SPE-178305-MS

Performance of Foriegn and Local Agents for Enhanced Oil Recovery of

Nigerian Crude
Naomi A. Ogolo, Shadrach O. Ogiriki, Victor I. D. Onyiri, Therisa C. Nwosu, and Mike O. Onyekonwu, Institute of
Petroleum Studies and Department of Petroleum and Gas Engineering, University of Port Harcourt, Rivers State,
Nigeria

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the Nigeria Annual International Conference and Exhibition held in Lagos, Nigeria, 4 – 6 August 2015.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Nigeria is gradually advancing into the secondary stage of oil recovery, necessitating preparation for
tertiary oil recovery especially enhanced oil recovery (EOR). Considering the high cost of EOR agents,
it is imperative to investigate the performance of available local EOR agents against foreign agents when
these agents (such as surfactants and polymers) are used in combination. Oil displacement experiments
were thus conducted using foreign and local surfactant-polymer (SP) and alkaline-polymer (AP) agents on
Nigerian crude and their results were compared. The experiments entailed using different percentage
ratios of surfactants to polymers and alkaline to polymer. Four kinds of Alkaline were also used to
displace residual oil from sand to find out what type of alkaline displaces oil better.
The displacement efficiencies obtained from experimental results showed that the foreign EOR agents
performed better than the local EOR agents. For the SP agents, the foreign SP displaced above 90% of
both light and medium crude at about 45/55 percentage and 0/100 percentage respectively. The local SP
displaced a maximum of about 35% of the light crude and 75% of medium crude at an SP ratio of about
20/80 for both cases. The use of Alkaline-Polymer results showed that the foreign agents performed better
than the local agents. The maximum displacement efficiency of the foreign AP was 78.13% at a ratio of
40/60 while the maximum displacement efficiency of the local AP was 64% at a ratio of 60/40. The
displacement of residual oil experiments performed using four kinds of alkaline showed that potassium
hydroxide (KOH) enhances recovery better than NaOH, Na2CO3 and Palm bunch ash (a local source of
alkaline). It was also observed that oil displacement efficiency increased as pH value of the alkaline
increased.

Introduction
Nigeria is gradually advancing into secondary oil recovery and the stage will soon be set for tertiary
recovery. Enhanced oil recovery (EOR) by introducing chemicals into oil reservoirs is a major tertiary oil
recovery technique that has been exploited. The content in some of these foreign chemicals that activate
displacement of trapped oil from reservoir pores can also be found in some local materials in the country.
Using extracts from local materials for EOR is beneficial mainly because it reduces over dependence on
2 SPE-178305-MS

foreign chemicals, reduces cost and encourages economic growth. This has necessitated research into
identification of local materials that contain extracts that can enhance oil recovery, but the performance
of these local EOR agents needs to be compared with the performance of foreign EOR agents.
Two kinds of EOR agents can be combined together (provided they are miscible) to compliment the
performance of each other aside from the usual practice of using one agent after the other. In the common
field practice, the first agents to use which is either a surfactant or an alkaline is aimed at microscopically
displacing oil from individual pores while the second agent is usually a polymer which targets macro-
scopic recovery or volumetric sweep along the contacted zone. In this work however, the two agents are
not used separately rather, they are used in combination (at varying ratios) to ascertain how effective such
combinations can be in displacing residual oil from formations. In actual field practice, such combinations
sometimes are used. It is expected that as the polymer sweeps the formation, the surfactant or alkaline
contained in it on contact with residual oil will reduce the interfacial tension between the oil and the
surrounding water that is already at a high saturation in the sand. The effect of these two mechanisms
(reduction of interfacial tension and mobility ratio) in displacing residual oil by a combination of
surfactants and polymers and alkaline and polymers is investigated in this work.
There are two primary objectives to this work. The first is to evaluate the performance of foreign EOR
agent to local EOR agent by comparison in order to ascertain if the local agents can substitute for the
foreign ones. The second objective is to identify the ideal ratio of local and foreign EOR agents that
optimally enhances oil recovery for light and medium crude obtained from the Niger Delta. Other
objectives include determining the most effective type of alkaline that can displace oil from sand pores
among the four kinds used and finding out if there is a relationship between displacement efficiency and
pH value.

Background
Surfactants, alkaline and polymers are good EOR agents. Alkalines and surfactants reduce interfacial
tension (IFT) between oil and water by forming emulsions, thereby allowing drops of oil to flow along
with water especially with reduced oil saturation and increased water saturation. Alkaline can reduce
interfacial tension just like surfactants but in addition can also change rock wettability. Polymers increase
the viscosity of the displacing fluid, thereby reducing the mobility ratio and improving sweep efficiency
to avoid viscous fingering and trapping of oil behind the flood front. There is a possibility for these agents
to perform better when they are used in combination necessity research into the ideal ratios that yield the
best results.
Alkaline
Alkaline when in contact with crude oil reacts with the acidic components of the crude to form a surfactant
hydroxide ion. The process is referred to as hydrolysis reaction. The hydrogen-bonding interaction
between the ionized and neutral acids can lead to the formation of complex materials called acid soap.
There are various possible mechanisms through which oil is displaced with the use of alkaline. These
include emulsification with entrainment, emulsification with entrapment, emulsification with coalescence,
wettability reversal, wettability gradients, oil-phase swelling, disruption of rigid films, and low interfacial
tensions (Ramakrishnan et al, 1983). Different crude oils in different reservoir rock can lead to widely
disparate behavior when they contact alkali under dissimilar environments such as temperature, salinity,
hardness concentration, and pH. However, all the researchers agree on the fact the acidic components in
the crude oil are the most important factor for alkali flooding. The alkali technique can be distinguished
from other recovery methods on the basis that the chemicals promoting oil recovery are generated in situ
by saponification. The acid number of a crude oil which is one of the most important quantities in alkaline
flooding characterizes the amount of natural soap that can be generated by the alkaline. One advantage
of alkaline over surfactants is that they are cheaper.
SPE-178305-MS 3

Jennings et al (1974) investigated the IFT of a large number of crude oil samples with NaOH solutions
of different concentration by using the pendant drop method at ambient temperature. They reported that
despite a few oil samples which changed only a little in IFT, many samples showed a very low IFT at only
one alkali concentration, while others displayed very low IFT over a broad range of alkali concentrations.
Cooke et al. (1974) also found that the addition of alkali could lower interfacial tension between oil and
water. Ramakrishnan and Wasan (1983) found that the IFT between oil and water are sensitive to both
NaOH concentration and salinity, and the minimum IFT can be obtained in the concentration range of
0.01– 0.1wt%NaOH. Qutubuddin and others (1984) also found that the ultra-low interfacial tensions were
observed with a suitable NaOH concentration which includes the high pH and electrolyte strength.
Wettability also plays an important role in oil recovery. The phenomenon that high-pH chemicals can
alter the wettability has been known for several decades (Wagner and Leach, 1959, Emery et al., 1970,
Ehrlich et al., 1977 and Olsen et al., 1990). Depending on the rock mineralogy, alkali can interact with
reservoir rock in several ways which can alter the wettability of the rock. These interactions include
surface exchange and hydrolysis, congruent and incongruent dissolution reactions and insoluble salt
formation by reaction with hardness ions in the fluid and rock surfaces (Somerton et al, 1983).
There are many alkali candidates for enhanced oil recovery. These include sodium hydroxide, sodium
orthophosphate, sodium carbonate, and sodium silicate. Cheng (1986) made a comparative evaluation of
chemical consumption during the alkaline flooding and results indicated that sodium carbonate might be
a good candidate for the alkali flooding because its buffering effect had less consumption and shorter
alkali breakthrough times than the other alkalis and it is more compatible with carbonate formations.
Cheng also found that sodium carbonate has less permeability damage compared to hydroxide and silicate.
By comparing the sodium carbonate with sodium hydroxide and sodium silicate, Burk (1987) found that
sodium carbonate is much less corrosive for sandstone. Compared to other alkalis, sodium carbonate is the
least expensive and it suppresses multivalent ion concentration which causes large surfactant consump-
tions. Sodium carbonate is shown to reduce the adsorption of anionic surfactant on calcite and dolomite
while sodium hydroxide does not have this surfactant adsorption reduction effect. Sodium carbonate also
retards the degradation of some anionic surfactant, e.g. sulfates, by increasing the pH. Zhang (1985) found
out that sodium carbonate reduces the absorption of anionic surfactants on carbornate minerals.

Surfactants
The basic function of a surfactant is reduction the interfacial tension between fluids so the oil and water
can create emulsion and flow in continuous phases, (Hirasaki, G 2008). Surfactants are usually organic
compounds that are amphiphilic, meaning they contain both hydrophobic groups (tails) and hydrophilic
groups (heads). Therefore, a surfactant molecule contains both water and oil soluble components.
Depending on the nature of the hydrophilic group, surfactants are classified into four (anionic, cationic,
zwitterionic and nonionic) groups (Rosen et al, 2012). Surfactants overcome the natural capillary forces
by lowering the crude oil-water IFT to an ultra-low level which allows oil globules (ganglia) in the
reservoir to flow through rock pores and coalesce to form a clean oil bank (Manu M. 2013).

Polymers
Two types of polymers, polyacrylamide and polysaccharides are commonly used in polymer enhanced oil
recovery (Sorbie, 1991). Polyacrylamides used in polymer EOR processes are partially Hydrolyzed
Polyacrylamides (HPAM). Thus, the HPAM is negatively charged, as is the anionic surfactants. HPAM
has been used in about 95% of the reported polymer tests (Lake, 1989). The commonly used polysac-
charide is xanthan gum, which is a bactarial polysaccharide. Compared to HPAM, xanthan gum has a
more rigid structure than HPAM and relatively nonionic. These properties make it relatively insensitive
to salinity and hardness. However, it is susceptible to bacterial degradation after it has been injected into
the field.
4 SPE-178305-MS

The use of polymers in enhanced oil recovery increases the viscosity of the displacing phase which
decreases mobility ratio. Adding polymers to waters that are used for flooding reservoirs increases the
viscosity of the water which reduces the water-to-oil mobility ratio, prevents viscous fingering into oil
banks and makes it easy to sweep the oil towards producing wells. The mobility ratio between displacing
and displaced fluids has to be as low as possible for an efficient displacement of oil to occur.

Alkaline/Polymer
In the Alkaline Polymer (AP) flooding, the alkali reacts with the acidic components in the crude oil to
form additional surfactant in-situ, thus, continuously providing ultra-low interfacial tension and freeing
the trapped oil. The polymer is used to increase the viscosity of the injection fluid, to minimize
channeling, and provide mobility control (Nedjhioui et al, 2005 and Horváth-Szabó et al, 2002).

Surfactant/Polymer
Currently, Surfactant-Polymer (SP) enhances oil recovery is considered one of the most promising
methods of EOR because it integrates the advantages of surfactant and polymer. The mechanisms of the
Surfactant-Polymer flooding are mainly IFT reduction and high sweep efficiency. The Surfactant reduces
the interfacial tension of the crude oil-water, while the polymer improves the sweep efficiency of the
flooding, thereby reducing fingering of the flooding reagents. In one study it was reported that a mixture
of 0.3 wt.% SLPS (petroleum sulfonate made from Shengli oil) and 0.1 wt.% co-surfactant had IFT of 2.95
⫻ 10⫺3 mN/m where the petroleum sulfonate alone had IFT of 4 ⫻ 10⫺2 mN/m (Zhang et al, 2004). Oil
production in the pilot area was increased about 3 times from 34 to 95 tons/day. And the water cut was
decreased 3.2% from 98.2% to 95%.

Materials and Experimental Procedure

The EOR agents experimented with in this work involved the use of local and foreign surfactant-
polymer (SP), Alkaline-polymer (AP) and four kinds of alkaline. For the SP case, the foreign and local
surfactants used were Sodium Dodecyl Sulphate and Soya bean respectively while the foreign and local
polymers used were Polyacrylamide and Irvingia gabonensis (locally known as Ogbonno) respectively.
For the AP case, the alkaline used was Sodium hydroxide (NaOH) while the foreign and local polymers
used were Polyanoic cellulose and Brachystegia eurycoma seed (locally known as Achi) respectively. The
same alkaline (NaOH) was used with the foreign and local polymers. The four kinds of alkaline
experimented with were palm bunch ash (PBA, a local alkaline), sodium carbonate (Na2CO3), potassium
hydroxide (KOH), and sodium hydroxide (NaOH).
Three sets of oil displacement experiments were conducted using foreign and local EOR agents. The
first set of experiments involved the use of foreign and local SP agents (Sodium Dodecyl Sulphate/
Polyacrylamide and Soya bean/Irvingia gabonensis respectively) at varying percentage combinations
presented on the first and second columns in Table 1. The properties of the two kinds of crude oil used
are presented on Table 2. In the second set of oil displacements experiments involving the use of alkaline
and polymer, sodium hydroxide (an alkaline) was used with a foreign and local polymer (Polyanoic
cellulose and Brachystegia eurycoma seed respectively). The varying percentages of the AP agents used
in the oil displacement experiments are presented on the third and fourth columns of Table 1. Only one
type of crude (medium) was used for this set of experiments and the oil properties are presented on Table
2. In the third set of experiments, four kinds of alkaline (PBA, Na2CO3, KOH and NaOH) were used to
displace residual oil from sand samples and the pH values of the different kinds of alkaline were
determined. Two kinds of oil (light and medium crude) were used in this part of the work and the oil
properties are also presented on Table 2.
SPE-178305-MS 5

Table 1—The Ratios of EOR Agents used in the Experimental Work

First Set of Experiments: Percentage mixture of surfactant and Second Set of Experiments: Percentage mixture of alkaline and
polymer (SP) used for foreign and local cases polymer (AP) used for foreign and local cases

Surfactants (%) Polymer (%) Alkaline (NaOH in %) Polymer (%)

100 0 0 100
80 20 10 90
60 40 20 80
40 60 30 70
20 80 40 60
0 100 50 50
- - 60 40
- - 70 30
- - 80 20
- - 90 10
- - 100 0

Table 2—Properties of the Crude Oil Used

SP Experiments AP Experiments Experiments with Alkaline

Crude Oil Properties Light Crude Medium Crude Medium Crude Light Crude Medium Crude

Density (g/cm3) 0.85 0.91 0.91 0.55 0.91

Specific Gravity 0.82 0.92 0.92 - -
API Gravity 40.64° 22.44° 23.58° 36.8° 26.4°
Viscosity (cp) 58.46 53.28 - 7.61 33.27

Different types of foreign and local EOR agents were used for oil displacement in this work. For each
of these agents, their properties and the concentrations used are presented on Table 3. Each of the local
agents used were dried, grinded and soaked in water for 48 hours. The solid materials were then separated
from the liquid by filtration.

Table 3—Properties of the EOR Agents

Type of EOR Agent Name of EOR Agent Concentration used (ppm) Density (g/cm3) Specific Gravity Viscosity (cp)

SP Foreign Surfactant Sodium Dodecyl Sulphate 167ml/L 1.03 1.1 -

Foreign Polymer polyacrylamide 2,500 1.02 1.00 -
Local Surfactant Soya Bean 13,000 1.02 1.00 0.93
Local Polymer Irvingia Gabonensis 13,000 1.02 1.00 1.11
AP Alkaline Sodium Hydroxide (NaOH) 20,000 1.01 1.00 -
Foreign Polymer Polyanoic cellulose 6,500 1.01 1.01 -
Local Polymer Brachystegia Eurycoma Seed 12,500 1.01 1.01 -
Alkaline Sodium Carbonate (NaCO3) 20,000 1.02 - 1.02
Sodium Hydroxide (NaOH) 20,000 1.03 - 1.11
Potassium Hydroxide (KOH) 20,000 1.02 - 0.81
Palm Bunch Ash 20,000 1.00 - 0.94

The experimental procedure for the three sets of experiments is the same. The schematic of the
experimental work is presented in Fig. 1. All experiments were conducted under standard conditions. The
porosities of the cleansed sand samples were determined and the samples were flooded with brine of
20,000ppm and left for 48 hours. Oil was injected into the samples and the residual water saturation was
determined. The injected oil was then displaced with brine until only water was produced, then the EOR
6 SPE-178305-MS

agents were introduced into the sand samples. The ratio of amount of oil produced to the residual oil (after
flooding with brine) was used to determine the displacement efficiency of the foreign and local EOR
agents.

Figure 1—Schematic of the Flooding Process

Results and Discussions

Results of oil displacement using foreign and local SP agents are presented in Figures 2 to 5. Figures 2
and 3 show that the ratios of foreign surfactant and polymer that gave the maximum oil displacement
efficiency of more than 90% are 50/50 and 0/100 for light and medium crude respectively. Figures 4 and
5 show that the ratio of local surfactant and polymer that gave the maximum oil displacement efficiency
of 40% and 75% was 20/80 for both light and medium crude respectively. Comparing the performance
of foreign and local SP agents as presented in Figure 6 for light crude shows that the foreign SP performs
better than the local SP from 0/100 up to a ratio of 30/70; the maximum foreign SP displacement
efficiency of 94% was obtained at a SP ratio 50/50. From Figure 7, the performance of the local SP was
better than the foreign SP from 0/100 to about 15/85 after which the foreign SP performed better, attaining
a maximum displacement efficiency of about 96% at a SP ratio of 0/100. Figure 8 compares the foreign
SP performance on light and medium crude while Figure 9 compares the local SP performance on light
and medium crude.
SPE-178305-MS 7

Figure 2—Results of Foreign SP on Light Crude

Figure 3—Results of Foreign SP on medium Crude

8 SPE-178305-MS

Figure 4 —Results of Local SP on Light Crude

Figure 5—Results of Local SP on medium Crude

SPE-178305-MS 9

Figure 6 —Results of Foreign and Local SP on Light Crude

Figure 7—Results of Foreign and Local SP on Medium Crude

10 SPE-178305-MS

Figure 8 —Performance of Foreign SP on Light and Medium Crude

Figure 9 —Performance of Local SP on Light and Medium Crude

Figures 10 and 11 show the results of the displacement efficiency using NaOH as an alkaline with a
foreign and local polymer. Figure 10 shows that in almost all the ratios (except for 60/40), the foreign
agent performed better than the local agent. The maximum oil displacement efficiency of 78% from the
foreign AP occurred at an AP ratio of 40/60 while the maximum oil displacement efficiency of 64% for
the local crude occurred at an AP ratio of 60/40. Presented on Figure 11 is the trend of the recovery
efficiency of increasing polymer and decreasing alkaline content of the AP agent.
SPE-178305-MS 11

Figure 10 —Results of Foreign and Local Polymer with Foreign and Alkaline on Displacement Efficiency

Figure 11—Trend of Displacement Efficiency of Local Polymer with Alkaline

Presented on Figure 12 are the results of oil displacement efficiency using four kinds of alkaline. The
results show that KOH displaces oil from sand better that NaOH, NaCO3 and PBA. KOH gave a
maximum oil displacement of 66.7% for light crude and 41.7% for medium crude. The values for the use
of other kinds of alkaline were lower. Figure 13 shows the observed relationship between pH values and
displacement efficiency. For the two kinds of oil used (light and medium crude), it was observed that
displacement efficiency increased as the pH values of the alkaline increased.
12 SPE-178305-MS

Figure 12—Performance of Different Kinds of Alkaline on Values Dissplacement Efficiency

Figure 13—Trend of Displacement Efficiency with pH

Conclusions
The conclusions drawn from this work are as follows:
1. Foreign surfactant and polymer EOR agents displace light and medium Nigerian crude oil better
than local surfactant and polymer EOR agents.
2. Alkaline and a foreign displaced light and medium Nigerian crude oil better than the same alkaline
and a local polymer.
3. Potassium hydroxide (KOH) displaces oil from sands better than sodium carbonate, sodium
hydroxide and palm bunch ash (a local alkaline).
4. Oil displacement tends to increase with increasing pH values.
5. Addition of polymers to surfactants and alkaline enhances the performance of these agents in
displacing oil from sand pores and gives better results than using these surfactants and alkaline
alone.
SPE-178305-MS 13

Recommendations
The recommendations made from this work are as follows:
1. Foreign surfactant/polymer and alkaline/polymer agents are recommended for EOR of Nigerian
light and medium crude because they give better oil displacement efficiency than local surfactant/
polymer and alkaline polymer.
2. For local EOR agents to be used in displacing Nigerian crude oil from reservoirs after secondary
recovery schemes, they need to be improved upon so that their performance can compete favorably
with foreign EOR agents; this constitute an area for further research work.
3. For EOR using alkaline, KOH gives better displacement efficiency than NaCO3, NaOH and PBA.

Summary
There is a need to investigate the performance of foreign EOR agents with local EOR agents in order to
depend less on imported chemicals and to reduce cost. Alkaline, surfactants and polymers sourced from
Nigeria that can enhance oil recovery and foreign sources of these agents were used to conduct oil
displacement experiments. An alkaline combined with different polymers and different surfactants
combined with different polymers in different ratios were used to determine the ratio combinations that
give optimum displacement efficiency. Experiments were performed using foreign and local agents. In
another set of experiments, four kinds of alkaline were used for oil displacement experiments and the best
performing type of alkaline was determined.
Experimental results showed that foreign EOR agents performed better than local EOR agents. For the
foreign SP agents, maximum values of displacement efficiency were above 90% for light and foreign
crude at a percentage surfactant/polymer mixture of 45/55 and 0/100 respectively. The local SP gave a
maximum displacement efficiency of 35% and 75% at 20/80 percentage ratio for light and medium crude
respectively. For the use of AP, the foreign agent gave a maximum displacement efficiency of 78% at
40/60 while the local agent gave a maximum of 64% at an alkaline/polymer ratio of 60/40. Results of
displacement efficiency using four kinds of alkaline showed that KOH displaces oil from sand better than
NaCO3, NaOH and palm bunch ash. It was also observed that displacement efficiency increases as pH
value increases.

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