Accepted Manuscript

Title: Use of Membrane technology for oil field and refinery

produced water treatment–A review

Author: Selvaraj Munirasu Mohammad Abu Haija Fawzi

Banat

PII: S0957-5820(16)00013-6
DOI: http://dx.doi.org/doi:10.1016/j.psep.2016.01.010
Reference: PSEP 679

To appear in: Process Safety and Environment Protection

Received date: 12-7-2015

Revised date: 16-12-2015
Accepted date: 14-1-2016

Please cite this article as: Munirasu, S., Haija, M.A., Banat, F.,Use of
Membrane technology for oil field and refinery produced water treatmentndashA
review, Process Safety and Environment Protection (2016),
http://dx.doi.org/10.1016/j.psep.2016.01.010

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Highlights

 The produced and refinery wastewater treatment by membrane

technology is reviewed.
 The primary and secondary treatment of the treatment are discussed.
 Merits and limits of micro, ultra, nano filtration and RO are discussed.
 Use of FO and MD as potential futuristic technology is discussed.
 Gaps are identified and the future perspectives are proposed

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Use of Membrane technology for oil field and refinery produced water treatment – A
review

Selvaraj Munirasu+, Mohammad Abu Haija$ and Fawzi Banat+*

+Department of Chemical Engineering, $Department of Applied

Chemistry. The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United

Arab Emirates.

*Author to whom all correspondence should be addressed. E-mail: fbanat@pi.ac.ae (F.

Banat).

ACKNOWLEDGEMENTS

The authors are grateful to The Petroleum Institute, Abu Dhabi for funding the project.

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Abstract:

With the advent of modern drilling technology namely sand-tar, hydraulic fracturing
and enhanced oil recovery, the amount of waste water to be treated before reuse
and/or discharge to the environment has increased manifold in recent time. The
treatment of produced water and refinery waste water from the oil industry has been
traditionally done by physical as well as chemical processes. The use of membrane
technology for the produced and refinery waste water treatment has been recent
phenomenon and active research has been focused to enhance the efficiency and life
time of the membrane during the operation of the waste water treatment. In this
review we briefly focus on the produced and refinery waste water treatment by
primary and secondary treatment in historical perspective followed by focusing on
various membrane technologies starting from microfiltration (MF), ultrafiltration
(UF), nanofiltration (NF) and reverse osmosis (RO). Finally we also focus on the
membrane distillation (MD) in combination with forward osmosis (FO) as potential
future technology.

Keywords:

Produced water, oil refinery waste water, membrane technology and water reuse.

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1. Introduction

It is no exaggeration to state that the modern life style depends on the reliable energy
supply. Among the various energy sources, the fossil fuel is the most convenient
source of energy for more than century and even today it is the primary energy source
for humankind. Among the fossil fuels, except coal, all other fuels namely oil, gas, coal
bed methane (CBM), and recent advent of hydraulic fracturing of shale oil and gas are
produced by deep drilling of the earth to recover the hydrocarbon energy sources. In
the drilling process, water has always been produced as by-product which is generally
known as produced water (PW) or co-produce water (co-PW) or flowback water. The
term co-produce water or flowback water refers the fresh water comes out with
formation water from the well. The fresh surface water was generally used for the
pressurization and thereby pumping out the crude oil and/or gas from the well. The
volume of PW is particularly vast quantity for the oil industry whereas the gas drilling
produces comparatively less quantity of water. The amount of PW varies from well to
well as well as the age of reservoir. The volume of PW typically increases with the age
of reservoir and in certain cases it can reach up to 98 % of the total fluid volume [1][1]
[1][1, 2]. However, it is generally recognised as 1:3 ratio for oil & water for most of the
oil well. The typical source of produced water is depicted in Figure 1a [1]. The
produced water is part of natural formation water existing beneath or within the
oil/gas reservoir. Thus the constituents of PW are based on natural geological
formation and it is often acidic in nature with various soluble mineral ions depending
on the geology of the particular the reservoir.

Invariably all the recovered crude oil and gas by drilling the reservoir are further
subjected to “refinery processing” before the final use. Thus the refinery processes for
oil and sweetening of the gas also produce large amount of waste water which is
generally called as “process water” (Figure 1b). Particularly the oil refinery industry
uses large volumes of fresh water for the processing. The major contributing
processes in the oil refinery are desalter effluent, sour water, tank bottom draw and
spent caustic [3]. The major difference between produced water and process water is
that the produced water contains the majority of the dissolved mineral ions whereas
the refinery process water generally contains comparatively less dissolved inorganic
(mineral) ions. However, the refinery process creates many breakdown chemical

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compounds during the chemical transformation which are generally less or
nonexistence in the produced water. The major notable constituent increment in the
process water due to the refinery processing is phenols, ammonia, H 2S and BTEX
(benzene, toluene, ethylbenzene and xylenes). The chemical structure of these
compounds are shown in Figure 2. Thus, the produced and process water differs
considerably in terms of concentration of the pollutant present. In general the
produced water contains high salt content whereas the refinery process water
contains high organic matters (see table 1& 2) [1, 4, 5]. The pre-treatment for both
produced and process water using MF and/or UF membrane can be considered
comparable because of the removal of macro constituents by these membrane
technologies. Since the quality and quantity of the produced water (and oil and gas
also) varies from well to well therefore accordingly the refinery processing, we discuss
the treatment of produced and processing water as single progression in this review.
In many literature, the model refinery process water is prepared using crude oil and
therefore it is considerably similar in nature compared to the produced water.[6, 7]
Additionally there are studies that deals with both produced and process water using
similar membrane treatment protocol for the water purification.[8] Therefore
hereafter in this review PW refers both produced and process (refinery) water.

In general, the treatment of PW can be simplified in the following three classes based
on the macro and molecular level separation. 1. Removal of organics which include
dispersed, dissolved and emulsified oil, grease and gases. 2. The removal of dissolved
inorganic matters which is commonly referenced as TDS. If naturally occurring
radioactive materials (NORM) is present in PW, then special care should be needed for
the removal and disposal of NORM.[9] 3. Removal of particulates which include
suspended particle, clay and sand. Depending on the oil and gas production well, the
production chemicals and chemicals used in the refinery process also should be
removed and it can be included in the above three categories based on its original
constituent. The treatment of PW typically involves primary and secondary treatment
and in some cases biological treatment followed by tertiary treatment. The use of
membrane technology as tertiary treatment for the PW is fast evolving application in
the oil and gas industry. There are literature reviews available concerning the
produced water or refinery waste water treatment as standalone treatment,[2, 4, 10-

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17], but to the best of our knowledge there is no review article universally deals with
both

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produced and process water in the oil industry. In this review article, after
emphasising the primary and secondary treatment, we focus on both produced and
process water treatment with main focus on the membrane technology as final
treatment process. We also discuss the development of FO-MD as potential
technology. Additionally, to the best of our knowledge, there are no review articles
discussing the futuristic aspect of surface wettability and its potential application and
this point also included in this review article for the first time. Thus this review covers
in holistic manner, for the first time, all the existing and potential future membrane
technologies for the treatment of PW.

1.1. Constituents of PW

The most commonly existing pollutant constituents from the produced and process
water are given in table 1& 2 [1, 4, 18, 19]. It can be largely divided into two
categories namely organic and inorganic substances and varying widely from well to
well. Therefore it influences the treatment process significantly. The inorganic
compounds are specific in nature and majority of the constituents exist as dissolved
anions and cations. The common cations in the PW are: Na, Ca, K, Mg, Fe, Al, B, Ba, Cu,
Li, Zn, Ti, Mn, and also toxic Cd, Cr, Pb, Hg, As, Sr, Be. Depending on the geological
condition, some wells contain NORM, like 226Ra, 228Ra, 238U and 235U in the PW. The
major anions in the PW are: chloride, sulphate, sulphite, (bi)carbonate, nitrate, nitrite,
etc. The organic components are very complex in nature starting from oil, grease, and
other organic compounds produced by Bactria. The organics can vary from aliphatic
to aromatic and changing from polar to non-polar characteristic with many possible
functional groups like alcoholic -OH, amino –NH 2, carboxylic –COOH, phenolic –OH etc.
Additionally the organic matters can also exist in the PW as dissolved, dispersed and
emulsified forms. In addition to the inherent composition of PW from its source,
additional chemical compounds are used for the oil recovery from the well. They are
namely corrosion and scale inhibitor, demulsifier, polyelectrolyte, methanol and
glycols[1]. Apart from dissolved and dispersed compounds, the PW also contains
solids which ranges from clay, waxes, bacteria, sand and other suspended solids based
on production chemicals. Additionally dissolved gases also present in the PW and the
three major gases are CO2, O2 and H2S.

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1.2. Challenges and needs for the PW treatment

The conventional way of dealing with the PW in the past was mainly physical
separation of oil and water using gravity and subsequent discharge to the
environment. However, the regulation is progressively becoming more stringent as
more evidence suggested that the impact of PW on the environment.[20] The PW
water discharged into sea should contain less than 40 ppm of OIW (oil-in-water) for
majority of the countries, however more countries are attempting for further
stringent regulatory standards[1]. Consequently most oil companies are attempting to
reach “zero-discharge” of harmful compounds to the environment. It was reported
that about 80% of PW has been re- injected to the well in order to manage the PW and
maintain the pressure of the oil well. Since many oil producing regions are in the
water stressed zone it makes more economical sense to utilize the PW for the
beneficial use of irrigation or live stocks.[1] Therefore, efficient treatment of PW
should meet the dual target of cleaning the polluted water as well as recovering the
purified water for the beneficial use. Among all the available water purification
technologies, the membranes can be cost effective water treatment method with
required criterions of the treated water for the final use or discharge.[21, 22] One of
the main issues in the PW treatment using membrane technology is to reduce and
solve the complexity of the organic matter in the pre- treatment stage in order to
reduce the fouling of the membranes. The high content of inorganic matters in the PW
on the other hand makes it inherently high osmatic and therefore high operating
pressure for the nanofiltration (NF) and reverse osmosis (RO) membrane process.
Additionally, the presence of high TDS is one of the main reason for the frequent scale
and silt formation on the membrane surface. Thus, it is imperative to reduce the
inorganic as well as organic matters as much as possible in the pretreatment stages in
order to make the membrane treatment practically feasible as well as economically
viable process. In this review article, we focus on the use of membrane technology for
the PW treatment in holistic manner in historical perspective followed by recent
developments in the membranes for the PW treatment. In the following section, we
first discuss the primary and secondary treatment of PW followed by membrane
technology.
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2. Primary and Secondary treatment of PW

The earlier use of membrane technology for the PW treatment has not been successful
due to the presence of high fouling constituents in the PW.[1] In order to overcome
this shortcoming due to the inherent nature of PW, the pretreatment of the PW before
feeding to the membrane process is most important aspect of any PW treatment
process. Most of the pre-treatment methods for the PW treatment were similar to the
municipality waste water treatment namely primary and secondary treatment.
Primary treatment includes screening, grit removal, gravity assisted sedimentation,
demulsification,[23] coagulation, adsorption, dissolved air precipitation[24] and
induced air flotation (IAF).[25] The secondary treatment involves the removal of
dissolved components through chemical and biological treatment. The chemical
treatment includes chemical oxidation,[26] including advance oxidation process
(AOP)[27, 28], biological oxidation,[29] electrodialysis,[30] electrocoagulation, electro
flocculation [31] etc. The biological treatment includes trickling filter and activated
sledge treatment etc. and, as a recent development, the biological treatment in
combination with membrane known as “membrane bioreactor” (MBR) technology is
one of the active research area. The principal aim of primary and secondary treatment
is to reduce the pollutant level as low as possible with cost effective manner. In many
cases, more than one primary or secondary treatment processes are combined in
order to have effective pollutant removal. In the following section we discuss selective
primary and secondary treatments for the PW from the literature followed by
summary of current status of technology.

The combination of Induced Air Flotation (IAF) as primary and photo-Fenton process
as secondary treatment has been reported for the treatment of oil in water.[32] The
real crude oil was mixed with standard synthetic saline water to mimic the PW. The
resulting synthetic effluent contained 300 ppm of oil. The IAF process in combination
with non-ionic surfactant, ethoxylated fatty alcohol, removed the oil content in the
effluent up to 90%. The remaining ~35 ppm oil in the water was removed by photo-
Fenton process using H2O2 and FeSO4.7H2O. The pH was maintained at 3.0 with the

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addition of H2SO4. The effect of surfactant concentration in the IAF and dissolved
oxygen in photo-Fenton process also studied. It was shown that at the optimum
condition of 10 min., IAF in combination with 45 min., photo-Fenton process, 99% of
the oil in the effluent can be removed. In an earlier work, the experimental conditions
were optimized using the same combination of IAF and photo-Fenton process for the
removal of xylene from the synthetic waste water.[33] Apart from usage of chemicals
in the photo oxidation process, the acidification of pH 3 and possible neutralization
later stage will be a major drawback of this process for the large scale application.

The judicial use of coagulant and flocculent is one of the robust options for the
primary treatment of PW. Based on the nature of PW, sometime the standalone
process of coagulation or flocculation alone was not effective. For example, the
removal of TSS from the PW using FeCl3 or Al2(SO4)3 alone as coagulant were showed
unsatisfactory result due to formation of smaller size flocs which was not removed by
sedimentation.[34] By combining with ionic polymers as flocculent, much improved
TSS removal was reported and the resulting water contained TSS within acceptable
limit of 80 mg/L. In the study, cationic polyelectrolyte DF 492 and anionic
polyelectrolyte DF 973 were used as flocculent. The cationic DF 492 using 5 ppm
showed better TSS removal in combination with 5 ppm Al 2(SO4)3. It was claimed that
the cationic polymer formed stronger attachment with the floc formed hence better
removal. The sequence of the pre-treatment also has considerable impact on the
outcome of the process. The effect of softening sequencing on electrocoagulation (EC)
for the treatment of PW was reported by Esmaeilirad et al. [35] The influence of
chemical softening on EC was studied and for the chemical softening the pH was
manipulated by addition of NaOH and HCl. About 99% of turbidity removal for one
month old PW was achieved by softening before EC, compared to 88% for the EC
followed by softening. It was reported that it was more effective to carry out chemical
softening followed by EC for the turbidity removal from the PW. Neither configuration
was effective for the fresh flowback PW (one and two day samples). It was
hypothesised that this might be due to the decrease in organic matter for the older
sample.

The combination of coagulation and bioaugmentation were used for treatment of oil
field wastewater originating from the use of alkaline, surfactant and polymer.[36] For

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coagulation, polymeric ferric sulfate (PFS), polymeric aluminum chloride,
polyaluminum ferric chloride (PAFC), aluminum sulfate (alum) and ferric sulfate were
used with varying dosage. The PFS showed about 80% COD removal at 600 mg/m 3
dosage. The indigenous bacterial communities were used for the biological
hydrolysis/acidification treatment and followed by bio-contact oxidation treatment.
The bacterial communities include Pseudomonas, Acinetobacter, Bacillus,
Flavobacterium, sulfate-reducing prokaryotes, a PAM-degrading bacterium (Bacillus
cereus NY001), a petroleum sulfonate-degrading strain (Burkholderia sp. NY003), and
a petroleum hydrocarbon-degrading organism (Pseudomonas spp. NY012). The
aerobic hydrolysis/acidification treatment removed more than 90% BOD 5 and 70%
COD after 40 h of hydraulic retention time. As the final stage of bio-contact oxidation

at HRT of 20 h, the average values of COD, BOD 5, oil, PAM, and NH3-N of the effluent
decreased to 116, 19, 4, 11, and 20 mg/L respectively from the PW, which corresponds
to the
removal efficiencies of 65.3%, 86.1%, 52.7%, 35.2%, and 78.4% respectively.

Though the use of electrolysis for PW treatment in large scale is uncommon, the COD
removal by electrolysis using Ti/RuO 2 electrode was reported for the real PW
treatment.[37] The two different types of samples, before flotation (BF) and after
flotation (AF), were collected from the refinery were subjected to the electrolysis.
Because of the partial elimination of COD during the flotation, the current density or
time required varied for these two samples. For example, with a current density of 10
mAcm-2 with 120 min electrolysis, 96% COD removal was observed for the AF sample
whereas only 87% observed for the BF sample. Complete COD removal was achieved
by increasing current density to 30 mAcm -2. At this current, the BF sample needed 60
min electrolysis and for the AF sample only 30 min electrolysis needed. The calculated
cost of complete COD removal based on this work is US$ 38/kg COD for the BF and
US$ 28/kg COD for the AF sample. Though the cost for AF is considerably less
compared to BF, at this cost, this process might be prohibitively expensive for PW
containing high COD especially from gas field which has COD of as high as 120,000
mg/L or refinery waste water (see table 1).

In an interesting study, the use of plasma gliding arc for the removal of bicarbonate in
PW was reported.[38] The aim of the work was to study the effect of plasma on the

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removal of bicarbonate and the effect of high concentration of calcium in the absence
of

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bicarbonate on scaling. The plasma treatment effectively removed the bicarbonate to
negligible level and no calcium scaling was observed up to 30 hours at high
temperature in the absence of bicarbonate. Although this method can be useful for
high scale forming PW, the cost effectiveness and large scale feasibility study were not
reported.

The beneficial use of combination of pre-treatment processes rather than single

process in order to achieve the effective treatment of PW was reported by El-Nass et
al. [39] A three-step process combination of electrocoagulation (EC), spouted bed
bioreactor (SBBR), and adsorption on activated carbon were the three methods used
for the study. The authors used the real PW for the COD and phenol removal by these
three combined methods by varying the process configuration. As a standalone
process, none of three methods provided the satisfactory treatment of PW for the
discharge. At first, the EC treatment followed by activated carbon and finally SBBR
were attempted for the PW treatment. In this configuration, the EC as first stage
removed 46% COD. The activated carbon as second stage removed the cumulative
COD of 83%. The final SBBR reactor did not improve the COD removal at al. Thus the
overall COD removal in this configuration was about 85%. The activated carbon
reduced the COD initially to Zero in the first 3 hours and then gradually saturated. The
same configuration showed the phenol reduction of 30% by EC followed by more than
85% reduction using activated carbon adsorption as second stage. The SBBR further
reduce the phenol to above 95%. In another configuration, the authors exchanged the
treatment sequence of SBBR and activate carbon. In this, the SBBR treatment was
done ahead of activated carbon adsorption. In this configuration, the SBBR removed
the COD by about 73% cumulatively with EC and activated carbon finally removed up
to 97% COD cumulatively. It is interesting to note that, SBBR as final treatment for the
COD does not show any improvement at all in the previous configuration. The SBBR as
second stage in the process removed the phenol up to 61% followed by activated
carbon process which essentially removed all the phenol completely. Thus it was
demonstrated that the superiority of the proper combination of the process
configuration and the COD was removed from initial 4190 ppm to 110 ppm and
phenol and cresols (originally 12.2 ppm & 75 ppm respectively) were removed
completely.

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The use of membrane sequencing batch reactor (MSBR) for the hypersaline oily waste
water treatment has been reported.[40] The effect of varying organic and salt

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concentrations was reported in the study. The organic loading was varied from 0.281 to
3.372 kg COD/m3.day and salt concentration from 35, 000 to 250, 000 mg/L with
MSBR cycle time of 12 to 48 h. Using synthetic PW with an organic loading of 1.124 kg
COD/m3.day with 35,000 mg/L of salt concentration, removal efficiencies of 97.5%,
97.2%, and 98.9% for the COD, total organic carbon (TOC), and oil and grease (O&G),
respectively, were achieved in 48 h reaction time. However, the real PW showed less
efficiency vis-aà -vis 86.2%, 90.8%, and 90% for the same conditions. At the highest
TDS of 250,000 ppm, the COD removal was only about 90.4% and 17.7% for synthetic
and real PW. It is important to note, in both cases of two different salinities, the
efficiency difference between real and synthetic PW by MSBR process is vast and more
so in the case of high salinity PW. The use of hollow fibre submerged membrane
bioreactor for the treatment of brackish oil and natural gas field PW was reported.[41]
After one year lab scale operation, stable performance was reported despite variations
in the influent at different sludge retention time (SRT). The COD removal was about
80-85% and the removal of oil and grease increased from 60% to 85% by increasing
the sludge age. The linear hydrocarbon C9-C13 was effectively removed up to 99%
efficiency. The physical cleaning restored 60% of initial flux and further 95% of initial
flux was re-established after subsequent chemical cleaning. In most cases the
biological treatments are more effective in less toxic PW and this can be facilitated by
the effective use primary and secondary chemical treatment.

In recent times the use of surface wettability by tuning the surface chemistry of filters
gained attention for the separation of immiscible liquids. By changing the surface
energy of the filter to very low or high, it is possible to change the wettability of the
surface in to superhydrophobic or superhydrophilic. With optimum porosity and
surface energy, one can separate the oil-water mixture based on the wettability of PW
on the filter. Using this principle, simple filtration method based on the surface energy
of the filter and medium has been studied as bench scale demonstration. Thus
superhydrophilic and underwater superoleophobic nature of the surface was used for
the oil-water separation.[42] To obtain the surface with specific wetting character,
TiO2 nanoparticles were spray coated on stainless steel mesh (50 & 100 micrometre).

Due to the TiO2 coating, the surface of SS mesh becomes superhydrophilic as well as
underwater superoleophobic. Thus the modified SS mesh showed the gravity driven
oil-water separation up to 99% separation efficiency. The hierarchical

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superhydrophobic surface made of layer-by-layer (LBL) self-assembly for the oil-
water separation has also been reported.[43] The SS mesh or SS fibers felt were used
to coat SiO2 nano particles having different size by serious of LBL method. After
obtaining the required rough surface, the silanol–OH group was surface modified
using perflourotriethoxysilane by chemical vapour deposition (CVD). The resulting
superhydrophobic fibers separated Hexane-in-water emulsion by non-sieving
coalescence mechanism with separation efficiency up to 99.4%.

Utilising similar concept, alumoxane modified Kevlar fabric has been reported for the
separation of oil/water (n-hexane in water).[44] The surface modified alumoxane was
attached to the Kevlar fabric using the hydrogen bond and the resulting enhanced
hydrophilic fabric was used for the dead-end filtration by the gravity force. The
neutral pH proved to be optimum with flux of 7392 LM -2h-1 at rejection of 89%. The
fouling gel layer formed on the surface was removed by distilled water and acidic
solution which resulted a flux recovery of 89%. The unmodified Kevlar fabric showed
oil rejection of less than 20% due to less hydrophilic in nature compared to the
alumoxane modified fabric. The highly hydrophilic nature of alumoxane modified
fabric induced the selective passage of water by acting as barrier to oil. However all
the reported surface energy based separations are laboratory scale studies and their
long term stability is an issue. The separations are not based on molecular level and
separation occurs wetting based sieving on macro scale. In future, wetting based
filters may compete and complement the physical separation methods like skimmer.
The main disadvantage of wetting based filters is when the oil droplet size is less than
20 µm size. These are effective when the size of droplets are more than 20 µm and it
is unclear the effectiveness for finely dispersed organic compounds. For obvious
reason, the dissolved organic compound separation is not possible by this
methodology. Additionally more research studies are needed at the pilot scale in order
to evaluate the suitability for the industrial scale application.

To summarize, for the primary and secondary treatment of PW many existing

technologies can be effectively applied for the PW treatment. After effective initial
screening and separation of oil based on gravity, the chemical treatments along with
coagulants could be the choice to reduce the contaminant further in order to have
reasonably good quality feed for further membrane filtration. Based on the nature of

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PW, especially for the less toxic PW, the biological treatments can be cost effective
method. Recent developments in advanced oxidation process and membrane
bioreactors will facilitate the future applications. After initial screening and gravity
separation, wetting based oil separation could also have potential application for the
PW treatment in future.

3. Produced water treatment by membrane technology

The principle of membrane separation of the constituents is based on exclusion,

mostly but not always, based on size using a selective barrier layer. Most of the
modern day membranes are prepared using synthetic organic polymers; nevertheless
inorganic ceramic membranes are also widely used. For water purification practice,
according to the pore size, the membranes can be classified as microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO). The pore size of the
selective layer decreases from MF to UF and then NF and finally RO, and therefore
hydrodynamic resistance for the liquid passage increases. Because of the pore size
change, the applied pressures for the membrane operations vary significantly and the
operating pressure increases dramatically as the pore size of the membrane decrease.
The MF and UF operation are based on convective pore-flow mechanism (Darcy’s
law) whereas the RO membrane operation is based on solution diffusion mechanism
(Fick’s law). The NF membrane is in between pore-flow and diffusion mechanism and
sometime it is called loose RO membrane.[22] As the name implies, the microfiltration
operates in the pore size range of 0.1-10 µm and accordingly it can reject suspended
solids, bacteria etc., but allows the passage of the virus, divalent ions etc. The pore size
of ultrafiltration is in the range of 2-100 nm and it rejects most of the macromolecular
colloids and virus, but most of the dissolved ionic species passes through the
membrane. It has been identified that the occurrence of transition between pore-flow
to solution-diffusion is about 0.5-1 nm diameter and this is the range where NF
membrane pore size should be for the ideal operation.[22] Thus, the ideal NF
membrane should reject the divalent and multivalent ions like Mg2+, Al3+, -SO4-2 etc.,
whereas it should allow the passage of monovalent ions like Na+, Cl- etc. Since RO
membrane operates based on solution diffusion mechanism, the ideal RO membrane
should reject all the ionic species and only water molecule
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should pass through the membrane and in most cases the rejection of solutes from
water is more than 99%. Based on these principles, in the following sections, we focus
the use of MF, UF, NF and RO membrane for the PW treatment. Apart from the
principle of separation based on the nature of pores, the major difference between MF,
UF and NF, RO, is the membrane preparation process. The MF and UF are usually
integral membrane, and most of modern UF membranes are asymmetric in nature too,
where whole membrane is a single polymeric material with or without mechanical
support. The mechanical support can be non-woven polyester or other supports. On
the other hand the RO and majority of the NF membranes are composite membranes
where the top thin separating layer in the range of 100-200 nm are usually cross-
linked polymers on the support of UF membrane. A typical RO or NF membrane can be
prepared on the top of the UF membrane by interfacial cross-linking polymerization.

There is one important factor to be considered when membrane technologies are used
in real application. There is a large gap between the intrinsic membrane capability
and actual membrane performance. For example, MF & UF can have high pure water
flux whereas in real life application like food and dairy industries, it can be less than
10% of pure water flux. This is mainly due to the concentration polarization and
fouling of the membrane. Therefore in reality, rather than membrane’s intrinsic
property, it is the feed factors like concentration polarization and fouling will decide
the performance of the membrane. In summary, most of the membranes can’t achieve
its theoretical limit in real application. One has to keep this is mind when membrane
technology is applied for the separation process. For more detailed information about
the basics of membrane technology the readers are directed to follow the books about
membrane science and technology.[21, 22]

Microfiltration (MF)

MF is a process of sieving particulates based on the pore size of the membrane. The
pore size of MF is about 0.1 µm or more, therefore its application in PW treatment
should be considered as a pre-treatment in order to enhance the effectiveness of UF,
NF or RO processes. Polymeric or ceramic MF [45, 46] membrane are widely available

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for the treatment of PW. One of the earliest report dealt with oil-water separation is
the

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use of ceramic and polyacrylonitrile (PAN)[21] MF membranes[47]. The ceramic MF
of 0.8, 0.2 µm and 0.1 µm PAN membranes were used for the study and the synthetic
PW was made by using heavy crude oil (API 12 weight, density 0.972 g cm -3) in the
concentration range of 250-1000 ppm. It has been observed that the increased oil
concentration decreased the water flux and cross flow velocity (CFV) and
transmembrane pressure (TMP) and temperature (T) had little impact on the final
flux. The permeate contained less than 6 ppm of oil and interestingly addition of
suspended solids (250 ppm diatomaceous earth) increased the final flux of the
membrane by one order of magnitude. It was hypothesised that that the suspended
solids adsorb the oil, break up the oil layer on the membrane surface thereby
increasing the permeation flux. The bigger pore size membranes, i.e., 0.8 and 0.2 µm
ceramic membranes were found to have both internal and external fouling whereas
the 0.1 µm PAN had only external fouling; i.e. membrane top surface layer fouling. All
the surfaces of the membranes were found to be hydrophobic due to oil fouling and
these oily layers were resistance to hydrodynamic shear method for the removal. In
another early work, Campos et al. reported the use of MF and biological process for
the PW treatment.[48] The coarse filtration was used as pre-treatment and the PW
was subjected to 0.1 µm commercial mixed cellulose esters MF. The MF process
removed the COD, TOC, oil & grease (O&G) and phenol of 35%, 25%, 92%, and 35%
respectively. Subsequently the polystyrene particle beads air-lift reactor was used as
biodegradation. The lowest studied hydraulic retention time (HRT) of 12 h showed
the COD, TOC, phenol and ammonium removal of 65%, 80%, 65% and 40%
respectively. The combined MF and biodegradation process showed the COD and TOC
within the discharge limit (230 and 55 mg/L respectively), but the phenol and
ammonium concentrations were above the permissible limit. It was clear from these
earlier studies that the use of MF alone will not be sufficient for the treatment of PW
and most importantly the high fouling of membrane discouraged the wide use in the
PW treatment.

The use of mullite and mullite–alumina ceramic MF membranes for the treatment of
PW was reported by Abbasi et al. [49] The mullite-alumina MF membranes were
prepared using kaolin clay with α-alumina by extruding the water mixture followed by
room temperature drying. Finally the room temperature dried membrane was

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calcinated at 1250 °C for 3 h followed by strong alkali leaching to remove the free
silica. The

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prepared MF ceramic membrane was subjected to study the effect of pressure,
temperature, CFV, oil and salt concentration. It has been observed that the permeation
flow increased with increasing flow rate, temperature, pressure and alumina content
of the mullite–alumina membranes whereas permeation decreased with increasing oil
concentration in the PW. At elevated temperature and high CFV, the fouling resistance
decreased. The rejection was slightly higher with the increased pressure, salt
concentration, oil concentration and alumina content of the mullite–alumina ceramic
membranes. It has been found that the TOC rejection of 94% for the synthetic oily
wastewater but only 84% of the TOC rejection for the real PW using the same
membrane. It is important to note that the reported study showed less permeation
flux and lower rejection for the real PW compared to synthetic PW. A tubular ceramic
α- Al2O3 MF was reported for the treatment of Tehran refinery.[50] The
microfiltration produced the water with oil and grease content of 4 mg/L which was
within allowed limit. The operating parameters like TMP, CFV and temp. on the effect
of permeate flux, TOC removal and fouling resistance were studied. It was also
reported that the backwashing could prevent the flux decline significantly.

Recently, Zhu et al. reported the use of hydrophilic and oleophobic PVDF hollow fiber
MF membranes for the oil-water separation.[51] For this novel membrane, the P(VDF-
co-CTFE)-g-(PMAA-co-fPEG) has been synthesized by grafting tert-butylmethacrylate
(tBMA) on poly(vinylidenefluoride-co-chlorotrifluoroethylene), P(VDF-co-CTFE),
using ATRP. Subsequent hydrolysis of tBMA segment resulted the PMAA grafted on
P(VDF- co-CTFE) backbone. The acid group of the grafted MAA was further esterified
either with perfluoroalkylpolyethyleneglycol(fPEG) or polyethyleneglycol (PEG) to
obtain the additive polymer of P(VDF-co-CTFE)-g-(PMAA-co-fPEG or P(VDF-co-CTFE)-g-
(PMAA-co- PEG). The modified polymers were added as additives to the PVDF dope
solution in order to make hydrophilic and oleophobic PVDF hollow fiber MF
membranes. Three different types of oils namely ‘H-oil’ (Hexane in water), ‘C-oil’
(crude oil in water) and ‘P-oil’ (palm oil in water) were studied for the oil-water
separation using the new hydrophilic and oleophobic PVDF hollow fiber membrane.
The ‘H-oil’ removal efficiency of > 98% was achieved and the ‘C-oil’ removal was
impressive, >99%. However the ‘P-oil’ showed only about 70% separation efficiency
due to the smaller size of oil droplet in the feed water. The main aim of the work was
fouling resistance and

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this novel membrane showed excellent flux recovery after back washing and
importantly the rate of flux reduction is considerably lower compared to the
controlled PVDF hollow fiber MF membrane which has been prepared without the
hydrophilic additive polymer (Figure 3). From the figure, it is clear that the PVDF
membrane without hydrophilic additive loses most it its water permeability
irreversibly within few hours of operation. However, the membranes prepared with
hydrophilic additives showed more than 95% flux recovery by simply washing and
backwashing with DI water at the membrane operating pressure, ca. 0.34 MPa.
Because of it excellent flux recovery using well known PVDF polymer, which has been
used as commercial membrane for long time and the notable exceptional property of
new membrane compared to the existing PVDF membrane makes it one of interesting
candidate for further pilot and industrial scale study .

The integration of coalescer bed and MF membrane process was reported by Motta et
al. for the synthetic oil/water separation.[52] The cation exchange resins were used
for the coalescer bed formation working in up-flow condition with polyetherimide
hollow fiber MF submerged module with permeation area of 0.5 m2. Using optimum
condition, the efficiency of 93.0% to 100% oil removal achieved and this
corresponded to an O&G concentration in the final effluent between 0.1 and 14.8mgL -
1. The coalescer bed first removed about half of the O&G and the remaining O&G was
removed by the membrane process. The combination of these two processes was
suggested as pretreatment to minimize the operational problems like fouling for
further treatment by UF and RO membrane. Additionally it was suggested that the
coalescer bed and MF processes can be made as a loop, thereby the retentate of the
MF membrane can be sent back to coalescer bed to recover the oil.

The use of Hollow fiber supported liquid membranes (HFSLM) for the removal of
mercury (II) from the PW water was reported by Chaturabul et al. [53] The HFSLM
was made by impregnating the commercial hollow fiber module with surfactant
Aliquat 336 by toluene solution circulation and thiourea was used as stripping agent.
It has been reported that 99.7% extraction with a recovery of 90% was possible using
the optimized condition. A theoretical model was developed and the prediction
agreed well with the experimental result. The treated water contained less than 5 ppb
of mercury which is within the limit for the discharge. In a similar previous study,
Cyanex® 923 (a
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mixture of phosphine oxide), tri-n-butylphosphate (TBP), bis(2, 4, 4-trimethylpentyl)
dithiophosphinic acid (Cyanex® 301), tri-n-octylamine (TOA) and
methyltrioctylammonium chloride (Aliquat 336) were used as the extractants and
NaOH solution as stripping agent.[54] Since Hg is highly toxic substance and its
removal is high importace in PW. However it might be interesting to check the
longevity and large scale viability of these types of system in long term operation.

Recently graphene oxide modified Al 2O3 based MF membrane was reported for the
synthetic oil/water separation by Hu et al. [55] It has been observed that the
efficiency of GO modified membrane was higher for the oil removal with ~28% higher
permeate flux compared to unmodified membrane. However, the membrane stability
to withstand the backwashing and chemical cleaning has not been reported. In the
future, more research on the applications of these new materials will assist to
understand the effect of these materials in the membrane technology.

The cost for the PW treatment using membrane technology is very important for any
viable application. Thus the cost estimation for the synthetic PW treatment using
zirconium oxide ceramic MF was reported by Weschenfelder et al. [56] The water flux
for the synthetic produced water with different oil and salt contents was studied with
varying CFV and TMP. The optimum CFV has been found at 2.0 m.s -1 and based on the
optimization, the capital and operating cost was calculated for the water recovery rate
of 50%, 80% and 95%. The cost of membrane regeneration by backwashing with
1000 mg.L-1 of each NaOH followed by sodium hypochlorite and finally distilled water
wash was also included. Based on the experimental results, the capital and operating
cost was calculated for the recovery rate of 95% water for CFV from 0.3 to 4 m.s -1 as a
function of the unit volume of treated water in m 3 for the PW treatment of 1000m 3.h-1.
A total US$ 3.21/m3 was reported as the lowest possible cost. The salt rejection has
not been reported in this study and it can be assumed that it should be negligible due
the use of microfiltration process. It should be also noted that it has been calculated
using NaCl alone as salt constituent with refinery oil. However the real PW samples
are much more complex in terms of oil contents, other organic and inorganic
pollutants. Nevertheless the cost estimation is useful tool for the oil removal and MF
treatment can be considered as pre-treatment and further cost estimation can be done
for NF and/or RO treatment for the salt removal.

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To summarize, the MF can be used as cost effective pre-treatment for the PW
treatment. It can be used after removing the bulk of the oil component by using the
primary treatment of sedimentation, coagulation, flocculation & sedimentation
process. The MF process can effectively remove the dispersed oil droplets and other
particulates with the size of more than 100 nm. However, the smaller droplets and
particulates can pass though the MF membrane and for more effective removal of
smaller size, the UF membrane can be employed. Another major limitation of MF is the
lack of removal of dissolved component.

3.1. Ultrafiltration

UF process is one of the initial methods attempted along with MF for the oil removal
from the petroleum industry waste water. However, due to high permeation flux, UF
membranes were easily susceptible to the fouling. Consequently one of the main
objectives in UF membrane study is to reduce the fouling on the surface of UF
membrane. Hence most of the literature dealing with UF membrane reports the effect
of fouling and how to manage or reduce it effectively. The most effective way of
reducing fouling is to make the membrane surface more hydrophilic and reduce the
roughness. Therefore, in the following section, we discuss some of the selective
reported literature dealing with UF membrane for the PW treatment. First we focus
on the new lab made hydrophilized UF membranes followed by the examples of
commercial UF membranes.

The fouling resistance hydrophilic cellulose based UF membrane for the synthetic PW
treatment was reported by Husson et al.[57] In this study, the low molecular weight
cutoff regenerated cellulose UF membranes was modified by surface initiated atom
transfer radical polymerization (ATRP). Firstly, thermos-sensitive poly(N-
isopropylacrylamide), PNIPAAm, was grafted followed by
poly(oligoethyleneglycolmethacrylate), (POEGMA) grafting. The resulting poly(N-
isopropylacrylamide)-block-oligoethyleneglycolmethacrylate), PNIPAAm-b-POEGMA,
and PNIPAAm homopolymer grafted membranes were compared with the unmodified
cellulose UF membrane. The synthetic PW was prepared using soybean oil (5g/L) and
NaCl (0.5 g/L). The modified membranes showed less water flux compared to
unmodified UF membrane due to the surface pore coverage by the grafted polymers.

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However, the slop of flux decline is far less for the modified membrane compared to
the unmodified membrane. Most interestingly, the modified membranes showed
100% permeation flux recovery by simple cold water rinse whereas the unmodified
membrane showed only 81% of initial flux recovery. Though it is 81% of initial flux
recovery, the water wash of unmodified membrane showed insignificant improvement
from the point of recovery point, i.e., the flux value before and after cold water wash is
nearly same. The TOC removal efficiency of >94% was achieved for all three
membranes and the most importantly, 100% flux recovery from the modified
membranes. Based on the complete flux recovery, it was claimed that the modified
membrane will be useful as fouling resistance membrane. The same group further
studied the effect of grafting density on the fouling resistance.[58] It was found that
the increasing grafting density decreased the permeate flux, but the flux decline over
continues operation is significantly less compared to sparsely grafted membrane and
this effect is more pronounced when compared with the unmodified membrane. It has
been determined that the initial lower permeation flux is better trade-off in long term
use when one considers the rate of flux decline and washing. In an another earlier
study, the commercial NF membrane (NF270) was subjected to the similar surface
initiated polymerization by anchoring the initiator on the NF membrane.[59] However
the modified membranes showed less permeate flux and importantly does not show
any improvement in flux recovery. The authors suggested that this might be due to
increase in hydrophobicity after the modification with dense polymer layer. Unlike the
NF membranes, the UF membranes showed better flux recovery and thus it was
claimed to have better fouling resistance compared to the unmodified membranes.

The effect of hydrophilic segment inclusion in the PAN UF membrane for the fouling
resistance in the PW treatment was reported.[8] The effect of the addition of 20 wt%
PAN-g-PEO in the PAN UF membrane preparation for the treatment of two different
PWs and one refinery waste water was studied. For the comparison, the commercial
Serpo PAN400 was used to differentiate the fouling resistance due to the hydrophilic
segment addition in the UF membrane. The dead-end filtrations of commercial and
manufactured PAN membranes were successful in removing free and dispersed oil &
grease. The hydrophilic PAN recovered the flux by backwashing whereas the PAN
membrane lost more than 25% initial flux irreversibly. Additionally the rate of flux

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decline for the hydrophilic UF membrane is significantly less compared to the plain
PAN UF membrane without hydrophilic PAN addition. This report clearly indicate the
superiority of hydrophilized membrane compared to the conventional commercial
PAN membranes for the PW treatment.

The effect of PEG grafting density on PSf-UF membrane for the oil separation from
water was reported for two different type oily waste waters, namely soybean oil and
industrial PW.[60] The azide-functionalized PSf-UF membrane was prepared by phase
inversion method. The azide group on the side chain of polysulfone backbone was
PEGlated by click chemistry using alkyne end-functionalized PEG. Two different
degrees of azide functionalities (17 % and 45%) and three different MWs of PEG (120,
750 & 1300) were used to study the effects of grafting density as well as molecular
weights of PEG. The high molecular weight PEG with densely grated PEG showed
more hydrophilic than the rest of the combinations. The membranes with high
grafting density using low molecular weight PEG showed better fouling resistance and
permeate flux. The optimized membrane showed complete oil rejection with a flux of
120 LMH with over 95% flux recovery by simple water rinsing. Since PSf is widely
used for the UF membrane manufacturing due to the exceptional pore formation with
good mechanical stability, the result might be interesting for the further study.

The lab-made polyethersulfone (PES) asymmetric UF membrane for the PW treatment

has been reported.[61] The hollow fiber membrane was prepared using 17 wt% PES
and 2.5 wt% PVP dope solution for the dry-jet-wet spinning process. The PVP was
added in order to make the membrane more hydrophilic and to change the surface
and subsurface morphology more porous. The real PW was used for the study and the
use of PES UF membrane showed TOC rejection of 96.3%, COD (83.1%), turbidity
(99.3%), and oil and grease content (99.7%), and complete rejection for TSS with a
reasonably high permeation flux of 84.1 L/m 2.h and fouling resistance of 63.0%. It was
reported that the quality of the UF treated PW is better than the cooling tower feed
water used in the Tehran oil refinery. The authors also used adaptive neuro-fuzzy
inference system (ANFIS) model to predict permeation flux in UF process and it was
found good agreement of the model with experimental data.

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The hybrid photocatalytic reactor and PVDF/MWCNT nanocomposite UF membrane
process for treatment of petroleum refinery wastewater has been reported.[62] The
pristine and oxidized MWCNT were used for the fabrication of PVDF nanocomposite
UF membrane. The waste water was subjected to photocatalytic reaction using UV
light in combination with 200 ppm TiO2. More than 90% of organic matters were
decomposed by the photocatalytic reaction in 6 h UV radiation. After the
photocatalytic reaction, the feed was passed through PVDF/MWCNT nanocomposite
UF membrane and the permeate showed >99% of organic pollutant removal.
Interestingly the TiO2 photocatalyst also recovered in single filtration process of UF
membrane with an efficiency of more than 99% from the catalytic reactor. Thus the UF
membrane was used for dual purpose to filter the water as well as to recover the
photocatalyst.

The physiochemical nature of membrane is important for the effective separation and
in addition to that the membrane operating conditions are also deciding factor for the
practical use of membrane technology. The effect of membrane operating conditions
like temperature (T), transmembrane pressure (TMP), and cross flow velocity (CFV)
on permeate flux, fouling resistance, and TOC rejection using commercial PAN350 UF
membrane was reported by Shahabadi and Reyhani.[63] According to this study, TMP
has high impact on the permeate flux and fouling resistance where as CFV has more
impact on the TOC removal. The experimental and full factorial design methodology
was used to optimize and narrow down the impact of each operating conditions. For
the PAN350 UF membrane, it was reported that the significance of operating
parameters on the outcome as follows: (a) For permeate flux: TMP > T > CFV > T–TMP
> T–CFV, (b) For fouling resistance: TMP > T > CFV > T–CFV > T–CFV > TMP–CFV, (c)
For TOC rejection: CFV > T > TMP > TMP–CFV > T–TMP. By utilizing best operating
conditions, 100% oil and grease, 100% TSS, 99% turbidity, and about 50% TOC
removal from real PW was reported. This result clearly indicates that it is important to
optimize the operating parameters of membrane unit based on the PW quality in
order to achieve the best result.

In similar operational parameter optimization, the refinery waste water from Tehran
API unit was subjected to UF process under different operating conditions and the

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permeate quality was compared with the existing conventional biological treatment
which has been used in the in refinery for the PW discharge.[64] Two commercial UF

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membranes, PAN (molecular weight cut-off – 20 kDa) and PSf (molecular weight cut-off
– 30 kDa) were studied for the pilot scale operational optimization. After studying the
effect of TMP, CFV, pH and temperature, it was found that the optimum conditions as
following: TMP -3 bar, CFV – 1 m/s, T – 40 °C and pH – 9. The PAN UF membrane
showed better water flux and fouling resistance than PSf UF membrane. The chemical
cleaning using EDTA as chelating agent and SDS as surfactant were effective to recover
the permeation flux up to 90%. It was demonstrated that all parameters, except COD
removal, were superior by UF process than the existing biological treatment in the
refinery. A pilot-scale plant involving aeration tank, air floatation, sand filter and UF
has been reported for the Daqing oilfield waste water treatment.[65] It was claimed
that the hybrid process removed the oil, SS contents in the oily wastewater to less than
0.5 mg/L, 1.0 mg/L, respectively. It was further claimed that Fe, reductive substances,
sulfate reduction bacteria (SRB), metatrophic bacteria (TGB) and iron bacteria (IB)
were also reduced to the level of discharging limit.

The combination of ceramic MF & UF with ion exchange resin for the PW treatment
was reported.[66] Three different MF membranes with pore size of 1.4, 0.8, 0.2 µm
and two UF membranes with pore size of 20 and 5 nm were used for the study. The
Marcellus shale gas PW water, with characteristic TOC of 720 mg/L, TSS of 881 mg/L,
TDS of 48,000 mg/L with conductivity of 67, 000 µs/cm, was passed through
combination of MF-MF or MF-UF membrane process. All the combination of
membranes removed the TSS >99% and MF-MF combination (1.4 µm & 0.02 µm pore
size) showed about 97% turbidity removal. The MF-UF combinations were effective to
remove the turbidity 100%. The TOC removal was in the range of 10-15 % with
negligible decrease in conductivity which suggests that nearly all the TDS remain in
the membrane treated PW. As a final stage cleaning, the ion exchange resins, DOWEX
G-26 with a mean diameter of 0.6 mm and Marathon A resin with a mean diameter of
0.5mm were used. After the ion exchange treatment, the quality of the water met the
criteria (Pennsylvania
– USA) for the surface water discharge. The cost estimation for the PW treatment
using the membranes and ion exchange resin will be about 18.4 US$/m 3. It was
highlighted that the ion exchange resin treatment alone has the share of nearly ¾ of
the treatment cost. Therefore it can be assumed that the reduction of cost should
come from ion exchange resins or using alternative final stage cleaning.

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The effect of pre-treatment on the performance of the ceramic UF membrane for the
treatment of oil sands tailings pond recycle water was reported in a pilot scale study.
[67] Two different methods of pre-treatment employed and the first pretreatment
step was the use of coagulant. It was reported that the coagulant removed the solids
completely. The second method was use of coagulant with softening agent (Multiflo™
system). The use of softening agent helped to reduce the membrane fouling by
removing the hardness causing ions to negligible level. More than 99% of turbidity
and less than 20 % of TOC were removed by the pretreatment. Thus pre-treated water
showed relatively high flux, ca. 120 L/m2.h, with a recovery of more than 90% water in
the ceramic UF. For improving the water quality further, it was suggested that the
ceramic UF treated water can be further subjected to RO process for the beneficial use.
In a direct comparison study, the polymeric and ceramic UF membranes
(polyaryletherketone and zirconia respectively) were used for the oil-in-water
emulsion separation.[68] These two membranes were compared under various
operating parameters and ceramic membranes are sensitive to oil penetration at
lower CFV and high TMP. Compared to the polymeric membrane, optimum
performance of the ceramic membranes were found under low feed flow rate and
TMP. It was reported that more studies needed in order to understand the systems
fully.

The use of rotating ceramic filter disc for the produced water treatment was reported.
[69] The commercially available MF (0.2 µm pore size) and UF (7 nm pore size)
ceramic membrane were used for the PW treatment. Two different PWs, namely tank
dewatering-produced water (TDPW) and oil model solution (OMS) prepared using
crude oil, were used for the study. The TDPW had high pollutant compared to OMS
with characteristic of dispersed oil 200-1,000 mg/L, conductivity 20,000-80,000
µS/cm, TOC 200-2000 mg/L, iron 66 mg/L and zinc 0.55 mg/L. It has been shown that
more than 99% oil and more than 98% of TOC can be removed for both TDPW and
OMS PW by the ceramic UF membrane. The rotational speed of the disc filter affected
the performance of the membrane. At high speed rotation, more permeation flux and
less fouling was observed. It was also reported that the rejection efficiency was
independent of membrane rotational speed.

In summary, the UF process can be effective membrane technology for the PW

treatment especially for the low saline and less toxic PW. If the PW is more benign in
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nature, then the UF treatment alone can be achieve closer to the discharge limit, for
example in offshore oil field. In more practical terms, the UF process can be ultimate
pretreatment for the NF or RO membrane where one can get the purified water with
reasonably acceptable quality for the beneficial use like irrigation or live stocks. The
main focus of UF membrane development will be fouling reduction and this alone will
be the major impediment to adapt the UF process in large scale. Therefore fouling
resistance, smart UF membrane development will be the ongoing and future research
development in membrane technology.

3.2. NF and RO membranes for PW treatment

Both NF and RO membranes are operated at relatively high pressure compared to MF

and UF membranes. In RO membrane, the water permeation flux is directly
proportional to the operating pressure whereas the salt permeation is independent of
pressure. Therefore, membrane is more selective when operated in high pressure.[22]
Both NF and RO membranes are effective in removing inorganic minerals. The major
difference between NF and RO membrane is the selectivity. The RO membrane rejects
all the ionic species including monovalent ions whereas the NF is more selective for
the divalent ions and partially allows the monovalent ions like Na + and Cl-. Most of the
NF and nearly all of the modern RO membranes are made as thin film composite (TFC)
membrane on an asymmetric UF membrane support. Since these membranes are
highly selective at the high pressure operation, these membranes are easily prone to
fouling and therefore require relatively clean feed water in terms of suspended solids,
clay, organic foulants etc. In this section we discuss selective literature report dealt
with the PW treatment using NF and RO membranes.

In one of the earliest study, Xu and Drewes studied RO, ultra-low pressure RO (ULPRO)
and NF membranes for the beneficial use of methane produce water.[70] The samples
were collected from sandstone aquifer and considered as brackish groundwater based
on the components in the PW, namely 5500 of TDS with conductance of 10000 µs/cm
with pH of 8.5. The following commercial membranes were used for the PW
treatment:
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One RO (TFC-HR, Koch Membrane Systems), three ULPRO membranes: XLE
(Dow/Filmtec), TFCULP (Koch) and TMG-10 (Toray America), and three NF
membranes: NF-90 (Dow/Filmtec), TFC-S (Koch), and ESNA (Hydranautics). All the
membranes were characterized for contact angle and mean roughness in order to
study the fouling of membranes by the PW. It was inferred that more hydrophilic and
less rough (smooth) surfaces showed better fouling resistance, and high permeation
flux membranes (for pure water) fouled faster than low permeation flux membranes.
Based on ESEM and ATR-FTIR study, it was hypothesised that the organic fouling
might not be the major mechanism for the flux decline. Various methods, like
hydraulic backwashing by DI water, acidic (HCl or citric acid) & basic (NaOH) wash,
EDTA and SDS cleaning were studied in order to obtain the original permeation flux.
Among all the studied membranes, TMG-10 showed better recovery by either basic or
SDS wash. The remaining membranes showed below 90% flux recovery. In a
continuation study, 2- stage laboratory scale membranes were employed to estimate
the cost-effectiveness and economic viability of the membrane treatment.[71] Based
on the previous optimizations, TFC-HR, TFC-ULP, TMG10 and NF90 selected for the
cost-estimation study. Among chosen membranes, NF90 required the lowest operating
pressure for high permeate flux and the rejection was lower than RO and ULPRO
membranes. Though NF membrane met the primary drinking water standard, it
lacked the secondary drinking water standards with high TDS and chloride. The two
ULPRO membranes showed high flux with comparable rejection of RO membrane. All
the tested membranes showed lower rejection of boron and it was suggested that
further treatment required meeting the drinking water standard. The PW water of this
particular well contained high iodine concentration (~50 mg/L) and it was suggested
that the concentrated brine with excess of 100 mg/L can be used for the iodine
recovery. And the final cost analysis showed about one US$/m 3 for operating energy
cost alone. The ULPRO membranes provided marginally better operation and
maintenance (O&M) cost than RO membrane and ULPRO will be more cost effective if
the cost of future energy is higher than the calculated period.

The effect of pretreatment on NF and RO membrane process for the desalination of oil
sands process-affected water (OSPW) was studied.[72] The commercial Dry flat-sheet
NF (DK and DL) and RO (AK and AG) membranes from GE-Osmonics were used for the

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PW treatment. A bench scale coagulation–flocculation–sedimentation (CFS) process
was performed for three different ways of pre-treated PW samples and these results
were compared; The three different methods of pretreatment procedures are as
follows: 1. Solid materials in PW were settled by gravity without chemical agents, 2.
OSPW was treated with CFS plus the coagulant alum as pretreatment, 3. OSPW was
treated with CFS, alum and coagulant aid – poly(dimethyldiallylammonium chloride).
Without pre-treatment, all four membranes were fouled within 4-5 h operation with
flux reduction of 80% or more. By utilizing gravity settling as pre-treatment, the flux
reduction about 50% observed for the same operating condition. It was shown that by
utilizing CFS with or without coagulant aid, the flux reduction can be reduced below
40
%. All four membranes showed similar behaviour in the flux reduction for all three
combinations of pre-treatments. The CFS pre-treatment with or without coagulant aid
reduced the turbidity to 0.45 NTU from 71.6 NTU thereby reducing the SDI15 to 1.5
from
6.13. However, the pre-treatments alone do not reduce any COD or TDS from the feed
water which suggests that the fouling reduction is due the solid content removal by
the CFS pre-treatment. Among the four studied membranes, the efficient AK-RO
membrane with alum pretreatment, achieved 98.5% desalination of OSPW. The
chemical cleaning, using acid and base, was required to remove the fouling layers on
the membranes. In a continuation work, using similar pre-treatment process, the 1
kDa molecular weight cutoff (MWCO) ceramic ultrafiltration membrane was subjected
for more detailed study of fouling by the PW on the UF membrane.[73] Expectedly, the
direct filtration of PW without pre-treatment caused irreversible membrane fouling.
Though permeation flux increased with increasing TMP, the higher flux decline was
observed for the highest TMP. The lower CFV caused more fouling than higher CFV.

The combination of surface modified UF & RO membranes for the treatment of

flowback water from the Barnett Shale region of Texas was reported.[74] The UF & RO
membrane surfaces were modified by in situ polymerization of dopamine in order to
make the membrane surface more hydrophilic and fouling resistance. Subsequently
the polydopamine modified UF membrane surface was further modified by reacting
with PEG-NH2. The polydopamine-PEG modified UF membranes showed relatively
higher permeate flux, lower transmembrane pressure and improved cleaning
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efficiency compared to the unmodified UF membrane. The polydopamine modified RO
membrane

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showed higher salt rejection than the unmodified RO membrane. Interestingly the
fouling behaviour of the modified RO membrane did not show any difference
compared to the unmodified RO membrane. It was hypothesized that it might be due
to removal of organic foulants in the feed by the modified UF membrane and the
authors did not report any further study to verify this claim.

Ebrahimi et al. reported the use of commercially available ceramic MF, UF and NF
membrane combination for the treatment of model (synthetic) and real PW.[75]
Though the ceramic membranes showed more than 99% oil removal, the TOC removal
was modest. It has been observed that different membranes showed different flux
reduction and the real PW showed more drastic flux reduction compared to synthetic
PW. In a follow up study, the authors used DAF as pretreatment in combination with
the ceramic membranes.[76] The DAF process alone removed the oil up to 90% in 90
min with airflow rate of 0.8 Nl/s. The ceramic membrane treatment process provided
up to 99.5% oil removal and TOC removal was about 50%. It was further reported
that the back flushing was more effective than chemical cleaning using lye solution for
the membrane cleaning.[77] The efficiency of ceramic NF membrane is not
comparable with the polymeric TFC-NF membrane and presumably it might be due to
the high MWCO of the ceramic membrane.

In one of the comparative study, Koyuncu et al. reported the use of combination of
various type membranes for the produced water treatment.[78] The primary
treatment namely Dissolved air floatation (DAF), acid cracking, coagulation with lime
and precipitation were utilized for the preliminary treatment. 5 and 1 µm cartridge
filters were also employed before subjecting the PW for the membrane treatment. All
four types of membranes namely MF (cellulose acetate), UF (ultrafilic – Osmanics), NF
(filmtech – NF200) in combination with RO membrane (ST10 & AG – Osmanics) were
used for the PW treatment. The MF and UF membranes were used as pre-treatment to
polish the PW and NF and/or RO membrane as final treatment. It was observed that
NF membrane did not produce the water quality for the direct beneficial use or
discharge due to high TDS, but the COD removal was within discharge limit. A
relatively stable flux was observed in NF process whereas the RO membranes showed
improved water quality with lesser permeation flux. Based on the study, it has been
proposed that the following configuration for the effective treatment of PW: Primary
sedimentation for
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the oil separation from water followed by DAF for the smaller oil particle removal,
then 1 µm cartridge filter followed by 0.2 µm MF then use of activated carbon and
finally RO membrane. It was reported that after studying various combination of
membrane systems, the PW treatment would cost about 5-6 US$/m 3 depending on the
configuration of the pretreatment and membrane units.

The comparative study of NF and RO membranes for the PW treatment was also
reported.[79, 80] In this study, the treated water quality and toxicity removal
efficiency of NF and RO membranes were assessed. The authors collected the
industrially treated PE before discharge in to the environment for further NF and RO
membrane treatment for the beneficial reuse. The hydrophilic nanofiltration NF1 and
reverse osmosis RO- BW30 from AMFOR INC®, China were used for the study. Based
on contact angle measurements, it was claimed that the studied membranes were the
most hydrophilic among the commercially available membranes. Admittedly, the NF
membrane removed the divalent cations more efficiently than monovalent ions with
efficiency ranging from 33 to 94% whereas the anion removal was in the range of 3 to
77%. The NF membrane showed poor removal of Cl and F anions compared to the RO
membrane. A similar trend was observed for the Na cation removal. The NF
membrane showed reasonably improved removal of Mn, Ba, and surprisingly Fe was
more efficiently removed by NF membrane than RO membrane. Among the 103
parameters studied for the water quality, 74 international standard parameters were
met by NF membrane alone. The notable exceptions, which NF membrane could not
be effective, were molybdenum, ammonia and boron. The RO membrane removed the
boron but failed to remove molybdenum and ammonia effectively. Thus treated water
further subjected for the toxicity study using marine luminescent bacterium
(V.fischeri). The NF treated water showed EC50 of 13.65% which is close to the raw PW
which has the EC50 of 14.27. After studying the TOC, COD and BOD removal by NF and
RO membranes, the authors postulated that it could be from the additive chemicals
and chemical product from the oil industry which might have contributed to the
toxicity of the treated PW by NF membranes. The RO membrane treated water
showed no toxicity towards V.fischeri. It was suggested that the NF membrane could be
used as pretreatment to the RO membrane in order to reduce the fouling.

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Mondal et al. reported the use of nanofiltration and reverse osmosis for the treatment
of co-PW.[81, 82] In this report, three commercially available FilmTec membranes
namely NF270, NF90 (nanofiltration) and BW30 (low pressure reverse osmosis) were
studied for three different PWs with varying concentration of contaminants. The high
flux NF270 nanofiltration membrane was most hydrophilic and displayed least
reduction in permeation flux. However it showed less effective in TDS removal
whereas the BW30, low pressure reverse osmosis membrane, provided better removal
of TDS. Based on the treated water quality, it was proposed that the membrane
treated water can be beneficially used in lives stock and crop watering. The fouling
behaviour of the three membranes based on its surface roughness and hydrophilicity
was compared. It was inferred that the smooth and more hydrophilic membranes are
less susceptible for the fouling.

The importance of the pre-treatment for the effective PW treatment can be

understood from the report of Zhao et al. [83] The authors studied the real PW for the
removal of hardness, COD and turbidity by electrocoagulation as pretreatment. The
pre-treated produced water was directly subjected to RO process. The pH, current
density and time were varied and optimized for the effective pretreatment. At
optimum condition of pH 7.36, 85.81% hardness, 66.64% of COD and 93.80% of
turbidity was removed. Thus the pre-treated water showed steady permeation flux of
87.83%, ca: 22 L/m2.h, whereas the raw produced water without pre-treatment
showed the flux decline of more than 80 % in less than 100 hours of RO membrane
operation. From the flux decline by fouling, it is imperative to carry out the effective
pretreatment in order to achieve effective membrane treatment.

In a pilot scale study, the use of RO membrane in combination with three different
types pretreatment was reported for the treatment of PW from Coal-bed
methane(CBM).[84] A stages of pretreatment namely Manganese sand filter, sand
filter and UF membrane were used before subjecting the PW to the RO membrane
treatment. The Manganese sand filter alone removed the Fe and Mn ~100%, which
was originally present at 0.22 and 0.04 ppm in the PW. The Manganese sand filter
reduced the turbidity up to 97%. Further use of sand filter, UF and finally RO filtration
combination showed complete removal of turbidity and F-. Further 98% of TDS,
81.6% of COD, 85.4% of NH 3-N and 96.99% of Cl- removal was reported for the
combined treatment. The authors used
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theoretical model to predict the performance membrane and the prediction agreed
well with the experimental result. Interestingly, it was claimed that the treated water
is well within the Chinese drinking water standard.

Salahi et al. reported the purification of biologically treated Tehran refinery waste
water using the RO membrane process.[85] The collected the refinery waste water
was subjected directly to the RO membrane as final treatment. The effect of
transmembrane pressure (TMP 8, 15 and 20 bar), cross flow velocity (CFV 0.5, 1 and
1.5 m/s), pH (4, 7,
10) and feed temperature (27.5, 37.5 and 50 °C) were studied at three different levels.
Except pH, all three parameters showed positive effect on the permeation flux with
small decrease in the rejection. The effect of pH on the permeate flux was reported as
complex. The characteristics of Tehran refinery waste water is given in Table 1. The
biologically pre-treated refinery waste water had the following characteristic (in
mg/L): TSS – 4, TDS – 1953, O&G – 7.2, COD – 160, BOD 5- 86, TOC – 48 and turbidity
1.1 NTU. The RO membrane process had the permeation flux of 50 LMH with

permeate water quality as follows: TSS – 0, TDS – 253, O&G – 1, COD – 8, BOD 5- 4, TOC
– 4.9 and turbidity 0.2 NTU. From the permeate water quality, it is clear that the
treated water quality is reasonable good. However as suggested in the report, the long
term membrane fouling behaviour needs to be studied further to evaluate the
practical feasibility of direct use of RO membrane from the biologically treated
refinery waste water. In an earlier study, the research group used the UF as pre-
treatment for the same refinery waste water.[86] In this case also the effect of
transmembrane pressure (TMP – 1.5, 3, 4.5 bar), cross flow velocity (CFV – 0.25, 0.75,
1.25 m/s), pH (4, 7, 10) and feed temperature (25, 37.5, 50 °C) were studied at three
different levels for the optimization of UF process. Using the optimum TMP (3 bar),
CFV (1 m/s), pH (9) at the temperature of 40 °C, the permeate from the UF membrane
was used as feed to the RO membrane. The RO permeate showed 100%, 98%, 98%,
95%, and 100% reduction for O&G, TOC, TDS and turbidity respectively. It was
reported that the permeate water quality from UF and RO membrane treatment was
better than the cooling water tower used in the Tehran refinery.

In a large scale demonstration of use of membrane technology, the use of biological

treatment in combination with UF and RO membrane process was reported for the
Sinopec Yanshan refinery plant waste water.[87] The treatment plant was run more
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than four years with the water treatment capacity above 100 m 3/h. The biological
treatment comprised of biological aerated filter (BAF), coagulation settlement, fibrous
filtration followed by activated carbon filter. After the biological treatment, the
refinery water was subjected to UF membrane which showed 34% TOC removal and
the COD removal was in the range of 0-60% depending on the molecular weights of
the organics. High molecular weight organics were effectively removed by coagulation
and multimedia filter, but low molecular weight organics easily passed through UF
membrane. The first module of three RO membrane train showed pressure drop more
than the second or third module due to the organic fouling. After more than 30
chemical cleanings, each per month, the RO membrane showed the rejection of more
than 97% with water recovery of 80%. It was reported that the membrane treated
refinery waste water met the entire parameters for the reuse in the plant. This is one
of the few report deals with reasonably large quantity of real waste water with long
period of plant operation. Most importantly, the treated water was very much within
reuse quality.

In summary, the use of NF can be very selective for the oil & gas industries. Many oil
fields use fresh water for the pressure maintenance and to pump out the crude. For
this purpose, the water quality may not necessarily high. The fresh water should be
free of corrosion, pore blocking and scale forming ions. To meet these criteria, the use
of sea water with free of above mentioned ions is the most cost effective way,
especially in off- shore oil field. The NF membrane can effectively remove all the
multivalent ions which cause the problems. Therefore the use of NF membrane for the
sea water softening for polymer flooding for oil recovery was reported.[88] The UF
membrane was used as pretreatment and four commercial NF membranes, namely
NF90-2540, NF200-2540, NF270-2540 and DL-2540, were used for the softening of
sea water. All the four NF membranes showed more than 95% removal of SO 42-.
However the divalent cations, Ca2+ and Mg2+, removal varied for each NF membrane.
The NF90-2450 showed the effective divalent ions, both cation and anion, removal of
more than 99%. Using the NF90-2540 treated sea water, the authors studied the
polymer viscosity and stability which was found to be stable for long time at oil-well
formation temperature. It was further reported that the core sensitivity and
compatibility test were used to prove the NF permeate water quality for the flooding

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of oil well. From the result, it is possible to use the NF membrane for the treatment of
sea water for the use in oil & gas industry.

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The same methodology can be easily adapted with appropriate modification for the
PW treatment and thus treated water can be beneficially reused by the oil & gas
industry. It is important to note that the operating pressure of NF membrane is
significantly less, therefore less operation cost, compared to the RO membrane.

3.3. Thermal desalination and Forward Osmosis (FO) for the PW treatment

One of the earliest desalination technology adopted in large scale is thermal

desalination. Two well-known desalination methods which are still in use (mostly in
the Middle East regions) are multistage flash distillation (MSF) and multiple effect
distillation (MED). Though these two distillation methods are energy intensive, it
scores two important points over membrane technology namely capability of very
large scale installation and long period of plant operation, in some cases over 20
years. However these thermal technologies are in the retreat due to high cost and
advent of more energy efficient membrane technologies. Recently a pilot scale study
for the coal seam gas (CSG) produced water treatment by combining ultrafiltration,
reverse osmosis and multi-effect distillation was reported.[89] The CSG PW water was
considered as brackish with moderate TDS. The UF membrane was operated as dead-
end mode with repeated 40 seconds of air scouring and 30 seconds of back-flushing
for each 17 min production cycle. About 76% of water recovered in the UF and
permeate was sent as feed for the RO filtration. The RO system was operated to
recover about 76% of feed water and the RO concentrate was send to MED for the
further water recovery. The MED process recovered about 80% of the feed from RO
retentate. Overall an impressive 95.2% of purified water recovered from the initial
PW. Since the RO and MED permeate waters are highly pure, it was suggested to use as
diluent for the UF permeate to the beneficial use in order to reduce energy
consumption.

The membrane distillation (MD) is another important thermal desalination technique

which acquired more attention by the research community in recent times [90-99].
The energy requirement, i.e. the heating requirement, is considerably less for the MD
and therefore it can be economically competitive in some special cases. The
membrane technologies discussed so far for the PW treatment use the pressure
difference as incentive to separate the constituents by using selective barrier layers.
On the other
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hand, the MD operates based on the thermal difference between the feed and
permeate which is separated by hydrophobic membrane layer. The MD can be a crucial
separation component for the PW treatment because of high water recovery. All the
pressure driven membranes separate the pollutants and at the end of the process it
has highly “concentrated brine” as retentate. It is assumed volume of waste water is
reduced to “manageable volume”. The majority of the literature reports deals with
water recovery from PW and no meaningful suggestions were made about the
“concentrated brine” retentate. Therefore in reality, what all the pressure driven
membrane separation does is the recovery of water as permeate and very highly
concentrated PW as retentate. The disposal or meaningful use of this concentrated
retentate of PW from pressure driven membranes will be the final frontier in the
treatment of PW. By its intrinsic nature, these saturated or “concentrated brine” is
beyond the practical operating pressure of NF or RO membranes due to very high
osmatic pressure. Since MD operation is not based on pressure driven but only
temperature difference between feed and permeate side is the driving force, the final
treatment of the “concentrated brine” can be effectively done using MD process. It has
been reported that the effect of salt concentration in the feed water is negligible on the
MD process compared to pressure driven process like RO or NF. Only 5 % flux decline
was observed in the MD when the TDS of the feed water was increased from 35, 000 to
75, 000 mg/L.[100] Therefore MD can be used as last stage recovery process and it
has been reported that near complete removal of salt is possible in the MD process
[93, 96]. However the presence of organic compounds in the feed water is problematic
for the successful MD process. The organic compounds, both polar and non-polar in
nature, firstly affect the wetting properties of the membrane. The non-wetting
phenomenon (contact angle) is one of the crucial requirements for the effective MD
process and the presence of organic compounds increases the wetting of the feed
water. Additionally, if the organic compounds are highly volatile, then these low
boiling compounds easily passes though the membrane during the distillation process.
Obviously, the gasses also easily pass through the MD. Therefore it is imperative that
the feed water for the MD process should contain as much as less organic compounds,
particularly the low boiling constituents, for the successful MD process. Otherwise
permeate might contain the organic and dissolved gases which might require further
post treatment before the beneficial use.

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There are four different modes of operation in the MD process which are: 1. Direct
contact MD (DCMD), 2. Air gap MD (AGMD), 3. Sweep gas MD (SGMD) and 4. Vacuum
MD (VMD). The operating principles of these methods are pictorially explained in the
figure 4. As the name implies, in the DCMD the feed and permeate is in direct contact
with the membrane (Fig. 4a). In VMD, instead of circulating cool water in the
permeate side, a vacuum has been applied and the resulting vapours are condensed
(Fig. 4b). In AGMD, air gap is created between membrane and condensing surface (Fig.
4c). In SGMD, cold air is circulated on the permeate side in order to collect the vapours
(Fig. 4d). In all these four variants, only the permeate collection side was varied
according to the condensation methods. The feed side remains similar for all four
processes which is hot circulating water. The permeate side should be at least 20 °C
cooler than feed side for the practically effective distillation and it can be liquid, air or
vacuum to collect the water vapours from the feed side.

The use of DCMD for treatment of real oilfield produced water was reported by
Macedonio et al. [101] The PW water was pre-treated using microfiltration and
activated carbon in order to remove the oil, suspended solids and H 2S. The pre-treated
PW was subjected for the DCMD using four different membranes namely two lab made
PVDF membranes and two commercially available PP membranes. The permeate flux
of 4-9 L/m2.h was obtained with feed temperature of 50 °C with permeate circulation
at 25
°C. After optimizing the operating conditions, the TDS removal of > 99.5% and >90%
of total carbon removal was obtained. The cost of the DCMD distillation process alone
has been calculated as 0.72 US$/m3 for the PW feed temperature of 50 °C and 1.28
US$/m3 if the PW feed starting temperature is 20 °C. Singh and Sirkar used DCMD for
the treatment of simulated produced water of steam assisted gravity drainage (SAGD).
[102] In this study, for the first time, the authors subjected the feed hot water up to
130 °C temperature for the circulation. The performance of commercial PTFE
membrane (W.
L. Gore and Associates), was studied in the presence of 45 ppm phenol, 45 ppm cresol,
10 ppm naphthenic acid 3000 ppm NaCl. Even at high temperature of 130 °C, there
was no leakage in the membrane and the highest permeation flux of 195 kg/m2 h was
observed. About ∼5 ppm of phenol and cresol and around 2 ppm of naphthenic acid

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passed through the PTFE membrane and it was attributed due to the fact that the
boiling of these compounds are in the range of 165–212 °C.

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Hilal et al. reported the study of three commercially available membranes for the
treatment of ARAMCO gulf PW by AGMD.[103] It was reported that as the pore size of
the membrane increased, the water flux also increased. As with typical MD process,
the permeate flux increased directly proportional to the feed temperature and
inversely proportional to the coolant temperature. It has been observed that
exponential increase in the permeate flux by rising the feed temperature. It also has
been reported that three membranes with different pore size showed no effect on the
energy consumption. However, the water flux is low and it has be increased at least an
order of magnitude for economically viable. One of the main advantages of MD process
is the capability to treat the high saline PW or concentrated PW. Utilizing this benefit,
Duong et al. reported a pilot study to treat the RO brine from coal seam gas PW by
spiral- wound air gap membrane distillation.[104] First UF&RO membranes were
used to recover 75 % fresh water from the raw CSG produced water. The concentrated
brine was subjected to AGMD. High packing density of spiral-wound module was used
to overcome the low permeate nature of membrane. By adding anti-scalant, a stable
80% recovery was achieved in AGMD. So far, the reported commercial membranes
showed very low permeate flux, around 20 LMH or less. At this rate of water flux, it
might be tall order to compete with the other purification methods. However the lab
made membranes for distillation showed much promising results and it needs to be
upscale to evaluate the comparative advantages of MD process.

Forward osmosis (FO) is another membrane technology which is getting more

attention recently for the treatment of PW.[105] In the RO process, pressure has to be
applied to overcome the osmotic pressure of the feed to force the water molecule to
pass through the membrane. In the FO, the permeate side contains very high osmotic
solution as draw solution and the separation occurs spontaneously due to osmotic
pressure difference between feed and draw solution. In FO, the draw solution should
have more osmatic pressure than the feed and the feed side osmotic pressure (from
the PW) should be less compared to the draw solution for the efficient separation. The
more osmotic pressure difference between feed and draw solution the more efficient
separation occurs. It should be noted that in some cases the PW itself contains high to
very high TDS and therefore the draw solution should have even more salt content
than the feed from PW. Various draw solutions starting from conventional salts like
NaCl &

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MgSO4 to novel chemical compounds including thermolytic salts and switchable
polarity solvents, were studied for the FO.[13, 105] The FO operates at low pressure,
normally at ambient condition, therefore the irreversible fouling should be less
compared to the RO process. Since the fouling formation likely to be less compact, it
was suggested that the removal of fouling layers in the FO processes should be easier
than high pressure membranes like RO.[13] During the FO process, the draw solution
becomes diluted as the osmosis occurs and it should be regenerated, i.e. should be
concentrated, in order to have practical viability. Since the draw solution contains very
high TDS and in many cases beyond the operating pressure of RO membrane, the MD
might be the viable option for the draw solution regeneration. It has been proposed
that the combination of FO and MD might be one of the potential options for the PW
treatment in the future.[13]

Indeed the combination of FO and MD has been reported by Zhang et al. for the water
recovery from synthetic PW.[106] The lab made CTA hollow fiber TFC membrane for
the FO and PVDF for the MD were used for the separation study. 2 M NaCl was used as
draw-solution in the FO process and synthetic oily water (4000 ppm) with 1000 ppm
acetic acid as feed. The FO membrane showed the fouling initially and after 24 h the
flux has been stabilized. The FO showed >99.9% oil and ~80% acetic acid rejection.
The MD showed 99.99% salt rejection and 47% acetic acid at operating temperature
of 60 °C.

These are the some promising results utilizing the combined advantage of FO and MD.
Since PW is considered as one of the “difficult to treat” waste water, the novel
combination of FO and MD will be further studied in future for the practical
application of PW treatment. In the FO process, high flux fouling resistance membrane
is the need of hour. In the MD process, the existing commercial membranes are having
uncompetitive low water permeation flux and here also the permeation flux has to be
increased at least an order of magnitude in order to be economically viable process.

In summary, for the successful treatment of PW using membrane technology, apart

from the effectiveness of each membrane process, the capital and operating cost might
be a deciding factor. For example, a typical operating cost of seawater RO membrane
replacement is less than 25 % whereas it can be 30-50% for the UF membrane due to
high fouling in the UF process.[22] The microfiltration process is well developed and
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mature technology with competitive price. Majority of the fluorine based MF
membranes like PVDF, PTFE were tested for MD process also, but the permeation flux
is very low. Therefore novel hydrophobic membranes need to be developed for the
cost effective MD process. For the FO, the existing thin film composite (TFC)
membranes are used and new membrane development might speedup for the
successful upscaling for the PW treatment. Apart from the production cost of
membranes, the operational condition and module design also play significant role in
the final cost. For example high pressure modules are more expensive than low
pressure module and hollow fiber modules are much cheaper than spiral-wound
module. The following cost estimation were reported for hollow fiber, capillary fiber,
spiral-wound, plate-and-frame and Tubular modules (in US$/m2): 5-20, 10-50, 5-100,
50-200 and 50-200.[22] The real cost of the membrane might be decided by the
demand-supply scenario too. At some point, the spiral-wound RO membranes were
cheaper than the UF module due to large volume production of RO membrane
compared to the few UF membrane manufacturer.[22] Therefore the true cost of
membrane is vibrant depending on market condition, nature of module and operating
conditions etc. The most important parameter that decides the effectiveness and
longevity of the membrane process is the feed quality of PW. Therefore, to select the
membrane process, it is imperative to keep all these conditions in mind to select the
membrane and the operating condition.

4. Summary and outlook

The complexity of the produced and process water from oil & gas industry makes it
one of the toughest waste water to manage within acceptable level of contamination at
affordable cost. The membrane technology is clearly one of the main contenders to
solve the intrinsic problem of produced waste water treatment. Because of high
complexity of PW, the future research development will have to be concurrently
developed with the advanced pretreatment methods and the success of the membrane
process will entirely depend on the initial quality of the PW feed after pretreatment.
The overall PW treatment processes and its final destination of the treated PW is given
in figure 5. It is clear from the reported literature that the potable water quality can be

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achieved only by employing RO membranes. If the water is used for drinking purpose,
then special post treatment might be needed to obtain the acceptable level of water

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quality. For example, presence of high level NORMs or boron will make it
unacceptable for the drinking purpose. Depending on the pre-treated PW quality, NF
membranes can be useful to achieve water quality for reuse in the oil industry itself,
irrigation and livestock. Though the RO membrane provides better water quality than
NF membranes, the NF membrane can be more cost effect for recycle and reuse in the
oil & gas industry. Recently the FO membranes in combination with thermal
distillation, particularly MD, are getting more attention. The combination of FO and
MD technology needs further study for the practical suitability for the PW treatment.
Finally, all the membrane technologies used for the PW treatment result highly
“concentrated brines” as final effluent at “manageable volume”. Very little study has
been focused on this concentrated brine and the recent development of MD will be an
ideal candidate for solving this problem. However the issue revolving around MD
process itself should be first resolved i.e. High cost (energy), scale forming, and heat
loss by thermal conduction etc. Finally, the literature reports dealing the real and
synthetic PW should be carefully evaluated. As demonstrated in few examples,[49, 75]
the effectiveness of membrane process for the real and synthetic PW is vast and the
real PW is invariably makes membrane less effective due to fouling. Therefore, the
choice of membrane technology has to be carefully chosen based on the real feed
water quality. Since produced and process water quality change according to the
geology of the oil & gas well and also with the age of well, each industrial need of
membrane has to be optimized for the effective treatment of PW. The real bottleneck
of PW treatment is the lack of large scale plant literature report. There are very few
literature reports that discuss about the large scale treatment plants.[79, 80, 87] The
three large scale examples using RO as final stage treatment are Chennai Petroleum
Company Limited (430,000 L/h), San Ardo water reclamation project in California
(50,000 bbl/d) and oilfield in Wellington, Colorado (93,600 g/d) and even the scarcely
available report does not provide complete details to understand the process and
thereby improving the technology. The operational data from of existing of large scale
plants will help to understand the current state of technology better and thereby
developing more adaptive smart membranes in the future. The results reported by
Zhu et al. [51] and hydrophilized PSf membranes [60] showed that it is possible to
reduce the fouling by designing the membrane appropriately. At the end, the cost of
PW treatment will be within

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acceptable level in order to make the oil industry waste water truly usable resource
instead of polluting water.

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[3] Petroleum refining water/wastewater use and management, IPIECA Operation Best Practice
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[4] A. Fakhru'l-Razi, A. Pendashteh, L.C. Abdullah, D.R. Biak, S.S. Madaeni, Z.Z. Abidin, Review of
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Constituents Oil field PW* Gas field PW* Damme 3 well#

TOC 0-1500 67-38,000 NA

COD 1200 2600-120,000 NA

TSS 1-1000 8-5484 NA

pH 4-10 3.1-7 NA

Total oil 2-565 NA NA

Volatiles (BTEX) 0.4-35 NA NA

Chloride 80-200000 1400-190,000 78200

Bicarbonate 77-3990 NA NA

Sulfate 2-1650 <0.1-47 8

Ammonia nitrogen 10-300 NA NA

Sulfite ~10 NA NA

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Phenols Up to 23 NA NA

Volatile fatty acids 2-4900 NA NA

Calcium 13- 25800 Up to 51,300 14100

Sodium 132-97000 520-120,000 30600

Potassium 24-4300 149-3870 110

Magnesium 8-6000 0.9-4300 1800

Iron <0.1-100 Up to 1100 91

Aluminum 310-410 <0.5-83 NA

Boron 5-95 Up to 56 NA

Barium 1.3-650 <1-1740 455

Cadmium <0.005-0.2 <0.02-1.21 NA

Chromium 0.02-1.1 Up to 0.03 0.3

Copper <0.002-105 Up to 5 NA

Lithium 3-50 18.6-235 5

Manganese <0.004-175 Up to 63 2.5

Lead 0.002-8.8 <0.2-10.2 1

Strontium 0.02-1000 Up to 6200 1455

Zinc 0.01-35 <0.02-5 0.4

Arsenic <0.3 Up to 151 NA

Mercury <0.002 NA NA

NA – Not available

Table 1. Commonly existing constituent of pollutants from the produced water

(adapted from [4, 5] (*JHM, 2009, 170, 530, # EES, 2013, 70, 3895).

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Contaminant Desalter* Sour Tank Cooling Sour Al
water* bottom* tower* water Ruwaisa
Brazil ~

COD 400-1000 600- 400- 150 850– 825

1200 1000 1020

Free Up to < 10 Up to <5 NA 750@

hydrocarbons 1000 1000

Suspended Up to 500 < 10 Up to Up to ND NA

solids 500 200

Phenols 10 to 100 Up to NA NA 98–128 25

200

Benzene 5 to 15 0 NA NA NA 85#

Sulphides Up to 100 < 10 Up to NA 15–23 3900^

100

Ammonia Up to 100 < 100 NA NA 5.1–21.1 75&

Dissolved solid NA NA NA Up to NA NA
700

NA – Not available, ND- non-detectable. & As Kjeldahl N, # as PAH, @ as TPH, ^ as sulfate

concentration.

Table 2. Commonly existing pollutant constituents from refinery waste water.

Data adapted from *[3]. ~ [18]. a [19].

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Figure 1. a). General schematic representation of oil & gas well with the formation
(produced) water in the reservoir and b). The refinery process which produces
process waste water (The figure is for representation only and not mentioned in the
true scale bar).

OH

S N
H H H H

phenol
hydrogen sulf ammonia
ide

Benzene Toluene Ethyl benzene Xylenes

BTEX

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Figure 2. The chemical structure of few selective compounds present in the
refinery waste water.

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Figure 3. Fouling resistance hydrophilic PVDF membrane for the oil-water separation.
M1 (blue line) represent the control and red and green lines (M2 & M3) represent the
hydrophilic additive PVDF membrane. Experimental condition: First 30 min DI water

Manus
filtration (conditioning) followed by 500 ppm crude oil in water. After 2 hour
filtration, the membrane washing 10 min followed by 20 min backwashing with DI
water and then second cycle of oil-water separation (Reproduced from [51])

cr

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Figure 4. Four different modes of membrane distillations: a) DCMD, b) VMD, c) AGMD,
d) SGMD

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Fig. 5. The schematic diagram of overall PW treatment processes and its final
destination of the treated PW.

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S. Membrane Membrane material and properties Water source Parameters studied Refere
No category nce

1 MF ceramic and polyacrylonitrile Synthetic Oil-water separation 41

PW

2 0.1 µm commercial mixed Real Pw COD, TOC, O&G removal 42

cellulose esters

3 mullite and mullite–alumina Synthetic TOC rejection 43

ceramic and real PW

4 hydrophilic and oleophobic Synthetic oil-water separation & fouling 44

PVDF hollow fiber and real PW resistance

5 graphene oxide modified Al2O3 Three oil-water separation 48

different
synthetic
waters

6 zirconium oxide ceramic MF Synthetic cost estimation 49

PW

7 UF hydrophilic cellulose based UF Synthetic TOC removal & Fouling 50 &

membrane PW resistance 51

8 PAN-g-PEO Produced O & G removal & fouling study 8

and refinery
water

9 PEGlated PSf-UF membrane PW and fouling resistance 53

soyabean oil

10 PVP hydrophilized real PW TSS, TOC, COD, O&G removal 54

polyethersulfone UF membrane

11 PVDF/MWCNT nanocomposite Refinery TiO2 Photocatalytic organic 55

UF membrane removal by membrane
Waste water

12 PAN350 UF membrane Real PW effect of membrane operating 56

conditions – T, TMP, CFV

13 commercial UF membranes, refinery membrane operational 57

PAN (MWCO – 20 kDa) and PSf waste water parameter optimization– T,
(MWCO – 30 kDa) TMP, CFV and pH

14 NF & RO Commercial NF & RO oil sands effect of pretreatment on NF 63

membranes (GE-Osmanics) process- and RO membrane process
affected
water

15 Dopamine-PEG hydrophilized flowback Effect of membrane 65

UF & RO water - modification for the fouling
Barnett resistance

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 Barnett resistance
Shale

16 Commercial ceramic MF, UF Synthetic & Effect of pretreatment, 66-68

and NF membrane real PW backwashing, chemical
cleaning & TOC removal

17 Commercial MF, UF, NF & RO Oil & gas Effect of various membrane 69
well PW combinations and cost
estimation

18 Commercial NF & RO Petroleum comparative study of NF and 70-71

refinery PW RO membranes

19 Commercial NF & RO PW comparative study of NF and 72-73

RO membranes & fouling study

20 Commercial RO membrane Real PW electrocoagulation as 74

pretreatment and then direct
RO process
-
21 Commercial UF & RO Coal-bed TDS, COD, NH3 and Cl removal 75
methane PW

22 Commercial RO refinery Effect of TMP, CFV, Temp., pH 76-77

waste water

23 Commercial UF and RO refinery Large scale demonstration (100 78

membrane waste water m3/h) for more than four years
operation

24 MD DCMD Oil field PW microfiltration and activated 92

carbon pretreatment and cost
calculation for the DCMD

25 FO & MD FO & MD synthetic FO showed >99.9% oil rejection 96

PW & MD showed 99.99% salt
rejection

Table 3. Selected summary of membrane treatment of produced and refinery waste water from the literature.

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