High Flux Recovery of Copper(II) from Ammoniacal Solution with

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High Flux Recovery of Copper(II) from Ammoniacal Solution with Stable Sandwich Supported Liquid Membrane Duo Wang, Qiyuan Chen, Jiugang Hu,* Mingbo Fu, and Yaling Luo College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China ABSTRACT: The recovery of Cu(II) from ammoniacal solutions with the sandwich supported liquid membrane was studied by using 4-ethyl-1-phenyl-1,3-octadione as the carrier. The transport behavior of Cu(II), membrane stability and selectivity were investigated. The transport efficiency of Cu(II) in the membrane module is evidently dependent on the feed pH, carrier concentration, phase ratio and temperature, but almost independent of the H2SO4 concentration in receiving phase. The increase of carrier concentration and temperature can simultaneously enhance Cu(II) transport and initial copper flux in the feed phase, while both of them decrease as the phase ratio increases. The initial copper flux can reach 759 mmol m−2 h−1 at 45 °C. A satisfied membrane stability was obtained, and the copper concentration in the receiving phase can reach 3.91 g L−1 via uphill transport after five cycles. The main transport resistance could derive from the diffusion process of the copper complexes through the receiving phase/membrane interface. Moreover, the Cu(II) can be selectively recovered over Ni(II) and Zn(II). The high flux and good membrane stability makes the system promising for recovering metal values from various industrial process effluents.

1. INTRODUCTION In recent years, ammoniacal systems have been frequently used to process low-grade copper oxidized ores1,2 and various wastes containing copper.3,4 Thus, the recovery of Cu(II) from ammoniacal solutions has attracted much attention, for economic and environmental reasons. Although solvent extraction is an attractive approach and successfully used to recover Cu(II),5,6 the recovery of low-concentration copper(II) in ammoniacal solutions inevitably required a large inventory of equipment and solvent. Alternatively, membrane separation, usually including bulk liquid membrane (BLM), emulsion liquid membrane (ELM), supported liquid membrane (SLM) and polymer inclusion membrane (PIM), etc., is a promising technology for the recovery of various low-concentration metal values.7−9 Among them, SLMs are typically used and have been studied for the recovery of metal ions.10−12 By combining extraction and stripping into a single step, membrane separation presents several attractive advantages in comparison with solvent extraction, such as a great potential to reduce costs and energy consumption, high selectivity and enrichment ratio, easy scaleup, and the possible usage of an expensive carrier, etc.13 However, the low membrane stability and flux are still the great hindrance for the large-scale application of SLMs. Many studies have shown that the low stability mainly results from the loss of membrane phase (carrier and/or solvent) into aqueous phases by dissolution or leaking, thus influencing both flux and stability.14,15 Several research efforts have been performed to enhance the membrane stability, such as by designing new membrane materials or by developing new membrane configurations.9,16−20 Kavitha et al. investigated the permeation of Cu(II) through polymer inclusion membrane containing D2EHPA as the carrier and cellulose triacetate as the polymer.9 Although an evident membrane stability can be obtained usign a polymer inclusion membrane, the low flux is still an issue, because of the high membrane hindrance. Alguacil et al. promoted the flux of Cu(II) in acidic media through a strip dispersion membrane, in which Acorga M5640 is used as © XXXX American Chemical Society

the organic phase mixed with H2SO4 to form a pseudoemulsion in the receiving phase.17 Nevertheless, the acidic pseudo-emulsion phase directly contacted with ammoniacal feed solution could induce a high ammonia transport, which is deleterious to the membrane circuit and subsequent electrowinning process. Another possible alternative to minimize the membrane instability is the use of a sandwich supported liquid membrane (sandwich SLM), in which a thin membrane phase is confined between two hydrophobic or hydrophilic membranes that separate the feed and receiving phases.18,21,22 Although this membrane module could increase the mass transfer resistance, the results reported by Molinari clearly indicated the higher metal flux and stability for the sandwich liquid membrane than the traditional SLMs.18 Moreover, the transport rate can be greatly improved by hollow fiber configuration. For example, by the pioneer work of Sirkar et al., the hollow fiber contained liquid membrane (HFCLM) has been greatly developed for the separation of gas,21 toxic volatile organics,22 and metal ions.23−25 The hybrid liquid membrane (HLM) also has a similar feature with the sandwich SLM and HFCLM.26 Mortaheb studied the removal of cadmium by a hybrid liquid membrane and found that the removal efficiency for HLM is superior to that of SLM under the same other conditions.27 In the present work, the sandwich SLM module constructed with two hydrophobic PVDF membranes was used for recovery of Cu(II) from ammoniacal solutions. The carrier used is 4ethyl-1-phenyl-1,3-octadione (denoted as HA), which was previously made for the solvent extraction of Cu(II) in ammoniacal solution and showed a superior copper recovery and low ammonia loading.6 The transport behavior of Cu(II) Received: January 22, 2015 Revised: April 14, 2015 Accepted: April 16, 2015

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DOI: 10.1021/acs.iecr.5b00297 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Industrial & Engineering Chemistry Research

phase (0.8 mL) was slowly injected into the interlayer of membrane module and the inside air can be well removed from another syringe needle. In order to decrease the loss of membrane phase induced by the shear force of continuous pumping of aqueous phases, the feed and receiving solutions were first pumped into a membrane module with a positive pressure differential applied on the sides of the aqueous phases,23 and then the added organic phase fills the membrane pores through capillary action. Because the hydrophobic PVDF membrane is easily wetted by the membrane phase,29 the positive pressure can suppress the loss of membrane phase; thus, it is beneficial to the membrane stability. Unless mentioned otherwise, the feed and receiving reservoirs were immersed in a thermostatic water bath at 30 °C. The volumes of the feed solution and stripping solution were 80 mL each, except for the phase ratio experiments. For membrane stability and uphill transport test, the membrane phase and receiving phase remained the same as in the first run, while the feed solution was periodically renewed after each 6 h. 2.3. Determination of Transport Efficiency and Flux. Equal volumes of samples were simultaneously withdrawn from both feed and receiving solutions for metal concentration analysis at a desired time interval of 60 min. The aqueous pH of feed solution was measured using a calibrated Rex-3C digital pH meter before and after membrane transport. The concentrations of Cu(II), Ni(II), and Zn(II) in the feed phase and the receiving phase were determined by standard EDTA titration method. All results are presented as the mean value of triplicate analysis. The concentrations of targeted ions in membrane phase were calculated by mass balance. The transport behavior of Cu(II) in the feed phase, the receiving phase, and the membrane phase were evaluated as follows:

through the sandwich SLM module was studied by consideration of various parameters including feed pH, carrier concentration, H2SO4 concentration in receiving phase, phase ratio, and temperature. The membrane stability and selectivity of copper over nickel and zinc was also determined.

2. EXPERIMENTAL SECTION 2.1. Materials and Reagents. The carrier (4-ethyl-1phenyl-1,3-octadione, HA), was made according to the procedure described earlier.28 All other reagents were of analytical grade and used as received. The ultrapure water (18.2 MΩ cm, Milli-Q system, Millipore, Bedford, MA, USA) was used throughout the experiments. The hydrophobic polyvinylidene fluoride (PVDF) film was purchased from Millipore, and used as the support of sandwich SLM. The membrane has a porosity of 75%, an average pore size of 0.2 μm, and a thickness of 125 μm. The desired amounts of carrier were dissolved in nonane and used as the membrane phase. Stock aqueous solutions were prepared by dissolving 0.02 mol L−1 MSO4 (M = Cu, Ni, Zn) in 1.0 mol L−1 (NH4)2SO4 solutions of various pH, which was adjusted using sodium hydroxide and sulfuric acid. 2.2. Transport Studies. All the transport experiments were performed by the self-designed three-compartment membrane module as presented in Figure 1. The setup consists of two

Cu(II) transport in the feed phase: xtf (%) =

C tf × 100 C0

(1)

Cu(II) transport in the receiving phase: xtr (%) =

C tr × 100 C0

(2)

Cu(II) retention in the membrane phase: xtm (%) =

C0 − C tf − C tr × 100 C0

(3)

where C0 is the initial concentration of Cu(II) in the feed phase; Ctf and Ctr are the Cu(II) concentrations in the feed phase and the receiving phase, respectively, at the desired time. The initial copper flux (J0, given in units of mmol m−2 h−1) was determined using the following equation:

Figure 1. Schematic diagram of sandwich SLM module. (a) Membrane transport setup, (b) sandwich SLM configuration: (1) permeation cell, (2) feed phase compartment, (3) membrane phase compartment, (4) receiving phase compartment, (5) stripping solution, (6) feed solution, (7) thermostatic water bath, (8) peristaltic pump, (9) syringe needle, (10) hydrophobic PVDF membrane, and (11) fluoro-rubber gasket.

J0 = −

V d[Cu 2 +] Aeff dt

(4)

2+

where d[Cu ] is the Cu(II) concentration change in the feed solution over the experimental time t (in hours), V the volume of feed phase, and Aeff the effective membrane surface (9.42 cm2), which was calculated from the geometrical area and the membrane porosity.

cylindrical cells with a volume of ∼10 mL each for the feed phase and the receiving phase. The sandwich SLM module consists of two hydrophobic PVDF membranes separated by a 1 mm fluorine rubber gasket as a spacer. Each membrane diameter is 4 cm. The feed and receiving phases were separately recirculated by peristaltic pumps with a constant flow rate of 80 mL min−1. After starting the peristaltic pumps, the organic

3. RESULTS AND DISCUSSION 3.1. Effect of pH on Cu(II) Transport. In ammoniacal solution, the Cu(II) transport is dependent on the pH of feed B


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Industrial & Engineering Chemistry Research solution. As shown in Figure 2, the transport efficiency of Cu(II) in both the feed phase and the receiving phase at pH 9.3

is evidently lower than that at pH 7.3 and pH 8.3. According to our previous results,6 the extraction efficiency of Cu(II) in ammoniacal solutions can remain stable in the pH range of 6.5−8.5, especially under the condition of the higher extractant concentration. However, the Cu(II) extraction efficiency evidently decreases because the more stable tetrammine copper species is predominant beyond pH 8.5. The Cu(II) transport through the sandwich SLM presents a similar behavior with solvent extraction. At pH 8.3, the 45% copper can be extracted into membrane phase and 37% copper can be stripped into receiving phase in the first 2 h. The transport efficiency of Cu(II) in the feed and receiving phases can reach to 88.5% and 75%, respectively, after 6 h. When the aqueous pH increases from 8.3 to 9.3, the transport time of 50% copper from feed solution increases from 2.3 h to 4 h. Meanwhile, the aforementioned 10% copper was still retained in the membrane phase at the sixth hour, which could result from the lower diffusion rate of copper complexes in the membrane phase, including the PVDF membrane substrates, thus inhibiting the copper transport. On the other hand, it is worth noting that the negligible pH change for feed solution at pH 8.3 is beneficial to the stability of Cu(II) transport. 3.2. Effect of Carrier Concentration on Cu(II) Transport. The effect of HA concentration on the transport efficiency of copper(II) at pH 8.3 is shown in Figure 3. It can be found that increasing the HA concentration is favorable to Cu(II) transport. When the HA concentration increases from 0.2 mol L−1 to 0.8 mol L−1, the transport efficiency of Cu(II) in the feed phase increases from 81.5% to 90.5% in 6 h, whereas the transport efficiency of Cu(II) in the receiving phase increases from 70.8% to 79.4%. Meanwhile, the residual

Figure 2. Effect of pH on the transport efficiency of Cu(II): (a) Cu(II) percentage in the feed phase, (b) Cu(II) percentage in the membrane phase, (c) Cu(II) percentage in the receiving phase, and (d) pH change of the feed solution. Conditions: [HA] = 0.4 mol L−1, phase ratio = 1, [H2SO4] = 2 mol L−1, T = 30 °C.]

Figure 3. Effect of HA concentration on the transport efficiency of Cu(II): (a) feed phase, (b) membrane phase, (c) receiving phase, and (d) initial copper flux in the feed phase . [Conditions: feed pH = 8.3, phase ratio = 1, [H2SO4] = 2 mol/L, and T = 30 °C.] C


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Figure 4. Effect of H2SO4 concentration on the transport efficiency of Cu(II): (a) feed phase, (b) membrane phase, and (c) receiving phase. [Conditions: feed pH = 8.3; [HA] = 0.4 mol L−1; phase ratio = 1; T = 30 °C.]

Figure 5. Effect of temperature on the transport efficiency of Cu(II): (a) feed phase, (b) membrane phase, (c) receiving phase, and (d) initial copper flux in the feed phase. [Conditions: feed pH = 8.3, [HA] = 0.4 mol/L, phase ratio = 1, [H2SO4] = 2 mol/L.]

H2SO4 concentration in the receiving phase on the transport efficiency of Cu(II) in the pH 8.3 feed solution is shown in Figure 4. It can be found that the transport efficiency of Cu(II) in the feed phase remains almost constant under the conditions of a H2SO4 concentration of 1−3 mol L−1. When H2SO4 concentration increases from 2 mol L−1 to 3 mol L−1, the Cu(II) transport efficiency in the receiving phase only increases by 1.6%. In several recent work, some authors concluded that the driving force in SLM is the pH difference between the feed and strip phases.18 Gameiro et al. also reported that the increase in the H2SO4 concentration induces a faster transport rate of

copper in the membrane phase does not increase during this 6 h. The initial copper flux also increases linearly from 446.5 mmol m2 h−1 to 676.5 mmol m2 h−1. These results indicate that the Cu(II) transport in the sandwich SLM is strongly dependent on the concentration gradient of both HA and copper complex at the feed/membrane and membrane/ receiving interfaces. 3.3. Effect of H2SO4 Concentration on Cu(II) Transport. The special uphill effect of ion transport in membrane module is usually dependent on an effective stripping process. When the HA concentration is maintained at 0.4 mol L−1, the effect of D


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Figure 6. Figure 6. Effect of phase ratio on the transport efficiency of Cu(II): (a) feed phase, (b) membrane phase, (c) receiving phase, and (d) initial copper flux in the feed phase. [Conditions: T = 30 °C.]

Figure 7. Selectivity tests of sandwich SLM: (a) feed phase and (b) receiving phase. [Conditions: feed pH = 8.3, [HA] = 0.4 mol/L, phase ratio = 1, [H2SO4] = 2 mol/L, T = 30 °C.]

copper(II) in the emulsion liquid membrane.30 However, the results in this work show that the proton concentration gradient is not the key driving force of Cu(II) transport in the sandwich SLM module. 3.4. Effect of Temperature on Cu(II) Transport. The effect of temperature on the transport efficiency of Cu(II) in the feed solution of pH 8.3 is shown in Figure 5. It was found that the increase of temperature is beneficial to the Cu(II) transport in both the feed and receiving phases. When temperature increases from 15 °C to 45 °C, the extraction

efficiency of copper(II) increases from 83.5% to 94% at the sixth hour, whereas the stripping efficiency increases from 66.8% to 82%. The residual copper in the membrane phase decreases from 16.8% to 11.8%. The results clearly showed that the increasing temperature is more favorable to the stripping process, because the acid stripping reaction is usually a definite endothermic process.31 Thus, the higher stripping efficiency can facilitate the formation of the greater concentration gradient of both HA and copper complex at the interfaces between the membrane and aqueous phases, thus promoting E


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Figure 8. Stability tests and uphill transport of sandwich SLM in successive four cycles. [Conditions: feed pH = 8.3, [HA] = 0.4 mol/L, phase ratio = 1, [H2SO4] = 2 mol/L, T = 30 °C.]

Table 1. Comparison on the Initial Flux of Cu(II) and Stability in Various Membrane Modules membrane module supported liquid membrane stagnant sandwich liquid membranes (with hydrophilic membrane) supported liquid membrane polymer inclusion membrane pseudo-emulsion-based membrane strip dispersion polymer inclusion membrane polymer inclusion membrane polymer inclusion membrane chemically modified SLM hollow fiber SLM hollow fiber SLM sandwich SLM (with hydrophobic membrane)

feed system

carrier

sulfate solutions sulfate solutions

D2EHPA D2EHPA

plating wastewater sulfate solutions acidic wastewaters sulfate solutions sulfate solutions sulfate solutions ammoniacal solutions ammoniacal solutions ammoniacal solutions ammoniacal solutions

D2EHPA D2EHPA Acorga M5640 LIX84I LIX984 LIX54 LIX54 LIX 54

initial flux (mmol m−2 h−1) 52.4 41.5 320.4 16.13 62.36 10.5 9.54 2.82 47.88

stability

source

183 h

ref 18 ref 20

>110 h >10 cycles

ref 16 ref 9 ref 17 ref 36 ref 36 ref 36 ref 37

>100 h

96.38

ref 38

LIX54

468

>3 cycles

ref 19

4-ethyl-1-phenyl-1,3octadione

759

>5 cycles

this work

almost present a linear dependence on time, indicating that the high phase ratio can provide a greater driving force in this membrane module. 3.6. Membrane Selectivity. The selectivity of the sandwich SLM was investigated by performing the transport of Cu(II), Ni(II), and Zn(II) in a pH 8.3 ammoniacal solution. The results shown in Figure 7 show that the copper(II) can be transported prior to Ni(II) and Zn(II). At pH 8.3, the transport efficiency of Cu(II), Ni(II), and Zn(II) in the receiving phase is 75%, 7.4%, and 3.9%, respectively. Because water and ammonia molecules coordinate more easily with both nickel and zinc extracts than copper extract in the organic phase,32−34 the extracted copper complex is more liable to transport in the hydrophobic sandwich SLM, because of its greater hydrophobic nature. Thus, the Cu(II) in the ammoniacal solutions can be selectively transported over nickel and zinc into sulfuric acid solutions. 3.7. Mechanism Stability and Uphill Transport. The stability tests and uphill transport of the sandwich SLM were carried out by successive transport experiments on a fixed SLM,

the Cu(II) transport. On the other hand, because the raising temperature can promote the diffusion of copper complexes and carrier in the membrane phase, the initial copper flux in the feed phase can increase from 479 mmol m2 h−1 to 759 mmol m2 h−1 with increasing temperature from 15 °C to 45 °C. Mortaheb et al. also found a similar phenomenon during the cadmium transport in the hybrid liquid membrane.27 3.5. Effect of Phase Ratio on Cu(II) Transport. The high phase ratio in membrane separation is economically beneficial for enriching the valuable metals from low-concentration solutions. As shown in Figure 6, the transport efficiency of Cu(II) in the feed solution of pH 8.3 evidently decreases as the volume ratio of feed solution to receiving solution increases. The initial copper flux also linearly decreases from 559 mmol m2 h−1 to 470 mmol m2 h−1. However, the overall transport of copper in the sandwich SLM module was promoted, especially after the third hour. The Cu(II) concentration in the receiving phase at the sixth hour is 1.62 g L−1 and 1.71 g L−1 for phase ratios of 2:1 and 4:1, respectively. When the phase ratio is larger than 2:1, the Cu(II) transport in the receiving phase F


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Although H2SO4 in the receiving solution was continuously reduced during the successive transport, the decrease of transport efficiency could not result from the decrease of driving force for interfacial stripping reaction, because a sufficiently high H2SO4 concentration was maintained in the receiving phase. On the other hand, it can be also found that more and more extracted copper complexes accumulate in the membrane phase, whereas the Cu(II) transport efficiency in the feed phase can still remain stable. Therefore, the Cu(II) transport resistance is not dependent on the coordination reaction between Cu(II) and carrier and the diffusion of the formed complex and carrier at the feed solution/membrane interface. Thus, the main transport resistance could be derived from the diffusion process of the copper complexes through the receiving phase/membrane interface. Based on the previous results,32 two carrier molecules can coordinate with per Cu ion to form the copper complexes with a planar square configuration, thereby increasing the molecular volume and viscidity of transport matters, which can increase their transport resistance.35 In practice, increasing temperature is favorable to the Cu(II) transport, because of the decrease of viscosity of the extracted copper complexes at the higher temperature. Furthermore, if enlarging the membrane area of the receiving side of sandwich SLM to reduce the effect of membrane resistance, a larger Cu(II) transport flux could be obtained. A similar phenomenon was found by Kislik when titanium(IV) in hydrochloric acid solutions transports through the hybrid liquid membrane module.26 The adjustable membrane area can be easily achieved in the hollow fiber membrane configuration. The promising hollow fiber contained liquid membrane permeator with different membrane areas of the feed and receiving sides had been reported to improve the ion transport rate.23

where only the feed phase was replaced with fresh feed solution after each 6 h. As shown in Figure 8, the Cu(II) transport efficiency in the feed phase can remain at ∼90% during five successive transports. The loss of carrier by dissolving or leaking into aqueous phases was hardly observed during the stability tests; thus, the sandwich SLM presents good membrane stability. Molinari el al. studied the removal of low-concentration copper from wastewater by sandwich SLM containing D2EHPA as carrier; a longer stability (187 h) can be also obtained.20 The comparison of membrane stability and the initial flux of Cu(II) in this work with some reported membrane modules is shown in Table 1. It can be found that the hydrophobic sandwich SLM for Cu(II) transport is comparable with hollow fiber SLM and is superior to the other membrane modules, with regard to both flux and stability. Meanwhile, although the initial flux is dependent on the ion concentration in feed solutions, the high flux of Cu(II) transport presents a good potential of sandwich SLM to recover metal values in the hydrometallurgical solutions. Via the uphill transport, the Cu(II) concentration in the receiving phase can reach 3.91 g L−1 after five cycles. The results suggest that the continuous enrichment of Cu(II) by the sandwich SLM is feasible and this membrane module is promising for the recovery of metal values from lowconcentration industrial process effluents. Meanwhile, it can be found that Cu(II) recovery in the receiving phase has an evident decreasing trend for the successive uphill transport. The transport process of Cu(II) through the sandwich SLM can be explained by the following five stages and the schematic transport mechanism is given in Figure 9:

4. CONCLUSIONS The recovery of Cu(II) from ammoniacal solutions with the sandwich supported liquid membrane was studied by using 4ethyl-1-phenyl-1,3-octadione as the carrier. The Cu(II) transport is dependent on the feed pH. Both transport efficiency and initial copper flux in the feed phase simultaneously increase as the carrier concentration and temperature each increase, while a decrease is observed with increasing phase ratio. When increasing the temperature from 15 °C to 45 °C, the initial copper flux can increase from 479 mmol m2 h−1 to 759 mmol m2 h−1. The transport efficiency of Cu(II) in the feed solution can almost keep constant during five successive cycles, indicating good membrane stability. By the uphill transport, the continuous enrichment of Cu(II) by the sandwich SLM is feasible and the copper concentration in the receiving phase can reach 3.91 g L−1 after five cycles. The overall results show that the transport resistance of Cu(II) is controlled by the diffusion process of the copper complexes through the receiving phase/ membrane interface. Moreover, the Cu(II) can be selectively recovered over Ni(II) and Zn(II). Therefore, the high flux recovery of Cu(II) in ammoniacal solution can be achieved with the stable sandwich SLM module, thus presenting good potential to recover metal values in the hydrometallurgical solutions.

Figure 9. Schematic transport mechanism of Cu(II) in the sandwich SLM.

(1) diffusion of copper ammonia complexes in the feed phase; (2) coordination reaction between Cu(II) and the carrier at the feed/membrane interface and the release of hydrogen ions into the feed phase; (3) diffusion of the formed complex and carrier through the sandwich membrane module including the PVDF membrane pores; (4) the Cu(II) release and carrier regeneration at the interface of membrane/receiving phases; and (5) diffusion of Cu(II) in the receiving phase.

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(18) Molinari, R.; Argurio, P.; Pirillo, F. Comparison between stagnant sandwich and supported liquid membranes in copper(II) removal from aqueous solutions: Flux, stability and model elaboration. J. Membr. Sci. 2005, 256, 158−168. (19) Yang, Q.; Kocherginsky, N. M. Copper recovery and spent ammoniacal etchant regeneration based on hollow fiber supported liquid membrane technology: From bench-scale to pilot-scale tests. J. Membr. Sci. 2006, 286, 301−309. (20) Molinari, R.; Argurio, P.; Poerio, T. Studies of various solid membrane supports to prepare stable sandwich liquid membranes and testing copper(II) removal from aqueous media. Sep. Purif. Technol. 2009, 70, 166−172. (21) Sengupta, A.; Basu, R.; Prasad, R.; Sirkar, K. K. Separation of Liquid Solutions by Contained Liquid Membranes. Sep. Purif. Technol. 1988, 23, 1735−1751. (22) Yang, D.; Majumdar, S.; Kovenklioglu, S.; Sirkar, K. K. Hollow fiber contained liquid membrane pervaporation system for the removal of toxic volatile organics from wastewater. J. Membr. Sci. 1995, 103, 195−210. (23) Guha, A. K.; Yun, C. H.; Basu, R.; Sirkar, K. K. Heavy metal removal and recovery by contained liquid membrane permeator. AIChE J. 1994, 40, 1223−1237. (24) Yun, C. H.; Prasad, R.; Guha, A. K.; Sirkar, K. K. Hollow fiber solvent extraction removal of toxic heavy metals from aqueous waste streams. Ind. Eng. Chem. Res. 1993, 32, 1186−1195. (25) Yang, Z.-F.; Guha, A. K.; Sirkar, K. K. Simultaneous and Synergistic Extraction of Cationic and Anionic Heavy Metallic Species by a Mixed Solvent Extraction System and a Novel Contained Liquid Membrane Device. Ind. Eng. Chem. Res. 1996, 35, 4214−4220. (26) Kislik, V. S.; Eyal, A. M. Hybrid liquid membrane (HLM) system in separation technologies. J. Membr. Sci. 1996, 111, 259−272. (27) Mortaheb, H. R.; Zolfaghari, A.; Mokhtarani, B.; Amini, M. H.; Mandanipour, V. Study on removal of cadmium by hybrid liquid membrane process. J. Hazard. Mater. 2010, 177, 660−667. (28) Fu, W.; Chen, Q.; Wu, Q.; Hu, H.; Bai, L. Solvent extraction of zinc from ammoniacal/ammonium chloride solutions by a sterically hindered β-diketone and its mixture with tri-n-octylphosphine oxide. Hydrometallurgy 2010, 100, 116−121. (29) Kocherginsky, N. M.; Yang, Q. Big Carrousel mechanism of copper removal from ammoniacal wastewater through supported liquid membrane. Sep. Purif. Technol. 2007, 54, 104−116. (30) Gameiro, M. L. F.; Bento, P.; Ismael, M. R. C.; Reis, M. T. A.; Carvalho, J. M. R. Extraction of copper from ammoniacal medium by emulsion liquid membranes using LIX 54. J. Membr. Sci. 2007, 293, 151−160. (31) Hoh, Y. C.; Chuang, W. S. Influence of temperature on the extraction of zinc by LIX 34. Hydrometallurgy 1983, 10, 123−128. (32) Hu, J.; Chen, Q.; Hu, H.; Jiang, Z.; Wang, D.; Wang, S.; Li, Y. Microscopic Insights Into Extraction Mechanism of Copper(II) in Ammoniacal Solutions Studied by X-ray Absorption Spectroscopy and Density Functional Theory Calculation. J. Phys. Chem. A 2013, 117, 12280−12287. (33) Hu, J.; Chen, Q.; Hu, H.; Qiu, B.; Xie, A.; Yin, Z. Extraction behavior of nickel(II) in ammoniacal sulfate solution with sterically hindered β-diketone. Sep. Purif. Technol. 2012, 95, 136−143. (34) Hu, J.; Chen, Q.; Hu, H.; Chen, X.; Hu, F.; Yin, Z. XAS investigation on the coordination structure and extraction mechanism of zinc(II) in ammoniacal solution. Sep. Purif. Technol. 2012, 98, 308− 314. (35) Molinari, R.; Poerio, T.; Argurio, P. Selective removal of Cu2+ versus Ni2+, Zn2+ and Mn2+ by using a new carrier in a supported liquid membrane. J. Membr. Sci. 2006, 280, 470−477. (36) Rodríguez de San Miguel, E.; Hernández-Andaluz, A. M.; Bañuelos, J. G.; Saniger, J. M.; Aguilar, J. C.; de Gyves, J. LIX-loaded polymer inclusion membrane for copper(II) transport: 1. Composition−performance relationships through membrane characterization and solubility diagrams. Mater. Sci. Eng. A 2006, 434, 30−38. (37) Yang, Q.; Chung, T.-S.; Xiao, Y.; Wang, K. The development of chemically modified P84 Co-polyimide membranes as supported

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Basic Research Program of China (No. 2014CB643401), National Natural Science Foundation of China (Nos. 51134007 and 51304244), China Postdoctoral Science Foundation (No. 2014M552152), and Hunan Provincial Natural Science Foundation of China (No. 2015JJ3154).

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REFERENCES

(1) Liu, W.; Tang, M.; Tang, C.; He, J.; Yang, S.; Yang, J. Dissolution kinetics of low grade complex copper ore in ammonia−ammonium chloride solution. Trans. Nonferrous Met. Soc. China 2010, 20, 910− 917. (2) Meng, X.; Han, K. The Principles and Applications of Ammonia Leaching of MetalsA Review. Miner. Process Extr. Metall. Rev. 1996, 16, 23−61. (3) Oishi, T.; Koyama, K.; Alam, S.; Tanaka, M.; Lee, J. C. Recovery of high purity copper cathode from printed circuit boards using ammoniacal sulfate or chloride solutions. Hydrometallurgy 2007, 89, 82−88. (4) Yang, J.; Wu, Y.; Li, J. Recovery of ultrafine copper particles from metal components of waste printed circuit boards. Hydrometallurgy 2012, 121, 1−6. (5) Panigrahi, S.; Parhi, P. K.; Sarangi, K.; Nathsarma, K. C. A study on extraction of copper using LIX 84-I and LIX 622N. Sep. Purif. Technol. 2009, 70, 58−62. (6) Hu, J.; Chen, Q.; Hu, H.; Chen, X.; Ma, Q.; Yin, Z. Extraction behavior and mechanism of Cu(II) in ammoniacal sulfate solution with β-diketone. Hydrometallurgy 2012, 127−128, 54−61. (7) Drioli, E.; Stankiewicz, A. I.; Macedonio, F. Membrane engineering in process intensificationAn overview. J. Membr. Sci. 2011, 380, 1−8. (8) San Román, M. F.; Bringas, E.; Ibañez, R.; Ortiz, I. Liquid membrane technology: Fundamentals and review of its applications. J. Chem. Technol. Biotechnol. 2010, 85, 2−10. (9) Kavitha, N.; Palanivelu, K. Recovery of copper(II) through polymer inclusion membrane with di(2-ethylhexyl)phosphoric acid as carrier from e-waste. J. Membr. Sci. 2012, 415−416, 663−669. (10) Panja, S.; Ruhela, R.; Das, A.; Tripathi, S. C.; Singh, A. K.; Gandhi, P. M.; Hubli, R. C. Carrier mediated transport of Pd(II) from nitric acid medium using dithiodiglycolamide (DTDGA) across a supported liquid membrane (SLM). J. Membr. Sci. 2014, 449, 67−73. (11) Solangi, I. B.; Ö zcan, F.; Arslan, G.; Ersöz, M. Transportation of Cr(VI) through calix[4]arene based supported liquid membrane. Sep. Purif. Technol. 2013, 118, 470−478. (12) Verbeken, K.; Vanheule, B.; Pinoy, L.; Verhaege, M. Cobalt removal from waste-water by means of supported liquid membranes. J. Chem. Technol. Biotechnol. 2009, 84, 711−715. (13) Kocherginsky, N. M.; Yang, Q.; Seelam, L. Recent advances in supported liquid membrane technology. Sep. Purif. Technol. 2007, 53, 171−177. (14) Dreher, T. M.; Stevens, G. W. Instability Mechanisms of Supported Liquid Membranes. Sep. Sci. Technol. 1998, 33, 835−853. (15) Hill, C.; Dozol, J. F.; Rouquette, H.; Eymard, S.; Tournois, B. Study of the stability of some supported liquid membranes. J. Membr. Sci. 1996, 114, 73−80. (16) Venkateswaran, P.; Gopalakrishnan, A. N.; Palanivelu, K. Di(2ethylhexyl)phosphoric acid−coconut oil supported liquid membrane for the separation of copper ions from copper plating wastewater. J. Environ. Sci. 2007, 19, 1446−1453. (17) Alguacil, F. J.; Lopez, F. A.; Garcia-Diaz, I. Copper removal from acidic wastewaters using 2-hydroxy-5-nonylbenzaldehyde oxime as ionophore in pseudo-emulsion membrane with strip dispersion (PEMSD) technology. J. Ind. Eng. Chem. 2012, 18, 255−259. H


Article

Industrial & Engineering Chemistry Research liquid membrane matrix for Cu(II) removal with prolonged stability. Chem. Eng. Sci. 2007, 62, 1721−1729. (38) Gameiro, M. L. F.; Ismael, M. R. C.; Reis, M. T. A.; Carvalho, J. M. R. Recovery of copper from ammoniacal medium using liquid membranes with LIX 54. Sep. Purif. Technol. 2008, 63, 287−296.

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High Flux Recovery of Copper(II) from Ammoniacal Solution with

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