Geosystem Eng.

, 3(2), 81-83, (June 2000)

Preparation of Ceric Hydroxide through Transformation of Cerium Compounds

Jiang-Tao Jia1), Chun-Hua Yan1), Jong-Kee Oh2)*, Chang-Hong Kim2) and Chong-Hong Pyun2)
1)

State Key Laboratory of Rare Earth Materials Chemistry and Applications, Peking University, Beijing 100871, China 2) Korea Institute of Science and Technology, Seoul 130-650, Korea (Received January 28, 2000 ; Accepted May 12, 2000)

ABSTRACT : The light rare earths, particularly cerium compounds, are becoming more and more important recently. The preparation method of Ce(OH)4 xH2O through transformation between cerium compounds was investigated. The process is compared with the direct routine by reacting Ce(III) with sodium hydroxide and hydrogen peroxide as a oxidant. The results show that transformation process is a potential preparation technique to produce Ce(OH)4 xH2O with better physical properties. Key words : preparation, ceric hydroxide, transformation process, cerium compounds

INTRODUCTION
Rare earth elements play more and more important roles in materials science and technology recently. Because of their extraordinary characteristics in viewpoints of optics, electric and magnetic properties, rare earths have more advantages than other elements as functional materials. Scientists of American and Japanese regard them as the keys of the new material treasure house. Some of the developed countries even store rare earth resources as strategic materials for the coming 21st century. In fact, some novel rare earth materials came out and were industrialized and commercialized every five or ten years during the past several decades. And the cycling has been intending shorter and shorter over the last several decades. Cerium of an important light rare earths occupies nearly half of the rare earth composition in bastnasite and is particularly a unique element with oxidation number of III and IV. Its compounds are also extensively used in glasses, abrasives, decolorant, and solid electrolytes. As the requirements of environment protection, the exhausted gas from vehicles should be cleaned by catalysts made of cerium oxide. The cerium, an active component of the catalyst(Crucq A. et al.), is rapidly increasing in consumption, recently. Zhang H.J. reviewed on China Rare Earth Information that near half of the cerium production is consumed in this area in the United States during

the past few years. This demands to scale up the metallurgical processes of bastnasite. Nowadays, many kinds of cerium compounds have been produced. They are, for instance, CeO2, Ce(OH)4, Ce(SO4)2, Ce(NO3)4, Ce2(CO3)3, CeF3, CeCl3, Ce2(C2O4)3, CePO4, and a series of ammonium and sodium complex salts. CeO2 is the most popular compound among them for industrial uses. However, it is often difficult to be treated in most cases because the precursor of cerium is generally obtained as cerium dioxide which has low solubility in some mineral acids. CeF3, Ce2(C2O4)3 and CePO4 are also insoluble in mineral acid. CeCl3 has hygroscopic property and ceric chloride is unstable. The carbonate is available as a precursor on account of its high solubility in mineral acid. However, it has a drawback to emit much more volume of carbon dioxide gas during the leaching process. Ce(OH)4 is becoming more and more popular as a precursor recently, which is a primary product from the process of treating rare earth minerals in general.

EXPERIMENTAL
Reagents The sample and reagents used for the experiments are listed as follows : Cerous carbonate, CeO2 /REO 99%, TREO~ 50%, Zibo Rare Earth Plant, China; Sodium sulfate anhydrous, 98.5%, Extra pure, Kanto Chemical Co. Inc.; Sodium hydroxide, 96%, Guaranteed Reagent, Junsei Chemical Co., Ltd.; Hydrogen peroxide, ~35%, Extra pure, Junsei Chemical Co., Ltd. Preparations Cerium carbonate is dissolved into hydrochloric acid solution. The solution is treated with proper reactants as neutralizers like NaOH and KOH to produce ceric hydroxide, which is filtered and calcined at high temperature through drying to get the ceric oxide. First of all, 20.5 g Ce2(CO3)3 xH2O in a 200 ml beaker is pulped with 20 ml distilled water and 20 ml HCl(11.3 mol/L) is added to dissolve the cerium carbonate. The reaction is progressing very fast in the strong acid solution. The solution

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become clear when all the Ce2(CO3)3 xH2O is dissolved in hydrochloric acid. 20 g Na2SO4 is dissolved in distilled water and the solution is poured into the cerous solution. The white precipitate is washed and filtered. The precipitate is dissolved into 100 ml alkaline solution with 80 g NaOH per liter of distilled water. And then the slurry is treated by gradually adding 30 ml H2O2(30 wt.%), kept reaction for 4 hours and then heated for one hour to prepare the ceric hydroxide which is washed, filtered and calcined to transform it into ceric oxide.

RESULTS AND DISCUSSION

The solubility products of ceric hydroxide[Ce(OH)4] is much lower(about 10-40) than most other insoluble cerium salts. This makes it possible to prepare Ce(OH)4 xH2O by transformation from other salts. Ce2(CO3)3 and Ce (III) complex salts are rather popular species for preparation of Ce(OH)4 xH2O. When the cerrous carbonate is dissolved with hydrochloric acid by the reaction (1) over generation of carbon dioxide. Ce2(CO3)3 xH2O + 6HCl = 2CeCl3 + 3CO2 + (3+ x)H2O (White powder) (1) Cerous solution is treated with sodium sulfate to precipitate the white powder of NaCe(SO4)2 nH2O like equation (2). The slurry is settled after heating and stirring for about 10 minutes and decanted to remove the upper clear solution. The condensed cerous sulfate slurry is washed with warm water. The cerium can be recoverd with high efficiency, because the solubility of such complex salt is quite low in excessive sodium sulfate solution. The dried product is identified to be NaCeSO4 by XRD, as shown in Fig. 1. CeCl3 + 2Na2SO4 + nH2O = NaCe(SO4)2 nH2O (White) + 3NaCl (2)

into alkaline solution, where cerous ion is partially oxidized by the air to show the gray color. Hydrogen peroxide reacts with sodium cerous sulfate into hydroperoxyl ceric hydroxide with dark brown as shown in equation (3). The product is identified to be amorphous as shown in Fig. 2, which is partially converted into ceric hydroxide on drying. The slurry containing dark brown precipitate of Ce(OH)3 OOH is kept reation for 4 hours and then heated for about half an hour to transform the cerous compound into bright yellow precipitate of ceric hydroxide as shown in equation (4). The ceric hydroxide can be confirmed to be Ce(OH)4 2H2O by XRD as shown in Fig. 3. 2NaCe(SO4)2 nH2O+6NaOH+3H2O2 = 2Ce(OH)3 OOH + 4Na2SO4 + 2(n+1)H2O (Dark brown) 2Ce(OH)3 OOH = 2Ce(OH)4 +O2 (Yellow)

(3) (4)

The recovered ceric hydroxide through thoroughly washing is calcined to produce the ceric oxide, which has the proper size and better filtrability. Besides the way of transformation described as above,

The white precipitate of NaCe(SO4)2 nH2O is pulped

Fig. 2. XRD pattern of Ce(OH)3 OOH xH2O as intermediate product.

Fig. 1. Crystal of NaCeSO4 to be produced by reaction (2).

Fig. 3. Crystallinity of ceric hydroxide as Ce(OH)4 2H2O produced.

Preparation of Ceric Hydroxide through Transformation of Cerium Compounds

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Ce(OH)4 xH2O can be directly prepared by reacting Ce(III) salts simultaneously with sodium hydroxide and hydrogen peroxide. Predetermined amount of Ce2(CO3)3 xH2O is made paste with water and dissolved in hydrochloric acid thoroughly. And then the residue is filtered out as insoluble impurities. The excessive amount of H2O2 poured into the filtrate in order to convert cerous to ceric ion and NaOH solution is dropped slowly. The dark brown precipitate appears according to equation (5). When the color changes to yellow on boiling, the precipite is filtered with washing to get the final product of ceric hydroxide. 2CeCl3 +6NaOH+3H2O2 = 2Ce(OH)3 OOH (Dark brown) + 2H2O +6NaCl (5)

Ni, J. Z. and Hong, G. Y., 1998, Progress on novel rare earth materials and flow sheets, Science Press, Beijing. Crucq A., 1991, Catalysis and automotive pollution control II: proceedings of the Second International Symposium (CAPoC 2), Brussels, Belgium, September 10-13, 1990, Elsevier, Amsterdam ; New York. Zhang H.J., 1999, Review and prospect on Rare Earth Market, China Rare Earth Information Center, Baotou. th Susan B., 1996, The Merck Index, 12 , Merck & Co. Inc.:Whitehouse Station, NJ, p1483.

Compared the two ways of preparation of ceric oxide, although the former process has more steps than the latter, Ce(OH)4 xH2O produced by the former method is more convenient to be rinsed and filtered than that obtained by the latter. So transformation process makes it quite easier to treat the product and to lessen the moisture content of the product.

Jiang-Tao Jia, received his B.S.(1991) in Chemistry and Ph.D. (1998) in Rare Earth Separation Chemistry from Peking University, China. He is currently postdoctoral researcher of Peking University and a visiting scientist in KIST, Korea. His main research interests are rare earth separation chemistry and engineering.

CONCLUSION
In order to make use of rare earths in functional materials conveniently, the preparation of Ce(OH)4 xH2O is investigated and reviewed through transformation process and direct precipitation. Compared with direct precipitation method of reacting Ce3+ with base after oxidation of cerous ion with hydrogen peroxide, complex salt of NaCe(SO4)2 is better to make Ce(OH)4 xH2O with better physical properties. The precipitates obtained by transformation is more convenient for washing and filtering the product. This process could be available in the industrialization for preparation of ceric oxide.

Chun-Hua Yan, received his B.S.(1982) in Chemistry, M.S.(1985), and Ph.D.(1988) in Inorganic Chemistry from Peking University, China. He is currently a professor of Chemistry in Peking University and a commissioner in ChinaKorea Advanced Materials Cooperation Center. His main interests are rare earth separation and materials chemistry. Jong Kee Oh, received his B.S.(1969) in the Mining Engineering Dept. and Ph.D.(1986) in Rare Earth Separation by Solvent Extraction from Seoul National University. He is currently principal researcher of Metal Processing Research Center at KIST and has mainly interests in recovery of metals from primary and/or secondary resources and hydrometallurgy.(ohjoko@kist.re.kr) Chang-Hong Kim, received his B.S. in Chemical Science from Seoul National Univeristy and Ph.D.(1979) in Chemistry from KAIS. He is currently principal researcher at KIST and has specialty in Solid Chemistry and preparation of luminescence materials. Also He takes charge of Korea-China New Material Corporation Center as Chief. Chong-Hong Pyun, received his B.S. in Chemical Science from Seoul National University and Ph.D.(1985) in Electrochemistry from New Mexico University. He is currently principal researcher at KIST and has specialty in characterization of luminescence materials and electrochemistry.

REFERENCES
Xu, G. X., 1995, Rare Earths, 2 try Press, Beijing, Vol. 1.
nd

Ed., Metallurgical Indus-

Jianf-Tao Jia

Chun-Hun Yan

Jong Kee Oh

Chang-Hong Kim

Chong-Hong Pyun