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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
es were used to target field chemicals,
membrane-distillation (MD) methods
were used to target salinity, membrane-
MBRs. MBRs are now considered by
the downstream petroleum industry
as an excellent solution to treat vari-
removal, using physical separation bioreactors (MBRs) were used to target ous wastewater streams. Although MBRs
technologies and injection in disposal organics, and ozonation was used to tar- have not yet been applied to treat PW at
wells. However, because of new get field chemicals. upstream oil and gas facilities, a num-
regulations, combined with geological ber of bench-scale and pilot studies re-
restrictions and local water scarcity, the Overview of AWTTs port that PW is biodegradable, achiev-
drive to have a greater fraction of the PW Membrane Processes. The potential for ing chemical-oxygen-demand (COD) and
treated more extensively and ultimately membrane processes to treat PW has oil-and-grease (O&G) removals greater
to be reused is increasing. This paper been demonstrated successfully in vari- than 95%. Moreover, full-scale MBRs
presents the results of a laboratory ous field studies; moreover, a number are also operating successfully in other
investigation in which treatment of upstream petroleum full-scale facil- industries, treating highly contaminat-
processes were evaluated as treatment ities have already installed membrane ed organic streams (COD greater than
methods for PW from different oil and processes to treat and reuse PW. The 15 000 mg/L) and achieving COD remov-
gas fields. treatment trains either are a combina- als greater than 95%.
tion of different membrane processes
or involve other conventional water- Advanced Oxidation Processes
Introduction treatment technologies such as media (AOPs). As is the case with MBRs, there
A combination of factors is putting great filtration or clarification. For two case is limited information on AOPs being
pressure on operators to find new ways studies involving the use of membrane applied to treat PW in full-scale facili-
of treating and managing PW that pro- processes, please see the complete paper. ties. One of the few studies assessed
mote water conservation and sustain- a combination of ozone/ultraviolet/
ability. However, treating PW to produce Thermal Evaporators. These entered titanium dioxide to treat PW with
a good-quality effluent is a challeng- the PW-treatment market by finding 38-g/L salinity; COD and O&G remov-
ing task. PW characteristics can vary niche opportunities. Moreover, because als of 74  and 95%, respectively, were
considerably. In order to treat PW to a almost all waste streams are recycled achieved after a 30-minute contact pe-
water-quality standard that enables it back to the evaporator, the volumes of riod. After a 60-minute contact period,
to be reused, advanced water-treatment fresh water required for makeup are dra- COD removal increased to 89%. Pub-
technologies (AWTTs) have to be applied, matically reduced. lished research investigating refinery-
alone or in combination. With the proliferation of shale-gas effluent treatment with AOPs appears to
To investigate the suitability of sev- wells in the past decade in the US, the de- be more common.
eral AWTTs to treat and reuse PW from mand for treating flowback water with Some of these studies assessed a
Qatari gas fields, the authors, in con- total-dissolved-solids (TDS) concentra- number of different AOPs and conclud-
junction with an operator’s research tions greater than 100 000 mg/L has ed that the Fenton reaction was able to
center, carried out a laboratory investi- expanded the opportunities for ther- achieve excellent organic removals. Ad-
gation in which various treatment pro- mal systems. Another niche market in ditionally, some companies have devel-
cesses were evaluated. Four treatment which the application of evaporators oped AOP-based patented technologies
methods were selected to target main has been very successful is the steam- with successful applications in the chem-
contaminants identified in PW from a assisted-gravity-drainage enhanced- ical, petrochemical, and pharmaceutical
Qatari gas field: Membrane process- recovery process. industries; COD removals of greater than
90% were obtained for systems with
CODs of 1 000 to 10 000 mg/L.
This article, written by JPT Technology Editor Chris Carpenter, contains highlights Despite the evidence that AOPs
of paper IPTC 17394, “Advanced Technologies for Produced-Water Treatment may be successful in treating PW, the
and Reuse,” by A. Hussain, J. Minier-Matar, A. Janson, S. Gharfeh, and S. upstream petroleum industry has yet
Adham, ConocoPhillips, prepared for the 2014 International Petroleum Technology to benefit from the many opportunities
Conference, Doha, Qatar, 20–22 January. The paper has not been peer reviewed. 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 desalination plant] were tested under mass balances and is reported as per-
Methods To Treat and Reuse PW different operating conditions and using cent removal.
Membrane Processes. The effective- different membranes. Salt rejection was In a third investigation, an MBR
ness of ultrafiltration (UF), nanofiltra- assessed by measuring conductivity and was fed with PW collected from a differ-
tion (NF), and reverse-osmosis (RO) TDS in the feed and product water. ent location in the plant. This PW was
membranes in rejecting kinetic hydrate lower in both salinity and organics than
inhibitor (KHI) was investigated by use MBRs. PW also contains soluble organ- that used for the salinity experiments.
of a test cell. The membranes were test- ics in various forms, including hydro- After acclimation, for 5 weeks under
ed with a solution of 1.5-wt% KHI pre- carbons, organic acids, and KHI (during steady-state conditions, biotreatability
pared in a synthetic-brine solution with the winter season). To assess the poten- was measured through COD mass bal-
a TDS concentration of approximately tial of the MBR process for removing ances and reported as percent COD re-
6 000 mg/L. The objective of the experi- organics, tests were conducted both in moval. The MBR effluent was also treat-
ment was to analyze KHI rejection for batch reactors and in an MBR, each of ed with a downstream RO process in
different membranes. 1-L working volume. The effect of salin- order to generate an effluent that can be
ity on biotreatability of PW was assessed reused for multiple applications.
MD. The PW collected from the Qatari over the range of salinities from 6 000
fields was high in salinity. The abil- to 31 750 mg/L. Biotreatability was cal- Ozonation. The removal of KHI in a
ity  of MD to treat high-salinity feed culated on the basis of total-organic- synthetic-brine solution with a TDS con-
waters can make it suitable for reduc- carbon (TOC) mass balances and is re- centration of approximately 6000 mg/L
ing the salinity of PWs. To investigate ported as percent TOC removal. To was tested by use of an ozone generator
further, the research team initiated an assess the biotreatability of KHI, the that bubbled ozone into a 1-L column.
extensive testing program in which batch bioreactor was fed with 0.25% The ozone concentrations at the inlet
various solutions with salinities compa- KHI (initial tests) or 1.5% KHI (later and outlet were monitored continuously
rable to those of PWs were tested with tests) added to a standardized brine with an ozone detector. The KHI solu-
an  MD direct- contact-configuration solution mimicking the inorganic con- tion was ozonated for 0.5, 1.5, 3, and 4
test cell. tent of PW. In this way, the biotreat- hours to evaluate ozonation as a func-
Various saline streams [synthet- ability of KHI could be measured di- tion of time. The removal of KHI was as-
ic sodium chloride (NaCl) solutions, rectly. Biotreatability was calculated sessed by calculating the percent of KHI
seawater, and brine from a thermal- on the basis of both COD and TOC 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 25
containing 1.5% KHI was tested for 22
hours, with the operating pressure kept 20
at 590 psi. Throughout the test, the flux
15
decreased from 15 to 10.5 LMH. At the Membrane E
end of the test, the solution of NaCl at Hot-side temperature: 70°C
10 Cold-side temperature: 30°C
10 g/L was introduced through the sys-
tem at 500 psi and the permeate flux
5
was 9 LMH, which confirmed that the
membrane can be restored to its origi- 0
nal compaction condition (10 LMH). The 0 50 100 150 200 250 300
KHI polymer was removed completely by Time (minutes)
the RO membrane (99.9% rejection). For
a discussion of similar test results seen Fig. 1—Results of MD tests on NaCl solutions (Membrane E).
with NF and UF membranes, please see
the complete paper. 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
MD. The initial tests were performed 70 g/L, a slight drop in flux was ob- conducted with five different MD mem-
with NaCl solutions prepared in deion- served (20 LMH), which may be related branes. Although the initial flux was sim-
ized water, using a single membrane to vapor-pressure variations and differ- ilar, all membranes showed a drop in flux
(Membrane E). Fig. 1 shows that flux re- ence in water viscosity that could impact with time, with the exception of Mem-
mained relatively constant at approxi- the thermal conditions at the membrane brane B (Fig. 2). This flux decline was
mately 25 LMH when testing NaCl solu- boundary layer. not observed when the membranes were

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JPT • DECEMBER 2014 133


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

www.meos2015.com
JPT • DECEMBER 2014