CN1288088C - Process for preparing high purity active nano ceria - Google Patents
Process for preparing high purity active nano ceria Download PDFInfo
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- CN1288088C CN1288088C CN 200410023273 CN200410023273A CN1288088C CN 1288088 C CN1288088 C CN 1288088C CN 200410023273 CN200410023273 CN 200410023273 CN 200410023273 A CN200410023273 A CN 200410023273A CN 1288088 C CN1288088 C CN 1288088C
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- cerium
- reaction
- tensio
- active
- roasting
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Abstract
The present invention relates to a method for preparing nanometer active cerium dioxide with high purity. The method uses cerium salts as cerium sources and carbonate, oxalate or oxalic acid as precipitating agents, and comprises the following steps of carrying out chemical precipitation reactions under the action of mechanical agitation by adding surface active agents to form precursors, and filtering, washing, dispersing, drying and calcining the precursors in a muffle furnace to obtain nanometer active CeO2 finished products with high purity. The present invention has the advantages of low price of raw materials, high product yield, easy operation process, simple required equipment and low preparation cost. The present invention utilizes a liquid phase chemical precipitation method to change reaction conditions to obtain the nanometer CeO2 which has different grain sizes, crystallization degrees, structure compaction degrees, specific surface areas and surface activity. The grain diameter of the obtained product crystal grains is from 5 to 30 nm, the CeO2 content is larger than 99.95%, and the specific surface area is from 40 to 140m<2>/g.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material.
Background technology
The present invention relates to a kind of highly pure active nano Ce O
2The preparation method of powder particularly adopts liquid phase method to prepare grain-size 5~30nm, specific surface area 40~140g/cm
2, purity is greater than 99.95% CeO
2The method of powder.
Oxide nano rare earth CeO
2Because of unique oxygen function and the quick oxygen of high temperature room diffusibility stored arranged, can be widely used in the redox reaction, become the purifying vehicle exhaust catalytic material, high temperature oxygen sensitive semiconductor, pH transmitter, Solid Oxide Fuel Cell (SOFC) electrode materials, electrochemical reaction promotor, metal oxidation resistance, erosion shield and additive and chemically machinery polished (CMP) abrasive etc. that have application prospect, huge development potentiality is arranged in modern high-tech field.Nano Ce O
2Performance directly influence its application, particle purity is high more, grain-size is more little, specific surface area is big more, activity is high more, particle is spherical in shape or class is spherical and be evenly distributed, then CeO
2Redox ability strong more, use wide more.
At present for obtaining nano Ce O
2Adopted preparation technology have: scorification (F.Bondioli etc. Nanosized CeO
2Powders obtained by flux method.Materials ResearchBulletin, 1999,34 (14/15): 2159~2166), the precipitator method (.Nanostructured Cerium Oxide:Preparation and Properties ofWeakly-agglomerated Powders.Journal of the European Ceramic Society such as Boro Djuriclic, 1999,19:1925~1934), the sonochemistry precipitator method (.SonochemicalSynthesis of Cerium Oxide Nanoparticles-Effect of Additives andQuantum Size Effect.Journal of Colloid and Interface Science such as Lunxiang Yin, 2002,246:78~84), sol-gel method (Hou Wenhua etc. adopt different methods to prepare CeO
2Ultrafine particle-sol-gel method. Nanjing University's journal (natural science), 1997,7:487~490), hydrothermal crystallization method (.Synthesis of cerium oxide nanoparticles byhydrothermal crystallization with citric acid.Journal of MaterialsScience Letters 2002 such as T.Masui, 21:489~49118; Dong Xiangting etc. hydrothermal crystallization method prepares .CeO
2Nanocrystalline. 312~314), microemulsion method (CeO in the .W/O microemulsion such as Shi Shuo Rare Metals Materials and engineering, 2002,1 (4):
2The preparation of ultrafine particle. chemistry circular, 1998,12:51)) and vapor phase process (.Microstructural studies of nanocrystalline CeO such as N.Guillou
2Producedby gas condensation.NanostructuredMaterials, 1997,8 (5): 545~557)
But above method all exists such as product performance are not good, production cost is high, severe reaction conditions, restive, the complex manufacturing of technology, fatal problem such as environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of product purity height, size of microcrystal is little, and specific surface area is big, and is active high, and cost is lower, and equipment and operating process are simple, can effectively remove impurity, the nano Ce O of environmentally safe
2The preparation method.
The present invention adopts cerium salt as the cerium source, adopt carbonate, oxalate or oxalic acid as precipitation agent, adopting polyoxyethylene glycol 100-10000 or ethylene glycol or Virahol or polyvinylpyrrolidone or polyvinyl alcohol is tensio-active agent, carries out the chemical precipitation reaction by mechanical agitation and generates presoma; Presoma after filtration, after the washing, carry out ultrasonic dispersing with raw spirit, more after filtration, 70 ℃ of dryings, roasting obtains highly pure active nano Ce O in retort furnace
2Finished product.
Employed cerium source is cerous nitrate or cerous sulfate among the present invention, preferred cerous nitrate; Precipitation agent is volatile salt, bicarbonate of ammonia, ammonium oxalate or oxalic acid, preferred volatile salt or bicarbonate of ammonia; Tensio-active agent is polyoxyethylene glycol 100-10000 or ethylene glycol or Virahol or polyvinylpyrrolidone or polyvinyl alcohol, preferred Macrogol 2000-6000, more preferably Macrogol 4000, the effect of these tensio-active agents is the reunions that help to prevent particle in subsequent processes.
The processing condition that adopted among the present invention are: precipitant solution is poured into fast carried out chemical reaction in the cerium solution that is added with tensio-active agent, tensio-active agent add-on 0~5g/L wherein, preferred 3~4g/L; Cerium solution concentration is 0.1~0.5mol/L, preferred 0.1~0.2mol/L; Precipitant solution concentration 0.1~0.5mol/L, preferred 0.1~0.2mol/L; Cerium salt and precipitation agent reaction mol ratio 0.5~3, preferred 1.5~2; Temperature of reaction is 20~80 ℃, preferred 30~40 ℃; Stir speed (S.S.) is 200~1200r/min, preferred 700~800r/min; Reaction times is 10~60min, preferred 10~20min.After the presoma that reaction forms carries out solid-liquid separation after filtration, must carry out ultrasonic dispersing with further increase particle dispersiveness with raw spirit again with deionized water wash for several times fully to remove impurity.Drying mode can be taked infrared warm air drying, vacuum-drying or frozen drying; What obtain after drying is finished is the presoma dry powder of white.
Presoma dry powder obtains light yellow to yellow product after roasting in retort furnace.Roasting condition should be able to carry out in the retort furnace of controlled atmosphere, and control furnace atmosphere and heat-up rate, and atmosphere can be that neutrality also can be inert atmosphere; Temperature rise rate is 1~15 ℃/min; Maturing temperature is 300~1000 ℃, and roasting time is 1~5h.The product that obtains under these conditions is that crystallinity is good, the size of microcrystal footpath between 5~30nm, specific surface area is at 40~140m
2Between/the g, purity is greater than 99.5% highly pure active nano Ce O
2
The present invention compares with existing Technology and has the following advantages:
(1) the present invention adopts cost of material cheap, the product yield height, and operating process is easy, and required equipment is simple, and preparation cost is low, helps saving human and material resources and financial resources;
(2) the present invention utilizes the liquid phase chemical precipitator method to prepare highly pure active nano Ce O
2, change reaction conditions and can obtain grain-size, crystallization degree, compact structure degree and the specific surface area nano Ce O all different with surfactivity with roasting condition
2, then can control these indexs by control reaction conditions and roasting system, control process is simple;
(3) presoma can effectively be removed impurity through deionized water wash and obtain high purity product among the present invention; Reaction process is introduced tensio-active agent as dispersion agent, and in washing process, carries out ultrasonic dispersing by dehydrated alcohol, can reduce the agglomeration of presoma in follow-up drying, calcination process process, helps obtaining the good nano Ce O of monodispersity
2The products obtained therefrom size of microcrystal is 5~30nm, purity height, CeO
2Content is greater than 99.95%, and size distribution is even, and active big, specific surface area reaches 40~140m
2/ g.
Description of drawings
Fig. 1: process flow diagram of the present invention;
Fig. 2: presoma Ce
2(CO
3)
3H
2The XRD figure of O products obtained therefrom behind 300 ℃ of roasting 1h;
Fig. 3: presoma Ce
2(CO
3)
3H
2The TEM photo of O products obtained therefrom behind 300 ℃ of roasting 1h;
Fig. 4: presoma Ce
2(CO
3)
3H
2The N of O products obtained therefrom behind 300 ℃ of roasting 1h
2Adsorption isotherm adsorption-desorption curve;
Fig. 5: presoma Ce
2(CO
3)
3H
2The BJH desorption pore size distribution of O products obtained therefrom behind 300 ℃ of roasting 1h.
Embodiment
Embodiment 1 takes by weighing Ce (NO
3)
36H
2O 8.68g is made into the 0.1mol/L solution of 100ml, and adds 1gPEG4000 therein; Take by weighing (NH
4)
2CO
3H
2O 5.13g is made into the 0.1mol/L solution of 150ml.Two kinds of solution that make are placed water-bath, and 40 ℃ of following preheating 10min are then with (NH
4)
2CO
3H
2O solution is poured Ce (NO fast into
3)
36H
2In the O mixing solutions, motor machine stirring reaction 10min under the 800r/min rotating speed, gained presoma Ce
2(CO
3)
3H
2O colloidal sol is used twice of deionized water water washing in the vacuum filtration process, to filter the dry labor thing and put into raw spirit ultrasonic dispersing 10min, vacuum filtration, repeat twice, then in 70 ℃ of vacuum-dryings, gained presoma dry powder is put into retort furnace in 300 ℃ of following roasting 1h of air, promptly gets light yellow highly pure active nano Ce O
2Product, its XRD figure is composed as shown in Figure 2, and size of microcrystal is 5.84nm; The TEM photo as shown in Figure 3, grain diameter is about 30nm, about; The BET specific surface area is 140.61m
2/ g, N
2Adsorption isotherm adsorption-desorption curve as shown in Figure 4, BJH desorption pore size distribution curve shows to have surface mesoporous structure as shown in Figure 5, the pore size majority is positioned at 5~15nm scope, the aperture peak value is 9.3nm; Foreign matter content is as shown in table 1, and product purity is greater than 99.5%.
Embodiment 2 takes by weighing Ce (NO
3)
36H
2O 8.68g is made into the 0.1mol/L solution of 100ml, and adds 1gPEG4000 therein; Take by weighing (NH
4)
2CO
3H
2O 5.13g is made into the 0.1mol/L solution of 150ml.Under 40 ℃, with (NH
4)
2CO
3H
2O solution is poured the Ce (NO that is added with PEG4000 fast into
3)
36H
2In the O mixing solutions, mechanical stirring reaction 10min under the 800rpm rotating speed, the gained precursor sol is used twice of distilled water wash in the vacuum filtration process, to filter the dry labor thing and put into raw spirit ultrasonic dispersing 10min, vacuum filtration, repeat twice, then in 70 ℃ of dryings, gained aqueous precursor gel powder 700 ℃ of roasting 3h in retort furnace promptly obtain yellow highly pure active nano Ce O
2Product, size of microcrystal are 15.26nm, and the BET specific surface area is 69.78m
2/ g, purity is greater than 99.5%.
Table 1 nano Ce O
2Middle foreign matter content (%)
La | Fe | Si | Ca | Mg | Al | Mn | W |
0.005 | 0.002 | 0.001 | <0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
Ni | Y | Mo | Ti | Cu | Zn | V | |
0.004 | 0.001 | 0.001 | 0.001 | <0.0001 | <0.001 | 0.002 |
Claims (2)
1. method for preparing the highly pure active nano ceric oxide, it is characterized in that: adopt cerium salt as the cerium source, adopt carbonate, oxalate or oxalic acid as precipitation agent, adopting polyoxyethylene glycol 100-10000 or ethylene glycol or Virahol or polyvinylpyrrolidone or polyvinyl alcohol is tensio-active agent, carries out the chemical precipitation reaction by mechanical stirring and generates presoma; Presoma after filtration, after the washing, carry out ultrasonic dispersing with raw spirit, more after filtration, 70 ℃ of dryings, roasting obtains highly pure active nano Ce O in retort furnace
2Finished product;
Employed cerium source is cerous nitrate or cerous sulfate, precipitation agent is volatile salt, bicarbonate of ammonia, ammonium oxalate or oxalic acid, tensio-active agent add-on 0~5g/L, cerium solution concentration is 0.1~0.5mol/L, precipitant solution concentration 0.1~0.5mol/L, cerium salt and precipitation agent reaction mol ratio 0.5~3, temperature of reaction is 20~80 ℃, mechanical stirring speed is 200~1200r/min, and the reaction times is 10~60min;
Roasting is carried out in retort furnace, and temperature rise rate is 1~15 ℃/min; Maturing temperature is 300~1000 ℃, and roasting time is 1~5h.
2. method according to claim 1, it is characterized in that: employed cerium source is a cerous nitrate, precipitation agent is volatile salt or bicarbonate of ammonia, and tensio-active agent is polyoxyethylene glycol 100-10000, and the tensio-active agent add-on is 3~4g/L, cerium solution concentration is 0.1~0.2mol/L, precipitant solution concentration is 0.1~0.2mol/L, and cerium salt and precipitation agent reaction mol ratio are 1.5~2, and temperature of reaction is 30~40 ℃, stir speed (S.S.) is 700~800r/min, and the reaction times is 10~20min.
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