Upstream Process

Engineering Course
1. Physical Properties

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Liquid Density
o
• Examples of Liquid and solid Compound Density @ 15 C
3
Densities (kg/m )
Water 1000
Ethyl alcohol 785
Butane 563.2
Octane 706.7
Heavy Crude 903
Medium Crude 859
Light Gas Condensate 734
Steel Approx. 7800
Concrete Approx. 2300

Calculation of mixture density

One of the simplest methods is the API corresponding states method which uses a correlation to obtain a correction
factor that adjusts the density at standard conditions to the actual conditions.
Below are the equations used:
Mi xi
m   Where:  - Molar Volume (m3/kmol)  - density (kg/m3)
i M - Molecular weight (kg/kmol) x - Mole fraction
C1 & C2 - Correlation factors for density correction
Mm   xiMi subscripts: m - mixed compound i - component i

 C1 
 actual   s tan dard . 
 C 2 
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Liquid Density - Example Calculation
Example:

Calculate the liquid density of a saturated mixture of 70% ethane, 20% propane and 10 %butane at 100 bara and 25oC

Working:
Obtain the density of components at standard conditions , here data is given relative to water.
C2    0.3581    358.1 kg/m 3 , M  30.07 
 Relativedensity(  ) at standard conditionsand
C3    0.5083    508.3 kg/m 3 , M  44.097 
 molecular weight (M) can be found in general databooks
C4    0.5637    563.7 kg/m 3 , M  58.124 

Using volume mixing equation

30.07  0.7 44.097  0.2 58.124  0.1
m     0.0865 m 3 / kmol
358.1 508.3 563.7
M m  (30.07  0.8)  (44.097  0.2)  (58.124  0.1)  35.68 kg/kmol

Mm 38.69
 m standard    412.6 kg/m 3 @Standard Conditions
m 0.0864
Now find the correlatio n factors to adjust the standard density to the actual conditions .

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Liquid Density - Example continued
Taking Critical Properties from standard databooks

Pcm   x i Pci  (0.7  48.8)  (0.2  42.49)  (0.1  36.49)  46.31 bara

Tcm   x i Tci  (0.7  305.43)  (0.2  369.82)  (0.1  408.13)  328.6 K

@ Standard Conditions ( 15 C & 1 bara)

288
Pr standard  Saturated Liquid Tr standard   0.876
328.6
From Correlatio n chart C1  0.745

@ Actual Conditions (25 C & 100 barg)

100 298
Pr actual   2.16 Tr actual   0.907
46.31 328.6
From Correlatio n Chart C2  0.764

 C2   0.764 
So  actual   s tan dard    412.6   423.11 kg/m
3

 C1   0.745  Chart: API correlation chart for liquid density

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Liquid Density - HYSYS Equations
• The computer simulation HYSYS uses an Equation of State by Hawkinson, Brombst & Thomson usually referred to
as COSTALD because it uses Corresponding Standard Liquid Tables.

Vs
*
 VR0 [1  SRK VR ]
V

VR0  1  a (1  Tr )1 3  b(1  Tr ) 2 3  c(1  Tr )  d(1  Tr ) 4 3 0.25  Tr  0.95

VR  [e  fT r  gT r2  hT r3 ] /( Tr  1.00001) 0.25  Tr  1.0

Where:
a = -1.52816 b = 1.43907 Vs  Saturated Liquid Volume
c = -0.81446 d = 0.190454 VR0 , VR  Functions of Tr
e = -0.296123 f = 0.386914
Tr  Reduced Temperatur e
g = -0.0427258 h = -0.0480645
V *  Molar Volume 
Found in COSTALD tables
SRK  Acentric factor 

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Liquid Density - Mixing Rules
• The mixing rules for the variables in the previous equations are as follows:

n n

 x x V T
i 1 j1
i j
*
ij cij

Tcm 
Vm*

Vm* 
1
4
 x V  3 x V  x V 
i i
*
i i
*2 3
i i
*1 3

 V T V T 
12
Vij* Tcij i
*
ci
*
j cj

SRK m   x i SRK i Acentric Factor (shape sensitive)

0.291  0.80 RT
Pcm 
SRK m cm
*
V
m

This is a much more complicated method and is not suitable for hand calculations.

Running the liquid density calculation in HYSYS returns a density of 456.5. kg/m3.
Using the API method we obtained a value of 423.11 kg/m3.

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Vapour Density
Compound Vapour Density
Example Gas Densities: 3
(kg/m )
@15oC, 1 bara Air 1.21
Oxygen 1.335
Carbon dioxide 1.873
Methane 0.6784
Propane 1.865

The main parameter in calculating vapour density is the compressibility. This can be calculated by either the appropriate equation of
state or activity model, or by generalised compressibility charts.

Calculation using compressibility charts is as follows:

Mixed critical properties are calculated using Kay' s rule and databook tables :
Pcm   y i Pci , Tcm   y i Tci where y i is mole fraction of vapour component
– Find reduced properties (Pr, Tr)
P T
Prm  , Trm 
Pcm Tcm
Use the reduced properties with a compressib ility chart to obtain the compressib ility, Z.
The Mean molecular mass is then calculated M m   yi Mi
and Density is calculated  m  M m P ZRT
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Vapour Density - Example Calculation
Calculate the density of vapour using the same composition as the previous example except with 15 bara pressure
and 25 C temperature. At these conditions the mixture is single phase gas.
Component Yi Tci (K) YTci Pci (MPa) YPci Zci Yzci M Myi
C2 0.7 305 213.5 4.88 3.416 0.28 0.196 30.07 21.049
C3 0.2 370 74 4.25 0.85 0.274 0.0548 44.097 8.8194
C4 0.1 408 40.8 3.65 0.365 0.277 0.0277 58.124 5.8124
Sum 328.3 4.631 0.2785 35.681
Compressibility Chart

We have the mixtures critical properties , next calculate

the reduced properties
P
Pr 
Pc
T
Tr 
Tc

Pr  15 / 46.3  0.324
Tr  298.15 / 328.6  0.907

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Vapour Density - Example

From generalise d compressib ility charts Z  0.84

 m  M m .P / ZRT
 35.68  1500/ 0.84  8.314  298.15
 25.7 kg/m 3

HYSYS uses the Equation of State selected by the user to calculate the compressibility factor.
This is an iterative process and is more accurate.

HYSYS result:
Density mixture = 26.58 kg/m3

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Viscosity
Example Viscosities:
Gas Compounds Viscosity Liquid Compounds Viscosity
(cP) (cP)
o o
Air @ 5 C .017 Octane @ 5 C 0.75
o o
Methane @ 5 C 0.01 Water @ 5 C 1.4
o o
Steam @ 100 C 0.012 Heavy crude @ 15 C 24
o
Medium crude @ 15 C 5
o
Light gas condensate @ 15 C 1

Accurate prediction of viscosity is very difficult due to the number and type of variables.

Nearly all methods rely on critical data developed from the equation of state and accuracy is greatly
affected by the equations chosen.

HYSYS uses the following methods for viscosity calculation.

System Vapour Phase Liquid Phase

Light Hydrocarbons Modified Ely & Hanley Modified Ely & Hanley
o
NBP < 155 F
Heavy Hydrocarbons Modified Ely & Hanley Twu
o
NBP > 155 F
Non Hydrocarbon Modified Ely & Hanley Modified Letsou-stiel
Systems

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Viscosity
Component viscosities can be found by using viscosity charts. Viscosity of Liquid
These can be found in data books along with co-ordinates which relate
to different compounds. There are separate charts for gases and liquids. Component X Y
Water 10.2 13
For viscos ity estimation of liquid mixtures the following rule can be used Pentane 14.9 5.2

m   x   
i i
13 3
Hexane
Heptane
14.7
14.1
7
8.4
Octane 13.7 10
where  m  mixture vis cos ity , x i  component mole fraction
 i  component viscosity
Example:
Estimate the viscosity of a mixture of 30% Pentane and 70% Octane
at 25 oC and 1 bar.

Working:
Find the co-ordinates for Pentane and Octane to be used with the chart.
Pentane - X=14.9, Y=5.2 Octane - X=13.7, Y=10
from the chart  (mPas)= 0.23 for pentane
= 0.54 for octane note: cP = mPas
3
 m   0.3 * (0.23) 3    0.7 * (0.54) 3 
1 1

   
 0.1838  0.5700
3

 0.428 (cP )
HYSYS returns a liquid viscosity of 0.416 (cP)
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Viscosity
Viscosity of Gases
For viscos ity estimation of gases the following rule can be used

m 
 y
i i Mi Component
Air
X
11
Y
20
y i Mi Carbon Dioxide 9.5 18.7
Methane 9.9 15.5
where  m - Mixture viscosity ,  i - Component viscosity Ethane 9.1 14.5
y i - Mole fraction of component M i - Component molecular weight Propane 9.7 12.9

Viscosities are found from viscosity charts. The charts give the viscosity at 1
atmosphere and the required temperature. Correction for pressure and
temperature can be made by using a viscosity correction chart. This requires the
reduced P & T from Kay’s rule.

Example:
Estimate the viscosity of a gas with composition 40% methane & 60% propane
at 25oC and 5 bara pressure.

Working:
Calculated the viscosity of the gas at 1 atmosphere and the required temperature
Using co-ordinates: methane - X= 9.9, Y= 15.5 propane - X= 9.7, Y= 12.9
from chart  (mPas) = 0.011 for methane
= 0.0084 for propane

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Viscosity
0.011 * 0.4 * 16.043  0.0084 * 0.6 * 44.097
m 
0.4 * 16.043  0.6 * 44.097
Chart: Viscosity Correction
0.0176  0.0335
  0.00915 (cP)
1.602  3.984

The viscosity at the required Pressure and

Temperature can then be calculated by multiplying by
the viscosity ratio (found from viscosity correction
chart).

In this case the correction factor is very small.

From Kay’s Method:

Pr = P / Pc = (5 / 44) = 0.114
Tr = T / Tc = (298 /298) =1

Reading From chart  / 1 will be very close to 1

therefore  = 1 x 0.00915
= 0.00915 cP

HYSYS returns a viscosity of 0.0097 cP

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Specific Heat Capacity
• Example Heat Capacity values:

Gas / solid Compound Isobaric Heat Capacity, Liquid Compound Isobaric Heat Capacity,
Cp (J/kgK) Cp (kJ/kgK)
Air 0.996 Water 4.187
Propane 2.467 Octane 2.177
Decane 1.758
Steel 0.502 Heavy Crude 1.718
Medium Crude 1.750
Gas Condensate 2.077

 The AIChE method can be applied to both gases and liquids. As in the other calculatio ns a correction term is found
to adjust the ideal value.

R  C p  C p 
0

Cp  C  0  which is the ideal heat capacity minus a correction term.

w  
p
R 

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Specific Heat Capacity

where :
C p  Actual Heat Capacity
C 0p  Ideal Heat Capacity
w  mass fraction
(0) (1)
 C p0  C p   C p0  C p   C p0  C p 
     
 R   R   R 
     
(0)
 C p0  C p 
   Simple fluid term found from tables. f(T r , Pr )
 R 
 
(1)
 C p0  C p 
   Correction term found from tables. f(T r , Pr )
 R 
 
  Acentric factor

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Specific Heat Capacity - Mixing Rules
The following mixing rules can be applied to the previous Heat Capacity Equations.

C opm   w i C opi - Ideal heat capacity

Tcm   x i Tci - Critical Temperatur e

Pcm   x i Pci - Critical Pressure

 m   x i i - Acentric factor

HYSYS Results from ethane, propane and butane mixture.

Gas Heat Capacity - 2 (kJ/kgC)

Liquid Heat Capacity - 2.971 (kJ/kgC)

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Thermal Conductivity
Example Conductivities
Gas / solid Thermal Conductivity Liquid Compound Thermal Conductivity
2 2
Compound (W/m K) (W/m K)
Methane 0.0286 Water 0.569
Propane 0.1181 Octane 0.144
Heavy crude 0.164
Carbon steel 51.9 Medium crude 0.146
Stainless steel 16.3 Gas condensate 0.132

• HYSYS uses the general guidelines of Reid, Prausnitz & Poling to determine which model best suits each class of
component.
– Hydrocarbon systems use the corresponding states method of Ely & Hanley
– Glycols & Acids are calculated by Sato-Reidel method
– Esters, alcohols and light hydrocarbons by Latini
– Others use the Missenard & Reidel method
– Vapour Phase is covered by Misic & Thodos and Chung covers the higher pressure range.

HYSYS results from ethane, propane and butane mixture.

Gas Conductivity - 0.0217 W/m2K

Liquid Conductivity - 0.0744 W/m2K

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Thermal Conductivity
Mixing rules for low pressure gases: Mixing rules for liquids:

n
yii
m   n n
 lm    i  j  lij
n
i 1
y A
j1
j ij i 1 j1

A ij  f (, M, Tb ) x i Vi
i 
where :  m  Thermal conductivi ty of mixture  x j Vj
2
 i  Thermal conductivi ty of pure component  li 
(1 /  li )  (1 /  lj )
  viscosity
where : n - number of components
y i , y j  mole fraction of components i and j
x i, j - component mole fractions
M  Molecular weight
 lm - Mixture thermal conductivi ty
Tb  Boiling point
 li - Pure component thermal conductivi ty
Vi - Pure component liquid molar volu me

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Surface Tension
Examples:
Component Surface Tension
(dyne/cm)

Water 73.82
Octane 25.05
Heavy crude 30.27
Medium crude 27.32
Gas condensate 23.39

HYSYS results from ethane, propane and butane mixture.

Liquid case Surface Tension - 2.733 (dyne/cm)

• A modified form of the Brock, Bird equation is used by HYSYS to calculate surface tension. This expresses surface
tension as a function of the reduced & critical properties of the compound.

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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 Surface Tension

2 1
  Pc 3 Tc 3 Q(1  TR ) a .b
Q  0.1207[1  TBR ln Pc /(1  TBR )]  0.281 
 Q and a can be modified to account for Polar molecules.
a  Parameter fitted for each chemical class 
b  C 0  C1  C 2  2  C 3 3 - Parameter fitted for each
chemical class dependent on molecular shape.
where :
 - Surface tension
 - acentric value
TBR - Reduced boiling temperatu re

•
Pcm   x i Pci
Mixing Rules

Tcm   x i Tci

Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Ltd Calculation of Mixture Properties
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