EFFECT OF VARYING SURFACTANT CONCENTRATION ON INTERFACIAL .
EFFECT OF VARYING SURFACTANT CONCENTRATION ONINTERFACIAL TENSION IN TERTIARY RECOVERY OF CRUDE OILbyJos Antony XavierSubmitted in partial fulfillment of the requirementsfor the degree of Master of EngineeringMajor Subject: Petroleum EngineeringatDalhousie UniversityHalifax, Nova ScotiaAugust, 2011
iiDALHOUSIE UNIVERSITYFaculty of Engineering,Petroleum Engineering ProgramThe undersigned hereby certify that they have read and recommend to the Faculty of GraduateStudies for acceptance a thesis entitled “EFFECT OF VARYING SURFACTANTCONCENTRATION ON INTERFACIAL TENSION IN TERTIARY RECOVERY OF CRUDEOIL” by Jos Antony Xavier in partial fulfilment of the requirements for the degree of Master ofEngineering.Dated: DEC 20th, 2011Supervisor:Readers:Departmental Representative:
iiiDALHOUSIE UNIVERSITYDATE:DEC 20th, 2011AUTHOR:Jos Antony XavierTITLE:Effect of Varying Surfactant Concentration on Interfacial Tension inTertiary Recovery of Crude OilDEPARTMENT OR SCHOOL:DEGREE:M.Eng.Faculty of Engineering, Petroleum EngineeringProgramCONVOCATION: MayYEAR:2012Permission is herewith granted to DalhousieUniversity to circulate and to have copied for noncommercial purposes, at its discretion, the above title upon the request of individuals orinstitutions. I understand that my thesis will be electronically available to the public.The author reserves other publication rights, and neither the thesis nor extensive extracts from itmay be printed or otherwise reproduced without the author’s written permission.The author attests that permission has been obtained for the use of any copyrighted materialappearing in the thesis (other than the brief excerpts requiring only proper acknowledgement inscholarly writing), and that all such use is clearly acknowledged.Signature of Author
ivDEDICATEDToMy Parents
vACKNOWLEDGEMENTSI wish to express profound gratitude to my supervisor, Dr. Michael Pegg for his support andencouragement throughout the duration of the project. I could not have wished for a moresupportive and inspirational supervisor. I am also thankful to Dr. Jan Haelssig for accepting to beon my examining committee.All members of the Petroleum Engineering laboratory, especially RazaqRaji for teaching andsharing his knowledge on how to operate the equipment used for this research; and also to Mr.MumuniAmadu for helping to review some of the technical content.To my numerous friends and colleagues who made the journey during this time enjoyable, Ithank you all.Finally, to my parents, for their love, support and encouragement.
1ContentsLIST OF TABLES.3LIST OF FIGURES .4ABSTRACT .5LIST OF ABBREVIATIONS USED .6CHAPTER1: INTRODUCTION .71.1 BACKGROUND . 71.2 OBJECTIVES . 8CHAPTER 2: LITERATURE REVIEW .92.1 OIL RECOVERY . 92.1.1 PRIMARY OIL RECOVERY . 91.Rock and liquid expansion drive . 92.Depletion drive. 103.Gas cap drive . 104.Water drive . 105.Gravity drainage drive. 106.Combination drive. 112.1.2 SECONDARY OIL RECOVERY . 11Water Flooding . 122.1.3 TERTIARY/ENHANCED OIL RECOVERY . 121.Miscible Flooding Process . 132.Chemical Flooding Process. 13a)Polymer Flooding . 14b)Micellar-Polymer Flooding . 14c)Alkaline Flooding . 143.Thermal Flooding Process . 14
24.Microbial Flooding Process . 15CHAPTER 3: LOW INTERFACIAL TENSION FOR OIL RECOVERY . 163.1 INTERFACIAL TENSION . 163.2 SURFACTANTS . 173.3 SURFACTANT AND INTERFACIAL TENSION . 183.4 CRITICAL MICELLE CONCENTRATION . 18CHAPTER 4: EXPERIMENTAL SETUP, APPARATUS AND PROCEDURE . 204.1 MATERIALS USED: . 204.2 APPARATUS . 204.3 DENSITY MEASUREMENT . 234.4EXPERIMENTAL PROCEDURE . 23CHAPTER 5: RESULTS AND DISCUSSION . 265.1 RESULTS. 265.2 DISCUSSION. 285.3 STATISTICAL ANALYSIS . 28CHAPTER 6: CONCLUSIONS AND RECOMMENDATIONS . 296.1 CONCLUSIONS . 296.2 RECOMMENDATIONS. 29REFERENCES . 30APPENDIX . 32
3LIST OF TABLESTable 4.2: Technical Data of Krüss SITE100 Spinning Drop Tensiometer . 22Table 4.3: Summary of the brine sample/Wabamun formation . 24
4LIST OF FIGURESFigure 2.1: Initial fluids distribution in an oil reservoir . 11Figure 3.4: Variation of IFT with surfactant concentration . 18Figure 4.2: Experimental setup showing spinning drop tensiometer . 21Figure 5.1: IFT measurements for kerosene-brine/surfactant system .26Figure 5.2: Average IFT measurements for kerosene-brine/surfactant system . .27
5ABSTRACTDuring the past several years significant and considerable research has been carried out on thetertiary recovery of trapped residual oil remaining within the producing formations. One methodthat has received much attention and intensive study over these years is the use of surfactantbased chemical flooding. The interfacial tension between heavy crude oil and injection waterunder reservoir conditions plays a significant role in the process of enhanced oil recovery. Thisinteraction between the oil and water phases is a function of temperature, pressure, andcomposition of both the hydrocarbon and aqueous phases.This study experimentally determines the influence of surfactant concentration on oil recovery.The interfacial tension between brine and kerosene was studied with the use of sodium dodecylsulphate (SDS) as a means of lowering the interfacial tension. The spinning drop tensiometer(Krüss, SITE 100) was used to measure the interfacial tension due to its ability to measureultralow interfacial tensions.This study reveals the variation of IFT with varying surfactant concentration. The IFT reduces asthe surfactant concentration increases and reaches a point (CMC) after which the IFT remainsmore or less constant. Thus we are able to find a critical surfactant concentration which is veryimportant from the economic point of tertiary recovery (chemical flooding) since the use ofsurfactants is expensive.
6LIST OF ABBREVIATIONS USEDCMC – Critical Micelle Concentration (mM)IFT – Interfacial Tension (mN/m)Nc – Capillary Number𝑣 - Flow rate (m3/s, bbl/day)𝜇 – Viscosity (Pa.s, cp)𝛾- Interfacial Tension (mN/m)- Radius of drop (m)– Rotational frequency (rpm)ρH - Density of heavy phase (kg/m3)ρL - Density of Light Phase (kg/m3)
7CHAPTER1: INTRODUCTION1.1 BACKGROUNDThe initial or primary phase of recovering oil from an underground reservoir takes advantage ofthe natural pressure existing in the reservoir, assisted by pumps (if needed) to lift the oil to thesurface. But only about 10 percent of a reservoir's original-oil-in-place (referred to as OOIP) istypically produced during primary recovery.To extend the productive life of an oil field, most oil producers have used secondary recoverymethods. Such secondary methods generally involve injecting water into the undergroundreservoir to displace the oil and drive it into the wellbore where it can be lifted to the surface bypumps. In some cases, natural gas (often produced simultaneously with the oil) is re-injected tomaintain reservoir pressure, thus driving the oil into the wellbore. Secondary recovery methodsgenerally raise the overall oil recovery to 20 – 40 percent of the original-oil-in-place. Thus, evenafter the secondary phase of recovery, about 60 – 80 percent of the oil still remains in thereservoir. (http://www.eoearth.org/article/Petroleum crude oil?topic 49478)As the world continues to use more crude oil and world oil reservoirs are depleted, new ways ofextracting oil and gas must be developed to get every drop possible from existing sources.Enhanced Oil Recovery (abbreviated EOR) is a generic term for tertiary techniques used tofurther increase the recovery of oil from an oil field. Using EOR, 30 – 60 %, or more of thereservoir’s original oil-in-place can be recovered compared with 20 – 40% using primary andsecondary recovery, effectively doubling or tripling the amount of the oil produced from thefield. It is estimated that the full use of enhanced oil recovery in United States could generate anadditional 240 billion barrels of oil (United States Department of Energy, 2011).
8Various enhanced oil recovery methods are being employed to overcome viscosity, interfacialtension and capillary forces that keep this vast amount of oil trapped in the reservoir. Thesemethods which are in use today are still under current development to achieve maximum oilrecovery at low cost. These techniques, employed to overcome forces that trap residual oil atdifferent depths, must be suitable to account for the effects of increasing temperature, pressureand salinity.Surfactant addition has become very attractive because of its ability to reduce surface/Interfacialtension between immiscible fluids thereby increasing the capillary number necessary formobilizing residual hydrocarbons in the reservoir. The behaviour of surfactants with varyingtemperature, pressure and salinity will determine the necessary concentrations to maximize oilrecovery.1.2 OBJECTIVESThe primary objectives of this project were to:1) Measure the IFT between Kerosene and brine using the spinning drop tensiometer.2) Measure the IFT between kerosene and brine with the addition of SDS surfactant.3) Determine a critical surfactant concentration (CMC) for very low IFT.
9CHAPTER 2: LITERATURE REVIEW2.1 OIL RECOVERYThe overall performance of oil reservoirs is largely determined by the nature of the energy, i.e.,driving mechanism, available for moving the oil to the wellbore. Oil recovery is separated intothree phases: primary, secondary and tertiary, which is also known as Enhanced Oil Recovery(EOR).2.1.1 PRIMARY OIL RECOVERYProducing reserves are called “primary” when they are produced by primary recovery methodsusing the natural energy inherent in the reservoir. The driving energy may be derived from theliberation and expansion of dissolved gas, from the expansion of the gas cap or of an activeaquifer, from gravity drainage, or from a combination of these effects. Ahmed (2006) defines sixbasic drive mechanisms that provide natural energy necessary for oil recovery: rock and liquidexpansion drive; depletion drive; gas cap drive; water drive; gravity drainage drive andcombination drive.1. Rock and liquid expansion drive: This occurs when an oil reservoir initially exists at apressure higher than the bubble-point pressure. Crude oil, connate water and rock are thematerials present in a reservoir at pressures above the bubble-point. Hence, as reservoirpressure declines, rock and fluids expand due to their compressibilities. This causes areduction in pore volume. As the expansion of the fluids and reduction in the pore volumeoccur with decreasing reservoir pressure, the crude oil and water will be forced out of thepore space to the well bore (Ahmed, 2006).
102. Depletion drive: This drive mechanism occurs when production of oil from the reservoir is aresult of the expansion of the original oil volume with its original dissolved gas (solutiongas). Due to declining pressure below the bubble point, gas bubbles are liberated within themicroscopic pore spaces; the bubbles expand and force the crude oil out of the porespace.(Ahmed, 2006).3. Gas cap drive: The formation of a gas cap in a reservoir is due to the presence of a largeamount of gas that could be dissolved in the oil at the pressure and temperature of thereservoir. The excess gas segregates to occupy the top part of the reservoir. As the oil isproduced, the expansion of the gas in the gas cap pushes down on the oil and fills the porespaces formerly occupied by the produced oil.(Ahmed, 2006).4. Water drive: Oil/gas reservoirs exist as large, continuous, porous formations with the oil/gasoccupying a portion of the formation. The formation below the oil/gas is saturated with brineat very high pressure. Thus when oil/gas is produced, lowering the pressure in the well, thebrine expands and moves upwards, pushing the oil/gas out of the formation and occupyingthe pore spaces vacated by the produced oil/gas. (Ahmed, 2006).5. Gravity drainage drive: The gravity drainage mechanism occurs in reservoirs due todifferences in densities of the reservoir fluids. The fluids in a petroleum reservoir have beensubjected to forces of gravity as evidenced by the positions of the fluids shown in figure 2.1.Gas on top, oil underlies the gas, and water underlying the oil.(Ahmed, 2006).
11Figure 2.1: Initial fluid distribution in an oil reservoir (Ahmed, 2006)6. Combination drive: It is possible that more than one of these drive mechanisms occursimultaneously; the most common combination being gas cap drive and natural aquifer drive,where both water and free gas are available in some degree to displace the oil toward theproducing wells.(Ahmed, 2006).2.1.2 SECONDARY OIL RECOVERY:The natural or primary driving mechanism is a relatively inefficient process and results in a lowoverall oil recovery. The lack of sufficient natural drive in most reservoirs has led to the practiceof supplementing the natural reservoir energy by introducing some form of artificial drive, themost basic method being the injection of gas or water, and other techniques to increase reservoirpressure, thereby replacing or increasing natural reservoir drive. Usually, the selected secondaryrecovery process follows the primary recovery but it can also be conducted concurrently with theprimary recovery. Water flooding is perhaps the most common method of secondary recovery.
12Water Flooding: Water Flooding is a method of secondary oil recovery in which water isinjected into the reservoir formation to displace the residual oil. The water sweeps some ofthe remaining oil through the reservoir into the producing wells and can recover 5-50% of theremaining oil in place. The injected water is usually oil field brine from separators or treatedwater from other sources. This injected water must be compatible with the producingformations, not causing reactions that decrease the permeability of the flooded formation.The injected water is either pumped under pressure down the well or is fed by gravity fromstorage tanks at a high elevation. Injection wells are either drilled or converted fromproducing wells. (Hyne, 2001)2.1.3 TERTIARY/ENHANCED OIL RECOVERYEnhanced Oil Recovery refers to the process of producing oil by methods other than theconventional use of the natural energy inherent in the reservoir or the reservoir repressurizingschemes with gas or water. On average, the primary and secondary recovery methods willproduce from a reservoir about 30% of the initial oil in place. The remaining oil, nearly 70% ofthe initial resource, is a large and attractive target for enhanced oil recovery methods. (Lake,1989)Enhanced oil recovery processes can be classified into four categories: (Terry, 2001)1. Miscible flooding process2. Chemical flooding process3. Thermal flooding process4. Microbial flooding process
131. Miscible Flooding Process: A miscible process is one in which the interfacial tension isreduced to zero; that is, t
The interfacial tension between brine and kerosene was studied with the use of sodium dodecyl sulphate (SDS) as a means of lowering the interfacial tension. The spinning drop tensiometer (Krüss, SITE 100) was used to measure the interfacial tension due to its ability to measure ultralow interfacial tensions.
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