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Abstract
Produced Water (PW) is the highest volume liquid waste stream generated by the petroleum industry. Historically, the
treatment of 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 more extensively treated and ultimately reused is increasing. Moreover, the growth in the
application of water intensive processes to extract unconventional oil&gas resources, in particular in shale plays and oil
sands, has increased the need for cost-effective treatment and reuse of PW to reduce fresh water uptakes.
Therefore, the petroleum industry is investigating new PW treatment technologies given that the physical separation
technologies traditionally used in the past are, in most cases, not capable of producing water of suitable quality to replace
fresh water uptakes.
This paper presents the results of a laboratory investigation carried out by the ConocoPhillips Global Water Sustainability
Center (GWSC), where various treatment processes (membrane processes, membrane-bioreactors (MBRs), membrane
distillation (MD) and ozonation) were evaluated as treatment methods for PW from different oil&gas fields.
The key conclusions of this paper are:
Membrane Processes and Thermal Evaporators are currently operating within the petroleum industry in full scale
PW treatment and reuse applications.
The preliminary results of investigations performed by GWSC confirmed the potential of Membrane Filtration,
MBRs and Ozonation to treat PW and produce an effluent suitable for reuse. Membrane Distillation may have
potential in the longer term. Further investigation is ongoing.
If successfully implemented, the above technologies will contribute to provide the petroleum industry with a
broad range of technologies to cost-effectively treat and reuse PW.
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1. Introduction
Produced Water (PW) is the highest volume liquid waste stream generated by the petroleum industry. The American
Petroleum Institute (API) estimated that in 1995, 18 billions of barrels of PW were generated in the US only from onshore
facilities [1]. Figures published in 2011 [2] and 2007 [3] show that globally, between 70 and 100 billion barrels of PW
were generated in 2007. The same report also projected a steady increase in PW generated in the US until 2025.
Currently, the majority of PW generated worldwide at onshore facilities is re-injected into the soil in disposal wells
and therefore, the treatment facilities are mostly designed to remove dispersed oil and grease (O&G) and suspended solids
(SS), to avoid formation plugging. In offshore operations, because the common practice is to discharge the treated PW to
sea, the main treatment objective is to reduce O&G to acceptable levels and mitigate toxicity impacts on aquatic fauna
and flora. As a consequence, the PW treatment methods applied in the petroleum industry are historically limited to
physical separation technologies such as the API separator, coalescers or hydrocyclones. These technologies are, in most
cases, not capable of producing an effluent compatible with water quality standards for beneficial recycling in the
petroleum industry itself or reuse in, for example, irrigation or other industrial processes.
A combination of factors including new regulations, geological restrictions and local water scarcity, is putting
enormous pressure on the petroleum industry operators to find new ways of treating and managing PW that promotes
water conservation and sustainability. As an example, Canadian oil sands operators using > 500,000 m3 of water per year
have to treat and recycle 75-90% of the PW generated. In 2008 for instance, mining operations in Canada withdrew 151
million m3 of fresh water from rivers [2]. Furthermore, for fracturing operations in shale gas fields, large volumes of
water (as high as 15,000 m3/well) are also required to drill the wells and to make up the fracturing liquids [4]. With
proper treatment, there is an opportunity for treated PW and flowback water to replace these significant volumes of water
extracted from lakes, rivers and aquifers in production operations.
Increasing efforts are being developed by the petroleum industry to develop and adopt advanced technologies that are
capable of further treating PW to produce an effluent compatible with water quality standards for beneficial reuse. This
will ultimately lead to significant water conservation benefits in several growing oil and gas key sectors:
Where PW is currently being injected in wells, the injection volumes will be reduced, diminishing environmental
impacts;
If wastewaters generated in water-intense operations (e.g. unconventional and oil sands resources) are treated and
reused, it will dramatically reduce the volumes of fresh water required;
There is growing evidence that enhanced oil recovery may become more efficient and productive if the injected
water is treated with advanced technologies to meet specific salinity levels.
However, treating PW and producing a good quality effluent is challenging. PW characteristics can vary considerably.
For instance, Total Dissolved Solids (TDS) can vary from >100,000 mg/L in Flowback waters from shale gas wells to less
than 3,000 mg/L in PWs from coal bed methane (CBM) wells [5,6]. However, as a broad generalization the constituents
that offer the greatest concerns from a treatment standpoint are organic content (in particular dissolved fraction) and
salinity. Also, PW from gas fields tend to have higher concentrations of low molecular weight aromatic hydrocarbons
than PW from oil fields, making these significantly more toxic [2]. Therefore, 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 combinations.
This paper discusses some of the AWTTs that are being applied in full scale oil and gas operations to treat and reuse
PW, or have the potential to do so. The technologies discussed are:
Membrane Processes (Microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF) and Reverse Osmosis
(RO));
Thermal Evaporator;
MBRs - Organics
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2. Research Conducted
2.1 Overview of AWTTs to treat and reuse PW
The first part of the paper reports case studies demonstrating the application of AWTTs in full scale oil and gas operation
facilities to treat and reuse PW. It also discusses some of the AWTTs that, although not yet applied, have to the potential
to treat PW in full scale operations.
2.1.1 Membrane Processes
The potential for membrane processes to treat PW has been successfully demonstrated in various field studies [7,8,9].
Moreover, a number of upstream petroleum full scale facilities (e.g. oil fields [2], CBM wells [10]) have already installed
membrane processes to treat and reuse PW. The treatment trains are either a combination of different membrane processes
(e.g. MF or UF + RO) or in combination with other conventional water treatment technologies such as media filtration or
clarification. UF & MF present several advantages over conventional media filters and clarifiers for SS and O&G removal
in PW.
Case study - San Ardo Oil Field, US[2]
The San Ardo PW treatment facility in California is considered the first large scale application of RO to treat PW.
Historically, the PW was disposed via deep well injection. However, the PW volumes generated in the field exceeded the
capacity of the disposal wells and the decision was made to install a system to treat and reuse the PW. The OPUSTM
process was installed in 2008 with an installed capacity of 50,000 bbd of PW. The PW generated in the field presented
significant challenges such as high levels of organics and silica. The treatment system was able to overcome these
challenges and the treated PW is now reused for aquifer recharge.
Case study - Arroyo Grande Oilfield, US [2]
The Arroyo Grande Oil field utilizes OPUS - II process for desalination of PW. This facility uses ceramic membrane in
the pretreatment stage before ion-exchange and reverse osmosis. The facility produces 45,000 barrels per day of water.
Over half of the treated water is used for once through steam generation, while the remaining 20,000 bpd capacity is
available as surface-water discharge.
2.1.2 Thermal Evaporators
Thermal evaporators entered the PW treatment market by looking at niche opportunities, particularly in remote locations
where other forms of traditional PW management tended to be more expensive, allowing the energy intensive thermal
processes an opportunity to be cost-effective. Moreover, since almost all waste streams are recycled back to the
evaporator, the volumes of fresh water required for makeup are dramatically reduced. With the proliferation of shale gas
wells in the past decade in the US, the demand for treating flowback water with TDS concentrations greater than 100,000
mg/L has expanded the opportunities for thermal systems. Another niche market where the application of evaporators has
been very successful is the SAGD enhancement recovery process. A leading technology company alone has developed 14
projects involving evaporators for SAGD in oil sands [11].
Case study - Connacher Great Divide Pod 1/ Algar Oil Field, Canada[12]
The Pod 1 Great Divide facility (Pod 1) and the Algar facility each produce 10,000 bbd of oil. Both facilities have
installed 2 parallel evaporators followed by a standard drum boiler to treat PW and generate stream for the SAGD
process. Pod 1 has been successfully operated since start-up in September 2007 and the evaporator treats de-oiled PW.
The Algar facility began operation in June 2010 and the evaporator in this facility treats a mixture of PW, source water
and blowdown generated from the Pod 1 evaporator. In both facilities, the evaporator produces a high quality distillate,
meeting the standards required for the boilers. In Algar for instance, the distillate produced has iron and copper
concentrations < 0.005 mg/L, total hardness < 0.013 mg/L, O&G < 1 mg/L and silica <0.02 mg/L. Furthermore, upsets in
the upstream de-oiling system have very little impact on the distillate quality. The main chemical dosed in the evaporators
system is caustic soda, necessary to keep the high levels of silica in the PW soluble, reducing the risk of scaling on the
evaporator heat transfer surfaces.
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2.2.4 Ozonation
The removal of KHI in a synthetic brine solution with a TDS around 6,000 mg/L was tested using an ozone generator
which was then bubbled ozone into a 1L column. The ozone concentrations at the inlet and outlet were continuously
monitored using an ozone detector. The KHI solution was ozonated for 0.5, 1.5, 3 and 4 hours to evaluate ozonation as a
function of time.
The removal of KHI was assessed by calculating the % of KHI oxidized and measuring cloud point.
3. RESULTS
3.1 Membrane Processes
A Toray brackish water RO (BWRO) membrane was used in the tests. Initially, the membrane was compacted with 10
g/L of NaCl at 500 psi, achieving a stable flux of 10LMH after 14 hours. The synthetic brine solution containing 1.5%
KHI was tested for 22 hours, with the operating pressure kept at 590psi. Throughout the test, the flux decreased from 15
LMH to 10.5 LMH. At the end of the test, the same solution of NaCl at 10 g/L was introduced through the system at
500psi and the permeate flux was 9 LMH, which confirmed that the membrane can be restored to its original compaction
condition (10 LMH). The KHI polymer was completely removed by the RO membrane (99.9% rejection).
A NF membrane from GE Osmonic (Desal-DK) was used in this investigation. The pore size of the membrane was 0.5
nm. The synthetic brine solution containing 1.5% KHI was tested at 150 175 psi for 29 hours. The initial permeate flux
was 33.6 LMH, which decreased to 11.3 LMH. The results show that the NF membrane tested rejected 99.7% of KHI
polymer.
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A UF membrane from GE Osmonic (GK series) was also tested. The molecular weight (MW) cut-off of the membrane
was 3,500 Daltons based on polyethylene glycol. The operating pressure was 50 65 psi and the test was carried out for
24 hours. The flux was constant at 12 LMH and the rejection of KHI polymer was about 83.3%.
The rejections for various elements during the above tests are summarized in Table 1 below.
Table 1 Rejections for tests with RO, NF and UF membranes
Parameter
Unit
Synthetic
brine + KHI
1.5%
RO Rejection
(%)
NF Rejection
(%)
UF
Rejection
(%)
KHI
mg/L
20,738
99.9
99.7
83.3
Chloride
mg/L
3,403
99.2
72.8
2.8
Sulphate
mg/L
40
99.0
100
25.0
Phosphate
mg/L
292
99.7
100
16.6
Sodium
mg/L
675
99.2
14.6
0.0
Magnesium
mg/L
245
99.7
98.9
4.2
Calcium
mg/L
1,017
99.7
97.7
1.2
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Figure 6 Results of MD tests on Seawater from the Arabian Gulf (Membrane A, B, C, D and E)
Figure 7 Results of MD tests on Brine from a local Thermal Desalination Plant (Membrane A, B and E)
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Table 2 Rejections for Seawater and Thermal Brine tests with Membrane B
Parameter
Unit
Seawater
Distillate
Rejection
(%)
Thermal
brine
Distillate
Rejection
(%)
Conductivity
S/cm
65,000
>99.99
100,000
>99.99
TDS
mg/L
43,247
<1
>99.99
71,981
<1
>99.99
Calcium
mg/L
416
<0.1
>99.97
718
<0.1
>99.99
Magnesium
mg/L
1879
<0.01
>99.99
3,120
<0.01
>99.99
Sodium
mg/L
13,384
<0.03
>99.99
22,604
<0.03
>99.99
Chloride
mg/L
23,715
<0.03
>99.99
39,274
<0.03
>99.99
The above results demonstrate the ability of MD in reducing the salinity of highly saline feed waters. Therefore, based on
the knowhow captured above, the research team at GWSC has started testing different MD membranes on various types
of PW collected from various oil and gas operations worldwide. These tests are still undergoing and therefore the results
cannot be included in this manuscript.
3.3 Membrane Bioreactors (MBRs)
The characteristics of the PW used during the salinity tests are summarized in Table 3 below.
Table 3 Characteristics of the PW during Salinity Tests
Parameter
Unit
Value
COD
mg/L
1,440
TOC
mg/L
403
O&G
mg/L
14
Conductivity
S/cm
46,000
TDS
mg/L
28,980
Salinity
The salinity of the bioreactor was gradually increased from 6,400 to 31,750 mg/L over an 8 week testing period. During
this period, the F:M increased from 0.01 to an estimated 0.04 gCOD/gMLVSS-d. The daily %TOC removals fluctuated
between 4080%, averaging 65%, over the entire range of salinities. There was no significant effect of salinity on %
TOC removal over this range of salinities.
KHI
Since all the organics present in the feed were attributed to KHI, the %COD removal results directly reflect the
biotreatability of KHI. The results indicate that over the 7 week test period, 50 - 60% of the COD associated with KHI is
removed through biotreatment. The % removal was similar for both at both the low and high KHI concentrations.
MBR
The %COD removal over the 5 weeks of steady state testing indicates that 63% of the COD could be removed through
biotreatment. The UF flux remained excellent over the entire testing period and no intermediate maintenance or soak
cleaning was required. In the posttreatment experiments with an RO, as expected, the effluent produced was excellent
with >98% removal of both the COD and inorganics. The effluent would be suitable for recycle or reuse within the gas
processing facility. Although the RO flux on MBR effluent was lower than the pretest benchmark water flux, upon
completion 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.
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3.4 Ozonation
The KHI solution was ozonated for 0.5, 1.5, 3 and 4 hours to evaluate ozonation as a function of time.
From Table 4 below we can see that a KHI removal of 11%, 60% and 75% was obtained 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 effectiveness of ozonation in oxidizing KHI is very dependent on the contact time and
significant removals (75%) can be achieved given the necessary contact time.
The cloud point (the temperature at which turbidity due to precipitation of polymer is observed) also varied with contact
time (Table 4). Visual examination of the treated effluent indicated that the treated effluent was turbid after ozonation.
However, after filtration through a 0.45 micron filter, the treated effluent solution was clear.
Table 4 Ozonation Test Results
Ozonation Time
(h)
KHI Oxidized
(%)
Cloud Point
(C)
40
0.5
33
1.5
11
ND
60
48
75
57
ND Not Detected
4. CONCLUSIONS
The key conclusions of this paper are:
Membrane Processes and Thermal Evaporators are currently operating within the petroleum industry in full scale
PW treatment and reuse applications.
The results of investigations performed by GWSC confirmed the potential of biological degradation and
ozonation to treat PW and produce an effluent suitable for recycle or reuse.
Membrane Distillation may have potential in the longer term as a method for producing a treated effluent also
suitable for recycle or reuse. Further investigation is warranted.
Overall, the AWTTs investigated confirm their potential to treat PW and produce an effluent than can potentially
be reused in various applications: crop irrigation, livestock watering, wildlife habitats and industrial applications.
This reuse could potentially leave more fresh water available for domestic use.
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