Int. J. Miner. Process. 82 (2007) 14 22 www.elsevier.

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Influence of alcohols on the extraction of cerium(IV) by Aliquat-336 in kerosene

Y.A. El-Nadi
Hot Laboratories Centre, Atomic Energy Authority, Post Code 13759, Cairo, Egypt Received 26 July 2006; received in revised form 2 November 2006; accepted 8 November 2006 Available online 20 December 2006

Abstract Tricaprylmethylammonium chloride (Aliquat-336) diluted with kerosene was used to extract cerium(IV) from nitric acid medium. Various alcohols were used as modifiers to overcome the third phase problem. The different parameters affecting the extraction process including nitric, nitrate, hydrogen ion, extractant and metal concentrations as well as the temperature were separately investigated. The effect of the investigated alcohols on the extraction process was also studied in detail at two different concentrations and correlated to their physical constants. Based on the obtained results, the extraction equilibrium was deduced and the optimum conditions for the extraction of cerium(IV) were proposed. The method was tested and applied to the separation of cerium from the hydrous oxide cake resulting from monazite sand. 2006 Elsevier B.V. All rights reserved.
Keywords: Cerium(IV); Extraction; Alcohols; Aliquat-336; Monazite

1. Introduction The mineral monazite is primarily composed of rare earth phosphates especially those of low atomic numbers (cerium group) along with numerous other minor constituents. The formula of this mineral may be written as (Ce,La,Nd,Th)PO4. Egyptian monazite has been analyzed and was found to assay 5.90% ThO2, 0.44% U3O8, 26.55% Ce2O3 and 34.35% other rare earths (RE2O3) (Osman, 1998). Swaminathan et al. (1988) developed a process for producing cerium depleted rare earth chloride, cerium, thorium and uranium from the hydrous oxide cake obtained from monazite. The process involves drying of the mixed rare earth-thorium hydroxide cake obtained by monazite-caustic soda process followed by stepwise
Tel.: +20 10 5031178; fax: +20 2 6352474. E-mail address: yael_nadi@yahoo.com. 0301-7516/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.minpro.2006.11.002

extraction. Methods for the group-separation of rare earths, thorium and uranium from hydrous metal oxide cake obtained by the alkaline digestion of monazite were studied (Chayavadhanangkur et al., 1986). Leaching of the hydrous metal oxide cake at pH 45 separates the elements under investigation into three major groups, which are suitable to be used as feed materials for further purification. Although some text books imply that the rare earth elements and yttrium are all produced by ion exchange, only a few heavy elements are purified commercially by such method. For large-scale production the chosen path is solvent extraction, usually in nitrate solutions (Kilbourn, 1994). The extraction of Am(III) and Eu(III) by 2,6-di(5,6dipropyl-1,2,4-triazin-3-yl)-pyridines (DPTP) from 1.9 M HNO3 + NH4NO3 was studied (Kolarik et al., 1999). The extraction and separation efficiency of DPTP strongly decreases in the order of diluents (each modified with 2-

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ethyl-1-hexanol): branched alkanes N cyclohexane N 2methyl-4-pentanone N 2-ethylhexyl acetate N benzene N chlorobenzene N xylene. 1-Octanol and 2-ethyl-1-hexanol modifiers appropriately support the solubility of protonated forms of DPTP in branched alkanes, and moderately enhance the extraction of Am(III) and Eu(III). The optimum extraction and separation efficiency is attained at 1020 vol.% modifier. Third phase formation in the extraction of Nd(III) by 0.2 M Octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (OPHICMPO) in ndodecane was studied with tri-n-butyl phosphate (TBP) and tri-n-amyl phosphate (TAP) as modifiers to provide a comparison between these two modifiers systems (Suresh et al., 1999). The effect of concentration of TAP as modifier for the extraction of Nd(III) by 0.2 M OPHICMPO was studied. The extraction of Nd(III) by TAP/n-dodecane in the absence of the extractant was also investigated and the results are reported. Tachimori et al. (2002) studied N, N,N,N-Tetraoctyl-3-oxapentanediamide (TODGA) in ndodecane solvent to clarify the characteristics of third phase formation in extraction of lanthanides(III) and to modify the solvent. Addition of N,N-dihexyloctanamide (DHOA) of more than 0.5 M to the solvent as modifier eliminated the third phase in the extraction of Nd(III). The modified solvent of 0.1 M or 0.2 M TODGA with 1 M DHOA exhibited a satisfactorily high metal loading and slightly lower extractability for Nd(III) and moderately higher extraction of HNO3 than neat TODGA. In the TRUEX process, CMPO is used as an extractant and TBP as a phase modifier. Sano et al. (2000) studied the coordination properties of light lanthanides (Ln) complexes in the CMPO/TBP systems by NMR measurements. The authors clarified the structure of the Ln complexes, their changes with CMPO concentration and the effect of TBP on the Ln complexes in such systems. Zhao et al. (2004) investigated the extraction behaviour of Ce(IV), Th(IV) and some RE(III), using di (2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP) in heptane as extractant and reported that extractability varies in the order: Ce(IV) N Th(IV) RE(III). Therefore, it was possible to find the appropriate conditions under which Ce(IV) can be effectively separated from Th(IV) and RE(III). In a previous work, a modified leaching and extraction process of uranium from hydrous oxide cake of Egyptian monazite was developed (El-Nadi et al., 2005) and later thorium was separated from rare earths by a countercurrent extraction system using a mixer settler contactor (Ali et al., in press). The present work is directed to study the separation of cerium(IV) from hydrous oxide cake after separation of uranium and thorium. In this respect, the extraction of Ce(IV) from nitric acid solution by

Aliquat-336 dissolved in kerosene was investigated. Different alcohols were added to the organic phase as modifiers and studied in detail. The results were evaluated and correlated to the physical constants of the investigated alcohols and the optimum extraction conditions were used for the extraction of Ce(IV) from monazite cake. 2. Experimental 2.1. Chemicals and reagents All chemicals and reagents used were analytical reagent grade. Ammonium ceric nitrate, Aliquat-336 and 1butanol were Merck products. Nitric acid, sodium bromate, 1-hexanol, 1-heptanol and 1-octanol were obtained from BDH. 1-nonanol was supplied from Reanal, while kerosene (non-aromatic) was supplied by Misr Petroleum Ltd. Company. 2.2. Procedure Cerium(IV) was kept in the tetravalent state by dissolving a certain weight of ammonium ceric nitrate giving 1 g Ce/L in 4 M HNO3 containing 0.3 M sodium bromate (Moore, 1969). The solution was stable for several hours and this concentration was used throughout the present work in all experiments unless otherwise stated. Cerium(IV) in the aqueous phase was spectrophotometrically determined by formaldoxime method (Marczenko, 1979) using Shimazu UV-Visible 160A spectrophotometer. Before extraction, the chloride form of Aliquat-336 was converted into nitrate form by shaking equal volumes of Aliquat-336/kerosene/alcohol solution with 1 M HNO3 several times for 5 min (Moore, 1969). The extraction procedure was performed by shaking equal volumes (5 ml) of the aqueous and organic phases in stoppered glass tubes for 30 min using a thermostated shaking water bath adjusted at 25 C. Preliminary experiments showed that a contact time of 15 min is sufficient to reach the extraction equilibrium. To determine the cerium concentration, known aliquot volumes were taken from the aqueous phase before and after extraction for spectrophotometric assay. The distribution ratio, D, was calculated from the relation: D Co C C 1

Where, Co is the original metal concentration in the aqueous phase before extraction and C is the metal concentration in the aqueous phase after extraction.

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3. Results and discussion Aliquat-336 dissolved in kerosene was used as extractant for Ce(IV) from nitrate medium. The alcohols used as phase modifier were 1-butanol, 1-hexanol, 1-heptanol, 1-octanol and 1-nonanol. Two concentrations of alcohols used through this work; namely, 10 vol.% and 20 vol.%. 3.1. 10% alcohol system 3.1.1. Effect of nitric acid concentration The influence of nitric acid concentration on the extraction of 1 g/L Ce(IV) was investigated in the range 0.54 M using 0.5 M Aliquat-336 in kerosene containing 10 vol.% of the alcohol modifiers. The relations between the nitric acid concentration in the aqueous phase and the respective extraction percent are represented in Fig. 1. Increasing nitric acid concentration was found to increase the extraction of cerium through the investigated range. This behaviour differs from that obtained by (Moore, 1969) who found that the extraction of Ce(IV) by Aliquat336 in xylene reached a maximum value at 2 M HNO3, then decreased with further increase in nitric acid concentration. This disagreement may be attributed to the difference in the diluent used. On the other hand, results for 1-butanol are not presented for the 10 vol.% alcohol system. The 10 vol.% 1-butanol concentration was insufficient to overcome third phase formation. 3.1.2. Effect of H+ concentration The effect of hydrogen ion concentration at 2 M [NO3 ] on the extraction of Ce(IV) from mixtures of HNO3 + NaNO3 by 0.5 M Aliquat-336 in kerosene with

Fig. 2. Effect on Aliquat-336 concentration dissolved in kerosene and 10% 1-hexanol, 1-heptanol, 1-octanol or 1-nonanol on the extraction of 1 g/L Ce(IV) from 2 M HNO3 solution at phase ratio (O/A) = 1 and 25 C.

the different alcohols was investigated in the range 0.1 to 2 M. The increase in H+ concentration in the investigated range had almost no influence on the extraction under the used experimental conditions. 3.1.3. Effect of Aliquat-336 concentration The effect of the variation of Aliquat-336 concentration within the range 0.10.7 M on the extraction of Ce(IV) from 2 M nitric acid was studied. It was found that the extraction of Ce(IV) increased by increasing Aliquat-336 concentration in the presence of 10% alcohol. The slopes of loglog linear relationships between the extractant concentrations with the corresponding distribution ratios were found to be around two in the investigated system (Fig. 2), which indicate the participation of two molecules of Aliquat-336 in the extracted Ce(IV) species. 3.1.4. Effect of nitrate concentration Increasing the nitrate concentration from 2 to 4 M at a given acidity (2 M) using 0.5 M Aliquat-336 in kerosene in presence of the investigated alcohols was found to decrease the extraction of Ce(IV). Plotting the nitrate concentration against the distribution ratio (D) as a log log relation (Fig. 3) gives a straight line with slope equals to about negative two. This slope indicates the release of two nitrate ions during the extraction reaction. 3.1.5. Effect of phase ratio The increasing tendency of the extraction of cerium from 2 M HNO3 solution by 0.5 M Aliquat-336 in kerosene in the presence of 10% alcohol was almost the same for all alcohol modifiers used when organic/ aqueous phase ratio increased from 1/3 to 3/1 (Fig. 4).

Fig. 1. Effect of nitric acid concentration on the extraction of 1 g/L Ce (IV) by 0.5 M Aliquat-336 dissolved in kerosene and 10% 1-hexanol, 1-heptanol, 1-octanol or 1-nonanol at phase ratio (O/A) = 1 and 25 C.

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Fig. 3. Effect of nitrate ion concentration on the extraction of 1 g/L Ce (IV) by 0.5 M Aliquat-336 dissolved in kerosene and 10% 1-hexanol, 1-heptanol, 1-octanol or 1-nonanol at phase ratio (O/A) = 1 and 25 C.

From the above results, it is clear that as the carbon chain number of the modifier increases and the dielectric constant decreases from hexanol to nonanol, the extraction of cerium(IV) increases. 3.2. 20% alcohol system The studied parameters in the previous system are also considered here in this system and the results are tabulated instead of represented graphically to avoid repetition. Thus, as nitric acid concentration increased from 0.5 to 4 M, the extraction percent of Ce(IV) by 0.5 M Aliquat-

336/kerosene/20 vol.% alcohol increased, Table 1. The trend of increase is the same for all alcohols except in case of butanol which shows a decrease in the extraction of Ce (IV) beyond 3 M HNO3. This may be due to the short chain of butanol and hence its large solubility in aqueous medium compared to other alcohols. The hydrogen ion concentration change was found to have a negligible effect on the extraction of cerium(IV) when extracted from nitric acid medium of 0.12 M [H+] by 0.5 M Aliquat-336/ kerosene/20% alcohol system. The change of extractant concentration was found to increase the extraction percent of Ce(IV) from 2 M HNO3 solution as observed in Table 1. The slopes of the straight lines obtained when the distribution ratio was plotted against the Aliquat-336 concentration were found to equal to about two indicating the participation of two Aliquat-336 molecules in the extracted species. On the other hand, the extraction percent and hence the distribution ratio of Ce(IV) were found to be inversely proportional to the increase in the nitrate ion concentration through the range 24 M, Table 1. The negative slope of two means the liberation of two nitrate ions through the reaction of extraction.
Table 1 Extraction percent values of 1 g/L Ce(IV) extraction by Aliquat-336 dissolved in kerosene and 20 vol.% alcohol as modifier under different parameters at 25 C Studied Extraction percent (%E) parameter, 1-Butanol 1-Hexanol 1-Heptanol 1-Octanol 1-Nonanol M HNO3 0.5 1 2 3 4 Aliquat 0.1 0.2 0.3 0.4 0.5 0.7 Nitrate 2.0 2.5 3.0 4.0 O /A a 0.33 0.5 1.0 2.0 3.0
a

21.75 35.5 52.3 65.6 57.6 6.1 20.0 35.5 48.4 59.8 74.5 59.8 47.9 39.7 25.9 21.6 38.6 52.3 66.3 71.8

12.3 21.9 42.5 67.2 73.5 4.6 15.9 28.0 44.4 53.3 71.0 53.3 40.5 30.1 20.0 26.3 36.1 42.5 54.7 57.6

38.3 56.7 68.0 80.3 86.8 6.5 22.5 38.3 49.2 60.8 75.8 60.8 47.4 39.4 27.0 26.8 38.8 68.0 70.0 71.5

24.8 35.4 68.8 72.0 88.6 8.9 25.9 43.8 55.5 68.4 79.0 68.4 58.0 47.1 35.5 24.6 40.1 68.8 69.0 71.0

26.7 45.1 73.4 90.9 91.7 10.31 29.1 46.8 60.6 71.8 81.8 71.8 63.6 53.3 40.8 24.7 44.3 72.4 74.5 78.0

Fig. 4. Effect of phase ratio (O/A) on the extraction of 1 g/L Ce(IV) by 0.5 M Aliquat-336 dissolved in kerosene and 10% 1-hexanol, 1heptanol, 1-octanol or 1-nonanol from 2 M HNO3 solution at phase ratio (O/A) = 1 and 25 C.

O/A is unitless (organic/aqueous) ratio.

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The effect of phase ratio is also illustrated in Table 1 and the trend of increase is almost the same as obtained in the previous 10% alcohol system. 3.3. Extraction equilibrium Based on the preceding results, the extraction equilibrium of Ce(IV) by Aliquat-336 in kerosene from nitrate medium can be written as:
CeNO3 2 6 P P 2 R3 CH3 NNO3 W R3 CH3 N2 CeNO3 6 2NO 3

Where R3CH3NNO3 = Aliquat-336 and the bars refer to the species in the organic phase. The extraction constant, Kex, for the above reaction can be expressed as: Kex
2 R3 CH3 N2 CeNO3 6 NO 3 2 CeNO3 2 6 R3 CH3 NNO3 2 DNO 3

Fig. 5. Relation between the average extraction constant of Ce(IV) extraction by 0.5 M Aliquat-336 dissolved in kerosene and 10% or 20% alcohol from 2 M HNO3 solution at phase ratio (O/A) = 1 and the alcohol carbon atom or dielectric constant.

Kex

R3 CH3 NNO3 2

The average values of the calculated extraction constant for Ce(IV) extraction at different Aliquat-336 and nitrate concentrations are illustrated in Table 2. As observed from this table, the extraction constant in general increases with decreasing the dielectric constants (Dean, 1985) of the alcohols and the values related to 10% alcohol-system are better than 20% system. Dipole moment values seem not to be correlated well with Kex values. The tabulated data are represented graphically in Fig. 5. As shown in this figure, the extraction constant values linearly increase with the number of carbon atoms of alcohols and decrease with their dielectric constant values. Butanol was deviated from the linear relation due to its relatively high solubility in the aqueous medium. Therefore, one could predict the value
Table 2 Extraction constants of Ce(IV) (1 g/L) from 2 M HNO3 extracted by Aliquat-336 in kerosene using different alcohols as modifiers Alcohol modifier 1-Butanol 1-Hexanol 1-Heptanol 1-Octanol 1-Nonanol Extraction constant (Kex) 10% 22.95 1.10 36.72 1.35 42.53 1.40 47.37 1.40 20% 23.85 0.81 17.81 1.11 25.07 1.22 34.25 1.33 41.46 1.36 Dipole moment () 1.66 1.55 Not found 1.68 Not found Dielectric constant () 17.50 13.30 11.32 10.34 8.60

of extraction constant of higher alcohols if used for the extraction of cerium(IV) under the same experimental conditions. Thus, the optimum concentration of the alcohol is 20%, giving appropriate solubilization of the extractant in the mixed diluent. Higher distribution ratios are obtained in the presence of 1-butanol compared to 1hexanol for example, which, however, solubilizes the extractant less effectively than other alcohols. 4. Effect of temperature The increase of temperature in the range 1545 C decreased the extraction of cerium when extracted by 0.5 M Aliquat-336 in kerosene with the different modifiers from 2 M HNO3 solution. The Van't Hoff equation (Kreyszig, 1979) used to calculate the enthalpy change (H) associated with the extraction of this metal is: lnKex DH =RT C 5

Where, R is the universal gas constant (8.314 J mol 1 K 1) and C is a constant. The plot of lnKex vs. 1 / T for the extraction of the metal gave straight lines (Fig. 6). The negative values of the enthalpy change for the extraction calculated from the slopes of the linear relations indicate the exothermic nature of the extraction process for all alcohol systems, Table 3. The free energy change (G) and the entropy

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Fig. 6. Effect of temperature on the average extraction constant of Ce (IV) extraction from 2 M HNO3 medium by 0.5 M Aliquat-336 dissolved in kerosene and 10% or 20% 1-butanol, 1-hexanol, 1heptanol, 1-octanol or 1-nonanol at phase ratio (O/A) = 1.

Fig. 7. Correlation of H and S of cerium(IV) extraction by 0.5 M Aliquat-336 dissolved in kerosene and 20% alcohol from 2 M HNO3 solution through the temperature range 1545 C at O/A = 1.

change (S) can be calculated using the following equations: DG RT lnKex DS DH DG=T 6 7

As shown in Table 3, the negative values of G for the extraction of cerium(IV) by Aliquat-336 from nitrate medium mean that the extraction reaction occurs spontaneously in all cases. The results show that increasing the chain length of the alcohols decreases the values of G and S which indicates that the system gets more spontaneous and more ordered in the direction: 1-butanol N 1-hexanol N 1-heptanol N 1-octanol N 1-nonanol. Such behaviour can suggest that water plays a role in the extraction system. In this concern, the dielectric constant values decrease for the different alcohols investigated with subsequent decrease in possible extraction of water with the extracted species. As a result, the ordering of the system with increasing the

chain length could be justified. Furthermore, the relation between H and S for the different modifiers used is linear as shown in Fig. 7. This indicates that entropy is dependent on the enthalpy change in the investigated system. It is known that (Rydberg et al., 1992), in organic solvents, solvation generally is weaker than for aqueous solutions. As a consequence, the desolvation reaction would result in small values of Hs and Ss (for solvation). Therefore, Hc and Sc (for combination of the metal and ligand) are Hs and Ss, respectively. This suggests that Hreaction is often negative, whereas Sreaction may be positive or negative, which is consistent with the values obtained and presented in Table 3. 5. Stripping investigations Stripping studies were carried out on organic solution consisting of 0.5 M Aliquat-336 in kerosene containing 20% octanol after extraction of 1 g/L Ce(IV) from 2 M HNO3 + 0.3 M NaBrO3 solution. The effect of water,

Table 3 Thermodynamic parameters for the Ce(IV) (1 g/L) extraction system using 0.5 M Aliquat-336 in kerosene using different alcohols as modifiers through the temperature range 1545 C Alcohol modifier 1-Butanol 1-Hexanol 1-Heptanol 1-Octanol 1-Nonanol H, kJ mol 1 10% 19.6 1.3 5.6 0.4 10.4 0.6 5.5 0.4 20% 51.0 2.3 47.3 2.7 53.5 2.9 65.3 3.7 79.0 4.5 G, kJ mol 1 10% 7.8 0.2 8.9 0.7 9.3 0.7 9.6 0.8 20% 7.9 0.5 7.1 0.3 8.0 0.5 8.8 0.7 9.2 0.7 S, J mol 1 K 1 10% 39 1 11 1 4 1 14 1 20% 144 2 135 3 153 3 189 2 234 2

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Table 4 Stripping of Ce(IV) with water, different concentrations of mineral acids and other reagents after extraction with 0.5 M Aliquat-336 in kerosene containing 20% 1-octanol at O/A = 1 and 25 C Stripping agent H2O HCl, 1 M H2SO4, 1 M HNO3 0.001 M 0.01 M 0.1 M 1M NaNO2 0.05 M 0.1 M NaOH, 0.1 M Stripping percent (%S ) 35.5 58.1 66.0 83.2 72.0 68.9 27.2 42.1 67.7 50.6

Subsequently, dilute nitric acid (0.001 M) can be considered as a promising stripping agent as it leads to better stripping of cerium. Two stripping steps were found sufficient to recover most of cerium(IV) from the loaded organic phase. 6. Separation of cerium from monazite cake The aforementioned results of cerium extraction were used to separate cerium from monazite sand. Egyptian monazite was found to contain uranium, thorium and rare earths in respective concentrations of 0.54, 5.26 and 54.70 wt.% (Saleh, 1966; El-Nadi et al., 2005). The rare earth elements in Egyptian monazite are essentially La, Ce and Nd, and the average concentration of cerium was determined as 24.89 wt.% using total X-ray fluorescence (TXRF) technique on a solution obtained from a fusion of two monazite samples with lithium metaborate or sodium pyrosulfate followed by dissolution in 1 M HNO3 (El-Nadi, 2002). In a previous work, a modified leaching and extraction process of uranium from hydrous oxide cake of Egyptian monazite was developed (El-Nadi et al., 2005). In this process, a monazite sample (25 g) was ground to mesh size 200270, then digested by boiling with sodium hydroxide (50%) for 4 h at 140 C. The

mineral acids as well as sodium nitrite and sodium hydroxide on the stripping of metal ions from the loaded organic solvents was investigated and the results are given in Table 4. The low stripping value obtained by water may be due to the formation of weak hydrolytic species of Ce(IV) (Baes and Mesmer, 1976), which cannot completely strip Ce(IV) from the organic phase. At slightly acidic solution, formation of cationic cerium in the acid medium prevails and stripping occurs easily.

Fig. 8. Flowchart of separation of cerium from Th/RE cake resulting from opening and digestion of monazite sand.

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Fig. 9. Absorbance spectra of Ce(IV) and Nd(III) in aqueous nitrate medium (a) and in organic phase (b) before and after extraction by 0.5 M Aliquat-336 in kerosene/octanol at O/A = 1 and 25 C.

was reduced to its trivalent state by standing the solution for 1 h after cooling. Thorium was extracted from above mixture by 2.5% Aliquat-336 in kerosene in a phase ratio (O/A) 1.5:1, stripped by shaking with 5 M HCl solution in a phase ratio 1:1 and precipitated as hydroxide by addition of ammonium hydroxide giving 1.212 g Th (Ali et al., in press). Based on the results of the present work, Cerium(III) was oxidized to the tetravalent state by addition of sodium bromate, extracted by 25% Aliquat-336 in kerosene containing 20% 1-octanol at O/A = 1 for three extraction stages and stripped by shaking the organic phase with 0.001 M HNO3 solution at the same phase ratio in two steps, then precipitated as hydroxide by addition of ammonia. The weight of cerium hydroxide was found to equal to 5.75 g indicating a recovery quantity of about 96%. The resulted solution after removal of thorium was scanned spectrophotometrically (Fig. 9a). Before extraction, the peaks related to Ce(IV) and Nd(III) (as example of trivalent rare earths) are found in the figure. After extraction, Ce(IV) peak decreased markedly while Nd (III) peaks had the same absorbance indicating the poor extraction of Nd(III) under these conditions. On the other hand, Fig. 9b represents the Ce(IV) peak in the organic phase referring to the purity of cerium and the efficiency of the method used. 7. Conclusions Ce(IV) can be extracted by Aliquat-336 dissolved in kerosene containing 10% or 20% of alcohol as phase modifier from nitric acid solution. Increasing the acid concentration increased the extraction while the change in H+ concentration had almost no effect on the extraction. Extraction percent increased with Aliquat-336 concentration and slope analysis in the different investigated systems indicated that two extractant molecules participate in the extracted metal species. Stripping of Ce(IV) from loaded Aliquat-336/kerosene/alcohol solution was successfully performed using diluted nitric acid. After complete digestion of Egyptian monazite sample and separation of uranium and thorium, the rare earths fraction was dissolved in nitric acid. Cerium was oxidized to Ce(IV) by sodium bromate, extracted with Aliquat-336/kerosene/octanol system, stripped by diluted HNO3 and finally precipitated as hydroxide using ammonia. The recovery of 96% of Ce(IV) indicates the efficiency and the applicability of the proposed process for separation of cerium from monazite sand.

solution was diluted to NaOH concentration of 20% and boiled again at 105 C for another hour, then filtered at 80 C. The filtrate can be recycled for recovery of sodium phosphate and excess sodium hydroxide whereas the precipitate was washed with water and dried. The dried precipitate, which consists mainly of thorium and rare earths as well as uranium hydrous oxides, was leached several times with alkaline solution (total 150 ml) composed of 40% sodium carbonate (1 M), 50% sodium hydroxide (1 M), and 10% hydrogen peroxide (30%) to separate uranium. The solution was filtered and the filtrate containing uranium was diluted (1 + 3 with water) and shaken with 5% Aliquat-336 in kerosene containing 5% octanol in one stage solvent extraction (1:1 phase ratio) to recover uranium. The resulted uranium which is mainly as tricarbonato complex was precipitated as hydroxide by decreasing pH of the solution by addition of nitric acid giving 0.123 g of uranium. As shown schematically in Fig. 8, thorium and rare earths precipitate was dissolved in 4 M nitric acid (100 ml) with heating at 60 C for 1 h and cerium(IV)

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Acknowledgement The author would like to express his deep thanks to Prof. Dr. H.F. Aly and Prof. Dr. J.A. Daoud for their valuable support and continuous guidance through this work. References
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