Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

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Process Safety and Environmental Protection

j o u r n a l h o m e p a g e : w w w. e l s e v i e r.c o m / l o c a t e / p s e p

Removal of chromium from tanning wastewater

and its reuse
Bianca Mella , Ana Cludia Glanert, Mariliz Gutterres
Federal University of Rio Grande do Sul UFRGS, Chemical Engineering Department, Laboratory for Leather and
Environmental Studies LACOURO, Eng. Luiz Englert Street, s/n., 90040-040 Porto Alegre, Rio Grande do Sul, Brazil

a r t i c l e i n f o
a b s t r a c t
Article history:
Received 10 September 2014
Received in revised form 3 March
2015
Accepted 6 March 2015
Available online 14 March 2015
Keywords: Chrome Wastewater Reuse
Chemical precipitation
Electrocoagulation
Cost comparison
The chromium (Cr) used in the manufacture of leather from hides has well-known adverse effects when inappropriately disposed in the
environment. The tanneries use large quanti- ties of water for processing hides. The recovery of Cr from the wastewater produced in the
tanning step is an environmentally friendly and economically viable alternative avoiding the disposal of large amount of Cr-containing
sludge in industrial hazardous waste landlls. This work aims at studying the removal of the Cr from the tanning wastewater through
chemical precipitation (CP) and electrocoagulation (EC) techniques and its reuse in tanning process. In the CP experiments, efcient Cr
removal from wastewater samples was achieved, with up to
99.74% removal efciencies. In the EC experiments, three different electrode materials, Al, Cu, and Fe were tested. The highest removal
efciency of 97.76% was obtained with Al elec- trodes by conducting electrolysis at 3.0 V for 110 min. This was followed by Fe electrodes
and Cu electrodes, which showed removal efciencies of 90.27% (at 2.5 V) and 69.91% (at 2.0 V), respectively, for an electrolysis of 100
min. The recovered Cr was reused as a tanning agent in leather processing, where good crossing of Cr was reached in leathers tanned
with the liquors prepared from the sludge, and the pH and ash content values were measured. While the hides tanned with the Crcontaining liquor recovered by CP and by EC with Cu electrodes showed good hydrothermal stability and Cr content above 2.5% Cr2 O3 , the
hides tanned with Cr-containing liquors recovered by chemical precipitation and by EC conducted with Fe and Cu electrodes showed
contents of Cr according to technical specications. However, the Cr samples obtained with the iron electrode showed a dark coloration
due to oxidation of the iron. It can be concluded that the tanning process with Cr recovered by CP and by EC with Cu electrodes showed
the best results.
2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1.

Introduction

Various environmental concerns are associated with the leather indus- try due to the generation of high quantities of solid and liquid wastes as
well as gaseous emissions and unpleasant odors (Andrioli et al.,
2015) during the manufacturing process. Processing of one metric ton of rawhide results in 200 kg of tanned leather, 190350 kg of non-tanned
waste, 200250 kg of tanned leather waste, and 50,000 kg of wastewater (Sundar et al., 2011). The tanning process in Brazil and worldwide is of
great economic importance. Brazil has the second largest herd overall
and the largest marketable herd in the world, consisting of approx- imately 210 million heads of cattle. The country is also the second largest
producer and exporter of leather and aims at achieving excel- lence in the industry with investments, qualication, and technology (ABQTIC,
2013).
The processing of hides involves three main phases, namely beam- house, tanning, and nishing, which are further subdivided into
several steps. Beamhouse operations are mainly responsible of clean- ing the hide and preparing it for subsequent tanning steps. Therefore, the
beamhouse process, carried out in the conventional manner, is

Corresponding author. Tel.: +55 5133083955.

E-mail address: bianca@enq.ufrgs.br (B. Mella).
http://dx.doi.org/10.1016/j.psep.2015.03.007
0957-5820/ 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

196

Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

responsible for producing 70% of the total pollution arising from leather processing (Li et al., 2010).
A large amount of chemicals are added in leather processing. Each of these operations gives rise to characteristic pollutant loads, as high
biological oxygen demand (BOD), high chemical oxygen demand (COD) and high concentrations of suspended solids, organic nitrogen, sulde and
chromium (Thorstensen, 1997).
Rao et al. (2003) and Gutterres et al. (2015) characterized the parameters of tannery wastewaters in all process operations nd- ing
the following values for tanning wastewaters: pH (2.53.0), BOD (350800), COD (10002500), total solids (25,00060,000), dissolved solids (24,000
57,500), suspended solids (10002500), chlorides (15,00025,000) and total chromium (20005000).
Roughly 3% of the reserves of chromium are used for the manufac- ture of tanning salts, dyestuffs and raw materials for chromium-plated
surfaces or pharmaceuticals, of which leather accounts for 12%. The use of chromium for leather tanning has no signicant impact on the
worlds chrome reserves. However, a recycling concept of chromium for leather would be an interesting and realistic approach which should be
considered and addressed, at least in countries with high consumption (Tegtmeyer and Rabe, 2014).
It is possible to recycle the tanning wastewater, passing them through a sieve, do a chromium solution analysis and replenish the
amount of chromium salt and chemical inputs required for the pro- cess. Tests were conducted on an industrial scale for reuse of tanning
wastewaters in a tannery in Brazil (Aquim, 2009; Aquim and Gutterres,
2012). Before the tanning wastewaters were recycled the pH value, the
concentration of Cr2 O3 and the content of oils and greases were meaformation of ocs by destabilizing the suspended particles. The result- ing ocs can be separated from the liquid by otation or sedimentation
depending on their density (Bensadok et al., 2007).
The most preferable electrode materials in electrochemical coag- ulation are Al or Fe (Mollah et al., 2004), creating a unique
chemical/physical environment, which allows destabilization of the pollutant matter and its subsequent coagulation and otation, thus
avoiding addition of another coagulant agent (Espinoza-Quin ones et al.,
2009).
Until now, little attention has being paid to other metals such as copper (Montero-Ocampo et al., 2007). Indeed, a recent study found that
the use of copper electrodes increased arsenite removal to 99.6% without any secondary contamination (Ali et al., 2013).
In the electrocoagulation (EC), to release the coagulating agent, the metal ions and hydroxyl radicals, a potential difference has to be
applied to the electrodes. As the sacricial anode corrodes, the active cation is released to the solution (Wimmer, 2007).
Using copper as constituent material of the electrode, the following reactions occur, according to Eqs. (1)(4):Anodic reaction:
Cu(s) Cu2+ (aq) + 2e
2H2 O(l) + 2e 2OH (aq) + H2(g)

(1) Cathodic reactions:

(2) Overall reaction:

sured. It was possible to reduce the supply of salt (sodium chloride) in

Cu + 2H O
Cu(OH)
+H
(3)
tests through recycling. As the recycled wastewaters already contained a certain amount of salt (necessary to avoid the swelling of the hide)
(s)
2 (l)
2(s)
2(g)

3.04.5% of sodium chloride was added in relation to the mass of hides, while usually 5.5% of sodium chloride is added to a new processing
water. In the recycling of tanning wastewaters the supply of chromium, was reduced from 5.5 to 4.0%. Water reuse in tanning not only saves
clean water but also proposes reusing a wastewater that would be han- dled and disposed of to the environment; thus the use of this input is
maximized. The proposed direct reuse of chrome baths is even more important because chromium is a chemical of great environmental impact
(Aquim, 2009).
The global leather industry is increasing attention for treating liq- uid efuents and providing adequate endpoints for the sludge and
residues generated in the processes. Conventional tanning necessitates use and discharge of about 810% of common salt on the weight of hides and
skins, resulting in high salinity of tannery efuents apart from large quantities of unxed chromium (Aslan, 2009 and Sundar et al.,
2002). Considering the level of Cr in the wastewater, the development of appropriate techniques to recover and recycle the residual Cr is rele- vant
(Gutterres and Mella, 2014). The uncontrolled release of chromium containing tannery efuent in natural water bodies increases environ- mental
pollution concerns and health risks (Khan, 2001 and Kimbrough et al., 1999). Residues containing Cr are classied as dangerous in Brazil
The formation of chrome complex occurs:
Cu(OH)2(s) + CrSO4 OH Cr(OH)3 + CrSO4

(4) After these processes, the Cr(OH)3 is redissolved with the controlled

addition of a strong acid. The Cr so obtained can be reused as an input in the tanning process.
This work aims at studying the removal of Cr present in the tanning wastewater through CP and EC techniques and its reuse in the tanning
process. After its recovery from wastewater, the Cr recovered is tested as a tanning agent in leather processing, and is veried the economic
viability of these processes.

2.

Materials and methods

2.1.

Analysis of wastewater

The tanning wastewater was collected directly (without any pretreatment) from the tanning drum of a tannery that performs beamhouse and tanning operations, processing 500 hides/day and generating a total average efuent ow of
and must be disposed of in dangerous industrial residues landlls. This

applies to wet-blue leather shavings and trimmings, semi-nished and nished leather cuts, and the sludge generated in wastewater treat-

ment plants (Gutterres and Mella, 2014).

Many methods are used to remove heavy metals from wastewater e.g., chemical precipitation, ion exchange, adsorption, reverse osmo- sis,
coagulationocculation, electrocoagulation, otation, membrane ltration, etc. (Fu and Qi, 2011; Kurniawan et al., 2006).
Chemical precipitation (CP) is widely used for heavy metal removal from inorganic wastewater (Kurniawan et al., 2006). By adjusting the pH to
basic conditions using an alkali, the dissolved metal ions are con- verted into an insoluble solid. In the case of Cr, chromium (III) hydroxide (Cr(OH)3
) is precipitated.
Another technique for wastewater treatment is by electrocoagulation (EC), where a sacricial anode undergoes oxidation, releasing metal ions, and the hydrolysis of water takes place at the cathode,
resulting in the formation of hydroxyl ions. Metal ions combine with the hydroxyl ions to form metal hydroxide compounds that favor the

200 m /day in addition to 60 m /day of Cr-containing wastewater. This wastewater was ltered with glass wool before the experiments, according to NBR 13336 (NBR, 1995) standards, to
remove the suspended solids (shavings and fats).
The pH and the electrical conductivity of the raw and treated wastewater were determined. The analyses of biolog- ical
oxidation demand (BOD) and chemical oxygen demand (COD) were carried out by the titration method and suldes were
analyzed using a spectrophotometer. The total amount of Cr in the wastewater was determined according to the ABNT NBR
13341 (2010) standard.

2.2.

Chromium recovery by CP and EC

The CP tests were performed with the same sample; 1000 mL

of efuent were added in each of the 12 vats of the jar test
Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

197

equipment; a medium speed of 50 rpm was applied, and stir- ring was performed for 1 h. In each vat, 2.024.0 mL NaOH (12
M) were measured in order to determine the inuence of pH on the precipitation of metals in the form of hydroxides. After
stirring, the system was allowed to rest for sedimentation of the sludge occur and samples of the supernatant (claried
liquid) and the sludge formed in each vat were collected.
The EC tests were performed in a laboratory-scale reactor made of glass, with a volume of 500 mL, with
provisions for magnetic stirring. Electrodes made of Fe,
Cu, and Al with dimensions of 150 mm 51 mm 0.9 mm,
150 mm 51 mm 0.9 mm, and 143 mm 50 mm 1.5 mm,
respectively, were used. The electrodes were spaced 2.0 cm apart. The submerged area of each electrode was 52 cm2 . An
Iminipa MPL-1303M power supply with adjustable settings with the voltage range 030 V and the current range 03 A was
Table 1 Cost of electric energy, aluminum, copper and iron.
Price
Electric energy (US$/kWh)
Aluminum (US$/g)
Copper (US$/g)
Iron (US$/g)

0.201
3.57
4.81
1.51

Considering Faradays laws of electrolysis, which can be used to relate the mass of the sacricial anode material consumed to the amount of charge passed and the equivalent weight of the material produced, the consumed electrode for
treatment was calculated according to Eq. (6) (Mollah et al.,
2004).
ItM

used.
w=
z F

(6)

Vr

2.3.

Tanning tests with recovered chromium

The liquors of recovered Cr were prepared for the tanning tests by stripping the sludge generated by CP and EC with sulfuric
acid. This sludge was previously densied in a cen- trifuge to obtain more concentrated Cr liquor when stripping with sulfuric
acid. Shen et al. (2001) compared three mineral acids (sulfuric, hydrochloric, and nitric acids) for the extrac- tion of Cr3+ and
demonstrated over 70% extraction of Cr3+ at low pH values of 3.0. They preferred sulfuric acid due to better solubilization of
chromium and lower solubility of calcium.
The tanning tests were conducted in a laboratory-scale tanning drum with a liming hide sample, whose mass was
calculated from the amount of chromium recovered. In order to verify the tanning power of the Cr salts obtained from the
sludge, the samples of leather were analyzed for chromium oxide. Further, to quantify the levels of Cr, Al, Fe, and Cu in the
tanned leather, the samples were calcined to ashes accord- ing to ASTM 2617 (Astm, 1998a) and the Cr content in the leather
was determined according to the standards prescribed in ASTM D 2807-93 (Astm, 1998b). In order to analyze for Al, Cu, and Fe, the
samples were subjected to acid digestion and then analyzed using atomic absorption spectrometry (AAS) with a ame. Tests to
determine the shrinkage temperature of the
leather samples (size 2 cm 5 cm) were performed according
to the standards prescribed in ABNT NBR 13335 (NBR, 2009).

2.4.

Cost analysis

In order to evaluate the economic viability of the CP and the EC processes, some parameters were considered. In the case of
CP, the costs of chemicals to be dosed (per m3 ) were cal- culated, whereas in the case of EC, the total cost (Eq. (7)) was
determined by factoring in the electrical energy consumed (Eq. (5)) and the consumed electrode for (Eq. (6)).
The cost of energy consumed was calculated as the product of the energy and the electrolysis time per unit volume of the
treated efuent, according to Eq. (5) (Kobya et al., 2006):
IVt
where w = mass of sacricial electrode consumed (g); I = current density (A); t = treatment time (s); M = molecular
weight of the sacricial electrode (g/mol); z = number of electrons involved; F = Faradays constant (96487 C) and Vr =
volume of treated efuent (m3 ).
The total cost of treatment by EC can be calculated as the sum of the energy costs calculated from Eq. (5) and the consumed electrode for treatment was calculated from Eq. (6), as follows.
Ct = (E CEE ) + (w CM )

(7)

where Ct = total cost of treatment ($/m3 ); CEE = energy cost ($/kWh); w = mass of worn electrode (g) and CM = cost of acquisition of metal ($/g).
The costs for procuring the metals were provided by local businesses and the value of electricity in MWh were obtained
from ANEEL (National Electric Energy Agency), in August 2014, according to the class consumption (industrial) and their
respective region (South) Brazil, as listed in Table 1.

3.

Results and discussion

3.1.

Chromium removal experiments from wastewater

The choice of treatment to be used and the parameters for operational control were determined from a preliminary charTable 2 Characterization of tanning wastewater.
Parameter
pH
Temperature
BOD
COD
Conductivity
Total chromiuma
Turbidity
Suspended solids
Suldes
a

Unit

mg O2 /L
mg O2 /L
m/Scm
mg/L
NTU
mg/L
mg/L

Value
4.07 0.04
20.00 0.01
116.20 0.1
387.20 3.0
71.91 0.9
2000.00 0.00055
14.56 0.01
456.00 0.1
0.05 0.004

Total chromium was determined in the form of Cr2 O3 .

acterization of the tanning wastewater are listed in Table 2.

The low pH values of the tanning wastewater were due to the presence of acids in the pickling bath, which is a step
=
before the tanning process. At the pickling step, sodium chlo- ride (NaCl) is also added to prevent acid swelling of the hide;
E
(5)
Vr
where E = electrical energy consumed
(kWh m3 );
I = intensity of electric current (A); V = voltage (V); t = time
of treatment (h) and Vr = volume of treated efuent (m3 ).

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Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

100%
90%
80%
Cr
re
mo
val
effi
cie
nc
y
70%

60%
50%
40%
30%
20%
10%
0%

Cr removal efficiency (%)

Final concentration Cr2O3 (mg/L)

2000
1900
Fin
al
con
cen
trat
ion
Cr2
O3
(m
g/
L)
1800
1700
1600
1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
3
6

9
11

10
12

pH

Fig. 1 Inuence of pH on the Cr removal efciency and nal concentration with CP.
therefore, the conductivity of the tanning wastewater is high. The BOD and the COD of the tanning wastewater are lower
compared to the samples from the other stages in the tan- ning process like wastewaters of all tannery process with COD
992210,180 mg O2 /L and BOD5 528 mg O2 /L (Isarain-Chvez et al., 2014). This is due to the low amounts of organic matter in
the wastewater, since the hide is cleaned
expected, since only the efuent from the
cess was analyzed, the amount of total Cr
collagen bers. The efuent from tanning
turbidity was low.

3.1.1.

and the proteins are removed during the previous beamhouse process steps. As
tanning prowas high, as well as the amount of suspended solids, which is largely a result of
showed a strong blue color due to the presence of chromium but the measured

Chromium recovery by chemical precipitation

Analysis of the wastewater samples obtained from the CP experiments revealed that Cr was removed efciently, with
efciencies of above 98% at pH values above 7.0, as shown in Fig. 1. The experimental results conrm the theoretical predictions made in the Pourbaix diagram, which shows that the precipitation of Cr(OH)3 can be expected to occur in the pH
range 8.011.0. In addition, the solubilities of various other metal hydroxides are also minimized in the pH range 8.011.0
(Baltpurvins et al., 1997).
The use of alkali to remove Cr from the tanning waste- water is a technology sometimes used in the tanneries. Guo et al.
(2006) performed a comparative study of ve different alkalis, NaOH, NaHCO3 , Na2 CO3 , MgO, and CaO, where they evaluated
the efciency of Cr removal, the inuence of pH, and the volume of sludge generated. All the alkalis used led to chromium
removal efciencies above 99%. However, the use of NaOH resulted in a higher volume of sludge.

3.1.2.

Chromium recovery by EC

Preliminary testing of EC using Al, Cu, and Fe electrode pairs (anode and cathode) were conducted using the raw efuent in the
potential range 0.53.0 V for 60 min in order to determine the best potential range for Cr removal. Suitable potential ranges
for Cr removal with Al and Fe electrodes were deter- mined to be 2.53.0 V, whereas the potential range for Cu electrodes
was determined to be 1.52.0 V. Once the optimum potential range for each type of electrode was identied, the EC tests were
conducted for longer time (at least 100 min), in order to obtain the best efciency of chromium removal (Mella et al., 2013).
While Al electrodes (Fig. 2) resulted higher removal ef- ciency of 97.76% at 3.0 V and 110 min, potential of 2.5 V were
matched. In the experiments performed by Benhadji et al.
(2011) under ideal conditions, removal efciencies greater
100%
90%
80%
Cr
re
mo
val
effi
cie
nc
y

70%
60%
50%
40%
30%
20%

68.08%
90.27%
82.57%

69.91%
97.76%

Al 2.5V Al 3.0V Cu 1.5V Cu 2.0V Fe 2.5V

Fe 3.0V
10%
0%
0
20

30

40

50

60

70

80

90

10

100
110
120
Time (min)

Fig. 2 Chromium removal in experiments of electrocoagulation with electrodes of aluminum, copper and iron at
different potentials with time.
Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

199

Table 3 Data from the tanning with recovered chromium salt generated in each process.
Parameters

Chemical precipitation (CP)

Water volume (mL)

Chromium concentration (g L1 )
Chromium offer (g)
Hide weight (g)

105
6.85
0.72
32.0

Electrocoagulation (EC)
AlAl

CuCu

FeFe

95.00
7.58
0.72
32.00

32.00
14.14
0.45
20.00

65.00
13.13
0.85
38.00

than 90% for various components in the tannery wastewater such as BOD5 , COD, turbidity, chromium, iron, and nitrate were
achieved with Al electrodes. Sengil et al. (2009) veried the removal of COD, sulde, and oilgrease from tannery liming
drum wastewater using direct current (DC) EC. The experi- mental results showed that COD, sulde, and oilgrease were
removed effectively when mild steel electrodes were used as the sacricial anode. In their study, the overall COD, sulde, and
oilgrease removal efciencies reached values of 82%,
90%, and 96%, respectively.
In the present study, the Cu electrodes (Fig. 2) did not show high Cr removal efciencies. Removal efciencies of 68.08% (at
1.5 V for 50 min) and 69.91% (at 2.0 V for 100 min) were obtained. In the case of Fe electrodes, removal efciencies of
90.27% and 82.57% were obtained at 2.5 V and 3.0 V, respec- tively for 100 min. Therefore, it can be concluded that the
increase in potential did not affect the removal of Cr.
Other authors have studied the effects of EC combined with other treatments in tannery efuents. Feng et al. (2007) tested
the mechanisms of removal of COD, ammonia, total organic carbon, sulde, and color with two soluble elec- trodes (mild
steel and Al). The tannery wastewater was rst treated using mild steel electrodes followed by ltration and nally by the
aluminum electrodes and the elimination rates of COD, ammonia, total organic carbon, sulde, and color were determined to
be 68.0%, 43.1%, 55.1%, 96.7%, and 84.3%, respectively. Sirajuddin et al. (2007) tested various combina- tions of electrodes and
determined the best electrode couple and optimal chromium removal and recovery conditions for the removal of Cr in the
forms of Cr(OH)3 and/or Na2 Cr2 O7
at the cathode and the anode, respectively. A Cr recovery of
99% was achieved after electrolysis for 2 h at cell potential of
1.0 V, pH value of 5.0, and stirring rate of 500 rpm using Pb sheet as the anode and Cu sheet as the cathode. Mdenes et al.
(2012) integrated the widely used photo-Fenton process and the EC process and applied to the treatment of tannery industrial
efuent. They showed that optimal performance of the photo-Fenton process was achieved by solar irradiation of the samples
for 120 min in acidic media, in broad concentration ranges Fe2+ (0.3750.50 g L1 ) and H2 O2 (2030 g L1 ).
The best response was achieved at the initial pH of 3 and
Fe2+ and H2 O2 concentrations of 0.5 and 30 g L1 , respectively.
Table 4 Shrinkage leather tests.
Sample

Linear shrinkage (%)

Pickled hidea
CP
EC AlAl
EC CuCu
EC FeFe
a

30.00
0.0
34.00
0.0
16.00

Supercial
shrinkage (%)
47.50
0.0
53.80
0.0
37.00

Hide before tanning treatment.

3.2.

Tanning with recovered chromium

The quantities of water, Cr, and hide used in each test are shown in Table 3.
In order to understand if there was total crossing of Cr in the hides, transverse cuts were made in the hides (Fig. 3).
As shown in Fig. 3, the three transverse sections (sam- ples bd) exhibited the blue chromium color trough the hide
thickness when compared to the pickled hide before tanning treatment (sample a). The last gure (sample e) presents a dark
brown color trough the hide thickness due to the presence of the metals chromium and oxidized Fe. Therefore, it may be
concluded that tanning was well executed ensuring the total crossing of Cr.
Another important parameter analyzed was the resistance of the leather to high temperatures. The leathers that are
resistant to boiling water normally have enough Cr in their structures (CTCCA, 2002). The hides natural collagen typically
exhibits retraction in boiling water. The retraction is due to the transition of the collagen from a triple helix structure to a
random coiled structure and this phenomenon is also known as denaturation. While the soluble collagen denatures in an
aqueous solution at 37 C, the insoluble collagen denatures
(shrinkages) at temperature of about 65 C. The shrinkage tem- perature of the helix depends mainly on the number and the
distribution of the amino acids, and their sequence in the col- lagen chain (Gutterres et al., 2005).
According to the shrinkage temperature tests, the leather samples tanned with Cr recovered by CP and by EC using Cu
electrodes showed good hydrothermal stability i.e. did not exhibit retraction, whereas the samples treated with Cr

Fig. 3 Tanning with recovered chromium salt of the tests: (a) hide before tanning tests; (b) CP; (c) EC AlAl; (d) EC CuCu;
(e) EC FeFe. (For interpretation of the references to color in text, the reader is referred to the web version of this article.)

200

Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

Table 5 Total chromium and other metals in the leather samples.

Sample

Cr2 O3 (%)

CP
AlAl
CuCu
FeFe

3.3075
1.0885
4.8650
3.3600

Al (%)

4.1650

Cu (%)

Fe (%)

Final pH

2.7965

7.9100

4.20
4.02
3.99
3.74

recovered by EC using Al and Fe electrodes showed retraction

(Table 4).
Table 5 shows the analytical results of the tanned leather samples. All the samples showed pH values that met the
minimum value of 3.5 required as per the NBR 13525/2005 standard. The contents of Cr2 O3 samples recovered by CP and by EC
using Cu and Fe electrodes showed satisfactory values and met the minimum required value of 2.5%, whereas the values
obtained in the case of Al electrodes were unsatisfac- tory. The shrinkage values obtained for leather tanned with Cr
recovered using Fe electrode is probably because the pH of the pickled skin, was above the ideal range 2.03.0 at the
beginning of the tanning process, which affected the Cr dis- tribution in the hide. According to Fuck (2008), pickled hides have
a pH in the range 2.03.0, as they enter at the tanning medium, resulting that the rate of reaction between the pro- tein and
Cr is greatly reduced. This condition allows the basic chromium sulfate to penetrate the collagen matrix without any
deposition on the surface.
The tanning tests with Cr recovered were well succeeded. The presence of other metals did not affect negatively the process, as well as it was previously described by other authors.
The recent history of chrome tanning has been centered on its alleged environmental impact. Therefore attention has been
turned to the possibility of nding an alternative tan- ning metal for the global leather industry, ideally to confer the same
properties as chrome (Covington, 2011). The only practical options as alternatives to chrome, which have some history of use
in the leather industry, are aluminum(III), tita- nium(IV) and zirconium(IV) [and to a lesser extent iron(II)] (Covington, 2011).
Heidemann (1993) also mentions that the effect of iron salts has been known since the middle of the last century and has
been applied for nearly a hundred years. Other tannages include copper salts and the salts of rare earths.
In Covingtons (2011) opinion, aluminum, titanium and zirconium cannot match the tanning power of chromium.
Copper(II) has a complex chemistry with oxy ligands, but with a tendency to form complex anions, which are not use- ful
for tanning. And all metal salts can be used together in all proportions. The benets of introducing another metal salt can
be summarized as follows: (a) the efciency of chrome uptake is improved by reducing the offer (Future Tanning
Chemistries, 2000); (b) the rate of chrome uptake can be improved by the presence of another weaker mineral tanning
agent, applied as a pretreatment (Simoncini et al.,
1978).

3.3.

Cost comparison of the treatment technologies tested

The analysis of cost to treat 1 m3 of wastewater was calcu- lated for the best experimental conditions determined in this
study. In this calculation, the price of chemicals (NaOH) and/or metals used in the process, the duration of the process, and
Table 6 Total costs for each treatment.
Sample
CP
AlAl
CuCu
FeFe

Costs (US$/m3 )
4.14
2.16
0.49
1.76

the price of electricity were considered. The costs determined for CP and for EC with Al, Cu, and Fe are shown in Table 6.
While CP continues to be the most widely used process for the removal of heavy metals owing to its operational simplicity, high removal efciencies, and the lack of a need for assisted operation and sophisticated equipment, the cost of
chemicals used is higher compared to EC processes.
Espinoza-Quin ones et al. (2009) tested in laboratory scale
EC with iron plates for 060 min and obtained operational costs of 1.64 US$ m3 . In comparison with the operational cost (only

reactants) of conventional method (US$ 3.50 m3 in Brazilian tannery factory), the EC method is evidently cheaper than the
conventional one.
Among the three metals used as electrodes in EC, Cu had the lowest total cost per cubic meter, even though the cost of the
electrode plate was the highest. Although the cost of the Fe and Al electrode plates were lower, higher wear was seen with these
electrodes. This is along expected lines, since employing higher potentials leads to increased wear of the electrode and increased
energy consumption, resulting in a higher total cost of operation.

4.

Conclusion

With CP technique the efcient removal of Cr from wastewa- ter samples reached values higher than 99%. In the EC tests, the
best removal efciency of Cr was 97.76% with Al elec- trodes (3.0 V for 110 min), 69.91% with Cu (2.0 V for 100 min) and
90.27% with Fe electrodes (2.5 V for 100 min).
In tanning tests with recovered chromium the hides tanned with Cr recovered by CP and by EC with Cu electrodes
showed good hydrothermal stability also showed the min- imum required amount of Cr2 O3 for the tanning technical
specications (2.5%).
It was concluded that the Cr recovered by EC with Cu elec- trodes presented a reduction of 88.16% of total cost when
compared to CP and both techniques showed satisfactory results of chromium removal efciency from tannery wastew- aters
too.

Acknowledgements
We would like to thank CAPES for granting doctoral schol- arship and FAPERGS (Edict FAPERGS 04/2012) and FINEP (MCTI/FINEP
CT-HIDRO 01/2013).
Process Safety and Environmental Protection 9 5 ( 2 0 1 5 ) 195201

201

References
Ali, I., Asim, M., Khan, T.A., 2013. Arsenite removal from water by electrocoagulation on zinczinc and coppercopper
electrodes. Int. J. Environ. Sci. Technol. 10, 377384. Andrioli, E., Petry, L., Gutterres, M., 2015. Environmentally
friendly hide unhairing: enzymaticoxidative unhairing as an alternative to use of lime and sodium sulde. Process Saf. Environ.
Prot. 93, 917.
Aquim, P.M., 2009. Gesto em Curtumes: Uso Integrado e Eciente da gua. Tese de Doutorado Universidade Federal do Rio Grande do
Sul, Programa de Ps Graduac o em Engenharia Qumica.
Aquim, P.M., Gutterres, M., 2012. Reuso de gua uma alternativa para minimizar o impacto ambiental do curtimento. Presented at XVIII
FLAQTIC, Montevideo.
Aslan, A., 2009. Determination of heavy metal toxicity of nished leather solid waste. Bull. Environ. Contam. Toxicol. 82,
633638.
Astm, D., 1998a. 2617-96 Annual Book of American Society for Testing and Materials Standard, Test Method for Total Ash in Leather,
272 e 2732.
Astm, D., 1998b. 2807-93 Annual Book of American Society for Testing and Materials Standard, Test Method for Chromic Oxide in
Leather (Perchloric Acid Oxidation)., pp. 280282.
Sundar, V.J., Gnanamani, A., Muralidharan, C., Chandrababu, N.K., Mandal, A.B., 2011. Recovery and utilization of proteinous wastes of
leather making: a review. Rev. Environ. Sci. Biotechnol. 10, 151163.
Baltpurvins, K.A., Burns, R.C., Lawrance, G.A., Stuart, A.D., 1997.
Effect of electrolyte composition on zinc hyd roxide precipitation by lime. Water Res. 31, 973980.
Benhadji, A., Ahmed, M.T., Maachi, R., 2011. Electrocoagulation and effect of cathode materials on the removal of pollutants from
tannery wastewater of Rouiba. Desalination 277,
128134.
Bensadok, K., Benammar, S., Lapicque, F., Nezzal, G., 2007.
Electrocoagulation of cutting oil emulsions using aluminium plate electrodes. J. Hazard. Mater. 152, 423430.
Brazilian Association of Chemists and Technicians Leather
Industry, 2013. Brazilian Leather Guide.
Covington, A.D., 2011. Tanning Chemistry: The Science of
Leather. RSC Publishing.
CTCCA, 2002. Materiais: Couro e Outros Materiais de Corte, Novo
Hamburgo.
Espinoza-Quin ones, F.R., Fornari, M.M.T., Mdenes, A.N., Palcio, S.M., Silva Jr., F.G.da., Szymanski, N., Kroumov, A.D., Trigueros, D.E.G.,
2009. Pollutant removal from tannery efuent by electrocoagulation. Chem. Eng. J. 151, 5965.
Feng, J., Sun, Y., Zheng, Z., Zhang, J., Li, S., Tian, Y., 2007.
Treatment of tannery wastewater by electrocoagulation. J. Environ. Sci. 19, 14091415.
Fu, F., Qi, W., 2011. Removal of heavy metal ions from wastewaters: a review. J. Environ. Manag. 92, 407418.
Fuck, W.F., 2008. Inuncia do teor de cromo e do tipo de leo na formac o de cromo hexavalente no couro. Dissertac o de Mestrado
UFRGS.
Future Tanning Chemistries, 2000, September. UNIDO Workshop, Casablanca.
Guo, Z., Zhang, G., Fang, J., Dou, X., 2006. Enhanced chromium recovery from tanning wastewater. J. Clean. Prod. 14, 7579.
Gutterres, M., Passos, J.B., Friedrich, D., 2005. Uso da gua e Caracterizac o das Correntes Parciais Residuais de Curtumes. Tecnicouro
27 (3), 6872.
Gutterres, M., Mella, B., 2014. Chapter 16: Chromium in Tannery Wastewater, Book Heavy Metals in Water: Presence, Removal and
Safety. Springer Publisher, Londres.
Gutterres, M., Benvenuti, J., Fontoura, J., Ortiz-Monsalve, S., 2015.
Characterization of raw wastewater from tanneries. J. Soc. Leather Technol. Chem. (in press).
Heidemann, E., 1993. Fundamentals of Leather Manufacturing.
Eduard Roether KG.

Isarain-Chvez, E., De La Rosa, C., Godnez, L.A., Brillas, E., Peralta-Hernndez, J.M., 2014. Comparative study of electrochemical
water treatment processes for a tannery wastewater efuent. J. Electroanal. Chem. 713,
6269.
Khan, A.G., 2001. Relationships between chromium biomagnications ratio, accumulation factor, and mycorrhizae in plants growing
on tannery efuent-polluted soil. Environ. Int. 26, 417423.
Kimbrough, D.E., Cohen, Y., Winer, A.M., Creelman, L., Mabuni, C.,
1999. A critical assessment of chromium in the environment. Crit. Rev. Environ. Sci. Technol. 29, 146.
Kobya, M., Hiz, H., Senturk, E., Aydiner, C., Demirbas, E., 2006, April. Treatment of potato chips manufacturing wastewater by
electrocoagulation. Desalination 190 (13), 201211.
Kurniawan, T.A., Chan, G.Y.S., Lo, W., Babel, S., 2006.
Physico-chemical treatment techniques for wastewater laden with heavy metals. Chem. Eng. J. 118, 8398.
Li, S., Li, J., Yi, J., Shan, Z., 2010. Cleaner beam house processes trial on cattle sofa leather. J. Clean. Prod. 18, 471477.
Mella, B., Glanert, A.C.C., Gutterres, M., 2013. Removal of chromium from tanning wastewater by chemical precipitation and
electrocoagulation. In: XXXII Congress of the IULTCS, Istanbul.
Mollah, M.Y.A., Morkovsky, P., Gomes, J.A.G., Kesmez, M., Parga, J., Cocke, D.L., 2004. Fundamentals, present and future perspectives of
electrocoagulation. J. Hazard. Mater. 114 (13),
199210.
Mdenes, A.N., Espinoza-Quin ones, F.R., Borba, F.H., Manenti, D.R., 2012. Performance evaluation of an integrated
photo-Fenton electrocoagulation process applied to pollutant removal from tannery efuent in batch system. Chem. Eng. J. 197,
19.
Montero-Ocampo, C., Maldonado, A., Solorza-Feria, O., 2007.
Arsenic removal from underground water by electrocoagulation with zinc, brass and iron. ECS Trans. 2,
7185.
NBR 13.341 ABNT, 1995, Couro, Calc ados e Artefatos de Couro Determinac o do teor de xido de cromo (III).
NBR 13.335 ABNT, 2009, Banho residual de curtimento e recurtimento Determinac o da retrac o.
NBR 13.336 ABNT, 2010, Banho residual e euente lquido Amostragem.
NBR 13.525 ABNT, 2005, Couro Requisitos quanto anlise qumica.
Rao, J.R., Chandrababu, N.K., Muralidharan, C., Nair, B.U., Rao, P.G., Ramasami, T., 2003. Recouping the wastewater: a way forward for
cleaner leather processing. J. Clean. Prod. 11,
591599.
Sengil, A., Kulac , S., Ozacar, M., 2009. Treatment of tannery liming drum wastewater by electrocoagulation. J. Hazard. Mater. 167,
940946.
Shen, S.B., Tyagi, R.D., Blais, J.F., 2001. Extraction of Cr(III) and other metals from tannery sludge by mineral acids. Environ. Technol. 22,
10071014.
Simoncini, A., et al., 1978. Cuoio 54 (4), 439.
Sirajuddin, Kakakhel, L., Lutfullah, G., Bhanger, M.I., Shah, A., Niaz, A., 2007. Electrolytic recovery of chromium salts from tannery
wastewater. J. Hazard. Mater. 148, 560565.
Sundar, V.J., Rao, J.R., Muralidharan, C., 2002. Cleaner chrome tanning emerging options. J. Clean. Prod. 10, 6974.
Tegtmeyer, D., Rabe, V., 2014, July/August. Modern Chrome
Tanning Is Safe. International Leather Maker.
Thorstensen, T., 1997. Pollution prevention and control for small tanneries. J. Am. Leather Chem. Assoc. 10, 245255.
Wimmer, A.C.S., 2007. Aplicac o do processo eletroltico no tratamento de euentes de uma indstria petroqumica. Dissertac o
Mestrado, PUC, Rio de Janeiro, RJ, Brasil.