Chemosphere 144 (2016) 671e680

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

An overview of oilewater separation using gas flotation systems

Jayaprakash Saththasivam, Kavithaa Loganathan, Sarper Sarp*
Qatar Environment and Energy Research Institute (QEERI), Hamad Bin Khalifa University, Qatar Foundation, Doha, Qatar

h i g h l i g h t s

Gas flotation is capable of reducing oil concentration from approximately below 1000 ppm to 10 ppm.

Oil-bubble attachment by the means of full encapsulation yields the best removal efficiency.

Flotation efficiency can be significantly enhanced by prior addition of coagulants-flocculants.

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

Article history: Oil concentration levels in municipal waste water effluent streams are stringently regulated in most parts
Received 27 August 2015 of the world. Apart from municipal waste, stricter oil/grease discharge limits are also enforced in oil and
Accepted 31 August 2015 gas sectors as large volumes of produced water is being discharged to open ocean. One of the feasible,
Available online xxx
practical and established methods to remove oil substances from waste water sources is by gas flotation.
In this overview, gas flotation technologies, namely dissolved and induced flotation systems, are dis-
Keywords:
cussed. Physico-chemical interaction between oilewater-gas during flotation is also summarized. In
Gas flotation
addition to a brief review on design advancements in flotation systems, enhancement of flotation effi-
Oilewater separation
Oilewateregas interactions
ciency by using pre-treatment methods, particularly coagulation-flocculation, is also presented.
Air flotation © 2015 Elsevier Ltd. All rights reserved.
Dissolved gas flotation
Induced gas flotation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
2. Gas flotation system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
2.1. Induced gas flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
2.2. Dissolved gas flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
3. GaseOilewater interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
3.1. Stokes law and rise rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
3.2. Interfacial tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
3.3. Oil droplet and bubble size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
3.4. Oil droplet-bubble attachment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
3.5. Spreading coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
4. Gas flotation design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
5. Pre-treatment for flotation system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
6. Latest development in gas flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678

* Corresponding author.
E-mail address: ssarp@qf.org.qa (S. Sarp).

http://dx.doi.org/10.1016/j.chemosphere.2015.08.087
0045-6535/© 2015 Elsevier Ltd. All rights reserved.
672 J. Saththasivam et al. / Chemosphere 144 (2016) 671e680

1. Introduction for flotation (Moosai and Dawe, 2003).

Oil and grease concentrations in municipal and industrial waste

effluents are strictly monitored (Diya'uddeen et al., 2011; Farmaki
2. Gas flotation system
et al., 2007; Mueller et al., 2003; Raha, 2007; Rinco
n and La
Motta, 2014) as they could lead to serious health and environ-
The working mechanism of gas flotation is primarily governed
mental related issues. For instance, discharge limits of these sub-
by the density differences between bubble-particle aggregate and
stances in produced water emanating from offshore petroleum
water (influent). Different types of gases are used in flotation sys-
plants are regulated at a monthly average of 29 mg L1 with a daily
tems with air being the most common. However, in specific flota-
maximum of 42 mg L1 (C. Hank Rawlins, 2009). Oil and gas pro-
tion processes (e.g. produced water treatment), air is not preferred
duction plants in North East Atlantic are required to meet the
due to the presence of oxygen in the air that could lead to possible
30 mg L1 oil and grease discharge standards set by Oslo Paris
metal precipitation and explosion. Methane is generally used in
Convention (OSPAR) (Atarah, 2011). To meet these stringent
produced water flotation systems due its availability and compat-
discharge limits, oil substance can be effectively separated from
ibility with the influent aqueous solution. Apart from these gases,
waste water using following practical technologies:-
nitrogen and carbon dioxide are also being used in some specific
gas flotation processes. Adhesion of gas bubbles with fine particles
i. Gravity settling (API tanks (Stewart and Arnold, 2009) and
(e.g suspended solid, oil and etc.) forms lighter agglomerates that
corrugated plate interceptors (NALCO Chemical Company,
can be easily floated and skimmed from the top surface. Wang et al.
2009))
(Wang et al., 2010) summarized the four key steps of a gas flotation
ii. Centrifugal separation using Hydrocyclone (Bai et al., 2011;
system:-
Belaidi et al., 2003; Husveg et al., 2007))
iii. Chemical pre-treatment (coagulation-flocculation) (Mostefa
i. Generation of gas bubbles e size and volume of gas bubbles
and Tir, 2004; Santo et al., 2012; Zouboulis and Avranas,
generated with respect to oil concentration and droplet size
2000),
are very important in forming a stable bubble-particle
iv. Coalescing media (Ma et al., 2013; Owens and Lee, 2007;
aggregate. Large bubbles and low gas volume generally
Zhang et al., 2014),
leads to poor capture efficiency.
v. Gas flotation (induced gas flotation (Castillo et al., 2012; El-
ii. Contact between gas bubbles and oil droplets e frequent
Kayar et al., 1993; Hoseini et al., 2013; Meyssami and
collision between gas bubbles and oil droplets is required to
Kasaeian, 2005; Painmanakul et al., 2010) and dissolved gas
promote the bubble-drop attachment/adhesion.
flotation (Abo-El Ela and Nawar, 1980; Behin and Bahrami,
iii. Attachment of gas bubbles e Establishing a strong adhesion
2012; Multon and Viraraghavan, 2008; Younker and Walsh,
between gas bubbles and oil droplets is important to
2014a)),
generate the required flotation buoyancy force. Improper or
vi. Biological processes (membrane bio-reactor (Kose et al.,
weak attachment leads to poor oilewater separation
2012; Pendashteh et al., 2012; Soltani et al., 2010; Zhidong
efficiency.
et al., 2009) and activated sludge (Tellez et al., 2002; Zhang
iv. Rise of the aggregates and the skimming of sludge e The
et al., 2009)),
floated aggregates form a contaminant-laden froth that
vii. Media Filtration (Resin, polymer, sand, clay, garnet, silica,
needs to be skimmed to ensure a continuous separation
walnut shell (Angelova et al., 2011; Blumenschein et al.,
process.
2001; C. Hank Rawlins, 2009; Franco et al., 2014; Reynolds
et al., 2001; Srinivasan and Viraraghavan, 2008)
Induced and dissolved gas flotation systems are the two most
viii. Membrane separation - micro-filtration (Hu and Scott, 2008;
commonly used flotation technologies (C. Hank Rawlins, 2009;
Motta et al., 2014); ultra-filtration (Li et al., 2013; Lipp et al.,
Wang et al., 2010). Both methods are very effective in floating
1988; Weschenfelder et al., 2015); Nano-filtration (Mondal
small suspended particles, organic matter, oil and grease. It has
and Wickramasinghe, 2008; Xu and Drewes, 2006) and
been reported that particles as fine as 3 mm can be removed with
reverse osmosis (Al-Jeshi and Neville, 2008; Mohammadi
the aid of coagulation (Drewes et al., 2009). These systems are
et al., 2003).
usually used to treat waste influent that has an oil concentration
lower than 1000 mg L1
A summary on these technologies is shown in Table 1. In most
cases, combinations of the above-mentioned technologies are
required to achieve the desired effluent quality.
Gravity based separation technologies (e.g. settling/sedimenta- 2.1. Induced gas flotation
tion and gas flotation) are widely used in various water treatment
plants to remove oil and grease. Gas flotation systems are generally Induced gas flotation (IGF) or, also known as dispersed gas
preferred over the setting methods due to the following significant flotation system, operates by inducing and dispersing gas bubbles
advantages:- (i) shorter retention time and higher loading rate (ii) into the influent. This can be achieved either by mechanical or
compact and smaller foot print (iii) better separation efficiency in hydraulic methods, as shown in Fig. 1. In mechanical based IGF, high
removing smaller and lighter particles and (iv) higher effluent speed impellers are used to generate a vortex that entrains and
quality in the presence of chemicals (coagulants and flocculants). It mixes gas into the water stream. On the other hand, hydraulic IGF
must be emphasized that removal of free and dispersed heavy oil is uses an educator/venturi to entrain gas bubbles. A portion of clean
not feasible using settling methods due to minor density differ- effluent is recycled to the flotation chamber via venturi to entrain
ences between the continuous fluid and heavy oil. Density differ- and deliver gas bubbles into the waste water. The flotation mech-
ence, which is the primary driving force for gravity separation, can anism that takes place after gas dispersion is the same for both IGF
be significantly enhanced using gas flotation systems. Then systems. Light aggregates, resulting from bubble-droplet attach-
attachment of gas bubbles on the heavy oil will reduce the net ments, will rise to the surface of the column before being skimmed
density of oil aggregates and provide the required buoyancy force off.
Table 1
Summary of common de-oiling methods.
No Technology
1 Gravity settling
(Skim vessels, API Tanks) ii. API tanks suitable for removal of oil droplets >150 mm
2 Gravity settling
(Parallel and Corrugated
Plate separators.)
3 Hydrocyclone
4 Chemical Treatment
5 Coalescing Media
6 Gas flotation
7 Biological Treatment
8 Media Filtration
9 Membrane separation
Working principle
i. Based on the specific gravity of the immiscible fluids.
(Alzahrani and Mohammad, 2014) with possible effluent
concentration in the range of 50e100 mg L1
(Judd et al., 2014).
i .Based on the specific gravity of the immiscible fluids
with the aid of plates to coalesce and remove free oil.
ii .Plate Interceptors are suitable for the removal of oil
droplets >50 mm (Owens and Lee, 2007) with an average
effluent concentration of 25e100 mg L1 (Bennett, 1988)
i. Centrifugal and centripetal forces are generated to separate
oil and water by accelerating the influent into the cyclonic
chamber using a tangential feed. Due to lower density, oil
will migrate to the core of the vortex and travel in the
opposite direction to the “denser” water.
ii. Suitable for removal of oil droplets down to 1e15 mm
(Owens and Lee, 2007) with average effluent concentration
of 20e30 mg L1 (Zangaeva, 2010).
i. Addition of coagulants and flocculants to de-emulsify,
coalesce and aggregate oil particles to form larger droplets.
i.Oleo-philic and hydrophobic coalescing medias are used to
collide and adhere small oil droplets to form larger droplets
(Arnold et al., n.d.; C. Hank Rawlins, 2009).
ii.These medias are capable of achieving low oil effluent levels
(e.g. <5 mg L1) (Owens and Lee, 2007)
i.A floating mechanism where the overall density of
oil/solid particles is significantly reduced by aggregating
them with gas bubbles. These aggregates will rise rapidly
and eventually skim off.
ii.Suitable for removal of oil droplets >20 mm with average
effluent concentration of 10e40 mg L1 (Zangaeva, 2010)
i.Biological treatment (activated sludge) coupled with
membrane separation (MBR) can be effectively used to
decompose and remove organic compounds and oil
substance in wastewater.
i.Medias such as walnut, sand, and anthracite are
commonly used in oilewater separation industry.
ii.Black walnut shell, which is highly hydrophilic and
oleophobic, can easily remove oil to very low concentration
(C. Hank Rawlins, 2009; Owens and Lee, 2007).
iii.Another adsorbent, organoclay, is capable of removing
insoluble and dispersed hydrocarbons (Jaji, 2012).
i.Pressure-driven membranes (microfiltration, ultrafiltration,
nanofiltration, reverse osmosis) play a significant role in
removing oil and grease from waste water.
ii.Micro filtration can be effectively used to remove suspended
solid and fine particulates while ultrafiltration can be used to
remove to colloids and emulsified oil.
Advantages
i. Suitable for removal of large suspended solids and free oil. i. Small droplets and stable oilewater emulsion require
ii. Simple equipment with minimum operating
costs and maintenance.
iii. Can be effectively used as the first treatment step in
removing oil and grease.
i. Smaller foot-print compared to skim vessels and API tanks. i. Possibility of plate clogging.
i. Non-moving parts.
ii. High throughput with very low retention time.
iii. Compact and capable of handling influent concentration
(up to 2000 mg L1) (Owens and Lee, 2007).
i. Enhanced oil coalescence and aggregation; Larger oil
droplets/flocs are much easier to remove.
ii. Contributes to the removal of solid and organic carbon.
i.Can be conjugated with flotation system for higher
separation efficiency.
i.Lighter and smaller particles that are difficult to settle
down and can be easily removed using gas flotation.
ii.Gas flotation systems are compact and have small foot
prints compared to gravity settling tanks.
iii.Better solid handling and good float thickening.
i.MBR has high effluent quality with low sludge
production (Dores et al., 2012).
ii.MBR is a compact system with high loading rate
and lower energy cost (Pendashteh et al., 2012).
i.Media filtration is not subjected to the salinity
(Igunnu and Chen, 2014) of the influent, which could
be an advantage in treating oil field produced water.
ii.Media filtration produces high quality effluent and is
usually used for final polishing.
iii.Efficiency can be further enhanced if coagulants are
added to the feed water prior to filtration.
i.Variation in feed water quality will have a minimal
impact on permeate quality.
ii.Compact unit with small foot print area.
iii.Modular design which makes it easier to operate.
Disadvantages
excessive settling time.
ii. Not suitable for removal of dissolved oil.
iii. Large foot print.
iv. Not suitable for heavy oil separation.
ii. Not suitable for heavy oil separation.
iii. Not suitable for removal of stable emulsion and
dissolved oil.
i. Possibility of fouling and clogging.
ii. Not suitable for heavy oil and stable emulsion
(small size droplets).
iii. Requires pressurized inlets and high maintenance.
J. Saththasivam et al. / Chemosphere 144 (2016) 671e680
i. Conventional inorganic coagulants (aluminium
and iron salts) could pose additional problems due to the
presence of metal content in effluent (Karhu et al., 2012).
ii. A large volume of sludge is produced (Karhu et al., 2014).
iii. Contributes significantly to the operating cost
(Chemical coagulant and pumping cost) (Atarah, 2011).
i.Could be susceptible to solid loading and clogging.
i.Difficult to remove dissolved oil and usually requires
chemical pre-treatment to remove emulsified oil.
ii.It is not cost effective to produce large volumes
of microbubbles that are smaller than oil droplets.
i.Hyper-saline oil contaminated water (e.g. oil-field
produced water) could affect the metabolism of
micro-organisms and lead to cell dehydration
(plasmolysis) (Pendashteh et al., 2012).
ii.Biological systems are sensitive to influent loading,
where abrupt changes in the loading could seriously
affect the biological balance in the reactor.
i.Regeneration of the media is one of the drawbacks
of this system.
ii.Not suitable for high inlet oil concentrations (>50 mg L1)
(Owens and Lee, 2007).
iii.Incapable of removing soluble hydrocarbons.
i.Membranes are subjected to fouling from oil/grease and
biological content in the influent.
ii.Polymeric membrane material degradation when
subjected to high temperature (>50  C).
673
674 J. Saththasivam et al. / Chemosphere 144 (2016) 671e680
Fig. 1. Two types of Induced Gas Flotation system (Stewart and Arnold, 2009).
2.2. Dissolved gas flotation
While the IGF system accelerates liquid velocity (e.g. radial ve-
locity for mechanical IGF and axial velocity for hydraulic IGF) to
entrain and disperse gas bubbles, dissolved gas flotation (DGF)
systems, on the other hand, produces gas bubbles by manipulating
the fluid pressure. Working principles of DGF systems have been
extensively discussed by many researchers before (Al-Zoubi et al.,
2009; Bennett, 1988; Stewart and Arnold, 2009; Wang et al.,
2010). Pressurized gas is dissolved in the liquid phase using satu-
rator before being de-pressurized to nucleate tiny micro-bubbles in
the range of 10e100 mm. Since gas solubility is a function of pres-
sure, larger amounts of gas micro-bubbles can be generated by
raising the saturator pressure. The gas saturated water is then
injected into the contact zone where collisions and agglomerations
of bubble-droplet occur. Then, the agglomerates enter the separa-
tion zone where flotation takes place. A skimmer is used on the
tank surface to remove the floated froth. A conventional DGF sys-
tem is shown in Fig. 2. Comparison distinguishing IGF and DGF is
shown in Table 2.
Fig. 2. Conventional Dissolved Gas Flotation system (Stewart and Arnold, 2009).
3. GaseOilewater interactions
Oil separation via flotation method depends on physicochemical
properties of the continuous phase (waste water), oil/grease and
gas bubbles. Grattoni et al. (Grattoni et al., 2003) highlighted the
importance of understanding the surface science of these proper-
ties to achieve an optimal flotation system. Properties such as vis-
cosity and density of the fluids, as well as interfacial tensions
between the fluids need to be carefully evaluated in order to design
an efficient flotation system (C. Hank Rawlins, 2009). In this section,
several important design parameters related to flotation (namely
rise rate, interfacial tension, oil-bubble droplet size and attach-
ment, sweep factor and spreading coefficient) are discussed.
3.1. Stokes law and rise rate
The effect on size, density and viscosity on the rise rate of par-
ticle can be understood from the Stokes law (Equation (1)).


gd2p rl  rp
u∞ ¼ (1)
18ml
whereu∞ is the terminal velocity (m/s), g is gravitational accel-
eration (9.81 m/s), dp is the bubble/droplet diameter (m),rl is the
liquiddensity (kg/mI3),rp is the bubble/droplet density (kg/mI3),
and ml is the liquid viscosity (kg/m$s).
Stokes Law is only applicable when the Reynolds number is less
than 1.0 with an assumption that the particle (bubble, droplet, or
bubble-droplet aggregate) is in a spherical shape (Wang et al.,
2010). It can be seen from Equation (1) that smaller diameter
(hence larger surface area) gas bubbles will rise more slowly than
big gas bubbles in a same liquid. Slower rise rate contributes to
higher collision rate with oil droplets; hence the flotation efficiency
is increased. (Robinson, 2013). It has to be emphasized that the rise
rate calculated from Stokes Law could differ from real conditions
due to the following reasons (i) particles could exist in many
various shapes (not necessarily sphere, as approximated by Stokes
Law) (II) particulates may exist in different sizes (diameter) due to
coalescence (iii) presence of turbulence and wake in the flow,
which makes it difficult to maintain laminar flow.
Rise rate is also directly proportional to the density difference,
and inversely proportional to the dynamic viscosity of the fluid. In
most cases, these two factors are strongly governed by temperature
and the amount of dissolved solid in the liquid. Rawlins (C. Hank
 J. Saththasivam et al. / Chemosphere 144 (2016) 671e680 675

Table 2
Comparison between induced and dissolved gas flotation system.

Parameters IGF DGF

Bubble Size 100e1000 mm 10e100 mm

Generation Method Velocity based; Entrainment and Dispersion Pressure based, Saturation and depressurization
Bubble Generation Quantity High Low (limited by saturation)
Operating Conditions Turbulent and less quiescent; multi cell configuration. Quiescent; usually single cell configuration.
Bubble Generation Method Entrainment and dispersion Saturation and depressurization
Retention Time <5 min (Wang et al., 2010) 5e15 min (Al-Shamrani et al., 2002)
Foot Prints Compact (due to high residence time) Large (due to high residence time)
Capital Cost Low High (large tank and saturator system)
Maintenance Significant; due to wear and tear in Mechanical IGF Low (non-moving parts)
and scaling in Hydraulic system

Rawlins, 2009) summarized that the rise rate was approximately
increased by half when liquid temperature is doubled for a given
droplet diameter. Nevertheless, rise rate only decreased by 10%
when the liquid's salinity was doubled.
3.2. Interfacial tension
Bubble-droplet attachment is primarily controlled by the
interfacial tensions (IFT) between the water, oil and gas bubble. IFT
difference between water-gas(gwg), oilewater(gow), and oil-gas
(gog) are used to calculate spreading coefficient, So. This coeffi-
cient indicates the strength of the bubble-droplet attachment and
will be covered in detail in the subsequent sections. Similar to
density and viscosity, interfacial tensions between the fluids are
also affected by the temperature and content of dissolved solid.
Temperature increment decreases interfacial tension, thus pro-
moting coalescence while the opposite is true for salinity variation
(C. Hank Rawlins, 2011).
3.3. Oil droplet and bubble size
As described earlier, size of the particles (e.g. bubble and oil
droplet) play a pre-dominant role in gas flotation. Small bubbles are
preferred due to their large surface areas which are useful for
droplet aggregation. On the other hand, large bubbles tend to rise
rapidly, which results to lower collision efficiency. It was also re-
ported that bubble sizes decrease with salinity (Eskin et al., 2015).
Hence, better separation efficiency can be expected in saline water.
In waste water, oil could exist in many forms (Wang et al., 2010).
These different forms are shown in Table 3. Oil droplets which are
bigger than 20 mm (Moosai and Dawe, 2003) are suitable for
flotation purposes. Small oil droplets (<10 um) might not rise due
to the Brownian motion (Atarah, 2011). It has been reported that by
using the smallest possible bubble to lift the biggest possible
droplet will lead to optimum flotation efficiency (Moosai and Dawe,
2003).
3.4. Oil droplet-bubble attachment
Droplet-bubble attachment is another key factor in the flotation
system. The aggregation of the droplet-bubble is preceded by the
collision between the matters as well as thinning and rupturing of
the interstitial film between the droplet and gas bubble. Formation
of stable aggregates are governed by various factors such as bubble/
droplet size ratio, bubble swarm density, mean bubble size, and
bubble distribution, salinity, oil viscosity, spreading coefficient,
fluid velocity, and turbulence. Of all these, gas related parameters
(e.g. bubble size, distribution, and dispersion) are considered to be
the controlling factor in oilewater separation (C. Hank Rawlins,
2009).
Probability of flotation, Pf (Oliveira et al., 1999) is formulated as
following:-
Pf ¼ Pc  Pa  Ps (2)
Where Pc is the collision probability, Pa is adhesion probability that
is determined by the thinning and rupturing of the interstitial film
between bubble-drop and Ps is stable aggregate probability (a
function of contact angle value) (Oliveira et al., 1999).
Collision probability depends on the concentration of oil drop-
lets and gas bubbles as well as the projected areas of the droplets
and gas bubbles (Walsh, 2012). Higher concentrations and surface
area leads to a higher collision rate (Bahadori et al., 2013). As
collision efficiency is directly proportional to droplet diameter and
inversely proportional to bubble diameter, better collision can be
realized by injecting finer gas bubbles (Oliveira et al., 1999). A
Sweep Factor, one of the design parameters used in gas flotation,
defines the number of times per minute gas bubbles will contact
with any particular volume element in the flotation cell (Juniel
et al., 2004; Lee and Frankiewicz, 2004; Walsh, 2012). Higher
collision probability can be realized by designing a flotation column
with a larger Sweep Factor. Sweep Factor is defined as:-
Agas  Fgas
SF ¼ (3)
Acell
Where SF denotes the Sweep Factor (min1), Agas is the total cross
sectional area of bubbles per unit volume (m2 gas/m3 gas), Fgas is
the gas volumetric flow rate (m3 min1) and Acell is the cross
sectional area of flotation cell (m2). As Agas is inversely propositional
to bubble diameter (Walsh, 2012), smaller gas bubbles will
contribute to a larger sweep factor which increases the flotation
efficiency.

Table 3
Different forms of Oil in Waste Water (Wang et al., 2010).

No Form Size Description

1 Free Oil/Dispersed Oil
2 Emulsified Oil e Physical
3 Emulsified Oil e Chemical
4 Dissolved/Soluble Oil
5 Oil Wet Solids
>20 mm Low specific density and easy to float and separate
5e20 mm Emulsion forms due to mechanical actions such as valve throttling, mixing in pump.
<5 mm Emulsion form due to presence of anionic surfactants.
e Common in produced water and consists of all hydrocarbons and other organic
compounds that have some solubility in produced water.
e Oil that is attached to the solid particles.
676 J. Saththasivam et al. / Chemosphere 144 (2016) 671e680
Nevertheless, it has to be clearly understood that effective
flotation efficiency cannot be achieved by merely increasing the
collision frequency. In other words, bubble-droplet adhesion will
not occur in all the collisions (Walsh, 2012). Collision has to occur in
a manner that it thins and ruptures the interstitial liquid/film be-
tween the droplet and bubble. This is the principal requirement for
an adhesion mechanism. It has been reported that droplet-bubble
adhesion happens when a film thickness of 0.1 mm is reached. At
this point, the film ruptures due to a stronger intermolecular force
between the droplet and bubble which eventually forms a droplet-
bubble aggregate (Oliveira et al., 1999). Rawlins (C. Hank Rawlins,
2011, 2009) explained the following four possible droplet-bubble
adhesion mechanisms:-
(i) Direct impingement with full or partial encapsulation by
chemical adhesion.
(ii) Hydrodynamic capture of oil droplets in the wake of a rising
gas bubble.
(iii) Clustering of gas bubbles to form a buoyant mat.
(iv) Nucleation, coalescence, and growth of gas bubbles on the
surface of an oil droplet to result in full or partial
encapsulation.
It was summarized that direct impingement with full encap-
sulation is the best adhesion mechanism for oil flotation. The
strongest bond between droplet and bubble occurs when the oil
fully encapsulates/coats the surface of the bubble. Unstable (e.g.
weak bond) droplet-bubble adhesion occurs when the oil droplet
makes a point contact rather encapsulating the gas bubble. The
second adhesion mechanism (hydrodynamic wake capture) also
creates a weak bond between the droplet and the bubble.
3.5. Spreading coefficient
As oil encapsulated bubbles yield the best oil separation effi-
ciency, it is important to understand the mechanism of oil
spreading on gas bubbles. Imbalance of interfacial tension (IFT)
differences between water-gas (gwg), oilewater (gow), and oil-gas
(gog) greatly influences oil spreading (Grattoni et al., 2003) and
are used to measure the spreading coefficient, So:-


So ¼ gwg  gow þ gog
Encapsulation of oil on the surface of a gas bubble occurs when
the spreading coefficient is greater than zero. Full encapsulation of
oil on a gas surface is shown in Fig. 3. A positive spreading coeffi-
cient can be obtained when the interfacial tension of water-gas is
larger than the summation of interfacial tension of oilewater and
oil-gas. In other words, an effective flotation can be conceived by
ensuring a continuous oil droplet film is formed between the gas
and the water (Moosai and Dawe, 2003). Smaller gas bubbles, larger
droplet size, and higher salinity lead to a higher spreading coeffi-
cient (C. Hank Rawlins, 2009; Grattoni et al., 2003; Moosai and
Dawe, 2003).
4. Gas flotation design
Many new and different concepts have been conceived to
improve the oil removal efficiency using gas flotation systems. Le
et al. (Le et al., 2013) evaluated oil flotation efficiency by using a
combined macro-micro bubble generation system. Macro bubbles
(diameter range between 0.5 mme20 mm) and fine micro-bubbles
(diameter ranging from 1 to 16 mm) were produced using a cyclone
and micro bubble generating nozzles respectively. A swarm of
macro-micro bubbles were injected to create a swirl flow in a
vertical oil separation column. Emulsified palm oil (diameter
<16 mm) of various concentrations were used in these batch
studies. It was found that the oil separation efficiency was
increased by 13% when the combined macro-micro-bubbles system
was used instead of the micro bubble generator only.
Liu et al. (Liu et al., 2013) studied the feasibility of using
cyclonic-static micro bubble flotation for oil removal. The proposed
system combines the principles of hydrocyclone and induced air
floatation to maximize the separation efficiency. In addition to that,
it was claimed that the hybrid system which is suitable for treating
large influent capacity, has lower operation costs and a shorter
separation time.
Modified Jet Flotation Cell (MJC) is another design that has been
proposed for oilewater emulsion separation. Jet floatation
(Jameson Cell) systems are usually compact in design, requires less
maintenance and operating power and have high throughput with
a low residence time (<3 min) (Santander et al., 2011). The con-
ventional jet floatation system mainly consists of a down comer
(vertical pipe) with a nozzle for air entrainment and a floatation
cell. Santander et al. (Santander et al., 2011) has retrofitted the
conventional system by adding a blind end internal cylinder and
packed bed (crowder) to reduce the hydraulic short circuit, stabilize
froth formation and minimize turbulence in the flotation cell.
Laboratory tests revealed that the modified MJC has slightly better
removal efficiency (improvement of 5%) than the convention jet
flotation system.
Apart from the above laboratory experimental studies, indus-
trial scale floatation systems are also summarized here. As there are
many industrial oilewater flotation treatment applications, we
have limited our summary to gas flotation technologies that are
available for treating produced water only. Table 4 shows some of
the common gas floatation technologies which are being marketed
in this field.
5. Pre-treatment for flotation system
Performance of gas flotation systems can be dramatically
improved by having a proper pre-treatment system. The role of
(4)
Fig. 3. Spreading oil on gas bubbles surface (Full Encapsulation) (Moosai and Dawe,
2003).
 J. Saththasivam et al. / Chemosphere 144 (2016) 671e680 677

coagulants in destabilizing oilewater emulsion to promote droplet
coalescence has been well documented (Bensadok et al., 2007; El-
Gohary et al., 2010; Karhu et al., 2014; Tansel and Pascual, 2011;
Zouboulis and Avranas, 2000). Effect of aluminium and ferric sul-
phates in oil separation using a dissolved gas flotation technique
has been studied by Al-Shamrani et al. (Al-Shamrani et al., 2002). It
has been reported that addition of these coagulants led to over 99%
removal efficiency. The addition of highly charged cations
neutralized the negatively charged oil droplets and enhanced
droplet coalescence. It was also highlighted that stability of emul-
sion is more sensitive to pH variation than coagulant concentration
(Al-Shamrani et al., 2002; Santo et al., 2012). Hoseini et al. (Hoseini
et al., 2013) reported that Total Petroleum Hydrocarbons (TPH)
removal of oil-in-water emulsions were obtained by using
aluminium sulphate at pH of 4 and concentration of 50 mg L1.
Another oilewater separation study reported that a maximum
removal of 99% COD was achieved at optimum pH value and alum
concentration range between pH 8e10 and 800 and 1400 mg L1,
respectively (Painmanakul et al., 2010). Zouboulis and Avra-
nas(Zouboulis and Avranas, 2000) stated that a 95% removal effi-
ciency can be achieved when the oilewater emulsion was treated
using dissolved air flotation with 100 mg L1 of Ferric Chloride at
pH 6. Bio-surfactants also have high potential in improving flota-
tion performance. Compared to synthetic coagulants, bio-
surfactant is more environmental friendly, less toxic and more
tolerant to pH, temperature and has lower salt variations (Menezes
et al., 2011). Bio-surfactant produced by C. sphaerica is reported to
have increased the oil separation efficiency from 80.0% to 98.0% (da
Rocha e Silva et al., 2014). In addition to coagulant, Younker and
Walsh (Younker and Walsh, 2014b) added organoclay prior to
flotation to remove both dispersed and dissolved oil. While main-
taining high separation oil and grease efficiency, organoclay was
able to improve the removal efficiency of naphthalene. A summary
of the coagulants used in conjunction with flotation units are
shown in Table 5.
6. Latest development in gas flotation
Current developments of flotation systems focus on the fol-
lowings (Eskin et al., 2015):-
(i) Reduction of aeration time (e.g. pressure vessel with porous
media partition, pressure accumulator, electric discharge
method, DAF pump and etc.)
(ii) Uniform distribution of gas bubbles (e.g. flotation cell inter-
nal structure modification, ring aerator for radial distribu-
tion, parabolic baffles and etc.)
(iii) Integrated framework (multi stage dissolved flotation, hybrid
combination with coalescer, cyclone, filter and etc.)
As the above-mentioned developments focus on increasing the
physical separation efficiency of emulsified and free oil from waste
influent, it is an undeniable fact that flotation systems are not
capable of removing dissolved oil. Effluent from flotation systems

Table 4
Gas flotation technology in produced water treatment.

No Model name Technology Additional remarks

1 Unicel (“UNICEL™ Vertical IGF™,” 2015)
2 Epcon DualCFU (“EPCON Dual Multistage
Compact Flotation Unit Technology,
Schlumberger,” 2015)
3 Quadricell (Siemens, 2015a)
4 Spinsep Vertical (Siemens, 2015b)
5 Veirsep Horizontal (Siemens, 2015c)
6 Hydrocell Hydraulic IAF (Siemens, n.d.)
7 AutoFloteMechanical (Technologies, n.d.)
10 Revolift VS Flotation (Exterran, 2015)
12 TST CFU (Cameron, 2015)
Vertical Induced Gas Flotation
Centrifugal Force and Flotation
Mechanical Induced Gas Flotation
Vertical column with Induced (Eductor),
Dissolved Gas (Brise) Pump or sparger
Horizontal configuration with Induced
(Eductor), Dissolved Gas (Brise)
Pump or sparger
Horizontal Hydraulic
(educator)induced air flotation
Horizontal Mechanical induced
air flotation
Induced gas flotation systems
Vertical Multi-stage separation with
dissolved or induced gas flotation
- Capacity: 160 m3 d1 to 25,400 m3 d1
- Effluent Oil Concentration: 5e10 mg L1
- Use of baffled central rise for better contact and radial
dispersion of oil-solid flocs
- Capacity: 72 m3 d1 to 24,000 m3 d1 e Single stage
- Effluent Oil Concentration: <10 mg L1
- Internal design enhancement to reuse the previously
lost excess gas for better oilewater separation efficiency
- Capacity: Up to 5000 mg L1
- Effluent Oil Concentration: <5 mg L1
- The Quadricell separator uses four cells in series
for maximum liquid/air contact
- Capacity: 654 m3 d1 to 15,808 m3 d1
- Coalescing device(SPIRALSEP) at the pipe inlet;
90O inlet angle to create circular motion for
better agglomeration; Packing scrub for oil
droplet coalescence
- Capacity: 164 m3 d1 to 23,984 m3 d1
- Coalescing device (SPIRALSEP) at the pipe inlet
- Multi cell flotation chamber; - Pressurized and
atmospheric configuration is possible
- Capacity: 556 m3 d1 to 15,900 m3 d1
- Patented educator induce and disperse gas bubbles
- Capacity: 1248 m3 d1 to 27,264 m3 d1
- Reduces free oil and solids by 90e95% with
maximum inlet concentrations of 200 mg L1
of free oil and less than 100 mg L1 of total
suspended solids
- Capacity: 795 m3 d1 to 4372 m3 d1 (possible
to reach 23,848 m3 d1 with other
configuration); e Effluent water quality
targets of <20 mg L1
- Multi-chambered design
- Capacity from 120 m3 d1 to 16,800 m3 d1
- Design consists of special internals that includes
static mixture, riser pipe, distribution arms and
guide vanes
- Capable of handling in oil content (1000 mg L1)
and can achieve below 10 mg L1 OIW through
multiple stages
678 J. Saththasivam et al. / Chemosphere 144 (2016) 671e680
Table 5
Coagulants used in Flotation Systems.
No Coagulant type Optimal dosage
(mg L1)
1 Aluminium Sulphate (Al-Shamrani et al., 2002) 100
2 Ferric Sulphate (Al-Shamrani et al., 2002) 120
3 Ferric Chloride (El-Gohary et al., 2010) 500e700
4 Alum (El-Gohary et al., 2010) 600e800
5 Ferrous Sulphate (El-Gohary et al., 2010) 700e1000
6 Aluminium Sulphate (Hoseini et al., 2013) 50
7 Alum (Painmanakul et al., 2010) 800e1400
8 Ferric Chloride (Zouboulis and Avranas, 2000) 100
need to be further treated in the presence of dissolved oil/hydro-
carbons. Several post treatment techniques such as advance
oxidation (Afzal et al., 2015), solvent sublation (Bayati et al., 2012),
photo-fenton (da Silva et al., 2015) and membrane filtration
(Alzahrani and Mohammad, 2014; Muraleedaaran et al., 2009) are
used to remove toxic dissolved hydrocarbon substances from water
(e.g. Gas field produced water).
7. Conclusion
Gas flotation is an effective method for removing oil-grease
from waste water. Higher separation efficiency can be achieved
by mainly increasing the collision and adhesion (capture) effi-
ciencies. Collision probability can be increased by increasing the
amount of gas used for flotation and reducing size of the gas bub-
bles. Small size bubbles also increases the capture (adhesion effi-
ciency). As oil droplets are usually smaller than gas bubbles, the
spreading of oil on a bubble's surface is much easier for smaller gas
bubbles. In reality, it is not cost effective to generate a large quantity
of small (micro) bubbles (Walsh, 2012). Apart from manipulating
the concentration and size of gas bubbles, floatation efficiency can
be enhanced by coalescing oil droplets. The addition of coagulants
promotes droplet coalescence, thus it has better collision and
adhesion probabilities with gas bubbles. Usage of coalescence
media also helps to form larger oil droplets. Fluid path during
flotation also contributes to greater oilewater separation. Mild
turbulence and swirl motion lead to better bubble-droplet collision
and capture. Swirl flow accelerates adhesion by forcing droplets
and bubbles to core of the chamber. The radial flow path travelled
by fluid in swirl motion is larger than axial flow, thus leads to longer
contact time between the droplets and bubbles. Post flotation
treatment techniques are usually required to remove dissolved
hydrocarbon from the waste water.
Acknowledgement
The authors would like to acknowledge the Qatar Environment
and Energy Research Institute (QEERI) for funding the Water Grand
Challenge Program, WGC 4004: Advanced Treatment of Waste
Water from Oil and Gas Industry.
Optimal pH Influent concentration Removal Additional details
(mg L1 oil) efficiency
8 1630 99.3% Flash mixing at 200 RPM for 1 min,
flocculation at 20 rpm for 15 min
and flotation for 7 min using a
saturation pressure of 80 psi and the
addition of 10% recycled water.
7 1630 99.94% Flash mixing at 200 RPM for 1 min,
flocculation at 20 rpm for 15 min and
flotation for 7 min using a saturation
pressure of 80 psi and the addition of
10% recycled water.
8.41 ± 0.15 169.7 ± 17 73 ± 5%
6.93 ± 0.2 169.7 ± 17 78.59 ± 0.8%
8.9 ± 0.2 169.7 ± 17 72 ± 4.2%
4 500 93% Flotation time of 10 min, impeller
speed of 1000 RPM, and airflow rate
of 4.5 Lpm.
8e10 e 99% COD Separation time <10 min and velocity
removal gradient ¼ 145 s1
6 500 >95% Addition of anionic collector sodium
oleate ¼ 50 mg L1; Recovery ratio ¼ 30%
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