Desalination 126 (1999) 219–226

Treatment of an industrial effluent by reverse osmosis

Antonio Pérez Padillaa*, Eduardo L. Tavanib
a
Instituto de Investigaciones en Tecnología Química (INTEQUI), Universidad Nacional de San Luis,
CONICET, CC 290, 5700 San Luis, Argentina
Fax +54 (2652) 26711; email: apadilla@unsl.edu.ar
b
Centro de Tecnología de Recursos Minerales y Cerámica (CETMIC), Comisión de Investigaciones Científicas de la
Provincia de Buenos Aires, CONICET, CC49, 1897 M.B. Gonnet, Argentina

Abstract
The treatment of tanning wastewater was studied by means of reverse osmosis and ultrafiltration. Tests were carried
out on laboratory scale using membranes of polyamide (reverse osmosis) and of polysulfone (ultrafiltration). The
evaluation of the system was performed by chemical analysis, pH measurements and visible spectrophotometry. Effects
of the protein contained in the industrial effluent, the applied pressure and the feed temperature on the permeate flux
were analyzed. The polyamide membrane used allowed us to obtain permeates with a low chromium (III) content
(7–10 mg/L) but with appreciable amounts of SO4= (1–3 g/l), Cl (9–14 g/L) and Na+ (5–10 g/L). The presence of
chromium (III) polymers was determined in the original effluent and in the concentrates obtained by reverse osmosis.
Finally, it was established that during the operation of reverse osmosis, the transport of H+(H3O+) from the concentrate
to the permeate was produced.

Keywords: Tanning wastewater; Reverse osmosis; Ultrafiltration; Chromium (III); Recovery; Leather

1. Introduction carboxylic groups of the protein fiber network of

Leather is a material that has a reasonable
mechanical resistance, good chemical stability
and acceptable thermal behaviour. This material
is obtained by means of specific reactions among
*Corresponding author.
animal skin (collagen) and tanning reagents. The
basic chromium (III) sulfate [Cr(OH)(H2O)5SO4]
is a primary tanning agent widely used at the
present time [1].
During the tanning process, large amounts of
wastewater; sludge; and solids containing
chromium, sodium, chloride and sulfate are

Presented at the Conference on Desalination and the Environment, Las Palmas, Gran Canaria, November 9–12, 1999.
European Desalination Society and the International Water Association.
0011-9164/99/$– See front matter © 1999 Elsevier Science B.V. All rights reserved
220 A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226
produced. In all these wastes the chromium is
present only in the trivalent form since the
tanning process not generate chromium (VI)
[1,2]. Both oxidation states of the chromium are
abundant in environment. Chromium (III) is the
form most stable and its presence is necessary, in
small amounts, for human health. Chromium (VI)
is found in several commercial products and its
presence may have immediate adverse effects for
human health [2,3].
Chromium (VI) is transformed rapidly to
chromium (III) under environmental normal
conditions, with only contamination risks near
direct emissions. However, under very specific
conditions, the oxidation of trivalent to hexa-
valent form may also occur [4,5]. Technical
regulations for disposal of wastes containing
chromium (III) are stringent and are based on the
probable presence of chromium (VI).
Wastewater is the effluent of the tannery that
has a fast interaction with the environment. The
amount of wastewater varies between 30 and 50L
per kilogram of processed skin [6,7]. From the
total amount of liquids, nearly 10% corresponds
to the tanning stage (tanning wastewater) and the
remainder to the other stages of processing
(dehairing, pickling, neutralization, fat-liquoring,
dyeing and washings). The greatest content of
chromium (III) is found in the tanning
wastewater.
The composition of this effluent varies
according to the tanning process used and to the
type of leather to be obtained. Most of the
components of the tanning wastewater and their
most frequent contents are: 16–25 g/L sulfate,
17–26 g/L chloride, 14–21 g/L sodium,
0.6–2.0 g/L of chromium (III) and a residual
acidity between pH 3.5 and 5.0.
Precipitation and adsorption are two alter-
native methods for the recovery of chromium (III)
contained in tanning wastewater. Chromium (III)
is easily precipitated by the addition of an alkali
(generally, calcium hydroxide) to the liquid
effluent. In this way a supernatant free of the
metallic element and a precipitate containing
chromium (III) hydroxide are obtained. From the
precipitate it is possible to recover the chromium
by calcination at 600(C (as hexavalent
chromium) or by acid leaching [8].
The adsorption occurs on the surface of a
substance called adsorbent and the addition of
any reagent is not required. To carry out under
favorable economic conditions, the separation of
chromium (III) by adsorption, it is necessary to
select an adequate adsorbent with high adsorption
capacity and able to remain stable at low pH.
Smectite is a natural adsorbent with good
adsorption capacity, but it does not have
selectivity [9]. Thus, adsorption of chromium
(III) (0.040 g/g of adsorbent) and of sodium
(0.006 g/g of adsorbent) were determined on the
smectite from tanning wastewater without
dilution [10]. The alteration of this adsorbent in
contact with sulfuric acid is produced at pH ~ 1.7
[11]. Activated clay (a kaolin amorphous deriva-
tive) with an adsorption capacity nearly three
times higher than the smectite is altered at lower
acid concentration (the chemical attack starts at
pH ~3.0) [12].
The separation (desorption) of chromium (III)
retained on the adsorbent surface requires the
addition of reagents. The facility of a cation
replacement depends on its valence, on the water
layer thickness surrounding it, and on its atomic
configuration [9]. Protons (hydronium) H+(H3O+)
have high capacity to replace to other cations, but
their use is not always convenient since some
adsorbents may be altered by acid attack. In brief,
the adsorption and the desorption must be made
under very specific operative conditions to
impede generation of new wastes.
According to the two methods mentioned
above, several operations and processes must be
used to separate chromium (III), but they are not
commonly utilized in the tannery. Based on these
facts, it was considered as appropriate to study
the separation of chromium (III) contained in a
tanning wastewater by means of reverse osmosis
 A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226
(RO). In this method that is easier to be fulfilled
than the precipitation and the adsorption, a
fraction of the tanning wastewater passes through
an adequate membrane under sufficient pressure
to overcome the osmotic pressure. The fraction
that passes through the membrane (permeate) is
constituted basically by water with a low content
of dissolved salts and the fraction retained by the
membrane (concentrate) contains most of the
dissolved salts in the original effluent [13–16].
2. Experimental
The tanning wastewater was obtained from a
typical tanning process. The suspended solids
were separated by ultrafiltration (UF). Table 1
shows the chemical analysis of the tanning
wastewater without suspended solids.
Chemical analyses were performed by atomic
absorption/emission (AA/AE), volumetry and
gravimetry. Analyses by AA/AE were made with
Jarell Ash equipment.
UF tests were carried out with Millipore
equipment using a membrane of polysulfone
Pellicon Cassette PTGC00005 of 10.000 NMWL,
with a surface of 0.46 m2 and operable between
pH 2.0 and 12.0.
RO tests were performed using Osmo
equipment, model 19E-HR 500, with a membrane
of polyamide Osmonics 192 HR, with a surface
of 1.68 m2 and operable between pH 2.0 and 12.0.
Table 1
Chemical analysis of the tanning wastewater without
suspended solids
Component g/L
SO4= 17.60
Cl 24.80
Na+ 17.80
Cr3+ 0.75
221
The high-pressure pump and the membrane of the
equipment allowed us to work with a maximum
pressure of 1.3 MPa and with recycling flow of
156 L/h.
The cleaning of the RO membrane was carried
out with water without salts and chlorine, H3PO4
solution at pH 2.0–2.5, NaOH solution at
pH 11.0–11.5 and a sodium lauryl sulfate solution
0.001 w/w. The cleaning operation was finished
when the initial permeate flux was recovered
using distilled water as feed.
The chromium species in solution were
determined by absorption within the visible range
(340–800 nm) with a Hewlett Packard 8453
spectrophotometer.
3. Results and discussion
3.1. UF and RO tests
At the beginning of the RO operation, the
convective flow of the solute associated with the
global flow of the dissolution originates an
accumulation of those species that do not pass
through the membrane (rejected species). The
accumulation of rejected species is produced near
the membrane. Under the effect of the concen-
tration gradient so generated, the diffusion of
these substances is produced towards the interior
of the dissolution in the opposite direction to that
of the convective flow. As the operation occurs,
the concentration of the rejected species
continues increasing up to reaching a certain
equilibrium value. This value remains constant
and the solute forms a layer over the membrane
(boundary layer). The boundary layer is formed
during the first moments of the operation and
disappears after interrupting the operation
pressure.
According to the system nature and under
determined operative conditions, a second layer
of rejected molecules may be formed on the
membrane surface. This formation occurs for
some materials like proteins or silica at a certain
222 A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226
concentration level. The layer near the membrane
surface is very stable and the other is more
dynamic. When the pump is disconnected, most
of the solute molecules disappear, although some
of them remain for some time. Thus, an
additional resistance to the transport through the
membrane is added.
The use of the pressure to overcome the
osmotic pressure induces the species of smaller
molecular size to pass through the membrane and
thus those species which are larger are
concentrated. In order to prevent any
accumulation of particles on the membrane
surface, the feed is performed by means of a
tangential flow with a high rate. If this action is
not sufficient, pretreatment of the feed must be
performed to remove the different particles of
suspended solids that may affect the system
behaviour [13].
In our case, the particles of suspended solids
were almost all of them proteins released from
the collagen during the tanning process. The
protein content in the tanning wastewater was
0.007 w/w, and its separation was performed by
UF at room temperature using a transmembrane
pressure of 0.15 MPa. Thus, it was possible to
separate more than 80% of the proteins contained
in the effluent.
To determine the influence of the suspended
solids on the permeate flux (L/m2h), tanning
wastewaters with and without proteins were used.
In each case the test was performed with an
effluent volume of 12 L, an applied pressure of
1.3 MPa and a feed temperature of 298 K. The
time required to obtain 1.8 L of permeate was
measured, and thus it was possible to determine
the corresponding flux. This determination was
performed six times (1–6) resulting in a final
concentrate volume of 1.2 L. Table 2 shows three
permeate fluxes (1, 3 and 6) obtained for tests
performed with and without pretreatment of the
effluent by UF. These values indicate that the
permeate flux was in each aliquot slightly higher
for the effluent without proteins, and this allowed
Table 2
Permeate fluxes obtained with and without pretreatment
of the effluent by UF
Permeate Effluent
flux, L/m2 h
With pretreatment Without
by UF pretreatment by UF
1 0.84 0.69
3 0.81 0.64
6 0.59 0.50
us to decrease the working time to obtain the
same final permeate volume. The low protein
content in the tanning wastewater would explain
the scarce difference of the permeate fluxes
obtained with and without pretreatment of the
effluent by UF.
The permeate flux depends on the applied
pressure and on the feed temperature. In order to
study the behaviour of both variables, tests were
made using three different pressures (0.9, 1.1 and
1.3 MPa) at constant temperature (288 K). With
these conditions, the permeate flux changed in a
linear way with the applied pressure (0.17 L/m2h
at 0.9 MPa, 0.34 L/m2h at 1.1 MPa and 0.50 L/m2h
at 1.3 MPa). When the tests were made using
three different temperatures (288, 298 and 308 K)
at constant pressure (1.0 MPa), the permeate flux
changed according to a parabolic law with the
feed temperature (0.27 L/m2h at 288 K;
0.54 L/m2h at 298 K and 0.71 L/m2h at 308 K).
Taking into account the results mentioned
above, a new RO test was carried out using the
effluent without proteins, an applied pressure of
1.3 MPa and a feed temperature of 298 K. The
test was performed with an effluent volume of
24 L and was finished when the concentrate
volume was 2.4 L. From each 1.8 L of permeate
obtained, an aliquot of 0.15 L was taken for
chemical analysis. In total, 12 aliquots of
 A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226
Table 3
Chemical analyses and pH of permeates and pH of the respective concentrates
Aliquot Permeate
SO4=, g/L Cl, g/L
1 0.9 8.5
6 1.9 10.9
12 3.3 13.7
permeate (1–12) were analyzed. The characteri-
zation was completed with the pH measurement
of each permeate aliquot and of the respective
concentrate. Table 3 shows the chemical analyses
and the pH of three permeate aliquots (1, 6 and
12) and the pH of the concentrates. The low
chromium (III) content in all permeate aliquots
shown in Table 3, similar to the values
mentioned by other authors [13–16], confirms
that the RO method is a valid alternative for the
treatment of the tanning wastewater.
3.2. Identification of chromium (III) species
present in the tanning wastewater and in the
concentrates obtained by RO
The separation of species by RO depends on
the difference of molecular size of the feed
components to be treated, among other aspects
[15]. The medium conditions (pH and
concentration of soluble species) are modified as
consequence of this separation, which may affect
the molecular size (structural changes) of some
component. Under the experimental conditions
used in this work, chromium (III) is the most
propitious component to present structural
changes [17–21]. According to these considera-
tions, the physicochemical characterization of
different solutions (chromium (III) content,
storage temperature and time) was made in order
to obtain evidence to explain the results attained
by RO.
223
Concentrate pH
Na+, g/L Cr3+, mg/L pH pH
5.3 10.4 4.42 4.50
8.4 7.5 4.61 4.67
9.7 6.8 4.72 4.75
The absorption spectrum of a diluted solution
of chromium (III) nitrate recently prepared and
maintained at room temperature has two bands at
408 and 575 nm. The anion nitrate is a weak
ligand, and it is very difficult that in diluted
solutions it may penetrate into the coordination
sphere of the chromium (III) complex. At the
same time, the possibility of hydrolytic polymeri-
zation of this cation (structural changes) in fresh
solutions and maintained at room temperature is
negligible. The above-mentioned facts suggest
the only presence of water groups into the sphere
of the complex [18–21]. Then the bands at 408
and 575 nm show the presence of a chromium
(III) mononuclear complex [Cr(H2O)63+].
The absorption spectrum of a solution recently
prepared from a commercial tanning salt
(Chromosal-BA Bayer), with a chromium (III)
concentration similar to the one of nitrate and
maintained at room temperature, has two bands at
432 and 594 nm. A shift of the absorption
maxima towards longer wavelengths was
attributed to the presence of hydroxide groups
and sulfate groups into the sphere of the
complex. The hydroxide groups produce
chromium (III) polymerization, and the sulfate
groups (with a ligand strength higher than the one
of nitrate) act as monodentate and bidentate
ligands [17–21]. Species in solution are
polynuclear (dimer), and they remain without
structural changes for some time when the
commercial salt is dissolved in cold water [17].
224 A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226
The tanning reagents of mineral origin react
with carboxylic groups of the collagen between
pH 2.9 and 4.1. A tanning improvement may be
achieved when the process is performed at a
temperature of 10 to 20(C higher than the room
one [22,23]. The pH of a fresh solution of the
commercial tanning salt (150 g/L) and maintained
at room temperature was ~2.7. When the pH and
the temperature of this solution were similar to
the usual values of the tanning process, certain
structural changes were produced, and at the end
the maxima of absorption bands decreased. These
changes originated from hydroxide groups that
act as ligands among central atoms of chromium
(III), which leads to a decrease in the initial
sulfate concentration into the sphere of the
complex. Hydroxide groups (as bridge or as
monodentate ligand) produce a shift of the
absorption bands lower than the sulfate groups
[17].
The pH of the tanning wastewater was ~4.3,
and the absorption spectrum of this effluent
without suspended solids, obtained under equal
operation conditions than the above-mentioned
spectra, has two bands at 414 and 582 nm. Both
maxima were increased when the pH was
decreased with successive additions of sulfuric
acid. The shift of the absorption maxima obtained
when lowering the medium pH (from 4.3 up to
2.7), while the sulfate concentration did not
present changes, was used as evidence of the
participation of hydroxide groups in the
structural changes produced in soluble chromium
(III) complexes. Despite the reversible character
of the shift, in none of the cases was it possible to
obtain an absorption spectrum of the tanning
wastewater similar to the absorption spectrum of
a fresh tanning solution. This behaviour was
attributed to the different chemical composition
of both liquids.
The transport of H2O from the concentrate
(the tanning wastewater at the test start) towards
the permeate produced an increase in the
chromium (III) concentration of the concentrate.
At the same time, the pH of each permeate was
lower than the pH of the respective concentrate.
According to these pH values, it is possible to
assume that during RO test, the transport of
H+(H3O+) was also produced in a similar
direction (from the concentrate to the permeate).
The increases of both parameters (concentration
of cation and pH) are aspects that favor the
hydrolytic polymerization of chromium (III)
[18,19].
At pH >4.7 a chromium (III) complex salt
started its precipitation (16% of Cr2O3), and as
the RO test occurred, the amount of precipitate
increased. The addition of sulfuric acid impeded
the precipitation progress and made possible the
start of the redissolution of the solid phase
already formed. However, the redissolution was
not complete, and an important part remained
retained in the filter placed previous to the high-
pressure pump. The chemical analysis of the
concentrate supernatant so obtained is indicated
in Table 4. The formation of the precipitate
during the RO test and its subsequent
redissolution with sulfuric acid was a new
evidence of the participation of hydroxide groups
in the chromium (III) polymerization. The
absorption spectra of concentrates obtained in the
successive stages of the RO test maintained the
band maxima at wavelengths lower than those
mentioned for the commercial tanning salt
recently dissolved.
The aspects above analyzed indicate that the
chromium (III) forms polynuclear complexes in
the tanning wastewater and in the concentrates
obtained by RO. These chromium (III) poly-
nuclear complexes have sizes larger than the
other ionic species (SO4=, Cl, Na+) present in the
system [17–21]. Consequently, chromium (III)
polymers would be the components of the system
with higher difficulty to pass through the
polyamide membrane used, and this would
explain the results obtained.
 A. Pérez Padilla, E.L. Tavani / Desalination 126 (1999) 219–226
Table 4
Chemical analysis of the concentrate supernatant
obtained in this work by RO
Component g/L
SO4= 35.90
Cl 16.67
Na+ 14.35
Cr3+ 4.09
4. Conclusions
The polyamide membrane used allowed us to
perform an efficient separation of chromium (III)
contained in the tanning wastewater, but the
other components of the system (SO4=, Cl and
Na+) could not be separated satisfactorily.
It was determined that a low protein content
(0.007 w/w) in the tanning wastewater had little
influence on the permeate flux. On the other
hand, it was established that the pressure changes
applied to overcome the osmotic pressure
produced variations of the permeate flux higher
than the temperature changes of the feed.
The presence of chromium (III) polymers in
the tanning wastewater and in the concentrates
obtained by RO was identified. These chromium
(III) polymers have a more complex molecular
structure than the other ionic species present in
the system which originates a size difference
among effluent components, and this would
contribute to explain results obtained in this
work.
It was determined that a transport of H+(H3O+)
from the concentrate towards the permeate was
produced. This ionic transfer was analyzed in
detail since the medium acidity affects the
chromium (III) polymerization (molecular
structure).
225
Acknowledgements
The authors thank N.A. Lacour (CIC–CITEC)
and J.A. Rodríguez (UNSL–INTEQUI) for their
collaboration in the development of this work.
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