Advanced Technologies

for Produced-Water Treatment and Reuse

H istorically, the treatment of

produced water (PW) has been
limited to free-oil and suspended-solids
removal, using physical separation
technologies and injection in disposal
wells. However, because of new
regulations, combined with geological
restrictions and local water scarcity, the
drive to have a greater fraction of the PW
treated more extensively and ultimately
to be reused is increasing. This paper
presents the results of a laboratory
investigation in which treatment
processes were evaluated as treatment
methods for PW from different oil and
gas fields.
Introduction
A combination of factors is putting great
pressure on operators to find new ways
of treating and managing PW that pro-
mote water conservation and sustain-
ability. However, treating PW to produce
a good-quality effluent is a challeng-
ing task. PW characteristics can vary
considerably. In order to treat PW to a
water-quality standard that enables it
to be reused, advanced water-treatment
technologies (AWTTs) have to be applied,
alone or in combination.
To investigate the suitability of sev-
eral AWTTs to treat and reuse PW from
Qatari gas fields, the authors, in con-
junction with an operator’s research
center, carried out a laboratory investi-
gation in which various treatment pro-
cesses were evaluated. Four treatment
methods were selected to target main
contaminants identified in PW from a
Qatari gas field: Membrane process-
This article, written by JPT Technology Editor Chris Carpenter, contains highlights
of paper IPTC 17394, “Advanced Technologies for Produced-Water Treatment
and Reuse,” by A. Hussain, J. Minier-Matar, A. Janson, S. Gharfeh, and S.
Adham, ConocoPhillips, prepared for the 2014 International Petroleum Technology
Conference, Doha, Qatar, 20–22 January. The paper has not been peer reviewed.
es were used to target field chemicals,
membrane-distillation (MD) methods
were used to target salinity, membrane-
bioreactors (MBRs) were used to target
organics, and ozonation was used to tar-
get field chemicals.
Overview of AWTTs
Membrane Processes. The potential for
membrane processes to treat PW has
been demonstrated successfully in vari-
ous field studies; moreover, a number
of upstream petroleum full-scale facil-
ities have already installed membrane
processes to treat and reuse PW. The
treatment trains either are a combina-
tion of different membrane processes
or involve other conventional water-
treatment technologies such as media
filtration or clarification. For two case
studies involving the use of membrane
processes, please see the complete paper.
Thermal Evaporators. These entered
the PW-treatment market by finding
niche opportunities. Moreover, because
almost all waste streams are recycled
back to the evaporator, the volumes of
fresh water required for makeup are dra-
matically reduced.
With the proliferation of shale-gas
wells in the past decade in the US, the de-
mand for treating flowback water with
total-dissolved-solids (TDS) concentra-
tions greater than 100 000 mg/L has
expanded the opportunities for ther-
mal systems. Another niche market in
which the application of evaporators
has been very successful is the steam-
assisted-gravity-drainage enhanced-
recovery process.
MBRs. MBRs are now considered by
the downstream petroleum industry
as an excellent solution to treat vari-
ous wastewater streams. Although MBRs
have not yet been applied to treat PW at
upstream oil and gas facilities, a num-
ber of bench-scale and pilot studies re-
port that PW is biodegradable, achiev-
ing chemical-oxygen-demand (COD) and
oil-and-grease (O&G) removals greater
than 95%. Moreover, full-scale MBRs
are also operating successfully in other
industries, treating highly contaminat-
ed organic streams (COD greater than
15 000 mg/L) and achieving COD remov-
als greater than 95%.
Advanced Oxidation Processes
(AOPs). As is the case with MBRs, there
is limited information on AOPs being
applied to treat PW in full-scale facili-
ties. One of the few studies assessed
a combination of ozone/ultraviolet/
titanium dioxide to treat PW with
38-g/L salinity; COD and O&G remov-
als of 74  and 95%, respectively, were
achieved after a 30-minute contact pe-
riod. After a 60-minute contact period,
COD removal increased to 89%. Pub-
lished research investigating refinery-
effluent treatment with AOPs appears to
be more common.
Some of these studies assessed a
number of different AOPs and conclud-
ed that the Fenton reaction was able to
achieve excellent organic removals. Ad-
ditionally, some companies have devel-
oped AOP-based patented technologies
with successful applications in the chem-
ical, petrochemical, and pharmaceutical
industries; COD removals of greater than
90% were obtained for systems with
CODs of 1 000 to 10 000 mg/L.
Despite the evidence that AOPs
may be successful in treating PW, the
upstream petroleum industry has yet
to benefit from the many opportunities
these processes offer.

For a limited time, the complete paper is free to SPE members at www.spe.org/jpt.

JPT • DECEMBER 2014 131

 Investigation of Various
Methods To Treat and Reuse PW
Membrane Processes. The effective-
ness of ultrafiltration (UF), nanofiltra-
tion (NF), and reverse-osmosis (RO)
membranes in rejecting kinetic hydrate
inhibitor (KHI) was investigated by use
of a test cell. The membranes were test-
ed with a solution of 1.5-wt% KHI pre-
pared in a synthetic-brine solution with
a TDS concentration of approximately
6 000 mg/L. The objective of the experi-
ment was to analyze KHI rejection for
different membranes.
MD. The PW collected from the Qatari
fields was high in salinity. The abil-
ity  of MD to treat high-salinity feed
waters can make it suitable for reduc-
ing the salinity of PWs. To investigate
further, the research team initiated an
extensive testing program in which
various solutions with salinities compa-
rable to those of PWs were tested with
an  MD direct- contact-configuration
test cell.
Various saline streams [synthet-
ic sodium chloride (NaCl) solutions,
seawater, and brine from a thermal-
desalination plant] were tested under
different operating conditions and using
different membranes. Salt rejection was
assessed by measuring conductivity and
TDS in the feed and product water.
MBRs. PW also contains soluble organ-
ics in various forms, including hydro-
carbons, organic acids, and KHI (during
the winter season). To assess the poten-
tial of the MBR process for removing
organics, tests were conducted both in
batch reactors and in an MBR, each of
1-L working volume. The effect of salin-
ity on biotreatability of PW was assessed
over the range of salinities from 6 000
to 31 750 mg/L. Biotreatability was cal-
culated on the basis of total-organic-
carbon (TOC) mass balances and is re-
ported as percent TOC removal. To
assess the biotreatability of KHI, the
batch bioreactor was fed with 0.25%
KHI (initial tests) or 1.5% KHI (later
tests) added to a standardized brine
solution mimicking the inorganic con-
tent of PW. In this way, the biotreat-
ability of KHI could be measured di-
rectly. Biotreatability was calculated
on the basis of both COD and TOC
mass balances and is reported as per-
cent removal.
In a third investigation, an MBR
was fed with PW collected from a differ-
ent location in the plant. This PW was
lower in both salinity and organics than
that used for the salinity experiments.
After acclimation, for 5 weeks under
steady-state conditions, biotreatability
was measured through COD mass bal-
ances and reported as percent COD re-
moval. The MBR effluent was also treat-
ed with a downstream RO process in
order to generate an effluent that can be
reused for multiple applications.
Ozonation. The removal of KHI in a
synthetic-brine solution with a TDS con-
centration of approximately 6000 mg/L
was tested by use of an ozone generator
that bubbled ozone into a 1-L column.
The ozone concentrations at the inlet
and outlet were monitored continuously
with an ozone detector. The KHI solu-
tion was ozonated for 0.5, 1.5, 3, and 4
hours to evaluate ozonation as a func-
tion of time. The removal of KHI was as-
sessed by calculating the percent of KHI
oxidized and by measuring cloud point.

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132 JPT • DECEMBER 2014

Results 40
Membrane Processes. A Toray brackish- NaCl 100 mg/L
water RO membrane was used in the tests. 35 NaCl 35 000 mg/L
NaCl 70 000 mg/L
Initially, the membrane was compacted
30 NaCl 100 000 mg/L
with 10 g/L of NaCl at 500 psi, achiev-

Distillate Flux (LMH)

ing a stable flux of 10 L/m2/h (LMH) after
14 hours. The synthetic brine solution
containing 1.5% KHI was tested for 22
hours, with the operating pressure kept
at 590 psi. Throughout the test, the flux
decreased from 15 to 10.5 LMH. At the
end of the test, the solution of NaCl at
10 g/L was introduced through the sys-
tem at 500 psi and the permeate flux
was 9 LMH, which confirmed that the
membrane can be restored to its origi-
nal compaction condition (10 LMH). The
KHI polymer was removed completely by
the RO membrane (99.9% rejection). For
a discussion of similar test results seen
with NF and UF membranes, please see
the complete paper.
MD. The initial tests were performed
with NaCl solutions prepared in deion-
ized water, using a single membrane
(Membrane E). Fig. 1 shows that flux re-
mained relatively constant at approxi-
mately 25 LMH when testing NaCl solu-
25
20
15
Membrane E
Hot-side temperature: 70°C
10 Cold-side temperature: 30°C
5
0
0 50 100 150 200 250 300
Time (minutes)
Fig. 1—Results of MD tests on NaCl solutions (Membrane E).
tions of 0.1–35 g/L. However, when the Tests on seawater collected from
salt concentration was increased above the Arabian Gulf offshore Qatar were
70 g/L, a slight drop in flux was ob- conducted with five different MD mem-
served (20 LMH), which may be related branes. Although the initial flux was sim-
to vapor-pressure variations and differ- ilar, all membranes showed a drop in flux
ence in water viscosity that could impact with time, with the exception of Mem-
the thermal conditions at the membrane brane B (Fig. 2). This flux decline was
boundary layer. not observed when the membranes were

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 40
Under the Patronage of Membrane A
Membrane B
His Royal Highness 35 Membrane C
Prince Khalifa bin Salman Al Khalifa Membrane D
Membrane E
Prime Minister of 30

Distillate Flux (LMH)

the Kingdom of Bahrain
25

20
Hot-side temperature: 70°C
Cold-side temperature: 30°C
15 Seawater

10

0
0 200 400 600 800 1,000 1,200 1,400 1,600
Time (minutes)
Fig. 2—Results of MD tests on seawater from the Arabian Gulf (Membranes A,
B, C, D, and E).

tested on NaCl solutions. It should be “maintenance” or “soak” cleaning was

noted that no antiscalant was added to
the seawater and the pH was not adjust-
ed before testing. The TDS rejection by
all membranes was greater than 99.99%.
For a discussion of experimen-
tal results using brine collected from a
local full-scale thermal-desalination
19th Middle East Oil & Gas plant operating in Qatar, please see the
Show and Conference complete paper.
BAHRAIN INTERNATIONAL EXHIBITION
AND CONVENTION CENTRE MBRs. Salinity. The salinity of the biore-
actor was gradually increased from 6400
to 31 750 mg/L over an 8-week testing
CONFERENCE: 8-11 March 2015 period. The daily percent TOC removals
fluctuated between 40 and 80%, averag-
ing 65%, over the entire range of salini-
EXHIBITION: 9-11 March 2015 ties. There was no significant effect of
salinity on percent TOC removal over this
range of salinities.
KHI. Because all the organics pres-
ent in the feed were attributed to KHI,
the percent COD-removal results direct-
ly reflect the biotreatability of KHI. The
CONFERENCE EXHIBITION results indicate that, over the 7-week test
ORGANISERS ORGANISERS
period, 50–60% of the COD associated
with KHI is removed through biotreat-
fawzi@aemallworld.com
ment. The percent removal was similar
dubprog@spe.org at low and high KHI concentrations.
MBR. The percent COD removal
WORLDWIDE FAR EAST
COORDINATORS COORDINATORS
over the 5 weeks of steady-state test-
ing indicates that 63% of the COD could
be removed through biotreatment. The
meos@oesallworld.com gerald@iemallworld.com UF flux remained excellent over the en-
tire testing period, and no intermediate
required. In the post-treatment experi-
ments with RO, as expected, the efflu-
ent produced was excellent, with greater
than 98% removal of both the COD and
inorganics. The effluent would be suit-
able for recycle or reuse within the gas-
processing facility. Although the RO flux
on MBR effluent was lower than the pre-
test benchmark-water flux, upon com-
pletion of the RO tests, a simple flush of
the system with tap water restored the
flux to the pretest level, indicating that
there was no irreversible fouling of the
RO membrane.
Ozonation. The KHI solution was ozon-
ated for 0.5, 1.5, 3, and 4 hours to eval-
uate ozonation as a function of time.
KHI removal of 11, 60, and 75% was ob-
tained with ozonation times of 1.5, 3,
and 4 hours, respectively. An ozonation
time of 0.5 hours did not remove any of
the KHI in the synthetic-brine solution.
The results clearly show that the effec-
tiveness of ozonation in oxidizing KHI
is dependent upon the contact time; sig-
nificant removals (75%) can be achieved
given the necessary contact time. The
cloud point also varied with contact time.
Visual examination of the treated effluent
indicated that the treated effluent was
turbid after ozonation. However, after
filtration through a 0.45-μm filter, the
treated effluent solution was clear. JPT

www.meos2015.com
JPT • DECEMBER 2014