SPE-169048-MS

Injection Water Chemistry Requirement Guidelines for IOR/EOR

S.C. Ayirala and A.A. Yousef, Saudi Aramco

Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, USA, 12-16 April 2014.

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
Water chemistry with selective ionic content and composition in the injection water plays a critical role to impact on several
oil recovery enhancement processes. Low ionic strength waters with threshold salinities lower than 5,000 ppm are desired for
SmartWater flooding in sandstones. Low to moderate salinity waters depleted in monovalents, but enriched in sulfates and
divalents are suited for SmartWater flooding in carbonates. Polymer floods mandate different low salinity water lacking both
monovalent and divalent ions to reduce polymer dosage and improve project economics. ASP floods require optimal salinity
water without the hardness ions to enable utilization of alkali and certain temperature tolerant surfactants in the chemical
formulation design. Lower salinity water is desired for carbonated water flooding to increase CO2 dissolved quantities for
better incremental oil recovery. Lower salinity waters could turn out to be a boon for even CO2 WAG where low salinity
benefits outweigh the adverse CO2 solubility effects. Thermal floods require fresh and hardness free water to generate steam
as injectant using boilers.

Injection waters of optimized salinity, ionic content and composition not only work on their own, but can also synergistically
combine with other EOR processes to result in higher incremental oil recoveries. Lower salinity waters have a beneficial
effect in polymer, surfactant, dilute surfactant and carbonated water floods to yield better oil recoveries when compared to
high salinity water. In this paper we first provide an overview on the benefits of tuning injection water salinity and
composition in different IOR/EOR processes with selected examples from published data and then propose a unique set of
injection water chemistry requirement guidelines for IOR/EOR. The present study findings also point out the need to develop
“water chemistry” as a specialty discipline within EOR portfolio and advocate for better integration of this emerging focus
area with other key surface and subsurface related disciplines to effectively improve upon IOR/EOR upstream value chain.

1. Introduction
Water injection is the widely used secondary recovery process since early 1950’s for pressure maintenance upon depletion of
natural energy in petroleum reservoirs. Typically water floods recover about 10-40% oil depending on oil properties such as
viscosity, geological and reservoir characteristics such as connectivity and heterogeneity, and well configuration such as
number of wells and type of well pattern etc. Hence water flooding has become a standard practice in oil industry today.
Almost all the conventional reservoirs, both onshore and offshore, go through water flood cycle to recover a portion of the
remaining oil after pressure depletion. A considerable amount of oil still remains trapped underground even after secondary
water floods. This is due to inefficient macroscopic sweep and microscopic capillary trapping caused by interfacial and
surface forces that retain crude oil within the pores. Currently oil industry is showing great interest in improved and enhanced
oil recovery technologies to either maximize the utlimate oil recovery by water flooding or recover additional oil from the
left behind water flood residual oil. The two main reasons for these renewed IOR/EOR interests in the industry today are: (1)
consistently higher oil prices maintained in the market over the past few years, and (2) to reverse the declining oil production
from the existing mature fields for sustainability and better profitability.
2 SPE-169048-MS

Enhanced oil recovery (EOR) processes can be broadly categorized into three types: (1) thermal, (2) gas, and (3) chemical.
Thermal processes apply heat (by injecting steam generated from water boilers) to recover very viscous oils and tar sands.
Both gas and chemical based methods are applicable to light to medium viscosity oils. Chemical EOR (cEOR) methods
include polymer (P), surfactant-polymer (SP), and alkaline-surfactant-polymer processes (ASP). In cEOR processes, each of
the constituent used in the chemical blend has its own effect to contribute on oil recovery enhancement. Polymer viscosifies
the water to provide mobility control; surfactant reduces oil-water IFT and alters wettability whereas alkali generates insitu
soaps by reacting with organic acid components present in the crude oil. Alkali also modifies surface charge characteristics of
the rock to reduce surfactant adsorption and causes some partial wettability alteration. Gas based methods constitute injection
of gases such as hydrocarbon, carbon dioxide, and nitrogen at immiscible or miscible conditions. Oil swelling and viscosity
reduction, zero gas-oil IFT, and changing gas/oil compositions due to mass transfer between fluid phases at reservoir
conditions are the important mechanisms that contribute to incremental oil recovery in a miscible gas flooding process. Gases
are injected either continuously or in alternate slugs with water known as water alternating gas (WAG) process. WAG
process is most popular compared to continuous gas injection due to resulting higher ultimate recovery from improved
mobility control. All three major EOR methods are thereby dependent on water either as a carrier fluid or in some other
indirect means to generate the injection fluid. For example, steam for thermal floods is generated with boilers using water, all
the chemicals are dissolved and injected with water for chemical EOR, and water is injected as alternate slugs with gas in
miscible WAG.

There has been significant research work and field tests reported during the last decade on the effects of water ionic
composition on oil recovery. These water compositional effects on oil recovery improvements were revealed in early 1990 at
University of Wyoming for sandstones1-2 and by University of Stavanger for chalks (pure and soft calcium rock type) in mid-
2000s3, and by Saudi Aramco for typical carbonates (Limestones/dolomites) in late-2000s4. The proposed enhanced water
flooding process relies on alteration of water ionic composition through removal of certain unwanted ions from injection
water to match with reservoir rock and fluids chemistry for releasing more oil from the pores. Nevertheless oil industry has
given different names to this technology such as SmartWater flooding (SWF), LoSalTM, and Low Salinity water flooding
(LSF), among several others (this process has been referred to as SmartWater flooding hereafter). Low ionic strength brines
with threshold salinities lower than 5,000 ppm showed oil recovery improvements in sandstone reservoirs. In contrast, low to
moderate salinity brines with reduced monovalent ions, but enriched in divalent ions showed beneficial effects on improved
oil recovery in carbonates. SmartWater flooding has huge upside when implemented in secondary mode and hence can be
potentially categorized as an improved oil recovery process.

Any injection water in terms of selective ionic content and composition customized for improved or enhanced oil recovery
can be termed as “SmartWater”. SmartWater is thereby a special type of water cocktail consisting of varying composition of
different water ions. Selection of certain water ions, their ionic content and relative distribution with respect to other in the
cocktail are critical depending on the nature of specific EOR process for optimum compatibility and interaction with both
injection fluids and resident rock and fluids present in the reservoir. SmartWater through its water chemistry plays an
important role to impact the performance of several IOR/EOR processes including the offshore water floods, as illustrated in
the following. Offshore water floods require a SmartWater with some sort of water treatment to remove certain detrimental
ions. Because these ions have adverse effects on resident insitu materials present in the reservoir to impact on injectivity,
scaling, and souring potential. Furthermore, not all the source waters are optimally suited for application in cEOR processes
due to the interference of specific ions present in the water with chemical additives. Hence a different SmartWater is required
for these processes to minimize on water ion interactions with chemicals and/or optimally match with reservoir fluids
chemistry. Thermal floods require another type of SmartWater that is essentially fresh with almost zero hardness ions to meet
the water quality requirements of boiler feed water to generate the steam. Interests in offshore EOR is gradually picking up in
oil industry, where it is much more complex to obtain desired SmartWater since injection water resource is limited to
seawater. Hence the main objectives of this paper are: (1) provide an overview of SmartWater flooding technology, (2)
describe the important roles played by injection water chemistry in IOR/EOR with supporting examples and extend the
applicability of SmartWater to different IOR/EOR processes, and (3) ultimately develop desired injection water chemistry
requirement guidelines for IOR/EOR.
SPE-169048-MS 3

2. SmartWater Flooding (SWF) Technology

Research work on the effects of water ionic composition on oil recovery was first started in early 1990’s at U. of Wyoming1-2.
Results from core flood tests showed the potential for oil recovery improvements by lowering water salinity. Optimizing
water flood recovery with SmartWater through tailoring of injection water salinity is very appealing to oil industry because of
its lower capital intensity compared to a full-fledged enhanced oil recovery method. Industry since then quickly tapped on
this technology and BP has carried out the first field test in Alaskan sandstone reservoir 5. It has initiated a systematic research
program that included more than 20 reservoir condition core floods on a range of sandstone reservoirs from its global
portfolio, both in secondary and tertiary modes. It has also conducted more than 10 single well chemical tracer tests and a
log-inject-log test. All the laboratory and field tests revealed some positive results, at least for sandstone reservoirs6-8. Oil
recovery has been shown to increase with a decrease in injected water salinity. Some field trials have also been reported later
by Shell and Statoil9-11. Lower salinity brines with salinities <5,000 ppm are desired to activate SmartWater benefits in
sandstones (with some dilvalents included to avoid clay swelling in the reservoir) and expected incremental oil recoveries
ranged 5-10% OOIP under favorable conditions.

Oil recovery by SmartWater flooding in sandstones is not a simple process. It involves complex and competing mechanisms
related to fluid-fluid and fluid-rock interactions. The primary mechanisms and the conditions necessary for increasing oil
recovery are still far from being adequately understood. However, it is well documented that the effect of low salinity water
is related to presence of clay minerals, and consequently, it is generally accepted that the effect is caused by wettability
alteration of clay minerals. The continuing research studies, however, have pointed out that the performance of SmartWater
flooding in sandstones is strongly affected by the composition of crude oils, the wettability of the rock surfaces, the migration
of clays, the salinity of the connate water in reservoirs, and the multicomponent ionic exchange12-18.

Based on the contrast in the surface charge between sandstones and carbonates, it is anticipated that injection of low salinity
water in carbonates is not sufficient to change the wettability and consequently increase oil recovery19. Unlike sandstone
reservoirs, carbonates do not contain clay minerals and usually exhibit a positively charged surface and because oil contains
negative carboxylic groups that adsorb on the surface, the system loses its natural wettability characteristics and become oil
wet in both drainage and imbibition. In this case, the only way to change the wettability of the reservoir rock is by increasing
the salinity in the formation so that more brine anions can replace negative carboxylic groups. Only multivalent anions will
be able to compete with these groups to wet the surface and change the wettability toward water wetness state. Therefore,
brine with monovalent anions will not affect recovery in carbonates, while multivalent brines are the ones able to unlock oil
through shifting wettability to a favorable state.

The research work by U. Stavanger in mid-2000 has shown that sulfate ions play important role in oil recovery from
carbonate reservoirs3,20. Because of adsorption, these ions change the wettability of carbonates and consequently increase
water-wetness as well as pH. Also, sulfate affinity on carbonate surface increase with higher temperatures. It is proposed that
injection brines with high sulfate, coupled with high temperature, will give higher recovery by spontaneous imbibition. These
researchers attributed the resulting increase in oil recovery to the release of carboxylic compounds via anionic exchange with
sulfates and by concomitant complexation of the carboxylate group by Ca2+. Increased oil recoveries were reported when
chalk cores imbibed with 2-4 times sulfates and 3-4 times calcium in seawater, respectively, at 100oC and 70oC21,22.
Imbibition oil recoveries also increased with seawater prepared in NaCl containing 4 times sulfates + 1 time magnesium and
2 times sulfates + 1 time calcium at 100oC23. Another study24 from the same research group pointed out that not only sulfates
and divalents such as Ca2+ and Mg2+ are important, but also the amounts of non-active salts (Na+ and Cl-) affect the
wettability alteration in carbonates. Spontaneous imbibition oil recoveries were increased by about 5-18% OOIP compared to
seawater when the concentration of sulfates was increased by about 4-times in the seawater depleted in non-active
monovalent ions. Because these non-active ions partly prevent the accessibility of active potential determining ions to the
carbonate rock surface thereby reducing the effectiveness of the process25. The process is sensitive to temperature and the
interactions between active ions and rock surface seem to trigger at temperatures above 70oC25,26. In a recent core flood
study27, highest incremental oil recoveries were seen for a limestone reservoir rock at 120oC with modified seawater
containing 4 times sulfates and seawater diluted to 50 times in both secondary and tertiary modes.
4 SPE-169048-MS

In view of huge carbonate oil resources in the Kingdom, Saudi Aramco initiated a strategic research program in 2006 to
investigate on the benefits of SmartWater flooding in carbonate reservoirs by tuning the ionic composition of the injection
water. Several reservoir condition core flood tests were conducted in-house using the cores and fluids from Saudi Arabian
carbonate reservoirs4,28. The injection fluid sequence consisted of first injecting seawater and then followed by injection of
various diluted seawater versions. These experimental results showed about 7.0-8.5% incremental oil recovery with twice
diluted seawater, 9.0-10.0% with 10-times diluted seawater, and 1.0-1.6% with 20-times diluted seawater with an overall
ultimate incremental oil recovery of about 17.0-20.1% (as shown in Figure 1). This is the first work in published literature
that demonstrated low ionic strength seawater does improve oil recovery in carbonates, which has led to much rigorous
subsequent research in this area by others in the industry and research Universities. Yousef et al.4, 29-30 also revealed that
connectivity between macropore and micropore systems is increased significantly during these floods in carbonates due to
microscopic dissolution of anhydrite. Later fundamental research studies by the same group30,31 pointed out the role of water
ions and confirmed that significant reduction in the ionic strength (Na+, Cl-) of field seawater is required to result in favorable
effect. The primary recovery mechanism for the observed incremental oil recovery was attributed in these studies to favorable
wettability alteration through the results of macroscopic measurements such as contact angle, IFT, zeta potential, and
laboratory NMR techniques. The relationship between the recovery mechanism and water chemistry in carbonates is depicted
in Figure 2. As can be seen, the increase in oil recovery is due to wettability alteration caused by adsorption/interaction of
key ions which is in turn strongly dependent on the water chemistry of the injection water. Hence water chemistry plays a
critical role on incremental oil recoveries observed in SmartWater flooding of carbonates. The three key ions present in the
seawater – sulfate, calcium, and magnesium alter rock-fluids chemistry in carbonates to result in reduced capillary trapping of
oil. SmartWater can also add more sulfate ions by dissolving anhydrites present in the formation32,33. Based on these
promising results, Saudi Aramco decided to take this technology into next phase and as a result industry's first SmartWater
field tests were performed in a carbonate reservoir34. Several single well tests were carried out in a carbonate reservoir with
various ionic strength brines and tuned ionic composition obtained using chemistry-optimized seawater. All field trials
confirmed the potential of SmartWater and showed about 7 saturation unit reduction in residual oil saturation beyond
conventional seawater. Saudi Aramco is presently investigating how ions affect oil-water-rock interactions at “microscopic
and atomic scales” to further optimize this advanced water flooding process for higher oil recovery. Several field trials are
also being planned to identify potential problems in the field application and consequently help the design of multi-well
demonstration pilot.

SmartWater has beneficial effects in both sandstones and carbonates for improved oil recovery. Desired SmartWater should
have lower ionic strength with threshold salinities less than 5000 ppm to result in oil recovery improvement for sandstone
reservoirs. Sandstones contain clays and hence small amounts of divalent cations (<500 ppm) can be included in the
SmartWater to avoid clay swelling in the reservoir. In contrast, low to moderate salinity diluted seawater (2-10 times
dilution/28000-6000 ppm) or modified seawaters depleted in monovalent ions, but enriched in potentially determining
divalent ions (4 times sulfates, 1 times calcium and magnesium) appear to be better suited for improved oil recovery in
carbonates. Of course the desired injection water chemistry in carbonates is dependent on temperature, rock mineralogy, and
initial formation fluids chemistry (as shown in Figure 3). Therefore selective water ionic composition with a specific
monovalent to divalent ion content and sulfates is required for carbonates, which constitutes complex water chemistry
compared to sandstones, and thereby requires better tuning and flexibility in the water chemistry of injection water.

3. IOR/EOR Injection Water Chemistry Requirements

Injection water chemistry requirements for different IOR/EOR processes including offshore water floods and their impact on
oil recovery due to interactions of water ions in the injection water with insitu rock and fluids present in the reservoir are
described in this section.

3.1 Offshore Secondary Water Floods

Water floods have been in practice for oil recovery since their accidental discovery in early 1900’s. The main objective of
water injection is to provide pressure maintenance and sweep efficiency to push oil into the production wells. The
requirement for altering injection water chemistry in offshore secondary recovery processes has been come to light until its
need has been strongly recognized in early 1990’s during North Sea South Brae oil field development35. Seawater is the only
SPE-169048-MS 5

available water resource for water injection in offshore and formation waters in these environments contain high salinities
with large amounts of divalent ions. Typical seawater and formation water compositions36 are shown in Table 1 for an
offshore environment. As can be seen, seawater contains significant amounts of sulfates and hardness. As a result, there is a
strong incompatibility between injection seawater and formation water due to the presence of substantial amounts of barium,
strontium, and calcium in formation water. Sulfates present in the injection water precipitate with barium and strontium to
result in barite (barium sulfate) and celestite (strontium sulfate) scales. The presence of calcium in formation water results in
the formation of calcium sulfate scale. These scales will deposit all over the place between injector and producer in the
formation to cause serious restrictions to flow. The formation of scale in the near well bore regions of the injection well can
also drastically reduce injectivity. These sulfate scales are very hard, difficult to remove and hence severely hamper
productivity from the producers. Sulfate scale effects could be much serious and instantaneous as evidenced by significant
drop in production from 4770 m3/d to almost zero observed within a day in one of the North Sea wells at Miller field36.

Presence of sulfate ions in the injection water poses another major risk called reservoir souring. As per Oilfield Wiki
definition, reservoir souring “is the phenomenon when there is an increase of mass of hydrogen sulfide (H2S) per unit mass of
total produced fluids due to activities of sulfate reducing bacteria (SRB) as a result of water flood”. Seawater contains
sulfates and sulfate reducing bacteria which provide the feed source for the reaction with organics present in the reservoir.
SRB’s could also be present in the reservoir. Sulfates react with organics in the presence of SRB to produce oxidized carbon
and hydrogen sulfide. Hydrogen sulfide is highly toxic and corrosive even at very low concentrations thereby causing severe
handing and safety concerns in oil field operations. Furthermore the resulting sour oil is difficult to refine and reduces its
monetary value. Less than 1 ppm hydrogen sulfide in the aqueous phase may result in high corrosion rates. When hydrogen
sulfide levels in the production reach beyond certain safety limit, the wells had to be shut down with costly remedial actions,
which may lead to losing several million dollars.

Stoichiometric calculations indicate that about 100 ppm of sulfate in the injection water could produce about 35.4 ppm of
hydrogen sulfide in the presence of SRB. But this effect may be exaggerated, since most of the current offshore water floods
did not show even trace levels of H2S in produced fluids with about 40 ppm of sulfates in the injection water37. Seawater
injection has been in practice in several North Sea projects during the past several decades and the experience from these
projects can provide good illustrative case histories on scaling and souring issues encountered in offshore water floods.
Lately higher concentrations of hydrogen sulfide were reported in at least two major North Sea oil fields38. Figure 4 shows
souring evaluation results for individual producers, both timing and concentrations, as predicted from a simulation model for
one of the Gulf of Mexico offshore projects with seawater injection39. As can be seen hydrogen sulfide was detected in most
wells after seawater breakthrough and the concentration levels were then quickly increased to more than 10 ppm. This
observation highlights the importance of mitigating souring potential with appropriate injection water treatment in water
floods. Hardness ions present in the injection water do not pose that much serious threat compared to sulfates, but they can
precipitate in pipes and foul the heating equipment when injection water is heated under some special circumstances.
Removal of hardness ions from injection water can also favorably impacts injectivity. Based on the discussion presented in
this section, it can be concluded that certain ions in the injection seawater (mainly sulfates) are detrimental for offshore water
floods due to their insitu biological reactions with the resident materials present in the reservoir. Hence water chemistry of
injection water needs to be tuned to remove these ions for optimal and environmentally safer offshore water flood operation.
SmartWater containing negligible sulfates (<40-100 ppm) and with moderate to low amounts of hardness ions (<500-600
ppm) can be specified as the desired water chemistry for offshore secondary water floods.

3.2 Polymer Flood

Polymer floods were widely employed in oil industry till 1980’s for enhanced oil recovery. It is a matured EOR technology
and reviews of several past successful polymer injection field projects can be found elsewhere40-42. This technology falls
under chemical EOR umbrella and uses viscosified water to achieve better mobility control in water floods. In addition, it
also reduces rock permeability to lower the mobility of the injected water. Typically polymer concentrations ranging from
250-2500 ppm are dissolved in water to reach desired injection viscosities in polymer floods. There are some recent theories
developed suggesting improvements in microscopic efficiency at high polymer concentrations due to polymer viscoelasticity,
but these mechanisms are not very well understood. Currently Daqing oil field in China is operating world’s largest
6 SPE-169048-MS

commercial polymer flood with up-to-date successful results43. Lately the operating envelope of polymer flooding technology
has been extended to even heavier viscosity oils up to 1000-2500 cP with some success reported in Canadian pilots44.
Attempts are also being made to evaluate polymer floods offshore to improve the reservoir sweep45,46.

Two types of commercial polymers are most popular in oil industry for enhanced oil recovery, hydrolyzed polyacrylamides
(HPAM) and xanthan gum. Among these, polyacrylamides are widely used. Only few projects used xanthan gum and most of
the commercial successes in polymer flooding reported so far have been with polyacrylamides. Xanthan gums are
biopolymers and they are prone to bacterial degradation to quickly loose mobility control as reported in Louden pilot
project47. Polyacrylamides are synthetic polymers and they are anionic in nature induced by negatively charged carboxyl
groups in the polymer chain. Due to this anionic nature, polyacrylamides are sensitive to salts present in the injection water.
Because positively charged cations in the water bind tightly to negatively charged carboxylic acid groups in the polymer
chain to make polymer molecules in the coiled state and consequently to affect its viscosifying characteristics. On the other
hand in low salinity water, there will be a strong repulsion between charges in polymer chain and as a result polymer
molecules are in swelled or elongated state to yield much higher viscosities for the same polymer concentration. Divalent
cations are much more detrimental when compared to monovalent ions because of their strong bridging effect with the
polymer chain and the ability to precipitate polymer even at low concentrations.

The comparison of FP3630S polymer solution viscosities prepared using seawater and 500-600 ppm TDS low salinity
SmartWater is shown in Figure 5 for different polymer concentrations at 7.3 sec-1 shear rate and 25oC48. As can be seen,
much reduced polymer consumption requirements are expected when lower salinity SmartWater is used for making up
polymer flood injection fluid instead of seawater. For achieving 80 cP polymer solution viscosity, about 1200 ppm polymer is
required with SmartWater whereas about 3,200 ppm polymer is required in seawater. About 3-times reduction in polymer
consumption is observed with SmartWater, which has significant impact on project operating costs to quickly pay out
incremental capital costs associated with SmartWater surface facilities. Ayirala et al.49 compared the surface facilities weight,
space and costs of low salinity SmartWater polymer flooding with that of seawater polymer flooding for a typical offshore
project. The results from this study showed that extra facilities costs in SmartWater flooding can be paid out within one year
for 45,000 m3/d injection capacity at 6 cP targeted injection water viscosities. Space requirements on the platform were
reduced by about 10% and the weight requirements by about 50% with SmartWater. These savings are mainly due to large
reduction in polymer consumption requirements obtained with SmartWater to reduce chemical storage space and weight on
the platform. It is important to note that incremental oil recovery benefit associated with SmartWater (i.e. improved
microscopic sweep efficiency) in SmartWater polymer flooding is not included in these cost comparisons while determining
the payout time and as a result these results can be treated as somewhat conservative.

SmartWater has synergistic effect in polymer flood. Low salinity SmartWater improves microscopic sweep to reduce
capillary trapping in addition to enhanced macroscopic sweep efficiency achieved with polymer due to better mobility
control. As a result higher incremental oil recoveries and relatively better timing are expected in SmartWater polymer flood
due to compounding of these two additive effects when compared to seawater polymer flood. The use of SmartWater in
polymer flood is also expected to yield other benefits such as reduced polymer adsorption, lower polymer cloud point, and
enhanced polymer temperature stability. The coreflood experimental study by Kozaki50 showed 5-10% reduction in residual
oil saturation with injection of low salinity polymer solutions compared to high salinity water flood. Less pore volumes were
injected in these core floods to achieve ultimate oil recoveries when polymer was present. Mohammadi and Jerauld51
modeled low salinity SmartWater polymer flooding to compare with high salinity polymer flooding and the results of this
study are shown in Figure 6. About 10% more incremental oil recovery was obtained in SmartWater polymer flooding when
compared to high salinity polymer flooding. It is also quite evident from Figure 6 that the incremental recovery (over water
flood) in SmartWater polymer flood is almost equal to the summation of incremental oil recoveries obtained in individual
SmartWater and high salinity polymer floods. The comparison of chemical costs between these two cases showed about 5
times reduction in chemical cost per bbl of oil recovered in SmartWater polymer flooding. A recent review study by
Vermolen et al.52 pointed out that low salinity polymer flooding can improve polymer flooding technical feasibility,
economics besides providing opportunities to extend polymer flooding to high-salinity and high-temperature reservoirs.
SPE-169048-MS 7

The use of SmartWater in polymer flooding has good upside potential, since improved oil recovery advantage associated with
SmartWater can effectively combine with polymer flood benefit to yield higher incremental oil recovery. As a result
SmartWater polymer flooding has some merit to be considered as a new hybrid EOR process. This hybrid EOR process could
turn out to be economically beneficial even without including oil recovery improvement associated with SmartWater due to
much lower usage of polymer quantities caused by decreased salinities. It would also complement ongoing interests in the
industry to extend the applicability of polymer flooding to heavier viscosity oils due to achievement of proper mobility ratio
with low salinity water using decent polymer concentrations. Desired injection water chemistry for polymer floods thereby
requires low salinity SmartWater lacking both monovalent and divalent ions to result in better incremental oil recovery and
favorably impact both project technical feasibility and operating costs. Typically injection water salinities lower than 5,000
ppm containing 100 ppm and below hardness (to avoid clay swelling and deflocculation) are preferred for polymer floods in
sandstones to synergize on the benefit from both reduced polymer concentration and low salinity effect.

3.3 Surfactant Flood

Surfactant pilots for EOR applications have been reported in oil industry as early as 1960’s53. The main mechanism
responsible for enhanced oil recovery in the process is generation of ultra-low interfacial tensions (to values less than
0.001 mN/m) and partial wetting alteration, both of which cause an increase in capillary number to result in mobilization of
residual oil. Formation of three phases is required (upper oil, middle microemulsion, and lower water) in a conventional
surfactant flood at the so-called optimal salinity to generate ultra-low interfacial tension environment in the reservoir.
Optimal salinity is defined as the salinity at which equal volumes of oil and water solubilized into the middle microemulsion
and is strongly dependent on surfactant type, concentration, oil composition, temperature, and pressure. The common practice
is to either condition the formation to optimal salinity with a pre-flush or match the optimal salinity with that of formation
water salinity by tuning surfactant chemicals in the formulation. Both these practices ensure chemical slug, the chase water
drive, and the formation brine to be at or close to “optimal salinity”. Salinity gradient concept was later developed for better
chemical flood design wherein chemical slug optimal salinity is less than formation brine and chase drive salinities are at
most kept equal to optimal salinities extrapolated to zero surfactant concentration54. In this approach, the salinity will be
overoptimum ahead of the chemical bank, underoptimum in the drive behind the chemical bank, and “optimum” at
someplace in the chemical bank thereby assuring the guaranteed passage of salinity profile through optimal salinity region.

Polymers were included in the process to achieve mobility control for better sweep55. Alkali was added to surfactant slug in
mid 1980’s and the proposed technology was called as cosurfactant-enhanced alkaline flooding56. The purpose of alkali
addition was to save on synthetic surfactant costs by reducing its concentration in the chemical slug. Because alkali reduces
surfactant adsorption on the rock and also creates natural soaps insitu by the reactions with organic acid components present
in the crude oil. Alkaline-surfactant-polymer (ASP) flooding process looks attractive for oil industry due to significantly
higher incremental oil recoveries in the range of 15-20% OOIP expected. Nevertheless the use of alkali in the chemical
formulation has some inherent disadvantages such as produced fluids emulsification and severe scale and corrosion issues in
the production systems. Sometimes, additional chemical agents such as co-solvents are used to provide quicker equilibrium
between the phases and prevent the formation of viscous phases at insitu subsurface conditions. The process looks much
complicated due to complex interaction of these various chemicals involved with each other and with reservoir rock and
fluids. As a result ASP process has not yet been fully commercialized and several pilots are currently ongoing worldwide to
field test, better understand, optimize and extend the technology to quite challenging environments.

Two types of synthetic surfactant chemical classes are available today for surfactant based EOR processes: (1) sulfates, and
(2) sulfonates. Both these surfactants are anionic in nature and hence are well suited for application in sandstone reservoirs
due to relatively lower surfactant adsorption resulting from the repulsive forces between the opposite charges of surfactant
molecule and the rock surface. Sulfates are tolerant to salt and divalent ions, but are unstable at temperatures above 60 oC. On
the other hand, sulfonates exhibit excellent temperature stability, but are sensitive to hardness ions. The current trend is to use
mixture of these two surfactant classes in the chemical formulation as a “blended surfactant system” to have a better
flexibility on adjusting optimal salinity and chemical phase behavior to match reservoir fluids chemistry57. The blends of
sulfates and sulfonates also found to exhibit much higher salinity tolerance levels when compared to respective individual
surfactant systems. Most of the early surfactant pilots reported in the literature during the last century had been with
8 SPE-169048-MS

petroleum sulfonate surfactants. As a result injection water was treated in majority of these projects to remove hardness and
chelating agents were included in the chemical slug to protect the surfactant from hardness ions present in the formation
water. Sulfonate stabilities are expected to deteriorate badly even with small amounts of divalent or hardness ions in the
makeup water. It is also believed that the properties of sulfonate surfactant solutions such as solubility, interfacial behavior,
and adsorption will be enormously improved when divalent cations are removed.

When the reservoir temperatures exceed 60oC, the use of salinity tolerant sulfates alone is not applicable and temperature
stable sulfonates provide one available option for the suitable constituent in the chemical formulation. Surfactant cost is one
of the largest cost items in chemical flooding technology and this can be considered as the main reason for declining
surfactant based EOR projects since mid-1980’s when oil prices of 20$/bbl or below were prevalent at that time in the
market. Reducing surfactant consumption is the key for economic success and use of alkali in the chemical formulation helps
to achieve that target. Soda ash is the most widely used alkali in ASP process since it is a weak alkali and hence causes less
reservoir damage. However it is highly sensitive to divalent ions and precipitates with hardness in the injection water. Hence
injection water must be softened to remove hardness ions to obtain optimal performance with sulfonate surfactants and to
enable utilization of alkali in ASP projects. Furthermore, removal of divalents from the injection water is highly desired to
obtain good viscosifying characteristics from conventional polyacrylamide HPAM polymers at much lower concentrations.
The importance for alteration of water chemistry to remove divalent ions from seawater using desalination to facilitate
offshore implementation of alkaline-surfactant (AS) and alkaline-surfactant-polymer (ASP) projects has also been
highlighted in recent works58,59.

There were some interesting studies that described the benefits of combining low salinity SmartWater with surfactant
flooding in sandstones60,61. An anionic internal olefin sulfonate surfactant was used in these studies at 1.0 wt% concentration
to have low interfacial tension (~0.01 mN/m) in the SmartWater containing 0.5 wt% NaCl. Core flood results with 13.8 cP
stocktank crude oil indicated about 5-10% OOIP higher oil recovery in secondary low salinity water floods when compared
seawater flood (shown in Figure 7). About 30-32% OOIP incremental oil (Sor = 4-6%) was obtained when surfactant was
used with lower salinity SmartWater in tertiary mode. Higher incremental oil recoveries in two of the tertiary surfactant
floods were due to pre-existing low salinity environment in the core from the secondary low salinity (LS) water flood. The
lower tertiary oil recovery (about 20% OOIP) observed in one of the core floods can be attributed to the interaction of
divalent ions with the surfactant resulting from previous high salinity water flood performed using seawater (SW). This
observation suggests that secondary low salinity/SmartWater floods, in addition to recovering extra incremental oil, could
also favorably condition the reservoir salinity to create a relatively better environment for the subsequent polymer and
surfactant floods to obtain higher oil recovery in the tertiary stage. However it seems that these post Smartwater flood
benefits on chemical EOR have not been captured in the recent studies. Improved surfactant aqueous stability and reduced
surfactant adsorption are other advantages associated with the low salinity surfactant flooding process. Destabilization of oil
resulting from lower brine salinity together with release of trapped oil due to low IFT was attributed to be the main
mechanism responsible for incremental oil recovery in SmartWater surfactant flooding60,61. Furthermore, the process was
designed to show optimal IFT behavior in Winsor type I region and as a result most of the difficult phenomena encountered
in conventional chemical flooding processes such as middle-phase formation, high emulsion viscosities, and three-phase
relative permeability effects are avoided to make the process simple and less cumbersome. Low surfactant adsorption
associated with the process may also improve its economic feasibility when compared to conventional chemical flooding.

The combination of SmartWater with dilute surfactant flooding looks more attractive for carbonate reservoirs. The addition
of minute quantities of surfactant (<0.1 wt%) to the injection water, in contrast to large surfactant concentrations as high as
1-2 wt% used in conventional surfactant flooding, can be termed as dilute surfactant flooding. Recent research work 62 has
shown that dilute surfactants in carbonates are able to imbibe into the rock and alter rock wettability leading to improved oil
recovery. This study showed that surfactant imbibition alone is capable of expelling above 35% of OOIP at the conditions of
study ranging up to 90oC. SmartWater dilute surfactant flooding in carbonates is expected to result in 5-10% OOIP
incremental oil recovery over SmartWater flooding due to additional surfactant induced mechanisms such as IFT reduction
and improved spontaneous imbibition coming into play. Core flood results performed using carbonate reservoir rock and
fluids and 0.1 wt% amphoteric surfactant containing ethylene glycol monobutyl ether cosurfactant in twice diluted seawater
are shown in Figure 863. As can be seen, about 15.5% OOIP incremental oil recovery was obtained with SmartWater
SPE-169048-MS 9

surfactant flooding when compared to water flooding with seawater. The core flood performed using the twice diluted
seawater in the similar rock-fluids system showed an incremental oil recovery of about 7% OOIP over seawater flooding.
Based on the comparison of these two core flood results, it was concluded that dilute surfactant flooding is beneficial for
carbonates and its contribution on oil recovery enhancement in the combined SmartWater surfactant flooding was about
8-9% OOIP in the specific rock-fluids system studied.

The following important guidelines can be drawn on the desired injection water chemistry requirements for surfactant
flooding processes: (1) injection water should to be treated/softened to remove divalent ions (<10 ppm) and match salinities
with those of optimal salinity (<50000-60000 ppm) for conventional ASP floods using sulfonate surfactants and/or alkali, (2)
SmartWater surfactant flooding is shown to be beneficial in both sandstones and carbonates and these processes require
lower salinity SmartWater (<5000 ppm in sandstones), and (3) lower salinity requirements in SmartWater surfactant flooding
may also warrant complete removal of divalent ions and partial removal of monovalent ions depending on source injection
water, surfactant type and to optimally synergize with SmartWater injection water chemistry in a specific reservoir rock-
fluids system.

3.4 Miscible CO2 WAG

Injected CO2 gas, under proper reservoir conditions of temperature and pressure and in the presence of favorable crude oil
composition, can become miscible with reservoir crude oil. This EOR process is gaining much attention in recent years due
to the added benefit of underground CO2 sequestration. The development of miscibility between oil and CO2 in the reservoir
remobilizes huge amounts of oil, otherwise that is trapped due to the capillary forces, thereby resulting in incremental oil
recovery. Gas-oil miscibility in the process is developed through in-situ compositional changes that occur due to multiple
contacts of injection gas with reservoir crude oil as the injected CO2 gas moves through the reservoir. The three main
mechanisms that contribute to enhanced oil recovery in CO2 miscible gas flooding process are: (1) zero interfacial tension,
(2) increase in oil volume due to swelling, and (3) oil viscosity reduction.

Two types of gas injection processes are commonly used in the field for EOR applications. One is continuous gas injection
(CGI) and the other is water-alternating-gas (WAG) injection. In CGI, the gas is injected as continuous slugs, whereas WAG
utilizes alternate slugs of gas and water aimed to somewhat offset gravity segregation in the reservoir. Few field projects used
hybrid WAG, a combination of CGI and WAG, where gas is injected continuously at the beginning to have faster response
and produce more oil and then WAG is initiated to prevent early gas breakthrough and to limit CO2 utilization. CO2 miscible
flooding can be considered as a matured technology with lot of prior experience reported in West Texas Permian basin and
currently there are about 112 miscible CO2 floods are under operation in United States64. A large miscible CO2 flood is also
presently under operation at Weyburn oil field located in Midale, Saskatchewan, Canada. Availability of CO2 source and
infrastructure for gas transportation are the major limiting factors for the technology. Severe corrosion with acid solutions,
loss of CO2 due solubility in water, asphaltene precipitation, and formation of hydrates are some other key challenges.

WAG theoretically combines the good microscopic displacement of gas injection with improved macroscopic sweep of the
water injection. It is the most widely applied miscible gas injection process in the field and has become a default for
commercial gas injection. But in reality, injected water provides good sweep in WAG only in the regions proximity to
injection well and poor macroscopic sweeps are envisioned at certain distance away from the injection well deep in the
reservoir due to natural tendencies of gas to over-ride and water to under-ride65. Furthermore injected CO2 viscosities at the
reservoir conditions are very low in the range of about 0.05 to 0.10 cP, which results in unfavorable mobility ratio leading to
viscous fingering and premature gas breakthrough. Hence attesting gravity segregation and viscous fingering in gas injection
has become a major challenge to improve the efficiency of miscible gas floods. Several newer advanced technologies are
being researched in oil industry today such as foams (using water/CO2 soluble surfactants and nanoparticles), gels, and CO2
thickeners to mitigate gravity over-ride/viscous fingering and reduce gas utilization in miscible CO2 floods. Christensen
et al.66 reviewed 59 WAG field projects, which include both onshore and offshore and non-CO2 gas injection processes such
as hydrocarbon and N2. Interestingly almost all the offshore projects used hydrocarbon gas for WAG due to the availability
of hydrocarbon gas from production. This study has reported an average incremental oil recovery of about 10% OOIP for
10 SPE-169048-MS

miscible WAG field projects. A review of 12 previously conduced field-scale CO2 miscible floods by Brock and Bryan67
showed incremental oil recoveries in the range of 8-10% OOIP.

There were not many studies reported in the literature studying on injection brine compositional effects in tertiary miscible
CO2 WAG processes. Based on the Berea core flood results obtained using a model oil (n-decane) and CO2 gas, Kulkarni
and Rao68 reported that WAG recoveries showed significant decrease in oil recovery when the brine composition was
changed from 5% NaCl to 0.9 wt% multivalent reservoir brine containing 650 ppm hardness ions. About 12% decrease in oil
recovery was observed in this study and these results were attributed to higher solubilities of CO2 in multivalent brines when
compared to monovalent brines. Al-Netaifi69 conducted CO2 WAG core floods using Berea sandstones, n-decane oil and two
different brine compositions, moderate salinity brine containing 2.55 wt% NaCl and 0.45% CaCl2 and higher salinity brine
containing 5.89 wt% NaCl, 2.24 wt% CaCl2, and 0.15 wt% MgCl2. Both these core floods showed almost similar ultimate oil
recoveries, but faster oil recovery response was observed with higher salinity brine. These two studies thereby pointed out
adverse effects of higher CO2 solubilities in miscible WAG with lower salinity brines. It is also important to note that
nothing much can be inferred about low salinity effect from these studies since non-reactive decane is used as oil phase
without providing much information on clay content details in Berea. Aleidan and Mamora70 carried out secondary miscible
CO2 core floods in heterogeneous carbonate cores with 31o API West Texas crude oil to evaluate the effects of injection
brine salinity (0, 6, and 20 wt%) in WAG. The results indicated better ultimate oil recoveries at lower injection brine
salinities and were attributed to better displacement efficiency of CO2-water mixture to mobilize the bypassed oil after the
CO2 slug in these highly heterogeneous systems. Zhang and Sarma71 summarized other favorable view points of lower
salinity and higher CO2 dissolution in tertiary miscible WAG such as reduced viscous fingering to result in delayed gas
breakthrough and access to the oil shielded by “water blocking” through diffusion. Jiang et al.72 performed both secondary
water and tertiary miscible CO2 WAG core floods using Berea sandstones of low clay content and crude oil at different
injection brine salinities and these results are shown in Figure 9. Water flood recoveries increased at lower salinities
(however wettability alteration effect is questionable) whereas WAG recoveries slightly decreased due to higher CO2
solubilities in brine. This is because, at lower salinities larger amounts of CO2 gas will be lost into the aqueous phase due to
increased solubility and as a result lower volumes of injected CO2 is available to interact with oil. Unlike continuous gas
injection, it is not possible to replenish CO2 gas lost into the water phase in WAG due to finite CO2 slug sizes used and
increased water saturation in the reservoir as the amount of water injected alternately with the gas increases with time. One
interesting conclusion that can be drawn from the data shown in Figure 9 is that the total oil recovery from low salinity
secondary water flood and low salinity tertiary miscible WAG is about 13-14% higher when compared to total oil recovery
obtained from these two floods at high salinity conditions. This result intuitively suggests that SmartWater benefits may
outweigh adverse CO2 solubility effects at lower salinities in some cases to provide an overall better incremental oil recovery
in SmartWater miscible WAG. However more systematic experimental work is required to confirm and accurately determine
on SmartWater effects in tertiary miscible CO2 WAG processes. A recent numerical simulation work by Dang et al.73 showed
about 9% OOIP increase in CO2 WAG recovery when low salinity water is used instead of high salinity water. Injection
scheme used consisted of 0.4 pore volumes of high salinity water followed by four WAG cycles of low salinity brine/CO2
(0.8 pore volumes) and finally 0.6 pore volumes of buffering low salinity water. When the high salinity injection water in the
first 0.4 pore volumes was replaced with low salinity water (LSW), even more incremental oil was observed compared to 9%
OOIP with early oil production. A one-dimensional linear model was used in this study and the conventional low salinity
model was integrated with a comprehensive geochemical model to simulate the LSW-WAG process. As a result, these
authors concluded that low salinity water can improve WAG performance in both oil-wet and mixed-wet reservoirs due to
favorable ion-exhange and wettability alteration. However adverse effects of low salinities on CO2 solubilities were not
discussed in this study.

Solubility of CO2 in brines containing divalent ions is higher compared to monovalent ions at the same ionic strength74.
Hence relatively less adverse CO2 solubility effects are expected in WAG with injection waters stripped of divalent cations.
Also the use of low salinity SmartWater in miscible WAG may yield better incremental oil recovery in a specific reservoir
rock-fluids system where SmartWater benefits overcome the competing adverse CO2 solubility effects. The largest
successful mobility control demonstration project using foams involved injecting alternate slugs of surfactant containing
water with injection gas at Norsk Hydro’s Snorre field in the North Sea75. The use of such advanced foam based mobility
SPE-169048-MS 11

control techniques, wherein water based surfactants are used to generate insitu foams in miscible WAG, may need better
compatibility with injection water (especially hardness removal) depending on the surfactant type chosen for the application.
Due to absence of any direct experimental evidence from published data to support the advantage of low salinity effect, no
specific water salinity requirements are suggested for CO2 WAG in this study (lower salinity could be advantageous in some
cases). However low to moderate hardness ions are desired to prevent adverse CO2 solubility effects in water from the
alternating CO2 slugs in WAG.

3.5 Carbonated Water Flooding (CWF)

Carbonated water flooding is another emerging IOR/EOR method where water chemistry limits the amount of CO2 dissolved
in the injection water. Presently some active research is pursued in this area with the rationale that carbonated water injection
can reduce gravity segregation encountered in conventional WAG processes. In this technology, CO2 is dissolved in water
until the solubility limit is reached depending upon pressure, temperature, and injection water salinity and the carbonated
water so obtained is then injected into the reservoir (as a finite slug) followed by chase water. Solubility of CO2 in water
decreases with increasing temperatures up to 100oC, increases with increasing pressures, and decreases with increasing water
salinities76.

The process can be treated as subdued WAG since the amount of CO2 injected is limited based on CO2 solubility in
carbonated water volumes injected. All the CO2 injected together with water, as dissolved phase, stays in either water or oil
phase in the reservoir and there will not be any free CO2 gas in the reservoir to result in gravity over-ride. Dissolved CO2 in
the injected carbonated water preferentially partitions into oil phase by diffusion as the water contacts the oil, since the
solubility of CO2 in oil is about 3-7 times higher than that of water at similar pressure and temperature conditions77,78. CO2
transfer between oil and water continues until the oil saturation pressure becomes equal to that of water. As a result of these
mass transfer interactions, oil swells and loses its viscosity. Both these effects have positive impact on mobility ratio to result
in incremental oil recovery. There are some studies that even reported up to 20% reduction in oil-water interfacial tension
with the dissolution of CO2 in water phase79, which can further cause an improvement in microscopic sweep. Dissolution of
CO2 in water phase would also increase water viscosity and density which will make the injected water mobility more
favorable compared to normal injection water80,81.

Oil industry experience with carbonated water flood dates back to 1960. Hickok et al.82 reported the first commercial
carbonated waterflood project, the K&S project. It was shown in this project that because of carbonated water, the oil
recovery in one year was more than the total oil produced for the past 29 years in that field. Also, substantial improvements
in injectivity were observed because of the carbonated water. Corrosion and/or emulsion were not noticed in the producing
wells, lines or tank batteries, though it was expected. In fact, CO2 lines have been re-used several times during the staging of
the CO2 project. Other field applications of carbonated water flooding can be found elsewhere 83-86. Several papers described
laboratory experimental results on carbonated water flooding and all these studies are reviewed in detail by Dong et al.78. It is
important to note that only few papers that showed relevance to injection water chemistry and CO2 solubility in carbonated
water flooding are described in this study. Holm87 reported an incremental oil recovery of about 20% for carbonated water
flood when compared to water flood from core flood experiments conducted using Berea sandstone cores and a West Texas
crude oil. Martin88 observed 12% improvement in oil recovery due to carbonated water flood. One interesting observation
from this study is that waters with reduced carbonation showed lower incremental oil recoveries when compared to waters
abundantly saturated with CO2, which points out the importance of dissolving more CO2 in injection water. Incremental oil
recovery in carbonated water flooding is thereby correlated to carbonation level in injection water. This could become a “big
boon” for using low salinity SmartWater in carbonated water flooding to increase dissolved CO2 quantities in water and
hence to improve upon oil recovery. Kechut et al.89 studied the tertiary injection of carbonated water in coreflood
experiments, numerical simulation and a high pressure micromodel. Similar to secondary injection, oil swelling, change in oil
color and reconnection of oil ganglia were observed during tertiary recovery. These changes indicate dissolution of CO2 in
the oil phase, viscosity reduction, and remobilization of oil, respectively. The incremental oil recovery after tertiary CWF
was quantified to be 9.2% for stocktank crude oil in the reservoir core with seawater as injection brine at 100oF and 2500 psig
(shown in Figure 10). Another reported advantage of carbonated water injection is the high retention factor of CO2 (46% in
tertiary core flood), which indicates the good potential of carbonated water for carbon storage. The use of SmartWater in
carbonated water flooding can be attractive due to improved CO2 solubilities in injection water and additional benefit of
12 SPE-169048-MS

combining the wettability alteration aspect associated with lower salinity ionic composition of the water. It also provides
some room to sequester higher volumes of CO2 underground with carbonated waters made with lower salinity SmartWater.
However, to the best of our knowledge there seem to be no direct experimental studies carried out in the literature to
investigate the advantage of using low salinity SmartWater in carbonated water flooding in a systematic approach to clearly
distinguish on the salinity effect. One recent simulation study71 investigated the effects of brine salinity in secondary
carbonated water injection using a compositional reservoir model in a hypothetical and homogeneous geological environment
and showed about 10% increase in oil recovery when the brine salinity was reduced from 250,000 ppm to 100,000 ppm.
These increments in oil recovery were solely attributed to higher CO2 volumes injected with lower salinities (increased CO2
solubilities), since the effects of CO2 diffusion from water to oil and permeability modification by carbonated water were not
captured in the model. The use of lower salinity water in carbonated water injection has good potential to augment CWF
performance and it could also synergize very well with the low salinity effect. Injection water salinities below 5,000 ppm
with about 500 ppm and less divalents could be advantageous for carbonated water flooding in sandstones to combine both
the benefits associated with increased CO2 volumes and low salinity effect.

3.6 Steam Flooding

Steam flooding has been the most successful and matured of all EOR technologies and they are in practice since 1950’s.
These methods are applied in shallow reservoirs (<3000-5000 ft) to recover heavy oils, bitumen and tar sands (10-20o API).
They currently contribute to about 50-60% of EOR oil production in United States. Oil viscosity reduces drastically with
temperature to result in decreased mobility ratio, which is the main mechanism responsible for oil recovery in thermal
methods. There are several types of thermal floods applied in the field and cyclic steam stimulation, steam flooding, and
steam-assisted-gravity-drainage (SAGD) are the most widely used methods among them.

All steam floods are energy intensive and need steam in huge quantities. The required steam for thermal floods is generated
with steam generators using fresh water. Two types of steam generators are typically used, (1) once through steam generator
(OTSG), and (2) drum boilers. OTSG provides 80% quality steam whereas drum boilers produce steam at 100% quality. The
steam qualities from OTSG can be further increased by employing a series of vapor liquid separators down steam of steam
generator. The natural gas consumption for steam generation could be as high as 500 tonnes/m3 of bitumen90. The steam oil
ratios (m3/m3) range from 1.9 to 2.5 for large scale SAGD field projects91. Luhning et al.92 estimated that for a 4000 m3/d oil
production, steam flood requires about 1,150,000 m3/d of natural gas and 1700 m3/d of fresh water.

Removal of hardness ions from source water is one critical parameter to satisfy the stringent boiler feed water quality
specification requirement. These ions precipitate and result in scale formation on the tubing surfaces to eventually lead to
tube failures in the steam generator. The deposited materials also act as an insulating layer to reduce heat transfer, thermal
efficiency and can result in thermal-stress cracking. Typical water quality requirements for OTSG and drum boilers given by
Pedenaud et al.93 are shown in Tables 2 and 3, respectively. As can be seen, both OTSG and drum boilers require essentially
zero hardness in the feed water. OTSG boilers have relatively higher tolerance for feed water contaminants compared to
drum boilers. This could be due to lower concentration factor and ease of mechanical cleaning to remove the deposits in
OTSG boilers94. The specification guidelines provided in Tables 2 and 3 are for produced water and as a result feed water
contains contaminants like silica and residual oil. During steam injection, silica within the reservoir dissolves at high
temperatures and produced with water. These contaminants will not be present when river /brackish water and seawater are
used as the source water for treatment. Boiler water quality requirements are a function of boiler pressure and they become
more stringent at increasing pressures. Feed water quality requirements shown in Tables 2 and 3 seem to represent the upper
limit values at lower pressures. Based on the data shown in these tables, it can be concluded that water chemistry
requirements to generate steam for thermal floods require low salinity waters (<10,000-12,000 ppm), but with almost zero
hardness (<0.5-1 ppm) to meet boiler feed water specification limits.

3.7 IOR/EOR Water Chemistry Requirement Guidelines

IOR/EOR water chemistry requirement guidelines proposed in this study are summarized in Table 4 and Figure 11. In Figure
11, total salinity is plotted against hardness and sulfates. Sulfates are considered to be 20-80% of total hardness and sulfates
SPE-169048-MS 13

in that they are 20% for a portion of the ordinate axis (region marked as A in Figure 11) and 80% for the rest (region marked
as B in Figure 11).

As can be seen, desired salinities for polymer and steam floods are less than 5,000 and 10,000-12000 ppm, respectively, with
low hardness. The major difference is that steam floods require essentially zero hardness (<0.5-1 ppm) whereas hardness ions
less than 100 pm are desired for polymer floods to mitigate adverse effects of these key detrimental ions on polymer solution
viscosities. Injection water containing 30,000-50,000 ppm salinity (based on source seawater compositions in different
geographic locations worldwide) with moderate hardness (500-600 ppm) and less than 40-100 ppm sulfates is suited for
offshore water floods. SmartWater flood in sandstones requires salinities less than 5000 ppm with low to moderate
hardness/sulfate ion content (<500 ppm). SmartWater flood in carbonates needs low to moderate salinities in the range 6000-
28000 ppm, but with high hardness and sulfate ion content. ASP floods require water salinities ranging from 10,000 ppm to
50,000 ppm (depending on optimal salinity and formation water salinity) with negligible hardness ions (<10 ppm). No
specific salinity requirement guidelines are evident from published data for CO2 WAG (lower salinity could be advantageous
in some cases), but low to moderate hardness ions are preferred (<500 ppm). Injection water salinities below 5,000 ppm with
about 500 ppm and less divalents could be suited for carbonated water flooding in sandstones to combine both the effects of
increased CO2 solubilities and low salinity.

4. Summary and Conclusions

In this paper, a detailed overview was provided to highlight on the importance of injection water chemistry in different
IOR/EOR processes. It was also shown using selected examples from published data that injection waters of optimized
salinity and composition could synergistically combine with several EOR processes to result in better incremental oil
recoveries. A unique set of IOR/EOR water chemistry requirement guidelines was proposed summarizing desired injection
water salinities and compositions for all IOR/EOR processes. The following are major conclusions from this study.

SmartWater through its water chemistry plays an important role to impact on several IOR/EOR processes including the
offshore water floods. SmartWater with modified seawater composition containing negligible sulfates (<40-100 ppm)
with low to moderate hardness (<500-600 ppm) is a prerequisite for offshore water floods to prevent scaling and souring
in reservoirs.

lower salinity SmartWaters with threshold salinities less than 5,000 ppm are desired for SmartWater flooding in
sandstones. In contrast low to moderate ionic strength SmartWaters (2-10 times seawater reduced salinity/28000-6000
ppm) or SmartWaters of modified seawater depleted in monovalent ions, but enriched in potentially determining divalent
ions (4 times sulfates, 1 times calcium and magnesium) are suited for improved oil recovery in carbonates.

Polymer floods prefer a low salinity SmartWater containing negligible monovalent and divalent cations (<5000 ppm
salinity and <100 ppm hardness). Specifically divalent cations have much more pronounced detrimental effect on
polymer solution viscosities compared to monovalent ions. SmartWater benefit compounds with polymer flood
advantage in SmartWater polymer flooding and hence higher incremental oil recoveries are expected.

Optimal salinity SmartWaters without hardness ions (<10 ppm) are required for conventional ASP chemical floods
involving surfactant and alkali chemicals. Low salinity SmartWaters may sometime work synergistically with surfactants
for improved performance in chemical floods. Dilute surfactant floods using low salinity SmartWater (seawater dilution)
have a definite edge for carbonate reservoirs due to compounding of these two additive effects to result in an overall
better incremental oil recovery.

Lower salinity SmartWater advantages in CO2 miscible WAG are not clearly identified due to the presence of two
opposing effects associated with low salinity and CO2 solubilities. There could be a benefit in some cases where
SmartWater effects outweigh adverse CO2 solubility effects. More systematic experimental work is required to
accurately determine SmartWater effects in tertiary CO2 miscible WAG.

The use of lower salinity SmartWater for carbonated water flooding looks promising due to increased CO2 carbonation
levels and the resulting additive effect of SmartWater on oil recovery.

Steam floods require a special type of SmartWater with essentially zero hardness (<0.5-1 ppm) to meet boiler feed water
quality specifications to generate the steam. SmartWater is used to make up the injectant for thermal floods in contrast to
other EOR processes where it was used as carrier fluid for additives.
14 SPE-169048-MS

The effects of salinity and water ionic composition on different recovery processes described in this study call for
development of fit-for-purpose water treatment technologies and novel blending schemes to adequately address injection
water chemistry requirements of a specific IOR/EOR process.

These results also point out the need to develop “water chemistry” as a specialty discipline within oil industry and
advocate for better integration of this emerging focus area with other key surface and subsurface related disciplines to
effectively improve upon IOR/EOR upstream value chain.

Acknowledgements
The authors would like to thank Saudi Aramco for providing permission to present and publish this work. The authors would
also like to acknowledge Society of Petroleum Engineers (SPE) for using most of the data and figures from their past and
recent papers in this review study. Finally they would like to thank management of EXPEC ARC for the great support.

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SPE-169048-MS 15

17) Doust, A.R., Puntervold, T.P., Strand, S. and Austad, T.A., “Smart Water as Wettability Modifier in Carbonate and Sandstone,” Paper
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16 SPE-169048-MS

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SPE-169048-MS 17

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18 SPE-169048-MS

92) Luhning, R.W., Das, S.K., Bakker, J., Engleman, J.R., Wong, S., Fisher, L.J., Grabowski, J., Sullivan, L.A. and Boyle, H.A., “Full
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Facilities”, Paper presented at the International Water Conference, San Antonio, TX, 24-28 Oct., 2010.

36
Table 1: Typical Seawater and Offshore Formation Water Compositions
(Data Source: Crabtree et al., 1999; Ref. 36)
Formation Water Seawater                                                                
Ion
(ppm) (ppm)
Sodium 31,275 10,890
Potassium 654 460
Magnesium 379 1368
Barium 269 0
Strontium 771 0
Sulfate 0 2960
Chloride 60412 19,766
Calcium 5038 428
 

93
Table 2: OTSG Boiler Feed Water Specification
(Data Source: Pedenaud et al., 2005; SPE; Ref. 93)

Parameter Specification limit

Total Hardness < 1 mg/l CaCO3

Barium < 0.1 mg/l
Iron <0.25 mg/l
Silica < 100 mg/l
Oxygen < 0.02 mg/l
Oil < 0.5 mg/l
TDS < 12,000 mg/l
 
93
Table 3: Drum Boiler Feed Water Specification
(Data Source: Pedenaud et al., 2005; SPE; Ref. 93)

Parameter Specification limit

Total Hardness < 0.5 mg/l CaCO3
Copper < 0.005 mg/l
Iron <0.02 mg/l
Silica < 20 ug/l
Oxygen < 0.02 mg/l
Oil < 0.3 mg/l
*
TDS < 3500 mg/l  
 
 
 
SPE-169048-MS 19

Table 4: IOR/EOR Injection Water Chemistry Requirement Summary

Total Salinity Hardness Sulfates

IOR/EOR Process
(ppm) (ppm) (ppm)
Offshore water floods 30000-50000 <500-600 <40-100
SWF in sandstones <5000 <500 n/a
SWF in carbonates 6000-28000 <2000-3000 <10000
Polymer flood <5000 <100 n/a
ASP flooding <50000-60000 <10 n/a
SW surfactant flooding in sandstones <5000 <100 n/a
Miscible CO2 WAG <50000-60000 <500 n/a
Carbonated water flooding <5000 <500 n/a
Steam flooding <10000-12000 <0.5-1.0 n/a

28
Figure 1: Core Flood Oil Recovery in a Carbonate SmartWater Flood
(Figure Source: Yousef et al., 2011; SPE; Ref. 28)
20 SPE-169048-MS

Figure 2: Recovery Mechanism Dependence on Water Chemistry in Carbonate SWF

Figure 3: Desired Injection Water Chemistry for SWF in Carbonates

SPE-169048-MS 21

39
Figure 4: Reservoir Souring Predictions with Seawater Injection

(Figure Source: Al-Kindi et al., 2008; SPE; Ref. 39)

48
Figure 5: Polymer Requirements for Seawater versus Low Salinity SmartWater

(Figure Source: Ayirala et al., 2008; SPE; Ref. 48)

22 SPE-169048-MS

51
Figure 6: Recovery Comparison between Low Salinity SmartWater and High Salinity Polymer Floods
(Figure Source: Mohammadi et al., 2012; SPE; Ref. 51)

100
90
Low Salinity
80 Surfactant

70
Oil  Recovery  (%OOIP)  

60
50
40
30
20
10
0
0 5 10 15 20
Volumes  Injected  (PV)  
Secondary  LS Secondary  LS  +  tertiary  surfactant  LS

Secondary  SW Secondary  SW  +  Tertiary  Surfactant  LS

60
Figure 7: Low Salinity SmartWater Surfactant Flooding in Sandstones

(Data Source: Alagic and Skauge, 2010; Ref. 60)

SPE-169048-MS 23

63
Figure 8: Low Salinity SmartWater Dilute Surfactant Flooding in Carbonates

(Data Source: Yousef et al., 2013; Ref. 63)

Low Salinity-CO2 Solubility Effect

72
Figure 9: Effect of Salinity on Water Flooding and Miscible CO2 WAG

(Figure Source: Jianag et al., 2010; SPE; Ref. 72)

24 SPE-169048-MS

CWI

89
Figure 10: Carbonated Water Flood Incremental Oil Recovery
(Figure Source: Kechut et al., 2010; SPE; Ref. 89)

10000
SWF  in  Carbonates
B
Hardness  +  Sulfates  (ppm)

1000
SWF  in  Sand  Stones
Offshore  Water  Flood
CO2  WAG
100
Polymer  
Flood
A 10
ASP  Flood

1
Steam   Sulfates  =  20-­‐80%  *  (hardness  +  sulfates)
Flood A  =  20%  ;  B  =  80%
0.1
0 10000 20000 30000 40000 50000
Salinity  TDS  (ppm)
Figure 11: IOR/EOR Water Chemistry Requirement Diagram