SPE 157108

Using Advanced Water Treatment Technologies To Treat Produced Water

From The Petroleum Industry
Raul Dores, Altaf Hussain, Mary Katebah, Samer Adham. ConocoPhillips - Global Water Sustainability Center
(GWSC), Doha, Qatar

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Production and Operations Conference and Exhibition held in Doha Qatar, 14–16 May 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract

Produced Water (PW) is the water trapped in underground formations that is brought to the surface along with oil or gas in
extraction operations and it 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 and subsequent discharge into water bodies or deep
injection in disposal wells. Only a small fraction of the PW is currently being treated to an extent that allows it to be recycled
& reused.

However, due to any of a variety of factors including legislation, geological restrictions and local water scarcity, the future
will require a greater fraction of the PW to be extensively treated and ultimately recycled & reused. The petroleum
industry will have to change how it has historically been managing PW and start to consider PW as a “by-product” of
strategic importance and value and not as an operational liability.

This paper focuses on the application of Advanced Water Treatment Technologies (AWTTs) for the treatment of PW. The
specific technologies presented include direct membrane filtration, biological treatment in membrane-bioreactors (MBRs),
thermal evaporators and advanced oxidation processes (AOPs). In addition to describing their respective advantages and
disadvantages, this paper also presents examples of case studies where PW is being treated and recycled & reused through the
application of AWTTs in full scale facilities.

This paper also presents a brief overview of a laboratory investigation carried out by ConocoPhillips GWSC, where various
treatment processes (membrane filtration, biological degradation, membrane distillation (MD) and ozonation) were evaluated
as PW treatment methods.

The case studies reported demonstrate that thermal evaporators and membrane filtration technologies have been proven at
various installations to be cost-effective at the full-scale for PW treatment. Data reported in this paper also reveal that PW can
be successfully biodegraded or chemically oxidized and hence processes such as MBRs and AOPs, which have been
successful in other industries but overlooked by the petroleum industry, will need to be considered. In the long term, hybrid
technologies such as MD may also become a cost-effective alternative to treat PW.
2 SPE 157108

1. Introduction

Currently, the majority of Produced Water (PW) generated worldwide at onshore facilities is reinjected into the soil, either for
disposal or for Enhanced Oil Recovery (EOR) processes. As a result, the treatment facilities in onshore oil and gas production
operations 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. This normally means
reducing the O&G concentrations in the treated PW to 30-40 ppm, depending on the location of the platform in the world1,2,3.
The PW treatment technologies 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 fresh water standards for beneficial reuse in for example irrigation or industrial processes.

To obtain a source of fresh water from treated PW, Advanced Water Treatment Technologies (AWTTs) have to be
applied, alone or in combinations, to remove soluble materials including emulsified oils, organics, chemical additives and
salts,.

1.1 Definition and Characteristics of PW

There are many definitions of PW in the literature. In simple terms, PW is any water that is present in a reservoir with the
hydrocarbon resource and is brought to the surface with the crude oil or natural gas2. PW characteristics and physical
properties vary considerably. For instance, Total Dissolved Solids (TDS) can vary from >100,000 ppm in Flowback waters
3,4
from shale gas wells to less than 3,000 ppm in PWs from coal bed methane (CBM) wells . 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 toxic2. Although the characteristics of PW vary considerably, as a broad generalization the constituents that
offer a major concern to achieve fresh water quality standards are organic content (in particular dissolved fraction) and
salinity.

1.2 Volumes of PW generated worldwide

PW represents the highest volume liquid waste stream for the petroleum industry. The cost of managing produced water is a
significant factor in the profitability of wells and excessive water production is one of the main reasons to abandon an oil or
gas well, leaving behind large volumes of hydrocarbons. Published data indicate that the volumes of PW generated worldwide
are steadily increasing. For instance, the American Petroleum Institute (API) estimated that in 1995, 18 billions of barrels of
2 1 5
PW were generated in the US only from onshore facilities . Figures published in 2011 and 2007 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. These numbers can be explained by the ageing
of many oil and gas fields across the world and hence the increase
in both water to oil ratios (WORs) and water to gas ratios (WGRs).
Published figures from 2007 seem to agree on a worldwide WOR
2,4,5
of 3:1 while data from 2011 attributes for onshore crude oil
operations in the US a WOR of approximately 8:1 and 12:1 for
1
2007 and 2025 respectively . In addition, according to the
International Energy Agency (IEA) 2011 World Energy Outlook,
both oil and gas will still represent a significant fraction of the
energy consumption by 2035 (Figure 1), further contributing to the
increase in PW volumes. 6
Figure 1- World primary energy demand

1.3 Drivers for PW treatment

There are a number of economical, environmental and even social drivers which are changing the way the petroleum industry
perceives PW. It is being considered more as a “by-product” of strategic importance and value and not as an operational
liability. This is expected to pave the way for PW to be more extensively treated and produce an effluent with quality
standards that enables it to be recycled & reused. Some of the most important drivers for this change are discussed below.

Local water scarcity - Fresh water scarcity is a problem in many regions with oil and gas production. Therefore, the
injection of substantial volumes of PW in disposal wells seems a waste of a valuable commodity in these regions. In Qatar for
instance, demand for fresh water has more than doubled in the past 5 years and based on current projections, demand may
7
exceed supply by 2013 .
 Legislation - Legislation related to PW treatment and disposal has become increasingly stringent. In the US for instance,
discharge of treated PW to surface water bodies is prohibited, with some minor exceptions. In Canada, for Oil Sands
operations using > 500,000 m3 of water per year, 75-90% of the PW generated has to be treated and recycled1. The trend will
be for similar legislation to be adopted in other regions which will ultimately lead to an increase in water reclamation projects.

Risk of formation plugging - Where pretreated PW is reinjected in disposal wells, the risk of plugging increases with
time and as a consequence so does the risk of hampering or stopping production. As a result, many operators are
reassigning their management strategies to treat and recycle & reuse the PW generated, reducing the risk of formation
plugging.

High costs associated with PW disposal - When onsite disposal is not possible for regulatory or geological reasons,
operators have to dispose the PW offsite. In some areas, the PW has to be trucked for hundreds of miles at prohibitive costs. A
$1/bbl is normally considered a benchmark but significantly higher costs are reported, depending on the treatment and disposal
1
method employed . Therefore, operators are considering new management strategies to treat the PW and recycle & reuse it on
site, reducing offsite disposal costs.

Quality of water used in EOR - Some research supports the benefits of using low salinity water (1,000-8,000 mg/l TDS)
3,8
in water flooding operations, advocating improvements in recovery up to 40% . A source for this low salinity can be treated
PW. Considering that a huge proportion of the world’s oil production is currently achieved via water flooding, an increase in
the water quality being reinjected could potentially represent a substantial increase in oil output volumes.

Increasing demand for water in production operations - The volumes of water required for oil and gas operations have
increased significantly, in particular in non-conventional oil and gas resources. In oil sands, as much as 12 bbl of water can be
required per 1 bbl of Synthetic Crude Oil (SCO) produced in surface mining operations while 3 bbl of water are needed to
generate 1 bbl of steam for in situ Steam Assisted Gravity Drainage (SAGD). For instance in 2008, mining operations in
3 1
Canada withdrew 151 million m of fresh water from rivers . Furthermore, for fracturing operations in Shale gas fields, large
3
volumes of water (as high as 15,000 m /well) are also required to drill the shale gas wells and to make up the fracturing
liquids9. 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.

Social perception - With fresh water resources becoming increasingly scarce, it may not be socially responsible to use
vast volumes of fresh water for oil and gas operations. Moreover, in regions where fresh water resources are not
available, the disposal of PW in wells rather than treating and reusing it in other activities (e.g. agricultural irrigation,
industrial processes) may not be socially acceptable.

2. Advanced Water Treatment Technologies (AWTTs)

This section will discuss some of the AWTTs that are either being applied in upstream oil and gas operations to treat PW or
have the potential to do so. The technologies discussed are:
 Membrane Filtration (Microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF) and Reverse Osmosis (RO));
 Membrane Bioreactor (MBR);
 Thermal Evaporator;
 Advanced Oxidation Processes (AOPs).

2.1 Membrane Filtration

In membrane filtration technologies, the separation of a pollutant from the water is accomplished using a thin semi-permeable
layer of material, when a driving force is applied across the membrane10. Membrane technologies can be classified in many
different ways, including membrane material, nature of driving force, separation mechanism or nominal size of membrane
pore. The most common is classification according to the nominal pore size of the membrane (Figure 2). The selection of
which technology to use (MF, UF, NF, RO) depends on the nature of the application, the characteristics of the water to be
treated, and the effluent water quality required.
 Figure 2 - Classification according to the nominal pore size of the membrane (AWWA)

Microfiltration (MF) and Ultrafiltration (UF)

Both MF and UF are low pressure membrane filtration processes with similar operating principles: pressure drives the water
through the membrane element while pollutants bigger than the pore size are retained. An MF membrane will reject
particulates, including bacteria and suspended solids while the UF membranes can reject these materials as well as some
10
macromolecules including emulsified oils. UF membranes have been used industrially in oily wastewater applications since
the early 1980’s. These early systems successfully concentrated oily wastewaters to reduce the volume of wastewater to be
disposed of off-site and to produce an effluent suitable for sewer discharge. There are two basic designs of UF/MF systems:
 Pressurized systems: membranes are housed in vessels and feed is forced through the membranes under positive
pressure, or
 Immersed membranes: filtration is done with hollow fiber or flat-sheet membranes in open tanks by creating a
negative pressure on the filtered water side and drawing the filtered water through under vacuum.

Compared with pressurized membrane systems, immersed membrane processes have significantly lower operating costs
because the transmembrane pressure (TMP) is only 0.3 – 0.6 bar compared with 3 to 6 bar typical of pressurized systems. The
extremely low operating energy required by immersed membranes has resulted in these plants being cost-effective and
commercially available at extremely large flows; up to 800,000 m3/d in municipal drinking water treatment. In wastewater
treatment, UF membranes can serve either of two roles:
 Tertiary filtration: to polish the effluent from an existing clarifier; critical if
the effluent is to be processed through an NF or RO, or
 Membrane bioreactor (MBR): to filter activated sludge directly, replacing
the clarifier entirely.

The use of immersed UF membranes for tertiary filtration in water reclamation

projects is practiced in Doha, Qatar, in at least three full scale facilities: Doha West
3
Wastewater Treatment plant (135,000 m /d), Doha North Wastewater Treatment plant
3
(440,000 m /d) and the Pearl Gas to Liquid (GTL) project.
Hollow fiber configurations with polymer membranes dominate the larger scale
market although ceramics have several advantages that might justify their use for certain
niche applications, despite the higher costs. It is the characteristics of the water to be
treated that ultimately dictates the best option.
Figure 3 - Immersed UF module for tertiary filtration

Nanofiltration (NF) and Reverse Osmosis (RO)

The difference in pressure across a membrane, between two streams with different salt concentration is referred to as osmotic
pressure. An external force is therefore required to overcome this pressure and allow the water passage (permeate) across the
membrane and hence salt separation. The salinity of the feed water is critical in defining the operating pressure for a NF and
RO system. As the salinity increases, the osmotic pressure increases accordingly and therefore more pressure is required to
achieve salt separation at a defined recovery. For instance, with brackish water 80% or more recovery can be achieved with an
operating pressure around 100-150 psi while seawater desalination requires higher pressures of 700-1000 psi and recoveries
are typically limited to 40%.

NF and RO technologies also differ in terms of their salt rejection characteristics. NF membranes only remove divalent
ions such as calcium, magnesium and sulfate (rejections 80-90%) while monovalent ions such as sodium and chloride pass
through the membrane to varying degrees. However, the low fouling tendency
and high rejection of divalent ions makes NF suitable for other applications
such as water softening and sulfate removal from sea water. RO membranes
can achieve high rejections of both mono and divalent ions (greater than
99%). The most common configuration of NF an RO is spiral wound.
Typically spiral wound membranes are 4”or 8” in diameter and 40” long and
are housed in horizontal pressure vessels. RO membrane technology is now
considered a mature technology and it is currently responsible for 60% of
worldwide seawater desalination installed capacity (Figure 4). Moreover, the
operating costs of RO systems continue to decrease, with seawater
3
desalination plants operating at a cost of 3 kWh/m . In 2010, 67.5 MIGD of
11
RO capacities were contracted in Ras Azzour, Saudi Arabia .
Figure 4 - Installed capacity for sea water desalination
11
worldwide
Membrane Filtration to Treat
PW

The potential for membrane filtration technologies to treat PW has been successfully demonstrated in various field
12,13,14 1 16
studies . Moreover, a number of upstream petroleum full scale facilities (e.g: oil fields , CBM wells ) have already
installed membrane filtration technologies to treat and reuse PW. The treatment trains are either a combination of different
membrane technologies (eg: MF or UF + RO) or a 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. For salt removal, NF&RO also have several advantages when compared to other desalination
technologies. The main advantages of membrane filtration technologies to treat PW can be summarized as1,12,15:
 Very compact systems; small footprint requirements, making it suitable for onshore and offshore operations;
 Modular and therefore easy to upgrade capacity;
 Reliable; consistent effluent quality that is not subject to upstream process conditions;
 Fully automated; minimal operator input required to control and operate;
 Can reduce the amount of treatment chemicals needed.

Moreover, UF membranes produce an effluent quality that can be further treated in a downstream NF or RO for water
reuse. For desalination, RO is also more cost-effective when compared to more energy intensive thermal desalination systems.
The main disadvantage normally reported for membrane filtration technologies is the capital and replacement cost of the
membranes. However, capital costs of membranes have decreased almost exponentially since the mid-1990 and membrane life
time has also increased (evidence of duration over 10 years) due to product enhancements, thereby reducing the cost of
membrane replacement. Also, better design and operation of the plants has decreased operating costs associated with the
technology10. Another disadvantage of NF & RO membranes is that they still require extensive pretreatment to avoid
membrane fouling. An example of a full scale facility where membrane filtration technologies are being used to treat PW is
presented and discussed below.
1
Case study – San Ardo Oil Field, US

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
TM
to install a system to treat and reuse the PW. The OPUS
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.
Figure 5 - Treatment process installed at San Ardo, US
 2.2 Membrane Bioreactors (MBRs)

A simple definition for MBR technology is a wastewater treatment process that integrates membrane filtration with a
10
biological process . In conventional biological wastewater treatment, the soluble organic pollutants in the water are oxidized
by the microorganisms producing carbon dioxide, water and biomass. Gravity settling in open tanks (clarifiers) is the standard
method in activated sludge systems for separating the treated water from the
biomass. In an MBR, membrane filtration replaces the clarifier, providing a
physical barrier that retains the biomass and other suspended solids in the
tank, producing an effluent stream with typically less than 0.1 NTU turbidity.
In addition to removing virtually all suspended solids, the membrane can
remove emulsified oils and other soluble organics that may not have been
degraded by the microorganisms, producing an effluent suitable for a
10,17,18
downstream RO process . In terms of commercial applications, the
hollow fiber configuration using polymer materials dominates the larger scale
municipal and industrial MBR markets.
Figure 6 - Schematic representation of an MBR

MBR is now considered a mature technology and several MBR plants are now treating volumes greater than 100 MLD10.
The cost of the membranes continue to decrease and newer membrane materials have produced service lives >10 years.
Moreover, better operating practices regarding aeration strategies allows municipal wastewater MBRs to operate with total
energy requirements as low as 1.4 kWh/m3 19. Nearly all MBRs currently operating worldwide are working under aerobic
conditions. However, intensive research is being carried out on anaerobic MBR20,21. The advantages over an aerobic-operated
MBR are significant: lower energy consumption and possible net positive energy production if methane generation is
achieved, capable of treating highly concentrated organic streams with less sludge generation. Another hybrid technology that
is the subject of active research is the integration of powdered activated carbon with an MBR (PAC/MBR). In a PAC/MBR,
soluble organics are adsorbed by the carbon and effectively removed from the wastewater, either through microbial oxidation
(bacteria attached to the carbon) or through direct wasting with the waste sludge. A very interesting work22 concluded that by
adding PAC to an aerobic MBR, higher COD removals were achieved (92 % compared to 81%) due to the high adsorption
capacity of PAC. Moreover, the system experienced lower tendency to foul the membranes.

MBR to Treat PW

Very little information is available on full scale MBRs treating PW. The application of MBRs in the petroleum industry has
not been considered as a standard treatment solution for mainly two reasons: cautiousness of the industry towards innovative
technologies and the lack of regulatory requirements for a high quality effluent. This has changed in recently years driven
mainly by factors mentioned earlier resulting in the implementation of more water reclamation projects. MBRs are now
frequently used in petroleum industry, although their application is confined to downstream applications, mainly refineries or
petrochemical facilities. MBRs are now considered by the downstream petroleum industry as an excellent solution to treat
23
various wastewater streams and MBRs treating 50MLD flows are presently operating . New MBRs are also being planned or
under construction such as the 100 MLD MBR plant at Teneco Refinery in Russia. MBRs present several advantages over
10
conventional biological treatment processes for PW treatment :
 As opposed to sedimentation tanks, effluent quality is not affected by the settleability of the biomass;
 Filtration benefits of UF membranes; produces a high quality effluent than can be used in a downstream RO;
 Long retention times allows microorganisms to degrade soluble organics otherwise not removed;
 Very little sludge is generated;
 Small footprint.

MBRs have not yet been applied to treat PW at upstream oil and gas facilities. This is mainly due to the bigger treatment
challenges that PW offers when compared to wastewaters from refineries, including higher salinities and organic
concentrations, and field chemicals. However, a number of bench scale and pilot studies report that PW is biodegradable,
achieving COD and O&G removals greater than 95%24,25. For instance, one of these works has shown that some
26
microorganisms can achieve organic removal even in hypersaline media containing 20% NaCl . Moreover, full scale MBRs
are successfully operating in other industries treating highly contaminated organic streams (COD > 15,000 ppm) achieving
COD removals > 95%10. This reinforces the vision that MBRs have the potential to treat PW. If the MBR technology is
proven successful in treating PW at a full scale, the opportunities for this technology in water reclamation projects in the oil
and gas industry are numerous.
 2.3 Thermal Evaporators

There are various designs of thermal evaporators available, i.e: horizontal

tube, vertical short tube, long tube rising film, vertical tube falling film
etc. Of these, the latter driven by mechanical vapor compressors (MVC)
has the highest heat transfer characteristics. A high heat transfer
coefficient is critical to efficiently evaporate the water and in a cost-
effective manner. The vertical tube falling film arrangement also allows
evaporation to occur with reduced fouling effects by keeping surfaces
27
wetted at all times . The vapor compression cycle is the key to the
energy efficiency in these systems. Compressed vapor flows to the
outside of the heat transfer tubes, where its latent heat is given up to the
cooler brine slurry falling inside. As the vapor gives up heat, it
condenses as high quality distilled water. The system provides distillate
quality water than can be used by downstream systems, e.g. once-through
steam generators (OTSG) or drum boilers for stream production. An
important aspect of an evaporator is the increase in solids concentration
inside the evaporator, leading to crystal precipitation. To prevent the
newly formed crystals from scaling the tube walls, the evaporators can be
seeded with calcium sulphate, which provides an alternative surface for
the crystals to adhere reducing scaling on the tubes walls.
Figure 7 - Typical falling film evaporator

Thermal Evaporators to Treat PW

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. 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 ppm has expanded the opportunities for
thermal systems. Another niche market where the application of evaporators has increased significantly is the SAGD
enhancement recovery process. Traditionally in SAGD operations, the PW was treated using warm lime softeners and ion
exchange systems and OTSG to produce steam1. This treatment process is complex, produces several waste streams requiring
disposal and has relatively high operations and maintenance costs. In addition, upsets in the equipment upstream of the OTSG
27
can affect the steam generation and therefore impact on the SAGD recovery rate . Therefore, a simpler alternative approach
was developed using vertical tube falling film evaporators driven by MVCs followed by drum boilers to produce a high
quality steam. Since 1998, GE alone has developed 14 projects involving evaporators for SAGD in oil sands28.

Using evaporators to treat PW has several key technical advantages1,27:

 A number of physical and chemical processes are eliminated; simpler process;
 Very little pretreatment is required;
 Disposal volumes are reduced since almost 100% of waste streams are recycled to the evaporator;
 Stream quality is virtually not affected by feed water characteristics and upsets upstream;
 Significantly less chemicals are needed.

Moreover, since almost all waste streams are recycled back to the evaporator, the volumes of fresh required for makeup
are dramatically reduced. In some cases where waste disposal or deep well injection is not possible, thermal evaporators can
also be coupled with crystallizers to achieve Zero Liquid Discharge (ZLD). Although the application of evaporators to treat
PW is relatively new, the installation of this technology in full scale facilities has significantly increased in recent
years and a example of these applications are discussed below.
 Case Study - Connacher Great Divide Pod 1/ Algar Oil Field, Canada29

The Pod 1 Great Divide facility (Pod 1) and the Algar facility each produce 10,000
bbl/day 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 deoiled 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 ppm,
total hardness < 0.013 ppm, O&G < 1 ppm and silica <0.02 ppm. Upsets in the
upstream deoiling 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.
Figure 8 - Evaporator at Algar facility

2.4 Advanced Oxidation Process (AOPs)

AOPs have been extensively investigated for the past 30 years and can be considered fully developed technologies. They
include a number of different processes such as O3 + H2O2, UV + H2O2, UV + O3, O3 + UV + TiO2, UV + O3 + H2O,
Fenton’s reagent and UV + Fenton’s30,31. In addition, there are so called non-conventional AOPs such as wet air oxidation and
humid oxidation with peroxide (OHP®). All AOPs share a common objective: to generate a powerful oxidizing hydroxyl
radical (HO•). This radical specie has a tremendous oxidation power, greater than ozone, hydrogen peroxide, chlorine or
oxygen, reacting rapidly and non-selectively with nearly all electron-rich organic compounds, completely mineralizing
dissolved organic pollutants. If the contact time provided is not sufficient to achieve complete mineralization, the process will
still crack down large molecular weight organic molecules to smaller organic molecules which can be easily further removed
by, for instance, a biological process or other processes such as activated carbon. Moreover, AOPs have been successfully
used to reduce the concentrations of toxic organic compounds that inhibit biological treatment processes.

AOPs to Treat PW

Similar to MBRs, there is very limited information on AOPs being applied to treat PW in full scale facilities. Bench scale and
field studies are also scarce. One of the few studies assessed a combination of O3/UV/TiO2 to treat PW with a 38 g/l salinity
and achieved COD and O&G removals of 74% and 95% respectively, after a 30 minute contact time. After a 60 minutes
contact time, COD removal increased to 89%. Phenol presented in the PW was completely removed after only a 5 minute
contact time32. Published research investigating refinery effluents treatment with AOPs appears to be more common. Some of
these assessed a number of different AOPs and concluded that the Fenton reaction was able to achieve excellent organic
33,34
removals (DOC=90%, TOC=70% and COD=98% at optimum conditions) . Another work extensively described the
degradation of petroleum refinery effluents with photocatalytic AOP and reported COD removals above 90%35. Other studies
published in the literature describe the capability of AOPs to effectively degrade and mineralize organics in heavily
contaminated effluents generated by different industries (olive-oil mill, textile dyes, oil recovery industry, pharmaceutical,
etc.), with COD concentrations as high as 10,000ppm30,31. There are also references of companies that have developed AOP-
based patented technologies with successful applications in full scale chemical, petrochemical and pharmaceutical industries;
COD removals >90% were obtained for systems with COD’s of 1,000-10,000 mg/l. Despite the evidence that AOPs may be
successful in treating PW, the petroleum industry has yet to benefit from the many opportunities these processes offer. AOPs
30,34,35
present significant advantages over other technologies that are applied to remove organics :
 Can achieve complete mineralization of organic compounds, including recalcitrant;
 Some AOPs produce virtually no sludge;
 Time required for degradation can be very short (i.e minutes) depending on the feed water characteristics.

The main disadvantage of AOPs is that chemical addition is required, which can make the treatment expensive. Also, the
reaction time needed for the process is highly affected by the organic matrix of the water. Even though AOPs have not been
applied commercially to treat PW, results of several works published in the literature and from experience in full scale
applications in other industries would indicate that there is potential for AOPs in niche PW market treatment applications.
 3. Laboratory Investigation by GWSC

3.1 Membrane Filtration

The effectiveness of UF, NF and RO membranes in removing Kinetic

Hydrate Inhibitors (KHI) was investigated using a SEPA CF II test cell.
KHI is a polymer commonly added in the petroleum industry that may
require removal before the PW is disposed. The membranes were tested on
a solution of 1.5 wt% KHI prepared in a synthetic brine solution with a
TDS around 6,000 ppm. The objective of the experiment was exclusively
to analyze KHI rejection for different membranes. All membranes tested
were effective in removing KHI from solution to varying degrees. The
removal efficiency was greater than 99% for RO and NF membranes and
83% for UF membranes tested.
Figure 9 - Membrane testing setup used for the experiments

3.2 Biological Degradation

Two types of tests were carried out to evaluate the biodegradability of process water from gas fields, with a COD
concentration of 870 ppm: manometric respirometry (OECD 301F) and Zahn-Wellens/EMPA (OECD 302B). Both tests are
widely used as indicators of biological activity and hence biotreatability of wastewaters. Respirometry tests were performed in
fed and non-fed batch reactors, with inoculum sampled from a municipal activated sludge wastewater treatment plant. Two
sets of test were performed: with and without adapted inoculums. In each case,
a biomass concentration (MLSS) of 5 g/l was used. In the tests performed
without adapted inoculums, an increase in accumulated oxygen uptakes was
observed and hence biological degradation of process water occurred. In the
second set of manometric respirometry tests with adapted inoculums, the
oxygen uptake increased significantly. The Zahn-Wellens/EMPA tests were
conducted exclusively in non fed batch reactors for a period of 28 days and the
process water was inoculated with non-adapted inoculum. Two sets of test were
performed: one with a MLSS concentration of 5 g/l and another set of test with
a MLSS concentration of 10g/l. The tests carried out with a MLSS
concentration of 5 g/l showed COD reductions of 54% while he test with 10 g/l
did not show any improvement in removal.
Figure 10 - Manometric respirometry tests setup

The results from the Zahn-Wellens/EMPA tests confirmed those of the manometric respirometry; that process water
investigated was highly biodegradable and it does not appear to be toxic to the activated sludge biomass used as inoculum.
Moreover, the results from the manometric respirometry test performed with adapted inoculum indicate that a much higher
COD reduction could have been achieved during the Zahn-Wellens/EMPA tests if adapted inoculum had been used.

3.3 Thermal Treatment

A new hybrid thermal-membrane desalination process called membrane distillation (MD) was investigated. MD is capable of
achieving salt separation through the vapour pressure difference between a “warm” stream and a “cool” stream, across a
hydrophobic membrane. Several MD configurations can be used (direct contact, air gap, vacuum or sweeping gas) but all
36,37
possess the same fundamental advantages :
 Operate at low pressures (< 5psi);
 Can treat streams with high salinities (> 50,000 ppm TDS);
 Water can be heated by low grade waste heat or renewable energy;
 High quality distillate is produced (conductivity < 10 μs/cm).
The tests performed at GWSC were carried out with a MD direct contact
configuration test cell (Figure 11). Various saline streams (seawater, thermal
desalination brine, 100,000 ppm sodium chloride solution) were tested under
different operating conditions. All tests reported excellent salt separation (>99
%), producing a distillate of constant quality with conductivity below 5 μS/cm.
Although the tests show that MD can separate salts from highly saline
solutions, its ability to treat PW has yet to be demonstrated.
Figure 11- MD bench scale unit used for the tests
10 SPE 157108

3.4 AOPs (Ozonation)

The removal of KHI with ozonation was assessed using the apparatus
illustrated in Figure 12. Ozone was created in an ozone generator and was
then bubbled into a 1L column. The ozone concentrations at the inlet and
outlet were continuously monitored using an ozone detector. A solution of
KHI prepared in a synthetic brine solution with a TDS around 6,000 ppm
was ozonated for 4 hours. The initial KHI concentration in the untreated
brine solution was 13,395 mg/l, which was reduced to 3,322 mg/l after the
ozonation period. This represents a KHI removal of 75%. Experiments were
also conducted with 3 and 1.5 hours ozonation time, achieving a KHI
removals of 60% and 11% respectively. The results demonstrate that
ozonation was effective in removing KHI, although removal was is directly
dependent on the ozonation time.
Figure 12 - Ozonation testing apparatus

4. Conclusions

The key conclusions of this paper are:

1. For a variety of commercial and environmental reasons, AWTTs will play an ever-increasing role in the treatment of
petroleum industry wastewaters.
2. Membrane filtration and thermal evaporators are currently operating within the petroleum industry in full scale PW
treatment applications. They are proven and ideally suited for applications needing immediate solutions.
3. MBRs and AOPs have the potential to be used successfully to treat PW in the medium term. MBRs will likely prove
to be the most cost-effective process for the majority of applications but for certain niche applications, AOPs may
prove more cost-effective.
4. The results of investigations performed by GWSC confirmed the potential of biological degradation and ozonation to
treat PW.
5. Membrane distillation, because of its ability to produce distillate quality water from high salinity brines, may have
potential in the longer term. Further investigation is warranted.
6. No single technology will likely be sufficient to treat PW for reuse. A hybrid solution with two or more AWTTs may
have to be implemented to effectively treat PW.

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