Journal of Water Process Engineering 4 (2014) 107–133

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Journal of Water Process Engineering

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

Review

Challenges and trends in membrane technology implementation for

produced water treatment: A review
Salem Alzahrani a,∗ , Abdul Wahab Mohammad b,c
a
Alamoudi Chair for Water Researches, King Saud University, 2460-11451 Riyadh, Saudi Arabia
b
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia
c
Research Centre for Sustainable Process Technology (CESPRO), Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

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

Article history: This review provides insight into the implementation of membrane technology in the petroleum industry
Received 25 May 2014 for treating produced water that is generated from conventional oilfields in upstream and downstream
Received in revised form 8 September 2014 processes. The ever-evolving and increasingly stringent regulatory standards for discharging produced
Accepted 25 September 2014
water pose colossal environmental and economic implications because the bulk of this produced water
Available online 18 October 2014
is disposed into the environment. Thus, a review of the implementation of membrane technology for
produced water treatment could contribute to the knowledge required for the increased introduction of
Keywords:
scaled-up membrane technology in the petroleum industry. This review encompasses the capabilities
Produced water
Membrane application
and performance optimization possibilities of microfiltration, ultrafiltration, nanofiltration, and reverse
Membrane fabrication osmosis membranes. The level of applications that these membrane technologies might attain within
Membrane fouling the petroleum industry were determined, and these implementations were correlated with the purpose,
Wastewater reuse performance efficiency, treatment system configurations, necessary pretreatment procedures, quality of
treated produced water, fouling occurrence and control, foulants, cleaning procedures, raw produced
water content, potential challenges with corresponding applied solutions, and economic factors. This
review also maps current and future trends and provides a perspective on the outlook for advances in
novel membrane applications for produced water treatment.
© 2014 Elsevier Ltd. All rights reserved.

Contents

1. Implementation of membrane technology for the treatment of produced water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

1.1. MF membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
1.2. UF membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
1.3. NF membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
1.4. RO membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2. Reuse of produced water in the petroleum industry using membrane technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
2.1. Drivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
2.2. Content of produced water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.3. Performance efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
2.4. Fouling occurrence and control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2.5. Economic factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
3. Potential applications of membrane technology in the petroleum industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
3.1. Upstream processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
3.2. Downstream processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4. Current trends and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

∗ Corresponding author. Tel.: +966 114673737; fax: +966 114673739.

E-mail addresses: sazahrani@ksu.edu.sa, salem4alzahrani@gmail.com (S. Alzahrani).

http://dx.doi.org/10.1016/j.jwpe.2014.09.007
2214-7144/© 2014 Elsevier Ltd. All rights reserved.
108 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
1. Implementation of membrane technology for the
treatment of produced water
The use of membrane technology in the petroleum industry
began in the early 20th century [1]. Preliminary experiments using
membrane technology involved separating certain gases and were
initially conducted in 1950 [2]. The pioneer and notable mem-
brane unit was installed in 1977 for adjusting the H2 /CO ratio.
Another application that was employed to recover hydrogen from
purge gases in petrochemical plants ensued in 1978 [3]. The suc-
cess of these membrane applications led to the development and
application of 219 membrane units in refineries around the world
until approximately 1993, after which additional applications have
been developed and employed [3]. Currently, the most important
membrane applications in the petroleum industry are employed
in nitrogen production, hydrogen recovery, natural gas sweeten-
ing, nitrogen removal, enhanced oil recovery via CO2 , monomer
recovery in polyolefin production, pervaporation processes, and
organic solvent nanofiltration (NF) [4]. Such advancements in gas
separation technologies have led to the adoption of membrane
technologies in liquid-liquid and solid-liquid stream separation
processes in the petroleum industry [5]. The first such technol-
ogy was employed in 1998 at a refinery in Beaumont, Texas, in
which the Mobil Oil Corporation installed a reverse osmosis (RO)
membrane (e.g., hyperfiltration, originally patented in 1993) [6] to
separate small molecules of methyl ethyl ketone solvent from lube
oil [5]. This application was also the first recorded industrial use of
pressure-driven membranes to separate organic solvent mixtures
in the petroleum industry [5]. These RO membranes are solvent
resistant (Starmem® ) [6] and are composed of Matrimid® . This
material is a polyamide membrane that is stable up to 305 ◦ C, and
the membrane structure remains glassy and unswollen [5]. Formed
essentially as spiral-wound modules, these RO membranes have a
flux of 10–20 gal/ft2 /d at pressures ranging from 450 to 650 psi,
and their successful application [7–9] has demonstrated the great
potential for the implementation of membrane technology in the
separation of organic liquids, such as the fractionation of linear from
branched paraffins and the separation of benzene and other aro-
matic compounds from paraffins [5]. Ongoing efforts to optimize
the performance of these membranes has achieved recent inno-
vative developments, including the filtration process developed
by Exxon that uses an ultrafiltration (UF) membrane [10] system
(patented in 2009) to upgrade visbroken residual products by UF
during thermal cracking [11] and the production of an enhanced
residual coker feed using an UF membrane [12]. Two novel appli-
cations [13,14] that exemplify membrane process applications in
the petrochemical industry were patented in 2009 [4].
Recent advancements have demonstrated the potential for
applying available commercial modules of such membranes to
produced water management in the petroleum industry. Success-
ful applications of such membranes in the gas separation and
desalination industries have demonstrated the reliability of these
technologies. To exploit their reliability, the most recent applica-
tion of membrane technology adopted in the petroleum industry
involved the treatment of produced water through pressure-driven
membrane technology [4]. Tremendous advancement and expan-
sion in oil production and refining have resulted in the consumption
of vast quantities of process water and the consequent genera-
tion of vast amounts of wastewater, termed produced water [15].
Existing management options for produced water are currently
restricted to re-injection, reuse or recycling, and discharge [16],
which are all heavily governed by regulations due to the com-
plexity of produced water contaminants [17]. Currently, traditional
methods of produced water management do not adequately sat-
isfy the petroleum industry requirements for treating produced
water in compliance with discharge and reuse standards [18,19].
Thus, there is a substantial need for innovative membrane pro-
cess technologies. To this end, this review highlights the on-going
implementations of pressure-driven membranes in the petroleum
industry for treating produced water generated from conventional
oil sources, as 85% oil is extracted from such sources [20]. The exist-
ing literature regarding these processes and recent advancements
in membrane technology applications in the petroleum industry
for produced water treatment is insufficient [19,21–26]. Hence,
to bridge this research gap, this review has screened the avail-
able literature to focus on different types of microfiltration (MF),
UF, NF, and RO membrane processes for treating actual produced
water that originated from conventional oil resources and treated
at the bench and industrial scales. In addition to the drivers of
such membrane processes and their performances, current trends
and future prospects are discussed. Therefore, this review of mem-
brane technology applications for produced water treatment in the
petroleum industry contributes to the expansion of such membrane
applications in treating produced water during different processes
of oil production and refining. This review may assist in advanc-
ing the industrialization of membrane technologies in produced
water treatment and improving the understanding of current prac-
tices in management by shifting the current view from produced
water as merely a source of pollution to its role as a renewable
water resource. Thus, this review aims to assist in intensifying more
effective produced water reuse efforts by employing membrane
technologies.
1.1. MF membranes
Several MF membrane studies were reviewed to establish the
characterization and effectiveness of MF membranes for produced
water treatment. A ceramic MF membrane for treating produced
water was reported in 1997 [27]. Two ␣-alumina ceramic mem-
branes with pore sizes of 0.2 and 0.8 ␮m and one modified ceramic
membrane surface composed of polyacrylonitrile (named 1MF,
2MF, and 3MF in this paper) were used to microfilter produced
water containing high levels of oil (up to 1000 mg/L). Mueller et al.
[27] claimed 99% removal efficiency using MF membranes that
were supplied by Membralox and Zenon Environmental in tubular
modules (Table 1). The membranes were operated at low pres-
sure (0.69 bar), and the following ranges of permeate flux values
were obtained for the MF membranes: MF1, 471–26 kg/m2 h, MF2,
301–25 kg/m2 h, and MF3, 438–6.9 kg/m2 h. This study reported
that solutions of NaOH (0.2 wt%) and nitric acid (1.0 wt%) were
applied for the chemical cleaning of MF1 and MF2 membranes,
whereas a caustic anionic detergent (pH 12.1) and citric acid (pH
1.4) were used to clean the 3MF membrane. Neither one of these
cleaning procedures was effective in cleaning the MF membranes
after utilization with high concentrations of oil, which caused sig-
nificant fouling and resulted in no recovery of flux (Figs. 1–3). The
modeling of the fouling mechanisms in Fig. 4 for the 1MF and
2MF membranes showed that they were internal and external,
respectively, whereas 3MF only exhibited external fouling due to
the high presence of foulants in the form of submicron-sized oil
droplets. Furthermore, varying the operational conditions did not
significantly affect the fouling mechanisms, thus indicating com-
plete blockage of the MF membrane pores; the analyses of the
fouling layer thickness demonstrated that layer thicknesses of 60
and 30 ␮m covered a 0.2 ␮m ceramic MF membrane and a 0.1 ␮m
PAN-MF membrane, respectively (Fig. 4). Such fouling layer thick-
nesses require a pre-treatment step before processing ceramic MF
membranes for produced water treatment [27].
Six years after this study, Zhong et al. [28] developed a
new generation of ceramic MF membrane composed of zirconia
(ZrO2 ). Produced water containing maximum oil concentrations of
200 mg/L was first mixed with flocculation as a pretreatment and
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 109

Table 1
MF membrane efficiency in treating produced water.

Experiment number Initial flux (kg/m2 h) Final flux (kg/m2 h) Flux change (%) Coil, feed (ppm) Coil, permeate (ppm) Oil removal (%)

0.8 ␮m ceramic (MF1)

1 678 ± 51 33 ± 6 −95.1 250 0.3 ± 0.2 99.9
2 998 ± 500 40 ± 22 (o) −95.6 250 0.6 ± 0.3 (o) 99.7
3 800 ± 128 46 ± 6 (+) −94.2 250 1.8 ± 0.5 (+) 99.3
4 471 ± 15 26 ± 11 (o) −94.5 1000 1.4 ± 0.2 (+) 99.4
0.2 ␮m ceramic (MF2)
5 525 ± 50 42 ± 19 −91.9 250 3.7 ± 1.9 98.5
6 657 ± 156 21 ± 2 (o) −96.8 250 5.1 ± 0.8 (o) 98.0
7 211 ± 19 32 ± 13 (o) −84.8 250 4.6 ± 0.2 (o) 98.2
8 301 ± 52 25 ± 6 (o) −91.7 1000 5.8 ± 1.0 (+) 99.4
9 305 312 +1.6 250 5 98.0
10 281 577 +105.4 250 5.4 98.5
0.1 ␮m PAN (MF3)
11 204 ± 27 34 ± 3 (o) −83.3 250 1.8 ± 0.6 99.3
12 287 ± 30 32 ± 3 (o) −88.9 250 0.5 ± 0.2 (–) 99.8
13 163 ± 5 31 ± 3 (o) −81.0 250 2.8 ± 1.4 (o) 98.9
14 438 ± 30 6.9 −98.4 1000 0.9 ± 0.3 (o) 99.9
15 455 ± 30 226 −50.3 250 0.9 99.7

The results are expressed as the average of three repetitions, plus and minus one standard deviation, with +, –, and o representing the respective positive, negative, and
insignificant differences from the baseline results at a 90% confidence level [27].

Fig. 1. Flux decline curves for a 0.8 ␮m ␣-alumina ceramic MF membrane during
the treatment of produced water containing 250–1000 mg/L of oil and operating at
0.69 bar, 40 ◦ C, and a mean cross-flow velocity of 0.24 m/s [27].
Fig. 3. Flux decline curves for a 0.1 ␮m PAN MF membrane during the treatment
of produced water containing 250–1000 mg/L of oil and operating at 0.69 bar, 40 ◦ C,
and a mean cross-flow velocity of 0.24 m/s [27].

Fig. 2. Flux decline curves for a 0.2 ␮m ␣-alumina ceramic MF membrane during Fig. 4. Total fouling resistance versus time curves for three different MF membranes
the treatment of produced water containing 250–1000 mg/L of oil and operating at used for produced water treatment at baseline conditions (operation conditions are
0.69 bar, 40 ◦ C, and a mean cross-flow velocity of 0.24 m/s [27]. analogous to those presented in Figs. 1–3) [27].
110 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Fig. 5. Effect of (a) flocculation pre-treatment, (b) transmembrane pressure, and (c) cross-flow velocity on MF membrane performance during the treatment of produced
water containing 200 mg/L of oil [28].

then passed through an MF membrane at an applied pressure of water treatment; when flocculation is used as a pre-treatment step
1.1 bar. The post-filtration permeate showed that the concentra- for a MF membrane, less fouling occurs and the removal efficiency
tion of oil had been reduced to 8.7 mg/L from 200 mg/L, and the is increased to 95.6%. In addition, the applied MF membrane suc-
treated produced water satisfied the Chinese national discharge cessfully met the Chinese standards for produced water discharge
standards [28]. Increased applied pressure and decreased cross- [28]. Similarly, integration of UF with MF membranes resulted in
flow velocity in the pre-treatment step have been optimized for the removal of suspended foulants and increased the flux recovery
the performance of ZrO2 MF membranes (Table 2, Fig. 5(a–c)). To to 61%, thereby demonstrating the potential of replacing conven-
supplement the previous investigation, in 2010, Ebrahimi et al. tional treatment technologies with MF membrane processes [29].
tested two Al2 O3 –ceramic MF membranes (0.1 and 0.2 ␮m) as a Simultaneously, with this system, 99% of the oil was removed from
post-treatment step in the MF of produced water [29], and an produced water containing 1000 mg/L of oil without an appropri-
UF membrane was utilized as a pre-treatment for the MF mem- ate pre-treatment step, resulting in complete blockage and no flux
brane. In this study, a feed of 0.1 ␮m MF membrane that contained recovery despite the application of several cleaning procedures.
148.6 mg/L of oil and 23 mg/L of TOC was filtered to reduce the oil This study also found that varying the operational conditions had
and TOC contaminant concentrations by 61.4% and 38.6%, respec- no effect on the control of the fouling mechanism [27].
tively. The flux of this MF membrane at an applied pressure range
of 0.5–2 bar was 715 L/m2 h bar at 5 mg/L of oil, and its recovery
increased to 61%. In contrast, a 0.2 ␮m MF membrane displayed
Table 3
low performance, as shown in Table 3. However, continuous and
Performance efficiency of Al2 O3 –ceramic MF membranes in produced water treat-
back flush cleaning has proven effective in restoring the flux of ment with an applied pressure of 1 bar and temperature of 60 ◦ C [29].
Al2 O3 –ceramic MF membranes (Fig. 6).
Parameter Al2 O3 –ceramic MF membranes
According to previous MF membrane studies that have captured
the attention of several researchers [27–29], inorganic membranes, Membrane cut-off (␮m) 0.2 0.1
Coil feed (%) 5 5
such as ceramic membranes, have been more effective against
Initial flux (L/h m2 bar) 2657 715
fouling if a pre-treatment step is applied. Table 4 presents a com- Final flux (L/h m2 bar) 771 319
parative assessment of different MF membranes used for produced Flux after chemical cleaning (L/h m2 bar) 878 446
Cleaning efficiency (%) 33 61

Table 2
Effects of various operation conditions on ZrO2 MF membrane performance during
produced water treatment.
a
Effect of flocculation pretreatment Removal efficiency

Parameter ZrO2 MF Flocculation + ZrO2 MF

2
Flux (L/m h) 120 173.5
COD (mg/L) 154 108
Oil (200 mg/L) 34.68 8.7

Effect of transmembrane pressure Removal efficiency

Pressure (MPa) COD (mg/L) Oil content (mg/L)

0.045 101 8.201

0.110 108 8.762
0.155 112 11.71

a
Cross-flow velocity (m/s) Removal efficiency

COD (mg/L) Oil content (mg/L)

0.58 123 10.82

1.75 113 9.533
2.56 108 8.762
a
Permeates collected after MF of produced water for 30 min with the following Fig. 6. Permeate flux rates as a function of operation time for continuous and
parameters: transmembrane pressure, 0.110 MPa; cross-flow velocity, 2.56 m/s−1 back flushed operations using an Al2 O3 –ceramic MF membrane (0.2 ␮m) during
and operation temperature, 25 ◦ C [28]. produced water treatment [29].
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 111

Table 4
Comparative assessment of five MF membranes used to treat produced water.

Reference

[28] [29] [27] [27] [27]

Membrane materials Zirconia (ZrO2 ) Al2 O3 –ceramic ␣-Alumina ceramic ␣-Alumina ceramic Surface-modified
polyacrylonitrile
Membrane name ZrO2 Al2 O3 0.2 ␮m 0.8 ␮m PNA
Membrane manufacturer – – Membralox Membralox Zenon
Environmental
Membrane module Tubular Tubular Tubular Tubular Tubular
Produced water content (oil mg/L) 200 148.6 1000 1000 1000
Removal efficiency (oil mg/L) 8.7 mg/L 61.4% 99% 99% 99%
Cleaning procedures – NaOH, Ultrasil NaOH 0.2 wt%, NaOH 0.2 wt%, Caustic anionic
P3–14, P3–10, back nitric acid 1.0 wt% nitric acid 1.0 wt% detergent (pH
flushing 12.1), citric acid
(pH 1.4)
Permeate flux (L/h m2 bar) 173.5 715
kg/m2 h 471–26 301–25 438–6.9
Applied pressure (bar) 1.1 0.5–2 0.69 0.69 0.69
Flux recovery – 61% Trace rate Trace rate Trace rate

1.2. UF membranes UF-PVDF is a cost-effective option for treating produced water,

Different types of UF membranes for produced water treat-
ment have been studied. Li et al. [30] modified polyvinylidene
fluoride (PVDF) made in a tubular module. Their study investi-
gated the capability of two unmodified UF membranes and the
combination of a modified UF membrane with nano-sized alumina
particles. The required standards for produced water re-injection
were satisfied using produced water containing 15.5 mg/L of oil,
15.8 mg/L of TSS, and 214.9 mg/L of TOC. The results revealed
that similar removal efficiencies were obtained for the two UF
membranes (Table 5) and that the modified membrane dis-
played higher performance in removing organic pollutants with
the following performance efficiencies: oil, 98.02%; TSS, 98.7%;
and TOC, 98%. However, the advantage of adding nano-sized alu-
mina particles for the modification of UF membranes resulted
in improved antifouling performance, a high permeate flux at
170 L/m2 h bar, and a complete flux recovery after testing sev-
eral chemical cleaning solutions (Table 5). The study proposed an
optimized chemical cleaning procedure to be applied via back-
wash with OP-10 surfactant (1 wt% at pH 10) to maintain UF
membrane performance when fouling occurs from the foulants
in produced water. Thus, this investigation implies that modified
Table 5
Comparison of the capabilities of modified and unmodified polymeric UF mem-
branes for produced water treatment [30].
Performance efficiency of UF membranes (PVDF) in treating produced water
Content of produced water Unmodified UF
rejection (%)
COD (637 mg/L) 87.82
Oil (15.5 mg/L) 98.7
TOC (214.9 mg/L) 90.49
Turbidity (98 NTU) 98.1
TSS (15.8 mg/L) 98.
Optimization of UF membrane performances via chemical cleaning
especially if applied as a pre-treatment step for treating discharged
produced water for reuse or compliance with disposal regula-
tions.
Another study by Salahi et al. [31] employed a hydrophilic
20 kDa UF membrane-PAN350 composed of polyacrylonitrile
materials to model fouling mechanisms during produced water
treatment. A flat sheet of this membrane was used to treat sampled
produced water from the Tehran Refinery containing 2028 mg/L of
TDS, 78 mg/L of oil, and 60 mg/L of TSS. The produced water filtra-
tion process was conducted at pressures ranging from 1.5 to 3 bar,
which reduced the concentration of oil and TSS by 99%, although
the UF membrane employed exhibited low levels of rejection for
TDS, which was only reduced by 30%. However, the hydrophilic UF
membrane (PAN350) effectively removed organic contaminants. In
terms of fouling studies, the fouling mechanisms and flux decline
were controlled and mitigated at higher levels with a pH of 10 and
temperature of 50 ◦ C and at lower levels with a transmembrane
pressure of 3 bar and a crossflow velocity of 1 m/s. These opti-
mal conditions were selected based on evaluation of nine different
operation conditions following the Taguchi L9 method, as shown in
Table 6 and Fig. 7. The fouling was attributed to cake layer formation
and the intermediate pore blocking mechanism in applied exper-
iments, as revealed by an application of Hermia’s model (Table 6;
Fig. 8).
In addition to previous studies that investigated polymeric UF
membranes, the inorganic UF membranes reported by Ebrahimi
et al. [29] were evaluated based on the performances of ceramic
UF membranes composed of TiO2 /Al2 O3 (0.05 ␮m, 20 kDa) for fil-
Modified UF tering produced water samples containing 32.2 mg/L of oil. The
rejection (%) results indicated an organic content removal rate of 78.2% when
90.14 the applied pressure was set to 2 bar. However, the TiO2 /Al2 O3
98.04 UF membranes were capable of removing salt content only at
98.73
98.6
98.7 Table 6
Application of the Taguchi L9 method for designing fouling study experiments during
produced water treatment using UF membranes [31].

Cleaning solution Permeate flux recovery (%) Experiment number T (◦ C) TMP (bar) CFV (m/s) pH

1 25 1.5 0.25 4
Unmodified UF Modified UF
2 25 3 0.75 7
Pure water 88.5 91.5 3 25 4.5 1.25 10
1% OP-10 surfactant 95 96.29 4 37.5 1.5 0.75 10
1% OP-10 surfactant, pH 10 97.67 100 5 37.5 3 1.25 4
2% sodium dodecylbenzenesulfate 93.67 96.9 6 37.5 4.5 0.25 7
2% sodium hydroxide 89.67 95.68 7 50 1.5 1.25 7
Citric acid, pH 3 81.67 73.73 8 50 3 0.25 10
0.1 mol hydrochloric acid 84.33 77.39 9 50 4.5 0.75 4
112 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

to reuse the treated produced water as process water in the refin-

Fig. 7. Correlation of the operational conditions (listed in Table 6) and filtration
times in controlling the flux decline in UF processes of produced water [31].
lower pressures (0.5 bar, Fig. 9(a)). Moreover, the productivity of
UF membranes was optimized by increasing the applied pressure
to 2 bar, rather than 0.5–1.5 bar at ambient pressure (Fig. 9(b)).
Furthermore, Teodosiu et al. [32] tested the performance of UF
membranes for post-treatment in a combined membrane system
and proposed an NaOH solution, back flushing, and certain chem-
ical additives (Ultrasil P3-14 and P3-10) for cleaning to optimize
the performance of two UF membranes composed of polyethersul-
fone (PES) and polyvinylpyrrolidone (PVP). These membranes were
used to treat produced water sampled from an oil refinery as a pre-
treatment step after secondary treatment for the RO feed in order
ery [32]. The results of this study revealed that 30.2 mg/L of TSS and
12.5–14.2 mg/L of turbidity were both removed to reduce to 98%,
whereas a lower performance was observed for the removal of COD
(70–90 to 55–125 mg/L) and TOC (8.8–10.3 to 6.97–10.3 mg/L). This
study suggests that the tested UF membranes are capable of being
employed as a pre-treatment step for RO membranes to remove
suspended foulants. In investigating the performance of PES-UF
membranes in detail, several applied pressure levels were tested,
and 1.5 bar was optimal for mitigating the effects of flux decline, as
shown in Fig. 10.
A comparative assessment of overall PES and PVP-UF membrane
performance in treating produced water is presented in Table 7. In
terms of chemical cleaning, citric acid and sodium hydroxide were
found to be the most effective cleaning agents, and the backwash-
ing of PVP-UF membranes was more efficient at recovering flux,
with a flux recovery rate of 87.6% compared to the 51.3% recov-
ery rate for PES-UF membranes (Figs. 11 and 12) [32]. In terms
of improving UF membrane performance by chemical modifica-
tion, Asatekin et al. [33] modified UF membranes by incorporating
an amphiphilic comb copolymer additive, polyacrylonitrile-graft-
poly (ethylene oxide) (PAN-g-PEO), for produced water treatment.
During their experiments, 96% of the dispersed and free oils were
successfully removed, which is a higher efficiency compared to
PAN-UF commercial membranes, for which the removal rate of
COD is only 41–44%. The comb copolymer-modified membranes
demonstrated full recovery of initial flux values after only physi-
cal cleaning methods, and this modification was believed to have
maximized the lifespan of the UF membranes in produced water
treatment [33].

Fig. 8. Application of (1) standard pore blocking [1/J1/2 = 1/J0 ½ + Kgt], complete pore blocking [Ln(J) = Ln(J0 ) − Kb t], (3) intermediate pore blocking [1/J = 1/J0 + Ki At], and (4)
cake formation [1/J2 = 1/J0 2 + Kc t] using Hermia’s models to predict permeate flux of hydrophilic PAN-UF membranes for controlling fouling caused by produced water
treatment. Legends: Lines represent predicted data; numbered symbols represent experimental results [31]. Details of operational conditions are presented in Table 6. A
[m2 ]: membrane area; J [l/m2 h]: filtration flux; J0 [l/m2 h]: initial filtration flux; Kb [1/s]: complete pore blocking model constant; Kc [s/m6 ]: cake filtration model constant;
Ki [l/m3 ]: intermediate pore blocking model constant; Ks [1/s3 ]: standard pore blocking model constant; n: blocking index; t [s]: filtration time; T [◦ C]: temperature [31].
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 113

Table 7
Comparative assessment of UF membrane performance in treating produced water
[32].

Characteristics PES-UF PVP-UF

membrane membrane

Operating pressure (bar) 0.3 1

Backwashing pressure (bar) 0.6 2
Clean water flux (CWF) of new 206.3 157.5
membrane (L/h m2 )
CWF at the beginning of UF tests (L/h m2 ) 147.5 157.5
Number of UF tests 9 9
Total UF time (h) 6.27 4.75
Number of backwashings (BW) 18 11
Number of enhanced backwashings 1 1
(EBW)
Total time BW and EBW (h) 0.75 0.4
Number of chemical cleanings (CHC) 8 1
Total time chemical cleanings (h) 2.88 0.3
Permeate volume (L) 40.19 47.5
Demineralized water consumed for BW 8.45 6.4
(L)
Flux recovery by BW (%) 51.3 87.6
Operating/cleaning time 1.73 6.78
Process efficiency (%) 78.9 86.5
Turbidity removal (%) – 30.2 mg/L 98.6 98.2
COD removal (%) – 70–90 mg/L 30.8 44.5

membranes (NF90 and NF2570) were evaluated. The overall rejec-

tion of salts was 93% [34]. In terms of treating produced water for
reuse, Mondal and Wickramasinghe studied the efficiency of two
NF membranes in 2008 [35]. Their findings showed that the NF270
membrane reduced the concentrations of TOC and TDS from 136.4

Fig. 9. (a) Effect of transmembrane pressure changes on the removal efficiency

and flux performance at ambient temperature and (b) 60 ◦ C for a TiO2 /Al2 O3 UF
membrane during produced water treatment [29].

Fig. 11. Optimization of the flux performance and restoration of PVP-UF membranes
during produced water treatment by backwashing (BW), chemical cleaning (CHC):
2% NaOH, 3%, 2(OH), 500 ppm, 2% citric acid; and enhanced backwashing (EBW).
*CWF: clean water flux (reference flux) [32].

Fig. 10. Correlation of the flux decline and transmembrane pressure effects for a
PES-UF membrane applied in produced water treatment [32].

1.3. NF membranes

Several investigations have proposed the use of NF membranes

for water treatment in the oil industry. Seland et al. [34] suggested
the nanofiltration of injected water by employing desulfated injec-
Fig. 12. Flux performance optimization and restoration of PES-UF membranes dur-
tion water in oilfields using a NF membrane. This treatment step
ing produced water treatment via backwashing (BW), chemical cleaning (CHC): 2%
was applied as a preventive measure for well souring and puri- NaOH, 3%, 2(OH), 500 ppm, 2% citric acid; and enhanced backwashing (EBW). *CWF:
fying injection water of scale compounds, and two types of NF clean water flux (reference flux) [32].
114 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
Fig. 13. Ceramic NF membrane (1000 and 750 Da) removal efficiency and flux sta-
bility performance results for produced water treatment at the transmembrane
pressure (1 bar) and high temperature (60 ◦ C) [29].
to 98.1 mg/L and from 2090 to 1760 mg/L, respectively. Herein, the
use of the NF90 membrane reduced the concentration of TOC to
89.7 mg/L and resulted in higher rejection than the NF270 mem-
brane for removing inorganic components; the concentration of
TDS was reduced from 2090 to 1340 mg/L. Fouled membrane recov-
ery after flushing with pure water ranged from 8 to 31% at applied
pressures ranging from 1.4 to 7 bar. In contrast, Ebrahimi et al. [29]
tested TiO2 /TiO2 (1000 Da) and TiO2 /Al2 O3 (750 Da) ceramic NF
membranes for produced water treatment containing an enriched
TOC content (292 mg/L) and 2.6 mg/L of oil as a post-treatment in
a combined system of membranes. These tubular NF membranes
completely removed the oil and reduced the TOC content by 49.8%
at a low applied pressure (1 bar). During these experiments, the
permeate flux average for the NF membranes was 123 L/m2 h bar
for 10 mg/L of oil at 60 ◦ C (Fig. 13).
1.4. RO membranes
Zeolite, polyvinylidene fluoride, polyethersulfone, and
polyamide are different types of RO membrane materials that
have been tested for produced water treatment. Interestingly, an
␣-alumina-supported, MFI-type zeolite membrane was reported
in two studies; both materials were synthesized as innovative
Fig. 15. Morphological structure of a MFI-silicate zeolite RO membrane developed for produced water treatment with an estimated membrane thickness of 1.2 ␮m: (a)
surface and (b) cross section [37].
Fig. 14. Assessment of the fabricated zeolite RO membrane flux performance while
desalinating produced water that contains 181,600 mg/L of TDS [36].
membranes for produced water treatment. In 2004, synthetic
zeolite RO membranes were employed to reduce the salinity of
produced water in upstream processes during the production of oil
[36]. The associated produced water was characterized with a high
content of TDS (181,600 mg/L), which was reduced to 11% (viz.,
32,700 mg/L was rejected) by a fabricated zeolite RO membrane.
Here, the applied pressure and permeate flux were set to 55 bar
and 0.018 kg/m2 h, respectively (Fig. 14).
Similarly, Liu et al. [37] developed a MFI silicate zeolite RO
membrane (Fig. 15) and tested the membrane with a synthesized
mixture of produced water samples containing three organic sol-
vents. The study reported that the membrane performance for
rejecting the organic mixture was approximately 96.5% at 27.6 bar
and 0.33 kg/m2 h for 100 mg/L of organic solution. For salts, this
zeolite membrane rejected 99.4% of 0.1 M NaCl salt (Fig. 16) [37]. In
terms of polymeric RO membranes, Fakhru’l-Razi et al. [38] uti-
lized two PVDF-RO and three PES-RO membranes for produced
water treatment [38]. These RO membranes were applied as a
post-treatment step at high pressures after a biological process of
treating produced water containing 33–43 mg/L of TOC. All of the
RO membranes exhibited high performances, with removal effi-
ciencies and fluxes ranging from 92 to 94% and 80 to 30 L/m2 h,
respectively (Table 8). The RO membrane system was operated for
18 d, after which chemical cleaning, consisting of 1% NaOH and 0.3%
HNO3 treatments, and sonication was applied; the RO membrane
recovery rate was 98%. The quality of the treated produced water
obtained from these membranes was acceptable for reuse [38].
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 115

undertaken to develop, optimize, and test technological solutions,

in which RO membrane technologies have been employed for pro-
duced water treatment, can mitigate membrane limitations for
handling the complex content of produced water. However, all of
these studies were performed on the bench scale and were pub-
lished from 2003 [39] to 2010 [38], emphasizing the need for novel,
effective technologies to remove small dissolved organic and inor-
ganic particulates from produced water, achieve environmental
compliance, and yield produced water for reuse. In this context, a
major conclusion from these studies is the current absence of com-
mercial [35] or fabricated RO membranes [36] to treat produced
water without pre-treatment steps, with the exception of the use
of these membranes as a final step for the treatment of pre-treated
(viz., disposal limits) produced water [38].
Fig. 16. Performance assessment of an MFI-silicate zeolite RO membrane developed
for produced water treatment with rejection of 0.1 M NaCl [37].
2. Reuse of produced water in the petroleum industry
using membrane technology

Compared to previous sections, in which most of the studies

were conducted at the research and development scale, this section
highlights membranes that were developed for actual application
to treat produced water in the petroleum industry with regard to
their drivers, performance efficiency, quality of the produced water,
pre-treatment steps, technical challenges, fouling occurrence, and
use in the production, and refining phases.
In upstream processes during the oil production phase, a typi-
cal surface-produced water treatment facility consists primarily of
oil, water, and gas separators; water-polishing systems; solid-filter
systems; and chemical treatment units (Fig. 18). This facility treats
produced water to satisfy the required standards for re-injection
or discharge [42]. In this process, treating one barrel of produced
water costs $0.50; this estimate is based on the following aspects:
an inland (onshore) oilfield location, a depth ranging from 6000 to
8000 ft, a well productivity that is higher than 1000 bb/d of oil, and
a produced water injection of 5000 bbl/d [42]. Currently, several
Fig. 17. BW-30 RO membrane flux capabilities in treating produced water. DI: ref- applications of membrane technology are utilized in surface facili-
erence flux of clean water; PW3: flux of the actual produced water sample; D1 (after ties for produced water treatment. In contrast, in the downstream
PW3): flux recovery of the fouled RO membrane and filtration time: 30 min [35]. process during the refining oil phase, petroleum refineries consume
large amounts of water to process different operations during refin-
Mondal and Wickramasinghe [35] also investigated the capabil- ing. According to the latest global survey conducted in 2011, 662
ity of RO membrane-BW30 to treat contaminated produced water refineries have a processing capacity of more than 88 million bbl/d
with 136.4 and 2090 mg/L of TOC and TDS, respectively. This mem- [43] using a wide variety of processes (150) to generate large quan-
brane reduced these TOC and TDS concentrations to 45.2 mg/L and tities of produced water [44]. In the following sections, several
1090 mg/L, respectively, at low pressures ranging from 1.4 to 7 bar studies in which advanced membrane technologies have shown
(Fig. 17). Similarly, Murray-Gulde et al. [39] employed a polymeric remarkable success in large pilot applications of produced water
RO membrane (AG 4040FF) to treat produced water for reuse by treatment in the petroleum industry are reviewed.
utilizing it as a post-treatment in a combined filtration system
before remediation for a constructed wetland. Characterization of 2.1. Drivers
the tested produced water was as follows: TDS, 6554 mg/L and TOC,
77.4 mg/L. During the experiments, at 18.61 bar, the TOC and TDS The implementation of membrane technology in upstream and
concentrations were successfully reduced to 18.4 and 295 mg/L, downstream processes in the petroleum industry has been driven
respectively. The flow rates ranged from 0.028 to 0.006 L/s. The RO by the desire to overcome water supply shortage through recycling
membrane was cleaned with a NaOH solution, and a flux recovery produced water while complying with environmental regulations,
rate of 90% was achieved. Previous studies [35,38–41] regarding as shown in Table 9. Among these uses, the largest application
the use of polymeric RO membranes have shown that the efforts in terms of demonstrating the need for membrane technology
occurred in Angola. Here, 0.5 million barrels of process water
Table 8 sourced from seawater and discharged produced water were fil-
RO membranes efficiency in produced water treatment [38]. trated using a NF membrane for the production of injection water
RO membrane Final flux Average Average TOC [45,46] to prevent the occurrence of well souring and sulfate scale
(L/m2 h) TOC (mg/L) removal (%) formation [47]. In fact, desulfated water obtained through NF mem-
EM006 30 33 93.9
brane technology in the petroleum industry is highly desirable
ES209 32 36 93.3 for injection purposes, as has been demonstrated in more than
ES625 37 38 93 50 large-scale applications in onshore and offshore oil production
FP100 65 40 92.6 platforms worldwide [48]. Similarly, the San Ardo water reclama-
FP200 80 43 92
tion project in California represents the largest-scale application
116 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Fig. 18. Schematic of a typical surface produced water treatment facility for upstream processes [42].

Table 9
Drivers and configurations of membrane treatment system implementations for produced water treatment in the oil industry.

Reference Membrane treatment system configuration Purpose of produced water reuse

[63] Walnut shell filter, warm lime softening, fin fan cooling, trickling To process waste sourced as municipal water and recycled as
filter, pressure filter, ion exchange, and RO membrane produced water
[53] Settlement tank, pH adjustment (5.8–5.9), temperature To reuse produced water for irrigation in compliance with
adjustment 85 ◦ C, cartridge filter, UF membrane, oil/water environmental disposal standards
separator, and NF and RO membranes
[49] Heat exchange, degasification, chemical softening, media filtration, To increase produced water quantity: 10 barrels of water
ion exchange softening, high pH adjustment, and double-pass RO generated against 1 barrel of oil for reuse as potable water and
units process water
[51] Dissolved air flotation, pre-filtration, ceramic MF membranes, To increase the treatment cost from 1923 to 2007. The content of
activated carbon adsorption, and RO membrane produced water in oil exceeded 98.5%, and the cost became $1 per
barrel for disposal, resulting in reusing produced water as potable
water
[54] Aeration tank, air flotation, sand filtration, and UF membrane To comply with environmental discharge standards
[55] Biological treatment process and MF membrane To comply with environmental discharge standards
[56] Primary sedimentation, oil/water separator, DAF system, ␮m To meet the COD discharge standard of <250 mg/L
ceramic or metallic cartridge filter, and 0.2 ␮m ceramic or metallic
MF and RO membranes
[50] Desanding, de-oiling hydrocyclones, and a hydrophilic UF To comply with environmental discharge standards
membrane
[59] UF and RO membranes To comply with environmental discharge standards
[45,46] NF membrane To desulfate 500,000 bbl/d for injection during oil production
recovery processes and prevent well souring
[57] Clarification, dissolved air flotation, biological process, an UF and To recycle produced water as process water
RO membranes
[57] UF and RO membranes To comply with environmental discharge standards for BTEX and
recycle produced water as cooling water and boiler feedwater
[58] MF, UF, NF, and RO membranes To comply with discharge standards for <1.3 ppt (Hg) and <280 ppb
(V)
[137] Lime clarification, dual media filtration, and UF and RO membranes To recycle produced water as cooling water, boiler feedwater, and
fire water
[154] UF and RO membranes To recycle produced water as boiler feedwater
[44] MF and RO membranes To reuse produced water as boiler feedwater
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 117

Fig. 19. Scheme illustrating the major uses of membrane technology for produced
water treatment.

Fig. 20. Timeline of selected membrane technology applications for produced water
of RO membrane technology for produced water treatment in the treatment in the oil industry.
petroleum industry [49]. This project demonstrated how the selec-
tion of membrane technology can manage massive quantities of
by several desires, as shown in Table 9, demonstrating that mem-
produced water from a technological perspective, with 10 bbl/d
brane technology has been primarily employed to either treat raw
of water from every barrel of oil extracted. The adoption of the
process water or discharge produced water. Several refineries have
water resource sustainability concept led to the establishment of
used membrane technology to treat secondary municipal efflu-
this membrane application by reusing the produced water to purify
ent to provide process water, as reported by Evans et al. [52] and
more than 50,000 barrels/d for recharging a groundwater basin to
Wong and [44]. In contrast, other studies have demonstrated the
supply potable water [49].
treatment of produced water through the use of membrane tech-
Other examples for the need of membrane processes include
nology as a post-treatment for discharge or reuse produced water.
an application in Texas in which 25,000 barrels were treated per
All of these drivers have demonstrated that ever-increasing envi-
day to investigate the possibility of integrated UF membranes as
ronmental regulations influence the implementation of membrane
a post-treatment step to meet the requirements for a permit for
technology [53–58], particularly because traditional technologies
produced water discharge [50]. Similarly, the treatment of pro-
have failed to deliver efficient and effective membrane technologies
duced water from the Wellington Oilfield met the standards of
(e.g., removing small dissolved particulates) [19]. However, some
discharge or reuse for oil production processes. The application of
applications have adopted even more advanced initiatives, such
membrane technology in this oilfield demonstrated the possibility
as the reuse of treated produced water via membrane technology,
of converting produced water from a pollution source to a usable
Table 9. In refineries that have used membrane technology to sat-
water resource through membrane technology and added eco-
isfy discharge standards, as recorded by Peeters and Theodoulou
nomic value to this water by providing potable water for domestic
[57] and Negri et al. [58], most of the employed membrane tech-
use in Wellington, CO, USA [51]. As previously mentioned, mature
nologies in these studies were initiated between 2000 and 2009.
oilfields produce high amounts of produced water, especially when
This fact indicates the emerging need for membrane technology
the oilfield has reached peak production, which results in higher
to meet the requirements of the petroleum industry for managing
treatment costs [42]. Wellington Oilfield, which is located in north-
produced water (Fig. 20).
ern Colorado, began production in 1923 and continued production
until 2007, at which time its produced water exceeded 98.5% of the
total yield with an increment of $1 per barrel of produced water 2.2. Content of produced water
in re-injection and disposal costs. Thus, membrane technology was
employed to treat 3000 barrels of produced water per day using By reviewing several membrane technology applications for
both ceramic MF and RO membranes to provide fresh water for reusing produced water on an industrial scale, certain concentra-
reuse [51]. In contrast, the use of membrane technology for pro- tions have been reported (Table 10), ranging from 1.2 to 200 mg/L
duced water treatment is driven by environmental regulations and for oil, 1000 to 15,000 mg/L for TDS, 20 to 2250 mg/L for COD,
the need for advanced technology to comply with such standards and 5–4200 mg/L for TSS, as shown in Table 10. These produced
by removing dissolved nano-sized particulates. As shown in Fig. 19, water contents may pose a substantial challenge for membrane
all current uses of treated produced water are categorized as dis- technologies, especially the organic content, in which the oil
charge, reinjection, or reuse. reached 200 mg/L [54], compared to other studies reported in
Similarly, in downstream processes, the implementation of Table 10. Furthermore, in a study by Drewes [59], organic fouling
membrane technology for produced water treatment was driven was observed and the TSS concentration exceeded 4000 mg/L,
118 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Table 10
Pre-treatment contents of produced water treated by selected applications of membrane technology.

Membrane application Content of produced water

Oil Silica TDS COD TOC TSS Fe BOD BTEX

Riyadh Refinery, Saudi Arabia [137] 2 10 1000 40 5 0.2

Daqing Oilfield, China [54] 50–200 2500–2900 380–490 30–160 2–8.4
Pemex’s Caderayta Refinery, Minatitlan, Mexico [57] 1.6 80.1 20.3 4.8
Marathon Ashland Refinery, Kentucky, U.S. [57] 165 66 775 30.2
12 oilfields in Texas [59] 15,000 4200 170
Sinopec Yanshan Refinery, China [66,67] 1.2 20–50
Bakersfield Oilfield, California [53] 10–50
Placerita Canyon Oilfield, California [63] 20–80
San Ardo produced water reclamation facility, California [49] 7000
Campos Oilfield, Brazil [55] 600–2250 250–550
Vakeflar Oilfield, Turkey [56] 6830 1523
West Texas Oilfield [50] 5–10 73

Units in mg/L.

possibly resulting in membrane pore blockage. In contrast, the salt
content was reported to be low, and the highest level reported
was 15,000 mg/L [59], which is low compared to the seawater
content of TDS, which may range from 20,000 to 50,000 mg/L [60].
However, because the reviewed studies have different purposes
for membrane technology in terms of reusing produced water
and the placement of membrane technology as pre-treatment or
post-treatment steps, the most likely parameter that is critical is oil
[54,57]. In contrast, other studies have reported on specific cases
for a certain parameter, which has resulted in technical challenges
and lowered membrane rejection performance. For example, an
application of UF, NF, and RO membranes for membrane feeds
in primary treatment processes, including a settlement tank, pH
adjustment (5.8–5.9) temperature adjustment (85 ◦ C), a cartridge
filter, and an oil/water separator, resulted in a relatively high
boron concentration (5–10 mg/L) because a low pH was used. This
obstacle was overcome through ion exchange, which lowered the
boron concentration to 0.75 mg/L [53]. This example demonstrated
that the presence of boron, unlike others substances that may
present in produced water, might present technical challenges
when utilizing membrane technologies for produced water
treatment if pre-treatment of the membrane feed is treated at a
low pH. Most commercial RO membranes are fixed, negatively
charged membranes [5], and boron is present in produced water as
boric acid (B(OH)3 ) and is non-ionized [60]. The ability of RO mem-
branes to reject boric acid is low because it is a neutral molecule.
Additionally, the RO membrane rejection mechanism depends
mainly on size exclusion, and small boric acid particles can pass
through the pores of RO membranes [61]. To address this issue, the
pH may be increased to convert boric acid into negatively charged,
larger borate ions (BOH4 − ), which enable the RO membrane to
reject it [62]. This technique achieves a boron rejection rate for RO
membranes in excess of 95%, which meets the permissible level
for produced water discharge (Fig. 21) [49]. In contrast, a boron
selective ion exchange resin, which costs approximately $1000 per
cubic foot, may be employed as an alternative but is certainly not
cost effective compared to merely increasing the pH to remove
boron from RO feeds [61].
Similarly, the abundant presence of silica in produced water
is another commonly reported challenge during the implementa-
tion of RO membranes for produced water treatment. This issue
was demonstrated in an actual industrial application in which

Fig. 21. Boron rejection versus pH effect during produced water treatment using an RO membrane [49].
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
Fig. 22. Effect of pH on the solubility of silica [49].
20–80 mg/L of silica affected the membrane performance due to the
inefficiency of the primary treatment processes applied (i.e., wal-
nut shell filter, warm lime softening, fin fan cooling, trickling filter,
pressure filter, and ion exchange) before utilizing the RO mem-
brane. A proposed measure to mitigate this challenge was applied
through softening, pH adjustment (8.5–9.5), and MgCl2 addition
(400 mg/L), enabling the RO membrane to reject the remaining
silica content and reduce it to 3 mg/L (Fig. 22) [63].
The presence of ammonia in produced water is yet another
challenge for membrane technology and is addressed in the
post-treatment stages of downstream processes in the petroleum
industry [53]. Ammonia concentrations typically remain high in
secondary effluent treatment before being pumped or fed into
membrane units; the ammonia concentration is maintained at
50 mg/L in the feed for secondary treatment to serve as a source
of nutrients in biological treatment processes in petroleum facil-
ities [44]. Thus, sufficient amounts of ammonia (milligrams) may
appear later in the membrane feed [64], not because of ammonia
degasification but because the non-ionization of ammonia pre-
vents membrane surfaces from becoming charged and rejecting
the ammonia [5], resulting in reduced membrane performance and
biofouling [60]. Thus, to optimize the membrane technology for
particular RO membranes that will remove ammonia, decreasing
the pH below 9 increases the solubility of ammonia and thereby
reduces the ammonia load on the RO membrane [63]. Incidentally,
operational conflicts might arise when simultaneously remov-
ing boron and ammonia with an RO membrane with respect to
pH adjustment. Alternatively, ammonia removal in primary or
secondary treatment processes can be addressed before the appli-
cation of membrane technology by employing different techniques,
such as chlorination breakpoint, air stripping, selective ammo-
nium ion exchange, and biological treatment [61]. Among these
methods, selective ammonium ion exchange is the most effective
pre-treatment step before utilizing the membrane unit for pro-
duced water that contains a high ammonia load [61]. In the context
of boron removal after pH adjustment, silica and ammonia will
greatly affect membrane fouling [60].
Aside from the aforementioned foulants, the presence of
organic compounds in produced water is largely attributed to the
119
concentrations of oil reaching 200 mg/L [28]. The solubility of such
soluble organics increases with increasing pH (Fig. 23) [60], and
therefore, operating membrane technology at high pH values may
eliminate the potential for membrane fouling [65]. This concept
was reported in an actual application using RO membranes at
high pH levels to treat produced water containing 60 mg/L of
free/dispersed oil [49]. However, the authors also found that
maintaining a steady pH in the feed is essential for this process
[49]. Fluctuations in pH occur when using alkaline solutions,
whereas the addition of H+ increases the pH while simultaneously
enabling the conversion of bicarbonate alkalinity to CO2 [53]. This
conversion results in a drop in the pH value of the permeate due to
the passage of CO2 through the membrane and the simultaneous
rejection of bicarbonate (HCO3 − ) [41]. In a study [41] using an
RO membrane to treat produced water at high pH (10.7), the RO
feed resulted in a pH of 11.5 in the permeate due to an increase
in the hydroxyl ion (OH− ) concentration, which repelled nega-
tively charged carboxyl groups on the membrane surface. In such
cases, membrane surface may be affected, subsequently causing an
increase in the passage of ions, such as OH− , and thereby increasing
the permeate pH [41]. CO2 degasification, which uses air stripping,
is recommended to avoid such a pH decrease, particularly because
it also reduces the potential for scale build-up [53].
2.3. Performance efficiency
In reusing produced water for beneficial applications, an assess-
ment of different membrane process efficiencies was conducted
with respect to configuration and performance, and the results
are presented in Table 11. RO membranes were utilized in the
largest number of applications, followed by UF membranes. Both
UF and RO membranes were used in several applications; the UF
membranes served as the pre-treatment for an RO feed, and the
latter was used as a post-treatment. MF membranes were used
in few applications. An MF membrane was employed also as a
pre-treatment and as a post-treatment, and there were limited
applications of NF processes [53,58]. However, approximately 50
applications of NF membranes to desulfate seawater prior to
injection into oil wells have been reported; however, insufficient
 120
Table 11
Analyses of membrane performance efficiencies for produced water reuse.

Parameter Oil SO4 2− Mg Ca K Na Cl NH3 Silica TDS TSS SRB1 TGB2 COD TOC BOD BTEX HCO− 3 Hardness Recovery%
◦
Bakersfield Oilfield [53], California: settlement tank + pH adjustment (5.8–5.9) + temperature adjustment 85 C + cartridge filter + UF membrane + Oil/water separator + NF membrane + RO membrane
Raw PW (mg/L) 10–50 1090 412 715 174 9610 8010 110
UF 90–98% 90–95
NF 100% 100% 72% 77.2% 55.7% 45% 41% 38%
RO 100% 100% 99.5% 99% 98.8% 98.5% 98.5% 98%

S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Placerita Canyon Oilfield [63]: walnut shell filter + warm lime softening + fin fan cooling, trickling filter + pressure filter, ion exchange + RO membrane
Raw PW (mg/L) 20–80 -
RO 3 95%
San Ardo produced water reclamation facility [49]: heat exchange + degasification + chemical softening + media filtration + ion exchange softening + high pH adjustment + double-pass RO system
Raw PW (mg/L) 133 2300 3400 7000
2nd pass of RO 0 43 0 76
Daqing Oilfield, China [54]: aeration tank + air flotation + sand filtration + UF membrane
Raw PW (mg/L) 1.5 4–8 2.5 × 101 6.0 × 101
UF <1 <0.1 0 <102
Campos Oilfield, Brazil [55]: biological treatment process + MF membrane
Raw PW (mg/L) 600–2250 250–550
MF 230 55
Vakeflar Oilfield, Turkey [56]: primary sedimentation + oil/water separator + dissolved air flotation system + ␮m ceramic or metallic cartridge filter + 0.2 ␮m ceramic or metallic MF
Raw PW (mg/L) 6830 1523
RO 170 <30
West Texas Oilfield [50]: desanding + de-oiling hydrocyclones + hydrophilic UF membrane
Raw PW (mg/L) 5–10 73
MF <2 54% 98
12 oilfields in Texas [59]: UF membrane + RO membrane
Raw PW (mg/L) 15,000
RO 98.7%
Pemex’s Caderayta Refinery, Mexico [57]: clarification + dissolved air flotation + biological process + immersed reinforced hollow-fiber UF + RO membrane
Raw PW (mg/L) 1.6 20.3 80.1 4.8
MF Pre-t. Pre-t. Pre-t. Pre-t. Pre-t.
RO 0.2 0.5 36.4 2.4 95
Marathon Ashland Refinery, USA [57]: immersed reinforced hollow-fiber UF membrane + RO membrane
Raw PW (mg/L) 165 66 775 30.21
MF Pre-t. Pre-t. Pre-t. Pre-t.
RO 97% 89% 99.7% 0.15
Riyadh Refinery, Saudi Arabia [137]: lime clarification + dual media filtration + UF membrane + RO membrane
Raw PW 906
MF Pre-t.
RO 17
Chevron’s El Segundo Refinery, Los Angeles [44]: MF membrane + RO membrane
Raw PW (mg/L) 1.5 60 27 <0.3
RO 0.1 5 3 <0.03 85–90%

One sulfate reduction bacteria (n/mL); Two metatrophic bacteria (␮m). Pre-t. = pre-treatment.
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
Fig. 23. Effect of pH on the solubility of organic substances (oil and grease) present in produced water [49].
information regarding these applications was provided in this
reference [48]. In terms of membrane applications, some were spe-
cial configurations for produced water treatment, whereas in the
remaining studies, intensive pre-treatment steps consisting of tra-
ditional treatment methods were employed as the primary and
secondary treatments with membranes to prevent membrane foul-
ing (Table 11). Overall membrane process performances in major
applications have decreased due to the complexity of the produced
water content, which is typically replete with organic contents
(Tables 10 and 11). For example, an RO membrane system with
primary and secondary treatment processes that included clarifi-
cation, dissolved air flotation, biological processes, and immersed
reinforced hollow fiber UF resulted in a TOC reduction from 80.1
to 36.4 mg/L, whereas the oil concentration pre-filtration was ini-
tially recorded at 1.6 and was reduced to 0.2 mg/L [57]. Utilizing
sufficient pre-treatment steps for membrane technology resulted
in excellent membrane performance for the production of oil-free
produced water, as reported in a study with a full membrane
treatment system that included a settlement tank, pH adjustment,
temperature adjustment (85 ◦ C), a cartridge filter, an UF mem-
brane, and an oil/water separator. This NF and RO membrane
system increased the oil content removal rate from 10–50% to
100%, thereby yielding reusable produced water [53]. However,
no standard configurations are utilized for different purposes for
produced water treatment, as shown in Table 9.
Each membrane application is specific to an oilfield and refinery
operator due to the different environmental and reuse regula-
tions worldwide and the lack of similarity in the produced water
content, which is reflected in the different performances of mem-
brane applications during the produced water treatments. Thus,
as shown in Table 11, the use of insufficient pre-treatment steps
for produced water treatment results in poor yields of treated
produced water. For example, biological treatment process appli-
cations with MF membranes are ineffective in removing high
COD and TOC contents, 600–2250 mg/L and 250–550 mg/L, respec-
tively, as these parameters were reduced to only 230 and 55 mg/L,
respectively [55]. However, integrating membranes with sufficient
conventional treatment processes can demonstrate high efficiency,
as demonstrated in Table 11. In a previous study [53], UF, NF,
121
and RO membranes recovered their permeates to 90–95%, and UF
and RO membrane placement as post-treatments in conventional
treatment processes recovered 95% of membrane permeates while
maintaining steady productivity. However, this system was ineffi-
cient with respect to complete organic substance rejection [57].
Other examples of membrane technology implementation per-
formed in large-scale units with long-term operation will now be
discussed.
One of the largest applications of reusing produced water is
the San Ardo produced water reclamation facility, which employed
double-pass RO membrane units for 14 months with feed and per-
meate flow rates of 550–900 and 550–700 gpm, respectively, and an
applied pressure range of 270–530 psi [49]. This membrane treat-
ment system has met all of the standards for reuse by recharging
underground water basins, with the exception for boron, where the
initial boron concentration was 26 mg/L, and the 2nd RO membrane
pass only rejected 16 mg/L instead of the required 0.75 mg/L. Fur-
thermore, post-treatment with a constructed wetland could not
remove the boron [49]. In terms of fouling, membrane surface
autopsies were performed using energy dispersive X-ray spec-
troscopy after 8 months of operation and revealed organics, silica,
and iron as the major foulants (Table 12); in addition, the 1st RO
membrane skid was apparently more affected than the 2nd skid
[49].
Çakmakce et al. [56] conducted appropriate pre-treatment
assessments for NF and RO membranes in produced water treat-
ment to overcome such technical limitations. These authors
investigated the technological capabilities of several primary
and secondary treatment processes to reduce the COD value
(1681 mg/L) below the allowable limits of discharge (viz.,
<250 mg/L). Several alternatives and strategies were tested,
as shown in Table 13, including dissolved air flotation (DAF),
acid cracking (AC), coagulation (CA) with lime, and precipitation.
Cartridge filters (CDF; 5 and 1 ␮m) and MF and UF membranes
were used as pre-treatment techniques before feeding NF and RO
membrane units with the influent from a secondary treatment [56].
The results of this study indicated that the optimal pre-treatment
technique before applying an NF or RO membrane utilizes a mem-
brane treatment system with primary sedimentation, an oil/water
122 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Table 12
Composition of membrane foulants after 8 months of operation based on energy
dispersive X-ray (EDAX) results [49].

wt%

Foulant membrane 1st pass of RO 2nd pass of RO

membrane membrane

Carbon 59.16 21.12

Sulfur 11.68 03.27
Oxygen 10.44 24.28
Nitrogen 8.35 3.98
Iron 5.94 11.00
Silicon 2.37 28.86
Magnesium 0.35 3.93
Calcium – 0.86
Aluminum – 1.26
Sodium – 1.43
Membrane recovery 76–82% 87–91%
Fig. 24. Assessment of membrane performance flux versus filtration time during
the treatment of produced water from the Vakeflar Oilfield in Turkey [56].
separator, a DAF system, a 1 ␮m ceramic cartridge filter, and a
0.2 ␮m MF membrane (Fig. 24). This system was the most effective
pre-treatment combination to obtain high-quality treated pro- of 1400–1900 ␮S/cm. These pollutants were successfully removed
duced water (viz., up to the disposal limit) and to yield optimal with a RO (BW30-365 FR) and UF (SFP-2660) membrane pre-
membrane performance in terms of the permeate flux (Fig. 24). The treatment prior to the RO feed. The UF membrane reduced the
analyses of the treated produced water obtained from this system turbidity from 5 to 0.3 NTU before RO feeding, and thereafter,
showed that the RO membrane reduced the concentration of COD 100 m3 /h of the RO permeate was reused as boiler feedwater in
to <30 mg/L [56]. These findings firmly established the ability of the refinery (Table 14) [66,67].
advanced membrane technology to effectively treat produced
water beyond the allowable environmental regulation standards 2.4. Fouling occurrence and control
and indicated that the integration of conventional treatment tech-
niques with membrane technology may provide promising results. The occurrence of membrane fouling during produced water
Another example of a membrane application for reusing pro- treatment is high because the presence of potential foulants in
duced water in downstream processes is the Sinopec Yanshan produced water, as listed in Table 15. Analysis of the fifty studies
Refinery which has successfully operated a combined mem- related to produced water [19,38,54,55,64,68–109] revealed that
brane system comprised of UF and RO membranes for more the most abundant foulants that may contribute to different foul-
than four years [66,67]. These UF and RO membranes treat sec- ing mechanisms result from the organic content, specifically oil
ondary biological treatment effluent with the following typical and organic substances (TOC), whose concentrations ranged from
stream characteristics: an oil content of 1.2 mg/L, a COD content 15 to 303 mg/L for oil and 6.9 to 540 mg/L for TOC in 272 analyzed
of 20–50 mg/L, a hardness of 300–500 mg/L, and a conductivity samples (Table 15). Compared to the content of these samples, in

Table 13
Assessment of several alternative pre-treatment steps for membrane performance optimization during produced water treatment [56] NF and RO membranes applied at 10
and 20 bar, respectively Membranes: MF (Cellulose acetate), UF (Osmonics), NF (NF-200, Film Tech), RO-1 (ST10, Osmonics) and RO-2 (AG, Osmonics).

Description COD Conductivity pH

Raw produced water content 1681 18,770 7.8

Alternatives
1
1–5 ␮m cartridge filters + RO membrane – ST10 180 11,130 7.4
2
1 ␮m cartridge filter + 0.2 ␮m MF membrane 1483 11,130 8
RO membrane – ST10 201 1164 7.4
3
1 ␮m cartridge filter + UF membrane 1446 9970 8
RO membrane – ST10 485 1094 7.4
4
1 ␮m cartridge filter + 0.2 ␮m MF membrane 1483 11,130 8
RO membrane – AG 34 373 8.8
5
1 ␮m cartridge filter + UF membrane 1446 9970 8
RO membrane – AG 53 621 7.9
6
1 ␮m cartridge filter + acid cracking + coagulation + 0.2 ␮m MF membrane + RO membrane – AG 145 340 8.8
7
1 ␮m cartridge filter + 0.2 ␮m MF membrane 1483 11,130 8
NF membrane – NF200 137 4320 7.6
8
1 ␮m cartridge filter + dissolved air floatation + 0.2 ␮m MF membrane 1532 12,680 8.35
RO membrane – AG <30 363 8.93
9
1 ␮m cartridge filter + dissolved air floatation + coagulation – lime 1740 12,680 8.59
0.2 ␮m MF membrane 1663 12,470 8.56
RO membrane – 2 <30 516 9.02
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 123

Table 14
UF and RO membrane application results in actual oil refinery for produced water reuse [66].

Parameter Unit UF RO

Membrane – SFP-2660 FBW 30-365FR

Capacity m3 /h 560 412
Number of skids – 10 (8R:2S) 4
Number of modules per skid – 60 –
Total number of modules – 600 –
Capacity per skid m3 /h 70 103
Recovery % >95 –
Design flux L/m2 h 37.2 –

Cleaning procedure for UF membranes

Parameter Frequency Duration Chemical consumption

Filtration – 55 min –
Air scour After every filtration 30 s 1152 N m3 /d (air)
Backwash After every filtration 50 s 10–15 ppm NaOCl
Forward flush After every backwash 70 s –
CEBa None None –
CIPb 3–6 months 8h Alkaline: 0.1% NaOH, 0.2% NaOCl + acid: 0.2% oxalic acid
a
Chemically enhanced backwash.
b
Clean-in-place.

other types of wastewater, such as those from municipality waste- applications in some of the studies described in Tables 3, 4, and 7
water, the contents of organic substances typically range from 10 and in Figs. 1–3, 6, 8, and 10–12. The organic foulants in produced
to 20 mg/L for TOC, and in surface water the content is <10 mg/L water primarily originated from oil and chemical additives that are
[60]. Thus, the potential for organic fouling is much higher in the used widely in oil production processes and remain at appreciable
levels, as exhibited in Table 12 [110].
Table 15 In comparison to municipal wastewater treatment using
Potential foulants present in raw produced water that may contribute to inorganic
membrane technology, common organic foulants, such as polysac-
or organic fouling for membrane technologies.
charides, natural organic matter, humic acid, proteins (bovine
Parameter Min Max No. of samples serum albumin), fatty acids and surfactants [65], have been
Organics reported. Similar to these types of wastewater, produced water,
TOC 6.9 540 76 municipal wastewater and seawater contain natural organic
Oil 15 303.2 196
foulants and organic acids. Differences in organic fouling can be
Anions, cations, and metals
Chloride <1 254,923 58,824
estimated in terms of quantity (i.e., more foulants are present), as
Sodium <1 149,836 58,743 shown in Table 15, and there is a wide range of chemical addi-
Calcium <1 74,185 58,880 tives, which have contributed to the occurrence of organic fouling
Magnesium <1 46,656 58,866 (Table 16). As for inorganic foulants, in seawater and municipal
Sulfate <1 15,000 58,991
wastewater, silica, ferric hydroxide, aluminum oxide and calcium
Bicarbonate <1 14,750 58,728
Potassium 1.6 4875 58,734 phosphate have been reported to be common [65]. In compari-
Iron 0.1 4770 88 son to produced water, as shown in Table 15, the high levels of
Strontium 0.05 1090 65 potential inorganic foulants may result in significant polarization
Carbonate 7.3 1030 3
concentration, scaling and colloidal accumulation [65].
Barium 0.07 468 25
Bromide 3.71 357 16
Fouling studies related to produced water are lacking and
Sulfide 0.4 118 72 might help to understand the mechanisms of this type of foul-
Phosphate 0.5 39.2 11 ing [33,65,74,111]. However, when controlling membrane fouling
Lithium 5.6 31.6 3 from produced water, some studies have developed different tech-
Silicon 1.4 31.2 9
niques through the application of cleaning procedures [27]. A
Nickel 0.015 9.5 36
Phosphorus 0.02 8.78 23
Manganese 0.7 8.1 59
Physico-chemical parameters Table 16
TDS 740 970,000 216 Examples of chemical additives used and discharged with produced water in the
Salinity 4110 100,000 20 Norwegian sector of the North Sea (unit in tons/year) [110].
TSS 90 4744 78
COD 80 2900 26 Category Used Injected Discharged
Turbidity 95 850 21 Biocides 2584 2446 81
BOD 4.4 695 78 Corrosion inhibitors 2471 – 216
Temperature 15 92 425 Oxygen scavengers 1277 1241 22
Ammonia 7 90 84 Scale inhibitors 1727 515 1143
pH 2.6 10.2 513 Demulsifiers 444 21 9
Natural occurrence of radioactive materials Coagulant/de-oiler 222 17 189
226-Radium 0.1 111.2 61 Antifoam 144 33 –
228-Radium 8.8 67.4 58 Flocculant 203 4 108
All units are expressed in mg/L with the exception of turbidity in NTU; temperature Fluid-loss control 103 – 15
in ◦ C; radium in Bq/L; and pH (unitless). The data were extracted from previ- Viscosifiers 24 – 10
ous reports [19,38,54,55,64,68–109] and represent raw produced water from 20 Surfactant/detergents 24 – 24
countries, including China, the USA, Brazil, Norway, Egypt, Iran, Malaysia, Algeria, Detergent/cleaners 92 – 87
Denmark, India, Mexico, Russia, Saudi Arabia, Sub-Saharan Africa, Syria, Taiwan, Gas treatment 9307 2800 2846
Turkey, the UAE, and the UK. Paraffin 202 – –
124 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
variety of such methods exist, such as mechanical or hydraulic
cleaning by membrane flushing and chemical cleaning with chem-
ical reagents. Hydrochloric acid, citric acid, and sodium hydroxide
are typically used for the chemical cleaning of membranes [112].
In addition, sodium ethylenediaminetetraacetate (EDTA) has been
employed as a metal chelating agent, and sodium dodecyl sul-
fate (SDS) represents the most common anionic surfactant used
[113]. The efficiency of these chemical cleaning agents on differ-
ent types of polymeric membranes for produced water treatment
has been explored. A chemical cleaning procedure utilizing caustic
and anionic surfactant solutions was more effective than acids and
metal chelating agents in terms of restoring membrane permeabil-
ity [113]. In contrast, Ashaghi et al. [25] listed the most common
methods of cleaning ceramic membranes during produced water
treatment, such as the addition of air bubbles to improve cross-
flushing and the use of 45 kHz ultrasound to increase the fouled
membrane permeability by breaking the cake layer and reducing
the adsorption of concentrated solutes in the fouled membrane sur-
face. In addition to the aforementioned chemical agents for cleaning
(e.g., acids, alkali, surfactants, and chelating agents), oxidants and
enzymes may also be used to oxidize organic material and bacteria,
thus degrading the foulants [25]. Furthermore, a recent study devel-
oped a chemical cleaning agent based on anionic derivatives of alkyl
polyglycosides and a micelle cleaning solution comprised of alpha
olefin sulfonates and additives materials that included polymer
particles with an organic based fluid; a surfactant-containing flu-
ids (polymer-containing solid surfactant suspensions with aqueous
carrier fluids) was formed and could clean UF membranes fouled
by produced water. Cleaning with this chemical agent has multiple
mechanisms through which the cleaning performance is optimized,
including lowering the critical micelle concentration and interfacial
tension [114]. Numerous reviews have focused on the membrane
fouling phenomena caused by municipal wastewater and seawa-
ter [65,115], whereas there are few studies regarding membrane
fouling caused by produced water.
2.5. Economic factor
One of the most common factors governing the implementation
of membrane technology in the petroleum industry is economic
factor [51]. From an industrial viewpoint, the estimated cost of
produced water management in an actual conventional produced
water treatment facility (capacity 20,000–200,000 bbl/d) during
oil production may cost an average of $0.578 per 1 bbl/d. This
estimate includes capital and operating expenses, utilities and
chemicals, lifting, separation, de-oiling, filtering, pumping, and
injection into disposal wells [42]. However, when employing mem-
brane technologies, this cost may increase to $0.94 with UF and
RO membranes [59] and decrease to 9.7 cents with UF membranes
[50]. When more stringent environmental regulations are enforced,
integrated hybrid membrane treatment systems are estimated to
be $0.62–0.71 for 1 bbl/d due to collection and capital costs for
the appropriate pre-treatment procedures in upstream processes
[56]. For downstream processes, Hum et al. [116] argued that the
treatment of produced water for beneficial uses, such as drinking
water, whether in-refinery or off-refinery, is not as expensive as
perceived. The cost of treating produced water is approximated to
be $0.47/bbl, and the cost of producing drinking water from this
yield is approximated to be $0.11–0.15/bbl, as achieved in Canada’s
petroleum industry. This study [116] emphasized that turning pro-
duced water into useable water is not prohibitively expensive by
comparing the price for 1 m3 among different commercial liquid
products sold in Canada. This investigation calculated the follow-
ing monetary outcomes per 1 m3 of produced water: coffee, $4000;
coca, $3000; skim milk, $1200; gasoline, $1000; and bottled water,
$2000. This comparison illustrates that the treatment of produced
water for beneficial uses by employing membrane technology is
highly effective, particularly as an alternative to environmental dis-
charge [116]. Membrane technology offers viable choices that can
reduce operational costs and energy requirements. For example,
a petroleum refinery applied RO membranes to replace hot lime
softeners for boiler feedwater [117]. This replacement reduced the
percent of steam produced from 13.3 to 1.5. In addition, in terms
of operational costs, approximately $165,000 was saved per year,
which included boiler treatment chemicals ($36,000), maintenance
($20,000), and waste disposal ($4300). RO membranes require
cleaning or maintenance approximately every 6 months [117].
These studies have shown that membrane technology for produced
water treatment is realistic and can result in cost-effective water
resource sustainability.
3. Potential applications of membrane technology in the
petroleum industry
The following sections provide an overview of the future preva-
lence of new membrane technology applications in the petroleum
industry, which are expected to become more prevalent.
3.1. Upstream processes
Several techniques are currently employed to minimize pro-
duced water production from oilfields. Mechanical techniques,
such as zonal isolation, and chemical techniques, such as the addi-
tion of additives for water-shut off, represent common methods;
however, chemical techniques are costly and quantity intensive
[47]. Oil producers are wary of managing produced water, espe-
cially in mature oilfields where the amount of produced water
generated per corresponding barrel of oil increases dramatically
over time [15]. However, from a strictly operational perspective,
minimization of produced water generation is desired to pre-
vent the occurrence of scale formation, fines migration, sandface
failure, tubular corrosion, and even well killing via hydrostatic
loading [118]. Therefore, the need for innovative technologies to
reduce this amount of produced water is substantial, as more
than 700,000 oilfield operations and 655 refineries exist worldwide
[119]. In this context, the potential for integrated membrane tech-
nology in downhole oil/water separation systems is promising in
the membrane industry, and it should be investigated thoroughly.
Unfortunately, research regarding this aspect is currently lacking
[120], with the exception of a few patents [121–124].
A simulation study was conducted to gauge the applicability
of using a device for separating oil and water downhole through
integrated hydrophobic MF membranes supported by submersible
electric pumps to produce oil-free water [125]. The results of
this simulation revealed that applying membrane technology
to separate oil and water downhole is possible. Comprehensive
details regarding this study in terms of oil well characterization,
operational conditions, and expected challenges were previously
reported [125]. In current practices of produced water man-
agement at oilfield processing facilities, water separated at the
demulsification stage contains high concentrations of residual oil
as oil-in-water emulsions (inverse emulsions) and finely dispersed
solids, thus necessitating treatment [47]. The concentration of
residual oil is typically higher than the discharge limits and holds
considerable economic value if extracted. Additionally, if this
water is re-injected, the solids may plug the throats of injection
wells or the filters and thus raise the backpressure, which wastes
energy, damages equipment, and can even lead to a facility shut-
down [47]. Thus, treatment processes consume high amounts of
chemical additives, such as flocculant, also termed water clarifier,
de-oiler, oil-in-water demulsifier, reserve emulsion breaker, or
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133 125

polyelectrolyte, to remove residual oils and dispersed solids Table 17

Comparison of the efficiencies of different technologies in oil removal [127].
[47]. Available physical technologies, other than flocculants,
for the removal of oil and other contaminants from produced Rate of oil removal by technology Minimum size of particles
water include a combined degassing and flotation tank, specially removed (␮m)
designed centrifuges or hydrocyclones, and C-Tour processes, a API gravity separator 150
combination of hydrocyclones and additional liquid hydrocarbon Corrugated plate separator 40
gases [126] that has been used in North Sea platforms [47]. How- Induced gas floatation (without flocculants) 25
Induced gas floatation (with flocculants) 3–5
ever, chemical additives, such as flocculants, remain indispensable,
Hydroclone 10–15
as reported in an application of hydrocyclones to increase floc Mesh coalesce 5
size because hydrocyclones are ineffective for oil diameters of Media filter 5
greater than 10 ␮m [47]. Thus, flotation cells are frequently used Centrifuge 2
Membrane filter 0.01
to complement flocculants, thereby enabling several rounds of
treatment with primary and secondary flocculants. However,
these techniques have no effect on dissolved hydrocarbons, which
often require biological oxidation (e.g., the removal of ammonia high quantities of ultra-pure water to inject high-pressure steam
and BOD) [47]. Therefore, membrane technology represents an and produce heavy crude (<15 API) by heating reservoir rocks to
alternative cost-effective option that can remove small dissolved sweep the oil [128]. Thus, oil sands demand a technology with
organic components in produced water compared to the tradi- the capability of producing ultra-pure water and treating frack-
tional methods shown in Table 17 [127]. With the exception of the ing wastewater, which may be accomplished using membrane
current applications reviewed in this paper, at surface facilities that technology that is specifically designed for this purpose.
use membrane technology to treat produced water for discharge,
the amount of oilfield injection water worldwide is increasing 3.2. Downstream processes
unabatedly to maximize well productivity [119]. Thus, the treat-
ment of injected water through membrane technology is expected In the past, the reuse of produced water in petroleum refineries
to increase rapidly, intensifying the need to conserve seawater or has been limited due to the absence of complete treatment sys-
surface water, which are the primary sources of injection water in tems that can provide high-quality treated wastewater. In contrast,
many cases, not only in the oil production phase of conventional some refineries have employed traditional methods to treat and
oilfields but also at new and unconventional oil sources [51]. Oil reuse municipal wastewater as process water [63]. However, sev-
sand initiatives have fully acknowledged the potential and utility eral technical obstacles were encountered when reusing the treated
of membrane technology because oil sand processing requires water due to the complex content of the municipal wastewater. A

Table 18
Requirements of water quality for water reuse in refining processes.

Description PWa PW-TMWb PW-SWb BFWa CQWa CCWa CRa CWa CWWa PCb

Anions
HCO3 − 480 9 5
Cl− 300 87 35 <1500
F− 1.2 0.4 0.4
NO3 − 10
SO4 2− 600 81 10
Cations
Ca2+ 75 57 10
Mg2+ 30 40
K+Na 230 77 40
Metals
Fea 1.0 0.3 <1 0.05–0.1
Cua <1 <0.015
S <10
Dissolved gases
H2 S Absent Absent
Various parameters
Alkalinity 500 9 5 2000 10 <1
Ammonia 40 0.2 0.04 <3000 <50
Biological solids
Color 25 Absent Absent
Conductivityc 400 100 20 <6000d <1
Hardness 350 97 10 0.1–1 1 <0.02
Odor Absent Absent
Oil 1–2
pH 6–9 7.0–12.0
SiO2 a 60 1.4 0.05 50–150
TDS 1000 238 60 7000 10 <200 <0.5
TSS 10 1–5 <100 <100 <150
Turbidity 3 4 5 <1

Reference [138] [129] [129] [73] [130] [130] [130] [130] [130] [129]

PW: process water; PW-TMW: process water as treated municipal water; PW-SW: process water as seawater; BFW: boiler feedwater (China, USA, and Canada); CQW: coker
quench water; CCW: coke cutting water; CR: condensate return; CW: cooling water; CWW: crude washwater; PC: polished condensate.
a
Unit = mg/L.
b
Unit = mg/L as CaCO3 .
c
Unit = ␮moh/cm.
d
Unit = ␮S/cm.
126 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Fig. 25. Typical configurations for refinery treatment plants [130].

refinery in Los Angeles used reclaimed municipal wastewater for
most of its cooling tower feeds [44]. In contrast, a refinery in the San
Francisco Bay Area used potable water as the source for its refinery
[44]. Both refineries employed traditional water treatment meth-
ods to meet their needs for supply water for cooling towers. The
Torrance Refinery experienced technical challenges in controlling
corrosion and scale formation in its cooling tower systems due to
inefficiencies in the system used, which consisted of chlorination,
dual media filtration with polyelectrolyte addition, dechlorination,
electrodialysis reversal, and two-bed ion exchange [44].
Following similar challenges, Chevron Refinery identified the
potential of reusing produced water instead of consuming fresh-
water, and subsequently employed lime/soda ash softening as a
secondary effluent treatment to produce high-quality water for
reuse in its refinery’s cooling towers, thus avoiding the occurrence
of corrosion, scale formation, and biofouling [44]. These two cases
illustrate the need for advanced technologies for petroleum refiner-
ies, such as membrane technology, to provide effective solutions
to technical challenges in the treatment and reuse of produced
water. Membrane technology is currently being applied for both
process water provision and produced water treatment in sev-
eral oil refineries, as shown in Table 9. However, the possibility
of applying membrane technology in new applications is particu-
larly high in the area of devising integrated membrane technologies
to treat produced water at the source, as opposed to segregating
different types of produced water in a refinery and then sending
the produced water to a central plant for treatment with mem-
brane technology [129]. In this context, the current segregation
and pretreatment practices of some of the produced water types in
refineries do not include membrane technology. The treatment and
management of produced water in petroleum refineries essentially
involves in-plant source control, pre-treatment, and end-of-pipe
treatment [44]. In-plant source control is the reduction of certain
pollutant concentrations before sending the pre-treated water to an
end-of-pipe treatment system. Pre-treatment is the removal of spe-
cific pollutants from produced water before mixing it with the main
produced water stream, wherein the recovery of some contami-
nants may occur. End-of-pipe treatment is the last step for meeting
discharge standards [44]. Different technologies have been applied
in refineries to reduce the amount of produced water and thus
contaminant flow [130]. Therefore, the integration of membrane
technologies in an in-plant source control or pre-treatment pro-
cess is critical for potential applications. Sour water stripping, spent
caustics treatment, ballast water separation, and slop oil recovery

Fig. 26. Comparison of different technologies that are applied in the oil industry and membrane technologies versus type of raw water.
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
Fig. 27. Total capacity of RO membrane technologies in the oil industry versus treated water type (% MGD).
represent four major pre-treatment processes that are applied to
individual wastewater streams at produced water treatment plants
in refineries [44,131]. As reported in previous sections, several stud-
ies [132–134] have detailed the possibility of recovering econom-
ically valuable hydrocarbon compounds that are abundant in sour
water and alkylated wastewater, such as phenol. Recovery can be
performed at an in-plant source, for instance, in the processing and
fractionation of crude oils, where the wastewater generated dur-
ing recirculation or transfer of hydrocarbons to other fractionators
results in produced water being drawn off from overhead accumu-
lators [44]. Similarly, during the separation of produced water from
hydrocarbon vapors in thermal cracking processes, produced water
can also be generated from the overhead accumulator on the frac-
tionator. In catalytic cracking units, the recovery and separation of
various hydrocarbon fractions produced in catalytic reactors gen-
erates sour water in the steam strippers and high amounts of pollu-
tants, especially phenols, in the overhead accumulators on fraction-
ators [44]. In hydrocracking, in which the sulfur content of crude
samples are reduced, the produced water stream contains dissolved
H2 S, phenols, and ammonia, and current technologies applied to
these waste-streams include stripping with steam, the use of flue
gas, or air oxidation [44]. Thus, membrane technology may be inte-
grated as part of a special pre-treatment step, and numerous studies
have focused on this topic. This integration can be highly effective
127
in cleaning produced water for reuse during refining processes that
require low-quality water (Table 18) or in the reduction and recov-
ery of certain amounts of pollutants before end-of-pipe treatment
[131]. For example, the phenol concentration of sour water ranged
from 200 to 400 mg/L [60]. Thus, as previously noted, utilizing
membranes to recover phenols represents a promising application.
Membrane technology is currently being used for this purpose in
a number of facilities to recover gases [4]; however, it is not being
implemented for produced water contents. In addition to the afore-
mentioned application, membrane-integrated pre-treatments are
being considered for produced water when crude wash processes
are utilized [44]. Similarly, the following opportunities describe
some of the potential future applications of membrane technol-
ogy in refinery processes. In steam systems, the potential exists
for applying membrane technology to treat (i) boiler blowdown
wastewater for return to the boiler feedwater supply rather than
discharging it to the treatment plant, (ii) non-contact steam con-
densate to be reused as boiler feedwater, and (iii) contaminated
steam condensate to supply the necessary washwater for crude
desalting or in alkylation solutions [128]. Such treatment steps may
be achieved by integrating membrane technology instead of dis-
charging the produced water to a treatment plant. In end-of-pipe
treatment, all streams of produced water generated from differ-
ent refining processes are collected and treated for discharge [44].
128 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133

Fig. 28. Comparison of the geographical distribution and applied technologies used for process water and produced water treatment in the petroleum industry and NF and
RO membrane technologies.

The current application of membrane technology is the final stage treatment processes in the petroleum refining industry [130]. An
of produced water treatment, as depicted in Fig. 25. Primary and attempt to standardize the integration of membrane technology
secondary oil-water separation, followed by biological and tertiary for this process would be difficult because each petroleum refinery
treatments, is typically applied in contemporary produced water has a different configuration and different unit treatment processes

Fig. 29. Timeline of different installed technologies in the oil industry for treatment and desalination process water and produced water (detailed in Fig. 26).
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
Fig. 30. Comparison of the total capacities for conventional technologies applied in the oil industry and NF and RO membranes for desalination and treatment versus output
water.
[131]. Generally, appropriate future applications of membrane
technology in this area would depend mainly on the additional effi-
ciency of any applied membrane pre-treatment step. Thus, conven-
tional membrane technology is well positioned to become the final
step in produced water treatment. To reiterate a key finding from
this section, current membrane technology has the greatest poten-
tial for use in the final stages of produced water treatment (viz.,
as a post-treatment or tertiary treatment). The complexity of pro-
duced water content requires multiple pre-treatment steps before
being fed to membranes, which is why membrane technologies as
standalone methods for produced water treatment may not show
sufficient efficiency. Thus, UF and RO membranes are optimal can-
didates for pre-and post-treatment, followed by membrane biore-
actors, to be used for treatment at future petroleum refineries [130].
Table 17 presents a comparison between such traditional tech-
nologies currently applied in petroleum refineries and membrane
technologies [127]. As shown, membrane technology is capa-
ble of removing very small dissolved oil and grease particulates
(<0.01 ␮m). Furthermore, recent membrane technologies, such as
NF and RO membranes, are more effective at removing dissolved
ions and small organic particulates compared to the traditional
technologies listed in Table 17 [130]. The demand for membrane
technologies to be applied as post-treatment steps in refineries
may increase with the increasingly stringent discharge standards.
Refineries that have taken strides in reusing treated produced water
as process water have quickly learned that optimizing the per-
formance of current applications first requires understanding the
quality requirements of the water to be reused (Tables 15 and 18).
For example, to reuse treated produced water or raw process water
from desalter units during crude washing processes in refiner-
ies, the concentrations of sulfate, ammonia, and TDS in the water
stream must be less than 10, 50, and 200 mg/L, respectively [130].
These values can be achieved using membrane technology. Sim-
ilarly, preparing quenched water, which is used to reduce the
temperature during refining processes, also has certain quality
requirements, such as a TSS concentration of greater than 100 mg/L
and non-detectable concentrations of BOD and H2 S [130]. In this
129
case, membrane technology can be integrated with degasification
units to meet these standards. Similarly, for cooling towers, pro-
duced water treated through membrane technology may meet the
allowable limits for the quality of cooling water which are as fol-
lows: a conductivity of <6000 ␮S/cm, an alkalinity <3000 mg/L,
a chloride concentration <1500 mg/L, and a TSS concentration
<150 mg/L [130]. These concentration levels can be met by utilizing
a combination of membrane types to treat produced or raw pro-
cess water. Therefore, the membrane research community should
consider the membrane units associated with pre-treatment steps
as hybrid technologies that can be integrated to address the spe-
cific source of wastewater in those refining processes (viz., in-plant
source control). Additional studies focusing on this topic are nec-
essary.
4. Current trends and future perspectives
The implementation of membrane technology in the petroleum
industry for produced water indicates the significant potential for
future wide-scale adoption, although the number of current appli-
cations worldwide is still considered insufficient against 700,000
existing active oil wells and 655 oil refineries (Fig. 26) [119].
A review of several studies conducted to reuse produced water
through membrane technologies has resulted in the timeline of
selected current applications presented in Fig. 20, with most
applications beginning in 2000 [55]; this emphasis has continued
throughout the last decade. At an industrial level, when comparing
the capacity of RO plants in the global desalination industry with
the capacity of NF and RO membrane applications applied in the
petroleum industry, the latter processes 1.57 million m3 /d versus
39 million m3 /d in the desalination industry (Fig. 27) [135,136]. This
finding was obtained from the analysis of 268 applications that
used five different technologies to treat process water and pro-
duced water in the petroleum industry in 32 countries (Fig. 28). A
comparison of their timelines (Fig. 29) indicated that from 1954 to
2014, RO membranes were used in 150 applications for multi-effect
distillation (44 applications), multi-stage flash (63 application),
130 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
Fig. 31. Geographical distribution of the implementation of RO membrane technology in the oil industry versus output water and the number of RO membrane technology
applications in different countries.
electrodialysis (10 applications), and hybrid technology processes
(1 application). This timeline indicates that RO membrane tech-
nology implementation has been increasing in recent decades
(Fig. 30) [136]. In contrast, the capacity (MGD) of NF and RO tech-
nologies utilized for process water and produced water treatment
have dominated the field, constituting 78% of applications (Fig. 30)
[136]. Most of the membrane technology implementations in the
petroleum industry are in oil-producing countries (Fig. 31) and
are mainly directed to the treatment of process water or injection
water originating from brackish water (inland water), brine (con-
centrated seawater), river water (low concentrated saline water),
and produced water (Fig. 27) [136]. Overall, as the global demand
for water increases, fresh water resources continue to be depleted
and increasing environmental awareness continues to drive new
regulatory discharge standards, the petroleum industry is com-
pelled to modify their strategies for produced water management.
Particular attention will be given to membrane technologies, and
current trends indicate that the desire for membrane technology
will expand as contemporary produced water management prac-
tices shift their focus from discharge and re-injection to reducing,
reusing, and recycling.
5. Conclusions
Membrane technology implementation in the petroleum indus-
try is in its infancy. Current applications of membrane technologies
have demonstrated their high potential for meeting the petroleum
industry’s needs and their feasibility for treating produced water.
The major functions of membrane technology for produced water
treatment are driven by environmental regulations and the require-
ment to meet strict reuse standards for beneficial applications and
re-injection in disposal wells. The findings of this review indi-
cate that despite the success of current membrane technology
applications, several challenges persist, such as membrane fouling,
which occurs due to the complex contaminants in produced water,
including organic matter, scale compounds, boron and silica, and
the absence of standard cleaning procedures. Ongoing research to
mitigate these challenges has suggested solutions, including suffi-
cient pre-treatment steps, the modification and development of
novel membrane materials, and the use of nano-sized particles
to construct membranes and optimize cleaning procedures. These
solutions have optimized the performance the production of anti-
fouling membranes and the development of new cleaning agents.
The current trends in membrane technology applications in the
petroleum industry indicate that the need for membrane tech-
nology will continue to grow, as contemporary produced water
management practices have shifted their focus from discharge
and re-injection to reducing, reusing, and recycling. Thus, oil pro-
ducers and petroleum refineries are being compelled to change
their strategies for produced water management, and much atten-
tion is shifting to membrane technologies. The future trends in
membrane technology clearly show that the potential of novel
membrane applications is particularly great in the area of devis-
ing integrated membrane technologies to treat produced water at
its source in contrast to post facto segregation by type and sub-
sequent membrane treatment in a central plant. Thus, the use of
membrane technology in these potential applications may signif-
icantly reduce this global cost and generate a sufficient amount
of water for resource sustainability. Thus, future efforts of the
membrane research community should shift their focus from appli-
cations to research and development in order to generate more
patented processes for widespread adoption. For such initiatives,
the advancement of current membrane applications requires (i) a
standard reference for produced water and fracking wastewater
composition, developed through comprehensive characterization
with respect to all natural and anthropogenic sources of contam-
ination. Additionally, (ii) the contribution of chemical additives in
discharged water to fouling membranes should be investigated.
Foulants in produced water differ from those in municipal waste-
water, which is being extensively studied. (iii) Most academic
studies and industrial solutions regard produced water as a pol-
lution source after being brought to the surface from oilfields in
upstream processes or when generated from oil refineries in down-
stream processes. A creative solution for minimizing the generation
of produced water or fracking wastewater may be preventing such
wastewaters from being brought to the surface by integrating
membrane technology. Furthermore, (iv) membrane technology is
currently being applied to produce post-treated water in oil refiner-
ies. Potential new membrane technology applications include the
development of integrated membrane technologies to treat pro-
duced water at its source, as opposed to segregating different types
of produced water in a refinery and then sending these streams to a
central plant for treatment with membrane technology. Therefore,
extensive research is necessary to achieve zero liquid discharge by
recycling treated produced water within refinery processes that
require low water quality levels, such as water for crude wash-
ing, quench water, and service water. Finally, (v) there is immense
potential for the recovery of by-products from produced water; one
such by-product is lithium, which is considered an essential ele-
ment in power generation. Future research in this area using liquid
membranes is recommended. Thus, membrane technology distinc-
tive, promising solution for treating produced water while meeting
 S. Alzahrani, A.W. Mohammad / Journal of Water Process Engineering 4 (2014) 107–133
discharge standards, yielding reusable water, and conserving scarce
water resources for sustainable development.
Acknowledgment
This project was supported by NSTIP strategic technologies pro-
grams (number 12-WAT2623-02) in the Kingdom of Saudi Arabia.
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