water research 43 (2009) 1464–1470

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The use of microemulsions to remove chromium

from industrial sludge

T.N. Castro Dantasa,*, K.R. Oliveiraa, A.A. Dantas Netob, M.C.P.A. Mourab
a
Departamento de Quı́mica, Universidade Federal do Rio Grande do Norte, Campus Universitário, CEP: 59072-970 Natal, RN, Brazil
b
Departamento de Engenharia Quı́mica, Universidade Federal do Rio Grande do Norte, Campus Universitário,
CEP: 59072-970 Natal, RN, Brazil

article info abstract

Article history: In this work microemulsion systems were used to remove chromium from leather tannery
Received 27 August 2008 sediments. The sludge was treated by a solid–liquid extraction process (acid digestion). The
Received in revised form effects of particle size, digestion temperature and digestion time with regards to the effi-
16 December 2008 ciency of chromium removal were considered. The raw sludge (3 Mesh) was dried,
Accepted 18 December 2008 grounded and sieved. Particles with 3, 14, 65, 100, 200, and 325 Mesh were evaluated. Sludge
Published online 8 January 2009 digestion solutions were prepared using each studied granule size at 25  C, 70  C, and 95  C.
Microemulsion extraction experiments to remove chromium III from the acid digestion
Keywords: solution were made according to a Scheffé Net experimental design methodology, using
Leather sediments microemulsion systems inside the Winsor II region (System I) and inside the micro-
Digestion process emulsion region (Winsor IV – System II). A statistical treatment was used to obtain the
Chromium isoresponse plots. Chromium extraction percentages were up to 73.3% for System I and up
Microemulsion to 93.4% for System II.
Scheffé Net ª 2008 Elsevier Ltd. All rights reserved.

1. Introduction organic matter, magnesium, calcium, high chromium

Heavy metals are introduced in many natural environments
mainly by industrial activities. They are not only harmful to
the receiving water bodies, but also to the living community of
these environments. These metals, in their elementary form,
generally are not absorbed by human gastrointestinal tract. Its
salts, however, can be absorbed by ingestion, inhalation or
contact with skin, negatively affecting human and animal
healths (WHO, 1988).
Leather tanneries transform raw animal skin in leather by
means of a series of mechanical operations and chemical
treatments. Chromium, in the form of basic chromium
sulfate, is used in mineral tanning due to its ability to give to
the final product a good stability and resistance. In the raw
state, chrome-tanned-skins are referred to as ‘‘wet blue’’.
Leather tannery sediments consist mainly of oil, grease,
content, skin fragments, and others (Basegio et al., 2002;
Jordão et al., 1998; Chuan and Liu, 1996).
Chromium is usually found in the environment in the (III)
and (VI) oxidation states [Cr(III) and Cr(VI)]. Of these more
common oxidation states of chromium, Cr(VI) is very soluble
and toxic, whereas Cr(III) is more stable and features lower
toxicity (Stasinakis et al., 2003; Kotás and Stasicka, 2000). In
the United States, the maximum permissible concentration of
chromium in wastewaters to be discharged in natural waters
is 2 mg L1 (USEPA, 2002).
Microemulsions have been an interesting subject because
they can be used in many fields, such as separation processes,
chemical reactions, and material preparation (Cheng et al.,
2007). A microemulsion is defined as a system formed by the
dispersion of microdroplets of two immiscible liquids, stabi-
lized by an interfacial membrane formed by surfactant and

* Corresponding author. Tel./fax: þ55 84 3215 3827.

E-mail address: tereza@eq.ufrn.br (T.N. Castro Dantas).
0043-1354/$ – see front matter ª 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2008.12.047
 water research 43 (2009) 1464–1470 1465

cosurfactant. They are thermodynamically stable, homoge-

Table 1 – Raw sludge composition (3 Mesh, by dry weight
neous and optically isotropic solutions (Winsor, 1954; Solans %, w/w).
and Ponds, 1997).
Parametera (%) Parameter (%)
In excess of oil, the microemulsion is water-continuous
(Winsor I – WI) and in excess of water it is said to be oil- Organic matter 49.86 Magnesium (Mg) 1.41
continuous (Winsor II – WII). In a Winsor III (WIII) system three Calcium (Ca) 20.05 Sulfur (S) 1.01
Chromium (Cr) 13.32 Manganese (Mn) 0.85
phases are present, where the middle phase microemulsion is
Aluminum (Al) 4.58 Iron (Fe) 0.77
in equilibrium with both excess aqueous and organic phases,
Sodium (Na) 3.61 Phosphorus (P) 0.54
and in a Winsor IV (WIV) system only a microemulsion phase Chlorine (Cl) 1.79 Potassium (K) 0.15
is formed (Castro Dantas et al., 2003). Silicon (Si) 1.72 Strontium (Sr) 0.06
Extraction of heavy metals by microemulsion systems can Zinc (Zn) 0.03 – –
be very advantageous as compared with conventional treat-
a Metals determined by using X-ray fluorescence spectrometry.
ment techniques, mainly related to contamination with
solvents and energy consumption. Castro Dantas et al. (2001,
2003) and Dantas Neto et al. (2004) applied microemulsion 2.3. Solid sludge digestion
systems to remove heavy metals from aqueous solutions.
They evaluated the efficiency of these systems in liquid–liquid Oliveira (2003) studied three acid digestion methods in the
extraction processes and as a surface modifier agent of solubilization of tannery sludge. The three methods were
natural clay. The results obtained by these authors showed tested and Method I, proposed by USEPA (1986), presented the
the potential of microemulsion systems to remediate heavy best digestion result (97.66% of the initial raw sediment mass),
metal pollution. followed by Method II, proposed by Chuan and Liu (1996), with
Venditti et al. (2007) developed a new adsorbent, CTAB- 72.97% digestion and Method III, proposed by Cunha and
silica gelatin composite, aiming its application to remove Simões (1999), with 68.25% digestion.
hexavalent chromium from aqueous solutions. The new Method I was applied in this work. The sludge sample was
adsorbent was obtained by adding the silica precursor tetra- digested using concentrated nitric acid (HNO3) and hydrogen
thoxysilane to a microemulsion-based gel. They concluded peroxide (H2O2 – 30%) at 95  C heating temperature. The
that a reasonable amount of chromium can be removed from following parameters were evaluated during the digestion
aqueous solutions at neutral pH (7.5). process: granule size, pH, digestion temperature, and diges-
Vijayalakshmi and Gulari (1992) studied the removal of tion time.
trivalent metals by using a water-in-oil microemulsion of
Aerosol-OT. They showed that it is possible to enhance the
2.4. Metal quantification
aqueous metal ion concentrations to a large extent by using
suitable microemulsions as extractant, being the process
The determination of chromium concentration was carried
more efficient for trivalent metals ions than for bivalent ones.
out before and after microemulsion extraction. It was used
The scope of the present study was to investigate the use of
a Varian SpectrAA-10-Plus atomic absorption spectropho-
two microemulsion systems to remove chromium from
tometer. Solutions were prepared with all studied granule
a chromium-rich solution obtained by acid digestion of
sizes and analyzed to determine the initial chromium
tannery sludge. The influence of granule size, digestion time,
concentration.
and heating temperature in the digestion process was
assessed.
2.5. Surfactant synthesis

2. Materials and methods The surfactant was derived from coconut oil (Rio Grande do
Norte regional production – chemical composition (%): octa-
2.1. Tannery sludge noic acid – 7.6, decanoic acid – 7.3, lauric acid – 48.2, myristic
acid – 16.6, palmitic acid – 8.0, stearic acid – 3.8, oleic acid – 5.0,
The material was collected from a local industry and used linoleic acid – 2.5) with the saponification reaction carried out
without further treatment. It was dried under free, normal with sodium hydroxide (NaOH) in a stoichiometric reaction
atmosphere (30  C). Raw sludge with 3-Mesh particle size was
obtained. This material was grounded in a common two-bladed
mill and analyzed to determine its composition (Table 1).
Table 2 – Size distribution of the sludge particles (by dry
weight %, w/w).
2.2. Granule size analysis
Tyler (Mesh) Size (mm) Retained (%)
The grounded sediment was sieved in a series of Tyler sieves 3 6.68 41.95
to separate the particles with different sizes (3, 14, 65, 100, 200, 14 1.17 50.01
and 325 Mesh), as shown in Table 2. This operation was per- 65 0.21 5.99
formed in a sieving column (Betel brand) during an allowed 100 0.15 0.77
200 0.07 0.50
time of 15 min, long enough to effect the separation according
325 0.03 0.43
to the studied granule sizes.
1466 water research 43 (2009) 1464–1470

(1:1 ratio). The surfactant, a soap mixture, was used without The extraction percentages were calculated by using the
further purification. following equations:
The anionic surfactant obtained (SCO – Saponified Coconut
Oil) has one or several functional groups ionized in aqueous
Madded ¼ VE.CE (1)
solution, supplying ions negatively charged in the active
surface which interacts with chromium ions. The surfactant is
Maqueous phase ¼ VAP.CAP (2)
of great importance in the used extraction system, being the
direct responsible by the interactions with the metal to be


extracted. Madded  Maqueous phase
ECr ¼  100 ð%Þ (3)
Madded
2.6. Heavy metal extraction
where: Madded is the total amount of metal added to the
Taking into account precipitated formation in the aqueous systems (g); Maqueous phase is the total amount of metal in
phase (digestion solution) during preliminary extraction the aqueous phase after extraction (g); VE is the volume of acid
rehearsals, it was decided to use two microemulsion extrac- digestion solution used in the system; VAP is the volume
tion systems: System I, in a Winsor II region, using as aqueous of aqueous phase after extraction; CE is the concentration of
phase the acid digestion solution, and System II, in a Winsor metal in the acid digestion solution; CAP is the concentration
IV region, being obtained by the addition of the acid digestion of metal in the aqueous phase after extraction and ECr is the
solution to a microemulsion phase, whose aqueous phase is percentage of chromium extracted.
distilled water, until the formation of a Winsor II system.
The Winsor’s systems regions were determined through
pseudoternary phase diagrams. To determine the Winsor’s 3. Results and discussion
regions, the oil phase (OP) was mixed with the cosurfactant
(C)/surfactant (S) phase (pseudo-constituent pure – C/S) and 3.1. Tannery sludge digestion
the mixture was titrated with the aqueous phase (AP) until it
turned clear. The volume of AP used was then recorded. Table 3 shows the obtained percentage of solid sludge diges-
Titration was continued until the mixture turned turbid and, tion for different granule sizes and temperatures by using the
again, the AP volume was recorded. The pseudoternary phase methodology described by USEPA (1986).
diagram was constructed by plotting the amounts of aqueous According to the results shown in Table 3 it can be
phase, oil phase, and C/S phase used in each experiment. observed that the used acid digestion methodology provided
After determination of Winsor’s systems, points were high percentage of solid sludge digestion, as high as 97.7%.
defined inside the WII (microemulsion þ aqueous phase in Relating to the influence of temperature and granule size
excess) and WIV (only microemulsion) regions with the on the acid digestion of the solid sludge, it was observed that
purpose to delimitate the region of interest (Scheffé Net). at 25  C and with 3-Mesh particle size (raw sediment) the
Thereafter, a Scheffé Net experimental design was applied in percentage of waste digestion was very low, in that a value as
order to describe the behavior of the system in a wider area low as 60% was obtained, as compared to the values obtained
with a reduced number of experiments. The systems used to when 70  C and 95  C were used. It can also be seen that the
obtain the pseudoternary phase diagrams were composed by:
System I (WII) – surfactant (SCO), cosurfactant (n-butanol), oil
phase (kerosene), aqueous phase (solid digestion solution, pH
Table 3 – Acid digestion of raw sediments.
3.5), C/S ¼ 4, at 27  C; System II (WIV) – surfactant (SCO),
cosurfactant (n-butanol), oil phase (kerosene), aqueous phase Experimental conditions
(distilled water), C/S ¼ 4, at 27  C. Temperature ( C) Granule size (Mesh) Yield (%)
The microemulsion extraction systems were obtained by
25 3 60. 9
mixing the surfactant, cosurfactant, oil phase, and aqueous
70 3 94.6
phase in compositions pre-defined by the experimental
95 3 95.8
design methodology (Scheffé Net). 25 14 87.3
In System I (WII) the pH of the acid digestion solution 70 14 94.3
(aqueous phase) was adjusted to 3.5 by using 0.1 N sodium 95 14 97.7
hydroxide solution (NaOH). The system was maintained in 25 65 93.9
constant stirring during 20 min and after that at rest until 70 65 97.0
95 65 97.1
complete phase separation. The aqueous phase in excess,
25 100 94.0
poor in heavy metal, was separated withdrawing by using 70 100 96.9
a syringe and taken for analysis by flame atomic absorption 95 100 97.5
spectroscopy (FAAS). 25 200 94.0
Chromium extraction with System II was performed by 70 200 96.8
adding the microemulsion with known composition, inside 95 200 96.9
25 325 95.5
the pseudoternary phase diagram and according to the points
70 325 96.4
selected in the experimental design, to the digestion solution
95 325 97.4
until phase separation (WII).
 water research 43 (2009) 1464–1470
best results were obtained at 95  C, with digestion percentages
higher than 98%. In fact, the best percentages were obtained
with 14-Mesh granule size and up, due to an increased
homogeneity as compared with 3-Mesh samples.
3.2. Influence of temperature and granule size on the
release of chromium from tannery sludge
To evaluate chromium release from tannery sediments,
experiments were performed at 25  C, 70  C, and 95  C, using
several granule sizes (14, 65, 100, 200, and 325 Mesh). The
results are shown in Fig. 1.
It can be observed that the release of chromium from
sludge was more efficient after 14-Mesh granule size, at 70  C
and 95  C, being this granule size used in chromium extraction
by microemulsion. The 65, 100, 200, and 325-Mesh granule
sizes can also be used, but implies in additional energy
consumption. It follows that particle size is a very important
parameter to be considered when acid digestion processes are
to be implemented.
The metal concentration in the acid digestion solution was
479.86 ppm (Table 4), much higher than the maximum allowed
by the environmental regulation from Brazilian Environ-
mental National Council (CONAMA, 2005). This study suggests
that the waste requires treatment and, in this case, the acid
digestion solution must be processed differently, for example
by means of a liquid–liquid extraction operation, so as to lower
the chromium concentration to the permissible levels.
3.3. Effect of digestion time in chromium release
To evaluate chromium release, in this study acid digestion
was accomplished using 14-Mesh tannery sludge during 30
and 60 min digestion time, at 25  C and 95  C. Table 4 shows
the obtained results.
By analyzing Table 4 it can be observed that the best result
was obtained with 60 min digestion time at 95  C, being these
conditions adopted in posterior experiments.
3.4. Influence of pH in chromium concentration
It was verified in preliminary experiments the necessity to
increase the pH of chromium acid solution to obtain a Winsor
Fig. 1 – Temperature and granule size influence in
chromium release.
1467
Table 4 – Effect of temperature and digestion time in
chromium release using 14-Mesh sediment.
T ( C) Digestion time (min) Chromium (ppm)
25 30 330.67
25 60 345.10
95 30 411.05
95 60 479.86
II system (System I). NaOH solution (1.0 N) was used for this
purpose. Chromium concentration of the acid solution was
obtained at pH 0.6 (initial acid digestion solution pH), 1.5 and
3.5, as can be observed in Table 5.
It can be noticed that when the pH of the acid digestion
solution is increased a reduction in chromium concentration
occurs due to precipitate formation. As in System I, the
aqueous phase of the microemulsion is the chromium acid
digestion solution and an increase in pH value is observed
when the surfactant is added to the system, it was decided to
use the solution at pH 3.5 to avoid any precipitation. In System
II, the microemulsion system was made using distilled water
as aqueous phase and the extraction of chromium is accom-
plished by contacting the microemulsion phase with the
chromium digestion solution in its original pH (pH 0.6).
3.5. Chromium extraction by microemulsion
The pseudoternary phase diagrams with the experimental
points (12 points) which form the Scheffé Net, for Systems I
and II, are shown in Figs. 2 and 3. The adopted compatibility
region for the experimental design study was the Winsor II
region for System I and Winsor IV region for System II.
Chromium extraction efficiency by microemulsions was
evaluated by using the selected experimental points. The
extraction process using System I was accomplished by
placing the aqueous solution with the metal to be extracted
(acid digestion solution) in contact with the oil phase and
active matter (cosurfactant þ surfactant) according to the
points selected by the experimental design. Table 6 shows
the composition of the studied points and the results obtained
for chromium extraction process by using System I.
The study using System I showed a low efficiency for
chromium removal in all studied points. This system doesn’t
represent a viable alternative for chromium waste treatment
due to the high chromium concentration levels remaining in
the aqueous phase.
The extraction process using System II was accomplished
by placing the aqueous solution (acid digestion solution), with
the metal to be extracted, in contact with the microemulsion
Table 5 – Chromium concentration in acid digestion
solution with varied pH.
pH Chromium (ppm)
0.6 479.86
1.5 219.80
3.5 163.16
1468 water research 43 (2009) 1464–1470

Fig. 2 – Pseudoternary phase diagram with Scheffé Net for System I.

phase obtained according to the points selected in the
experimental design to obtain a two-phase system (WII).
Table 7 shows the composition of the studied points and the
results obtained for chromium extraction process by using
System II.
By analyzing the results showed in Table 7 it can be
observed that chromium was extracted with percentages up
to 93.4%, without any metal loss by precipitation. It was used
the experimental results to obtain a mathematical model for
chromium removal (SAS System Software, version 6.12). The
used software provides values for the coefficients of the three
studied parameters (XOP, XC/S and XAP), as well as their
interactions. The best mathematical model obtained for
chromium extraction by microemulsion using System II was
the quadratic reduced one (Equation (4)).
ECr ¼ 92:07XAP þ 90:04XOP þ 87:65XC=S þ 14:05XOP XC=S ð%Þ (4)
From the analysis of Equation (4) it can be verified that only
XOP XC/S interaction was significant for chromium extraction
process, having a positive influence in the extraction
percentage. The used model presents a small standard error
(0.33) being considered satisfactory.
The isoresponse surface (Fig. 4) was built from the obtained
extraction equation (ECr). It allows a better evaluation of the

Fig. 3 – Pseudoternary phase diagram with Scheffé Net for System II.
 water research 43 (2009) 1464–1470 1469

Table 6 – Composition of the studied points and the
obtained results for chromium extraction process (%) by
using System I (pH 3.5 L Chromium initial
concentration [ 163.16 ppm, T [ 27 8C).
Experimental point Composition Chromium extraction
(mass fraction)
Table 7 – Composition of the studied points and the
obtained results for chromium extraction process (%) by
using System II (pH 0.6 L Chromium initial
concentration [ 479.86 ppm, T [ 27 8C).
Experimental point Composition Chromium extraction
(mass fraction)

XC/S XOP XAP (%) XC/S XOP XAP (%)

1 30.0 5.0 65.0 57.0 1 40.0 10.0 50.0 91.7

2 31.0 17.0 52.0 64.7 2 40.0 25.0 35.0 90.5
3 30.0 30.0 40.0 62.5 3 40.0 45.0 15.0 90.7
4 35.0 10.0 55.0 63.4 4 50.0 15.0 35.0 91.1
5 35.0 20.0 45.0 57.2 5 50.0 30.0 20.0 91.6
6 38.0 14.0 48.0 64.7 6 55.0 10.0 35.0 90.6
7 43.0 5.0 52.0 66.2 7 55.0 20.0 25.0 91.9
8 40.0 20.0 40.0 68.8 8 60.0 25.0 15.0 93.4
9 42.5 15.0 42.5 57.0 9 65.0 15.0 20.0 88.9
10 45.0 10.0 45.0 61.0 10 75.0 10.0 15.0 86.9
11 50.5 8.5 41.0 63.5 11 50.0 35.0 15.0 91.1
12 55.0 5.0 40.0 55.1 12 60.0 10.0 30.0 90.8

Fig. 4 – Isoresponse surface for chromium extraction process using System II.

behavior of chromium extraction within the studied domain
(Scheffé Net).
From Fig. 4 it can be verified that chromium extraction
percentile is higher in the aqueous phase-rich region. It is also
observed an increase in the extraction percentage in C/S–OP
binary direction, especially using intermediary amounts of
C/S–OP.
acid digestion solution until the appearing of a WII system
(WIV / WII), very high efficiency was obtained, reaching
chromium extraction percentages up to 93.4% with only one
extraction stage, showing the high potential of micro-
emulsions to treat tannery sediments.
references

4. Conclusions
Basegio, T., Berutti, F., Bernardes, A., Bergmann, C.P., 2002.
It can be concluded that System I, a microemulsion containing Environmental and technical aspects of the utilization of
tannery sludge as a raw material for clay products. Journal of
chromium solution as aqueous phase in equilibrium with an
the European Ceramic Society 22, 2251–2259.
aqueous phase in excess (WII), was not a viable alternative for
Castro Dantas, T.N., Dantas Neto, A.A., Moura, M.C.P.A., 2001.
chromium waste treatment due to the high concentration Removal of chromium from aqueous solutions by diatomite
levels of metal remaining in the aqueous phase. With System treated with microemulsion. Water Research 35 (9),
II, a microemulsion phase in which is added the chromium 2219–2224.
1470 water research 43 (2009) 1464–1470
Castro Dantas, T.N., Dantas Neto, A.A., Moura, M.C.P.A., Barros
Neto, E.L., Forte, K.R., Leite, R.H.L., 2003. Heavy metals
extraction by microemulsions. Water Research 37, 2709–2717.
Cheng, S., Fu, X., Liu, J., Zhang, J., Zhang, Z., Wei, Y., Han, B., 2007.
Study of ethylene glycol/TX-100/ionic liquid microemulsions.
Colloids and Surfaces A: Physicochemical and Engineering
Aspects 302, 211–215.
Chuan, M.C., Liu, J.C., 1996. Release behavior of chromium from
tannery sludge. Water Research 30 (4), 932–938.
CONAMA – National Environmental Council, March 17, 2005.
Resolution 357.
Cunha, A.L., Simões, A.M., 1999. Removal and Recovery of Cr (III)
from Wastewaters and Residues of a Tannery Industry.
Undergraduate final work, Universidade Técnica de Lisboa –
Instituto Superior Técnico, Portugal (in Portuguese).
Dantas Neto, A.A., Castro Dantas, T.N., Moura, M.C.P.A., 2004.
Evaluation and optimization of chromium removal from
tannery effluent by microemulsion in the Morris extractor.
Journal of Hazardous Materials B114, 115–122.
Jordão, C.P., Pereira, J.L., Jham, G.N., 1998. Chromium
contamination in sediment, vegetation and fish caused by
tanneries in the state of Minas Gerais, Brazil. The Science of
the Total Environment 207, 1–11.
Kotás, J., Stasicka, Z., 2000. Chromium occurrence in the
environment and methods of its speciation. Environmental
Pollution 107, 263–283.
Oliveira, K.R., 2003. The Use of Microemulsions to Extract Heavy
Metals from Tannery Sludge. Master of Science Thesis. Rio
Grande do Norte University UFRN-PPGQ, Natal, Brazil (in
Portuguese).
Solans, C., Ponds, R., 1997. Overview of basic aspects of
microemulsions. In: Solans, C., Kunieda, H. (Eds.), Industrial
Applications of Microemulsions, Surfactant Science Series,
vol. 66, pp. 1–18.
Stasinakis, A.S., Thomaidis, N.S., Mamais, D., Karivali, M.,
Lekkas, T.D., 2003. Chromium species behavior in the
activated sludge process. Chemosphere 52, 1059–1067.
USEPA, 2002. United States Environmental Protection Agency,
Effluent Guidelines and Standards. Sub-Chapter N, Parts
400–424.
USEPA, Environmental Protection Agency Method, 1986. Acid
Digestion of Sediments, Sludges and Soils. Method 3050, Test
Method for Evaluating Solid Waste, Washington.
Venditti, F., Ceglie, A., Palazzo, G., Colafemmina, G., Lopez, F.,
2007. Removal of chromate from water by a new CTAB-silica
gelatin composite. Journal of Colloid and Interface Science
310, 353–361.
Vijayalakshmi, C.S., Gulari, E., 1992. Extraction of trivalent metals
and separation of binary mixtures of metals using Winsor II
microemulsion systems. Separation Science and Technology
27 (2), 173–198.
WHO – World Health Organization, 1988. Chromium.
Environmental Health Criteria, 61. World Health Organization,
Finland.
Winsor, P.A., 1954. Solvent Properties of Amphiphilic Compounds.
Butterworths Scientific Publications, London. 207p.