Solvent extraction of copper and ammonia from

ammoniacal solutions using sterically hindered β-diketone

HU Hui-ping(胡慧萍), LIU Chun-xuan(刘春轩), HAN Xue-tao(韩雪涛),
LIANG Qi-wen(梁啟文), CHEN Qi-yuan(陈启元)
School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
Received 13 November 2009; accepted 2 March 2010

Abstract: Extraction of copper and ammonia from Cu2+-NH3-Cl−-H2O solution using laboratorialy synthesized sterically hindered
β-diketone (4,4-dimethyl-1-(4-dodecylphenyl)-1,3-pentanedione) was studied. The effects of the copper concentration, the total
ammonia concentration, the initial pH in the aqueous phase, the phase ratio, and the temperature on copper extraction ratio and
ammonia extraction in loaded organic phase were investigated using this sterically hindered β-diketone. Under the conditions of
temperature 25 °C, contact time of two phases 30 min, phase ratio 1‫׃‬1, concentration of copper 3 g/L, concentration of total ammonia
3 mol/L, aqueous pH 8.43, and the concentration of β-diketone in organic phase 20% (volume fraction), ammonia in aqueous phase is
much lower to be extracted by organic phase (just 14.5 mg/L), while the extraction rate of copper is 95.09%.
Key words: ammoniacal solution; 4, 4-dimethyl-1-(4-dodecylphenyl)-1, 3-pentanedione; copper; solvent extraction

extraction−electrowinning” process, the commonly used

1 Introduction extractants are P204, LIX54 and LIX84. P204
(di-2-ethylhexyl phosphate) is an acidic
Tangdan copper mine, located near Dongchuan organophosphorous extractant. It is reported that under
City in Yunnan Province, China, having 1.16×106 t the conditions of temperature 25 °C, the contact time of
copper reserve, is a refractory oxidized ore with two phases 10 min, phase ratio 1:1, ammoniacal solution
high-alkaline gangues. Its average copper content is (pH 10) and the concentration of P204 20% (volume
0.46% (mass fraction, the same below if not mentioned). fraction), the extraction rate of copper was 93.9%[4].
This oxidized copper mineral has high alkaline gangue However, P204 is so soluble in alkaline solution that it is
content (w(CaO+MgO)>40%) with above 50% of impossible to be commercially used in ammoniacal
malachite and chrysocolla, and the rest of it is raw solution (pH >9). LIX54, a β-diketone extractant, has the
vulcanized copper, such as digenite, chalocite and virtue of higher saturation capacity of copper and lower
bornite. Ammonia leaching method is applied to deal ammonia extraction during the solvent extraction in
with this oxidized copper mineral, which has some ammoniacal solution[5]. But in 1995, Escondida of Chile
advantages, e.g., high copper leaching ratio and low applied LIX54 to extract copper from ammoniacal
production cost. If acid-leaching method is adopted, it solution in a pilot scale. As a result of LIX54
has high production cost because of huge acid deterioration, which might be led by the reaction
consumption for the existence of alkaline gangue. In between a keto group of LIX54 and ammonia to generate
1990s, to deal with Tangdan oxidized copper mineral, ketimine, the copper in loaded organic phase was
Beijing General Research Institute of Mining and difficult to back extract, and finally this pilot plant was
Metallurgy cooperated with Dongchuan Copper Mines forced to be closed[6]. Therefore, it is inappropriate to
Administration used the “ammonia leaching−solvent choose LIX54 to extract copper in ammoniacal system.
extraction−electrowinning” process. A pilot plant with LIX84, a hydroxyoxime extractant, has been proved to
500 t cathode copper production per year was built in be the main extractant for the extraction of copper from
1995[1−3]. In the “ammonia leaching−solvent ammoniacal solution[7−11]. However, hydroxyoxime

Foundation item: Project(2007CB613601) supported by the National Basic Research Program of China; Project(NCET-08) supported by Program for New
Century Excellent Talents in University, China
Corresponding author: HU Hui-ping; Tel: +86-731-88876034; E-mail: [email protected]
DOI: 10.1016/S1003-6326(09)60412-X
 HU Hui-ping, et al/Trans. Nonferrous Met. Soc. China 20(2010) 2026−2031 2027
such as LIX84 has a problem of serious ammonia in the aqueous phase before and after extraction. The
extraction in ammoniacal solution[12−13]. The ammonia loaded organic phases were centrifuged to remove all
present in the loaded organic phase should be removed possible content of aqueous entrainment, stripped with
before attempting copper stripping with the spent distilled water at a phase ratio (O/A) of 1‫׃‬5. Then, the
electrolyte. Otherwise, ammonia in the loaded organic two phases were separated with separatory funnel. The
phase is transferred to the pregnant electrolyte after ammonia content of the aqueous phase was determined
copper stripping, which may result in the accumulation by the Nessler's Reagent Spectrophotometry[18].
and the precipitation of (NH4)2SO4 in the pregnant
electrolyte[14]. In our research, TBP was added to 3 Results and discussion
LIX84, which just partially decreased ammonia
extraction in the loaded organic phase[15].
The extraction equilibrium for a divalent metal Cu2+
In this work, a laboratory synthesized sterically
and a chelating extractant, such as sterically hindered
hindered β-diketone was applied to reduce the ammonia
β-diketone, is generally given by[19]
extraction in the loaded organic phase. The effects of the
concentration of copper ion, the total ammonia Cu 2+ (aq) + 2HR (org) CuR 2 (org) + 2H + (aq) (1)
concentration, the initial pH in the aqueous phase, and
the phase ratio on copper extraction ratio and ammonia If the aqueous solution contains copper ions and
extraction in loaded organic phase were also studied. ammonium ions, at sufficiently high pH value where free
ammonia is produced, copper ammine complexes in
2 Experimental aqueous phase will be formed, which subjects to the
following equilibrium[19]:
2.1 Reagents
Sterically hindered β-diketone (4, 4-dimethyl-1-(4- Cu 2+ (aq) + mNH 3 (aq) [Cu(NH 3 ) m ]2+ (aq) (2)
dodecylphenyl)-1, 3-pentanedione) used as extractant for
the extraction of copper ions was laboratorialy When the two phases contact, ammonia in aqueous
synthesized according to Ref.[16]. The diluent (260# phase may be extracted into the organic phase as
kerosene) was supplied by Shanghai Rare-earth [Cu(NH3)m]R2(org) which is extracted into the organic
Chemical Co, Ltd, China. Aqueous phase was prepared phase by β-diketone, which subjects to the following
with proper molar ratio of CuCl2·2H2O, NH3·H2O and equilibrium[20]:
NH4Cl. All the other reagents used were in AR grade.
[Cu(NH 3 ) m ]2+ (aq) + 2HR(org)
2.2 Apparatus [Cu(NH 3 ) m ]R 2 (org) + 2H + (aq) (3)
Extraction studies were carried out in conical flask
with a thermostatic water bath shaker to equilibrate the where HR(org) refers to sterically hindered β-diketone in
samples for 30 min to study the copper extraction or the organic phase; CuR2(org) refers to complexing
ammonia stripping. The pH of aqueous solutions was compound of copper and sterically hindered β-diketone
measured with a digital Rex pH meter Model pHS-3C in organic phase; [Cu(NH3)m2+](aq) refers to the
provided with combined glass electrode. The Pgeneral complexing species between ammine and copper ion in
Model TAS-990 atomic absorption spectrophotometer aqueous phase; and Cu(NH3)m2+]R2(org) refers to the
(AAS) was used for analyzing copper content after extraction compound between Cu(NH3)m2+ and sterically
proper dilutions with 0.3 mol/L HNO3. The ammonia hindered β-diketone in organic phase.
content was determined with Nessler's Reagent
spectrophotometry method using Model 722 visible 3.1 Rate of copper extraction
spectrophotometer. The extraction experiments were carried out for
3−20 min. The operating conditions of extraction were:
2.3 General extraction experiments [Cu2+]=3 g/L, [NH3]=1 mol/L, [NH4Cl]=2 mol/L, the
Desired volumes of the aqueous phase and organic concentration of β-diketone in organic phase 20%
phase were equilibrated in a thermostatic water bath (volume fraction) and phase ratio (O/A)=1 at room
shaker for 30 min and after phase disengagement, the temperature. The results are represented in Fig.1.
aqueous phase was separated followed by the In Fig.1, the extraction rate of copper increases with
determination of copper concentrations in the raffinate the increase of the contact time. The extraction
by atomic absorption spectrophotometer[17]. The equilibrium is established after 10 min. In all the
concentration of copper ions in the organic phase was extraction experiments, a contact time of 30 min was
calculated from the difference between the concentration chosen to ensure that the equilibrium could be reached.
2028 HU Hui-ping, et al/Trans. Nonferrous Met. Soc. China 20(2010) 2026−2031

Fig. 1 Effect of contact time on copper extraction rate Fig.3 Effect of copper concentration of aqueous phase on
ammonia concentration in loaded organic phase
3.2 Effect of copper concentration on copper
extraction rate and ammonia extraction In Fig.3, the variation of the initial copper
The effects of the initial copper concentration in the concentration from 2.8 to 7.1 g/L leads to an increase of
aqueous phase on the extraction of copper and ammonia extracted ammonia in loaded organic phase from 20.8 to
in the loaded organic phase were studied (See Fig.2 and 35.8 mg/L. Ammonia in aqueous phase is probably
Fig.3). The operating conditions used were [NH3]=1 extracted to the organic phase by β-diketone as the
mol/L, [NH4Cl]=2 mol/L, the concentration of β- species [Cu(NH3)m]R2(org). With the increase of the
diketone in organic phase 20% (volume fraction), O/A initial copper concentration in aqueous phase, the content
phase ratio 1 and contact time 30 min at room
of [Cu(NH3)m](aq) increases. And it is beneficial to the
temperature.
formation of [Cu(NH3)x]R2(org) when the two phases are
contacted. Hence, there is a significant increase of the
extracted ammonia content in the loaded organic phase.

3.3 Effect of total ammonia concentration on copper

extraction rate and ammonia extraction
The effects of total ammonia concentration in the
initial aqueous phase on the extraction of copper and
ammonia are shown in Fig. 4 and Fig.5. The operating
conditions used were [Cu2+]=3 g/L, the molar ratio of
NH3 to NH4Cl =1:2, the concentration of β-diketone in
organic phase 20% (volume fraction), phase ratio
(O/A)=1 and contact time 30 min at room temperature.
In Fig.4, it can be observed that the extraction rate
Fig.2 Effect of copper concentration of aqueous phase on of copper decreases with the increase of the total
copper extraction rate ammonia concentration in the initial aqueous phase. The
variation of the total ammonia concentration from 1.5 to
In Fig.2, the extraction rate of copper decreases 6 mol/L leads to an decrease of the extraction rate of
with the increase of the initial copper concentration in copper from 98.7% to 17.2%. The decrease of extracted
the aqueous phase. The variation of the initial copper copper percentage can be explained that the ammine
concentration from 2.8 to 7.1 g/L leads to a decrease of copper species formation of [Cu(NH3)m]2+ occurs in the
copper extraction rate from 80.4% to 53.4%. The aqueous solution and this formation affects the metal
possible reason may be that the concentration of extraction by virtue of the resulting decrease in the
β-diketone in the initial organic phase is constant, while concentration of free copper ions.
the concentration of β-diketone is declined with the In Fig.5, the extracted ammonia concentration
increasing initial copper concentration in the aqueous increases with the increase of the total ammonia
phase, which results in the decrease of copper extraction concentration in the aqueous phase. The variation of the
rate. total ammonia concentration from 1.5 to 6 mol/L leads to
 HU Hui-ping, et al/Trans. Nonferrous Met. Soc. China 20(2010) 2026−2031 2029
Table 1 Effect of pH on copper extraction rate and ammonia
extraction
Copper extraction Ammonia
PH
rate/% concentration/(mg·L−1)
7.77 98.76 9.5

8.43 95.09 14.5

10.03 95.89 16.7

increasing pH value of the aqueous phase. As the initial

pH value increases from 7.77 to 10.03, the highest
extracted ammonia concentration in loaded organic phase
is just 16.7 mg/L. These phenomena can be explained
Fig.4 Effect of total ammonia concentration of aqueous phase that the concentration of [Cu(NH3)m]2+(aq) increases with
on copper extraction rate the increase of the pH value, which results in the increase
of extracted ammonia content in loaded organic phase.

3.5 Effect of O/A phase ratio on copper extraction

rate and ammonia extraction
The effect of O/A phase ratio on copper extraction
ratio and ammonia extraction is shown in Fig.8 and Table
2. The operating conditions used were [Cu2+]=3 g/L,
[NH3]=1 mol/L, [NH4Cl]=2 mol/L, the concentration of
β-diketone in organic phase 20% (volume fraction) and
contact time 30 min at room temperature. The O/A phase
ratio is from 1‫׃‬5 to 10‫׃‬1.
In Fig.6, the extraction rate of copper increases with
the increase of the phase ratio (O/A). The variation of the
phase ratio from 1‫׃‬10 to 2‫׃‬1 leads to an increase in the
Fig.5 Effect of total ammonia concentration of aqueous phase rate of extracted copper from 28.0% to 94.2%. When the
on ammonia concentration in loaded organic phase phase ratio is more than 2, the phase ratio has almost no
effect on the extraction rate of copper. These phenomena
an increase of extracted ammonia concentration from 5.6 can be explained by the equilibrium (1). The
to 16.2 mg/L. These phenomena can be explained by the concentration of HR(org) in organic phase increases with
above equilibriums (2) and (3). The concentration of the increase of the phase ratio (O/A), which results in the
[Cu(NH3)m]2+(aq) increases with the increase of total increase of copper extraction ratio.
ammonia concentration, which results in the increase of
extracted ammonia in loaded organic phase.

3.4 Effect of initial pH on copper extraction rate and

ammonia extraction
The extraction of copper and ammonia from
ammoniacal medium was studied using β-diketone
within the initial pH range from 7.77 to 10.03 (see Table
1). The operating conditions of extraction were: [Cu2+]=3
g/L, [NH3]+[NH4Cl]=3 mol/L, the concentration of
β-diketone in organic phase 20% (volume fraction),
phase ratio (O/A) =1 and contact time 30 min at room
temperature.
In Table 1, when the pH value of the aqueous phase
ranges from 7.77 to 10.03, pH has little effect on the
extraction rate of copper. While the extracted ammonia
concentration in loaded organic phase increases with Fig.6 Effect of phase ratio on copper extraction rate
2030 HU Hui-ping, et al/Trans. Nonferrous Met. Soc. China 20(2010) 2026−2031
Table 2 shows that the extracted ammonia content rate decreases. With the increase of initial pH value and
in the loaded organic phase decreases from 29.0 to 7.8 phase ratio, the copper extraction rate increases.
mg/L as the phase ratio (O/A) descends from 5‫׃‬1 to 1‫׃‬2. Temperature has almost no effect on the copper
However, the extracted ammonia concentration in loaded extraction rate. The extracted ammonia concentration in
organic phase increases from 7.8 mg/L to 33.6 mg/L as loaded organic phase increases with the increase of
the phase ratio (O/A) descends from 1‫׃‬2 to 1‫׃‬10. The copper concentration, total ammonia concentration and
lowest extracted ammonia concentration in loaded initial pH value in the aqueous phase.
organic phase was achieved at O/A ratio of 1‫׃‬2. 2) Under the conditions of temperature 25 °C,
contact time of two phases 30 min, phase ratio 1‫׃‬1,
Table 2 Effect of phase ratio on ammonia extraction concentration of copper 3 g/L, concentration of total
Phase ratio (O/A) Ammonia content/(mg·L−1) ammonia 3 mol/L, aqueous pH 8.43, and concentration
5‫׃‬1 29.0
of β-diketone in organic phase 20% (volume fraction),
ammonia in aqueous phase is much lower to be extracted
2‫׃‬1 26.2 by the organic phase (just 14.5 mg/L), while the
1‫׃‬1 18.1 extraction rate of copper is 95.09%. Though the extracted
copper rate of β-diketone is a little lower than that of
1‫׃‬2 7.8
LIX84, the extracted ammonia concentration of
1‫׃‬5 17.9 β-diketone is much lower than that of LIX84.
1‫׃‬7 22.0
References
1‫׃‬10 33.6

[1] CHENG Qiong, ZHANG Xiao-lin, LIU Dian-wen, ZHANG Wen-bin.

3.6 Effect of temperature on copper extraction rate Ammonia leaching of oxidized copper ore at normal temperature and
and ammonia extraction pressure [J]. Hydrometallurgy of China, 2006, 25(2): 74−77. (in
The effects of temperature on copper extraction Chinese)
ratio and ammonia extraction are shown in Table 3. The [2] CHENG Qiong, ZHANG Wen-bi. Tedmieal progress in ammonia
operating conditions used were [Cu2+]=3 g/L, [NH3]=1 leaching of Tangdan oxidized copper ore containing alkaline gangues
mol/L, [NH4Cl]=2 mol/L, the concentration of [J]. Yunnan Metallurgy, 2005, 34(6): 17−20. (in Chinese)
[3] LIU Da-xing, ZHAO Bing-zhi, JIANG Kai-xi. Study on treatment of
β-diketone in organic phase 20% (volume fraction),
Tangdan refractory copper oxide ore with high content of alkali
phase ratio (O/A) =1 and contact time 30 min. The
gangues [J]. Mining and Metallurgy of China, 2003, 12(2): 49−52.
temperature was 25−50 °C.
(in Chinese)
[4] QIAN Dong, WANG Kai-yi, CAI Chun-lin, PAN Chun-yue, TANG
Table 3 Effect of temperature on copper extraction rate You-gen, JIANG Jin-zhi. Separation of nickel, cobalt and copper by
Temperature/°C Copper extraction rate/% solvent extraction with P204 [J]. Transactions of Nonferrous Metals
Society of China, 2001, 11(5): 803−805.
25 94.29
[5] ALGUACIL F J, ALONSO M. Recovery of copper from ammoniacal
30 94.27 ammonium sulfate medium by LIX 54 [J]. Journal of Chemical
Technology and Biotechnology, 1999, 74(12): 1171−1175.
50 94.95
[6] ZHU Tun. Extraction and ion exchange [M]. Beijing: Metallurgical
Industry Press, 2005: 280−281. (in Chinese)
Table 3 shows that the extraction rate of copper [7] REDDY R B, PRIYA N D. Process development for the separation of
basically unchanged in the temperature range of 25−50 copper(II), nickel(II) and zinc(II) from sulphate solutions by solvent
°C. The extracted ammonia concentrations in loaded extraction using LIX84I [J]. Separation and Purification Technology,

organic phases are very low (less than 12 mg/L) at 25, 30 2005, 45(2): 163−167.
[8] MACKENZIE M, VIRNIG M, FEATHER A. The recovery of nickel
and 50 °C.
from high-pressure acid leach solutions using mixed hydroxide
product-LIX®84-INS technology [J]. Minerals Engineering, 2006,
4 Conclusions 19(12): 1220−1233.
[9] SARANGI K, PARHI P K, PADHAN E, PALAI A K, NATHSARMA
1) The laboratorialy synthesized sterically hindered K C, PARK K H. Separation of iron(III), copper(II) and zinc(II) from
β-diketone has been proved to be an effective extractant a mixed sulphate/chloride solution using TBP, LIX84I and Cyanex
for the extraction of copper with much lower ammonia 923 [J]. Separation and Purification Technology, 2007, 55(1): 44−49.
concentration extracted in loaded organic phase. With the [10] PARHIA P K, SARANGI K. Separation of copper, zinc, cobalt and
increase of copper concentration and total ammonia nickel ions by supported liquid membrane technique using LIX 84I,

concentration in the aqueous phase, the copper extraction TOPS-99 and Cyanex 272 [J]. Separation and Purification
 HU Hui-ping, et al/Trans. Nonferrous Met. Soc. China 20(2010) 2026−2031 2031
Technology, 2008, 59(2): 169−174. mixture of LIX84 and TBP [J]. The Chinese Journal of Process
[11] SENGUPTA B, BHAKHAR M S, SENGUPTA R. Extraction of Engineering. 2009, 9(6): 86−92. (in Chinese)
copper from ammoniacal solutions into emulsion liquid membranes [16] FU Weng. The synthesis and characterization of four kinds of
using LIX 84 I® [J] Hydrometallurgy, 2007, 89(3/4): 311−318. beta-diketone [D]. Changsha: Central South University. 2008: 35−56.
[12] PARIJA C, REDDY B R, BHASKARA SARMA P V R. Recovery of (in Chinese)
nickel from solutions containing ammonium sulphate using LIX 84-I [17] GB/T 2466. 1−1996. Pyrites and concentrate-determination of copper
[J]. Hydrometallurgy, 1998, 49(3): 255−261. content [S]. (in Chinese)
[13] PARIJA C, BHASKARA SARMA P V R. Separation of nickel and [18] GB/T18204. 25−2000. Methods for determination of ammonia in air
copper from ammoniacal solutions through co-extraction and of public places [S]. (in Chinese)
selective stripping using LIX84 as the extractant [J]. [19] ALGUACIL F J, ALONSO M. The effect of ammonium sulphate and
Hydrometallurgy, 2000, 54(2/3): 195−204. ammonia on the liquid-liquid extraction of zinc using LIX 54 [J].
[14] RITCEY G M, ASHBROOK A W. Solvent extraction: Principles and Hydrometallurgy, 1999, 53: 203−209.
applications to process metallurgy [M]. SUN Fang-jiu, transl. Beijing: [20] FLETT D S, MELLING J. Extraction of ammonia by commercial
Atomic Energy Press, 1985: 111−119. (in Chinese) copper chelating extractants [J]. Hydrometallurgy, 1979, 4: 135−146.
[15] LIU Chun-xuan, HU Hui-ping, HAN Xue-tao. Study on the copper (Edited by LI Xiang-qun)
and ammonia extraction from Cu2+-NH3-Cl--H2O solutions with the