POLYMER FLOODING

PETROLEUM ENGINEERING DEPARTMENT

Group 3 – 1st March 2021.
 ABSTRACT

When a reservoir is flooded with polymer, the mobility ratio between the displaced fluid and the displacing
fluid become favourable compared to the conventional water flooding. Natural polymers are abundant in
nature, cheap and environmentally friendly. These agricultural and forest produce contain starch and cellulose
which are known to have rigid and long polysaccharide chains that can withstand the harsh reservoir
conditions. But the design of a polymer flood or a permeability-modified process involving polymer requires
knowledge about the polymer flow mechanism and the rheological behaviour of the porous media. This paper,
therefore, reviews two new natural polymers that can be used for enhanced oil recovery applications.
Environmental application issues associated with the application of natural polymers have opened new frontier
for research and are also highlighted herein.

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 TABLE OF CONTENTS
ABSTRACT............................................................................................................................. 2
CHAPTER 1 - INTRODUCTION ........................................................................................ 4
1.0 ENHANCED OIL RECOVERY................................................................................................ 4
1.1 WHAT IS A POLYMER? ....................................................................................................... 5
1.2 THE PHYSICAL PROPERTIES OF POLYMERS INCLUDE .......................................................... 5
CHAPTER 2 - POLYMER FOR ENHANCED OIL RECOVERY .................................. 7
2.0 PRINCIPLE AND MECHANISM ............................................................................................. 7
2.1 POLYMER CHARACTERISTICS FOR EOR............................................................................. 9
2.2 CHARACTERISTICS OF A RESERVOIR ADVANTAGEOUS TO POLYMER FLOODING ............... 11
2.3 NATURAL POLYMERS ...................................................................................................... 13
2.4 RHEOLOGY IN POROUS MEDIA ......................................................................................... 14
2.5 CONVENTIONAL POLYMERS ............................................................................................ 16
CHAPTER 3 SCLEROGLUCAN – MICROBIAL POLYSACCHARIDE .................... 19
3.0 PROPERTIES OF SCLEROGLUCAN ..................................................................................... 20
3.1 SCLEROGLUCAN RHEOLOGY ........................................................................................... 20
3.2 IRVINGIA GABONENSIS (DIKANUT) ..................................................................... 22
3.3 MUSHROOM POLYSACCHARIDE ........................................................................... 23
3.4 ENVIRONMENTAL APPLICATIONS ISSUES ASSOCIATED WITH NATURAL POLYMERS .......... 24
CHAPTER 4 – CONCLUSIONS ........................................................................................ 25
REFERENCES ..................................................................................................................... 26
AUTHORS............................................................................................................................. 27

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 CHAPTER 1 - INTRODUCTION

1.0 Enhanced oil recovery

Application of Enhanced oil recovery (EOR) technology gives an additional chance to produce more oil from
the reservoir. The world continues to rely heavily on oil for primary energy. As the extraction of oil becomes
more challenging, new techniques are put in place to increase the amount of oil extracted. Polymers play major
role in the Enhanced Oil Recovery; they help extract up 5-30% of the original oil in place. Polymers help
increase the viscosity of the displacing liquid (water) to drive the displaced liquid (oil) to the production well.
A variety of polymers is used in different oil fields depending on working conditions of that field. Before the
right polymer is chosen, a careful analysis should be conducted to ensure that the polymer is effective during
an extensive period of time. The common expectation from polymer flooding is to obtain 50% ultimate
recovery with 15 to 20% incremental recovery over secondary water flooding. Both naturally derived
polymers like xanthan gum and synthetic polymers like partially hydrolysed polyacrylamide (HPAM) have
been used for this purpose. Salinity and temperature are the major issues with the synthetic polymers that lead
to polymer degradation and adsorption on the rock surface. Microbial degradation and concentration are major
issues with naturally derived polymers leading to loss of viscosity and pore throat plugging. Polymer flooding
is a very mature method with years of applications. It has been shown to be effective in recovering un-swept
oil by improving the mobility ratio. The total cost of polymer flooding is actually less than for water flooding
due to decreased water production and increased oil production. The main reason for its introduction is to
remedy the problem pose by waterflooding such as heterogeneity and high mobility ratio (M). Polymer
flooding is aimed at reducing the mobility ratio by increasing the water viscosity and reducing the formation
permeability. The beauty of using polymer to reduce mobility ratio is that they can increase the viscosity of
the injected brine by factors of between 3 and 20 at low concentration of a few hundred parts-per-million
(ppm) by weight.
During the first stage of oil production, the differential pressure between the reservoir and wellbore is
responsible for driving oil out of the production well. This process recovers only about 10% of the original oil
in place (OOIP) and is referred as primary production. With a decline in reservoir pressure, oil recovery also
decreases, leading to the implementation of secondary recovery. Secondary recovery involves the injection of
an external fluid (such as water and gas) through the injection wells for maintaining reservoir pressure and
displacing oil towards the wellbore. During this process, there is a physical sweeping of oil by water, which
produces 15–60% of the OOIP. Further, the oil industries adopt enhanced oil recovery (EOR) process to
increase oil production by improving oil flow and sweep efficiency in the reservoir (figure 1). The EOR
method comprises four methods: chemical, thermal, miscible and immiscible gas flooding, and microbial to
increase recovery of remaining oil. Chemical EOR (cEOR) is one of the promising methods of EOR in which
surfactants, polymers, and/or alkali are used. Polymer-based cEOR can improve the sweep efficiency by
lowering water to oil mobility ratio.

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1.1 What is a polymer?

A polymer is a substance or material consisting of very large molecules, or macromolecules, composed of

many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play
essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as
polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and
function. Polymers, both natural and synthetic, are created via polymerization of many small molecules,
known as monomers. Their consequently large molecular mass, relative to small molecule compounds,
produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to
form amorphous and semi crystalline structures rather than crystals.
Polymer, any of a class of natural or synthetic substances composed of very large molecules, called
macromolecules, that are multiples of simpler chemical units called monomers. Polymers make up many of
the materials in living organisms, including, for example, proteins, cellulose, and nucleic acids. Moreover,
they constitute the basis of such minerals as diamond, quartz, and feldspar and such man-made materials as
concrete, glass, paper, plastics, and rubbers. The word polymer designates an unspecified number of monomer
units. When the number of monomers is very large, the compound is sometimes called a high polymer.
Polymers are not restricted to monomers of the same chemical composition or molecular weight and structure.
Some natural polymers are composed of one kind of monomer. Most natural and synthetic polymers, however,
are made up of two or more different types of monomers; such polymers are known as copolymers. Organic
polymers play a crucial role in living things, providing basic structural materials and participating in vital life
processes. For example, the solid parts of all plants are made up of polymers. These include cellulose, lignin,
and various resins. Cellulose is a polysaccharide, a polymer that is composed of sugar molecules. Lignin
consists of a complicated three-dimensional network of polymers. Wood resins are polymers of a simple
hydrocarbon, isoprene. Another familiar isoprene polymer is rubber.

1.2 The physical properties of polymers include:

1. Strength and Flexibility: these properties depend on

• chain length - in general, the longer the chains the stronger the polymer;

• side groups - polar side groups (including those that lead to hydrogen bonding) give stronger
attraction between polymer chains, making the polymer stronger;

• branching - straight, unbranched chains can pack together more closely than highly branched chains,
giving polymers that have higher density, are more crystalline and therefore stronger;

• cross-linking - if polymer chains are linked together extensively by covalent bonds, the polymer is
harder and more difficult to melt.
2. Tensile Strength: the tensile strength measures the forces needed to snap a polymer or how much stress
the polymer will endure before permanent deformation occurs. Polymers have poor tensile strength.
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3. Melting Point: polymers are said to melt when they change state from crystalline to semi-crystalline.
4. Density: Polymers are very light in weight, that is, low density but are comparatively stiff and strong.
5. Lack of conductivity: polymers can be both thermal and electrical insulators.
6. Corrosion resistance: Polymers have good resistance to corrosion.
7. Temperature resistance: polymers have poor temperature resistance. They are considered unstable under
high temperature.
8. Viscosity:

The physical properties (such as transition temperature, viscosity, etc.) and mechanical properties (such as
strength, stiffness, and toughness) depend on the molecular weight of polymer. The lower the molecular
weight, lower the transition temperature, viscosity, and the mechanical properties. Due to increased
entanglement of chains with increased molecular weight, the polymer gets higher viscosity in molten state,
which makes the processing of polymer difficult. Currently, two different types of polymers are used:

• a synthetic polymer such as polyacrylamide and

• a biologically produced polymer (biopolymer) such as xanthan gum and cellulose.

Figure 1 - Enhanced oil recovery/ improved oil recovery definition (Journal of Petroleum Exploration and
Production Technology (2018) 8:1349–1362)

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 Figure 2 – Polymer flooding mechanism (Source: G. Zerkalov)

CHAPTER 2 - Polymer for Enhanced Oil Recovery

2.0 Principle and mechanism

Polymer is the material that plays an important role in the application of EOR technology, especially for
hydrogel polymer. The difference between the oil and aqueous phase mobilities is one of the factors
responsible for poor sweep efficiency. Compared to oil, water tends to move rapidly resulting in an irregular
front with water reaching the production well first. Higher mobility ratio results in water channelling through
the same pathway across the oil phase leaving behind regions of unswept oil. However, mobility ratio <1
favour higher oil recovery with a uniform displacement of oil. Hence, when a polymer is added to the injection
water, there is an increase in viscosity of the water phase, which decreases its mobility and further improves
the overall sweep efficiency of polymer flood. In traditional water flood systems, water is pumped through
injector wells to push oil towards production wells. In many reservoirs, the water flood narrows its course
between the injector wells and the producers. This results in ‘coning’ or ‘fingering’ patterns whereby
potentially large volumes of oil-saturated rock are bypassed by the water flood and the oil therein is not
recovered.
To improve water flood sweep efficiency, an operator can increase the viscosity of injected water with
polymers. This reduces the tendency of water to bypass or finger through oil, thereby sweeping more oil
toward production wells to significantly improve recovery. Two most commonly used types of polymers have
been mentioned in page. A typical polymer flood project involves mixing and injecting polymer over an

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extended period of time until about 1/3-1/2 of the reservoir pore volume has been injected. This polymer
“slug” is then followed by continued long-term water flooding to drive the polymer slug and the oil bank in
front of it toward the production wells (figure2). Polymer is injected continuously over a period of years to
reach the desired pore volume. When water is injected into a reservoir, it seeks the path of least resistance
(usually the layers of highest permeability) to the lower pressure region of the offset producing wells. If the
oil in place has a higher viscosity than the injected water, the water will finger through this oil and result in a
low sweep efficiency, or bypassed oil. One of the routine screening parameters used for a preliminary analysis
of a reservoir is the mobility ratio that represents effects of relative permeability and viscosity of water and
oil on fractional flow. Addition of polymer into reservoir increases the viscosity of water and reduces relative
permeability of water in the reservoir then increases oil recovery due to increase of fractional flow. If the
mobility ratio is one or slightly less, the displacement of the oil by the water will be efficient and pistons like.

By contrast, if the mobility ratio is greater than one, the more mobile water will finger through the oil and
leave behind regions of unswept oil. Based on the principle of mobility ratio, water-soluble polymer can be
used to increase the viscosity of the water phase while reducing the permeability of water to the porous rock
and thereby creating a more efficient and uniform front to displace oil from the reservoir. The effect can be
obtained at various reservoir conditions with mobile oil saturation is greater than zero. However, significant
effect is only obtained at reservoir with a great value of ko which means a high mobile oil saturation,
meanwhile from the oil characteristic aspect, the value will be significant at light oil reservoir, so its viscosity
is low, and its permeability is great. Ideal properties for mobility control agents can be summarized as follow
low cost or high cost effectiveness, allow high injectivity, effective when mixed with reservoir brines (up to
20% total dissolved solids), resistant to mechanical degradation (up to 1000 m3/m2/d flux when entering
porous rock), 5 to 10 years stability at reservoir temperature (up to 200 C), resistant to microbial degradation,
low retention (e.g., adsorption) in porous rock, effective in presence of oil or gas, and not sensitive to O2,
H2S, pH or oilfield chemicals.

The fingering effect in figure 3 is highly undesirable as it promotes itself more and more and sharply reduces
the production as soon as the finger reaches the production well site. In an endeavor to decrease the mobility
ratio below one, the approach of using viscous fluid (polymer) to increase the viscosity of displacing fluid has
been developed. This helps to promote the displacing fluid in a stable, uniform manner and decrease the chance
of fingering effect thus increasing the efficiency of oil recovery.

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 Figure 3 – Viscous fingering (above) & favourable mobility ratio (below)

2.1 Polymer characteristics for EOR

For different polymer solutions, properties are affected by a number of elements, whether it is the viscosity of
the solution, the influence of shear stress, temperature stability and sensitivity towards a range of factors, pH,
metal ions, O2, and most important being salinity. The screening criteria is based on polymer and reservoir
characteristics that are explained below in details.

Filtration properties
During preparation of polymer solutions, ineffective hydration of polymer and debris in the solution can affect
injectivity, resulting in near wellbore plugging. While dissolving polymers, rapid wetting of the exterior of
the particles could cause swelling of polymers and creates a barrier to inner particles. Wellbore plugging
problems may be caused by crosslinking of polymers (catalysed by impurities in the polymer or in the makeup
water). This can be avoided by using good quality water and filtration of the polymer solution before injection.

Suitable viscosity
For oil field purposes, one of the most imperative properties of a polymer solution is its ability to generate
viscosity at a minimum concentration. In addition, it is known that the uniform movement of a displacement
fluid in a uniform permeable reservoir can be discontinued if the displacement fluid is less viscous compared
to that of the crude in situ. This is called adverse mobility effect. Also, the phenomenon where the less viscous
displacing fluid penetrates the oil front is referred as the viscous fingering. Both of these phenomena lead to
poor sweep efficiency which could be addressed by a suitable polymer use.

Salinity and calcium tolerance

During polymer flooding, the injected solution must maintain its viscosity for a longer duration till the transit
of oil towards the producer well. However, there is a loss in viscosity in the presence of salt with an increasing

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percent of hydrolysis. Attraction and repulsion of molecular charges are responsible for the resultant solution
viscosity. During the oil displacement process, oil and brine form the moving front in contact with the leading
edge of polymer slug as shown in Fig. An exchange of polyvalent ions takes place at this point of contact, but
the presence of exchangeable divalent metal cations like calcium and magnesium in the rock constituents can
affect the displacement process substantially. Besides, anionic polymer or surfactant gets adsorbed to rock
surfaces leading to losing mobility control during displacement. Also, an increase in mobility of buffer
solution of high concentrated reservoir brine and divalent cations (Ca+2) with a loss in viscosity can lead to
fingering and other displacement inefficiencies

Injectivity, retention, and polymer adsorption

The viscosity of the polymer solution increases with the increase in molecular weight leading to higher
production of oil. Though if the molecular weight is too high, it can cause plugging of the pore throat lowering
the flow through it. Low injectivity can be another big issue in the path of EOR, especially for shallow
reservoirs with low water permeability, which when flooded with a polymer solution can further reduce the
permeability, making the injectivity very low. This, in the end, makes it harder to maintain pressure in low-
permeability shallow reservoirs. Compared to oil, water moves rapidly in the reservoir, resulting in water
reaching the produced well first. Polymer flooding increases overall sweep efficiency of the water flood by
decreasing its mobility and increasing the viscosity of water, thereby preventing the formation of an irregular
front. The reduction in permeability to water with the flow of polymer is a function of polymer retention and
can prove deleterious to oil recovery (permeability of polymer solution decreases when polymer retention
occurs on rock surfaces). The presence of an adsorbed polymer layer, almost impenetrable to water, reduces
the crossflow section in pore throats. Propagation of polymers is thus expected to be more difficult than in
nonadsorbing conditions, especially as pore size becomes closer to macromolecular length. In this case, the
polymer generally does not propagate at the same rate as brine, if injection is performed at low shear rates.
Polymer adsorption on pore wall has three major effects:
§ The steric effect to adsorbed layer of polymer significant to pore size, limiting further penetration of
polymer containing brine
§ The lubrication effect that favours flow of nonwetting fluids such as oil
§ Enhancing wettability of rock surface and improving oil mobility

Microbial degradation
While using the biopolymers for EOR, caution must be taken that it should not degrade before downhole
injection. This can be prevented by preparation of biopolymer solution precisely before injecting. On the other
hand, utilization of biopolymer by resident bacteria inside the reservoir can lead to bio plugging and increased
oil recovery. This is also an advantage over synthetic polymers as degradation of synthetic polymer leads to

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formation damage whereas degraded biopolymer is the source of microbial growth leading to bio plugging.
Bio plugging can also be enhanced by giving another slug of multivalent cations that can bind the residual
biopolymer molecules together for preferential partial plugging.

Oxygen, hydrogen sulphide, and pH sensitivity

Naturally occurring agents such as oxygen can react with small amounts of dissolved iron, generating oxygen-
centred free radicals (example, °OH), leading to degradation of the long-chain polymers into simpler units.
Mostly, the biogenic sulphide production takes place in the oil reservoirs going through secondary recovery.
This sulphide production (also known as reservoir souring) is due to the reduction of sulphate to sulphide by
sulphate-reducing bacteria (SRB) in oil reservoirs. Souring is very deleterious to oil recovery in terms of
reduced oil quality, harmful to workers, leaks in the pipelines, and effect viscoelasticity of polymer solution.
pH has an added effect on the adsorption of polymer on rock surfaces. This depends on the nature of the
solution, as with an acidic pH, the sand surface becomes more positive and electrostatically attracts negatively
charge groups of an anionic polymer. However, the adsorption decreases for an alkaline solution repelling the
sand surfaces with same charge.

2.2 Characteristics of a reservoir advantageous to polymer flooding

Lithology
The existence of different minerals could affect the efficiency of the polymer being implemented in the
reservoirs. Clays are known to swell when contacted with water; thus, it can affect polymer mobility during
injection. Calcium and other minerals increase polymer adsorption, thereby reducing the effectiveness of
flooding. Hence, for the success of oil recovery, a thorough understanding of reservoir formation and
architecture is needed.

Reservoir salinity
The viscosity of polyacrylamide-based polymers is quite sensitive to divalent cations, with a majority being
affected with increasing salinity of reservoir brine. When a polymer solution comes in contact with these salts,
there is an increase in mobility of buffer solution with a decrease in polymer viscosity. This can lead to
fingering and other displacement inefficiencies. As mentioned earlier, HPAM is also more sensitive to salinity
compared to other polymers like xanthan gum. A polymer solution shall thus be designed to be compatible
with reservoir brine.

Permeability
Higher viscosity and reduced mobility of polymer solution lower its injectivity compared to solvent brine.
This can be a problem in low-permeability reservoir because slow injection rate would increase the life of the
polymer flood without substantial economic gain, high shear rate around injection wellbore could lead to

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polymer degradation, and low rate of polymer injection could result in reduced pressure conditions. This is
generally a problem in shallow reservoir due to reduced pressure conditions. A polymer flood can have a
larger effect for EOR in a reservoir with a higher oil viscosity (up to 126 cp) compared to a reservoir with oil
viscosity nearer to that of water. The oil water mobility ratio is an important parameter controlling the flow
of oil in front of polymer slug and deciding the concentration of polymer to be used. Excess oil viscosity
requires a higher amount of polymer to improve mobility control. Besides, the mobility ratio can be much
more improved if the initial ratio between oil and water is high.

2.4 Polymer flow behaviour

The major reason for adding polymer to displacing fluids is to make the fluid viscous, but there may be some
reaction between the polymer and the reservoir which cause some of the polymer to be retained by the
reservoir. This will form a barrier for any other polymer to be injected into the reservoir; the fluid forming a
barrier will have a lower viscosity than any other injected polymer which will make the polymer
to be less effective. Also, this may lead to reduction in permeability of the rock, which will in turn affect
recovery. With view of the highlighted facts, the success of a polymer flood depends on how you can minimise
the amount of polymer retained.

Polymer adsorption
Polymer adsorption can simply be defined as the interaction between the solid surface (soft rock) and the
polymer molecules. It allows the polymer to be physical adsorbed to the surface of the solid, hydrogen bond
and van der Waal’s forces acting on the molecules and solid surface. The polymer usually adsorbs on the
surface of the solid, and if the surface area of the solid is large, the higher the level of adsorption.

Mechanical entrapment
Mechanical entrapment and hydrodynamic retention are similar, and both only occur in porous media. They
are not involved in free powder/bulk solution experiments. Mechanical entrapment occurs when large
molecules of polymer are trapped in narrow flow channels. The concentration at the end of the core would fail
to reach the desired input concentration or will do so when a lot of polymer pore volume passes through which
could lead to blockage and allowing polymer to flow through other channels that are bigger. Also, the
distribution of the polymer will not be uniform allowing large polymers at the core close to the inlet and
decreasing in that order. Finally, there are several entrapment areas, the media will be completely blocked,
and the permeability will fall to zero.

Synthetic Polymers

Synthetic polymers are those materials that are a result of a process that takes place in a laboratory. As the
name suggests, synthetic is something that is not natural. So, we can say that it is made in laboratories and
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factories by human beings. The persons who make this material can be scientists or engineers. The most
common examples of synthetic polymers are PVC, acrylic, Teflon, and polythene. Synthetic polymers are
polymers developed of formulated in laboratories by chemists or engineers. Synthetic polymers are human-
made polymers. They can be classified into four main categories: thermoplastics, thermosets, elastomers,
and synthetic fibers. They are commonly found in a variety of consumer products. Various main chains and
side chains are used to make different synthetic organic polymers. Synthetic polymers are derived from
petroleum oil and made by scientists and engineers. Examples of synthetic polymers include nylon,
polyethylene, polyester, Teflon, and epoxy. Synthetic polymers are produced by chemical reactions, termed
"polymerizations." Polymerizations occur in varied forms--far too many to examine here--but such reactions
consist of the repetitive chemical bonding of individual molecules, or monomers. Co-polymers can
be formed using two or more different monomers.

Synthetic polymers are sometimes referred as “plastics”, of which the well-known ones are nylon and
polyethylene. The polymers which are formed by linking monomer units, without the any change of material,
are known to as addition polymers or also called as chain-growth polymers. All these are said to be synthetic
polymers. Some synthetic polymers which we use in our everyday life include nylons used in fabrics and
textiles, Teflon used in non-stick pans, polyvinyl chloride used in pipes. The PET bottles we use are commonly
made up of synthetic polymer called as polyethylene terephthalate. The covers and plastic kits comprise
synthetic polymers such as polythene, and the tyres of vehicles are manufactured from the Buna rubbers. But
on the other side, there also arises environmental issues by the use of these synthetic polymers such as the bio
plastics and those made from petroleum as they are said to be non-biodegradable.

2.3 Natural polymers

Also called biopolymers. They possess a rigid, unique helical structure (double or triple), and charge-free
chains and as a result display a higher tolerance to temperature and salts which stands them out as having
stability in harsh condition reservoirs. They also exhibit good thickening capability. For polymers to be
successfully used, they must be assessed for important characteristics such as solubility, long-term stability,
injectivity, viscoelasticity, adsorption, rheology. Natural polymers are available in nature by the biological
process. Most of the chemical compounds that are present in biological systems are polymer compounds.
These natural polymers are primarily found in our environment, in our surroundings, and within the human
system. Now, these polymers of the natural kind have three classifications – polysaccharides, polyamides, and
polynucleotides. Polysaccharides are polymers that are made of monosaccharide particles. Common
monosaccharides are glucose, fructose, galactose, and others. Polysaccharides are also found in animals and
plant life. In plants, it is present as starch as stored carbohydrate, and in animals, it is storage carbohydrate
present as glycogen.

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Some of the polymers are a result of condensation whereas some polymers are products of addition. Polymers
obtained from condensation are known as condensation polymers and from addition, polymerization is known
as addition polymers. Besides, some of the synthetic polymers get a classification as organic and inorganic
polymers. Organic polymers are made of hydrocarbon particles whereas inorganic polymers are not made
from hydrocarbons. Starches and cellulose are the most abundant natural polymers in the world. The
advantages of selecting them as a starting raw material to produce polymers for EOR is because they are in
abundance, readily available, environmentally friendly, and biodegradable (figure 5). Also, easy to handle,
their rigid structure and long polysaccharides chains make them suitable to withstand the harsh reservoir
conditions.

2.4 Rheology in porous media

Viscosity is also one of the important parameters when discussing polymer rheology, the bulk viscosity is
measured with a viscometer, while the in-situ viscosity is measured in the porous media. It is not directly
measured, but instead it is calculated according to the Darcy equation using core flood data, the calculated
viscosity is called the apparent viscosity. In porous media, fluid rheology can be classified as Newtonian and
non-Newtonian. For Newtonian fluid, the viscosity is expressed by the relationship between the stress and
shear rate. In Newtonian fluid, the viscosity remains constant, no matter the amount of shear applied; therefore,
the relationship between the viscosity and shear stress is linear. Viscosity of non-Newtonian fluid thus not

have a constant viscosity at all shear rate, as such effective or apparent viscosity is used to describe the
viscosity of fluid at a shear rate. Therefore, non-Newtonian fluid is fluid where the proportionality between
the stress and strain is not linear. Non-Newtonian fluids can be classified into four major group: the dilatant
where the viscosity of the fluid increases when shear is applied, for example, quicksand, corn flour, and water;
the pseudoplastic (figure 4), in this case, the more shear is applied, the fluid become less viscous, for example,
ketchup, polymer, which is our area of interest; this is similar to dilatant but the difference is when shear is
applied, the viscosity increases with time, that is, it is time-dependent example: we have cream, gypsum paste;
thixotropic here where shear is applied, the viscosity decreases with time, which makes it also time-dependent
examples: paint, cosmetic, asphalt, and glue. We can, therefore, conclude that non-Newtonian fluid is either
time dependent or non-time dependent.

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 Figure 4 – The graph of stress versus strain in shear flow (Journal of Petroleum Exploration and
Production Technology (2018) 8:1349–1362)

Table 1 - Difference Between Natural and Synthetic Polymers

Natural Polymers Synthetic Polymers

Natural polymers are polymers that are Synthetic polymers are polymers that are
found naturally in our environment. produced artificially by humans in a lab.

They occur naturally Do not occur naturally.

It is produced from biological processes. It is produced from chemical processes.

Most polymers are easily degradable by Most polymers are hard to degrade by natural
biological process. process.

The main similarity between natural and synthetic polymer is that they are made up of monomers. A monomer
is a molecule that can react together with other monomer molecules to form larger polymer chain or three-
dimensional network in a process called polymerization. All polymers are made from the polymerization
process.

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2.5 Conventional polymers

Hydrogel polymers to control the mobility of injected water have been used for many years in EOR
applications. These polymers are non-Newtonian (also called pseudoplastic) fluids, because their viscosity is
a function of shear rate. They are usually used with surfactants and alkali agents for increasing the sweep
efficiency of these tertiary recovery floods. A synthetic polymer almost always means polyacrylamides. In
general, performances of a polyacrylamide will depend on its molecular weight and its degree of hydrolysis.
Partially hydrolysed polyacrylamide (HPAM) is one of the polyacrylamide group, has the shape of straight
chain polymer of acrylamide monomers which some of it has been hydrolysed. HPAM is the most often used
polymer in EOR applications especially because of its relatively low price with good viscosifying properties,
and well-known physicochemical characteristics. The implementation of HPAM is relatively easy and can
improve significantly the oil recovery rate under standard reservoir conditions. Xanthan Gum/Biopolymer.
Xanthan gum is a polysaccharide or usually called as biopolymer. It is produced by the microbial action of
Xanthomonascampestris on a substrate of carbohydrate media, with a protein supplement and an inorganic
source of nitrogen. The Bio polymer is an extracellular slime, which forms on the surface of the cells. The
fermented broth is pasteurized to kill the microbes and precipitated from the broth by alcohol, then
concentrated. Xanthan gum is well known to have excellent performance in high salinity brine. It is relatively
compatible with most surfactants and other injection fluid additives used in tertiary oil recovery formulations.

Needs of new advanced polymer

HPAM currently used as polymers for EOR has some drawbacks, especially from their sensitivity to salinity
and high temperatures. The HPAM, which is currently in use in the industries, is susceptible to high
temperature and salinity and its synthetic nature makes it harmful to the environment. The biopolymer xanthan
has the problem of degradation, and both are very expensive. With the shortfall in crude oil price and the high
cost of exploitation and drilling new wells, there is need for us to formulate new improved polymers that can
combat the problems aforementioned. Many unprofitable projects were the result of inadequate reservoir
description or problems with the polymer system being used. However, there are limitations with the existing
polymer technology such as degradation (thermal, physical, bacterial, and chemical) or polymer rheological.
HPAM as the most common used polymer recently also suffers from strict temperature and salinity limitations.
Reservoir permeability and oil viscosity are used to determine the optimum molecular weight polymer. Rock
composition and polymer adsorption level are used to determine the best anionicity (degree of hydrolysis).
New generation of polymer has to tolerate high salinity and temperature so there is no practical limit for high
salinity reservoir.

Table 2 to 4 shows basic properties, rheological behaviour, and recovery factors of some natural sources that
have been previously investigated for polymer production.

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 Table 2 - Basic properties of natural polymers

Table 3 - List of studies on natural polymer flow behaviour in porous media

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 Table 4 – Investigated oil recovery using natural polymer sources

(Journal of Petroleum Exploration and Production Technology (2018) 8:1349–1362)

Figure 5 – Natural Polysaccharide sources (wikipedia)

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 CHAPTER 3 – MICROBIAL & MUSHROOM POLYSACCHARIDE

Scleroglucan – microbial polysaccharide

This is a non-ionic triple helix polysaccharide biopolymer (Figure 6) that is naturally produced and secreted
by a fungal plant pathogen of genus Sclerotium during fermentation. Polysaccharide precipitation is done with
an organic solvent, then it is filtered, centrifuged, dried, and milled It easily dissolves in cold and hot water.
Due to its nonionic nature, acids and alkalis do not affect scleroglucan solution over a wide range of pH (2.5–
12). Ions also have no impact on solution viscosity. Scleroglucan solution is thermostable and exhibits
pseudoplastic behavior with a high yield value. Scleroglucan has a good emulsifying capability and acts as a
foam stabilizer. Due to its good rheological properties and stability over a wide range of pH values, salinities,
and temperature, the performance of scleroglucan will not drastically change with temperature, salinity and
hardness. These characteristics make scleroglucan an ideal solution for enhanced oil recovery. Post-
fermentation scleroglucan can be purified to either dried powder or liquid forms to create commercial
products. The most common commercially available grades of scleroglucan are typically employed as
viscosifying agents. The unique properties include

• High thermal stability

• High yield value and viscosity

• Anti-settling properties

• High shear stability and Controls viscosity in a wide pH range

• Non-ionic: compatible with salts and surfactants

Figure 6 - Scleroglucan repeating units (SPE-200335-MS)

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3.0 Properties of scleroglucan

It is an extracellular polysaccharide and possesses non-ionic and water-soluble capabilities. It is obtained from
species of the genus Sclerotium glucanicum and Sclerotium rolfsii. Its rigid chain and triple-helical structure
gives credence to its good temperature resistance and excellent shear resistance. They are also resistant to pH
and high mineralization because of its non-ionic property. A pH value of above 13 leads to a sharp decrease
in the apparent viscosity as the triple helical structure disintegrates when subjected to extreme conditions. An
addition of FeCl3 in water caused an increase in viscosity. In addition to its high stability, solutions of
scleroglucan display high viscosifying ability at minimal concentrations because of its rigid chain and high
molecular weight. Scleroglucan solutions also exhibit pseudoplastic behaviors with an exponential
relationship between polymer concentration and apparent viscosity. Scleroglucan solutions of 0.5 and 2.0%
viscosity remain constant between about 10 and 90℃; however, thermo-reversible gels are synthesized at
minimal temperatures, near 7℃. It was also found to be compatible with various electrolytes, although gel
formation or flocculation of solution was likely to occur at greater concentrations of electrolyte. Scleroglucan
solutions of 0.8% concentration were observed to come short in terms of displaying thixotropic behavior
except when the temperature drops to or below 10℃. It also can act as a suspending agent for very fine
particles because of its pseudoplastic behavior.

Scleroglucan is less temperature sensitive than xanthan gum because the melting temperature of the triple-
helix structure is approximately 135℃, hence denaturation fails to occur, and the helix structure is retained.
All favorable characteristics including high thermal tolerance, high shear tolerance and high salt tolerance
testify that Scleroglucan is a promising subject for EOR polymer flooding. Some of the downsides of
Scleroglucan is its poor filterability, biodegradation, and oxidation. Also, it has been noted that the solutions
of this polymer have poor injectivity, possibly because of aggregate formation in solution. It is probable that
because of this behavior, extremely high levels of scleroglucan retention have been collated in core flow
studies using this polymer and this is a property that is not appreciated. Also, the clean-up process for
producing high quality solutions of this polymer is very costly now.

3.1 Scleroglucan Rheology

Scleroglucan solution rheology at multiple salinities and temperatures of 20 °C and 70 °C is shown in Figure
2 along with an AMPS reference polymer. Note the negligible change in viscosity of scleroglucan solutions
as the salinity is increased to up to 10 % sea salt. AMPS by comparison has a substantial drop in viscosity
when salinity is increased from 0.35% to 1%. Both polymers were evaluated at the same concentrations, and
the rheology in Figure 2 indicates that at the same concentration, scleroglucan solutions offer a higher final
viscosity than that seen with the AMPS solution.

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 Figure 7 - Rheology curves of scleroglucan solutions at different polymer concentrations and different salt
concentrations (SPE-200335-MS)

The full shear curves for scleroglucan solutions at various concentrations at 70 °C are shown in Figure 7.
These data demonstrate the shear thinning behavior of scleroglucan and its near complete rheological
independence from solution salinity (Figure 7).

Scleroglucan Thermal Stability

Thermal stability is critical for successful polymer flooding at high temperatures. The figures below show
stable viscosity at 105°C with synthetic sea salt under anaerobic conditions (left graph of Figure 8).
Additionally, initial data indicates no loss in viscosity through 90 days at 120°C (right graph of Figure 8).

Figure 8 - Scleroglucan rheology after anaerobic thermal exposure in synthetic sea salt. The graph on the
leftindicates no loss in viscosity for 2 years at 105°C. The graph on the right shows 90 days of stable
viscosity at 120°C (SPE-200335-MS)

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Hydrogen Sulphide Compatibility
Reservoir souring is a common issue in the EOR industry. There are known issues with existing synthetic
polymers being degraded in the presence of H2S and oxygen. Figure 9 show more extreme conditions for a
longer duration.

Figure 9 - Rheology curves of a 1000 ppm scleroglucan solution exposed to 2000 ppm H2S
(SPE-200335-MS)

3.2 IRVINGIA GABONENSIS (DIKANUT)

Dikanut seed is obtained from the fleshy fruit of Irvingia gabonensis. It is locally known in Yoruba land (South
West of Nigeria) as “Apon” and “Ogbono” in Igbo land (South East of Nigeria). In Nigeria, dikanut is
poplularly used as soup ingredient. The tree of dikanut grows well in tropical rainforests of Africa. The
plant Irvingia gabonensis contains lipids and polymer extractives that are usually extracted from the seeds
with the aid of either organic solvents or enzymes. The seed of the plant contains lipids and polymeric
constituents and are usually harvested during the dry season when ripe. The mucilage from the kernel can be
used as a binding agent, an emulsifying and suspending agent. The pseudoplastic behaviour of dikanut in
solutions at high temperature confers on it the preservative and stabilizing properties. Irvingia gabonensis is a
good displacing agent owing to its viscosity which decreases the mobility of the displacing fluid. To achieve
better oil recovery, the best sequence to use is waterflooding, followed by nanofluids flooding and finally,
polymer flooding.

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3.3 MUSHROOM POLYSACCHARIDE

The figure below clearly shows that by raising the polymer concentration it increases the viscosity. The
polymer was unstable at lower concentrations due to low viscosity. The polymer started to show stability
where the viscosity reading is high at approximately and kept increasing with increase in the polymer
concentration. Like other polysaccharides, the viscosity of this extracted biopolymer increases with increasing
polymer concentration (Figure 10a). As a polysaccharide, this biopolymer can behave as a non-Newtonian
and pseudoplastic fluid, exhibiting shear thinning behavior like other polysaccharide biopolymers such as
Irvingia gabonensis. From the previous study, a higher concentration of polymer, which could provide higher
viscosity is required to recover more oil from the reservoir, as the mobility ratio between the displacing fluid
to the displaced fluid is more favorable, resulting in improvement of sweep efficiency. Moreover, a high
concentration of polymer can withstand high temperatures and salinity reservoir environments.

Temperature Fig. 10(b) shows the results of the temperature effect on the viscosity of extracted biopolymer at
1500 and 3000 ppm. Polymer at 1500 ppm concentration degraded earlier than that at 3000 ppm concentration.
In addition, the 3000 ppm polymer can withstand higher temperature up to 80 °C before it was fully degraded,
compared to 1500 ppm polymer, which was completely degraded at 60 °C. Thus, this extracted biopolymer is
most applicable at low temperature like xanthan biopolymers, which are mostly limited to applications where
the temperature is lower than 60 °C. However, the polymer is likely unstable and immature to react at low
temperature, while at high reservoir temperature, the polymer loses its viscosity and degrades. This situation
shows that very high polymer concentration is required at high-temperature reservoir conditions to minimize
the loss of its viscosity efficiency.

The addition of salt affects the viscosity of the polymer solution. When the salinity is high, the polymer
performance decreases as it losses its viscosity. Most of the reservoir is in high salinity condition. The viscosity
of the biopolymer was not much affected by the change in salinity and divalent ions (figure 10(c) & 10(d))
compared with a synthetic polymer. However, the presence of divalent ions (Ca2+ and Mg2+) have further
reduced the polymer viscosity compared to monovalent ion (Na+), while Ca2+ provided a more significant
reduction effect on polymer viscosity than the Mg2+. The oil recovery tests in figure 11 showed that polymers
at a higher concentration of 3000 ppm have recovered more oil with the incremental recovery of 25.8% after
waterflooding, while 1500 ppm polymer yielded lower oil recovery with incremental 22.2% of OOIP. The oil
recovery from waterflooding was approximately 25.4 and 24.2% of the OOIP, respectively. Therefore,
mushroom polysaccharide is an environmentally friendly biopolymer, which is a potential for enhanced oil
recovery (EOR) application, but it will lose its viscosity performance at certain reservoir conditions.

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 Figure 10 - The polymer viscosity at various (a) polymer concentration (ppm), (b) temperature (°C), (c)
brine concentration (ppm), (d) divalent ion concentration (ppm)
(Indones. J. Chem., 2020, 20 (6), 1382 – 1391)

Figure 11 - Oil recovery from waterflooding and co-injection of polymer

(Indones. J. Chem., 2020, 20 (6), 1382 – 1391)

3.4 Environmental applications issues associated with natural polymers

The environmental application problems associated with natural polymers are few compared to the synthetic
polymers. Industrial waste represents the main source of environmental pollution. Processing of natural
polymers especially starch has gone beyond the traditional methods and requires enough water and yet often
sited in areas of water scarcity.
Wastewater
The water produced from starch derivatives are directed into pits for conversion; this may lead to leaching and
contaminate groundwater, while overflow may affect surface water. In most cases, it is returned into land or

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shallow streams. The environmental impact may be as a result of addition of substances, heat or micro-
organism to the water, the addition of microorganism can affect the quality of the water, alter the aquatic
ecology, which will in turn affect plants, animal and human health.
Solid waste and chemical use
Solid waste might be in the form of peels, pulp waste, and shells. Inappropriate storage for a long period can
lead to foul smell and during the raining season; it can accumulate to form leachate to contaminate ground
water. Most cassava starch factory uses, sulphur dioxide as anti-microbial and bleaching agent. The sulphur
is released into groundwater as waste; the rest is released into the atmosphere.
Atmospheric pollution
Most of the cyanide released during processing of starch end up in wastewater and are evaporated into the
atmosphere; however, hydrogen cyanide (HCN) is released during processing and is harmful to health. Dust
from shafts in the case of aqueous beans is also a problem, and the odour from beans, fermentation of organic
matter in cassava waste.

CHAPTER 4 – Conclusions

Scleroglucan is a highly viscosifying material with rheology that is extremely insensitive to solutions of most
common reservoir salt types: NaCl, KCl, CaCl2, MgCl2, Na2SO4, and FeCl3. This tends to make scleroglucan
EOR solutions largely immune to high hardness, variable incoming water source, and ion heterogeneity in
potential applications. These traits coupled with scleroglucan's excellent thermal stability make it an excellent
choice for harsh reservoir EOR. This study therefore indicates that scleroglucan and mushroom polysaccharide
could be an excellent EOR candidate for challenging high temp, high salinity, high hardness, and sour oil
reservoirs. There is a big hope that polymer can play an important role in increasing production of oil since
applications of polymer flooding in the enhanced oil recovery (EOR) field has shown some successes to
recover more than 20% additional oil from OOIP.

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AUTHORS

• ADETOLA JOSEPH OPEYEMI 16CE021699

• IYAMAH OSEREMEN EDDIE 16CN021092
• OFIME SMITH RALPH 16CN021110
• CHUKWUKA SOMTO VICTORY 16CN021072
• TORI USMAN SALEH 16CN021125
• AKA-OKOYE AMARACHI JOHANNA 16CN021060
• ADEWOYIN OLUWADARA OMOTOOKE 16CN021055
• AJAGUNNA SAMUEL 16CN021058
• AJAYI ANUOLUWAPO FRANCISCA 16CN021059
• PUPRE DIWENI PRINCESS 16CN021119
• AKINTAN OLUWATOSIN BLESSING 16CN021065
• EMMANUEL DEBORAH ONUAWUCHI 15CN03245
• SEBASTIAN UCHECHI ESTHER 16CN021121
• OLUYORI OLUWATOMIPE 15CN03293
• ADEKANOLA EMMANUEL OLALEKAN 16CN021052

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