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This paper was prepared for presentation at the PAPG/SPE Pakistan Section Annual Technical Conference and Exhibition held in Islamabad, Pakistan, 21-23
November 2016.
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
Alkali-Surfactant-Polymer (ASP) flooding is the most effective Chemical Enhanced Oil Recovery
(CEOR) method applied in sandstone reservoirs. After the successful results in sandstone formations, its
usage has been widened to carbonate reservoirs as well. However, ASP application in carbonate
reservoirs is less well understood. The main limitation of ASP flooding in carbonate reservoirs is the
presence of carbonate minerals. These minerals react with the added chemicals to form insoluble
materials called precipitations. Therefore, an ASP formulation was developed by incorporating acrylic
acid as a precipitation inhibitor to overcome the precipitation problems.
The performance of the Acrylic Acid (AA) with an ASP formulation was evaluated using sodium
metaborate, surfactant and polymer. Feasibility of applying AA with ASP formula was demonstrated by
comprehensive fluid-fluid compatibility tests, interfacial tension tests, viscosity measurements and
coreflooding experiments. Hardbrine composition of 59,940 ppm was used to prepare the ASP
formulations in the presence and absence of AA. All the chemicals including, alkalis, surfactants, and
polymers were compatible with the hard brine used in this study. The presence of acrylic acid exhibited
excellent properties in preventing precipitations as the all solutions remained clear for 30 days at 80 oC.
The weight ratio of optimum acid concentration of acid to alkali was found to be 0.6:1.0. No
precipitation was observed when using this acid to alkali ratio. Interfacial tension and viscosity tests
screened the best chemical formulations which were validated by coreflooding. The core flooding tests
showed significant improvement in the oil recovery with the use of AASP and ASP flooding by
accomplishing a total oil recovery of 75.7% and 88.7% OOIP respectively.
Although, total recovery efficiency of AASP formulation is relatively lower than with ASP, the new
AASP formulation can be prepared with any water source such as formation water or seawater. The
precipitation inhibitor makes the conventional ASP system more flexible and advantageous for offshore
applications by eliminating the need of softening or desalting the seawater. Furthermore, there is no
need to remove the calcium and magnesium ions from the injected water as it can be done by using the
appropriate concentration of acid and alkali. This eliminates the cost of water treatment equipment and
minimizes the use of surface equipment as well.
2 SPE-185313-MS
Introduction
Chemical flooding is considered as one of the important technologies for enhanced oil recovery over the
last decades. Various chemical methods are used to increase the macroscopic sweep efficiency and
microscopic displacement efficiency in the porous spaces. ASP flooding has shown encouraging
economic consequences for the field applications in sandstone reservoirs around the world [1][2]. The
successful results of ASP flooding have opened the ways to exploit this technology in carbonate
reservoirs [3]. Carbonate reservoirs (limestone, dolomite and gypsum) account for about 50% of world
oil reserves. They are classified as highly heterogeneous, naturally fractured and oil-wet or neutral-wet
[4][5]. There are several problems associated with ASP flooding in carbonate reservoirs. The major
problem is the formation of precipitates (calcium carbonate and calcium hydroxide) caused by the
reaction of alkali (sodium hydroxide or sodium carbonate) with calcium and magnesium ions. These
solids in the form of precipitates cause formation damage and pore plugging in the carbonate reservoirs
[6].
Previously, ASP slug was combined with Sodium tripolyphosphate (SPTT) to prevent precipitation [7].
Reservoirs were preflushed with softened brine or fresh water prior to ASP slug injection to mitigate
hardness effect [8][9]. Preparation of softened water from sea water is an expensive process. Therefore,
ethylene-diaamine-tetra-ecetate (EDTA) has sometimes been used in place of softened water to acquire
the same results in a cost effective way [6]. However, these methods are not found to be effective in
mitigating these challenges in high salinity and high hardness carbonate reservoirs.
In this study, a new chemical flooding formula was designed by introducing acrylic acid (AA) to
generate in-situ inhibitor. The in-situ inhibitor has the potential to overcome the precipitation problems
caused by reservoir minerals and brine compositions. Sodium acrylate (SA) as an in-situ inhibitor is
produced by the reaction of acrylic acid with sodium ion (Na+) and alkali. Sodium acrylate accumulates
on the surfaces of the divalent cations to prevent them from precipitating [10]. Sodium metaborate was
blended with acid to generate acrylate. Sodium metaborate is a novel alkali that has high tolerance to
multivalent ions. Its borate ion reacts with these cationic minerals and forms amorphous crystals that are
effectively dissolvable in aqueous solution [11]. Hence, when acrylic acid and sodium metaborate were
blended in the presence of synthetic hard brine, the combination worked more effectively to sequester
these minerals from any precipitation [12].
Experimental Methodology
Materials
In this study, crude oil was collected from the Dulang oil field reservoir, Malaysia. The density of
the crude oil was 0.799 g/cc (80 °C) and the API gravity was 35.5°. Sodium metaborate was supplied by
Rio Tinto Minerals. Acrylic acid was supplied by Sigma Aldrich. C14-16 Alpha olefin sulfonate (AOS)
was supplied by Stepan Chemical Co. AN-125 SH copolymer was supplied by SNF Floerger. Carbonate
core samples were purchased from Kocurek Industries/Hard Rock Division (USA). The basic properties
of core samples were determined and are as given in Table 3. Different synthetic brines were utilized to
prepare all solutions and the main compositions for each brine are as given in Table 1.
Methods
Fluid-Fluid Compatibility Tests
The extensive fluid-fluid compatibility tests were performed to find the most compatible solutions
with the hard brine. The tests were conducted at 80 °C for a specific period of time, and the solids
formation in the solutions indicated the incompatibility of the solution. All interaction tests were
observed by visual evaluation.
Viscosity Measurement
In order to measure the viscosities of copolymer AN-125 SH solutions with respect to different shear
rates; high pressure high temperature viscometer (OFITE 1100 model, USA) was used. The polymer
concentration of 2000ppm was employed to conduct the tests at 80 °C.
Coreflooding Experiments
All core flood experiments were conducted using Relative Permeability System (RPS) equipment.
All experiments were performed in carbonate core samples using the promising chemical formulations.
The detailed procedure of coreflooding experiments has been presented in the published article [13].
Figure 1: IFT between crude oil and various alpha olefin Figure 2: IFT between crude oil and various acid-alkali
sulfonate concentrations in the presence of 0.6% sodium concentrations in the presence of 0.8% surfactant using
metaborate using softened water. synthetic hard brine.
Viscosity Measurements
In chemical enhanced oil recovery, viscosity is the most important parameter for effective mobility
control. In general, surfactant slugs tend to decrease capillary forces and cause fingering. Therefore,
polymers are combined with the chemical slugs to increase the slug viscosity and maintain mobility
control. In this study, viscosity of various chemical solutions was measured using softened water and
synthetic hard brine.
Figure 3: Effect of various surfactant concentrations on shear viscosity of the polymer at 80 °C.
6 SPE-185313-MS
Figure 4: Effect of various surfactant concentrations and constant acid-alkali concentration on shear viscosity of the polymer at
80°C.
Coreflooding Experiments
Core flooding experiments were aimed to examine the residual oil displacement by the best chemical
formulations. Two core flooding tests were performed to investigate the impact of different injection
strategies on the residual oil displacement. The core tests included Acid-Alkali-Surfactant-Polymer
(AASP) combination and Alkali-Surfactant-Polymer (ASP) prepared with synthetic hard brine and
softened brine respectively. The screening tests performed were IFT and viscosity measurements for
selecting the best ASP concentrations. The core’s properties, core flood results for the AASP system and
ASP system are summarized in Table 3.
Figure 5 shows the comparison of recovery results between AASP and ASP as a function of pore
volume injected. The optimum chemical concentration for the AASP system was determined as 0.48%
acid, 0.8% alkali, 0.8% surfactant and 2000 ppm polymer. On the other hand, the optimum
concentration for the ASP system was found to be 0.6% alkali, 0.8% surfactant and 2000 ppm polymer.
These concentrations had the best performance in mobilizing and driving the crude oil after
waterflooding. Injection of 0.5 PV of the formulated slugs of AASP and ASP followed by chase water
produced an additional 18.9% OOIP and 25.1% OOIP over water flooding respectively. Further,
SPE-185313-MS 7
injecting 0.3 PV of polymer drive followed by chase water recovered additional 3.0% OOIP and 4.6%
OOIP over AASP and ASP flooding correspondingly.
Given in the Figure 5, oil recovery results of AASP flooding are comparable to ASP flooding after
waterflooding. Although, recovery efficiency for ASP flooding is much higher, the main advantage of
AASP lies in its feasibility of preparing chemical slugs with hard brine.
Table 3 Summary of core flood tests for ASP and AASP using synthetic hard brine and softened brine
respectively.
Figure 5: Comparison of oil recovery profile between ASP and AASP flooding.
Conclusions
Both sodium metaborate and sodium carbonate precipitated in presence of synthetic hard brine.
However, generated precipitation inhibitor sequestered divalent cations from precipitating. The
ratio of acrylic acid to sodium metaborate of 0.6:1.0 was found to be optimum. No precipitation
was detected for 30 days at 80 oC temperature using the optimum ratio.
The precipitation inhibitor significantly lowered interfacial tension in the presence of hard brine.
The addition of acrylic acid and sodium metaborate with polymer solutions negligibly decreased
the polymer performance. The shear viscosity was improved when surfactant was combined with
acid-alkali-polymer solution.
Results from the optimization process in coreflood tests indicated that 0.48% acid with 0.8%
alkali, 0.8% surfactant and 2000 ppm polymer performaned the best for enhanced oil recovery
using AASP, while 0.6% alkali, 0.8% surfactant and 2000 ppm polymer were found to be the
optimum condition for ASP system. These concentrations had the best performance in mobilizing
and driving the crude oil after waterflooding. Injection of 0.5 PV of the formulated slugs followed
by chase water produced an additional 18.9% and 25.1% OOIP to waterflooding for AASP
system and ASP system respectively.
Hence, AASP flooding formulation has the potential to enhance oil recovery from carbonates.
The principal advantage of this new system is its use of hard brine rather than softened water
while preserving the required slug properties. This makes the new AASP formula promising for
chemical EOR particularly in offshore field applications.
Acknowledgements
The authors are thankful to Universiti Teknologi PETRONAS for supporting this work. We also thank
RIO Tinto Minerals, Stepan Chemical Co. and SNF Floerger for providing some of the materials for this
project.
SPE-185313-MS 9
References
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10 SPE-185313-MS
Shuaib Ahmed
Shuaib Ahmed is associated with Weatherford as an Application Engineer in Artificial Lift Systems and is
mainly responsible for Nodal Analysis and Designs of several lifts including Capillary Soap injection, Jet
Pump, Gas Lift and Plunger Lift. He has also worked on different National & International Field Projects
for Jet Pumps and Capillary Soap injections, and has remained associated with almost every E&P
Company in Pakistan for devising optimum Artificial Lift Solutions for various clients to enhance
production via world’s proven ALS techniques. Shuaib has accomplished Master of Science in Petroleum
Engineering from Universiti Teknologi PETRONAS, Malaysia and has 2.5 years of research experience
worked in “Center of Excellence for Enhanced Oil Recovery” PETRONAS. He has published 15+ research
articles in worldwide SPE conferences on different subjects of Petroleum Engineering – Artificial Lift
Systems and Enhanced Oil Recovery.
Ghulam Abbas
Ghulam Abbas holds MSc degree in Petroleum Engineering from Universiti Teknologi PETRONAS,
Malaysia. He had B.E degree in Petroleum from Mehran University of Engineering and Technology,
Pakistan. He has five years diversified experience of Petroleum Industry and research in an auspicious
manner. He worked as Petroleum Engineer at different fieldsof OGDCL, Pakistan as well as Research
Assistant in Petroleum Engineering department, Universiti Teknologi PETRONAS, Malaysia. His area of
interest includes, chemical EOR, drilling optimization, drilling fluid and cementing. Currently, he is
working as Lecturer in Mehran University of Engineering and Technology, S.Z.A.B Campus, Khairpur
Mirs, Pakistan.
Sandeep Kumar
Performance-Driven Petroleum Engineering Professional with 4+ years of diversified experience in Oil
and Gas Industry. Scope of the experience includes production optimization, research, consultancy,
servicing as well as exploration & production. Accomplished expert with specialty in Artificial Lift System,
Production Engineering and Enhanced Oil Recovery. 2.5 years of valuable research experience gained
through working as Research Graduate at “Center of Excellence for Enhanced Oil Recovery” PETRONAS
and completed Master of Science in Petroleum Engineering from UniversitiTeknologi PETRONAS,
Malaysia. Published 20+ research articles in worldwide SPE conferences on different subjects of
Petroleum Engineering – Artificial Lift System, Nodal Analysis and Enhanced Oil Recovery.
Khurram Farouque
Khurram Farouque is currently working as Country Productline Manager Artificial Lift Systems (ALS) for
Weatherford International and looking after Production Systems, Flow Measurement & Assurance,
Reservoir Monitoring, Automation and Software. He earned his B.E in Mechanical from National
University o f Sciences & Technology (NUST) and started his career with Baker Hughes Pakistan in 2001
and then transferred to BHI Qatar, where he worked in Mud Logging unit. He then joined Tullow Pakistan
as Production Engineer in 2001 and served for approx. 2-1/2 years. Later on, after serving MOL Pakistan
for another 2-1/2 years, he did his MS in Oil & Gas from Seoul National University, South Korea in 2007.
After returning from Korea, Khurram joined Weatherford Oil Tools Pakistan as Projects Coordinator and
worked on installation and commissioning of Production Facility. Thereafter, he has been given various
tasks within the organization before he was appointed as Production Optimization Team Leader since Jan
2013.