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Review of ASP EOR Technology in The Petroleum Industry. Olajire2014
Review of ASP EOR Technology in The Petroleum Industry. Olajire2014
Energy
journal homepage: www.elsevier.com/locate/energy
Review
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.
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
aqueous phase [23], so that the mobility of aqueous phase de- produced fluid [33e37] also limited its further application in the
creases. Thus, the decrease in mobility ratio greatly increases sweep field. This study reviewed and assessed some of the recent ad-
efficiency. vances and prospects made by the application of ASP flooding
Substantial research works are being carried out worldwide on process in oil recovery in the petroleum industry and its limitations
ASP flooding process by different researchers [24e29]. The devel- to maximizing oil recovery from onshore and offshore reservoirs.
opment of ASP EOR technology and advances on surfactant Also discussed is how these challenges could be technically
chemistry have brought a renewed attention for chemical floods addressed.
[30], especially to boost oil production in mature and waterflooded
fields. Currently, there are numerous active ASP flooding projects 2. Enhanced oil recovery (EOR) processes
worldwide, with the ASP flooding implemented at the Daqing field
in China considered as one of the largest ASP ongoing projects [31]. The ultimate goal of EOR processes is to increase the overall oil
Several current ASP oilfield applications are reported in the litera- displacement efficiency, which is a function of microscopic and
ture [31,32]. Meanwhile, disadvantages identified during the macroscopic displacement efficiency. Based on the overall mate-
implementation process of the ASP flooding technology, such as, rials balance of the reservoir, the overall oil recovery efficiency (Ero)
severe scaling in the injection lines and strong emulsification of the can be defined as:
A.A. Olajire / Energy 77 (2014) 963e982 965
forces due to the high interfacial tension (IFT) between water and
Np oil. Summarily, microscopic efficiency can be increased by reducing
Ero ¼ (1)
N capillary forces or interfacial tension between the displacing fluid
and oil or by decreasing the oil viscosity [39]. The displacement
where N is the original oil in place, Np is the accumulative oil
efficiency is characterized by the capillary number Nc, a ratio of
recovered after recovery process. The overall efficiency consists of
viscous to local capillary forces. It can be increased by increasing
microscopic or displacement efficiency (Edo) and macroscopic or
the viscous force and reducing the capillary forces. The viscous
volumetric sweep efficiency (Evo) as the given in equation below.
force will help oil mobilization, while the capillary forces favor oil
Ero ¼ Evo Edo ¼ Ea Ev Edo (2) trapping [40].
Macroscopic or volumetric sweep efficiency refers to the effec-
where, Ea is the areal displacement efficiency, Ev is vertical tiveness of the displacing fluid(s) in contacting the reservoir in a
displacement efficiency. volumetric sense. Volumetric sweep efficiency indicates the effec-
Microscopic or displacement efficiency refers to the displace- tiveness of the displacing fluid in sweeping out the volume of a
ment or mobilization of oil at the pore scale and measures the reservoir, both areally and vertically, as well as how effectively the
effectiveness of the displacing fluid in moving the oil at those places displacing fluid moves the displaced oil toward production wells
in the rock when the displacing fluid contacts the oil [38]. It is the [38]. It depends on the selected injection pattern, character and
ratio of the amount of oil recovered to the oil initially present in the locations of the wells, fractures in the reservoir, position of gaseoil
swept volume and can be expressed in terms of saturation as; and oilewater contacts, reservoir thickness, heterogeneity,
mobility ratio, density difference between the displacing and the
Soi Sor displaced fluid, and flow rate etc. Usually, sweep efficiency can be
Edo ¼ (3)
Soi decomposed as the product of areal sweep efficiency and vertical
sweep efficiency. Areal sweep efficiency represents the fraction of
where Soi is the initial oil saturation, Sor is the residual oil saturation total formation area swept by the injected displacing agent; vertical
after oil recovery process. sweep efficiency denotes the fraction of the total formation volume
The displacement efficiency is a function of time, liquid viscos- in the vertical plane swept by the injected displacing agent. Sweep
ities, relative permeabilities, interfacial tensions, wettabilities and efficiency can be greatly improved with mobility control methods,
capillary pressures. Even if all the oil were contacted with injected such as polymers, foams and WAG injection (water alternating gas)
water during waterflooding, some oil would still remain in the process. The polymer in ASP process could significantly increase the
reservoir. This is due to the trapping of oil droplets by capillary sweep efficiency. Fig. 1 presents a schematic of sweep efficiencies:
Microscopic Sweep
RESERVOIR ROCK
Vertical Sweep or Macroscopic Sweep Efficiency
Areal Sweep
PRODUCING
INJECTION WELL
WELL
Vertical Sweep
WATER
OIL
microscopic and macroscopic (areal sweep and vertical sweep). The overcome by either viscous or gravity forces. The two dimension-
overall displacement efficiency of any oil recovery displacement less numbers that are used to compare these forces include capil-
process can be increased by improving the mobility ratio or by lary number (Nc) and bond number (Nb).
increasing the capillary number or both [39], which are the focal The capillary number (Nc) is a ratio of viscous to capillary forces
points of most recovery methods including ASP. and is given as;
Fig. 2. (a) Waterflooding with unfavorable mobility ratio (M > 1), (b) Polymer augmented waterflooding with favorable mobility ratio (M 1) [44].
A.A. Olajire / Energy 77 (2014) 963e982 967
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
Alkaline/Surfactant/
Polymer Solutions
(ASP)
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
may or may not be branched, while the hydrophilic group is formed AAS > IOS > AOS > PS > EA
by moieties such as carboxylates, sulfates, sulfonates (anionic), al- Decreasing order of thermal stability
!
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 3.1.2. Mechanism of surfactant flooding
formation of oil banks. IFT reduction lowers capillary forces and The aim of surfactant flooding is to recover the capillary-trapped
allows for the oil bank to flow more freely without renewed trap- residual oil after waterflooding. By the injection of surfactant so-
ping [36,40,48,54]. The selection of appropriate surfactant for EOR lution, the residual oil can be mobilized through a strong reduction
purposes is based on ability to reduce IFT between crude and brine, in the interfacial tension (IFT) between oil and water. Crude oil
thermal stability, tolerance to salinity and hardness of brine, solu- contains organic acids and salts, alcohols and other natural surface-
bility in brine, phase behavior parameters, adsorption test under active agents. When crude oil is brought in contact with brine or
static and dynamic condition and displacement studies under water, these natural surfactants accumulate at the interface and
reservoir conditions. form an adsorbed film which lowers the interfacial tension of the
crude oil/water interface. Depending on the type of crude oil, the
3.1.1. Types of surfactant and their structure adsorbed film at the interface can be either fluid or very viscoelastic
Surfactants are usually organic compounds that are amphiphilic, and able to form a skin. Depending on the properties of the crude
meaning they contain both hydrophobic groups (tails) and
Polar head
soluble in water
Water
Hydrophobic (oil-soluble)
C8 - C18
Oil
Hydrophilic (water-soluble)
+ Hydrocarbon tail
SO3 Na soluble in oil
Table 3
Classification of surfactants.
Propylene oxide-modified
oil (e.g. API (American Petroleum Institute) gravity, sulfur, salt and temperature, must be evaluated to avoid precipitation on the
metals content, viscosity, pour point, etc.), the structure of the film chemical equipment during injection, or during the flow through
can vary significantly [57]. Therefore, the molecular packing, sur- the reservoir [58,59]. An incremental recovery factor of 5% OOIP
face viscosity, surface elasticity and surface charge of the adsorbed (original oil in place) or more has been reported as a successful
film are very important parameters that determine various phe- polymer application [60e62].
nomena such as coalescence of emulsion droplets, as well as oil
drop migration in porous media. 3.2.1. Polymer types used in EOR
The two sets that are extensively used for enhancing oil recovery
3.2. Polymer flooding include synthetic polymers and biopolymers [63]. The most utilized
polymers today are the synthetic and partially HPAM (hydrolyzed
Polymer flooding may involve addition of polymer to the water polyacrylamide), the modified natural polymers and the biological
of a waterflood to decrease its mobility. Polymer increases the polysaccharide, Xanthan [64,65]. The natural polymers and their de-
viscosity of the aqueous phase as well as reduces water perme- rivatives include HEC (hydroxyl ethyl cellulose), guar gum and sodium
ability due to mechanical entrapment, consequently resulting in carboxymethyl cellulose, carboxyethoxyhydroxyethylcellulose.
more favorable mobility ratio. With a more viscous phase, the
collected oil bank can be more easily moved through the reservoir 3.2.1.1. PAM (Polyacrylamide). Polyacrylamide (Fig. 6a) was the first
and eventually into the producing well [16]. polymer used as a thickening agent for aqueous solutions. The
Before any polymer applications the cloud point of the polymer thickening capability (increase of the corresponding solution vis-
solution, i.e., polymer thermal stability in high salt brine and high cosity) of PAM resides mainly in its high molecular weight, which
Table 4 reaches relatively high values (>1 106 g/mol). Generally, the
Properties of surfactants used in EOR. performance of a polyacrylamide in a flooding process will depend
on its molecular weight and its degree of hydrolysis.
Surfactant type Property
the oil components responsible for surface active materials have sweep efficiency by emulsions [94]. The combination of alkali,
been identified as carboxylic acids and to a lesser extent as car- surfactants and polymers leads to synergistic effects between the
boxyphenols, porphyrins or asphaltene fractions. The acidic com- chemicals resulting in less surfactant required to recover signifi-
ponents of oil are measured and referred to as acid number. The cantly incremental oil. Typical ASP formulations involve 0.2 PV
acid number is defined as the milligrams of potassium hydroxide (pore volume) of 1% surfactant and 0.5% alkali, chased by 0.3 PV or
required to neutralize 1 g of crude oil. However, the acid number more of a solution containing 1000 ppm polymer. Here again, in-
may not be a good indicator of the acid components present in cremental oil recoveries of up to 25% or even more have been re-
crude oil that generate soap. Fan and Buckley [92] and Hirasaki [93] ported, depending upon specific geology, well spacing and
discuss new protocols for acid number measurements that better injectivity [95e98]. A common ASP EOR injection sequence is
reflect the generation of soap. The generation of soap was modeled shown in Fig. 8. An ASP flood includes several flood stages. A brine
by partitioning of acid in the crude oil (HAo) to water according to preflush is sometimes used to change the salinity or other rock or
the following solubility as; fluid properties. The first chemical slug injected is a combination of
alkali and surfactant. That slug mixes with the oil and changes its
KD
HAo ⇔HAw (10) properties, decreasing the IFT and altering the rock wettability.
Surfactants (detergents) mobilize oil that waterflooding alone
HAo and HAw are the concentrations of acid in oil and water leaves trapped in the reservoir while the alkali added increases the
respectively; and KD is the partition coefficient of HA between oil efficiency of the injected surfactants (alkali and surfactant act
and water. together to mobilize oil trapped in the reservoir). These effects
The acid in water will then dissociate in the aqueous phase to mobilize more oil. A polymer slug follows to improve the mobility
produce soluble anionic surfactant (Ae) referred to as soap ac- differential between the oil and the injected fluids. The polymer
cording to the expression: thickens the injected fluid to increase the volume of reservoir
contacted and improves reservoir sweep. This slug is typically fol-
Ka
HAw ⇔Hþ þ A (11) lowed by a freshwater slug to optimize recovery of the chemicals,
and then a flood with drive water.
where, Ka is the reaction constant following the equilibrium
relationship: 4. Status of ASP application
H Aþ
Alkaline/surfactant/polymer (ASP) combinations can be
Ka ¼ (12)
½HAw considered as candidates to improve the recovery from some of the
geologically challenging reservoirs. In particular, ASP flooding can
This reaction is one of the sources of alkali consumption since be economically attractive for reservoirs in which the gravity and
the alkali uses OHe to generate soap by the following reaction: imbibition processes play a significant role in recovering the oil.
Kb
Several ASP EOR methods have been extensively documented in the
HAw þ OH ⇔H2 O þ A (13) 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
3.4. Synergistic mechanisms of ASP flooding of different scales [96e100]. Gudong [101], Karamay [95,102], Lia-
hoe and Shengli [96] fields are other examples of Chinese ASP EOR
Alkaliesurfactantepolymer (ASP) flooding owes its success to projects documented in the literature. Additional ASP EOR flooding
the synergy of the individual components of enhanced-oil recov- reported during the last decade includes ASP flooding in Viraj field,
ery (EOR) blends. ASP flooding involves initial injection of a India [103] and West Kiehl [104], Sho-Vel-Tum [105], Cambridge
combined AlkalineeSurfactantePolymer slug for improving Minnelusa [52] and Tanner [106] fields in the U.S.
displacement efficiency by mobilizing more of the residual oil in
the pore spaces, followed by a straight polymer slug to improve 4.1. ASP in China
volumetric sweep by improving mobility ratio and volumetric
sweep. The goals are improved oil rates and reduced water pro- Most of the field pilots and commercial applications have been
duction as shown in the following equation for the overall oil conducted in China. From China alone, 13 field cases (pilots and
recovery (Ero): commercial scale) have been reported. Among them, five are from
Daqing. Most of the cases are in small scale operations, all in
So Vp sandstone reservoirs. One Daqing commercial application that
Ero ¼ Edo Ea Ev $ (14)
Bo began in 2000 had 17 injectors and 27 producers [107,108]. Among
where, Edo is the microscopic displacement efficiency improved these 13 fields tested, the highest reservoir temperature was 86 C.
with alkali and surfactant, while Ea is the areal displacement effi- In most cases, the oil viscosities were 6e13 mPa s. Only in two
ciency improved with polymer and Ev is the vertical displacement cases, the oil viscosities were 42 and 70 mPa s. The salinity was less
efficiency improved with polymer, Bo is the formation volume than 7000 ppm (parts per million) in Daqing.
factor of the oil, So is the oil saturation, Vp is the permeability
variation. 4.1.1. ASP flooding in Daqing oilfield
An important mechanism is the synergy between in situ A tertiary pilot application of the alkaline/surfactant/polymer
generated soap and synthetic surfactant. Generally, the optimum (ASP) process was initiated in Sept. 1994 in the west central area of
salinity for the soap is unrealistically low, and the optimum salinity Daqing oilfield [51]. The pilot pattern consists of four inverted five-
for the surfactant is high. When they function together, the salinity spots, including four injectors, nine producers, and two observation
range in which IFT reaches its low values is increased [10]. The alkali wells, encompassing an area of 90,000 m2 and with a pore volume
and the surfactant will produce synergistic interfacial tension (PV) of 203,300 m3. The target layer is the Saertu, consisting of
reduction while polymer improved microscopic and macroscopic sandstone, with an average porosity of 26% and permeability of
A.A. Olajire / Energy 77 (2014) 963e982 973
Polymer Oil
Drive fluid solution bank
(water) Preflush
Freshwater Alkaline-
buffer surfactant solution
l i
1.426 mm2. The crude oil viscosity is 11.5 mPa s at reservoir tem- test began in 1992 in the Gudong reservoir. Incremental recovery
perature and the connate-water salinity is 6800 mg/L. The pilot was reported to be 26% OOIP [109]. The second ASP pilot test was
performance shows a pronounced response from ASP injection. The conducted in 1997 in the western part of the Gudao reservoir in an
average pilot area oil production rate increased from 36.7 to area of 150 acres. The well spacing and net pay were 695 ft and
91.5 m3/d, while water cut decreased from 82.7 to 59.7%. A sum- 53 ft, respectively. The reservoir is a channel-sand deposit with
mary of these pilot tests is given in Table 5. In this table, Slug 1 average porosity and permeability of 32% and 1520 md, respec-
refers to a preflush with polymer, Slugs 2 and 3 usually are ASP tively. The pilot area has six injection wells and 10 producing wells
slugs with different chemical compositions, and Slug 4 is the with an average daily oil rate of 46 b/d. The waterflooding recovery
polymer drive. However, Slug 3 may not be used in some cases. The efficiency was 22.4% OOIP before ASP flooding. The ASP process was
size of these tests varied from well spacing of 246e820 ft. Three of conducted in a three-slug sequence:
the tests are still ongoing. Sodium hydroxide was used in most of
these tests, but sodium carbonate also was tried. Several types of 1. Preflush: A 0.1-Vp 2000-ppm polymer solution was injected for
surfactants, including alkyl benzene sulfonates, petroleum sulfo- 306 days.
nates, lignosulfonates, petroleum carboxylates, and biologically 2. ASP slug: A total of 0.3-Vp ASP slug containing 1.2% Na2CO3, 0.2%
produced surfactants, were tested. Hydrolyzed polyacrylamide Surfactant A, 0.1% Surfactant B, and 1700 ppm polymer was
(HPAM) polymers with different molecular weights were used in injected for 948 days.
the preflush, ASP slug, and driving slug. Incremental recovery ef- 3. Polymer drive: A 0.05-Vp 1500-ppm polymer solution was
ficiencies from the five completed projects varied from 19 to 25% injected for 158 days.
OOIP.
The injection of chemical slugs was completed in 2002. The oil
rate increased from 630 to 1490 b/d at peak production, and cor-
4.1.2. ASP process in other oilfields of China
responding water cuts decreased from 96 to 83%. The total incre-
In addition to the tests conducted in Daqing, the ASP process
mental recovery was 15.5% OOIP.
was tested in other fields including Shengli and Karamay.
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)
spacing of 164 ft and four five-spot patterns [95]. A three-slug heavy oils. One of the objectives was to determine if freshwater
process was designed as follows: requirements could be minimized during preparation of chemical
solutions for injection. This objective was successfully met (though
1. A 0.40-Vp slug of 1.5% NaCl brine preflush. with several problems which were successfully resolved). Another
2. A 0.34-Vp slug of ASP containing 1.4% Na2CO3, 0.3% crude oil objective was to determine if the produced water could be reused
sulfonates, and 0.13% polymer. and this objective was not successfully met during this pilot. It also
3. A 0.15-Vp slug of 0.1% polymer and a 0.4% NaCl drive fluid. reported that at Suffield, Cenovus determined ASP flooding to be
successful and are moving towards commercialization.
The waterflooding recovery efficiency in the pilot area before
ASP slug injection was approximately 50% OOIP at 99% water cut. 4.3. ASP projects in USA
The ASP slug was injected from July 1996 to June 1997 with
continued water drive to early 1999. The increased recovery started The ASP flooding reported in the US fields include West Kiehl
after approximately 0.04 Vp of the ASP slug had been injected and [104], Sho-Vel-Tum [105], Cambridge Minnelusa [52], Tanner [106]
got to the peak when approximately 0.2 Vp of the ASP slug had been and Lawrence field Illinois [111].
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% 4.3.1. West Kiehl, Wyoming
OOIP. Severe emulsions in produced fluids were observed, and The earliest field testing of ASP flooding was implemented at
difficulties were encountered in breaking the emulsions. West Kiehl, Wyoming [104,112] beginning in September 1987. The
incremental oil recovery over the next 2.5 years had reached 26%
4.2. Canadian ASP projects OOIP. At West Kiehl they used soda ash (Na2CO3) as the alkali. The
West Kiehl AlkalineeSurfactantePolymer flood produces incre-
Husky implemented the first “field-wide ASP flood” in Canada in mental oil greater than waterflooding at a cost of less than $2.00
May 2006. Information about this EOR scheme was obtained largely per incremental barrel.
through the company's participation in Alberta Energy's IEPT [110].
4.3.2. Cambridge Minnelusa
4.2.1. Taber South ASP project, Alberta The next ASP pilot test came from the Cambridge field, a Min-
Taber South was producing 300 bbl/day before the ASP flood. nesula field located contiguous to the Kiehl field. In this case, ASP
ASP injection started in June 2006. Production increased to flooding increased recovery by 28% of OOIP (1,143,000 bbls) and
1502 bbl/day as of December 2007. Oil cuts increased from 1.7 to incremental costs were estimated at 2.42 $/bbl.
7.3% over the same period. This project demonstrates feasibility of
tertiary application of ASP flood in a mature waterflood in a me- 4.3.3. Tanner field
dium gravity oil pool. Severe problems of equipment scaling and The Tanner field formulation contained 1 wt% sodium hydroxide
injectivity loss were encountered; these were solved using treating (NaOH) and 0.1% active ORS-41HF. The projected incremental OOIP
chemicals with varying degrees of success. This pilot also high- was 17%, based on experiments and results from pilot tests [106].
lighted that due to variability of reservoir properties, some parts of
the pool may not effectively respond to ASP injection. The challenge 4.3.4. Sho-Vel-Tum field ASP project
was to identify such areas early in the life of an ASP flooding project An ASP flood in the Sho-Vel-Tum field sponsored by the US
to optimize cost-effectiveness of chemicals. Department of Energy was conducted beginning in 1998 [105]. The
well is located in Oklahoma, USA and the reservoir is only 700 ft
4.2.2. Taber Glauconitic ASP project (214 m) deep making it the shallowest well in the United States
Husky Oil Operations Limited implemented the first field-wide where an ASP flood has been initiated. The well has been producing
AlkalineeSurfactantePolymer (ASP) flood using surfactants for over 40 years and was producing 4 bbl/day before the ASP
derived from renewable resources on January 23, 2008. The co- project was initiated. The ASP system consisted of 0.5 wt% ORS-62,
surfactants are a blend of sodium lignosulfonate (lignin) and APG 2.20 wt% Na2CO3 and 1000 mg/l Alcoflood 1275A polymer in soft-
(alkyl polyglycosides). Lignin is a natural polymer that binds a tree ened water. The ASP project increased average oil recovery from
together. Lignosulfonates can act as both a binder and a dispersant 4 bbl/day to 20 bbl/day. The pilot project added 10,444 barrels of
and these qualities can enhance the efficiency of ASP systems. incremental oil over a period of 1.3 years.
APG are an agricultural crop based combination of fatty alcohols
and glucose, mostly used in personal care formulations, cleaners, 4.3.5. Lawrence field Illinois
and agricultural formulations, and are readily biodegradable. In- Most of the unrecovered oil in Lawrence Field is contained in
cremental oil production was expected to be 762 103 m3 from the Pennsylvanian Age Bridgeport sandstones and Mississippian Age
Taber Glauconitic K pool, an incremental oil recovery factor of 15.0% Cypress sandstones [111]. During 2007, core floods resulted in an oil
OOIP. Ultimate production was estimated to be 10% higher using recovery rate of 21% OOIP for Cypress, and 24% OOIP for Bridgeport.
green chemistry based surfactants than the ASP system using In 2008-pilot ASP injection started. Bridgeport Sandstone demon-
conventional surfactants. strated an initial response to the ASP chemical injection as indi-
Pool oil production was 26 m3/dm with an oil cut of 0.9% when cated by an increase in the oil cut ratio in the pilot wells while
ASP injection began in January 2008 and in April 2010 oil produc- Cypress Sandstone ASP pilot demonstrated a continuous response
tion was 127 m3/d with a 5.3% oil cut. Total incremental oil pro- to the ASP chemical injection.
duction above the base decline at the end of April 2010 to
22 103 m3 or 0.4% OOIP incremental recovery factor. 5. Prospects of ASP EOR technology
essence, a predetermined volume or slug mixture of ASP is injected so desalination or alternative chemicals may be required. Scaling
into the reservoir, often followed by an additional injection or problem is caused during ASP injection due to the high content of
“push” of polymer, which help to reduce the slope of the oil pro- divalent ions.
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 6.1. Operational difficulties
solutions. Such surfactants, when enhanced by additional surfac-
tants, have the capability of mobilizing additional oil. The combi- ASP flooding is associated with several operational issues.
nation of injected surfactant and soap created by interaction Problems like low injectivity or complete plugging of injection
between the injected alkali and the oil can generate watereoil in- wells, polymer degradation, pump failures, incomplete polymer
terfaces with ultra-low interfacial tensions [113]. The presence of dissolution, corrosion and scaling have been encountered [5]. ASP is
alkalis also increases the surface charge on the rock surface and also complex to design, requiring analysis of oil, water and rock
hence decreases surfactant loss due to adsorption on the rock [11]. chemistry as well as geological heterogeneity, cost due to large
Polymer is added to protect the chemical slug from early dissipa- volumes of chemicals required and may not be feasible in hot
tion by the driving water phase. The three, generally non-toxic (in reservoirs, carbonate reservoirs or those with saline water.
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 6.2. Scaling issues during ASP flooding
components [114]. The ASP chemicals reduce interfacial tension
and scrub the reservoir, releasing some of the oil which remains Scaling of the well bore equipment is caused by reaction be-
locked in the reservoir after waterflooding. Alkaline surfactant tween the alkali and divalent metal cations such as calcium and
polymer (ASP) technology not only increases oil production but magnesium that result in excessive alkali consumption and sur-
also reduces water production. ASP floods are also attractive in that factant precipitation [117,118]. The precipitated material under
the chemicals used are non-toxic which reduces disposal liability. certain conditions of pH, temperature and pressure deposits on the
In selecting chemicals for an ASP flood, it is necessary to well equipment as a ‘scale’, thereby ‘fouling’ it. In the process,
consider availability, quantities required, cost, performance, and calcium as well as, silicate scales form that may play havoc with the
logistics. All of these factors are critical due to the large quantities well bore equipment. Many substances are found in the injection
usually required to flood one field, which can run into the hundreds lines. Some of them will propagate into the first phase of the
of millions of pounds. Therefore in order to minimize costs, it is reservoir: rust, sand, clay, ferrous sulfate, sulfur, calcium carbonate,
critical that: magnesium hydroxide, barium and strontium sulfates and molds.
During ASP flooding, the alkali reacts with the rock minerals and
C There should be chemical manufacturing plants large formation water thereby increasing the concentration of scaling
3
enough to accommodate the capacity needed and in close ions ðCa2þ ; CO2 3 ; SiO2 Þ in the system. Scales can originate from
proximity to the field being flooded to reduce transportation the reactions of alkalis with the carbonate minerals in the rock.
costs,
C Chemical cost should be low enough to make the sizable FeCO3ðsÞ þ SiO2 2
3 ⇔FeSiO3 Y þ CO3 (15)
investment in chemicals profitable in the long term.
MgCO3ðsÞ þ 2OH ⇔MgðOHÞ2 Y þ CO2
3 (16)
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 CaCO3ðsÞ þ SiO2 2
3 ⇔CaSiO3 Y þ CO3 (17)
cost alternative to other chemical flooding methods.
A study into ASP scaling has shown that it is a mixture of car-
bonate and silicate. The major mineralogical compositions are
6. Challenges associated with ASP EOR technology
amorphous state silicon dioxide, hexagonal-spherical calcite and
conventional calcite. The minor mineralogical compositions are
ASP flooding is still facing some major challenges in produced
clastic quartz, clastic feldspar, clastic clay particles and pyrite [117].
fluid handling on its way to commercial application. While a sig-
Silicate scale formation, though believed to be a very complex
nificant decrease in water cut of produced fluid and an increase in
mechanism, silica polymerization is believed to follow the base
oil production have been achieved, alkaline (A), surfactant (S), and
catalyzed reaction as proposed by Amjad and Zuhl [119].
polymer (P) in produced fluid have resulted in very tight oil-in-
water (O/W) emulsion, causing great troubles in surface oil/water SiðOHÞ4 þ OH /SiðOHÞ
3 þ H2 O þ 1=2O2 (18)
separation [115]. There are a number of difficulties which have
limited widespread field application, especially offshore [116]. SiðOHÞ
3 þ SiðOHÞ4 /ðOHÞ3 Si O SiðOHÞ3 þ OH
(19)
Operational difficulties include the large volumes of chemicals that
have to be transported to remote sites and then stored on platforms Dimer/Cyclic/Colloidal/Amophous silica scale
where space is limited. Additional produced fluid processing is
needed as ASP flooding results in the production of emulsions with The issues associated with silicates are potentially different
droplets as small as 10 mm in diameter. Finally produced fluids from those of traditional scales. Its formation in the oilfield is a
(containing the ASP chemicals) need to be disposed of without complex and poorly understood process [120]. The ASP flood has
impacting the environment. Technical difficulties include the fact a high pH of 11 or above. As it moves through the reservoir,
that the chemical mix needs to be carefully designed for the fluids quartz silica is dissolved [121] and the dissolved silica becomes
to be encountered in the field. ASP flooding works best with rela- stable in the high pH alkaline flood. However, as the ASP flows to
tively low-salinity water (often optimal performance is achieved by the production well, it encounters neutral pH connate water
the use of a salinity gradient during injection of the different either near the well bore or in the well and thus neutralizes the
stages), but, offshore, seawater is the only source of injection water 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 anionic, electrostatic and steric effects can result in enhanced
nanoparticle [120,122]. emulsion stability [129,130], which might not be easy to demulsify.
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 6.5. ASP produced water disposal treatment
a buffer in the reservoir between the existing waters (a mixture
of connate water and flood water at later field life). The presence In the field practice of alkaline/surfactant/polymer (ASP)
of any residual magnesium after the softening will precipitate as flooding, many produced water disposal methods faced the chal-
magnesium hydroxide (Mg(OH)2) in the ASP. Magnesium (Mg) is lenges of purifying effect, facilities pollution, healthy and environ-
then introduced into the neutral pH connate water. In the mental threat, and economical justification with the water cut
absence of divalent cations, the colloidal silicate particles may rising of the benefited oil wells and the appearance of alkali, sur-
continue to grow and form amorphous silica scale [118,120]. factant and polymer in produced water. During the application of
Silicates precipitates are generally hydrated, flocculent and ASP floods, especially on the benefited oil wells, breakthrough of
highly plugging even at low concentrations. Carbonate pre- the injection chemicals such as alkali, surfactant and polymer
cipitates are relatively granular and less adhering on colloid periodically occurs resulting in stable emulsions [129,130].
surface [123]. Accordingly the emulsified water exhibited a high oily and sus-
Cenovus in their reports on the IETP project at Suffield UU stated pended solids content, which is different from that produced from
that there were two types of scales generated during ASP projects- the other flooding technologies, and is difficult to be disposed due
initially calcium carbonate based and later, amorphous silica based. to the adsorption of the injection chemicals onto the surface of the
Scaling problems have also been reported from ASP projects in oil droplets. The separation of oil and suspended solids in ASP
China (Daqing) and elsewhere [96,100,124,125]. 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
6.3. Surfactant precipitation to be put in place.
Table 6
Effect of offshore challenges on ASP EOR technology [58].
7.1. Use of scale inhibitors inherent and consequent environmental hazards of using these
toxic and non-biodegradable scale inhibitors, has hindered the use
Scale inhibitors are chemicals that delay, reduce or prevent scale of phosphonates due to their poor ecotoxicity and many polymers,
formation when added in small amounts to normally scaling water. due to their failure to meet minimum biodegradation requirements
Most of scale inhibitors function via one of the following inhibition [145].
mechanisms [136], absorbing onto the crystal surface to prevent Many of the organic phosphates and phosphonates that are
further growth of very tiny crystals that precipitates out of the widely in use as scale inhibitors are quite toxic to the environ-
water, or by preventing the scale crystals from adhering to solid ment. These have been replaced by some organic phosphorus
surfaces such as pipes and vessels. compounds which are less toxic such as dibutylphosphor-
Chemical scale removal has been adopted as the lowest cost odithoic acid and carboxyhydromethylphosphonic acids. All
method of scale treatment especially when access to the scale is these inhibitors are based on phosphorus chemistry, but envi-
very difficult or scale exists where conventional mechanical ronmental regulatory bodies worldwide are encouraging oper-
removal methods are ineffective or expensive to install [137]. Effi- ators to use greener chemicals, hence the popularity of
ciency of chemical treatment of scale removal is measured by how phosphorous free and non-toxic scale inhibitors [143]. The
well the reagents access the scale surface. The speed and efficiency phosphorus based inhibitors have been replaced by the acrylate
with which the chemical inhibitors treat the scale are attributed to based polymers such as polyacrylic acid, polyacrylamide and
the surface-area-to-volume ratio or the equivalent surface-area-to- various polyacrylates. Results of research into greener chemicals
mass ratio [137]. proposed poly amino acids, in particular PASP (polyaspartates),
which have been tested and commercialized as scale inhibitors
7.1.1. Conventional scale inhibitors in a variety of industries [146]. Structures of some green scale
Conventional scale inhibitors are hydrophilic, that is, they inhibitors are shown in Fig. 9b.
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
7.2. Use of precipitation inhibitor
the chemical before acting as desired [138]. The most common
inhibitor chemicals are inorganic phosphates, organophosphorous
The precipitation inhibitor (sodium acrylate) could be generated
compounds, and organic polymers. PPCA (Poly phosphono car-
in situ by introducing acrylic acid and alkali to the injection water
boxylic acid) and DETPMP (diethylenetriaminepenta (methylene
[150]. When the acid was added to injection water that contains
phosphonic acid)) (Fig. 9a) are two common commercial scale in-
large quantities of divalent metal cations, the acrylic acid reacts
hibitors used in the oil and gas industry [139]. By inhibition
with the sodium ion to form sodium acrylate with an excess
mechanism, PPCA is said to inhibit by nucleation while DETPMP
amount of acrylic acid. By adding the alkali (sodium carbonate) to
operates by crystal growth inhibition [140].
the mixture, more sodium acrylate would be generated. The so-
dium acrylate would adsorb at the active growth sites of the metal
7.1.2. Green scale inhibitors
cations to prevent them from precipitating. The expected reactions
Green chemistry, or pollution prevention at molecular level is
that may occur during the preparation are shown below [150].
the chemistry designed to minimize or eliminate the use or
regeneration of hazardous materials associated with manufacture C3 H4 O2 þ Na/C3 H3 NaO2 þ H2 O (23)
and application of chemicals. It combines critical elements of
environmental improvement, economic performance and social
C3 H4 O2 þ Na2 CO3 /C3 H3 NaO þ CO2 þ H2 O (24)
responsibility [141,142]. The number of chemicals allowed to be
used as inhibitors has thus been limited mainly to three criteria-tier When the calcium and magnesium ions are disabled in the so-
level of biodegradability, bioaccumulation and toxicity. According lution, then the surfactant introduced to the system was without
to the PARCOM (Paris Commission), an ideal green inhibitor should any precipitation problems [151]. The influence of the inhibitor on
be non-toxic, readily biodegradable and shows no bioaccumulation precipitation reaction may be explained in terms of three effects:
[141]. (a) direct complexation of sodium acrylate with crystal lattice ions
Though the use of green scale inhibitors to inhibit scale in oil in solution; (b) adsorption of sodium acrylate on the crystal surface
and gas wells is relatively an unexplored area [143], there have or at the active growth sites; (c) sodium acrylate may change the
been several works on this promising alternative [144]. 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
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 Hard water containing high amounts of Ca2þ and Mg2þ ions can
[152]. The advantage of the in situ inhibitor is the use of hard brines be treated by SAC (strong acid cation) resins or, by WAC (weak acid
without the need for softening the injection water. This could cation) resins. This method requires the feed water to contain very
reduce the cost of chemical EOR process and make it more suitable small amount of oil/grease (<50 ppm). Alternative treatment could
for environmentally sensitive applications, particularly offshore be by SIS (select ion sequestration) method that can tolerate rela-
application. tively more oil carryover (up to 500 ppm).
One of the major issues to be addressed when designing an ASP Petroleum industry is currently investigating the limiting fac-
flood is the prevention of scale formation. The increase in pH due to tors pertinent to offshore ASP EOR. The sector is examining new
the injection of alkali will lead to the precipitation of divalent ions enabling chemistries and technologies for improving surface op-
such as Ca2þ and Mg2þ, which will form carbonate and/or hy- erations to allow cost-effective offshore ASP EOR to be performed in
droxide. To prevent or at least significantly reduce these reactions, an environmentally sound and safer manner. Some of the recent
it is necessary to soften the injection water to reduce the concen- chemical and fluid processing developments are described in the
tration of divalent ions. following section.
A.A. Olajire / Energy 77 (2014) 963e982 979
7.4.1. Logistics-chemical transport, storage and cost degraded polymer, etc.) on subsurface performance must be taken
Table 7 gives typical consumption levels for an offshore ASP into account. Also, online measurement methods for residual
injection process at 30,000 m3 injection fluid per day [58]. The large polymer and surfactant are needed to allow correct dosing of make-
storage volume and weight shown in the last two columns can be up chemicals into injection stream [158].
prohibitive for many projects due to restrictions on available deck ASP chemicals can also enter the ocean during transport and
space [153]. The largest requirements are for surfactant and alka- transfer to the offshore facility or during production upsets when
line soda ash. Surfactants are typically delivered as aqueous solu- injection or re-injection is not possible [135,155]. All these sce-
tions with low active level resulting in shipping and storage of large narios must be considered and accounted for when designing an
quantities of water. Development of low-adsorbing, high-active environmentally-sound offshore ASP EOR project.
surfactants would help in reducing the storage requirements for
the surfactant component. Also, use of surfactants that do not 8. Conclusion
require co-solvents would be particularly beneficial in reducing
chemical logistics costs [154]. Use of the SP process rather than ASP ASP EOR technology is a versatile tertiary oil recovery technique
would not reduce overall chemical volume requirements as elimi- that should be considered for future application in both offshore
nation of alkalinity typically results in the usage of 3e5 times and onshore assets to maximize total oil production and meet
higher concentration of surfactant [155]. However, an SP process increasing energy needs. China is the country with the largest oil
may look attractive for some cases where the oils have low acid production benefiting from ASP EOR projects. However, there are
numbers and to avoid excessive scale issues in production facilities. an increasing number of ongoing and planned ASP evaluations at
Shipment and storage of large amounts of chemicals may pilot scale, especially in Canada and the U.S. ASP flooding is gaining
necessitate the use of dedicated supply vessels. Also, floating interest for heavy crude oil reservoirs (i.e., Canada) and offshore
storage and offloading vessels (FSO) or additional deck space on fields. However, ASP EOR is not expected to impact world's oil
new offshore structure may be appropriate for some projects where production for at least two decades, if not implemented at com-
insufficient space and/or weight restrictions exist on the pre- mercial scales. Although, ASP EOR has already been widely and
existing floating production facilities [153]. successfully applied onshore in pilot and field applications
More weight-efficient surfactants and elimination of co-sol- [14,31,131], the design and operational experiences acquired from
vents would also likely reduce the overall cost of chemicals, a onshore applications should be exploited in development efforts to
factor that can inhibit implementation of ASP EOR in an offshore enable offshore ASP EOR to impact global oil production in the near
environment where large well-spacing often delays the financial future. In order to take this technology to the next level, there is
benefit of enhanced production. In fact, the overall economics of need to develop better ASP systems with more cost-effective sur-
an ASP project is dominated by the cost of the injected chemical factants in weak alkaline systems and with pH-tolerant polymers.
slug which in turn dominated by cost of the surfactant, the Subsurface and surface challenges also need to be addressed to
highest-cost chemical in the slug [155,156]. Any changes in sur- allow cost-effective and environmentally-acceptable application of
factant chemistry to lower OPEX and logistics costs must be onshore and offshore ASP EOR processes.
balanced with the changes which would lead to effective recovery
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