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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.
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
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.
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
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