, behind catalyst system, the transformation efficiency of o-Xylol is about 10%.In the time of 210 ℃, the transformation efficiency of o-Xylol is reached 100%.
Table three CeO
2Nanocubes catalyst activity evaluation result
Embodiment 9: it is the quartz tube reactor of 6mm that the catalyzer of getting a certain amount of 40～60 order embodiment 4 places internal diameter, feeds O
220mlmin
-1, N
280mlmin
-1With the reactant gases of 500ppm o-Xylol, reaction velocity (GHSV) is 10,000h
-1Down, the temperature of reaction interval is from 160 ℃～220 ℃.O-Xylol concentration utilizes GC-MS to measure, and product utilization GC measures.
Reaction result shows, in the time of 160 ℃, behind catalyst system, is 8.9% to the transformation efficiency of o-Xylol.In the time of 220 ℃, the transformation efficiency of o-Xylol is reached 100%.
Table four CeO
2Nanocubes catalyst activity evaluation result
Embodiment 10: it is the quartz tube reactor of 6mm that the catalyzer of getting a certain amount of 40～60 order embodiment 5 places internal diameter, feeds O
220mlmin
-1, N
280mlmin
-1With the reactant gases of 500ppm o-Xylol, reaction velocity (GHSV) is 10,000h
-1Down, the temperature of reaction interval is from 160 ℃～220 ℃.O-Xylol concentration utilizes GC-MS to measure, and product utilization GC measures.
Reaction result shows, in the time of 160 ℃, behind catalyst system, is 6.7% to the transformation efficiency of o-Xylol.In the time of 220 ℃, the transformation efficiency of o-Xylol is reached 100%.
Table five CeO
2Nanocubes catalyst activity evaluation result
Claims (3)
1. cerium oxide nano materials that thermostability is high is characterized in that:
Described cerium oxide is a nanocubes;
Described cerium oxide nano cubes presents favorable uniformity, monodispersity and thermostability through 350-750 ℃ of temperature roasting;
Described nanocubes specific surface area is 19-83m
2/ g;
The size of described nanocubes is 7-50nm.
2. prepare the described nano-cerium oxide cubes of claim 1 material, its key step is:
Getting solubility cerium salt and sodium hydroxide is dissolved in respectively in an amount of water, sodium hydroxide solution is added drop-wise in the solubility cerium solution, dropwise the back and continue reaction 10-30min, then it is transferred in the reactor, place thermostat container constant temperature 8-12h, the throw out that obtains is through deionized water wash, 60 ℃ of dried overnight, and roasting 4h obtains cerium oxide nano materials in retort furnace;
Described preparation method, solubility cerium salt is a kind of in cerous nitrate or Cerium II Chloride or the cerous acetate, its concentration is 0.1～1mol/L;
Described preparation method, concentration of sodium hydroxide solution is at 0.1～15mol/L;
Described preparation method, its hydro-thermal synthesis temperature is preferably 80～120 ℃;
Described preparation method, maturing temperature is 350～750 ℃.
3. the described cerium oxide nano cubes of claim 1 is as catalyzer or support of the catalyst, the application in the catalyzing and oxidizing ortho-xylene reaction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886261A (en) * | 2012-09-10 | 2013-01-23 | 北京工业大学 | Alcohol-water solvent thermal synthetic method of flower-shaped Pd/CeO2 three-way catalyst |
| CN103127933A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院生态环境研究中心 | Nano cerium oxide silver-loaded catalyst, manufacturing method and purpose thereof |
| CN105126808A (en) * | 2015-07-03 | 2015-12-09 | 河海大学 | Alumina supported type cerium oxide powder material preparation method |
| CN105731514A (en) * | 2016-01-28 | 2016-07-06 | 郑州航空工业管理学院 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
| CN106353267A (en) * | 2016-08-29 | 2017-01-25 | 浙江中检测研究院股份有限公司 | Method for detecting content of lead in blood by aid of nanometer cerium oxide-atomic absorption spectra |
-
2009
- 2009-12-24 CN CN200910243061A patent/CN101734707A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886261A (en) * | 2012-09-10 | 2013-01-23 | 北京工业大学 | Alcohol-water solvent thermal synthetic method of flower-shaped Pd/CeO2 three-way catalyst |
| CN103127933A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院生态环境研究中心 | Nano cerium oxide silver-loaded catalyst, manufacturing method and purpose thereof |
| CN105126808A (en) * | 2015-07-03 | 2015-12-09 | 河海大学 | Alumina supported type cerium oxide powder material preparation method |
| CN105731514A (en) * | 2016-01-28 | 2016-07-06 | 郑州航空工业管理学院 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
| CN106353267A (en) * | 2016-08-29 | 2017-01-25 | 浙江中检测研究院股份有限公司 | Method for detecting content of lead in blood by aid of nanometer cerium oxide-atomic absorption spectra |
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Open date: 20100616 |