Properties of Reservoir Fluids

Phase Behavior

Fall2010

Shahab Gerami

System & Surrounding

Thermodynamic studies are generally focused on arbitrarily chosen systems while the rest of the universe is assumed as surroundings. System Boundary: the surface of the system - real or imaginary - is called a boundary.

A system is a region of space or quantity of matter we want to study.

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Closed & Open Systems

A system is called a closed system if it does not exchange matter with the surroundings, in opposite to an open system which exchanges matter with the surroundings. Both systems may exchange energy with the surroundings.

Closed system (or control mass)

Open system (or control volume)

Closed System with Moving Boundary

Open System (Control Volume)

Phase
The concept of a closed system is of major interest in applied hydrocarbon thermodynamics. It is called a homogeneous closed system if it contains a single phase, e.g. a natural gas phase or an oil phase. A heterogeneous closed system contains more than one phase. Phase: a phase is defined as a physically homogeneous portion of matter.

The phases of a heterogeneous system are separated by interfaces and are optically distinguishable. It is not obligatory that a phase is chemically homogeneous. It may consists of several compounds, e.g. of a large number of various hydrocarbons.

Property
A property is a characteristic of a system to which numerical values can be assigned to describe the system (Mass, Temperature, Pressure ,Density,...) Property: 1. Extensive Property: Extensive properties are properties which can be counted and their value for the whole system is the sum of the value for subdivisions of the system. They depend on the extent of the system. Examples: Volume, Mass

2. Intensive Property: Intensive properties are independent of the size (mass or volume) of the system. Examples: Density, Temperature

Property

State
The state of a system is defined by the values of its properties. A system is in equilibrium if its properties are not changing at any given location in the system. This is also known as thermodynamic equilibrium or total equilibrium. Equilibrium implies balance--no unbalanced potentials (driving forces) in the system. We will distinguish four different types of equilibrium

State and Equilibrium

Thermodynamics deals with equilibrium states A system is in thermodynamic equilibrium if it maintains thermal, mechanical, phase, and chemical equilibrium.

1. 2. 3. 4.

Thermal equilibrium -- the temperature does not change with time Mechanical equilibrium -- Pressure does not change with time Chemical equilibrium -- molecular structure does not change with time Phase equilibrium mass and composition of each phase is unchanging with time (i.e., same liquid/gas or liquid/solid composition)

State Functions
State functions or state variables are those properties for which the change in state only depends on the respective initial and final state. It is this path-independent characteristic of the state functions that makes it possible to quantify any change of a system.

1 Path 2 Path 1

2 Path 3

V
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Equilibrium
Equilibrium has been defined as a state of rest. In an equilibrium state, no further change or - more precisely - no net-flux will take place unless one or more properties of the system are altered. On the other side, a system changes until it reaches its equilibrium state. Any change of a system is called a thermodynamic interest in the thermodynamic study of the system: adiabatic (no heat added to or removed from the system), isothermal (constant temperature), isobaric (constant pressure), isochoric (constant volume). A process is called reversible if it proceeds through a series of equilibrium states in such a way that the work done by forward change along the path is identical to the work attained from the backward change along the same path. However, all real processes are irreversible with varying degrees of departure from a reversible one.
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Temperature Scales

Atmospheric, Absolute, Gage, and Vacuum Pressures

Phase Behavior
Hydrocarbon reservoirs = Rock + Fluids Reservoir Fluid: Water in brine form and a gaseous and/or liquid hydrocarbon phase are regarded as reservoir fluids. The phase behavior of the actual hydrocarbon mixture in the reservoir can be described as a function of the state of the system. A system in thermodynamic equilibrium possesses an accurately defined relationship between the state variables. These are united in the so-called equation of state:

By specification of two variables, the third will be stipulated.

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Phase Diagram
A phase diagram is a concise graphical method of representing phase behavior of fluids. It provides an effective tool for communicating a large amount of information about how fluids behave at different conditions. Two Classes of Fluids 1. Pure-component systems: the composition is not a variable and therefore cannot influence behavior. 2. Mixtures: the behavior of a mixture is strongly controlled by composition. In fact, as the number of components in the system increases, the complexity of the phase diagram increases as well. Two components Multi components

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Single or Pure-Component System

Figure1

The curve in Figure 1 is called the vapor pressure curve or boiling point curve. The line also represents the dew point curve and the bubble point curve; one on top of the other. This curve represents the transition between the vapor and liquid states.
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Definition of Basic Terms

Vapor Pressure: The pressure that the vapor phase of a fluid exerts over its own liquid at equilibrium at a given temperature. Dew Point: The pressure and temperature condition at which an infinitesimal quantity of liquid (a droplet) exists in equilibrium with vapor. It represents the condition of incipient liquid formation in an initially gaseous system. Notice that it can be also visualized as a liquid system where all but an infinitesimal quantity of liquid has been vaporized. Bubble Point: The pressure and temperature condition at which the system is all liquid, and in equilibrium with an infinitesimal quantity (a bubble) of gas. This situation is, in essence, the opposite of that of the dew point.

Figure1
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Definition of Basic Terms

NOTE: For single-component systems, one single curve represents all three of these conditions (vapor pressure, dew point and bubble point conditions) simply because Vapor Pressure = Dew Point = Bubble Point for unary systems.

Figure1

In Figure 1, once a saturation pressure has been selected, there is one (and only one) saturation temperature associated with it. This is only true for a single component system. In other words, this is the only temperature (at the given pressure), at which liquid and gas phase will co-exist in equilibrium. The rule that governs the uniqueness of this point, for a single-component system, is called the Gibbs Phase Rule. 18

Complete P-T Diagram for Pure-component Systems

Figure2

Two very important thermodynamic points bound the vapor pressure curve: the Critical Point at its upper end and the Triple Point at its lower end.

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Triple Point
The Triple Point is the meeting point of the vapor pressure, solidification and sublimation curves; hence, it represents the only condition at which all three phases of a pure substance (solid, liquid and gas) can co-exist in equilibrium.

Figure2 For water, the triple point is at 273.16 K (0.01 C or 32.018 F) and 0.6113 kPa (0.0887 psia).
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Critical Point
At the Critical Point, gas and liquid are in equilibrium without any interface to differentiate them; they are no longer distinguishable in terms of their properties. As we recall, the only location on the P-T diagram where liquid and gas can be found together in equilibrium is along the vapor pressure curve. Hence, the critical point is clearly the maximum value of temperature and pressure at which liquid and vapor can be at equilibrium. This maximum temperature is called the critical temperature (Tc); the corresponding maximum pressure is called the critical pressure (Pc). The critical point is the point at which all intensive properties of the gas and liquid phases are equal. An intensive property is a property independent of the quantity of the system. Pressure, temperature, density, composition, and viscosity are examples of intensive properties.

Figure3
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Properties Of The Critical Point (Tc,Pc) (For Pure Substances)

Temperature and pressure for which liquid and vapor are no longer distinguishable. For T > Tc, liquid and vapor will not co-exist, no matter what the pressure is. For P > Pc, liquid and vapor will not co-exist, no matter what the temperature is
The vaporliquid critical point in a pressure temperature phase diagram is at the high temperature extreme of the liquidgas phase boundary. The dotted green line gives the anomalous behavior of water.

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Two Thermodynamic Path to Go from A to B

isobaricheating

Thephaseboundaryrepresents asharpdiscontinuityindensity (andotherphysicalproperties)

thephaseboundaryiscrossed

thephaseboundaryisNOTcrossedatall Path AD: Isothermal compression Path DE: Isobaric heating Path EB: Isothermal expansion We went from an all-liquid condition (point A) to an all-vapor condition (point B) without any sharp phase transition.
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Sensible Heat: Its main purpose is to cause an increase in temperature of the system. Latent Heat: It serves only one purpose: to convert the liquid into vapor. It does not cause a temperature increase.

PV Diagram for Pure Systems

Where is path F-G in this figure?

L+V

The temperature is being held constant; Isothermal compression process path F-G: two-phase condition, the liquid (L) and vapor (V) co-exist in equilibrium E: all-vapor condition F: saturated vapor condition (vapor in equilibrium with an infinitesimal amount of liquid; dew pint G: saturated liquid condition (liquid in equilibrium with an infinitesimal amount of vapor; bubble point
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Family of P-V Isotherms for a Pure Component

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P-V Phase Diagram for a Pure Component

The critical point has a point of inflexion (change of curvature). The critical point also represents the maximum point (apex) of the Pv envelope The criticality conditions:

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Three-dimensional Diagram of Single-Component System

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GIBBS Phase Rule

When referring to the number of phases coexisting in the thermodynamical equilibrium, the phase rule introduced by GIBBS (1928) is applied.

where P: number of phases, C: number of components, F: number of degrees of freedom.

Gibbs, JosiahWillard(18391903)

C is defined as the smallest number of constituents by which the coexisting phases can be completely described. F is defined as the number of quantities such as pressure, temperature, concentrations which can be varied within finite boundaries without changing the number of phases in the system.

Equation describes the system in a qualitative and very general manner. However, no reference to the state variables (p,T), to the composition of the particular phases or to the proportions of the phases are given.
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Waterphasediagram

a)Atthetriplepoint: P=3(solid,liquid,andgas) C=1(water) P+F=C+2 F=0(nodegreeoffreedom) b)liquidsolidcurve P=2 2+F=1+2 F=1 Onevariable(TorP)canbechanged c)Liquid P=1 SoF=2 Twovariables(TandP)canbevariedindependently andthesystemwillremainsa singlephase

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BinarySystem
The real-life systems are never single-component; they are multicomponent systems. The presence of one or more additional components bring the additional complexity in description of phase diagram. The good news: the behavior of multicomponent systems are quite similar to that of binary systems.

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Why is pressure increasing during the phase transition?

When a mixture exists in a twophase condition, different molecules of different species are present and they can be either in a liquid or vapor state (two-phase condition). Some of them would prefer to be in the gas phase while the others would prefer to be in the liquid phase. This preference is controlled by the volatility of the given component.
P-v Diagram for a Binary Mixture

P-v Diagram for a Pure Component

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Pressure/volume diagram for the n-C5 and n-C7 system containing 52.4 wt % n-C7.

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Family of Isotherms on a P-V diagram Binary Mixture

Can we say now that the critical point is the maximum value of pressure and temperature where liquid and gas can coexist? Critical Point (Pc,Tc): The temperature and pressure for which liquid and vapor are indistinguishable. Cricondentherm (Tcc): 1. The highest temperature in the twophase envelope. 2. For T > Tcc, liquid and vapor cannot co-exist at equilibrium, no matter what the pressure is. Cricondenbar (Pcc): 1. The highest pressure in the twophase envelope. 2. For P > Pcc, liquid and vapor cannot co-exist at equilibrium, no matter what the temperature is.

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P-V diagram of a Binary Mixture

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P-T diagram of a Binary Mixture

PT diagram for two pure components and PT diagram for a 50:50 mixture of the same components

Quality lines describe the pressure and temperature conditions of equal volumes of liquid. Obviously, the bubble-point curve and the dew-point curve represent 100% and 0% liquid, respectively.

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Retrograde Phenomenon
Regarding multi-component mixtures (where the binary system is the simplest case), some interesting phenomenon profoundly differentiate their behavior from the behavior of single-component systems. We are now talking about retrograde phenomena.

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Retrograde Phenomenon
Let us now consider the isothermal processes taking place at T = T1 and T = T2

T1 < Tc

Tc < T2 < Tcc

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A Typical Liquid Shrinkage Volume Curve for a Relatively Rich Condensate System.
The curve is commonly called the liquid dropout curve. The maximum liquid dropout (LDO) is 26.5%, which occurs when the reservoir pressure drops from a dew-point pressure of 5900 psi to 2800 psi. In most gascondensate reservoirs, the condensed liquid volume seldom exceeds more than 1519% of the pore volume. This liquid saturation is not large enough to allow any liquid flow through the bulk of reservoir.

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Effect of Composition on Phase Behavior

We would expect that the P-T diagram of each pure component will have some sort of influence on the P-T diagram of any mixture in which it is found. it would be reasonable to think that as the presence of a given component A dominates over B, the P-T graph of that mixture (A+B) should get closer and closer to that of A as a pure component. What this is telling us is that a new variable is coming into the picture: composition.

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Phase Diagram of a Methane/Ethane Mixture

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Lightest components Tc < Mixture components Tc < Heaviest components Tc A mixtures Pc can be found to be higher than the critical pressures of both pure components hence, we see a concave shape for the critical locus. In general, the more dissimilar the two substances, the farther the upward reach of the critical locus. When the substances making up the mixture are similar in molecular complexity, the shape of the critical locus flattens down.

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P-x and T-x Diagrams

Inadditiontoconsidering variationswithpressure, temperature, andvolume,aswehave donesofar,itisalsoveryconstructivetoconsidervariationswithcomposition.Most literatureonthesubjectcallsthesediagramsthePxandTxdiagramsrespectively

InaPxdiagram, the bubble point anddewpoint curvesbound the twophase region atits topand itsbottom, respectively In the Tx diagram, this happens in the reverse order; vapor is found at high temperatures and liquid at low temperatures
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TheLeverRule px&TxDiagrams
For a binary system Px and Tx diagrams phase diagrams can give quantitative information pertaining to the amounts of each phase present, as well as the composition of each phase. At a given temperature or pressure in a Tx or Px diagram (respectively), a horizontal line may be drawn through the twophase region that will connect the composition of the liquid (xA) and vapor (yA) in equilibrium at such condition that is, the bubble and dew points at the given temperature or pressure, respectively. If, at the given pressure and temperature, the overall composition of the system (zA) is found within these values (xA < zA < yA in the Tx diagram or yA < zA < xA in the Px diagram), the system will be in a two phase condition and the vapor fraction (G) and liquid fraction (L) can be determined by the lever rule:

NotethatL andG arenotindependent ofeachother,sinceL +G =1.

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TheLeverRulepVDiagram

Considering point D within the 2phase region of the system (specific volume of the system in total), the mass ratio of the liquid and vapor phase being in equilibrium with one another can be calculated by the principle of the lever:
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Ternary Systems

Atriangularcoordinatesystem Features: Anypointwithinthistrianglerepresents theoverallcompositionofaternarysystemat afixedtemperature andpressure. Byconvention,thelightest component(L)islocatedattheapexortopofthetriangle. Theheavy(H)andmedium(M)componentsareplacedatthelefthandcornerandright handcorner,respectively. Everycornerrepresents apurecondition.Hence,atthetopwehave100%L,andat eachside,100%Hand100%M,respectively. Eachsideofthetrianglerepresents allpossible binarycombinationsofthethree components. Onanyofthosesides,thefractionofthethirdcomponentiszero(0%). Asyoumovefromoneside(0%)tothe100%orpurecondition,thecompositionof thegivencomponentisincreasinggradually andproportionally.Attheverycenterofthe triangle,wefind33.33%ofeachofthecomponent. 48

Overall Composition Theconcentration ofeachofthethreecomponents Canbeexpressed aseitherwt.%ormolar% Sumoftheconcentration ofthethreecomponentsmustaddupto100% TheGibbsTriangleisalwaysusedtodetermine theoverallcomposition TheGibbsTriangle: Anequilateral triangleonwhichthepurecomponentsare represented byeachcorner

Therearethreewaysofdetermining the overallcomposition

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Method 1
RefertoFiguresOC1andOC2Lettheoverallcompositionberepresented bythepointX DrawlinespassingthroughX,andparalleltoeachofthesides WherethelineACintersects thesideABtellsustheconcentration ofcomponentBinX Theconcentrations ofAandC,inX,canbedetermined inanidentical manner

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Method Two
DrawlinesthroughX,paralleltothesidesoftheGibbsTriangle ACintersectsABatA BCintersectsABatB ConcentrationofB=AA ConcentrationofC=AB ConcentrationofA=BB Thismethodcanbesomewhatconfusing,andisnotrecommended

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Method3
ApplicationoftheInverseLeverRuleDrawstraightlinesfromeachcorner,throughX %A=AX/AM %B=BX/BN %C=CX/CL ImportantNote: Alwaysdetermine theconcentration ofthecomponentsindependently, thencheckby addingthemuptoobtain100%

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Todifferentiate withinthetwophaseregionandsinglephase regionintheternary diagram,pressure andtemperature mustbefixed.Therewillbedifferent envelopes (binodal curves)atdifferent pressures andtemperatures. Thebinodal curve isthe boundarybetween the2phaseconditionandthesinglephase condition.Insidethe binodal curveorphaseenvelope,thetwophaseconditionprevails.Ifwefollowthe conventiongivenabove(lightsatthetop,heaviesandmediumsatthesides),thetwo phaseregionwillbefoundatthetop.ThiscanbeseenmoreclearlyinFigure5.7.

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ClassificationofClassificationofReservoir andReservoirFluids
Reservoir fluids can be categorized into: dry gas wet gas retrograde gas volatile oil black oil heavy oil

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PTDiagramofaDryGas

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PTDiagramofaWetgas

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PTDiagramofaRetrogradegas

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p-T Diagram of a Low-shrinkage Oil

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P-T Diagram of a High-shrinkage Oil

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Generalized P-T diagram of a gas and oil

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