5 The Five Reservoir Fluids Before reading this chapter, go back to the last pages of Chapter 2 and review imulticomponent phase diagrams. Remember that all five of Figures 2-32 through 2-36 are for petroleum mixtures, Examination of these figures shows the wide variety of shapes and sizes of petroleum phase diagrams. Numerous components make up these petroleum mixtures. Diverse chemical species are found in them. And the types and quantities of the components of a particular mixture fix the shape of its phase diagram. The behavior of a reservoir fluid during production is determined by . the shape of its phase diagram and the position of its critical point. Our knowledge of the behavior of two-component mixtures will serve as a guide to the behavior of these multicomponent mixtures; a quick review of the first few pages of the two-component mixtures section of Chapter 2 might be useful. Unmistakable similarity exists between the phase diagrams of two-component and multicomponent mixtures. Chapter 5 begins with a short discussion of the relationship of composition to the shape of the phase diagram as evidenced by two-component mixtures. However, the major purpose of this chapter is to define and describe the five types of petroleum reservoir fluids. Each will be defined by reference to the shape of its typical phase diagram. Several rules of thumb wil! be given to assist in determining fluid type from normally available production data. Many of the producing characteristics of each type of fluid will be discussed. Ensuing chapters will address the physical properties of these five reservoir fluids,with emphasis on black oils, dry gases, and wet gases. Multicomponent Phase Diagrams Figure 2-37 shows phase diagrams for several mixtures of ethane and n-heptane. These are two-component mixtures; however, the shapes of the phase diagrams can.be used in understanding the behavior of multicomponent mixtures. 147148 PETROLEUM FLUIDS Mixture 2 on Figure 2-37 illustrates a mixture containing a large quantity of the light component. The phase envelope is relatively small and is located at low temperatures. The critical point is located far down the left-hand side of the phase envelope and is fairly close to the critical point of the pure light component. There is a large area in which retrograde condensation can occur. As heavy component is added to the mixtures—lines 3 and 4, for instance—the phase envelope increases in size and covers wider ranges of temperature and pressure. The critical point moves up closer to the top of the envelope. Phase behavior of multicomponent reservoir fluids is similar. Reser- voir gases, which are predominately methane, have relatively small phase diagrams with critical temperatures not much higher than the critical Temperaturé “of methane. The ‘critical ‘point’is “far down the left slope of the envelope. Reservoir liquids contain some methane, normally the lightest compo- nent of any significance. Reservoir liquids also contain a wide variety of intermediate and very large molecules. Their phase diagrams are extremely large and cover a wide range of temperature, analogous to mixture 6 of Figure 2-37. However, in naturally occurring petroleum liquids, the critical point does not normally appear to the right of the top of the phase envelope. Only those reservoir liquids which are deficient in intermediate components (often found in south Louisiana) or which have considerable dissolved nitrogen will have critical points to the right of the top of the phase envelope. The Five Reservoir Fluids There are five types of reservoir fluids. These are usually called black oil, volatile oil, retrograde gas, wet-gas, and dry gas. The five types of reservoir fluids have been defined because each requires different approaches by reservoir engineers and production engineers. ‘The petroleum engineer should determine the type of fluid very early in the life of his reservoir. Fluid type is the deciding factor in many of the decisions which must be made regarding the reservoir. The method of fluid sampling, the types and sizes of surface equipment, the calcula- tional procedures for determining oil and gas in place, the techniques of predicting oil and gas reserves, the plan of depletion, and the selection of enhanced recovery method are all dependent on the type of reservoir fluid.The Five Reservoir Fluids 149 Identification of Fluid Type Reservoir fluid type can be confirmed only by observation in the laboratory. Yet, readily available production information usually will indicate the type of fluid in the reservoir. Rules of thumb will be given for identification of each of the five fluid types. Three properties are readily available: the initial producing gas-oil ratio, the gravity of the stock-tank liquid, and the color of the stock-tank liquid. Initial producing gas-oil ratio is by far the most important indicator of fluid type. The color of stock-tank liquid alone is not a good indicator of fluid type. However, stock-tank liquid gravity and color are useful in confirming the fluid type indicated by the producing gas-oil ratio. If all three indicators—initial gas-oil ratio, stock-tank liquid gravity, and stock-tank liquid color—do not fit within the ranges given in the rules of thumb, the rules fail and the reservoir fluid must be observed in the laboratory to determine its type. Do not attempt to compare fluid types as defined here with the reservoir descriptions as defined by the state regulatory agencies which have jurisdiction over the petroleum industry. The legal and regulatory definitions of oil, crude oil, gas, natural gas, condensate, etc., usually do- not bear any relationship to. the engineering definitions given here. In fact, the regulatory definitions are often contradictory. Black Oils Black oils consist of a wide variety of chemical species including large, heavy, nonvolatile molecules. ‘The phase diagram predictably covers a wide temperature range. The critical point is well up the slope of the phase envelope. . Black Oil Phase Diagram The phase diagram of a typical black oil is shown in Figure 5-1. The lines within the phase envelope represent constant liquid volume, measured as percent of total volume. These lines are called iso-vols or quality lines. Note that the iso-vols are spaced fairly evenly within the envelope. _ The vertical line 123 indicates the reduction in pressure at constant temperature that occurs in the reservoir during production. The pressure and temperature of the separator located at the surface are indicated too. ‘When reservoir pressure ies anywhere along line 12 , the oil is said to be undersaturated. The word undersaturated is used in this sense to150 PETROLEUM FLUIDS Black oil Prosaure path In rasorvole Critical point Temperature Fig. 5-1. Phase diagram of a typical black ail with line of isothermal reduction of reservoir pressure, 128, and surface separator conditions. indicate that the oil could dissolve more gas if more gas were present. If the reservoir pressure is at point 2, the oil is at its bubble point and is said to be saturated. The oil contains as much dissolved gas as it can hold. A reduction in pressure will release gas to form a free gas phase in the reservoir. _ As reservoir pressure declines along line 23 , additional gas is evolved in the reservoir. The volume of gas on a percentage basis is one hundred minus the percent liquid. Water is always present in a petroleum reservoir but is not included in this discussion. _ Actually, the oil is “‘saturated”’ anywhere along line 23 . The bubble point, point 2, is a special case of saturation at which the first bubble of gas forms. Unfortunately, the word ‘‘saturated’’ is often used to mean “bubble point.’”” Additional gas evolves from the oil as it moves from the reservoir to the surface. This causes some shrinkage of the oil. However, separator conditions lie well within the phase envelope, indicating that a relatively large amount of liquid arrives at the surface.‘The Five Reservoir Fluids 151 Comments The name black oil is a misnomer since the color of this type of oil is not always black. This type of reservoir fluid has also been called low- shrinkage crude oil or ordinary oil.) Field identification of Black Oils Black oils are characterized as having initial producing gas-oil ratios of 2000 scf/STB or less.* Producing gas-oil ratio will increase during production when reservoir pressure falls below the bubble-point pressure of the oil. The stock-tank oil usually wil] have a gravity below 45°API. Stock-tank oil gravity will slightly decrease with time until late in the life of the reservoir when it will increase. The stock-tank oil is very dark, indicating the presence of heavy hydrocarbons, often black, sometimes with a greenish cast, or brown. Laboratory Analysis of Black Oils Laboratory analysis wil] indicate an initial oil formation volume factor of 2.0 res bbI/STB or less. Oil formation volume factor is the quantity of reservoir liquid in barrels required to produce one stock-tank barrel. Thus, the volume of oi] at point 2 of Figure 5-1 shrinks by one-half or Jess on its trip to the stock tank. Laboratory determined composition of heptanes plus will be higher than 30 mole percent, an indication of the large quantity of heavy hydrocarbons in black oils. Volatile Oils Volatile oils contain relatively fewer heavy molecules and more intermediates (defined as ethane through hexanes) than black oils. Volatite Oil Phase Diagram The phase diagram for a typical volatile oil, Figure S—2, is somewhat > different from the black-oil phase diagram. The temperature range covered by the phase envelope is somewhat smaller, but of more interest is the position of the critical point. The critical temperature is much lower than for a black oil and, in fact, is close to reservoir temperature. Also, the iso-vols are not evenly spaced but are shifted upwards toward the bubble-point line.152 PETROLEUM FLUIDS Volatile oll Preasure Temperature Fig. 5-2. Phase diagram of a typical volatile oil with line of isothermal reduction of reservoir pressure, 123, and surface separator conditions. The vertical line shows the path taken by the constant-temperature reduction in pressure during production. Notice that a small reduction in pressure below the bubble point, point 2, causes the release of a large amount of gas in the reservoir. A volatile oil may become as much as 50 percent gas in the reservoir at only a few hundred psi below the bubble-point pressure. Also, an iso-vol with a much lower percent liquid crosses the separator conditions. Hence the name volatile oil. Comments Volatile oils also have been called high-shrinkage crude oils, and near-critical oils." The set of equations known collectively as “material balance equa- tions” which are used for black oils will not work for volatile oils. These equations were derived under the assumption that the gas associated with the reservoir liquid is a dry gas (defined later). This is true for black oilsThe Five Reservoir Fluids 153 except at low reservoir pressures. However, the gas associated with a volatile oil is very rich, usually a retrograde gas (defined later). This rich gas releases a large quantity of liquid as it moves to the surface. Often over one-half of the stock-tank liquid produced during the life of a volatile oil reservoir entered the wellbore as part of the gas. This situation causes the material balance equations to be invalid for volatile oils. Field Identification of Volatile Oils The dividing line between black oils and volatile oils is somewhat arbitrary. The difference depends largely on the point at which the material balance equations begin to have intolerable inaccuracy. The dividing line between volatile oils and retrograde gases is clear. For a fluid to be a volatile oil its critical temperature must be greater than reservoir temperature. Volatile oils are identified as having initial producing gas-oil ratios between 2000 and 3300 scf/STB.? The producing gas-oil ratio increases as production proceeds and reservoir pressure falls below the bubble- point pressure of the oil. The stock-tank oil gravity is usually 40°API or higher and increases during production as reservoir pressure falls below the bubble point. The stock-tank oil is colored (usually brown, orange, or sometimes green). Laboratory Analysis of Volatile Oils Laboratory observation of volatile oils will reveal an initial oil formation volume factor greater than 2.0 res bbI/STB. The oil produced at point 2 of Figure 5—2 will shrink by more than one-half, often three- quarters, on the trip to the stock tank. Volatile oils should be produced through three or more stages of surface separation to minimize this shrinkage. Laboratory determined compositions of volatile oils will have 12.5 to 30 mole percent hepianes plus. The dividing line between volatile oils and retrograde gases of 12.5 mole percent heptanes plus is fairly definite.” When the heptanes plus concentration is greater than 12.5 mole percent, the reservoir fluid is almost always liquid and exhibits a bubble point. When the heptanes plus concentration is less than 12.5 mole percent, the reservoir fluid is almost always gas and exhibits a dew point. Any exceptions to this rule normally do not meet the rules of thumb with regard to stock-tank oil gravity and color.154 PETROLEUM FLUIDS Prousure path in regarvotr 1 Retrograde gas Pressure 2 Separator Temperature Fig. 5-3. Phase diagram of a typical retrograde gas with line of isothermal reduction of reservoir pressure, 123, and surface separator conditions. Retrograde Gases The third type of reservoir fluid we will consider is retrograde gas. Retrograde Gas Phase Diagram The phase diagram of a retrograde gas is somewhat smaller than that for oils, and the critical point is further down the left side of the envelope. These changes are a result of retrograde gases containing fewer of the heavy hydrocarbons than do the oils. The phase diagram of a retrograde gas has a critical temperature less than reservoir temiperature and a cricondentherm greater than reservoir temperature. See Figure 5—3. Initially, the retrograde gas is totally gas in the reservoir, point 1. As reservoir pressure decreases, the retrograde gas exhibits a dew point, point 2. As pressure is reduced, liquid condenses from the gas to form a free liquid in the reservoir. This liquid will normally not flow and cannot be produced.The Five Reservoir Fluids 155 The reservoir pressure path on the phase diagram, Figure S—3, indicates that at some low pressure the liquid begins to revaporize. This occurs in the laboratory; however, it probably does not occur to much extent in the reservoir because during production the overall composition of the reservoir fluid changes. Field Identification of Retrograde Gases The lower limit of the initial producing gas-oil ratio for a retrograde gas is approximately 3300 scf/STB.” The upper limit is not well defined; values of over 150,000 scf/STB have been observed. Gas-oil ratios this high indicate that the phase diagram is much smaller than shown in Figure 5—3. Gases with high gas-oil ratios have cricondentherms close to reservoir temperature and. drop very little retrograde liquid in the reservoir. As a practical matter, when producing gas-oil ratio is above 50,000 scf/STB, the quantity of retrograde liquid in the reservoir is very small and the reservoir fluid can be treated as if it were a wet gas (defined later). o Producing gas-oil ratios for a retrograde gas will increase after production begins when reservoir pressure falls below the dew-point pressure of the gas. Stock-tank liquid gravities are between 40° and 60°API and increase as reservoir pressure falls below the dew-point pressure.” The liquid can be lightly colored, brown, orange, greenish, or water-white. Laboratory Analysis of Retrograde Gases Retrograde gases exhibit a dew point when pressure is reduced at reservoir temperature. The heptanes plus fraction is less than 12.5 mole percent. Retrograde behavior will occur at reservoir conditions for gases with less than one percent heptanes plus, but for these gases the quantity of retrograde liquid is negligible. Comments Retrograde gases are also called retrograde gas-condensates, retro- grade condensate gases, gas condensates, or condensates.' The use of the word “condensate” in the name of this reservoir fluid leads to much confusion. Initially, the fluid is gas in the reservoir and exhibits retrograde behavior. Hence, the correct name is retrograde gas.156 PETROLEUM FLUIDS Stock-tank liquid produced from retrograde gas reservoirs often is called condensate. The liquid produced in the reservoir is called condensate also. A better name is retrograde liquid. An initial producing gas-oil ratio of 3300 to 5000 scf/STB indicates a very rich retrograde gas, one which will condense sufficient liquid to fill 35 percent or more of the reservoir volume. Even this quantity of liquid seldom will flow and normally cannot be produced. The surface gas is very rich in intermediates and often is processed to remove liquid propane, butanes, pentanes, and heavier hydrocarbons. These liquids often are called plant liquids. The gas-oil ratios in the rules of thumb discussed above do not include any of these plant liquids. Wet Gases The fourth type of reservoir fluid we will discuss is wet gas. Wet Gas Phase Diagram ‘The entire phase diagram of a hydrocarbon mixture of predominately smaller molecules will lie below reservoir temperature. An example of the phase diagram of a wet gas is given in Figure 5-4. A wet gas exists solely as a gas in the reservoir throughout the reduction in reservoir pressure. ‘The pressure path, line 12 , does not enter the phase envelope. Thus, no liquid is formed in the reservoir. However, separator conditions lie within the phase envelope, causing some liquid to be formed at the surface. Comments The surface liquid normally is called condensate, and the reservoir gas sometimes is called condensate-gas. This leads to a great deal of confusion between wet gases and retrograde gases. The word “wet” in wet gas does not mean that the gas is wet with water but refers to the hydrocarbon liquid which condenses at surface conditions, In fact, reservoir gas is normally saturated with water. Field Identification of Wet Gases ‘Wet gases produce stock-tank liquids with the same range of gravities as the liquids from retrograde gases. However, the gravity of the stock- tank liquid does not change during the life of the reservoir. The stock- tank liquid is usually water-white. True wet gases have very highThe Five Reservoir Fluids 187 Prossure path i renervalt 1 Wet gas Pressure ‘° Separator Temperature Fig. 5-4. Phase diagram of a typical wet gas with line of isothermal reduction of reservoir pressure, 12 , and surface separator conditions. producing gas-oil ratios. Producing gas-oil ratios will remain constant during the life of a wet gas reservoir. For engineering purposes, a gas which produces more than 50,000 scf/STB can be treated as if it were a wet gas. Dry Gases The fifth type of reservoir fluid we will consider is dry gas. Dry Gas Phase Diagram Dry gas is primarily methane with some intermediates. Figure 55 shows that the hydrocarbon mixture is solely gas in the reservoir and that normal surface separator conditions fall outside the phase envelope. Thus, no liquid is formed at the surface.158 PETROLEUM FLUIDS Prosaure path In reservoir Dry gas Pressure s Separator Temperature Fig. 5-5. Phase diagram of a typical dry gas with line of isothermal reduction of reservoir pressure, 12 , and surface conditions. Comments The word “dry” in dry gas indicates that the gas does not contain enough of the heavier molecules to form hydrocarbon liquid at the surface. Usually some liquid water is condensed at the surface. A dry gas reservoir often is called simply a gas reservoir. This leads to confusion because wet gas reservoirs sometimes are called gas reser- voirs. Further, a retrograde gas initially exists as gas in the reservoir. A set of equations known collectively as gas material balance equations has been devised to determine original gas in place and predict gas reserves. These equations were derived for dry gases and can be used for wet gases, if care is taken in defining the properties of the wet gases. The equations are applicable to retrograde gases only at reservoir pressures above the dew point.