597776

research-article2015
WMR0010.1177/0734242X15597776Waste Management & ResearchKwon and Lee

Short Communication

Waste Management & Research

Options for reducing oil content of

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DOI: 10.1177/0734242X15597776

treatment plant wmr.sagepub.com

Tae-Soon Kwon and Jae-Young Lee

Abstract
Wastewater treatment plants at petroleum refineries often produce substantial quantities of sludge with relatively high concentrations
of oil. Disposal of this waste is costly, in part because the high oil content requires use of secure disposal methods akin to handling of
hazardous wastes. This article examines the properties of oily sludge and evaluates optional methods for reducing the oil content of
this sludge to enable use of lower cost disposal methods. To reduce the oil content or break the structure of oily sludge, preliminary
lab-scale experiments involving mechanical treatment, surfactant extraction, and oxidation are conducted. By applying surfactants,
approximately 36% to 45% of oils are extracted from oily sludge. Of this, about 33% of oils are rapidly oxidised via radiation by an
electron beam within 10 s of exposure. The Fenton reaction is effective for destruction of oily sludge. It is also found that 56% of oils
were removed by reacting oily sludge with water containing ozone of 0.5 mg l-1 over a period of 24 h. Oxidation using ozone thus can
also be effectively used as a pretreatment for oily sludge.

Keywords
Oily sludge, shear force, surfactants, Fenton reaction, electron beam, ozone

Introduction
While industrialisation has been facilitated by the discovery,
refinement, and use of petroleum, the production and use of petro-
leum also contributes to environmental pollution. Among all envi-
ronmental pollutants, petroleum accounts for about 70% of the
total environmental pollution. In the Republic of Korea, petro-
leum is the major pollutant in 75% of sites that have been remedi-
ated from 2005 to 2011. It is estimated that the number of
petroleum-contaminated sites in South Korea exceeds 5000
(Korea Ministry of Environment, 2009). Annually, over 800 mil-
lion barrels of petroleum are consumed in South Korea, leading to
2 million tonnes of toxic waste containing oil residuals (Korea
Ministry of Environment, 2014). In particular, inappropriately
managed oily sludge generated at modern petroleum refineries
can pollute the environment (such as surface and groundwater and
soils). In wastewater treatment plants, equalisation tanks are gen-
erally used for the efficient disposal of wastewater. The sludge
that continuously flows into these tanks causes operational prob-
lems and large volumes of waste sludge are produced. To reduce
the total volume, waste sludge is dehydrated by centrifugation.
The resultant sludge cake is then incinerated. However, the oil
content of the cake generally exceeds 5% and it is categorised as
a specified waste by the current Korean waste management legis-
lation. The disposal cost of specified waste is about five times
higher than that of non-specified waste in the Republic of Korea.
If the oil content of the sludge is reduced below the legal standard
of 5%, about 80% of the disposal cost can be saved. It is therefore
necessary to develop suitable disposal methods for cost-effective
disposal of oily sludge. The oily sludge includes 30% to 90%
water, 4% to 7% sediments, and 5% to 60% waste oil; the waste
oil in turn contains 40% to 60% saturates, 25% to 40% aromatics,
10% to 15% resins, and 10% to 15% asphaltenes (Da Silva et al.,
2012). This complex structure of oily sludge inhibits the separa-
tion and degradation of waste oil.
The traditional technique is to reduce the oil and water content
below the level suitable for land disposal restriction criteria by
thermal treatment. Heat treatment of 500~1000 °C is currently
applicable, but multi-step processes are required for efficient dis-
posal, which is a notable drawback for large scale facilities (Ayen
and Swanstrom, 1992; Swanberg, 1993; Zang et al., 2014). As
alternatives, freezing/thawing and biological treatment have been
reported (Jean et al., 1999; Lin et al., 2008). Freezing/thawing
recovers the oil from sludge through separation of oily sludge into
oil, water, and a precipitate by the process of freezing and thawing
the sludge. The equipment and operating costs of freezing/thaw-
ing, however, are high and the recovery rate of oil is low. To
Transportation Environmental Research Team, Korea Railroad
Research Institute, Gyeonggi-Do, Republic of Korea
Corresponding author:
Tae-Soon Kwon, Transportation Environmental Research Team,
Korea Railroad Research Institute, #176, Railroad museum road,
Uiwang-si, Gyeonggi-Do 437-757, Republic of Korea.
Email: klez@krri.re.kr

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2 Waste Management & Research
address this and enhance the recovery rate of oil, a combination of
freezing/thawing and other methods (such as solvent extraction
and ultrasonic treatment) have been examined (Hu et al., 2015;
Zang et al., 2012). Meanwhile, biological treatment using a spe-
cific microorganism is cost-effective and environmentally friendly
compared with other recovery techniques (Jasmine and Mukherji,
2015; Mishra et al., 2001). However, the high oil content of the
sludge limits the activities of the microorganisms. Various other
approaches (including electrokinetic methods, filtration, flotation,
microwave irradiation, and centrifugation) to treat the oily sludge
have been reported in the literature, but they showed low treat-
ment efficiency or high costs (Abdulbari et al., 2011; Elektorowicz
et al., 2006; Huang et al., 2014; Qi et al., 2011; Ramaswamy et al.,
2007; Xu et al., 2009; Zubaidy and Abouelnasr, 2010). In this
study, the properties of oily sludge discharged from petroleum
refinery plants are observed and the preliminary feasibilities of
several technologies to reduce the costs for disposal of oily sludge
are investigated. As options for reducing the oil content of oily
sludge below the Korean standard for specified waste via the addi-
tional installation of simple facilities to the existing wastewater
plants in petroleum refineries, mechanical treatment, oil extraction
by surfactants, and oxidative degradation are adopted. The liquid
(oil and water) and solid can be separated by mechanical treatment
applying shear forces, and thus it becomes feasible to reduce the oil
content in the solid component of the sludge. The effectiveness of
various methods to apply shear forces is examined in this work.
The oil extraction from sludge by a surfactant is also evaluated.
Surfactants have been widely used to recover or separate the
hydrophobic contaminants from water, soil, and other wastes (Mao
et al., 2015). Furthermore, separation using a surfactant is simple,
fast, and efficient. Lastly, the representative oxidative degradation
methods, including the Fenton reaction, ozone, and electron beam
radiation, are applied to reduce the oil content of sludge in a short
time. Rapid oxidative degradation can be used for the direct dis-
posal of sludge waste or pretreatment before the dehydration step.
Materials and methods
Characterisation of oily sludge
The sludge used in this study was obtained from a wastewater
treatment plant of a petroleum refinery in the Republic of Korea.
The oil and water content of the sludge analysed by the EPA
9011B method were 15.4 ±4.5 wt% and 15.7 ±0.8 wt%, respec-
tively. The peaks were not fully separated in the chromatogram of
HPLC/UV (high performance liquid chromatography with ultra-
violet dectetor, Waters, USA), but the diesel oil concentrations at
254 nm (622,715 mg diesel oil/kg sludge) were higher than that at
210 nm (264,300 mg diesel oil/kg sludge). This indicates that the
ratio of polyaromatic hydrocarbons (PAHs) to total oil is rela-
tively high in oily sludge. The detailed composition of oil in the
sludge was analysed by TLC/FID (thin layer chromatography
with flame Ionization detection, Iatroscan, USA) and described
in Table 1. Compared with general oils, the aromatic content is
high and many impurities (resins, asphaltenes) exist.
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Table 1. Composition of oily sludge by TLC/FID.
Saturates (%) Aromatics (%) Resins (%) Asphaltenes (%)
30.1 11.6 54.7 3.6
Methods for reducing oil content of
sludge
For mechanical treatment of the sludge, a sonicator, a ball mill,
and a homogeniser were used to separate the phases of the
sludge by applying shear force. The amount of sludge used in
the mechanical treatment was 100 g. Sonication was conducted
with a rod-type sonicator for 30 min. Ball-milling was imple-
mented for 48 h. To increase the shear force on the sludge struc-
ture, the homogeniser was used. The oily sludge was
homogenised at a rate of 10,000 r min-1 for 2 h. After applying
the shear force, all samples were centrifuged and separated into
bottom solids, middle liquids, and top solids. The surfactant has
both hydrophobic and hydrophilic components and hence can
be used for extraction of oil from sludge. In this study, anionic
and non-ionic surfactants were selected to minimise the adsorp-
tion of the surfactants on solid surfaces that are charged posi-
tively. SDS (sodium dodecyl sulphate, Sigma Aldrich, USA) for
an anionic surfactant and Brij and Tween series (Sigma Aldrich,
USA) for a non-ionic surfactant were selected. Non-ionic sur-
factants of various hydrophilic/lipophilic balance (HLB) num-
bers were used to confirm the effects of the hydrophilic/
hydrophobic properties on the extraction of oils. The properties
of the surfactants used in this study are listed in Table 2.
Surfactants of 5 wt% were added to 30 g of sludge and mixed
over a period of 24 h. The solid phase of the sludge was then
separated by centrifugation at 10,000 r min-1 for 20 min and the
amount of oil in the solid phase was measured. For the degrada-
tion of oils by hydroxyl (OH) radicals, an electron beam radia-
tor (EB tech, Korea) and oxidising agents, including Fenton
reagents and ozone, were used. For the Fenton reaction, hydro-
gen peroxide and FeSO4 (Junsei, Japan) were purchased, and
the ozone generator (Chayon tech, Korea) was employed to pro-
duce the water containing ozone of 0.5 mg l-1.
Results and discussion
Mechanical treatment for the separation
of oils
The oil content of each solid in the top and bottom phases was
measured and the results are listed in Table 3. If the structure of
the sludge is influenced by shear force, the oil in the solid pre-
cipitants will decrease. In all experiments applying shear force,
oil content in the top and bottom phases changed slightly, but the
application of shear force did not show significant performance
in the separation of oils from the sludge. Therefore, the use of
shear force did not cause a change in the phase structure of the
oily sludge.
Kwon and Lee 3

Table 2. Properties of surfactants and results of oil extraction by surfactants (initial oil contents in sludge: 19.9 wt%).

Surfactants Molecular weight (g mol-1) HLB No. Residual oil contents

in solid (wt%)
SDS 288 – 20.4
Brij 30 362 9.7 16.2
Brij 35 1198 16.9 12.8
Tween 85 1839 11 15.2
Tween 80 1310 15 11.0

HLB: hydrophilic/lipophilic balance; SDS: sodium dodecyl sulphate.Brij 30: polyoxyethylene(4) lauryl ether, Brij 35: polyoxyethylene (10) lauryl
ether, Tween 85 : polyoxyethylene sorbitan trioleate, Tween 80: polyoxyethylene sorbitan monooleate.

Table 3. Oil contents in top and bottom solids after applying
shear forces to oily sludge.
Oil contents (wt%) Oil contents (wt%) in
in solid of top phase solid of bottom phase
Untreated sludge 7.6 ±0.3 6.6 ±0.6
Sonication 7.5 ±0.4 4.9 ±0.3
Ball-milling 8.8 ±0.5 5.8 ±0.5
Homogenisation 7.3 ±0.3 6.2 ±0.6
Oil extraction by surfactants
Table 2 shows the residual oil content in the solid phase of sludge
after extraction by surfactants. SDS did not separate the oil from
the sludge and it is considered that the anionic charge of SDS was
not effective owing to the solid surface of the sludge that is
charged negatively. On the other hand, non-ionic surfactants
were effective for the extraction of oils from the oily sludge.
Considering the properties of non-ionic surfactants related to
HLB number, it is expected that Brij 30 and Tween 85 are more
suitable for extracting oils than Brij 35 and Tween 80, because
non-ionic surfactants of low HLB number have high hydropho-
bicity. However, the non-ionic surfactants of a high HLB number,
Brij 35 and Tween 80, showed better extraction performance.
The results thus indicate that non-ionic surfactants of a high HLB
number, which are more hydrophilic, are effective for extracting
oils from oily sludge.
Degradation of oils by electron beam and
oxidising agents
Electron beams have been applied to wastewater and NOx and
SOx of exhaust gas (Han et al., 2012; Pikaev, 2002a, 2002b).
Oxidising agents such as hydrogen peroxide and ozone are also
widely used for many environmental purposes. First, a 50 kJ kg-1
electron beam was used to degrade oils in the sludge. A 50% dilu-
tion of sludge was conducted to minimise the inhibition of solid
particles. By applying an electron beam for 10 s, the total petro-
leum hydrocarbon (TPH) concentration was reduced from
44,662 mg oil/kg sludge to 30,100 mg oil/kg sludge. Generally,
OH radicals react more easily with the double bond of aromatic
hydrocarbons than the single bond of saturated hydrocarbons. If
the major reason for the removal of oils is degradation by OH
radicals, the ratio of saturates/aromatics should increase. The
ratio of saturates/aromatics of the sludge, however, did not
change by electron beam radiation (Figure 1). It is thus assumed
that the degradation by OH radicals and volatilisation by the high
energy of the electron beam occurred simultaneously.
The radiation of the electron beam was effective for reducing
the oil concentration of the sludge. However, the facility costs are
high and many volatile gases can be emitted during the applica-
tion. Fenton reagents and ozone were thus used for easy oxida-
tive disposal of the sludge in this study. For the Fenton reaction,
35% (v/v) hydrogen peroxide, 0.1 M FeSO4, and 10 g of oily
sludge were used. The ratios of sludge to hydrogen peroxide were
1:2, 1:4, and 1:8. The structure of the oily sludge was destroyed
by the Fenton reaction and the sludge was easily separated into
liquid and solid precipitants by centrifugation. To confirm the
effectiveness of oxidation by the Fenton reaction, the chemical
oxygen demand (COD) of the residual liquids was measured. The
CODs of liquids according to the treatment ratio of sludge and
hydrogen oxide (1:2, 1:4, and 1:8) were 184, 80, and 36 mg l-1,
respectively. All CODs were below 200 mg l-1 and thus oxidation
by the Fenton reaction was effective for degradation of the oils in
the sludge. However, hydrogen peroxide is costly and it should
be handled with caution owing to its instability. As an alternative
for Fenton reagents, ozone was selected and water containing a
low concentration of ozone (0.5 mg l-1) was used to reduce the
application costs. For 10 g of sludge, the ratios of ozone and
sludge used were 1:5 and 1:10. By contacting the ozone and the
sludge for 24 h, oil content in the sludge was reduced from
15.4 wt% to 11.5 wt% (ratio of 1:5) and 6.7 wt% (ratio of 1:10).
Considering the results, oxidation by ozone in low concentrations
can be used for a pretreatment process to lower the oil content.
Conclusions
Oily sludge considered in this study had a relatively high oil con-
tent of over 15 wt%, and a large portion of oil in the sludge was
resins and asphaltenes with high viscosity. These conditions led
to strong binding of the oil and the sludge. To lower the oil con-
tent of sludge, this study focused on three techniques: using shear
force, surfactants, and oxidative degradation. The results indicate
that the extraction of oils by surfactants and oxidative degrada-
tion is effective for lowering the oil content of sludge. Non-ionic
surfactants of a high HLB number, having more hydrophilic
properties, were suitable for the extraction of oils, and about 36%

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4 Waste Management & Research
60
Before radiation
After radiation
50
40
Composition (%)
30
20
10
0
Saturates Aromatics
Figure 1. Change in composition of oily sludge after exposure to electron beam radiation.
to 45% of oils were recovered by the use of Brij 35 and Tween 80.
Oxidative degradation of oily sludge had a significant impact on
lowering the oil content. The application of an electron beam and
Fenton reaction are also possible approaches for rapidly treating
sludge with high concentrations of oil. Finally, degradation using
ozone can be applied as a pretreatment to reduce the oil content
at lower cost.
Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with respect
to the research, authorship, and/or publication of this article.
Funding
The author(s) disclosed receipt of the following financial support for
the research, authorship, and/or publication of this article: This
research was supported by a grant from R&D Program of the Korea
Railroad Research Institute, Republic of Korea.
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