DESALINATION

ELSEVIER

Desalination 164 (2004) 249-259

Treatment of tannery wastewater by chemical coagulation

Z. Song a*, C.J. Williams b, R.G.J.

Edyvean

~PRC, School of Biomedical and Molecular Sciences, University of Surrey, Guildford, GU2 7XH, UK
Tel. +44 (1483) 686821; Fax +44 (1483) 689555; email: z.song@surrey.ac.uk
bYorkshire Forward, Victoria House, Victoria Place, Leeds LS11 5AE, UK
CDepartment of Chemical and Process Engineering, University of Sheffield, Sheffield $1 3JD, UK
Received 21 May 2003; accepted 3 November 2003

Abstract

The objective of this study was to develop a treatment system that can effectively reduce the concentration of
pollutants in tannery wastewater to environmentally acceptable levels and that can greatly reduce the cost of
discharging the effluents. Aluminium sulphate and ferric chloride were used as a coagulant in the process. The
influence of pH and coagulant dosages on the coagulation process was studied and conditions were optimised
corresponding to the best removal of organic matters, suspended solids as well as chromium. The COD and chromium
were removed mainly through coagulation: 38-46% removal of suspended solids, 30-37% removal of total COD from
settled tannery wastewaters and 74-99% removal of chromium at an initial concentration of 12 mg/1 can be achieved
by using the optimum coagulant dosage (800 mg/1) in the optimum pH range (around 7.5). Ferric chloride produced
better results than aluminium sulphate. The initial chromium concentrations and pH values of the wastewater had a
great effect on chromium removal efficiency. Low chromium concentrations and high pH produced a more effective
result on chromium removal than high chromium concentrations and low pH. Higher dosages did not significantly
increase pollutant removal and were not economical. Coagulation combined with centrifugation improved the removal
efficiency of suspended solids (70%). A high degree of clarification is attained as indicated by an excess of 85-86%
colour removal. The results provide useful information for tannery wastewater treatment.
Keywords: Tannery wastewater; Coagulation; Chromium; Aluminium sulphate; Ferric chloride; Purification

1. I n t r o d u c t i o n

The leather industry is well known as a high

consumer of water. It can create heavy pollution
from effluents containing high levels of salinity,
organic loading, inorganic matter, dissolved and
*Corresponding author.

suspended solids, ammonia, organic nitrogen and

specific pollutants (sulphide, chromium and other
toxic metal salt residues) [I ]. In order to sustain
our global water supply, many environmental
action programmes have been established to
address pollution issues and numerous Environmental Directives, regulations and legislation
have been issued in order to define quality

0011-9164/04/$- See front matter 2004 Elsevier B.V. All rights reserved
PII: S 0 0 1 1 - 9 1 6 4 ( 0 4 ) 0 0 1 9 3 - 6

250

Z. Song et al. / Desalination 164 (2004) 249259

standards for water, set emission standards for

discharges to water and to control emissions of
dangerous pollutants. In the UK, tanners have
generally been able to meet the discharge limits
set by regional water companies. However, the
high chemical oxygen demand (COD) and suspended solids (SS) loading still pose an
economical problem for tanneries since they have
been employed by the water companies as major
parameters for effluent discharge [2]. Furthermore, lowering of the legal limits can be expected
in the future, providing ever more stringent
targets which the tannery industry will be required to meet [3].
Various physico-chemical techniques have
been studied for their applicability to the treatment of tannery wastewater [4,5]. Among these
are coagulation, flocculation, ozonation, reverse
osmosis, ion exchange and activated carbon
adsorption [6]. Coagulation is by far the most
widely used process to remove the substances
producing turbidity in water. These substances
normally consist largely of clay minerals and
proteinous matter in widely varying sizes. The
settling rates of the colloidal and finely divided
(approximately 0.001-1 /zm) suspended matter
are so slow that removing them from wastewater
by plain sedimentation is impossible [7]. These
finer particles will not settle in any reasonable
time and must be flocculated to produce larger
particles. It is usually cost effective to apply
coagulation to remove colloidal and small
particles that settle slowly. Current research is
oriented toward using natural coagulants of
vegetable and mineral origin in water treatment,
but they have not been able to compete effectively because of the fact that they tend to increase
the concentration of organic matter in the treated
water [8,9]. Aluminium and ferric salts are widely
used as coagulants in water and wastewater
treatment and in some other applications [12].
Although some researchers have pointed out
several drawbacks of using aluminium and ferric
salts such as residual metal in treated waters and

synthetic polymers have considerably improved

the coagulation process [ 10-13 ], so far, no readily
available alternative coagulants have been developed to replace aluminium or ferric salts.
The coagulation process, promoted by using
aluminium and ferric salts, is not a novel concept,
and many researchers have investigated the coagulation ofwastewater [4,6,14,15]. However, as
far as is known, no attempt has been made to
fully investigate the optimisation of coagulation
in conjunction with subsequent biological treatability of coagulated tannery wastewater. Each
coagulant operates most effectively in a specific
pH range and displays maximum pollutant
removal at an optimum pH. The extent of the pH
range is affected by the type of coagulant used
and by the characteristics of the wastewater as
well as by the dosage of coagulant.
This paper describes experimental studies that
were conducted on plain settling of tannery
wastewaters in order to evaluate coagulation
efficiencies in terms of COD, SS, chromium and
colour removal at various pH and coagulant doses
with regard to pretreatment standards, and to
optimise the operating conditions for coagulation
of tannery wastewaters.

2. Materials and methods

2. l. Tannery wastewater pretreatment system,
wastewater characteristics and coagulants

Fig. 1 shows the wastewater pretreatment

system that is generally used in the tannery. All
the wastewater from the different processing
phases of leather production are mixed and settled
in the balancing tank (also called the collecting
tank). At the end of each day the wastewater is
agitated with the addition of acids or lime for pH
correction and then allowed to settle. The
supernatant is then directly discharged to the
sewers and the settled solids are pumped to
another tank (sludge settling tanks) for further
settling. The supernatant from the sludge settling

Z. Song et al. /Desalination ] 64 (2004) 249-259

Effluent from
Processing

Supematant to Sewer

Sludg~ I
]

Sludge from
Collecting
Tank

251

Table 1
Composition of pre-settled wastewaters

1I--4
] ]M

Slu~rom
Settling Tank

Solid waste to

Niter Press

Fig. 1. Tannery wastewater pretreatment system.

tanks is discharged to the sewer and the sludge is
pumped to the filter press for further dewatering.
After the filter press, the liquor is discharged to
the sewers while the filter cake is sent to landfill.
The mixed samples were collected from the
main wastewater collection tank and brought into
the laboratory. After 3 h of plain settling [16], the
supernatants were transferred to a clear container
and then they were ready to be used for the
experimental runs. The mean composition and
features of the supernatants are shown in Table 1.
Aluminium sulphate (A12(SO4)318H20 ) and ferric
chloride hexahydrate (FeC136H20) (Fluka Chemicals, UK) were used for the experimental procedure. Both coagulants were prepared as a
solution (50 g/l) using tap water.

2.2. Experimental procedure

2.2.1. Effect of adding coagulants on pH
A known volume of prepared aluminium sulphate or ferric chloride solution was added to a
100-ml jar containing 50 ml of settled wastewater. The coagulant dosages ranged from 0 to
2000 rag/1 as aluminium sulphate (A12(SO4)3
8H20 ) or ferric chloride hexahydrate (FeC13 H20 )
at increments of 100 mg/1. The jars were sealed
and shaken on an orbital shaker for 15 min at
50 rpm, after which the pH value of each sample
was measured.

Parameters

Concentration

pH
COD, mg/1
TS, mg/1
SS, mg/1
Chromium, mg/1

9.2 =~0.2
3,300 + 150
15,000 + 550
260 + 45
16.8 2.3

2.2.2. Optimisation of pH and coagulant dose

in the coagulation process
The chemical coagulation experiments were
performed in triplicate by a series of standard jar
tests [17] at room temperature. A known volume
of prepared aluminium sulphate or ferric chloride
solution was added to a jar containing 1 L of
settled wastewater at different pH values adjuste d
with concentrated H3PO 4 and NaOH. The coagulation experiments proceeded with rapid mixing
of water samples at 100 rpm for 5 rain, followed
by slow mixing at 50 rpm for 15 min, and then
standstill for 60 rain. After 60-min settling, the
settled sludge volume [4,16] was determined and
the supernatant was withdrawn for pH, COD, SS,
Cr and colour analyses. In order to evaluate the
actual improvement determined by wastewater
centrifugation, the other additional sample was
placed in a 50-ml plastic centrifuge tube and
centrifuged (Fisher Scientific, Marathon 3200
bench-top centrifuge) for 10 rain at 3000 rpm.
To optimise the pH of the coagulation process,
jar tests were conducted over the pH range of
4-10 and coagulant dosages of 400-I200 rag/1 at
increments of 200 rag/1. To investigate the optim u m coagulant dose, the pH value of the wastewater was maintained at an optimum pH as
determined above. Coagulant doses ranging from
0 to 2000 mg/1 at 100 rag/1 increments in concentration were added to each jar. In order to
determine the effect of initial chromium concentration on the chromium removal efficiency by
coagulation, prior to the addition of the

252

Z. Song et al. / Desalination 164 (2004) 249-259

coagulants, a calculated amount of prepared

chromium chloride (Aldrich Chemicals, UK)
solution was added to the settled wastewater to
make up the chromium concentration, ranging
from 0 to 150 mg/1 at varying increments.
2.3. Analytical methods
SS and COD were determined according to
standard methods [18]. Settled sludge volume
was measured using an Imhoffcone. One litre of
a well mixed sample was placed in an Imhoff
cone and allowed to settle for 3 h. The volume of
settleble sludge in the cone was recorded as a
percentage (ml/100 ml of mixed sample). The
concentrations of chromium in the liquid phase
were determined using inductively coupled
plasma atomic emission spectrophotometry (ICPAES). All colour analyses were conducted using
a Camspec M330 UV-visible spectrophotometer
in a 1-cm silica cell at 390 nm. Distilled water
was used as a blank sample. Settled and untreated
samples were used as the control. The untreated
samples were diluted using distilled water into
10% to 90% concentration at increments of 10%.
The standard calibration curve was made by using
these diluted samples together with the blank and
the control samples. The removal of colour was
quoted as a percentage relative to the values
measured for the untreated and diluted wastewater. Prior to colour measurements, the water
samples were filtered through filter paper
(Whatman No. 1).

3. Results and discussion

3.1. Effect o f coagulants on p H o f the wastewater

The solution pH is an important factor in
determining the physical and chemical properties
of the sample, and it can be affected by the
coagulants. Fig. 2 shows that an increase in the
coagulant dose is associated with a decrease in
the solution pH. The initial pH of the sample was

8
7

-'6

35

3
2
1
0

- o - Ferric Chloride
- o - Alum

400

,
800

1200 1600 2000

Concentration of Coagulants (mg/I)

Fig. 2. Effectof coagulantdose on pH of the wastewater.

9.21. After the addition of A12(SOg)3and FeC13at

a concentration of 100 mg/1, the pH decreased to
8.9. The maximum rate of pH reduction occurs
where the concentration of coagulant is in the
range of 500-900 rag/l, which gives a final pH
value of 6.57 (A12(804)3)and 5.72 (FeC13.6H20).
As the coagulant level rises, the pH decreases
further although the degree of reduction declines.
This can be explained by the acid character of
Fe 3+or A13+(Lewis acid) [4], which reacting with
OH- ions of wastewaters precipitate in the form
of Fe(OH)3 or AI(OH)3. The pH decrease indicates that coagulation of tannery wastewater
could offer a possibility for treated wastewaters
which may have a neutral or lower pH value.
However, in practice, coagulation is uneconomical as a direct replacement of acid for pH
correction only. It may benefit tanneries where
the pH correction of a highly alkaline stream is
required in order to meet discharge requirements
(pH 6-10). On the other hand, if tanneries do not
have lime dehairing operations, the wastewater
tends to be acidic, and caustic or lime chemical
addition is necessary in order to correct the pH
drop due to coagulation. Some tanneries produce
both highly alkaline and acidic streams; both can
be mutually treated, possibly with further additions of acid and coagulants.

Z. Song et al. /Desalination 164 (2004) 249-259

3.2. Determination of the optimal coagulation pH

3.2.1 Effects of pH on percentage sludge
volume and COD removal
The effects of pH on percentage sludge
volume and COD removal from jar tests for
coagulation of tannery wastewater using aluminium sulphate and ferric chloride are shown in
Figs. 3 and 4. It can be seen that COD removal is
most effective at a pH range between 6.5 and 7.5
for aluminium sulphate and between 6.5 and 8.5
for ferric chloride, but optimally at pH 7.0-7.5.
The rate of COD removal decreased if the pH was
lower than 6.0 or higher than 8.5. All the curves
at each coagulant dosage for both coagulants
have a similar pattern. Ferric chloride has a
broader optimum pH range compared to aluminium sulphate. At a lower pH, ferric chloride

E
03
rr
c3

g 12

-o-- 400mg/I
+
800mg/I
- o - - 1200mg/I

-'- 600mglt
1000rngtl

0J

30
25
20
15

E 10
"~
> 8
03
6
O3
== 4
oz 2

10
5
0

"- 14

35

50
45
40

(Fig. 3B) has little effect whilst aluminium sulphate (Fig. 3A) consistently brought about COD
reductions by 27%. At a high pH ferric chloride
addition resulted in a larger reduction of COD
compared with aluminium sulphate. The percentage of COD removal at a dosage range of
800-1,200 mg/1 was higher than at the extreme
ranges for both aluminium sulphate and ferric
chloride. The maximum COD removal was
36-37% at a dosage of 800 mg/1 corresponding to
the optimum pH (7.0-7.5).
The interrelationship between pH and sludge
volume is shown in Fig. 4. The settled sludge
volume is highly influenced by pH values. With
decreasing pH (from pH 10 to 4), the percentage
sludge volume decreased considerably, giving a
minimum for each coagulant dose at near optimal
pH and then increased gradually at lower pH.
20
_=-.18

5O
45
40
O

253

A
,,,

---,>-400 mg/I
.-.-.zx--800 mg/I
- . o - - 1200 mg/I

"
+

600 mg/I
1000 mg/I

20
18

oE
O

16
14
g 12
03
E 10
"5
8
>
03
6
O3
"O
4
co
2
0
Z

35

E
30
I1)
a: 25
20
0
15
10
5
0

,,

B
234

2 3 4 5 6 7 8 9 1011 12

9 10 11 12

pH Value

pH Value

Fig. 3. COD removal effects at different pH and coagulant dosages. (A) aluminium sulphate; (B) ferric chloride.

Fig. 4. Percentage sludge volume vs. pH value at different

coagulant doses. (A) aluminium sulphate; (B) ferric
chloride.

254

Z. Song et al. /Desalination 164 (2004) 249-259

These results were not expected since more

sludge was expected to be produced with
improved SS and COD reduction. This may be
explained if different qualities of sludge formed
at different solution pH as a result of high density
of floes forming during coagulation. The plot
shows that the dosage near 800 rag/1 produced the
highest settled sludge volume for both aluminium
sulphate and ferric chloride, but aluminium sulphate produced less sludge than ferric chloride.

3.2.2. Effect of pH on chromium removal

Fig. 5 shows that pH is a predominant factor
affecting the removal of chromium. Higher
amounts of chromium are removed when the pH
increased under all coagulant doses: 90-95% of
chromium was removed at pH 10 while 10-21%
at pH 4. This can partly be explained by the
occurrence of competition between protons and
metal ions under acid conditions [9]. Moreover,

an increase in pH from 6 to 8.5 showed a more

visible effect on chromium removal than that
found in the extreme range (i.e., <6 or >8.5).
Therefore, coagulation should be operated at an
alkaline range to achieve maximum chromium
removal [ 1,19].

3.2.3. Effect of p H on SS removal and eolour

change
Fig. 6 shows that SS removal reaches its maximum at pH 6-8 for aluminium sulphate (up to
38%) and at pH 7-8 for ferric chloride (up to
46%). The effects of coagulant dose on the SS
removal are more significant than the effects of
pH. It was observed that from pH 6 to 8, the
supernatant of the samples (after sludge separation) was the clearest (clear yellow) for both
coagulants at different coagulant doses. At the
extremes ofpH, the colour turned to yellow, then
to brown and became dark brown. Samples

100

50

8O

40

'~ 60

"~ 30

E
rY 20

g: 40

O3
CO

20

10

0
100

0
50

80
40
"~ 60

'~ 30

mg/I
g/I
g/I
mg/I
- o - 1200mg/I

g, 4o
20

3 4

5 6 7 8 9 10 11 12
pH Value

Fig. 5. Chromium removal effects at different pH and

coagulant dosages. (A) aluminium sulphate; (B) ferric
chloride.

~, 2o
CO
CO

lO

--c-- 600mg/I
800mg/I
1000mg/I
--o.-- 1200mg/I

2 3 4 5 6 7 8 9 10 11 12
pH Value

Fig. 6. SS removal effects at different pH and coagulant

dosages. (A) aluminium sulphate; (B) ferric chloride.

Z. Song et al. /Desalination 164 (2004) 249-259

treated with aluminium sulphate were also significantly lighter in colour than those treated with
ferric chloride.
Considering this result together with the pH
influence on the removal of COD and chromium,
the pH value in the coagulating process appears
to be extremely important with an optimal pH
range near 7.5. Failure to operate within the
optimum pH may result in lower wastewater
quality. In addition, with such optimum pH
conditions, the soluble residual aluminium and
iron content in the wastewater will be lower than
0.5 mg/1 and 2 mg/1, respectively [4,7,11 ].
3.3. Optimisation of the coagulant dose and the
performance in the coagulation process
3.3. I. Reduction o f suspended solids (SS)
Fig. 7 shows the influence of coagulant dose
on the removal of SS at optimum pH 7.5. After
the addition of aluminium sulphate or ferric
chloride at a concentration of 100 rag/l, the SS
concentration decreased by 3-4%. As the coagulant dose increased, the reduction of SS increased.
Considering an initial SS concentration of
260 rag/l, a maximum removal efficiency of
37.6% (remaining SS of 156 mg/1) and 45.6%
(138 rag/l) was reached at a dosage of 800 mg/1
for aluminium sulphate and ferric chloride,
respectively.
100

Centrifuged (AI)
--o-- settled(AI)
~
Centrifuged (Fe)
Settled(Fe)

90
80

Fig. 7 also shows that centrifugation improve

the efficiency of SS removal. Centrifugation
removed 55.4% of the initial SS without the
addition of coagulants. With the addition of
coagulants, the percentage SS removal reached
64.0% and 70.0% at the optimal dose of 800mg/1
for aluminium sulphate and ferric chloride,
respectively. Therefore, a maximum SS removal
(70%) was achieved by optimal coagulation
(pH 7.5; 800 mg/1 of ferric chloride) followed by
centrifugation.
3.3.2. Reduction o f COD
Fig. 8 shows the effect of coagulant addition
on the percentage removal of COD. After the
addition of the coagulants at a concentration of
!00 rag/l, the COD concentration decreased by
5%. On the basis of an average initial COD
concentration of 3,300 mg/1, the results indicate
that a maximum COD removal of 27.0% after
settling and of 32.0% after centrifuging can be
achieved by using aluminium sulphate (at
800 rag/l). The maximum percentage COD removal that ferric chloride could remove is 30.0%
after settling and 37% after centrifuging. The
residual COD concentration was 2,244 mg/1 and
2,125 mg/1 for aluminium sulphate and ferric
chloride, respectively. Kabdasli et al. [20] reported the results and claimed that chemical
5 I

255

4o I
-~30
>
o

60
50

ED
o
o 10

.~ 40
ao
20
10
o~
0

--~--$etu~ (Fe)

~ Centrifuged (Fe)

0
0
300 600 900 1200 1500
Coagulants dosage (mgll)

Fig. 7. SS removal vs. coagulant dose.

300

600

900

1200 1500

Coagulants dosage(mg/I)
Fig. 8. Effect of coagulant dose on percentage removal of
COD.

256

Z. Song et al. / Desalination 164 (2004) 249-259

coagulation produces wastewater with a COD of

around 2000 mg/1 almost independent of raw
tannery wastewater quality. In this study the
optimum dose was dependent on the type of
tannery wastewater, the amount of SS, the concentrations of pollutants (such as Cr, S=), and it
was better determined by jar testing on site.
Nevertheless, in terms of COD removal, the
optimum coagulant dose is similar for A12(SO4) 3
and FeC% at about 800 mg/1, but ferric chloride is
more effective than aluminium sulphate. Another
benefit of using ferric coagulant is the sulphide
removal, which is an extremely important factor
in the anaerobic treatment of wastewater [21 ].
Unlike the effect on SS removal, centrifugation does not offer a great improvement in
COD removal efficiency (an improvement from
4.0 to 5.6%). This is due to the solubility of the
large part of COD in the tannery wastewater so it
cannot be removed by centrifugation. Nevertheless, 30-35% of COD removal can be
achieved if the process is operated at an optimal
coagulant dosage (800 mg/1) and pH 7.5. A
further increase in the coagulant dose is associated with an increase in the COD so that COD
removal efficiency declined. The calculation of
the costs for chemical treatment resulted in a unit
cost of $0.05-0.10/kg.COD removed. If this is
compared with the discharge costs for $0.330.73/kg'COD (depending on the regions) [22],
this would significantly reduce the discharge fee
for a tannery since COD is the main parameter
used by water companies for calculating effluent
discharge charges.

3.3.3. Removal of colour by coagulation

Fig. 9 shows the effect of coagulation on
colour removal. The percentage of colour removal increased when the coagulant dose was
raised. The maximum percentage of colour
removal was 85% (at 900 rag/1 of ferric chloride)
and 86% (800 mg/1 of aluminium sulphate). As
the coagulant dose increased, the percentage of

100
90
70
60
50

40
30
8 20
10 F
0

al miniurnsilplate
s Ip a
- - aluminium
'

0 300 600 900 1200 1500

Coagulantsconcentration(mg/I)
Fig. 9. Effect of coagulant dose on colour removal.

colour removal dropped significantly. Thus,

900 mg/l of ferric chloride and 800 mg/1 ofaluminium sulphate were the optimal doses in terms of
colour removal. Coagulation using aluminium
sulphate appeared to be a little more effective
than ferric chloride in removing colour. This
might be explained assuming the fact that coagulants containing Fe produce colour problems in
effluents with amounts of sulphide or vegetable
tannins [23].
Substances producing colour consist either of
colloidal metallic hydroxides (e.g., iron hydroxides) or of organic compounds (e.g., dyestuff),
which have a much smaller particle size. These
substances can be removed by coagulation, which
serves to agglomerate the very small particles into
sizes that are settleble or can be removed by
filters or absorption [6,7,24]. A correlation
analysis of the data points from Figs. 8 and 9
shows that the average correlation between the
reduction of COD and colour removal, for both
aluminium sulphate and ferric chloride, was r =
0.964-0.05 when the coagulant dose is less than
900 mg/1. This indicates that part of COD in the
tannery wastewater is related to some organic
compounds present in the wastewater in which
they cause the colour. However, when the coagulant dose is increased, there is very little
correlation between colour removal and COD

257

Z. Song et al. / Desalination 164 (2004) 249-259

removal. This could be the result of chemical

changes of the effluent promoted by high
concentrations of coagulants.
A significant proportion of the soluble matter
in the effluent is not removed by the physicochemical treatment. In order to achieve a higher
quality of treated water, further treatments will be
needed prior to discharge. It is likely that a
biological treatment would need to be incorporated for maximum treatment. Current research
[25] shows that some colourless and soluble
chemicals present in tannery wastewater (i.e.,
naphthalenesulfonates) contribute significantly to
the remaining COD. Their biodegradations by
bacterial isolates are being investigated.

100
v

80

:>
O

E 60

40

20

cO

100
80

60
40
20

3.3.4. Effect of initial chromium concentration

and coagulant dose on chromium removal
Several chromium concentrations were tested
at pH 7.5 by adding coagulants ranging from 0 to
2000 rag/1 at increments of 100 mg/1. Fig. 10
shows that chromium removal is dependent on
coagulant dose and initial chromium concentrations. After the addition of the aluminium
sulphate or ferric chloride at concentrations of
100 mg/1, chromium concentrations were reduced
by up to 70%, especially at the lower initial
chromium concentrations (e.g., 2 mg/1). When the
dose of coagulants increased, more chromium
was removed from solution. The trend remained
until maximum removal efficiency was reached
for each initial chromium concentration.
The effect of varying the initial chromium
concentrations on chromium removal was found
to be significant for both aluminium sulphate and
ferric chloride (Fig. 10). The results indicate that
there is a relationship between the initial
chromium concentration and the residual concentration. At each coagulant dose the percentage of
chromium removal is dependent on the initial
chromium concentration. The maximum chromium removal at each initial chromium concentration was achieved at a different coagulant

0
0

500

1000

1500

2000

Coagulants dose (mg/I)

- 0 - 2 mg/I Cr
6 mg/I C r
--4F- 40mgll Cr

--c-- 4 mg/I Cr
~
12mg/I Cr
--o- 150 rng/I Cr

Fig. 10. Effect of coagulant dose on chromium removal

at various initial chromium concentrations. (A) aluminium sulphate; (B) ferric chloride.
dose. For instance, the maximum percentage of
chromium removal from 2, 4, 6, 12, 40 and
150 rag/1 initial wastewater concentrations was
99.2%, 92.3%, 95.2%, 78.8%, 24.9% and 21.8%,
respectively, at a ferric chloride dose from
600 mg/1 to 900 mg/1 (Fig. 10B). Similarly, the
maximum percentage of chromium removal from
2, 4, 6, 12, 40 and 150 mg/1 initial wastewater
concentrations was 83.0%, 86.6%, 83.2%, 74.4%,
25.6% and 20.6%, respectively, at an aluminium
sulphate dose from 700 mg/1 to 900 mg/1
(Fig. 10A). Therefore, a higher initial chromium
concentration exhibits a lower percentage of
chromium removal. These results are in accordance with findings obtained by Williams and
Edyvean [26]. By comparing Fig. 10A with
Fig. 10B, it can be seen that the optimal coagulant

258

Z. Song et al. / Desalination 164 (2004) 249-259

dose, in terms of chromium removal, is similar

for both aluminium sulphate and ferric chloride,
at near 800 rag/l, but ferric chloride is slightly
more effective than aluminium sulphate.
In practice, since chromium, to some extent,
also acts as a coagulant, some tanneries just add
the waste lime liquors to chrome liquors, which
then provide flocs for clarification with or without additional coagulants. The results on chromium separation and recovery from sludges are
inconclusive in this work. However, chromium
can be separated and recovered by its quantitative
precipitation as hydroxide at pH 8 [27,28] or by
incineration and acid extraction [29]. Different
chromium discharge limits apply for different
tanneries, ranging from 1 mg/1 up to 40 mg/1
(typically 5-10 mg/1 to sewer). Considering the
optimum efficiency for each initial wastewater
concentration, the residual chromium concentration after treatment was less than 4 mg/1, which
meets the current UK discharge limits if the
initial chromium concentration is less than
12 mg/1. When the initial chromium concentration
is higher than 12 mg/1, the residual chromium
concentration is beyond the discharge limits.
However, the problem could be solved by applying plain settling with pH correction and effective
solids separation before coagulation, as described
by Song et al. [16].

4. Conclusions

This investigation has demonstrated that

coagulation with aluminium sulphate and ferric
chloride is an effective method to clarify tannery
wastewater by reducing the COD, SS and
chromium content of the wastewaters and will
lead to reduce waste disposal costs for tannery
companies. Pollutant removal efficiency at
various pH and coagulant doses was evaluated.
Ferric chloride produced better results than
aluminium sulphate in terms of COD and chromium removal. The efficiency of the coagulation of

settled tannery wastewater is highly dependent on

the control of pH (7.5) and coagulant dose
(800 mg/l) within an optimum range. The results
show a significant reduction of waste pollution of
about 40% for COD, 69% for SS and 86% for
colour removal. Applying centrifugation after
coagulation does not offer much of an advantage
over chemical settling in terms of COD removal,
but does improve the SS removal by 15%.
Chromium removal has been shown to be very
effective with both aluminium sulphate and ferric
chloride exhibiting a range from 74% to 99%
removal at optimal conditions. If the initial
chromium concentration is much higher, plain
settling [16] is required before applying coagulation to meet the current discharge standard.
Coagulation, with the advantage of removing the
pollutants of wastewater, also benefits tanneries
for pH correction of highly alkaline streams in
order to meet the discharge requirements.

References

[1] M. Ros and A. Gantar, Possibilities of reduction of

recipient loading of tannery wastewater in Slovenia.
Wat. Sci. Tech., 37(8) (1998) 145-152.
[2] Z. Song, C.J. Williams and R.G.J. Edyvean,
Characteristics of the tannery waste water. IChemE
Research Event 98, Newcastle, UK, 1998.
[3] D.J. Eye and S.P. Graef, Pilot plant studies on the
treatment of beamhouse wastes from a sole leather
tannery. J. Am. Leather Chem. Ass., 63 (1986) 396409.
[4] A. Amokrane, C. Cornel J. and Veron, Landfill
leachates pretreatment by coagulation-flocculation.
Wat. Res., 31(11) (1997) 2775-2782.
[5] D. Orhon, S. Sgzen, E. Ubay Cokg~r and E. Ates,
The effect of chemical settling on the kinetics and
design of activated sludge for tannery wastewater.
IAWQ 19thBiennialInternationalConference,1998,
pp. 256-363.
[6] I. Arvanitoyammis,I. Eleftheriadisand E. Tsatsaroni,
Influence of pH on adsorption of @e-containing
effluents with different bentonites. Chemosphere,
18(9/10) (1989) 1707-1711.

Z. Song et al. / Desalination 164 (2004) 249-259

[7] R.A. Corbitt, in: H.B. Crawford and D. Gleason,
eds., Stand Handbook of Environment Engineering,
McGraw Hill, New York, 1989, pp. 671-698.
[8] S.A.A. Jahn and D. Hammed, Studies of natural
water coagulants in Sudan, with special reference to
Moringa oleifera seeds. Wat. SA, 5 (1979) 90-97.
[9] J.P. Sutherland, G.K. Folkard and W.D. Grand,
Seeds of Moringa species as naturally occurring
flocculants for water treatment. Sci., Technol. Dev,,
7 (1989) 191-197.
[10] A. Ndabigengesere and K.S. Narasiah, Quality of
water treated by coagulation using Moringa oleifera
seeds. Wat. Res., 32(3) (1998) 2775-2782.
[11] R.D. Letterman and C.T. Driscoll, Survey ofresidual
aluminium in filtered water. J. AWWA, 80 (1988)
154-158.
[ 12] J. Duan and J. Gregory, Coagulation by hydrolysing
metal salts, Adv. Colloid Interface Sci., 100-102
(2003) 475-502.
[13] J. Mallevialle, A. Bruchet and F. Fiessinger, How
safe are organic polymers in water treatment. J.
AWWA, 76 (1984) 87-93.
[14] B. Vanukuru, J,R.V. Flora, M.F. Petrou and C.M.
Aelion, Control of pH during denitrication using an
encapsulated phosphate buffer. Wat. Res., 32(9)
(1998) 2735-2745.
[15] J. Duan, J. Wang, N. Graham and F. Wilson,
Coagulation ofhumic acid by aluminium sulphate in
saline water conditions, Desalination, 150 (2002)
1-14.
[16] Z. Song, C.J. Williams and R.G.J. Edyvean,
Sedimentation of tannery wastewater. Wat. Res.,
34(7) (2000) 2171-2176.
[17] M.J. Hammer, Water and Wastewater Technology,
2nd ed., Prentice Hall Career & Technology,
Englewood Cliffs, NJ, 1986.
[18] APHA, Standard Methods for the Examination of
Water and Wastewater, 18th ed., American Public
Health Association, Washington DC, 1992.
[19] D.G. Bailey, M.H. Tunick and M.A. Huzma, Effect
of sulfide, chromium, and phosphate ions on methane

259

production by an anaerobic siudge acclimated to

tannery beamhouse effluent. 14th Mid-Atlantic Ind.
Waste Conference Proceedings, Maryland University, Maryland, 1982, pp. 202-211.
[20] I. Kabdasli, O. Ttinay and D. Orhon, The treatability
of chromium tannery wastes. Wat. Sci. Tech., 28(2)
(1993) 97-105.
[21 ] Z. Song, R.G. Edyvean and C. Willams, Coagulation
and anaerobic digestion of tannery wastewater.
Process Safety and Environmental Protection: Trans
IChemE B, 79(1) (2001) 23-28.
[22] D.R. Coming, Trade effluent and water charges
England and Wales. BLC J., 33(7) (1990) 83-85.
[23] A. Bousher, X. Shen and R.G.J. Edyvean, Removal
of coloured organic matter by adsorption onto lowcost waste materials. Wat. Res., 31(8) (1997) 20842092.
[24] H. Springer, Treatment of industrial waste of the
leather industry - - Is it still a major problem? J. Am.
Leather Chem. Ass., 89 (1994)153-187.
[25] Z. Song, S. Edwards, K. Howland and R.G. Bums,
Analysis of a retan agent used in the tanning process
and its determination in tannery wastewater. Anal.
Chem., 75 (2003) 1285-1293.
[26] C.J. Williams and R.G.J. Edyvean, Optimization of
metal adsorption by seaweeds and seaweed derivatives. Trans IChemE, 75(B) (1997) 19-26.
[27] A. Macchi, M. Pagano, M. Pettine, M. Santori and
G. Tiravanti, Bench study on chromium recovery
from tannery sludge. Wat. Res., 25(11) (1991) 10191025.
[28] T. Aoki and M. Munimori, Recovery of chromium
from wastewater with iron(III) hydroxide - - I.
Wat. Res., 16 (1982) 793-796.
[29] M. Beccari, L. Campanellla, E. Cardarelli, M.
Maione and E. Rolle, Chromium recovery from
tannery sludge by incineration and acid extraction,
in: J.W. Patterson and R. Passino, eds., 2nd Internat.
Symp. of Metal Speciation, Separation and
Recovery, Lewis, Chelsea, MI, 1990, pp. 587-602.