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PRETREATMENT AND CLARIFICATION OF TANNERY

WASTEWATER

Z Song
BSc., MSc., Mres.
C.J. Williams
BSc., PhD, MRAWQ, CBIOL.
R.G.J. Edyvean
BSc., MSc., PhD, CBIOL.

Address: Department of Chemical and Processing Engineering, The

University of Sheffield, Sheffield - S1 3JD UK - Tel: (0044-114-
2227558) - Fax: (0044-114-2227501) - e-mail: mep96zs@sheffield

ABSTRACT

Tannery wastewater is a powerful pollutant. It presents severe environmental problems

related to its high COD (Chemical Oxygen Demand) together with an elevated chrome
and deep colour content. Restrictions on the discharge of tannery effluents have been set
in many countries in an effort to protect aquatic environments. The strength parameters
employed are COD and SS (Suspended Solids). The objective of this study is to
investigate pretreatment of a tannery wastewater, typified by the mixed effluent from
tannery operations. The behaviour of plain settling is described. The results demonstrate
33-41% removal of total COD, 53-80% removal of Chromium, 70 - 80% removal of
suspended solid and 5-15% removal of total solids.

KEYWORDS: Tannery Wastewater, Pre-treatment, Plain Settling, COD.

INTRODUCTION

Waste treatment is concerned with environmental protection and with the reduction of
production costs by reducing waste. In the light of growing concern about the environmental
impact of industrial discharges it is likely that ever tightening regulatory requirements will
inevitably lead to increasing waste disposal costs (Eye, 1986). Therefore waste treatment is
important for long term company profitability. The treatment of tannery wastewater has been
very important issue for pollution control in leather producing countries due to its heavy
pollutants. Different sets of leather manufacturing operations and processes will result in
different liquid effluents. A variation in liquid residue volume will have relevant effects on
pollutant concentrations (Springer, 1994). In the most general case where tannery waste
water is a directly discharged to sewer, there is no well established model which provides a
solution for wastewater treatment in all tanneries. Thus, it is necessary to investigate each
specific situation. The treatment systems employed in a tannery have to be multi-staged so as
to meet pretreatment requirements and due to the small to medium scale of the industry
investment in effluent treatment is limited (Tunay, 1994).

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Tannery effluents are generally treated biologically for the removal of biodegradable
organics before discharge to receiving waters. However before carrying out studies to
investigate the options for the cost-effective treatment of tannery wastewater, it is
necessary to first examine the behaviour of the pre-treatment. This paper is concerned
with plain settling carried out on effluent sampled from a medium sized tannery.

MATERIALS & METHODS

Typical Tannery Effluent Pretreatment System

The diagram below shows typical tannery effluent pretreatment employed by tannery.

Effluent from
Processing Supernatant to Sewer

Liqueur to Sewer
Sludge Solid waste to
Collecting
Sludge Skip
T k

Sludge from Sludge from Filter Press

Collecting Tank Settling Tank

Figure ¡Error!Argumento de modificador desconocido. A - Typical Tannery Effluent

Pretreatment System.

All of the effluent from the different processing phase of the leather production is mixed
and settled in the collecting tank (also called balancing tank). At the end of each day the
effluent is agitated and then allowed to settle. The supernatant is then discharged to the
sewers directly and the settled solids are pumped to another tank (sludge settling tanks)
for further settling. The supernatant from the sludge settling tanks is discharged to 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 or may be
used as fertilisers.

Characteristics of the Mixed Tannery Wastewater

For the purpose of the assessment, a tannery with a full production profile has been
considered, that is, one producing full chrome upper leather from an input of
predominantly dry salted bovine hides. The characterization was made by collecting
samples weekly from the balancing tank in which all of the effluent from the different
processing phase of the leather production is mixed and settled. Table 1 (Song et
al.,1998) shows the characteristics of the tannery wastewater.

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In this experiment, two different typical samples X and Y were used. Both of them were
collected from the collecting tank at different time and brought into the laboratory. The
characteristics of the raw effluent are show in Table 2 in terms of the average values of
the different parameters. The concentration of chromium was made artificially by adding
chromium chloride (CrCl3) (Aldrich Chemicals Ltd, UK) to the collected effluent.

Table ¡Error!Argumento de modificador desconocido.: Typical Characteristics of the

Effluent from a Balancing Tank.
Parameter Unit Average
pH - 10.50
COD mg / l 5,000
TS mg / l 25,000
FTS mg / l 20,500
SS mg / l 700
FSS mg / l 400
DS mg / l 25,000
Grease mg / l 200
Chloride mg / l 7,000
Chromium mg / l 60

Table ¡Error!Argumento de modificador desconocido. Wastewater Sample

Characterisation.
Parameter Sample X Sample Y Parameter Sample X Sample Y
pH 9.0 7.5 Chromium 100,00mg/l ---
SS 1,500mg/l 4,000 mg/l COD 5,000 mg/l >10,000 mg/l
TS 29,000 mg/l 45,000 mg/l BOD5 1,500 mg/l 2,000 mg/l

Waste Water Analysis

Total, fixed solids (TS, FTS), Suspended and fixed solids (SS, FSS), dissolved solids
(DS) chemical oxygen demand (COD) and pH value were measured with standard
methods (APHA, 1992). Chromium concentration was determined by Inductively
Coupled Plasma Atomic Emission Spectrophotometry (ICP-AES).

Plain Settling
The settling column is made of a cylinder of perpex tubing. Sampling ports are uniformly
spaced along the length of the column at 30 cm intervals and at a height of 10 cm, 40 cm,
70 cm, 100 cm and 130 cm from the bottom of the column. The effective settling depth is
the depth above of the lowest point. The column is 16cm in internal diameter and 1.6m
high which is the same heights as used in the settling tank height at the tannery. Because
the flocculent is time-depth dependent, more representative settling curves are obtained
when the column depth is near the tank depth. Samples were collected from each
sampling point at time increments of 10 mins, 20 mins, 30 mins, 40 mins, 60 mins, 2
hours, 3 hours and 20 hours. The column was filled initially with a well mixed sample of
effluent in which the parameters of TS, TSS, COD, BOD and chromium concentration
had already been determined (Table 2). At the start of experiment the same concentration
exists throughout the depth of the column. Analysis of the samples collected throughout

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the experiment allowed the change in concentration against time and height (cm) to be
determined.
RESULTS

Sedimentation Curve

The behaviour of two types of samples over time in the column settling test is plotted in
Figure 2. The variation in the settling performance of sample X and Sample Y has been
attributed to their different characteristics (Table 2).

Top 180
160 Reflocculate Sample X
Height of Interface (cm)

Sample Y
140
120
Initial Settling
100
Transition
80
Compression
60
40
20
Bottom 0
0 20 40 60 80 100 120 140 160 180

Settling Time (minutes)

Figure ¡Error!Argumento de modificador desconocido. - Batch Settling Curve for 2

Different Samples of Tannery Wastewater.

Sample X has relatively high concentration of suspended solids, 1,500 mg/l of SS and
29,000 mg/l of total solids, the suspensions settle in the zone-settling regime which
represents the typical characteristics of tannery wastewater. In the settling process, the
solids settle as a mass, producing a distinct interface between the sludge and clarified
water zone (Bye and Dold, 1998). The height of this distinct sludge interface is
determined as the movement of the interface through the graduated settling column over
time.

At the start of the experiment there is a very short period during which little settling takes
place. During this phase, the mixed solids reflocculate and a solids-water interface forms.
A clarified zone exists in the upper portion of the column, followed by a linear (or
hindered) settling portion in which the solids-water interface settles at a constant velocity.
It takes about 20 minutes. This zone-settling phase is followed by a half-hour curvilinear -
transition stage in which the suspension is moving down and concentrating towards the
bottom of the column where a slowly compacting sludge forms.

The volume of sludge produced constitutes about 37% of the total waste water sample 1
hour after commencing of the settling process. After the completion of zone settling, the

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final compression settling period is reached within one hour. As the settling continues,
minimal further settling takes place because the solids have been compacted to the
highest degree possible under gravity settling conditions. The sludge volume was 30 %
and 28% of the original sample volume after 2 and 3 hours settling respectively. The
residue was still 15% of the original volume even after settling overnight. No significant
difference was observed when comparing with the sludge volume measured after 3 hours
with that at the beginning of the settling process. This indicated that most solids had
settled within three hours and further prolonged settling does not reduce the settling
sludge volume to any economic extent.

Sample Y contained much higher solid contents, 4,000 mg/l of SS and 45,000 mg/l of
total solids, compared with sample X which had 1,500 mg/l of SS and 29,000 mg / l of
total solids. This results in a different settling process which is called thickening
dewatering or compression of the sludges. In this process, particles are in physical contact
with each other, thus reducing the rate of subsidence. After 1 hour of settling, the sludge
at the bottom of settling column constitutes 81% of the original sample volume. Even
after 2 hours and 3 hours of settling, 70% and 67% of the original sample volume was
calculated to be as sludge respectively. The conclusion can be made that plain settling is
not an effective treatment for an effluent such as sample Y due to its higher solids
content. It would be better to treat this as a sludge rather than as an effluent. The
remainder of this paper will deal with the tannery effluent characterised as sample X and
not cover the sludge treatment process.

Removal of Suspended Solids (SS) and Total Solids (TS)

The initial concentration of SS and TS of the tannery wastewater sample X were

examined. They are 1,500 mg/l and 29,000 mg/l respectively. The concentration of SS
and TS in each of the five sampling points at the time 20 mins, 30 mins, 40 mins, 60
mins, 2 hours, 3 hours and 20 hours that were determined are illustrated in Fig. 3 and Fig.
4.

The overall percentage removal of SS was from 75% (bottom: 40cm) to 78% (top: 130
cm ) with an average of 76.1 % after a one hour period of settling while the removal
efficiency of SS was only 78.4 % even after 20 hours settling. The removal efficiency of
SS after 3 hours of plain settling was about 77.2 % . This indicated that further settling
process does not improve the efficiency of the MLSS removal very much.

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30000

25000

20000

SS (mg/l)
15000

10000
10
5000 40
70
0 100
S a m pling

0
130

10mins

20mins

30mins
He ight (cm )

40mins

1 hr

2 hrs

3 hrs

20 hrs
S e ttling Tim e (M ins or Hrs)

Figure ¡Error!Argumento de modificador desconocido. - Suspended Solids Change

During Settling Presses.

45000
40000
35000
30000
TS (mg/l)

25000
20000
15000
10000 10c m
40c m
5000 70c m
0 100c m
Sampling
0
10mins

20mins

130c m
30mins

40mins

1 hr

H e ight
2 hr

3 hrs

20hrs

Se ttling T ime (M ins or H rs)

Figure ¡Error!Argumento de modificador desconocido. - Total Solid Change During

Settling Process.

As can also be seen from Fig. 4 and table 3, the total solids concentration of the
supernatant does not change much along the height of the column and over time. This
indicates that only a small part of the total solids can be removed during plain settling
process. The maximum removal of total solids is only about 12% of the initial wastewater
content and even this is reached after 20 hours of plain settling. This means that a large
part of the solids in waste water are dissolved, unsettlable colloidal and finely divided
suspended matter. This matter presents a major difficulty in the treatment and handling of
the effluent. The sludge produced at the bottom of the settling column contains about
7,500 mg/l of SS, 36,000 mg/l of TS after one hour of settling, 12,000 mg/l of SS, 38,000
mg/l of TS after 3 hours of settling and 28,000 mg/l of SS, 41,000 of TS after 20 hours of
settling.

The concentration of SS and TS decreased from 1,500 mg/l and 29,000 mg/l of initial
content to 375 mg/l or less and 27,651 mg/l after 1 hour settling process, 358 mg/l and

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26,589 mg/l after 3 hours settling process and 339 mg/l and 25,222 mg/l after 20 hours of
settling process respectively.

Reduction of COD and BOD

During the plain settling process, additional benefits occur, such as reducing the
concentration of COD, BOD5 . The results are presented in Figure 5 and Figure 6. They
show that most of the COD and BOD5 reduction occurred in the first hour. Within one
hour of commencing the settling process, the average COD and BOD5 of the mixed
effluent had levelled out at about 3,116 mg/l and 1,112 mg/l respectively (Table 3). On the
basis of an average COD concentration of 5,000 mg/l and BOD5 concentration of 1,500
mg /l, the results indicate a removal efficiency of 34.9 % for COD and of 18.0 % for
BOD5. After 3 hours of settling, the average percentage of COD and BOD5 removal were
38.9% and 22.9% respectively. After 20 hours of plain settling the average of COD and
BOD5 of the mixed effluent still remained at 2,864 mg/l and 1,010 mg/l respectively. The
results show that only 40.2 % of COD and 25.5 % of BOD5 were removed even after 20
hours of settling. This indicates that a duration of between 1 and 3 hours of plain settling
provides optimal settling time. Longer periods of settling reduce process economy and
result in only a slight increase in the COD and BOD5 removal. It appears therefore that a
significant proportion of the poorly degradable matter in tannery wastewater is not
removed by sedimentation.

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Although the COD

content of the effluent
200 00 after plain settling
180 00
160 00
meets the discharge
140 00 consent to sewer, it is
120 00 much higher than
COD (mg/l)
100 00
800 0 many limits on the
600 0
10 direct discharge of
400 0
200 0
40 effluent to a river or
70
0 100 other water body.
0

COD standards are

10mins
130
20mins Sampling
30mins

40mins

1 hr

2 hrs

3 hrs
He ight (cm) 1,000 mg/l in the UK

20 hrs
and 500 mg/l in Italy
Se ttling T ime (M ins or Hrs) (Tunay, 1994). In
addition, COD is the
Figure ¡Error!Argumento de modificador desconocido. - COD main parameter
Change During Settling Process. employed by UK
water companies for
calculating the
charges for effluent
3000 discharge. This means
that if the company
2500
discharges an effluent
BOD Concentration

2000 which contains 2,926

mg/l (3 hours settling)
(mg/l)

1500
or 2,864 (20 hours
1000
10 settling) of COD
40
500
70
directly to the sewer,
0 100 they need to pay
Sampling
0

considerable charges
10mins

130
20mins

30mins

40mins

1 hr

Height (cm)
2 hrs

3 hrs

for the further

20 hrs

treatment carried out

Settling Time (Mins or Hrs)
by the water company.
This represents a
Figure ¡Error!Argumento de modificador desconocido. - BOD5
considerable sum for a
Change During Settling Process.
small or medium size
company. Thus, further treatments are needed prior to discharge not only in terms of
environmental impact but also in terms of economics.

Reduction of Chromium

The remaining concentration of chromium over time at various height in the settling column
are presented in Figure 7. The concentration of chromium decreases gradually over time at
the top of the column, but the chromium concentration increases greatly in the first 10 mins
then increases gradually afterward at the bottom of the column where the sludges are
compacting. In the middle of column, 40 cm to 70 cm from the bottom, the chromium
concentration increases slightly at the beginning of settling process. After 10 to 30 mins, the
concentration of chromium begins to decrease slightly. This can be seen in Figure 7 and
Table 3. Within half an hour and one hour of commencement of the settling process, the

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average concentration of chromium of the mixed effluent had levelled out at about 30.26mg/l
and 28.8 mg/l respectively where they remained. On the basis of an average chromium level
of 100 mg/ l, the results indicate that plain sedimentation provides a removal efficiency of
70.4 % and of 71.2 % for chromium at half an hour and 1 hour respectively. After 20 hours
of plain settling the average concentration of chromium in the mixed effluent remained at
about 14.0 mg/l. The
results show that 86.4 %
chromium removal has
1000 been obtained after 20
900
hours of settling. The
Concentration (mg/l)

800
700 results indicate that the
Chromium

600 fastest period of

500
400
chromium removal
300
10
Bottom occurred in the first hour.
200
100
40 However, in relation to
70
0 100 the solids, COD and BOD
Sampling
0mins

removal, recommend that

10mins

130
20mins
30mins
40mins

Height (cm)
1 hrs
2 hrs

3 hrs

most appropriate settling

20hours

Top
time would still be 3
Time (Mins or Hrs)
hours. This gives 83.6 %
Figure ¡Error!Argumento de modificador desconocido. - of removal of total
Chromium Concentration Change During Settling chromium leaving 16.78
mg/l of chromium in the
P
supernatant.
Finally, the chromium
concentration in the compressed sludge is relatively high. The value from the lowest sampling
point of the settling column shows that 639.4 mg/l and 886.0 mg/l and 1000 mg/l of chromium are
remain in the sludge after one hour, 3 hours and 20 hours of settling process respectively. Other
studies on chromium recovery and treatment from tannery sludge have been reported elsewhere
(Macchi, 1991; Spahrmann, 1979).

General Characteristics of Supernatants from the Settling Column

Samples of the supernatant were collected from each sample point, except for the two
sludge points at the bottom of the column, after 1 hour, 3 hours and 20 hours. These
supernatants samples were mixed and analysed to determine the characteristics of the
supernatants from settling process over time 1 hour, 3 hours and 20 hours respectively.
Table 3 lists the mean characteristics of each sample.

Table ¡Error!Argumento de modificador desconocido. Characteristics of Supernatants

from the Settling Column.
Initial 1 Hour 3 hours 20 Hours
Parameter Conc. Conc. Remov Conc. Removal Conc. Removal
(mg / l) (mg/l) al % (mg/l) % (mg/l) %
pH 9.0 8.6 -- 8.5 -- 8.2 --
MLSS 1,500 375 76.1 358 77.2 339 78.4
TS 29,000 27,651 3.6 26,589 7.3 25,222 12.0
Chromium 100 28.80 71.2 16.78 83.6 13.95 86.4
COD 5,000 3,116 34.9 2,926 38.9 2,864 40.2

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BOD5 1,500 1,112 18.0 10,46 22.9 1,010 25.5

CONCLUSION

In this paper, the performance of sedimentation of wastewater from a leather tannery and
removal efficiencies in terms of solids, COD, BOD5 and toxic chromium with regard to
pretreatment standards were investigated. In general the pretreatment standards for the
leather tanning industry are stringent in almost all countries and necessitate the
application of biological treatment. The investigation indicated that although coarser
components, such as sand and silt and high concentrations of settleable solids, can be
removed from wastewater by plain sedimentation without coagulant addition or by a
roughing filter, these standards cannot be met by only applying plain sedimentation. Even
though higher efficiencies have been obtained further treatment is still considered to be
needed. The following conclusions can be drawn from the investigation:

Depending on the test condition (column height, solids settleability, and compatibility),
the behaviour of the plain settling system may show a marked dependence on the solids
concentration.

The compression phase of settling is reached within one hour period and the most solids
are settled properly within 3 hours. Further prolonged settling does not reduce the settling
sludge volume efficiently. The sludge volume remains at 28% of the original sample
volume within 3 hours of settling. 3 hours or slightly longer after the beginning of plain
settling is the optimum settling time. Longer periods of settling reduce process economy
with only a slight increase in the solid, COD, BOD5 and chromium removals.

A removal of 76.1 % and 77.2% of SS, 3.6 % and 7.3% of TS, 34.9% and 38.9 of COD,
18.0 % and 22.9 % of BOD5 and 71.2 % and 83.6 % of chromium were obtained after
one hour and 3 hours of plain settling process

A significant proportion of the poorly degradable matter in tannery wastewater is not

removed by the sedimentation. Thus, further treatments are needed prior to discharge not
only in terms of environmental impact (COD, chromium) but also in terms of economics.

BIBLIOGRAPHIC REFERENCES

1. APHA (1992), Standard methods for the examination of water and wastewater, 18th ed., APHA,
Washington DC.
2. Bye C. M. and Dold P. L. (1998) Sludge Volume Index Settleability Measures: Effect of Solids
Characteristics and Test Parameters. Water Environment Research, 70 (1), 87-93.
3. Eye D. J. and Graef S. P., 1986, Pilot plant studies on the treatment of beamhouse wastes from a
sole leather tannery, J. America Leather Chemistry Association, Vol. 63: 396-409.
4. Song Z., Williams C. J. and Edyvean R.G.J. (1998) Characteristics of the Tannery Waste Water.
IChemE Research Event 98, Newcastle, U.K..
5. Spahrmann J. (1979) Direct and Indirect recycling of Tannery Waste Water, JALCA, Vol.74, pp418-
421.
6. Springer H. (1994) Treatment of Industrial Waste of the Leather Industry - Is It Still a Major
Problem ? JALCA, Vol.89. pp153-187.
7. Tunay O., Orhon D. and Kabdasli I (1994) Pretreatment Requirements for Leather Tanning Industry
Wastewaters, Waste Water, 29 (9), 121-128.
8. Macchi G. Pagano M. et al (1991) A bench Study on Chromium Recovery from Tannery Sludge.
Water Research, Vol. 25., 11, pp 1019-1026.

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