Accepted Manuscript

Review
Oil and grease removal from wastewaters: Sorption treatment as an alternative
to state-of-the-art technologies. A critical review
Ariana M.A. Pintor, Vtor J.P. Vilar, Cidlia M.S. Botelho, Rui A.R. Boaventura
PII:
DOI:
Reference:

S1385-8947(16)30385-0
http://dx.doi.org/10.1016/j.cej.2016.03.121
CEJ 14973

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Chemical Engineering Journal

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Revised Date:
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19 November 2015
22 March 2016
23 March 2016

Please cite this article as: A.M.A. Pintor, V.J.P. Vilar, C.M.S. Botelho, R.A.R. Boaventura, Oil and grease removal
from wastewaters: Sorption treatment as an alternative to state-of-the-art technologies. A critical review, Chemical
Engineering Journal (2016), doi: http://dx.doi.org/10.1016/j.cej.2016.03.121

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Oil and grease removal from wastewaters: Sorption treatment as

an alternative to state-of-the-art technologies. A critical review

Ariana M. A. Pintor*, Vtor J. P. Vilar, Cidlia M. S. Botelho, Rui A. R. Boaventura*

LSRE-Laboratory of Separation and Reaction Engineering Associate Laboratory
LSRE/LCM, Departamento de Engenharia Qumica, Faculdade de Engenharia da
Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

Authors to whom correspondence should be addressed

Tel. +351 225081669; Fax: +351 225081674; E-mail address: ampintor@fe.up.pt

(Ariana M. A. Pintor); bventura@fe.up.pt (Rui A. R. Boaventura).

Abstract

Oil and grease (O&G) is a class of pollutants with very low affinity to water. Their
removal from wastewaters is often challenging and involves the combination of
different treatment technologies, according to the specifications for the treated water
and the O&G substances involved. O&G can be classified according to its type and
source and this influences the choice of the treatment process.
This paper presents a review of the state-of-the-art technology on O&G removal.
Treatment usually involves several steps, including primary, secondary and tertiary
treatment. Gravity separators accomplish removal of free oil as a primary treatment.
Secondary treatments include chemical, electrical and physical methods which target
emulsified oil, such as, coagulation/flocculation, dissolved air flotation, electrocoagulation/flotation, and membrane separation. Tighter membranes and advanced
oxidation processes can refine treatment in a tertiary step.
Many of these treatments present, however, disadvantages such as production of
hazardous sludge or high energy requirements. In this context, sorption as a secondary
treatment is gaining focus in the literature, especially using natural organic sorbents.
These present the advantages of lower cost and biodegradability, and may enable the
recovery or recycling of sorbed O&G. Additionally, some of them may be reused up to
a limited number of working cycles. Several kinds of sorbents and mechanisms for oil
sorption and recovery are reviewed in this article.

Keywords: Oil and grease; Wastewater; Treatment; Sorption; Coagulation; Membrane

separation

1. Introduction

Growth in industrial production and urbanization, which had its onset in the 18th century
with the Industrial Revolution and increased considerably in the last decades, brought
about great improvements in manufacturing processes and in the living conditions of
populations. However, as a result of overexploitation and inadequate waste
management, it has also led to the emergence of many environmental impacts. Among
these, contamination of water resources has been one of the most afflicting.
Among the many classes of pollutants, one regularly found in waters and wastewaters is
Oil and Grease (O&G). O&G is a group of organic substances whose defining
characteristic consists in a very low affinity to water. Allocation of contaminants to the
O&G category is usually determined by the method of chemical analysis, in particular
the solvent used for extraction from the aqueous phase. Substances typically classified
as O&G include hydrocarbons, fatty acids, soaps, lipids and waxes [1]. Such a wide
range of compounds constitutes a class of complex nature; therefore, it is not surprising
that Rhee et al. [2] consider O&G one of the most complicated pollutants to remove
in oil processing wastewaters.
Since most substances in this class have very low biodegradability, their release to the
environment via wastewaters may impact the biosphere [3]. Even the thinnest layer of
oil will affect aquatic life by decreasing both the penetration of light and the oxygen
transfer between air and water [4]. For this reason, discharge limits for oil and grease
are imposed by environmental law in most countries.
In addition to its ecological impact, O&G affects the operation of traditional wastewater
treatment plants, inhibiting biological activity in activated sludge reactors and causing
clogging and fouling of pumps and piping [2]. Furthermore, the presence of oily matter

in wastewaters is often indicative of the occurrence of toxic micro pollutants, especially

those which are hydrophobic in nature. High concentrations of benzene, toluene and
xylene have been associated with discharges of petroleum refinery wastewaters in the
municipal system [2], and mono- and polyaromatics have been detected alongside other
long-chain hydrocarbons in stormwater runoff [5]. To protect the normal functioning of
sewage treatment plants, emissions of oil and grease to the local wastewater drainage
system are also subject to regulation.
For the aforementioned reasons, wastewaters heavily loaded with oil and grease can
neither be directly discharged onto the environment nor collected by the municipal
system; an alternative treatment strategy must be sought. There is a large body of
literature on how to remove oil and grease from water, including results of the
application of several technologies, but oily wastewaters remain a challenge. O&G may
vary in chemical constitution, physical properties and industrial source, and treatment
design depends on these specifications, along with each wastewaters characteristics and
pollution parameters.
One of the most promising technologies for the removal of O&G from wastewaters is
sorption. The use of organic sorbents is particularly relevant because these materials are
easily accessible, cost-effective and present reduced environmental impact [3]. This
paper aims to establish the state-of-the-art on O&G, its origin, analysis and
composition, and the best available technologies for O&G removal. For the latter, a
review of the literature has been done in order to point out the advantages and
disadvantages of each method and identify possible applications. Special focus is given
to sorption as an alternative process to the most common technologies.

2. The O&G class of pollutants

2.1.Types of O&G

O&G substances can be divided into two great classes, differing in origin and in
chemical constitution. A first category has mineral provenance, namely from petroleum
and its derivatives, and consists of a mixture of hydrocarbons of different chemical
configurations; a second group is from biological origin (animal or vegetable), and is
mainly composed of triglycerides, i.e. esters of glycerin and fatty acids.
It is not clear whether further chemical differences can be assigned to the two types.
Patterson [1] maintains that there is a dichotomy between mineral and biological oils in
which polarity and biodegradability are a characteristic of the latter group. However, it
might be an oversimplification to correlate these chemical properties with the previous
classification. In fact, OBrien [6] points out that all edible fats and oils are waterinsoluble, because of the large nonpolar hydrocarbon tails of fatty acids which govern
triglycerides polarity, despite the slightly polar carbon-oxygen bonds in glycerol.
Therefore, as a rule, oils of biological origin behave like nonpolar molecules. Likewise,
it is difficult to establish a priori whether any O&G present in a wastewater will be
biodegradable; it tends to depend on external factors which influence microbiological
activity.
Regardless of chemical classification, O&G in water and wastewater can be examined
with regards to their physical characteristics, which are fundamental for appropriate
treatment design. The level of dispersion and stability of oil droplets in aqueous medium
will influence the readiness of separation and the resources which need to be put
forward to achieve the treatment objective. Here, Patterson [1] defines five other classes

of O&G, which were later complemented by Rhee et al. [2] by attributing a droplet size
range to each class. Their description is presented in Table 1. Other authors who have
directly or indirectly classified O&G regarding their physical characteristics [4, 7, 8]
provide only variations of the aforementioned classification, either by considering only
a few classes or by giving emphasis on the role of surfactants in the emulsification of oil
in water.

2.2.Sources of O&G

O&G is present in municipal wastewaters, but not in high concentrations: provided

industrial discharges are under control, the entrance of oil in the system is restricted to
domestic activities such as cooking or cleaning, and the problem is usually controlled at
the source through the installation of grease traps. Domestic wastewaters were reported
to vary in O&G content between 50 and 150 mg L-1 [9]. Similarly, O&G in
stormwaters, consisting of leached hydrocarbons from automobile vehicles and related
activities such as parking lots and gas stations, was rarely found to exceed a few
milligrams per liter in a study by Stenstrom et al. [5].
So how does oil and grease end up in high concentrations in wastewaters? The answer
to this question lies in industrial activity. Liquid waste rejected by plants mixes oily
matter with water used at all steps of operation, resulting in colloidal suspensions with
oil droplets in different physical forms. As far as industrial wastewaters are concerned,
O&G concentrations may reach a few dozens of grams per liter.
In his book about industrial wastewater treatment, Patterson [1] presents a
comprehensive list of industrial processes which generate oily wastewater, from which
three prevailing activities are singled out as representative of different realities:

Petroleum wastewaters originate from both crude oil extraction and oil
refineries. On-field exploitations of crude oil reservoirs originate oil-field
brine, a wastewater that, besides being loaded with hydrocarbons, presents very
high salinity [10]. Wastewaters from oil refineries also contain other nonconventional pollutants such as ammonia, sulphides, chlorides, mercaptans and
phenols [2, 11, 12];

Metalworking wastewaters result from metal piece manufacturing in materials

ranging from aluminum to steel. Cutting, cooling and lubricating oils are often
applied in the process to serve as interface between tools and workpieces. These
fluids usually do not consist of pure oils, but of oil-in-water emulsions which
combine the properties of both liquids under the stabilising action of a surfactant
[13, 14]. In rinsing, cooling and cleaning operations, they are carried away to the
facilitys wastewaters. Moreover, when spent, the diluted metalworking fluids
themselves consist in wastewaters with O&G concentrations that may reach
dozens of grams per liter only in the emulsified form [1, 15];

Food processing wastewaters derive from the transformation of both animal and
vegetable products. Operations of slaughtering and cleaning generate oily
wastewaters in meat processing [16]. Extraction and refinery of vegetable oils
discharge great volumes of oily wastewaters as well. In Southern Asia, palm oil
mill effluent (POME) is a growing concern [17-19], while in Mediterranean
countries, olive mill wastewaters production is high, due to strong activity in
this sector [20-22]. Refining of vegetable oils originates vegetable oil refinery
wastewaters (VORWs) from different origins, for example, sunflower,
cottonseed, soybean and rapeseed [23].

Table 2 presents several types of wastewaters characterized in the literature, in terms of

their O&G content and discharge levels.

3. Treatment of wastewaters with O&G

Treatment of oily wastewater is, according to Patterson [1], similar in concept to

treatment of domestic sewage, since it consists of a primary treatment followed by a
secondary step and, when needed, a tertiary stage for the refinement of quality
parameters for discharge and/or reuse. However, treatment technology differs in its
specifications for each situation.
In wastewaters where O&G is the central pollutant of concern, primary treatment
generally consists of a gravity separation tank with quiescent flow conditions which
allow free oil to float to the surface. Different tank configurations can be used for this
effect, from the traditional American Petroleum Institute (API) separator to parallelplate interceptors (PPIs) which take advantage of tilted plates inside the tank to promote
oil droplet aggregation and ascension [7].
For wastewaters with high solids content, sedimentation of solids is also enabled by the
stagnant conditions of a gravity separator, or alternatively by sedimentation tanks [20,
24].
After the first treatment step, the secondary unit aims to separate the remaining oil,
which is mostly in the emulsified form and therefore does not spontaneously separate
under the action of gravity and buoyancy forces. The breaking of the oil/water emulsion
can be externally promoted through a variety of treatment methods, which can be
classified as chemical, electrical or physical. Chemical methods are the most common
and work by destabilising the emulsified oil droplets through the addition of coagulants
such as aluminum or iron salts. The sludge generated in this process can then be
separated by a physical method, most commonly sedimentation or flotation. Electrical
methods include electroflotation and electrocoagulation: the former replaces traditional

flotation by creating gas bubbles by the electrolysis of water, and the latter induces
coagulation by means of consumable electrodes, which upon oxidation release metallic
coagulants into the wastewater. Finally, physical methods act by changing physical
properties or applying forces to promote coalescence and agglomeration of oil droplets.
Techniques in this category include heating, centrifugation, filtration, dissolved air
flotation (DAF) and coalescing beds [1, 4].
When biodegradable oil and grease is present in wastewater, the secondary treatment
step may be a biological reactor, operating in a very similar way to a municipal
wastewater treatment plant (WWTP). With this methodology, removal of nonbiodegradable oils occurs by sorption or incorporation in the biological sludge [1].
Therefore the presence of the latter type of oils must not be prevailing in order not to
interfere with the normal functioning of the process.
After the secondary treatment, the effluent may need refinement if the previous methods
were not efficient enough to reduce O&G concentration below the discharge limit, or if
a higher water quality is desired to allow reuse. In such cases, a tertiary step will involve
a more selective technology, such as adsorption, membrane filtration or advanced
oxidation processes (AOPs).
In the next sections the different steps in oily wastewater treatment and the
corresponding technologies for O&G removal at each stage will be explored in more
detail, referencing the literature in each segment as appropriate.

3.1.Primary treatment

Primary treatment of oily wastewaters aims for both the removal of O&G in free oil
form and the sedimentation of solids and unstable colloidal particles. Separation of
these substances from the aqueous matrix is usually performed by taking advantage of
10

gravitational forces and differential densities, which cause oil globules to float and solid
granules to settle [1].
Quiescence of the wastewater can be achieved in gravity separators, which consist in
tanks and/or channels where horizontal flows are low enough not to interfere with oil
rise or solid deposition. The first separator to be designed for this effect, back in the
1950s, was the API separator. It consists in a simple rectangular channel coupled with
an oil skimmer and a sludge pump. The design parameters limit horizontal water
velocity to 3 ft min-1 (approx. 1.5 cm s-1), hence allowing a reduced surface-loading rate
(flowrate divided by surface area) which in turn increases oil removal. Theoretically,
any oil droplet whose rise rate exceeds the surface-loading rate will reach the top of the
separator and be skimmed off from the surface [7].
The rise rate of oil globules can be estimated taking into account the balance of the
forces that act upon them [25]. The most important factors governing the rise rate are
differential density and viscosity. It is clear that the closer the specific gravities of oil
and water, the slower the separation. Similarly, the more viscous the fluid the lower the
rising rate. The decrease in viscosity can be achieved with an increase in temperature.
Therefore, heating is a possible mechanism of enhancing phase separation.
Another possibility for the improvement of separation involves the adoption of a
different separator design. Sometimes, to achieve the desired removal efficiency, large
surface areas are required to decrease the surface-loading rate. With a simple
rectangular channel configuration this may involve unfeasible land occupation. In order
to solve this problem, plate separators were conceived. The inclined plates added inside
this reactor configuration enable an increase in surface area avoiding the enlargement of
the reactor itself.

11

In a PPI, plates are distributed inside the reactor at angles between 45 and 60 from the
horizontal and a spacing of 0.75-1.5 in between them (approx. 2 to 4 cm). Das and
Biswas [26] found that a baffled separator with 4 cm spacing between baffles positioned
at a 45 angle was the most suitable configuration for the separation of a 5% diesel oilwater mixture. Parallel plates promote collision between oil droplets near the solid
surface, leading to the occurrence of coalescence [1]. The increase in droplet size
implies that the rise rate will also increase, speeding up the separation process.
Coalescence can be further improved by using corrugated plates in the place of standard
smooth parallel plates; this configuration is called a corrugated-plate interceptor (CPI)
[27].
PPI and CPI units present many advantages over the traditional API separator, the most
obvious of which is the improvement of efficiency in a same limited space. According
to API [7], plate separators can handle flows two or three times higher than equivalent
traditional units. Moreover, these configurations can be designed to remove oil globules
as small as 60 m diameter, often meeting treatment requirements of O&G
concentration as low as 50 mg L-1. Traditional separators are dimensioned for a
diameter threshold of 150 m and are only expected to remove O&G down to a
concentration of 100 mg L-1. A summary of the advantages and disadvantages of each
method is presented in Table 3.
In all gravity separators, at the end of the quiescence period, both oil and sludge have to
be collected, respectively, from the top and bottom of the separator. At the surface, an
oil-skimming device gathers the less dense phase, which can be either discarded or
reprocessed. The sediment, on the other hand, is removed from the bottom of the
separator either manually or using a scraper and a sludge pump, depending on the
concentration of solids in the wastewater [7].

12

The effect of gravity separation can be enhanced by several methods, namely DAF,
centrifugation, coalescing beds, and heating [4]. Benito et al. [13] have also improved
the removal of settleable solids using filtration with mesh and magnetic filters.

3.2.Secondary treatment: chemical methods

As it has been covered in the previous section, the removal of free O&G is fairly
straightforward once a good grasp of the physical forces acting on the oil droplets is
acquired. A bigger challenge remains: the removal of the remaining oil, which is
dispersed in very small droplets and stabilised by interparticle forces and/or surface
active agents. This type of stable O&G is often found in industrial wastewaters, and
must be targeted by a secondary treatment, since gravity separation is ineffective [28].
Chemical methods of secondary treatment consist in the addition of a reagent to remove
O&G by taking advantage of a chemical process [1]. A summary of the applications of
chemical treatments found in the literature and their results is presented in Table 4.
Ahmad et al. [29] propose solvent addition (n-hexane having the best performance) to
extract oil from POME. However, this methodology seems rather unfeasible in practice
due to the high associated costs, unless the recovered product should prove to have very
high added value.
The most common reagents used in emulsified O&G treatment aim to break the oilwater emulsion, regardless of the possibility of recovery [30]. Emulsion breakage can be
achieved using detergents, acids, coagulants and polymers [31]. Acidification, per se, is
usually not enough to foster the aggregation of oil droplets in a short time frame.
Nevertheless, it may prove to be beneficial if it takes advantage of processes already
under way at the industrial facility. An example is presented by Boyer [32] in the

13

treatment of edible oil wastewater, where separation of oil is enhanced at the WWTP by
taking advantage of residual acidity and heat from acidulation wastewater. The main
disadvantage of acidification may consist in the robust construction materials needed for
tanks, which may increase the installations cost.
Using acidification to break the oil-water emulsion leads us in the right direction
towards faster and more effective techniques of oil separation. Zouboulis and Avranas
[28] and Welz et al. [8] state that oil droplets are stable as a colloidal phase due to the
adsorption of surface active agents or hydroxyl ions at their surface, which promote the
negative charging of the particles and the occurrence of electrostatic repulsion between
them. Therefore, positively charged particles, such as the hydrogen ions released to
solution upon the addition of an acid, will destabilise the dispersion by means of charge
neutralisation. But while H+ will only promote coalescence of oil droplets, metallic
cations cause a much stronger effect of coagulation, since apart from neutralisation, they
can stimulate other mechanisms of destabilisation, such as double layer compression,
precipitation and bridging flocculation [8, 28, 30, 33]. Several authors [14, 28, 33, 34]
successfully monitor the stability of the oil-water emulsion by measurement of the zeta
potential or surface charge, reporting that effective coagulation is achieved when zeta
potential is brought to zero.
The most common coagulants used in oily wastewater treatment are iron and aluminium
salts [2, 28, 29, 33, 35, 36], which are cheap and widely available. Chipasa [37], Pandey
et al. [23] and Benito et al. [14] have also used calcium salts as coagulants, namely
calcium chloride and lime, and Suzuki and Maruyama [38] the inorganic polymer
polyaluminium chloride (PAC). PAC has a higher net charge than monomer aluminium
salts, thus being more effective in emulsion breaking; furthermore, polymers promote

14

flocculation by bridging between coagulated particles, forming flocs which are easier to
separate from the aqueous phase.
The separation of the coagulated sludge from the supernatant can be achieved by several
methods, the most popular of which is DAF [16, 28, 34]. This separation technique can,
by itself, remove particles over 40 m diameter, but its performance is boosted by the
use of coagulant and flocculant aids, with which it is able to achieve an effluent quality
of 1 to 20 mg L-1 O&G. Coagulants not only promote the aggregation of oil droplets, as
it has been previously described, but they also increase the adhesion between air
bubbles and oil droplets, easing the flotation of oily matter [2]. DAF performance can
also be enhanced by surfactants, due to the formation of positively charged air bubbles
which attract negatively charged flocs and oil droplets [34, 39] A technique with similar
characteristics is induced air flotation (IAF), though it relies on the production of larger
bubbles and higher turbulence [40].
Other flotation techniques which have just recently been introduced in wastewater
treatment have been tested. Foam separation, a method widely applied in ore flotation,
relies in the spontaneous formation of air bubbles in the presence of a foaming agent
that enhances adhesion between flocs and bubbles. The generated foam brings to the
surface not only the coagulated oily matter but also suspended solids [38]. Another
technology, mechanically agitated flotation cell (MFC), promotes higher turbulence
than DAF or IAF and has higher capacity than those traditional flotation methods.
Despite the increase in energy efficiency, MFC treatment could not achieve O&G
concentrations below 50 mg L-1 [8]. In another approach, Santander et al. [41] could
achieve 80 to 85% O&G removal from petroleum wastewaters in conventional and
modified jet flotation cells. Finally, it is worth mentioning that centrifugation has also
been used to separate coagulated sludge from treated effluent [14], but the expensive

15

energy costs associated with this method compare rather unfavorably to flotation
techniques.
The biggest disadvantage which is often pointed out in the literature regarding
traditional chemical methods such as coagulation with inorganic salts is the production
of large amounts of hazardous sludge [32, 42]. Since the oil is trapped among
aluminium and iron precipitates, it is unrecoverable [43]. The handling of the
oily/metallic sludge usually involves costly treatment or deposition. In this sense,
organic and biodegradable coagulants have been tested in place of inorganic salts, in
order to minimise the hazardousness of the sludge and develop a cleaner process.
Synthetic organic polymers have been used for this purpose by Karhu et al. [34] and
Cristvo et al. [44]. Boyer [32] had previously advocated the use of food-grade organic
compounds as coagulants, while Benito et al. [13] have used a biodegradable
demulsifier to destabilise oil-water emulsions and separate them by centrifugation.
The most popular organic coagulant presented in the literature for the treatment of oily
wastewater is chitosan [24, 42, 45]. It is a natural polymer of marine origin with
widespread applications. The treatment of oily wastewater by chitosan powder is
believed to work by both mechanisms of coagulation and adsorption [42, 46]. The
positive charge of chitosan particles attracts negatively charged oil droplets and other
suspended solids [24]. Ahmad et al. [42] have concluded that chitosan is more efficient
than traditional coagulants alum and PAC in a study on the treatment of POME: to
achieve the same treatment objectives, operation with the natural polymer requires
lower coagulant dosage, less mixing time and less sedimentation time. Chi and Cheng
[45] have achieved similar conclusions in the treatment of milk processing wastewater
samples; following a cost-benefit analysis, they concluded that the use of chitosan does
not increase costs while providing operating benefits. More recently, chemical

16

transformations have been carried out on chitosan in order to enhance its flocculating
properties [47].
Regardless of the type of coagulant used, it must be noted that chemical treatment may
not lead to full compliance with wastewater discharge limits. For stricter regulations, the
remaining O&G will still need further reduction, and coagulation is ineffective in the
removal of dissolved organic matter [37, 45]. Aslan et al. [48] have shown, through
chemical oxygen demand (COD) fraction analysis, that the effluent from
physicochemical treatment of VORW has high biodegradability. For this reason, the
coupling of coagulation/flocculation and DAF processes with subsequent biological
reactors is a common solution to achieve the desired effluent quality for discharge [23,
37].

3.3.Secondary treatment: electrical methods

Electrical methods take advantage of electrochemistry to increase the efficiency of

coagulation and flotation processes. In electrocoagulation, the coagulants are generated
in situ, by means of consumable electrodes. Electroflotation, on the other hand, is based
on the generation of gas bubbles by the electrolysis of water, mimicking an air flotation
process [1]. The main advantage of electrical treatment methods derives from the fact
that both electrocoagulation and electroflotation often coexist in a treatment process.
This leads to high efficiency gains, since while metallic cations are being released to the
solution, promoting the aggregation of oil droplets, hydrogen gas bubbles are being
formed, improving agitation conditions and carrying the flocs to the surface [30].
A summary of electrocoagulation/electroflotation applications found in the literature for
O&G removal is presented in Table 5.

17

The study of electrocoagulation has been carried out mostly in real wastewater matrices,
such as refectory wastewater [49], olive mill wastewaters [50], VORW [51], POME
[52], biodiesel wastewater [53], slaughterhouse wastewaters [54, 55], restaurant
wastewater [56], and bilge water [57]. Nevertheless, recent studies have also
approached the destabilisation of oil-in-water emulsions by this method in order to
study more fundamental principles of the technology [58, 59].
Aluminium is the most common material for sacrificial electrodes [51, 52, 58], even
though some studies have found iron electrodes more efficient [50]. The efficacy of a
consumable electrode depends on the specifics of each application, including, for
instance, the supporting electrolytes. Izquierdo et al. [60] have found that chlorides are
the most advantageous types of salts for energy-efficient dissolution of both aluminium
and iron electrodes, while nitrates and sulfates cause large decreases of efficiency for
treatment with the latter.
Electrocoagulation has been compared to chemical coagulation with inconclusive
results. While some authors report definite efficiency gains with electrocoagulation
[55], others observe that electro and chemical coagulation lead to similar O&G
removals, with other mechanisms coming into play. Caizares et al. [33, 61] have
argued that pH is a very important factor when choosing between electrocoagulation
and chemical coagulation, since each process causes different variations in this
parameter along time. The deviation of pH from an optimum range of operation can
then compromise treatment effectiveness. In another approach, Phalakornkule et al. [52]
demonstrate that, for a similar treatment of POME, electrocoagulation is cheaper than
chemical coagulation, due to the elimination of reactant consumption. However, in the
same study, it is reported that electrocoagulation generates twice the mass of sludge

18

from chemical coagulation, so this environmental impact is not minimised by the

electrical method, but it is even worsened.
The use of electroflotation methods with insoluble electrodes can reduce the production
of hazardous sludge [62, 63]. These processes work solely on the basis of hydrogen and
oxygen bubble generation. The size of the bubbles and their surface charge influence
strongly the treatment efficiency. Nevertheless, despite attempts to optimise flotation
performance, to achieve the desired effluent concentrations coagulant and flocculant
agents often need to be added to the electroflotation unit [63, 64].
Recent studies have approached the treatment of oily wastewaters by optimizing both
electrocoagulation and electroflotation performance in the same unit [56].

3.4.Secondary treatment: physical methods

The control of the physical properties of oil and water can be fundamental in devising
alternative treatments where gravity separation and chemical and electrochemical
methods have proven unsatisfactory or hazardous [65]. One way to achieve this is by
tweaking the operating conditions of processes which have been described earlier to
separate coagulated flocs from water so that they are able to perform oil droplet
separation without coagulant addition. The other option is to apply other physical
separation methods, such as heating, coalescence and filtration, and optimise them for
oil/water separation [2, 4, 30]. A summary of the physical methods which have been
applied to O&G removal in the literature and their results is presented in Table 6.
Instead of working as a method of carrying floatable flocs to the surface, DAF can be
used as a method of oil droplet separation alone [38, 39]. As it has been mentioned
earlier in section 3.2., Zouboulis and Avranas [28] have found that the technology is

19

able to separate all droplets with diameters over 40 m; however, this did not result in
good removal efficiencies.
In a previous work, Angelidou et al. [39] were able to achieve high treatment quality of
other oil-water emulsions using DAF, and could even describe the process accurately
using theoretical models of first-order kinetics. Tansel and Pascual [66] also applied
DAF without coagulants with success in the treatment of brackish and pond waters
contaminated with emulsified oil. One of the parameters often highlighted for optimal
performance is the size distribution of air bubbles. In this sense, designs which promote
microbubble formation, such as cyclone-based technologies, have been tested [67, 68].
Centrifugation is also a method used to separate coagulated sludge and treated water
that can be applied directly to oil-water emulsions [69]. However, without the addition
of coagulants or demulsifiers, the technology is unable to remove the smallest
emulsified oil particles [30], nor can it reduce COD levels associated with dissolved
organic matter [20].
Vacuum evaporation is a technique that is very effective in producing a purified
aqueous phase, and can be used when there is a goal of water reuse. However, the
operating costs are inhibitory for a large-scale application [14].
Roques and Aurelle [4] propose coalescence in a granular medium bed as treatment
strategy. This method works by fostering the aggregation of small oil droplets onto
larger particles, so that they will easily be separated by gravity once they flow out of the
coalescing bed. The mechanism unfolds in three steps: first, the oil droplets are attracted
to the granules surface; then, they adhere to the solids by means of weak interactions;
finally, the oil salts out of the bed in larger droplets, which easily float to the surface in
a free resting space at the top of the bed. This technology is usually based on resin
materials [70], but it has also been done with other granular and fibrous media, such as

20

polypropylene and nylon fibres [71], sand [72], polyurethane, poly(ethylene

terephthalate) and polypropylene granules [73] and glass microfibres [74].
Instead of promoting coalescence in view of downstream gravity separation, a filtration
bed will provide oil removal by both retention and coalescence [1]. However, the study
of filtration beds is very complex, since several mechanisms occur simultaneously,
including sorption, which will be approached in further sections of this article.
Therefore, in this section only an overview of membrane separation is presented.
Membrane filtration has the ability to achieve high effluent purity, and often allows the
recovery of the separated oily phase [43]. The biggest constraint to good membrane
performance is maintenance and fouling, which can be minimised by adequate
pretreatments for high removals of O&G and suspended solids, and by careful choice of
the membrane characteristics and operating conditions [29].
In oil-water separation, the affinity of the membrane material towards oil and water is
one of the most important characteristics influencing filtration performance. Membranes
can range from superhydrophobic (contact angle with water = 0) to superhydrophilic
(contact angle with water > 150) and from superoleophilic (contact angle with oil = 0)
to superoleophobic (contact angle with oil > 150) [75]. Another important parameter is
the membrane pore size, which determines whether we are working with microfiltration
(MF), ultrafiltration (UF), nanofiltration (NF) or reverse osmosis (RO) processes.
Decloux et al. [43] have accomplished the treatment of a real acidic VORW using a MF
hydrophilic mineral membrane operating at low transmembrane pressure. Removal
efficiencies of over 90% for suspended solids and O&G and 60% for COD were
achieved. Good O&G removal efficiencies were also obtained in the treatment of
petroleum refinery wastewaters with a MF membrane [76]. However, due to its large
pores, MF is often used in a two-step membrane treatment as a pretreatment before

21

tighter membranes. Peng and Tremblay [77] used MF in combination with UF, where
the MF membrane works as a coalescence medium for smaller particles and is very
effective in the separation of surfactants and detergents.
A more recent approach to MF membranes has been to improve their surface properties
in order to combine hydrophilicity with oleophobicity and take advantage of these
affinities to improve separation performance and avoid fouling problems [78]. A
remarkable study by Kota et al. [75] has reported on the creation of a
superhydrophilic/superoleophobic membrane (stainless steel mesh coated with
fluorodecyl polyhedral oligomeric silsequioxane and cross-linked poly(ethylene glycol)
diacrylate) which keeps its properties after water wetting. The differential density
between water and oil makes it possible for the process to be driven by gravity forces
alone. The authors demonstrate the feasibility of the method with successful separations
(99.9% purity for each phase) of oil-in-water and water-in-oil emulsions, even when
stabilised by surfactants, maintaining operation for over 100 h without fouling or losing
membrane permeation. This line of research has progressed onto the development of
superhydrophobic membranes with higher durability and whose production can be
easily scaled up, such as poly(ethylene terephthalate) (PET) textiles coated with
polydimethylsiloxane and polyvinyl chloride [79]. Zhang et al. [80] have developed
superoleophobic kapok membranes which simultaneously remove water-soluble dyes
while performing oil-water separation.
UF has been used both as secondary and tertiary treatment, for oil-in-water emulsions
[13, 14, 81] and for oily wastewaters [82-84]. Still, high operating pressures and
specific methods of cleaning and regeneration are often needed for UF to run smoothly
[77]. Therefore, the effectiveness of this technology comes at the expense of elevated
costs.

22

3.5.Tertiary treatment

Tertiary treatment is often designed with the perspective of water reuse, so a great
effluent quality is expected. The results of different methods employed in the literature
can be reviewed in Table 7.
NF and RO membranes are in this category, since they can deliver even higher quality
permeates than MF and UF systems; however, they are also more expensive to operate.
NF membranes have been used successfully at end-of-line treatments of petroleum
wastewaters [85] and olive mill wastewaters [86]. Mondal and Wickramasinghe [85]
have also shown that RO membranes can achieve greater permeate quality than NF
ones. Al-Jeshi and Neville [87] have achieved over 99% O&G removal in the separation
of oil-in-water emulsions with oil contents ranging from 0.15% to 50% with a RO
membrane. In a recent study, anti-fouling nanofiltration membranes could separate
engine oil in water at a concentration of 500-1000 ppm with efficiencies of 95.5-99.5%
[88].
An advantage of RO membranes is that they also enable the separation of salts, which
are commonly found in oily wastewaters from the petroleum and food industries.
However, the efficiency of salt rejection is influenced by the feeds oil concentration.
Oxidation technologies, namely AOPs, are also emerging as tertiary treatment
alternatives for oily wastewaters, in particular due to their ability to destroy dissolved
organic matter and thus reduce the remaining COD content after secondary treatment.
Many methodologies, from chemical oxidation to solar ultraviolet (UV) radiation
photocatalysis, have been studied for this purpose, for instance, Fentons reagent
(Fe2+/H2O2)

[89,

90],

H2O2/UV

[89-91],

electro-Fenton

[57],

photo-Fenton

23

(Fe2+/H2O2/UV) [89, 92], O3/UV [91], aerated heterogeneous Fenton with nano
zerovalent iron [93] and solar photo-Fenton [22].

3.6.Biological treatment

The use of biological reactors in wastewater treatment is very common, since it is a very
cheap and easily accessible technology. Previously, on section 1., the reasons why O&G
is not so easily treated by biological methods and how it interferes with their normal
functioning have been presented. Nevertheless, in a few particular cases, it is possible to
use biological treatment to remove O&G from wastewaters.
Untreated industrial wastewater containing high concentrations of oil is rarely fit for
biological degradation. Aslan et al. [48] evaluated the biodegradability of VORWs,
inferring that they cannot be treated by biological methods alone, due to their low
BOD5/COD ratio. Biodegradable O&G is, therefore, mostly constituted by soluble
substances and very finely divided droplets at very low concentration [2, 37]. Oils of
biological origin (such as vegetable and animal oils) are, in general, easier to biodegrade
than those of mineral origin [1].
For proper functioning of a biological reactor as a secondary treatment, upstream
treatments must enable removal of all coarse O&G and substances which are not subject
to biodegradation. It is a common strategy to use a physicochemical treatment
(coagulation/flocculation followed by sedimentation/flotation) preceding an activated
sludge reactor. This has been successfully tested for the treatment of VORWs [23, 37].
Aslan et al. [48] have confirmed that the effluent of a physicochemical treatment leads
to increased biodegradability in these types of wastewaters.

24

Other typologies of biological reactors have also been tested for oily wastewater
remediation, such as anaerobic/aerobic systems [94], biological filters with supported
biomass on granular activated carbon (GAC) [10, 91], biological aerated filters [95, 96]
and membrane biological reactors [97]. A summary of the results found in the literature
is presented in Table 8.

3.7.Combination of treatment strategies

As it has been introduced in the beginning of this section (3.), the removal of O&G and
the full decontamination of wastewaters is only achieved by a combination of different
methodologies in sequential steps. In the literature, it is more common to find studies
exploring the possibilities of each technology at once, but a few authors have proposed
combinations of treatment strategies which have proved successful in the removal of
O&G from oil-in-water emulsions and real wastewaters.
Pandey et al. [23] have examined a real VORW treatment plant, giving suggestions to
improve its operation and performance. The basis of the proposed treatment is the
common combination of physicochemical and biological treatment, which has been
mentioned in section 3.6. and studied by other authors [37, 48]. Upstream from the
coagulation/flocculation unit, the industrial WWTP has an equalisation tank, and
downstream from two activated sludge processes, the plant completes treatment with
secondary clarification and chlorination (Figure 1). The final effluent is compliant with
limits of discharge.
In a different study, Benito et al. [13] report on the design of a pilot plant for the
treatment of a cutting oil residue from metalworking with very high levels of O&G and
COD. The authors were able to achieve quality for discharge into the local wastewater

25

drainage system by a sequence of filtration, demulsification/centrifugation, UF and peat

bed filtration.
Ahmad et al. [29] and Peng and Tremblay [77] also advocate treatment strategies
centered on one or more membrane separation units. But while the first group of authors
recommends the use of different pretreatments to remove suspended solids and O&G
and prevent fouling, the latter combines different types of membranes for more efficient
operation.
In another study with more sophisticated technologies, Souza et al. [91] have combined
AOPs with a biological filter supported on GAC for the treatment of petroleum
wastewaters. The effluent after both units had enough quality for water reuse.
Finally, there are many authors that center the treatment line on a sorption unit. This
methodology, which is the main focus of this article, will be covered in greater detail in
the next section. Al-Malah et al. [20] propose treatment of olive mill effluent by
sequential sedimentation, centrifugation, filtration and sorption onto activated clay.
Previously, Alther [98] had suggested that sorption of O&G onto organoclays could be
positioned either as a pretreatment for more sensitive adsorption and membrane
separation or as a post treatment for primary units such as gravity separators. Ahmad et
al. [99] have studied O&G removal by sorption as a follow-up to coagulation and
sedimentation. Dalmacija et al. [10] and Hami et al. [11] have used sorbents as a direct
complement to other technologies, such as activated sludge processes and DAF, with
improvements in O&G and COD removal efficiency.
The emergence of sorption as an alternative to other treatments presented in this section
consisted in an effort to minimize disadvantages presented by the technologies
presented thus far in this article. A table comparing advantages and disadvantages of the
main available technologies for O&G removal is presented in Table 9.

26

4. Treatment of wastewaters with O&G by sorption

Thirty years ago, in an overview of O&G removal methodologies in industrial

wastewater treatment, Patterson [1] mentioned adsorption as an emerging technology,
mostly used in tertiary treatment. In the past two decades the importance of (ad)sorption
in oily wastewater treatment has changed immensely. Alther [98] was a pioneer in this
matter, demonstrating the versatility of organoclays in oil removal, either as a
pretreatment for membrane separation processes or as a secondary treatment following
gravity separators. These sorbents can be used both in the powdered and granular forms,
the former in batch systems and the latter in filtration units, mixed with other media,
such as anthracite.
In more recent studies, activated clay and other mineral sorbents have been shown to
provide successful treatment for olive mill wastewaters [20, 21]. Besides capturing
O&G, they also sorb other organics, such as polyphenols. Santi et al. [21] have tested
both batch and percolating column configurations, finding no difference between them
in terms of treatment efficiency. The authors tried to improve effluent quality by
performing sequential sorption treatments, but it was ineffective.
The result of coupling sorption units toward better overall treatment is more valuable
when each unit is designed with a different objective in mind. Zhou et al. [65]
performed a successful two-step treatment of a synthetic oil-in-water emulsion using
modified resin for removing high concentrations of oil and GAC for treatment
polishing. Dalmacija et al. [10] and Hami et al. [11] have used activated carbon in the
powdered form as an aid of coagulation/flocculation/DAF and activated sludge
processes, and in the granular form as a tertiary step, in refinery wastewater treatment.
However, despite the demonstrated increase in efficiency in biochemical oxygen

27

demand (BOD5) and COD removal, adsorption onto activated carbon can be an
expensive technology. If higher O&G concentrations are present, pore clogging effects
can occur [100].
The use of granular media in a column configuration also needs to take into account the
occurrence of coalescence [4]. Wang et al. [101] have tried to circumvent this problem
by using a fluidised bed of hydrophobic nanogels. Since nanogels are less dense than
water, the configuration used was inverse fluidisation (Figure 2). In order to improve
operation, the authors tested combinations of both fixed and fluidised bed in the same
run, by switching between flowrates under and above the minimum fluidisation
velocity. The main disadvantage of a fluidised bed is the high flowrate it requires for
proper bed expansion.
Since activated carbon and other synthetic materials such as nanogels are expensive to
manufacture, many authors have been turning to natural materials, including agroindustrial wastes, in the search for a cheaper technology of O&G removal by sorption.
Most of these low-cost materials have been tested solely on batch mode for a
preliminary screening of sorption capacity; examples include rubber powder [29, 99],
fungal biomass [102], walnut shell [102], and chitosan powder and flake [24, 46, 103].
Since some materials did not present high affinity for oil by themselves, they have been
submitted to pretreatments to improve oil sorption capacity, such as surface
modification with cationic surfactant [104, 105] or silica nanoparticles [106]. Other
treatments, such as the deposition of iron oxide on the sorbents surface, have aimed to
facilitate their separation from water using magnetic properties [18]. Finally, sorption
units have been designed, such as biosorption columns of Salvinia sp. [107] and M.
rouxii [108] dead biomass.

28

Experimental sorption tests have been carried out both in oil-in-water emulsions and in
real wastewaters from several provenances. Besides oil sorption, some materials, such
as chitosan, also trigger coagulation-like mechanisms. This has been previously
addressed in section 3.2., where chitosan was mentioned as a natural coagulant. Beyond
outperforming traditional coagulants PAC and alum, chitosan powder has also been
proven to overcome adsorbents bentonite and activated carbon in oil sorption capacity
[24]. Aside from improving oil removal efficiency, chitosan also works at lower
dosages than conventional coagulants and sorbents [42].
Finally, it is worth mentioning that a lot of research in oil-absorbing materials has been
done outside of wastewater treatment technologies, with oil spill management
applications in mind instead. In this field of research, authors have focused either on
increasing oil sorption capacity by improved material synthesis, or in reducing costs of
spill decontamination by finding natural high-uptake materials. Sorbents tested with this
purpose include carbon fibre felts [109], vegetable fibres [110], walnut shell [111],
polymers [112] and iron oxide nanoparticles [113, 114]. These sorbents are of interest
since if their high affinity for oil is coupled with durability and high hydrophobicity
they may be quite effective for O&G removal from wastewaters.
Tables 10 and 11 present a summary of sorbents previously employed in oil removal
and the results obtained. In the next two sections the properties of oil sorbents and the
corresponding uptake mechanisms will be reviewed. A final section will present some
examples of desorption and oil recovery found in the literature.

4.1.Types and characteristics of sorbents

29

Several materials are reported in the literature as sorbents of O&G. As it has been
mentioned, their experimental applications range from separation of synthetic oil-inwater emulsions to real wastewaters of complex composition. Therefore, it is not easy to
establish a pattern that identifies the best types of sorbents and the respective
physicochemical characteristics and sorption capacities. Nevertheless, a review of the
studied sorbents is important to frame the proposal of a new O&G sorption treatment in
the context of the existing knowledge.
One of the most common adsorbents, which has been widely tested for many
applications, is activated carbon. However, its production is expensive due to low yields
of carbonisation coupled to high energy requirements. One of the ways to reduce the
cost of activated carbon production is to use natural carbonaceous materials as
precursors. Ngarmkam et al. [18] have used palm shell, a local resource, as a precursor
of activated carbons for the treatment of POME. Even though removals of over 90%
were achieved for ZnCl2-treated carbons, the absolute sorption capacity of either the
raw palm shell sorbents or the best performing carbons did not exceed 30-90 mg L-1, a
low value. Similar sorption capacities per mass of raw material were used in a study
with cork-based activated carbons treated with phosphoric acid [115]. Adsorption onto
commercial activated carbon has been more successfully used as a complement to other
treatment methods, improving BOD5 and COD removal in refinery wastewaters and oilfield brine [10, 11].
The main disadvantage of the use of activated carbons in O&G sorption is that oil
droplets sit at the entrance of the pores, blocking a great part of available surface area in
these materials, and not taking advantage of their most distinct property, the
development of microporosity [98, 100]. Zhou et al. [65] have advocated the use of
synthetic polymeric sorbents instead, highlighting their higher stability, selectivity and

30

lower cost. They propose a treatment with an organophilic resin modified by cationic
surfactant. Other sorbents of the same type include ethanol-grafted polyacrylonitrile
[116] and polystyrene resin [117], which were used in oil-in-water emulsion treatment,
and polyurethane foams [112] and polyester non-woven matrices [118], which were
used for oil spill management. More recently, modified polymers with incorporated
mineral adsorbents have been an innovation for the latter, with studies presenting
materials such as polyurethane foam with immobilized carbon nanotubes [119],
polyurethane foam modified with nanoclay [120] and polystyrene/polyvinylidene
fluoride nanofiber composite magnetic mats [121]. Furthermore, other synthetic
materials such as hydrophobic nanogels [101, 122, 123] have been used for both
emulsion treatment and oil spill cleanup. More recently, synthetic iron oxide
nanomaterials have been tested for oil sorption in spill situations, due to their ease of
recovery by magnetic means [113, 114] (Figure 3).
Other authors have opted for the use of natural mineral sorbents such as bentonite clay
[20, 124], vermiculite [125], sepiolite [126], clay soil and zeolite [21]. These materials
do not present high porosity but, as it has been mentioned, this is not an essential aspect
in oil sorption [98]. They work best when modified with surfactants, so that their
lipophilicity is enhanced, and in this case they are denominated as organoclays. Alther
[98] defines organoclays as clays whose surface sodium and calcium have been
exchanged for the nitrogen end of a quaternary amine. The hydrophobic tail of the
surfactant is left to contact with the solution or emulsion, thereby granting organophilic
properties to the sorbent. For the removal of oil and organic contaminants, the use of
surfactants with a long alkyl chain is preferred, since it is believed that these tails
possess more affinity towards these contaminants than short ones [127, 128]. The
modification of clays with quaternary ammonium cations has been extensively studied

31

and several applications have been researched besides the removal of oil and grease
[129, 130]. These materials can be used both in powdered and granular form [98].
Some authors have applied the idea behind clay modification with cationic surfactants
to organic materials. This was first reported by Namasivayam and Sureshkumar [131]
on coconut coir pith but only used later by Ibrahim et al. [104, 105] on barley straw with
oil sorption in mind. These researchers verified that raw barely straw had a very low
affinity towards oil and managed to improve it almost nine-fold through modification
with cetylpyridinium chloride.
Wang et al. [106] have recently proposed a superhydrophobic coating with silica
nanoparticles for kapok fibre. Even though kapok fibre presents oil affinity by itself,
this was highly enhanced by the pretreatment, with increased sorption capacities for
several types of oils and organic substances.
Organic materials with natural oil affinity can be used as O&G sorbents without any
surface modifications. Chitosan powder and flake have both been used in the treatment
of POME with better performance than coagulants alum and PAC [42] and sorbents
bentonite and activated carbon [24], as it has been previously mentioned in sections 3.2.
and 4.. Chitosan powder seems to work especially well due to its high surface area and
charge density [17]. It has been tested successfully in the removal of COD, turbidity and
electrical conductivity from VORWs [46]. Chitosan flakes have also been used in the
treatment of biodiesel wastewater [103].
Several types of dead biomass have been used in the treatment of oil-in-water
emulsions, for instance hydrophobic aquatic plant Salvinia sp. [107], non-viable fungal
cultures M. rouxii and A. coerulea [102, 108], fruiting bodies of macro-fungus
Auricularia polytricha [132], kapok (Ceiba pentandra (L.) Gaertn.) [19] and rice husks
[133]. Srinivasan and Viraraghavan [102] have suggested that the affinity of M. rouxii

32

towards oil might be partly caused by the presence of chitosan in its constitution.
Ribeiro et al. [107] evaluated sorbent hydrophobicity through a methodology that
measures the partition between an organic phase and water. Hydrophobicity has also
been used as a justification for the use of rubber powder as a sorbent in POME
treatment [99]. However, the dosages required for effective treatment by sorption onto
this material are very high.
In oil spill management, natural fibrous sorbents are an increasingly common option for
oil sorption.
A recent review by Wahi et al. [3] highlights the advantages of natural fibrous sorbents,
namely their high buoyancy and low processing cost. Abdullah et al. [134] further point
out that natural organic sorbents are easier to dispose after use and can be co-applied
with other techniques such as bioremediation. Sorption onto natural fibres has had
attention from researchers for several decades [135], but many materials, such as silk
floss [110], walnut shell [111], kapok fibres [134], and rice husks [136] have only
recently been shown to be fit for this application. Common characteristics that are
described by the authors as conducive to high oil sorption include hydrophobicity and
low specific gravity. This last feature means that the material will have tendency
towards floating in water, just like oil, therefore facilitating contact between sorbent and
pollutant when the spills occur in aqueous environments [110]. Inagaki et al. [109]
demonstrate, through different types of carbon materials, that there is an inversely
proportional correlation between apparent density and sorption capacity.
Both hydrophobicity and low specific gravity are characteristics of cork, a
lignocellulosic material (bark of Quercus suber L.). Therefore, this material is also a
natural organic sorbent indicated for the clean-up of oil spills [137]. Recent studies have

33

also demonstrated the ability of cork to sorb oil from oil-in-water emulsions [138] and
VORWs [139].

4.2.Oil sorption mechanism onto natural organic materials

There are two great types of oil/sorbent interactions to be taken into account when
examining oil sorption: absorption and adsorption. While the latter refers only to surface
interactions, namely the accumulation of adsorbate at the liquid/solid interface, the
former involves the penetration of the sorbate into the sorbent material, even if just for a
few nanometers [110]. When contacting sorbents with pure oil, i.e. in oil spill cleanup,
it is believed that both processes occur. In this scenario, oil accumulates almost
instantaneously at the surface through lipophilic interactions or coalescence, the latter
being prominent in hydrophilic materials, which do not bond easily with oil [111].
Then, absorption into the material is promoted by capillary forces [109]. These forces
are especially relevant in sorbents with hair-like features [107, 132]. Wahi et al. [3]
suggest that oil sorption occurs in a three-phase mechanism consisting of diffusion,
capillary action and agglomeration in porous and rough structures.
When the contact between oil and sorbent happens in an aqueous medium, competition
between water and oil may take place [110, 111]. Interactions between oil and water
must be taken into account, and this is often done by measuring the oils interfacial
tension. Srinivasan and Viraraghavan [111] suggest that oils with lower interfacial
tension exhibit higher uptake because they reach the pores of the sorbent more easily.
However, when the oil is emulsified, low interfacial tension will lead to the formation of
smaller oil droplets and higher kinetic stability. Emulsion stability is most commonly
evaluated through droplet size distribution and zeta potential measurements [102].

34

Surface active agents (surfactants) also influence emulsion stability and, as a

consequence, oil sorption. Benito et al. [14] have studied the influence of surfactant type
and concentration, observing higher stability in emulsions prepared with increased
surfactant dosages. Wang et al. [101, 123] have also identified the presence of surfactant
as a hindering influence in oil sorption by nanogels and Pintor et al. [139] have shown
the hindering effect of soap presence in vegetable oil-in-water emulsions.
It has been previously mentioned in section 3.2. that destabilisation of emulsions can be
carried out by charge neutralisation of oil droplets, thus promoting their aggregation.
Most authors agree that the decrease of pH contributes to emulsion destabilization, most
noticeably by bringing the zeta potential closer to zero, resulting in an improvement in
oil sorption onto several sorbent materials [17, 24, 42, 102, 138]. This works even better
when the sorbent also becomes positively charged via protonation of surface
functionalities, as in the case of amino groups in chitosan [46], thereby attracting
negatively charged colloidal particles. In this case, the action of the sorbent resembles
that of a coagulant, aggregating the oil droplets at its surface [24].
Apart from favourable electrostatic conditions, adequate agitation is also essential to
overcome surface film resistance, which is suggested by Ahmad et al. [29] to be the
main factor in the rate of sorption, due to an observation of faster kinetics with higher
mixing speed. High agitation velocities and times lead to a desirable breakage of the oil
droplets, increasing the surface area available for contact between oil and sorbent [17].
Nevertheless, speed should not be too intense to avoid redispersion of the oil droplets in
a stabilised state [24, 138]. The risk is higher when there is excess sorbent that may
promote charge reversal [46]; optimisation of sorbent dosage and mixing conditions
should be done for every application. If the film resistance is easily overcome by proper
agitation, then oil bonding to the sorbate may consist in the rate-controlling step.

35

Intraparticle diffusion and adsorption onto the porosity is then presented by some
authors as the main mass transfer mechanism [17, 99].
Many researchers agree that chemisorption occurs between oil and most sorbent
materials. Hydrophobic interactions lead to the uptake of oil and organics from the
aqueous medium by a partitioning process [98, 138, 139]. In surfactant-modified
materials, these interactions occur between the oil and the oleophilic tails at the solids
surface. These surface-modified sorbents can be regenerated without losing surface
properties since the ionic bond between solid and surfactant is stronger than the weak
bonds between surfactant and oil [4, 65].
The fact that oil sorption usually occurs by partitioning may mean that the presence of
other organic substances in solution may hinder oil uptake. However, Mirshahghassemi
et al. [114] have shown good uptake of oil by iron oxide nanoparticles even in the
presence of fulvic acids, as representatives of environmentally relevant conditions.
Oil sorption equilibria and kinetics have been described using mathematical models
which are commonly employed in the literature to interpret adsorption processes. The
Freundlich isotherm [140], which is illustrative of heterogeneous multilayer adsorption,
is the model applied by most authors to describe equilibrium data [17, 99, 107].
Nevertheless, Ibrahim et al. [104, 105] have also successfully fitted the Langmuir
isotherm equation [141], which represents monolayer adsorption, and Yang et al. [132]
have used the Langmuir-Freundlich isotherm with better results than both Langmuir and
Freundlich equations separately. As far as kinetics are concerned, oil sorption is usually
fast. In an aqueous mixture, kinetics can usually be described by pseudo-first-order
[132] or pseudo-second-order [17] empirical equations, or a combination of both [103].
Recently, Pintor et al. [138, 139] proposed a kinetic model based on an external fluid
film resistance and instantaneous partitioning at the sorbents surface.

36

4.3.Desorption/recovery

A great advantage of sorption technologies is the possibility of sorbent regeneration and

oil recovery, expanding the life cycle of the technology and creating the possibility of
product recovery. Oil desorption and recovery, especially from natural sorbents, has
plenty of room for exploration, since so far it has only been superficially covered in the
literature.
Sorbent regeneration and oil recovery has been studied by both chemical and physical
methods. Chemical methods include elution of oil using aqueous solutions and other
chemical agents. Physical methods include compression, centrifugation and other
methods using physical forces to separate the oil phase from the solid sorbent. A
summary of chemical and physical methods and the results found in the literature is
presented in Table 12.
When the oil can be recovered from the sorbent, it may be with quality enough for
reintroduction into the production line, or it may be fit for other purposes. If trace
hazardous elements are not present, the oil may be burned as an energy source [14,
111].

37

5. Conclusions

O&G is a serious concern in wastewater treatment. Its main sources are industrial
wastewaters from petroleum, metalworking and food processing facilities. Conventional
wastewater treatment plants do not decontaminate O&G effectively and may even be
affected by large concentrations of these pollutants, because they create superficial films
that can lead to clogging in pumps and piping and inhibition of microbiological activity
in activated sludge reactors.
Therefore, removal of O&G in industrial wastewaters requires specific treatment. It
usually consists of two or three sequential steps with different objectives. The primary
treatment has the goal of eliminating the free oil and suspended solids which constitute
the largest load of organic pollution. Secondary treatment aims at removing the
emulsified oil, which is dispersed so finely that it cannot be separated easily only by
buoyancy forces. Finally, tertiary treatment separates residual O&G and COD and even
other substances such as salts, using more sophisticated technologies.
Primary treatment is, in general, achieved by gravity separation. Secondary treatment,
however,

comprises

many

methodologies.

Chemical

treatment

includes

coagulation/flocculation with DAF, a common method used in practice. Effluents of

such treatment can often be forwarded to biological reactors. Electrical methods are
improvements of chemical and physical methods such as electrocoagulation and
electroflotation. The main disadvantage of chemical/electro coagulation is the
production of large amounts of hazardous sludge, which is unrecoverable and must be
disposed of. Physical methods, namely membrane separation, can achieve very high
O&G removal rates, and the retained oil in the membrane may be recovered. The main
disadvantage of this method consists in the frequent clogging of membrane pores and

38

the high energy demands. Finally, tertiary treatment can be carried out with NF, RO
membranes or AOPs, toward a goal of water reuse.
Sorption is an emerging technology that can avoid production of hazardous sludge and
avoid the large costs associated with membrane operation. Natural sorbents from either
mineral or organic provenance have the additional advantage of low cost and
environmental friendliness and have been shown to provide good O&G removal
efficiencies. High surface area, charge density and hydrophobicity are desirable
characteristics of oil sorbents, and corrugations and hair-like features can also be
advantageous by promoting oil uptake by capillary forces. Oil sorption usually occurs
by partitioning between the sorbent and the sorbate and this process has been enhanced
by surface modification of some sorbents. It has been shown that oil droplets in an
emulsion exhibit negative charge and are stabilised by the resulting droplet-droplet
repulsive forces, and the neutralisation of these droplet surface charges can be done by
reducing the pH or by positive charges at the sorbents surface. Oil sorbents may be
regenerated after saturation, especially by solvent extraction, compression and vacuum
filtration.
Sorption is therefore an emerging alternative to other O&G removal methods and more
research aiming to establish this technology in this field of wastewater treatment should
be expected in the near future. The investigation of natural sorbents and agro-industrial
residues as sorbents will continue in search for low-cost methods with environmental
benefits. At the same time, the development of sophisticated coatings with
superhydrophobic/superoleophilic properties may result in the enhancement of existing
low-cost sorbents, and with easily scaled-up technologies, may create products with
high sorption capacity and therefore high commercial interest.

39

More studies need to be carried out with different sorption reactor configurations, in
order to establish the most appropriate set-ups for the desired treatment objectives.
There is still a scarcity of published research on pilot-scale O&G sorption systems,
since most are still carried out in lab-scale batch mode. These studies are very important
in O&G removal, as O&G sorption columns are prone to problems with clogging and
sorbent swelling. Studies with these and other reactor configurations are essential to test
the efficacy of the proposed sorbents in real settings.

40

Nomenclature

List of acronyms
AOP

Advanced oxidation process

API

American Petroleum Institute

BOD5

Biochemical oxygen demand (5 days)

COD

Chemical oxygen demand

CPC

Cetylpyridinium chloride

CPI

Corrugated-plate interceptor

CTAB

Cetyltrimethylammonium bromide

DAF

Dissolved air flotation

GAC

Granular activated carbon

GP

Granular palm shell

IAF

Induced air flotation

MF

Microfiltration

MFC

Mechanically agitated flotation cell

NF

Nanofiltration

O&G

Oil and grease

PAC

Polyaluminium chloride

PEG

Polyethylene glycol

PES

Polyethersulfone

PET

Poly(ethylene terephthalate)

POME

Palm oil mill effluent

POSS

Polyhedral oligomeric silsesquioxane

PPI

Parallel-plate interceptor

41

PVDF

Polyvinylidene fluoride

PVP

Polyvinylpyrrolidone

TDI

Toluene diisocyanate

TMp

Trimethyloylpropane

TSS

Total suspended solids

UF

Ultrafiltration

UV

Ultraviolet

VORW

Vegetable oil refinery wastewater

WWTP

Wastewater treatment plant

x-PEGDA

Cross-linked poly(ethylene glycol) diacrylate

42

Acknowledgements
This work was supported by the HidroCork project Utilization of cork wastes and
byproducts for elimination of oils and fats from water financed by National Innovation
Agency (QREN-National Strategic Reference Framework), as also co-financed by
FCT/MEC and FEDER under Programme PT2020 (Project UID/EQU/50020/2013). A.
Pintor acknowledges her PhD scholarship by FCT (SFRH/BD/70142/2010). V.J.P. Vilar
acknowledges the FCT Investigator 2013 Programme (IF/01501/2013).

43

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52

Legends
Figure 1. Schematic representation of the treatment sequency in a real WWTP for
VORW. Reprinted (adapted) with permission from Pandey et al., 2003 [23]. Copyright
2003 Elsevier, License Number: 3830141313982.
Figure 2. Schematic representation of an inverse fluidization experimental setup used
for sorption of O&G from water. Reprinted (adapted) with permission from Wang et al.,
2010 [101]. Copyright 2010 Elsevier, License Number: 3830141077929.
Figure 3. Sorption of O&G using magnetically-recoverable sorbents. Reprinted
(adapted) with permission from Mirshahghassemi et al., 2015 [114]. Copyright 2015,
American Chemical Society.

53

Table 1. Physical classification of O&G droplets (adapted from Patterson [1] and Rhee
et al. [2]).

Physical class

Diameter
range

Free oil

> 150 m

Dispersed oil

20-150 m

Emulsified oil

< 20 m

Soluble or
dissolved oil
Oil-wet solids

< 5 m

Description
Droplets that rise quickly to the surface in quiescent
conditions, due to the imbalance of forces caused by
the differential density between oil and water
Droplets stabilised by electric charges and other
interparticle forces
Droplets stabilised by the chemical action of surface
active agents
Dissolved or very finely dispersed droplets
Suspended solids with oil adhered to their surface

54

Table 2. Amount produced and O&G characteristics and legislation for different sources of oily wastewaters reported in the literature.
Source of
wastewater
Oil and gas
produced water

Petroleum refinery
effluent
Metalworking
fluids

POME

VORW

Amount
produced
>300 106
barrels d-1,
World
33.6 106
barrels d-1
(minimum),
World
2 109 L y-1,
World
30 109 kg y-1
(2004), 44 109
kg y-1 (2008),
Malaysia (about
40% of world
production)
-

O&G
(mg L-1)

Limit of O&G discharge in country

Reference

Natural gas: 2.3-60

Oilfield: 2-565

30 mg L-1 (daily), 50 mg L-1

(instantaneous), Australia; 29 mg L-1
(monthly), 42 mg L-1 (daily), U.S.A.; 10
mg L-1, China; 40 mg L-1, North-East
Atlantic

[142]

1.1-3,000

10 mg L-1, China; 23 mg L-1, Brazil

[143]

20-200,000

17 mg L-1 (monthly), 35 mg L-1 (daily),

U.S.A.

[144, 145]

4,000-8,000

50 mg L-1, Malaysia

[17, 18, 146-148]

480-7,782

10 mg L-1, India; 15 mg L-1, Portugal

[23, 43, 139]

Table 3. Summary of primary treatment methods, with their advantages and disadvantages.
Method

Advantages

API separator

Simple design, easy

predictability of results

PPI separator

CPI separator

Increased capacity of
handling large flows in the
same space, increased
efficiency
Increased efficiency by
improving coalescence,
removing O&G down to
50 mg L-1 and droplets as
small as 60 m

Disadvantages
Limited capacity to handle large
flows, limited O&G removal
down to 100 mg L-1, removing
only free oil (droplet diameter
>150 m)
More sophisticated design than
the API separator

Need for more sophisticated

design and corrugated materials

Table 4. Results of chemical treatment reported in the literature.

Method

Reagent

Type of
wastewater/emulsion

O&Ginitial
(mg L-1)

O&Gfinal
(mg L-1)

O&G removal
(%)

Reference

Solvent
addition

n-hexane (ratio 6:10)

POME (pH 9)

1,089

54

95.3%

[29]

Aluminium chloride (60 mg

L-1 Al)
Ferric sulfate (50 mg L-1)
Ferric sulfate (10 mg L-1)
Ferric chloride (100 mg L-1
Fe3+) with sodium oleate (50
mg L-1) as flocculant

Lubricant/soluble oil
emulsions (50:50 w/w)
Oil processing wastewater
(pH 8.5)

3,000

90% (as COD)

[33]

200

>95%
85%

[2]

500

< 30

95%

[28]

200

>95%

[2]

345-800

104-320

48-73%

[37]

14,297

n/d

100%; 98% (as

TSS)

[16]

Coagulation

Coagulation/
flocculation
with DAF

Alum (100 mg L-1)

Coagulation/
flocculation
with
sedimentation

Alum
Ferric chloride (800 mg L-1)
with Floccin (900 mg L-1) as
flocculant
PAX-18 (polyaluminium
chloride) (27 mg L-1 Al2O3)
Aluminium sulfate (40 mg
L-1 Al2(SO4)3)
Ferric sulfate (56 mg L-1
Fe2(SO4)3
PAX-18 (polyaluminium
chloride) (200 mg L-1)

n-octane emulsion (pH 6)

with or without Tween 80
Oil processing wastewater
(pH 8.5)
VORW (technological)
Poultry processing
wastewater

87% (as COD)

Petroleum refinery
wastewater (pH 7.0)

87% (as COD)

[35]

85% (as COD)

Fish canning wastewater

759

99.5%

[36, 44]

Aluminum sulfate (200 mg

L-1 Al2(SO4)3.16H2O)
Ferric sulfate (200 mg L-1)
Ferric chloride (200 mg L-1)
Calcium chloride (100 mg L1
)
RIFLOC 1815 (organic
coagulant) (150 mg L-1)
Lime (16.6 kg d-1), Alum (5
kg d-1)

99.4%
99.5%
99.2%
97.0%
Fish canning wastewater
(pH 9.0)

405

98.6%

[44]

VORW

1,150 90

10.6 2.5

[23]

PAC (20 mg L-1 Al)

Semi-synthetic motor oil

emulsion

102.5

<5

[38]

Alum (8.0 g L-1)

PAC (6.0 g L-1)
Chitosan (0.5 g L-1)

POME

2,000

99%

[42]

Biodiesel wastewater (fatty

acids removal with acid)
(pH 6.0)

18,00022,000 (raw);
210-421
(after fatty
acids
removal)

105

98.8%

[53]

Aluminum sulfate (2 g L-1),

calcium oxide (for
neutralization)
Alum (Al2(SO4)3.18H2O
(200 mg L-1 Al3+)
Ferrous sulfate
(FeSO4.7H2O) (200 mg L-1
Fe2+)
Ferric chloride (FeCl3.6H2O)

93.6%
Slaughterhouse wastewater
(pH 7)
Slaughterhouse wastewater

275-376

88.6%

[55]

89.9%

58

Coagulation
with
sedimentation
and DAF
Coagulation
with IAF
Flocculation
with DAF

Surfactantenhanced DAF

Coagulation
with foam
separation

(100 mg L-1 Fe3+)

(pH 6)

Calcium chloride

VORW (acidulation)

2,896-4,750

104-320

Chitosan (100 mg L-1)

Olive oil-in-water emulsions

5,000

Cat-Floc K-10
(poly(dimethyl-dialylammonium chloride)) (5 mL
L-1 of a 1% v/v stock
solution)
Cetyltrimethylammonium
bromide (CTAB) (100 mg L1
)
CTAB (25 mg L-1),
Octylphenol ethylene oxide
condensate (Nonidet P.42)
(25 mg L-1)
PAC (3 mg L-1 Al), casein
(30 mg L-1)
PAC (3 mg L-1 Al), casein (3
mg L-1), linear dodecyl
benzene sulfonic acid
sodium (LAS) (10 mg L-1)
PAC (30 mg L-1 Al), casein
(10 mg L-1)

Fuel oil-in-pond water

emulsions

150
1,500
150

0
0
0

>90% (as
turbidity)
-

1,500

Fuel oil-in-brackish water

emulsions
Turpentine substitute oil-inwater emulsions

Turpentine substitute oil-inseawater emulsions

Steel manufacturing
wastewater (pH 7.0)

[37]

[40]

[66]

100%
50-100

Semi-synthetic motor oil

emulsion (pH 7)

93-97%

[39]
100%

87.4

<3

83.7

<1

445

6.7

170.0
430.5

2.2
4.1

98.7%
99.0%

[38]

59

Coagulation/
flocculation
with MFC
Flocculation in
a conventional
jet flotation cell

Flocculation in
a modified jet
flotation cell

Demulsification
with
centrifugation

PAC (50 mg L-1 Al), casein

(30 mg L-1)
PAC (20 mg L-1 Al), casein
(100 mg L-1)
PAC (30 mg L-1 Al), casein
(10 mg L-1)
Lime (170 mg L-1), with
anionic polyacrylamide (1.5
mg L-1) as flocculant
Alum (50 mg L-1), with
anionic polyacrylamide (0.5
mg L-1) as flocculant
Polyvinyl alcohol (3 mg L-1)
with sodium dodecyl sulfate
(27 mg L-1) as a frother
Polyvinyl alcohol (3 mg L-1)
with sodium dodecyl sulfate
(27 mg L-1) as a frother

Petroleum refining
wastewater (pH 8.2)
Vehicles repairing
wastewater (pH 7.0)

143.2

2.8

98.0%

1,900

58.8

96.9%

20.8

0.9

95.7%
94%

Petroleum refinery
wastewater (pH 5.5)

2,000

50-100

[8]
97%

Heavy oil-in-water
emulsions
Heavy oil-in-water
emulsions

Polyvinyl alcohol (3 mg L1
), Dismulgan (cationic
polyacrylamide) (10 mg L-1)

Produced water (effluent

from degassing vessel)
Produced water (effluent
from production separator)

Biodegradable demulsifier
WS009 (Alfa Laval) (1,000
mg L-1)

Waste cutting oil

100-400

80%

98.1

16.9

83%

161.2

21.8

86%

68.7

29.7

56.8%

123

30

76%

22,425

1,500

[41]

[41]

[13]

60

Table 5. Results from electrical methods reported in the literature.

Method

Electrodes, reagents

Iron electrodes

Electrocoagulation

Aluminum electrodes

Type of
wastewater/emulsion
Motor oil-in-water
emulsions

O&Ginitial
(mg L-1)

O&Gfinal
(mg L-1)

1,000

Refectory wastewater

45-450

>90%

[49]

Olive mill wastewater

99%

[50]

Biodiesel wastewater
(fatty acids removal with
acid) (pH > 4)

18,000-22,000
(raw); 210-421
(after fatty acids
removal)

80

99.5%

[53]

Slaughterhouse
wastewater (pH 6)

275-376

92.8%

[55]

Bilge water

93

81.4

12.5%

[57]

Soluble cutting oil-inwater emulsions

1% wt.

82% (as COD)

[60]

Olive mill wastewater

99%

[50]

VORW

98.9% (as
COD)

[51]

3,000

830

72%

[52]

143.1

>80%; 83% (as

COD)

[54]

275-376

94.7%

[55]

POME (pH 5, addition

of NaNO3 electrolyte)
Poultry slaughterhouse
wastewater (pH 2-4)
Slaughterhouse
wastewater (pH 4)

O&G removal
(%)
99% (as
turbidity)

Reference
[30]

61

Bilge water
Cutting oil-in-water
emulsions
Soluble cutting oil-inwater emulsions
Lubricant/soluble oil
emulsions (50:50 w/w)

Electroflotation

Electrocoagulation
with
electroflotation

Electroflotation
with flocculation

Electroflotation

93

40

57%

[57]

9,600

>99%

[58]

1% wt.

82% (as COD)

[60]

3,000

90% (as COD)

[33]

Cathode: stainless steel

gauze; anode: graphite
sheet

Motor oil-in-water
emulsions

1,000

40% (as
turbidity)

[30]

Cathode: stainless steel

screen; anode: lead

Crude oil-in-water
emulsions

490
1,050
1,990

55%
65%
70%

[62]

Cathode: stainless steel;

anode: aluminum

Restaurant wastewater

180-280

>95%

[56]

Crude oil-in-water
emulsions

1,050

92%

[62]

Cutting oil-in-water
emulsions

4% wt.

99%

[64]

Crude oil-in-water

1,000

99.5%

[63]

Cathode: stainless steel

screen; anode: lead;
flocculant: cationic
emulsifier Nalco 7720
(16 mg L-1)
Cathode: continuous flat
sheet of stainless steel;
anode: perforated flat
sheet of steel; flocculant:
non-ionic polyacrylamide
Cathode: stainless steel

62

with coagulation

screen; anode: titanium

coated with ruthenium
oxide; coagulant: ferric
sulfate (30 mg L-1)
Cathode: continuous flat
sheet of stainless steel;
anode: perforated flat
sheet of steel; coagulant:
ferric sulfate (200 mg L-1
Fe3+)
Cathode: continuous flat
sheet of stainless steel;
anode: perforated flat
sheet of steel; coagulant:
aluminum sulfate (200
mg L-1 Al3+)

emulsions

Cutting oil-in-water
emulsions

4% wt.

99%

[64]

Type of
wastewater/emulsion

O&Ginitial
(mg L-1)

O&Gfinal
(mg L-1)

O&G removal
(%)

Reference

Fuel oil-in-pond water

emulsions

150

1,500

150

1,500

Table 6. Results from physical methods reported in the literature.

Method

DAF

Materials

Fuel oil-in-brackish
water emulsions

[66]

63

DAF with
microbubbles

Centrifugation

Coalescence on
granular bed

Palm oil-in-water
emulsions (NaCl 30 mg
L-1)

1,009

90%

[67]

Oilfield wastewater

1,616.53

97.03%

[68]

Fuel oil (1:1:1 ratio of jet

fuel, diesel, unleaded
regular gasoline)-inpond water emulsions
Fuel oil (1:1:1 ratio of jet
fuel, diesel, unleaded
regular gasoline)-inbrackish water
emulsions
Motor oil-in-water
emulsions

142

82.42%

2,900

68.83%

142

84.62%

2,900

72.57%

1,000

50% (as
turbidity)

[30]

500

89%

[70]

264

13.3

95.8%

212

7.1

96.9%

200-3,000

4.89-53.04

96.4-99.8%

Commercial resin (Gel

polystyrene crosslinked
with divinyl benzene)

Diesel oil-in-water
emulsions

Sand (treated to achieve

oil-wet surface)

Produced water

Glass microfibers

Diesel oil-in-water
emulsions

Polyacrylonitrile fibre
Modified
polyacrylonitrile fibre
Ion-exchange resin

[69]

[72]
[74]

71-95%

Diesel oil-in-water
emulsions

630

Diesel oil-in-water

30% v/v

84.9-97.3%
83.4%

[116]
[117]
64

Membrane
separation

(Purolite OL 100, gel

polystyrene crosslinked
with divinyl benzene)
Microfiltration
membrane (Membralox
ceramic multichannel
monoliths)
Microfiltration
superhydrophilic/
superoleophobic
membranes (stainless
steel mesh 400 coated
with 20% wt fluorodecyl
polyhedral oligomeric
silsesquioxane (POSS)
and cross-linked
poly(ethylene glycol)
diacrylate (x-PEGDA))

emulsions

Acidic VORWs

2,020-3,900

93-97%

[43]

Hexadecane-in-water
emulsions

50% v/v

>99%

[75]

Microfiltration
superhydrophobic
membranes (PET textiles
coated with
polydimethylsiloxane and
polyvinyl chloride)

Sunflower oil-in-water
emulsions
n-hexane-in-water
emulsions
Crude oil-in-water
emulsions
Diesel oil-in-water
emulsions

>97%

[79]

Microfiltration

Toluene-in-water

5% v/v

>98.5%

[80]

65

superoleophobic kapok
membranes
Microfiltration tubular
ceramic membrane (Al2O3)
Microfiltration
membrane (hydrophilic
polyvinylidene fluoride
(PVDF))
Micro/ultrafiltration
membranes (hollow fiber
membranes prepared
from PVDF with
hydrophilic and
oleophobic segments)
Microfiltration (PVDF
membrane) with
ultrafiltration
(polyethersulfone (PES)
membrane) membranes
Ultrafiltration
membranes (G-series)
Ultrafiltration
membranes (tubular
ceramic membrane
Membralox, composite of
microporous zirconia

emulsions (with aqueous

dye methylene blue)
Effluent from API in
petroleum refinery

26

85%

[76]

Oil refining wastewater

(desalter plant)

3,591

21.5

99.4%

[84]

500

>98%

500

>99%

POME

91

70%

Oil refining wastewater

(desalter plant)

3,591

0.4

99.9%

[84]

POME

100

51

50%

[29]

Waste cutting oil

1,500

500

[13]

Hexadecane-in-water
emulsions
Used crude oil-in-water
emulsions

[78]

66

(ZrO2) on -Al2O3
Ultrafiltration
membranes (polysulfone
membranes with
enhanced hydrophilicity
by polyvinylpyrrolidone
(PVP) and polyethylene
glycol (PEG))
Ultrafiltration membrane
(UFPHT20-6338,
polysulfone membrane)
Ultrafiltration membrane
(polyvinylidinedifluoride)
Ultrafiltration membrane
(Ultrafilic)
Ultrafiltration membrane
(PES membrane)

100

>90%

Crude oil-in-water
emulsions

200

98.9%

VORW

90% (as COD)

370

Olive mill wastewater

Oil refining wastewater

(desalter plant)

[81]

25,100

[82]

[83]

3,591

270

18.5

99.5%

[84]

Table 7. Results from tertiary treatment reported in the literature.

Method

Materials/reagents

Type of
wastewater/emulsion

O&Ginitial
(mg L-1)

O&Gfinal
(mg L-1)

O&G removal
(%)

Reference

Membrane
separation

Nanofiltration membrane
(DK2540F polyamide/polysulfone
membrane)

Olive mill/olive wash

wastewaters

69.4-84.5% (as
COD)

[86]

67

AOPs

Nanofiltration membranes
(polysulfone membranes
containing penta-block
copolymer)
Reverse osmosis membrane
(TriSep X20 (aromatic polyamideurea suported in polysulfone))
Reverse osmosis membrane
(Osmonics SG (polyamide))
Fentons reagent (Fe2+ 23.16 g L-1,
H2O2 200.52 g L-1)
Fentons reagent (Fe2+ 30 mg L-1,
H2O2 400 mg L-1)
H2O2 (2:1 of COD)/ UV (low
pressure mercury vapor lamp, 12
W, 254 nm)
H2O2 (400 mg L-1)/UV (medium
pressure mercury vapor lamp, 400
W)
H2O2 (2:1 of C)/UV (germicidal
lamp, UV-C, 254 nm)
O3 (30 mg L-1)/UV (germicidal
lamp, UV-C, 254 nm)
Photo-Fenton (Fe2+ 50 mg L-1,
H2O2 8.4 g L-1, UV (low pressure

Engine oil-in-water
emulsions

Petroleum oil-in-water
emulsions

500-1,000

95.2-99.5%

0.15-0.6% v/v

>99%

[88]

[87]
0.15-50% v/v

>99%

1,140

86% (as COD)

[89]

480

46% (as COD)

[90]

Oil recovery industry

wastewater

1,140

55% (as COD)

[89]

Synthetic fatliquor (pH

3.5)

480

37% (as COD)

[90]

18% (as TOC)

[91]

37% (as TOC)

[91]

1,140

81% (as COD)

[89]

Oil recovery industry

wastewater
Synthetic fatliquor (pH
3.5)

Effluent from
membrane bioreactor
treatment at oil refinery
Effluent from
membrane bioreactor
treatment at oil refinery
Oil recovery industry
wastewater

68

mercury vapor lamp, 12 W, 254

nm))
Photo-Fenton (Fe2+ 0.44 mM,
H2O2 10 mM)
Electro-Fenton (Iron electrodes,
H2O2 5,000 mg L-1)
Aerated heterogeneous Fenton
process (3.91 g L-1 nano-zerovalent iron (nZVI), 1.84 g L-1
H2O2)
Solar photo-Fenton (Fe2+ 80 mg L1
, H2O2 1 g L-1 solar light from
pilot plant with compound
parabolic collectors)

Crude oil-in-water
emulsions

30

85%

[92]

Bilge water

93

29

68.8%

[57]

Anaerobically-treated
POME

1,100

75% (as COD)

[93]

Olive mill wastewater

87.3%

[22]

O&Ginitial
(mg L-1)

O&Gfinal
(mg L-1)

O&G removal
(%)

Reference

10.6

4.5

[23]

4.5

2.8

Heavy oil field wastewater

11

40% (as COD)

[96]

Ultrafiltration permeate
from metal manufacturing

92-530

93% (as COD)

(82% anaerobic/

[94]

Table 8. Results from biological treatment reported in the literature.

Type of reactor

Activated sludge
reactors

Anaerobic reactor +
aerobic reactor

Microbial consortia

Type of
wastewater/emulsion

Philodina (rotifera) and

Vorticella (protozoa) as
dominant fauna

VORW

Seed from an activated sludge

pond (mostly Pseudomonas sp.
and Bacillus sp.)
Inoculated with activated
sludge

69

11% aerobic)
Biologically
activated carbon
column

Biologically
aerated filter

Membrane
bioreactor

Acclimated sludge in
bituminous F400 GAC
Groups B350 and B350M,
immobilized on self-made
patented FPUFPS carrier
Groups B350 and B925,
immobilized on a polycin
urepan (FPU) carrier (mostly
Acinetobacter sp. and
Agrococcus sp.
Mixed halophilic bacterial
culture in a polyethylene flatsheet microfiltration membrane

Effluent from membrane

bioreactor treatment at oil
refinery

60-76%

[91]

Oilfield wastewater

20

<3

75-99%

[95]

Heavy oil field wastewater

11

24% (as COD)

[96]

Synthetic produced water

115-346

13.5-17.5

89.2-95.5%

[97]

Table 9. Comparison between methods for O&G removal in terms of advantages and disadvantages (adapted from Wahi et al. [3]).
Method

Advantages

Chemical
coagulation/flocculation
(with DAF/sedimentation/
others)

High removal efficiency

Usually easy to operate

Electrochemical
coagulation/flotation

High removal efficiency

Low reactant consumption

Disadvantages

High consumption of reactants

Production of hazardous sludge
High operative costs for higher
efficiencies (reactants, air diffusers,
etc)
Production of hazardous sludge
(possibly larger than with chemical

70

Cheaper than chemical coagulation

Physical methods (DAF,

centrifugation)

Low reactant consumption

No production of byproducts

Coalescence on granular bed

No reactant consumption
Cheap and easy to operate

Membrane separation

AOPs

High removal efficiency

Low/no reactant consumption
No production of byproducts
Possibility of recovery of the oily
retentate
Possibility of removing other pollutants
simultaneously
Possibility of total elimination of organic
pollution
Possibility of removing other pollutants
simultaneously

Biological treatment

High removal efficiency

Low reactant consumption
Cheap and easy to operate

Sorption

High removal efficiency

coagulation [52])
High installation cost
High energy requirements
Lower removal efficiency
Slow oil removal
May not be possible for all types of
wastewaters due to interference of
other pollutants (e.g. suspended
solids)
Lower removal efficiency
High energy requirements
May require pretreatment (another
upstream secondary treatment) of
wastewater
High maintenance costs due to
occurrence of membrane fouling
Lower removal efficiency
Only adequate for low-pollution
wastewaters
High reactant consumption
Production of sludge
Only adequate for biodegradable
wastewaters (may require pretreatment
(another upstream secondary
treatment))
May not be adequate for finely
71

No reactant consumption
Cheap (especially with low cost
materials)
Easy to operate
No production of byproducts
Possibility of regeneration

dispersed emulsions
May suffer interference of other
pollutants

Table 10. Results of sorption in pure oil medium reported in the literature.
Sorbent

Sorbent treatment and

characteristics
Dried biomass, > 1 mm size

Salvinia sp.
biomass
Dried biomass, < 1 mm size

Peat

Commercial, Peat Sorb, < 4

mm size
Bulk density 53.6 kg m-3

Carbon fibre felts

Bulk density 65.3 kg m-3

Bulk density 77.0 kg m-3

Type of oil

Medium of contact

qoil (g g-1)

Vaseline (aliphatic oil)

7.3

Nujol (aliphatic oil)

Marlin oil (heavy oil)
Vaseline (aliphatic oil)
Nujol (aliphatic oil)
Marlin oil (heavy oil)
Vaseline (aliphatic oil)
Nujol (aliphatic oil)
Marlin oil (heavy oil)
Heavy oil (A-grade)
Heavy oil (C-grade)
Heavy oil (A-grade)
Heavy oil (C-grade)
Heavy oil (A-grade)
Heavy oil (C-grade)

8.6
11.6
3.6
4.7
4.8
3.0
3.3
2.7
17
22
14
16
13
17

Absence of water

Absence of water

Absence of water

Reference

[107]

[107]

[109]

72

Bulk density 74.6 kg m-3

Activated carbon
fibres

Carbon fibre
fabrics
Exfoliated
graphite
Carbonized fir
fibres
Sisal (Agave
sisalana)
Mixed leaves
residues
Mixed sawdust
Coir fibre (Cocos
nucifera)
Sponge gourd
(Luffa cylindrica)
Silk floss (Chorisia
speciosa)

Bulk density 76.5 kg m-3,

surface area 720 m2 g-1
Bulk density 36.7 kg m-3,
surface area 920 m2 g-1
Bulk density 42.7 kg m-3,
surface area 1220 m2 g-1
Bulk density 190 kg m-3
Bulk density 109 kg m-3
Bulk density 7.2 kg m-3
Bulk density 5.6 kg m-3,
carbonized at 900 C
Granulometry >3.35 mm
Granulometry 0.85-1.70 mm
Granulometry >3.35 mm
Granulometry 0.85-1.70 mm
Granulometry >3.35 mm
Granulometry 0.85-1.70 mm
Granulometry >3.35 mm
Granulometry 0.85-1.70 mm
Granulometry >3.35 mm
Granulometry 0.85-1.70 mm
Specific gravity, < 0.62 g cm-3

Heavy oil (A-grade)

Heavy oil (C-grade)

11
12
10

Heavy oil (A-grade)

Absence of water

20

[109]

19
Heavy oil (A-grade)
Heavy oil (A-grade)
Heavy oil (C-grade)
Heavy oil (A-grade)
Heavy oil (C-grade)
Crude heavy oil
Crude heavy oil
Crude heavy oil
Crude heavy oil
Crude heavy oil

Crude heavy oil

Absence of water
Absence of water
Absence of water
Oil on top of deionized
water
Oil on top of deionized
water
Oil on top of deionized
water
Oil on top of deionized
water
Oil on top of deionized
water
Oil on top of deionized
water
Oil in stirred system with

6.1
7.4
83
67
78
66
3.0
6.4
1.4
2.7
4.1
6.4
1.8
5.4
1.8
4.6
87.1

[109]
[109]
[109]
[110]
[110]
[110]
[110]
[110]

[110]

85.8
73

Toluene

84.9
0.56
0.30
0.58
0.51
0.74
0.58
16

Crude oil

20

Toluene

20

Standard mineral oil

Walnut shell
media

Mean size 56.28 mm, surface

area 0.1713 m2 g-1

Canola oil
Cutting oil

Polyurethane
foams

Produced from recycled

poly(ethylene terephthalate)
(PET) bottles, glycolysed with
trimethyloylpropane (TMp)
(molar ratio 1.1), reacted with
toluene diisocyanate (TDI) (wt
ratio 1.1)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 1.1), reacted with
TDI (wt ratio 1.2)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 1.1), reacted with
TDI (wt ratio 1.3)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 2.0), reacted with
TDI (wt ratio 1.1)

deionized water
Absence of water
Oil on top of water
Absence of water
Oil on top of water
Absence of water
Oil on top of water
Absence of water

Crude oil

Absence of water

25

Toluene

Crude oil

Toluene

19

Crude oil

25

[111]

[112]

74

Produced from recycled PET

bottles, glycolysed with TMp
(molar ratio 2.0), reacted with
TDI (wt ratio 1.2)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 2.0), reacted with
TDI (wt ratio 1.3)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 3.0), reacted with
TDI (wt ratio 1.1)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 3.0), reacted with
TDI (wt ratio 1.2)
Produced from recycled PET
bottles, glycolysed with TMp
(molar ratio 3.0), reacted with
TDI (wt ratio 1.3)
Produced from recycled PET
bottles, glycolysed with
pentaerytheritol (PEr) (molar
ratio 2.0), reacted with TDI (wt
ratio 1.1)
Produced from recycled PET
bottles, glycolysed with PEr
(molar ratio 2.0), reacted with

Toluene

22

Crude oil

35

Toluene

Crude oil

Toluene

22

Crude oil

35

Toluene

28

Crude oil

40

Toluene

10

Crude oil

Toluene

14

Crude oil

20

Toluene

18

Crude oil

22

75

Polyurethane
foams with
immobilized

TDI (wt ratio 1.2)

Produced from recycled PET
bottles, glycolysed with PEr
(molar ratio 2.0), reacted with
TDI (wt ratio 1.3)
Produced from recycled PET
bottles, glycolysed with PEr
(molar ratio 3.0), reacted with
TDI (wt ratio 1.1)
Produced from recycled PET
bottles, glycolysed with PEr
(molar ratio 3.0), reacted with
TDI (wt ratio 1.2)
Produced from recycled PET
bottles, glycolysed with PEr
(molar ratio 3.0), reacted with
TDI (wt ratio 1.3)
Produced from polyol and 1,1dichloro-1-fluoroethane
Produced from polyol and 1,1dichloro-1-fluoroethane,
regenerated with toluene and
petroleum ether after first cycle
of sorption
Immobilized at 0.5% wt
Immobilized at 1% wt
Immobilized at 2% wt

Toluene

Crude oil

Toluene

10

Crude oil

15

Toluene

Crude oil

15

Toluene

Crude oil

Crude oil
Light crude oil

Oil on top of water, stirred

Oil on top of water, stirred

21.44
19.569

[119]
[120]

Light crude oil

Oil on top of water, stirred

21.692

[120]

Oil on top of water, stirred

22.66
23.39
22.86

[119]

Crude oil

76

multi-walled
carbon nanotubes

Immobilized at 3% wt

Polyurethane
foams modified
with nanoclay

Cloisite 20A, incorporated in

the structure, at 2% wt
Cloisite 20A, incorporated in
the structure, at 3% wt
Cloisite 20A, incorporated in
the structure, at 3% wt,
regenerated with toluene and
petroleum ether after first cycle
of sorption
Cloisite 20A, incorporated in
the structure, at 4% wt
Cloisite 20A, incorporated in
the structure, at 4% wt,
regenerated with toluene and
petroleum ether after first cycle
of sorption

Light crude oil

Grafting degree 25.22%

Diesel oil

PET non-woven
grafted with
lauryl acrylate
Polyvinylidene
fluoride mats

Fabricated by electrospinning

Polystyrene mats

Fabricated by electrospinning

Composite
polyvinylidene

Fabricated by electrospinning

23.67
20.325
20.408

20.284
Oil on top of water, stirred

[120]
17.699

14.970

Sunflower oil, motor oil,

soybean oil, diesel oil
Sunflower oil, motor oil,
soybean oil, diesel oil
Sunflower oil, motor oil,
soybean oil, diesel oil

Oil on top of water

17.38

[118]

Oil on top of water

11-14

[121]

Oil on top of water

74-75

[121]

Oil on top of water

44-46

[121]

77

fluoride/
polystyrene mats
Magnetic
composite
polyvinylidene
fluoride/
polystyrene mats
Hydrophobic
aerogels

Fabricated by electrospinning,
with incorporated Fe3O4
nanoparticles ( 200 nm
diameter)
Commercial, Nanogel TLD302 (1.7-2.35 mm size),
surface area 671 m2 g-1

Raw, dried
Kapok fibre

Sunflower oil, motor oil,

soybean oil, diesel oil
Vegetable oil
Motor oil
Light crude oil
Diesel oil
Crude palm oil
Diesel oil
Used engine oil
New engine oil
n-hexane
Toluene
Chloroform
Gasoline
Diesel oil

Soybean oil

Treated with NaOH

Diesel oil
Crude palm oil
Diesel oil

Oil on top of water

Absence of water

Absence of water, in a
wire-mesh basket

Absence of water, in a
stainless steel mesh

Oil on top of water

Absence of water, in a
stainless steel mesh
Oil on top of water
Absence of water, in a
wire-mesh basket

35-36

14.6
15.1
11.7
31.3
51.2
36.7
50.8
47.4
22.8
30.4
41.9
34.1
38.1
32

[121]

[123]

[19]

[134]

[106]

49.1
48.9
20.1
49
15.4-17.7

[19]
[134]
78

Surface-modified
kapok fibre

Superhydrophobic
kapok fibre

Treated with chloroform

Diesel oil

Treated with NaCl solution,

tetratethylorthosilicate, sodium
dodecyl benzene sulfonate

Diesel oil

Treated with NaClO2,

tetraethylorthosilicate, sodium
dodecyl benzene sulfonate,
ammonia and
dodecyltrimethoxysilane

Crude palm oil

n-hexane
Toluene
Chloroform
Gasoline
Diesel oil

Soybean oil
HCl-treated
bentonite
Alkali-treated rice
husks

Exfoliated
graphite

Thermallyreduced graphene

Size < 0.2 m, treated with 5%

HCl

Diesel oil

Treated with 1 M NaOH

Marine residual fuel

Commercial, bulk density 6 kg

m-3
Commercial, bulk density 10
kg m-3
Produced from graphite
following the thermal
exfoliation method, 17.9 C/O

Heavy oil (A-grade)

Crude oil
Heavy oil (B-grade)
Heavy oil (C-grade)
Heavy oil (A-grade)
Crude oil
Crude oil
Residual oil

Absence of water, in a
wire-mesh basket
Absence of water, in a
wire-mesh basket

Absence of water, in a
stainless steel mesh

Oil on top of water

Absence of water, in a
stainless steel mesh
Oil on top of water
Absence of water, in a
wire-mesh basket
Absence of water, in a
stainless steel net

Oil on top of water

Oil on top of water

Oil on top of water

20.4-20.5
33.7
56.7
41.8
56
85.5
50.5
54.2
46.9

[19]

[106]

59.8
58.8
60

[19]

19.27

[136]

83
75
75
67
70
65
131
108

[149]

[150]

79

atomic ratio

Table 11. Results of sorption in oil-water emulsions or wastewater reported in the literature.

Sorbent

Sorbent treatment and

characteristics

Clays modified with

quaternary amines

Organoclays

Commercial Cloisite
15A, modified with
dimethyl,
dehydrogenated tallow,
quaternary ammonium
Commercial Cloisite
30B, modified with
methyl, tallow, bis-2hydroxyethyl, quaternary
ammonium
Commercial sodium
montmorillonite
(Cloisite Na+), modified
with

Treatment
configuration

Organoclay/anthrazite
mix downflow filters

Type of
wastewater/
emulsion
Air compressor
condensate
containing
automatic
transmission
fluid oil

q (O&G)
(mg g-1)

O&Ginitial
(mg L-1)

O&Gfinal
(mg L-1)

3,300

240

240

O&G
removal
(%)

Reference

[98]

95.3%

Batch mode (50 mL,

sorbent dosage 2 g L1
)

Crude oil-inwater emulsions

850

97.5%

[128]

98.78%

80

tetramethylammonium
chloride
Local bentonite clay,
modified with
tetramethylammonium
chloride
Powdered
organoclay

Commercial Cloisite
30B (2-13 m size)

Mesh size < 100

Bentonite

Granules 3 mm
Raw powder, size < 0.2
m

HCl-treated
bentonite

Size < 0.2 m, treated

with 5% HCl

Bentonite
organoclay

Organoclay/anthracite
mixture with 30%
bentonite organoclay

73.41%
Fixed bed adsorption
column with
organoclay/sand
particles mix
Batch mode (1 L,
sorbent dosage 8 g L1
)
Batch mode (300 mL,
sorbent dosage 2.75.3 g L-1)
Batch mode (400 mL,
sorbent in a wiremesh basket)
Batch mode (400 mL,
sorbent in a wiremesh basket)
Batch mode (100 mL,
sorbent dosage 100 g
L-1)

Crude oil-insalty water

emulsions

100-1,200

29

[100]

POME

2,000

< 10

99%

[24]

Motor oil-inwater emulsions

150-176

15,000

19.219.6%

[126]

POME

4,200

92% (as
COD)

[19]

POME

4,200

75% (as
COD)

[19]

Mineral oil-inwater emulsions

235.2

66.5

71.7%
[124]

Cutting oil-inwater emulsions

330

6.0

98.2%

81

Expanded
vermiculite

Hydrophobized
vermiculite

Mean size 2.3 mm,

surface area 134.4 m2 g-1

Vermiculite mixed with

carnauba wax at 200 C

Batch mode (100 mL,

sorbent dosage 15 g
L-1)

Batch mode (100 mL,

sorbent dosage 15 g
L-1)

328

23.5

92.8%

Refinery effluent

5.2

0.3

94.2%

Produced water

230.9

29.7

87.2%

Mineral oil-inwater emulsions

162.95

218

45

79.0%

Canola oil-inwater emulsions

127.8

[125]

Cutting oil-inwater emulsions

102.35

170

18.0

89.4%

Refinery effluent

4.35

11.5

4.9

57.0%

Mineral oil-inwater emulsions

108.4

218

65

56.0%

Canola oil-inwater emulsions

78.14

[125]

Cutting oil-inwater emulsions

86.54

170

90

49.0%

Refinery effluent

3.07

11.5

6.5

43.0%

82

Batch mode (300 mL,

sorbent dosage 2.75.3 g L-1)
Batch mode (300 mL,
sorbent dosage 2.75.3 g L-1)

Motor oil-inwater emulsions

174-184

15,000

19.220.7%

[126]

Motor oil-inwater emulsions

166-192

15,000

18.421.4%

[126]

200

48.8%

Sepiolite

Granules 0.5-3 mm

Zeolite

Fine powder

Polystyrene
resin

Washed in hot water

Modified
polystyrene
resin

Contact of polystyrene
resin with
cetyltrimethylammonium
bromide (CTAB)

Granular
activated
carbon (GAC)

Mesh size 8 30

Adsorption column
(glass)

n-octane-inwater emulsions

Mesh size < 100

Batch mode (1 L,
sorbent dosage 12 g
L-1)

POME

Activated
carbon

Activated
carbon from
palm shell

Commercial, CGC 200

P, surface area 906 m2
g-1
Carbonization of
granular palm shell (GP)
under N2 flow, 400 C,
surface area 2.7 m2 g-1
Carbonization of GP
under N2 flow, 600 C,

Adsorption column
(glass)

n-octane-inwater emulsions

[65]
100-1,000

80%

100

90%

[65]

2,000

< 10

99%

[24]

84%
Batch mode (50 mL,
sorbent dosage 80 g
L-1)

POME

8,100

54%

[18]

57%

83

surface area 127 m2 g-1

Carbonization of GP
under N2 flow, 800 C,
surface area 365 m2 g-1
Carbonization and
physical activation of GP
with CO2, 400 C,
surface area 41 m2 g-1
Carbonization and
physical activation of GP
with CO2, 600 C,
surface area 213 m2 g-1
Carbonization and
physical activation of GP
with CO2, 800 C,
surface area 511 m2 g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 400 C,
surface area 368 m2 g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 600 C,
surface area 414 m2 g-1

62%

57%

66%

74%

63%

67%

84

Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 800 C,
2 h, surface area 1041 m2
g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 800 C,
3 h, surface area 1334 m2
g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 800 C,
4 h, surface area 1066 m2
g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 900 C,
2 h, surface area 1017 m2
g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 900 C,

86%

90%

88%

84%

86%

85

3 h, surface area 1053 m2

g-1

Activated
carbon from
cork

Magnetized
activated
carbon from
palm shell

Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 900 C,
4 h, surface area 1080 m2
g-1
Carbonization and
chemical activation of
cork granulates with
phosphoric acid, 450 C,
surface area 620 m2 g-1
Carbonization and
physical and chemical
activation of GP with
CO2 and ZnCl2, 800 C,
3 h, coated with iron
oxides (ratio 1:6),
surface area 544 m2 g-1

88%

Batch mode (45 mL,

sorbent dosage 0.5 g
L-1)

Sunflower oil-inwater emulsions

233

150-200

82%

[115]

Batch mode (50 mL,

sorbent dosage 80 g
L-1)

POME

8,100

80%

[18]

100

90.9%

n-octane-inwater emulsions

GAC +
Modified
polystyrene
resin

GAC (mesh size 8 30)

and polystyrene resin
modified with CTAB

Adsorption columns
(glass)

Modified
polystyrene

Polystyrene resin
modified with CTAB +

Adsorption columns
(glass)

n-octane-inwater emulsions

[65]
1,000

78.2%

100

81.8%

[65]

86

resin + GAC

GAC (mesh size 8 30)

Nanogel TLD 301 (0.71.2 mm size), surface

area 686 m2 g-1

Inverse fluidized bed

Batch mode (100 mL,

sorbent dosage 1 g L1
)
Hydrophobic
aerogels
Inverse fluidized bed

Nanogel TLD 302 (1.72.3 mm size), surface

area 671 m2 g-1

Inverse
packed/fluidized bed

Inverse
fluidized/packed bed

Vegetable oil-inwater emulsions

stabilized by
Tween 80 (4%)
Vegetable oil-inwater emulsions
stabilized by
Tween 80 (1%)

1,2601,430

1,000

93.6%

[101]

1,5102,130

Oily wastewater
(with jet fuel)

20

400

[123]

Vegetable oil-inwater emulsions

stabilized by
Tween 80 (4%)

1,840

[101]

Soybean oil-inwater emulsions

3,300

260

[122]

2,2602,770

Vegetable oil-inwater emulsions

stabilized by
Tween 80 (4%)
Vegetable oil-inwater emulsions
stabilized by
Tween 80 (1%)

[101]
1,910

87

Nanogel OGD 303 (1.72.3 mm size)

3,500

390

1,900

260

5,300

360

Nanogel OGD 303 (0.50.85 mm size)

Inverse fluidized bed

Soybean oil-inwater emulsions

Nanogel TLD 101 (0.50.85 mm size)

Polymercoated iron
oxide
nanoparticles
Rubber
powder

M. rouxii dead
biomass

Synthetic iron oxide

nanoparticles coated
with
polyvinylpyrrolidone
Synthetic rubber latex
powder, 60.2% w/w
dried rubber, surface
area 15.98 m2 g-1
Fungal strains cultivated
and inactivated, surface
area 20.55 m2 g-1

[122]
4,300

360

7,100

450

6,500

480

Batch mode

Crude oil-inwater emulsions

600-900

>93%

[113]

Batch mode (100 mL,

sorbent dosage 300 g
L-1)

POME (pH 7-9)

828

100

88%

[29, 99]

Mineral oil-inwater emulsions

(pH 5)

77.2

200

45.6

77%

Canola oil-inwater emulsions

92.5

Batch mode (100 mL,

sorbent dosage 2 g L1
)

[102]
200

15.0

93%

88

(pH 5)
Cutting oil-inwater emulsions
(pH 5)
Mineral oil-inwater emulsions

Powdered biomass,
immobilized in
polysulfone matrix
(0.42-2.36 mm size
beads)

Canola oil-inwater emulsions

Adsorption column
(glass)
Powdered biomass,
immobilized in
polysulfone matrix
(0.42-2.36 mm size
beads), regenerated after
first sorption cycle

A. coerulea
dead biomass

Fungal strains cultivated

and inactivated, surface
area 0.68 m2 g-1

Cutting oil-inwater emulsions

Mineral oil-inwater emulsions
Canola oil-inwater emulsions
Cutting oil-inwater emulsions

Batch mode (100 mL,

sorbent dosage 2 g L1
)

Mineral oil-inwater emulsions

(pH 5)

84

200

32.0

84%

14.67
(Thomas
model)
9.87
(Thomas
model)
10.67
(Thomas
model)
2.5
(Thomas
model)
0.03
(Thomas
model)
0.5
(Thomas
model)

50

[108]

72.1

200

55.8

72%

[102]

89

From crab shells, >85%

deacetylation, surface
area 0.65 m2 g-1

Chitosan

Batch mode (100 mL,

sorbent dosage 2 g L1
)

Canola oil-inwater emulsions

(pH 5)
Cutting oil-inwater emulsions
(pH 5)
Mineral oil-inwater emulsions
(pH 5)
Canola oil-inwater emulsions
(pH 5)
Cutting oil-inwater emulsions
(pH 5)

90.5

200

18.9

91%

200

39.8

80%

99.6

200

0.8

99%

99.9

200

0.3

99%

200

6.3

97%

[102]

White fine powder, mesh

size < 120

Batch mode (1 L,
sorbent dosage 0.5 g
L-1)

POME

2,000

< 10

99%

[24]

White fine powder, mesh

size < 120, 90%
deacetylation, surface
area 20-30 m2 g-1

Batch mode (1 L,
sorbent dosage 0.5 g
L-1)

POME

2,000

99%

[17]

VORW

79% (as
COD)

[46]

Pre-treated
biodiesel
wastewater (pH

680-1,130

160-200

66.276.0%

[103]

Powder, 80%
deacetylation
Flakes, commercial

Batch mode (500 mL,

sorbent dosage 800
mg L-1)
Batch mode (100 mL,
sorbent dosage 3.5 g
L-1)

90

4)

Flakes, size < 2.0 mm,

surface area 5-10 m2 g-1

Walnut shell
media

Surfactantmodified
barley straw

Mean size 56.28 mm,

surface area 0.17 m2 g-1

Barley straw treated with

0.05 M NaOH solution
and surfactant
cetylpyridinium chloride
(CPC), 0.5-1.18 mm
size, surface area 63.2
m2 g-1

4 consecutive batch
mode runs (100 mL,
sorbent dosage 3.5 g
L-1)
Batch mode (1 L,
sorbent dosage 0.5 g
L-1)

Batch mode (100 mL,

sorbent dosage 2 g L1
)

Batch mode (100 mL,

sorbent dosage 4-16 g
L-1)
Batch mode (100 mL,
sorbent dosage 10 g
L-1)
Batch mode (100 mL,
sorbent dosage 4-16 g
L-1))

Pre-treated
biodiesel
wastewater (pH
4)

680-1,130

40-60

95.8%

POME

2,000

80-85%

82.5

200

35.0

83%

96

200

8.0

96%

200

9.3

96%

Mineral oil-inwater emulsions

584.2
(qmax,
Langmuir)

Mineral oil-inwater emulsions

821

96%

Canola oil-inwater emulsions

613.3
(qmax,
Langmuir)

Mineral oil-inwater emulsions

(pH 5)
Canola oil-inwater emulsions
(pH 5)
Cutting oil-inwater emulsions
(pH 5)

[17]

[102]

[104]

91

Palm shell

Salvinia sp.
biomass

Peat

Regranulated
cork

Barley straw treated with

CPC, surface area 75.70
m2 g-1
Powdered, size < 355
m, surface area 1.5 m2
g-1
Dried biomass, size < 4
mm, surface area 274 m2
g-1

Commercial, Peat Sorb,

size < 4 mm, surface
area 270 m2 g-1

Produced from raw cork

by injection of steam at
380 C, size 1.0-2.0 mm

Batch mode (100 mL,

Canola oil-insorbent dosage 10 g
water emulsions
L-1)
Batch mode (100 mL,
Canola oil-insorbent dosage 4-13 g
water emulsions
L-1)
Batch mode (50 mL,
sorbent dosage 80 g
POME
L-1)
Batch mode (200 mL,
sorbent dosage 0.5 g
L-1))
Heavy oil-inCompressed filter (8 water emulsions
cm diameter, 0.5 cm
thickness)
Compressed filter (8
Heavy oil-incm diameter, 0.5 cm
water emulsions
thickness)
Batch mode (45 mL,
Sunflower oil-insorbent dosage 0.5 g
water emulsions
L-1)
Batch mode (45 mL,
Sunflower oil-insorbent dosage 1.6 g
water emulsions
L-1)
Batch mode (45 mL,
sorbent dosage 1.5VORW
-1
4.0 g L )

860

90%

576.0
(qmax,
Langmuir)

[105]

33

8,100

32%

[18]

950

800

240

[107]

1,330

90%

260

62%

[107]

79

150-200

[115]

150

15

90%

[138]

1,400

40

96%

[139]

92

Batch mode (45 mL,

sorbent dosage 1.0 g
L-1)
Batch mode (45 mL,
sorbent dosage 1.0 g
L-1)
Continuous mode in a
stirred tank
Natural wool
fibres
Recycled woolbased
nonwoven
material
Fruiting bodies
of
macrofungus
Auricularia
polytricha

Simulated
VORW (60%
soap)
Simulated
VORW (60%
soap)

210

480

92%

200

85.4%

192

200

< 15

Originated from
domestic sheep

Batch mode (300 mL,

sorbent dosage 0.10.13 g L-1)

Motor oil-inwater emulsions

33,00043,000

15,000

73-95%

[126]

Batch mode (300 mL,

sorbent dosage 0.10.13 g L-1)

Motor oil-inwater emulsions

15,00019,000

15,000

33-43%

[126]

Fruiting bodies dead

biomass, pieces 0.5 0.5
cm

Batch mode (50 mL,

sorbent dosage 4-20 g
L-1)

Mineral oil-inwater emulsions

398 (qmax,
LangmuirFreundlich)

200-3,500

[132]

POME

4,200

98% (as
COD)

Raw, dried
Kapok fibre
Treated with NaOH
Rice husks

VORW

Raw, particle size < 2

Batch mode (400 mL,

sorbent in a wiremesh basket)
Batch mode (400 mL,
sorbent in a wiremesh basket)
Batch mode (250 mL,

[19]
POME

4,200

76% (as
COD)

Crude oil-in-

454.55

10,000

49%

[133]
93

mm

sorbent dosage 10 g
L-1)

Engine oil-inwater emulsions

Raw, particle size 1-2

mm

White rice husks ash,

thermally treated at 600
C with circulation of
air, particle size < 2 mm

Thermally
treated rice
husks

Black rice husks ash,

thermally treated at 600
C with N2 flow, particle
size < 2 mm

Black rice husks ash,

thermally treated at 600
C with N2 flow, particle
size 1-2 mm

water emulsions
Spent engine oilin-water
emulsions

Batch mode (250 mL,

sorbent dosage 10 g
L-1)

Batch mode (250 mL,

sorbent dosage 10 g
L-1)

Batch mode (250 mL,

sorbent dosage 10 g
L-1)

Crude oil-inwater emulsions

Spent engine oilin-water
emulsions
Engine oil-inwater emulsions
Crude oil-inwater emulsions
Spent engine oilin-water
emulsions
Engine oil-inwater emulsions
Crude oil-inwater emulsions
Spent engine oilin-water

666.70

63%

500.00
1,250
(qmax,
Langmuir)

57%
1,00050,000

200.00
250.00

20%

10,000

23%

303.30

30%

495.05

45%
[133]

769.20

10,000

769.20
1,000
(qmax,
Langmuir)
1,250
(qmax,

75%
77%

1,00050,000

94

emulsions
Engine oil-inwater emulsions

Langmuir)
2,000
(qmax,
Langmuir)

95

Table 12. Summary of oil desorption and recovery methods found in the literature.

Method

Material

Observations

Vermiculite
Contact with
clean water

Barley straw
Dead
biomass

Contact with
NaOH solution

Chitosan

Activated
carbon
Extraction with
n-hexane
Carbon fibre
felts
Carbon fibre
Centrifugation
felts
Walnut shell
Compression Polyurethane
foams
Cotton fibres
Squeezing

Vacuum
filtration

Carbon fibre
felts
Carbon fibre
felts
Kapok fibre
Exfoliated
graphite
Thermally
reduced
graphene

Reference
[125]

Release of oil by contact with water

is very low due to hydrophobicity
of the sorbents

[104]
[108]

Significant removal of oil, but the

capacity of the sorbent declines in
the second cycle

[103]
[18]

Good oil removal and recovery

[109]
Good oil removal and sorbent
regeneration for several cycles
Good oil removal and possibility of
sorbent regeneration
Possibility of sorbent regeneration,
but with decreased capacity; too
aggressive for fragile sorbents
Good oil recovery and good
stability of sorbent regeneration for
8 to 15 cycles
Good oil recovery and no damage
to the fragile sorbent structure;
gradual loss of capacity when
regenerated

[109]
[111]
[112]
[135]
[109]
[109]
[134]
[149]
[150]

Figure 1.

Figure 2.

Figure 3.

Graphical Abstract (for review)

Primary
treatment

Secondary
treatment
Flotation, e.g. with
dissolved air (DAF)
Coagulation /
Flocculation and DAF
Electrocoagulation /
Electroflotation

Gravity separation

Oil & Grease

Other secondary/
Tertiary
treatment
Biological treatment
(activated sludge)
Advanced oxidation
(AOPs)

Centrifugation
Coalescence in a
granular bed
Membrane separation
(MF/UF)
Adsorption /
Biosorption

Membrane separation
(NF/RO)

Highlights

Oil and grease is a widespread pollutant of several types and sources;

Review of state-of-the-art technologies for oil and grease removal;

Sorption is an emerging technology with high efficiency and low cost;

Review of natural and synthetic sorbents for oil and grease removal;

Comparison of advantages and disadvantages of oil and grease removal

technologies.