Chemical Engineering Journal Advances 4 (2020) 100049

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Chemical Engineering Journal Advances

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

Review article

Recent advances on the treatment technology of oil and gas produced

water for sustainable energy industry-mechanistic aspects and process
chemistry perspectives
Abass A. Olajire
Industrial/Environmental Unit, Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, Ogbomoso, Nigeria

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

Keywords: Produced water (PW) is the largest volume of wastewater generated during oil and gas recovery operations. It
Oil and gas produced water is a complex mixture of dissolved and particulate inorganic and organic matters ranging from near freshwater
Treatment technology quality to concentrated saline brine. The management of PW has been the main focus of oil and gas industry in
Process chemistry
view of the stringent legislations on the discharge of oil and gas PW into the environment and the potential of
Environmental legislation
PW as a source of fresh water, which hitherto comes from surface water, groundwater or municipal water, for
water deficient oil producing countries. This article reviews current technologies for the management of oil and
gas PW with a view of not only for more efficient removal and recovery of oils and other toxic agents, but also for
environmental sustainability and fit-for-purpose reuse. The purpose of this article is to present some of the main
technologies including primary treatment, secondary treatment including biological and membrane treatment
and tertiary treatment especially advanced oxidation processes (AOPs) that have been used for the treatment of
PW from oil and gas extraction; and to provide an overview of treatment technologies. The future developmental
research needs for management of PW is also discussed.

1. Introduction
Oil and gas produced water (PW) is the largest wastewater stream
(brine) that is brought up from the hydrocarbon bearing formation strata
during oil and gas exploration and production activities. It is a mixture
of formation water, a seawater or fresh water that has been trapped
for millions of years beneath hydrocarbons in porous reservoir medium
[1]; injection water; small volumes of condensed water from gas pro-
duction and residues of treatment chemicals that have been added to
ensure effective hydro-fracture operations. In gas fields, water injection
is not used, which thus implies that the PW in a gas field is a mixture of
formation water and condensed water. Consequently, the volume of PW
from a gas field has been reported to be less than that of oilfields [2].
Furthermore, the acidity of PW from a gas field has been reported to be
higher than that of the oilfield, and this might be due to the dissolved
CO2 and H2 S acidic gasses that are contained in the former [3].
An array of different solvents and chemicals are used in oil and gas
fields for exploration and production (E & P) activities [4], where about
one-third of these chemicals has been reported to be discharged in PW
[5]. The volume of oil and water generated or the water cut (the ratio of
water produced to the total fluid produced) has been found to increase
with the age of the well [6,7], where production capacity in a nearly
depleted field was reported to decrease to as low as 98% water cut [8,9].
The oil and gas PW treatment needs to meet the quality requirement
of water as set by regulatory bodies either for discharge/reuse and for
sustainability of the energy sector. The disposal of untreated oil and gas
PW containing many hazardous materials can interfere with the envi-
ronmental sustainability. The characteristics in term of the chemical and
physical composition of PW must be known to provide an appropriate
way of reducing the content of these hazardous substances in the PW
to a permissible level prior to disposal or fit-for-purpose reuse. Appro-
priate management strategy is therefore necessary to be put in place so
that oil and gas PW can be safely disposed to the environment and/or
reused without interfering with the environment and for the sustainabil-
ity of the energy sector. Recent papers have reviewed technologies for
the treatment of PW [10–13], however, review of technology develop-
ment by different research groups and detailed mechanistic aspects and
process chemistry of the technology are scanty. It is necessary to under-
stand the mechanistic chemistry of the process to provide information
on reaction pathways during treatment, and possible impacts of the by-
products formed on the environment. The main objectives of this review
are:
a To provide details of recent technologies available for the manage-
ment of oil and gas PW in view of significant challenge posed by
water scarcity in recent times,

E-mail addresses: olajireaa@yahoo.com, aaolajire@lautech.edu.ng

https://doi.org/10.1016/j.ceja.2020.100049
Received 23 August 2020; Received in revised form 28 October 2020; Accepted 31 October 2020
2666-8211/© 2020 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
Abass A. Olajire
b To focus on the use of combined methods for improving the quality
of PW for environmental and energy industry sustainability,
c To provide detailed mechanistic aspects and process chemistry of
the technology, thus giving information on reaction pathways dur-
ing treatment and the impacts of the by-products formed on the en-
vironment,
d To review the technology development by different research groups,
e To highlight the pros and cons of various treatment technologies,
f Finally, to discuss the future developmental needs that will recognize
produced water as part of the industry’s strategic water reserves for
reuse rather than as effluent.
2. Produced water volume
Globally, the estimated production volume of produced formation
water was around 250 million barrels per day compared with around
80 million barrels of oil produced per day, which gave a water cut of
around ∼ 80% [14]. However, the new report updates which expands
the 2007 report to provide a more recent estimate for the global volume
of PW generated from all onshore and offshore oil and gas production
gave a higher water cut of close to 85% [15]. Apart from site-specific
nature of the PW volume, it also depends on other parameters such as
age of the well, geographical location, reservoir history and production
technologies. The volume of PW generated every year keeps increasing
as production well ages [16], with the production capacity in a nearly
depleted oil field decreasing to as low as 2% oil to PW [8,9]. The an-
nual estimates of PW in the United States was around 890 billion gallons
(3.37 billion m3 ), thus making it the largest waste stream associated
with oil and gas activities [15]. The volume of PW generated tends to
increase on a yearly basis as old fields mature and as new oil fields
emerge [14,17], and these can be attributed to the expansion of uncon-
ventional oil and gas development, which produced more than 50% of
crude oil and natural gas in recent time [18]. The flow rate of PW varies
throughout the life of an oil and gas well, where little or no PW is gen-
erated by conventional oil and gas at the beginning, with increase in the
flow rate over time. However, a high PW flow rate is being generated
at the beginning by most unconventional hydraulically fractured wells
due to the flowback of the fracturing fluids, which then leveled up at a
relatively steady lower level with a decline in the flow rate [19].
3. Composition of oil and gas produced water
Composition of oil and gas PW is complex, and it includes dissolved
oil, dissolved hydrocarbons, dissolved gasses (particularly hydrogen sul-
fide and carbon dioxide), organic acids, phenols, metals [20]. Also, PW
contains traces of production chemicals (additives), which are strictly
regulated in most countries and their compositions do not contribute
to increased pollution load in PW. These oil-indigenous dissolved com-
ponents contain a wide range of recalcitrant organic compounds such
benzene, toluene, ethylbenzene, xylene (BTEX), polycyclic aromatic hy-
drocarbons (PAHs), phenols, organic acids, waxes, surfactants, biocides,
which are finally deposited as main contaminants in PW [21,22]. The
chemical structure of some of these compounds are shown in Fig. 1.
These substances have great influence on physico-chemical proper-
ties of PW and they vary widely depending on the geological location
of the field, geological age, geological formation, reservoir history, and
type of hydrocarbon product being produced [26,27]. Hence, “no two
PW are equivalent in properties”, which thus necessitates the need to
carry out studies on regional basis to address the impacts of PW dis-
charges on the environment [28]. The classification of various con-
stituents of oil and gas produced water is given in Fig. 2.
The chemical and physical properties of oil and gas PW have sig-
nificant impacts on its quality. The concentration range worldwide and
limits of main constituents of oil and gas PW are summarized in Table 1.
Chemical Engineering Journal Advances 4 (2020) 100049
3.1. Environmental footprints of produced water
Environmental footprints of PW are the environmental impacts
caused by disposal of PW and to clean up contamination related to the
improper disposal of PW. BTEX group exhibits a range of side effects
including poisoning, inhalation injuries, skin disorders, headaches, neu-
rological problems, aplastic anaemia, leukaemia etc. on humans, which
are acute or chronic, and may be deadly [32]. BTEX are rarely involved
when considering the ecotoxicological effects of PW on marine envi-
ronments [33] due to their high volatility and rapid degradation in the
seawater [25,34]. The discharge of PAHs has been given high prior-
ity in environmental pollution regulations and in risk assessment of in-
dustrial discharges because of their carcinogenic properties and other
health related issues including deoxyribonucleic acid (DNA) damage
[35], oxidative stress [36], cardiac function defects [37], or embyrotox-
icity [38]. Higher molecular weight PAHs have been reported to cause
various adverse effects in fish, including carcinogenicity, impairment
to genetic, reproductive and growth systems [39]. Alkyphenols have
constituted a greatest concern due their strong endocrine disruption ef-
fects, where the long-chained alkylphenols (C7 –C9 ) are considered the
most toxic but rarely exist in PW [34, 40]. The estrogenic effects in
vertebrates have been linked to the moderately and highly alkylated
phenols such as nonylphenol [25,41–43] and to a lesser degree, in al-
gae, clams, shrimps and crustaceans [41]. The high chronic toxicity of
highly alkylated alkyphenols, especially octyl- and nonyl-phenols, after
prolonged period of exposure has been predicated on their endocrine
disruption properties [44,45], though rarely exist at environmentally
acceptable concentration levels. Naphthenic acid is another constituent
of PW which have been reported to function as xeno-estrogens [46].
Naphthenic acids have been implicated in tailings pond water as they
pose a high risk to aquatic organisms and wildlife, mainly birds that en-
counter these tailings pond waters [47]. The levels of trace metals in fish
and shellfish collected close to offshore installations have been reported
to be significantly less than natural background concentration due to di-
lution and chemical processes that occur on entering the sea resulting to
rapid reduction in the concentration of these inorganic elements [48].
The environmental impact of PW is predicated on the chemical com-
pounds in PW which are potentially toxic to marine organisms due to
their inherent toxicity potentials. Studies have indicated low risk of
acute toxicity to marine environment from discharged PW [49,50], and
the main risk factor has been related to the concentration of constituents
rather than total discharge volumes of PW containing potentially impor-
tant hazardous components [49]. However, discharge volumes remain a
relevant factor that needs to be given consideration because operational
discharge associated with production drilling is related to PW influent
volumes.
4. Treatment technology of oil and gas produced water
Oil and gas PW need to undergo effective treatments in order to
fit into the current legislation with a view to its final disposal [51].
The treatment technology must meet the regulatory standard before dis-
charging into the environment or recycled for oil stimulation, civil us-
age, or use in cooling tower [52]. Stringent environmental regulations
require extensive treatment of oilfield PW prior to discharge into the
environment. Consequently, the treatment technology must be robust
and able to eliminate substantial amounts of contaminants such as sus-
pended solid particles and organic materials from oil and gas PW so as
to make the beneficial reuse of PW an attractive opportunity for oil and
gas industry [53].
The treatment technology for oil and gas PW is complex and thus
the strategy to be adopted for the treatment process must be appropri-
ately evaluated before deployment. The combinatory treatments involv-
ing physical and/or biological and chemical treatments, which are less
energy-intensive processes have been used to improve the water quality
in compliance with the regulatory body [54].
Abass A. Olajire
Various treatment methods are recently used in the oil and gas indus-
try, with the objectives of removing substantial amounts of pollutants
from PW prior to disposal to the sea or re-use for re-injection, irrigation,
wildlife consumption and habitat, and industrial water [55–57]. Fig. 3
is a process flow diagram for the treatment pilot plant system, where
PW to be treated is gathered directly from the oil/water separator unit
and/or the water storage tank [58].
Chemical Engineering Journal Advances 4 (2020) 100049
Fig. 1. Structures of compounds in oil and
gas PW [23-25].
The treatment processes are discussed below:
4.1. Primary treatment
The primary (physical) treatment processes entail elimination of
solid particles and hydrocarbon compounds from oil and gas PW [59].
The gravity separator (American Petroleum Institute (API) separator) is
Abass A. Olajire
Fig. 2. Constituents of oil and gas PW based on previous study [20].
used to separate oil and light fractions with lower density than water
from the PW generated from well head (Fig. 4). The settles sludge parti-
cles at the bottom of the separator will then be transferred to desanding
hydrocyclones for further treatment by gravity separation. The oily frac-
tions will be transferred to deoiling hydrocyclones to remove any traces
of oil from the PW by liquid-liquid separation. The polymeric flocculants
will be added to the separated water stream in a mixing reaction tank
to facilitate coalescence of particles by sedimentation. However, the use
of synthetic organic polymers such as polyacrylamides and polyamines
for PW clarification has been discouraged due to their toxicity under
certain conditions [60]. These restrictions have led to search for eco-
friendly, cost-effective and biodegradable coagulants such as bentonite
(coagulant aid) and chitosan (coagulants/flocculants) for clarification
of industrial wastewaters. The clarified water will then be sent for sec-
ondary treatment for further reduction of pollutants from the PW.
4.2. Secondary treatment
The secondary treatment entails removal of dissolved components
using various treatment options, including flotation method, biological,
and membrane treatment processes. However, combination of biological
treatment with membrane, referred to as ‘membrane bioreactor’ (MBR)
technology has recently been developed. The membrane treatments that
are commonly employed include microfiltration (MF) and ultrafiltration
(UF), nanofiltration (NF), and reverse osmosis (RO) methods. However,
NF/RO membrane techniques are often employed at tertiary treatment
Chemical Engineering Journal Advances 4 (2020) 100049
level for desalination of treated water to obtain ultra-pure water for fit-
for-purpose reuse.
4.2.1. Flotation method
Floatation technique is used to separate large and small oil droplets
from PW by injecting the air flotation chamber such as induced air flota-
tion or dissolved air flotation with nitrogen or natural gas (Fig. 5), which
enhances the floatability of the oil and reduces the separation time [61].
The efficiency of oil removal can be enhanced by optimizing the flota-
tion parameters such as gas flowrate, feed flowrates, gas bubble size,
flotation period and temperature. The separation of oil and water by
flotation technique is based on the Stokes’ law as expressed as follows:
2 𝑅 ( 𝜌𝑤 − 𝜌𝑜 )
2
𝑣= (1)
9 𝜇
where, v is the velocity of oil droplets rising to the surface, R is the radius
of the oil droplets, 𝜌w is the water density, 𝜌o is the oil density, 𝜇is the
water viscosity.
The larger the size of oil droplet, the greater the velocity. The larger
variance in density and lower viscosity of water increase the vertical
velocity and enhances the separation process. The effectiveness of gas
flotation can be determined by four steps, including generation of gas
bubbles, collision between gas bubbles and oil droplets, attachment of
gas bubbles with oil droplets and rise of the attachments to the surface,
giving rise to separation of water and oil at their outlets [62].
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 1
Main constituents in produced water worldwide [29,30].

Parameter
(mg/L) Oilfield PW Gas field PW Limit [31] Metals (mg/L) Oilfield PW Gas field PW Limit [31]

pH 4.3–10 3.1–7 6.5–8.5 Ca 18–132,687 Up to 51,300 100

Density 1014–1140 NA NA Na 316–134,652 520–120,000 NA
(kg/m3 ) 3.4–5960 67–38,000 NA K 8.6–14,649 149–3870 NA
TOC 1200 2600–120,000 ≤50 Mg 4–18,145 0.9–4300 100
COD NA 75–2870 ≤30 Fe < 0.1–100 Up to 1100 0.3
BOD 1.2–21,820 8–5484 30 Al 310–410 <0.5–83 ≤0.2
TSS 1 × 103 –4 × 105 2600–360,000 1200 B 5–95 Up to 56 1.0
TDS 8.2 NA <4.0 Ba 0–22,400 <1–1740 1.0
DO 2–565 NA NA Cd < 0.005–0.2 <0.02–1.21 0.005
TPH 0.39–35 NA NA Cr 0.02–1.1 Up to 0.03 ≤0.1
BTEX < 140 NA NA Cu < 0.002–1.5 Up to 5 1.3
Base/neutrals 80–310,561 1400–190,000 250 Li 3–50 18.6–235 NA
Cl 0–12,000 150–1149 NA Mn < 0.004–175 Up to 63 0.05
Br 0–500 NA NA Ni NA <1–9.2 0.30 0.015
I 1.9–7355 NA NA Pb 0.002–8.8 <0.2–10.2 NA
HCO3 0–800 NA NA Sr 0.02–1000 Up to 6200 NA
CO3 0.5–7851 <0.1–47 250 Ti < 0.01–0.7 NA 7.4
SO4 ∼10 NA NA Zn 0.01–35 <0.02–5 0.02
SO3 0–0.10 NA 5 As <0.005–0.3 Up to 151 0.005
PO4 0–3.5 NA 10 Hg <0.001–0.002 NA 0.10
NO3 0.05 NA 1.0 Ag <0.001–0.15 0.047–7.0 NA
NO2 10–300 NA 100 Be <0.001–0.004 NA 5
NH3 –N 9.7–600 NA NA NORM (pCi/L) 0.054–32,400 NA NA
Total polar < 1–63 NA NA Total Ra 238 U 0.008–2.7 NA 15
232
Higher acids Up to 23 NA 0.001 Th 0.008–0.027 NA NA
210
Phenol 2–4900 NA NA Pb 1.35–5130 NA NA
210
VFA 6.9–210 2.3–60 20 Po 0.005–0.17 NA
Oil and grease 0.015–0.611 NA NA
m-xylene 1.41–1.71 0.02 NA
MC 0.01–54 NA NA
MBAS 0.6–2000 NA 5
HEM 6.1–200 NA NA
Alkalinity
(CaCO3 )
MC, methylene chloride; VFA, volatile fatty acids; MBAS, methylene blue active substances (anionic surfactants); HEM, hexane extractable materials; NORM,
naturally occurring radioactive materials; pCi/L, picocuries per liter; mg/L, milligrams per liter; 𝜇g/L, micrograms per liter; NA, not available; TOC, total
organic carbon; COD, chemical oxygen demand; BOD, biological oxygen demand; TSS, total suspended solid; TPH, total petroleum hydrocarbons; BTEX,
benzene, toluene, ethylbenzene and xylene;.

4.2.2. Biological treatment method
The biodegradable organic matter contained in wastewater can be
converted into simpler substances and additional mass (biomass) by
a wide variety of microorganisms and the biomass is separated from
treated wastewater through sedimentation. The bioconversion equation
is represented as follows:
COHNS+O2 +bacteria → CO2 +NH3 +Energy + other end − products
Organic mat t er
The thick biomass is formed from the biosynthetic transformation of
the colloidal and dissolved organic matter into new cell as represented
below:
COHNS+O2 +bacteria → C5 H7 NO2 → biomass
Dissolved New cell sludge
organic mat t er
These microorganisms consumed the dissolve contaminants in the
wastewater in the bioreactor tank to form additional biomass (sludge).
The water is washed out of the reactor for clarification leaving behind
the sludge (solid waste) containing both live and dead bacteria, at the
bottom of reactor. The effluent from clarifier enters a filtration unit,
from where it is discharged or recycled. A typical flowchart of biological
treatment process is shown in Fig. 6.
Several studies have been conducted to evaluate the effectiveness of
biological treatment of PW. Recently, Kuyukina et al. [64] evaluated the
feasibility of a fluidized-bed bioreactor (FBB) process using sawdust co-
immobilized Rhodococcus cultures for the concentrated oilfield PW pu-
rification. The FBBs with developed biofilms were reported to perform
better in the removal of petroleum hydrocarbons, giving 70% biodegra-
dation efficiencies for alkanes and PAHs within two weeks compared
to corresponding 24 and 37% for non-inoculated FBBs. Also, 75–96%
removal efficiency of heavy metals (Al, Cr, Cu, Fe, Hg, Zn, Mn) was re-
ported from combined effects of physical sorption by the sawdust and
biosorption by the Rhodococcus biomass. In a related study, Serebren-
nikova et al. [65] investigated the possibility of using a consortium of
(2a) actinobacteria from the genus Rhodococcus immobilized on a polymeric
carrier for oilfield PW treatment in a bioreactor. Their study revealed
that Rhodococcus opacus IEGM 263 and Rhodococcus ruber IEGM 231
cells remained viable at high concentrations of mineral salts in water
and were able to oxidize oil hydrocarbons up to 62–81%. The study
further showed that the consortium of Rhodococci was more efficient in
the elimination of hydrocarbons from wastewater than monocultures.
(2b)
Camarillo and Stringfellow [66] reviewed biological processes for the
treatment of oil and gas PW, where the process was adjudged to be
promising and could be incorporated into a larger treatment train for
production of effluents suitable for reuse. Recently, Pendashteh et al.
[67] evaluated the potential of acclimated halophilic microorganisms,
commercial microorganisms, and microorganisms from polluted soil
to degrade crude oil of high salinity oily wastewater (synthetic pro-
duced water) in a batch stirred tank reactor at different salt concen-
trations ranging from zero to 250,000 mg/L of total dissolved solids
(TDS). The removal efficiency of commercial microorganisms was re-
ported to be less than that of acclimated halophilic microorganisms,
that was found to have the highest degradation of crude oil (> 60%) at
TDS of 35,000 mg/L. In a related study, Sudmalis et al. [68] investigated
simultaneous n–alkane biodegradation and production of neutral lipids
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Fig. 3. Treatment processes of oilfield produced water based on the previous study [58].

in a concentrated PW stream with Alcanivorax borkumensis SK2 as the
sole reactor inoculum. N-alkane removal efficiency of up to 99.6%, with
influent alkane COD of 7.4 g/L was achieved in a continuously oper-
ated reactor system. Their results also showed that most other non-polar
compounds present in the PW were biodegraded. Biodegradation of n-
alkanes was reported to be accompanied by simultaneous production of
neutral lipids, mostly wax ester-alike compounds. Silva et al. [69] ex-
amined mixed cultures for heterotrophic nitrification/aerobic denitri-
fication by microbiota from oil PW biological treatment system in hy-
persaline conditions. Their findings showed that acclimated mixed cul-
ture salts exhibited high efficiency in heterotrophic nitrification/aerobic
denitrification process in hypersaline conditions and they were able to
remove 80% of ammonium in heterotrophic nitrification medium with
12 and 14% of salt and up to 40% ammonium removal in hypersalinity
conditions, such as 20% of salt. Thus, these mixed acclimated cultures
were reported to have a potential for application in hypersaline efflu-

Fig. 4. Primary treatment scheme based on the previous study [59].

Abass A. Olajire
Fig. 5. Principle of flotation method based on the previous study [61].
ent treatment. The potentials of five local microalgae strains including
Monoraphidium, Chlorella, Neochloris, Scenedesmus, and Dictyosphaerium
for the removal of pollutants from PW of a local petroleum industry were
evaluated by Hakim et al. [70]. The five microalgae strains species were
reported to show a significant amount of biomass generation within
different concentrations of PW. Although biomass yield was found to
vary significantly among the microalgae strains, nitrogen removal effi-
ciency was reported to be similar for all strains while organic carbon
removal differs. Scenedesmus sp. was reported to achieve 63.76% to-
tal nitrogen removal efficiency from PW, while Dictyosphaerium sp. was
able to achieve 88.83% phosphorus and various metals removal effi-
ciencies. Neochloris sp. was reported to remove 41.61% of TOC from
different concentrations of PW despite its low biomass generation. All
the five microalgae strains were reported to achieve 100% benzene and
ethylbenzene removals for different concentrations of PW, with reten-
tion of small amount of toluene and xylene in the PW. In a separate
study, Riley et al. [71] examined the effectiveness of biologically ac-
tive filtration (BAF) and three granular active carbon (GAC) media (one
spent and two new) and two nutrient mix supplements for the removal
of chemical oxygen demand (COD) and dissolved organic carbon (DOC)
from PW. Their findings revealed considerable removal efficiencies of
92% and 81% of DOC and COD respectively in 24 h by the spent GAC
with extant biofilm, indicating the use of BAF as a pre-treatment for sub-
sequent desalination. The performances of microbial fuel cells (MFCs)
and microbial capacitive deionization cells (MCDCs) for the treatment of
PW from the Bakken shale were compared by Shrestha et al. [72]. MFCs
were reported to achieve COD removal efficiency of 88% while MCDCs
were limited to 76% COD removal efficiency. However, the MCDCs were
reported to achieve two-fold higher removal efficiency of total dissolved
solids (69%) than MFCs (32%).
Bioreactor-based methods have been found to be suitable for the
treatment of industrial hydrocarbon-containing wastewater. Very re-
cently, Kuyukina et al. [73] reviewed various bioreactor-based meth-
ods, including stirred-tank, membrane, packed-bed and fluidized-bed
constructions, for the treatment of industrial hydrocarbon-containing
wastewater. The method was reported to have substantial advantages,
including more precise control and management of biodegradation pa-
rameters, increased mass transfer between the aqueous, hydrocarbons,
and biocatalyst phase and higher resistance of the immobilized biomass
to toxic effects, over the traditional activated sludge (AS) systems. In a
related study, the bio-treatability of PW Qatari gas fields in a membrane
bioreactor (MBR) under varying conditions of hydraulic retention time
(HRT: 16–32 h), solid retention time (SRT: 60–120 d), and temperature,
(22–38 °C) was evaluated by Janson et al. [74]. Their results indicated a
removal efficiency of 60% of COD from PW at HRT of 16 h. Alsalhy et al.
[75] investigated the effects of mixed liquor suspended solid (MLSS) of
concentrations 500 and 1000 mg/L at pre-heating temperatures of 25,
Chemical Engineering Journal Advances 4 (2020) 100049
45 and 55 °C of the influent wastewater and different pre-heating peri-
ods of 15, 30 and 45 min on the performance of MBR for the removal of
COD, BOD, oil content, phenol and turbidity from industrial wastewa-
ter in Daura refinery in Baghdad. Their results showed that the removal
efficiencies of 71, 60, 100 and 100% of COD, BOD, oil content and phe-
nol respectively could be enhanced by increasing MLSS concentration to
1000 mg/L and at pre-heating temperature of 55 °C. Recently, the behav-
ior of a hollow fiber MBR system for the treatment of wastewater con-
taminated by petroleum hydrocarbons in terms of removal efficiency,
microbial activity and membrane fouling was investigated by Capodici
et al. [76]. Their results showed good performances in terms of COD
removal and nitrification, thus suggesting the adaptation of the biomass
to hydrocarbons. Table 2 summarizes the recent studies on biological
treatment of oil and gas PW.
4.2.3. Membrane technology
Membranes are microporous films with specific pore ratings, which
selectively separate a fluid from its components. Membranes can be clas-
sified according to the pore size as microfiltration (MF), ultrafiltration
(UF), nanofiltration (NF) and reverse osmosis (RO) [77]. The hydrody-
namic resistance for the passage of the liquid increases as the pore size
decreases, which thus implies that the applied pressure for the opera-
tion of the membrane will dramatically increase as the pore size of the
membrane decreases (Table 3). The operational principles of MF and UF
are based on convective pore -flow mechanism (Darcy’s law) whereas
RO operates on solution diffusion mechanism (Fick’s law) and NF mem-
brane is in between pore-flow and diffusion mechanism [78]. Membrane
technology has been applied by various researchers to achieve different
separations in the PW treatment [79-81]. The application of membrane
technology in the treatment of PW range from mild treatment target-
ing at removing suspended solids to desalination. A better-quality water
with less sludge generation is provided by this technology. More details
about basics of membrane technology can be found in the books on
membrane science and technology [78,82].
4.2.3.1. Microfiltration. The nominal pore size of the membrane filter
is 0.1–10 μm, which allows movement of water, metal ions (mono- and
multivalent) and viruses through its membrane filter with the retention
(rejection) of most bacteria and protozoa cysts and suspended solids. It
is employed in the removal of color, odor, viruses and colloidal organic
matter [83]. The susceptibility of the membrane to biofouling and even-
tual clogging due to a build-up of microorganisms on the membrane
filter reduces the flow through the membrane and thus results to poor
quality of the permeate. Therefore, periodic backwashing and chemical
cleaning of the membrane filter will guarantee the sustenance of the
performance of MF.
MF has been reported to be effective for the removal of suspended
particles and turbidity in effluents [84,85]. The membrane fouling has
been reduced by combining the MF process with pre- and post-treatment
steps to achieve the desired permeate quality [86,87]. The MF process
has also been used as a pre-treatment step for other membrane opera-
tions like ultrafiltration (UF) and nanofiltration (NF) for PW treatment
and for the removal oil from wastewater before final discharge or sub-
sequent treatment [86,88,89].
A lot of studies have been carried out to investigate the effective-
ness of MF membrane on treatment of PW. Chaturabul et al. [90] used
Hollow fiber supported liquid membranes (HFSLM) to remove mer-
cury (II) from PW. Their study revealed that it was possible to extract
99.7% of mercury (II) from PW with 90% recovery at maximum op-
erating condition. The treated PW was reported to contain < 5 ppb
Hg, which falls within the regulatory limit for discharge into the en-
vironment. In another related study, Hu et al. [91] separated synthetic
oil/water using graphene oxide (GO) modified Al2 O3 based MF mem-
brane. The modified GO membrane was found to have higher oil re-
moval efficiency with ∼ 28% permeate flux than the unmodified mem-
brane. Recently, the performances of an integrated microfiltration (MF)
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 2
Recent studies of bioreactors used for the treatment of oil and gas produced water.

Bioreactor configuration Operational conditions Treatment efficiency Reference

FBB Hydrophobized saw-dust immobilized 70% removal of alkanes and [64]

Rhodococcus ruber IEGM 615 and PAHs,75–96% removal of heavy metals
Rhodococcus opacus IEGM 249.
FBB Poly(vinyl alcohol) cryogel Removal of 64–82% TPH [65]
immobilized Rhodococcus ruber IEGM
231 and Rhodococcus opacus IEGM
263.
BAF/GAC Spent and new GAC carriers as 81% COD and 92% DOC removals in 24 [71]
indigenous biofilm. h
Batch stirred tank Bioreactor Acclimated indigenous halophilic >60% degradation of crude oil [67]
microorganisms
Continuously operated stirred tank Simultaneous n-alkane biodegradation Alkane removal up to 99.6% [68]
reactor and production of neutral lipids by
Alcanivorax borkumensis SK2.
ASP Each mixed culture was inoculated 80% removal of Ammonium [69]
into culture medium for nitrifying
heterotrophic bacteria (HNM) and
were subjected to treatment I) HNM
medium without NaCl and treatment
II) HNN medium with 6–20% NaCl.
MFCs and MCDCs Two-compartment MFCs and three 88% COD (MFCs) and 76% COD [72]
compartment MCDCs were evaluated (MCDCs) removal efficiencies.
under batch-fed mode using mixed
microbial consortia in the anode,
ferricyanide in the cathode, and
produced water as the electrolyte in
the anode and capacitive deionization
units.
32%TDS (MFCs) and 69% TDS(MCDCs)
removal efficiencies
MBR The bench-scale continuous 60% COD removal efficiency at HRT of [74]
membrane bioreactor (MBR) system 16 h
consisting of three parallel
bioreactors, each with 1 L working
volume and designated as bioreactors
800 L of PW was processed. (HRT:
16–32 h, SRT: 60–120d; Temp.:
22–38 °C)
Submerged MBR Submerged MBR (PVC pipes joined 71%COD, 60% BOD, 100% oil content, [75]
with PVC fittings). and 100% phenol removal efficiencies
MLSS concentrations: 500 and
1000 mg/l; Initial preheating
temperatures of wastewater: 25, 45,
55 °C, Preheating periods:15, 30 and
45 min.; Voily wastewater =18 L; VAS = 2 L
MBR plant MBR plant equipped with an Good performance for COD removal [76]
ultrafiltration (UF) hollow fiber and total reduction in the membrane
membrane module. fouling
Permeate flux (L. m–2 h–1 ): 15, Flow
rate (L h–1 ): 0.8 HRT (h): 27;
Voily wastewater = 20 L; MLSS conc.: 4 g
TSS L–1
FBB = fluidized-bed bioreactor; BAF = biological aerated filter; GAC = granular active carbon; ASP, activated sludge process;
MFCs = microbial fuel cells; MCDCs = microbial capacitive deionization cells; MBR = membrane bioreactor.

Fig. 6. flowchart of biological treatment pro-

cess based on the previous study [63].
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 3
Properties of membrane technologies for the treatment of produced water.

Technology Porosity (μm) Pressure (bar) Mechanism of separation Material type Removal

Microfiltration 0.1–1.0 1–5 Separation by sieving through Polymeric & Suspended solids, large organic
macropores ≥ 50 nm inorganic/porous molecules and large colloidal
particles including
microorganisms such as bacteria,
macromolecules (used for
reducing colloidal suspension and
turbidity)
Ultrafiltration 0.01–0.1 1–7 Separation by sieving through Polymeric & Dissolved solute molecules and
mesopores (2 – 50 nm) inorganic/porous suspended colloidal particles
including bacteria and
macromolecules such as proteins,
viruses, humic acids„
Nanofiltration 0.001–0.01 5 – 10 Separation through polymeric/dense color, voc, pesticides, mtbe
combination of charge (methyl tert-butyl ether),
rejection, solubility-diffusion multivalent ions like mg2+ , al3+ ,
and sieving through so4 2− , po4 3− etc., and specific
micropores (< 2 nm) charged or polar molecules.
Reverse osmosis < 0.001 15 – 70 Separation is based on the Polymeric/Dense Low molecular weight
difference in solubility and components such as inorganic
diffusion rates of water and ions and metals (arsenic, lead).
solutes.

and direct contact membrane distillation (DCMD)/membrane crystal-
lization (MCr) systems were evaluated for the recovery of freshwater
and minerals from PW by Ali et al. [55]. They carried out thermody-
namic/exergetic/quantitative analysis based on the experimental data.
Their results showed efficient conversion of PW into salt and freshwa-
ter with the integrated system, thus reducing waste disposal issue, as
indicated from the very low values of mass and waste intensities, re-
spectively.
4.2.3.2. Ultrafiltration. Ultrafiltration (UF) has smaller pore size rang-
ing from 0.01 – 0.1 μm, and allows total removal (rejection) of bacteria,
viruses, protozoa, silica, proteins, plastics, endotoxins and smog and/or
fumes. A slightly higher pressure than MF is needed for its operation. UF
is an effective method for the removal of oil from PW when compared
with the traditional separation methods [92], and has been reported to
be more efficient than MF for the removal of hydrocarbons, suspended
solids and dissolved constituents from oilfield PW [93].
Studies have been carried out by various researchers to evaluate the
effectiveness of UF for the treatment of PW. Salahi et al. [94] used a
polyether sulfone (PES) asymmetric UF membrane to treat PW. The pre-
pared PES UF membrane was reported to show rejection of total organic
carbon (TOC) (96.3%), chemical oxygen demand (COD) (83.1%), tur-
bidity (99.3%), oil and grease content (99.7%), and total suspended
solid (TSS) (100%) with high permeation flow of 84.1 L/m2 h and
fouling resistance of 63.0%. The quality of PW treated with UF pro-
cess was reported to be better than the quality of feed water used for
cooling tower in the Tehran oil refinery. In a related study, Mosle-
hyani et al. [95] used hybrid photocatalytic reactor and polyvinylidene
difluoride/multi-walled carbon nanotubes (PVDF/MWCNT) UF mem-
brane process to treat refinery wastewater. After the pre-treatment by
photocatalytic reaction, the feed was passed through PVDF/MWCNT
nanocomposite UF membrane to give the permeate, which indicated
>99% removal efficiency of organic pollutant.
Recently, Ahmad et al. [96] prepared a cost-effective polyvinyl chlo-
ride/bentonite (PVC/bentonite) UF membranes and evaluated their per-
formance for the treatment of oilfield PW. Their study indicated a max-
imum oil rejection of 98.6% at maximum permeation flux with the use
of the membranes.
4.2.3.3. Nanofiltration. Nanofiltration (NF) is a pressure-driven mem-
brane filtration process with a pore-size range of 0.001–0.01 μm, larger
than that of RO. It effectively retains only divalent and bigger particles,
providing > 99% rejection of divalent ions while monovalent particles
such as sodium chloride permeate through the NF film, hence not useful
in water desalination process but a robust technology for water soften-
ing, metal removal and contaminants as small as 0.001 μm [83].
Few studies have been conducted of late to investigate the effective-
ness of NF membrane for the treatment of PW. Sherhan et al. [97] in-
vestigated the application of ultrafiltration (UF) and nanofiltration (NF)
processes in the treatment of raw PW. Various types of hollow fiber
membranes including poly vinyl chloride (PVC) UF membrane, two dif-
ferent polyether sulfone (PES) NF membranes, and poly phenyl sulfone
PPS NF membrane were utilized in their study. Their results showed
that these types of membrane can be used to remove all contaminants
including COD, oil content, 𝑆𝑂42− , 𝑁𝑂3− , and all heavy metals except
conductivity, TDS and Cl− . Recently, Sadrzadeh et al. [98] provided
proof of-concept for NF treatment of the following PW streams in the
steam-assisted gravity drainage (SAGD) operation: warm lime softener
inlet water, boiler feed water, and boiler blowdown water. Their re-
sults showed that commercial NF membrane could remove up to 98%
of the total dissolved solids (TDS), total organic carbon (TOC) and
dissolved silica compared to the removal efficiencies of conventional
SAGD-produced water treatment processes. Their finding further in-
dicated that more than 99% removal efficiency of divalent ions was
achieved with the use of tight NF membranes, thus confirming the po-
tential of NF softening for oil sands PW streams. In a related study, Riley
et al. [99] evaluated the use of close circuit desalination with nanofiltra-
tion (NF) and reverse osmosis (RO) to remove TDS and organic matter
from pre-treated PW. Their results showed removal efficiencies of 99.6%
and 89% for TDS and dissolved organic carbon (DOC), respectively from
PW to produce high quality permeate, thus suggesting close circuit de-
salination as a promising method to facilitate the reuse of PW.
4.2.3.4. Reverse osmosis. Reverse osmosis (RO) has pore size of
<0.001 μm, smaller than NF. It effectively removes contaminants as
small as 0.0001 μm. RO membrane technology with adequate pre-
treatment has been reported to be efficient for PW treatment [100],
with a life expectancy of 3–7 years [101]. RO rejects all ionic species
and only water molecules pass through the membrane and rejection of
solutes from water was mostly more than 99% [100,101].
Several researchers have carried out studies to evaluate the effec-
tiveness of RO membrane for PW treatment. Piemonte et al. [102] per-
formed the RO process simulation for three different salinities using
the IMSDesign Software by HydranauticsTM [103]. Their results showed
that the RO process decreased the concentrations of TDS in all stud-
ied cases to 160.2, 449.5 and 55.1 mg/L from 35,546, 71,127, and
Abass A. Olajire
106,670 mg/L in the feed stream, respectively, which are all within the
limits for reuse, thus suggesting the viability of the RO process in get-
ting high quality water for multipurpose reuse. Recently, a combined
forward osmosis (FO)/reverse osmosis (RO) in a pilot system was used
by Maltos et al. [104] to treat raw PW from the Denver-Julesburg basin
(Colorado) for over a period of four weeks. Their results indicated that
the FO-RO pilot system achieved > 99% rejection of nearly all measured
ions and > 95% rejection of hydrocarbons. However, high concentra-
tions of organic compounds were reported to cause severe fouling of
the FO membrane, which thus reduced the water flux by 68% within
21 days. In a related study, Guo et al. [105] evaluated the performance
of a combined UF/RO membrane process for the treatment of flowback
and produced water from Weiyuan shale gas play, China. Their results
showed that the RO process decreased the concentrations of TDS, chemi-
cal oxygen demand (COD) and chloride (Cl− ) to 192, 267.5 and 97 mg/L
from 18,900, 530 and 11,000 mg/L in the feed, respectively under a con-
stant pressure of 4.5 MPa.
The PW quality, the load of solids and the formation of fouling during
the treatment are the major parameters that determine the efficiency of
the membrane technologies. These challenges can be addressed by using
a combined system that comprises of a low-pressure membrane filtration
followed by high-pressure membrane filtration [106]. Table 3 summa-
rizes the operational principles and removal potential of the commonly
used membrane technologies.
In summary, membrane separation technology has shown a great
promise for the treatment of produced water due to excellent efflu-
ent quality, higher organic loading, reduced sludge production, long-
term reusability and compact footprint over the conventional activated
sludge process [107–110]. However, membrane fouling that reduces the
quality of effluent, increase energy consumption and cleaning frequency
which might lead to a shorten life span of the membrane and higher op-
eration costs (OPEX), still remains one of the major concerns of mem-
brane separation technology [111–113]. Therefore, membrane surface
modification should be the future focus in membrane technology to en-
hance its antifouling property that has attracted scientific interest in
recent times [114–118].
4.2.4. “Schmoo” handling methods
The “schmoo” is a viscous oil-wet tar-like substance that is formed
when the primary solids in oilfields PW (silica, iron oxides, iron sulfides,
and sulfate and/or carbonate scale deposits with or without NORM) are
bound with oil contents, residual production chemicals (corrosion in-
hibitors, emulsion breakers, scale inhibitors and scale dissolvers), and
biomass (bacteria and bacterial products). Oil contents cause the adher-
ence of suspended solids with residual chemical and biomass, and the
sum of these species quickly deteriorates water quality as the produc-
tion of treated oilfield PW approaches the design limit of the effluent
treatment plant (ETP).
The treatment of “schmoo” deposits is complex and it consists of
three extensive stages. The first stage involves mechanical removal of
some of the “schmoo” from the bottom of the wellbore and tubular
lining using coiled tubing fitted with a jetting nozzle with alternating
fluids. The first cleaning fluid is either seawater or oil-free brine wa-
ter or makeup brine water mixed with a selected material to break up
“schmoo” while the second fluid is gelled water to assist in lifting the
dispersed “schmoo” out of the treated well. The mechanical stage is
then followed by acid treatment to remove some of the oil contents and
rust from the tubing. The extensive chemical treatment using a vari-
ety of surfactants, miscible solvents, oxidizers, and acids to disperse the
“schmoo” will then be carried out immediately after the acidification
stage. The mechanical and acidification stages serve as a pre-treatment
for the extensive chemical treatment stage. The stabilized “schmoo” can
therefore be easily handled without any health hazard. The disposal of
“schmoo” directly into the landfill or ocean after treatment is not a sus-
tainable disposal option. It is therefore imperative to establish a suit-
able “schmoo” management strategy that is environmentally friendly,
Chemical Engineering Journal Advances 4 (2020) 100049
Table 4
Oxidation potential of common ROS used in
AOPs [136,137].
ROS Potential (Eϑ /V)
•
Hydroxyl radical (HO ) 2.86
𝑆𝑢𝑙𝑝ℎ𝑎𝑡𝑒 𝑖𝑜𝑛 𝑟𝑎𝑑𝑖𝑐𝑎𝑙 (𝑆𝑂4∙ − ) 2.60
Oxygen atom (O) 2.42
Ozone molecules (O3 ) 2.07
𝑂𝑧𝑜𝑛𝑒 𝑖𝑜𝑛 𝑟𝑎𝑑𝑖𝑐𝑎𝑙 (𝑂3∙ − ) 1.80
Hydrogen peroxide (H2 O2 ) 1.78
Oxygen molecules (O2 ) 1.23
𝑃 𝑒𝑟ℎ𝑦𝑑 𝑟𝑜𝑥𝑦𝑙 𝑟𝑎𝑑 𝑖𝑐𝑎𝑙 (𝐻𝑂2∙ ) 1.06
𝑆𝑢𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒 𝑎𝑛𝑖𝑜𝑛 (𝑂2∙ − ) 0.94
Sin𝑔 𝑙𝑒𝑡 𝑜𝑥𝑦𝑔 𝑒𝑛 (1 𝑂2 ) 0.6
ROS, reactive oxygen species; AOPs, advanced ox-
idation processes.
sustainable and cost-effective. This can be achieved through character-
ization of the treated “schmoo” that will permit effective utilization
of the “schmoo” through recycling and reuse either for brick making
[119,120], ceramic making [121,122], cement production [123,124],
cementitious material [125,126] and light weight aggregate [127,128].
4.3. Tertiary treatment
Tertiary PW treatment (also called water polishing technique) in-
volves a series of additional steps after secondary treatment to further
reduce organics, turbidity, nitrogen phosphorus, metals and pathogens.
The oxidation and degradation-based techniques including advanced ox-
idation processes (AOPs) have been developed as an emerging destruc-
tion technology for the total mineralization of most of the organic con-
taminants in PW to improve its quality prior to discharge or reuse in
specific industrial applications.
4.3.1. Chemical treatment technology
This entails the use of chemical oxidants for the oxidation of organic
contaminants in oil and gas PW to less harmful products like CO2 and
H2 O [129]. The oxidants such as pure oxygen, ozone (O3 ), hydrogen
peroxide (H2 O2 ) etc. or combination thereof are used for conventional
oxidation process. However, the oil and gas PW contains recalcitrant
pollutants [130], such as BTEX, phenols and acetic with a low reaction
rate with radicals, and thus are difficult to decompose [22] by these
oxidants. This then necessitates the need for a novel technique such as
advanced oxidation processes (AOPs), which is cost-effective and effi-
cient, for complete oxidation of contaminants including recalcitrant or-
ganic compounds in PW. In AOPs, extremely reactive hydroxyl radicals
are generated for the degradation of contaminants in PW to produce a
less toxic intermediate product.
4.3.1.1. Advanced oxidation processes. The insufficient oxidation poten-
tial of natural air and oxygen, as well as other conventional oxidants
such as NaOCl and H2 O2 has necessitated the need to develop a simple
and effective treatment process which can effectively remove contam-
inants in PW. The use of AOPs for the treatment of wastewater and
PW has therefore attracted the attention of many investigators in re-
cent times [131–133]. In AOPs, highly reactive radicals are generated
for complete oxidation of organic pollutants in wastewaters [133–135],
where the radicals attack the electron-rich organic compounds for their
complete degradation. The oxidation potential of some ROS used in
AOPs in decreasing order of their oxidizing power is listed in Table 4.
The degradation potential of hydroxyl radical(HO• ) could be at-
tributed to its higher oxidizing power compared to other oxidants
(Table 4). The special features of AOPs has to do with the eco-friendly
end-product generated by the process, coupled with the ability to min-
eralize a wide range of organic pollutants. Apart from the artificial light
sources, which is costly and hazardous, solar energy can also be used to
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

generate hydroxyl radicals, which thus makes AOPs to be highly cost-

effective. The mechanistic aspects for the degradation of organic com- 𝑂3− ∙ + 𝐻 + → 𝐻𝑂3∙ (6e)
pounds in PW by the hydroxyl radicals (HO• )are highlighted below:
Step 1: Initiation reactions during which alky radical species (R• ) 𝐻 𝑂3∙ → 𝐻 𝑂∙ + 𝑂2 (6f)
and water are formed via dehydrogenation or abstraction of a hydrogen
atom from hydrocarbon compounds such as alkane as shown in Eq. (3).
𝐻 𝑂∙ + 𝑂3 → 𝐻𝑂2∙ + 𝑂2 (6g)
RH + HO → H2 O+R
∙ ∙
(3) Ozone can also be catalytically decomposed to generate hydroxyl
Step 2: Propagation reactions involving the reaction of alkyl radical radicals (called catalytic ozonation processes). The process can be sub-
species (R• ) with molecular oxygen to generate alkoxyl radical, 𝑅𝑂2∙ divided into homogeneous and heterogeneous catalytic ozonation. In
(Eq. (4a)) or reaction of alkyl radical species with other neutral organic the former, transition metal ions such as Cr3+ , Zn2+ , Fe2+ etc. are used
molecules (Eq. (4b)) as follows: as catalysts to speed up the ozonation process, aiming at degrading the
organic pollutants in PW [139–141]. The generation of hydroxyl radical
𝑅∙ + 𝑂2 → 𝑅𝑂2∙ (4a) from decomposition of ozone using Fe2+ as a catalyst (Eq. 7) is shown
in the reaction below [142]:
𝑅∙ + 𝑅∕ 𝐻 → 𝑅𝐻 + 𝑅∕∙ (4b)
𝐹 𝑒2+ 𝑂3 → 𝐹 𝑒𝑂2+ + 𝑂2 (7a)
Electron transfer reaction in terms of redox reaction also occurs,
which ionizes the hydroxyl radical to hydroxide ion (Eq. (4c)) as fol- 𝐹 𝑒𝑂2+ + 𝐻2 𝑂 → 𝐹 𝑒3+ + 𝐻 𝑂∙ + 𝑂𝐻 − (7b)
lows:
However, in heterogeneous catalytic ozonation, a solid catalyst in-
𝑅𝑋 + 𝐻 𝑂∙ → 𝑅𝑋 ∙ + 𝑂𝐻 − (4c) cluding solid metals, metal oxides or metal supported metal oxides such
The organic compound is hydroxylated through the attack of the high as Fe, Cu, Pd, TiO2 , ZnO, MgO Al2 O3 , Cu/Al2 O3 , or Pt/Al2 O3 , etc. are
electron density sites by the HO• , leading to the formation of aromatic used to catalyze the decomposition of ozone [141,142], which occur on
or unsaturated aliphatic compounds, thus initiating oxidative chain re- the surface of the catalyst where the efficiency depends on the number
actions (eqns. 4d–f) as depicted below. of surface-active sites, pH of medium, water composition and proper-
ties of organic contaminants. Ozone decomposition in aqueous solution
𝐴𝑟𝐻 + 𝐻 𝑂∙ → 𝐴𝑟𝐻 (𝐻 𝑂)∙ (4d) in the presence of a solid catalyst is as given in the following reaction
sequence (Eq. (8a)–(8g)):
𝐴𝑟𝐻 (𝐻 𝑂)∙ + 𝑂2 → 𝐴𝑟𝐻 (𝐻 𝑂)𝑂2∙ (4e)
𝐼𝑛𝑖𝑡𝑖𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑒𝑝 ∶ 𝑂3 + 𝐻2 𝑂 → 2 𝐻 𝑂∙ + 𝑂2 (8a)

𝐴𝑟𝐻 (𝐻 𝑂)𝑂2∙ → 𝐴𝑟(𝐻𝑂) + 𝐻𝑂2− (4f)

Propagation step ∶ 𝑂3 + 𝑂𝐻 − → 𝑂2− ∙ + 𝐻𝑂2∙ (8b)
Step 3: Termination reactions where radicals combine to form neu-
tral molecules (eqns. 5a–d) as given below. 𝑂3 + 𝐻 𝑂∙ → 𝐻𝑂2∙ + 𝑂2 (8c)

𝑅 +𝑅 →𝑅−𝑅
∙ ∙
(5a)
𝑂3 + 𝐻 𝑂2∙ → 𝐻 𝑂∙ + 2 𝑂2 (8d)

𝑅 + 𝐻 𝑂 → 𝑅 − 𝑂𝐻
∙ ∙
(5b)
Termination step ∶ 2 𝐻𝑂2∙ → 𝐻2 𝑂2 + 𝑂2 (8e)

𝐻 𝑂 + 𝐻 𝑂 → 𝐻2 𝑂2
∙ ∙
(5c)
2 𝐻 𝑂 ∙ → 𝐻2 𝑂2 (8f)
𝑦
𝑅𝑂2∙ + 𝑦 (𝐻 𝑂 ∕𝑂2 ) → 𝑥 𝐶 𝑂2 + 𝐻2 𝑂
∙
(5d)
2 𝐻 𝑂2∙ + 𝐻 𝑂∙ → 𝐻2 𝑂 + 𝑂2 (8g)
The AOPs are classified according to the source of hydroxy radicals.
Ozone can also be decomposed in the presence of hydrogen peroxide
4.3.1.1.1. Chemical-based AOPs. The radicals are generated
(called peroxonation process), where hydrogen peroxide is partially dis-
through the interaction of the chemicals within the reactor and without
sociated into its conjugate base, the hydroperoxide ion(𝐻𝑂2− ) in aqueous
the involvement of energy. The various types are as discussed below:
solution (Eq. (9a)). The hydroperoxide ion reacts with ozone leading to
its decomposition (Eq. (9b)), with resultant series of chain reactions in-
4.3.1.1.1.1. Ozone-mediated AOPs. Ozone is unstable in aqueous
volving the radicals (eqns.6c, 9d–f) [143,144]. Ozone further reacts with
medium and it spontaneously decomposes via a complex mechanism to
hydroxyl radicals (Eq. (9f)) to produce more hydroperoxide radical that
generate hydroxy radical that is used for the oxidation of many organic
decomposes as shown in Eq. (6c), thus making it a continuous process.
and inorganic compounds in produced water [138]. Ozone decomposes
The pollutant is therefore susceptible to attack by direct route (reaction
into free radical either in alkaline medium, in the presence of a catalyst
with O3 ) or indirect radical pathway (reaction with HO• ).
or hydrogen peroxide. The decomposition of ozone in aqueous solution
into free radical is favoured at high pH and proceeds via the following
𝐻2 𝑂2 → 𝐻 𝑂2− + 𝐻 + (9a)
equations (eqns. 6a-g) as follows:

𝑂𝐻 − + 𝑂3 → 𝑂2 + 𝐻𝑂2− (6a) 𝐻 𝑂2− + 𝑂3 → 𝐻 𝑂2∙ + 𝑂3∙ (9b)

𝐻 𝑂2− + 𝑂3 → 𝐻 𝑂2∙ + 𝑂3− ∙ (6b) 𝑂2∙ − + 𝑂3 → 𝑂2 + 𝑂3− ∙ (9c)

𝐻 𝑂2∙ ⇄ 𝐻 + + 𝑂2− ∙ { 𝑝𝐾𝑤 = 4.8} (6c) 𝑂3− ∙ + 𝐻 + → 𝐻𝑂3∙ (9d)

𝑂2− ∙ + 𝑂3 → 𝑂2 + 𝑂3− ∙ (6d) 𝐻 𝑂3∙ → 𝐻 𝑂∙ + 𝑂2 (9e)

Abass A. Olajire
𝐻 𝑂∙ + 𝑂3 → 𝐻𝑂2∙ + 𝑂2 (9f)
Furthermore, direct reaction of ozone with hydrogen peroxide to
generate more hydroxyl radical may occur as shown in the following
equation (Eq. (9g)):
2 𝐻2 𝑂2 + 2 𝑂3 → 4 𝐻 𝑂 ∙ + 3 𝑂2 (9g)
A complete mineralization of recalcitrant organic contaminants in
wastewater can be quickly achieved by the highly reactive O3 /H2 O2
system [145,146]. The addition of H2 O2 accelerates the decomposition
of O3 with subsequent generation of hydroxyl radical (Eq. (9g)).
Various studies have been conducted to evaluate the effectiveness
of ozone for the treatment of oil and gas PW. The recent development
of ozone and biological aerated filter (O3 /BAF) was studied and ap-
plied in polishing different bio-treated secondary effluents [147]. Their
results showed that the combination of ozone and BAF was effective
for the removal of recalcitrant organic pollutants from wastewaters and
could obviously reduce their toxicity. Recently, Jing et al. [148] used
experimental and modeling approaches to study ozonation as a treat-
ment technology for the removal of polycyclic aromatic hydrocarbons
(PAHs) from offshore PW. Both elevated ozone dose and temperature
were found to have positive impacts on the rate at which PAHs are re-
moved from offshore PW due to improved mass transfer of ozone, high
yield of hydroxyl radical generated and high rate of decomposition of
ozone. Recently, Jiménez et al. [133] used AOPs for the treatment of PW,
where all organic components including a high percentage of acetic acid
(78%) and TOC (74%) were removed by ozonation combined with H2 O2
(peroxonation process). However, the authors suggested that doses of
ozone and H2 O2 could still be optimized for a larger scale operation.
4.3.1.1.1.2. Fenton-related AOPs
Fenton [149] described a process of enhancing the oxidizing power
of H2 O2 by mixing with a catalyst iron (II) (Fe2+ ), also called Fenton
reagent. A mixture of Fe2+ and H2 O2 is added to the wastewater, where
Fe2+ acts as a catalyst to generate the oxidant (HO• ) in accordance with
the following equation (Eq. (10a)) [150].
{ }
𝐹 𝑒2+ + 𝐻2 𝑂2 → 𝐹 𝑒3+ + 𝑂𝐻 − + 𝐻 𝑂∙ 𝑘 = 40 − 80 𝐿 mol−1 𝑠−1 (10a)
The Fe3 + produced in the above reaction (Eq. (10a)) reacts with
H2 O2 to regenerate Fe2 + (Eqs. (10b) and (10c)) [151]. This implies that
the Fenton process is catalytic with respect to Fe2 + salt and the gen-
eration of hydroxy radical (HO• ) can continuously take place in the
presence of H2 O2 in the reaction medium.
(10b)
{ }
𝐹 𝑒 − 𝑂𝑂𝐻 2+ → 𝐻𝑂2∙ + 𝐹 𝑒2+ 𝑘 = 2.7 × 10−3 𝑠−1 (10c)
The oxidation of many organic compounds including aromatic (phe-
nols, polyphenols, etc.) and aliphatic compounds (alcohols, aldehydes,
etc.) can be carried out with the use of Fenton reagent. The mechanis-
tic aspects of oxidation of organic compounds by Fenton reagent was
reported to be complex and unknown, but the following reaction steps
(Eqs. (10a) & (11)) were assumed to occur [152]:
𝐹 𝑒2+ + 𝐻2 𝑂2 → 𝐹 𝑒3+ + 𝑂𝐻 − + 𝐻 𝑂∙ (10𝑎)
𝑅𝐻 + 𝐻2 𝑂2 → 𝑃 1 (11a)
𝑅𝐻 + 𝐻 𝑂∙ → 𝑃 2 (11b)
where ′RH′is the organic compound, and ‘P1’ and ‘P2’ are respectively
intermediates and final oxidation products.
Chemical Engineering Journal Advances 4 (2020) 100049
Studies have been conducted to evaluate the effectiveness of Fen-
ton’s process for the treatment of oil and gas produced water. Recently,
Jiménez et al. [133] investigated the use of AOPs for the treatment of
PW, where the conventional Fenton process was reported to rapidly
eliminate 40% TOC at 70 °C without salts and 18% TOC at 20 °C but
slightly removed the recalcitrant acetic acid. Very recently, Yang et al.
[153] evaluated the effectiveness of the optimized in situ chemical oxida-
tion process using Fenton and activated persulfate oxidation for the re-
mediation of petroleum-hydrocarbon contaminated groundwater in the
batch and column experiments using benzene and toluene as the tar-
get compounds. Their study revealed that Fenton oxidation process has
higher reaction rates of 1.65 and 1.28 l/h for benzene and toluene, re-
spectively than activated persulphate oxidation with respective reaction
rates of 0.13 and 0.1 l/h for benzene and toluene.
Despite these promising results, Fenton reaction was reported to
have its own shortcomings including the slow regeneration rate of Fe2 + ,
use of high dosage of reagents, the need for separation of dissolved iron
from the medium and high accumulation of iron sludge which requires
additional cost of treatment for the generated secondary sludge and op-
eration of the process in acidic medium.
4.3.1.1.2. Photochemical AOPs. The complete mineralization of or-
ganic compounds in PW can be enhanced by the combination of UV ra-
diation or solar light irradiation with chemical-based AOPs, where the
hydroxyl radicals are photogenerated with UV lamps in the wavelength
of 200–380 nm range or by harnessing solar light energy (Eq. 12 a–d) as
given below.
(12a)
𝑒− + 𝑂2 → 𝑂2− (12b)
(𝑎𝑞)
𝐻 ∙ + 𝑂2 → 𝐻𝑂2∙ (12c)
𝐻𝑂2∙ + 𝑅𝐻 → oxidation products (12d)
4.3.1.1.2.1. Photolysis of ROS
Reactive oxygen species (ROS) such as O3 , H2 O2 or O3 /H2 O2 can be
photolyzed to generate hydroxyl radicals required for the degradation
of organic compounds in PW [145, 154]. Ozone has strong ability to
absorb UV light at wavelength of 254 nm (𝜆 = 254 nm)with molar ex-
tinction coefficient of 3300 M−1 cm−1 , where it undergoes homolysis in
the presence of UV light (Eq. (13a)), followed by generation of hydroxyl
radical by the reaction of excited oxygen (O∗ ) with water at the second
stage (Eq. (13b)) [155] as follows:
(13a)
𝑂 ∗ + 𝐻2 𝑂 → 2 𝐻 𝑂 ∙ (13b)
•
The hydroxyl radical (HO ) generated will now react with the or-
ganic compound (Eqs. (14a) & b) as shown below:
𝑅𝐻 + 𝐻 𝑂∙ → 𝐻2 𝑂 + 𝑅∙ (14a)
𝑅∙ + 𝑂2 → 𝑅𝑂2∙ (14b)
However, the major shortcoming of O3 /UV has to do with the high
cost of generating ozone, which consumes large amounts of electrical
energy and selectivity of molecular ozone.
The hydroxyl radicals can also be generated by the symmetrical split-
ting of H2 O2 in the presence of UV light (Eq. (15a)), also called pho-
toperoxidation process [156].
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

refinery wastewater. Their finding revealed that the UV/H2 O2 was able
(15a) to achieve 70.9% and 4.39% removal efficiencies of phenol and COD,
respectively after the reaction time of 3 h. In a similar study, Bustillo-
The quantum yield of the process has been reported to be very sub- Lecompte et al. [160] evaluated the potentials of UV-185/H2 O2 and
stantial, producing two moles of hydroxyl radicals as adsorbed [156]. UV-254/H2 O2 processes for the photochemical degradation of BTEX in
This is then followed by a series of radical reactions (Eqs. 8e-g & 15b, petrochemical wastewater in a continuous photoreactor. Their findings
c) as follows [157]: revealed that 80 and 90% of TOC were removed by UV-254/H2 O2 and
UV-185/H2 O2 respectively, at the residence time of 6 h and pH of 3. Az-
𝐻2 𝑂2 + 𝐻 𝑂∙ → 𝐻𝑂2∙ + 𝐻2 𝑂 (15b)
izah and Widasa [159] used UV/O3 /H2 O2 for the degradation of phenol
and removal of COD from residual fluid catalytic cracking (RFCC) refin-
𝐻2 𝑂2 + 𝐻 𝑂2∙ → 𝐻 𝑂∙ + 𝑂2 + 𝐻2 𝑂 (15c) ery wastewater. Their finding indicated that the UV/O3 /H2 O2 system
was able to achieve 93.75% and 12.2% removal efficiencies of phenol
2 𝐻𝑂2∙ → 𝐻2 𝑂2 + 𝑂2 (8𝑒) and COD respectively, after the reaction time of 2 h.
4.3.1.1.2.2. Photo-, electro- and sono-Fenton processes
2 𝐻 𝑂 ∙ → 𝐻2 𝑂2 (8𝑓 ) Photo-Fenton is based on Fenton reaction between H2 O2 and
Fe2 + or Fe3 + in the presence of UV irradiation. The UV light ac-
celerates both the formation of hydroxyl radical(HO• ) via photolysis
𝐻 𝑂∙ + 𝐻𝑂2∙ → 𝐻2 𝑂 + 𝑂2 (8𝑔)
of H2 O2 (Eq. (15a)) [161] and regeneration of Fe2 + via reduction of
The radicals generated (𝐻 𝑂2∙ and 𝐻 𝑂∙ )are good oxidants that can re- Fe3 + (Eq. (17a)) as follows:
act with organic compounds in PW. The dissociation of organic com-
pounds (Eq. (15d)) as well as the intermediates formed such as hydrogen
peroxides (Eq. (9a)), hydroperoxide radicals (Eq. (6c)) etc. are shown
below:
(17a)
𝑅𝐻 ↔ 𝑅− + 𝐻 + (15d)

The conversion of Fe3 + to Fe2 + by UV light (Eq. (17a)) also con-

𝐻2 𝑂2 → 𝐻 𝑂2− + 𝐻 + (9𝑎) tributes to the generation of hydroxyl radicals and the Fe2 + formed also
reacts rapidly with H2 O2 by the conventional Fenton reaction to yield
𝐻 𝑂2∙ ⇄ 𝐻 + + 𝑂2−∙ {𝑝𝐾𝑎 = 4.8} (6𝑐) more of the HO• radicals (Eq. (17b)) as follows:

The major shortcoming of the process is that the oxidation process 𝐹 𝑒2+ + 𝐻2 𝑂2 → 𝐹 𝑒(𝑂𝐻)2+ + 𝐻 𝑂∙ (17b)
uses a very small fraction of the incident UV light due to the small ex-
Electro-Fenton (EF) is based on electrochemical in situ generation of
tinction coefficient (18.6 M−1 cm−1 ) of H2 O2 at 257 nm [143].
Fenton’s reagents- a mixture of Fe2+ and H2 O2 to produce hydroxyl rad-
Since a single O3 /UV or H2 O2 /UV process may not often be suffi-
ical (HO• ) for the oxidation of organic pollutants in wastewater [162].
cient to meet the targets of PW treatment, it is therefore necessary to
The EF treatments can be classified into four different types depending
use combination of O3 /H2 O2 with UV in a ternary process comprising
on the addition or in situ generation of Fenton’s reagents [163]. It is type
of O3 /H2 O2 /UV (photoperoxonation process) to generate hydroxyl rad-
1 when both H2 O2 and Fe2 + are electro-generated while type 2 involves
icals (HO• )for the oxidation of recalcitrant organic pollutants in PW.
generation of hydroxyl radical by externally added Fenton reagent and
These radicals(HO• ) are generated through a sequence of reactions Eqs.
Fe2 + is regenerated through reduction of Fe3 + on the cathode. It is a
(9g) & ((16)) as follows:
type 3 EF, when Fe2 + is externally added and H2 O2 is electro-generated
while it is type 4, when H2 O2 is externally added and Fe2 + is electro-
(16) generated. The types 3 and 4 EF treatments are easier to control with
generation of substantial amount of HO• and the reactions for types 3
and 4 EF are as follows:
Type 3 EF treatment:
2 𝐻2 𝑂2 + 2 𝑂3 → 4𝐻 𝑂 ∙ + 3 𝑂2 (9𝑔) Cathode:
The H2 O2 is generated from the electrochemical oxidation of O2 as
The photoperoxidation process is advantageous because the presence
follows:
of both the UV light and hydrogen peroxide enhances the decomposition
of ozone and thus results to increased rate of HO• generation. However, 𝑂2 + 2 𝐻 + + 2 𝑒− → 𝐻2 𝑂2 (18a)
the major drawback that limits the wide application of the process is the
high prices of ozone, hydrogen peroxide and UV light involved in the The oxidizing power of electro-generated H2 O2 is enhanced by the
process. Therefore, the system is limited to a highly polluted wastewater. externally added Fe2 + catalyst to the acidic solution to generate free
Studies have been conducted to evaluate the effectiveness of photol- HO• radical and Fe3 + as follows:
ysis of reactive oxygen species (ROS) for the treatment of oil and gas 𝐹 𝑒2+ + 𝐻2 𝑂2 + 𝐻 + → 𝐹 𝑒3+ + 𝐻2 𝑂 + 𝐻 𝑂∙ (18b)
PW. Souza et al. [158] investigated O3 , H2 O2 , UV/O3 and UV/H2 O2 for
the enhancement of the quality of the oil refinery biotreated wastewater Fe2 + is regenerated at the cathode from the reduction of Fe3 + as fol-
before reverse osmosis (RO) treatment to generate water of high-quality lows:
standard for fit-for-purpose reuse. Their findings revealed that UV/O3
𝐹 𝑒3+ + 𝑒− → 𝐹 𝑒2+ (18c)
and UV/H2 O2 processes were able to achieve a high mineralization level
with 95% and 74% removal efficiencies of TOC, respectively better than Anode:
either O3 or H2 O2 process alone that showed a low degree of mineral- Oxidation of water occurs as follows:
ization of less than 20% removal efficiency of TOC even at the highest
ozone concentration (60 mg L−1 ) after 60 min of reaction. In a related 2𝐻2 𝑂 → 4 𝐻 + + 𝑂2 ↑ +4 𝑒− (18d)
study, Azizah and Widasa [159] used UV/H2 O2 for the degradation of
phenol and removal of COD in residual fluid catalytic cracking (RFCC) The overall reaction is ∶ 𝐹 𝑒3+ + 𝐻2 𝑂 → 𝐹 𝑒2+ + 𝐻 + + 𝐻 𝑂∙ (18e)
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Type 4 EF treatment
Anode:
(22a)
Fe2 + is electro-generated as follows:

𝐹 𝑒 → 𝐹 𝑒2+ + 2 𝑒− (19a)
(22b)

4 𝑂𝐻 − → 𝑂2 ↑ +2 𝐻2 𝑂 + 4 𝑒− (19b)
(22c)
Cathode:

2 𝐻2 𝑂 → 2 𝐻 + + 2 𝑂 𝐻 − (19c) The simplicity, cost-effectiveness and high efficiency of photo-

𝐹 𝑒3+ + 𝑒− → 𝐹 𝑒2+ (19d)
𝑇 ℎ𝑒 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑠 ∶
(19e)
𝐹 𝑒 + 2 𝐻2 𝑂 + 6 𝐹 𝑒3+ → 7 𝐹 𝑒2+ + 4 𝐻 + + 𝑂2 ↑
The H2 O2 is externally added to the electro-generated Fe2 + to pro-
duce the hydroxyl radical andFe3 + as follows:
𝐻2 𝑂2 + 𝐹 𝑒2+ → 𝐹 𝑒3+ + 𝑂𝐻 − + 𝐻 𝑂∙ (19f)
• in same order of pollutants. Their study revealed that removal efficien-
The HO generated in either of the treatments will react with the
organic pollutants in wastewater as follows:
𝑅𝐻 + 𝐻 𝑂∙ → 𝑅∙ + 𝐻2 𝑂 (14𝑎)
𝑅∙ + 𝑂2 → 𝑅𝑂2∙ (14𝑏)
𝑅∙ + 𝐻 𝑂∙ → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (19𝑔)
The efficiency of electro-Fenton process can be further improved
in the presence of UV irradiation by a process called photoelectro-
Fenton (PEF). The catalytic effect of Fe2 + can be enhanced by sup-
porting electro-Fenton process with UV irradiation. The photoelectro-
Fenton process can increase the regeneration rate of Fe2 + in the pres-
ence of UV. The photocatalytic splitting of H2 O2 generates two moles
of HO• (Eq. (15a)) [162], thus increases the oxidative capability of the
process.
Ultrasound (US) is another promising AOP for the degradation of
organic pollutant because it is economical, safe, sludge-free and envi-
ronmentally friendly. The organic pollutants are degraded through di-
rect thermolysis (Eq. (20a)) (pyrolytic mechanism) and/or HO• attack
(Eq. (20b) and 20c) (oxidative mechanism) [164].
(20a)
(20b)
Pollutant + 𝐻 𝑂∙ → degradation product (20c)
where, ))) represents ultrasound
However, the shortcoming of US, including low efficiency and a high
energy consumption, thus necessitates the need to combine US with
other AOPs such as Fenton reaction [165] in the so-called sono-Fenton
(SF) process. The SF process promotes faster mineralization of pollu-
tant due to faster generation of HO• (Eqs. (10a) and 20b) [166], closer
contact between HO• and the pollutant [165,167] and improved regen-
eration of Fe2 + (Eq. (21)) [168].
(21)
It can also be combined with H2 O2 to generate reactive oxygen
species (ROS) (Eqs. (22a)-c) as proposed by Shemer and Narkis [169] as
follows:
Fenton-related processes have made various researchers to conduct stud-
ies on the use of the process for the treatment of oil and gas PW. Re-
cently, Zhai et al. [170] compared the performances of three differ-
ent processes, including Fenton, ultraviolet (UV) Fenton and ultrasonic
(US)-Fenton, for the removal of organics and color from pre-treated nat-
ural gas PW. The UV-Fenton system was found to be the most efficient
with 82, 73, 68 and 95% removal efficiencies of COD, TOC, BOD5 and
color respectively, from the natural gas field PW; followed by US-Fenton
with removal efficiencies of 79, 70, 66 and 95% of COD, TOC, BOD5 and
color respectively, and then Fenton treatment (70, 58, 51 and 92%), also
cies of carbon and color from PW were satisfactory, however biological
treatment or low cost constructed wetland was suggested for the final
polishing of PW before recycling or discharging the treated PW into the
environment. In a related investigation, Novais Mota et al. [171] used
photo-Fenton process in a reactor under solar and artificial UVA irradia-
tion to degrade organic compounds of phenolic effluent and oilfield PW.
Solar irradiation was found to be more efficient than lamplight with up
to 76% removal efficiency of organic components. The authors further
suggested the possibility of harnessing solar light as a way of reducing
operation costs (OPEX) of the system. Silva et al. [172] used photocatal-
ysis (with TiO2 as catalyst) and photo-Fenton (using FeSO4 •7H2 O as cat-
alyst) to treat simulated PW prepared with phenol solution in seawater
and a real sample of oilfield PW from Rio Grande do Norte, Brazil us-
ing UV irradiation at 254 nm. Their results indicated that photo-Fenton
gave the best results with 99% removal efficiency of phenol despite the
high salt contents of the seawater. Very recently, Ji and Davarpanah
[173] used photo-Fenton and flotation method to treat PW from 8 differ-
ent production wells in the same formation for the sustainable manage-
ment of flowback PW reuse. Their results indicated 85%, 70% and 75%
of saved water for hydraulic fracturing flow-back water, water flood-
ing processes and chemical enhanced oil recovery methods respectively.
Thus, implying that it only requires 15%, 30% and 25% of freshwater
to continue fracturing process, water flooding processes and chemical
enhanced oil recovery methods respectively, each day. In a separate
study, Adimi et al. [174] used electro-Fenton for the removal of COD
from petrochemical wastewater by varying the effects of different pa-
rameters using nanoporous aluminum electrode. Their results indicated
optimum COD removal efficiency of 65.03% at the pH, reaction time,
current density, H2 O2 /Fe2+ molar ratio and volume fraction of H2 O2
to petrochemical wastewaters of 2.96, 89.51 min., 69.57 mA, 3.42 and
1.93 ml/l, respectively. The use of modified electrode (nanoporous alu-
minum oxide) was found to accelerate decomposition of H2 O2 and led
to increasing generation of hydroxyl ions compared to plain aluminum
electrodes. Recently, Al-Khafaji and Mohammed [175] used dimension-
ally stable anode Ti-RuO2 /IrO2 and activated carbon fiber felt cathode
to investigate continuous electro-Fenton processes for the degradation
of organic pollutants in PW. Their results indicated 73.33% removal ef-
ficiency of COD with electrical energy consumption of 0.901 kWh/kg
COD for continuous EF experiments using multiple response optimiza-
tion. The COD removal efficiency for continuous EF was found to in-
crease to 81.1% and 86.0% with the use of one and two UVA lamps of
3 Watts each, respectively. In a related study, Wang et al. [176] applied
the EF process to treat mother liquor of gas field wastewater using Fe-
Fe electrodes with addition of H2 O2 to the EF system and varying the
effects of different parameters. Their results indicated the maximum of
Abass A. Olajire
71.9% removal efficiency of COD at the pH, current density, H2 O2 vol-
ume at half-hour, reaction time of 3, 2.0 A, 7 mL and 3 h, respectively.
The lowest values of specific electrical energy consumptions and specific
electrical plate consumption were reported to be 4.73 kWh/kg COD and
0.82 kg Fe/kg COD, respectively, at pH of 3.
Recently Sivagami et al. [177] used the combination of ultrasound
(US) and Fenton’s process for the treatment of total hydrocarbon in
oil spill sludge. Their results showed that maximum petroleum hydro-
carbons reduction of 84.5% and 23.58% (nC7 –C10 & nC11 –C20 ) were
achieved at a pH of 3, sludge/water ratio of 1:100, 40% ultrasound am-
plitude, H2 O2 /Fe2+ weight ratio of 10:1 and ultrasonic treatment time
of 10 min. They concluded that the combined SF process significantly
enhanced the degradation of oil spill sludge better than the ultrasound
(US) treatment and Fenton oxidation alone. In another related study,
Shokri [178] used Sono-photo-Fenton process for the degradation and
mineralization of petrochemical wastewater containing phenol and ni-
trophenol with chemical oxygen demand (COD) of 260 mg/L and total
organic carbon (TOC) of 100 mg/L. The influence of operational vari-
ables was evaluated by using full factorial design of the experiment.
The results of the study indicated 76.1% and 68.7% removal efficien-
cies of COD and TOC respectively, at predicted optimum conditions of
[Fe2 + ], pH and [H2 O2 ]of 24 mg/L, 3 and 500 mg/L, respectively after
60 min of reaction.
4.3.1.1.2.3. Photocatalytic oxidation process
Photocatalytic oxidation process is a promising AOP technology for
environmental remediation [179,180] in view of the minimal consump-
tion of chemical with subsequent reduction in the generation of waste
sludge, which are major concerns inhibiting PW treatment. In addition
to degradation of recalcitrant organic contaminants in PW, the technol-
ogy has also been proven to transform all metallic ions and metalloids to
less toxic species or species that can easily be separated from the system
in a subsequent treatment stage [181,182]. The technology is based on
the excitation of TiO2 in the presence of UV or visible light leading to the
production of electrons and holes respectively at the conduction and va-
lence bands (Eqs. (23a) & b), which in turn initiates the reduction and
oxidation reactions (Eqs. (23c)–h). These hollow-electron (e– /h+ ) will
react with adsorbed organic species on the surface of the TiO2 catalyst,
where oxidation and reduction reactions co-occur [183,184].
(23a)
𝑇 𝑖𝑂2 (𝑒− ) + 𝑂2 → 𝑇 𝑖𝑂2 + 𝑂2− ∙ (23b)
𝑇 𝑖𝑂2 (ℎ+ ) + 𝐻2 𝑂 → 𝑇 𝑖𝑂2 + 𝐻 𝑂 ∙ + 𝐻 + (23c)
𝑇 𝑖𝑂2 (ℎ+ ) + 𝑂 𝐻 − → 𝑇 𝑖𝑂2 + 𝐻 𝑂 ∙ (23d)
𝐻 𝑂∙ + 𝑅𝐻 → 𝑅𝐻2 𝑂∙ (23e)
𝐻 𝑂∙ + 𝑅𝐻 → 𝑅∙ + 𝐻2 𝑂 (23f)
𝑇 𝑖𝑂2 (ℎ+ ) + 𝑅𝐻 → 𝑇 𝑖𝑂2 + 𝑅𝐻 +∙ (23g)
The possible use of sunlight as source of irradiation, regenerability,
operability at standard pressure and temperature and ability of the sys-
tem to achieve complete mineralization of many organic compounds
are the advantages of this system. However, it is not without its short-
comings, which include problem of attaining uniform irradiation over
the entire surface of the catalyst on industrial scale and recovery of the
suspended catalyst, thus making the process uneconomical.
The application of photocatalytic oxidation process for the treatment
of PW is quite sparse in recent times [185]. However, few studies have
proven the effectiveness of this process for the treatment of PW. Liu et al.
Chemical Engineering Journal Advances 4 (2020) 100049
[186] compared the photocatalytic efficiencies of Aeroxide@ P25 nano-
scale TiO2 powder immobilized on glass slides by the heat attachment
method and the original suspended TiO2 for the removal of naphthalene
from offshore PW. Their results of adsorption revealed that immobi-
lized catalyst had a better performance in photo-oxidation and a higher
resistant to the substrates effects of offshore PW than the suspended
TiO2 powder. Recently, Silva et al. [172] used photocatalysis process
(TiO2 /UV) to remove dissolved organic matter from oil PW. Their results
showed effective removal of phenol in PW at pH of 7. The effectiveness
of the heterogeneous photocatalysis method (TiO2 /UV) for the treat-
ment of oily industrial influent was investigated by Mokhbi et al. [187].
Their study showed a marked improvement in efficiency on the treated
water quality in terms of color, turbidity, and COD under optimized con-
ditions of oil concentration, quantity of catalysts, temperature, Fenton’s
reagent concentration, and the pH of the solution. Their results indicated
80% and 98% COD removal efficiencies with TiO2 /UV (photocatalysis)
and TiO2 /UV/Fe2+/ H2 O2 (photocatalysis-Fenton reagent) respectively.
In a related study, Hassan and Mousa Al-zobai [188] conducted photo-
catalytic degradation of oil in glass reactors under UV irradiation using
titanium dioxide as a nano-photocatalyst by batch and continuous tech-
niques. Their results showed that all the oil (100%) was removed in
the batch system while 71% of the oil was removed in the continuous
system.
4.3.1.1.2.4. Electrooxidation and electrocoagulation processes
Electrooxidation occurs by direct or indirect anodic oxidation pro-
cess. The pollutant is adsorbed onto the electrode at a low potential
before the evolution of O2 in the direct anodic oxidation (DAO) or di-
rect electrochemical oxidation (DEO) process, where the mineralization
of the organic compound in the pollutant can occur by any of the fol-
lowing processes (Eq. (24a) & b) [189]:
𝑅 + 𝑥𝐻2 𝑂 → 𝑅𝑂𝑥 + 2𝑥 𝐻 + + 2𝑥 𝑒− (24a)
𝑅 + 𝑥𝐻2 𝑂 → 𝑥∕2 𝐶 𝑂2 + 2𝑥𝐻 + + 2𝑥 𝑒− (24b)
In indirect or mediated electrochemical oxidation (MEO), the oxi-
dation of the pollutant in the bulk solution is mediated by the strong
oxidizing species, mostly a transition metal in a higher oxidation state
[190] that is electro-generated at the electrode. The re-oxidation of the
reduced mediator takes place at the anode, for further oxidation of the
organic molecules in the wastewater. The common electrode materials
used for wastewater include platinum (Pt) and boron doped diamond
(BDD) electrodes, where the former is very expensive and subject to
fouling [191]. However, the high anodic stability, broad working po-
tential range, and excellent mineralization efficiencies of BDD electrodes
[192] have made them to gain wide acceptability for wastewater treat-
ment. The weakly adsorbed HO• that is formed during electrolysis of
water at the anodic surface (Eq. (25)) facilitates the oxidation of organic
compound [193].
(25)
The electrogenerated HO• may then trigger the formation of or-
ganic radicals (R• ), which in the presence of O2 form organic peroxy
radicals (𝑅𝑂2∙ ) [194]. The peroxy radicals can initiate subsequent chain
reactions leading to a non-Faradaic enhancement of the rate of elec-
trooxidation of organic compounds. In addition to the oxidation of or-
ganic pollutants, BDD anodes can generate other reactive species such as
O3 , H2 O2 ,anionic salts and ferrate [195], which also play an important
role in the bulk oxidation [196].
Mechanistic aspects of electrooxidation process
Organic compounds in wastewater are electrochemically combusted
on the metal oxide anode (MOx ), where adsorbed hydroxyl radicals are
generated (Eq. (26a)) by the discharge of H2 O in acid or alkali solution
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

at the anode as follows: Mechanism 1:

Anode:
(26a)
4 𝐹 𝑒(𝑠) → 4 𝐹 𝑒2+
(𝑎𝑞)
+ 8 𝑒− (28a)
where, k1 = electrochemical rate constant for H2 O discharge.
The higher oxide (MOx + 1 )is formed (Eq. (26b)) by the transfer of 4 𝐹 𝑒2+
(𝑎𝑞)
+ 10 𝐻2 𝑂(𝑙) + 𝑂2 → 4 𝐹 𝑒 (𝑂𝐻)3 + 8 𝐻(+𝑎𝑞) (28b)
oxygen from the adsorbed hydroxyl radical to the lattice of the metal
oxide anode as follows: Cathode:

8 𝐻(+𝑎𝑞) + 8 𝑒− → 4 𝐻2(𝑔) (28c)

(26b)
The overall reaction is:
k2 = electrochemical rate constant for transition of oxygen into the oxide
lattice. 4 𝐹 𝑒(𝑠) + 10 𝐻2 𝑂(𝑙) + 𝑂2(𝑔) → 4 𝐹 𝑒(𝑂𝐻)3 (𝑠) + 4 𝐻2 (𝑔) (28d)
Both the physisorbed (adsorbed HO• ) and chemisorbed (oxygen in
Mechanism 2:
the oxide lattice, MOx + 1 ) active oxygen that are present on the surface
Anode:
of the anode will respectively produce oxygen molecules in the absence
of any oxidizable organics (Eqs. (26c) & d) as follows: 𝐹 𝑒(𝑠) → 𝐹 𝑒2+
(𝑎𝑞)
+ 2 𝑒− (29a)

𝐹 𝑒2+
(𝑎𝑞)
+ 2 𝑂𝐻(−𝑎𝑞) → 𝐹 𝑒(𝑂𝐻)2(𝑠) (29b)
(26c)
Cathode:

2 𝐻2 𝑂(𝑙) + 2 𝑒− → 𝐻2(𝑔) + 2 𝑂𝐻(−𝑎𝑞) (29c)

(26d) The overall reaction is:

where, k0 and kd are the electrochemical rate constants for O2 evolu-
tion.
However, the physisorbed active oxygen HO• has been speculated
to cause complete mineralization of organics (Eq. (27a)) in the pres-
ence of oxidizable organic compound, which often takes place on sur-
faces containing PbO2 , SnO2 or Sb2 O5 while chemisorbed active oxygen
MOx + 1 takes part in the selective oxidation of organics (Eq. (27b)) as
follows [194,195]:
𝐹 𝑒(𝑠) + 2 𝐻2 𝑂(𝑙) → 𝐹 𝑒(𝑂𝐻)2(𝑠) + 𝐻2(𝑔) (29d)
The gelatinous suspension of Fe(OH)x (x = 2 or 3)that is formed
(Eq. (29b)) removes pollutants from the wastewater, either by complex-
ation or by electrostatic attraction, followed by coagulation. The fol-
lowing reactions (Eqs. (30a) & b) occur when aluminum is used as the
electrode.
Mechanism:
Anode:

2 𝐴𝑙(𝑠) → 2 𝐴𝑙(3+
𝑎𝑞)
+ 6 𝑒− (30a)
(27a) Cathode:

(27b) 6 𝐻2 𝑂(𝑙) + 6 𝑒− → 3 𝐻2 + 6 𝐻 + (30b)

The overall reaction is:

where, kc and ks are the electrochemical rate constants for the complete
combustion and selective oxidation of organics respectively, R is an or-
ganic compound with Z/2 carbon atoms and without any heteroatom,
which needs Z(=Z + Y) oxygen atoms to be totally mineralized to CO2 .
The use of chemical coagulants for wastewater treatment tend to
generate large volumes of sludge with high bound water content which
can be difficult to dewater and thus tend to increase total dissolve solid
(TDS) content of the effluent and makes it unacceptable for reuse and/or
discharge. This then necessitates the need for a robust novel and innova-
tive alternative such as electrocoagulation (EC) with several benefits, in-
cluding low sludge production, cost-effectiveness, safety and versatility
over the conventional chemical coagulation technique [197]. Electroco-
agulation (EC) process is based on the coagulation of the contaminants
from the aqueous medium by the cation produced from the electrolytic
oxidation of iron and/or aluminum anode. Thus, a highly charged poly-
meric metal hydroxide species is produced during the process, where the
negative surfaces of the solid hydroxides, oxyhydroxides and solid ox-
ides are responsible for the adsorption of polluting species [198]. Elec-
trocoagulation is a complex process with a multitude of mechanisms
including oxidation, reduction, decomposition, deposition, coagulation,
adsorption, precipitation and flotation operating synergistically to re-
move pollutants from wastewater [198].
Mechanistic aspects of electrocoagulation process
The process utilizes iron and aluminum as electrode materials. The
two proposed mechanisms involving iron electrode process (Eqs. 28 &
29) are as follows [199,200]:
2 𝐴𝑙(𝑠) + 6 𝐻2 𝑂(𝑙) → 2 𝐴𝑙(3+ + 3 𝐻2(𝑔) + 6 𝐻(+𝑎𝑞) (30c)
𝑎𝑞)
A lot of studies have recently been carried out to evaluate the effec-
tiveness of electrooxidation and electrocoagulation technologies for the
treatment of oil and gas PW. Recently, Abdel Salam et al. [201] used
electrochemical cell with a flow-by porous graphite as an electrode for
the oxidation of organic matter in PW from a natural gas processing
field. Their results indicated maximum removal efficiencies of 66.52%,
68.2% and 100% for COD, TDS and organic compounds up to C18 respec-
tively, at a current density of 1.41 mA cm−2 with energy consumption
of 2.12 Kwh/kg COD. Their study showed that when the current den-
sity increases, the COD and TDS removal efficiencies also increase. This
was attributed to direct electrooxidation, where the electrolysis of PW
generated hydroxyl radical group that acted as the oxidant. In a similar
study, Campos et al. [202] evaluated the applicability of electrochem-
ical oxidation (EO) for the treatment of a real petrochemical effluent
using a laboratory electrochemical cell and a pre-pilot plant scale re-
actor with Ti/Pt and BDD anode materials. Their results showed that
more than 97% of dissolved organic matter were removed using BDD
with the electrochemical pre-pilot reactor by applying 15 mA cm–2 at
pH 6.0 and 25 °C after 30 min of electrolysis, with energy consumption
of 3.37 kWh/m3 and incurred cost of around 0.57 USD m–3 . Their find-
ings agreed closely with the previous studies on the economic benefits of
using BDD as the anode for achieving satisfactory abatement of organic
pollutants within a short time [203,204].
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 5
Recent studies on the application various AOPs for the treatment of oil and gas PW.

Process Operation condition Removal efficiency Remark Ref.

O3 𝑄𝑂3 = 250 𝑚𝐿∕ min . Effective removal of PAHs from Elevated ozone dose and temperature
offshore PW via the pseudo first-order had positive effects on the removal [148]
kinetic model. rate of PAHs due to enhanced ozone
mass transfer, ozone decomposition,
and radical yield.
O3 /H2 O2 VPW = 1.0 L;𝑄𝑂3 = 4𝑔∕ℎ and [H2 O2 ] 74% TOC removal, 78% acetic acid Lowest electric energy consumption
=1500 mg/L, pH =10, Time = 2 h elimination per order of TOC removal [133]
H2 O2 /Fe2+ (Fenton’s pH = 3, Temp. = 20 °C, 40 °C and 70 °C. 40% TOC removal at 70 °C in the The temperature needed would
reagent) Time = 2h absence of salts, and 18% at 20 °C hamper the scale-up of this process. [142]
UV/O3 Lamp=15 W, O3 = 60 mg O3 /L, 95% TOC removal The combined process was found to
UV/H2 O2 EEO =5.4 Wh L−1 , pH ∼ 7 74% TOC removal increase the TOC removal than the [158]
Time= 60 min single processes due to presence of
Lamp = 95 W higher concentrations of hydroxyl
EEO =81 Wh L−1 , pH ∼ 7 radicals in the former for the
C:H2 O2 = 1:4 degradation of wastewater
Time =60 min compounds. The UV/H2 O2 also
reduced microbial growth on the RO
membrane surface which
consequently reduced the risk of
membrane fouling by biofilm
formation
UV/H2 O2 UV Lamp (110–240 V, 50/60 Hz); 70.9% phenol and 4.39% COD removal Exceeding the optimum concentration
H2 O2 /UV/O3 Time= 3 h; efficiencies. of H2 O2 was found to lead to [159]
[H2 O2 ] = 1000 mg/L; reduction in the amount of phenol
[H2 O2 ]=1000 ppm; UV process 93.75% phenol and 12.2% COD removal and COD removal efficiencies of the
equipped with an ozone generator; efficiencies. process.
Time = 2 h

UV-185/H2 O2 [H2 O2 ] =250 mg/L; UV lamp = 6 W; 80% TOC removal; Increasing [H2 O2 ] beyond optimum
UV-254/H2 O2 Time = 6 h 90% TOC removal concentration had a negative impact [160]
pH = 3 because the extra [H2 O2 ] acts as
•
[H2 O2 ] =300 mg/L; UV lamp = 6 W; HO scavenger and this compete with
•
Time = 6 h BTEX for HO . Also, the
pH = 3 photochemical degradation of BTEX
was found to generate intermediates
which did not improve its
biodegradability.
Fe2+ /H2 O2 VPW = 250 mL; 70% COD, 58% TOC, 51% BOD5 and 92% Most of the carbon removal was
(Fenton’s H2 O2 /COD (1–10), color removal efficiencies. achieved [170]
reagent) H2 O2 /Fe2+ (5–30), within 60 min and remained almost
pH =3 stable in the later period
UV/H2 O2 /Fe2+ Hg UV lamp=15 W, 82% COD, 73% TOC, 68% BOD5 and 95% UV–Fenton showed a Significant
(UV-Fenton) pH=3, Time =120 min color removal efficiencies. increase in removal rate along with [170]
the reaction time.
2+
US/H2 O2 /Fe US power: 200 W, 79% COD, 70% TOC, 66% BOD5 , and The US–Fenton process had better
(US–Fenton Time: 120 min, 95% color performance on pollutants than [170]
process) Removal efficiencies. conventional Fenton treatment, and
COD, BOD5 removal efficiency
increased significantly along with the
reaction time.
UV/H2 O2 /Fe2+ VPW = 6.0 L; Solar and UV lamp 76% TOC (Solar) and 45% TOC (UV Solar irradiation was more efficient
(Photo-Fenton process) ((320–400 nm; 40 W; 250 W/m2 ), irradiation) removal efficiencies. than UV lamp, and it corresponds an [171]
pH = 3, [Fe2+ ] = 1 mM, important factor for the reduction of
[H2 O2 ] = 100 mM, operating costs of this process.
UV/H2 O2 /Fe2+ [Fe2+ ]:[H2 O2 ]=1:10; UV irradiation= 99% Phenol removals Less effective at pH 10 due to low
(Photo-Fenton process) 254 nm; pH = 3; solubility of H2 O2 in basic media, [172]
which thus hindered the interaction
with Fe2+ and Fe3+ . Photo-Fenton is
more effective than photocatalytic
process
Anodic Al2 O3 /H2 O2 /Fe2+ [H2 O2 ]/[Fe2+ ]=3.42; ID = 69.57 mA; 65.03% COD removal; The use of nanoporous aluminum
(Electro-Fenton process) Time= 89.51 min; oxide (modified electrodes) as an [174]
[H2 O2 ]/Petrochemical waste auxiliary agent accelerated the
(v/v) = 1.93 ml/l; pH=2.96; decomposition of H2 O2 and lead
increasing generation of hydroxyl ions.
Electro-Fenton process Anode: DSA TiRuO2 /IrO2 mesh 73.33% COD removal; The COD removal efficiency was found
to increase with increasing applied [175]
current intensity from 100 to 340 mA,
and beyond 340 mA the removal
efficiency decreased due to increased
reaction that scavenged the hydroxyl
radicals.
(continued on next page)
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 5 (continued)

Process Operation condition Removal efficiency Remark Ref.

Cathode: activated carbon filter felt;

Two UVA lamps (3 Watt each);
[Fe2+ ]= 0.1–0.5 mM; ID =(100–500 mA),
Tr = 22–81 min;
Electro-Fenton process VML-GFW = 500 mL; ID = 2 A;𝑉𝐻2 𝑂2 =
7 mL/30 min; Fe electrodes; T = 3 h;
period reversal time = 10 min.; pH =3
Sono–photo-Fenton Hg Lamp (15 W); UV-C = 254 nm;
process US = 20 kHz; [Fe2+ ] = 24 mg/L;
[H2 O2 ] = 500 mg/L; pH = 3
TiO2 /UV VPW = 250 mL, UV hollow equipped
with eight UV tubes; [TiO2 ] (25, 35,
50, and 150 ppm), Temp. = 25 °C.
pH=6.5, Time=1.5 h.
TiO2 /UV VPW = 25 mL, six UV lamps (253.7 nm,
15 W, 220 V); pH = 3
TiO2 /H2 O2 /UV VPW = 25 mL, six UV lamps (253.7 nm,
15 W, 220 V); pH = 3
Fe2+ /H2 O2 /UV VPW = 25 mL, six UV lamps (253.7 nm,
(Photo-Fenton) 15 W, 220 V); pH = 3
TiO2 /UV (Photocatalysis) UV lamp (365 nm, 3.4 eV),
[TiO2 ] = 0.8 g/L, pH = 6–7
TiO2 /UV/Fe2+ /H2 O2 [UV lamp (365 nm, 3.4 eV), [Fe2+ ]=
(photocatalysis –Fenton’s 40 mg/L, [H2 O2 ] = 400 mg/L, pH = 6–7
reagent)
Electrooxidation, 𝐸 𝑂𝑄𝑓 = 50 𝑚𝐿∕ min .
(EO) j = 1.41 mA/cm2 , pH
= 7.3, initial COD= 2845 mg O2 /L,
E = 2.12 kWh/kg COD, graphite
electrodes.
71.9% COD removal
76.1% COD and 68.7% TOC removal
efficiencies
100% oil removal in the batch system,
and 71% oil removal in the continuous
system.
33% (pH 3), 11% (pH 7) and 7% (pH
10) phenol removal efficiencies.
87% (pH 3), 94% (pH 7) and 71% (pH
10) phenol removal efficiencies.
99% phenol removal.
80% COD removal
98% COD removal.
66.52% COD, 68.2% TDS
and 100% organic
compounds up
to C18 removal efficiencies.
Oxidation was found to be the major
pathway to remove organic matter in [176]
the EF process, which was found to be
enhanced at pH of 3.
Their study revealed that ultrasonic
treatment can be suitable technique of [178]
improving the Fenton and
photo-Fenton as a higher amount of
degradation was achieved for
Sono-photo-Fenton (US+UV+Fenton)
than either photo-Fenton (UV+Fenton)
and Sono-Fenton (US + Fenton).
The number of lamps, light radiation,
and time and process type have [188]
impact on the percentage of oil
removal.
The low pH promotes high phenol
removal rates even in the presence of [172]
high salinity of the seawater
The photocatalytic process is effective
even in the presence of high seawater [172]
salinity.
Fe3+ and Fe2+ are very stable in acidic
media, thus, favouring their [172]
interaction with H2 O2 , generating
•
HO radicals that oxidize phenolic
compounds in water.
The study demonstrates an
economical and effective strategy for [187]
removing both a large portion of oily
organic pollutants and oils that
generally, coexist in industrial
wastewater.
The combined photocatalysis and
Fenton’s reagent enhanced COD [187]
removal. Solar light would
significantly reduce the cost of
treatment, thus providing avenue for
industrial applications.
The graphite is cheaper than other
electrodes and gives a higher surface [201]
area for anodic oxidation reactions
and require low energy consumption.

Electrooxidation (EO) VPW = 500 mL and 1000 mL, j = 60 mA VPW =500 mL Lower energy consumption and higher
cm−2 , pH =6, Temp. =25 °C, Anodes: 84% COD COD removal were achieved when the [202]
Ti/Pt and BDD, E = 4.84 kWh m–3 (Ti/Pt), 99% flow cell was employed with the BDD
(Ti/Pt), 78 kWh m–3 (BDD) (BDD) removal efficiencies after 2 h. electrode, thus making EO a
VPW =1000 mL promising technology to reduce the
96% COD environmental impact of discharging
(Ti/Pt) removal PW in aquatic system with affordable
after 2 h; 100% costs.
COD (BDD)
removal after
0.5 h
Electrooxidation (EO) VPW = 5000 mL, j = 40 mA cm–2 , 90.7% COD Higher mineralization efficiency was
Anodes: Ti/Pt and BDD, E = 140 kWh (Ti/Pt), 94.5% reported to be obtained with BDD [203]
dm–3 (Ti/Pt), 191 kWh dm–3 (BDD) COD (BDD) electrocatalytic material.
Removal efficiencies after 8 h.
Electrooxidation (EO) VPW = 200 mL, j = 30 mA cm–2 , 85% COD BDD was reported to be the most
Time = 11 and 8 h, Anodes: Ta/PbO2 (Ta/PbO2 ) efficient [204]
and BDD, E = 46.6 kWh dm–3 removal after Electrocatalytic material.
(Ta/PbO2 ), 38.0 kWh dm–3 (BDD) 11 h, 96% COD
(BDD) removal after 8 h.
(continued on next page)
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 5 (continued)

Process Operation condition Removal efficiency Remark Ref.

Pulse electrocoagulation VAFPW = 250 mL; Electrode: Fe; pulse
(PE) process duty cycle= 0.3; ID = 35 mA/cm2 ;
Time = 40 min; pulse frequency=
3.0 kHz; Electrode distance = 1.0 cm;
Econsup. = 0.19 kWh/kg CODremoved ;
Electrode consumption =3.1 kg Fe/kg
CODremoved
Electrocoagulation (EC) Anode: Al, Time = 15
min, j = 45.5 mA.
cm–2, pH = 11, Temp.
= 25 °C, Batch system,
ECQ = 1 mL/min .
Hybrid electrocoagulation VPW = 1.5 L, I = 0.34 A, Al electrode,
chemical coagulation Confg. = bipolar (BP), pH =8,
(EC–CC) Process Temp. = 60 °C, coagulant conc. (AlCl3 )=
200 mg/L, mixing rate = 700 rpm,
Time = 90 min.
98.3% COD, 99.0% oil & grease, 98.8%
turbidity, 98.1% TSS, and 94.3%
polyacrylamide removal Efficiencies
≥ 90% oil Removal
39.8% TOC removal
The PE process was reported to be an
energy saving process compared with [205]
the traditional direct current method.
The internal loop airlift
electrochemical reactor used in this [206]
study was reported to be highly
efficient with less energy consumption
when compared to conventional
existing electrochemical cells which
used mechanical agitation.
Of all the design parameters, chemical
coagulant concentration and the [207]
treatment time were reported to have
significant contribution to TOC
removal efficiency, thus revealing the
capability of integrating chemical
coagulation with electrical coagulation
for the removal of the suspended and
dissolved organic matter from the
contaminated water.

Fig. 7. flowchart of combined process for PW treatment based on this review.

The technical and economic feasibility of the pulse elec-
trocoagulation (PEC) process for the treatment of oilfield al-
kali/surfactant/polymer flooding PW was investigated by Zheng
[205] using an Fe electrode to analyze the performance of PEC process
in terms of operating parameters. Their results indicated removal
efficiencies of 98.3, 99.0, 98.8, 98.1 and 94.3%, for COD, oil and
greases, turbidity, TSS, and polyacrylamide, respectively under the
optimum operating conditions of pulse density cycle, current den-
sity, pulse frequency, electrode distance and reaction time of 0.3,
35 mA/cm2 , 3.0 kHz, 1.0 cm and 40 min, respectively, with an energy
consumption of 3.1 kg Fe/kg CODremoved . Recently, Ammar & Akbar
[206] used electrocoagulation method to treat oilfield PW. Their study
revealed that the electrocoagulation time required to achieve 90% oil
removal efficiency decreased from 46 to 15 min while the operating
Abass A. Olajire Chemical Engineering Journal Advances 4 (2020) 100049

Table 6
Pros and cons of the current technologies used for the treatment of produced water.

Process Main features Pros Cons

Primary treatment
API separation Gravity separation ● Separation of oil and light fractions with ● Requires sludge
Coagulation and Uptake of the lower density than water dewatering unit, energy intensive and not
Flocculation pollutant and ● Simple process, wide range of chemicals economically feasible
Induced air flotation separation of product formed are available, but biopolymers are more ● Non-regenerable chemicals
(IAF)/Dissolved air advantageous (eco-friendly and (coagulants/flocculants).
flotation (DAF) Separation process biodegradable). ● Physicochemical
● Very efficient for removal of SS, colloidal monitoring of effluent
particles, reduction in COD, BOD, and TOC. pH.
● Simple, rapid and efficient process for ● Increased sludge
removal of insoluble contaminants. volume generation,
● Robust and durable. Efficient for removal of leading to sludge
small particles that require long settling disposal problems
periods. ● Generation of large
● Separation of oil (deoiling), suspended, amount of air.
macromolecules, and removal of metals. ● Retention time for
●Useful for primary clarification. separation, skim
● Mechanism volume.
involves true flotation, ● Maintenance and operation cost are
entrainment and aggregation. high.
● Requires chemical
for maintenance of proper froth
characteristics.
● Production, transport
and maintenance of the
oxidants.
Secondary treatment
Biological treatment Use of biological ● Simple, economically ● Requires management
Method cultures (pure or attractive and widely used. and maintenance of the
Membrane technology mixed, consortium) ● Allow the use of consortiums or pure microorganisms and/or
(Microfiltration, for the cultures (White-rot physicochemical pretreatment.
Ultrafiltration, biodegradation of fungus). ● Inefficient for
Nanofiltration and organic contaminants ● Efficiently eliminates biodegradable organic non-degradable or toxic
Reverse osmosis) Nondestructive matter, NH3, NH4 + , iron. ● High removal of compounds.
separation. BOD and SS ●Low biodegradability of certain
Semipermeable ● Availability of wide range of commercial molecules.
barrier membrane from several manufacturers. ●The process is slow, poor decolorization.
●Large number of application and ● Generation of biological sludge, hence,
Module configurations. creates disposal problems.
●Small space requirement. ● The microbiological mechanisms are
●Simple, rapid and efficient, even at high complex.
concentrations. ● High investment cost for small and
●Produce high quality treated effluent. medium
● No chemical required. industries.
● Low solid waste generation. ●High energy requirement.
● Eliminates all types of salt and mineral ●High maintenance and
derivatives. operation costs.
● Efficient elimination of particles, SS and ● Rapid membrane fouling with high
Microorganisms (MF,UF, NF, concentrations, hence, requires frequent
RO), volatile and non-volatile organics (NF, backwashing.
RO). ●Limited flow rates.
● Separation of multivalent ions (NF). ●Choice of membrane depends on
●Production of pure water (RO). specific application.
● Elimination of the
concentrate.

current density increased from 6.8 to 45.5 mA cm−2 . The reactor type
was also found to be highly efficient with less energy consumption
compared to conventional existing electrochemical cells which used
mechanical agitation. In a related study, Shamaei et al. [207] used
hybrid electrocoagulation–chemical coagulation (EC–CC) process for
the treatment of steam assisted gravity drainage (SAGD) produced
water. They evaluated the influence of eight parameters on the organic
matter removal from SAGD produced water using analysis of variance
(ANOVA). Their study indicated that among these parameters, the
chemical coagulant and the treatment time had the most significant
contribution to the TOC removal efficiency with each having 40%
and 26%, respectively. The optimum condition for the highest TOC
removal efficiency of 39.8% was reported to be achieved when 0.34A
was applied to aluminum electrode in a bipolar (BP) configuration
at the pH, temperature, coagulant concentration, mixing rate and
reaction time of 8, 60 °C, 200 mg/L, 700 rpm and 90 min, respectively.
Very recently, Manilal et al. [208] used electrocoagulation in a batch
process with a mild steel anode to remove oil and grease (O & G) from
synthetically PW. The effects of various parameters were investigated
with a response surface methodology. Their results indicated removal
efficiencies of 99.7% and 96.43% for COD and O&G respectively, from
an influent oil-in-water (O/W) emulsion concentration of 1250 mg/L
under optimal operating conditions. Table 5 summarizes the recent
studies conducted by various researchers on the application of various
AOPs for the treatment of oil and gas PW.
5. Overview of produced water treatment technology
Raw produced water is commonly regarded as a high-volume toxic
waste which can be beneficial to humans if properly managed. The treat-
Abass A. Olajire
ment of PW is of paramount importance to oil and gas industry due to
legislation, environmental and energy industry sustainability as well as
reducing stress on fresh water sources. The PW must meet the required
quality standards prior to reuse or disposal to the environment. In this
review article, different technologies including physical (primary treat-
ment); biological, membrane technology (secondary treatment); chemi-
cal and advanced oxidation processes (tertiary treatment) that are used
for the treatment of PW as well as their applications in future man-
agement strategies have been extensively reviewed. The review is also
supported with the mechanism and process chemistry involved in each
of the technology.
Bioreactor-based methods were suggested to be more suitable than
the traditional activated sludge systems for the biological treatment of
oil and gas PW because of some inherent advantages of the former,
which include precise management and control of the biodegradation
parameters, toxic resistant of the immobilized biomass, increased mass
transfer between all phases in the bioreactor.
Membrane technologies are used as filtration techniques using mem-
branes of different pore sizes as filter medium for PW treatment. How-
ever, significant progress must be made to reduce membrane fouling
for them to compete in the future management of PW. The readiness of
membrane technology to be customized and retrofitted into other exist-
ing technologies makes it possible to treat the complex oil and gas PW.
The technology has been greatly improved in recent time for the sepa-
ration of different components in oil and gas PW [114–118]. It has been
the greatest contender in terms of purification performance compared
to other conventional and existing technology. It is a highly promising
technology that should be explored more in the future management of
PW.
AOPs came on board as a promising technology for the removal
of recalcitrant organic compounds in wastewater including those that
are contained oil and gas PW. Different types of AOPs used in oil-
field wastewater treatment and mechanistic chemistry of their processes
are critically reviewed, and these include ozonation, peroxone, hetero-
geneous and homogeneous photocatalysis, photo-Fenton and Fenton-
like processes, sonolysis, and electrochemical processes. Several con-
clusions were drawn from various studies on the applications of AOPs
for the treatment of oil and gas PW. The analysis results of ozona-
tion revealed that it gave better performance under alkaline conditions,
as high pH favours free radical generation from ozone decomposition
and could also be combined with other catalysts to achieve better re-
sult than pure ozone alone. Excellent results have been achieved re-
cently with photo-Fenton, and photo-Fenton-like oxidation processes
such as photoelectro-Fenton (PEF), electro-Fenton (EF), pulse electro-
coagulation (PEC) and sono-photo-Fenton for treatment of oil and gas
PW. Results of some researchers indicated that factors such as the ra-
tio of Fe2+ /H2 O2 , Fe2+ /COD, temperature and reaction time have ef-
fects on the treatment of oil and gas PW. Their results also suggested
the possibility of harnessing solar light in the photo-Fenton process as
a key factor to reducing operation costs (OPEX) of the system. How-
ever, the implementation of AOPs at the industrial scale is still at its in-
fant because of high operational cost, compared to the commonly used
oxidation process. TiO2 is a common semiconductor material used for
photocatalytic process because of its high chemical stability, and cost-
effectiveness. Studies have shown that the amount of semiconductor
material has great influence on removal efficiency of pollutants from
PW. Thus, it is imperative for researchers to find out about the proper
dosage of semiconductor material required for different applications.
The flowchart of proposed combined process for PW treatment is given
in Fig. 7. It has been reported that two or more technologies must be
combined or employed in a hybrid system in order to optimize PW
treatment [13]. However, a cost-effective technology with zero pollu-
tant discharge should be the major priority for the future management
of PW. Table 6 summarizes the pros and cons of different technologies
[209,210].
Chemical Engineering Journal Advances 4 (2020) 100049
6. Future developmental needs of PW treatment technology
Oil and gas industry generates the most significant quantity of co-
produced water during oil and gas extraction, where about 40% is being
discharged into seas or oceans [40] while the remaining can be used as
pressure support for secondary recovery processes, disposes onto sur-
face waters, or underground reservoirs, etc. [211]. Currently, the use
of cost-effective and efficient treatment technology to produce water
quality that will meet regulatory standards for discharge and/or fit-for-
purpose reuse constitute a big challenge for oil and gas industry. A spe-
cific technique cannot be recommended to satisfy all requirements such
as environmental compliance, recycling and reuse for sustainable energy
industry because PW characteristics depend on reservoir history, types
of field (gas or oil), platform types (onshore or offshore) and chemical
composition of production chemicals.
The projected growth of oil and gas sector and future sustainability
of the sector may be potentially hindered by water usage, water qual-
ity and disposal, due to the new environmental legislation and public
perception [212]. Therefore, management of flowback and produced
water in a cost-effective manner is sacrosanct for the operator for to-
tal compliance with regulatory requirements and sustainability of the
energy sector. Thus, the treatment process must be robust, mobile and
modular, sustainable, inexpensive and low energy demand. Also, treat-
ment process should be versatile and flexible and capable of treating
water of large volumes, containing different contaminants with differ-
ent characteristics. Various treatment technologies have been used or
under development to address the large volume of PW produced dur-
ing oil and gas developments. However, the efficiency and feasibility of
emerging technology for future deployment must satisfy certain criteria
for technical assessment, including commercial status of the technol-
ogy and applications, feed stream quantity and expected water qual-
ity produced, removal efficiencies of major contaminants, considera-
tion of infrastructure (modularity, mobility etc.), resource consumption
(energy use, chemical demand etc.) to achieve desired treatment, eco-
friendliness of the technology, consideration of life cycle and costs of
operation and maintenance (simplicity, reliability etc.), consideration of
space facilities, consideration of platform types (offshore or onshore),
necessity of pre/post-treatment and waste disposal management. This
then translates into the demand for more advanced technology to tackle
challenges faced by oil and gas industry with regards to the manage-
ment of PW. In offshore platform for example, operators use physical
and chemical methods due to lack of space while biological treatment
combined with physico-chemical pre-treatment is preferred in onshore
platform due to availability of enough space. However, not all hazardous
pollutants can be removed by neither of the above two methods. The
final polishing of the effluent that will satisfy all requirement can be
achieved with membrane technology especially RO [213], thus necessi-
tating the needs for future research on membrane technology to focus
on resistance of membrane to fouling and development of smart mem-
branes. Overall, the use of cost-effective and efficient as well as eco-
friendly technology with consideration of the above-mentioned techni-
cal issues, is recommended for future research.
7. Conclusion
Treatment of PW has been extensively reviewed in this paper and are
proven to be effective options of handling oil and gas PW. The review
has been able to identify and compile existing and recently developed
technologies which are economically viable for oil and gas PW. In PW
treatment, two or more treatment systems might be combined as no
single technology can satisfy all the water quality requirements. The
choice of best technology depends on the chemistry and origin of PW,
cost effectiveness, eco-friendliness, space limitation for equipment in-
stallation, fit-for-purpose reuse, durability of operation and by-product
of the treatment process. Also, consideration of the geological and hy-
Abass A. Olajire
drologic setting for oil fields should be part of description of applications
of these technologies.
The first step in the selection of the best treatment option is to charac-
terize the PW to determine its major components in a table test. The re-
sults of such characterization with the rest of other components will then
be used to determine if physical pre-treatment is required, or thermal
treatment is ideal, or chemical dosing could be avoided etc. Therefore,
the selection of optimal option for the treatment of PW entails charac-
terization of PW together with environmental factors, economic consid-
eration, resource consumption (energy, chemicals etc.), space availabil-
ity, and local regulatory framework. Furthermore, applications of these
technologies should include the treatment objectives and the desired
beneficial use or disposal route to be employed.
Declaration of Competing Interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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