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Article history:
Received 20 January 2009
Received in revised form 14 October 2009
Accepted 16 October 2009
Keywords:
Tannery
Unhairing wastewater
Ultraltration
Membrane cleaning
a b s t r a c t
Tanneries wastewaters are characterized by high organic matter and salt concentrations. Beamhouse
operations, in particular unhairing, are the processes that provide the most concentrated efuents concerning the organic matter. Besides, the unhairing wastewater includes a high sulphides concentration.
Thus, the separated management of the unhairing efuents has been considered in the last 20 years with
the aim of their recycling and reuse. Ultraltration was a promising technique to separate the organic
matter from the chemicals (lime and sulphides) that could be reused in the unhairing process. However,
the membrane fouling has avoided its application at an industrial scale. The main aims of this paper
are to study the inuence of the reuse of the ultraltration permeate on the quality of the nal leather
and the comparison among different types of membrane cleaning. Ultraltration experiments, including
cleaning procedures, were carried out in a module for plane membranes with 30 cm2 of active surface.
Sodium dodecyl sulphate, two different enzymes and sodium hypochlorite were used as cleaning chemicals. In addition, the module conguration with only a plane membrane let the study of the effect of
providing air from the permeate side. Laboratory drums with a 5 L maximum capacity were used for the
permeate reuse and further hide samples processing in order to study the nal quality of the leathers.
Results showed that the nal quality of the leather was not modied by using ultraltration permeate
for the unhairing process. Concerning the membrane cleaning, the best results in terms of ux recovery
were achieved with 1000 mg L1 of sodium hypochlorite (92% of ux recovery) and with the air dosing
from the permeate side. Flux recovery with enzymatic cleaning hardly reached an efciency of 35%.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Tanneries generate high wastewaters ow rates including high
organic matter and salts concentrations and other pollutants such
as trivalent chromium. The rst phase in the hide processing is
called the beamhouse operations. In this phase, hides undergo some
processes whose main aims are to re-hydrate the hide, to remove
the conservation salt and blood and to separate the hair, the epidermis and the esh layer from the hide. In this way, beamhouse
operations are the most water consuming and organic matter generating ones.
By means of the unhairing process hair and epidermis are separated from the hide [1].
This process is performed in a drum by mixing the hides with
an alkaline solution containing lime (used to swallow the hide) and
reduction agents such as sulphides. Immediately after the unhairing, the residual bath is taken out of the drum and driven to a grid to
separate hair before its solubilisation. At the end of the operation,
a residual bath with a pH value of about 12 and with a high content
297
298
Operating
time (min)
15a
180
15
15
15
The operating time for the rst use of a membrane was 30 min.
Table 3
Unhairing wastewater characterization.
Parameter (units)
1
COD (mg L )
TS (mg L1 )
S2 (mg L1 )
pH
COND (mS/cm)
Fig. 2. Laboratory drums for the hide samples processing using UF permeate for the,
unhairing.
Standard procedure
BS EN ISO 2589 [25]
ISO 3379 [26]
BS EN ISO 3377-2 [27]
ISO 3376 [28]
ISO 3376
Value
18,00022,000
58,00060,000
6,5007,000
1212.2
4045
COD (mg L )
TS (mg L1 )
S2 (mg L1 )
pH
COND (mS/cm)
Value
12,00014,000 mg L1
50,00052,000 mg L1
5,5006,500 mg L1
12.012.2
3640 mS/cm
299
Table 5
Physical characteristics of the nished leather after unhairing with fresh liquor and with UF permeate.
Physical test
Fibre
direction
Minimal value
required
A
B
15
15
17
15
16
15
A
B
40
60
40
60
45
69
A
B
60
60
86
112
112
154
7.5
8.7
Unhairing with
UF permeate
9.1
Table 6
Permeate uxes measured after the different stages of the cleaning procedure with
DDS (ux values in L m2 h1 ).
Test
% DDS
Jiw
Jww
Jr1
Jc
Jfr
1
2
3
4
5
6
2.0
2.0
1.0
1.0
0.5
0.5
375.0
215.7
310.3
240.0
227.4
190.3
17.0
15.7
16.3
16.0
14.1
15.0
98.8
65.0
62.1
60.3
54.2
52.3
190.5
157.2
145.0
137.7
92.8
83.4
206.9
162.2
153.8
148.1
97.2
89.6
branes. They stated that the surface charge depends only on the
ability of the membranes to adsorb ions. The main ions adsorbed in
their work were OH , giving rise a negative membrane charge.
However, the authors reported that the streaming potential
through the membrane pores decreased considerably with the ionic
strength. Thus, at 1 mol L1 KCl, the zeta potential was 0.
In this way, the effect of the electrostatic repulsion will be very
limited in the UF of unhairing wastewater, since its ionic strength
is high due to the sodium chloride that has not been removed in
the previous soaking process. Thus, it can be concluded that severe
fouling can be produced both by adsorption onto the membrane
surface and especially by pore blocking caused by the fraction of
small peptides that goes into the membrane pores.
3.3.2. Membrane cleaning with surfactant
Table 6 shows the permeate uxes measured after the different
stages of the UF and cleaning procedures according to Section 2.4.
The maximum concentration of DDS was 2%, since higher DDS
concentrations drove to scum formation that avoided a correct
operation of the plant. It was tested the same membrane for the
tests using the same DDS concentrations.
In Fig. 3, nal ux recovery after each experiment can be
observed.
Extremely low ux recoveries were obtained from the rst
experiment with each DDS concentration, due to the high ux
Fig. 3. Final ux recovery after the experiments with DDS as cleaning chemical.
300
Table 7
Results of the enzymatic cleaning experiments (ux values in L m2 h1 ).
Test
Enzyme
Conc. (g L1 )
Jiw
Jww
Jr1
Jc
Jfr
1
2
3
4
5
D
D
R
R
M
1
10
1
10
1+1+5
108.0
98.0
87.0
82.5
86.7
15.5
16.2
13.6
12.4
8.7
29.0
28.4
20.2
19.0
12.8
31.6
32.6
21.1
14.8
21.7
33.0
33.8
24.2
22.5
32.4
decline after the rst test of each membrane. Better results were
obtained by increasing the DDS concentration. Thus, the higher DDS
concentration, the higher ux recovery. However, the maximum
DDS concentration was limited as it was explained above.
3.3.3. Membrane cleaning with enzymes
The enzymes used in the cleaning of the membranes were the
same that those usually applied in the processes carried out in a tannery industry. These enzymes were DEFAT 50 and RIBERZIM MPX.
Besides, an additional experiment was carried out using a mixture
of both enzymes and EDTA-Na4 that was added to the cleaning
solution in case the low ux recovery efciency was due to scaling phenomena. The results of this group of tests are described in
Table 6, where D means DEFAT enzyme, R means RIBERZIM and M
means the mixture of the 2 enzymes and EDTA-Na4 . The composition of the mixture solution was the following: 1 g L1 of DEFAT 50,
1 g L1 of RIBERZIM and 5 g L1 of EDTA-Na4 . The concentrations
of the enzymes in the cleaning solutions were determined after
consulting the technical sheets of the product.
The tests whose results are showed in the table were carried
out with the same membrane. Due to the low ux recoveries, it
was necessary to prolong the cleaning time and then to take the
membrane out of the module and to put it into a cleaning bath
in order to achieve afterwards an initial water permeate ux high
enough to compare the tests carried out with the same membrane.
It can be observed (Table 7) that the ux recovery was very
low. These values were substantially lower than the ones achieved
with other cleaning procedures. The maximum value was 37.4%
and it was achieved for the mixture solution. This was due
to the EDTA-Na4 that improved the ux recovery by eliminating the scaling caused by calcium deposition. This improvement
was not substantial, since the ux recovery values obtained in
the other experiments carried out only with enzymatic solutions ranged between 27.2 and 34.5%. The performance of the
enzyme DEFAT was slightly higher than that achieved with
RIBERZIM.
3.3.4. Membrane cleaning with sodium hypochlorite
The results of the cleaning experiments with sodium hypochlorite are detailed in Table 8.
The highest ux recoveries were obtained in the experiments
3 and 4, reaching values of 92% using a NaOCl concentration of
1000 mg L1 and of 87% with a concentration of 750 mg L1 . The
cleaning effect was produced by the protein oxidation.
Other authors (for example Tasselli et al. for the UF of kiwifruit
juice [36]) have equally reported very high permeability recovery
using NaOCl in the membrane cleaning.
Table 8
Results of the cleaning with sodium hypochlorite (ux values in L m2 h1 ).
Test
Jiw
Jww
Jr1
Jc
Jfr
1
2
3
4
1000
750
1000
750
119.0
114.3
103.7
95.3
13.0
13.0
12.9
11.7
54.5
48.2
46.2
39.2
99.2
96.4
92.4
81.0
101.2
99.2
95.3
83.7
301
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