You are on page 1of 7

Article

pubs.acs.org/IECR

Selective Recovery of Zinc over Iron from Spent Pickling Wastes by


Different Membrane-based Solvent Extraction Process
Configurations
J. Laso, V. García, E. Bringas, A. M. Urtiaga,* and I. Ortiz
Department of Chemical and Biomolecular Engineering, University of Cantabria, Av. de los Castros s/n, 39005 Santander, Spain

ABSTRACT: This paper reports the selective separation of zinc over iron from spent pickling wastes or effluents using two
different membrane-based solvent extraction process configurations, Nondispersive solvent extraction (NDSX) and emulsion
pertraction technology (EPT). The process aims to obtain a highly concentrated zinc solution with a negligible content of iron to
allow for Zn electrowinning. The effect of the following process variables on the kinetics and selectivity of zinc separation has
been evaluated: (i) process configuration NDSX and EPT, (ii) extractant concentration, tributylphosphate (TBP) in the range of
20−100% v/v and (iii) stripping phase/feed phase volume ratio in the range Vs/Va 0.2−2. The transport of iron, chloride and
free acid has been also monitored to gain insight into the separation fundamentals. EPT configuration overcame NDSX in terms
of zinc and iron separation kinetics, although separation selectivity (at 30 min) was higher for NDSX configuration, αZn/Fe = 22,
compared to EPT process αZn/Fe = 15. The optimum TBP content in the extractant phase was found to be 50% v/v. A further
increase did not improve the Zn recovery kinetics and reduced the Zn/Fe selectivity. The increase of the Vs/Va ratio improved
the process efficacy in terms of kinetics and zinc recovery.

1. INTRODUCTION because the oxidation of chloride to chlorine promotes the


Hot-dip galvanizing is the most extensively used surface chemical oxidation of Fe2+ to Fe3+ and ferric iron competes
treatment to protect steel pieces against corrosion. It is with Zn2+ ions in the cathode.9,10 Further, acidic pH values
reported that steelwork plants in the EU produce 300 000 m3 favor zinc electrodeposition. Consequently, the separation
per year of spent pickling solutions (SPS), which are of process should be selective toward zinc versus iron and
environmental concern due to their high content in heavy chloride and allow the permeation of protons.
metals and acids. Typical concentrations of zinc, iron and In the zinc-based surface treatment sector, conventional
hydrochloric acid are in the ranges of 20−120, 100−130 and solvent extraction and MBSX are being used for the
1−6 mol L−1, respectively.1−4 management of passivation baths11−14 and SPS.15−22 Regarding
To move toward an industry with a high level of resource the latter, previous works have focused on the viability of the
efficiency, the Waste Management Hierarchy must be carefully MBSX process configurations, i.e., nondispersive solvent
considered. Resource efficiency by means of recovery practices extraction (NDSX) and emulsion pertraction technology
is a key strategy to reduce the environmental impact of (EPT) also referred as pseudoemulsion based hollow fiber
processes that utilize nonrenewable materials and produce strip dispersion (PEHFSD). These configurations differ in the
hazardous effluents. Further on, process eco-efficiency is way of contacting the fluid phases and the number of the
enhanced. Galvanizing of steel pieces is high demanding in membrane contactors involved.8 In most of the reported works,
terms of zinc, which is one of the highest operational costs. The water was used as a stripping agent and tributylphosphate
recovery of zinc from SPS decreases the need for virgin zinc (TBP) was selected as an organic extractant because it
metal that has a market value of 1600 € per ton in 2013,5 and selectively removes zinc from iron containing solutions. This
reduces the toxicity of the effluents generated in the hot-dip is due to the combined effect of the zinc and iron speciation in
galvanizing process. the SPS and the extraction nature of the TBP, i.e., TBP extracts
Regel-Rosocka6 reviewed different separation alternatives to neutral or anionic compounds and the speciation of zinc and
regenerate SPS from steel processing aiming at metal recovery. iron in SPS at high chloride concentration and low pH is
The studied techniques were ion-exchange resins, crystallization ZnCl42− and ZnCl3− for zinc, and Fe2+ and a slight ratio of
and classical and membrane based solvent extraction. In the FeCl+ for iron.23,24
past few years, membrane based solvent extraction (MBSX) has The kinetics of zinc removal and recovery from SPS using
drawn the attention of researchers due to the low inventory of NDSX and EPT has been well studied from a theoretical and
extractant, low energy requirement, process selectivity and the experimental perspective.16,21 However, little attention has
possibility of simultaneous extraction and stripping of the target been paid to the behavior and transport of other major species
compounds.7,8 The integration of MBSX within the hot-dip
galvanizing process considers SPS a source of zinc, as this metal Received: January 8, 2015
can be selectively transferred to an enriched stream to allow for Revised: March 6, 2015
its further electrowinning recovery. The latter operation is Accepted: March 9, 2015
negatively affected by the presence of iron and chloride, Published: March 9, 2015

© 2015 American Chemical Society 3218 DOI: 10.1021/acs.iecr.5b00099


Ind. Eng. Chem. Res. 2015, 54, 3218−3224
Industrial & Engineering Chemistry Research Article

namely iron, chloride and protons, which are of key importance


for the assessment of the viability of zinc recovery.
This work reports the performance of the membrane-based
configurations, nondispersive solvent extraction and emulsion
pertraction technology, for the recovery of zinc over iron from
real spent pickling solutions using tributylphosphate as liquid
membrane and tap water as stripping agent. The aim is to
evaluate and assess the appropriate operation conditions of the
process in order to promote the selective separation of zinc
from iron containing SPS. Further, the progress of the
concentration of iron, chloride and free acid in the feed SPS
and in the stripping phase was monitored in order to select
suitable conditions for obtaining a stream of enough quality for
zinc electrowinning.

2. MATERIALS AND METHODS Figure 1. Configurations of the membrane-based solvent extraction


process for the recovery of zinc from SPS using HFMC: (a) NDSX
2.1. Materials. Samples of SPS were provided by a local and (b) EPT. EX, extraction; BEX, back-extraction.
industry and contained mainly zinc, iron, chloride and free acid
(Table 1). Further, synthetic solutions were prepared using fluid into the feed aqueous phases. In the EPT experiments, the
pseudoemulsion was prepared using an MRVS-08 stirrer (SBS).
Table 1. Composition of the Samples Studied The organic and the stripping phases can be easily separated by
gravity settling. Further details of the experimental procedure
real SPS synthetic SPS
−1
can be found elsewhere.12,14,21
+
[H ] (mol L ) 1.1 ± 0.04 1 Table 2 lists the experiments conducted for the analysis of
[Zn2+] (g L−1) 122 ± 3 149 ±5 the influence of the process variables on the kinetics and on the
[Fe]TOTAL (g L−1) 95.6 ± 3 121 ±3
[Fe2+] (g L−1) 92.6 ± 2 121 ±3
Table 2. Experimental Conditions of the Kinetic
[Fe3+] (g L−1) 3 ± 2 0
Experiments
[Cl−] (g L−1) 301 ± 3 354 ± 10
organic phase volume (L)a
ZnCl2 (97%, Panreac), FeCl2·4H2O (99%, Sigma-Aldrich) and Shellsol
no. of TBP D70
HCl (37%, Panreac) in order to simulate the composition of exp replicates configuration (% v/v)b (% v/v)c Va Vo Vs
SPS in terms of Zn2+, Fe2+, Cl− and H+. The organic liquid
1 2 NDSX 100 0.5 1 1
membranes consisted of the pure extractant TBP (97%, Sigma-
2d 4 NDSX 50 50 0.5 1 1
Aldrich) or of the TBP diluted in the aliphatic solvent Shellsol
3 2 NDSX 20 80 0.5 1 1
D70 (Kremer Pigmente). Tap water was utilized as stripping
4 2 EPT 80 20 1 0.8 0.2
solution in all the experiments.
5 2 EPT 80 20 0.5 1 1
2.2. Membrane-based Solvent Extraction Experi-
6d 4 EPT 50 50 0.5 1 1
ments. The experiments were performed at laboratory scale a
using mesoporous hollow fiber membrane contactors (HFMC, Va, feed solution volume; Vo, organic phase volume; Vs, stripping
solution volume. bTBP (%v/v): volume percent of TBP (carrier) in
Liqui-Cel Extra-Flow 2.5 × 8, Hoechst Celanese). The HFMC
the organic phase. cShellsol D70 (%v/v): volume percent of Shellsol
presented an effective mass-transfer area of 1.4 m2 and an D70 (solvent) in the organic phase. dExperiments performed with real
effective mass-transfer length of 0.15 m, and contained 10 200 and synthetic SPS.
polypropylene fibers. The fibers had a nominal porosity of 40%,
an average pore size of 0.03 μm and an internal diameter of 240
μm with a wall thickness of 30 μm. Figure 1 shows the selectivity of the separation process toward zinc over iron. Prior
experimental setup used for the extraction and back-extraction to each experiment, the organic solution was in contact with tap
of zinc from the aqueous systems using (a) NDSX and (b) EPT water for 30 min in order to (i) reach the maximum intake of
configurations. In NDSX configuration, the extraction and the water by fresh TBP and consequently, to minimize the water
back-extraction of the targeted compound were conducted in transport through the membrane and (ii) to wash the loaded
two different membrane modules and the nondispersive contact organic solution to be reused. During the NDSX and EPT
occurred between the spent acid and the organic extractant experiments the feed and stripping samples were taken
solutions and between the organic and the aqueous stripping regularly from the corresponding stirred tanks in order to
solutions, whereas in EPT, the extraction and the back- follow the development of zinc, iron, chloride and free acid
extraction were conducted in a single membrane module and concentration with time. The concentrations of the different
the nondispersive contact occurred between the feed SPS and species in the organic phase were calculated according to the
the pseudoemulsion prepared by dispersing the stripping mass balances.
solution into the organic phase. In both configurations, the The following methods were used for the sample
temperature of the experiments ranged from 22 to 35 °C due to quantification: atomic absorption spectrometry (PerkinElmer
the heating produced by fluid pumping. The difference in the 3110) for the determination of zinc and total iron, titration with
transmembrane pressure between the aqueous phase and the NaOH 0.1 mol L−1 and bromophenol blue solution 0.04% for
organic/emulsion phase was maintained constant at approx- the determination of H+, UV−vis spectroscopy (Spectroquant-
imately 0.15 bar in order to avoid the dispersion of the organic Pharo 100, λ = 500 nm) for the determination of Fe2+ and Fe3+
3219 DOI: 10.1021/acs.iecr.5b00099
Ind. Eng. Chem. Res. 2015, 54, 3218−3224
Industrial & Engineering Chemistry Research Article

by the Standard Method 3500-Fe B and Cl− by the Standard


Method 4500-Cl− E.25 When the experiments were repeated
the presented data are the mean values of the replications and
the related figures incorporate the corresponding error bars.

3. RESULTS AND DISCUSSION


3.1. Effect of Process Configuration. The effect of
process configuration, NDSX or EPT, on the selectivity of the
liquid membrane toward zinc versus iron separation was
evaluated by the comparison of experiments 2 and 6 listed in
Table 2. Figure 2 illustrates the development of zinc

Figure 3. Development of the concentration of iron with experimental


time in the (a) feed phase and (b) stripping phase using NDSX and
EPT configuration, and real and synthetic feed phase; [Fe]o = 97−103
g L−1, [TBP] = 50% (v/v).

total iron is present mainly as iron(II) in the forms of Fe2+ and


a minor amount of FeCl+ and both cationic species should be
rejected by TBP due to its solvating nature.32 However, TBP
may act also as a surfactant and Regel-Rosocka and co-
workers29−31 suggested that iron(II) was transported from the
aqueous solution to the stripping phase by means of
nonselective micromicelles. When the process separation was
Figure 2. Development of the concentration of zinc with experimental carried out using EPT, the concentration of iron in SPS
time in the (a) feed phase and (b) stripping phase using NDSX and decreased by 30%, whereas when using NDSX, it only
EPT configuration, and real and synthetic feed phase; [Zn]o = 115− decreased by 10%. On the other hand, the concentration of
121 g L−1, [TBP] = 50% (v/v). iron in the stripping phase when experiments were carried out
using EPT configuration reached 4 g L−1, whereas when using
concentration in the feed and stripping phases with NDSX, it was 1.5 g L−1. The higher interfacial area between the
experimental time. The results point out that the extraction dispersed stripping agent into the organic solution exhibited by
and stripping of zinc took place with higher rate when the EPT the EPT configuration compared to NDSX, enhanced the back-
configuration was used. The faster extraction and back- extraction of iron to the stripping agent and consequently the
extraction kinetics are related to the higher interfacial area extraction yield. The difference in the extracted and back-
between the dispersed stripping agent and the continuous extracted mass of iron was assigned to the metal accumulation
organic phase in EPT compared to NDSX.16,17,26 in the organic phase.
Chemical equilibrium is reached between the zinc species The selectivity (α) of the process toward zinc over iron in
contained in the liquid phases destroying the driving force for the stripping solution was calculated in the constant range of
zinc transport. The system equilibration was reached after 120 the back-extraction fluxes (J) (t < 30 min) in order to further
min when the separation was conducted with EPT whereas compare the performance of both configurations according to
more than 3 h of experimental run were required to achieve a the following equation:
similar performance when NDSX was employed. When
equilibrium conditions were reached, the concentration of JZn
αZn/Fe|t < 30 =
zinc in the feed phase had decreased from 120 to 25 g L−1, i.e., JFe (1)
79% of zinc removal, and the final concentration of zinc t < 30

reached in the stripping solution was 45 g L−1 independently The obtained results indicated that NDSX configuration
on the process configuration. promoted the selectivity of the separation process toward zinc
Figure 3 shows the development of iron concentration in the versus iron compared to EPT:αZn/Fe|NDSX = 2.2 × 10−6 kg Zn
feed and stripping phases with experimental time. The results m−2 s−1/9.9 × 10−8 kg Fe m−2 s−1 = 22 and αZn/Fe|EPT = 1.2 ×
indicate that iron is extracted and the rate is affected by process 10−5 kg Zn m−2 s−1/8.0 × 10−7 kg Fe m−2 s−1 = 15. The flux
configuration. Several studies have reported extraction of and selectivity values obtained in this work when using NDSX
iron(II) from 0.5% to 10% using TBP.1,3,24,27−31 In SPS, the were of similar level of magnitude than values previously
3220 DOI: 10.1021/acs.iecr.5b00099
Ind. Eng. Chem. Res. 2015, 54, 3218−3224
Industrial & Engineering Chemistry Research Article

observed in literature.20,33 To the best knowledge of the


authors, there is not available data to evaluate the selectivity of
the EPT configuration toward zinc over iron. The difference
between the selectivity values in EPT and NDSX is attributed
to the way in which the process configuration affects the zinc
and iron back-extraction fluxes. Due to the smaller driving
forces involved in the back-extraction of iron as compared to
zinc, the higher interfacial area provided by EPT in comparison
to NDSX reported a higher relative iron kinetics increase
(JFe,EPT/JFe,NDSX = 8.1) than the observed for zinc ((JZn,EPT/
JZn,NDSX = 5.4) in the constant range of the back-extraction
fluxes (t < 30 min).
Depending on the galvanic process, SPS may contain
different type and concentration of impurities such as metals,
ammonia and organic impurities. EPT and NDSX experiments
using synthetic samples were performed and compared with
experiments 2 and 6 in order to evaluate the effect of the matrix
composition on the process selectivity. The experiments were
conducted using 50% (v/v) of TBP and 180 min of
experimental time. Figures 2 and 3 illustrate the development
of the zinc and iron concentration respectively in aqueous and
stripping phase when synthetic solutions were used. The results
point out that the influence of the SPS complex matrix of in the Figure 4. Development of the concentration of zinc with experimental
extraction and back-extraction of zinc and iron was minor for time in the (a) feed phase and (b) stripping phase using different
both EPT and NDSX configurations. The lack of iron(III) in concentrations of TBP and the NDSX configuration; [Zn]o = 120 g
synthetic samples and the existence of iron in the obtained L−1.
stripping phase indicate that Fe2+ is the transported species
from the feed phase to the stripping phase. This fact could be stripping phase after 240 min, compared to the use of a 20%
supported by the micellar transport theory, in which Fe2+ is (v/v) extractant solution, 35 g Zn L−1. However, the utilization
transported from the aqueous solution to the stripping phase by of 100% (v/v) TBP solutions as extractant did not further
means of nonselective micromicelles.29−31 enhance zinc concentration in spite of the fact that the liquid
3.2. Effect of Extractant Concentration. The study of the membrane consisting of 100% (v/v) TBP extracted more zinc
effect of TBP concentration on the extraction of zinc was than when it was composed of 50% (v/v) TBP. This may be
carried out using the NDSX configuration. This was because of due to the fact that more stripping solution would be needed
the better selectivity of the process toward zinc when NDSX for back-extracting the accumulated zinc in the organic phase.
was used compared to EPT. Three experiments were From the operational process perspective, this need of more
performed using different concentrations of TBP: 100% (v/ volume of stripping could be tackled by the implementation of
v), 50% (v/v) and 20% (v/v) that correspond to experiments a semicontinuous system provided with a purge. This system
1−3. Table 2 indicates the experimental conditions. would allow the intake of a stripping agent during the process
Figure 4 shows the development of the concentration of zinc that will shift the chemical equilibrium between organic/
in the aqueous and stripping phases when different stripping phases. This fact could allow reaching higher
concentrations of TBP were used. The results showed that percentages of zinc extraction and back-extraction.
increasing TBP concentration promoted the extraction kinetics Figure 5 shows the development of the concentration of iron
of zinc. The use of 20% (v/v) of TBP implied that the in the aqueous and stripping phase using different concen-
equilibrium conditions were not attained after 240 min of trations of TBP. The amount of total iron in the stripping phase
experimental run and led to an extraction of 47% of zinc. On ranged from 1 to 2 g L−1, indicating that TBP concentration
the other hand, the use of 50% (v/v) and 100% (v/v) of TBP affected iron extraction. This may be due to the surfactant
implied an extraction of zinc about 80% when equilibrium properties of TBP; the higher the TBP concentration, the
between the liquid phases was reached at 180 and 120 min, closer to the critical micelle concentration (CMC) and the
respectively. The difference in the extraction kinetics at higher the possibilities of the iron transport by means of
different TBP levels was due to the fact that more TBP was nonselective micromicelles. This was also observed by Regel-
available for the generation of the zinc-TBP complex. The Rosocka and co-workers.29−31 On the other hand, the
removal of zinc from SPS was limited by the chemical extraction values for iron varied from 10 to 15% and the effect
equilibrium between the aqueous and organic phases; of TBP concentration on iron extraction from SPS could not be
consequently, increasing TBP concentration impacted on the accurately identified due to the fact that the amount of iron
time needed to reach the equilibrium. Mansur et al.3 reported extracted from SPS was minor compared to the remaining iron
that the extraction of zinc was 3 times higher when TBP in solution.
concentration increased from 25% (v/v) to 100% (v/v). In Further, high concentrations of chloride and free acidity in
accordance with Figure 4, Regel-Rosocka31 observed that the the presence of zinc enhance the formation of acid-complexes
influence of the concentration of TBP on the extraction of zinc with the general formula Hn+[ZnCln+2]−n with n = 0, 1, 2.32
was minor in the range of 80% (v/v) to 100% (v/v). Morris and Short33 proposed that at low acidity the formed
Further, the use of organic solution containing 50% (v/v) of zinc/TBP complexes were HZnCl3 and ZnCl2·2TBP, and at
TBP entailed a higher concentration of zinc, 45 g Zn L−1, in the acidity above 2.7 mol L−1 the complex H2ZnCl4·2TBP was
3221 DOI: 10.1021/acs.iecr.5b00099
Ind. Eng. Chem. Res. 2015, 54, 3218−3224
Industrial & Engineering Chemistry Research Article

Figure 5. Development of the concentration of iron with experimental Figure 6. Molar ratio of chloride/zinc during the (a) extraction and
time in the (a) feed phase and (b) stripping phase using different (b) back-extraction processes using different TBP concentrations as
concentrations of TBP and the NDSX configuration; [Fe]o = 90−100 liquid membrane.
g L−1.

detected. Regel-Rosocka et al.24 reported that at low acidity of


the feed phase ZnCl2 was the predominant species and at
higher acidity HZnCl3 and H2ZnCl4 were found. Several
researchers determined that the predominant zinc−chloro
complex in the SPS was H 2 ZnCl 4 using MEDUSA
software.23,24,27,34−38
The analysis of the molar ratios between the extracted and
back-extracted chloride and zinc, and protons and zinc
concentrations attained in the present experimental study
allows the evaluation of the main zinc chlorocomplexes
involved in the separation process. From the results depicted
in Figure 6, it is confirmed that all the values of the molar ratio
chloride/zinc obtained in the extraction and back-extraction
experiments were within the range from 2 to 4, as expected
from the general formula of zinc chlorocomplexes. However,
most of the data varied in the range from 3 to 2, thus
confirming, as expected from the literature, that HZnCl3 and
ZnCl2 were the preferable extracted species that react with TBP
as follows38
HZnCl3 + 3TBP ⇔ HZnCl3·3TBP (2)

ZnCl 2 + 2TBP ⇔ ZnCl 2·2TBP (3)


Figure 7 illustrates that the values of the molar ratio protons/ Figure 7. Molar ratio of free acid/zinc during (a) extraction and (b)
zinc in the extracted and back-extracted species, HZnCl3·3TBP back-extraction processes using different TBP concentrations as liquid
and ZnCl2·2TBP, were in the range between 0 and 1. These membrane.
values confirm the extraction mechanisms given by eqs 2 and 3.
The presence of H+ in the stripping solution may affect
positively the electrodeposition of zinc. Further, the existence that observed in the case of zinc performance. However, these
of Cl− can have a negative impact on the effectiveness of the values depend on the zinc concentration achieved in the
process because it is oxidized to chlorine. Therefore, the stripping solution.
concentration of the former species should be maximized and 3.3. Effect of Phase Volume. EPT was selected to perform
minimized, respectively. The concentration of H+ in the the study of the influence of the volume of the liquid phases on
stripping solution varied from 0.12 to 0.6 and that of Cl− the process performance because of the higher rates of zinc and
from 1.1 to 1.8 when the concentration of TBP was modified iron extraction when EPT was used compared to NDSX. Table
from 20% (v/v) to 100% (v/v) following a similar trend than 2 shows the experimental conditions of experiments 4 and 5
3222 DOI: 10.1021/acs.iecr.5b00099
Ind. Eng. Chem. Res. 2015, 54, 3218−3224
Industrial & Engineering Chemistry Research Article

where the volumes of feed (Va → 1 and 0.5 L), organic (Vo → 4. CONCLUSIONS
0.8 and 1 L) and stripping (Vs → 0.2 and 1 L) phases had been The separation of zinc from spent pickling solutions (SPS)
changed. Therefore, the variation of the volume of the organic versus iron is a key strategy to improve the resource recovery
phase was minor and the volume ratio of the stripping to the efficacy in hot-dip galvanizing processes. Zinc may be further
feed aqueous phase Vs/Va was varied between 0.2 (experiment recovered by electrowinning and the viability will depend on
4) and 2 (experiment 5). Figure 8 illustrates the development the presence of iron, chloride and free acid. This study shows
that emulsion pertraction technology (EPT) and nondispersive
solvent extraction (NDSX) are effective when removing zinc
versus iron from SPS using tributylphosphate (TBP) as an
extractant and water as a stripping agent. The kinetics of the
extraction and back-extraction of zinc were demonstrated to be
promoted by EPT, increasing the TBP concentration in the
range between 20% (v/v) and 50% (v/v) and increasing the
stripping volume from 0.2 to 1 L. On the other hand, the
transport of iron was enhanced by EPT, high TBP
concentration and increasing stripping volume. The efficacy
of the separation process was established to be mainly limited
by the chemical equilibria between the feed/organic and
organic/stripping phases. Therefore, this works highlights first
Figure 8. Development of the concentration of zinc with experimental the mechanisms and kinetics responsible of the transport of
time in the feed phase and stripping phase using 80% (v/v) of TBP zinc and iron from SPS and second the importance of
and the EPT configuration. implementing a semicontinuous system that allows a
continuous replacement of stripping in order to further
of the mass of zinc in the feed and stripping phases with improve the zinc recovery rate. Additionally, the species
experimental time. The comparison of the results obtained in involved in zinc transfer through the organic liquid membrane
both experiments indicates that increasing the volume of the were confirmed to be HZnCl3·3TBP and ZnCl 2·2TBP. Further
stripping phase promoted the extraction kinetics of zinc. After 2 research should be driven by the definition of the maximum
h of experimental running, the extraction percentages of zinc acceptable values of pH, chloride and iron concentration for
were 35% and 81% in experiments 4 and 5, respectively; conducting the recovery of zinc by electrodeposition. The
however, the mass of zinc extracted was around 40 g in both results obtained in the present study contribute to the design of
experiments. On the other hand, the concentration of zinc in the zinc separation process considering this complex scenario.


the stripping phase obtained in experiment 4 was 102 g L−1,
whereas in experiment 5, the concentration was 36 g L−1, with AUTHOR INFORMATION
the mass of back-extracted zinc being 20 and 36 g, respectively.
Therefore, the increase of the volume ratio Vs/Va positively Corresponding Author
influenced the effectiveness of the back-extraction stage which *Ane Urtiaga. E-mail: urtiaga@unican.es. Phone: +34
varied from ≈50% (experiment 4) to ≈90% (experiment 5). 942201587. Fax: +34 942201591.
The improvement on the stripping performance at high volume Notes
ratios minimizes the accumulation of zinc in the organic The authors declare no competing financial interest.
solution and it is related to the closeness between the extraction
and back-extraction rates.
The improvement in the back-extraction step promoted the
■ ACKNOWLEDGMENTS
Financial support of the Spanish Ministry of Economy and
regeneration of TBP. Thus, the amount of free extractant Competitiveness under the project CTQ2012-31639 (FEDER
contained in the organic phase is increased. This fact affected 2007-2013) and under Juan de la Cierva programme, and of the
positively the extraction step, obtaining faster kinetics of zinc company is gratefully acknowledged.


extraction. This was in agreement with results previously
obtained by Carrera et al.17 REFERENCES
The extraction of iron from SPS was verified by its (1) Cook, S. J.; Perera, J. M.; Stevens, G. W.; Kentish, S. E. The
quantification in the stripping phase in the final conditions. screening of extractants for the separation of Zn(II) from Australian
The final concentration of iron in experiment 4 was 2.5 g L−1, hot-dip galvanizing effluent. Sep. Sci. Technol. 2011, 46, 2066.
whereas in experiment 5, it was 6.6 g L−1. The promotion of (2) Csicsovszki, G.; Kékesi, T.; Török, T. I. Selective recovery of Zn
iron extraction followed a similar behavior as that observed for and Fe from spent pickling solutions by the combination of anion
zinc, which was related to the better washing of the organic exchange and membrane electrowinning techniques. Hydrometallurgy
solution at higher water volumes. 2005, 77, 19.
Consequently, a balance among the phases volume must be (3) Mansur, M. B.; Ferreira Rocha, S. D.; Silva Magalhaes, F.; dos
considered in order to obtain the maximum extraction of zinc Santos Benedetto, J. Selective extraction of zinc(II) over iron(II) from
from SPS and the maximum recovery of zinc in the stripping spent hydrochloric acid pickling effluents by liquid-liquid extraction. J.
Hazard. Mater. 2008, 150, 669.
phase with the lowest amount of iron impurities. As was (4) Regel-Rosocka, M.; Wisniewski, M. Selective removal on zinc(II)
pointed out in Section 3.2, the implementation of a from spent pickling solutions in the presence of iron ions with
semicontinuous system with continuous replacement of phosphonium ionic liquid Cyphos IL 101. Hydrometallurgy 2011, 110,
stripping phase seems to be the more convenient process 85.
configuration to handle the volume ratios needed to achieve the (5) Infomine. Mining intelligence & technology. http://www.
separation and recovery objectives. infomine.com/ (accessed September 2014).

3223 DOI: 10.1021/acs.iecr.5b00099


Ind. Eng. Chem. Res. 2015, 54, 3218−3224
Industrial & Engineering Chemistry Research Article

(6) Regel-Rosocka, M. A review on methods of regeneration of spent (24) Regel-Rosocka, M.; Sastre, A. M.; Szymanowski, J. Recovery of
pickling solutions from steel processing. J. Hazard. Mater. 2010, 177, zinc(II) from HCl spent pickling solutions by solvent extraction.
57. Environ. Sci. Technol. 2001, 35, 630.
(7) Mohapatra, P. K.; Bhattacharyya, A.; Manchanda, V. K. Selective (25) Clesceri, L. S. Standard Methods for the Examination of Water
separation of radio-cesium from acidic solutions using supported liquid and Wastewater, 20th ed.; American Public Health Association:
membrane containing chlorinated cobalt dicarbollide (CCD) in Washington, DC, 1998.
phenyltrifluoromethylsulphone (PTMS). J. Hazard. Mater. 2010, (26) Bringas, E.; San Román, M. F.; Ortiz, I. Separation and recovery
181, 679. of anionic pollutants by emulsion pertraction technology. Remediation
(8) San Román, M. F.; Bringas, E.; Ibañez, R.; Ortiz, I. Liquid of polluted groundwaters with Cr(VI). Ind. Eng. Chem. Res. 2006, 45,
membrane technology: Fundamentals and review of its applications. J. 4295.
Chem. Technol. Biotechnol. 2010, 85, 2. (27) Bartkowska, M.; Regel-Rosocka, M.; Szymanowski, J. Extraction
(9) Carrillo-Abad, J.; García-Gabaldón, M.; Ortega, E.; Pérez- of zinc(II), iron(III) and iron(II) with binary mixtures containing
tributyl phosphate and di(2-ethylhexyl) phosphoric acid or cyanex 302.
Herranz, V. Electrochemical recovery of zinc from the spent pickling
Physicochem. Probl. Miner. Process. 2002, 36, 217.
baths coming from the hot dip galvanizing industry. Potentiostatic
(28) Miesiac, I.; Kirschling, P.; Szymanowski, J. Extraction of zinc(II)
operation. Sep. Purif. Technol. 2011, 81, 200. from hydrochloric acid solutions in membrane contactors. In
(10) Carrillo-Abad, J.; García-Gabaldón, M.; Ortega, E.; Pérez- International Conference on Metallurgical High Technology New Materials
Herranz, V. Recovery of zinc from spent pickling solutions using an Heavy Nonferrous Metals, Kunming, China, April 3−5, 2002.
electrochemical reactor in presence and absence of an anion-exchange (29) Regel-Rosocka, M.; Sastre, A. M.; Szymanowski, J. Zinc(II)
membrane: Galvanostatic operation. Sep. Purif. Technol. 2012, 98, 366. Extraction from Hydrochloric Acid Solutions with Basic and Solvating
(11) Diban, N.; Mediavilla, R.; Urtiaga, A.; Ortiz, I. Zinc recovery and Extractants; XVII-th ARS SEPARATORIA: Borowno, Poland, 2002.
waste sludge minimization from chromium passivation baths. J. (30) Regel-Rosocka, M.; Miesiac, I.; Cierpiszewski, R.; Mishonov, I.;
Hazard. Mater. 2011, 192, 801. Alejski, K.; Sastre, A. M.; Szymanowski, J. Recovery of zinc(II) from
(12) Diban, N.; García, V.; Alguacil, F.; Ortiz, I.; Urtiaga, A. spent hydrochloric acid solutions from zinc hot-dip galvanizing plants.
Temperature enhancement of zinc and iron separation from Hydrometallurgy 2003, 2, 1577.
chromium(III) passivation baths by emulsion pertraction technology. (31) Regel-Rosocka, M.; Szymanowski, J. Iron(II) transfer to the
Ind. Eng. Chem. Res. 2012, 51, 9867. organic phase during zinc(II) extraction from spent pickling solutions
(13) García, V.; Steeghs, W.; Bouten, M.; Ortiz, I.; Urtiaga, A. with tributyl phosphate. Solvent Extr. Ion Exch. 2005, 23, 411.
Implementation of an eco-innovative separation process for a cleaner (32) Samaniego, H. Valorización de efluentes de decapado ácido
chromium passivation in the galvanic industry. J. Clean. Prod. 2013, 59, metálico. Recuperación de zinc. Doctoral Thesis, Universidad de
274. Cantabria, Santander, Spain, 2006.
(14) Urtiaga, A. M.; Bringas, E.; Mediavilla, R.; Ortiz, I. The role of (33) Morris, D. F. C.; Short, E. L. Zinc chloride and zinc bromide
liquid membranes in the selective separation and recovery of zinc for complexes. Part II. Solvent-extraction studies with zinc-65 as tracer. J.
the regeneration of Cr(III) passivation baths. J. Membr. Sci. 2010, 356, Chem. Soc. 1962, 2662.
88. (34) Lum, K. H.; Stevens, G. W.; Perera, J. M.; Kentish, S. E. The
(15) Bringas, E.; San Román, M. F.; Urtiaga, A. M.; Ortiz, I. modelling of ZnCl2 extraction and HCl co-extraction by TBP diluted
Membrane contactors (NDSX and EPT): An innovative alternative for in ShellSol 2046. Hydrometallurgy 2013, 133, 64.
the treatment of effluents containing metallic pollutants. Inter. J. (35) Mishonov, I. V.; Alejski, K.; Szymanowski, J. A contributive
study on the stripping of zinc(II) from loaded TBP using an
Environ. Waste Manage. 2012, 9, 201.
ammonia/ammonium chloride solution. Solv. Extr. Ion. Exch. 2004, 22,
(16) Carrera, J. A.; Bringas, E.; San Román, M. F.; Ortiz, I. Selective
219.
membrane alternative to the recovery of zinc from hot-dip galvanizing
(36) Niemczewska, J.; Cierpiszewski, R.; Szymanowski, J. Mass
effluents. J. Membr. Sci. 2009, 326, 672. transfer of zinc(II) extraction from hydrochloric acid solution in the
(17) Carrera, J. A.; Muñoz, E.; Bringas, E.; San Román, M. F.; Ortiz, Lewis cell. Desalination 2004, 162, 169.
I. Influence of operational variables on the recovery of zinc from spent (37) Rice, N. M.; Smith, M. R. Recovery of zinc, cadmium, and
pickling effluents using the emulsion pertraction technology. mercury(II) from chloride and sulphate membrane by solvent
Desalination 2009, 245, 675. extraction. J. Appl. Chem. Biotechnol. 1975, 25, 379.
(18) Lum, K. H.; Cook, S. J.; Stevens, G. W.; Perera, J. M.; Kentish, (38) Samaniego, H.; San Román, M. F.; Ortiz, I. Modelling of the
S. E. Zinc chloride and hydrochloric acid coextraction from galvanizing extraction and back-extraction equilibria of zinc from spent pickling
pickling waste in the presence of iron(II). Results with hollow fiber solutions. Sep. Sci. Technol. 2006, 41, 757.
membrane contactors. Ind. Eng. Chem. Res. 2014, 53, 4453.
(19) Lum, K. H.; Stevens, G. W.; Kentish, S. E. Development of a
process for the recovery of zinc sulphate from hot-dip galvanizing
spent pickling liquor via two solvent extraction steps. Hydrometallurgy
2014, 142, 108.
(20) Ortiz, I.; Bringas, E.; San Román, M. F.; Urtiaga, A. M. Selective
separation of zinc and iron from spent pickling solutions by
membrane-base solvent extraction: Process viability. Sep. Sci. Technol.
2004, 39, 1.
(21) Samaniego, H.; San Román, M. F.; Ortiz, I. Kinetics of zinc
recovery from spent pickling effluents. Ind. Eng. Chem. Res. 2007, 46,
907.
(22) Sinha, M. K.; Sahu, S. K.; Meshram, P.; Pandey, B. D. Solvent
extraction and separation of zinc and iron from spent pickle liquor.
Hydrometallurgy 2014, 147−148, 103.
(23) Cierpiszewski, R.; Miesiac, I.; Regel-Rosocka, M.; Sastre, A. M.;
Szymanowski, J. Removal of zinc(II) from spent hydrochloric acid
solutions from zinc hot galvanizing plants. Ind. Eng. Chem. Res. 2002,
41, 598.

3224 DOI: 10.1021/acs.iecr.5b00099


Ind. Eng. Chem. Res. 2015, 54, 3218−3224