USE OF SOLVENT EXTRACTION TECHNIQUE IN BRAZILLIAN URANIUM MILLS AN OVERVIEW Luiz A. Gomiero,1 and Carlos A.

. Morais2 Indstrias Nucleares do Brasil S/A INB, Unidade de Caetit, P.O. Box 7, 46400 000, Caetit, BA, Brazil. 2Centro de Desenvolvimento da Tecnologia Nuclear CDTN / CNEN, Rua Mrio Werneck, s/n, Campus da UFMG, Pampulha, 30123-970, Belo Horizonte, MG, Brazil. Corresponding author email address: gomiero@inb.gov.br; cmorais@cdtn.br
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ABSTRACT
Solvent extraction has been applied to uranium concentrate production in Brazil. At the first plant, uranium minerals associated to Zr and Mo were acid leached. Extraction were done by a mixture of Alamine 336 and Alamine 304, followed by selective Zr, U and Mo stripping. At the currently operating facilities a single U mineral is processed by acid heap leaching. Uranium is extracted with Alamine 336 and stripped with NaCl solution. As all water is recycled, chloride contents in the liquor has increased causing detrimental effect to the extraction process. The currently plant operating conditions and the improvements arisen from the researches developed to solve these problems are presented.

INTRODUCTION The first Brazilian mining and milling facilities for uranium concentrate production started operating in 1982, in the Municipality of Caldas, Minas Gerais State. Uranium ore containing zirconium and molybdenum minerals were crushed, grinded and leached in agitated tanks with high sulphuric acid consumption. A pregnant leach solution (PLS) containing these both contaminants among others of lower significance were produced. To solve some operating and product specifications troubles due to the Zr and Mo presence in the PLS, some changes in the previous extraction/stripping process were introduced. It will be shown that after introducing such improvements the facilities were operated with good results till 1995, when the shut down process started. A new mining and milling facilities started operating at the beginning of 2000 processing a single U mineral containing ore by the sulphuric acid heap leaching technique as shown by Matos & Gomiero [1]. It is located in the Municipality of Caetit, Bahia State. Uranium is separated from the other species present in the PLS by solvent extraction/stripping techniques. In this plant all aqueous effluent generated in the process is reused after treatment with lime and solid/liquid separation. As a consequence of using sodium chlorate as an oxidizing agent during leaching and an acidified sodium chloride

(NaCl) solution for U stripping in a process where chloride ions is not removed in the lime treatment, chloride content increased in the PLS causing a detrimental effect on the U extraction/stripping process. The currently plant operating conditions and the results of researches developed and introduced to solve this problem will be discussed in the corresponding section. CALDAS SOLVENT EXTRACTION PROCESS EXPERIENCE Caldas mine is formed by three main ore bodies named A, B and E. All of them have Mo and Zr associated to the U mineral but A and B bodies have higher Mo and Zr content than E body. Otherwise E body has higher U content than the others Mine exploitation was started by the E body giving PLS with the typical analysis shown in Table 1. Table 1. U, Mo and Zr content in a typical PLS from E Body. Chemical Content Specie (g/L) U3O8 0.475 MoO3 0.062 ZrO2 0.044 Extraction Uranium recovery from the PLS was done by solvent extraction in 5-stage mixersettlers arrangement with a C8-C10 tertiary amine. At the beginning of the plant operation the solvent composition was 5 vol% Alamine 336, 3 vol% tridecanol and commercial kerosene. At these conditions Mo is fully extracted from the PLS and Zr is only partially extracted. Raffinate was treated with lime up to pH 10 and disposed in a tailing dam. Liquid phase was released to the environment after barium chloride treatment and monitoring. Caldas plant did not face water shortage problems but the following undesirable results were observed along the first operating year: U load reducion on the solvent when MoO3/U3O8 > 0.5, leading to a lower U production, High Zr extraction causing high Zr/U ratio in the final uranium precipitate Stripping U and Mo were stripped separately. U was stripped from the loaded solvent in 5stage mixer-settlers by a 1.75 mol/L NaCl aqueous solution acidified to pH 1.2 1.5 with sulphuric acid. Zr and Mo were also partially stripped causing final U-precipitate contamination. Mo was stripped in one stage mixer-settler after U stripping by using a 0.75 mol/L sodium carbonate (Na2CO3).aqueous solution. It was observed the formation of organic insoluble Mo-amine complex leading to emulsion formation and solvent losses.

Solving the problems Researches were carried out to overcome such mentioned chemical and operational problems. The process flowsheet presented in Figure 1 shows the previous and the end operating solvent extraction process at Caldas facilities.
Solvent PLS U + Mo + Zr EXTRACTION Ammonia

Raffinate

Hidrogen Peroxide

Zr STRIPPING

Ammonium Sulfate

Zr PRECIPITATION

Zr Hidroxide

Hidrogen Peroxide
Sodium Chloride

U STRIPPING

U Strip Solution

Ammonium Diuranate

Sodium Carbonate

Mo STRIPPING

Mo Strip Solution

Calcium Molybdate

Water

SOLVENT SCRUB

Effluent Treatment y

Figure 1. Caldas extraction flowsheet. Unit operations rounded by branched line were introduced after plant start-up.

The following improvements were introduced to the process: solvent flow increasing in the extraction to overcome the reduction of the U loading on the solvent when MoO3/U3O8 > 0.5, use of a mixture of decyl and dodecyl tertiary amines to increase Mo solubility on loaded solvent and overcome the organic insoluble Mo-amine complex forming in the Mo stripping. A mixture of 70 vol% Alamine 304, 30 vol% Alamine 336 and 3.5 vol% tridecanol in commercial kerosene was adopted. addition of a proper amount of phosphate ore concentrate (raw apatite) to the grinding step of the U ore from E body to precipitate the soluble zirconium as a Zr-phosphate complex during the leaching step to avoid Zr contamination of the final U precipitate. After introducing the improvement,

Zr analysis in the PLS was reduced from 0.044 g/L ZrO2, as shown in Table 1, to 0.002 g/L. Introduction of a Zr stripping step from the loaded solvent before U and Mo stripping to operate with the A and B uranium ore bodies processing.: Bench and pilot essays with such ore gave a loaded solvent containing 2.55 g/L U3O8, 5.60 g/L MoO3 and 0.40 g/L ZrO2. After Zr stripping as indicated in Figure 1, the analysis of these species on the loaded solvent were 2.54 g/L U3O8, 5.60 g/L MoO3 and 0.008 g/L ZrO2. Zr was stripped by a 1 mol/L ammonium sulfate solution containing 3 g/L H2O2 100 wt% in 3 stages at pH 4.5. This unit was built up but it was not operated because bodies A and B were not exploited. Addition of 50 wt% H2O2 solution at a rate of 0.1 kg 100 wt% H2O2/kg U3O8 to the mixer of the first U extraction stage in order to oxidise Mo to reduce its solubility on the U stripping solution and thus overcoming Mo contamination of the U concentrate. CAETIT SOLVENT EXTRACTION PROCESS EXPERIENCE

Mining and milling facilities are constituted of an open-pit mine and a physical and chemical processing plant. Uranium is acid leached by heap leaching technique and purified by solvent extraction. U Extraction/Stripping U extraction is carried out in a circuit configuration consisted of a series of mixersettlers arranged as a 4-stage extraction, 4-stage U strip and a single stage solvent scrub or regeneration. The solvent consists of a mixture of 5 vol% Alamine 336 and 3 vol% tridecanol, both supplied by Cognis do Brasil Ltda, in a paraffin type diluent SOLBRAX ECO 175/235 supplied by Petrobras Distribuidora S/A. Aqueous raffinate from the extraction step is treated with lime up to pH 10 and disposed in lined settling ponds equipped with a botton water drainage system named sub-aerial drains. As Caetits facilities are located in a region with low water availability, all the used plant water must be recovered , treated and recycled to the leach process. U stripping is carried out by an aqueous NaCl solution acidified to pH 1.2-1.5 with sulphuric acid. At the start-up operation the stripped solvent was recycled to the extraction circuit without any prior treatment. At such operating conditions the tertiary amine on the recycled solvent was in the chloride form and the U extraction and stripping process may be represented by equations (1) and (2). 4R3NHCl(org) + [UO2(SO4)3]4-(aq) (R3NH4)4UO2(SO4)3(org) + 4(Na+Cl-)(aq) (R3NH4)4UO2(SO4)3(org) + 4Cl-(aq) (1) 4R3NHCl(org) + [UO2(SO4)3]4-(aq) + 4Na+(aq) (2)

Equation (1) shows that the chloride ion from the amine is released to the aqueous raffinate. U is precipitated from the aqueous chloride strip solution as ADU by ammonium hydroxide solution addition according to equation (3).

2[UO2(SO4)3]4-(aq) + 6NH4OH(aq)

(NH4)2U2O7(s) + 6SO42-(aq) + 4NH4+(aq) + 3H2O(l) (3)

Some 70 vol% of the ADU filtrate is recycled to the preparation of a new NaCl stripping solution. At the plant start-up the excess ADU filtrate was joined to the raffinate before lime treatment. As the chloride ion is not removed by the lime treatment, its content in liquor has increased causing a strong reduction of solvent U-loading capacity and effectively reducing plant throughput. To overcome such problem it was introduced a new 1-stage mixer-settler system to carry out the stripped solvent scrub with a 1 mol/L Na2CO3 solution. The resulting aqueous strip solution is joined to the excess ADU filtrate and disposed in a specific lined pond for future reuse. Some alternative U-stripping systems were also investigated [2, 3]. Ammonium sulfate/ammonia system showed to be also high sensitive to the presence of chloride ions in the liquor, since chloride competes with uranyl sulfate anions being partially extracted by the amine [4]. U stripping with a concentrated sulfuric acid solution is not affected by the presence of chloride ion in the liquor and is a good alternative to be considered for a future change in the Caetits process. Stable Emulsion Another undesirable experience faced by the Caetits plant operating staff was a strong emulsion formation in the extraction circuit. The phenomena was hardly evaluated [5] showing that the main causes were the high sulfate, chloride and suspended solids content in the liquor. From that experience these variables were carefully controlled to avoid another emulsion formation. Currently Caetits process flowsheet is shown in Figure 2.
Solvent

PLS

U EXTRACTION

Raffinate

Effluent Treatment y Ammonium Diuranate

Sodium Chloride

U STRIPPING

U Strip Solution

Sodium Carbonate

SOLVENT SCRUB

Specific Settling Pond

Figure 2. Caetit extraction flowsheet. Unit operation rounded by branched line were introduced after plant start-up.

FINAL CONSIDERATIONS Solvent extraction has proven to be a good choice for uranium recovery and purification in the processing of Brazilian urainum ores. In the first operating milling facilitie simultaneous U and Mo extraction were conducted with good operating conditions by using a proper mixture of Alamine 304 and Alamine 336. U, Mo and Zr separation were well achieved by selective stripping of each metal from the loaded solvent . Otherwise the use of NaCl solution for U stripping in a process where water must be recycled implies in the need of segregating the chloride ions by regenerating the stripped solvent before its recycle to the extraction step. Also all excess filtrate from the U precipitation and the aqueous phase from the solvent regeneration step must be segregated. Care must be taken on the control of chloride, sulphate and suspended solids contents in the PLS to avoid emulsion formation and to mantain the solvent load capacity. ACKNOWLEDGMENTS This work is published with the permission of the Indstrias Nucleares do Brasil S/A INB. The authors would like to acknowledge to Mr. Renato Rosa Pinto for its very important help on this report edition. REFERENCES
1 E. C. Matos and L. A Gomiero, Uranium Ore Concentrate Production in Caetit BA, Brazil, VI International Conference on Clean Technologies for the Mining Industry, Concepcin, Chile, 2004. C. A Morais and L. A Gomiero, !Uranium Stripping From Tertiary Amine Loaded Solution by Ammonium Sulfate, Mineral Engineering, 18, 1277-1281 (2005). C. A Morais, L. A Gomiero, W. Scassiotti Filho and H. Rangel Jr., Uranium Stripping From Tertiary Amine by Sulfuric Acid Solution and its Precipitation as Uranium Peroxide, Mineral Engineering, 18, 1331-1333 (2005). K. Soldenhoff, D. Wilkins, M. Shamieh and R. Ring, Solvent Extraction of Uranium in the Presence of Chloride, Proc. International Symposium on the Process Metallurgy of Uranium, E. zberk and A J. Oliver, Eds., Saskatoon, Saskatchewan, Canada, 2000; pp. 339-351. C. A Morais, J. S. Benedetto and L. A Gomiero, Emulsion in Uranium Solvent Extraction Plant Case Study, International Solvent Extraction Conference, Beijing, The Peoples Republic of China, 2005.

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