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DOI: 10.2298/APT0839121V BIBLID: 1450-7188 (2008) 39, 121-129
Original scientific paper

GRAVITATIONAL SEDIMENTATION – AN EFFICIENT CHROMIUM

REMOVAL METHOD FROM THE TANNING INDUSTRY WASTEWATERS

Ljiljana M. Vukić, Petar M. Gvero and Milorad D. Maksimović

Wastewaters generated in different phases of the technological process of leather

treatment have a significant organic load as well as containing toxic substances like salts
of chromium and sulfides. In order to preserve the environment and natural resources, it
is necessary to purify the effluents by using adequate treatment technologies.
In the scope of preliminary treatment, the influences of gravitational sedimentation
on the changes of the relevant characteristics of cumulative wastewaters were investi-
gated. The best effects were achieved during the removal of chromium and suspended
matter. The level of chromium removal was exceptionally high, 88%-96%. A special
column for gravitational sedimentation was constructed in order to achieve the high qua-
lity experimental result. This enabled monitoring of the setting process in time, with the
possibility of mathematical interpretation of the process changes by polynomial and
exponential functions.

KEYWORDS: Tanning industry, wastewater, chromium, sedimentation

INTRODUCTION

Raw leather loses about 30% of organic matter (proteins and lipids) during proces-
sing. Also, as a consequence of the nature of the process and insufficient binding on
leather, a significant amount of inorganic salts is released into the wastewater, which
makes them toxic and highly loaded.
Wastewaters form in all wet operations and the amount of these waste flows are dis-
tinctly different in quantity and content. The most loaded flows originate from the opera-
tions of leaching and tanning of the leather.
Before the purification process it is necessary to perform a detailed analysis of the se-
parate waste flows as well as the cumulative wastewaters (1-3). The basic characteristics
of wastewater from the leather industry are: content of chromium (III) salts, sulfides,

Dr. Ljiljana M. Vukić, Assist. Prof., vukicmadv@blic.net, Dr. Milorad D. Maksimović, Assoc. Prof., University
of Banjaluka, Faculty of Technology, V. S.Stepanovića 73, 78000 Banjaluka, Bosnia and Herzegovina; Dr.
Petar M. Gvero, Assist. Prof., University of Banjaluka, Faculty of Mechanical Engineering, V. S. Stepanovića
75, Banjaluka, Bosnia and Herzegovina.

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grease and oil, COD (Chemical Oxygen Demand) and BOD (Biochemical Oxygen De-
mand). Entry and type of raw material as well as the individual process operations deter-
mines the number and type of wastewater treatment methods needed, since total removal
of waste flows is not possible using only one treatment process. Hence, it is necessary to
apply a multistage scheme of the wastewater treatment.
The wastewaters can be treated either as a cumulative effluent or as separate waste
flows from each individual process unit.
The usual way of treating cumulative wastewaters from the leather industry, which
has already been largely accepted in the World, is a biological treatment process, for
which it is necessary to make preliminary preparations. Pretreatment of wastewaters
contains several physico-chemical techniques (4-7):
- equalizations with homogenization of wastewaters;
- gravitational sedimentation;
- chemical sedimentation (coagulation and flocculation).
Elimination of sulfides is mainly carried out by catalytic oxidation, foregoing to the
procedure of coagulation and flocculation or it is carried as a separate waste flow from
the leaching process (3,8,9).
During the process of gravitational sedimentation, as an important phase of the waste
water pretreatment, useful information about pollutant distribution was provided, as to
the definition of yielding components in the wastewater (10). There is a noticeable re-
duction of chromium content as well as COD and BOD values (11). As for chromium eli-
mination, more alternative methods exist, which are characterized with high efficiency, as
ion exchange, absorption of natural absorbents or industrial waste biomass or membrane
processes (12-20). However, all mentioned techniques, because of their complexity or
price, are in use in the treatment of waste flows from tanning processes, or for chromium
residual removal in the tertiary treatment.
The results presented in this paper are part of an integral investigation of the physico-
chemical treatment of cumulative wastewaters in the leather industry, with the aim of
being suitable for biological purification. For that purpose chromium elimination achie-
ved by gravitational sedimentation, was entirely satisfactory.

EXPERIMENTAL

Investigations were carried out on the cumulative wastewater samples of leather fac-
tory "Proleks" Kotor Varoš. After equalization, samples of cumulative wastewaters were
treated by the method of gravitational sedimentation. Experiments were carried out in
laboratory conditions on the column specially constructed for this investigation, accor-
ding to the principle of the ideal precipitator (2,22). Scheme of the experimental setup is
presented in Figure 2.
Samples were taken from each sampling point after 15, 30, 60, 120 and 180 minutes.
The effects of gravitational sedimentation were investigated via following parameters:
chromium(III) content, total solid matter, suspended matter, BOD and COD values. The
effects were observed as a function of the sampling time and of the column height. Sam-
ples of supernatants (the clarified part of wastewater) were prepared by mixing the frac-

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tions from the sampling points at 70, 100 and 130 cm, after 15, 30, 60, 120 and 180 mi-
nutes and analyzed too.
Chromium was determined using the AAS method by flame techniques (N2O/C2H2,
λ=357,9 nm); BOD by the method of dilution; COD dichromate method along to pho-
tometer detection; total solid matter and suspended matter by gravitational method (21).

RESULTS AND DISSCUSION

Gravitational sedimentation in the tested samples of water is carried out by the prin-
ciple of zonal sedimentation. During the sedimentation process, solid particles were for-
med in the zone with a distinct boundary surface (intermediate phase) between the sedi-
ment and clarified part of the wastewater. The height of this boundary is defined by mo-
ving the boundary surface of the phases through the graded sedimentation column as a
function of time. After a certain period of sediment motion, a concentration of sediments
occurred towards the bottom of the column. The final compression of the sediments was
increased at the end of the third hour of sedimentation, when the sludge volume was re-
duced.
On the basis of the series of experiments which performed, it was determined that a
period of 3 hours is completely sufficient to provide the process of gravitational sedimen-
tation and that any prolongation of sedimentation process (10 to 12 hours) does not lead
to notably better effects. Neither have the influence on the volume reduction of the sludge
as it has already settled. This behavior is in agreement with the literature data (22).
Treated sample of wastewater has characteristics typical for wastewaters from leather
processing and the course of sedimentation process in the period of 3 hours corresponds
to the behavior of this type of suspension (22). Results of wastewater purification by gra-
vitational sedimentation method are presented in Table 1.

Table 1. Influence of gravitational sedimenation process on cumulative wastewater

physico-chemical parameters

Cumulative Effects of
Parameter Supernatant
wastewater purification
pH 9,71 9,70 -
Chromium mg/L 192,7 7,8 95,95
Total solid matter mg/L 15.22 13.38 12,09
Suspend. matter mg/L 2.470 230 90,69
BOD mgO2/L 1.571 1.161 26,10
COD mfO2/L 3.744 2.920 22,0
BOD/COD 0,42 0,40 -

It can be seen that the influence of gravitational sedimentation on certain parameters

is different and of different efficiency. Taking into consideration that gravitational sedi-
mentation is a physical process, satisfactory effects were achieved only during the remo-
val of suspended component of pollution - suspended matter and chromium as Cr(III)-
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hydroxide. Optimal pH for Cr(III)-hydroxide sedimentation is 8,0 to 9,5 (23) so that,

almost complete sedimentation of Cr(III) and its removal in the form of precipitate were
achieved.
Considering the changes of particular parameters of the wastewater sample during the
sedimentation process it comes out that the best effects have been obtained in the removal
of chromium and suspended matter. From Figure 1e it is evident that chromium concen-
trations decrease rapidly from the top of the sedimentation column, at the same time
chromium concentrations increase at the bottom of the column, even after first 15 minu-
tes of sedimentation. After that the chromium concentration gradually decreases toward
the top, respectively gradually increases of the bottom of the column. The rate of chro-
minom sedimentaiton depends primarily on the pH of the wastewater and of the quantity
of suspended matter which will ‘pull’ the chromium(III)–hydroxide formed towards the
bottom of the sedimentation column (1,3,23).)
The other parameters were reduced according to the similar sedimentation regime,
with the difference that the degree of removal depended on the pollution form (Figure 1a,
1b, 1c, 1d).

130cm
35
100cm
Total. solid matter (mg/L)

30
70cm
25 40cm
20 10cm

15
Place of
10 sampling(cm)
10cm
5
70cm
0
15 130cm
30
60
120
180
Time of sampling (min)

Figure 1a. Total solid matter concentration change as a function of the site and time of
sampling

130cm
25
100cm
Suspended matter (mg/L)

20 70cm
40cm
15 10cm

10 Place of
sampling (cm)
5
40cm
0
15 30 130cm
60 120180
Time of sampling (min)

Figure 1b. Suspended matter concentration change as a function of the site and time of
sampling
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Original scientific paper

130cm
6000
100cm
5000 70cm
40cm

BOD (mgO/L)
4000
10cm
3000

2000 Place of
sampling (cm)
1000
40cm
0
15 30 130cm
60 120 180
Time of sampling (min)

Figure 1c. BOD change as a function of the site and time of sampling

130cm
16000
100cm
14000
70cm
12000 40cm
COD (mg/L)

10000 10cm
8000
6000 Place of
4000 sampling (cm)

2000 40cm
0
15 30 130cm
60 120 180
Time of sampling (min)

Figure 1d. COD change as a function of the site and time of sampling

130cm
1800
100cm
1600
1400 70cm
1200
Cr (mg/L)

40cm
1000
10cm
800
Place of
600
sampling (cm)
400
200 40cm
0
15

130cm
60

180

Time of sampling (min)

Figure 1e. Chromium concentration change as a function of the site and time of sampling
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Original scientific paper

Approximation of the curves which represent the changes in the chromium concen-
tration (y) versus time (x) for all sampling sites in the frame of defined conditions of the
experiment, mathematical expressions were obtained in the form of the polynomials of
the 3rd and 4th order (sampling height 10 cm and 130 cm, respectively) and exponential
functions (sampling height: 40 cm, 70 cm and 100 cm), which correlate very well with
the trend of chromium content change along the all sampling heights of the sedimentation
column (Figure 2).

Figure 2. Chromium concentration change in the sendimentation column as a function of

sampling site
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Besides, the conditions in the clarification zone of the column, where chromium con-
centration falls (sampling height: 40, 70, 100 and 130 cm), give the possibility of con-
structing a resultant curve based on the curves of chromium concentration change at the
different sampling heights (Figure 3a). This resultant curve and its approximation (Figure
3b) give chromium concentration (y) as a function of time (x) for total clarification zone
in the form of the following exponential equation:

y = 0.4111 + 43.42418e (− ( x −15 ) / 3.36951) + 15.62811e (− ( x −15 ) / 90.21418) + 7.00438e (− ( x −15 ) / 5.69574 ) [1]

It is necessary to mention that all presented equations hold for the sedimentation
period in the range from 15 to 180 minutes.

180
130 cm
160 100 cm
140 70 cm
40 cm
120
Cr (mg/L)

100
resultant curve
80

60

40

20

0 20 40 60 80 100 120 140 160 180 200

Time of sampling (min)

Figure 3a. Chromium concentrations change as a function of the sampling time in the
clarification zone of the gravitational column

80

Experimental
Mathematical
60
Cr (mg/L)

40

20

0 20 40 60 80 100 120 140 160 180 200

Time of sampling (min)

Figure 3b. Mathematical aproximation of the resultant curve for chromium concentration
change in the clarification zone of the gravitational column

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CONCLUSION
On the basis of the obtained results it is possible to conclude the following:
- the gravitational sedimentation process is an important phase of the cumulative
wastewaters preparation for further biological treatment;
- thanks to the high pH of wastewater (pH = 9.71) almost complete chromium(III)
was precipitated as Cr(OH)3;
- sedimentation period of three hours was contributed to additional sludge compres-
sion and more efficient reduction of the other physico-chemical parameters;
- the experiment in the sedimentation column enabled monitoring of the sedimenta-
tion process with possibility of mathematical interpretation of chromium concen-
tration change along the column height.

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ГРАВИТАЦИОНО ТАЛОЖЕЊЕ – ЕФИКАСАН ПОСТУПАК ЗА

УКЛАЊАЊЕ ХРОМА ИЗ ОТПАДНИХ ВОДА КОЖАРСКЕ ИНДУСТРИЈЕ

Љиљана М. Вукић, Петар М. Гверо и Милорад Д. Максимовић

Отпадне воде које настају у различитим фазама технолошког процеса прераде

коже, осим знатног органског оптерећења, садрже и токсичне супстанце, попут со-
ли хрома и сулфидe. У циљу очувања животне средине и природних ресурса eфлу-
ент је неопходно пречистити одговарајућим поступцима обраде.
У оквиру примарне обраде, испитан је утицај гравитационог таложења на пром-
јене релевантних карактеристика збирне отпадне воде. Најбољи ефекти су постиг-
нути код уклањања хрома и суспендованих материја. Степен елиминације хрома
изузетно је висок и износио је 88%-96%. За извођење експеримента конструисана је
специјална колона за гравитационо таложење, која је омогућила праћење таложног
процеса, уз могућност мaтематичке интерпретације промјене концентрације хрома
по висини колоне. Урађена је математичка апроксимација промјена помоћу поли-
нома и експоненцијалних функција.

Received 17 July 2008

Accepted 29 September 2008

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