Energy 77 (2014) 963e982

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Energy
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Review

Review of ASP EOR (alkaline surfactant polymer enhanced oil

recovery) technology in the petroleum industry: Prospects and
challenges
Abass A. Olajire*
Industrial and Environmental Chemistry Unit, Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, P. M. B 4000,
Ogbomoso, Oyo State, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: Owing to the inefficiency of the conventional primary and secondary recovery methods to yield above
Received 10 July 2014 20e40% of the OOIP (original oil in place) as incremental oil, the need for EOR (Enhanced Oil Recovery)
Received in revised form techniques to recover a higher proportion of the OOIP has become imperative. ASP (Alkaline/Surfactant/
24 August 2014
Polymer) is one of such techniques that has proven successful due to its ability to improve displacement
Accepted 2 September 2014
Available online 12 October 2014
and sweep efficiency. Alkalineesurfactantepolymer (ASP) flooding is a combination process in which
alkali, surfactant and polymer are injected at the same slug. Because of the synergy of these three
components, ASP is widely practiced in both pilot and field operations with the objective of achieving
Keywords:
Petroleum industry
optimum chemistry at large injection volumes for minimum cost. Despite its popularity as a potentially
Enhanced oil recovery cost-effective chemical flooding method, it is not without its limitations. This paper therefore focuses on
Alkaline/surfactant/polymer flooding the reviews of the application of ASP flooding process in oil recovery in the petroleum industry and its
Interfacial properties limitations in maximizing oil recovery from onshore and offshore reservoirs. Also discussed are technical
Synergy in ASP flooding solutions to some of these challenges.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction ASP flooding is a technique which is developed out on the basis

The high prices of crude oil and the future energy demand
worldwide have necessitated the needs for EOR (Enhanced Oil
Recovery) processes. Surfactant-based process, especially ASP
(Alkaline/Surfactant/Polymer) method has been identified as a
cost-effective CEOR (Chemical Enhanced Oil Recovery) process
yielding high recovery rates of above 20% in some oilfields like
Daqing oilfield in China [1,2]. While the other chemical enhanced
oil recovery (CEOR) methods have suffered several drawbacks like
adsorptive surfactant loss in a plain surfactant flood or long dura-
tion of a dilute alkaline flood, the ASP promises to alleviate such
problems [3]. The possession of a combined chemical phase
behavior of the injected surfactant and the in-situ generated natural
surfactant is one of key advantages of the ASP flood over other
CEOR methods. Thus, significant developments have made ASP
flooding a viable option for field enhanced oil recovery and more
attractive than other CEOR methods [4,5].
* Tel.: þ234 8033824264.
E-mail address: olajireaa@yahoo.com.
of alkali flooding, surfactant flooding and polymer flooding [6e8]
with gradual enhancement of oil recovery by decreasing IFT
(interfacial tension), increasing capillary number, enhancing
microscopic displacing efficiency, improving mobility ratio and
increasing macroscopic sweep efficiency [9]. ASP flooding utilizes
three types of chemicals e alkali, surfactant and polymer to recover
large amounts of waterflood residual oil. This process combines the
macroscopic volumetric sweep efficiency improvement from the
polymer due to reduction in watereoil mobility ratio with the
ability of surfactants (both added and in situ soaps) to enhance
microscopic sweep efficiency [10e12]. This enhancement results
from dramatic reduction of oilewater interfacial tension (IFT)
which increases capillary number (Nc) by orders of magnitude to
the required range for efficient oil recovery [13,14]. Alkali forms
soaps by reacting with naturally occurring organic acid in the crude
oil, which interacts synergistically with added surfactant to pro-
duce ultra-low IFT [15e17]. The ultra-low IFT is obtained by sur-
factant distribution between oil and water phase, and surfactant
arrangement at interface of oil/water. This is controlled by pH value
and ionic strength [18,19]. The alkali injected with surfactant can
reduce surfactant adsorption, play the role of ionic strength and
lower IFT [20e22]. Addition of polymer increases the viscosity of its

http://dx.doi.org/10.1016/j.energy.2014.09.005
0360-5442/© 2014 Elsevier Ltd. All rights reserved.
964 A.A. Olajire / Energy 77 (2014) 963e982

Nomenclature N67 Neodol 67-7PO (propoxylated) sulfate

NaOH sodium hydroxide (or caustic soda)
AAS alkylearyl sulphonate Na2CO3 sodium carbonate (or soda ash)
A alkaline NaHCO3 sodium bicarbonate
AOS a-olefin sulphonate NaBO2 sodium metaborate
AP alkaliepolymer Na2SO4 sodium sulfate
APG alkyl polyglycosides Nc capillary number
API American Petroleum Institute N original oil in place
ASP alkaline/surfactant/polymer Np accumulative oil recovered
AS alkaliesurfactant Nb bond number
Bo formation volume factor of the oil Nt total trapping number
CaSO4 anhydrite (calcium sulfate) OOIP original oil in place
CaSO4.2H2O gypsum (calcium sulfate dihydrate) O/W oil-in-water
CaCO3 calcium carbonate OPEX operating cost
Ca(OH)2 calcium hydroxide P polymer
CEOR chemical enhanced oil recovery Pr permeability reduction factor
DETPMP diethylenetriaminepenta (methylene phosphonic acid) PAA polyacrylic acid
EA ethoxylated alcohol PAM polyacrylamide
EOR enhanced oil recovery PARCOM Paris Commission
EO ethoxylate PASP polyaspartates
Ero oil recovery efficiency PO propoxylate
Edo microscopic or displacement efficiency PPCA poly phosphono carboxylic acid
Evo macroscopic or volumetric sweep efficiency PS petroleum sulphonate
Ea areal displacement efficiency PV pore volume
Ev vertical displacement efficiency R resistance factor
FPSO floating, production, storage and offloading Rr residual resistance factor
FSO floating storage and offloading S surfactant
g acceleration due to gravity SAC strong acid cation
HAo concentration of acid in oil SIS select ion sequestration
HAw concentration of acid in water Soi initial oil saturation
HEC hydroxyl ethyl cellulose Sor residual oil saturation
HPAM partially hydrolyzed polyacrylamide Vp permeability variation
IFT interfacial tension WAG water alternating gas injection
IOS internal olefin sulfonate WAC weak acid cation
KD partition coefficient of HA between oil and water mo oil viscosity
Ka reaction constant mw water viscosity
krw relative permeability of water n brine velocity (or Darcy's velocity)
kro relative permeability of oil lw water mobility
ka single phase permeability (absolute permeability) lo oil mobility
kp permeability of polymer solution lp polymer solution mobility
kw permeability of water lwp mobility of water after polymer injection
kwp permeability of water after polymer injection sow oil/water interfacial tension
M mobility ratio q contact angle between the wetting phase and the rock
Mg(OH)2 magnesium hydroxide Dr oil/water density difference
Mg magnesium

aqueous phase [23], so that the mobility of aqueous phase de-
creases. Thus, the decrease in mobility ratio greatly increases sweep
efficiency.
Substantial research works are being carried out worldwide on
ASP flooding process by different researchers [24e29]. The devel-
opment of ASP EOR technology and advances on surfactant
chemistry have brought a renewed attention for chemical floods
[30], especially to boost oil production in mature and waterflooded
fields. Currently, there are numerous active ASP flooding projects
worldwide, with the ASP flooding implemented at the Daqing field
in China considered as one of the largest ASP ongoing projects [31].
Several current ASP oilfield applications are reported in the litera-
ture [31,32]. Meanwhile, disadvantages identified during the
implementation process of the ASP flooding technology, such as,
severe scaling in the injection lines and strong emulsification of the
produced fluid [33e37] also limited its further application in the
field. This study reviewed and assessed some of the recent ad-
vances and prospects made by the application of ASP flooding
process in oil recovery in the petroleum industry and its limitations
to maximizing oil recovery from onshore and offshore reservoirs.
Also discussed is how these challenges could be technically
addressed.
2. Enhanced oil recovery (EOR) processes
The ultimate goal of EOR processes is to increase the overall oil
displacement efficiency, which is a function of microscopic and
macroscopic displacement efficiency. Based on the overall mate-
rials balance of the reservoir, the overall oil recovery efficiency (Ero)
can be defined as:
 A.A. Olajire / Energy 77 (2014) 963e982
Np
Ero ¼
N capillary forces or interfacial tension between the displacing fluid
where N is the original oil in place, Np is the accumulative oil
recovered after recovery process. The overall efficiency consists of
microscopic or displacement efficiency (Edo) and macroscopic or
volumetric sweep efficiency (Evo) as the given in equation below.
Ero ¼ Evo Edo ¼ Ea Ev Edo
where, Ea is the areal displacement efficiency, Ev is vertical
displacement efficiency.
Microscopic or displacement efficiency refers to the displace-
ment or mobilization of oil at the pore scale and measures the
effectiveness of the displacing fluid in moving the oil at those places
in the rock when the displacing fluid contacts the oil [38]. It is the
ratio of the amount of oil recovered to the oil initially present in the
swept volume and can be expressed in terms of saturation as;
Soi  Sor
Edo ¼
Soi
where Soi is the initial oil saturation, Sor is the residual oil saturation
after oil recovery process.
The displacement efficiency is a function of time, liquid viscos-
ities, relative permeabilities, interfacial tensions, wettabilities and
capillary pressures. Even if all the oil were contacted with injected
water during waterflooding, some oil would still remain in the
reservoir. This is due to the trapping of oil droplets by capillary
WATER
Vertical Sweep or Macroscopic Sweep Efficiency
INJECTION
WELL
WATER
Vertical Sweep
WATER
INJECTION WELL
Fig. 1. Schematics of microscopic and macroscopic sweep efficiencies [41].
965
forces due to the high interfacial tension (IFT) between water and
oil. Summarily, microscopic efficiency can be increased by reducing
(1)
and oil or by decreasing the oil viscosity [39]. The displacement
efficiency is characterized by the capillary number Nc, a ratio of
viscous to local capillary forces. It can be increased by increasing
the viscous force and reducing the capillary forces. The viscous
force will help oil mobilization, while the capillary forces favor oil
(2) trapping [40].
Macroscopic or volumetric sweep efficiency refers to the effec-
tiveness of the displacing fluid(s) in contacting the reservoir in a
volumetric sense. Volumetric sweep efficiency indicates the effec-
tiveness of the displacing fluid in sweeping out the volume of a
reservoir, both areally and vertically, as well as how effectively the
displacing fluid moves the displaced oil toward production wells
[38]. It depends on the selected injection pattern, character and
locations of the wells, fractures in the reservoir, position of gaseoil
and oilewater contacts, reservoir thickness, heterogeneity,
mobility ratio, density difference between the displacing and the
displaced fluid, and flow rate etc. Usually, sweep efficiency can be
(3)
decomposed as the product of areal sweep efficiency and vertical
sweep efficiency. Areal sweep efficiency represents the fraction of
total formation area swept by the injected displacing agent; vertical
sweep efficiency denotes the fraction of the total formation volume
in the vertical plane swept by the injected displacing agent. Sweep
efficiency can be greatly improved with mobility control methods,
such as polymers, foams and WAG injection (water alternating gas)
process. The polymer in ASP process could significantly increase the
sweep efficiency. Fig. 1 presents a schematic of sweep efficiencies:
Microscopic Sweep
OIL OIL
RESERVOIR ROCK
Areal Sweep
PRODUCING
WELL
OIL AND WATER
OIL
PRODUCING WELL
966 A.A. Olajire / Energy 77 (2014) 963e982
microscopic and macroscopic (areal sweep and vertical sweep). The
overall displacement efficiency of any oil recovery displacement
process can be increased by improving the mobility ratio or by
increasing the capillary number or both [39], which are the focal
points of most recovery methods including ASP.
2.1. Mobility control mechanism
Mobility ratio is defined as the mobility of the displacing fluid
(i.e. water) divided by the mobility of the displaced fluid (i.e. oil). In
a waterflooding system, this is the ratio of water to oil mobilities.
The mobility ratio, M, for a waterflood is given by the following
expression:
Mobilitywater lw krw =mw krw mo
M¼ ¼ ¼ ¼ (4)
Mobilityoil lo kro =mo kro mw
where lw and lo are water and oil mobilities, respectively, in mD/
cp; krw and kro are relative permeabilities of water and oil,
respectively; mo and mw are oil and water viscosities, respectively
[41].
Volumetric sweep (or macroscopic sweep) efficiency increases
as M decreases, therefore mobility ratio is an indication of the
stability of a displacement process, with flow becoming unstable
(non-uniform displacement front or viscous fingering) when
M > 1.0. Thus, a large viscosity contrast between the displacing fluid
(i.e. water) and the displaced fluid (i.e. oil) causes a large mobility
ratio (unfavorable M) which promotes the fingering of water
through the more viscous oil (Fig. 2) and reduces the oil recovery
efficiency. For maximum displacement efficacy, M should be less
than or equal to 1. Viscous fluid (polymer) is used in ASP project to
achieve M being less than unity and this is achievable by improving
relative permeabilities (water and oil), increasing the viscosity of
displacing fluid (i.e. water) and decreasing the viscosity of dis-
placed fluid (i.e. oil).
2.2. Capillary forces mechanism
The capillary forces have great influence on oil recovery effi-
ciency, but the influence differs fundamentally for non-fractured
and fractured reservoirs. In a non-fractured reservoir, strong
capillary forces during waterflooding will trap oil and cause rela-
tively high residual oil saturation. Therefore, to remobilize residual
oil, there is need to reduce the oilewater IFT. While in fractured
reservoirs, spontaneous imbibition of water due to strong capillary
forces is an important and necessary mechanism to attain high
displacement efficiency [42]. Generally, capillary forces are
Fig. 2. (a) Waterflooding with unfavorable mobility ratio (M > 1), (b) Polymer augmented waterflooding with favorable mobility ratio (M  1) [44].
overcome by either viscous or gravity forces. The two dimension-
less numbers that are used to compare these forces include capil-
lary number (Nc) and bond number (Nb).
The capillary number (Nc) is a ratio of viscous to capillary forces
and is given as;
viscous forces vmw
Nc ¼ ¼ (5)
capillary forces sow cos q
where n is the brine velocity (or Darcy's velocity), mw is the brine
viscosity, sow is oil/water interfacial tension and q is contact angle
between the wetting phase and the rock.
Capillary numbers for a mature waterflooding process have
been reported to be in the order of 107e106 [38]. At the end of the
waterflooding process, experience has shown that at these low
capillary numbers an important amount of oil is still left behind in
the reservoir trapped by capillary forces at the pore scale. To
mobilize the oil, either the brine velocity must be increased or the
oil/water IFT must be brought near zero, which produces a large
value of capillary number. Thus, if the capillary number is increased
through the application of EOR processes, residual oil will be
mobilized and recovered. The most practical alternative to signifi-
cantly increase the capillary number is through the application
chemical flooding, particularly ASP flooding [43,44].
In a system where gravity is more important, such as gravity
stabilized flow, the relevant quantity to maximize is the bond
number (Nb) [45], and is given as;
Drgka krw
Nb ¼ (6)
sow cos q
where, Dr is the oil/water density difference, g is acceleration due
to gravity and ka is the single phase permeability (absolute
permeability), krw is the displacing fluid relative permeability. Total
trapping number (Nt) was introduced to combine capillary and
bond effect [46]; it is expressed by the following equation:
Nt ¼ Nc þ Nb (7)
2.3. Classification of EOR processes
Fig. 3 is a simplified chart of some EOR methods normally car-
ried out in petroleum exploitation activities. The four major types
of enhanced oil recovery operations are chemical flooding, gas in-
jection, thermal recovery and others. Many secondary methods
basically involve perturbation of the unproductive reservoir via
 A.A. Olajire / Energy 77 (2014) 963e982 967

ENHANCED OIL RECOVERY

METHODS

Thermal Gaseous Chemical Others

Hot Electro Cyclic Continous In-situ

Water magnetic Vapor Vapor Combus- Alternated
Microbiological Vibration injection of
tion
water and gas

Ore
Explosives
Prospection
Miscible Miscible Miscible Miscible
CO2 N2 Rich gas Dry gas
Water injection at
the gas-oil interface
Immiscible Immiscible Miscible
CO2 N2 LPG

Polymers Foams Surfactants Alkaline

Solutions

Alkaline/Surfactant/
Polymer Solutions
(ASP)

Fig. 3. Classification of EOR processes.

some physical modification, for example, water, gas or steam matching the oil and water mobility through the addition of
flooding, however with low final oil recovery. polymer [48]. Alkali is also added to the water to reduce adsorption
Oil extraction activities can be greatly optimized by EOR of the surfactant onto the pore walls and to control the local salinity
methods that employ some kind of chemical technique, and find to ensure minimum IFT and alter the rock wettability [48e50]. ASP
huge applicability when secondary methods fail to improve reser- flooding can significantly improve oil recovery [3,51,52] with in-
voir productivity. Some of these techniques are cited in Fig. 3, cremental costs reported to be as low as $2.42 per incremental
with particular emphasis to the ASP methods (Alkalin- barrel for an onshore field [53]. The following sections discuss what
eeSurfactantePolymer). The lowering of tensions between water each component accomplishes-on its own and in combination with
and oil is the main driving force that enables the use of such each others (synergistic mechanisms).
methods. Traditionally, many EOR techniques target the oil
remaining after waterflooding. Waterflooding is generally not
considered an EOR method unless it is combined with some other 3.1. Surfactant flooding
flooding methods. EOR methods generate various physical effects
that help recover remaining oil that is trapped in the reservoir rock. A surfactant (Surface Active Agent) molecule has two functional
The incremental recovery factor has a large range of values when groups, namely a hydrophilic (water-soluble) or polar group and a
compared with waterflooding, which is typically not considered an hydrophobic (oil-soluble) or non-polar group (Fig. 4). The hydro-
EOR method. Incremental recovery factor also varies with the rock phobic group is usually a long hydrocarbon chain (C8eC18), which
properties, therefore recovery factor (Table 1) is presented as low,
moderate, high, very high or highest with respect to waterflooding,
Table 1
which provides the base case for different EOR methods.
Incremental recovery factors of EOR methods.
Table 2 also summarizes some of the advantages and disad-
vantages of ASP EOR over other EOR methods. EOR method Variety of forms Incremental recovery
factor
a
Waterflood Waterflood Base case
3. Mechanisms of alkaline surfactant polymer flooding Engineered water Low
technology Gas flood immiscible Hydrocarbon Moderate
CO2 High
Nitrogen or flue gas Moderate
Alkaline surfactant polymer (ASP) involves the injection of a Gas flood miscible Hydrocarbon High
solution containing polymer, alkali and surfactant into a depleted Hydrocarbon WAG Very high
or matured oilfield with the objective of achieving optimum CO2 High
CO2 WAG Highest
chemistry at large injection volumes for minimum cost. The alka-
Thermal Steam High
liesurfactant mixture forms an emulsion with the oil, which is then High pressure air High
swept and displaced from the reservoir using a polymer drive. Chemical Polymer Low
Alkaline surfactant polymer (ASP) flooding improves microscopic Surfactant Moderate
displacement efficiency by reducing the IFT between the water and ASP High
a
oil through the addition of a surfactant to the water, while Waterflooding provides the base case for comparison of the EOR methods.
968 A.A. Olajire / Energy 77 (2014) 963e982

Table 2 hydrophilic groups (heads). Therefore, a surfactant molecule con-

Advantages and disadvantages of ASP EOR over other EOR methods.
Advantages
1. Cost-effective chemical flooding
process for light and medium oils,
and in particular for offshore field
application.
2. Effectively mobilize the residual oil
and economically increase the re-
covery factor from a reservoir.
3. The synergy between the chem-
icals reduces the interfacial ten-
sion (IFT) between the brine and
residual oil causing capillary
number to increase.
4. The synergistic effects of alkali,
surfactant and polymer in ASP
flooding also give higher recovery
compared to other EOR methods
except CO2 WAG and hydrocarbon
WAG.
5. It utilizes low cost alkali to sup-
plement expensive synthetic
surfactant.
6. The presence of alkali also in-
creases the surface charge on the
rock surface and hence decreases
the surfactant loss due to adsorp-
tion on the rock [11].
7. Increased well run lifetimes at
least 4-fold.
Disadvantages
1. Severe silicate scaling in produce
wells, and thus leads to costly
workovers and well abandonment.
2. Excessive alkali consumption and
surfactant precipitation due to the
presence of divalent cations (Ca2þ
and Mg2þ) in injection water.
3. Salinity optimization and water
softening are required
4. A strong alkali has a detrimental
effect on polymer performance.
5. Reaction of alkali with clays, zeo-
lites and swelling causes perme-
ability reduction and makes the
process less effective.
6. Corrosion is also a problem asso-
ciated with the alkali process
7. Formation of tough emulsions are
observed in many ASP process,
leading to difficulties in processing
the produced fluid [5,8,47].
tains either a water insoluble or oil soluble component and a water
soluble component (Fig. 5).
Depending on the nature of the hydrophilic group, surfactants
are classified into four (anionic, cationic, zwitterionic and nonionic)
groups [55]. The surface-active portion of anionic surfactants bears
a negative charge, e.g. carboxylate (COO), sulfate ðSO 4 Þ; or sulfo-
nate ðSO3 Þ: Cationic surfactants have a hydrophilic part that bears a
positive charge, cetyl ammonium bromide (C16H33N(CH3)Br).
When this surfactant dissolves in water, the positive charge will be
on the N-atom. Zwitterionic surfactants have both a positive and a
þ
negative charge, e.g. RN H2 CH2 COO (long chain amino acid),
C17H37NSO3 (alkyldimethylpropanesultaine). Nonionic surfactants
bear no apparent ionic charge. However the hydrophilic part is
soluble in water because of polar groups. These groups can be hy-
droxyl (OH) or polyethylene oxides (OCH2CH2)n [56]. The structures
of various classes are given in Table 3.
Anionic surfactants are used for EOR applications. Some blends
of different surfactants are also used to get low IFT conditions and
favorable wettability changes. Examples of such blend are blends of
N67 (Neodol 67-7PO sulfate) and C15eC18 IOS (internal olefin sul-
fonate). Surfactants that are used in EOR include PS (petroleum
sulphonate), AOS (a-olefin sulphonate) and internal olefin sulph-
onate (IOS), AAS (alkylearyl sulphonate) and EA (ethoxylated
alcohol) [32]. Table 4 summarizes some properties of these sur-
factants. Thermal stability of the surfactants is in the following
order

may or may not be branched, while the hydrophilic group is formed
by moieties such as carboxylates, sulfates, sulfonates (anionic), al-
cohols, polyoxyethylenated chains (nonionic) and quaternary
ammonium salts (cationic).
Surfactants work in ASP flooding to lower the IFT between
trapped oil and brine, to aid mobilization and contribute to the
formation of oil banks. IFT reduction lowers capillary forces and
allows for the oil bank to flow more freely without renewed trap-
ping [36,40,48,54]. The selection of appropriate surfactant for EOR
purposes is based on ability to reduce IFT between crude and brine,
thermal stability, tolerance to salinity and hardness of brine, solu-
bility in brine, phase behavior parameters, adsorption test under
static and dynamic condition and displacement studies under
reservoir conditions.
3.1.1. Types of surfactant and their structure
Surfactants are usually organic compounds that are amphiphilic,
meaning they contain both hydrophobic groups (tails) and
AAS > IOS > AOS > PS > EA
Decreasing order of thermal stability
ƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒƒ!
3.1.2. Mechanism of surfactant flooding
The aim of surfactant flooding is to recover the capillary-trapped
residual oil after waterflooding. By the injection of surfactant so-
lution, the residual oil can be mobilized through a strong reduction
in the interfacial tension (IFT) between oil and water. Crude oil
contains organic acids and salts, alcohols and other natural surface-
active agents. When crude oil is brought in contact with brine or
water, these natural surfactants accumulate at the interface and
form an adsorbed film which lowers the interfacial tension of the
crude oil/water interface. Depending on the type of crude oil, the
adsorbed film at the interface can be either fluid or very viscoelastic
and able to form a skin. Depending on the properties of the crude

Polar head
soluble in water
Water
Hydrophobic (oil-soluble)
C8 - C18

Oil

Hydrophilic (water-soluble)
+ Hydrocarbon tail
SO3 Na soluble in oil

Fig. 4. Surfactant molecule. Fig. 5. Principles of surfactants.

 A.A. Olajire / Energy 77 (2014) 963e982 969

Table 3
Classification of surfactants.

Class Examples Structures

Anionic Na stearate CH3 ðCH2 Þ16 COO Naþ

Na dodecyl sulfate CH3 ðCH2 Þ11 SO
4 Na
þ

Na dodecylbenzenesulphonate CH3 ðCH2 Þ11 C6 H4 SO

3 Na
þ

Cationic Laurylamine hydrochloride CH3 ðCH2 Þ11 NHþ
3 Cl
Trimethyl dodecylammonium chloride C12 H25 Nþ ðCH3 Þ3 Cl
Cetyl trimethylammonium bromide CH3 ðCH2 Þ15 Nþ ðCH3 Þ3 Br
Cn H2nþ1 ðOCH2 CH2 Þm OH
Non-ionic Polyoxyethylene alcohol
n ¼ 8  18; m ¼ 3  15
C19 H19 C6 H4  ðOCH2 CH2 Þn OH
Alkylphenol ethoxylate
n ¼ 5  10
Polysorbate 80
w þ x þ y þ z ¼ 20
R](C17H33)COO

Propylene oxide-modified

Ethylene glycol distearate

Propylene glycol monostearate

Amphoteric or Dodecyl betaine C12 H25 Nþ ðCH3 Þ2 CH2 COO

zwitterionic Lauramidopropyl betaine C11 H25 CONHðCH2 Þ3 Nþ ðCH3 Þ2 CH2 COO
Cocoamido-2-hydroxypropyl sulfo betaine Cn H2nþ1 CONHðCH2 Þ3 Nþ ðCH3 Þ2 CH2 CHðOHÞCH2 SO
3

oil (e.g. API (American Petroleum Institute) gravity, sulfur, salt and
metals content, viscosity, pour point, etc.), the structure of the film
can vary significantly [57]. Therefore, the molecular packing, sur-
face viscosity, surface elasticity and surface charge of the adsorbed
film are very important parameters that determine various phe-
nomena such as coalescence of emulsion droplets, as well as oil
drop migration in porous media.
3.2. Polymer flooding
Polymer flooding may involve addition of polymer to the water
of a waterflood to decrease its mobility. Polymer increases the
viscosity of the aqueous phase as well as reduces water perme-
ability due to mechanical entrapment, consequently resulting in
more favorable mobility ratio. With a more viscous phase, the
collected oil bank can be more easily moved through the reservoir
and eventually into the producing well [16].
Before any polymer applications the cloud point of the polymer
solution, i.e., polymer thermal stability in high salt brine and high
Table 4
Properties of surfactants used in EOR.
Surfactant type Property
temperature, must be evaluated to avoid precipitation on the
chemical equipment during injection, or during the flow through
the reservoir [58,59]. An incremental recovery factor of 5% OOIP
(original oil in place) or more has been reported as a successful
polymer application [60e62].
3.2.1. Polymer types used in EOR
The two sets that are extensively used for enhancing oil recovery
include synthetic polymers and biopolymers [63]. The most utilized
polymers today are the synthetic and partially HPAM (hydrolyzed
polyacrylamide), the modified natural polymers and the biological
polysaccharide, Xanthan [64,65]. The natural polymers and their de-
rivatives include HEC (hydroxyl ethyl cellulose), guar gum and sodium
carboxymethyl cellulose, carboxyethoxyhydroxyethylcellulose.
3.2.1.1. PAM (Polyacrylamide). Polyacrylamide (Fig. 6a) was the first
polymer used as a thickening agent for aqueous solutions. The
thickening capability (increase of the corresponding solution vis-
cosity) of PAM resides mainly in its high molecular weight, which
reaches relatively high values (>1  106 g/mol). Generally, the
performance of a polyacrylamide in a flooding process will depend
on its molecular weight and its degree of hydrolysis.

Petroleum sulphonates (PSs) For reservoirs with temperature, low

a-Olefin sulphonates (AOS) and
internal olefin sulphonate (IOS)
Alkylearyl sulphonate (AAS)
Ethoxylated alcohol (EA)
salinity and bivalent cations
Better tolerance to salinity and hardness,
high temperature stability
For high temperature applications
For low temperature application
3.2.1.2. Partially hydrolyzed polyacrylamide (HPAM). HPAM
(Fig. 6b), by far the most used polymer in EOR applications, is a
copolymer of PAM and PAA (polyacrylic acid) obtained by partial
hydrolysis of PAM or by copolymerization of sodium acrylate with
acrylamide [66,67]. HPAM is preferred in EOR applications since it
970 A.A. Olajire / Energy 77 (2014) 963e982
Fig. 6. a. Structure of polyacrylamide. b. Structure of HPAM. c. Structure of xanthan
gum. d. Intra- and inter-molecular associations occurring between the hydrophobic
groups [64].
can tolerate the high mechanical forces present during the flooding
of a reservoir [68]. In addition, HPAM is a low cost polymer and is
resistant to bacterial attack [40]. HPAM is very sensitive to the brine
salinity and hardness. The viscosity enhancement property is
significantly reduced when it dissolves in high salinity or hardness
brine. This characteristic represents the disadvantage of using this
kind of polymer in the oil and gas reservoir, which generally ex-
hibits some degree of salinity. Besides the salt dependency, other
factors influencing the viscosity of HPAM solutions are the degree
of hydrolysis, solution temperature, molecular weight and solvent
quality [69]. Pressure also affects the viscosity of HPAM solutions
[70].
3.2.1.3. Xanthan gum. Xanthan gum is a polysaccharide, which is
produced through fermentation of glucose or fructose by different
bacteria [71]. The most efficient xanthan gum producer is the
Xanthomonas campestris bacterium [71,72]. The chemical structure
of xanthan gum (Fig. 6c) displays the presence of two glucose units,
two mannose units and one glucuronic acid unit with a molar ratio
of 2.8e2.0e2.0 [73]. The backbone of xanthan gum is similar to
cellulose. The side chains of the polymer contain charged moieties,
i.e. acetate and pyruvate groups, and the polymer is thus a poly-
electrolyte. The thickening capability of xanthan gum lies in its high
molecular weight, which ranges from 2 to 50  106 g/mol [73,74]
and in the rigidity of the polymer chains. Compared to HPAM,
xanthan gum has a more rigid structure than HPAM and relatively
nonionic. These properties make it relatively insensitive to salinity
and hardness. However, it is susceptible to bacterial degradation
after it has been injected into the field.
3.2.1.4. Associative polymers. The associative water-soluble poly-
mer is a relatively new class of polymers, which has recently been
introduced for oilfield applications. Essentially, these polymers
consist of a hydrophilic long-chain backbone, with a small number
of hydrophobic groups localized either randomly along the chain or
at the chain ends [75,76]. When these polymers are dissolved in
water, hydrophobic groups aggregate to minimize their water
exposure. The association effect depends on the properties of the
aqueous solution like content, pH and temperature, and also the
polymer structure, composition and concentration [64]. The
incorporated groups associate due the intramolecular hydrophobic
interactions and the intermolecular hydrophobic interactions.
Intramolecular hydrophobic associations occur between hydro-
phobic groups within the macromolecule, whereas intermolecular
hydrophobic associations are hydrophobic interactions occurring
between neighboring macromolecules in the aqueous solution [64].
Fig. 6d illustrates the different physical interactions occurring be-
tween hydrophobic groups.
Another important fact is that the functional groups on this
polymer is less sensitive to brine salinity compared to poly-
acrylamide, whose viscosity dramatically decreases with increasing
salinity.
3.2.2. Polymer rheology
Rheology is a study of the flow behavior and properties, and
deformation of all kinds of materials exposed to external stress.
When materials are under deformation stress they all show a
viscoelastic behavior, which is a mixture of viscous and elastic
properties [77]. Polymer solutions behave like Newtonian fluids at
very low and at very high shear rates [78,79]. However, at inter-
mediate shear rates they behave as pseudo-plastics obeying the
power law of the dependency of their viscosity on the shear rate.
3.2.2.1. Stability of polymers. HPAM is susceptible to mechanical
degradation because of an elastic behavior of PAM which easily
degraded by high shear rates in porous media. PAM is stable up to
90  C at normal salinity and up to 62  C at seawater salinity, which
put certain restrictions to their use in off-shore operations. Tem-
perature stability for xanthan is reported in the range 70  C to
above 90  C, and above 105  C for scleroglucan. The polymers and
especially the biopolymers are susceptible to bacterial attack in the
low-temperature region in the reservoir. Biocides like formalde-
hyde in concentrations 500e1000 ppm are effectively used to
prevent biological degradation [80].
3.2.2.2. Retention of polymers. Retention is a term used to cover all
the mechanisms responsible for the reduction of mean velocity of
polymer molecules during their propagation through porous me-
dia. Retention of polymer is mostly consists of polymer adsorption.
Sometimes it may involve mechanical entrapment of polymer
macromolecules in porous medium, and to some extent hydrody-
namically trapped polymer molecules in stagnant zones (Fig. 7).
The entrapment of polymer molecules in porous medium is simply
due to the size of polymer molecules which may be larger than the
size of pore throat.
3.2.2.3. Apparent viscosity and shear rates. Due to the micro-
heterogeneity of formation and the fact that polymer solution has
non-Newtonian properties the shear rate and thus, the viscosity of
the solution will vary within the porous medium. The viscosity is
therefore dependent upon the shear rate. In order to predict
effectiveness of polymer flooding one has to deal with apparent
values of a polymer solution viscosity. The rheological character-
ization of polymer solutions must include determination of their
viscosity in both shear and extensional flows, since these
 A.A. Olajire / Energy 77 (2014) 963e982
Fig. 7. Types of polymer retention in porous media.
macromolecules are subjected to both shear and extensional
stresses inside an oil reservoir [81,82]. Polymer solutions at low
concentration can act as non-Newtonian time-independent fluids
[83], which indicates that the strain rate at a given point only de-
pends on the instantaneous stress at that point.
3.2.2.4. Resistance and permeability reduction factors. The two
important factors that must be taken into account while simulating
polymer flooding are resistant factor and residual resistance factor.
Resistance factor (R), defined as the ratio of mobility of water
(brine) lw to that of polymer solution lp under the same conditions
is shown in equation below.
lw
R¼
lp
Residual resistance factor (Rr) is the mobility ratio of water (lw)
before and after polymer injection lwp under the same conditions,
where kp and kw are permeabilities of polymer solution and water
respectively.
lw kw kw
Rr ¼ ¼ z
lwp kwp kp
The last term of equation (9) is called permeability reduction
factor (Pr) and often used for the quality estimation of polymer
solution.
3.3. Alkali flooding
Alkali is a basic, ionic salt of an alkali metal or alkaline earth
metal element. The use of alkali in a chemical flood offers several
benefits including promoting crude oil emulsification, increasing
aqueous-phase ionic strength leading to regulation of phase
behavior of the injected surfactant, and lowering interfacial tension
(IFT) to ultralow values in presence of surfactant. Alkali can also
reduce costs by limiting the amount of surfactant needed in two
ways. First, alkali reduces surfactant adsorption by increasing the
rock surface's negative charge density, making it preferentially
water-wet [14,50,84]. Second, alkali reacts with the acids in the
crude oils to produce in situ soaps, which in turn broadens the
optimal salinity range. The soap generated creates a micro-
emulsion phase that can co-exist with oil and water, thus extend-
ing the three-phase region (or ultra-low IFT region) [14,40,48,85].
Finally, alkali is relatively inexpensive. Common alkaline agents
include sodium hydroxide (NaOH, or caustic soda), sodium car-
bonate (Na2CO3, or soda ash), sodium bicarbonate (NaHCO3) and
sodium metaborate (NaBO2).
3.3.1. Selection of alkali
Selection of alkali is guided by the type of formation, clay type
and divalent cations. Sodium hydroxide solutions have been
971
reported to strongly interact with sandstone at elevated tempera-
ture (185  F), resulting in sandstone weight loss and increased
porosity [86]. The author also concluded that caustic consumption
resulting from NaOH dissolution of silicate minerals can be a sig-
nificant and detrimental factor during field application. Hirasaki
and Zhang [87] gave another strong reason why NaOH should not
be used as an alkali agent. They observed that anionic surfactants
showed much smaller adsorption in the presence of Na2CO3
compared to NaOH. They concluded that the hydroxide is not a
potential determining ion for carbonate surfaces.
Calcium and other divalent cations can cause precipitation of
alkalis such as Na2CO3 unless soft brine is used. This is limitation of
Na2CO3. The use of NaBO2 as a replacement for Na2CO3 has been
reported [88,89]. This alkali gave pH values of about 11 at 1 wt%
alkali concentration and generated soap for acidic crude oils.
Another major advantage of NaBO2 species are their tolerance to
divalent cations. In carbonate reservoirs Na metaborate is used in
place of other alkalis. If reservoir contains clays NaHCO3 is
preferred. Na2CO3 is the most commonly used alkali because it is
cheap and transports better in porous media.
3.3.2. Mechanisms
In ASP flooding, alkaline or caustic solutions are injected into the
reservoir. These caustic chemicals react with the natural acids
(naphthenic acids) present in crude oils to form surfactants in-situ
(sodium naphthenate) that work in the same way as injected syn-
thetic surfactants to reduce interfacial tension (IFT) between oil/
(8) water and move additional amounts of oil to the producing well.
The role of the alkali in the ASP process is to reduce the adsorption
of the surfactant during displacement through the formation and
sequestering of divalent ions. The presence of alkali can also alter
formation wettability to reach either more water-wet or more oil-
wet states. For instance, in fractured oil-wet reservoirs, the com-
bined effect of alkali and surfactant in making the matrix prefer-
entially water-wet is essential for an effective process. These
(9) benefits can be exploited only when alkali is present [48].
Alkaline flooding can be applied to oils in the API gravity range
of 13 e35 , particularly in oils having high content of organic acids.
The preferred oil formations for alkaline flooding are sandstone
reservoirs rather than carbonate formations that contain anhydrite
(calcium sulfate) (CaSO4) or gypsum (calcium sulfate dehydrate)
(CaSO4.2H2O), which can consume large amounts of alkaline
chemicals. Also, in carbonate reservoirs the calcium carbonate
(CaCO3) or calcium hydroxide (Ca(OH)2) precipitation occurs when
Na2CO3 or NaOH is added. Carbonate reservoirs also contain brine
with a higher concentration of divalents and could cause precipi-
tation. To overcome this problem, Liu [54] suggested NaHCO3 and
sodium sulfate (Na2SO4). NaHCO3 has a much lower carbonate ion
concentration, and additional sulfate ions can decrease calcium ion
concentration in the solution.
These chemicals are also consumed by clays, minerals, or silica,
and the higher the temperature of the reservoir the higher the al-
kali consumption. Another common problem during caustic
flooding is scale formation in the producing wells. During alkaline
flooding, the injection sequence usually includes: (1) a preflush to
condition the reservoir before injection of the primary slug, (2)
primary slug (alkaline chemicals), (3) polymer as a mobility buffer
to displace the primary slug. Alkaline flooding can be modified as
the AP (alkaliepolymer), AS (alkaliesurfactant), and Alka-
lieSurfactantePolymer (ASP) processes [38,39,90].
3.3.3. Oilealkali chemistry
Soap produced from the reaction between the acidic compo-
nents of a crude oil and the injected alkali is the principal mecha-
nism of oil recovery in alkaline flooding. Mayer [91] discussed how
972 A.A. Olajire / Energy 77 (2014) 963e982
the oil components responsible for surface active materials have
been identified as carboxylic acids and to a lesser extent as car-
boxyphenols, porphyrins or asphaltene fractions. The acidic com-
ponents of oil are measured and referred to as acid number. The
acid number is defined as the milligrams of potassium hydroxide
required to neutralize 1 g of crude oil. However, the acid number
may not be a good indicator of the acid components present in
crude oil that generate soap. Fan and Buckley [92] and Hirasaki [93]
discuss new protocols for acid number measurements that better
reflect the generation of soap. The generation of soap was modeled
by partitioning of acid in the crude oil (HAo) to water according to
the following solubility as;
KD
HAo ⇔HAw (10)
HAo and HAw are the concentrations of acid in oil and water
respectively; and KD is the partition coefficient of HA between oil
and water.
The acid in water will then dissociate in the aqueous phase to
produce soluble anionic surfactant (Ae) referred to as soap ac-
cording to the expression:
Ka
HAw ⇔Hþ þ A (11)
where, Ka is the reaction constant following the equilibrium
relationship:
 

H Aþ
Ka ¼ (12)
½HAw 
This reaction is one of the sources of alkali consumption since
the alkali uses OHe to generate soap by the following reaction:
Kb
HAw þ OH ⇔H2 O þ A (13)
3.4. Synergistic mechanisms of ASP flooding
Alkaliesurfactantepolymer (ASP) flooding owes its success to
the synergy of the individual components of enhanced-oil recov-
ery (EOR) blends. ASP flooding involves initial injection of a
combined AlkalineeSurfactantePolymer slug for improving
displacement efficiency by mobilizing more of the residual oil in
the pore spaces, followed by a straight polymer slug to improve
volumetric sweep by improving mobility ratio and volumetric
sweep. The goals are improved oil rates and reduced water pro-
duction as shown in the following equation for the overall oil
recovery (Ero):
So Vp
Ero ¼ Edo Ea Ev $ (14)
Bo
where, Edo is the microscopic displacement efficiency improved
with alkali and surfactant, while Ea is the areal displacement effi-
ciency improved with polymer and Ev is the vertical displacement
efficiency improved with polymer, Bo is the formation volume
factor of the oil, So is the oil saturation, Vp is the permeability
variation.
An important mechanism is the synergy between in situ
generated soap and synthetic surfactant. Generally, the optimum
salinity for the soap is unrealistically low, and the optimum salinity
for the surfactant is high. When they function together, the salinity
range in which IFT reaches its low values is increased [10]. The alkali
and the surfactant will produce synergistic interfacial tension
reduction while polymer improved microscopic and macroscopic
sweep efficiency by emulsions [94]. The combination of alkali,
surfactants and polymers leads to synergistic effects between the
chemicals resulting in less surfactant required to recover signifi-
cantly incremental oil. Typical ASP formulations involve 0.2 PV
(pore volume) of 1% surfactant and 0.5% alkali, chased by 0.3 PV or
more of a solution containing 1000 ppm polymer. Here again, in-
cremental oil recoveries of up to 25% or even more have been re-
ported, depending upon specific geology, well spacing and
injectivity [95e98]. A common ASP EOR injection sequence is
shown in Fig. 8. An ASP flood includes several flood stages. A brine
preflush is sometimes used to change the salinity or other rock or
fluid properties. The first chemical slug injected is a combination of
alkali and surfactant. That slug mixes with the oil and changes its
properties, decreasing the IFT and altering the rock wettability.
Surfactants (detergents) mobilize oil that waterflooding alone
leaves trapped in the reservoir while the alkali added increases the
efficiency of the injected surfactants (alkali and surfactant act
together to mobilize oil trapped in the reservoir). These effects
mobilize more oil. A polymer slug follows to improve the mobility
differential between the oil and the injected fluids. The polymer
thickens the injected fluid to increase the volume of reservoir
contacted and improves reservoir sweep. This slug is typically fol-
lowed by a freshwater slug to optimize recovery of the chemicals,
and then a flood with drive water.
4. Status of ASP application
Alkaline/surfactant/polymer (ASP) combinations can be
considered as candidates to improve the recovery from some of the
geologically challenging reservoirs. In particular, ASP flooding can
be economically attractive for reservoirs in which the gravity and
imbibition processes play a significant role in recovering the oil.
Several ASP EOR methods have been extensively documented in the
literature during the last two decades. However, at the present time
Daqing field represents one of the largest, if not the largest, ASP
flood implemented as of today. ASP flooding has been studied and
tested in Daqing for more than 20 years though with several pilots
of different scales [96e100]. Gudong [101], Karamay [95,102], Lia-
hoe and Shengli [96] fields are other examples of Chinese ASP EOR
projects documented in the literature. Additional ASP EOR flooding
reported during the last decade includes ASP flooding in Viraj field,
India [103] and West Kiehl [104], Sho-Vel-Tum [105], Cambridge
Minnelusa [52] and Tanner [106] fields in the U.S.
4.1. ASP in China
Most of the field pilots and commercial applications have been
conducted in China. From China alone, 13 field cases (pilots and
commercial scale) have been reported. Among them, five are from
Daqing. Most of the cases are in small scale operations, all in
sandstone reservoirs. One Daqing commercial application that
began in 2000 had 17 injectors and 27 producers [107,108]. Among
these 13 fields tested, the highest reservoir temperature was 86  C.
In most cases, the oil viscosities were 6e13 mPa s. Only in two
cases, the oil viscosities were 42 and 70 mPa s. The salinity was less
than 7000 ppm (parts per million) in Daqing.
4.1.1. ASP flooding in Daqing oilfield
A tertiary pilot application of the alkaline/surfactant/polymer
(ASP) process was initiated in Sept. 1994 in the west central area of
Daqing oilfield [51]. The pilot pattern consists of four inverted five-
spots, including four injectors, nine producers, and two observation
wells, encompassing an area of 90,000 m2 and with a pore volume
(PV) of 203,300 m3. The target layer is the Saertu, consisting of
sandstone, with an average porosity of 26% and permeability of
 A.A. Olajire / Energy 77 (2014) 963e982 973

Injection well oil

Polymer Oil
Drive fluid solution bank
(water) Preflush

Freshwater Alkaline-
buffer surfactant solution
l i

Fig. 8. ASP flooding process.

1.426 mm2. The crude oil viscosity is 11.5 mPa s at reservoir tem-
perature and the connate-water salinity is 6800 mg/L. The pilot
performance shows a pronounced response from ASP injection. The
average pilot area oil production rate increased from 36.7 to
91.5 m3/d, while water cut decreased from 82.7 to 59.7%. A sum-
mary of these pilot tests is given in Table 5. In this table, Slug 1
refers to a preflush with polymer, Slugs 2 and 3 usually are ASP
slugs with different chemical compositions, and Slug 4 is the
polymer drive. However, Slug 3 may not be used in some cases. The
size of these tests varied from well spacing of 246e820 ft. Three of
the tests are still ongoing. Sodium hydroxide was used in most of
these tests, but sodium carbonate also was tried. Several types of
surfactants, including alkyl benzene sulfonates, petroleum sulfo-
nates, lignosulfonates, petroleum carboxylates, and biologically
produced surfactants, were tested. Hydrolyzed polyacrylamide
(HPAM) polymers with different molecular weights were used in
the preflush, ASP slug, and driving slug. Incremental recovery ef-
ficiencies from the five completed projects varied from 19 to 25%
OOIP.
4.1.2. ASP process in other oilfields of China
In addition to the tests conducted in Daqing, the ASP process
was tested in other fields including Shengli and Karamay.
test began in 1992 in the Gudong reservoir. Incremental recovery
was reported to be 26% OOIP [109]. The second ASP pilot test was
conducted in 1997 in the western part of the Gudao reservoir in an
area of 150 acres. The well spacing and net pay were 695 ft and
53 ft, respectively. The reservoir is a channel-sand deposit with
average porosity and permeability of 32% and 1520 md, respec-
tively. The pilot area has six injection wells and 10 producing wells
with an average daily oil rate of 46 b/d. The waterflooding recovery
efficiency was 22.4% OOIP before ASP flooding. The ASP process was
conducted in a three-slug sequence:
1. Preflush: A 0.1-Vp 2000-ppm polymer solution was injected for
306 days.
2. ASP slug: A total of 0.3-Vp ASP slug containing 1.2% Na2CO3, 0.2%
Surfactant A, 0.1% Surfactant B, and 1700 ppm polymer was
injected for 948 days.
3. Polymer drive: A 0.05-Vp 1500-ppm polymer solution was
injected for 158 days.
The injection of chemical slugs was completed in 2002. The oil
rate increased from 630 to 1490 b/d at peak production, and cor-
responding water cuts decreased from 96 to 83%. The total incre-
mental recovery was 15.5% OOIP.

4.1.2.1. Shengli. Shengli started experimental research in ASP 4.1.2.2. Karamay. An ASP pilot test was conducted in Karamay in
flooding in the early 1980s, and the first small-well-spacing field 1995 in a heterogeneous conglomerate reservoir with a well

Table 5
Summary of ASP pilot tests conducted in Daqing oilfield [96].

No. Location Spacing (ft) Wells Starting date Slug 1 (Vp) Slug 2 (Vp) Slug 3 (Vp) Slug 4 (Vp) Incremental
(Inj./prod.) recovery (%OOIP)

ASP1 S-ZX 348 4/9 Sep. 1994 0.30 0.29 21.40

ASP2 X5-Z 462 1/4 Jan. 1995 0.30 0.30 0.18 25.00
ASP3 X2-X 656 4/12 Sep. 1996 0.04 0.35 0.10 0.25 19.40
ASP4 S-B 246 3/4 Dec. 1997 0.33 0.15 0.25 23.24
ASP5 B1-FBX 820 6/12 Mar. 1997 0.30 0.15 0.20 20.63
ASP6 X2-Z 820 17/27 Apr. 2000 0.04 0.35 0.10 0.20 Ongoing
ASP7 SB-B2-Z 246 3/4 Oct. 2004 0.04 0.35 0.15 0.20 Ongoing
ASP8 S-B3X 820 e/13 Aug. 2002 0.04 0.35 0.10 0.20 Ongoing

inj., Injector; prod., producer.

974 A.A. Olajire / Energy 77 (2014) 963e982
spacing of 164 ft and four five-spot patterns [95]. A three-slug
process was designed as follows:
1. A 0.40-Vp slug of 1.5% NaCl brine preflush.
2. A 0.34-Vp slug of ASP containing 1.4% Na2CO3, 0.3% crude oil
sulfonates, and 0.13% polymer.
3. A 0.15-Vp slug of 0.1% polymer and a 0.4% NaCl drive fluid.
The waterflooding recovery efficiency in the pilot area before
ASP slug injection was approximately 50% OOIP at 99% water cut.
The ASP slug was injected from July 1996 to June 1997 with
continued water drive to early 1999. The increased recovery started
after approximately 0.04 Vp of the ASP slug had been injected and
got to the peak when approximately 0.2 Vp of the ASP slug had been
injected, with a six-fold increase in oil rate and water-cut reduction
from 99 to 79%. Incremental recovery in the central well was 25%
OOIP. Severe emulsions in produced fluids were observed, and
difficulties were encountered in breaking the emulsions.
4.2. Canadian ASP projects
Husky implemented the first “field-wide ASP flood” in Canada in
May 2006. Information about this EOR scheme was obtained largely
through the company's participation in Alberta Energy's IEPT [110].
4.2.1. Taber South ASP project, Alberta
Taber South was producing 300 bbl/day before the ASP flood.
ASP injection started in June 2006. Production increased to
1502 bbl/day as of December 2007. Oil cuts increased from 1.7 to
7.3% over the same period. This project demonstrates feasibility of
tertiary application of ASP flood in a mature waterflood in a me-
dium gravity oil pool. Severe problems of equipment scaling and
injectivity loss were encountered; these were solved using treating
chemicals with varying degrees of success. This pilot also high-
lighted that due to variability of reservoir properties, some parts of
the pool may not effectively respond to ASP injection. The challenge
was to identify such areas early in the life of an ASP flooding project
to optimize cost-effectiveness of chemicals.
4.2.2. Taber Glauconitic ASP project
Husky Oil Operations Limited implemented the first field-wide
AlkalineeSurfactantePolymer (ASP) flood using surfactants
derived from renewable resources on January 23, 2008. The co-
surfactants are a blend of sodium lignosulfonate (lignin) and APG
(alkyl polyglycosides). Lignin is a natural polymer that binds a tree
together. Lignosulfonates can act as both a binder and a dispersant
and these qualities can enhance the efficiency of ASP systems.
APG are an agricultural crop based combination of fatty alcohols
and glucose, mostly used in personal care formulations, cleaners,
and agricultural formulations, and are readily biodegradable. In-
cremental oil production was expected to be 762  103 m3 from the
Taber Glauconitic K pool, an incremental oil recovery factor of 15.0%
OOIP. Ultimate production was estimated to be 10% higher using
green chemistry based surfactants than the ASP system using
conventional surfactants.
Pool oil production was 26 m3/dm with an oil cut of 0.9% when
ASP injection began in January 2008 and in April 2010 oil produc-
tion was 127 m3/d with a 5.3% oil cut. Total incremental oil pro-
duction above the base decline at the end of April 2010 to
22  103 m3 or 0.4% OOIP incremental recovery factor.
4.2.3. Suffield ASP project
This project demonstrates feasibility of tertiary application of a
“green” ASP flood in a mature waterflood in a medium gravity oil
pool but with a high oil viscosity (181 mPa s) approaching that for
heavy oils. One of the objectives was to determine if freshwater
requirements could be minimized during preparation of chemical
solutions for injection. This objective was successfully met (though
with several problems which were successfully resolved). Another
objective was to determine if the produced water could be reused
and this objective was not successfully met during this pilot. It also
reported that at Suffield, Cenovus determined ASP flooding to be
successful and are moving towards commercialization.
4.3. ASP projects in USA
The ASP flooding reported in the US fields include West Kiehl
[104], Sho-Vel-Tum [105], Cambridge Minnelusa [52], Tanner [106]
and Lawrence field Illinois [111].
4.3.1. West Kiehl, Wyoming
The earliest field testing of ASP flooding was implemented at
West Kiehl, Wyoming [104,112] beginning in September 1987. The
incremental oil recovery over the next 2.5 years had reached 26%
OOIP. At West Kiehl they used soda ash (Na2CO3) as the alkali. The
West Kiehl AlkalineeSurfactantePolymer flood produces incre-
mental oil greater than waterflooding at a cost of less than $2.00
per incremental barrel.
4.3.2. Cambridge Minnelusa
The next ASP pilot test came from the Cambridge field, a Min-
nesula field located contiguous to the Kiehl field. In this case, ASP
flooding increased recovery by 28% of OOIP (1,143,000 bbls) and
incremental costs were estimated at 2.42 $/bbl.
4.3.3. Tanner field
The Tanner field formulation contained 1 wt% sodium hydroxide
(NaOH) and 0.1% active ORS-41HF. The projected incremental OOIP
was 17%, based on experiments and results from pilot tests [106].
4.3.4. Sho-Vel-Tum field ASP project
An ASP flood in the Sho-Vel-Tum field sponsored by the US
Department of Energy was conducted beginning in 1998 [105]. The
well is located in Oklahoma, USA and the reservoir is only 700 ft
(214 m) deep making it the shallowest well in the United States
where an ASP flood has been initiated. The well has been producing
for over 40 years and was producing 4 bbl/day before the ASP
project was initiated. The ASP system consisted of 0.5 wt% ORS-62,
2.20 wt% Na2CO3 and 1000 mg/l Alcoflood 1275A polymer in soft-
ened water. The ASP project increased average oil recovery from
4 bbl/day to 20 bbl/day. The pilot project added 10,444 barrels of
incremental oil over a period of 1.3 years.
4.3.5. Lawrence field Illinois
Most of the unrecovered oil in Lawrence Field is contained in
Pennsylvanian Age Bridgeport sandstones and Mississippian Age
Cypress sandstones [111]. During 2007, core floods resulted in an oil
recovery rate of 21% OOIP for Cypress, and 24% OOIP for Bridgeport.
In 2008-pilot ASP injection started. Bridgeport Sandstone demon-
strated an initial response to the ASP chemical injection as indi-
cated by an increase in the oil cut ratio in the pilot wells while
Cypress Sandstone ASP pilot demonstrated a continuous response
to the ASP chemical injection.
5. Prospects of ASP EOR technology
AlkalineeSurfactantePolymer flooding, or ASP flooding, is a
relatively new and still evolving chemical enhanced oil recovery
technology. The process was developed in the early 1980s as a
lower-cost alternative to other chemical flooding methods. In
 A.A. Olajire / Energy 77 (2014) 963e982
essence, a predetermined volume or slug mixture of ASP is injected
into the reservoir, often followed by an additional injection or
“push” of polymer, which help to reduce the slope of the oil pro-
duction decline and thus extends the production period. ASP pro-
cess is based upon the generation of surfactants that occurs when
certain crude oils that contain organic acids react with alkaline
solutions. Such surfactants, when enhanced by additional surfac-
tants, have the capability of mobilizing additional oil. The combi-
nation of injected surfactant and soap created by interaction
between the injected alkali and the oil can generate watereoil in-
terfaces with ultra-low interfacial tensions [113]. The presence of
alkalis also increases the surface charge on the rock surface and
hence decreases surfactant loss due to adsorption on the rock [11].
Polymer is added to protect the chemical slug from early dissipa-
tion by the driving water phase. The three, generally non-toxic (in
dilute solution) chemicals act together, or synergistically, to in-
crease the capillary number, improve the mobility ratio and to
effectively sweep more petroleum than if they were used as lone
components [114]. The ASP chemicals reduce interfacial tension
and scrub the reservoir, releasing some of the oil which remains
locked in the reservoir after waterflooding. Alkaline surfactant
polymer (ASP) technology not only increases oil production but
also reduces water production. ASP floods are also attractive in that
the chemicals used are non-toxic which reduces disposal liability.
In selecting chemicals for an ASP flood, it is necessary to
consider availability, quantities required, cost, performance, and
logistics. All of these factors are critical due to the large quantities
usually required to flood one field, which can run into the hundreds
of millions of pounds. Therefore in order to minimize costs, it is
critical that:
C There should be chemical manufacturing plants large
enough to accommodate the capacity needed and in close
proximity to the field being flooded to reduce transportation
costs,
C Chemical cost should be low enough to make the sizable
investment in chemicals profitable in the long term.
Low cost alkali such as sodium carbonate reduces surfactant
adsorption and for this and other reasons Alkalin-
eeSurfactantePolymer (ASP) flooding was developed as a lower
cost alternative to other chemical flooding methods.
6. Challenges associated with ASP EOR technology
ASP flooding is still facing some major challenges in produced
fluid handling on its way to commercial application. While a sig-
nificant decrease in water cut of produced fluid and an increase in
oil production have been achieved, alkaline (A), surfactant (S), and
polymer (P) in produced fluid have resulted in very tight oil-in-
water (O/W) emulsion, causing great troubles in surface oil/water
separation [115]. There are a number of difficulties which have
limited widespread field application, especially offshore [116].
Operational difficulties include the large volumes of chemicals that
have to be transported to remote sites and then stored on platforms
where space is limited. Additional produced fluid processing is
needed as ASP flooding results in the production of emulsions with
droplets as small as 10 mm in diameter. Finally produced fluids
(containing the ASP chemicals) need to be disposed of without
impacting the environment. Technical difficulties include the fact
that the chemical mix needs to be carefully designed for the fluids
to be encountered in the field. ASP flooding works best with rela-
tively low-salinity water (often optimal performance is achieved by
the use of a salinity gradient during injection of the different
stages), but, offshore, seawater is the only source of injection water
975
so desalination or alternative chemicals may be required. Scaling
problem is caused during ASP injection due to the high content of
divalent ions.
6.1. Operational difficulties
ASP flooding is associated with several operational issues.
Problems like low injectivity or complete plugging of injection
wells, polymer degradation, pump failures, incomplete polymer
dissolution, corrosion and scaling have been encountered [5]. ASP is
also complex to design, requiring analysis of oil, water and rock
chemistry as well as geological heterogeneity, cost due to large
volumes of chemicals required and may not be feasible in hot
reservoirs, carbonate reservoirs or those with saline water.
6.2. Scaling issues during ASP flooding
Scaling of the well bore equipment is caused by reaction be-
tween the alkali and divalent metal cations such as calcium and
magnesium that result in excessive alkali consumption and sur-
factant precipitation [117,118]. The precipitated material under
certain conditions of pH, temperature and pressure deposits on the
well equipment as a ‘scale’, thereby ‘fouling’ it. In the process,
calcium as well as, silicate scales form that may play havoc with the
well bore equipment. Many substances are found in the injection
lines. Some of them will propagate into the first phase of the
reservoir: rust, sand, clay, ferrous sulfate, sulfur, calcium carbonate,
magnesium hydroxide, barium and strontium sulfates and molds.
During ASP flooding, the alkali reacts with the rock minerals and
formation water thereby increasing the concentration of scaling
3
ions ðCa2þ ; CO2 3 ; SiO2 Þ in the system. Scales can originate from
the reactions of alkalis with the carbonate minerals in the rock.
FeCO3ðsÞ þ SiO2 2
3 ⇔FeSiO3 Y þ CO3 (15)
MgCO3ðsÞ þ 2OH ⇔MgðOHÞ2 Y þ CO2
3 (16)
CaCO3ðsÞ þ SiO2 2
3 ⇔CaSiO3 Y þ CO3 (17)
A study into ASP scaling has shown that it is a mixture of car-
bonate and silicate. The major mineralogical compositions are
amorphous state silicon dioxide, hexagonal-spherical calcite and
conventional calcite. The minor mineralogical compositions are
clastic quartz, clastic feldspar, clastic clay particles and pyrite [117].
Silicate scale formation, though believed to be a very complex
mechanism, silica polymerization is believed to follow the base
catalyzed reaction as proposed by Amjad and Zuhl [119].
SiðOHÞ4 þ OH /SiðOHÞ
3 þ H2 O þ 1=2O2 (18)
SiðOHÞ
3 þ SiðOHÞ4 /ðOHÞ3 Si  O  SiðOHÞ3 þ OH

(19)
Dimer/Cyclic/Colloidal/Amophous silica scale
The issues associated with silicates are potentially different
from those of traditional scales. Its formation in the oilfield is a
complex and poorly understood process [120]. The ASP flood has
a high pH of 11 or above. As it moves through the reservoir,
quartz silica is dissolved [121] and the dissolved silica becomes
stable in the high pH alkaline flood. However, as the ASP flows to
the production well, it encounters neutral pH connate water
either near the well bore or in the well and thus neutralizes the
high pH alkaline water. This pH reduction results in
976 A.A. Olajire / Energy 77 (2014) 963e982
polymerization of dissolved silica and form colloidal silica
nanoparticle [120,122].
The presence of magnesium can bridge the colloidal silicate
particles and form an amorphous magnesium silicate. Usually, in
the sequence of ASP injection, water is softened [119] to provide
a buffer in the reservoir between the existing waters (a mixture
of connate water and flood water at later field life). The presence
of any residual magnesium after the softening will precipitate as
magnesium hydroxide (Mg(OH)2) in the ASP. Magnesium (Mg) is
then introduced into the neutral pH connate water. In the
absence of divalent cations, the colloidal silicate particles may
continue to grow and form amorphous silica scale [118,120].
Silicates precipitates are generally hydrated, flocculent and
highly plugging even at low concentrations. Carbonate pre-
cipitates are relatively granular and less adhering on colloid
surface [123].
Cenovus in their reports on the IETP project at Suffield UU stated
that there were two types of scales generated during ASP projects-
initially calcium carbonate based and later, amorphous silica based.
Scaling problems have also been reported from ASP projects in
China (Daqing) and elsewhere [96,100,124,125].
6.3. Surfactant precipitation
In hard brines, the presence of divalent cations causes surfactant
precipitation as shown in equation below.
2R þ M2þ /MR2 Y (20)
R is the anionic surfactant, MR2 is the surfactantedivalent cation
complex that has a low solubility in brine.
This reaction leads to retention. Factors that influence the pre-
cipitation of anionic surfactants include cation valence, salt con-
centration, surfactant concentration, alcohol concentration,
temperature, etc. [38]. When oil is present, it can compete for
surfactant; that is, addition of oil can reduce (in some cases
completely eliminate) surfactant precipitation. Also, the ethoxylate
(EO) and propoxylate (PO) groups will help the surfactant to
have tolerance to divalent cations typically present in reservoir
brines.
At lower hardness level, the multivalent cation will react with
the anionic surfactant to form a monovalent cation that can
chemically exchange with cations originally bound to the reservoir
clays [126].
R þ M2þ /MRþ (21)
Na  Clay þ MRþ /MR  Clay þ Naþ (22)
6.4. Difficulties in treating produced emulsions
The formation of persistent and stable emulsions and excessive
formation of silicate scale especially with the higher concentration
of alkali should not come as surprise when one considers the
chemistry of ASP injected for CEOR [3,118,120,122,127,128]. As these
injected chemicals breakthrough into producing wells, the strong
synergistic interaction of the chemicals especially surfactants, at-
tracts them to the oil/water interface, stabilizing emulsions and
preventing agglomeration, creaming and even settling. Produced
O/W emulsions from ASP EOR processes differ from conventional
crude oil emulsions in that the injected surfactants and, in alkaline/
surfactant processes for oils with significant acid content, acids and
corresponding soaps can be concentrated at the oilewater in-
terfaces. Also the injected surfactants, soaps, and polymers are
anionic, electrostatic and steric effects can result in enhanced
emulsion stability [129,130], which might not be easy to demulsify.
6.5. ASP produced water disposal treatment
In the field practice of alkaline/surfactant/polymer (ASP)
flooding, many produced water disposal methods faced the chal-
lenges of purifying effect, facilities pollution, healthy and environ-
mental threat, and economical justification with the water cut
rising of the benefited oil wells and the appearance of alkali, sur-
factant and polymer in produced water. During the application of
ASP floods, especially on the benefited oil wells, breakthrough of
the injection chemicals such as alkali, surfactant and polymer
periodically occurs resulting in stable emulsions [129,130].
Accordingly the emulsified water exhibited a high oily and sus-
pended solids content, which is different from that produced from
the other flooding technologies, and is difficult to be disposed due
to the adsorption of the injection chemicals onto the surface of the
oil droplets. The separation of oil and suspended solids in ASP
produced water to meet the re-injection standard of high perme-
ability reservoir after disposal is a big challenge. Therefore, an
environmentally-friendly produced water disposal method needs
to be put in place.
6.6. Challenges unique to offshore application of ASP EOR
technology
Although the techniques are still evolving, ASP EOR has already
been widely and successfully applied onshore in pilot and field
applications [14,31,131]. A particularly high level of field activity has
occurred onshore in China [96,132] in contrast, offshore application
of ASP EOR has been much less prevalent and limited to pilot ac-
tivities due to several unique challenges in that setting [24,133,134]
which include:
Remote location e The remote location of many offshore pro-
duction facilities can make shipment and storage of chemicals
difficult and expensive [133].
Expensive wells and large well spacings e High well drilling
costs result in large well spacings making monitoring and control of
the ASP EOR process more difficult than in an onshore environment
where higher well density is often possible. In addition the pay-
back time is longer for offshore EOR as incremental oil is often
produced only after several years of chemical injection.
Space and weight limitations in the deck e Offshore production
facilities like the FPSO vessel (floating production, storage and
offloading) are often crowded with little deck space available for
the required equipment and storage needed for ASP EOR [135].
Seawater injection source e Seawater is often used as the in-
jection fluid and is commonly supplemented by produced water
since strict overboarding exists for produced water disposal. Table 6
summarizes challenges of offshore ASP EOR and their effects on
aspects of the process [58].
All the above-listed challenges affect subsurface efficiency, lo-
gistics, injection, production, and environmental aspects of ASP
EOR and, so far, have limited offshore activities to relatively few
pilots and partial field projects.
7. Technical solutions to challenges in the application of ASP
EOR
Below are some of the technical solutions to some of the chal-
lenges associated with ASP EOR technology and those that are
specific to offshore applications.
 A.A. Olajire / Energy 77 (2014) 963e982
Table 6
Effect of offshore challenges on ASP EOR technology [58].
Challenges Process effects
Subsurface efficiency Logistics
Remote locations Surfactant availability
and cost
Poor weather Effect of interrupted supply Large storage requirements
Expensive wells Fewer injection wells to Distribution of ASP solutions
monitor process over long distances
Space weight Low adsorbing surfactants High-active chemicals
Seawater Salt-tolerant surfactants
Disposal Effects of reinjection on Recycle surfactants
chemical efficacy
7.1. Use of scale inhibitors
Scale inhibitors are chemicals that delay, reduce or prevent scale
formation when added in small amounts to normally scaling water.
Most of scale inhibitors function via one of the following inhibition
mechanisms [136], absorbing onto the crystal surface to prevent
further growth of very tiny crystals that precipitates out of the
water, or by preventing the scale crystals from adhering to solid
surfaces such as pipes and vessels.
Chemical scale removal has been adopted as the lowest cost
method of scale treatment especially when access to the scale is
very difficult or scale exists where conventional mechanical
removal methods are ineffective or expensive to install [137]. Effi-
ciency of chemical treatment of scale removal is measured by how
well the reagents access the scale surface. The speed and efficiency
with which the chemical inhibitors treat the scale are attributed to
the surface-area-to-volume ratio or the equivalent surface-area-to-
mass ratio [137].
7.1.1. Conventional scale inhibitors
Conventional scale inhibitors are hydrophilic, that is, they
dissolve in water. In the case of down-hole squeezing, it is desirable
that the scale inhibitor is adsorbed on the rock to avoid washing out
the chemical before acting as desired [138]. The most common
inhibitor chemicals are inorganic phosphates, organophosphorous
compounds, and organic polymers. PPCA (Poly phosphono car-
boxylic acid) and DETPMP (diethylenetriaminepenta (methylene
phosphonic acid)) (Fig. 9a) are two common commercial scale in-
hibitors used in the oil and gas industry [139]. By inhibition
mechanism, PPCA is said to inhibit by nucleation while DETPMP
operates by crystal growth inhibition [140].
7.1.2. Green scale inhibitors
Green chemistry, or pollution prevention at molecular level is
the chemistry designed to minimize or eliminate the use or
regeneration of hazardous materials associated with manufacture
and application of chemicals. It combines critical elements of
environmental improvement, economic performance and social
responsibility [141,142]. The number of chemicals allowed to be
used as inhibitors has thus been limited mainly to three criteria-tier
level of biodegradability, bioaccumulation and toxicity. According
to the PARCOM (Paris Commission), an ideal green inhibitor should
be non-toxic, readily biodegradable and shows no bioaccumulation
[141].
Though the use of green scale inhibitors to inhibit scale in oil
and gas wells is relatively an unexplored area [143], there have
been several works on this promising alternative [144]. The
977
Injection Production Environment
On-site separation
preferred
Reliability, intermittent Accidental chemical
injection releases
Produced water reinjection No disposal wells for
likely produced water
Space-efficient
separation equipment
Water softening and deaeration
Produced water reinjection Overboarding toxic
surfactants
inherent and consequent environmental hazards of using these
toxic and non-biodegradable scale inhibitors, has hindered the use
of phosphonates due to their poor ecotoxicity and many polymers,
due to their failure to meet minimum biodegradation requirements
[145].
Many of the organic phosphates and phosphonates that are
widely in use as scale inhibitors are quite toxic to the environ-
ment. These have been replaced by some organic phosphorus
compounds which are less toxic such as dibutylphosphor-
odithoic acid and carboxyhydromethylphosphonic acids. All
these inhibitors are based on phosphorus chemistry, but envi-
ronmental regulatory bodies worldwide are encouraging oper-
ators to use greener chemicals, hence the popularity of
phosphorous free and non-toxic scale inhibitors [143]. The
phosphorus based inhibitors have been replaced by the acrylate
based polymers such as polyacrylic acid, polyacrylamide and
various polyacrylates. Results of research into greener chemicals
proposed poly amino acids, in particular PASP (polyaspartates),
which have been tested and commercialized as scale inhibitors
in a variety of industries [146]. Structures of some green scale
inhibitors are shown in Fig. 9b.
7.2. Use of precipitation inhibitor
The precipitation inhibitor (sodium acrylate) could be generated
in situ by introducing acrylic acid and alkali to the injection water
[150]. When the acid was added to injection water that contains
large quantities of divalent metal cations, the acrylic acid reacts
with the sodium ion to form sodium acrylate with an excess
amount of acrylic acid. By adding the alkali (sodium carbonate) to
the mixture, more sodium acrylate would be generated. The so-
dium acrylate would adsorb at the active growth sites of the metal
cations to prevent them from precipitating. The expected reactions
that may occur during the preparation are shown below [150].
C3 H4 O2 þ Na/C3 H3 NaO2 þ H2 O (23)
C3 H4 O2 þ Na2 CO3 /C3 H3 NaO þ CO2 þ H2 O (24)
When the calcium and magnesium ions are disabled in the so-
lution, then the surfactant introduced to the system was without
any precipitation problems [151]. The influence of the inhibitor on
precipitation reaction may be explained in terms of three effects:
(a) direct complexation of sodium acrylate with crystal lattice ions
in solution; (b) adsorption of sodium acrylate on the crystal surface
or at the active growth sites; (c) sodium acrylate may change the
ionic strength of the solution and hence increasing the effective
978 A.A. Olajire / Energy 77 (2014) 963e982

a O OH O OH
OH O
OH
OH P
O P
O OH O
P N
H N P
H m n N
HO OH
HO
OH
OH P
P HO
HO O
PPCA O
DETPMP

b O
H
H N
N
O O O O
O OH OH HO

n m Maleic acid
alpha beta

Poly-alpha, beta-D, L-aspartate

OH

O OH
OH O

HO OH
HO HN
O O
HO
O
HO

HN
HO CH2
x
N
(x = 1 - 50)
HO O N
O N
HO
H2N N OH
CH2
HO
Pteroyl-L-glutamic acid
OH
Inulin

Fig. 9. a Molecular structures of commercial scale inhibitors. b. Molecular structures of some green scale inhibitors [147e149].

solubilities of the calcium and magnesium ions in brine solution
[152]. The advantage of the in situ inhibitor is the use of hard brines
without the need for softening the injection water. This could
reduce the cost of chemical EOR process and make it more suitable
for environmentally sensitive applications, particularly offshore
application.
Hard water containing high amounts of Ca2þ and Mg2þ ions can
be treated by SAC (strong acid cation) resins or, by WAC (weak acid
cation) resins. This method requires the feed water to contain very
small amount of oil/grease (<50 ppm). Alternative treatment could
be by SIS (select ion sequestration) method that can tolerate rela-
tively more oil carryover (up to 500 ppm).

7.3. Water treatment in ASP 7.4. Offshore application of ASP EOR

One of the major issues to be addressed when designing an ASP
flood is the prevention of scale formation. The increase in pH due to
the injection of alkali will lead to the precipitation of divalent ions
such as Ca2þ and Mg2þ, which will form carbonate and/or hy-
droxide. To prevent or at least significantly reduce these reactions,
it is necessary to soften the injection water to reduce the concen-
tration of divalent ions.
Petroleum industry is currently investigating the limiting fac-
tors pertinent to offshore ASP EOR. The sector is examining new
enabling chemistries and technologies for improving surface op-
erations to allow cost-effective offshore ASP EOR to be performed in
an environmentally sound and safer manner. Some of the recent
chemical and fluid processing developments are described in the
following section.
 A.A. Olajire / Energy 77 (2014) 963e982
7.4.1. Logistics-chemical transport, storage and cost
Table 7 gives typical consumption levels for an offshore ASP
injection process at 30,000 m3 injection fluid per day [58]. The large
storage volume and weight shown in the last two columns can be
prohibitive for many projects due to restrictions on available deck
space [153]. The largest requirements are for surfactant and alka-
line soda ash. Surfactants are typically delivered as aqueous solu-
tions with low active level resulting in shipping and storage of large
quantities of water. Development of low-adsorbing, high-active
surfactants would help in reducing the storage requirements for
the surfactant component. Also, use of surfactants that do not
require co-solvents would be particularly beneficial in reducing
chemical logistics costs [154]. Use of the SP process rather than ASP
would not reduce overall chemical volume requirements as elimi-
nation of alkalinity typically results in the usage of 3e5 times
higher concentration of surfactant [155]. However, an SP process
may look attractive for some cases where the oils have low acid
numbers and to avoid excessive scale issues in production facilities.
Shipment and storage of large amounts of chemicals may
necessitate the use of dedicated supply vessels. Also, floating
storage and offloading vessels (FSO) or additional deck space on
new offshore structure may be appropriate for some projects where
insufficient space and/or weight restrictions exist on the pre-
existing floating production facilities [153].
More weight-efficient surfactants and elimination of co-sol-
vents would also likely reduce the overall cost of chemicals, a
factor that can inhibit implementation of ASP EOR in an offshore
environment where large well-spacing often delays the financial
benefit of enhanced production. In fact, the overall economics of
an ASP project is dominated by the cost of the injected chemical
slug which in turn dominated by cost of the surfactant, the
highest-cost chemical in the slug [155,156]. Any changes in sur-
factant chemistry to lower OPEX and logistics costs must be
balanced with the changes which would lead to effective recovery
of subsurface oil.
7.4.2. Environment e chemical effects
Offshore ASP EOR requires environmentally sound methods to
dispose or reuse produced water and chemicals. In some situations,
produced fluids can be shipped to onshore facilities [157]. However,
for remote offshore locations where overboard disposal of pro-
duced water is common, the properties of the ASP emulsions are
problematic. ASP EOR produced water is difficult to deoil to the
commonly legislated oil-in-water emulsion limit of 29 ppm for
overboard disposal [58]. Therefore, especially for deepwater pro-
jects, disposal wells for produced water containing ASP chemicals
are not an option as they are expensive and will affect project
economics.
In view of the above reasons, re-injection of produced water for
offshore ASP EOR is an attractive option since it minimizes envi-
ronmental impact and also reduces chemical costs [158]. When
doing so, the effects of residual oil on injectivity and other process
chemicals (demulsifiers, scale inhibitors, recycled surfactants,
Table 7
Typical chemical consumption for ASP injection-30,000 m3/day [58].
Component Typical concentration 21-day Storage 21-day Storage
range (ppm) (weight/tonnes) (volume/m3)
Surfactant 3000e7000 10,500 10,500
(30%-active)
Co-solvent 0e5000 1600 2000
Soda ash 10,000e15,000 7900 13,100
Polymer (powder) 500e3000 1100 1500
Total e 21,100 27,100
979
degraded polymer, etc.) on subsurface performance must be taken
into account. Also, online measurement methods for residual
polymer and surfactant are needed to allow correct dosing of make-
up chemicals into injection stream [158].
ASP chemicals can also enter the ocean during transport and
transfer to the offshore facility or during production upsets when
injection or re-injection is not possible [135,155]. All these sce-
narios must be considered and accounted for when designing an
environmentally-sound offshore ASP EOR project.
8. Conclusion
ASP EOR technology is a versatile tertiary oil recovery technique
that should be considered for future application in both offshore
and onshore assets to maximize total oil production and meet
increasing energy needs. China is the country with the largest oil
production benefiting from ASP EOR projects. However, there are
an increasing number of ongoing and planned ASP evaluations at
pilot scale, especially in Canada and the U.S. ASP flooding is gaining
interest for heavy crude oil reservoirs (i.e., Canada) and offshore
fields. However, ASP EOR is not expected to impact world's oil
production for at least two decades, if not implemented at com-
mercial scales. Although, ASP EOR has already been widely and
successfully applied onshore in pilot and field applications
[14,31,131], the design and operational experiences acquired from
onshore applications should be exploited in development efforts to
enable offshore ASP EOR to impact global oil production in the near
future. In order to take this technology to the next level, there is
need to develop better ASP systems with more cost-effective sur-
factants in weak alkaline systems and with pH-tolerant polymers.
Subsurface and surface challenges also need to be addressed to
allow cost-effective and environmentally-acceptable application of
onshore and offshore ASP EOR processes.
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