energies

Review
An Overview on Polymer Retention in Porous Media
Sameer Al-Hajri * , Syed M. Mahmood * , Hesham Abdulelah and Saeed Akbari
Department of Petroleum Engineering, Universiti Teknologi PETRONAS, Seri Iskandar 32610, Perak, Malaysia;
heshamsaif09@gmail.com (H.A.); akbari.sa70@gmail.com (S.A.)
* Correspondence: ensamyo87@gmail.com (S.A.-H.); mohammad.mahmood@utp.edu.my (S.M.M.);
Tel.: +60-111-667-5972 (S.A.-H.); Tel.: +60-5368-7103 (S.M.M.)




Received: 8 September 2018; Accepted: 8 October 2018; Published: 14 October 2018


Abstract: Polymer flooding is an important enhanced oil recovery technology introduced in field
projects since the late 1960s. The key to a successful polymer flood project depends upon proper
estimation of polymer retention. The aims of this paper are twofold. First, to show the mechanism of
polymer flooding and how this mechanism is affected by polymer retention. Based on the literature,
the mobility ratio significantly increases as a result of the interactions between the injected polymer
molecules and the reservoir rock. Secondly, to provide a better understanding of the polymer
retention, we discussed polymer retention types, mechanisms, factors promoting or inhibiting
polymer retention, methods and modeling techniques used for estimating polymer retention.

Keywords: polymer flooding; polymer retention; mobility ratio

1. Introduction
Implementing enhanced oil recovery (EOR) techniques has become more significant to recover
more hydrocarbons, with the continuation of exploration and development of new oil reserves.
Vladimir et al. indicated that the lifetime of a reservoir mostly consists of three phases [1]: primary
recovery as oil is extracted by naturally driven mechanisms, secondary recovery with reservoir pressure
maintaining techniques through water and gas injection, and enhanced oil recovery often called tertiary
recovery with a wide range of advanced technologies [2]. In primary recovery and secondary recovery,
only 20–40% of the potential oil can be extracted. It is possible to extract up to 30% of the original oil
reserve in the well by the implementation of EOR techniques [1,3–5].
Furthermore, as of 2017, it has been estimated by the organization of the petroleum exporting countries
that approximately 1.5 trillion barrels of proven crude oil remain in reservoirs globally. After the exhaustion
of the applications of conventional recovery methods, enhanced oil recovery helps not only extract these
reserves but also guarantees a continued supply of oil in the future [6]. EOR mechanisms broadly include
chemical flooding, gas injection and thermal recovery. In chemical flooding, some chemicals such as
polymers are added to the injected water to enhance the oil displacement ability.
The ability of water to displace oil and increase production was first noticed in the Pithole city
area of Pennsylvania in 1865 as an accidental water injection to the hydrocarbon zone [7]. In 1924,
petroleum companies realized the problem of insufficient oil recovery by natural energy and the need
to sweep more oil from reservoirs, and first five spot pattern water injection was first implemented
in Bradford oil field, Pennsylvania [7,8]. More hydrocarbon was extracted using waterflooding
techniques. However, in 1949, Muskat first indicated that waterflood performance would be affected
by fluid mobility [9], which was an essential discovery that helped other researchers start studying
new techniques for improving water mobility. Stiles, Dykstra, and Parsons used permeability and
distribution capacity in waterflooding calculations, and the latter two researchers pointed out the effect
of the mobility ratio and permeability variation on recovery [10,11]. The mobility ratio’s effect on water

Energies 2018, 11, 2751; doi:10.3390/en11102751 www.mdpi.com/journal/energies

Energies 2018, 11, 2751 2 of 19

encroachment for a specific flood patter was also studied. Moreover, the mobility ratio impacts on
injection and production histories in a five-spot waterflood were also investigated [12,13]. Furthermore,
Dyes showed the effect of the mobility ratio on the production of oil after a breakthrough [14]. By 1962
Caudle, Witte and Barnes suggested that by increasing water viscosity, waterflood sweep efficiency
can be improved [15,16]. In 1964, Pye and Sandiford conducted a fruitful study showing that adding
a small amount of water-soluble the polymer can efficiently reduce the mobility of water used in
waterflooding which in turn will reduce the mobility ratio thus improving sweep of oil [17,18].
Since then, studies were directed towards the polymer flooding efficiency, affecting factors, limitations,
challenges, measurements and modeling techniques of polymer flooding.

1.1. Mechanism of Polymer Flooding

It is not possible for oil and water to completely displace one another in a reservoir as oil and water
are immiscible fluid [19,20]. Immiscibility of both fluids is reflected in the residual oil saturation and
irreducible water in the relative permeability curve. As indicated by Mridul results, for a waterflood
system, despite the injected quantity of water into the reservoir, the oil saturation is not reduced below
the residual oil saturation [21]. Introducing the injected water with a water-soluble polymer will
increase the water viscosity [20,22–27]. Moreover, the effective permeability of water in the swept zone
can be reduced depending on the type and concentration of the polymer used [28–30]. Polymer flooding
is an enhanced oil recovery process in which a specified polymer concentration (usually 200–1500 ppm)
is added to the injected water. Polymer increases the viscosity of the injected solution and therefore
preferably decreases the water to oil mobility ratio which results in improving the displacement
efficiency of the injected displacing solution [31–33]. Polymer flooding does not significantly improve
displacement (microscopic) efficiently because the change in capillary number (NC ) is rather small.
However, residual oil saturation can be reached more quickly and economically [34].

1.2. Mobility Ratio

The mobility ratio concept is widely utilized in literature for describing the displacement process
efficiency such as waterflooding displacement efficiency [7,35,36]. The mobility ratio provides
measurements of the fluid’s relative movement for the displacement process. It is defined as the
ratio of the mobility of the displacing fluid to the mobility of the displaced fluid [37]. The term mobility
of a fluid is a measure of the ratio of the effective permeability of a particular fluid to its viscosity [21].
For a specific flood application, if the mobility ratio is higher than one, the flood is considered unstable,
and viscous fingering is expected. In contrast, a flood is deemed to be stable for a mobility ratio of less
than one and displacement is efficient [37]. The following equation defines the mobility ratio.

Krw Kro
M= / (1)
µw µo

It is important to mention here that mobility ratio is calculated before the breakthrough. From the
equation Krw is considered the value at average water saturation behind the flood front in the water
contacted portion of the reservoir. This means that polymer flooding application is more efficient if
started at earlier stages of the reservoir, particularly before breakthrough. However, lots of polymer
flood operations are initiated after water breakthrough [7,31]. As a result, to calculate the mobility
ratio during polymer flooding, we use the equation:

Krp
  
Kro Krw
M po = λrp /λ T = + (2)
µp µo µw

which defines the mobility ratio as the relative mobility of the polymer slug λrp to the total relative
mobility of the oil water bank λ T . In order to obtain these values, the relative permeability curves need
to be measured on native state cores in the laboratory, whereas, the mobility of the polymer is usually
Energies 2018, 11, 2751 3 of 19

determined at the residual oil saturation. Furthermore, just before the breakthrough, the relative
mobility of the water Kµrw w
is assumed to be zero.
During polymer flooding, the direction of the saturation changes. Therefore, the mobility ratio
during polymer flooding for the same polymer concentration increases from a low to a maximum
value in the medium saturation range [31]. Jewett and Schurz concluded that improvement in oil
recovery using polymer flooding is mainly implemented for cases with waterflooding mobility ratio at
a range of 1:10, and the oil recovery increment seems to fall off more quickly below a mobility ratio of
one rather than a mobility ratio above ten [38].
The idea of using polymer flooding is to use a polymer that functions as a mobility control agent
that will provide a better displacement and sweep efficiencies. It is estimated that the efficiency of
Energies 2018, 11, x FOR PEER REVIEW 3 of 18
polymer flood is in the range of 0.7–1.75 lb polymer per bbl of incremental oil production [3]. Therefore,
polymer89floodingDuring target polymer
is theflooding, the direction
oil saturation aboveof the
thesaturation
residual changes. Therefore, the
oil saturation mobilityPolymer
[39–41]. ratio flooding
90 during polymer flooding for the same polymer concentration increases from a low to a maximum
has shown
91 to be successful in a variety of types of reservoirs. Moreover,
value in the medium saturation range [31]. Jewett and Schurz concluded that improvement in oil
comparing to other enhanced
oil recovery
92 techniques,
recovery usingpolymer flooding
polymer flooding is simpler
is mainly and efficient
implemented for cases with[42,43]. However,
waterflooding there
mobility are significant
ratio
93 between
interactions at a range ofthe1:10, and the oil
injected recovery increment
polymer molecules seemsandto fall
theoffreservoir
more quickly below
rock a mobility
[44–46]. ratio interactions
These
94 of one rather than a mobility ratio above ten [38].
may cause
95 the polymer to be retained by the reservoir rock and may cause a bank of injection fluid to
The idea of using polymer flooding is to use a polymer that functions as a mobility control agent
form wholly
96 or partially
that will providedenuded of the polymer.
a better displacement and sweep The viscosity
efficiencies. It isof this fluid
estimated that bank will be
the efficiency of much lower
than the97injected
polymer flood is solution.
polymer in the rangeGenerally,
of 0.7–1.75 lb polymer
this per bbl of
will reduce theincremental
efficiency oilof
production
the polymer [3]. flood [47].
98 Therefore, polymer flooding target is the oil saturation above the residual oil saturation [39–41].
This
99 paper provides an overview of recent advances in polymer retention in porous media.
Polymer flooding has shown to be successful in a variety of types of reservoirs. Moreover, comparing
This overview
100 consists
to other of aoil
enhanced discussion on polymer
recovery techniques, polymer retention
flooding isconcept,
simpler andthe three
efficient mechanisms
[42,43]. However, of polymer
101 there are significant interactions between the injected polymer
retention, factors influencing polymer retention, methods used to estimate polymer molecules and the reservoir rock [44–46].
retention and
102 These interactions may cause the polymer to be retained by the reservoir rock and may cause a bank
modelling
103 techniques for polymer adsorption. Furthermore, this paper shows
of injection fluid to form wholly or partially denuded of the polymer. The viscosity of this fluid bank
the advantages and
technical
104issues of much
will be eachlower of the thanmeasuring methods.
the injected polymer Therefore,
solution. Generally,thisthis review
will reduce paper intends
the efficiency of to provide a
105
comprehensive the polymer
reference floodfor[47].
researchers investigating polymer retention to enhance the understanding
106 This paper provides an overview of recent advances in polymer retention in porous media. This
of polymer
107 retention and its relevance to polymer flooding projects.
overview consists of a discussion on polymer retention concept, the three mechanisms of polymer
108 retention, factors influencing polymer retention, methods used to estimate polymer retention and
2. Polymer
109 Retention
modelling techniques for polymer adsorption. Furthermore, this paper shows the advantages and
110 technical issues of each of the measuring methods. Therefore, this review paper intends to provide a
Polymer
111 retention has
comprehensive a majorforimpact
reference on the
researchers rate of polymer
investigating polymer propagation throughtheporous media
retention to enhance
during112
polymer flooding,ofand
understanding polymerconsequently, onrelevance
retention and its oil recovery [48,49].
to polymer floodingIt has a substantial effect in porous
projects.

media113on the2. transport and performance of polymer solution [50,51]. Consequently, high polymer
Polymer Retention
retention can dramatically delay oil movement and recovery during polymer flooding. To illustrate
114 Polymer retention has a major impact on the rate of polymer propagation through porous media
this behavior,
115 Green
during and flooding,
polymer Willhiteand (1998) showed
consequently, on a oildelay
recoveryfactor
[48,49].ranging from very
It has a substantial low
effect in retention of
116
10 µg/g to as high as 200 µg/g as shown in Figure 1. For one pore volume, at low retention rates
porous media on the transport and performance of polymer solution [50,51]. Consequently, high
117 polymer retention can dramatically delay oil movement and recovery during polymer flooding. To
and a polymer concentration of 2000 ppm, the delay factor is approximately 0.03 (3%). In the case of
118 illustrate this behavior, Green and Willhite (1998) showed a delay factor ranging from very low
moderate
119 polymer
retentionretention
of 10 µ g/g to of 100asµg/g
as high and
200 µ g/g a polymer
as shown in Figureconcentration of 1500
1. For one pore volume, ppm,
at low the delay factor
retention
120
is about 0.35 (35%), which means that 35% more of the polymer needs to be injected
rates and a polymer concentration of 2000 ppm, the delay factor is approximately 0.03 (3%). In the for reaching
121 case of moderate polymer retention of 100 µ g/g and a polymer concentration of 1500 ppm, the delay
the targeted formation, compared to the case with no polymer retention. With very high polymer
122 factor is about 0.35 (35%), which means that 35% more of the polymer needs to be injected for reaching
retention
123 of 200 µg/g and
the targeted above,
formation, polymer
compared to theretention
case with no might have
polymer a tremendous
retention. With very high impact
polymeron the rates of
124 retention of 200 µ g/g and above, polymer retention
oil displacement and the economic feasibility of polymer flooding. might have a tremendous impact on the rates of
125 oil displacement and the economic feasibility of polymer flooding.

126
127 Figure 1.Figure 1. Polymer
Polymer bankbank delayfactor
delay factor caused
causedby polymer retention
by polymer [52].
retention [52].
 Energies 2018, 11, 2751 4 of 19
Energies 2018, 11, x FOR PEER REVIEW 4 of 18

128 For aa successful

successfulimplementation
implementation of of polymer
polymer flooding,
flooding, polymer
polymer retention
retention must must be evaluated
be evaluated before
129 before field application.
field application. It is to
It is vital vital to understand
understand and predict
and predict the influence
the influence of retention
of retention on on
thethe transport
transport of
130 of
thethe polymer
polymer solution
solution toto havea aproper
have properdesign
designofoffield
fieldscale
scaleprojects
projects[53].
[53].Polymer
Polymer retention
retention has been
131 identified
identified as
as one of the major
major concerns
concerns in
in the
the polymer
polymer flooding
flooding operating
operating process.
process. Polymer retention
132 includes
includesadsorption,
adsorption,mechanical
mechanicalentrapment,
entrapment, and hydrodynamic
and hydrodynamic retention as shown
retention in Figure
as shown 2. 2.
in Figure

133
Figure 2. Polymer retention mechanism in porous media [47].
134 Figure 2. Polymer retention mechanism in porous media [47].
2.1. Adsorption
135 2.1. Adsorption
The interaction between the polymer molecules and the solid surface is referred to as
136 The interaction
adsorption [54]. Thisbetween the polymer
interaction makes the molecules
molecules andofthe
thesolid surface
polymer is referred
bind onto thetosurface
as adsorption [54].
of the solid
137 This interaction
rock largely makes the
by physical molecules
adsorption (vanof der
the Waal’s
polymer andbind onto the
hydrogen surface instead
bonding) of the solid rock largely
of chemisorption,
138 by physical adsorption (van der Waal’s and hydrogen bonding)
which means a full chemical bond between the polymer molecules and the solid surface is unlikelyinstead of chemisorption, which
139 means a full chemical bond between the polymer molecules and the solid
to form [47]. Therefore, molecules generally are adsorbed onto the rock surface by the mean of surface is unlikely to form [47].
an
140 Therefore, molecules generally are adsorbed onto the rock surface by
overall low free energy as shown in Figure 3. The low free energy is formed first by an entropic the mean of an overall low free
141 energy as shown
contribution, in Figure
as water 3. Theare
molecules low free energy
released fromis theformed
polymer firstsolution
by an entropic contribution,
or rock surface due to as water
polymer
142 molecules
adsorption,are released
this, in turn,from
will the polymer
cause solution
an increase or rock[55].
in entropy surface due to polymer
Reduction of the bulk adsorption, this, in
polymer solution
143 turn, will cause an increase in entropy [55]. Reduction of the bulk polymer
concentration by adsorption also increases entropy. In contrast, there is an entropy loss that counters solution concentration by
144 adsorption also increases entropy. In contrast, there is an entropy
the previous entropy gains, resulting from the loss of the configurational freedom of the polymer loss that counters the previous
145 entropy
when it isgains,
adsorbedresulting
on the from the [56].
surface loss Enthalpy
of the configurational
also contributes freedom of the
to the low freepolymer
energy of when it is
polymer
146 adsorbed on the surface [56]. Enthalpy also contributes to the low free energy
adsorption, that occurs for ionic polymers. This contribution is due to polymer electrostatic attraction of polymer adsorption,
147 that occurs fordepending
or repulsion, ionic polymers. on theThis contribution
surface net ionicischarge.
due to polymer electrostatic attraction or repulsion,
148 depending
Polymerson the aresurface net ionicbycharge.
characterized having high molecular weights and long chains; these chains
149 Polymers are characterized
contain many polar groups, which bywill
having
attachhigh molecular
to the available weights and long
polar points chains;
on the rockthese
surface chains
[48].
150 contain many polar groups, which will attach to the available polar
Essentially, the polymer occupies the adsorption sites at the rock surface, so the larger availablepoints on the rock surface [48].
151 Essentially,
surface area theto thepolymer
polymer occupies
molecule the
willadsorption
have a highersiteslevel
at the rock surface,
of adsorption. so the larger
Adsorption can beavailable
severe,
152 surface area to the polymer molecule will have a higher level of adsorption.
as polymer adsorption is irreversible [52,57]. If the adsorbed polymer occupies a large pore volume, Adsorption can be severe,
153 as polymer
it will adsorption
be difficult is irreversible
to recover [52,57].
a considerable If the adsorbed
amount polymer occupies
of oil. Furthermore, a largepermeability
the formation pore volume, is
154 it will be difficult to recover a considerable
decreased, leading to a lower recovery factor. amount of oil. Furthermore, the formation permeability
155 is decreased, leading to a lower recovery factor.
 Energies 2018, 11, x FOR PEER REVIEW 5 of 18
Energies 2018, 11, 2751 5 of 19
Energies 2018, 11, x FOR PEER REVIEW 5 of 18

156
156
157 Figure 3. Polymer adsorption in porous media [56].
157 Figure 3.
Figure 3. Polymer adsorption in porous media [56]. [56].
158 2.2. Mechanical Entrapment
2.2. Mechanical Entrapment
158
159 2.2. Mechanical
MechanicalEntrapment
entrapment has been studied by several researchers (Gogarty, Smith, Szabo,
160 Mechanical
Dominguez entrapment
and Willhite) has been studied
[58–62]. by several researchers
large in(Gogarty, Smith, Szabo,
159 Mechanical entrapment has Polymer
been studied molecules are relatively
by several researchers solution. Entrapment
(Gogarty, Smith, Szabo, of
161 Dominguez
polymers and Willhite)
occurs in porous [58–62].
media Polymer
as the molecules
polymer moleculesare relatively
are large large in solution.
relative to the sizeEntrapment
of the pores.of
160 Dominguez and Willhite) [58–62]. Polymer molecules are relatively large in solution. Entrapment of
162 polymers
Several occurs in porous
mechanisms media
contribute to as
thethe netpolymer
effect termedmolecules are large relative to the
mechanical size of the pores.
161 polymers occurs in porous media as the polymer molecules are largeentrapment.
relative to the Gogarty
size ofvisualized
the pores.
163 Several
mechanical mechanisms
entrapment contribute
as an end to the net effect termed mechanical entrapment. Gogarty visualized
162 Several mechanisms contribute toresult
the net ofeffect
plugged smallmechanical
termed pores by polymerentrapment. molecules
Gogarty which are too
visualized
164 mechanical
large to enter entrapment
them [58]. as an end
Water and result
salt of plugged
molecules which small
are pores
consideredby polymer
to be molecules
small in size which
can are
travel
163 mechanical entrapment as an end result of plugged small pores by polymer molecules which are too
165 too large
through to enter
porous them
media, [58].
but Water
large and salt
molecules molecules
such aswhich
polymer are considered
molecules to be
will small
be in
trapped size can
and
164 large to enter them [58]. Water and salt molecules which are considered to be small in size can travel
166 travel through
accumulate porous
in these media,
small pores.butGogarty
large molecules
determined such as polymer molecules will be trapped and
165 through porous media, but large molecules such asthat there ismolecules
polymer an effective willpolymer
be trappedmolecular and
167 accumulate
size, for in these small
hydrolyzed pores. Gogarty
polyacrylamide determined
molecules by that there
filtering 400 is an
ppm effective
of polymer
polymer molecular
solution size,
through
166 accumulate in these small pores. Gogarty determined that there is an effective polymer molecular
168 for hydrolyzed
different ofpolyacrylamide filters,molecules by filtering 400 ppm of polymer solution through and 2 different
167 size, for size
hydrolyzednuclepore
polyacrylamide Figure 4 shows
molecules the
by effective
filtering size400 ranging
ppm of between
polymer 0.4 solution µthrough
m [58].
169 size
Smith’sof nuclepore
results filters,
were Figure 4similar
somehow showsto theGogarty’s
effective size ranging
results. The between size
effective 0.4 andof 2 µm [58].
HPAM Smith’s
(Molecular
168 different size of nuclepore filters, Figure 4 shows the effective size ranging between 0.4 and 2 µ m [58].
170 results
weight were3 × somehow
=results106were
) in 0.5% similar
NaCltowas Gogarty’s
in the results.
range of The
0.3 effective
to µ m.size
1.0The of HPAM
According (Molecular weight =
169 Smith’s somehow similar to Gogarty’s results. effective sizetoofthe HPAMliterature, some
(Molecular
171 × 106 ) inthat
3reported 0.5% NaCl
adsorption was in
6) in 0.5% might
the range
be the of 0.3
major to 1.0
dominantµm. According to the literature, some reported that
170 weight = 3 × 10 NaCl was in the range of 0.3 tofor1.0polymer retentiontointhe
µ m. According high permeability
literature, some
172 adsorption
sands [63]. might
On be the
the major
other dominant
hand, mechanicalfor polymer
entrapmentretention is indominant
high permeability
in sands [63]. Onrock
low-permeability the
171 reported that adsorption might be the major dominant for polymer retention in high permeability
173 other hand,
[60,61,63,64]. mechanical
In contrast, entrapment is dominant in low-permeability rock [60,61,63,64]. In contrast,
172 sands [63]. On the otherCohen hand,and Christ suggested
mechanical entrapment that isfordominant
a 5.6 Darcy in silica pack, adsorption
low-permeability rock
174 Cohen
dominated and Christ
35.2% suggested
of the that for
polymer a 5.6 Darcy
retention, whereas silicathepack, adsorption
remainder dominated
retention was 35.2% of the
dominated by
173 [60,61,63,64]. In contrast, Cohen and Christ suggested that for a 5.6 Darcy silica pack, adsorption
175 polymer
mechanical retention,
entrapment whereas
[65]; the remainder
this can be as retention
a result of was
high dominated
heterogeneity. by mechanical
It is worth entrapment
noting that, [65];
for
174 dominated 35.2% of the polymer retention, whereas the remainder retention was dominated by
176 this
better canpolymer
be as a flooding
result of high heterogeneity.
performance most ofIt the
is worth
currentnoting that, for
polymer better
floods arepolymer
implemented flooding in
175 mechanical entrapment [65]; this can be as a result of high heterogeneity. It is worth noting that, for
177 performance
reservoirs withmost of the current
permeability higherpolymer
than floods
0.5 Darcy are implemented
such as Daqing in reservoirs
field with 800 with
md; permeability
Pelican lake:
176 better polymer flooding performance most of the current polymer floods are implemented in
178 higher
with than
1–3 0.5 Darcy
Darcy; Mangala such as Daqing
with field with
approximately 800 md;
5 Darcy; Pelicanwith
Marmul lake:15with
Darcy; 1–3 Darcy; Mangala with
177 reservoirs with permeability higher than 0.5 Darcy such as Daqing field with and 800 Tambaredjo
md; Pelican lake:
179 approximately
awith
range 5 Darcy; Marmul with 15 Darcy; and Tambaredjo with a range of 4–12 Darcys.
178 1–3ofDarcy;
4–12 Darcys.
Mangala with approximately 5 Darcy; Marmul with 15 Darcy; and Tambaredjo with
179 a range of 4–12 Darcys.

180
180
181 Figure 4.
Figure Polymer filteration
4. Polymer filteration with different size nuclepore filters [58]
with different [58]..
181 Figure 4. Polymer filteration with different size nuclepore filters [58].
182 2.3. Hydrodynamic Retention
182 2.3. Hydrodynamic Retention
Energies 2018, 11, 2751 6 of 19

2.3. Hydrodynamic Retention

Another type of polymer retention is hydrodynamic retention. Chauveteau and Kohler
experimentally showed the effect of hydrodynamic retention while running an HPAM core flooding
experiment. They noticed that polymer retention changed with the change in flow rates [66]. The idea
came after observing that, after reaching steady state in a polymer retention experiment in a core,
the retention level changed when a new value of the flow rate was adjusted [61,66,67]. In their
experiment, as the flow rate increased from 3 cubic meters per day to 10.3 cubic meters per day,
more polymer was lost in the porous media from the injected solution, as seen by a dip in the polymer
effluent concentration. As the flow rate was lowered again to 3 cubic meters per day, the effluent
polymer concentration rose above 400 ppm which was the input value, denoting a drop in the
retained level. Hydrodynamic retention of the polymer is the least well defined and understood
retention mechanism. The physical picture of the hydrodynamic retention mechanism is thought to be
temporarily trapped in stagnant regions by hydrodynamic drag forces called osmotic forces. It may be
possible for the polymer concentration in this region to exceed that of the injected fluid. If the flow
stops, these polymer molecules may diffuse out of the stagnant region into the main flow channels,
so when the flow is retrieved, they are produced as a peak in polymer concentration [47].

2.4. Inaccessible Pore Volume

Inaccessible pore volume (IPV) has been widely reported in the literature [61,68–80] as a
phenomenon that needs to be considered in polymer flooding applications. When the polymer
molecular size is larger than some pores in a porous medium, the polymer molecules cannot flow
through those pores. The volume of those pores that cannot be accessed by polymer molecules is
called inaccessible pore volume (IPV) [47,70,81]. This IPV is occupied by water (brine) that contains
no polymer, and this allows polymer concentration to be propagated through porous media more
rapidly than water does [70]. IPV depends on the hydrodynamic size of the polymer in the solution,
medium permeability, porosity, and pore size distribution and becomes more pronounced as molecular
weight increases and the ratio of permeability to porosity (characteristic pore size) decreases. In extreme
cases, IPV can be 30% of the total pore space [73].

2.5. A Combination of Adsorption and Inaccessible Pore Volume

As mentioned in the previous section IPV reduces the volume of the porous media that the
polymer flows through. Therefore, polymer adsorption can be decreased due to the presence of IPV
since less polymer solution will be in contact with the rock surface than total pore volume. Dawson
and Lantz (1972) first illustrated the effect of both polymer adsorption and IPV. Figure 5 shows four
possible scenarios for this effect as follows:

Scenario A: No retention nor IPV. The polymer will break through at 1 PV.
Scenario B: No retention, IPV represents 0.25 PV of the total pore volume. The polymer will break
through at 0.75 PV.
Scenario C: Retention is 0.25 PV and no IPV. The polymer will break through at 1.25 PV.
Scenario D: Retention is 0.2 PV, IPV is 0.25 PV. The polymer will break through at 0.95 PV.

In the case of no retention and no IPV, ideally, we expect the polymer to break out after injecting
one PV of the polymer as shown in scenario A. Polymer bank emerges early as shown in scenario B
in the case of the inaccessible pore volume and breakout curve will shift forward. On the contrary,
the front edge will be affected and break out will be delayed by adsorption. Moreover, the back edge
is not affected; hence, the polymer bank becomes smaller as shown in scenario C. the combination
adsorption and IPV in porous media shifts the polymer bank forward and reduces the amount of the
polymer at the effluent as a result of adsorption in the porous media as shown in Figure 2 Scenario D.
 Energies 2018, 11, 2751 7 of 19
Energies 2018, 11, x FOR PEER REVIEW 7 of 18

227
Figure 5. Ideal breakout curves [70].
228 Figure 5. Ideal breakout curves [70].
2.6. Static Versus Dynamic Retention
229 2.6. Static Versus Dynamic Retention
There are large differences between the level of static adsorption of polymers and dynamically
230 There
retained areinlarge
level differences
a core between
or pack [82] the level
as shown of static
in Table adsorption
1. These of polymers
differences and dynamically
are the result of changes
231 in the specific surface area of consolidated and unconsolidated packs and the accessibility of
retained level in a core or pack [82] as shown in Table 1. These differences are the result of changes
certain
232 in the specific surface area of consolidated and unconsolidated packs and the accessibility
portions of the pore space. These differences also depend on the extent of mechanical retention that of certain
is
233 portions of the pore space. These differences
present in the dynamic core flood experiment [81,83].also depend on the extent of mechanical retention that
234 is present in the dynamic core flood experiment [81,83].
Table 1. Comparison of polymer adsorption in static and dynamic test for three polymers at a polymer
235 Table 1. Comparison
concentration of polymer adsorption in static and dynamic test for three polymers at a polymer
of 1500 mg/L.
236 concentration of 1500 mg/l.
Polymer FP6040 DQ3500 KYPAM-2
Polymer FP6040 DQ3500 KYPAM-2
Static Test
Static Test
Adsorption amount µg/g 1492 876 1172
Adsorption amount µ g/g 1492 Test 876
Dynamic 1172
Adsorption amount µg/g Dynamic Test
196 125 159
Adsorption amount µ g/g 196 125 159

3. Factors Effecting Polymer Retention

237 3. Factors Effecting Polymer Retention
3.1. Polymer Type Effect
238 3.1. Polymer Type Effect
In early studies by Szabo for dynamic polymer adsorption, it was shown that 2-acrylamido-
239 In early studies by Szabo for dynamic polymer adsorption, it was shown that 2-acrylamido-
2methyl propane sulfonate (AMPS) adsorption is lower than HPAM [60]. Broadly, xanthan adsorption
240 2methyl propane sulfonate (AMPS) adsorption is lower than HPAM [60]. Broadly, xanthan
in porous media is much lower than that of HPAM and tends to show less sensitivity to the
241 adsorption in porous media is much lower than that of HPAM and tends to show less sensitivity to
salinity/hardness conditions of the solvent [47,52]. In another study by Szabo, adsorption and
242 the salinity/hardness conditions of the solvent [47,52]. In another study by Szabo, adsorption and
retention measurements in Berea cores were carried out on different types of polymers, including
243 retention measurements in Berea cores were carried out on different types of polymers, including
AMPS polymers, HPAMs, a xanthan and other polymers. The range of measured retention was lower
244 AMPS polymers, HPAMs, a xanthan and other polymers. The range of measured retention was lower
for the AMPS polymers (35–72 lb/AF) than for the HPAM polymers (88–196 lb/AF) in similar Berea
245 for the AMPS polymers (35–72 lb/AF) than for the HPAM polymers (88–196 lb/AF) in similar Berea
cores (k = 0.328–0.679 Darcy) [60]. Figure 6 shows more adsorption examples for different types of
246 cores (k = 0.328–0.679 Darcy) [60]. Figure 6 shows more adsorption examples for different types of
polymers which illustrates the vast variation in adsorption as a function of the type of the polymer.
247 polymers which illustrates the vast variation in adsorption as a function of the type of the polymer.
 Energies 2018, 11, 2751 8 of 19
Energies 2018, 11, x FOR PEER REVIEW 8 of 18

248
249 Figure
Figure 6.
6. Polymer
Polymer adsorption
adsorption for different types of polymers [81]
for different [81]..

250 3.2. Molecular Weight

3.2. Molecular Weight Effect
Effect

251 Reported results considering

Reported results considering the the effect
effect of
of molecular weight on
molecular weight on polymer
polymer static
static adsorption
adsorption for for
252 sulfonated polyacrylamide polymers
sulfonated polyacrylamide polymers showedshowed thatthat level
level of
of adsorption
adsorption waswas increased
increased byby increasing
increasing
253 molecular
molecular weight [84,85]. This is in accordance with theory since a polymer with a higher molecular
weight [84,85]. This is in accordance with theory since a polymer with a higher molecular
254 weight
weight would
would form
form aa thicker
thicker layer
layer of of the
the polymer
polymer when
when adsorbed
adsorbed on on aa surface
surface [84].
[84]. In
In dynamic
dynamic
255 polymer adsorption studies, sometimes higher levels of adsorption were
polymer adsorption studies, sometimes higher levels of adsorption were seen for higher molecularseen for higher molecular
256 weight
weight polymers,
polymers, butbut this
this adsorption
adsorption leveled
leveled off
off after
after aa specific
specific value
value of
of the
the molecular
molecular weight
weight [86].
[86].
257 However, dynamic adsorption in silica sand decreased with increasing molecular
However, dynamic adsorption in silica sand decreased with increasing molecular weight, although weight, although
258 the
the effect
effect was
was not
not large. Studies on
large. Studies on the
the effect
effect of
of molecular
molecular weight
weight on on retention
retention of
of sulfonated
sulfonated
259 polyacrylamide
polyacrylamide copolymers studied by Rashidi (2009, 2011) led to the conclusion that increasing
copolymers studied by Rashidi (2009, 2011) led to the conclusion that by by increasingthe
260 molecular weight
the molecular of the of
weight polymer, less polymer
the polymer, was retained
less polymer was[83,85].
retainedThe[83,85].
observation
The was explainedwas
observation by
261 inaccessible pore volume concept; larger polymers are unable to enter the smaller
explained by inaccessible pore volume concept; larger polymers are unable to enter the smaller pores pores of the rock.
262 Lakatos et al.
of the rock. (1979)et
Lakatos found that found
al. (1979) the levelthatofthe
HPAM
levelretention
of HPAMfor a 500 ppm
retention for asolution
500 ppminsolution
the sandpack
in the
263 decreased slightly with increasing molecular mass but decreased even more
sandpack decreased slightly with increasing molecular mass but decreased even more sharply as the sharply as the degree of
264 hydrolysis increased [82]. They considered the degree of hydrolysis and the
degree of hydrolysis increased [82]. They considered the degree of hydrolysis and the electrolyte electrolyte concentration
265 to have the most
concentration influence
to have the moston molecular
influence size (coil density)
on molecular and hence
size (coil theand
density) adsorption
hence the level. In this
adsorption
266 respect,
level. In they noted that
this respect, theythenoted
role of thethe
that molecular mass
role of the is very small.
molecular mass is very small.
3.3. Polymer Concentration Effect
267 3.3. Polymer Concentration Effect
The adsorption amount dependence on the polymer concentration for a typical unhydrolyzed and
268 The adsorption amount dependence on the polymer concentration for a typical unhydrolyzed
a partially hydrolyzed polyacrylamide shows similar behavior. Despite the considerable differences
269 and a partially hydrolyzed polyacrylamide shows similar behavior. Despite the considerable
in the absolute values, it is characteristic that the adsorption increases with the increase in polymer
270 differences in the absolute values, it is characteristic that the adsorption increases with the increase
concentration [52,79,87]. Zheng claimed that the Langmuir isotherm was applied to his results.
271 in polymer concentration [52,79,87]. Zheng claimed that the Langmuir isotherm was applied to his
However, he only measured retention for 250 ppm, 750 ppm and 1500 ppm polymer solutions [87].
272 results. However, he only measured retention for 250 ppm, 750 ppm and 1500 ppm polymer solutions
Moreover, his results showed that the highest retention was at 1500 ppm, that is only less than 1.5 times
273 [87]. Moreover, his results showed that the highest retention was at 1500 ppm, that is only less than
than that from the 250 ppm. Szabo measured retention by injecting polymer solution into a 1.2 Darcy
274 1.5 times than that from the 250 ppm. Szabo measured retention by injecting polymer solution into a
unconsolidated core. Initially, polymer retention was 3.50 µg/g at 300 ppm; then by increasing polymer
275 1.2 Darcy unconsolidated core. Initially, polymer retention was 3.50 µg/g at 300 ppm; then by
concentration to 600 ppm, retention was measured at 6 µg/g [60]. Another retention study by Huang
276 increasing polymer concentration to 600 ppm, retention was measured at 6 µg/g [60]. Another
and Sorbie (1993) for Scleroglucan in Bollotini packed columns showed an increase from 8.21 µg/g to
277 retention study by Huang and Sorbie (1993) for Scleroglucan in Bollotini packed columns showed an
11.71 µg/g as the concentration rose from 50 to 200 ppm [79]. A summary of the results of the polymer
278 increase from 8.21 µg/g to 11.71 µg/g as the concentration rose from 50 to 200 ppm [79]. A summary
concentration effect on adsorption is shown in Table 2.
279 of the results of the polymer concentration effect on adsorption is shown in Table 2.

280 Table 2. Polymer retention dependency on polymer concentration.

Polymer Concentration Type of Retention

Reference
(ppm) Polymer (µg/g)
10–6000 HPAM 20–420 Zhang and Seright (2013)
20–1000 HPAM 21–30 Green and Willhite (1988)
 Energies 2018, 11, 2751 9 of 19

Table 2. Polymer retention dependency on polymer concentration.

Polymer
Energies Concentration
2018, 11, (ppm)
x FOR PEER REVIEW Type of Polymer Retention (µg/g) Reference 9 of 18
10–6000 HPAM 20–420 Zhang and Seright (2013)
20–1000
250–1500 HPAM
HPAM 40–5821–30 Green
Zhengand Willhite (1988)
(2000)
250–1500
50–200 HPAM
Scleroglucan 40–58
8.2–11.7 Huang andZheng
Sorbie (2000)
(1993)
50–200 Scleroglucan 8.2–11.7 Huang and Sorbie (1993)
281 Another study by Zhang and Seright (2014) for both static and dynamic retention on the polymer
282 concentration effectbyon
Another study adsorption
Zhang concluded
and Seright the both
(2014) for overall behavior
static of concentration
and dynamic retention ondependency.
the polymer
283 They concluded
concentration that on
effect different polymer
adsorption adsorption
concluded thebehavior
overall exists in three
behavior regions dilute,dependency.
of concentration semi-dilute
284 and concentrated regions [51]. Polymer adsorption has a small dependency in the
They concluded that different polymer adsorption behavior exists in three regions dilute, semi-dilute dilute and
285 concentrated
and regions,
concentrated whereas,
regions [51].polymer adsorption
Polymer has has
adsorption a high
a dependency on polymer
small dependency in theconcentration
dilute and
286 in the semi-dilute region as shown in Figure 7. This might be a fruitful conclusion for
concentrated regions, whereas, polymer adsorption has a high dependency on polymer concentration the adsorption
287 dependency on concentration as previous reports showed a very small increase in adsorption
in the semi-dilute region as shown in Figure 7. This might be a fruitful conclusion for the adsorption for low
288 and high polymer
dependency concentration
on concentration compared
as previous to polymer
reports showedmedium concentration
a very small increase inbetween
adsorption(500–2000)
for low
289 ppm.
and high polymer concentration compared to polymer medium concentration between (500–2000) ppm.

290
291 Figure
Figure 7. Polymer adsorption
7. Polymer adsorption in
in different
different concentration
concentration regions
regions [51].
[51].
3.4. Rock Surface Effect
292 3.4. Rock Surface Effect
The iron and clay content of the porous medium has a strong effect on retention. The HPAM
293 The iron
adsorption and
level onclay content
calcium of the isporous
carbonate medium
significantly has athan
higher strong effect on
adsorption onretention. The HPAM
the silica surface [81].
294 Higher adsorption might be due to the vigorous interactions between the carboxylate groups on[81].
adsorption level on calcium carbonate is significantly higher than adsorption on the silica surface the
295 Higher adsorption might be
2 + due to the vigorous interactions between the carboxylate
HPAM and the surface Ca [59,64,82]. More experimental examples on iron and clay content effect groups on the
2+
296 HPAM and the surface
are shown in Table 3. 𝐶𝑎 [59,64,82]. More experimental examples on iron and clay content effect
297 are shown in Table 3.
Table 3. Polymer retention dependency on mineralogy.
298 Table 3. Polymer retention dependency on mineralogy.
Mineral Polymer Type Retention (µg/g) Reference
Mineral
Kaolinite Polymer
HPAMType Retention
339–1217(µg/g) Meister (1980)
Reference
[88]
Kaolinite
Baker dolomite HPAM 339–1217
1.9–17.8 Meister
Meister (1980) [88]
(1980)
Kaolinite
Baker dolomite Xanthan
HPAM 16,900
1.9–17.8 Hughes (1990)
Meister (1980)
Siderite
Kaolinite Xanthan
Xanthan 15,600
16,900 Hughes (1990)
Hughes (1990)
Montmorillonite
Siderite CPAM
Xanthan 180,000
15,600 Chiappa (1999)
Hughes (1990)
Quartzite CPAM 610 Chiappa (1999)
Montmorillonite CPAM 180,000 Chiappa (1999)
Calcium carbonate HPAM 20–100 Szabo (1975)
Quartzite CPAM 610 Chiappa (1999)
Calcium carbonate HPAM 20–100 Szabo (1975)
3.5. Salinity Effect
299 3.5. Salinity Effectthe salinity concentration generally increases the level of polymer adsorption.
Increasing
300 ManyIncreasing
physical the
andsalinity
chemical properties generally
concentration of the injected chemical
increases agents
the level are affected
of polymer by salinity,
adsorption. Many
301 physical and chemical properties of the injected chemical agents are affected by salinity, like viscosity,
302 chemical activity, stability, and adsorption [12]. Charge type (positive, negative, or neutral) of the
303 rock surface is disturbed in the presence of salinity, which leads to different behavior of the rock
304 surface [12]. Smith (1970) showed that a low concentration of calcium ion 𝐶𝑎2+ will promote HPAM
305 adsorption on silica, as the divalent ions compress/squeeze the size of the molecules of the flexible
Energies 2018, 11, 2751 10 of 19

like viscosity, chemical activity, stability, and adsorption [12]. Charge type (positive, negative,
or neutral) of the rock surface is disturbed in the presence of salinity, which leads to different behavior
of the rock surface [12]. Smith (1970) showed that a low concentration of calcium ion Ca2+ will promote
HPAM adsorption on silica, as the divalent ions compress/squeeze the size of the molecules of the
flexible HPAM and reduce the static repulsion between the silica surface and the polymer carboxyl
group [59]. Smith results also showed that polymer retention increased from about 11 g/m2 at 1%
NaCl to 60 g/m2 at 10% NaCl.

3.6. Hydrolysis Effect

As the degree of hydrolysis increases, the level of HPAM retention in the sand pack decreases [82].
Adsorption decreases with hydrolysis until adsorption reaches a minimum. Minimum adsorption is
because of the charge interaction between the carboxyl group on the polymer (negative charge) and
the silica surface on the sand (negative charge). Therefore, an electrostatic repulsion occurs causing a
decrease in adsorption.

3.7. Permeability Effect

Polymer retention decreases with higher permeability. This is due to mechanical entrapment in a
low permeability rock compared to that in a high permeability rock. Moreover, a high clay content in
low permeability rocks is also another possible reason for higher retention. Table 4 shows two types of
rocks with a high dependency on permeability below 0.2 Darcy.

Table 4. Polymer retention dependency on polymer concentration.

Rock Type and

Polymer Type Retention (µg/g) Reference
Permeability
Vosges sandstone 2100 md HPAM 155 Zaitoun and Kohler (1987) [89]
Vosges sandstone 520 md HPAM 140 Zaitoun & Kohler (1987)
Reservoir sandstone 137 md HPAM 12 Vela (1976)
Reservoir sandstone 12 md HPAM 130 Vela (1976)

3.8. Wetting Phase Effect

The wetting phase of the rock also affects polymer retention; in an oil-wet system, polymer
retention of polyacrylamide at residual oil saturation will considerably decrease by factors of 2 to 5
compared to the retention if the core is 100% water-saturated [90]. However, in a water-wet system,
the effect of residual oil saturation is less noticeable. For example, the retention with residual oil
saturation of 0.2 is almost 7.5 µg/g compared to zero residual oil saturation with a retention of 10 µg/g.

3.9. Temperature Effect

Adsorption decreases with temperature because of a combined physical and chemical reasons such as
electrostatic repulsion, hydrophobicity, van der Waals forces and hydrogen bonds. For nonionic polymers,
adsorption is more related to hydrogen bond, whereas adsorption is more related to electrostatic repulsion
in ionic polymers. Increasing the temperature facilitates the hydrogen bond to break up, causing a
decrease in polymer adsorption. Increasing temperature increases the negative charge on the rock surface,
leading to higher electrostatic repulsion, so, the ionic polymer adsorption is reduced [81].

4. Polymer Retention Measurement

Many factors need to be considered in polymer retention measurements which makes polymer
retention measurement a very long and complicated process. A broad range of methods for calculating
polymer retention in porous media was investigated by many researchers. We summarize these
methods into three categories.
Energies 2018, 11, 2751 11 of 19

4.1. Static Method

Generally, static methods are used to measure polymer adsorption to estimate the effect of
different parameters on polymer adsorption [85,91,92]. In this method, crushed sand is prepared,
and a known concentration of polymer is added to the crushed core, then the polymer concentration
is measured after separation of the polymer solution from the sand. Knowing the initial mass of the
sand, polymer
Energiesadoption
2018, 11, x FORisPEER
calculated
REVIEW by dividing the lost mass of the solution by the sand 11 of 18 weight as
shown in Equation (3).
342 Generally, static methods are used q =toVmeasure
(Co − Ce polymer
)/W adsorption to estimate the effect of (3)
343 different parameters on polymer adsorption[85,91,92]. In this method, crushed sand is prepared, and
344 q isa the
where known concentration
adsorption of polymer is added
concentration; V is tothethevolume
crushed core, thenpolymer
of the the polymer concentration
solution; Co isis the initial
345 measured after separation of the polymer solution from the sand. Knowing the initial mass of the
polymer concentration; Ce is the polymer concentration after the static adsorption.
346 sand, polymer adoption is calculated by dividing the lost mass of the solution by the sand weight as
As mentioned
347 in the (3).
shown in Equation static versus dynamic retention section, static and dynamic retention will
give different results. Mostly, static results will be higher than dynamic results unless the dominant
𝑞 = 𝑉(𝐶𝑜 − 𝐶𝑒)⁄𝑊 (3)
retention mechanism is the mechanical entrapment in very low permeability cores. The static method
348 where q is the adsorption concentration; V is the volume of the polymer solution; Co is the initial
relies
349on only two polymer concentration measurements. Therefore, errors in these measurements
polymer concentration; Ce is the polymer concentration after the static adsorption.
have350an essential impact on
As mentioned thestatic
in the adsorption value.retention
versus dynamic Moreover, tostatic
section, make andthe sand,retention
dynamic the rockwill needs to be
351
pulverized, which
give exposes
different results.more
Mostly,surface areawill
static results andbeminerals
higher thanwhich
dynamicmight
resultsnot be available
unless the dominant in the main
352
rock. One retention mechanism
more limitation inisusing
the mechanical
the static entrapment
test is thatin very
the low permeability
mechanical cores. The static
entrapment method
cannot be measured.
353 relies on only two polymer concentration measurements. Therefore, errors in these measurements
354 have an essential impact on the adsorption value. Moreover, to make the sand, the rock needs to be
4.2. Single Polymer Injection Method
355 pulverized, which exposes more surface area and minerals which might not be available in the main
356
One ofrock.
theOne more methods
earliest limitation in usingtothe
used static test
estimate is that the
polymer mechanical
retention in entrapment
porous media cannotwasbe based on
357 measured.
the calculation of the remaining polymer concentration in porous media after measuring the effluent
polymer
358 [51,63,93].
4.2. Single Polymer Injection Method
In
359 this method,
One of thetheearliest
polymer is injected
methods through
used to estimate cores retention
polymer or sand in packs
porous along
mediawith a tracer.
was based on Material
balance
360 calculation
the calculationis performed
of the remainingforpolymer
the effluent concentration
concentration profiles
in porous media afterin to determine
measuring the retention
the effluent
361
level polymer
as shown in [51,63,93].
Equation (4).
362 In this method, the polymer is injected through cores or sand packs along with a tracer. Material
363 balance calculation is performed for the effluent concentration dCsprofiles indCto determine the retention
364 level as shown in Equation ∆φVC + ∆DV = (1 − φ)
− (4). + φp (4)
dt dt
𝑑𝐶𝑠 𝑑𝐶
−∆ϕ𝑉𝐶 + ∆𝐷𝑉 = (1 − ϕ) + ϕ𝑝 (4)
Polymer retention is calculated from the difference𝑑𝑡between 𝑑𝑡 the area under the curves of the
polymer
365 and tracerPolymer slug. Moreover,
retention the inaccessible
is calculated from the differenceporebetween
volume the(IPV) can be
area under theestimated by the back
curves of the
edge366area polymer
between and tracer
the twoslug. Moreover,
curves the inaccessible
as shown in Figure pore volume (IPV) can be estimated by the back
8 [70].
367 edge area between the two curves as shown in Figure 8 [70].
It is difficult
368 to retrieve the polymer from the porous media with the injection of a few pore volumes,
It is difficult to retrieve the polymer from the porous media with the injection of a few pore
thus369
the amount of the polymer
volumes, thus the amount retained
of the in the porous
polymer media
retained can
in the be overestimated.
porous Therefore an extended
media can be overestimated.
370 ofTherefore
injection brine toanrecover
extended the polymer
injection is required
of brine to recover[48]. This isisarequired
the polymer result of[48].
theThis
unfavorable
is a result ofdisplacement.
the
371 unfavorable displacement. However, it is important to indicate that a very low polymer
However, it is important to indicate that a very low polymer concentration at the effluent will be associated concentration
372 at the effluent will be associated with polymer detection errors which again will overestimate the
with373
polymer detection errors which again will overestimate the amount of the retained polymer.
amount of the retained polymer.

374
Figure 8. Polymer retention measurement using a single polymer injection method.
 Energies 2018, 11, x FOR PEER REVIEW 12 of 18
Energies 2018, 11, 2751 12 of 19
375 Figure 8. Polymer retention measurement using a single polymer injection method.

376 4.3.
4.3. Extended
Extended Injectivity
Injectivity Method
Method
377 This
This method
method is is the
the most
most used
used method
method in in the
the literature
literature to
to determine
determine thethe polymer
polymer retention
retention inin
378 porous media [74,94,95]. In this method, a polymer solution along with a tracer is
porous media [74,94,95]. In this method, a polymer solution along with a tracer is injected into the injected into the
379 porous
porous media.
media. Injection continues until
Injection continues until the
the polymer
polymer andand tracer
tracer concentrations
concentrations produced
produced reach
reach the
the
380 injected polymer and tracer concentrations, followed by extended brine injectivity
injected polymer and tracer concentrations, followed by extended brine injectivity (~100) pore (~100) pore volumes
381 of brine. The
volumes mobileThe
of brine. polymer
mobile and tracer will
polymer andbetracer
displaced from
will be porous media.
displaced Finally,media.
from porous a second bank ofa
Finally,
382 polymer and tracer
second bank solution
of polymer andistracer
injected. Measurements
solution is injected.ofMeasurements
polymer retention and IPVretention
of polymer (inaccessible
andpore
IPV
383 volume) use only the front part of the break out curves from the two injected slugs, which
(inaccessible pore volume) use only the front part of the break out curves from the two injected slugs, eliminates
384 the problems
which associated
eliminates with the low
the problems concentration
associated with the extended production and
low concentration viscous fingering.
extended productionIPV andis
385 measured from the area
viscous fingering. IPV between the second
is measured from polymer
the areacurve and the
between thefirst/second
second polymertracer curve.
curve Polymer
and the
386 retention is measured from the area between the first polymer curve and the second
first/second tracer curve. Polymer retention is measured from the area between the first polymer polymer curve as
387 shown in Figure
curve and 9.
the second polymer curve as shown in Figure 9.

388
389 Figure 9. Polymer retention measurement using extended injectivity method.

390 Equation
Equation (5)
(5) shows
shows the
the mathematical
mathematical expression
expression for
for polymer
polymer retention
retention and
and IPV
IPV calculation.
calculation.
     
Cp𝐶𝑝 𝐶𝑡
Ct 𝑃𝑉 PV
R= 𝑅= ∑{[∑ [(
Cpo
𝐶𝑝𝑜
∗ ∆PV
∗ ∆PV)−
−(
Cto
𝐶𝑡𝑜
∆PV + IPV}
∗∗∆PV)]] + IPV ∗ ∗
𝐶𝑝𝑜Cpo
𝑀𝑟 Mr
(5)
(5)

391 where R
where retention in porous media; Cp and Cpo are the produced and injected polymer
R is the polymer retention
392 consecutively; PV is the pore volume in the porous media; Ct and Cto are the produced and injected
393 tracer,
tracer, respectively;
respectively; IPV
IPV is
is the
the inaccessible
inaccessible pore volumeMr
porevolume Mrisisthe
themass
massof
ofthe
therock.
rock.

394 4.4.
4.4. Concentration
Concentration Profile
Profile Method
Method
395 Another
Another method
method usedused toto calculate
calculate polymer
polymer retention
retention and
and IPVIPV isis by
by creating
creating the
the breakout
breakout curves
curves
396 in the same manner as in the extended injectivity test for the first and second polymer
in the same manner as in the extended injectivity test for the first and second polymer slug. According slug. According
397 to
to Huh
Huh (1990),
(1990),TheThedynamic
dynamicretention
retention can be be
can determined
determined by plotting
by plottingthe effluent profile
the effluent of a core
profile of aflood
core
398 experiment [63]. With
flood experiment [63].regard to the to
With regard theory of diffuse
the theory percolation,
of diffuse when awhen
percolation, solution flows through
a solution a core
flows through
399 at a constant
a core velocity, the
at a constant point, where
velocity, the normalized
the point, where the concentration (Ce/Cinj) on the
normalized concentration concentration
(Ce/Cinj) on the
400 profile at any time is 0.5 [94,96]. Retention and IPV can be directly measured
concentration profile at any time is 0.5 [94,96]. Retention and IPV can be directly measured by by reading thereading
values
401 corresponding to the point
the values corresponding toof
thenormalized concentration
point of normalized at 0.5 as shown
concentration inshown
at 0.5 as Figurein 10.Figure
This method
10. This
402 is the least used and reported in the literature. However, it showed comparatively
method is the least used and reported in the literature. However, it showed comparatively identical identical results
403 with thewith
results extended injectivity
the extended test. Thetest.
injectivity mainTheadvantage of usingof
main advantage this method
using is that IPV
this method can IPV
is that be directly
can be
404 estimated from the cut off value of the normalized concentration at 0.5 from
directly estimated from the cut off value of the normalized concentration at 0.5 from the second the second polymer slug
405 polymer slug without the need to plot the tracer curve using Equation (6). Retention is estimated
Energies 2018, 11, 2751 13 of 19

without the need to plot the tracer curve using Equation (6). Retention is estimated from the cut off
value of the normalized concentration at 0.5 from the first and second polymer slug using Equation (7).

IPV = 1 − PVsecond slug Ce (6)

Cinj =0.5

Retention = PV f irst slug Ce − PVsecond slug Ce (7)

Cinj =0.5 Cinj =0.5

Figure 10. Polymer retention measurement using concentration profile method.

5. Modeling of Polymer Retention in Porous Media

In polymer flooding, the polymer solution effectively reduces the displacing fluid mobility
whereas the effective permeability of the reservoir is reduced by polymer retention [50]. Polymer
retention simulation is primarily part of the polymer flood simulation that is extensively based on
modeling parameters such as viscosity depending on polymer concentration, polymer solution shear
thinning, shear degradation, permeability reduction, and polymer adsorption. Several simulators are
being used to model polymer flooding processes such as Eclipse, CMG and UTCHEM. The imposed
assumptions for flow equations development are equilibrium thermodynamic except for organic
component dissolution and tracers, immobile solid phases, Fickian dispersion, slightly compressible
fluids and soil, Darcy’s law and ideal mixing [95]. The boundary conditions are no dispersive flux and
no flow across the impermeable boundaries. For a component k, the continuity of mass in combination
with Darcy’s law is represented in terms of the overall volume of the component k per unit pore
volume as shown in Equation (8).

p n
∂ 
− ∅Čk ρk = ∇·[ ∑ ρk (Ckl ul − Dkl )] (8)
∂t l =1

where k is the component species index number (k for polymer = 4); l is the phase index number
for water and oil (water = 1, oil = 2); O is the porosity; Čk represents the overall concentration of the
component k; ρk is the density of the component k; n p is the number of the phases; Ckl is the component
k concentration in phase l; ul is the phase l darcy velocity; and Dkl represents the dispersion tensor.
Polymer retention in porous media results from adsorption of polymer molecules onto solid
surfaces and trapping of the polymer within small pores. As mentioned in the previous sections,
polymer retention slows the polymer breakout and depletes the polymer slug. To model polymer
Energies 2018, 11, 2751 14 of 19

adsorption level, simulators use a Langmuir-type isotherm as shown in Equation (9) which mainly
takes into account only the polymer concentration, salinity, and permeability.
   
ap Cp − Ĉp
Ĉp = minCp   (9)
1 + bp Cp − Ĉp

where Cp and Ĉp is the injected and adsorbed polymer concentration, respectively. (Cp − Ĉp) represents
the equilibrium concentration in the rock-polymer system. The minimum adsorption value is taken to
ensure that the adsorption is no greater than the total polymer concentration. ap and bp are the fitting
parameters. The parameter ap is calculated from Equation (10).


p = ap1 + ap2Csep (10)

where Kre f and Csep is the reference permeability (at which adsorption parameters input are specified)
and effective salinity respectively. The unit for ap is dimensionless. The effective salinity of the polymer
adsorption Csep is defined by Equation (11).

C51 + (ßp − 1)C61

Csep = (11)
C11
where C51, C61 and C11 are the anion, divalent, and water concentrations in the aqueous phase,
respectively. ßp is the covalent coefficient. It is noteworthy to mention that the Langmuir model is
an equilibrium relationship, and its application assumes polymer adsorption is instantaneous and
reversible. When polymer adsorption is considered to be irreversible, the Langmuir model cannot be
used directly as the polymer concentration is declining [81].

6. Scope of This Research

This paper presents a complete review of polymer retention phenomenon with an aim to provide
a comprehensive reference for researchers investigating polymer retention and field practitioner
designing a polymer slug for their project:

• A discussion on the strength and limitation of polymer flooding and the mechanism of mobility
ratio improvement was provided.
• A review of the polymer retention phenomenon, highlighting its importance, was presented.
• The factors influencing polymer adsorption, mechanical entrapment and hydrodynamic retention
were identified.
• The commonly used techniques for polymer retention measurements and their cons and pros
viz’a viz other techniques were discussed.
• The commonly used techniques for modeling were described.

7. Key Observation
• The flow of polymer solutions through porous media is a complex phenomenon requiring an
understanding of retention, flow capacity alteration, and inaccessible pore volume. Estimation of
these factors is important for economic evaluation and slug design for a successful implementation
of polymer flooding EOR.
• Polymer retention is caused by adsorption on the surfaces, mechanical entrapment due to narrow
passageways in porous media, and hydrodynamic entrapment due to high flow rates.
• The retained polymer reduces the flow area, thus the flow capacity (permeability) of the porous
media. The mobility of polymer is therefore reduced by both increased viscosity and reduced
flow capacity.
Energies 2018, 11, 2751 15 of 19

• Inaccessible pore volume allows the polymer to propagate through porous media more rapidly
and reduces the amount of polymer retention.
• Each measurement method has some limitations and cannot be relied upon solely. Therefore,
a combination of at least two methods for static and dynamic measurements is often needed.

Author Contributions: Conceptualization, S.A.-H. and S.M.M.; Methodology, S.A.-H.; Software, H.A.; Validation,
S.A.-H., S.M.M. and S.A.; Formal Analysis, S.A.-H.; Investigation, S.A.-H.; Resources, S.M.M.; Data Curation, H.A.
and S.A.; Writing-Original Draft Preparation, S.A.-H.; Writing-Review & Editing, S.M.M.; Visualization, S.A.-H.;
Supervision, S.M.M.; Project Administration, S.A.-H. and S.M.M.; Funding Acquisition, S.M.M.
Funding: This research was funded by Universiti Teknologi PETRONAS and Yaysan UTP-Fundamental Research
Grant (Cost Center 0153AA-E84).
Acknowledgments: The authors wish to thank Universiti Teknologi PETRONAS for providing monetary support
and an intellectual platform during this research.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Alvarado, V.; Manrique, E. Enhanced oil recovery: An update review. Energies 2010, 3, 1529–1575. [CrossRef]
2. Bilak, R. Enhanced Oil Recovery Methods. U.S. Patent US706,999,0B1, 4 July 2006.
3. Abidin, A.; Puspasari, T.; Nugroho, W.A. Polymers for enhanced oil recovery technology. Procedia Chem.
2012, 4, 11–16. [CrossRef]
4. Gao, C. Experiences of microbial enhanced oil recovery in Chinese oil fields. J. Pet. Sci. Eng. 2018, 166, 55–62.
[CrossRef]
5. Gao, C.; Shi, J.; Zhao, F. Successful polymer flooding and surfactant-polymer flooding projects at Shengli
Oilfield from 1992 to 2012. J. Pet. Explor. Prod. Technol. 2014, 4, 1–8. [CrossRef]
6. Surguchev, L.; Manrique, E.; Alvarado, V. Improved oil recovery: Status and opportunities. In Proceedings
of the 18th World Petroleum Congress, Johannesburg, South Africa, 25–29 September 2005.
7. Craig, F.F., Jr. The Reservoir Engineering Aspects of Waterflooding; H.L. Doherty Memorial Fund of AIME:
New York, NY, USA, 1971.
8. Fettke, C.R. The Bradford oil field Pennsylvania and New York; Department of Internal Affairs, Topographic and
Geologic Survey: Harrisburg, PA, USA, 1938.
9. Muskat, M. Physical Principles of Oil Production; McGraw-Hill Book Co.: New York, NY, USA, 1981.
10. Stiles, W.E. Use of permeability distribution in water flood calculations. J. Pet. Technol. 1949, 1, 9–13.
[CrossRef]
11. Johnson, C.E., Jr. Prediction of oil recovery by waterflood—A simplified graphical treatment of the
Dykstra-Parsons method. J. Pet. Technol. 1956, 8. [CrossRef]
12. Aronofsky, J.S. Mobility ratio—Its influence on flood patterns during water encroachment. J. Pet. Technol.
1952, 4, 15–24. [CrossRef]
13. Aronofsky, J.; Ramey, H.J., Jr. Mobility ratio—Its influence on injection or production histories in five-spot
water flood. J. Pet. Technol. 1956, 8, 205–210. [CrossRef]
14. Dyes, A.; Caudle, B.; Erickson, R. Oil production after breakthrough as influenced by mobility ratio.
J. Pet. Technol. 1954, 6, 27–32. [CrossRef]
15. Caudle, B.H.; Witte, M.D. Production potential changes during sweep-out in a five-spot system. J. Pet. Technol.
1959, 12. [CrossRef]
16. Barnes, A.L. The use of a viscous slug to improve waterflood efficiency in a reservoir partially invaded by
bottom water. J. Pet. Technol. 1962, 14. [CrossRef]
17. Pye, D.J. Improved secondary recovery by control of water mobility. J. Pet. Technol. 1964, 16, 911–916.
[CrossRef]
18. Sandiford, B.B. Laboratory and field studies of water floods using polymer solutions to increase oil recoveries.
J. Pet. Technol. 1964, 16, 917–922. [CrossRef]
19. Chaudhuri, A.; Vishnudas, R. A systematic numerical modeling study of various polymer injection conditions
on immiscible and miscible viscous fingering and oil recovery in a five-spot setup. Fuel 2018, 232, 431–443.
[CrossRef]
Energies 2018, 11, 2751 16 of 19

20. Lake, L.W.; Johns, R.; Rossen, B.; Pope, G. Fundamentals of enhanced oil recovery. In Enhanced Oil Recovery;
Society of Petroleum Engineers: Richardson, TX, USA, 2014.
21. Kumar, M.; Hoang, V.T.; Satik, C.; Rojas, D.H. High-Mobility-Ratio waterflood performance prediction:
Challenges and new insights. SPE Reserv. Eval. Eng. 2008, 11. [CrossRef]
22. Amirian, E.; Dejam, M.; Chen, Z. Performance forecasting for polymer flooding in heavy oil reservoirs. Fuel
2018, 216, 83–100. [CrossRef]
23. Salehi, M.M.; Hekmatzadeh, A.; Sajjadian, V.A.; Masoumi, M. Simulation of polymer flooding in one of the
Iranian oil fields. Egypt. J. Pet. 2017, 26, 325–330. [CrossRef]
24. Morelato, P.; Rodrigues, L.; Romero, O.J. Effect of polymer injection on the mobility ratio and oil recovery.
In Proceedings of the SPE Heavy Oil Conference and Exhibition, Kuwait City, Kuwait, 12–14 December 2011.
25. Akbari, S.; Mahmood, S.M.; Tan, I.M.; Ghaedi, H.; Ling, L. Assessment of polyacrylamide based co-polymers
enhanced by functional group modifications with regards to salinity and hardness. Polymers 2017, 9, 647.
[CrossRef]
26. Akbari, S.; Mahmood, S.M.; Tan, I.M.; Ling, O.L.; Ghaedi, H. Effect of aging, antioxidant, and mono- and
divalent ions at high temperature on the rheology of new polyacrylamide-based co-polymers. Polymers 2017,
9, 480. [CrossRef]
27. Akbari, S.; Mahmood, S.M.; Tan, I.M.; Bharadwaj, A.M.; Hematpour, H. Experimental investigation of the
effect of different process variables on the viscosity of sulfonated polyacrylamide copolymers. J. Pet. Explor.
Prod. Technol. 2017, 7, 87–101. [CrossRef]
28. Ogunberu, A.L.; Asghari, K. Water Permeability reduction under flow-induced polymer adsorption.
In Proceedings of the SPE Annual Technical Conference and Exhibition, Houston, TX, USA, 26–29 September 2004.
29. Barreau, P.; Bertin, H.; Lasseux, D.; Glénat, P.; Zaitoun, A. Water control in producing wells: Influence of an
adsorbed-polymer layer on relative permeabilities and capillary pressure. SPE Reserv. Eval. Eng. 1997, 12.
[CrossRef]
30. Chauveteau, G.; Denys, K.; Zaitoun, A. New insight on polymer adsorption under high flow rates.
In Proceedings of the SPE/DOE Improved Oil Recovery Symposium, Tulsa, OK, USA, 13–17 April 2002.
31. Chang, H.L. Polymer flooding technology yesterday, today, and tomorrow. J. Pet. Technol. 1978, 30. [CrossRef]
32. Wang, D.; Cheng, J.; Yang, Q.; Wenchao, G.; Qun, L.; Chen, F. Viscous-Elastic polymer can increase microscale
displacement efficiency in cores. In Proceedings of the SPE annual technical conference and exhibition,
Dallas, TX, USA, 1–4 October 2000.
33. Wang, D.; Cheng, J.; Xia, H.; Li, Q.; Shi, J. Viscous-Elastic fluids can mobilize oil remaining after water-flood
by force parallel to the oil-water interface. In Proceedings of the SPE Asia Pacific Improved Oil Recovery
Conference, Kuala Lumpur, Malaysia, 6–9 October 2001.
34. Needham, R.B.; Doe, P.H. Polymer flooding review. J. Pet. Technol. 1987, 39, 1503–1507. [CrossRef]
35. Dake, L. Fundamentals of Petroleum Engineering; Elsivier Science B.V.: Amsterdam, The Netherlands, 1978.
36. Willhite, G.P. Waterflooding; Society of Petroleum Engineers: Richardson, TX, USA, 1986.
37. Wang, Y.; Kovscek, A.R.; Brigham, W.E. Effect of mobility ratio on pattern behavior of a homogeneous porous
medium. In Situ 1999, 23, 1–20.
38. Jewett, R.L.; Schurz, G.F. Polymer flooding—A current appraisal. J. Pet. Technol. 1970, 22. [CrossRef]
39. He, J. An Innovative Closed Fracture Acidizing Technique for Deep Carbonate Reservoirs Using GLDA.
Ph.D. Thesis, Texas A&M University, College Station, TX, USA, 2015.
40. Maxey, J.E.; Van Zanten, R. Novel method to characterize formation damage caused by polymers.
In Proceedings of the SPE International Symposium and Exhibition on Formation Damage Control, Lafayette,
LA, USA, 15–17 February 2012.
41. He, J.; Arensman, D.; Nasr-El-Din, H. Effectiveness of calcium sulfate scale inhibitors in spent hydrochloric
acid/seawater system. J. Pet. Environ. Biotechnol. 2013, 4. [CrossRef]
42. Omar, A.E. Effect of polymer adsorption on mobility ratio. In Proceedings of the Middle East Oil Technical
Conference and Exhibition, Manama, Bahrain, 14–17 March 1983.
43. Sheng, J.J.; Leonhardt, B.; Azri, N. Status of polymer-flooding technology. J. Can. Pet. Technol. 2015, 54,
116–126. [CrossRef]
44. Banerjee, S.; Abdulsattar, Z.R.; Agim, K.; Lane, R.H.; Hascakir, B. Mechanism of polymer adsorption on shale
surfaces: Effect of polymer type and presence of monovalent and divalent salts. Petroleum 2017, 3, 384–390.
[CrossRef]
Energies 2018, 11, 2751 17 of 19

45. Cheraghian, G.; Nezhad, S.S.K.; Kamari, M.; Hemmati, M.; Masihi, M.; Bazgir, S. Adsorption polymer on
reservoir rock and role of the nanoparticles, clay and SiO2 . Int. Nano Lett. 2014, 4, 114. [CrossRef]
46. AlSofi, A.M.; Wang, J.; Leng, Z.; Abbad, M.; Kaidar, Z.F. Assessment of polymer interactions with carbonate
rocks and implications for EOR applications. In Proceedings of the SPE Kingdom of Saudi Arabia Annual
Technical Symposium and Exhibition, Dammam, Saudi Arabia, 24–27 April 2017.
47. Sorbie, K.S. Polymer-Improved Oil Recovery; Springer Science & Business Media: Berlin/Heidelberg, Germany, 2013.
48. Manichand, R.N.; Seright, R. Field vs. laboratory polymer-retention values for a polymer flood in the
tambaredjo field. SPE Reserv. Eval. Eng. 2014, 17. [CrossRef]
49. Zhao, J.; Fan, H.; You, Q.; Jia, Y. Distribution and presence of polymers in porous media. Energies 2017, 10,
2118. [CrossRef]
50. Lee, K.S. Simulation of polymer flood processes in heterogeneous layered systems with crossflow and
adsorption. J. Jpn. Pet. Inst. 2009, 52, 190–197. [CrossRef]
51. Zhang, G.; Seright, R. Effect of concentration on HPAM retention in porous media. SPE J. 2014, 19, 373–380.
[CrossRef]
52. Green, D.W.; Willhite, G.P. Enhanced Oil Recovery; Society of Petroleum Engineers: Richardson, TX, USA, 1998.
53. Choi, B.; Yu, K.; Lee, K.S. Modelling of polymer retention during low concentrated HPAM polymer flooding
in the heterogeneous reservoirs. Int. J. Oil Gas Coal Technol. 2016, 11, 249–263. [CrossRef]
54. Theng, B.K.G. Chapter 2: Polymer Behaviour at Clay and Solid Surfaces. In Developments in Soil Science,
Formation and Properties of Clay-Polymer Complexes; Elsivier Science B.V.: Amsterdam, The Netherlands, 1979.
55. Kolodziej, E.J. Transport mechanisms of Xanthan biopolymer solutions in porous media. In Proceedings of
the SPE Annual Technical Conference and Exhibition, Houston, TX, USA, 2–5 October 1988.
56. Dang, T.Q.C.; Chen, Z.; Nguyen, T.B.N.; Bae, W. Investigation of isotherm polymer adsorption in porous
media. Pet. Sci. Technol. 2014, 32, 1626–1640. [CrossRef]
57. Lee, J.-J.; Fuller, G.G. Adsorption and desorption of flexible polymer chains in flowing systems. J. Colloid
Interface Sci. 1985, 103, 569–577. [CrossRef]
58. Gogarty, W.B. Mobility control with polymer solutions. Soc. Pet. Eng. J. 1967, 7, 161–173. [CrossRef]
59. Smith, F.W. The behavior of partially hydrolyzed polyacrylamide solutions in porous media. J. Pet. Technol.
1970, 22, 148–156. [CrossRef]
60. Szabo, M.T. Some aspects of polymer retention in porous media using a C14-tagged hydrolyzed
polyacrylamide. Soc. Pet. Eng. J. 1975, 15, 323–337. [CrossRef]
61. Dominguez, J.G.; Willhite, G.P. Retention and flow characteristics of polymer solutions in porous media.
Soc. Pet. Eng. J. 1977, 17, 111–121. [CrossRef]
62. Zitha, P.L.J.; Botermans, C.W. Bridging-Adsorption of flexible polymers in low permeability porous media.
SPE Prod. Facil. 1998, 13. [CrossRef]
63. Huh, C.; Lange, E.A.; Cannella, W.J. Polymer retention in porous media. In Proceedings of the SPE/DOE
Enhanced Oil Recovery Symposium, Tulsa, OK, USA, 22–25 April 1990.
64. Szabo, M.T. An evaluation of water-soluble polymers for secondary oil recovery—Parts 1 and 2. J. Pet. Technol.
1979, 31, 553–570. [CrossRef]
65. Cohen, Y.; Christ, F.R. Polymer retention and adsorption in the flow of polymer solutions through porous
media. SPE Reserv. Eng. 1986, 1, 113–118. [CrossRef]
66. Chauveteau, G.; Kohler, N. Polymer flooding: The essential elements for laboratory evaluation.
In Proceedings of the SPE Improved Oil Recovery Symposium, Tulsa, OK, USA, 22–24 April 1974.
67. Marker, J.M. Dependence of polymer retention on flow rate. J. Pet. Technol. 1973, 25, 1307–1308. [CrossRef]
68. Shah, B.N.; Lawrence, G.; Willhite, P.; Green, D.W. The effect of inaccessible pore volume on the flow of
polymer and solvent through porous media. In Proceedings of the SPE Annual Fall Technical Conference
and Exhibition, Houston, TX, USA, 1–3 October 1978.
69. Zampieri, M.F. Evaluation of Polymer Flooding through Small Scale Simulation Models for Enhanced Oil
Recovery. Ph.D. Thesis, State University of Campinas, Campinas, Brazil, 2017. (In Portuguese)
70. Dawson, R.; Lantz, R.B. Inaccessible pore volume in polymer flooding. Soc. Pet. Eng. J. 1972, 12, 448–452.
[CrossRef]
71. Vela, S.; Peaceman, D.W.; Sandvik, E.I. Evaluation of polymer flooding in a layered reservoir with crossflow,
retention, and degradation. Soc. Pet. Eng. J. 1976, 16, 82–96. [CrossRef]
Energies 2018, 11, 2751 18 of 19

72. Dabbous, M.K. Displacement of polymers in waterflooded porous media and its effects on a subsequent
micellar flood. Soc. Pet. Eng. J. 1977, 17, 358–368. [CrossRef]
73. Pancharoen, M.; Thiele, M.R.; Kovscek, A.R. Inaccessible pore volume of associative polymer floods.
In Proceedings of the SPE Improved Oil Recovery Symposium, Tulsa, OK, USA, 24–28 April 2010.
74. Osterloh, W.T.; Law, E.J. Polymer transport and rheological properties for polymer flooding in the north sea.
In Proceedings of the SPE/DOE Improved Oil Recovery Symposium, Tulsa, OK, USA, 19–22 April 1998.
75. Hughes, D.S.; Teeuw, D.; Cottrell, C.W.; Tollas, J.M. Appraisal of the use of polymer injection to suppress
aquifer influx and to improve volumetric sweep in a viscous oil reservoir. SPE Reserv. Eng. 1990, 5, 33–40.
[CrossRef]
76. Gupta, S.P. Micellar flooding the propagation of the polymer mobility buffer bank. Soc. Pet. Eng. J. 1978, 18,
5–12. [CrossRef]
77. Fletcher, A.J.P.; Flew, S.R.G.; Lamb, S.P.; Lund, T.; Bjornestad, E.; Stavland, A.; Gjovikli, N.B. Measurements
of polysaccharide polymer properties in porous media. In Proceedings of the SPE International Symposium
on Oilfield Chemistry, Anaheim, CA, USA, 20–22 February 1991.
78. Lotsch, T.; Muller, T.; Pusch, G. The effect of inaccessible pore volume on polymer coreflood experiments.
In Proceedings of the SPE Oilfield and Geothermal Chemistry Symposium, Phoenix, AZ, USA, 9–11 March 1985.
79. Huang, Y.; Sorbie, K.S. Scleroglucan behavior in flow through porous media: Comparison of adsorption and
in-situ rheology with xanthan. In Proceedings of the SPE International Symposium on Oilfield Chemistry,
New Orleans, LA, USA, 2–5 March 1993.
80. Liauh, W.C.; Duda, J.L.; Klaus, E.E. An Investigation of the Inaccessible Pore Volume Phenomena. 1979.
Available online: https://www.onepetro.org/general/SPE-8751-MS (accessed on 1 September 2018).
81. Sheng, J. Modern Chemical Enhanced Oil Recovery: Theory And Practice, 1st ed.; Gulf Professional Publishing:
Houston, TX, USA, 2010.
82. Lakatos, I.; Lakatos-Szabó, J.; Tóth, J. Factors influencing polyacrylamide adsorption in porous media and
their effect on flow behavior. In Surface Phenomena in Enhanced Oil Recovery; Shah, D.O., Ed.; Springer: Boston,
MA, USA, 1981.
83. Rashidi, M.; Blokhus, A.M.; Skauge, A. Viscosity and retention of sulfonated polyacrylamide polymers at
high temperature. J. Appl. Polym. Sci. 2011, 119, 3623–3629. [CrossRef]
84. Hlady, V.; Lyklema, J.; Fleer, G.J. Effect of polydispersity on the adsorption of dextran on silver iodide.
J. Colloid Interface Sci. 1982, 87, 395–406. [CrossRef]
85. Rashidi, M.; Sandvik, S.; Blokhus, A.; Skauge, A. Static and dynamic adsorption of salt tolerant polymers.
In Proceedings of the IOR 2009-15th European Symposium on Improved Oil Recovery, Paris, France,
27–29 April 2009.
86. Gramain, P.; Myard, P. Polyacrylamides with coloured groups for trace analysis in water. Polym. Bull. 1980,
3, 627–631. [CrossRef]
87. Zheng, C.G.; Gall, B.L.; Gao, H.W.; Miller, A.E.; Bryant, R.S. Effects of polymer adsorption and flow behavior
on two-phase flow in porous. In Proceedings of the SPE/DOE Improved Oil Recovery Symposium, Tulsa,
OK, USA, 19–22 April 1998.
88. Meister, J.J.; Pledger, H., Jr.; Hogen-Esch, T.E.; Butler, G.B. Retention of polyacrylamide by berea sandstone,
baker dolomite, and sodium kaolinite during polymer flooding. In Proceedings of the SPE Oilfield and
Geothermal Chemistry Symposium, Stanford, CA, USA, 28–30 May 1980.
89. Zaitoun, A.; Kohler, N. The role of adsorption in polymer propagation through reservoir rocks. In Proceedings
of the SPE International Symposium on Oilfield Chemistry, San Antonio, TX, USA, 4–6 February 1987.
90. Broseta, D.; Medjahed, F.; Lecourtier, J.; Robin, M. Polymer adsorption/retention in porous media: Effects of
core wettability and residual oil. SPE Adv. Technol. Ser. 1995, 3. [CrossRef]
91. Chiappa, L.; Mennella, A.; Lockhart, T.P.; Burrafato, G. Polymer adsorption at the brine/rock interface:
The role of electrostatic interactions and wettability. J. Pet. Sci. Eng. 1999, 24, 113–122. [CrossRef]
92. Li, Q.; Pu, W.; Wei, B.; Jin, F.; Li, K. Static adsorption and dynamic retention of an anti-salinity polymer in
low permeability sandstone core. J. Appl. Polym. Sci. 2017, 134. [CrossRef]
93. Mezzomo, R.F.; Moczydlower, P.; Sanmartin, A.N.; Araujo, C.H.V. A new approach to the determination of
polymer concentration in reservoir rock adsorption tests. In Proceedings of the SPE/DOE Improved Oil
Recovery Symposium, Tulsa, OK, USA, 13–17 April 2002.
Energies 2018, 11, 2751 19 of 19

94. Li, K.; Jing, X.; He, S.; Wei, B. Static adsorption and retention of viscoelastic surfactant in porous media:
EOR implication. Energy Fuels 2016, 30, 9089–9096. [CrossRef]
95. Delshad, M.; Pope, G.A.; Sepehrnoori, K. A compositional simulator for modeling surfactant enhanced
aquifer remediation, 1 formulation. J. Contam. Hydrol. 1996, 23, 303–327. [CrossRef]
96. Wang, J.; Lu, H.; Luo, P. Determination of Inaccessible Pore Volume and Retention Pore Volume by the Use
of Effluent Concentration Profile Model. 2003. Available online: http://caod.oriprobe.com/articles/6373693/
Determination_of_inaccessible_pore_volume_and_retention_pore_volume_by.htm (accessed on 25 August 2018).

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).