DESALINATION

ELSEVIER

Desalination

108 (1996)

193-203

Quality improvement of recycled chromium in the

tanning operation by membrane processes
A. Cassanol,

E. Drioli1v2*, R. Molinaril,

and C. Bertolutti3

IDepartment of Chemical Engineering and Materials, University of Calabria, 87030 Arcavacata di Rende (CS),
Tel.: +39-984-492039; Fax.: +39-984-492058;
Research Institute on Membranes and Modelling of Chemical
Reactors, c/o Department of Chemical Engineering and Maferials, University of Calabria, 87030 Arcavacata di Rende
(CS); and 3Consorzio Recupero Cromo, via Nuova Francesca I, 56029 S. Croce S/Amo (PI), Italy
Received

30 August 1996; accepted 5 September

1996

Abstract
Use of pressure-driven membrane processes integrated with conventional precipitation/dissolution operations
is described in order to reduce chromium content in waste water from the tanning process and simultaneously
improve the quality of the recycled chromium by means of elimination/reduction of organic lipolytic
components, metals and other impurities that accompany the chromium recovered by traditional processes. The
results obtained in the identification of types of membranes and modules, chemical-physical parameters, pretreatment of fluids, cleaning procedures and fluid dynamic conditions are reported and discussed. According to
the obtained results, it is possible to suggest a process scheme that, starting from the exhausted chromium
solution, through a nanofiltration membrane purification/concentration permits to obtain solutions that can be
reused in tanning and/or retanning operations. The concentrate solution seems to guarantee improved
characteristics of tanned and retanned skins with respect the skins treated witb the traditional techniques as
showed by chemical and physical essays on leather samples. The process permits also the reuse of the permeate
from the nanofiltration in the pickling phase, considering the high content of chlorides in me solution.
Keywords:

Membrane processes; Ultrafiltration, Nanofiltration; Reverse osmosis; Chromium recovery

1. Introduction

the skin is treated with substances

The transformation
of animal skin into
hide requires
a series
of chemical
and
mechanical
treatments.
In one of these
chemical processes, that is the tanning process,
Presented at the Second Annual Meetin of the Euro ean
Desalination
Society (EDS) on Desa K
mation
an Bthe
.
Environment,
Genoa, Italy, October 20-23, 1996.
*Corresponding

author.

OOll-9164/97/$17.00
Copyright
PZZ SOOll-9164(97)00027-l

preventing
its putrefaction.
Chromium
salts, particularly
the basic
sulphate, are the most widely used tanning
substances today. The skins that have been
tanned with chromium salts present a good
mechanical
resistance,
an extraordinary
dyeing suitability and a better hydrothermic

resistance in comparison with the skins treated

with vegetal substances (the contraction
tempera&e
of a chromium-tanned
hide is

e 1997 Elsevier Science B.V. All rights reserved.

194

A. Camano et al. /Desalination

lOOC, while a vegetal-tanned hide has a

contraction temperature
of 7580C)
[ 11.
salts
are
the
chromium
Moreover,
characterised by a high rate of penetration
into the interfibrillar spaces of the skin: this
involves a saving in terms of production time
and a better control of the process.
Unfortunately only a part of the chromium
salts (about 60-70% of the initial one) used in
the tanning process reacts with the skins; the
residual quantity remains in the tanning
exhaust bath that is normally sent to a
depuration plant. Here the chromium salts
end up into the sludges, creating serious
problems for their disposal and/or for their
agricultural use [2].
Chromium recovery from tanning exhaust
baths means a significant
economical
advantage for tanning industry both in terms
of its reuse and for the simplification
of
depuration processes of global wastes. Some
proposed recovery techniques are adsorption
[3], redox-adsorption
[4] and ion-exchange

[51.
associated
leather
In Italy various
companies created the Consorzio Recupero
Cromo, located in S. Croce sullArno (Pisa), to

recover chromium [6]. The treatment process

(Fig. 1) is based on the precipitation of the
exhaust chromium with the addition of basic
substances. Particularly, the waste solution
originating from tanning and/or retanning
processes (containing a quantity of chromium
as CrzOs from 0.3 to 0.8% in weight) is
treated with NaOH in order to allow the
precipitation of chromium as hydroxide. The
precipitate is sent to the filtration plant where
panels of sludges containing
lo-12% of
chromium hydroxide on average are obtained
through filter-pressing.
The panels are
dissolved again in sulphuric acid and the
obtained solution is then adsorbed on fossil
flour in order to eliminate the suspended
particles
and the fat substances.
The
separation of fossil flour from chromium
basic sulphate happens through a final
procedure
of filter-pressing.
The final
obtained solution with a content in Cr2Os of
14-15% is reused in tannery for the
preparation of new tanning baths.
A problem observed by tanners is the poor
quality of this chromium due to the presence
of organic lipolytic components, metals and
In order to improve the
other impurities.

Recupero

1 Chromiumwaste water
2 sieving
3 Solid waste
4 Equalizationtank
5 Neutralizationtank
6 Flocculationtank
7 Hydroxidefiltratiin

pe4v]

Fig. 1. Plant scheme of Consorzio

108 (1996) 193-203

Cromo

8 First dissolution
9 Second dissolution
10 Adsorptionon fossilflour
11 Miirodosage NaOH
12 Micmdosage sulphwic acM
13 Storingfinal producl

(S. Croce WArno, Italy).

A. Cassano et al. /Desalination

quality of the recycled chromium or to test

alternative
to these
recovery
methods,
chemical methods a study using membrane
processes has been carried out.
Preliminary tests on microfiltration
and
ultrafiltration membranes were carried out in
order to find the type of pretreatment of the
feed, type of membranes, operating pressures
cleaning conditions of
and temperatures,
The optimisation
of the
membranes.
ultrafiltration operation was carried out by
ENEA [7] on a pilot plant at the Consorzio
Recupero Cromo. The permeate from this
plant was then used for concentration tests
using reverse osmosis and nanofiltration
membranes
and the optimal
chemicalphysical
parameters,
fluid-dynamics
conditions and cleaning procedures on these
modules were determined.
The concentrated chromium was tested as
such in the retanning of sheepskins and, after
further concentration by precipitation, also in
a tanning operation. The treated sheepskins
were compared by means some chemical and
physical tests on both the groups of skins
using control samples obtained with standard
tanning and retanning methods, respectively.

2. Experimental
Exhaust solutions of chromium used in all
the experiments
were drawn from the
equalization tank of Consorzio Recupero
Cromo.
Sepaclean
EZ- 1, Sepaclean
AC- 1,
Sepaclean
AL-l (Separem),
Ultrasil 50
(Henkel) and other reagents of commercial
grade were used in membrane cleaning.
Chloride,
pH, ammoniacal
nitrogen,
organic nitrogen and COD values were
determined according to the CNR-IRSAmethods.
Chromium was determined by Atomic
Absorption Spectrophotometer; sulphate was
determined by calorimetric method; oils and
fats were determined
by extraction
in
petroleum ether at 40-60C. Total suspended
solids (TSS) were determined by filtration on

108 (1996) 193-203

195

0.45 pm acetate cellulose membrane. Other

species (Ca 2+, Fe2+, Mg2+, Mn2+, A13+) were
determined
according
to conventional
methods. Turbidity of samples was determined by a turbidimeter (Velp Scientifica).
Flat sheets polysulphone (PS) membranes
(NMWCO > 3,000 kDa, 15 kDa, 40 kDa)
from Separem (Italy), PVDF (50 kDa) also
from Separem and PEEK-WC 12% (PEEK)
prepared in the Membrane Laboratory of the
Department of Chemical Engineering and
Materials using PVD 5% in DMF solvent were
used in preliminary tests.
Reverse osmosis (Table 1) and nanofiltration (Table 2) spiral wound modules
obtained
from Separem
were used. A
laboratory
plant able to operate simultaneously on five flat sheet membranes was
used in the preliminary tests. Two types of
pilot plant, Acqua Aria mod. 1081 A - 1983
and Separem (Fig. 2), were used to carry out
nanofiltration and reverse osmosis tests on
spiral-wound modules.

Table 1
Main technical characteristics
reverse osmosis module

of

MSCB 4040 Separem

Configuration
Spiral-wound
Membrane polymer
Composite/polyamide
Membrane surface area, m2
6.6
Typical salt rejection, %
99.2
42
Max. operating pressure, bar
Max. operating temperature, C 50
pH operating range
4-11
Axial flow rate, m3/h
1.5-4

Table 2
Main technical
characteristics
Separem nanofiltration module

of MOCD

Configuration
Membrane polymer
Membrane surface area, m2
Nominal cut-off, Da
Minimum rejection with MgS04,
Max. operating pressure, bar
Max. operating temperature, C
pH operating range
Axial flow rate, l/h
Water permeability,
Um2.h

Spiral-wound
Polyamide
5.5
150
96
%
28
50
2-11
1,200-4,500
47.21

4040 N50

A. Cmsano

196

of pilot nanofiltration

IO8 (1996) 193-203

prefilter (10 pm)

prefiller (5pm)

Fig. 2. Scheme

et al. /Desalination

/\

I
feed tank

plant.

3. Results and discussion

In the preliminary
phase
of the
experimental study, micro- and ultrafiltration
tests on five types of flat sheet membranes
using basic sulphate chromium solutions from
the equalization tank of Consorzio Recupero
Cromo were carried out. The microfiltration
tests on the PS > 3,000 kDa membrane,
carried out at pressures of 2 and 4 bar, gave a
permeate flux between 32 and 48 L/m2.h
using solutions prefiltered on rapid filtration
The chromium
rejection
was
paper.
respectively variable from 5 1% to 41%.
The tests carried out on ultrafiltration flat
sheets membranes
gave a sequence
of
chromium removal decreasing in the order:
PS 40 kDa > PEEK > PS 15 kDa > PVDF 50
kDa, calculated by the product permeate flow
rate times
concentration.
Rejections,
determinated at pressures of 2 and 4 bar, were
variable from 36% to 54% giving a lower
value at a pressure of 4 bar.
Comparing the data of microfiltration and
ultrafiltration tests an increase of the fouling

phenomena for the microfiltration membrane

greater than the ultrafiltration membrane was
observed.
Cleaning procedures using in sequence
solutions of Ultrasil 50 (1%) at 37C, HCl at
30C and NaOH at 30C gave positive results.
The results obtained in these preliminary
tests were used to carry out experiments on
pilot scale. The permeate obtained by ENEA
[7] from its ultrafiltration pilot plant was used
to perform concentration tests on reverse
osmosis and nanotiltration modules. In Table
3 the chemical characteristics of the initial
equalized chromium solution and of the final
permeate and concentrate obtained from the
ultrafiltration
plant by ENEA using an
Osmonics 411 TA spiral-wound
module
(PVDF, NMWCO 15-25 kDa, 3 m2, pressure
max. 3.8 bar, temperature max. 45C, pH 211, water permeability 60 l/h.m2.bar) are
reported. It is evident that this step already
leads to a strong reduction of suspended solid
components and of the fat substances. The
rejection of the membrane toward these
species with reference to the initial feed is of

A. Cassano et al. / Desdintiion

Table 3
Analytical
determinations
ultrafiltration
tests
Parameter
mg/l
PH
TSS
COD
Chloride
Sulfate
Chromium
Ammon. nitrogen
Organic nitrogen
Iron
Calcium
Manganese
Aluminium
Magnesium
Oils and fats

on samples

Feed

from

Retentate

Permeate

3.7
428
6,413
11,098
27,239
5,269
420
301
29
948
2.5
97
822
148

3.8
100
5,241
11,348
21,561
3,121
422
148
25
1,007
2.4
84
787
2.5

3.7
612
5,960
11,136
26,137
4,343
422
250
24
1,100
2.2
91
867
116

Table 4
Analytical
determinations
osmosis tests

obtained

on

samples

from

Sample

PH

COD
mg/l

Chloride
mg/l

Feed
Initial permeate
Final concentrate
Final permeate

3.5
3.4
3.3
3.3

4,316
272
6,055
461

8,224
85
13,045
301

reverse

Chromium
mg/l
2,219
<2
3,468
<2

84% and 98%, respectively. About 40% of

organic nitrogen is retained by the membrane
while the rejection for the chromium is 28%.
When the permeate from ultrafiltration was
processed in reverse osmosis spiral-wound
module the working pressure was 38 bar and
the average temperature 35C. The axial flow
rate was maintained a little higher than 2,500
l/h obtaining a permeate flux decreasing from
10.48 l/m*.h to 3.43 l/m*.h in a period of time
of about 70 minutes; this was also caused by
the high osmotic pressure of the concentrate
solution
which
is increased
by the
concentration of sulphate and chloride ions.
The results of analytical determinations are
reported in Table 4. It can be observed that
chromium concentration increases of 1.5 with
respect to the initial one. The COD ratio with
respect to the initial value increased of 1.4.
The nanofiltration was carried out at a
temperature of 25C an applied pressure of
14 bar and an axial feed flow rate of 2,200
l/h. The initial volume, about 160 liters, was
reduced to about 66 liters. The initial
permeate flux was 25 l/m*.h, then decreased in
the time to 4.92 l/m*.h, remaining constant in
the last hours of operation,
In Table 5 the chemical analyses carried
out on the permeate and the concentrate

Table 5
Analytical determinations
on samples from nanofiltration
concentration
by precipitationkedissolution
method)

tests (final concentrate

Parameter
mg/l

Half-run
concentrate

PH
TSS
COD
Chloride
Sulfate
Chromium
Ammoniacal
nitrogen
Organic nitrogen
Iron
Calcium
Manganese
Aluminium
Magnesium
Oils and fats

Feed

4.2
114
5,349
11,230
22,813
3,113
420
136
25
1,005
2.3
91
867
116

Initial
permeate
4.0
18
1,868
10,794
220
n.v.
223
61
1.3
58
0.6
1.7
0.4
n.v.

197

108 (1996) 193-203

4.0
190
5,320
10,195
28,019
3,668
402
199
32
1,329
9.1
98
998
n.v.

used as tanning

solution

after further

Half-run
permeate

Final
concentrate

Final
permeate

3.9
8
2,492
11,210
386
n.v.
231
74
1.4
320
0.8
3.6
76
n.v.

3.9
196
6,443
8,151
45,997
7,712
560
259
51
1,946
7.9
166
1,835
2.6

3.9
21
2,674
11,931
684
n.v.
238
76
1.5
65
1.3
2.3
10
n.v.

198

A. Cassano et al. /Desalination

samples at different time are reported.

The comparative examination of the feed
and of the final concentrate underlines in the
latter a concentration factor for chromium of
2.5 and for COD of 1.2. This means that
organic matter are reduced of about 50% as
10000~

o-

3 Cr

I,

10

I,,

20

30

40

50

60

70

Ume (min)
Fig. 3. Concentration
nanofiltration
tests.

8za
I
W

of chromium

and COD vs. time in

feed
permeate
concentrate

Chromium
Fig. 4. Chromium concentration
and COD values in the
final samples from nanofiltration
tests as compared to
the feed.

108 (1996) 193-203

shown by the ratio COD/chromium concentration. For this reason all the successive
experiments
were done on nanofiltration
modules.
In Fig. 3, the temporal course of chromium
concentration and COD in the concentrate
and permeate streams are represented. In Fig.
4 the relative values of COD and chromium in
the final samples withdrawn in nanofiltration
tests are shown.
In Fig. 5, the scheme of the two approaches
followed to reuse the concentrate
from
nanofiltration is reported.
In all the permeate fractions the chromium
concentration is not experimentally detectable
(the membrane rejection toward this species is
99.9%);
moreover,
the high chloride
concentration reached suggests to reuse this
solution in the pickling step, which precedes
the tanning operation.
In the first alternative the chromium
solution was subjected to a precipitation/
flocculation process through the addition of
NaOH (solution at 50%). The solution so
obtained
was filtered
to separate
the
chromium hydroxide from the water phase.
The panel of chromium hydroxide was then
dissolved in concentrate sulphuric acid (98%)
stirring the solution for about 6 hours. The
final product (containing 9.2% of chromium
as CrzO 3) was employed in tannery to
perform experimental tanning essays. For
these essays two groups of sheepskins (named
Sample A and B) were cut in two halves: one
half was tanned with the experimental solution
and the other with the conventional method
which envisages the use of pure chromium
basic sulphate.
In Tables 6 and 7, the results of the
chemical and physical analyses carried out on
the leather samples are reported. They show:
_ higher values of tensile strength and tear
strength for the skins tanned with the
nanofiltrated product;
_ the same content of chromium oxide in
both samples;
_ contraction temperature higher than 105C
in both groups of treated skins.

A. Cassano et al. /Desalination

108 (1996) 193-203

199

permeate

2nd alternative

concentrate

retanning

1st alternative
1
further concentration
pfldpletknlanddlglohlaan
k wlphulic add

tanning

In the second alternative, the concentrate

from the nanofiltration was used as retanning
product; it was obtained starting from an

T = 25C
P,rl6bar

35 -

Q,

30-

=22covh

25 P
3 20_)
15 -

10 -

S-

OL~
0

20

40

60

80

loo

120

140

160

time (min)

Fig. 6. Permeate

flux vs. time in nanofiltration

tests.

180

Fig. 5. Temptative process scheme for the reuse of

the concentrate from nanofiltration.

exhaust chromium bath containing 3,447 mg/l

of chromium that, after ultrafiltration, gave a
permeate with a chromium concentration of
2,861 mg/l used as feed for the nanofiltration.
In this last operation, the initial feed volume
of about 178 liters was reduced to 55 liters.
The solution temperature (25(Z), the applied
pressure (16 bar) and the axial flow rate of
the feed (2,200 l/h) were kept constant during
the nanofiltration. The permeate flux, starting
from an initial value of 36 l/m*.h, was reduced
to 3.63 l/m*.h and remained constant in the
last hour of operation (Fig. 6).
In Table 8, the concentration
of the
chemical species determined in the permeate
and the concentrate fractions are reported.
The Table shows a value of 9,285 mg/l of
chromium in the final concentrate (containing
1.35% of chromium
as Cr203) with a
concentration factor of 3.2 in comparison
with the feed. On the other hand, for the COD
the concentration factor is 1.5. As in the
previous case, the concentration of chromium

200

A. Cassano et al. /Desalination

Table 6
Physical analyses on leather samples tanned
Cr203) and with a standard chromium solution

with the recovered

highly

concentrated

Sample A

Parameter

Tensile
strength,
kg/mm2
Longitudinal drawing direction
Transversal drawing direction
Breaking
load, kg
1.d.d.
t.d.d.
Alongation
at break, %
1.d.d.
t.d.d.
Tear strength, kg
1.d.d.
t.d.d.
Tear load, kg
1.d.d.
t.d.d.
Contraction
temperature,
1.d.d.
t.d.d.
Bursting
essay
Thickness, mm
Chapping load, kg
Stretching at chapping, mm
Burst load, kg
Stretching at burst, mm

Experimental

2.0
0.86

54.0
17.0

3.15
1.30

49.0
22.0

40
134

solution

(9.2% as

39.0
14.3

32
156

26
120

Control

2.38
1.30
31.0
17.2
36
110

4.5
4.6

3.7
3.6

5.2
4.8

4.6
3.8

7.5
7.7

8.6
8.2

6.0
5.8

6.2
4.8

C
>105
>105

>105
>105

>105
>105

2.49
45
12.7
46
13.5

1.65
35
11.4
40
13.0

*Values referred conventionally

Control

2.16
0.94

Table 7
Chemical analyses on leather samples tanned
Cr203) and with a standard chromium solution

Humidity and volatile substances

Total sulfate ash at 8OOC
Chromium oxide
Total nitrogen
Leather substance**

chromium

Sample B

Experimental

Parameter,

108 (1996) 193-203

with the recovered

1.50
39
11.3
42
11.9

highly

concentrated

1.35
39
11.7
40
11.9

solution

(9.2% as

Sample B

Sample A

at 102C

chromium

> 105
> 105

Experimental

Control

Experimental

Control

22.4-14.0*
10.8-12.0
3.6-4.0
10.2-11.3
57.3-63.5

22.5-14.0*
7.3-8.1
3.6-4.0
10.9-12.1
62.3-68.0

20.6-14.0*
8.2-9.0
4.0-4.3
11.0-l 1.9
61.8-66.9

21.6-14.0*
8.8-9.6
3.9-4.3
10.6-11.6
59.6-65.2

to 14% humidity;

**calculated

and of the other metal species in the permeate

fractions are not relevant.

from N x 5.62.

The concentrate solution was employed to

carry out retanning essays on sheepskins.

A. Cassano et al. /Desalination

Table 8
Analytical

determinations

on samples

from nanofiltration

Parameter
mg/l

Feed

Initial
permeate

PH
TSS
COD
Chloride
Sulfate
Chromium
Ammoniacal
nitrogen
Organic nitrogen
Iron
Calcium
Manganese
Aluminium
Magnesium

4.1
88
5,028
11,552
26,815
2,861
441
126
32
1,390
2.3
90
856

4.1
17
2,063
11,330
252
n.v.
233
76
3.2
42
0.1
1.2
5

Table 9
Physical analyses on leather samples retanned
and with a standard chromium solution
Parameter

Tensile
strength,
kg/mm2
Longitudinal drawing direction
Transversal drawing direction
Breaking
load, kg
1.d.d.
t.d.d.
Alongation
at break, %
1.d.d.
t.d.d.
Tear strength, kg
1.d.d.
t.d.d.
Tear load, kg
1.d.d.
t.d.d.
Contraction
temperature,
1.d.d.
t.d.d.
Bursting
essay
Thickness, mm
Chapping load, kg
Stretching at chapping, mm
Burst load, kg
Stretching at burst, mm

tests (final concentrate

Half-run
concentrate
4.2
192
6,300
9,792
38,289
5,342
551
147
52
1,755
3.8
161
1,398

with the recovered

Sample C
Experimental

2.73
1.21
29.5
13.5
24
140

201

108 (1996) 193-203

used as retanning

solution)

Half-run
permeate

Final
concentrate

Final
permeate

3.9
8
2,492
11,210
386

4.0
370
7,641
7,390
83,455
9,285
720
209
81
1,367
6.3
259
6,162

4.0
28
3,315
13,190
10,550
30
320
98
8
12
0.4
5
60

concentrated

n .\I.

231
74
1.4
320
0.8
3 .ti
76

chromium

solution

(1.35% as Cr203)

Sample D
Control

1.92
1.06
23.0
14.8
32
136

Experimental

1.54
1.16
18.5
13.7
40
162

Control

1.72
0.77
22.0
9.2
36
204

4.6
4.1

5.4
3.7

3.5
2.9

3.6
3.1

5.3
4.3

6.7
4.9

5.8
5.2

6.0
5.0

C
>105
>105
1.19
25
10.8
35
12.8

>105
>105
1.26
29
10.5
40
12.3

>105
>105
1.57
15
9.3
29
12.9

>105
>105
1.69
16
9.7
32
13.1

202

A. Cassano et al. /Desalination

Table 10
Chemical analyses on leather samples retanned
and with a standard chromium solution
Parameter,

with the recovered

*Values referred conventionally

concentrated

Sample C
Experimental

Humidity and volatile substances

Total sulfate ash at 8OOC
Chromium oxide
Total nitrogen
Leather substance**

IO8 (1996) 193-203

at 102C

19.4-14.0*
6.0-6.4
3.6-3.8
12.3-13.1
69.1-73.6

to 14% humidity;

**calculated

Even in this case two groups of skins (named

Sample C and D) were cut in two halves: one
half was treated with the examined solution
(experimental
group); the other half was
retanned according
to the conventional
method (control group).
The chemical and physical tests performed
on the skin samples drawn in the course of the
treatment (Tables 9 and 10) reveal higher
values of tensile
strength
and leather
substance in comparison with the skins treated
with the experimental
solution.
The
contraction temperature is higher than 105C
in both the groups of skins.
On the basis of the chemical and physical
tests on tanned and retanned sheepskins the
concentrate solution from nanotiltration can
be used in two alternative ways as proposed in
Fig. 7.
Tests of membrane modules cleaning using
two solutions of Sepaclean (AC-l and EZ-1 at
1%) showed a good restore of the initial flux
using the AC-l solution (Fig. 8).
4. Conclusions
Use of a nanofiltration
membrane
operation, after ultrafiltration as a solution
pretreatment, permits to concentrate exhaust
chromium tanning baths. The quality of the
concentrated chromium solutions was im-

chromium

solution

(1.35% as Cr203)

Sample D
Control
18.6-14.0*
5.9-6.2
4.1-4.3
11.7-12.4
65.7-69.7

Experimental
21.0-14.0*
5.8-6.3
3.8-4.1
11.8-12.8
66.3-72.0

Control
20.3-14.0*
5.5-5.9
3.5-3.8
11.6-12.5
65.2-70.3

from N x 5.62.

proved with respect to the conventional

recovery process, based on precipitation and
dissolution, as showed by the low ratio of
organic lipolytic components/chromium.
A further concentration of the recovered
chromium
solution
was done by the
conventional
method of precipitation
and
dissolution enabling the highly concentrated
solution to be used directly in tanning
operations.
According to the obtained results, it is
possible to suggest a process scheme that,
starting from the exhausted
chromium
solution, through a nanofiltration membrane
purification/concentration
permits to obtain
solutions that can be reused in tanning and/or
retanning
operations.
The concentrate
solution
seems to guarantee
improved
characteristics of tanned and retanned skins
with respect the skins treated with the
traditional techniques as showed by chemical
and physical essays on leather samples.
The process permits also the reuse of the
permeate from the nanofiltration
in the
pickling phase, considering the high content
of chlorides in the solution.
The advantages are particularly in terms of
reduction
of environmental
impact,
simplification
of depuration processes of
waste waters, easy reuse of sludges and
decrease of disposal costs.

Cassano et al. /Desalination

108 (1996) 193-203

180 -

_
160-

Fine sieving
(0.5 mm)

203

bdomteotswiul
chmmiMsoluiml

&erte6mwith
chluniumwMkn

aftwwuymauc~ing
a afteracid washii

140 -

5
-I

120 loo SO-

201,
6
8

10

12

14

16

18

20

22

24

P (bar)

Fig. 8. Effect of membrane cleaning at various applied

pressures on water permeate flux (operating conditions.
T= 25C. Qfeed = 2,200 l/h).

preparationOfllW
pickling baths

muaa for

fulther

ratanning baths

concentration
inallmmcsed)

preparatknofm
tanning baths

Fig. 7. Scheme of the proposed process for reuse of

exhausted chromium solutions from tanning operation.

Acknowledgment
We would like to thank Conciaricerca Italia
S.r.L. which supported this work within the
MURST National Project Piano Nazionale
per la Chimica - Tema 6.

References
[l]

G. Mart&none. Conceria Pratica, 2nd ed., Editrice

Universitaria Levrotto e Bella, Torino, 1974.

121 R.

Molinari, Application
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