(59) The characteristic of phase behavior The equilibrium gas and liquid phases The dissolution() and separation of system Terminology: Phase behavior: Bubble point
Critical ponit Two phase region Phase diagram: Dew point
Phase envelope Quality lines: Cricondentherm: Cricondenbar: Locus Shrinkage Condensate gas Curve Volatile Depletion Retrograde gas condensate: Separator Equilibrium ratio
Reservoirs may be radically different from each other in fluid composition.
diversified forms: gas reservoir oil reservoir oil reservoir with gas-cap
3.1.1Phase and the descriptive approaches of phase
Theoretically based on the thermodynamics() and the physical chemistry,the theory of reservoir- fluid-phase usually takes a system as the object of study. The term system refers to the object which is artificially divided from the others for study and conceived as a space enveloped() by boundaries.
3.1 Phase behavior of reservoir hydrovarbon fluids
For a constant() composition system, the relationship between pressure, temperature and volume can be represented by EOSequation of state
f(PvT)0
Phase diagram is the graphic display of EOS.
( ) 3.1.1.1 3D phase diagram(PVT) (
22D diagram or Plane phase diagram The P-T diagram is most convenient P-V(-) and P-T(-) phase diagram are generally used in petroleum industry. 2D phase diagram of propane () C 1 % C 2 % C 3 % C 4 % C 5 % C 6 % C 7 % 4 8 .8 3 2 .7 5 1 .9 3 1 .6 0 1 .11 5 1 .5 9 4 11 5 6 4 .3 6 7 .5 2 4 .4 7 4 .1 2 2 .99 7 1 .3 8 1 4 .9 1 8 7 .0 1 4 .3 9 2 .2 9 1 .0 8 0 .88 3 0 .6 0 3 .8 0 9 5 .8 5 2 .6 7 0 .3 4 0 .5 2 0 .00 8 0 .1 2 0 .4 2 % 1 0 0 .0 0 1 0 0 .0 0 1 0 0 .0 0 1 0 0 .0 0 C 7+ 3 3 m m 3 g cm
M1 M2 M3 ? 3.1.2Phase behavior of single/two-component system(P62) 3.1.2.1 The characteristic of single component system
1Key parameters (1)Bubble point pressure(): refers to pressure at which the first bubble occurs under constant temperature when pressure decreases (2)Dew point pressure() refers to pressure at which the first liquid dew occurs under constant temperature when pressure increases (3)Saturated vapor pressure curve() refers to the line showing that vapor and liquid phase coexist for single component system (4)Critical point()refers to the end of saturated vapor pressure curve (point C). (5)Critical temperature (Tc)critical pressure (Pc) refers to the corresponding temperature and pressure at the critical point aMPa P-T diagram for ethane
C 5 Pc
F
4
3
2
1
0 -150 -100 -50 0 50 100 150 D
BE
A
Tc C
33 P-T
(30C, 4.88MPa) H2 S CO2 N2 CH4 C2 H6 C3 H8 C4 H1 0 C5 H1 2 aMPa 3P-T diagram for different pure system 10 9 8 7 6 5 4 3 2 1 0 -200 -100 0 100 200 300
35 1.2 The characteristic of binary() component system
1Key parameters (1)Bubble point curve(): is defined as the line separating the liquid phase region from the two phase region (2)Dew point curve():is defined as the line separating the vapor phase region from the two phase region (3)Cricondentherm(): is defined as the maximum temperature above which liquid can not be formed regardless of pressure. (4)Cricondenbar(): is defined as the maximum pressure above which no gas can be formed regardless of temperature. (5)Phase envelope (): the region enclosed by the bubble-point curve and the dew-point curve, wherein gas and liquid coexist in equilibrium, is defined as the phase envelope of the hydrocarbon system. (6)Quality lines(): refers to the dash lines within the phase diagram. They describe the pressure and temperature conditions for equal volumes of liquids. cricondenbar 2P-T diagram for binary system cricondentherm 3Typical P-T diagram for a binary system 1) The two-phase region is between the saturated vapor line of individual pure substance. 2) The Pc is higher than one of pure substance, while Tc is between that of both pure substance. 3) Point C will migrate to the side closer to the heavy substance with the content increase of heavy one, accompanied with the P-T drifting to the saturated vapor pressure curve of heavy substance 4)The two phase region is larger if the proportion of both component is close, contrary to the bigger proportion 1.3 The characteristic of multi-component hydrocarbon system(P66) 1The key points: 1.Three phase regions: liquid
region, vapor region, two phase region 2.Three points: cricondenbar, critical point, cricondentherm 3. Three lines: bubble point curve, dew point curve, quality lines 4.Two iso-regions: isothermal PT diagram decompression retrograde region(), isobaric cooling retrograde region() Critical point()intersection of bubble point curve and dew point curve. The Pc is the maximum pressure above which no gas can be formed regardless of temperature (cricondenbar), The Tc is defined as the maximum temperature above which liquid cannot be formed regardless of pressure (Cricondentherm). isothermal decompression retrograde region( ) isobaric cooling retrograde region() 2The particular (P68) isothermal decompression retrograde region() 3 Judgment of reservoir types Gas Volatile oil Condensate gas Black oil Oil reservoirsIf the reservoir temperature T is less than the critical temperature Tc of the reservoir fluid, the reservoir is classified as an oil reservoir. Gas reservoirsIf the reservoir temperature is greater than the critical temperature of the hydrocarbon fluid, the reservoir is considered a gas reservoir. 4 Phase behaviors of Typical reservoirs(P70) 1. Under-saturated oil reservoir. 2. Saturated oil reservoir. 3. Gas-cap reservoir. 1Phase diagram of conventional heavy oil reservoir( low shrinkage oil)
1. The quality lines are closely spaced near the dew-point curve, 2. The gas oil ratio is generally lower than 90 m3/m3, and the relative density is higher than 0.876. The color of this type of oil is generally black or dark brown. 3. The dash line simulates the path of pressure and temperature variation from wellbore to surface. Oil accounts for about 85% at the condition of separator. 2) Phase diagram of light oil reservoir (high shrinkage) 1. The phase diagram of
volatile oil reservoir is similar to that of black oil. But the quality lines are close together near the bubble-point and are more widely spaced at lower pressures. 2. The relative density is lower than 0.78, and gas oil ratio is lower than 1800 m3/m3 3. Oil accounts for about 65% at ,.the condition of separator 5 Gas reservoirs On the basis of their phase diagrams and the prevailing reservoir conditions, natural gases can be classified into four categories: -Retrograde gas-condensate -Near-critical gas-condensate -Wet gas -Dry gas 1Phase diagram of retrograde condensate gas reservoir(P72)
1. The initial reservoir pressure is higher than critical pressure , but its temperature is between critical temperature and cricondentherm 2. The gas oil ratio of condensate gas reservoir could reach 12600 m3/m3. The relative density of condensate oil could reach 0.74. The color is light and transparent. 33. liquid accounts for about 25% under the condition of surface separator. The produced liquid is called as condensate oil 2Phase diagram of near critical gas condensate reservoir
1. The initial reservoir temperature is near the critical temperature 2. All the quality lines converge (/)at the critical point, 3.a rapid liquid buildup will immediately occur below the dew point as the pressure is reduced to point 2.
3)Phase diagram of wet gas reservoir () 1.The reservoir temperature is above the cricondentherm of the hydrocarbon mixture, and it will always keep gas status when pressure decreases from point 1 to point 2. 2.It will be in two phase region under separator condition, therefore, there will be some light oil in separator. 3.The relative density of light oil is lower than 0.78, and the surface gas oil ratio is lower than 18000 m3/m3. 4)Phase diagram of dry gas reservoir() 1.The natural gas with high methane content(70 ~98 is referred as dry gas. 2.The reservoir temperature and separator temperature are outside two phase region. There is no liquid released in underground and surface condition. The gas oil ratio is higher than 18,000 m3/m3. 3.2 Gas-liquid phase equilibriumP73 - 1 Ideal solution 1) complete mixed between different constituents of solutions; 2) no chemical reaction during mixing; 3) particle volume of each constituent is equal (that isthe repulsion force and attractive force between different particle are equal) 2 Raoults Law () The equilibrium partial pressure of any component in a multi- component system is the product of its mole fraction xi in the liquid phase and the vapor pressure of the pure component pi: pi = xi pvi where :pi = partial pressure of ith component. pvi = vapor pressure of ith pure component. xi= mole fraction of ith component in the liquid. 3 Daltons Law () The partial pressure pi of any component is the product of its mole fraction yi in the vapor phase and the total pressure of the system p pi = yi p whereyimole fraction of component i p- total pressure of the system. k = 4Vapor-liquid phase equilibrium of ideal solution - 1) The equilibrium ratio
Raoult's and Dalton's law may be combined and written as yi p = xi Pvi yi
xi Pvi
P = k = f Li
f gi yi
xi = Real solution at high pressure yi ( f gi ) pure = xi ( f Li ) pure fugacity The equilibrium ratio k: The equilibrium ratio occurs under equilibrium conditions between vapor and liquid at any specified temperature and pressure. zi Ki yi = 2) Development of equations for calculating equilibrium relations z j n = x j nL + y j ng zi = xi L + yiV xi = zi L + KiV xi = 1 yi = 1 zi
i n n = 1 Where : i =1 i =1 VKi + L L = moles of liquid at equilibrium V = moles of vapor at equilibrium zi xi yi = mole fraction of the ith component in the total/ liquid/ vapor phase Ki = yi/xi = equilibrium ratio of the ith component at the pressure and temperature of the system
0.610
0.280
0.110 Sum 1.000 Ex. 3-1: The composition of ideal liquor is listed in table 3-1, calculate the composition of vapor and liquid phase under 65.5 (150) and 200 psia. 3-1
Zj mole fraction Pv j ,
Psia yj ,
mole fraction xj ,
mole fraction C3 0.610 350 0.771 0.441 n-C4 0.280 105 0.194 0.370 n-C5 0.110 37 0.035 0.189 sum 1.0 y j 1 . 000 x j = 1 .000 Solution: Step 1: Based on the chart of vapor pressure vs. T, presented the component vapor 3-2 pressure, list at the 3th column;;
Zj mole fraction Pv j ,
Psia yj ,
mole fraction xj ,
mole fraction C3 0.610 350 0.771 0.441 n-C4 0.280 105 0.194 0.370 n-C5 0.110 37 0.035 0.189 sum 1.0 y j 1 . 000 x j = 1 .000 j =1 y j = j =1 1 + nL ( indicated that y j = 1 Step 4: The composition of each j =1 x j = 1 + ng ( m m = 1 1) z j p
pvjj Step 2: Assumed that nL=0. 487, use the equation yi to trial calculate, list at the 4th; Step 3: If trial calculation is satisfied, = 1 1) m
j =1 m m
j =1
component in liquid xi is obtained. z j pvj p 3-2 zi y = L V + zi Ki = z K zi = xi Ki = pb = zi pvi 3) Calculate the bubble pressure At the bubble-point pressure, p=pb ,it is considered as a single phase liquid. L=1,V0 Based on the vapor equation i
= 1 pvi
pb Ki
n
i =1 VKi + L i i = 1 n n
i =1 i =1
n
i =1 n
i =1 zj
Fractlon mole
PvjPsia zj Pv j C3 0.610 350 213.5 n-C4 0.280 105 29.4 n-C5 0.110 37 4.1 Pb=247Psia Ex. 3-2: Calculate the bubble point pressure of the above- mentioned mixture (regarding as ideal liquor). 3-3 zi =i 1 xi = =i 1 VK + L = 1 z / K Ki = pd = zi
4) Calculate the dew pressure At the dew-point pressure, p=pd ,it is considered as a single vapor phase. V=1,L0 Based on the vapor equation n n
i zi = yi
= 1 pvi
pd i i n
i =1 n 1 i =1 pvi zj fraction mole ,
Pvj, Psia zjpvj C3 0.610 350 0.00174 n-C4 0.280 105 0.00267 n-C5 0.110 37 0.00297 sum 1.000 0.00738 Ex. 3-3: Calculate the dew point pressure of the above- mentioned mixture (regarding as ideal liquor).
1 0 .00738 = 136 Psia Pd = Calculating steps for saturated pressure Yes Given assumed Pb
Ki is obtained at Pb
No
calculatingniki=1
Yes
Output Pb Given assumed Pd
Ki is obtained at Pd
No
ni/ki=1
Output Pd
p5 p4 3 3 The solution and liberation of hydrocarbonsystem (P88) 3.1 liberation of system p p2 p1 1Flash liberation
V5
V4
V3 Vb V2 V1
pb
The solution gas that is liberated from an oil sample during a step decline in pressure stays in the cell by contact with the oil, and the change in the total hydrocarbon volume Vt is measured for each pressure increment. (CCE) 1Flash liberation (CCE Constant Composition Expansion) Saturation pressure (bubble-point or dew-point pressure) Isothermal compressibility coefficients of the single- phase fluid in excess of saturation pressure Compressibility factors of the gas phase Total hydrocarbon volume as a function of pressure 2Differential liberation
The solution gas that is liberated from an oil
sample during a decline in pressure is continuously removed from contact with the oil, and before establishing equilibrium with the b c a total hydrocarbon system. (CVD) 2Differential liberation (CVD Constant Volume Depletion) Amount of gas in solution as a function of pressure The shrinkage in the oil volume as a function of pressure Properties of the evolved gas including the composition of the liberated gas, the gas compressibility factor, and the gas specific gravity Density of the remaining oil as a function of pressure 3multi-stage liberation (or separator)
The solution gas that is liberated from an oil sample during a step decline in pressure is removed from contact with the oil, and the cell is constant. A scheme using three stage separation at a fixed temperature Optimum separation conditions A maximum stock-tank API gravity A minimum oil formation volume factor (i.e., less oil shrinkage)
A minimum producing gasoil ratio (gas solubility) Schematic illustration of n separation stages. 4Comparison between flash liberation and multi-stage separator reservoirs oil sample at the gas oil ratio m3m3 Gas volume increment in bottom hole of producing well
Flash
59.6 83.0 175.4 Multi- stage
41.4 71.5 144.5 different mothod
V
30.6 13.9 17.6 In the flash (equilibrium) separation, the liberated gas remains in contact with oil until its instantaneous removal at the final separation pressure. A maximum proportion of intermediate and heavy components is attracted into the gas phase by this process, and this results in a maximum oil shrinkage and, thus, a lower oilil recovery. In the differential separation, or multi-stage separator, the liberated gas (mainly composed of lighter components) is removed from contact with the oil as the pressure on the oil is reduced. The maximum amount of heavy and intermediate components will remain in the liquid, minimum shrinkage of the oil will occur, and, therefore, greater stock-tank oil recovery will occur. The gas volume released from oil sample by flash liberation is more than by multi-stage separation, that is the more gas oil ratio measured The specific gravity of gas liberated from oil sample by flash liberation is higher because of the more molar fraction of light oil 3.2 The gas solution 1Solubility The gas solubility Rs is defined as the number of standard cubic feet of gas which will dissolve in one stock-tank barrel of crude oil at certain pressure and temperature. The solubility of a natural gas in a crude oil is a strong function of the pressure, temperature, API gravity, and gas gravity. 2influential factor about gas solubility 1) Temperature factor Gas solution volume reduces as the temperature is increased, especially at high pressure. 2) Pressure and API oil gravity factor Gas solution volume increases as the pressure is increased With the increase of API oil gravity, gas solution increases,
because of the composition of
hydrocarbon liquid is extremely
dynamic as P and T change. 3) Gas gravity (or component) factor Gas solution volume increases as gas gravity is increased 4The relationship between solution and liberation 1)The processes of solution and liberation are opposite and uniform. These two processes occur at a specified condition. liberation curve and solution curve by flash liberation are all the same Solution curve and liberation curve by differential liberation , two lines do not coincide with each other 2) Two process lines of light component are nearly the same whereas lines of heavier component are just the opposite, especially at low pressure.