ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. 2014; 9: 471–489

Published online 30 May 2014 in Wiley Online Library
(wileyonlinelibrary.com) DOI: 10.1002/apj.1824

Review
A comprehensive review of alkaline–surfactant–polymer
(ASP) flooding
James J. Sheng*
Bob L. Herd Department of Petroleum Engineering, Texas Tech University, P.O. Box 43111, Lubbock, TX 79409, USA

Received 28 January 2014; Revised 29 March 2014; Accepted 15 April 2014

ABSTRACT: Alkaline–surfactant–polymer (ASP) flooding is a combination process in which alkali, surfactant, and polymer
are injected in the same slug. Because of the synergy of these three components, ASP is the current worldwide focus of
research and field trial in chemical enhanced oil recovery (EOR).
This paper is to provide a comprehensive review of the ASP process. The reviewed topics include the following:
• ASP synergy and its EOR mechanisms
• Screening criteria
• Laboratory work
• Numerical simulation work
• Summary of pilots and large-scale applications
• Project economics
• Chemicals used
• Water quality
• Mobility control requirement
• Problems associated with ASP flooding and possible solutions

In addition to the comprehensive review, future developments are also discussed. Data and analyzed results presented in
this review will provide the reader with the updated information about ASP and a guide to read relevant papers for those who
are new to chemical EOR. The survey data also provide operators with some reference data for their project design and
optimization. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.

KEYWORDS: ASP; alkaline–surfactant–polymer flooding; EOR; IOR; chemical enhanced oil recovery

INTRODUCTION In this paper, a comprehensive review of the issues

With growing global energy demand and depleting
reserves, enhanced oil recovery (EOR) from existing brown
fields becomes more and more important. Because most of
oil fields have been under waterflooding, chemical EOR
method may be implemented with less additional facilities
needed, compared with other EOR methods. Among
chemical methods, alkaline–surfactant–polymer (ASP) is
the most promising method because it has the synergy of
alkaline, surfactant, and polymer. In an ASP process, alkali,
surfactant, and polymer are added in the same solution slug.
However, it should be pointed out that if produced water
with oil and suspensions is used, or the water has high total
dissolved solids (TDS) and high divalent cations, quite
complex and expensive facilities have to be used.
*Correspondence to: James J. Sheng, Bob L. Herd Department of
Petroleum Engineering, Texas Tech University, P.O. Box 43111,
Lubbock, TX 79409, USA. E-mail: james.sheng@ttu.edu
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Curtin University is a trademark of Curtin University of Technology
related to ASP flooding is provided. Future developments
are also recommended. The effect of wettability alteration
is discussed in this paper, although it is an important
component of chemical EOR especially in carbonates,
because it has been reviewed in another publication of
the authors; see Sheng.[1]
ASP MECHANISMS
Before presenting the synergy of ASP process, the mecha-
nisms of each individual component are discussed first.
Mechanisms of polymer flooding
The process of polymer flooding is same as water-
flooding except that polymer is added in the water so that
the solution viscosity is increased. Sometimes, it is called
thickened waterflooding. It is well known that when the
472 J. J. SHENG
viscosity of polymer solution is increased, the sweep
efficiency is improved by reducing viscous fingering.
According to the fractional flow equation,
1 1
fw ¼   ¼ (1)
1þ k ro μw 1 þ λλwo
k rw μo
if the water viscosity μw is increased by adding polymer,
the water cut will be decreased. As a result, more oil can
be recovered at the same amount of water injected
compared with waterflooding. When polymer is injected
in vertically heterogeneous layers, crossflow between
layers improves polymer allocation in the vertical layers
so that the vertical sweep efficiency is improved.[2] In
polymer treatment, another mechanism is called dispro-
portionate permeability reduction. Through the use of
this mechanism, polymer can reduce water relative per-
meability krw much more than oil permeability kro. The
increased water viscosity and reduced water relative
permeability result in reduced water mobility λw. Thus,
the mobility ratio of water to oil (λo) is reduced. It is well
known that as the mobility ratio is reduced, more oil will
be recovered.
Because of polymer adsorption, the permeability in the
polymer flowing paths or zones is reduced. Thus, water
flow velocity is reduced. This is called the permeability
reduction effect. After polymer flooding, the permea-
bility of the subsequent water still remains low because
polymer adsorption is an irreversible process so that the
adsorbed polymer cannot be simply flushed away. This
is called residual permeability effect. Such effect will
make the subsequent waterflooding more effective.
The aforementioned mechanisms are fundamentally
important in polymer flooding in terms of oil recovery.
A secondary mechanism is related to polymer visco-
elastic behavior. Because of polymer viscoelastic pro-
perties, there is normal stress between oil and polymer
solution. Thus, polymer exerts a larger pull force on
oil droplets or oil films. Oil is ‘pushed and pulled’ out
of dead-end pores. Thus, residual oil saturation is
decreased. This mechanism was rarely discussed until
recently (e.g., Wang et al.[3,4]). The significance of this
mechanism needs more investigation.
It can be easily understood that the polymer solution
viscosity increases with polymer concentration. The
added salt will reduce the intra-chain repulsion of
polymer molecules [e.g., hydrolyzed polyacrylamide
(HPAM)], so that polymer solution viscosity is reduced.
This concentration and salinity dependency of polymer
solution viscosity can be described by the Flory–
Huggins equation.[5] Under typical reservoir conditions,
polymer solution is shear-thinning, and the viscosity
can be described by a power law function of shear rate.[6]
Some small pores cannot be accessed by large polymer
molecules. This phenomenon is called inaccessible pore
volume (IPV). IPV makes polymer molecules transport
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
faster than its solvent (solution). But the velocity is
retarded by adsorption. The resultant transport velocity
is the balance between the two. Polymer adsorption may
be described by the Langmuir-type isotherm. It increases
with salinity but decreases with permeability. As the
polymer molecular weight (MW) becomes higher, the
solution viscosity is higher compared with a lower-MW
solution at the same concentration. Therefore, in high-
permeability reservoirs, high-MW polymer is preferred.
Polymer solution viscosity may decrease as the pH
is increased owing to the increased salt effect of an
alkali.[7,8] However, Mungan[9] reported that the HAPM
viscosity at 50 s1 shear rate significantly decreased
when lowering pH. And Szabo[10] reported the increase
in the viscosity of AM/2-acrylamido-2-methyl propane
sulfonate copolymer solution when NaOH was added.
Those observations are probably related to the early-time
hydrolysis effect. The effect of pH is complex consi-
dering different hydrolysis effect and salt effect.
The aforementioned effects on polymer solution vis-
cosity are mainly addressed to the HPAM type, but most
of them are generally valid to biopolymers as well.
Biopolymers will be more tolerant to salinity but more
sensitive to temperature.
One economic impact of polymer flooding that has
been less discussed is the reduced amount of water
injected and produced, compared with waterflooding.[11]
Because polymer improves the sweep efficiency, less
water is produced and injected. In some situations like
an offshore environment and a desert area, water and
the treatment of water could be costly.
Mechanisms of surfactant flooding
The key mechanism for surfactant flooding is low
interfacial-tension (IFT) effect. To discuss this mechanism,
the concept of capillary number vs residual oil saturation
is discussed first. The capillary number, Nc, is defined as
uμ
Nc ¼ (2)
σð cosθÞ
where μ is the displacing fluid, u is the displacing Darcy
velocity, θ is the contact angle, and σ is the IFT between
the displacing fluid and the displaced fluid (oil). Many
experimental data show that as the capillary number is
increased, the residual oil saturation is decreased,[12] as
summarized by Stegemeier.[13] Please note that the
capillary number defined by Eqn (2) is a semi-empirical
parameter. Different forms have been used in the
literature. In particular, cosθ is omitted in some forms
for simplicity. However, the contact angle can be an
essential parameter when the mechanism of adding
surfactants is to change wettability, such as using
surfactants in oil-wet carbonate reservoirs.[14] Sheng[11]
provided a lengthy discussion regarding the forms of
the capillary number.
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
A typical capillary number for waterflooding is about
107. To reduce waterflooding residual oil saturation,
the capillary number must be significantly higher than
107, typically in the order of 104. How can the
capillary number be increased? From the definition of
capillary number (Eqn (2) with cosθ omitted, there are
three ways: (1) increasing injection fluid velocity u, (2)
increasing displacing fluid viscosity μ, and (3) reducing
the IFT σ. The injection fluid velocity is limited by pump
capacity or formation injectivity. Even though the pump
capacity is not a problem, if the injection velocity is too
high, the injection pressure may be higher than the form-
ation fracture pressure. Increasing injection fluid visco-
sity is limited at least by economics, because increasing
polymer solution viscosity needs a higher polymer con-
centration. The way left is to reduce IFT. It is known that
the IFT between a surfactant solution and oil can be
reduced from 20–30 to 103 mN/m. In other words, by
adding surfactants, the capillary number can be practi-
cally increased by more than 1000 times. Because of
the lowest IFT, oil droplets can flow more easily through
pore throats because of reduced capillary pressure. The
oil droplets move forward and merge with the oil down
the stream to form oil bank. In some circumstances,
wettability alteration and emulsion flooding could also
be important.
Sometimes, cosolvents are added to a surfactant for-
mulation to minimize the occurrence of gels, liquid
crystals, emulsions, or polymer-rich phase separating
from the surfactant solution, to lower the equilibration
time, and/or to reduce microemulsion viscosity.
Cosolvents like alcohol can also serve as a cosurfactant
to alter the optimum salinity required to achieve ultralow
IFT.[15] Usually, the volumetric ratio of surfactant to
cosolvent is about 2–3. However, cosolvents like alcohol
may decrease solubilization of oil and water in micro-
emulsions, thus increases the minimum value of IFT
achievable by a surfactant without a cosolvent.[16,17]
Also, it destabilizes foam that may be desired for
mobility control.[15]
Mechanisms of alkaline flooding
One mechanism of alkaline flooding is that a surfactant
(called soap to differentiate it from an injected synthetic
surfactant) is generated in situ when an alkaline solution
reacts with the acid component in a crude oil. The
reaction equation is
HA þ OH  →A þ H 2 O (3)
where HA is a pseudo-acid component and A is the
soap component.
More importantly, when an alkali is added with a
surfactant like in an ASP process, the alkali can reduce
the adsorption of surfactant on the grain surfaces. This
makes surfactant work more efficiently, and less
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
A COMPREHENSIVE REVIEW OF ASP FLOODING 473
surfactant needs to be injected. Other mechanisms
include emulsification, oil entrainment, bubble entrap-
ment, and wettability reversal.[18]
Synergy in ASP
An important mechanism of ASP flooding is the synergy
between in situ generated soap and an injected surfactant.
Generally, the optimum salinity for the soap is unrea-
listically low. To satisfy the low optimum salinity, the
injected alkaline concentration must be so low that the
injected alkali is lower than the amount of consumption;
thus the alkali cannot propagate forward. To solve this
problem, a synthetic surfactant is added because the
optimum salinity for a surfactant is high. When the soap
and the surfactant are mixed, the optimum salinity range
in which IFT reaches its low values is increased and is
widened.[19]
An incomplete list of the synergies and interactions
of ASP may be summarized as follows.
(1) Alkaline injection reduces the adsorption of
surfactant and polymer.
(2) Alkali reacts with crude oil to generate soap. Soap
has low optimum salinity, whereas a synthetic
surfactant has relatively high optimum salinity. The
mixture of soap and the synthetic surfactant has a
wider range of salinity in which the IFT is low.
(3) Emulsions improve the sweep efficiency. Soap and
surfactant make emulsions stable owing to the
reduced IFT. Polymer may help to stabilize emul-
sions owing to its high viscosity to retard
coalescence.
(4) There is a competition of adsorption sites between
polymer and surfactant. Therefore, adding polymer
reduces surfactant adsorption, or vice versa.
(5) Adding polymer improves the sweep efficiency.
SCREENING CRITERIA
Enhanced oil recovery screening criteria address two
questions: (1) Which EOR methods can be applicable in
the target reservoir? (2) Which EOR method is the most
suitable or most economic? To answer the second ques-
tion, detailed studies need to be performed. Dickson
et al.[20] presented a methodology to rank a variety of
EOR methods. More often, the first question is addressed.
The literature generally focuses on the technical appli-
cability of an EOR method. More importantly, the resour-
ces for the EOR project must be available, the project is
supported by the company management, and it will meet
local environmental regulations.
Screening criteria for broader EOR processes were
discussed by several researchers, e.g. Lake et al.,[21]
Taber et al.,[22,23] Al-Bahar et al.,[24] Dickson et al.,[20]
and Al-Adasani and Bai (2010).[25] Some of the
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474 J. J. SHENG Asia-Pacific Journal of Chemical Engineering

500–9000
Depth, ft
screening criteria for ASP are summarized in Table 1.

<9000

3238

NC
Here, several critical parameters are briefly discussed
regarding ASP application conditions. Many parameters
could affect chemical EOR processes. However, the

gravity
most critical parameters should be reservoir temperature,

>20

>20
26.6
API
formation water salinity, and divalent contents, clay
contents, oil viscosity, and formation permeability, as
discussed in the succeeding text. In Table 1, the average

coefficient
values of the parameters important to an ASP process

0.56
DP-

NC
from the real ASP projects are listed. The values of each
parameter are analyzed using the method of rank and
percentile, and the average value for each parameter is

Weak
taken at the 50% percentile.

Gas
cap

No

No
Formation

few cases
Aquifer

Weak in
Almost all of the chemical EOR applications have been

Weak
No
in sandstone reservoirs, except a few stimulation projects

In the table, μo is oil viscosity, So is oil saturation before ASP, Tr is reservoir temperature, NC means not critical for oil recovery.
that were conducted in carbonate reservoirs. One reason
for fewer applications in carbonate reservoirs is that

Spacing

<656
403.6
Well
anionic surfactants have high adsorption in carbonates

(ft)
and cationic surfactants are expensive. Another reason
is that anhydrite often exists in carbonates, which causes
precipitation[26] and high alkaline consumption.[27,28]
Clay

Low

Low

Low

Low
Clays in sandstones also cause high surfactant adsorption
and high alkaline consumption (Holm and Robertson,

Sandstone

Sandstone

Sandstone
Lithology
1981; Johnson et al., 1988; Shen and Chen, 1996).[29–
31]
Therefore, clay contents must be low for a chemical

ASP, alkaline–surfactant–polymer API; American Petroleum Institute; DP, Dykstra and Parsons.
EOR application.
Table 1. Summary of screening criteria for alkaline–surfactant–polymer.

Oil composition and oil viscosity

Divalent
(ppm)

<500

<100
1000

178
Oil composition is very important to alkalis and
surfactants, but it is not critical to polymer. According
to Taber et al.,[22,23] oil viscosity should be less than
<200 000 if TR
water salinity,
(TDS, ppm)

35 cP for an alkaline–surfactant (AS) project. In most

Formation

TR > 60 °C
<50 000 if

of Chinese ASP projects, the oil viscosity is around

<20 000

<50 000
< 60 °C,

10 cP, with a maximum of 70 cP. There is an increasing

50 000

interest in applying polymer flooding in heavy oil

7993

reservoirs with the viscosity up to 2000 cP.[32,33] Some

research has been performed in alkaline injection in
<93.3

<93.3

heavy oil reservoirs as well.[34] If the technology can be

Tr (°

<70

<95
52
C)

advanced in alkaline and polymer injection in heavy oil

reservoirs, the viscosity range for an ASP application
>100

473.0
(mD)

could become wider.

>10

>50

>50
k

Formation water salinity and divalents

>0.35

>0.45
(frac.)

>0.3
So

0.3

Most of ASP projects were carried out in low-salinity

reservoirs of about 10 000 ppm. Al-Bahar et al.[24]
<200

<150
(cP)

criterion is 50 000 ppm salinity and 1000 ppm hard-

<35

<35

<50
12.9
μo

ness. This 1000 ppm hardness is probably too high

and needs extra chelating agents. Alkalis will react with
Proposed by

Proposed in

multivalent cations to result in precipitation. Some

From ASP
et al.[22,23]

this paper
Al-Bahar

Dickson
et al.[21]

et al.[24]

et al.[20]

high-pH chelating agents such as Na4EDTA and

projects
Taber

Na3NTA may replace alkalis to avoid this problem.

Lake

Holm and Robertson[29] reported that the addition of

© 2014 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
7% Na4EDTA in micellar solutions did not result in
precipitation but improved oil recovery similar to
addition of Na4SiO4.
Although the formation water salinity and divalents
are important to ASP EOR, the salinity and divalent
content in the water used to dissolving chemicals
are much more important. This is because the salinity
and divalents in the formation water can only affect
the chemical slug performance through mixing with
the chemical slug, but the salinity and divalents
in the chemical slug will directly affect the chemical
slug performance. For example, the salinity of for-
mation water in the Oerrel and Hankensbuettel fields
were 167 000 ppm and 175 000 ppm. Fresh water was
used in dissolving polymer, and 0.044 PV and
0.182 PV of fresh water preflushed the formations,
respectively, in the two fields. Both polymer floods
were useful.[35]
Reservoir temperature
According to Taber et al.,[22,23] the reservoir tem-
perature should be lower than 93 ºC for A/S/P projects,
but the average temperature for actual A/S field
projects was 27 ºC, and the average temperature for
polymer projects was 60 ºC.[22] Daqing reservoir tem-
perature is about 45 ºC. The maximum temperature
for few Chinese projects was in the order of 80 ºC. It
should be noted that people preferred to apply chemical
projects in favorable reservoirs first subsequently move
to more difficult reservoirs, as Daqing did and reported
by Zhu et al.[36] Therefore, the temperature from
executed projects may not represent chemical EOR
applicable conditions.
Researchers tried to find chemicals, especially poly-
mers, which can be tolerant to high temperature,
high salinity, and divalent. For example, Vermolen
et al.[37] found that a ter-polymer containing anionic
monomer 2-acrylamido-2-methyl propane sulfonate
and 30–50% n-vinyl pyrrolidone could be stable for
more than 180 days at 120 °C, 20% TDS, and 1.8%
divalent. Puerto et al.[38] screened alkoxyglycidylether
sulfonates with n-octane/NaCl-brine systems. They
found that the systems could be stable up to 120 °C
with optimal salinities up to 20% NaCl with suitable
combinations of hydrophone and alkoxy chain type
(ethylene oxide or propylene oxide and chain length).
And some chemical suppliers state that polymer
can be applied up to 120 ºC. Barnes et al.[39] presented
internal olefin sulfonates, which could be stable even
up to 150 °C. However, these results are laboratory
not field applications. The application conditions of
a chemical mean that not only is the chemical stable
at these conditions, but it also must be able to satisfy
other conditions, which can lead to a high oil recovery
at a low cost, such as low adsorption and higher
solubilization ratios.
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
A COMPREHENSIVE REVIEW OF ASP FLOODING 475
Formation permeability
High permeability is favorable to ASP flooding, and it is
critical to polymer injection. Simply, polymer may not
be able to flow through low permeability formations.
Interestingly, Taber et al.[22] showed that although the
criteria for chemical projects is >10 md, the average
permeabilities in actual projects were 450 md for A/S,
and 800 md for polymer flooding. In Chinese chemical
EOR projects, the permeabilities are 100s to 100s md.
The data presented in the preceding paragraphs can
serve as a reference for potential projects. Among the
parameters discussed, reservoir temperature and water
salinity are the most critical parameters. However, as
chemical products are improved, the screening criteria
will be changed. From the current chemical EOR
technology, extensive laboratory measurements are still
needed for every project. Simulation work is needed to
analyze laboratory data and upscale to a field model for
potential prediction. ASP EOR in high temperature and
high salinity is a challenge.
LABORATORY WORK
There are so many kinds of laboratory tests that need to be
performed, but we could not afford to do every laboratory
test needed in practice. However, minimum laboratory
tests for almost every ASP project are needed. The tests
for polymer include the aqueous stability test, filtration
test, and viscosity measurements at different shear rates.
To select surfactants, in additional to the aqueous stability
test, one necessary test is the phase behavior test using
pipettes called the salinity scan test as shown in Fig. 1—
a photograph of such a test. From Fig. 1, it can be seen that
there are three types of microemulsions depending on
salinity: type I—oil-in-water microemulsion, type II—
water-in-oil microemulsion, and type III—bi-continuous
middle-phase microemulsion. One important objective
from such test is to select a surfactant or surfactants that
can have high solubilization ratios of oil to surfactant
volumes and water to surfactant volumes, which will be
achieved if the middle-phase volume in Fig. 1 is high, or
select the optimal salinity if the surfactants have been
chosen. The optimal salinity corresponds to the maximum
middle-phase volume in Fig. 1. According to Huh’s[40]
equations, high solubilization ratios will generate very
low IFT, preferably in the order of 103 mN/m. Selection
of surfactants based on the solubilization ratios may be
an alternative to the IFT measurement as Huh’s[40] equat-
ions may be used to calculate IFT from the solubilization
ratios. Apparently, measuring IFT directly in the labora-
tory was preferred in China because they always reported
IFT measurements in the Chinese literature for their
projects.
For the salinity scan test, a fixed water–oil volume
ratio that is generally one is used. For an ASP solution,
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
476 J. J. SHENG
Figure 1. Photograph of a salinity scan test for
phase behavior. The top numbers are salinity in
weight percent. Different types of microemulsions
are shown in the picture as the salinity is
increased. This figure is available in colour online
at www.apjChemEng.com.
an additional test called oil scan needs to be run. In this
test, the water–oil volume ratio is changed, because
alkali reacts with the acid component in the crude oil
and different saturations of oil in the reservoir in diffe-
rent phases of the project will result in different amount
of soap generated in situ; thus the phase behavior of the
mixed soap and injected surfactant will change with the
water–oil ratio (or oil saturation). The oil scan test results
are generally presented in the called activity map.[19] For
a detailed description of these tests, see Sheng.[11] At the
end, coreflood tests are needed to see whether a signifi-
cant oil recovery could be recovered. Because we can
only afford to do very limited experiments, a database
built from the existing projects and the literature will be
very useful.
Many laboratory-measured data such as the salinity
scan data, polymer viscosity data, and polymer and
surfactant adsorption data are input in a simulation
model to history-match coreflood tests. By history-
matching coreflood tests, the flow parameters and
chemical parameters are calibrated, and these para-
meters are then used in field-scale models to predict
field oil recovery performance. A good example of
such practice was presented by Delshad et al.[41]
Generally, all those tests mentioned earlier are conduc-
ted using dead oils because of the difficulty to do the tests
using live oils. It is the industry interest to know the
effect of dissolved gas. There are few papers that present
the experimental work using live oils. Nelson[42] obser-
ved little difference in phase behavior as a function
of equilibrated dissolved methane. Puerto and Reed[43]
and Southwick et al.[44] observed that surfactant was
relatively more soluble in the live oil phase compared
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
with in the dead oil, and the optimum salinity decreased
to a lower value. Kahlweit et al.,[45] Skauge and
Fotland,[46] Sassen et al.,[47] Austad and Strand,[48] and
Roshanfekr et al.[49] all observed that the increased
pressure reduced surfactant solubility in crude oils
and the optimum salinity increased. Roshanfekr
et al.[49] also found that adding methane to dead oil at a
constant pressure decreased the optimum salinity. The
effect of pressure was opposite to that of added methane
(live oil). And dissolution of methane dominated the
pressure effect.
NUMERICAL SIMULATION WORK
A proper numerical simulation work includes history-
matching laboratory coreflood tests to calibrate ASP
flow parameters, using the calibrated or up-scaled para-
meters in a pilot-scale, field-scale or sector model to
optimize the injection schemes and to predict ASP
performance, and using both the coreflood scale model
and the up-scaled model to do sensitivity studies and
perform engineering analysis. There are not many good
examples of such detailed simulation work, which have
been presented in the literature, partly because a good
simulator that captures ASP mechanisms and is user-
friendly is not available. UTCHEM, a chemical flood
simulator developed by the University of Texas, is the
best simulator to capture the mechanisms, but it is diffi-
cult to simulate a large field-scale case because of slow
computation algorithm (sometimes solutions are not
convergent) and lack of functions to include real geolo-
gical features. Another weakness is that UTCHEM itself
does not have a visualization package equipped for post-
processing analysis. External softwares such as S3GRAF
(http://www.sciencesoft.com/products/s3graf/) and
KRAKEM (https://www.esss.com.br/kraken/) are needed.
Simulating geochemical reactions is really tedious in
UTCHEM. To overcome this problem, a simplified
model was proposed to simulate ASP floods.[50] Karpan
et al.[51] proposed two ASP models. One is the effective
ASP model in which the water and oil solubilization
ratios are simulated as a function of salinity, and soap
is calculated based on the amount of acid in the oil and
the amount of alkali in the water. The other model is
the Shell’s dynamic reservoir simulator MoReS coupled
to PHREEQC, which is a geochemistry software including
the reactions between an aqueous solution and minerals,
gasses, exchangers, and sorption surfaces.[52] The coup-
ling process is performed block by block.[53] Soap and
surfactant are partitioned into oil and water phases accor-
ding to the salinity following the model proposed by Liu
et al.[54] In both of their models, basically, water and oil
phases are considered. In other words, the type III micro-
emulsion phase is not included.
In the past, a simulator called GCOMP developed by
PHH Petroleum Consultants Ltd. was used in simulating
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
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Asia-Pacific Journal of Chemical Engineering
ASP projects. These days, people start to use STARS
developed by Computer Modeling Group, and ECLIPSE
developed by Schlumberger. In ECLIPSE, the ASP
process is simulated using three models of alkaline,
surfactant, and polymer. The main lacking features of
these commercial simulators are that detailed geoche-
mistry reactions related to alkaline injection are not
included and that the surfactant solution is not treated
by the three types of microemulsions. These features
may be included in REVEAL developed by Petroleum
Experts.
A fundamental mechanism of surfactant-related EOR
methods is low IFT, which leads to a high capillary
number and thus a low residual oil saturation. IFT is
mainly a function of the amount of oil solubilized in the
microemulsion phase.[40] However, ECLIPSE models a
two-phase system with the IFT as a function of surfactant
and/or alkaline concentrations in the water phase. Surfac-
tant and alkali are assumed to be only in the aqueous
phase (type I microemulsion), and interactions with the
oleic phase are neglected. The type III microemulsion is
not simulated in the STARS. A new version of STARS,
STARS-ME, is a commercial adaption of UTCHEM. It
models the type III microemulsion. According to an
author’s benchmark work (not published), ECLIPSE
can simulate polymer flooding reasonably well. Chemical
injection like surfactant injection can reduce residual oil
saturations, resulting in increased relative permeabilities.
Therefore, commercial simulators without detailed
mechanisms included are used to simulate chemical
processes by modifying relative permeabilities.
Description of a chemical process requires many
parameters. Ideally, these parameters need to be mea-
sured in laboratory. However, it is not practical to
measure all of these parameters, because of limited time,
high cost, and/or lack of laboratory equipment. Some-
times, some of these parameters are obtained by adjus-
ting these parameters to history-match experiments
using simulation. Therefore, numerical simulation could
be very useful.
SUMMARY OF PILOTS AND LARGE-SCALE
APPLICATIONS
It is impossible to present detailed project description
and results in this paper. A chemical EOR knowledge
database is being developed. It includes the reservoir
and fluid data, chemical injection data, and perfor-
mance data of all field chemical EOR projects. Here,
only the main results of pilots and large-scale field
applications are summarized.
Single well tracer test before a pilot
Before carrying out a field pilot, generally, a single well
(chemical) tracer test (SWTT) is conducted. The SWTT
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
A COMPREHENSIVE REVIEW OF ASP FLOODING 477
is sometimes called chemical huff and puff. During an
SWTT, a slug of ASP solution is injected in a well, and
the oil saturation before and after the chemical injection
is measured. The main objective is to see how much oil
saturation can be reduced. Such test is less expensive,
but there is an uncertainty in estimating oil saturation,
and limited information regarding inter-well connec-
tivity, sweep efficiency, and injectivity can be obtained.
When a field pilot is conducted, more expensive observa-
tion wells may be drilled.
Summary of ASP projects
About 32 ASP field pilots and large-scale applications
have been reported with performance data so far world-
wide. These projects are listed in Table 2. Note that other
combination processes such as AS, alkaline–polymer
(AP), and ASP-foam are not included in this review.
The former Soviet Union was active in chemical EOR,
but the current status is unknown because field case
studies have not appeared in the modern English litera-
ture. Thus the Russian projects are not included in this
review. Among these 32 ASP projects, 21 projects were
carried out in China, seven in USA, one in Canada, two
in India, and one in Venezuela. All the projects were
carried out in onshore reservoirs except the Lagomar
project in Venezuela, which is in offshore. It was also
reported that ASP flooding was conducted recently in
the Elk Hills field in California and the Mooney field in
Canada, but the detailed results are not available. Zargon
Oil & Gas Ltd. has initiated an ASP project in the Little
Bow field. By May 2013, ASP chemical supply contracts
and construction contracts had awarded, and major
equipment had delivered on site. ASP injection may
begin on January 2014. From the paper by Ansarizadeh
et al.,[55] an ASP project was carried out in the Instow
field in Canada. But detailed data were not found in
searching the SPE OnePetro. The Marmul field has been
put in polymer flooding. It was reported that an ASP pilot
is being planned. Mangala was reported to have an ASP
project.[56] The EOR studies on the Caracara Sur field in
Llanos Basin, Columbia were conducted,[57] but a field
pilot or an application has not been seen reported.
Several papers have been presented about the design
and preparation of the offshore ASP pilots in two fields,
St. Joseph in Malaysia[58,53] and La Salina in
Venezuela.[59–61] The field application results have not
been seen reported in the literature. In Daqing, after
several pilot tests, ASP projects have been expanded to
several large-scale field applications, which are listed at
the end of Table 2.
Most of the field ASP projects were conducted in either
five-spot patterns or inverted five-spot patterns. The
Lagomar pilot was in an inverted seven-spot pattern, the
Jilin Hong-Gang pilot was in an inverted 13-spot pattern,
and the Sa-bei was in a four-spot pattern. Most of the
pilots were in small scales with a few injectors used.
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
478 J. J. SHENG Asia-Pacific Journal of Chemical Engineering
Table 2. Summary of alkaline–surfactant–polymer projects worldwide.

Inter-well
Case # Field Country Start date P* I* distance, ft References
[103–105]
1 Daqing Sa-zhong-xi (S-ZX) China 01-Sep-1994 9 4 347.8
[88,103,106]
2 Daqing Xing-wu-zhong (X5-Z) China 29-Jan-1995 4 1 459.3
[107]
3 Daqing Xing-2-xi (X2-X) China 28-Sep-1996 9 4 656.2
[108]
4 Daqing Sa-bei-1-xi (S-B) China 15-Dec-1997 4 3 246.1
[109,88]
5 Daqing Xing-bei xing-Daqing, X2-Z China 01-Apr-2000 27 17 820.2
[110]
6 Daqing Sabei-bei-2-dong (SB-B2-D) China 03-Oct-2004 4 3 246.1
[103,111,112]
7 Shengli Gudong China 01-Aug-1992 9 4 164.0
[113–115]
8 Shengli Gudao-xi China 01-May-1997 13 6 695.5
[41,106,115–117]
9 Karamay China 22-Jul-1996 9 4 164.0
[118]
10 Jilin Hong-gang China 01-Sep-1997 656.2
[119]
11 Zhong-yuan Hu-zhuang-ji China 12-Jan-2000 5 5
[120]
12 Yumen Lao-jun-miao China 01-Mar-1994 4 1 229.7
[121]
13 Cambridge USA 01-Feb-1993
[122,123]
14 West Kiehl USA 03-Dec-1987
[124]
15 Tanner USA 01-May-2000 2 1 656.2
[125]
16 Mellot Ranch USA 01-Aug-2000 3 2
[126,127]
17 Lawrence USA 01-Aug-2010 6 12 230.0
[128]
18 Sho-Vel-Tum USA 4 1 233.3
[129,130]
19 Lagomar Venezuela
[131]
20 Viraj India 10-Aug-2002 9 4 738.2
[132]
21 Jhalora India 07-Feb-2010 6 1
[133]
22 Brookshire Dome USA 02-Sept-2011 4 1
[134]
23 Little Bow Canada Jan-2014
[135]
24 Taber South Canada 17-May-2006 45 18
[54]
25 Mooney Canada 3rd quarter 2011
[36]
26 DQ-South-5 China Jul-2005 39 29 574.1
[36]
27 DQ-North-1 East China Jun-2006 63 49 410.0
[36]
28 DQ-North-2 West China Nov-2008 44 35 410.0
[36]
29 DQ-South 6 China Jan-2009 160 144 574.1
[36]
30 DQ-Xin 1-2 China Aug-2007 143 112 492.1
[36]
31 DQ-Xin 6-East I China Jun-2009 129 102 462.6
[36]
32 DQ-Xin 6-East II China 1-Oct-2009 109 105 462.2

*P and I mean the number of producers and injectors, respectively.

There have been ten large-scale field projects (each
project having more than ten injectors). Among these
projects, seven projects in Daqing have 29–144 injectors.
Among these seven projects, four projects have more
than 100 injectors. The average well spacing is 484 ft.
The surfactant used in these large-scale projects is heavy
alkylbenzene sulfonate made in China. The IFT achieved
103 to 104 mN/m, when 0.05–0.3 wt% surfactant is
mixed with 0.4–1.2 wt% alkali. The surfactant adsorp-
tion is less than 1 mg/g sand. The field performance
showed significant increase in oil rate increase and
reduction in water cut. The problems are scaling and
corrosion, which damaged the lifting system and
shortened pump working life; and strong emulsification,
which made liquid treatment difficult.[36]
For chemical EOR in carbonate reservoirs, many
polymer projects were conducted in 60s–90s. During
this period, there were only a few surfactant-polymer
(SP) projects, but no ASP project was reported. From
1990s–2000s, no chemical flood projects were
reported, except four surfactant stimulation projects
reported.[14] These projects are the Mauddud in the
Bahrain field,[62] the Cottonwood Creek in the Bighom
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Basin of Wyoming,[63,64] the Yates field in Texas,[65,66]
and the Baturaja formation in the Semoga field in
Indonesia.[67] A laboratory study was conducted to
study the feasibility of ASP in the Cretaceous Upper
Edwards reservoir, located in Central Texas, but no
field trial was reported.[68]
Injection scheme and amount of chemicals
injected
The injection schemes and amount of chemicals injected
in all the ASP projects are shown in Table 3. A typical
ASP injection process has three slugs: pre-slug, main
ASP slug, and post-slug. The function of a pre-slug is
to inject polymer solution for profile improvement.
Sometimes, alkaline slug is injected as a pre-slug. Its
objective is to remove high-concentration divalents to
avoid association of these divalent with the subsequent
surfactants. Sometimes, the injected alkalis can react
with divalents so that insoluble precipitates are
generated. The precipitates reduce permeability; thus
sweep efficiency is improved, as suggested by Sarem.[69]
This process is known as mobility-controlled caustic
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
 Table 3. Injection schemes and amount of chemicals injected in alkaline–surfactant–polymer projects.

Pre-slug Main slug Post-slug Total chemicals, PV × concentration

Case ID PV (%) P (wt%) PV (%) A (wt%) S (wt%) P (wt%) PV (%) P (wt%) A S P
Daqing Sa-zhong-xi (S-ZX) 32.0 1.25 0.30 0.1200 28.30 0.0600 40.00 9.60 5.54
Daqing Xing-wu-zhong (X5-Z) 37.0 1.31 0.32 0.1400 30.80 0.1100 48.47 11.84 8.57
Daqing Xing-2-xi (X2-X) 3.75 0.1284 45.6 2.90 0.46 0.2074 0.20 0.0872 132.24 20.79 9.96
Asia-Pacific Journal of Chemical Engineering

Daqing, Sa-bei-1-xi (S-B) 47.5 1.20 0.27 0.1800 20.00 0.0800 57.60 12.96 10.24
Daqing Xing-bei xing- 12.80 0.1538 45.4 1.02 0.18 0.1400 20.00 0.0800 46.31 8.17 9.92
2-zhong (X2-Z)
Daqing Sabei-bei-2-dong 4.00 0.1400 50.0 1.54 0.21 0.1800 20.00 0.1400 77.00 10.50 12.36
(SB-B2-D)
Shengli Gudong 5.00 0.1000 40.0 1.50 0.38 0.0900 10.00 0.0500 60.00 15.20 4.60
Shengli Gudao-xi 9.70 0.2000 30.9 1.20 0.30 0.1700 5.00 0.1500 37.08 9.27 8.07
Karamay 33.7 1.40 0.30 0.1300 16.60 0.1000 47.18 10.11 6.04

© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Jilin Hong-gang 18.0 0.75 0.06 0.1500 13.50 1.08 2.70
Zhong-yuan Hu-zhuang-ji 0.1500 0.50 1.58 0.0800 0.1000
Yumen, Lao-jun-miao 28.00 0.57 (A)* 17.0 4.70 12.60 52.00 0.0810 95.86 214.20 4.21
Cambridge 30.7 1.25 0.10 0.1475 29.70 38.38 3.07 4.53
West Kiehl 25.0 0.80 0.10 0.1050 20.00 2.50 2.63
Tanner 25.1 1.00 0.10 0.1000 25.10 2.51 2.51
Mellot Ranch 30.1 1.00 0.10 0.1300 20.00 30.10 3.01 3.91
Lawrence 25.0 1.00 1.75 0.2200 25.00 43.75 5.50
Sho-Vel-Tum 10.00 2.2 (A)* 30.0 2.20 0.50 0.1000 50.00 0.0276 88.00 15.00 4.38
Lagomar 35.0 0.50 0.20 0.1000 15.00 0.1000 17.50 7.00 5.00
Viraj 20.0 1.50 0.20 0.0800 30.00 0.0400 30.00 4.00 2.80
Jhalora 30.0 2.50 0.25 0.1500 30.00 0.0800 75.00 7.50 6.90
Little Bow 5.00 0.2200 30.0 0.80 0.50 0.2700 70.00 0.2700 24.00 15.00 27.00
Taber South 34.0 0.77 0.15 0.1200 25.50 5.10 4.08
Average (rank and percentile) 9.70 0.1450 30.8 1.25 0.27 0.1350 24.20 0.0800 43.16 9.44 5.25

*Alkaline pre-slug
A COMPREHENSIVE REVIEW OF ASP FLOODING

Asia-Pac. J. Chem. Eng. 2014; 9: 471–489

DOI: 10.1002/apj
479
480 J. J. SHENG Asia-Pacific Journal of Chemical Engineering

flood. However, as shown in Table 3, not all the projects

had pre-slugs. The average injected pre-slug pore
volume (PV) was 9.7% PV, and the average polymer
(P) concentration was 0.145 wt%.
The main slug consists of alkali (A), surfactant (S),
and polymer (P). The average injection concentrations
of these chemicals were 1.25 wt% A, 0.27 wt% S, and
0.135 wt% P, respectively, and 30.8% PV was injected.
After the main slug is injected, if only water is injected,
the water will finger into the main ASP slug, because
water mobility is much high than that of ASP slug. To
Figure 2. Incremental oil recovery factors available
avoid the fingering, a post-slug of polymer is injected for the projects and their average. This figure is
immediately following the main ASP slug. In some available in colour online at www.apjChemEng.com.
cases, a graded or tapered scheme that is an empirical
model[70] is used to reduce the amount of polymer
injected. The simplest model assumes that the polymer
concentration declines exponentially. Claridge[70] and
Stoneberger and Claridge[71] developed a method based
on the method by Koval[72] to design graded viscosity
banks. However, as the amount of polymer injected
becomes larger, such a graded scheme becomes less
important, as proved by experimental data.[73] The
reason is that the chase water would have less
opportunity to break through the polymer slug ahead of
it if the polymer slug is large. The average injected
post-slug was 24.2% PV and the average polymer
concentration was 0.08 wt%. In general, incremental oil
recovery over waterflooding would increase with the
Figure 3. Water cut reduction available from the
amount of chemicals injected,[74,73] also as shown later projects and their average. This figure is available in
in Fig. 4. Although post-slug polymer flooding is more colour online at www.apjChemEng.com.
practiced, for the same amount of polymer to be injected,
analyzing field data indicated that placing polymer in the
pre-slug was better than placing in the post-slug.[73]
The total chemical injected can be described by the
injection PV multiplied by the chemical concentration.
For all the projects, the injected alkali, surfactant, and
polymer averaged 43.16, 9.44, and 5.25, respectively, if
both the PV and chemical concentrations were in the unit
of percentage (%).
When designing a chemical injection scheme, forma-
tion injectivity needs to be considered. If the chemical
slug is too viscous, the injection pressure builds up and
the formation could be fractured. If the fractures extend
from an injector to a producer, the chemical slug could
quickly breakthrough.
Figure 4. Incremental oil recovery factors vs the
Field performance total amount of weighted chemicals injected. This
figure is available in colour online at www.
apjChemEng.com.
The incremental oil recovery factors over water-
flooding available for the projects are shown in Fig. 2.
The average incremental recovery factor was 21.8%
original oil in place (OOIP). The decreases in water weighted sum of alkali, surfactant, and polymer injected
cut after ASP injection available for the projects are in PVs multiplied by their respective concentrations. The
shown in Fig. 3. The average decrease was 18%. weights for A, S, and P are 0.1, 1, and 0.5, respectively,
Figure 4 shows the incremental oil recovery factors vs which is based on their approximate prices in the market.
the total amount of weighted chemicals injected. The In this figure, the highest amount of chemicals injected in
total amount of weighted chemicals is calculated by the the Yumen Lao-jun-miao field is not included. The figure
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering A COMPREHENSIVE REVIEW OF ASP FLOODING 481

shows that with more chemicals injected, higher incre- Table 4. Estimation of chemical costs based on the
mental oil recovery factors were obtained overall. average chemical concentrations and slug volumes of
surveyed projects.
Only limited data in the field cases 1–4, 5, 7, and 13
are available about produced chemical concentrations. Item Chemical slugs
The averages of the normalized produced alkali, surfac-
Pre-flush Main slug Post-flush
tant, and polymer concentrations for these field cases
were 0.07, 0.05, and 0.38, respectively. The normalized Slug size, PV (1 L) 0.097 0.308 0.242
concentration is defined as the produced concentration Polymer, ppm 1450 1350 800
divided by the injected concentration for each field case. Alkaline agents, % 1.25
Surfactants, % 0.27
Alkaline cost, US$/lb 0.15
HPAM cost, US$/lb 1.5
PROJECT ECONOMICS Surfactant cost, 3
US$/lb
Figure 5 shows the available chemical cost per barrel of Incremental oil, % 17.44
OOIP
incremental oil from the surveyed ASP projects. The Individual chemical 0.42 7.43 0.58
average was about $6/bbl. An estimate is further made slug cost, US$/bbl
based on 21.8% incremental oil recovery and the average Inc. oil
chemical slug sizes and concentrations from actual ASP Total chemical cost, 8.44
projects as reported in the preceding text. The incre- US$/bbl Inc. oil
Total chemical cost, 6.32
mental oil recovery factor is based on the OOIP which US$/bbl Inc. oil*
is 0.8 PV assuming the connate water saturation is 0.2.
The polymer cost of $1.5/lb is from Pope.[75] The prices PV, pore volume; HPAM, hydrolyzed polyacrylamide.
of alkalis and surfactants are assumed to be 0.1 and two *Chemical cost discounted at 10% per year, and the injection
velocity assumed 0.1 PV/year.
times the polymer price, respectively. The results are
shown in Table 4. It shows that the average chemical cost
is $8.44/bbl of incremental oil, which is higher than the calculate project elapse time in years), the discounted
actual average cost. This is only the chemical cost. The cost is $6.32/bbl of incremental oil, which is close to
facility cost and operation cost are not included. In some the average cost from the existing projects.
ASP projects, it is difficult to break produced emulsions. From the actual projects, the average incremental oil
Then the costs of facilities and demulsifiers will be recovery factor is 21.8% corresponding to the average
significant. Sometimes, more wells need to be drilled to amount of injected chemicals of 16.4 PV multiplied by
complete injection patterns. Thus more drilling cost will concentrations (Fig. 4). If the injection PV is reduced by
have to be added. As discussed later, the work life of half, then the amount of injected chemicals is reduced
equipment will be shorter compared with waterflooding, by half. From Fig. 4, the incremental oil recovery factor
Then the cost for production facilities and production will be 18%. Following the same calculation used in
chemicals will be higher. When ASP is injected, less Table 4, the chemical cost will become $5.11/bbl of
water will be produced. Here, the cost saving from less incremental oil. If the injection PV is doubled, the
water injection is not included. chemical cost becomes $11.5/bbl of incremental oil. It
If the chemical costs are changed, we can simply use shows that if less PV (chemicals) is injected, the chemical
this table to have an estimate. For example, if the chemi- cost per barrel of incremental oil will be lower. In other
cal cost is discounted at 10% per year and the injection words, Fig. 4 and Table 4 can be used in evaluating
velocity is assumed 0.1 PV/year (which is used to and/or designing a field project in this way: from the
designed amount of chemicals (injection volume and
concentrations), incremental oil recovery may be
estimated from Fig. 4, then Table 4 is used to estimate
the total chemical cost in terms of $/bbl incremental oil.

CHEMICALS USED

For the 23 ASP field projects presented in Table 3,

Figure 5. Chemical costs in actual alkaline–surfactant–
polymer projects. This figure is available in colour
online at www.apjChemEng.com.
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Na2CO3 was used in 14 cases, NaOH was used in seven
cases, and NaOH and Na2CO3 were combined in one
case. The alkali used in Little Bow was not published.
In earlier projects, NaOH was used in Daqing projects.
Silicate precipitates are generally hydrated, flocculent,
and highly plugging even at low concentrations.
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
482 J. J. SHENG
Carbonate precipitates are relatively granular and less
adhering on solid surfaces.[76] Thus sodium carbonate
shows less degree of permeability damage in the
presence of hard water under similar conditions. More-
over, carbonate scales can be successfully removed at
production wells by acidizing or by using inhibitors,
but no long-term treatment exists to control silicate-
containing precipitation. This is probably one reason that
sodium orthosilicate was not frequently used in chemical
flooding. Sodium orthosilicate is a water soluble alkali.
As the scaling problem was experienced in some
projects, the weak alkali has been more and more used.
To minimize the corrosion and scale problems associated
with inorganic alkalis, Berger and Lee[77] proposed an
organic alkali. The organic alkali is derived from the
sodium salts of certain weak polymer acids. No field test
using organic alkali was reported.
Different surfactants were used in the field ASP
projects. The surfactants used included ORS-41HF,
ORS-46HF, ORS-62, a bio-surfactant, OP10 and CY1
(local Chinese products), BES (an anionic surfactant),
lignosulfonate, KPS-1 (anionic surfactant which was a
local Chinese product), dodecyl sulfobetaine, YPS-3A
(local petroleum sulfonate), Petrostep B-100, TDA-
13PO-SO4, and C20–24 IOS. Some cosurfactants were
used, for example, isobutanol, n-butanol, and isopropyl
alcohol. In terms of chemical EOR in carbonates, much
more surfactants were tested in laboratory and some were
used in fields; see Sheng.[14]
Only in one case was a biopolymer, xanthan, used. In
the rest of projects, HPAM type of polymers was used.
The commercial names of these polymers included
1275A, 3530S, Alcoflood 1175A, and Pusher 700.
WATER QUALITY
In Daqing ASP projects, fresh water was used initially.
In some cases, produced water was re-injected at later
stages of the projects. Hernandez et al.[60] proposed
that the water to be used in the ASP preparation should
meet the following requirements:
• Suspended solids limit: <0.5 ppm
• Particle size: <5 μm
• Dissolved oxygen: <20 ppb
• Iron concentration (Fe3+): <1 ppm
• Total hardness (Ca2+ and Mg2+): <10 ppm
• Microorganisms and bacteria control
The aforementioned specification for the limit of
suspended solids seems to be too low compared with
Chinese specifications, which are 5 ppm for k < 100 md,
10 ppm for 100 < k < 300, 15 ppm for 300 < k < 600,
and 20 ppm for k > 600 md.[73] The particle size < 5 μm
is lower than what is specified in Daqing. The size of
filters used in water source lines in Daqing is 20 μm.
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
The oxygen content in solution specified earlier is
lower than what is required in China, which is 50 ppb.
The dissolved oxygen in the Daqing mixing and
injection system was high, and it seemed that such high
oxygen did not cause serious problem. Seright[78] gave
an explanation. Daqing sand has 0.25% pyrite and
0.5% siderite. These minerals effectively removed the
dissolved oxygen within a day and in a short moving
distance from the injector. Similarly, the dissolved
oxygen content (3–8 ppm) in the Suriname Tambaredjo
polymer project might not cause a serious problem
because the sand has up to 12% siderite and pyrite.[33]
Iron concentration should be low, especially in an
open system. The aforementioned specification is in line
with that used in Daqing, which is 0.5 ppm. The speci-
fications for oxygen, iron concentration, microorganisms
and bacteria control, and total hardness are made to
protect polymer stability. High hardness may cause
chemical precipitation.
MOBILITY CONTROL REQUIREMENT
In conventional waterflooding, a favorable mobility control
requirement is that the displacing phase mobility (water)
should be equal to or less than the sum of the mobilities
of several displaced phases (water and oil).[79–81] Such
mobility control requirement was basically extended
from the theory derived for a single-phase displacement
(a single phase displaces another single phase). When
the oil mobility is much lower than the water mobility,
the sum of the displaced phase mobilities (water and
oil) will be almost the same as the water mobility. Then
according to the conventional criterion, the displacing
ASP mobility is almost the same as the water mobility.
As a result, the ASP solution will flow preferentially
along water channels, leaving oil undisplaced. In
practical ASP projects, the ASP solution viscosities were
much higher than the total mobility of displaced water
and oil. For example, the ASP solution viscosities in
Daqing ASP projects were 2–4 times the oil viscosity.[82]
It was reported that the viscosity ratio of chemical fluid to
crude oil should be more than 4.[36] Sheng[83] propose
that the displacing ASP mobility should be equal to or
less than the lowest mobility of displaced phases
(generally, oil phase mobility) multiplied by the
normalized oil saturation, which is defined as So ¼
So Sor
1Sor Swc : Here So, Sor, and Swc are oil saturation, residual
oil saturation, and connate water saturation, respectively.
The proposed mobility control requirement provides a
criterion for mobility control design for an ASP project.
PROBLEMS ASSOCIATED WITH ASP FLOODING
Common operational problems in an ASP project are low
injectivity, polymer degradation, difficulty to separate
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
produced water from oil, pump failures, bacterial growth,
corrosion, problems related logistics, and handling,
especially in an offshore environment.[84] This section
discusses issues resulting from ASP applications, inclu-
ding produced emulsion, chromatographic separation,
precipitation and scaling, and others.
Produced emulsions
Stable emulsions can be formed in surfactant, alkaline,
and even in water injection. In water injection, stable
emulsions can be formed because crude oil has natural
emulsifiers such as asphaltene. In surfactant injection,
surfactant reduces the water/oil IFT so that stable
emulsions can be formed. In alkaline flooding, stable
emulsions can be formed because alkali reacts with
crude oil to generate in situ surfactant (soap). Although
polymer helps to stabilize emulsions, it cannot form
emulsions with oils. According to their structures, there
are four types of emulsions: W/O, O/W, W/O/W, and
O/W/O. Sometimes, W/O/W and/or O/W/O are called
multiple types. Generally, W/O emulsion was much
more stable than O/W emulsion. More factors that
affect emulsion stability were discussed by Sheng.[11]
Emulsification is an important mechanism in alkaline
flooding.[18] In other words, emulsion in ASP flooding
could improve oil recovery. Cheng et al.[85] reported
that emulsification increased the oil recovery factor
by about 5% in their corefloods. Many wells in Daqing
ASP applications showed that if the produced fluids
were more emulsified, the decrease in water cut would
be higher. The disadvantages of emulsification are that
it increases injection pressure and decreases water
injection rate and liquid production rate. It also can
cause difficulties in transportation and oil/water
separation. In a Shengli Gudong ASP pilot test started
in 1992, it was difficult to separate water from oil even
though the weak alkali Na2CO3 was injected. Overall,
the advantages of emulsions appear to be greater than
the disadvantages.[85]
Typical demulsifiers used in Chinese projects were
SP169, AE1910, and JS-8.[73] SP169 is a linear
molecule, AE1910 is a molecule with multi-branched
chains, and JS-8 is of a complex type. The ability of
demulsifiers is related to how well it is absorbed at the
oil/water interface, how it spreads toward the interface
to form a film, and how much it can affect the interfacial
intensity. Linear molecules are liable to be absorbed and
spread to form a film, while branched molecules tend to
weaken the intensity of the interfacial film. Molecules
of JS-8 molecules have aspects of linear and branched
ones.[86] Wylde et al.[87] tested other demulsifiers. They
found a mixtured demulsifier of diepoxide, amine poly-
ester, amine block-polymer, and a nonyl acid catalyzed
resin worked best for an ASP project in a heavy oil
reservoir. The selected demulsifiers also depend on
the surfactants used. For example, the demulsifier
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
A COMPREHENSIVE REVIEW OF ASP FLOODING 483
FD408-01 worked well when the surfactant ORS-41
was used; GFD310-10 was a good demulsifier for the
emulsion when the surfactant alkyl benzene sulfonate
is used.[88]
Chromatographic separation of alkali,
surfactant, and polymer
Figure 6 is the effluent concentration histories of an ASP
slug injection. The vertical axis shows the normalized
concentrations of polymer, alkali, and surfactant. The
horizontal axis is the injection PV. First, we can see that
polymer broke through first, then alkali followed by
surfactant. Second, each maximum relative concen-
tration depended on its retention or consumption in the
pore medium. The maximum polymer concentration
was 1, the maximum alkali concentration was 0.9, and
the maximum surfactant concentration was 0.09 in this
case. Third, their concentration ratios in the system were
constantly changing. In other words, the chemical
injection concentrations will not be proportionally
decreased. In general, actual effluent concentrations and
breakthrough times depend on their individual balance
between the injection concentration and the retention or
consumption.
To have the ASP synergy, the three components
should transport at the same velocity. IPV is intrinsic,
and retentions cannot be changed too much to solve the
separation problem. What we can do is to change the
injection concentrations. Here is a simulated example
using UTCHEM. It is a one-dimensional homogeneous
model of 1 ft long, 2 in wide and 2 in high. Grid blocks
of 100 × 1 × 1 are used. The porosity is 0.4, and the
permeability is 1500 md. The initial oil saturation is at
the residual oil saturation of 0.35. But the residual oil
saturation can be decreased as low as zero depending
on the capillary number. Soap generation is included.
Initially, the injection scheme is 0.5 PV slug of 0.7%
Na2CO3, 1% surfactant, and 0.15% polymer. Figure 7
shows the pH, which represents alkaline concentration,
and surfactant and polymer concentrations of the produ-
ced fluids. Polymer breaks through first, followed by
surfactant and alkali.
1.2
1.0
0.8
C/Cinj
0.6
0.4
0.2
0.0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Injection PV
Figure 6. Effluent concentration histories of polymer,
alkali, and surfactant (Huang and Yu, 2002).
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
484 J. J. SHENG Asia-Pacific Journal of Chemical Engineering
13 0.16
pH observed in Daqing. The scaling and precipitates may
Surfactant 0.14 cause formation damage.
12

Cs (fraction), Cp (%)
Polymer
0.12 Chinese operators have experienced severe scaling
11 and emulsion problems in their surface facilities caused
0.10
by strong alkalis such as NaOH. In addition, high-
pH

10
9 viscoelasticity. To avoid the preceding problems,
8
7 0.00
0.0 0.5 1.0 1.5 2.0 2.5
Injection PV
Figure 7. Concentration histories of the produced
fluid at the initial injection concentration. This figure
is available in colour online at www.apjChemEng.
com.
If only the alkaline concentration is changed from
0.7% to 1.8%, and the other injection concentrations
and the slug volume are kept the same as those in the
initial case, the produced concentrations are shown in
Fig. 8. Now the alkali and surfactant break although
the production ends at the same time, although polymer
still transports ahead of them. This example demons-
trates that injection concentrations can be changed to
solve the separation problem.
Precipitation and scale problems
When an alkaline solution is injected into a formation,
OH concentration is raised. The raised OH converts
HCO3 into CO32. Alkaline reaction with formation
minerals may produce SiO32. Seawater has a high
concentration of SO24 . When divalents such as Ca ,
2+
2+ 3+
Mg , and Al exist in the formation, the divalents react
with OH, CO32, and SiO32. Several inorganic scales
and precipitates can be formed. Frequent operation
failures of production wells due to these problems were
13
pH
Surfactant
12
0.08
concentration alkalis reduce SP solution viscosity and
0.06
0.04 Chinese companies are proposing the following: (1)
0.02 alkali-free SP flooding and (2) dynamic IFT of
102 mN/m, not 103 mN/m. IFT of 102 mN/m may
be low enough to reach a high incremental oil recovery
factor. The main reason is that it is quite difficult to reach
103 mN/m IFT. To achieve such low IFT, sometimes
high surfactant and alkaline concentrations need to be
used. Thus, the chemical cost will go up. A high alkaline
concentration will cause more problems, such as
emulsion, scaling, precipitation, formation damage, and
so on. A high alkaline concentration will also reduce
polymer viscosity. As a result, more polymer will be
needed to reach a required viscosity.
Although ASP outperformed any other combinations
of alkaline, surfactant, and polymer flooding, the
problems with produced emulsions (difficult to demul-
sify or increased cost), scaling, and corrosion have led
the industry to seek alkaline-free options like SP process.
Or a week alkali is preferred to a strong alkali.
Problems associated with facility
Because of scaling problem of ASP solution, the average
work life of screw pumps in Daqing ASP flooding was
shortened to 97 days, compared with 375 days in poly-
mer flooding and 618 days in waterflooding.[88]
Other facility problems associated with ASP are
related to polymer viscoelastic behavior. Because of
polymer solution viscoelastic behavior, when polymer
solution flows into a branch line (at a tee section), a
‘pulling force’ tries to pull the solution back into the
main supply line. This pulling force increases with
the increase in velocities of the branch and main supply
lines. The velocity in the branch line oscillates, when
0.14
the triplex pump pumps. The oscillation of the velocity
0.12 changes normal stress and extension viscosity, thus
Cs (fraction), Cp (%)

Polymer

0.10 causing the pump vibration. The solution was to

11
increase pipe size.[89]
0.08
The polymer solution causes a larger blind area in the
pH

10
0.06 bottom of a maturation tank, which makes mixing more
9
0.04
difficult and consumes more energy to mix polymer
solution. Re-design of the mixing blades mitigated the
8 0.02 problem. For beam pumps, polymer solution enhances
7 0.00 the sucker-rod eccentric wear. The centralizers were
0.0 0.5 1.0 1.5 2.0 2.5
used to solve the problem.[90]
Injection PV

Figure 8. Concentration histories of the produced

Other technical challenges
fluid when alkaline injection concentration is
increased. This figure is available in colour online at Other important problems include polymer degradation
www.apjChemEng.com. and produced water cleanup. Polymer degradation could
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
be due to mechanical shear through pumps, perforation,
pore throats, and so on. Pang et al.[91] found that the
viscosity losses due to mechanic shearing at the high-
pressure metering pump, transportation pump, and filter
were about 5%, 2%, and 1%, respectively. The viscosity
loss at perforation due to mechanic shearing was about
9%. Polymer could also be degraded by contamination
such as oxygen and iron in surface injection facilities,
and by hydrolysis. It can also be degraded by bacteria.
The polymer viscosity will be lower at higher salinity,
especially if divalent concentrations are high. Adding
alkalis in the SP solution will result in higher salt
concentration, thus reducing polymer viscosity.
To reduce mechanical shearing, screw pumps are
used for transporting polymer solution, plunger pumps
are used to inject polymer solution at high pressures,
and polymer injection wells are commonly completed
through perforation. In some cases, hydraulic fractu-
ring may be used to reduce mechanic shearing near
the wellbore. To reduce shear effect in measuring rates,
electromagnetic flow meters, or spring scraped-blade
flow meters are used. In vertically heterogeneous multi-
layer reservoirs, multiple tubings are used to inject
polymer solution into different layers based on their
injectivities.[92]
To prevent the polymer degradation by oxygen, the
polymer makeup water, and dissolution equipment
need to be kept under a nitrogen blanket.[93] Luo
et al.[94] reported that the combination of thiourea and
cobalt salt could prevent oxidation reduction more
effectively than using the individual alone. A polymer
viscosity was retained at 69% after 360 h by using such
a combination, whereas the polymer viscosity was
retained at 20% if using thiourea only, and at 27% if
using cobalt salt only. A typical preservation package
includes isopropyl alcohol and thiourea, which miti-
gates degradation of polymer due to oxygen, ions such
as iron, and H2S.[95]
It has been observed in polymer-injected field
projects that the presence of polymer in produced water
causes decline in suspended particles but dramatic
increase in oil concentration (typical oil concentrations
were 160–800 ppm in Daqing).[96] Produced water
cleanup equipment such as gravity settling, induced
gas floatation, electrodialysis, porous medium separa-
tion, membrane separation, and hydrocyclones fail to
effectively clean up the produced water in chemical
flooding, because of stable O/W emulsions owing to
the small sizes of oil droplets, reduced IFT, and higher
water viscosity with polymer added, or because of
economic and environmental issues. Wang et al.[96]
combined biodegradation and filtration for removal of
oil and suspended solids in polymer-containing pro-
duced water. Their integrated process includes four
stages: cross-flow separation, biodegradation, post-
biotreatment cross-flow sedimentation, and medium
filtration. Zhang et al.[97] treated produced water by a
© 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
A COMPREHENSIVE REVIEW OF ASP FLOODING 485
combined method of hydrolysis acidification-dynamic
membrane bioreactor-coagulation process. Jiang et al.[98]
presented a design of three cubed curve hydrocyclone
tube, and Liu et al.[99] proposed to use a double-cone
air-sparged hydrocyclone to treat produced water from
polymer flooding.
Wu et al.[100] developed a mixture of nonionic reverse
demulsifier and demulsifier, a product named SP1002.
The mixture consists of both water soluble and oil soluble
active components for water clarification and water-in-oil
emulsion breaking, respectively. The dual-function che-
mical was injected into a high water-cut produced fluid
containing O/W emulsions before the produced fluid goes
through oil–water separation. It greatly enhanced floccu-
lation and coalescence of the oil droplets in the reverse
crude oil emulsion, while maintaining adequate emulsion
breaking capacity for downstream crude oil dehydration,
so that less oil was carried-over and looser emulsion was
formed in the influent water of produced water treatment
facilities. The reverse demulsifier (deoiling) and demul-
sifier must be compatible to each other.
A new commercial water-processing technology deve-
loped by Cambridge Water Technology combines chemi-
cal coagulation and flocculation with high-rate magnetic-
ballasted clarification and magnetic filtration for the
removal of dispersed oil.[101] Coagulant (metal salt) and
caustic are added to start the precipitation of contaminants
present in the produced water. Flocculant (polymer) is
added in the next stage to precipitate all the coagulated
mass as a ‘floc’, which is the ballasted with magnetite
(Fe3O4) addition for intense clarification. The magnetite
is positively charged and hence attracts the negatively
charged oil and solids to the flocs to settle and remove
as sludge.
Typically, surfactants are delivered in liquid form with
30–35% active concentrations. The associated problems
are a large storage space needed, higher shipping cost,
and heating needed at low temperature environments
(<10 °C, e.g.). Also, different facilities to prepare
chemical solutions are needed. These problems are
especially important in offshore environments. To solve
these problems, Barnes et al.[102] proposed to use AS or
ASP powder.
Future developments
Based on this comprehensive review study, the follo-
wing are our recommendations on future developments.
(1) High temperature and high salinity (and high-
divalents) limit ASP applications. Surfactants and
polymers that can be used in such reservoirs need to
be developed.
(2) The ASP problems are related to alkaline injection.
Therefore, we want to see whether alkalis have to
be used. In other words, we need to answer the
following: can SP be a better option than ASP?
Asia-Pac. J. Chem. Eng. 2014; 9: 471–489
DOI: 10.1002/apj
486 J. J. SHENG
(3) Alkali can react with the crude oil to generate soap.
This function is attractive. However, most of the
field projects conducted until 1983 offered the incre-
mental oil recovery factors of only 1–2% (Sheng,
2013c). The question is, is the generated soap impor-
tant in improving oil recovery? More broadly, we
also need to answer the following: are the advantages
of alkaline addition more than disadvantages?
(4) The potential benefit of ASP over the individual A,
S, or P process relies on the synergistic effect. To
have this synergistic effect, the components of A,
S, and P must be in the same slug (no chromato-
graphic separation). Few papers have been published
to address this issue. Future research effort should be
placed on it.
Acknowledgements
This work, especially field data collection part, was
financially supported by the Joint Industry Project
(JIP), Chemical EOR Knowledge Database. The finan-
cial support from the member companies in this JIP is
gratefully appreciated.
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