Wat. Res. Vol. 32, No. 11, pp.

3495±3499, 1998
# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(98)00111-0 0043-1354/98 $19.00 + 0.00

TECHNICAL NOTE

WASTEWATER TREATMENT AT THE PETROLEUM

REFINERY, KIRIKKALE, TURKEY USING SOME
COAGULANTS AND TURKISH CLAYS AS
COAGULANT AIDS
S° AHIÇ NDE DEMIÇ RCIÇ 1*, BAKIÇ ERDOGÆAN2 and RECEP OÈZCIÇ MDER3
1
Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey; 2Department of
Chemistry, Gazi University, Ankara, Turkey and 3Department of Chemical Engineering,
Kirikkale University, Kirikkale, Turkey

AbstractÐIn this study, waste water of Kirikkale Re®nery (Turkey) was treated with coagulants (alum,
ferric chloride, ferrous sulfate and lime) and coagulant aids (polyelectrolytes: anionic, cationic,
nonionic) and some Turkish clays namely Samas° , C° anbensan, Ceylan, Hasandede and Keskin in order
to see their e€ects in clarifying the waste water before biopuri®cation. The results showed that local
clays (Hasandede and Keskin) are as ecient as bentonites (Samas° , C° anbensan and Ceylan). The
clarifying eciency of clays in combination with coagulants shows almost the same results of about
90%. The e€ect of coagulants, FeCl3, FeSO4 and CaO, was similar to that obtained with Al2(SO4)3.
The eciency of polymeric materials especially cationic and anionic polymers was found to be better
than that obtained with clays. # 1998 Elsevier Science Ltd. All rights reserved

Key wordsÐwastewater treatment, coagulant aids, polyelectrolytes, clays

INTRODUCTION and some Turkish clays namely Samas° , C° anbensan

Waste water treatment in larger chemical and petro-
chemical plants including petroleum re®nery a€ords
the application of all available technologies for
pollution abatement (Huber, 1988). Waste water
facilities in these systems usually rely on many
interdependent steps; extensive pretreatment is very
often a basic requirement for ®nal biological
puri®cation.
In Kirikkale Re®nery, Kirikkale, Turkey, bio-
logical wastewater treatment has been applied and
after puri®cation it is discharged into the
Kizilirmak River that provides water to
Kapulukaya Dam which supplies water to the re®n-
ery. Therefore waste water of the plant should be
treated quite well in order to prevent occurrence of
an environmental problem.
The pollutant concentration of waste water
should be decreased as much as possible before bio-
degradation. This pretreatment may be carried out
by using coagulants and coagulant aids (ASTM,
1978; Huber, 1988; Gagnon et al., 1992; Rebhun
et al., 1992).
The aim of this study is to treat the waste water
of Kirikkale Re®nery with coagulants (alum, ferric
chloride, ferrous sulfate and lime) and coagulant
aids (polyelectrolytes: anionic, cationic, nonionic)
*Author to whom all correspondence should be addressed.
and Ceylan bentonites, Hasandede and Keskin
clays in order to see their e€ects in clarifying the
waste water before biopuri®cation.
MATERIALS AND METHODS
Wastewater for treatment was taken from the ¯occu-
lation pool where waste water was collected after some
treatments such as sieving, oil collection and stripping.
Chemical characteristics of this waste water are given in
Table 1. Treatment was followed by using the jar test of
water (ASTM, 1978) and measuring pollution parameters
(COD, NTU), pH and temperature.
The jar test machine used was Plipps and Bird U.S.A.
¯oc illuminator, model 302.
A ratio turbidimeter (Hach, model 18900) was used for
turbidity measurement in nephelometric turbidity unit,
NTU. The pH meter used was WTW, pH 530 (100-240).
COD determination was carried out by using a COD
spectrometer (Hach, Dr/3 100-20, single beam) and the
standard method from APHA (1980).
Trace element analysis was done by means of a Philips
model P49285 atomic absorption spectrometer. Reagent
grade chemicals, alum [or Al2(SO4)3
18H2O], FeCl3
6H2O,
FeSO4
7H2O, CaO, were used in all tests. The polyelectro-
lytes, anionic, cationic and nonionic, from Dearborn were
added as coagulant aids. Commercial bentonites, Samas° ,
C° anbensan and Ceylan and local clays, Hasandede and
Keskin, were also used as coagulant aids.
Clays were used with and without pretreatment.
Pretreatment means acid activation. For this purpose the
dry activation process was applied (C° akirogÆlu et al.,
1985).

3495
3496 Technical Note

Table 1. Chemical characteristics of wastewater of Kirikkale

re®nery
Parameter Valuea

COD (mg O2/l) 800

BOD 350
COD/BOD ratio 2.3
Oil (mg/l) 3000
Phenols (mg/l) 8
Sul®tes (mg/l) 17
Suspended solids (mg/l) 100
pH 6.5±8.5
a
Values given in the table show the average values.

Mineralogical composition of clays was determined by

X-ray di€raction analysis (XRD). The XRD patterns of
random and oriented mounts of the samples were obtained
with a Jeol JDX80 di€ractometer using Ni-®ltered Cu Ka
radiation and a Philips PW 1140 model di€ractometer
using again Ni-®ltered Cu Ka radiation.
Chemical compositions of the clays were determined by
X-ray ¯uorescence spectrometry (XRF) using a Philips PV
1480 spectrometer with lithium tetraborate fused discs.
In the waste water treatment three di€erent sets of
experiments were carried out.
In the ®rst set, to the beakers containing a sample,
100 mg CaO was added and fast-mixed (100±120 rpm) and
100 mg of a clay (Samas° , C° anbensan, Ceylan, Hasandede
or Keskin) was added and fast-mixed for 3±5 min. Then
stirring was continued slowly (30±50 rpm) for 10±15 min
for ¯occule growth. Finally stirring was stopped to permit
¯ocs to settle. During this quiescent period (up to 70 min),
samples were taken out and their turbidity was measured.
Results showed that the quiescent period of 30 min is
quite enough for ¯ocs to settle as expected from previous
experiences.
The second set of experiments were run similar to that
of the ®rst set. Here COD and NTU measurements were
done at 30 min of the quiescent period using coagulants
and clays by keeping the concentration of one of the two
constant and varying the concentration of the other one.
In this set, ®rst the amount of Al2(SO4)3 added was kept
constant at 100 mg and the amount of clays was varied in
the range (50±300) mg. Secondly, the amount of clays was
kept constant at 100 mg and the amount of coagulant was
varied in the range (50±300) mg. Measurements of COD
and NTU were carried out at 30 min of quiescent period.
The same experiments were repeated by replacing
Al2(SO4)3 by FeCl3, FeSO4 and CaO.
In the third set of experiments treatment was repeated
by using 100 mg Al2(SO4)3 and varying the amount of
polyelectrolytes in the range (4±25) mg.
In order to see the change in amounts of trace metals
(Mn, Ni and Zn), the concentration of them in untreated
and treated waste water with coagulant [Al2(SO4)3] and
clays were determined.
RESULTS AND DISCUSSION
Mineralogical analysis showed that all bentonites
are essentially montmorillonite as expected. XRD
patterns of samples in an air dried state gave
Fig. 1. Change in turbidity of waste water treated with
CaO and di€erent clays as a function of time.
a peak at around 13 AÊ which corresponds to
montmorillonite with predominantly Na+ as an
interlayer cation. Upon saturation with ethylene
glycol this peak shifted toward 17±18 AÊ which is
expected from a smectite. Calcite, feldspar, quartz,
opal-CT, zeolite and gypsum were identi®ed as the
main impurities in these bentonites (ErdogÆan and
Demirci, 1996).
Keskin and Hasandede clays also have smectite
group clay mineral montmorillonite, In addition,
Hasandede clay has sepiolite and Keskin clay has
kaolinite and chlorite clay minerals. A reduced
intensity of the chlorite peak (7.2 AÊ) due to collapse
of kaolinite by heating to 5508C indicates clearly
the presence of kaolinite. Both clays have a
negligible amount of impurities.
Values obtained in XRF analysis showed that
Al2O3/SiO2 ratios were 1/3 to 1/4 in bentonites
(Table 2) but not in Hasandede and Keskin clays.
According to XRF data Samas° bentonite carries a
little more Na2O (2.49%) than Ceylan bentonite
(1.90%) with C° anbensan clay containing 2.24%
Na2O. Iron oxide shows signi®cant variations
between the bentonite samples with Samas° carrying
3.78% Fe2O3, Ceylan has an unusually high Fe2O3
content (9.32%) and C° anbensan has 5.38% Fe2O3.
In Hasandede clay the MgO content is very high
(12.77%) due to the presence of sepiolite. The
amount of Na2O is also high (5.45%) which is
expected for the presence of Na montmorillonite.
Keskin clay has an unusually high Fe2O3 content
(10.95%) which may be due to the presence of
chlorite as Fe-chlorite (Carroll, 1974).

Table 2. Results of XRF analysis (%)

Sample SiO2 Al2O3 Fe2O3 Na2O CaO MgO MnO TiO2 K2O P2O5

Samas° 61.43 17.32 3.73 2.49 3.16 1.98 0.11 0.32 1.01 0.17
C° anbensan 61.83 17.36 5.38 2.24 1.39 2.64 0.04 0.73 0.95 0.03
Ceylan 55.35 16.63 9.32 1.90 3.26 2.29 0.15 1.32 0.68 0.46
Hasandede 52.28 8.13 3.10 5.45 3.50 12.77 0.05 0.33 1.73 0.10
Keskin 49.11 18.66 10.95 1.01 3.12 2.98 0.02 0.67 0.26 0.03
 Technical Note 3497

Fig. 2. Change in turbidity of waste water treated with Fig. 3. Change in COD of waste water treated with
Al2(SO4)3 and di€erent amounts of di€erent clays. Al2(SO4)3 and di€erent amounts of di€erent clays.

medium, clay itself forms a colloidal suspension and

In the ®rst set the results showed that local
causes somewhat turbidity which should not be
clays (Hasandede and Keskin) are as ecient as
troublesome (Fig. 2). The e€ect of coagulants,
bentonites (Samas° , C° anbensan and Ceylan). In
FeCl3, FeSO4 and CaO was similar to that obtained
Hasandede and Keskin clays the turbidity did not
with Al2(SO4)3 (Table 3).
change up to 10 min, but then decreased drastically
Changing the sequence of coagulant and clay did
like all other clays up to about 30 min. After this
not make any signi®cant change in the clarifying
the turbidity decreased slightly. The initial increase
eciency of the system.
in turbidity may be related to the formation of a
Activated clays have a higher eciency than
colloidal suspension of clay before settlement
those of untreated clays (Table 3). This is an
started (Fig. 1).
expected result. In acid activation, the adsorption
In the second set the results showed that the
capacity of the clays increases with an increasing
clarifying eciency (reducing in turbidity) of clays
acid/clay ratio upto about 0.50 (Sarikaya et al.,
in combination with coagulants shows almost the
1989).
same results. The coagulant concentration was kept
The eciency of local clays on COD reduction
constant at 100 mg considering the results of a pre-
seems to be better than that of bentonites (Fig. 3).
vious study related to the removal of dissolved
Among bentonites, Ceylan is better than Samas°
organic matter in water by treatment with alum
and C° anbensan. This may be due to the presence of
(Kuo and Amy, 1988). The turbidity was reduced
CaO and Fe2O3 in higher amounts. Iron and
to about 80% of the initial value upon application
calcium ions may produce complexes or salts with
of 50 mg clay by 30 min treatment. The increase in
organic molecules.
the amount of clays upto 300 mg caused only a
Many clay minerals, especially montmorillonites,
small increase in the clarifying eciency (090%).
readily adsorb organic molecules. Adsorption
This is true for all bentonites and local clays.
depends upon various factors including molecular
Complete clari®cation was not obtained. This is due
size of the adsorbate, its concentration in the med-
to the fact that while hydrocarbon pollutants are
ium, e€ect of van der Waals forces, chain length,
adsorbed on clay surfaces and removed from the
CH activity and entropy e€ect (Theng, 1974, 1982).

Table 3. COD and NTU values (in ppm) of waste water treated with di€erent coagulants and coagulant aids (clays)a
Coagulant (100 mg)
Al2(SO4)3 FeCl3 FeSO4 CaO
Clay (100 mg) COD NTU COD NTU COD NTU COD NTU

Samas° 61 20 44 12 65 21 65 17
Activated Samas° 57 11 33 11 52 11 57 13
C° anbensan 55 35 23 18 64 32 22 19
Activated C° ambensan 53 27 44 22 58 27 48 25
Ceylan 62 33 46 14 60 15 50 12
Activated Ceylan 60 30 42 13 57 12 48 11
Hasandede 29 16 17 13 32 17 29 17
Activated Hasandede 23 9 14 9 26 11 14 11
Keskin 32 28 37 30 38 34 34 28
Activated Keskin 30 25 30 32 25 22 30 29
a
Initial parameters; COD; 130 ppm, NTU; 35 ppm.
3498 Technical Note

Table 4. COD and NTU values for waste water treated with Al2(SO4)3 and changing amount of cationic, anionic and nonionic polymersa
Type of polymer added Weight of polymer added (mg) COD (ppm) NTU (ppm)

Cationic 4 23 0.75
5 20 0.67
6 19 1.50
15 15 1.20
25 16 1.08

Anionic 4 18 0.65
5 17 0.56
6 16 0.56
15 10 1.00
25 11 1.05

Nonionic 4 40 0.80
5 38 0.75
6 35 2.20
15 30 3.00
25 31 3.20
a
Initial parameters; COD; 50 ppm, NTU; 22 ppm.

Adsorption is usually increased by raising the
solute (organic) concentrations, or in the extreme
case by elimination of water from the system. This
was also the case in our study. The adsorption of
pollutants increased or more turbidity or COD re-
duction was observed on addition of the clays
which means that water is eliminated.
The presence of metal salts increases the e€ect of
clays on removal of pollutants in several ways
including double layer compression and speci®c-ion
adsorption. Metal ions such as Fe2+, Fe3+ and
Al3+ hydrolyse to produce multinuclear ions such
as Fe2(OH)2+ 2 , Fe3(OH)5+
4 , Al3(OH)4+
8 and
4+
Al8(OH)20 which exhibit speci®c adsorption onto
many types of solid surfaces. When the surface
charge of suspended particles is negative, a typical
situation in common substrates, these hydrolysis
species can decrease the magnitude of the charge
and even cause charge reversal (James et al., 1977).
At high coagulant doses, metal hydroxides are pro-
duced and organic substances are removed by in-
corporation into or sorption onto hydroxide ¯ocs
(Kuo and Amy, 1988). In the presence of initial
particles a ``seed'' surface exists for promoting het-
erogeneous nucleation and formation of M(OH)3/
clay aggregates. A signi®cant sorption of pollutant
molecules can be expected onto the surface of these
aggregates, since they have both hydrophobic and
hydrophilic characters.
In the third set the results showed that the e-
ciency of polymeric materials, especially cationic
and anionic polymers, as coagulant aid was found
to be better than that obtained with clays (Table 4).
For 15 mg polymer accompanied with 100 mg
Al2(SO4)3 the percentage decrease in NTU is 95, 96,
86 for cationic, anionic and nonionic polymers, re-
spectively. Similarly the percentage decrease in
COD is 70, 80 and 40. The e€ect of polymers also
depends upon their concentrations; at low concen-
tration they form a bridge between particles and
cause ¯occulation. At high concentration they form
an envelope on the suspending particles and cause
them to remain in suspension. Thus, at optimum
concentration (here 15 mg) they give the best results
for both COD and NTU. Although polymers gave
better results for the waste water treatment, they
are not advised and used for this purpose because
they may have toxic monomeric components
(S° enguÈl, 1989).
The concentration of trace metals, Mn, Ni and
Zn after treatment decreased considerably (Table 5).
Local clays, Hasandede and Keskin were found to
be more ecient in the sorption of trace metals
than bentonites.
The cost of the annual waste water treatment of
2.16  106 m3 using the common coagulant alum
together with clay or polymer was calculated. The
results are as follows; with clay the cost is 050 000
dollars and with polymer, 01 600 000 dollars.

Table 5. Concentrations of trace metals (Mn, Ni and Zn) in untreated and treated waste water
Concentration of trace metal (ppm)*
Sample of waste water studied Mn Ni Zn

Prior to treatment 0.114 0.220 0.752

Al2(SO4)3 added 0.062 0.085 0.106
Al2(SO4)3 and Samas° added 0.066 0.005 0.021
Al2(SO4)3 and C° anbensan added 0.090 0.010 0.033
Al2(SO4)3 and Ceylan added 0.085 0.013 0.030
Al2(SO4)3 and Keskin added 0.060 0.067 0.027
Al2(SO4)3 and Hasandede added 0.044 0.018 0.027
Untreated but with biodegradation 0.035 0.142 0.095
a
Values given are the average of at least three analysis results.
 Technical Note
CONCLUSIONS
Petroleum re®neries generate a considerable
amount of waste water and release a complex set of
oxygen demanding materials into the natural en-
vironment. Since these waste waters also contain
priority pollutants, treatment of these complex
wastes is a great problem. In Kirikkale Re®nery,
Turkey, an ecient biopuri®cation for waste water
has been developed. In order to use it more
eciently for longer time, additional pretreatment
should be carried out. This is especially required
when the cracking unit of the plant will start
working.
For this purpose some coagulants, Al2(SO4)3,
FeCl3, FeSO4 and CaO, accompanied with some
commercial bentonites, Samas° , C° anbensan and
Ceylan, and local clays, Hasandede and Keskin
have been used. Results showed that local clays
with optimum values of 100 mg/l accompanied with
100 mg/l coagulant can give a sucient decrease in
COD and NTU values (about 90%). Concen-
trations of trace metals (Mn, Ni and Zn) can be
decreased considerably especially with local clays.
In addition, using local clays doesn't need too
much investment. The cost of the annual waste
water treatment of 2.16  106 m3 using alum and
clay is about 50 000 dollars.
Comparing all the results and possibilities, using
clays especially local clays, Hasandede and Keskin,
accompanied with alum can be advisable in waste
water treatment before biopuri®cation in Kirikkale
Re®nery.
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