Separation and Purication Technology 70 (2010) 296301

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Separation and Purication Technology

journal homepage: www.elsevier.com/locate/seppur

Purication of tannery efuents by ultraltration in view of permeate reuse

J.A. Mendoza-Roca , M.V. Galiana-Aleixandre, J. Lora-Garca, A. Bes-Pi
Department of Chemical and Nuclear Engineering, Universidad Politcnica of Valencia, Camino de Vera s/n, 46022 Valencia, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Tanneries wastewaters are characterized by high organic matter and salt concentrations. Beamhouse
Received 20 January 2009 operations, in particular unhairing, are the processes that provide the most concentrated efuents con-
Received in revised form 14 October 2009 cerning the organic matter. Besides, the unhairing wastewater includes a high sulphides concentration.
Accepted 16 October 2009
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
Keywords:
matter from the chemicals (lime and sulphides) that could be reused in the unhairing process. However,
Tannery
the membrane fouling has avoided its application at an industrial scale. The main aims of this paper
Unhairing wastewater
Ultraltration
are to study the inuence of the reuse of the ultraltration permeate on the quality of the nal leather
Membrane cleaning 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 chem-
icals. 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 of organic substances (proteins), lime and sulphur as (S2 and SH )

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 epi-
dermis and the esh layer from the hide. In this way, beamhouse
operations are the most water consuming and organic matter gen-
erating ones.
By means of the unhairing process hair and epidermis are sep-
arated 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 unhair-
ing, 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
Corresponding author. Tel.: +34 963877630; fax: +34 963877639.
E-mail address: jamendoz@iqn.upv.es (J.A. Mendoza-Roca).
is left.
This residual bath contributes to the Chemical Oxygen
Demand (COD) of the total tannery wastewater in approximately
100120 kg of COD per ton of raw hide [2], i.e. approximately the
55% of the COD of the global efuent. Thus, this is the process efu-
ent with the highest COD in a tannery.
Separation of the organic matter from the residual bath drives to
a residual solution containing the chemicals used for the unhairing.
By means of ultraltration (UF) this separation can be achieved. The
protein concentrate of the reject stream could be precipitated and
further treated by evaporation.
The application of UF to the unhairing waste stream was already
proposed by some authors in the two last decades of the 20th cen-
tury [3,4].
Only few authors reported about the membrane cleaning and
the permeate reuse in the application of the UF to the unhairing
process. Collivignarelli and Barducci [5] concluded that UF was
the best technique for water and chemicals reuse and pointed
out the necessity of a daily cleaning with slightly acidic and
basic solutions (pH 5 and 11) in the cleaning process. The oper-
ation of an industrial ultraltration plant treating the residual
bath of the scale removal stage for crocodile skin was reported

1383-5866/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2009.10.010
 J.A. Mendoza-Roca et al. / Separation and Purication Technology 70 (2010) 296301
in the literature [6,7]. However, cleaning procedures were barely
explained.
Silva et al. (2001) carried out a pilot plant study with UF
membranes from Polyvinylidene Diuoride (PVDF) in a tannery
processing sheep skins. Costs were also estimated [8]. These
authors stated that the economical feasibility were based on per-
meate uxes higher than 40 L m2 h1 and process volumes higher
than 10 m3 d1 . Brites and Silva (2006) also studied the UF of the
unhairing wastewater, pointing out the importance of evaluating
the inuence of the permeate reuse on the nal leather quality [9].
These authors did not report about the membrane cleaning.
Tnay et al. (2001), reported that tanning industry had an
immense potential for materials recovery but was the least studied
branch in this aspect. Tanneries use to be small factories and inver-
sions are often not possible if they were not collected in industrial
parks [10]. The elimination of the beamhouse operations in some
tanneries together with the problem of the membrane cleaning did
not enhance the study of the purication and reuse of the tannery
wastewaters by means of UF.
However, for large size tanneries the purication of unhairing
wastewater with UF membranes is very interesting. The key points
to apply this process in an industrial scale are the study of the effect
of the hide unhairing with UF permeate on the nal leather and
the membrane cleaning, due to the tremendous membrane fouling
caused by the proteins of the unhairing wastewater.
The amino-acids content in the proteins of the unhairing
wastewaters is characterized by the presence of small concen-
trations of a wide spectrum of these compounds. Cuadros et al.
[11] reported that arginine and asparagine were the main amino-
acids of these wastewaters. In this way, the peptidic chains in
the wastewater come from soluble proteins as albumin, globu-
lin and keratin. The isoelectric point of the proteins from the
unhairing wastewater is around pH 3. Thereby, the proteins are
negatively charged in the unhairing wastewater, since its pH is
around 12.
Other papers have also been published pointing out the neces-
sity of minimizing the pollution coming from the unhairing process.
Other solutions such as replacement of the sulphur by other chemi-
cals [12,13] and direct reuse of the residual bath [14] are proposed.
However, most of tanneries maintain the traditional process. As
an example, the enzymatic processes can entails possible collagen
degradation phenomena [9] and they require further research as
well.
In the last years, UF of other types of efuents, which are sim-
ilar to the unhairing liquors in terms of difculty to be treated
like textile wastewaters and landll leachates has been studied.
Both contain a complex mixture of organic and inorganic pollu-
tants in high concentrations [15]. For textile wastewaters, Van der
Bruggen et al. [16] studied both the nanoltration of exhausted
dyes bath and the use of UF for the removal of spin nish from
wastewater resulting from rinsing of textile bres. These two
applications are feasible if membrane fouling can be controlled.
These authors concluded that the main fouling mechanism was the
adsorption of the organic compound. The penetration of low molec-
ular compounds into the membrane could enhance this fouling
phenomenon considerably. Concerning landll leachates, reverse
osmosis and nanoltration are considered the best techniques for
treating landll leachates. UF is proposed as pre-treatment [17].
Other examples are the UF of the black liquor from the pulp
and paper industry [18] and the whey protein concentrate in dairy
industries [19].
On the other hand, it has to be commented that notable advances
in the knowledge about the fouling phenomena of the UF mem-
branes caused by proteins have been developed in the last years
with the enormous growth of the membrane bioreactor market
[20,21].
297
Concerning the cleaning of the ultraltration membranes, it has
to be highlighted that the cleaning efciency depends on clean-
ing cycle, type of cleaner, concentration, hydrodynamics, pressure
and temperature [22]. A comparative study of different cleaning
agents for UF membranes fouled by surface waters was carried out
by Zondervan and Roffel [23], classifying the cleaning agents into
six categories (acidic, caustic, sequestering/complexing, enzymatic,
oxidizing, disinfecting and blend). For these authors, the more pos-
itive effects in the cleaning of membranes fouled with proteins are
produced by enzymes and oxidizers like sodium hypochlorite.
This work aims to advance in the purication and reuse of the
unhairing wastewater with UF. For that, the inuence of the unhair-
ing with the UF permeate on the nal leather quality is discussed
and different membrane cleaning procedures at laboratory scale
are compared.
2. Material and methods
2.1. Analytical methods
Unhairing wastewater samples were taken from a tannery
processing cattle hides. In order to characterize the unhairing
wastewater (feed solution) and the membrane permeate, COD, total
solids (TS), concentration of reduction agents (calculated as S2 ),
pH and conductivity were measured.
COD (by the dichromate reux method) and TS were determined
according to the Standard Methods [24]. Chlorides interference was
eliminated by the addition of HgSO4 . Thus, COD was a measurement
comprising both the oxygen demand of the organic matter and the
oxygen demand of the S2 and SH . Due to the high COD values,
samples of the feed solution were diluted in a 1:50 ratio. The value
adopted was the mean value after analyzing three samples.
The concentration of reduction agents (as mg L1 of S2 ) was
determined by titration of the excess of iodine, added after titration
of the sample with HCl, with a solution of Na2 S2 O3 . pH values were
measured using a GLP 22 CRISON pH-meter, while conductivity was
measured using a conductivity-meter model 524 from CRISON.
The particle size distribution of the pre-ltrated unhairing
wastewater was analyzed in Mastersizer 2000 from Malvern Instru-
ments.
2.2. Laboratory plant
The experiments were performed in a laboratory plant (Fig. 1).
The feed solution (unhairing wastewater pretreated with a 50-m
mesh size lter) was maintained at 25 C by the thermostatic bath.
Fig. 1. Scheme of the laboratory plant.
298 J.A. Mendoza-Roca et al. / Separation and Purication Technology 70 (2010) 296301

Table 2
Experimental procedure to evaluate the different types of cleaning.

Stage Operating
time (min)

Test using distilled water 15a

Unhairing wastewater ultraltration: (operating conditions: 180
P = 2.0 bar, v = 0.23 m/s, T = 25 C)
Distilled water rinse (P = 0.0 bar, v = 0.23 m/s, T = 25 C) 15
Washing with cleaning agent (P = 1.0 bar, v = 0.23 m/s, 15
T = 25 C)
Distilled water rinse (P = 0.0 bar, v = 0.23 m/s, T = 25 C) 15
a
The operating time for the rst use of a membrane was 30 min.

Table 3
Unhairing wastewater characterization.

Parameter (units) Value

1
COD (mg L ) 18,00022,000
TS (mg L1 ) 58,00060,000
S2 (mg L1 ) 6,5007,000
Fig. 2. Laboratory drums for the hide samples processing using UF permeate for the, pH 1212.2
unhairing. COND (mS/cm) 4045

It was pumped to the UF module, controlling the pressure by means mined by measuring the volume of collected permeates during a
of the valve at the retentate side. determinate time interval. The notation used was as follows:
The UF module was the MINITAN-S of MILLIPORE for a mem-
brane sheet with an active surface of 30 cm2 . The used membranes Jwi : initial water permeate ux
were IRIS 3065 (Molecular weight cut-off = 40,000 Da) from ORELIS. Jww : permeate ux at the end of the UF step
Jr1 : permeate ux after the rst rinse
2.3. Experimental procedure for the permeate reuse Jc : permeate ux after washing with cleaning agent
Jfr : permeate ux after the nal rinse
Hide samples were unhaired with the UF permeate solution and
further processed in laboratory drums (Fig. 2) of 5 L of maximum
The cleaning agents were:
capacity.
Table 1 shows the physical quality parameters measured for the
Sodium dodecyl sulphate (DDS) (PANREAC).
nal leathers. These parameters were measured with the aim of
Enzymes: DEFAT 50 (CROMOGENIA UNITS, S.A.) and RIBERZIM
nding out if using the UF permeate as unhairing bath affected the
MPX (CROMOGENIA UNITS, S.A.), used in the tannery in the beam-
leather characteristics.
house operations.
Sodium hypochlorite (PANREAC).
2.4. Experimental procedure for the membrane cleaning study

Cleaning procedures were tested after UF experiments. In UF
experiments, the reject stream was driven to the feed tank again
whereas the permeate stream was stored in a separated tank for its
reuse in the laboratory drums. The volume concentration factor at
the end of each test was of 2. The procedure used (except for the
cleaning procedure with air back ushing) is illustrated in Table 2.
UF pressure was chosen from previous experimental works, while
the cross-ow velocity was maintained low in order to enhance the
fouling of the membrane. The values of the operating time, pressure
and cross-ow velocity set up during the different stages of the
cleaning procedure were set up after the literature data revision
[2932].
In the case of the physical cleaning (with compressed air), 10 s
of gas with a pressure of 1.5 bar was supplied. The last stage in this
cleaning procedure was a water rinse [33].
After each cleaning step, the permeate ux at 2 bar pressure
was measured using distilled water as feed. Flow rates were deter-
Experiments with DDS and sodium hypochlorite were carried
out at different concentrations, replicating the tests.
Concerning the cleaning with NaOCl, the maximum con-
centration recommended by the membrane manufacturer was
1500 mg L1 for a weekly use of this chemical cleaning. In the exper-
iments the maximum concentration of sodium hypochlorite was
1000 mg L1 in order to prevent the membrane from any damage.
All experiments were carried out with the same membrane.
3. Results and discussion
3.1. Wastewater and permeate characterization
Tables 3 and 4 show the results of the analysis of wastewa-
ter and permeate samples. Due to the high concentration values,
samples dilution had to be carried out for the most of the analysis
generating an error source. Thus, results are expressed as ranges

Table 1 Table 4
Leather quality parameters and their standard procedures. UF permeate characterization.

Parameter Standard procedure Parameter (units) Value

1
Thickness, mm BS EN ISO 2589 [25] COD (mg L ) 12,00014,000 mg L1
Grain stretch, mm ISO 3379 [26] TS (mg L1 ) 50,00052,000 mg L1
Tear strength, N BS EN ISO 3377-2 [27] S2 (mg L1 ) 5,5006,500 mg L1
Elongation, % ISO 3376 [28] pH 12.012.2
Tensile strength, N/mm2 ISO 3376 COND (mS/cm) 3640 mS/cm
 J.A. Mendoza-Roca et al. / Separation and Purication Technology 70 (2010) 296301 299

Table 5
Physical characteristics of the nished leather after unhairing with fresh liquor and with UF permeate.

Physical test Fibre Minimal value Normal unhairing process Unhairing with
direction required (fresh liquor) UF permeate

Tensile strength (N/mm2 ) A 15 17 16

B 15 15 15

Breaking elongation (%) A 40 40 45

B 60 60 69

Tear strength (N) A 60 86 112

B 60 112 154

Grain stretch (mm) 7.5 8.7 9.1

according to the analysis data expressing minimum and maximum Table 6

Permeate uxes measured after the different stages of the cleaning procedure with
values measured.
DDS (ux values in L m2 h1 ).
For the unhairing wastewater was also measured the particle
size distribution. The particle size measured as volume weighted Test % DDS Jiw Jww Jr1 Jc Jfr
mean was 1.594 m. If the results are converted from particle vol- 1 2.0 375.0 17.0 98.8 190.5 206.9
ume into particle number, the percentile 90 for the particles size 2 2.0 215.7 15.7 65.0 157.2 162.2
was 0.346 m. 3 1.0 310.3 16.3 62.1 145.0 153.8
4 1.0 240.0 16.0 60.3 137.7 148.1
If mean values are considered, membrane COD retention index
5 0.5 227.4 14.1 54.2 92.8 97.2
was only 35%. However, as commented in Section 2, S2 and SH 6 0.5 190.3 15.0 52.3 83.4 89.6
are oxidized by dichromate, contributing signicantly to the COD
(1 S2 mol is oxidized to SO4 2 by 2 mol O2 , thereby it can be
expected a total oxygen demand up to 11,00013,000 mg L1 due to branes. They stated that the surface charge depends only on the
sulphides), what explains the high permeate COD. A protein analy- ability of the membranes to adsorb ions. The main ions adsorbed in
sis by the Bradford method conrmed that the protein rejection by their work were OH , giving rise a negative membrane charge.
the membrane was around 90%. However, the authors reported that the streaming potential
Therefore, since the UF separates mainly the organic matter, per- through the membrane pores decreased considerably with the ionic
meate contains the chemicals required for the unhairing process strength. Thus, at 1 mol L1 KCl, the zeta potential was 0.
(lime and sulphur). In this way, the effect of the electrostatic repulsion will be very
Thus, unhairing with the permeate solution had to be performed limited in the UF of unhairing wastewater, since its ionic strength
in order to check the eventual inuence of the residual proteins in is high due to the sodium chloride that has not been removed in
the hide processing. the previous soaking process. Thus, it can be concluded that severe
fouling can be produced both by adsorption onto the membrane
3.2. Hide processing with UF permeate surface and especially by pore blocking caused by the fraction of
small peptides that goes into the membrane pores.
In Table 5 the physical examination results of the leather sam-
ples can be observed. Those samples were processed after unhairing 3.3.2. Membrane cleaning with surfactant
with the fresh liquor (column 3) and with the UF permeate (column Table 6 shows the permeate uxes measured after the different
4). Besides, results are compared with the minimum acceptable stages of the UF and cleaning procedures according to Section 2.4.
values according to the standardized values required for leather The maximum concentration of DDS was 2%, since higher DDS
for shoes making (column 2). Samples thickness were in the range concentrations drove to scum formation that avoided a correct
of 1.41.6 mm. Results showed in the tables correspond with the operation of the plant. It was tested the same membrane for the
mean values obtained for three leather samples. tests using the same DDS concentrations.
It can be observed that the leather unhaired with UF permeate In Fig. 3, nal ux recovery after each experiment can be
meets the standards required concerning physical properties. The observed.
values correspond with average values after three tests. Compared Extremely low ux recoveries were obtained from the rst
to leather samples unhaired with fresh liquor, samples processed experiment with each DDS concentration, due to the high ux
with UF permeate even showed better tear strength values.
According to the results, 10,500 m3 of water and 6300 kg S2
can be saved in a tannery processing 25 tons of cattle hide per
day. Lime and other chemicals savings should be also considered.
These results have been calculated considering 222 working days,
the necessity of preparing a new unhairing solution every 10 days
and a UF plant recovery of 75%.

3.3. UF membrane fouling and cleaning

3.3.1. Membrane fouling

At the operating pH both the proteins (due to their isoelectric
point) and the membranes are negatively charged [34]. Process-
ing and cleaning can be optimised if the attraction between feed
components and membrane surfaces are kept to a minimum.
The charge of UF membranes was studied by Ponti et al. [35].
These authors studied the streaming potential of some UF mem- Fig. 3. Final ux recovery after the experiments with DDS as cleaning chemical.
300 J.A. Mendoza-Roca et al. / Separation and Purication Technology 70 (2010) 296301

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 D 1 108.0 15.5 29.0 31.6 33.0

2 D 10 98.0 16.2 28.4 32.6 33.8
3 R 1 87.0 13.6 20.2 21.1 24.2
4 R 10 82.5 12.4 19.0 14.8 22.5
5 M 1+1+5 86.7 8.7 12.8 21.7 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.

Fig. 4. Flux recovery after cleaning using air back ushing.

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 tan-
nery 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 scal-
ing 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 composi-
tion 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
Fig. 5. Effect of the application of air back ushing during UF.
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 3.3.5. Membrane cleaning with air back ushing
enough to compare the tests carried out with the same membrane. The results that were obtained in this group of experiments can
It can be observed (Table 7) that the ux recovery was very be observed in Fig. 4. All experiments were carried out with the
low. These values were substantially lower than the ones achieved same membrane.
with other cleaning procedures. The maximum value was 37.4% As it can be observed, the obtained ux recovery was very high,
and it was achieved for the mixture solution. This was due reaching values higher than 90% except from the rst experiment,
to the EDTA-Na4 that improved the ux recovery by eliminat- in that the ux recovery is lower as it was explained above. In com-
ing the scaling caused by calcium deposition. This improvement parison with the other cleaning procedures, particles that block the
was not substantial, since the ux recovery values obtained in pores of the membrane were removed due to the air back ushing.
the other experiments carried out only with enzymatic solu- These results drove us to think about the application of the back
tions ranged between 27.2 and 34.5%. The performance of the ushing with air during the UF process. In this way, the variation
enzyme DEFAT was slightly higher than that achieved with of the ux during the UF of unhairing wastewater can be observed
RIBERZIM. in Fig. 5. The increase of the ux is signicant in comparison with
the test without applying the back ushing with air.
3.3.4. Membrane cleaning with sodium hypochlorite These data cannot be extrapolated into an industrial scale, since
The results of the cleaning experiments with sodium hypochlo- normally the conguration of the plane membrane modules does
rite are detailed in Table 8. not let the air back ushing, that would break the membranes.
The highest ux recoveries were obtained in the experiments However, the higher ux values yielded drive to think about the
3 and 4, reaching values of 92% using a NaOCl concentration of possibility of designing special plane membrane modules that
1000 mg L1 and of 87% with a concentration of 750 mg L1 . The could work with back air ushing. In fact, for membrane bioreactor
cleaning effect was produced by the protein oxidation. applications have been recently developed plane membranes that
Other authors (for example Tasselli et al. for the UF of kiwifruit can be cleaned by means of back ushing.
juice [36]) have equally reported very high permeability recovery
using NaOCl in the membrane cleaning. 4. Conclusions

After the experiments carried out, it can be concluded that UF

Table 8 can be applied to the treatment of unhairing wastewater of a tan-
Results of the cleaning with sodium hypochlorite (ux values in L m2 h1 ).
ning industry to separate the chemicals. These chemicals can be
Test NaOCl conc. (mg L1 ) Jiw Jww Jr1 Jc Jfr reused in the process drum, since the hide processing reusing UF
1 1000 119.0 13.0 54.5 99.2 101.2 permeate yielded leather samples that met the quality standards.
2 750 114.3 13.0 48.2 96.4 99.2 Compared to leather samples unhaired with fresh liquor, samples
3 1000 103.7 12.9 46.2 92.4 95.3 processed with UF permeate even showed better tear strength val-
4 750 95.3 11.7 39.2 81.0 83.7
ues.
 J.A. Mendoza-Roca et al. / Separation and Purication Technology 70 (2010) 296301
However, the fouling of the membranes is very severe. Thus, it
is essential to develop a cleaning procedure in order to achieve the
best ux recovery of the membrane. In this way, the UF process
could be performed in a higher scale.
Among the different types of cleaning that were studied, the
procedures that showed the best results included cleaning with
air pulses from the membrane permeate side or with sodium
hypochlorite solution. Cleaning procedures using surfactant or
enzymes did not yield a sufcient ux recovery. The implemen-
tation of chemical cleaning with sodium hypochlorite is very
simple if the membrane resistance to chlorine is high. How-
ever, further experiments in higher scales have to be carried
out in order to check that frequent chemicals cleanings do not
degrade the membrane and to study the economical feasibility
of the process. The other effective solution, the air back ush-
ing, is only possible if the membrane conguration is appropriate
for it.
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