Chemical Engineering Journal 297 (2016) 229–255

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

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 ⇑, Vítor J.P. Vilar, Cidália M.S. Botelho, Rui A.R. Boaventura ⇑
LSRE-Laboratory of Separation and Reaction Engineering – Associate Laboratory LSRE/LCM, Departamento de Engenharia Química, Faculdade de Engenharia da Universidade do
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Oil and grease is a widespread

pollutant of several types and Other secondary/
Primary Secondary
sources. treatment treatment Terary
treatment
 Review of state-of-the-art
Flotaon, e.g. with
technologies for oil and grease dissolved air (DAF) Biological treatment
Coagulaon / (acvated sludge)
removal. Flocculaon and DAF Advanced oxidaon
Electrocoagulaon / (AOPs)
 Sorption is an emerging technology Electroflotaon
with high efficiency and low cost. Gravity separaon
Centrifugaon
 Review of natural and synthetic Coalescence in a
granular bed
sorbents for oil and grease removal. Membrane separaon Membrane separaon
(MF/UF) (NF/RO)
 Comparison of advantages and Oil & Grease Adsorpon /
Biosorpon
disadvantages of oil and grease
removal technologies.

a r t i c l e i n f o a b s t r a c t

Article history: Oil and grease (O&G) is a class of pollutants with very low affinity to water. Their removal from
Received 19 November 2015 wastewaters is often challenging and involves the combination of different treatment technologies,
Received in revised form 22 March 2016 according to the specifications for the treated water and the O&G substances involved. O&G can be
Accepted 23 March 2016
classified according to its type and source and this influences the choice of the treatment process.
Available online 29 March 2016
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
Keywords:
accomplish removal of free oil as a primary treatment. Secondary treatments include chemical, electrical
Oil and grease
Wastewater
and physical methods which target emulsified oil, such as, coagulation/flocculation, dissolved air
Treatment flotation, electro-coagulation/flotation, and membrane separation. Tighter membranes and advanced
Sorption oxidation processes can refine treatment in a tertiary step.
Coagulation Many of these treatments present, however, disadvantages such as production of hazardous sludge
Membrane separation 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.
Ó 2016 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2. The O&G class of pollutants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

⇑ Corresponding authors. Tel.: +351 225081669; fax: +351 225081674.

E-mail addresses: ampintor@fe.up.pt (A.M.A. Pintor), bventura@fe.up.pt (R.A.R. Boaventura).

http://dx.doi.org/10.1016/j.cej.2016.03.121
1385-8947/Ó 2016 Published by Elsevier B.V.
230 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

Nomenclature

List of acronyms PEG polyethylene glycol

AOP advanced oxidation process PES polyethersulfone
API American Petroleum Institute PET poly(ethylene terephthalate)
BOD5 biochemical oxygen demand (5 days) POME palm oil mill effluent
COD chemical oxygen demand POSS polyhedral oligomeric silsesquioxane
CPC cetylpyridinium chloride PPI parallel-plate interceptor
CPI corrugated-plate interceptor PVDF polyvinylidene fluoride
CTAB cetyltrimethylammonium bromide PVP polyvinylpyrrolidone
DAF dissolved air flotation TDI toluene diisocyanate
GAC granular activated carbon TMp trimethyloylpropane
GP granular palm shell TSS total suspended solids
IAF induced air flotation UF ultrafiltration
MF microfiltration UV ultraviolet
MFC mechanically agitated flotation cell VORW vegetable oil refinery wastewater
NF nanofiltration WWTP wastewater treatment plant
O&G oil and grease x-PEGDA cross-linked poly(ethylene glycol) diacrylate
PAC polyaluminium chloride

2.1. Types of O&G . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

2.2. Sources of O&G . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
3. Treatment of wastewaters with O&G . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3.1. Primary treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3.2. Secondary treatment: chemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3.3. Secondary treatment: electrical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
3.4. Secondary treatment: physical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.5. Tertiary treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.6. Biological treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.7. Combination of treatment strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
4. Treatment of wastewaters with O&G by sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4.1. Types and characteristics of sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
4.2. Oil sorption mechanism onto natural organic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
4.3. Desorption/recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253

1. Introduction
Growth in industrial production and urbanisation, 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 overexploita-
tion 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 hydrocar-
bons, 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 process-
ing wastewaters.
Since most substances in this class have very low biodegrad-
ability, 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 biologi-
cal 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
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
Table 1
Physical classification of O&G droplets (adapted from Patterson [1] and Rhee et al. [2]).
Physical class Diameter range
Free oil >150 lm
Dispersed oil 20–150 lm
Emulsified oil <20 lm
Soluble or ‘‘dissolved” oil <5 lm
‘‘Oil-wet solids”
environment nor collected by the municipal system; an alternative
treatment strategy must be sought. There is a large body of litera-
ture 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 wastewater’s
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. How-
ever, it might be an oversimplification to correlate these chemical
properties with the previous classification. In fact, O’Brien [6]
points out that ‘‘all edible fats and oils are water-insoluble”,
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 bio-
logical origin behave like nonpolar molecules. Likewise, it is diffi-
cult 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 charac-
teristics, 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
231
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
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 consider-
ing only a few classes or by giving emphasis on the role of surfac-
tants in the emulsification of oil in water.
2.2. Sources of O&G
O&G is present in municipal wastewaters, but not in high con-
centrations: 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 activ-
ities 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 activ-
ity. 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 ‘‘non-
conventional pollutants” such as ammonia, sulphides, chlorides,
mercaptans and phenols [2,11,12].
 Metalworking wastewaters result from metal piece manufactur-
ing in materials ranging from aluminium 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 facility’s
wastewaters. Moreover, when spent, the diluted metalworking
fluids themselves consist in wastewaters with O&G concentra-
tions 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
232 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
Table 2
Amount produced and O&G characteristics and legislation for different sources of oily wastewaters reported in the literature.
Source of wastewater Amount produced
6 1
Oil and gas produced water >300  10 barrels d , World
Petroleum refinery effluent 33.6  106 barrels d 1 (minimum),
World
Metalworking fluids 2  109 L y 1, World
POME 30  109 kg y 1 (2004), 44  109 kg y
(2008), Malaysia (about 40% of world
production)
VORW – 480–7782
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, cotton-
seed, soybean and rapeseed [23].
Table 2 presents several types of wastewaters characterised 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 parallel-plate 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 emul-
sion 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 aluminium 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 electroflota-
tion 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, operat-
ing in a very similar way to a municipal wastewater treatment
1
O&G (mg L ) Limit of O&G discharge in country Reference
1 1
Natural gas: 30 mg L (daily), 50 mg L (instantaneous), Australia; [142]
1
2.3–60 Oilfield: 29 mg L (monthly), 42 mg L 1 (daily), U.S.A.;
1
2–565 10 mg L , China; 40 mg L 1, North-East Atlantic
1.1–3000 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]
1
4000–8000 50 mg L 1, Malaysia [17,18,146–148]
1 1
10 mg L , India; 15 mg L , Portugal [23,43,139]
plant (WWTP). With this methodology, removal of non-
biodegradable 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 refine-
ment 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 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 horizon-
tal 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 rectan-
gular channel coupled with an oil skimmer and a sludge pump. The
design parameters limit horizontal water velocity to 3 ft min 1
(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 impor-
tant factors governing the rise rate are differential density and vis-
cosity. 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 chan-
nel 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
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
Table 3
Summary of primary treatment methods, with their advantages and disadvantages.
Method Advantages
API separator Simple design, easy predictability of results
PPI separator Increased capacity of handling large flows in the same space,
increased efficiency
CPI separator Increased efficiency by improving coalescence, removing O&G
down to 50 mg L 1 and droplets as small as 60 lm
increase in surface area avoiding the enlargement of the reactor
itself.
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 (2–4 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 oil–water mixture. Parallel plates pro-
mote 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 lm 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 lm 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].
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 treat-
ment, since gravity separation is ineffective [28].
Chemical methods of secondary treatment consist in the addi-
tion 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
233
Disadvantages
Limited capacity to handle large flows, limited O&G removal down to
100 mg L 1, removing only free oil (droplet diameter > 150 lm)
More sophisticated design than the API separator
Need for more sophisticated design and corrugated materials
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 oil–water 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 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 installation’s 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 neutralisa-
tion, they can stimulate other mechanisms of destabilisation, such
as double layer compression, precipitation and bridging floccula-
tion [8,28,30,33]. Several authors [14,28,33,34] successfully moni-
tor the stability of the oil–water emulsion by measurement of the
zeta potential or surface charge, reporting that effective coagula-
tion is achieved when zeta potential is brought to zero.
The most common coagulants used in oily wastewater treat-
ment 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 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 lm 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 1–20 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
Table 4

234
Results of chemical treatment reported in the literature.
1
Method Reagent Type of wastewater/emulsion O&Ginitial (mg L ) O&Gfinal O&G removal (%) Reference
(mg L 1)
Solvent addition n-hexane (ratio 6:10) POME (pH 9) 1089 54 95.3% [29]
Coagulation Aluminium chloride (60 mg L 1 Al) Lubricant/soluble oil emulsions (50:50 w/w) 3000 – 90% (as COD) [33]
Coagulation/flocculation with DAF Ferric sulfate (50 mg L 1) Oil processing wastewater (pH 8.5) 200 – >95% [2]
Ferric sulfate (10 mg L 1) 85%
Ferric chloride (100 mg L 1 Fe3+) with sodium n-octane emulsion (pH  6) with or without Tween 500 <30 95% [28]
oleate (50 mg L 1) as flocculant 80
Alum (100 mg L 1) Oil processing wastewater (pH 8.5) 200 – >95% [2]
Alum VORW (technological) 345–800 104–320 48–73% [37]
Ferric chloride (800 mg L 1) with Floccin Poultry processing wastewater 14,297 n/d 100%; 98% (as [16]
(900 mg L 1) as flocculant TSS)
Coagulation/flocculation with PAX-18 (polyaluminium chloride) Petroleum refinery wastewater (pH 7.0) – – 87% (as COD) [35]
sedimentation (27 mg L 1 Al2O3)
Aluminium sulfate (40 mg L 1 Al2(SO4)3) 87% (as COD)
Ferric sulfate (56 mg L 1 Fe2(SO4)3) 85% (as COD)

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

PAX-18 (polyaluminium chloride) (200 mg L 1) Fish canning wastewater 759 – 99.5% [36,44]
Aluminium sulfate (200 mg L 1 Al2(SO4)3.16H2O) 99.4%
Ferric sulfate (200 mg L 1) 99.5%
Ferric chloride (200 mg L 1) 99.2%
Calcium chloride (100 mg L 1) 97.0%
RIFLOC 1815 (organic coagulant) (150 mg L 1) Fish canning wastewater (pH 9.0) 405 – 98.6% [44]
Lime (16.6 kg d 1), Alum (5 kg d 1) VORW 1150 ± 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) POME 2000 – 99% [42]
PAC (6.0 g L 1)
Chitosan (0.5 g L 1)
Aluminum sulfate (2 g L 1), calcium oxide (for Biodiesel wastewater (fatty acids removal with acid) 18,000–22,000 (raw); 105 98.8% [53]
neutralization) (pH 6.0) 210–421 (after fatty
acids removal)
Alum (Al2(SO4)3.18H2O (200 mg L 1 Al3+) Slaughterhouse wastewater (pH 7) 275–376 – 93.6% [55]
Ferrous sulfate (FeSO4.7H2O) (200 mg L 1 Fe2+) 88.6%
Ferric chloride (FeCl3.6H2O) (100 mg L 1 Fe3+) Slaughterhouse wastewater (pH 6) 89.9%
Coagulation with sedimentation and Calcium chloride VORW (acidulation) 2896–4750 104–320 93–97% [37]
DAF
1
Coagulation with IAF Chitosan (100 mg L ) Olive oil-in-water emulsions 5000 – >90% (as [40]
turbidity)
Flocculation with DAF Cat-Floc K-10 (poly(dimethyl-dialyl-ammonium Fuel oil-in-pond water emulsions 150 0 – [66]
chloride)) (5 mL L 1 of a 1% v/v stock solution) 1500 0 –
Fuel oil-in-brackish water emulsions 150 0 –
1500 5 –
Surfactant-enhanced DAF Cetyltrimethylammonium bromide (CTAB) Turpentine substitute oil-in-water emulsions 50–100 – 100% [39]
(100 mg L 1)
CTAB (25 mg L 1), Octylphenol ethylene oxide Turpentine substitute oil-in-seawater emulsions 100%
condensate (Nonidet P.42) (25 mg L 1)
Coagulation with foam separation PAC (3 mg L 1 Al), casein (30 mg L 1) Semi-synthetic motor oil emulsion (pH 7) 87.4 <3 – [38]
PAC (3 mg L 1 Al), casein (3 mg L 1), linear dodecyl 83.7 <1 –
benzene sulfonic acid sodium (LAS) (10 mg L 1) 445 6.7 –
PAC (30 mg L 1 Al), casein (10 mg L 1) Steel manufacturing wastewater (pH 7.0) 170.0 2.2 98.7%
430.5 4.1 99.0%
1
PAC (50 mg L Al), casein (30 mg L 1) 143.2 2.8 98.0%
1
PAC (20 mg L Al), casein (100 mg L 1) Petroleum refining wastewater (pH 8.2) 1900 58.8 96.9%
1
PAC (30 mg L Al), casein (10 mg L 1) Vehicles repairing wastewater (pH 7.0) 20.8 0.9 95.7%
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255 235

similar characteristics is induced air flotation (IAF), though it relies

Reference

on the production of larger bubbles and higher turbulence [40].

Other flotation techniques which have just recently been intro-

[41]

[41]

[13]
[8]

duced in wastewater treatment have been tested. Foam separation,

a method widely applied in ore flotation, relies in the spontaneous
O&G removal (%)

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
56.8%
suspended solids [38]. Another technology, mechanically agitated
94%

97%

83%
86%

76%
80%

– flotation cell (MFC), promotes higher turbulence than DAF or IAF

and has higher capacity than those traditional flotation methods.
(mg L 1)
O&Gfinal

50–100

Despite the increase in energy efficiency, MFC treatment could

1500
16.9
21.8
29.7

not achieve O&G concentrations below 50 mg L 1 [8]. In another

30
–

approach, Santander et al. [41] could achieve 80–85% O&G removal

from petroleum wastewaters in conventional and modified jet
flotation cells. Finally, it is worth mentioning that centrifugation
)
1

has also been used to separate coagulated sludge from treated

O&Ginitial (mg L

effluent [14], but the expensive energy costs associated with this
method compare rather unfavorably to flotation techniques.
100–400

22,425

The biggest disadvantage which is often pointed out in the liter-

161.2
2000

98.1

68.7
123

ature regarding traditional chemical methods such as coagulation

with inorganic salts is the production of large amounts of hazardous
Produced water (effluent from production separator)

sludge [32,42]. Since the oil is trapped among aluminium and iron
Produced water (effluent from degassing vessel)

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
Petroleum refinery wastewater (pH 5.5)

in place of inorganic salts, in order to minimise the hazardousness

of the sludge and develop a cleaner process. Synthetic organic poly-
mers have been used for this purpose by Karhu et al. [34] and
Heavy oil-in-water emulsions

Heavy oil-in-water emulsions

Type of wastewater/emulsion

Cristóvão 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
Waste cutting oil

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
Polyvinyl alcohol (3 mg L 1) with sodium dodecyl

Polyvinyl alcohol (3 mg L 1) with sodium dodecyl

[42,46]. The positive charge of chitosan particles attracts negatively

Polyvinyl alcohol (3 mg L 1), Dismulgan (cationic
Lime (170 mg L 1), with anionic polyacrylamide

Alum (50 mg L 1), with anionic polyacrylamide

charged oil droplets and other suspended solids [24]. Ahmad et al.
Biodegradable demulsifier WS009 (Alfa Laval)

[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
sulfate (27 mg L 1) as a frother

sulfate (27 mg L 1) as a frother

sedimentation time. Chi and Cheng [45] have achieved similar con-
polyacrylamide) (10 mg L 1)

clusions in the treatment of milk processing wastewater samples;

(0.5 mg L 1) as flocculant
(1.5 mg L 1) as flocculant

following a cost-benefit analysis, they concluded that the use of

chitosan does not increase costs while providing operating benefits.
More recently, chemical transformations have been carried out on
(1000 mg L 1)

chitosan in order to enhance its flocculating properties [47].

Regardless of the type of coagulant used, it must be noted
Reagent

that chemical treatment may not lead to full compliance with

wastewater discharge limits. For stricter regulations, the remain-
ing O&G will still need further reduction, and coagulation is
Flocculation in a modified jet flotation

ineffective in the removal of dissolved organic matter [37,45].

Demulsification with centrifugation
Coagulation/flocculation with MFC

Aslan et al. [48] have shown, through chemical oxygen demand

Flocculation in a conventional jet

(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].
Table 4 (continued)

flotation cell

3.3. Secondary treatment: electrical methods

Method

cell

Electrical methods take advantage of electrochemistry to

increase the efficiency of coagulation and flotation processes. In
 236
Table 5
Results from electrical methods reported in the literature.
1
Method Electrodes, reagents Type of wastewater/emulsion O&Ginitial (mg L ) O&Gfinal O&G removal (%) Refs.
(mg L 1)
Electrocoagulation Iron electrodes Motor oil-in-water emulsions 1000 – 99% (as turbidity) [30]
Refectory wastewater 45–450 – >90% [49]
Olive mill wastewater – – 99% [50]
Biodiesel wastewater (fatty acids removal with 18,000–22,000 (raw); 80 99.5% [53]
acid) (pH > 4) 210–421 (after fatty acids
removal)

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

Slaughterhouse wastewater (pH 6) 275–376 – 92.8% [55]
Bilge water 93 81.4 12.5% [57]
Soluble cutting oil-in-water emulsions 1% wt. – 82% (as COD) [60]
Aluminium electrodes Olive mill wastewater – – 99% [50]
VORW – – 98.9% (as COD) [51]
POME (pH 5, addition of NaNO3 electrolyte) 3000 830 72% [52]
Poultry slaughterhouse wastewater (pH 2–4) 143.1 – >80%; 83% (as [54]
COD)
Slaughterhouse wastewater (pH 4) 275–376 – 94.7% [55]
Bilge water 93 40 57% [57]
Cutting oil-in-water emulsions 9600 – >99% [58]
Soluble cutting oil-in-water emulsions 1% wt. – 82% (as COD) [60]
Lubricant/soluble oil emulsions (50:50 w/w) 3000 – 90% (as COD) [33]
Electroflotation Cathode: stainless steel gauze; anode: graphite sheet Motor oil-in-water emulsions 1000 – 40% (as turbidity) [30]
Cathode: stainless steel screen; anode: lead Crude oil-in-water emulsions 490 – 55% [62]
1050 – 65%
1990 – 70%
Electrocoagulation with Cathode: stainless steel; anode: aluminium Restaurant wastewater 180–280 – >95% [56]
electroflotation
Electroflotation with flocculation Cathode: stainless steel screen; anode: lead; flocculant: Crude oil-in-water emulsions 1050 – 92% [62]
cationic emulsifier Nalco 7720 (16 mg L 1)
Cathode: continuous flat sheet of stainless steel; anode: Cutting oil-in-water emulsions 4% wt. – 99% [64]
perforated flat sheet of steel; flocculant: non-ionic
polyacrylamide
Electroflotation with coagulation Cathode: stainless steel screen; anode: titanium coated Crude oil-in-water emulsions 1000 – 99.5% [63]
with ruthenium oxide; coagulant: ferric sulfate
(30 mg L 1)
Cathode: continuous flat sheet of stainless steel; anode: Cutting oil-in-water emulsions 4% wt. – 99% [64]
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: aluminium
sulfate (200 mg L 1 Al3+)
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
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 electro-
coagulation 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 agita-
tion 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.
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. Cañizares 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 devia-
tion 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, electrocoag-
ulation 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 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 optimising both electrocoagulation and electro-
flotation 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 pro-
ven 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 coag-
237
ulant addition. The other option is to apply other physical separa-
tion 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 able
to separate all droplets with diameters over 40 lm; 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 pro-
ducing 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 med-
ium 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 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 grav-
ity 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 operat-
ing 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 superhy-
drophilic (contact angle with water > 150°) and from super-
oleophilic (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
 238
Table 6
Results from physical methods reported in the literature.
1
Method Materials Type of wastewater/emulsion O&Ginitial (mg L ) O&Gfinal O&G Refs.
(mg L 1) removal (%)
DAF – Fuel oil-in-pond water emulsions 150 5 – [66]
1500 5 –
Fuel oil-in-brackish water emulsions 150 0 –
1500 5 -
DAF with microbubbles – Palm oil-in-water emulsions (NaCl 30 mg L 1) 1009 – 90% [67]
Oilfield wastewater 1616.53 – 97.03% [68]
Centrifugation – Fuel oil (1:1:1 ratio of jet fuel, diesel, unleaded 142 – 82.42% [69]
regular gasoline)-in-pond water emulsions 2900 – 68.83%
Fuel oil (1:1:1 ratio of jet fuel, diesel, unleaded 142 – 84.62%
regular gasoline)-in-brackish water emulsions 2900 – 72.57%
Motor oil-in-water emulsions 1000 – 50% (as turbidity) [30]

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

Coalescence on Commercial resin (Gel polystyrene crosslinked with divinyl Diesel oil-in-water emulsions 500 – 89% [70]
granular bed benzene)
Sand (treated to achieve oil-wet surface) Produced water 264 13.3 95.8% [72]
212 7.1 96.9%
Glass microfibers Diesel oil-in-water emulsions 200–3000 4.89–53.04 96.4–99.8% [74]
Polyacrylonitrile fibre Diesel oil-in-water emulsions 630 – 71–95% [116]
Modified polyacrylonitrile fibre 84.9–97.3%
Ion-exchange resin (Purolite OL 100, gel polystyrene crosslinked Diesel oil-in-water emulsions 30% v/v – 83.4% [117]
with divinyl benzene)
Membrane separation Microfiltration membrane (Membralox ceramic multichannel Acidic VORWs 2020–3900 – 93–97% [43]
monoliths)
Microfiltration superhydrophilic/superoleophobic membranes Hexadecane-in-water emulsions 50% v/v – >99% [75]
(stainless steel mesh 400 coated with 20% wt fluorodecyl
polyhedral oligomeric silsesquioxane (POSS) and cross-linked
poly(ethylene glycol) diacrylate (x-PEGDA))
Microfiltration superhydrophobic membranes (PET textiles coated Sunflower oil-in-water emulsions – – >97% [79]
with polydimethylsiloxane and polyvinyl chloride) n-hexane-in-water emulsions
Crude oil-in-water emulsions
Diesel oil-in-water emulsions
Microfiltration superoleophobic kapok membranes Toluene-in-water emulsions (with aqueous 5% v/v – >98.5% [80]
dye methylene blue)
Microfiltration tubular ceramic membrane (a-Al2O3) Effluent from API in petroleum refinery 26 4 85% [76]
Microfiltration membrane (hydrophilic polyvinylidene fluoride Oil refining wastewater (desalter plant) 3591 21.5 99.4% [84]
(PVDF))
Micro/ultrafiltration membranes (hollow fiber membranes Hexadecane-in-water emulsions 500 – >98% [78]
prepared from PVDF with hydrophilic and oleophobic segments) Used crude oil-in-water emulsions 500 – >99%
POME 91 – 70%
Microfiltration (PVDF membrane) with ultrafiltration Oil refining wastewater (desalter plant) 3591 0.4 99.9% [84]
(polyethersulfone (PES) membrane) membranes
Ultrafiltration membranes (G-series) POME 100 51 50% [29]
Ultrafiltration membranes (tubular ceramic membrane Waste cutting oil 1500 500 – [13]
Membralox, composite of microporous zirconia (ZrO2) on a-Al2O3
Ultrafiltration membranes (polysulfone membranes with Crude oil-in-water emulsions 100 – >90% [81]
enhanced hydrophilicity by polyvinylpyrrolidone (PVP) and 200 – 98.9%
polyethylene glycol (PEG))
Ultrafiltration membrane (UFPHT20-6338, polysulfone VORW – – 90% (as COD) [82]
membrane)
Ultrafiltration membrane (polyvinylidine-difluoride) Olive mill wastewater 25100 370 – [83]
Ultrafiltration membrane (Ultrafilic) 270 –
Ultrafiltration membrane (PES membrane) Oil refining wastewater (desalter plant) 3591 18.5 99.5% [84]
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
working with microfiltration (MF), ultrafiltration (UF), nanofiltra-
tion (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 treat-
ment 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 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 superhydropho-
bic 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.
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 petro-
leum 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 nanofil-
tration membranes could separate engine oil in water at a concen-
tration 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 feed’s oil concentration.
239
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 treat-
ment. Many methodologies, from chemical oxidation to solar ultra-
violet (UV) radiation photocatalysis, have been studied for this
purpose, for instance, Fenton’s reagent (Fe2+/H2O2) [89,90], H2O2/
UV [89–91], electro-Fenton [57], photo-Fenton (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 concentra-
tions 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 consti-
tuted 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 (coagula-
tion/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.
Other typologies of biological reactors have also been tested
for oily wastewater remediation, such as anaerobic/aerobic sys-
tems [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 men-
tioned 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 (Fig. 1). The final effluent
is compliant with limits of discharge.
 240
Table 7
Results from tertiary treatment reported in the literature.

Method Materials/reagents Type of wastewater/emulsion O&Ginitial O&Gfinal O&G removal Refs.

(mg L 1) (mg L 1) (%)
Membrane separation Nanofiltration membrane (DK2540F polyamide/polysulfone membrane) Olive mill/olive wash wastewaters – – 69.4–84.5% (as [86]
COD)
Nanofiltration membranes (polysulfone membranes containing penta-block copolymer) Engine oil-in-water emulsions 500–1000 – 95.2–99.5% [88]
Reverse osmosis membrane (TriSep X20 (aromatic polyamide-urea suported in polysulfone)) Petroleum oil-in-water emulsions 0.15–0.6% – >99% [87]
v/v
Reverse osmosis membrane (Osmonics SG (polyamide)) 0.15–50% – >99%
v/v
AOPs Fenton’s reagent (Fe2+ 23.16 g L 1, H2O2 200.52 g L 1) Oil recovery industry wastewater 1140 – 86% (as COD) [89]
Fenton’s reagent (Fe2+ 30 mg L 1, H2O2 400 mg L 1) Synthetic fatliquor (pH 3.5) 480 – 46% (as COD) [90]
H2O2 (2:1 of COD)/UV (low pressure mercury vapour lamp, 12 W, 254 nm) Oil recovery industry wastewater 1140 – 55% (as COD) [89]
H2O2 (400 mg L 1)/UV (medium pressure mercury vapour lamp, 400 W) Synthetic fatliquor (pH 3.5) 480 – 37% (as COD) [90]
H2O2 (2:1 of C)/UV (germicidal lamp, UV-C, 254 nm) Effluent from membrane bioreactor treatment at – – 18% (as TOC) [91]
oil refinery

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1
O3 (30 mg L )/UV (germicidal lamp, UV-C, 254 nm) Effluent from membrane bioreactor treatment at – – 37% (as TOC) [91]
oil refinery
Photo-Fenton (Fe2+ 50 mg L 1, H2O2 8.4 g L 1, UV (low pressure mercury vapour lamp, 12 W, Oil recovery industry wastewater 1140 – 81% (as COD) [89]
254 nm))
Photo-Fenton (Fe2+ 0.44 mM, H2O2 10 mM) Crude oil-in-water emulsions 30 5 85% [92]
Electro-Fenton (Iron electrodes, H2O2 5000 mg L 1) Bilge water 93 29 68.8% [57]
Aerated heterogeneous Fenton process (3.91 g L 1 nano-zero-valent iron (nZVI), 1.84 g L 1 Anaerobically-treated POME 1100 – 75% (as COD) [93]
H2O2)
Solar photo-Fenton (Fe2+ 80 mg L 1, H2O2 1 g L 1 solar light from pilot plant with compound Olive mill wastewater – – 87.3% [22]
parabolic collectors)

Table 8
Results from biological treatment reported in the literature.

Type of reactor Microbial consortia Type of wastewater/emulsion O&Ginitial O&Gfinal O&G removal (%) Refs.
(mg L 1) (mg L 1)
Activated sludge reactors Philodina (rotifera) and Vorticella (protozoa) as dominant fauna VORW 10.6 4.5 – [23]
4.5 2.8
Seed from an activated sludge pond (mostly Pseudomonas sp. and Bacillus sp.) Heavy oil field wastewater 11 – 40% (as COD) [96]
Anaerobic reactor Inoculated with activated sludge Ultrafiltration permeate from metal 92–530 – 93% (as COD) (82% [94]
+ aerobic reactor manufacturing anaerobic/11% aerobic)
Biologically activated Acclimated sludge in bituminous F400 GAC Effluent from membrane bioreactor – – 60–76% [91]
carbon column treatment at oil refinery
Biologically aerated filter Groups B350 and B350M, immobilized on self-made patented FPUFPS carrier Oilfield wastewater 20 <3 75–99% [95]
Groups B350 and B925, immobilized on a polycin urepan (FPU) carrier (mostly Heavy oil field wastewater 11 – 24% (as COD) [96]
Acinetobacter sp. and Agrococcus sp.
Membrane bioreactor Mixed halophilic bacterial culture in a polyethylene flat-sheet microfiltration Synthetic produced water 115–346 13.5–17.5 89.2–95.5% [97]
membrane
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
Fig. 1. Schematic representation of the treatment sequency in a real WWTP for VORW. Reprinted (adapted) with permission from Pandey et al., 2003 [23]. Copyright Ó 2003
Elsevier, License Number: 3830141313982.
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 drainage system by a sequence of filtration, demulsifi
cation/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 separa-
tion 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 sorp-
tion as a follow-up to coagulation and sedimentation. Dalmacija
et al. [10] and Hami et al. [11] have used sorbents as a direct com-
plement 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 disad-
vantages 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.
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
241
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 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 (Fig. 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.
242 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

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

Method Advantages Disadvantages

Chemical coagulation/flocculation (with
DAF/sedimentation/others)
Electrochemical coagulation/flotation
Physical methods (DAF, centrifugation)
Coalescence on granular bed
Membrane separation
AOPs
Biological treatment
Sorption
 High removal efficiency
 Usually easy to operate
 High removal efficiency
 Low reactant consumption
 Cheaper than chemical coagulation
 Low reactant consumption
 No production of byproducts
 No reactant consumption
 Cheap and easy to operate
 High removal efficiency
 Low/no reactant consumption
 No production of byproducts
 Possibility of recovery of the oily
retentate
 Possibility of removing other pol-
lutants simultaneously
 Possibility of total elimination of
organic pollution
 Possibility of removing other pol-
lutants simultaneously
 High removal efficiency
 Low reactant consumption
 Cheap and easy to operate
 High removal efficiency
 No reactant consumption
 Cheap (especially with low cost
materials)
 Easy to operate
 No production of byproducts
 Possibility of regeneration
 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 coag-
ulation [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 dispersed emulsions
 May suffer interference of other pollutants

[104,105] or silica nanoparticles [106]. Other treatments, such as

Fig. 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 Ó 2010 Elsevier, License Number: 3830141077929.
Since activated carbon and other synthetic materials such as
nanogels are expensive to manufacture, many authors have been
turning to natural materials, including agro-industrial 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
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 biosorp-
tion columns of Salvinia sp. [107] and M. rouxii [108] dead biomass.
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 coagu-
lant. 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 treat-
ment 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.
Table 10
Results of sorption in pure oil medium reported in the literature.

Sorbent Sorbent treatment and characteristics Type of oil Medium of contact qoil Refs.
1
(g g )
Salvinia sp. biomass Dried biomass, >1 mm size Vaseline (aliphatic oil) Absence of water 7.3 [107]
Nujol (aliphatic oil) 8.6
Marlin oil (heavy oil) 11.6
Dried biomass, <1 mm size Vaseline (aliphatic oil) 3.6
Nujol (aliphatic oil) 4.7
Marlin oil (heavy oil) 4.8
Peat Commercial, Peat Sorb, <4 mm size Vaseline (aliphatic oil) Absence of water 3.0 [107]
Nujol (aliphatic oil) 3.3
Marlin oil (heavy oil) 2.7
3
Carbon fibre felts Bulk density 53.6 kg m Heavy oil (A-grade) Absence of water 17 [109]
Heavy oil (C-grade) 22
3
Bulk density 65.3 kg m Heavy oil (A-grade) 14
Heavy oil (C-grade) 16
3
Bulk density 77.0 kg m Heavy oil (A-grade) 13

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Heavy oil (C-grade) 17
3
Bulk density 74.6 kg m Heavy oil (A-grade) 11
Heavy oil (C-grade) 12
Activated carbon fibres Bulk density 76.5 kg m 3, surface area 720 m2 g 1 Heavy oil (A-grade) Absence of water 10 [109]
Bulk density 36.7 kg m 3, surface area 920 m2 g 1 20
Bulk density 42.7 kg m 3, surface area 1220 m2 g 1 19
Carbon fibre fabrics Bulk density 190 kg m 3 Heavy oil (A-grade) Absence of water 6.1 [109]
Bulk density 109 kg m 3 7.4
Exfoliated graphite Bulk density 7.2 kg m 3 Heavy oil (A-grade) Absence of water 83 [109]
Heavy oil (C-grade) 67
3
Carbonised fir fibres Bulk density 5.6 kg m , carbonised at 900 °C Heavy oil (A-grade) Absence of water 78 [109]
Heavy oil (C-grade) 66
Sisal (Agave sisalana) Granulometry > 3.35 mm Crude heavy oil Oil on top of deionized 3.0 [110]
Granulometry 0.85–1.70 mm water 6.4
Mixed leaves residues Granulometry > 3.35 mm Crude heavy oil Oil on top of deionized 1.4 [110]
Granulometry 0.85–1.70 mm water 2.7
Mixed sawdust Granulometry > 3.35 mm Crude heavy oil Oil on top of deionized 4.1 [110]
Granulometry 0.85–1.70 mm water 6.4
Coir fibre (Cocos nucifera) Granulometry > 3.35 mm Crude heavy oil Oil on top of deionized 1.8 [110]
Granulometry 0.85–1.70 mm water 5.4
Sponge gourd (Luffa cylindrica) Granulometry > 3.35 mm Crude heavy oil Oil on top of deionized 1.8 [110]
Granulometry 0.85–1.70 mm water 4.6
Silk floss (Chorisia speciosa) Specific gravity, <0.62 g cm 3 Crude heavy oil Oil on top of deionized 87.1 [110]
water
Oil in stirred system with 85.8
deionized water
Absence of water 84.9
Walnut shell media Mean size 56.28 mm, surface area 0.1713 m2 g 1
Standard mineral oil Oil on top of water 0.56 [111]
Absence of water 0.30
Canola oil Oil on top of water 0.58
Absence of water 0.51
Cutting oil Oil on top of water 0.74
Absence of water 0.58
Polyurethane foams Produced from recycled poly(ethylene terephthalate) (PET) bottles, glycolysed with Toluene Absence of water 16 [112]
trimethyloylpropane (TMp) (molar ratio 1.1), reacted with toluene diisocyanate (TDI) Crude oil 20
(wt ratio 1.1)
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 1.1), reacted Toluene 20
with TDI (wt ratio 1.2) Crude oil 25
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 1.1), reacted Toluene 6
with TDI (wt ratio 1.3) Crude oil 4

243
(continued on next page)
 244
Table 10 (continued)

Sorbent Sorbent treatment and characteristics Type of oil Medium of contact qoil Refs.
1
(g g )
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 2.0), reacted Toluene 19
with TDI (wt ratio 1.1) Crude oil 25
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 2.0), reacted Toluene 22
with TDI (wt ratio 1.2) Crude oil 35
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 2.0), reacted Toluene 8
with TDI (wt ratio 1.3) Crude oil 6
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 3.0), reacted Toluene 22
with TDI (wt ratio 1.1) Crude oil 35
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 3.0), reacted Toluene 28
with TDI (wt ratio 1.2) Crude oil 40
Produced from recycled PET bottles, glycolysed with TMp (molar ratio 3.0), reacted Toluene 10
with TDI (wt ratio 1.3) Crude oil 8
Produced from recycled PET bottles, glycolysed with pentaerytheritol (PEr) (molar Toluene 14
ratio 2.0), reacted with TDI (wt ratio 1.1) Crude oil 20
Produced from recycled PET bottles, glycolysed with PEr (molar ratio 2.0), reacted Toluene 18

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

with TDI (wt ratio 1.2) Crude oil 22
Produced from recycled PET bottles, glycolysed with PEr (molar ratio 2.0), reacted Toluene 9
with TDI (wt ratio 1.3) Crude oil 7
Produced from recycled PET bottles, glycolysed with PEr (molar ratio 3.0), reacted Toluene 10
with TDI (wt ratio 1.1) Crude oil 15
Produced from recycled PET bottles, glycolysed with PEr (molar ratio 3.0), reacted Toluene 8
with TDI (wt ratio 1.2) Crude oil 15
Produced from recycled PET bottles, glycolysed with PEr (molar ratio 3.0), reacted Toluene 4
with TDI (wt ratio 1.3) Crude oil 3
Produced from polyol and 1,1-dichloro-1-fluoroethane Crude oil Oil on top of water, stirred 21.44 [119]
Light crude oil Oil on top of water, stirred 19.569 [120]
Produced from polyol and 1,1-dichloro-1-fluoroethane, regenerated with toluene and Light crude oil Oil on top of water, stirred 21.692 [120]
petroleum ether after first cycle of sorption
Polyurethane foams with immobilized multi-walled Immobilized at 0.5% wt Crude oil Oil on top of water, stirred 22.66 [119]
carbon nanotubes Immobilized at 1% wt 23.39
Immobilized at 2% wt 22.86
Immobilized at 3% wt 23.67
Polyurethane foams modified with nanoclay Cloisite 20A, incorporated in the structure, at 2% wt Light crude oil Oil on top of water, stirred 20.325 [120]
Cloisite 20A, incorporated in the structure, at 3% wt 20.408
Cloisite 20A, incorporated in the structure, at 3% wt, regenerated with toluene and 20.284
petroleum ether after first cycle of sorption
Cloisite 20A, incorporated in the structure, at 4% wt 17.699
Cloisite 20A, incorporated in the structure, at 4% wt, regenerated with toluene and 14.970
petroleum ether after first cycle of sorption
PET non-woven grafted with lauryl acrylate Grafting degree 25.22% Diesel oil Oil on top of water 17.38 [118]
Polyvinylidene fluoride mats Fabricated by electrospinning Sunflower oil, motor oil, Oil on top of water 11–14 [121]
soybean oil, diesel oil
Polystyrene mats Fabricated by electrospinning Sunflower oil, motor oil, Oil on top of water 74–75 [121]
soybean oil, diesel oil
Composite polyvinylidene fluoride/polystyrene mats Fabricated by electrospinning Sunflower oil, motor oil, Oil on top of water 44–46 [121]
soybean oil, diesel oil
Magnetic composite polyvinylidene fluoride/ Fabricated by electrospinning, with incorporated Fe3O4 nanoparticles (200 nm Sunflower oil, motor oil, Oil on top of water 35–36 [121]
polystyrene mats diameter) soybean oil, diesel oil
Hydrophobic aerogels Commercial, Nanogel TLD-302 (1.7–2.35 mm size), surface area 671 m2 g 1 Vegetable oil Absence of water 14.6 [123]
Motor oil 15.1
Light crude oil 11.7
Table 10 (continued)

Sorbent Sorbent treatment and characteristics Type of oil Medium of contact qoil Refs.
1
(g g )
Kapok fibre Raw, dried Diesel oil Absence of water, in a 31.3 [19]
Crude palm oil wire-mesh basket 51.2
Diesel oil 36.7 [134]
Used engine oil 50.8
New engine oil 47.4
n-hexane Absence of water, in a 22.8 [106]
Toluene stainless steel mesh 30.4
Chloroform 41.9
Gasoline 34.1
Diesel oil 38.1
Oil on top of water 32
Soybean oil Absence of water, in a 49.1
stainless steel mesh
Oil on top of water 48.9
Treated with NaOH Diesel oil Absence of water, in a 20.1 [19]

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Crude palm oil wire-mesh basket 49
Diesel oil 15.4– [134]
17.7
Treated with chloroform Diesel oil Absence of water, in a 20.4–
wire-mesh basket 20.5
Surface-modified kapok fibre Treated with NaCl solution, tetratethylorthosilicate, sodium dodecyl benzene Diesel oil Absence of water, in a 33.7 [19]
sulfonate Crude palm oil wire-mesh basket 56.7
Superhydrophobic kapok fibre Treated with NaClO2, tetraethylorthosilicate, sodium dodecyl benzene sulfonate, n-hexane Absence of water, in a 41.8 [106]
ammonia and dodecyltrimethoxysilane Toluene stainless steel mesh 56
Chloroform 85.5
Gasoline 50.5
Diesel oil 54.2
Oil on top of water 46.9
Soybean oil Absence of water, in a 59.8
stainless steel mesh
Oil on top of water 58.8
HCl-treated bentonite Size < 0.2 lm, treated with 5% HCl Diesel oil Absence of water, in a 60 [19]
wire-mesh basket
Alkali-treated rice husks Treated with 1 M NaOH Marine residual fuel Absence of water, in a 19.27 [136]
stainless steel net
3
Exfoliated graphite Commercial, bulk density 6 kg m Heavy oil (A-grade) Oil on top of water 83 [149]
Crude oil 75
Heavy oil (B-grade) 75
Heavy oil (C-grade) 67
3
Commercial, bulk density 10 kg m Heavy oil (A-grade) Oil on top of water 70
Crude oil 65
Thermally-reduced graphene Produced from graphite following the thermal exfoliation method, 17.9 C/O atomic Crude oil Oil on top of water 131 [150]
ratio Residual oil 108

245
Table 11

246
Results of sorption in oil-water emulsions or wastewater reported in the literature.

Sorbent Sorbent treatment and characteristics Treatment configuration Type of wastewater/emulsion q (O&G) O&Ginitial O&Gfinal O&G Refs.
(mg g 1) (mg L 1) (mg removal (%)
L 1)
Organoclays Clays modified with quaternary amines Organoclay/anthrazite mix Air compressor condensate – 3300 240 – [98]
downflow filters containing automatic 240 1
transmission fluid oil
Commercial Cloisite 15A, modified with dimethyl, Batch mode (50 mL, sorbent Crude oil-in-water emulsions – 850 – 95.3% [128]
dehydrogenated tallow, quaternary ammonium dosage 2 g L 1)
Commercial Cloisite 30B, modified with methyl, tallow, 97.5%
bis-2-hydroxyethyl, quaternary ammonium
Commercial sodium montmorillonite (Cloisite Na+), 98.78%
modified with tetramethylammonium chloride
Local bentonite clay, modified with 73.41%
tetramethylammonium chloride
Powdered organoclay Commercial Cloisite 30B (2–13 lm size) Fixed bed adsorption column Crude oil-in-salty water – 100– 29 – [100]
with organoclay/sand particles emulsions 1200

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

mix
Bentonite Mesh size < 100 Batch mode (1 L, sorbent POME – 2000 <10 99% [24]
dosage 8 g L 1)
Granules 3 mm Batch mode (300 mL, sorbent Motor oil-in-water emulsions 150–176 15,000 – 19.2–19.6% [126]
dosage 2.7–5.3 g L 1)
Raw powder, size < 0.2 lm Batch mode (400 mL, sorbent POME – 4200 – 92% (as COD) [19]
in a wire-mesh basket)
HCl-treated bentonite Size < 0.2 lm, treated with 5% HCl Batch mode (400 mL, sorbent POME – 4200 – 75% (as COD) [19]
in a wire-mesh basket)
Bentonite organoclay Organoclay/anthracite mixture with 30% bentonite Batch mode (100 mL, sorbent Mineral oil-in-water emulsions – 235.2 66.5 71.7% [124]
organoclay dosage 100 g L 1) Cutting oil-in-water emulsions – 330 6.0 98.2%
328 23.5 92.8%
Refinery effluent – 5.2 0.3 94.2%
Produced water – 230.9 29.7 87.2%
2 1
Expanded vermiculite Mean size 2.3 mm, surface area 134.4 m g Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 162.95 218 45 79.0% [125]
dosage 15 g L 1) Canola oil-in-water emulsions 127.8 – – –
Cutting oil-in-water emulsions 102.35 170 18.0 89.4%
Refinery effluent 4.35 11.5 4.9 57.0%
Hydrophobized Vermiculite mixed with carnauba wax at 200 °C Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 108.4 218 65 56.0% [125]
vermiculite dosage 15 g L 1) Canola oil-in-water emulsions 78.14 – – –
Cutting oil-in-water emulsions 86.54 170 90 49.0%
Refinery effluent 3.07 11.5 6.5 43.0%
Sepiolite Granules 0.5–3 mm Batch mode (300 mL, sorbent Motor oil-in-water emulsions 174–184 15,000 – 19.2–20.7% [126]
dosage 2.7–5.3 g L 1)
Zeolite Fine powder Batch mode (300 mL, sorbent Motor oil-in-water emulsions 166–192 15,000 – 18.4–21.4% [126]
dosage 2.7–5.3 g L 1)
Polystyrene resin Washed in hot water Adsorption column (glass) n-octane-in-water emulsions – 200 – 48.8% [65]
Modified polystyrene Contact of polystyrene resin with 100– – 80%
resin cetyltrimethylammonium bromide (CTAB) 1000
Granular activated Mesh size 8  30 Adsorption column (glass) n-octane-in-water emulsions – 100 – 90% [65]
carbon (GAC)
Activated carbon Mesh size < 100 Batch mode (1 L, sorbent POME – 2000 <10 99% [24]
dosage 12 g L 1)
Activated carbon from Commercial, CGC 200 PÒ, surface area 906 m2 g 1 Batch mode (50 mL, sorbent POME – 8100 – 84% [18]
palm shell Carbonisation of granular palm shell (GP) under N2 flow, dosage 80 g L 1) 54%
400 °C, surface area 2.7 m2 g 1
Carbonisation of GP under N2 flow, 600 °C, surface area 57%
127 m2 g 1
Carbonisation of GP under N2 flow, 800 °C, surface area 62%
365 m2 g 1
Carbonisation and physical activation of GP with CO2, 57%
400 °C, surface area 41 m2 g 1
Table 11 (continued)

Sorbent Sorbent treatment and characteristics Treatment configuration Type of wastewater/emulsion q (O&G) O&Ginitial O&Gfinal O&G Refs.
(mg g 1) (mg L 1) (mg removal (%)
L 1)
Carbonisation and physical activation of GP with CO2, 66%
600 °C, surface area 213 m2 g 1
Carbonisation and physical activation of GP with CO2, 74%
800 °C, surface area 511 m2 g 1
Carbonisation and physical and chemical activation of 63%
GP with CO2 and ZnCl2, 400 °C, surface area 368 m2 g 1
Carbonisation and physical and chemical activation of 67%
GP with CO2 and ZnCl2, 600 °C, surface area 414 m2 g 1
Carbonisation and physical and chemical activation of 86%
GP with CO2 and ZnCl2, 800 °C, 2 h, surface area 1041 m2
g 1
Carbonisation and physical and chemical activation of 90%
GP with CO2 and ZnCl2, 800 °C, 3 h, surface area
1334 m2 g 1

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

Carbonisation and physical and chemical activation of 88%
GP with CO2 and ZnCl2, 800 °C, 4 h, surface area
1066 m2 g 1
Carbonisation and physical and chemical activation of 84%
GP with CO2 and ZnCl2, 900 °C, 2 h, surface area 1017 m2
g 1
Carbonisation and physical and chemical activation of 86%
GP with CO2 and ZnCl2, 900 °C, 3 h, surface area
1053 m2 g 1
Carbonisation and physical and chemical activation of 88%
GP with CO2 and ZnCl2, 900 °C, 4 h, surface area
1080 m2 g 1
Activated carbon from Carbonisation and chemical activation of cork granulates Batch mode (45 mL, sorbent Sunflower oil-in-water emulsions 233 150–200 – 82% [115]
cork with phosphoric acid, 450 °C, surface area 620 m2 g 1 dosage 0.5 g L 1)
Magnetised activated Carbonisation and physical and chemical activation of Batch mode (50 mL, sorbent POME – 8100 – 80% [18]
carbon from palm GP with CO2 and ZnCl2, 800 °C, 3 h, coated with iron dosage 80 g L 1)
shell oxides (ratio 1:6), surface area 544 m2 g 1
GAC + Modified GAC (mesh size 8  30) and polystyrene resin modified Adsorption columns (glass) n-octane-in-water emulsions – 100 – 90.9% [65]
polystyrene resin with CTAB 1000 – 78.2%
Modified polystyrene Polystyrene resin modified with CTAB + GAC (mesh size Adsorption columns (glass) n-octane-in-water emulsions – 100 – 81.8% [65]
resin + GAC 8  30) 1000 – 93.6%
Hydrophobic aerogels Nanogel TLD 301 (0.7–1.2 mm size), surface area Inverse fluidized bed Vegetable oil-in-water emulsions 1260–1430 – – – [101]
686 m2 g 1 stabilized by Tween 80 (4%)
Vegetable oil-in-water emulsions 1510–2130 – – –
stabilized by Tween 80 (1%)
Batch mode (100 mL, sorbent Oily wastewater (with jet fuel) 20 400 – – [123]
dosage 1 g L 1)
Nanogel TLD 302 (1.7–2.3 mm size), surface area 671 m2 Inverse fluidized bed Vegetable oil-in-water emulsions 1840 – – – [101]
g 1 stabilized by Tween 80 (4%)
Soybean oil-in-water emulsions 3300 260 – – [122]
Inverse packed/fluidized bed Vegetable oil-in-water emulsions 2260–2770 – – – [101]
stabilized by Tween 80 (4%)
Inverse fluidized/packed bed Vegetable oil-in-water emulsions 1910 - – –
stabilized by Tween 80 (1%)
Nanogel OGD 303 (1.7–2.3 mm size) Inverse fluidized bed Soybean oil-in-water emulsions 3500 390 – – [122]
Nanogel OGD 303 (0.5–0.85 mm size) 1900 260 – –
5300 360 – –
Nanogel TLD 101 (0.5–0.85 mm size) 4300 360 – –
7100 450 – –
6500 480 – –

247
(continued on next page)
 248
Table 11 (continued)

Sorbent Sorbent treatment and characteristics Treatment configuration Type of wastewater/emulsion q (O&G) O&Ginitial O&Gfinal O&G Refs.
(mg g 1) (mg L 1) (mg removal (%)
L 1)
Polymer-coated iron Synthetic iron oxide nanoparticles coated with Batch mode Crude oil-in-water emulsions – 600–900 – >93% [113]
oxide nanoparticles polyvinylpyrrolidone
Rubber powder Synthetic rubber latex powder, 60.2% w/w dried rubber, Batch mode (100 mL, sorbent POME (pH 7–9) – 828 100 88% [29,99]
surface area 15.98 m2 g 1 dosage 300 g L 1)
M. rouxii dead biomass Fungal strains cultivated and inactivated, surface area Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 77.2 200 45.6 77% [102]
20.55 m2 g 1 dosage 2 g L 1) (pH 5)
Canola oil-in-water emulsions 92.5 200 15.0 93%
(pH 5)
Cutting oil-in-water emulsions 84 200 32.0 84%
(pH 5)
Powdered biomass, immobilized in polysulfone matrix Adsorption column (glass) Mineral oil-in-water emulsions 14.67 (Thomas 50 – – [108]
(0.42–2.36 mm size beads) model)
Canola oil-in-water emulsions 9.87 (Thomas
model)

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

Cutting oil-in-water emulsions 10.67 (Thomas
model)
Powdered biomass, immobilized in polysulfone matrix Mineral oil-in-water emulsions 2.5 (Thomas
(0.42–2.36 mm size beads), regenerated after first model)
sorption cycle Canola oil-in-water emulsions 0.03 (Thomas
model)
Cutting oil-in-water emulsions 0.5 (Thomas
model)
A. coerulea dead biomass Fungal strains cultivated and inactivated, surface area Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 72.1 200 55.8 72% [102]
0.68 m2 g 1 dosage 2 g L 1) (pH 5)
Canola oil-in-water emulsions 90.5 200 18.9 91%
(pH 5)
Cutting oil-in-water emulsions – 200 39.8 80%
(pH 5)
Chitosan From crab shells,>85% deacetylation, surface area Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 99.6 200 0.8 99% [102]
0.65 m2 g 1 dosage 2 g L 1) (pH 5)
Canola oil-in-water emulsions 99.9 200 0.3 99%
(pH 5)
Cutting oil-in-water emulsions – 200 6.3 97%
(pH 5)
White fine powder, mesh size < 120 Batch mode (1 L, sorbent POME - 2000 <10 99% [24]
dosage 0.5 g L 1)
White fine powder, mesh size < 120, 90% deacetylation, Batch mode (1 L, sorbent POME – 2000 – 99% [17]
surface area 20–30 m2 g 1 dosage 0.5 g L 1)
Powder, 80% deacetylation Batch mode (500 mL, sorbent VORW – – – 79% (as COD) [46]
dosage 800 mg L 1)
Flakes, commercial Batch mode (100 mL, sorbent Pre-treated biodiesel wastewater – 680– 160– 66.2–76.0% [103]
dosage 3.5 g L 1) (pH 4) 1130 200
4 consecutive batch mode runs Pre-treated biodiesel wastewater – 680– 40–60 95.8%
(100 mL, sorbent dosage (pH 4) 1130
3.5 g L 1)
Flakes, size < 2.0 mm, surface area 5–10 m2 g 1
Batch mode (1 L, sorbent POME – 2000 – 80–85% [17]
dosage 0.5 g L 1)
2 1
Walnut shell media Mean size 56.28 mm, surface area 0.17 m g Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 82.5 200 35.0 83% [102]
dosage 2 g L 1) (pH 5)
Canola oil-in-water emulsions 96 200 8.0 96%
(pH 5)
Cutting oil-in-water emulsions – 200 9.3 96%
(pH 5)
Table 11 (continued)

Sorbent Sorbent treatment and characteristics Treatment configuration Type of wastewater/emulsion q (O&G) O&Ginitial O&Gfinal O&G Refs.
(mg g 1) (mg L 1) (mg removal (%)
L 1)
Surfactant-modified Barley straw treated with 0.05 M NaOH solution and Batch mode (100 mL, sorbent Mineral oil-in-water emulsions 584.2 (qmax, – – – [104]
barley straw surfactant cetylpyridinium chloride (CPC), 0.5–1.18 mm dosage 4–16 g L 1) Langmuir)
size, surface area 63.2 m2 g 1 Batch mode (100 mL, sorbent Mineral oil-in-water emulsions – 821 – 96%
dosage 10 g L 1)
Batch mode (100 mL, sorbent Canola oil-in-water emulsions 613.3 (qmax, – – –
dosage 4–16 g L 1)) Langmuir)
Batch mode (100 mL, sorbent Canola oil-in-water emulsions – 860 – 90%
dosage 10 g L 1)
2 1
Barley straw treated with CPC, surface area 75.70 m g Batch mode (100 mL, sorbent Canola oil-in-water emulsions 576.0 (qmax, – – – [105]
dosage 4–13 g L 1) Langmuir)
Palm shell Powdered, size < 355 lm, surface area 1.5 m g
2 1
Batch mode (50 mL, sorbent POME 33 8100 – 32% [18]
dosage 80 g L 1)
Salvinia sp. biomass Dried biomass, size < 4 mm, surface area 274 m2 g 1
Batch mode (200 mL, sorbent Heavy oil-in-water emulsions 950 800 240 – [107]
dosage 0.5 g L 1))

A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

Compressed filter (8 cm 1330 – – 90%
diameter, 0.5 cm thickness)
Peat Commercial, Peat Sorb, size < 4 mm, surface area Compressed filter (8 cm Heavy oil-in-water emulsions 260 – – 62% [107]
270 m2 g 1 diameter, 0.5 cm thickness)
Regranulated cork Produced from raw cork by injection of steam at 380 °C, Batch mode (45 mL, sorbent Sunflower oil-in-water emulsions 79 150–200 – – [115]
size 1.0–2.0 mm dosage 0.5 g L 1)
Batch mode (45 mL, sorbent Sunflower oil-in-water emulsions – 150 15 90% [138]
dosage 1.6 g L 1)
Batch mode (45 mL, sorbent VORW – 1400 40 96% [139]
dosage 1.5–4.0 g L 1)
Batch mode (45 mL, sorbent VORW 210 480 – 92%
dosage 1.0 g L 1)
Batch mode (45 mL, sorbent Simulated VORW (60% soap) – 200 – 85.4%
dosage 1.0 g L 1)
Continuous mode in a stirred Simulated VORW (60% soap) 192 200 <15 –
tank
Natural wool fibres Originated from domestic sheep Batch mode (300 mL, sorbent Motor oil-in-water emulsions 33,000–43,000 15,000 – 73–95% [126]
dosage 0.1–0.13 g L 1)
Recycled wool-based – Batch mode (300 mL, sorbent Motor oil-in-water emulsions 15,000–19,000 15,000 – 33–43% [126]
nonwoven material dosage 0.1–0.13 g L 1)
Fruiting bodies of Fruiting bodies dead biomass, pieces 0.5  0.5 cm Batch mode (50 mL, sorbent Mineral oil-in-water emulsions 398 (qmax, 200– - - [132]
macrofungus dosage 4–20 g L 1) Langmuir– 3500
Auricularia polytricha Freundlich)
Kapok fibre Raw, dried Batch mode (400 mL, sorbent POME – 4200 – 98% (as COD) [19]
in a wire-mesh basket)
Treated with NaOH Batch mode (400 mL, sorbent POME – 4200 – 76% (as COD)
in a wire-mesh basket)
Rice husks Raw, particle size < 2 mm Batch mode (250 mL, sorbent Crude oil-in-water emulsions 454.55 10000 – 49% [133]
dosage 10 g L 1) Spent engine oil-in-water 666.70 63%
emulsions
Engine oil-in-water emulsions 500.00 57%
Raw, particle size 1–2 mm 1250 (qmax, 1000– – –
Langmuir) 50,000
Thermally treated rice White rice husks ash, thermally treated at 600 °C with Batch mode (250 mL, sorbent Crude oil-in-water emulsions 200.00 10,000 – 20% [133]
husks circulation of air, particle size < 2 mm dosage 10 g L 1) Spent engine oil-in-water 250.00 23%
emulsions
Engine oil-in-water emulsions 303.30 30%

(continued on next page)

249
250 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

4.1. Types and characteristics of sorbents

Refs.

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-in-water emulsions to real
removal (%)

wastewaters of complex composition. Therefore, it is not easy to

establish a pattern that identifies the best types of sorbents
O&G

45%
75%

77%

and the respective physicochemical characteristics and sorption

–

capacities. Nevertheless, a review of the studied sorbents is

O&Gfinal

important to frame the proposal of a new O&G sorption treatment

L 1)
(mg

in the context of the existing knowledge.

–

One of the most common adsorbents, which has been widely

O&Ginitial
(mg L 1)

tested for many applications, is activated carbon. However, its pro-

10,000

50,000
1000–

duction 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 mate-
rials as precursors. Ngarmkam et al. [18] have used palm shell, a
1250 (qmax,
1000 (qmax,

2000 (qmax,
Langmuir)

Langmuir)

Langmuir)
(mg g 1)

local resource, as a precursor of activated carbons for the treatment

q (O&G)

495.05
769.20

769.20

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
Engine oil-in-water emulsions

Engine oil-in-water emulsions

Type of wastewater/emulsion

Crude oil-in-water emulsions

Crude oil-in-water emulsions

per mass of raw material were used in a study with cork-based

Spent engine oil-in-water

Spent engine oil-in-water

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 oil-field brine [10,11].
The main disadvantage of the use of activated carbons in O&G
emulsions

emulsions

sorption is that oil droplets sit at the entrance of the pores, block-
ing 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
Batch mode (250 mL, sorbent

Batch mode (250 mL, sorbent

of synthetic polymeric sorbents instead, highlighting their higher

Treatment configuration

stability, selectivity and lower cost. They propose a treatment with

an organophilic resin modified by cationic surfactant. Other sor-
bents of the same type include ethanol-grafted polyacrylonitrile
dosage 10 g L 1)

dosage 10 g L 1)

[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
Black rice husks ash, thermally treated at 600 °C with N2

Black rice husks ash, thermally treated at 600 °C with N2

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 syn-
thetic materials such as hydrophobic nanogels [101,122,123] have
Sorbent treatment and characteristics

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] (Fig. 3).
flow, particle size 1–2 mm
flow, particle size < 2 mm

Other authors have opted for the use of natural mineral sor-
bents 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
Table 11 (continued)

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
Sorbent

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
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
Fig. 3. Sorption of O&G using magnetically-recoverable sorbents. Reprinted
(adapted) with permission from Mirshahghassemi et al., 2015 [114]. Copyright Ó
2015, American Chemical Society.
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 ninefold 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 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 increas-
ingly 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
251
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 charac-
teristics 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.). There-
fore, this material is also a natural organic sorbent indicated for the
clean-up of oil spills [137]. Recent studies have 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 adsorp-
tion. 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 instanta-
neously at the surface through lipophilic interactions or coales-
cence, 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 agglomer-
ation 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 oil’s
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. Emul-
sion stability is most commonly evaluated through droplet size
distribution and zeta potential measurements [102].
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 destabilisa-
tion 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 sor-
bent 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
252 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255

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

Method Material Observations Refs.

Contact with clean water Vermiculite Release of oil by contact with water is very low due to hydrophobicity of the sorbents [125]
Barley straw [104]
Dead biomass [108]
Contact with NaOH Chitosan Significant removal of oil, but the capacity of the sorbent declines in the second cycle [103]
solution
Extraction with n-hexane Activated carbon Good oil removal and recovery [18]
Carbon fibre felts [109]
Centrifugation Carbon fibre felts Good oil removal and sorbent regeneration for several cycles [109]
Compression Walnut shell Good oil removal and possibility of sorbent regeneration [111]
Polyurethane foams [112]
Squeezing Cotton fibres Possibility of sorbent regeneration, but with decreased capacity; too aggressive for fragile sorbents [135]
Carbon fibre felts [109]
Vacuum filtration Carbon fibre felts Good oil recovery and good stability of sorbent regeneration for 8 to 15 cycles [109]
Kapok fibre [134]
Exfoliated graphite Good oil recovery and no damage to the fragile sorbent structure; gradual loss of capacity when [149]
Thermally reduced regenerated [150]
graphene

case, the action of the sorbent resembles that of a coagulant, aggre-
gating the oil droplets at its surface [24].
Apart from favourable electrostatic conditions, adequate agita-
tion 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]; optimisa-
tion 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. 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 parti-
tioning process [98,138,139]. In surfactant-modified materials,
these interactions occur between the oil and the oleophilic tails
at the solid’s 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 environmen-
tally relevant conditions.
Oil sorption equilibria and kinetics have been described using
mathematical models which are commonly employed in the liter-
ature 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 sorbent’s surface.
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].
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
 A.M.A. Pintor et al. / Chemical Engineering Journal 297 (2016) 229–255
can often be forwarded to biological reactors. Electrical methods
are improvements of chemical and physical methods such as elec-
trocoagulation 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 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 pro-
cess 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 sorbent’s
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 superhydro
phobic/superoleophilic properties may result in the enhancement
of existing low-cost sorbents, and with easily scaled-up technolo-
gies, may create products with high sorption capacity and
therefore high commercial interest.
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.
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).
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