Minerals Engineering 20 (2007) 694700 This article is also available online at: www.elsevier.

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Simulated small-scale pilot plant heap leaching of low-grade oxide zinc ore with integrated selective extraction of zinc
Qin Wen-qing *, Li Wei-zhong, Lan Zhuo-yue, Qiu Guan-zhou
School of Resource Processing and Bioengineering, Central South University, Changsha 410083, China Received 9 July 2006; accepted 5 January 2007 Available online 21 February 2007

Abstract The leaching of low-grade oxide zinc ore and simultaneous integrated selective extraction of zinc were investigated using a small-scale leaching column and laboratory scale box mixer-settlers. Di-2-ethythexyl phosphoric acid (D2EHPA) dissolved in kerosene was used as an extractant. The results showed that it was possible to selectively leach zinc from the ores by heap leaching. The zinc concentration of the leach liquor in the rst leachingextraction circuit was 32.57 g/L, and in the 16th cycle the zinc concentration was 8.27 g/L after the solvent extraction. The leach liquor was subjected to solvent extraction, scrubbing and selective stripping for the enrichment of zinc and the removal of impurities. The pregnant zinc sulfate solution produced from the stripping cycle was suitable for zinc electrowinning. 2007 Elsevier Ltd. All rights reserved.
Keywords: Zinc; Low-grade zinc oxide ores; Heap leaching; Solvent extraction; Di-2-ethythexyl phosphoric acid (D2EHPA)

1. Introduction Zinc oxide ore is an important source of zinc metal after zinc sulde ores. With the escalating depletion of zinc sulde ores, the zinc-bearing minerals such as willemite (Zn2SiO4), hemimorphite [Zn4(Si2O7)(OH) H2O] and smithsonite (ZnCO3), etc., have become an important source of zinc (Abdel-Aal, 2000). In China, zinc oxidized ores are relatively abundant, and are mainly founded in south-west and north-west China, in places such as Yunnan, Sichuan, Guangxi and Gansu provinces, etc. (Duan and Luo, 2000). Many studies have been done on concentration of zinc oxide ores, yet very little progress has been made. Usually zinc oxide ores are concentrated by otation or gravity, where the metal recovery is low and the operating cost is high (Duan and Luo, 2000). Zinc oxide ores can be treated by acidic leaching processes (Bodas, 1996). However, zinc is dissolved following the dissolution of many other metals

Corresponding author. E-mail address: csuqwq@hotmail.com (W.-q. Qin).

such as Fe, Ca, Mg, and SiO2, etc. As a result, the acid consumption is high, and complex purication processes are required. The large quantity of silica may transform into a gel and prevent the separation of zinc sulfate from the slurry. Furthermore acidic leaching processes are uneconomic for treating low-grade zinc oxide ores. Zinc oxide ores can also be treated by pyrometallurgical process (Chen and Qu, 1998). The high-grade zinc concentrate is produced from low-grade ores by volatilization techniques at high temperature in blast furnaces or Waelz-type kilns, and then subjected to a hydrometallurgical process. Though the pyrometallurgical process can treat low-grade ores, it is not acceptable because of heavy pollution and high capital investment (Choi et al., 1993). Solvent extraction is regarded as a highly eective technique of separation and purication, which has been used in the extraction of gold, copper, cobalt and nickel, etc. (Qiu et al., 2002, 2003; Hsu and Harrison, 1995). The extraction of zinc by various reagents including di-2-ethylhexyl phosphoric acid was studied in detail by Rice and Smith (1975). Conventional zinc extractants belong to the group of acidic reagents. Alkylphosphoric acids have been used for many years, and among them

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di-2-ethythexyl phosphoric acid (D2EHPA) is the extractant most used (Bart et al., 1992; Forrest and Hughes, 1978; Sato et al., 1978). The recovery of zinc from the leach liquors of the CENIM-LNETI process by solvent extraction with di-2-ethylhexyl phosphoric acid is performed by Amer and Luis (1995). Kongolo eciently performed the removal of zinc and manganese from industrial cobalt sulphate solutions by solvent extraction and they also investigated the recovery of Cobalt and zinc from copper sulphate solution by solvent extraction with D2EHPA, which has been successfully used to separate cobalt and zinc into their respective solutions (Kongolo et al., 2000, 2003). The solvent extraction of zinc and cadmium from phosphoric acid solutions using di-2-ethylhexyl phosphoric acid (D2EHPA) in treated kerosene as diluent has been investigated by Mellah and Benachour (2006). The dimerization constant of D2EHPA is about 106 in polar solvents and the equation of the dimerized form can be written in the following way: 2HR ! HR2 The mechanism of extraction by the D2EHPA and the nature of the formed metal complexes depend on several factors such as concentration of the metal cations, the nature of organic solvent, the acidity of the aqueous phase and the type of extracted cations (Pinipenko, 1974).

For zinc extraction with di-2-ethylhexyl phosphoric acid (D2EHPA) as extractant dissolved in aliphatic diluents, the equilibrium is given by the following scheme reactions (Mansur et al., 2002): Zn2 aq 1:5RH2 org ZnR2 RHorg 2H aq at the liquidliquid interface 2ZnR2 RHorg 2ZnR2 org RH2 org in the extract phase where RH represents the extractant species D2EHPA that acts like a liquid cationic ion exchanger, and subscripts (aq) and (org) refers to aqueous and organic species, respectively (Mellah and Benachour, 2006). Solvent extraction may be used for the selective extraction of impurities or valuable metal from process streams into an organic phase. The loaded organic is often stripped with an acid (aqueous) solution to back extract the Zn2+. The organic is regenerated, reconditioned and recycled. In this paper, the solvent extraction of zinc from leach liquor using D2EHPA in treated kerosene as diluent has been investigated. It presents the results of a study carried out to determine if solvent extraction could be used to selectively extract zinc from the leach liquor of low-grade zinc oxide ore, which was treated in a large diameter column (4 m high 0.2 m diameter) simulating a unit cell of a commercial operation. The organic extractant used was

Column Leaching of zinc oxidized ore

Leach liquor Organic feed Organic recycling Scrubbing water waste

Solvent extraction

Raffinate

Scrubbing

Scrubbing water

Stripping

H2SO4

Organic

Pregnant zinc electrolyte

HCl

Stripping

Organic HCl H2SO4

Stripping

H2SO4

Fig. 1. Schematic diagram of the leach-solvent extraction process.

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di-2-ethylhexyl phosphoric acid (D2EHPA). The pregnant zinc sulfate solution produced from the stripping cycle was suitable for electrowinning. Fig. 1 shows the schematic diagram for the leaching of low-grade zinc oxide ore, the zinc solvent extraction process in this paper. 2. Experimental 2.1. Zinc oxide ore The zinc oxide ore was obtained from Gaofeng mine in Guangxi province in China, whose chemical composition is given in Table 1. The Pb, Cd, Cu, Ni, Ag and Co content were analyzed by an atomic absorption spectrophotometer (Japan, Shimadzu AA-6800), and the Zn, Fe, MgO, CaO, Mn, Al2O3 were analyzed by titrimetric analysis. The S was analyzed by combustion analysis. The As was analyzed by colorimetric analysis and the SiO2 were analyzed by gravimetric analysis. Microscopic examination in thin slides of the groundmass showed that the zinc minerals are mainly willemite (Zn2SiO4), hemimorphite [Zn4(Si2O7)(OH) H2O] and smithsonite (ZnCO3), and gangue minerals are quartz, gypsum, dickite, and sericite (ne grained mica) in both crystalline and microcrystalline forms. Table 2 shows the mineral composition. 2.2. Column leaching Leaching of zinc oxide ore by sulfuric acid can be illustrated as ZnCO3 H2 SO4 ! ZnSO4 H2 O CO2 Zn4 Si2 O7 OH2 H2 O 4H2 SO4 ! 4ZnSO4 2SiOH4 2H2 O Zn2 SiO4 2H2 SO4 ! 2ZnSO4 SiOH4 1 2 3

reduce the dissolved silica and other impurities or make them precipitate in the leach residues. Column leaching was adopted for the sulfuric acid leaching of zinc oxide ores. The size distribution of the zinc oxide ore was 90% passing 20 mm and 42% passing 3 mm. The chemical analysis is shown in Table 1. The original concentration of H2SO4 in the lixiviant was 0.306 mol/L. The leach liquor was recycled without addition of acid after solvent extraction of zinc. 2.2.1. Column construction The experiments were carried out in a column reactor that was fabricated from 5 mm thick 304 L stainless steel. The column was 4 m high with an internal diameter of 0.2 m, and it stood in a shallow tank with a capacity of 0.1 m3, which collected the PLS solution draining from the column. The liquor level was maintained at a sucient height to provide a seal, forcing the air upwards through the column charge. Solution was applied to the surface of the column charge using a simple garden sprinkler head of the type used in drip irrigation systems. Support rock selection for use in column leaching process requires the rock be competent, low in carbonate and other acid-consuming minerals, and sized at 30 + 10 mm. A granite rock was sourced from a local supplier. Mineralogical analysis showed that the major minerals were quartz. Sizing was 80% passing 2530 mm with only 0.6% passing 10 mm. The rock contained <0.03% Zn, 1.7% Fe. Fig. 2 shows the schematic of the heap reactor. 2.2.2. Column operation The original concentration of H2SO4 was 0.306 mol/L. A tank with a capacity of 0.1 m3 was used to collect the PLS solution draining from the column. Leach liquor was sampled from this tank, and was analyzed to determine solution concentrations, metal dissolution and the acid balance by an atomic absorption spectrophotometer. Ore was coated onto the support rock by tumbling weighed batches. A layer of uncoated support rock,

With high acidity both the zinc leach rate and the zinc extraction rate increases. However, iron and silica are also dissolved in large quantities (Tang and Ouyang, 1998; Doepker and OConnor, 1990). Silica forms a gel, which decreases the ltration rate or even results in the collapse of the operation. Controlling the acidity of leaching can
Table 1 Chemical composition of the zinc oxide ore Element w/% Element w/% Zn 14.24 Mn 1.42 Pb 0.25 Al2O3 8.52 Cd 0.035 Co Mim. Cu 0.046 Ni 0.032 Fe 23.12 Ag 0.0028 MgO 1.35 S 2.55 CaO SiO2 3.64 36.29 As 0.23

Table 2 Minerals composition of the zinc oxide ore Mineral Willemite Hemimorphite Smithsonite Quartz Gypsum Composition 10.24 8.15 8.35 32.12 12.08 (%)

Fig. 2. Schematic of the heap reactor. (1) Peristaltic pump; (2) water bath; (3) mixer; (4) feed vessel; (5) liquid distributor.

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100 mm deep, was placed in the bottom of the column before the coated ore was loaded. The leach liquor was passed through the ore sample by gravity and re-circulated through a side loop with a peristaltic pump. In the leaching experiments, the column system was comprised of 100 kg of ore. For all of the tests the initial temperature and pH of the feed were 25 C and 1.2, respectively. Solution and ranate were fed to the top of the column from a feed container by means of a peristaltic pump at a rate of approximately 0.5 L/min, and collected at the base into the PLS stock tank by a pump controlled by a level sensor in the solution reservoir. The volume of liquid in the actual column was 80 L. From this and the ow rate, the apparent residence time was calculated to be about 160 min. The zinc from the PLS was recovered by solvent extraction with D2EHPA. Evaporation losses and sample removal were made up with water (pH 1.2) to a total circulation volume of 80 L per column. After leaching, liquor in the column was allowed to drain, and the column contents were then rinsed to remove residual zinc and other soluble species. The column charge was rinsed rst with dilute sulphuric acid solution (pH 1.2) followed by a water rinse. The column was then unloaded through the sampling ports, and the residue was separated from the support rock by wet screening. The residue was ltered, dried, and prepared for nal chemical analysis with similar chemical analysis methods used for zinc ore (Section 2.1). 2.3. Extraction and stripping processes Di-2-ethylhexyl phosphoric acid was obtained from Tianjing Chemistry Reagent Factory in China. It had a purity of 95%. Kerosene (260#) was obtained from Sinopec Shanghai Gpc Oil Renery in China and distilled to collect the fraction distilling over 260 C. It was mostly aliphatic in nature. The pH-extraction isotherms of zinc, calcium, copper, cadmium, cobalt and nickel were determined by

shakeout test at dierent equilibrium pH values. The metal concentration in aqueous solution was 3 g/L separately, which was prepared with AR grade sulfate, and was each studied separately. Extraction experiments were carried out in mechanically agitated beakers. The solution was agitated by a mechanical stirrer with a constant stirring rate. After shaking beakers for 10 min, the organic phase was separated from the aqueous phase. The pH of the aqueous solution was adjusted to the desired value by adding a small amount of HNO3 or NaOH. After phase disengagement, the aqueous phase was separated and its equilibrium pH was measured with a pH meter. The D2EHPA concentration was 10%, the phase ratio (VO/VA) was 1:1, and the contact time was 10 min. Fig. 3 shows the schematic diagram for the zinc solvent extraction process. The extraction-stripping process of zinc sulphate with D2EHPA had been studied at laboratory scale according to the following operating variables: pH of the aqueous phase, concentration of D2EHPA, equilibration time and O/A volumetric ratio (Qin et al., 2003). The D2EHPA concentration was about 30% v/v diluted in a kerosene-type diluents, the phase ratio (VO/VA) was 1.5:1, and the contact time was 5 min. The concentration of H2SO4 in the stripping aqueous feed is 1.53 mol/L. The mixer-settler cascade used in this work was composed of box-type mixer-settlers made of Teon with similar internal arrangement and dimension (width = 860 mm, depth = 250 mm and height = 500 mm). The active volume of one mixer-settler or stage was 6.0 L, while the ratio of the mixer and settler volumes was 1:4 (1.2 and 4.8 L, respectively). The stirring speed used was 1200 rpm. The connection between mixer and settler units was made by a central hole. Each mixer unit was provided with a pump-mixer impeller made of Teon. The mixer-settlers were tightly connected into three sections of two stages each, one for extraction, one for scrubbing and other for stripping of zinc. The residence time of each phase in the mixer was 5 min, so the ow rate for the feed and solvent streams

Organic feed

E1

E2
Leach liquor

SB1

SB2
Scrubbing water

Scrubbing water waste

Raffinate

S1

S2

S3

S4
HCl

S5

S6

H2SO4 Pregnant zinc electrolyte HCl, FeCl3 H2SO4

H2SO4

Fig. 3. The schematic diagram for the zinc solvent extraction process.

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was 120 mL/min in the extraction section, and 30 mL/min for the stripping solution stream in the stripping section. When the zinc loaded organic was stripped by sulfuric acid, zinc transfers from organic phase to aqueous phase and iron(III) remains in the organic phase, which is directly stripped by concentrated hydrochloric acid in two-stages. After the iron(III) is removed, the organic phase is again stripped by sulfuric acid in two-stages. A similar mixer-settler cascade was used for stripping. It was composed of box-type mixer-settlers that were connected into two sections of two stages each, one for hydrochloric acid stripping and other for sulfuric acid stripping. The active volume of one mixer-settler was 6.0 L while the ratio of the mixer and settler volumes was 1:4. 3. Results and discussion 3.1. Column leaching of zinc oxidized ores In these experiments, the column was set up initially with pH 1.2 medium, but no pH control was exercised during the experiment. And the leach liquor was recycled without adding compensating acid after the solvent extraction process. After about 16 days, solution pH level for the experiment was typically about pH 1.6. Zinc extraction from the column was determined from solution assays, mass of concentrate lled and the initial head grade, as well as on the basis of assays of the residual solids. The extractions of zinc, iron and silica as a function of time are shown in Fig. 4a and b, respectively. The results of column leaching are shown in Fig. 4. In the 16th day (cycle) the recovery of zinc was above 95% (Fig. 4a). It can be seen in the 16-cycle closed circuit leaching, that the pH of solution where less iron and silica were extracted was from pH 1 to 2. The recovery of iron and silica were 0.6% and 2.4%, respectively. From Fig. 1, some leach liquor was recovered by solvent extraction, and the ranate was recycled back to leaching. So the zinc extraction % values become lower. The chemical components of the leach liquor were analyzed by an atomic absorption spectrophotometer (Japan, Shimadzu
100 80 Recovery/% 60 40 20 0

AA-6800). The results are shown in Tables 3 and 4 respectively, when the leach time is one or 16 days. The zinc content was between 12 g/L and 33 g/L, and iron; calcium and silica content were lower than 0.40, 1.20 and 3.00 g/L respectively. The other impurities such as copper, cadmium, nickel, antimony and arsenic, etc., which are deleterious to zinc electrowinning, were at very low level. Hence, the leach liquor obtained from column leaching was suitable to the next process. Compared with agitation leaching, the leaching time of column (heap) leaching is longer. In this case the optimum recovery of zinc was observed after 10 days. The reasons are, the particle size of ores is relatively larger and the acidity of lixiviant is moderate, which decreases the speed of leaching. However, heap leaching of zinc oxide ores has some advantages, such as low acid consumption and low dissolved impurities. Above all, the ltration process is not needed in heap leaching, which is free from the negative eect of silica on solid liquid separation. In the leaching circuit, the accumulation of iron, silica and other impurities was not observed. This is probably because of the absorption in the accumulated ores. In fact, the pH value of the solution soaked into the ores particles increases while the leaching reaction occurs, which results in iron and silica precipitating in the residues.

Table 3 Chemical components of leach liquor (leach time 1 day) Composition Content/(g/L) Composition Content/(mg/L) Zn 32.57 Cu 84.34 Fe 0.38 Cd 0.85 SiO2 2.84 Ni 0.02 CaO 1.17 Sb 0.16 MgO 0.60 As 3.01

Table 4 Chemical components of leach liquor (leach time 16 days) Composition Content/(g/L) Composition Content/(mg/L) Zn 12.36 Cu 82.43 Fe 0.22 Cd 0.45 SiO2 2.45 Ni 0.02 CaO 1.00 Sb 0.11 MgO 0.43 As 2.84

3.0 2.5 Recovery/% 2.0 1.5 1.0 0.5 0 2 4 8 6 10 12 Leaching time/d 14 16 0.0
0 2 4

Si Fe

8 6 10 12 Leaching time/d

14 16

Fig. 4. Column leaching of zinc oxide ores (a) % recovery of zinc; (b) % recovery of iron and silica.

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3.2. Extraction and stripping The results for the extraction of various metals with 10% D2EHPA are shown in Fig. 5. At the equilibrium pH values about 2.0, the %zinc and calcium extraction were 90% and 70%, respectively, while both of the %copper and cadmium extraction were less than 5%, and the %cobalt and nickel extraction were negligible. Therefore, it may be seen that zinc is easily separated from copper, cadmium, cobalt and nickel at an equilibrium pH value of 2.0. However, zinc cannot be easily separated from calcium. At an equilibrium pH value of low than 1.5, Ca concentration will be around its saturation value under the conditions in the liquor owing to precipitation of gypsum on the bed. Low calcium was extracted than zinc. Fortunately, calcium at less concentration has no eect on zinc electrowinning. The solvent extraction process is shown in Fig. 3. One extraction process was carried out in each leaching circuit, and about 30 L leach liquor was used in each extraction process. The data for a closed loop leachingextraction circuit are shown in Table 5. The pH value of the extraction solution was less than 2.0, after zinc extraction the aqueous pH value decreases to about 1.0, so the ranate can be

recycled to leaching without the addition of acid, which reduces the acid consumption. The zinc concentration of the leach liquor in the rst leaching cycle was 32.57 g/L. From Fig. 1, some of the leach liquor was treated by solvent extraction, and the rainate is recycled back to leaching section. After the zinc extraction operation, a amount of zinc (about 8.27 g/l) is not extracted and remains in the ranate when an O/A ratio close to 1.5 is chosen. So the zinc concentration of leach liquor was decreased to 12.36 g/L in the 16th cycle. The co-extraction of impurity metals with D2EHPA is inevitable particularly at high concentrations. Therefore to obtain a pregnant solution with low contamination the loaded organic phase must be scrubbed to remove impurities. The scrubbing solution was zinc sulfate solution at a pH value of 1.5. To maintain the water balance, a high phase ratio (O/A) was necessary. It was found that the coextracted calcium and the entrainment of silica in loaded organic can be removed by scrubbing, and a phase ratio (O/A) of 10:1 was acceptable. Iron cannot be removed by scrubbing. Hence, zinc was separated from iron by selective stripping. The stripping is the reverse process of extraction, in which zinc transfers from organic phase to aqueous phase, the equation is as follow: ZnR2 2HRorg 2H ( 2H2 R2org Zn ) aq aq 4

100 80 Extracted / % 60 40 20 0 1 2 3 4 Equilibrium pH 5 Zn Ca Cu Cd Co Ni 6

Fig. 5. D2EHPA pH-extraction isotherms for six elements at 25.

Hence the aqueous phase in stripping must be of high acidity to keep the equilibrium move rightwards. The zinc loaded organic phase contained iron(III), and minim of calcium and silica. The percentage stripping increased with the increase of acidity. It was found the iron in the loaded organic phase was hardly stripped by 1.53 mol/L sulphuric acid. When the zinc loaded organic was stripped by sulfuric acid, zinc transfers from organic phase to aqueous phase while iron(III) remains in the organic phase.

Table 5 Closed loop of leachingextraction circuit Cycle pH Leach liquor 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1.84 1.80 1.70 1.75 1.60 1.82 1.63 1.68 1.55 1.63 1.58 1.49 1.56 1.70 1.55 1.60 Ranate 0.98 0.97 0.98 0.96 1.00 0.98 0.99 0.98 1.05 1.03 0.97 0.98 0.97 0.96 1.00 0.98 q(Zn)/g/L Leach liquor 32.57 28.62 24.87 22.49 22.20 24.80 22.79 21.23 18.18 17.87 16.02 14.94 13.64 13.95 12.63 12.36 Ranate 22.15 19.99 17.40 15.36 15.65 17.36 16.34 15.24 13.36 12.69 11.05 10.76 9.71 9.54 8.80 8.27 30.51 36.51 41.14 45.91 51.94 58.98 63.99 68.56 71.32 75.55 78.67 82.31 85.01 88.98 91.88 95.21 32.00 30.14 30.00 31.70 29.50 30.00 28.00 28.20 26.50 29.00 31.00 28.00 28.80 31.60 30.30 33.10 Recovery of zinc (%) Extraction of zinc (%)

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W.-q. Qin et al. / Minerals Engineering 20 (2007) 694700 Amer, S., Figueiredo, Luis, A., 1995. The recovery of zinc from the leach liquors of the CENIM-LNETI process by solvent extraction with di(2-ethylhexyl)phosphoric acid. Hydrometallurgy (37), 323337. Bart, H.H., Marr, R., Scheks, J., Koncar, M., 1992. Modelling of solvent extraction equilibria of Zn(II) from sulfate solutions with bis(-2ethylhexyl)phosphoric acid. Hydrometallurgy (31), 1328. Bodas, M.G., 1996. Hydrometallurgical treatment of zinc silicate ore from Thailand [J]. Hydrometallurgy 35 (1), 3749. Chen, Shi-ming, Qu, Kai-liu, 1998. On the treatment of oxidized zinc ore in lanping [J]. Yunnan Metallurgy 27 (5), 3135. Choi, W.K., Torma, A.E., Ohline, R.W., 1993. Electrochemical aspects of zinc sulphide leaching by Thiobacillus ferrooxidans. Hydrometallurgy 33 (1), 137152. Doepker, R.D., OConnor, W.K., 1990. Column leach study II. Heavy metal dissolution characteristics from selected leadzinc mine tailings. In: Proceedings of the Western Regional Symposium on Mining and Mineral Processing Wastes, May 30, Berkeley, CA, USA, pp. 6980. Duan, Xiu-mei, Lou, Lin, 2000. Review on present situation of the otation of oxidized zinc ore [J]. Mining and Metallurgy 9 (4), 4751. Forrest, C., Hughes, M.A., 1978. The separation of Zn from Cu by DZEHPA an equilibrium study. Hydrometallurgy (3), 327342. Gu, H., Chang, C.-M., et al., 2000. Preliminary design of a solvent extraction processing for the galvanic stripping of iron from D2EHPA [J]. Mineral and Metallurgical Processing 17 (1), 1622. Hsu, C.H., Harrison, R.G., 1995. Bacterial leaching of zinc and copper from mining wastes. Hydrometallurgy 37 (2), 169179. Kongolo, K., Mwema, D.M., Kyony, P.M., Mfumu, K., 2000. Manganese and zinc removal from cobalt sulphate solutions by means of solvent extraction. In: Proceedings of the 21st IMPC, July 2327, Rome, Italy. Kongolo, K., Mwema, M.D., Banza, A.N., Gock, E., 2003. Cobalt and zinc recovery from copper sulphate solution by solvent extraction. Minerals Engineering 16 (12), 13711374. Mansur, M.B., Slater, M.J., Biscaia Jr., E.C., 2002. Equilibrium analysis of the reactive liquidliquid test system ZnSO4/D2EHPA/n-heptane. Hydrometallurgy (63), 117126. Mellah, A., Benachour, D., 2006. The solvent extraction of zinc and cadmium from phosphoric acid solution by di-2-ethyl hexyl phosphoric acid in kerosene diluent. Chemical Engineering and Processing (45), 684690. Peng, Rong-qiu, 1992. Nonferrous Metal Extraction Metallurgy ManualZn, Cd, Pb, Bi [M]. Metallurgical Industry Press, Beijing. Pinipenko, A.T., 1974. Use of diphenyldabiocarbazone (dithizone) in analysis. III. Dissociation of thallium and cadmium dithizonate and zinc dithizonate. Zhur. Anal. Khim. (5), 1420. Qin, Wen-qing, Lan, Zhuo-yue, Li, Weizhong, 2003. Selective extraction of zinc from sulfate leach solution of zinc ore. Trans. Nonferrous Met. Soc. China 13 (6), 14351439. Qiu, Guan-zhou, Wu, Bo-zeng, Qin, Wen-qing, Lan, Zhuo-yue, 2002. Bioleaching of marmatite in high concentration of iron. Trans. Nonferrous Met. Soc. China 12 (6), 14351439. Qiu, Guan-zhou, Qin, Wen-qing, Lan, Zhuo-yue, Wu, Bo-zeng, 2003. Elective culture of bacteria in bioleaching on pyrrhotite. Trans. Nonferrous Met. Soc. China 13 (1), 175179. Rice, N.M., Smith, M.R., 1975. The recovery of zinc, cadmium and mercury(II) by solvent extraction. J. Appl. Chem. Biotechnol. 25, 379 402. Sato, T., Kawamura, M., Ueda, M., 1978. The extraction of divalent manganese, iron, cobalt, nickel copper and zinc from hydrochloric acid solutions by di(-2-ethylhexyl)phosphoric acid. J. Appl. Chem. Biotechnol. (28), 8594. Tang, Mo-tang, Ouyang, Min, 1998. Preparation of grade zinc oxide by using ammonium sulfate and ammonia complex leaching process. Zhongguo Youse Jinshu Xuebao/Chinese, Journal of Nonferrous Metals 8 (1), 118121. Yang, Jiao-yong, Liu, Da-xing, 1988. Extraction [M]. Metallurgy Industry Press, Beijing.

Table 6 Chemical components of pregnant solution q/(mg/L) Zn 68000.00 Ge 0.02 Fe 0.30 F <5.00 Cu 0.03 Cl <10.00 Mn 25.00 Ni 0.09 Co 0.03 Sb 0.02 Cd 0.11 As 0.04 CaO 0.48 SiO2 0.18 MgO 0.13 H2SO4 150.00

Though the iron concentration in the leach liquor was low, it accumulated in the recycle organic, which decreased the loading capacity of the extractant. Hence the recycle organic must be treated periodically to remove the iron(III). The conventional method is that the Fe3+ is directly stripped by strong hydrochloric acid. It was found that a strong acid solution (6 mol/L) was required to strip Fe3+ from D2EHPA (Gu et al., 2000). The long run test indicated that the performance of organic phase is stable in the recycle process and neither emulsion nor third phase formation was observed in the solvent extraction process. The chemical analysis of the pregnant zinc sulfate produced from solvent extraction is shown in Table 6. Zinc electrowinning is dependent on high hydrogen over potential on the zinc metal; a small quantity of impurities can result in the decrease of this hydrogen overpotential, which decreases the current eciency and the quality of cathode zinc. The impurities in the electrolyte were at levels as follows (mg/L): Cu < 0.10, Ni < 0.30, Co < 0.30, Fe < 10.00, Cd < 0.30, Sb < 0.03, As < 1.00, Ge < 0.03, Sn < 0.10, the electrolyte is suitable to electrowinning (Peng, 1992; Yang and Liu, 1988). It can be seen that the impurities in the pregnant solution are less than the above standards. 4. Conclusions This leaching-solvent extraction study has indicated the potential to selectively extract Zn from a low-grade zinc oxide ore. The zinc concentration in leach liquor in the rst leachingextraction circuit was 32.57 g/L, and in the 16th cycle the zinc concentration was 8.27 g/L after solvent extraction. The pregnant zinc sulfate solution obtained must be suitable to electrowinning. Therefore, the leach liquor was subjected to solvent extraction with D2EHPA as extractant, scrubbing and selective stripping for the enrichment of zinc and the removal of impurities. Fig. 1 shows the conceptual ow sheet for treating a typical a low-grade zinc oxide ore using the process described in this paper. Acknowledgements This work was aided by the National Natural Science Foundation of China (Project No. 50321402) and National Basic Research Program of China (2004CB619205). References
Abdel-Aal, E.A., 2000. Kinetic of sulfuric acid leaching of low-grade zinc silicate ore [J]. Hydrometallurgy 39 (2), 247254.