Desalination 216 (2007) 116–122

Effect of activated carbon on BOD and COD removal in a

dissolved air flotation unit treating refinery wastewater
Malik L. Hamia*, M.A. Al-Hashimib, M.M. Al-Dooric
a
Chemical Engineering Department, University of Mutah, Karak, Jordan
Tel. +963 (79) 685-7899; email: hamiml@yahoo.com
b
Building and Construction Department, University of Technology, Baghdad, Iraq
c
Chemical Engineering Department, University of Tikrit, Tikrit, Iraq

Received 20 April 2005; Accepted 28 January 2007

Abstract
The effects of powdered activated carbon (PAC) on the performance of a pilot-scale laboratory dissolved air
flotation (DAF) unit were investigated. Refinery wastewater of different pollutant concentrations was treated and
the effects of different operating parameters on the removal efficiency of pollutants in terms of biological oxygen
demand (BOD) and chemical oxygen demand (COD) were studied. A circular pilot-scale DAF unit with conical
bottom was used and the operating parameters investigated included flow rate, recycle ratio, saturation pressure and
the concentration of PAC added. It was found that for dosages of activated carbon in the range of 50–150 mg/l, the
removal efficiencies for BOD increased from 27–70% to 76–94% while those for COD increased from 16–64% to
72–92.5% for inlet values of 45–95 mg/l and 110–200 mg/l for BOD and COD respectively. Such findings represent
considerable improvement in the performance of the dissolved air flotation unit.

Keywords: BOD; COD; Air flotation; Activated carbon

1. Introduction wastewater effluent. Such requirements and con-

Refineries are high water consumers and,
consequently, large wastewater producers. Good
quality water is often required in order to comply
with environmental standards and regulations.
Additionally, in areas of limited water resources,
water economics may dictate the possible reuse of
*Corresponding author.
siderations necessitate the efficient treatment of
the wastewater for the removal of hazardous con-
taminants. Various physicochemical and micro-
biological treatment methods have been used for
the treatment of refinery wastewaters [1–7]. Such
methods include pretreatment by gravity oil
separator followed by flocculation followed by
dissolved air flotation (DAF) to reduce the con-
centration of suspended solids in addition to oil

0011-9164/07/$– See front matter © 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2007.01.003
 M.L. Hami et al. / Desalination 216 (2007) 116–122
and grease. The removal of dissolved organics
requires biological treatment. Activated carbon
treatment adsorption can be applied via tertiary
granular activated carbon (GAC) columns or
powdered activated carbon (PAC) integrated into
the activated sludge process [8–10].
The flotation method for removing suspended
solids has been used with considerable success in
the mining industry, treatment of surface raw
water, thickening of waste activated sludge and
pretreatment of industrial wastewater [11–22].
Flotation is a very effective method of liquid
solid separation and has distinct advantage for the
removal of low density particles which have a
tendency to float. There are different types of
flotation processes but the DAF is the most
applicable [22]. The DAF technology has been
reviewed in the literature [23,24] whereby a brief
description of the development of DAF as a unit
operation for the removal of solids in water and
wastewater treatment [24] and an excellent
review of the current DAF technology and its
application to drinking and, to a lesser extent,
wastewater treatment [23] are presented.
A petroleum refinery is a complex combina-
tion of interdependent industrial processes that
generate wastewater effluent containing oil,
ammonia, sulfides, chlorides, mercaptans, phe-
nols and other hydrocarbons [3]. The most
important pollutants are organics, oils, suspended
solids and other toxic materials referred to as
priority pollutants [5]. The presence of toxic
organic compounds in receiving waters and water
supplies has modified the emphasis of wastewater
treatment during the past several decades. Rather
low effluent concentrations are required especi-
ally for the organic priority pollutants [6]. Thus,
the complete range of available treatment tech-
nologies has been applied in this field, very often
with disregard to high treatment costs [6].
Recent studies indicated that conventional bio-
logical treatment which is capable of removing
many organic compounds, is not effective in
removing all compounds to acceptable discharge
117
standards. Consequently, extensive pretreatment
often constitutes a basic requirement for final
biological purification. In addition, modifications
and alternatives to conventional treatment
schemes for more efficient removal of these
compounds have been sought. The Environmental
Protection Agency (EPA) stated that there is
ample evidence in the literature to suggest that
activated carbon should be considered when
evaluating treatment alternatives for petro-
chemical wastewater treatment [8]. A variety of
modifications and alternatives to conventional
biological treatment methods has been suggested
and evaluated in bench, pilot and full-scale
systems [3,6,7,9]. Among such modifications has
been the addition of powdered activated carbon to
the aeration basin of activated sludge facilities
and the use of granular activated carbon columns
to treat the secondary effluents of an activated
sludge petrochemical wastewater [1,2,7,10].
Other modifications are reported elsewhere
[3,5,14].
Despite significant efforts made on the modi-
fication of various units by using activated
carbon, no reported attempt has been made on the
modification of the DAF unit which is regarded
as the most common pretreatment method for
industrial wastewater. In the present work, the
effect of activated carbon on the performance of
a conventional DAF unit operating with a recycle
is studied. Operating parameters such as flow
rate, recycle ratio, saturation pressure and the
dosage of activated carbon are investigated. The
results indicate that considerable improvement in
the performance of the conventional DAF unit
can be obtained when activated carbon is used.
The present work can be regarded as a pioneer in
this respect.
2. Experimental set-up and procedure
The DAF pilot plant constructed to perform
this study is sketched in Fig. 1. The plant consists
118 M.L. Hami et al. / Desalination 216 (2007) 116–122

Fig. 1. Schematic diagram for the experimental set-up.

of a feed storage tank, two feed pumps, rapid Table 1

mixing and flocculating chambers, a circular Capacities of various units
DAF unit with a conical bottom, a recycle pump,
a saturation vessel equipped with an air com- Tank/vessel Capacity, L
pressor, a dosing system for chemicals consisting Feed tank 50
of dilution tanks with mixers and dosing pumps Mixer flocculator 2
for alum, polyelectrolyte and activated carbon DAF unit 3.5
and, finally, an effluent receiving tank. All tanks Saturator 2.2
and vessels were made of steel with internal Effluent tank 50
coating. PVC material was used for piping and
fittings. The capacities of the various units and Pumps Pumping rate
flow rates of pumps are given in Table 1. Flocculator feed 1.0–5.0 L/h
Alum, polyelectrolyte and activated carbon DAF feed 1.0–5.0 L/h
were added into the rapid mixing chamber by Recycle 1.0–2.0 L/h
means of the appropriate dosing pumps. Concen- Alum dosing 1.0–10.0 mL/h
trated alum and polyelectrolyte liquid solutions Polyelectrolyte dosing 0.1–1.0 mL/h
were diluted to 1% solutions in the dilution tanks AC slurry 4.0–70.0 mL/h
which were equipped with mixers before being
dosed to the mixer-flocculator chamber. PAC was
dosed to the system as a diluted (1%) slurry. the refinery. Part of the effluent was pressurized
Alum, polyelectrolyte and AC dosages were in and recycled to the flotation tank through the
the range of 10–20, 1–2 and 50–150 mg/l, respec- saturation vessel. Pressures of 2, 3 and 5 atmos-
tively. The influent wastewater to the plant was pheres were used in the investigation which were
obtained from a nearby refinery where samples sustained by an air compressor. Flow rate mea-
were collected from the effluent of the API sepa- surements were obtained from flow character-
rator at the oily wastewater treatment facilities of istics of the pumps. Pressure gauges were placed
 M.L. Hami et al. / Desalination 216 (2007) 116–122 119

at the discharge ends of pumps, the saturation

vessel and downstream the de-pressuring valve.
The BOD and COD were measured using
standard incubation method over a period of
5 days for the former and an oxidation method
using potassium dichromate for the latter. All
experiments were conducted at room temperature
(20–22EC) and the pH was kept in the range of
6.5–8.0. When changing the conditions of the
experiment, the effluent samples were taken after
displacing the whole water contained in the
flotation tank. Fig. 2. Effect of flow rate variation on effluent BOD
For each wastewater sample used in this study, without activated carbon.
two sets of experiments were conducted. The first
set was conducted with ordinary DAF experi-
ments under various operating conditions of flow
rate, recycle ratio and saturation pressure. The
operating pressure which gave the best results for
each sample was used to conduct the second set
of experiments with the addition of different
quantities of activated carbon.

3. Results and discussion

3.1. Flow rate effect on effluent BOD and COD
Variation of effluent BOD with flow rate for
an inlet BOD of 95 mg/l at the operating pres-
sures of 2, 3, and 5 atmospheres is presented in
Fig. 2 and the corresponding results for COD
with an inlet value of 198 mg/l in Fig. 3. In both
cases, it can be seen that the effluent value
increases with flow rate at a given saturation
pressure and the increase is non-linear, particu-
larly at low flow rates. This behaviour may be
attributed to the combined effect of residence
time and recycle ratio. Higher flow rate leads to
shorter residence time and smaller recycled water
of lower pollutant concentration and dispersed air
bubbles. The organic pollutants now spend
shorter time in the flotation tank and, coupled
with the effect of less mixing with smaller
recycled water, the effluent concentration is
expected to increase. Furthermore, as the relative
Fig. 3. Effect of flow rate variation on effluent COD
without activated carbon.
significance of each of the above effects changes
with residence time decrease (flow rate increase),
the combined effect may assume different behav-
iour over the range of flow rates investigated as
indicated in the figures. It can also be observed
that the effect of increased saturation pressure is
to lower the effluent concentration, which is
expected since the dispersed air, which acts as a
stripper to pollutants, increases with saturation
pressure increase. According to the results for
BOD in Fig. 2 and those for COD in Fig. 3, it is
apparent that all three effects are significant at
low flow rates, while at higher flow rates the
residence time effect predominates leading to the
less non-linear behaviour.
120 M.L. Hami et al. / Desalination 216 (2007) 116–122

3.2. Effect of activated carbon on BOD and COD order. These findings may indicate that the
removal adsorption action of activated carbon is con-
siderably appreciable and the amount of adsorbed
Results for the effects of activated carbon
pollutants is seen to increase with surface area
which are presented in Figs. 4 and 5 indicate that
available for adsorption.
the pollutant effluent concentration of both BOD
The results also indicate that the effluent
and COD is decreased to a considerable extent,
pollutant concentration increases when inlet
for a given inlet value, when using activated
concentration of pollutants is increased. However,
carbon. Such findings are indeed reflected by the
careful investigation of the results obtained from
increase in removal efficiencies shown in Figs. 6
experiments indicate that the adsorbed quantity of
and 7 for BOD and COD respectively. It can be
pollutants as well as its residual concentration
seen that, without activated carbon, the removal
both increase with increase of inlet pollutants.
efficiencies were found to be in the range of 27–
This trend is in good agreement with both
70% and 19–64% for BOD and COD respectively
Freundlich and Langmuir models which give a
for the cases considered in the investigation.
direct proportionality relationship between the
When activated carbon was added, such values
residual and adsorbed concentration for a given
rose to 76-94% and 72-92.5% in their respective

Fig. 6. Effect of activated carbon on BOD removal

efficiency.
Fig. 4. Effect of activated carbon on effluent BOD.

Fig. 7. Effect of activated carbon on COD removal

Fig. 5. Effect of activated carbon on effluent COD. efficiency.
 M.L. Hami et al. / Desalination 216 (2007) 116–122
adsorbent (carbon in this application)
concentration.
It is apparent that, while the conventional
flotation schemes seem to be unable to reduce the
pollutant concentration for most of the operating
conditions below the standard limits of 40 and
100 ppm (mg/l) for BOD and COD respectively,
the addition of 50 ppm of activated carbon, on the
other hand, will enable the concentration of
pollutants to be reduced to well below such
limits. In such cases the effluent water can be
safely discharged into rivers without further
treatment or it can be reused thus compensating
for the cost of activated carbon.
4. Conclusions
The following conclusions can be drawn from
the present work:
C Activated carbon has been used in the DAF
unit and the effect on unit performance is
investigated.
C It has been found that effluent pollutant con-
centration for the DAF unit increases with
flow rate increase and decreases with satura-
tion pressure.
C The addition of activated carbon was found to
reduce the BOD and COD concentrations of
effluent pollutants to a considerable extent.
Furthermore, the improvement in effluent
water quality increases with increasing the
concentration of activated carbon added.
C The adsorbed pollutants and their residual
concentrations were found to increase with
increased inlet concentration of pollutants, in
good agreement with the Freundlich and
Langmuir adsorption models.
C The addition of suitable quantities of activated
carbon can reduce the BOD and COD concen-
trations of effluent pollutants below the maxi-
mum acceptable limits for disposal.
However, more investigations are needed on
121
different types of industrial wastes and different
operating conditions before such conclusions can
be generalized.
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