Modern Chemical Enhanced Oil Recovery: Theory and Practice

Front Matter

Modern Chemical Enhanced Oil Recovery

Theory and Practice

James J. Sheng, Ph. D.

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Library of Congress Cataloging-in-Publication Data

Sheng, James J.

  Modern chemical enhanced oil recovery : theory and practice / James J. Sheng.

       p.  cm.

  ISBN 978-1-85617-745-0

  1. Enhanced oil recovery. 2.  Oil reservoir engineering. 3.  Oil fields—

Production methods. I.  Title.

  TN871.S516 2010

  622′.33827–dc22                                                                            2010026763

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A catalogue record for this book is available from the British Library.

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Table of Contents

Preface

Acknowledgments

Nomenclature

Chapter 1: Introduction

Chapter 2: Transport of Chemicals and Fractional Flow Curve Analysis

Chapter 3: Salinity Effect and Ion Exchange

Chapter 4: Mobility Control Requirement in EOR Processes

Chapter 5: Polymer Flooding

Chapter 6: Polymer Viscoelastic Behavior and Its Effect on Field Facilities and Operations

Chapter 7: Surfactant Flooding

Chapter 8: Optimum Phase Type and Optimum Salinity Profile in Surfactant Flooding

Chapter 9: Surfactant-Polymer Flooding

Chapter 10: Alkaline Flooding

Chapter 11: Alkaline-Polymer Flooding

Chapter 12: Alkaline-Surfactant Flooding

Chapter 13: Alkaline-Surfactant-Polymer Flooding

References

Index

Preface

With growing global energy demand and depleting reserves, enhanced oil recovery (EOR) from existing or brown fields has become more and more important. Among the various enhanced oil recovery methods, chemical EOR has been labeled an expensive method, and field applications have been almost completely stopped during the past two decades worldwide except China, although limited university research was continued. Because we are facing the difficulty of replacing depleting reserves with cheap oil and rising oil price, chemical EOR has drawn increasing interest from oil companies, especially national oil companies.

In particular, technical references on chemical EOR are needed because petroleum professionals have not been trained in this area in the past 20 years. Except for some chapters in a few books that discuss general EOR, a comprehensive and systematic chemical EOR book has not been published. The purpose of this book is to complement the current literature on EOR. More important, it summarizes the results of research, pilot tests, and field applications in China because oil companies and research organizations there have continually made the effort to develop and apply chemical EOR technology during the past three decades.

This book is written mainly for petroleum professionals. Because overwhelming parameters are needed to describe a chemical EOR process, it is not practical to measure every one of them; therefore an effort has been made to collect, synthesize, and summarize available data, especially Chinese information that is inaccessible in Western literature. An effort has also been made to cover comprehensively the fundamental theories and practices related to alkaline (A), surfactant (S), and polymer (P) flooding processes, especially alkaline-surfactant-polymer (ASP) flooding that has barely been discussed in any enhanced oil recovery book in English.

Many pilot studies and field cases have been summarized; an effort has been made to select these studies and cases so that each one addresses unique issues. This book also proposes some new concepts and ideas or hypotheses. Several of them need to be validated by further research, and some may stimulate other research interests. From this standpoint, this book could be useful to researchers. The basic theories and sample calculations should help students and professionals who are less experienced in this area. This book also may be used by environmental engineering professionals who work on cleaning up wastes and nonaqueous phase liquids (NAPL). In addition, an effort has been made to strike an ideal balance between theory and practice; in addition, extensive references are provided.

The flow of logic of this book is as follows:

Chapter 1 introduces general EOR and how this book is organized.

Chapter 2 discusses the fundamentals of chemical transport and fractional flow analysis.

Chapter 3 reviews salinity and ion exchange, and the effect of salinity on waterflooding.

Chapter 4 proposes a new mobility control requirement for enhanced oil recovery processes.

Chapter 5 presents fundamentals and field practices of polymer flooding.

Chapter 6 reviews polymer viscoelastic behavior.

Chapter 7 discusses the fundamentals, concepts, and issues related to surfactant flooding.

Chapter 8 proposes new concepts of optimum salinity type and optimum salinity profile in surfactant flooding.

Chapter 9 discusses surfactant-polymer interactions.

Chapter 10 presents the fundamentals and modeling of alkaline flooding.

Chapter 11 discusses alkaline-polymer interactions.

Chapter 12 discusses alkaline-surfactant synergy.

Chapter 13 focuses on emulsion and ASP field applications.

Acknowledgments

While doing research on chemical EOR, I had opportunities to discuss the subject with several gurus and many experts. I sincerely appreciate those opportunities. Most of all, I greatly appreciate the insights gained from Dr. Gary Pope, professor at the University of Texas at Austin, through his explanation and stimulating discussion of some controversial and sometimes confusing issues. Such appreciation is extended to Dr. Larry Lake, professor at the University of Texas at Austin, and Dr. George Hirasaki, professor at Rice University. I am grateful to Dr. Mojdeh Delshad, professor at the University of Texas at Austin, for her help in using UTCHEM, a chemical simulator developed at the University of Texas at Austin.

I also appreciate the stimulating and valuable discussions I have had with these chemical EOR experts: Larry N. Britton, University of Texas at Austin; Maurice Bourrel, TOTAL Petrochemical; Danielle Morel, Pascal Gauer, and Gilles Bourdarot, TOTAL E&P; Ramon Bentsen, University of Alberta; Brij Maini, University of Calgary; Michael Prats and Scott Wellington, Shell E&P; Tor Austad, University of Stavanger; Shunhua Liu, Occidental Oil and Gas; and Harry L. Chang, Chemor Tech International. I am also grateful to Wilson Chin of StrataMagnetic Software for his advice to write a book. My thanks also go to Kenneth P. McCombs, Irene Hosey, Marilyn Rash, and the staff at Elsevier for their support, which made this book’s writing more enjoyable.

My biggest thanks must go to my wife, Ying Zhang, for her patience, understanding, and support. I owe much to my daughters, Emily and Selena, for the time I should have shared with them as their father. I am also thankful to my greater family for their continuing support. Finally, I am indebted to the authors and publishers who have given me the permission to use their results and copyrighted materials.

Nomenclature

Greek Symbols

Superscripts

Subscripts

Introduction

1.1 Enhanced Oil Recovery’s Potential

Today fossil fuels supply more than 85% of the world’s energy. Currently, we are producing roughly 87 million barrels per day—32 billion barrels per year in the world. That means every year the industry has to find twice the remaining volume of oil in the North Sea just to meet the target to replace the depleted reserves. Of the 32 billion barrels produced each year, almost 22 billion come out of sandstone reservoirs. The reserves and production ratios in sandstone fields have around 20 years of production time left. The proven and probable reserves in carbonate fields have around 80 years of production time left (Montaron, 2008). With global energy demand and consumption forecast to grow rapidly during the next 20 years, a more realistic solution to meet this need lies in sustaining production from existing fields for several reasons:

• The industry cannot guarantee new discoveries.

• New discoveries are most likely to lie in offshore, deep offshore, or difficult-to-produce areas.

• Producing unconventional resources would be more expensive than producing from existing brown fields by enhanced oil recovery (EOR) methods.

Figure 1.1 shows the US oil volume distribution in 1993 (Green and Willhite, 1998). The total oil discovered up to 1993 was 536 billion barrels, with the total produced being 162 billion barrels (30% of the total discovered) and the reserves being 23 billion barrels (4% of the total discovered). This is the number that could be produced economically using conventional methods. The remaining oil in the reservoirs was 351 billion barrels, or 66% of the total discovered. If EOR can recover half of the remaining (i.e., 176 billion barrels), then we could double the currently projected recoverable reserves. Similarly, we could have additional reserves of 2 trillion barrels worldwide.

FIGURE 1.1 US oil volume distribution in 1993.

1.2 Definitions of EOR and IOR

Depending on the producing life of a reservoir, oil recovery can be defined in three phases: primary, secondary, and tertiary. Primary recovery is recovery by natural drive energy initially available in the reservoir. It does not require injection of any external fluids or heat as a driving energy. The natural energy sources include rock and fluid expansion, solution gas, water influx, gas cap, and gravity drainage. Secondary recovery is recovery by injection of external fluids, such as water and/or gas, mainly for the purpose of pressure maintenance and volumetric sweep efficiency. Tertiary recovery refers to the recovery after secondary recovery. It is characterized by injection of special fluids such as chemicals, miscible gases, and/or the injection of thermal energy.

Enhanced oil recovery is oil recovery by injection of gases or chemicals and/or thermal energy into the reservoir. It is not restricted to a particular phase, as defined previously, in the producing life of the reservoir. Another term, improved oil recovery (IOR), is also used in the petroleum industry. The terms EOR and IOR have been used loosely and interchangeably at times. Some feel that the two terms are synonymous; others feel that IOR covers just about anything, including infill drilling and reservoir characterization.

Workable definitions of EOR and IOR are necessary not just for improved communication, but also to recoverable reserves booking, contract negotiations, government incentives, taxation, and regulatory authorities when looking at fiscal issues (Stosur et al., 2003). The following sections summarize the existing definitions used in the petroleum industry and then propose this book’s definitions of EOR and IOR.

1.2.1 Existing Definitions

Apparently, it has been agreed among petroleum professionals that IOR is a general term that implies improving oil recovery by any means; EOR is more specific in concept and can be considered a subset of IOR. According to Taber et al. (1997a), EOR simply means that something other than plain water or brine is injected into the oil reservoir, whereas IOR is a term used more broadly. According to Green and Willhite (1998), the term EOR is used to replace tertiary recovery because the chronological term does not describe some actual operation such as thermal recovery in a viscous oil reservoir. In this case, thermal recovery might be the only way to be able to recover significant oil. EOR results principally from the injection of gases and chemicals and/or the use of thermal energy. IOR includes EOR but also encompasses a broader range of activities—for example, reservoir characterization, improved reservoir management, infill drilling, horizontal well drilling, and sweep efficiency improvement. Selamat et al. (2008) included workover, step-out drilling, and infill drilling into IOR. Jørgenvåg and Sagli (2008) included any activity into IOR programs that may improve oil rate and recovery, whereas EOR refers to reservoir processes that recover oil not produced by secondary processes (Stosur et al., 2003).

High-pressure nitrogen injection is considered an EOR process (Manrique et al., 2007). Some authors (e.g., Moritis, 2000) classify immiscible gas injection as EOR too. In those cases, processes other than pressure maintenance are involved, and the processes result in more oil recovered.

Thomas (2008) defined EOR as a process to reduce oil saturation below the residual oil saturation (Sor). Recovery of oils retained due to capillary forces (after waterflooding in light oil reservoirs) and oils that are immobile or nearly immobile due to high viscosity (heavy oils and tar sands) can be achieved only by lowering the oil saturation below Sor. Such a case needs a definition of residual oil saturation different from the conventional one.

1.2.2 Proposed Definitions

The terms EOR and IOR should refer to reservoir processes. Any practices that are independent of the recovery process itself should not be grouped into either EOR or IOR. Such practices include reservoir characterization, reservoir simulation, use of hardware and equipment (pumps, down-hole separators, etc.), use of special well types (horizontal wells, multilaterals, smart wells, etc.), improved reservoir management, infill drilling, and so on. Oil here means hydrocarbon, including oil and natural gas.

Improved oil recovery refers to any reservoir process to improve oil recovery. Virtually, this term comprises all but the primary processes (Stosur et al., 2003). The following is an incomplete list:

• EOR processes

• Near wellbore conformance control (cement plug/gel treatment for water and gas shutoff)

• Immiscible gas injection (dry gas, CO2, nitrogen, alternating or co-injection with water)

• Water injection, cyclic water injection

• Well stimulation (acidizing and fracturing)

Enhanced oil recovery refers to any reservoir process to change the existing rock/oil/brine interactions in the reservoir. Here is an incomplete list:

• Thermal recovery: in situ combustion—forward: dry, wet, Toe-to-Heel Air Injection (THAI), and CAPRI (i.e., variation of THAI with a catalyst for in situ upgrading); reverse, high-pressure air injection; steam soak and cyclic huff-and-puff steam flood; SAGD, VAPEX (solvent gas VAPor EXtraction), Expanding Solvent VAPEX (ES-VAPEX) or ES-SAGD; Steam And Gas Push (SAGP); hot water drive; electromagnetic

• Miscible flooding: CO2, nitrogen, flue gas, hydrocarbon, solvent

• Chemical flooding: polymer, deep-formation profile control using gels, surfactant, alkaline, emulsion, foam, and their combinations

• Microbial

The classification could never be satisfactory because several processes can be combined. For example, chemicals are added to thermal and miscible EOR processes. Conformance control near wellbore zones, such as cement plug/gel treatment for water and gas shutoff, and acidizing and fracturing well stimulation are grouped into IOR because these processes are not in the reservoir scale even though there are some interactions near the wellbore.

1.3 General Description of Chemical EOR Processes

This book focuses on chemical EOR processes, including alkaline (A), surfactant (S), polymer (P), and any combination of these processes. We discuss emulsion whenever it relates to any chemical processes. In addition, we briefly describe foam when presenting an application of ASP with foam. Emulsion and foam are more related to mobility control. These two processes are not discussed in detail because they are thermodynamically unstable processes quite different from the stable processes we deal with here. Rather, we discuss the general mobility control requirement in EOR processes in Chapter 4.

The mobility control process is based primarily on maintaining a favorable mobility ratio to improve sweep efficiency. Figure 1.2 provides an example of macroscopic displacement efficiency improvement by polymer flooding over waterflooding. The mobility control process is closely coupled with every chemical process. There is hardly any chemical application without injecting a mobility controlling agent. Another fact that further justifies using a mobility control agent (e.g., polymer) is that water phase relative permeability is increased in surfactant flooding. Therefore, this book first discusses the general concept of mobility control, followed by polymer flooding.

FIGURE 1.2 Schematic of macroscopic displacement efficiency improvement by polymer flooding (b) over waterflooding (a).

Source: Courtesy of Surtek, a chemical EOR service company in Golden, Colorado.

A fundamental chemical process is surfactant flooding in which the key mechanism is to reduce interfacial tension (IFT) between oil and the displacing fluid. The mechanism, because of the reduced IFT, is associated with the increased capillary number, which is a dimensionless ratio of viscous-to-local capillary forces. Experimental data show that as the capillary number increases, the residual oil saturation decreases (Lake, 1989). Therefore, as IFT is reduced through the addition of surfactants, the ultimate oil recovery is increased. In alkaline flooding, the surfactant required to reduce IFT is generated in situ by the chemical reaction between injected alkali and naphthenic acids in the crude oil. However, more important mechanisms in alkaline injection are its synergy with surfactant and its function to reduce surfactant (even polymer) adsorption.

The synergy makes the alkaline-surfactant process more robust and results in a wider range of application conditions. In modern chemical EOR, the most important processes are to reduce the amount of injected chemicals and to fully explore the synergy of different processes. This effort has resulted in the alkaline-surfactant-polymer (ASP) process. Laboratory studies, pilot tests, and field applications have demonstrated the greatest potential for enhancing oil recovery. However, some problems, such as scaling and emulsion, have also emerged in practical applications. Although ASP has the greatest potential, the practical problems lead operators to consider chemical processes without alkaline injection. Other factors challenging chemical EOR processes include expensive water treatment such as filtering, softening, and post-filtering; disposal of produced chemical solution; initial capital investment for facilities and equipment; and so on.

1.4 Performance Evaluation of EOR Processes

A common measure of the success of an EOR process is the incremental oil recovery factor. Figure 1.3 shows the schematic of incremental oil recovery from an EOR process. The oil production rates from B to C are extrapolated rates, and the cumulative oil at D is the predicted ultimate oil recovery had the EOR process not been initiated at B. The time from B to C is required to respond to an EOR process. The cumulative oil at E is the ultimate oil recovery at the end of the EOR process. Consequently, the difference of cumulative oil between E and D is the incremental EOR oil recovery. For a chemical EOR process, the EOR oil is generally the incremental over waterflooding. Incremental enhanced oil recovery is commonly represented by the incremental oil recovery factor, which is the incremental oil recovered divided by the original oil in place (OOIP). Be aware that instead of using OOIP, we sometimes use the remaining oil after waterflooding to calculate the incremental oil recovery factor.

FIGURE 1.3 Incremental oil recovery from an EOR process.

Another measure of the success of chemical EOR is the amount of chemical injected in pounds per barrel of incremental oil produced (lb/bbl), or tons of oil produced per ton of chemical injected, a figure often used in China to represent polymer flooding efficiency. Chang et al. (2006) reported that incremental oil recovery factors of up to 14% of the OOIP have been obtained in polymer flooding good-quality reservoirs, and incremental oil recovery factors of up to 25% of OOIP have been reported in ASP pilot areas.

To estimate ultimate oil recovery, we have to extrapolate the production rate to an economic cutoff at which the production wells are shut-in. In waterflooding and chemical flooding, the economic cutoff is generally 98% water cut. The ultimate oil recovery will be the cumulative oil production by the cutoff.

If the economic cutoff of 98% water cut is used for both waterflooding and chemical flooding, then the total injection pore volumes (PVs) from these two processes could be different. Generally, the total injection PV in waterflooding is larger than that in chemical flooding. To compare the performance of the two processes at any time t, we should normalize the injection pore volume using the equation

is the normalized injection PV, PV(t) is the injection PV of waterflood or chemical flood at any time, PV0 is the start time of chemical flood, and PV1 is the total injection PV of waterflood or chemical food at the final cutoff.

The schematic interpretation of the idea is shown in and 1 corresponding to PV0 and PV1C, respectively, for it), the normalized water-cut curve for waterflooding is shown in the figure. We can see that the normalized water-cut curve for waterflooding is above the original curve. It is implied that waterflood performance is actually worse (a higher water cut) if we take into account that more water is injected compared with the chemical flood.

FIGURE 1.4 Schematic of water-cut curves of waterflooding, chemical flooding, and normalized waterflooding.

1.5 Screening Criteria for Chemical EOR Processes

A publication that specifically focuses on the screening criteria for chemical processes has not been seen in the literature. Screening criteria for broader EOR processes have been discussed by several researchers—for example, Taber et al. (1997a, 1997b), Al-Bahar et al. (2004), and Dickson et al. (2010). This section briefly summarizes several critical parameters regarding chemical EOR application conditions. Many parameters could affect chemical EOR processes; however, the most critical parameters should be reservoir temperature, formation salinity and divalent contents, clay contents, and oil viscosity. For polymer flooding, permeability is another critical parameter.

1.5.1 Formation

Almost all chemical EOR applications have been in sandstone reservoirs, except a few stimulation projects and a few that have not been published have been in carbonate reservoirs. One reason for fewer applications in carbonate reservoirs is that anionic surfactants have high adsorption in carbonates. Another reason is that anhydrite often exists in carbonates, which causes precipitation and high alkaline consumption. Clays also cause high surfactant and polymer adsorption and high alkaline consumption. Therefore, clay contents must be low for a chemical EOR application to be effective.

1.5.2 Oil Composition and Oil Viscosity

Oil composition is very important to alkaline-surfactant flooding because different surfactants must be selected for different oils, but it is not critical to polymer flooding. According to Taber et al. (1997a, 1997b), oil viscosity should be less than 35 mPa·s for A/S projects. For polymer flooding, oil viscosity could be 10 to 150 mPa·s. Sorbie (1991) defined 30 mPa·s as the upper limit of oil viscosity for polymer flooding, and 70 mPa·s as the maximum. In Chinese ASP projects, the oil viscosity is around 10 mPa·s, whereas for polymer projects, the median viscosity is about 20 mPa·s with the maximum viscosity being about 90 mPa·s. Recently, there has been an increasing research interest in chemical EOR for oils with higher viscosities.

1.5.3 Formation Water Salinity and Divalents

Formation water salinity and divalents are critical to chemical EOR processes for both surfactants and polymers. Although chemical suppliers claim their products can be tolerant to high salinity, most of the chemical EOR processes have been applied in low-salinity reservoirs. For most of the Chinese EOR projects, the formation water salinity is below 10,000 ppm, and fresh water is injected. The criterion Al-Bahar et al. (2004) discussed is 50,000 ppm salinity and 1000 ppm hardness. This 1000 ppm hardness is probably too high or needs extra chelating agents. It must be emphasized that the salinity and divalent limits depend on the type of polymer used. Biopolymer xanthan is much more salinity or hardness tolerant than HPAM.

1.5.4 Reservoir Temperature

According to Taber et al. (1997a, 1997b), the reservoir temperature should be lower than 93°C for A/S/P projects, but the average temperature for the actual A/S field projects they reported was 27°C. The average temperature for their reviewed 171 polymer projects was 49°C for the projects (Taber et al., 1997b); however, some chemical suppliers state that polymer can be applied up to 120°C. Daqing reservoir temperature is about 45°C. The maximum temperature for a few Chinese projects was in the order of 80°C. The criterion Al-Bahar et al. (2004) used is 70°C, which is on the lower side. Sorbie’s (1991) upper limit for polymer is 80°C, and the maximum is 95°C.

1.5.5 Formation Permeability

High permeability is favorable to chemical flooding, and it is critical to polymer flooding. Low-permeability formation will have injectivity and excess retention problems. Interestingly, Taber et al. (1997a) showed that although the criterion for chemical projects is greater than 10 md, the average permeabilities in their reviewed actual projects were 450 md for A/S and 800 md for polymer flooding. In Chinese chemical EOR projects, the permeability is 100 to 1000s md.

The data provided here can serve as a reference for potential projects. Among the parameters discussed in the preceding paragraphs, reservoir temperature and water salinity are the most critical parameters. However, as chemical products are improved, the criteria will be changed. From the current chemical EOR technology, extensive laboratory measurements still are needed for every project. Simulation work is needed to analyze laboratory data and upscale to a field model for potential prediction. The chemical EOR application in fields of high temperature and high salinity is still a challenging task.

1.6 Naming Conventions and Units

The chapters in this book are organized based on individual processes and combinations of individual processes. The individual processes are mainly polymer flooding (P), surfactant flooding (S), and alkaline flooding (A). A mixed process can be any combination of these individual processes—for example, surfactant-polymer flooding (SP) and alkaline-surfactant-polymer flooding (ASP). Here, the hyphen (-) between individual processes represents a combination. In the literature, a forward slash (/) is used more often—for example, alkaline/surfactant/polymer (A/S/P). We propose that if chemicals are mixed and injected in a single slug, a hyphen should be used; if chemicals are injected in sequential slugs, a forward slash should be used. For example, if surfactant and polymer are mixed and injected in a single slug, the term surfactant-polymer (SP or S-P) should be used. If surfactant and polymer are injected in sequentially separate slugs, the term surfactant/polymer (S/P) should be used. In this book, the numerical and alphabetical notations for phases are as shown in Table 1.1. The numerical and alphabetical notations for components (species) are as shown in Table 1.2.

TABLE 1.1 Numerical and Alphabetical Phases Notations

TABLE 1.2 Numerical and Alphabetical Components Notations

A parameter Vij means Parameter V, Component i in Phase j; for example, V13 means the water volume in the microemulsion phase. For this example, Vwm is the alphabetical form. The numerical and alphabetical notations for total concentrations of components are as shown in Table 1.3.

TABLE 1.3 Numerical and Alphabetical Total Concentrations of Components Notations

Sometimes the fluid concentration is expressed in the units M, m, and N. M is an abbreviation of the solubility unit, molarity, which is the number of moles (or gram formula weights) of solute in one liter (L) of solution. The abbreviation m is another unit, molality, which is the number of moles (or gram formula weights) of solute in one kilogram of solvent. A molar concentration is labeled with a square bracket. The unit of N is meq/mL. The unit of meq/mL is equivalent mole/L, or the equivalent milimole/mL. The general units of parameters are listed in the Nomenclature section at the beginning of this book. Some of the units used frequently in this book are listed there as well. For some formulas or equations, if the units are not specified, use of consistent units or the SI units should be assumed.

1.7 Organization of This Book

The basic chemical processes are polymer flooding (Chapter 5), surfactant flooding (Chapter 7), and alkaline flooding (Chapter 10). The fundamentals of these processes are detailed in their respective chapters. There are a few combinations of these basic processes. The important aspects of each combination are their interactions and their synergies. Therefore, we have dedicated specific chapters to these interactions and synergies: Chapter 9 for the surfactant-polymer interaction and compatibility, Chapter 11 for the alkali-polymer interaction and synergy, and Chapter 12 for the alkali-surfactant synergy. Chapter 13 describes alkaline-surfactant-polymer flooding; it focuses on the practical issues of the ASP process and discusses pilot tests and field applications.

Understanding the mechanisms of chemical flow helps us design chemical flooding. The transport of chemicals and fractional flow theories are summarized in Chapter 2. Salinity plays an important role in chemical flooding, so we discuss the salinity effects and ion exchange in Chapter 3 and the optimum salinity profile in Chapter 8. Mobility control is compulsory for a chemical flooding process. Consequently, we discuss the general mobility control requirement in EOR processes in Chapter 4. It has been observed in Daqing that polymer viscoelastic properties can reduce residual oil saturation and further improve polymer performance; therefore, this issue is reviewed in Chapter 6.

Transport of Chemicals and Fractional Flow Curve Analysis

2.1 Introduction

Diffusion and dispersion are important mechanisms for the transport of chemicals. This chapter first addresses diffusion and dispersion in the single phase flow. Then it discusses the fractional flow curve analysis in the water/oil two-phase flow. Fractional flow curve analysis may not provide an accurate estimate of actual field flood performance, but it is a good tool for mechanism analysis.

2.2 Diffusion

This section discusses diffusion coefficients in a bulk phase and a porous medium. It also briefly introduces a statistical representation of diffusion. Diffusion is less significant in reservoir flow than dispersion and their mechanisms are different, but the discussion of diffusion provides an analog to the formulation of dispersion.

2.2.1 Diffusion in a Bulk Liquid or Gas Phase

The basic concept of diffusion refers to the net transport of material within a single phase in the absence of mixing (by mechanical means or by convection). Both experiment and theory have shown that diffusion can result from pressure gradients (pressure diffusion), temperature gradients (thermal diffusion), external force fields (forced diffusion), and concentration gradients. Only the last type is considered in this book; that is, the discussion is limited to diffusion caused by the concentration difference between two points in a stagnant solution. This process, called molecular diffusion, is described by Fick’s laws. His first law relates the flux of a chemical to the concentration gradient:

where F is the flux (mol/s/cm²), C is the concentration (mol/cm³), and D0 is the diffusion coefficient (cm²/s) in a bulk liquid or gas phase. The values of diffusion coefficients of ions in water are reported in Appelo and Postma (2007). For multicomponent solutions, an average diffusion coefficient of 1.3 × 10−5 cm²/s may be used. According to these authors, the values at any temperature can be obtained using Eq. 2.2,

where T is the absolute temperature in degrees Kelvin (°K), and µ is the water viscosity in mPa·s. In the equation, the reference temperature is 298 °K. For neutral organic molecules, the diffusion coefficient can be estimated from Eq. 2.3 (Lyman et al., 1990; Schwartzenbach et al., 1993),

where Vl is the liquid molar volume of the substance in cm³/mol.

2.2.2 Diffusion in a Tortuous Pore

Equation 2.1 defines the flux in a bulk liquid or gas phase (with unit porosity or in a straight capillary). The effect of tortuous paths has to be considered in a porous medium. We use the effective diffusion coefficient, Dτ, to replace D0 in Eq. 2.1 to consider the effect of tortuosity. The relationship between Dτ and D0 may be defined (Childs, 1969) using Eq. 2.4,

where τ is the tortuosity of the porous medium, which is defined as the length of the actual travel path taken by a solute divided by the straight line distance. And the tortuosity is related to the formation electrical resistivity factor, FR, defined as the electrical resistivity of a porous medium with a liquid that conducts electricity divided by the electrical resistivity of the liquid in the porous medium,

where φ is the porosity in fraction. The empirical relationship between the formation electrical resistivity factor and porosity takes the form of Archie’s law,

where the exponent n varies from 1.4 to 2.0 (McNeil, 1980). When n is taken to be 2, we have

For a small volume as shown in Figure 2.1, the mass that enters from the left side is

FIGURE 2.1 Concentration changes in a small volume due to diffusion.

and the mass that leaves from the right side is

(2.9)

The mass balance for the small volume is

(2.10)

Thus, we have

Equation 2.11 is known as Fick’s second law of diffusion.

2.2.3 Statistical Representation of Diffusion

The diffusion process is molecular in nature. It results from the random Brownian motion of molecules in solution. Appelo and Postma (2007) showed that the solution of Eq. 2.11 can be related to the normal density function. Consider the initial condition where no chemical is present at time t < 0, N moles are injected at the origin, x = 0. This is known as a single shot input or Dirac delta function. As t → 0, C = 0 everywhere except at the origin where C → ∞. The solution of Eq. 2.11 for the initial conditions stated is

where N is the input mass (moles) at time t = 0 at x = 0. C(x, t) is expressed in mol/cm for convenience because we consider only one dimension.

Fundamentally, Eq. 2.12 is analogous to the normal density function (the Gaussian curve),

where x0 is the average location (in Eq. 2.12, x0 = 0), and σ² is the variance of the distribution. Diffusion can therefore be treated as a statistical process. Because Eqs. 2.12 and 2.13 are fundamentally the same, the variance σ² is related to the diffusion coefficient by

, the sphere where 68% of a point source is located has a radius r = σxyz:

2.3 Dispersion

Dispersion is an important issue in chemical processes in porous media, but we are really challenged to quantify this parameter because of its scale dependency. This section presents the empirical correlations to estimate dispersion coefficients in the laboratory scale and discusses the methods to estimate dispersivities in the large field scale.

2.3.1 Concept of Dispersion

The previous section discussed diffusion in the absence of gross fluid movement. If fluids are flowing through a porous medium, some additional mixing may be taking place. This increased mixing caused by uneven fluid flow or caused by concentration gradients resulting from fluid flow will be designated dispersion. In other words, dispersion is caused by variations (heterogeneity) in the velocity, whereas molecular diffusion is caused by the concentration gradient. There are two types of dispersion. One is the dispersion in the longitudinal direction or in the direction of gross fluid movement, and it is represented by DL (Kℓ in the petroleum literature), the longitudinal dispersion coefficient. The other one is the dispersion transverse to the direction of gross fluid movement, and it is represented by DT (Kt in the petroleum literature), the transverse dispersion coefficient.

Bear (1972) suggested hydrodynamic dispersion is the macroscopic outcome of the actual movements of the individual tracer particles through the pores and various physical and chemical phenomena that take place within the pores. This movement can arise from a variety of causes. Dispersion is the mixing of two miscible fluids caused by diffusion, local velocity gradients (as between a pore wall and a pore center), locally heterogeneous streamline lengths, and mechanical mixing in pore bodies, according to Lake (1989). The physical process behind dispersion is different from diffusion, which will be more evident in the subsequent discussion; however, we still use the form of Fick’s law (Eq. 2.1) to quantify dispersion:

Here, we have substituted DL, the longitudinal dispersion coefficient, in Eq. 2.16 for Dτ, the diffusion coefficient, in Eq. 2.1.

2.3.2 Estimate Longitudinal Dispersion Coefficient from Experimental Data

When we derived the diffusion equation (Eq. 2.11), there was no bulk fluid flow. Referring to Figure 2.1, in the case of bulk flow, the mass that enters from the left side is the sum of the dispersion component and the flow component:

(2.17)

Here, the longitudinal dispersion coefficient DL is used, and v is the interstitial velocity equal to the Darcy velocity, u, divided by the porosity, φ. Similarly, the mass that leaves from the right side is

(2.18)

The mass balance for the small volume is

(2.19)

Thus, we have

Equation 2.20 is the advection-dispersion (AD) equation. In the petroleum literature, the term convection-diffusion (CD) equation is used, or simply diffusion equation (Brigham, 1974). When a reaction term is included, the term advection-reaction-dispersion (ARD) equation is used elsewhere. When the adsorption term is expressed as a reaction term, the ARD equation is as discussed later in Section 2.4. Several solutions of Eq. 2.20 have been presented in