Upstream Process Engineering Course: 1. Hydrocarbon Phase Behaviour

Upstream Process
Engineering Course
1. Hydrocarbon Phase Behaviour
Upstream Process Engineering Course Prepared by Genesis Oil and Gas Consultants Hydrocarbon Phase Behaviour 1
Ltd
Reservoir Barrel
CARBON DIOXIDE
HYDROGEN SULPHIDE
METHANE &
ETHANE
SUBSTANCE USES
LOWEST Propane and butane gas for lighter fuel
gases
& camping stoves
BOILING POINT
Chemicals for medicines, plastics, paints,
naphtha
cosmetics & clothing materials
gasoline Petrol for vehicles
kerosene Jet fuel and paraffin
diesel oils Diesel fuel
Lubricating
Machine oil, waxes and polishes
oils
Fuel oil Fuel for ships and central heating

HIGHEST
BOILING POINT Bitumen for road surfaces and roofing
residue
materials
WATER
SAND
Ltd
Reservoir Fluid Types
• Four general types of reservoir
fluids
– Black Oil - Forties
– Volatile Oil - Gyda
– Condensate - Bruce
– Gas - SNS Villages
Typical P-T diagrams showing the position of

the critical point for all four reservoir fluid types
Ltd
Phase Equilibrium Definitions
• Phase Diagram
– A record of the effects of temperature, pressure and composition on the kinds and numbers of
phases that can exist in equilibrium with each other
• Bubble Point
– The point at which the first infinitesimally small vapour bubble appears in a liquid system. The
bubble point curve on a phase diagram represents 0% vapour
• Dew Point
– The point at which the first infinitesimally small droplet of condensation forms in a gaseous
system. The dew point curve on a phase diagram represents 0% liquid
• Phase Envelope
– The area on a pressure-temperature phase diagram for a mixture enclosed by the bubble and
dew point curves. This area represents the set of conditions for the mixture were vapour and
liquid phases co-exist in equilibrium.
• Cricondenbar
– The maximum pressure at which vapour and liquid can co-exist in equilibrium
Ltd
• Cricondentherm
– The maximum temperature at which vapour and liquid can co-exist in equilibrium
• Critical Point
– At the critical point, liquid and vapour phases of a fluid have identical physical properties
• Quality Lines
– Lines through the two-phase region showing a constant percentage of liquid and vapour
• Retrograde
– The name given to phase behaviour above the critical temperature and pressure were vapour
and liquid phases coexist and the amount of vaporisation or condensation changes with
pressure and temperature in the opposite direction to normal behaviour.
• Equation of State
– An equation which describes the relationship between pressure, temperature and molar volume
of any homogenous fluid at equilibrium
Ltd
• Fugacity
– A thermodynamic concept arising from the consideration of the change in Gibbs free energy
with changes in pressure and temperature for non-ideal mixtures and substances. Three types
of fugacity can be defined: pure component fugacity, mixture fugacity , partial fugacity .
Fugacity must have the same units as pressure by definition but will only be equal to pressure
under ideal conditions (e.g. low pressure gases).
• Binary Interaction Coefficient
– A constant which accounts for the deviation from ideality for component pairs in mixtures.
These are specific to one equation of state as they are calculated by the regression of measured
data. The coefficients used in a liquid activity method are essentially regression constants used
to calculate the liquid activity coefficient
• Liquid activity coefficient
– The ratio of the partial fugacity of a component in a mixture to its pure component fugacity at
the same physical conditions, divided by its mole fraction in the mixture.
Ltd
HYSYS EOS Set Up
Ltd
Black Oil
Component Mol %
Methane (CH4) 48.83
Ethane (C2H6) 2.75
Propane (C3H8) 1.93
Butanes (C4H10) 1.6
Pentanes (C 5H12) 1.15
Hexane (C6H14) 1.59
C7+ 42.15
Molecular Weight of C7+ 225
GOR (scf/bbl) 625
Oil Gravity (º API) 34.3
Colour Black
Ltd
Volatile Oil
Component Mol %
Methane (CH4) 64.36
Ethane (C 2H6) 7.52
Propane (C3H8) 4.74
Butanes (C4H10) 4.12
Hexane (C6H14) 1.38
C7+ 14.91
GOR (scf/bbl) 2000
Colour Brown
HYSYS is not
flawless
Ltd
Gas Condensate
Component Mol %
Methane (CH4) 87.07
Ethane (C 2H6) 4.39
Propane (C3H8) 2.29
Hexane (C6H14) 0.6
C7+ 3.8
GOR (scf/bbl) 18200
Colour Straw
Ltd
Dry Gas
Component Mol %
Methane (CH4) 95.85
Ethane (C 2H6) 2.67
Propane (C3H8) 0.34
Hexane (C6H14) 0.12
C7+ 0.42
GOR (scf/bbl) 105000
Oil Gravity (º API) -54.7
Colour White
Ltd
Fluid Sampling
• Drill Stem Tests
– Carried out on appraisal wells to provide sub-surface
information and data for facilities design
– Laboratory and field measurements made
– Basis for verifying simulation models
• Extended Well Test
– Testing over many months
– Sub-surface uncertainty reduced
– Opportunities to undertake extensive facilities testing
– Environmental implications require to be evaluated • Bottom Hole Samples
• Topsides Samples – Capture pressurised reservoir
– Regular samples are taken to maintain product sample e.g asphaltene analysis
quality and ensure levels of chemical treatment are – QA for drilling fluid
sufficient contamination
– Pressurised samples are taken of crude at normal – For fast track development
operating conditions for laboratory analysis and sometimes only sample
atmospheric samples
Ltd
Fluid Analysis
• Reservoir fluids consist of a mixture of mainly hydrocarbon components and
water. Other commonly found components of reservoir fluids include carbon
dioxide(CO2), hydrogen (H2), hydrogen sulphide (H2S) and nitrogen (N2).
• Common hydrocarbon components include the following classes of compound.
– Alkanes or Paraffins (both straight chain and isomeric)
– Cycloparaffins
– Aromatics
– Naphthalenics
• It is not practical to model every component of a reservoir fluid due to the large
numbers of components that are present. Generally, for acceptable phase behaviour
prediction, it is sufficient to specify the mole fractions of the main light end
paraffins, typically C1 to C10 for black oils. If dealing with gas condensate
systems, however, more rigorous compositional data may be required, particularly
if modelling retrograde behaviour.
Ltd
Crude Oil Composition Schematic
Ltd
Pseudo-Components
• For the heavier components in a reservoir fluid mix one or more pseudo-
components (or hypothetical components) can be used.
• Pseudo-Components are a mixture of many components with different properties
but modelled as one component with generalised physical properties.
• Pseudo-Components are generally defined either by the critical properties or by
average molecular weight, specific gravity and normal boiling point. For most
computer simulations a minimum of two of these must be specified. Acentricity
factors and binary interaction parameters can also be entered; most simulation
packages will estimate these if not supplied by the user. The more information
that is given on a pseudo component, however, the more accurate the phase
prediction can be.
• The pseudo component facility can also be used to enter data into a simulation for
a component not contained in the component library of the simulation package
being used.
Ltd
Heavy End Fluid Characterisation
• Prediction of heavy end physical properties is Stabilised Crude Boiling Curve
important to good prediction of phase
behaviour; incomplete or inaccurate data can 90
80
radically affect phase calculations. For
Total Distillate Wt%

70
example the prediction of bubble and dew 60
points. 50
40
• Standard fractional distillation tests can be 30
used to produce boiling point curves and 20
10
physical properties so that the heavy ends can 0
be split into a number of pseudo components.
90
0
0
0
12
15
18
27
30
36
39
50
21
24
33
44
• Some simulation packages have the facility TBP Cut Deg C
to take in distillation test data directly and to

produce the pseudo-components
automatically.
• Some ‘tuning’ may be required to match the
properties of the modelled reservoir fluids to
well test data.
Ltd
Pseudo-Components
Component Analysis
50
40
30
Mol %
20
10
0
Component
43 Components – simplify for

simulation
Ltd
Pseudo-Components
C7 plus Components
8
7
6
5
4
ol%
3
M
2
1
0
Component Pseudo Component Simplification
16
14
12
Mol %
10
8
6
4
2
0
C7 C8 C9 C13 C17 C19 C23 C27 C31 C37 C45 C62

do do do o o o o o o o o o
eu seu seu eu d eu d eu d eu d eu d eu d eu d eu d eu d
Ps P P P s P s P s P s P s P s P s P s P s
Ltd
Fluid Modelling
• The choice of thermodynamic model is critical when evaluating phase behaviour
• Fluid phase behaviour and properties can be predicted using a either a ‘Black Oil’ model or a
‘Compositional’ model
• Black Oil models are generally used for multiphase modelling in flowlines and wellbores. They
predict phase behaviour and bulk properties for varying conditions by relating the fluid
volumetric properties at the surface (e.g. Bo, GOR, Oil Gravity and Gas Gravity) to the down-
hole conditions. No detailed knowledge of fluid composition is required. Black oil models are
not recommended for gas condensate systems particularly where there is retrograde
condensation.
• Compositional models are used for rigorous heat and mass balance work. They use a property
package and a composition specified in terms of individual components which are available in
the package database or ‘component library’. If required, pseudo-components can be specified
for non-library components or for boiling point cuts. Binary interaction parameters for
components pairs can be used to give improved VLE property predictions.
• Modern simulation packages generally have several of property packages available for selection
including both equations of state and activity models.
Ltd
Property Package Selection
• Selection of the property package must take into account the components and the operating
conditions
• For most purposes, Peng Robinson (PR), Soave-Redlich-Kwong (SRK), or a modified version
of these methods, will provide sufficiently accurate modelling for oil and gas field
applications.
• The PR and SRK equations of state give accurate modelling for systems containing up to 5%
N2, CO2 or H2S. For systems with greater than 5% N2, CO2 or H2S these equations of state are
still recommended if the system does not include free water. It may be advisable, however, to
utilise user defined binary interaction parameters if available. This will depend upon the
simulation/flash package being used and the quality of the data in its components library. It is
recommended to consult the user guide (or help desk) for the particular package being used.
• Polar compounds can be problematic for EOS methods - methanol, glycol and water -
empirical correction factors are often required to improve accuracy. Most simulation packages
offer specialised property packages to handle such systems which utilise a combination of an
EOS to predict vapour phase fugacity coefficients and an activity coefficient model for the
liquid phase.
Ltd
Fugacity
• Fugacity is a conceptual term which is related to Gibb’s free energy, temperature,
volume and pressure, the units of fugacity are the same as pressure
• Although fugacity has the same units as pressure it will only be equal to pressure under
ideal conditions
• The fugacity coefficient for a pure component is defined as:
fi
i
P
• For a component in a gas mixture, the fugacity coefficient is:
fi
 i
yiP
• Where yi is the mole fraction of component y in the vapour phase
Ltd
Equilibrium Ratios
• The vapour-liquid equilibrium constant (K) is defined as the mole fraction of any
component in the vapour phase divided by the mole fraction of the same component in
the liquid phase
• Ki = yi / xi
• An equation of state can be used to calculate accurate K values when the vapour and
liquid phases co-exist in equilibrium
• For equilibrium, the fugacity of a component in the vapour phase must be equal to the
fugacity of the component in the liquid phase, when this criterion is met:
Ki = iL / iv
• Use of Equilibrium Ratios is key to the preparation of oil and gas processing heat and
mass balances
Ltd
Application of K Values
• The basic application of K values is the calculation of dew points, bubble points and the
vapour-liquid behaviour inside the phase envelope (flash calculations)
• Bubble Point Calculation
Ki xi = yi = 1.0
– Assume a temperature for the known pressure (or assume pressure if temperature is known)
– Find Ki at pressure and temperature known and assumed
– Multiply Ki by the corresponding xi (eqn. 1)
– If summation of values is 1.0, then pressure and temperature is correct, if not repeat until Ki
xi = 1.0, within accuracy limits
• Dew Point Calculation
(yi/Ki) = xi = 1.0
– The steps involved in a dew point calculation are the same as for the bubble point calculation, using eqn. 2 in
place of eqn. 1
• A dew point calculation is less exact than a bubble point calculation, especially for lean
gases containing a small amount of heavy ends
Ltd
Flash Calculation
• Flash calculations determine the amount of vapour and liquid in a two phase
system
– F = V + L (Overall)
– F z i = V yi + L x i (For each component)
– Where
• F = mols of total feed
• V = mols of gas leaving system for F mols of feed
• L = mols of liquid leaving system for F mols of feed
• zi = mols of component ‘i’ in the feed stream per mol total feed
• yi = mol fraction of component ‘i’ in the gas stream (V)
• xi = mol fraction of component ‘i’ in the liquid stream (L)
– Let F = 1 and substitute yi = Ki xi
  xi   zi  1.0  yi   1 .0
z i
V
( L  VK i ) (L  )
and Ki
– if xi or yi = 1.0 then a solution has been obtained
Ltd
Soave-Redlich-Kwong
• SRK is robust and well proven, ideal for use in oil & gas and refinery
applications. It is suitable for cryogenic conditions and pressures up to 300 bara.
• For the highest accuracy binary interaction parameters for component pairs
should be used. Correlations can be used to generate binary interaction
parameters for pseudo-components.
• Results for mixtures of hydrogen and hydrocarbons are good; those for
aromatics less so but these can be improved using appropriate binary interaction
parameters.
• Can handle up to 25% H2S with acceptable degree of accuracy if binary
interaction parameters are used.
• Generally not considered suitable where accuracy is required for systems with
polar compounds.
• Liquid compressibility predictions are accurate enough for fugacity calculations
but not for accurate liquid densities (can be 10 - 20% low).
Ltd
Soave-Redlich-Kwong
• Phase behaviour in the critical region can be predicted although calculations
are somewhat unstable at the critical point itself.
• SRK is not considered to be accurate for heavy end VLE prediction and
vacuum systems
• The variables ‘a’ and ‘b’ are derived from the Van-der-Waals equation, which
was based on a model where molecules were represented by hard spheres
which behaved in a classical and predictable fashion
• The parameter ‘b’ represents the hard-sphere volume of the molecules
• The parameter ‘a’ represents the intermolecular attraction
Ltd
Soave-Redlich-Kwong
Standard Form The temperature dependant term a/T of the
P
RT

aα Redlich-Kwong equation was replaced by a
(V  b) V(V  b) function a(T, ) involving the temperature
Polynomial Compressibility Form and acentric factor by Soave
z3 - z2 + (A - B- B2) z - AB = 0
Parameters Fugacity Coefficient
A = (aP)/(R2T2) = 0.42748Pr/Tr2 ln z - 1 - ln (z - B) - A/B ln (1 + B/z)
B = (b P)/(RT) = 0.08664Pr/Tr Mixtures
a = aR2Tc2/Pc = 0.42748R2Tc2/Pc a = yiyj(aij
b = bRTc/Pc = 0.08664RTc/Pc b = yibi
α  1  m(1  Tr 0.5 ) where A = yiyjAij

m  0.48  1.574  0.172 2 B = yiBi
(aij = (1 - kij)[(ai)(a)j]0.5
Ltd
Peng-Robinson
• Peng-Robinson is robust and well proven, ideal for use in oil & gas and
refinery applications. It is generally similar in performance and applicability
to SRK except as follows.
• It is generally accurate over a wider range of conditions.
• It is more accurate around the critical point.
• Liquid phase density prediction is more accurate.
• Improved PR packages can be used for heavy end VLE prediction and vacuum
distillation
Ltd
Peng-Robinson
Standard Form
RT aα
Validity is roughly the same as S-
P  2
(V  b) ( V  2bV - b2 ) R-K, but is more accurate near the
Polynomial Compressibility Form critical point
z3 - (1- B)z2 + (A - 3B2 - 2B)z - (AB - B2 - B3) = 0

Mixtures
Parameters a = yiyj (a)ij
a= 0.45724 [(R2Tc2)/Pc] b = yibi
(aij = (1 - kij) [(a )i(a )j]0.5
b = 0.07780 RTc/Pc
A = yiyjAij
(0.37464 + 1.54226 - 0.26992  (1-Tr )]
 0.5 2
B = yiBi
A = (aP)/(R2T2) = 0.45724Pr/Tr2 Aij = (1 - kij)(AiAj)0.5
B = (bP)/(RT) = 0.07780Pr/Tr kii = 0
Fugacity Coefficient
ln = z - 1 - ln (z - B) - [A/2(2B)0.5] ln [(z+2.414B)/(z-0.414B)]
Ltd
Notation
• Definitions • Greek Symbols
a Attraction parameter Parameter
b Residual volume parameter ij Volatility of species i relative to that of
SRK Parameter (numerical coefficient) species j
A Derived parameter = fi/P, Fugacity Coefficient
B Derived parameter Acentric Factor
z = PV/RT, compressibility factor  Molar Density
ai = ^fi/f0 , activity of a species in a aixi,Activity Coefficient of species i
mixture • Subscripts
^f Partial fugacity of species i
i
c Value of any variable at the critical
kij Binary Interaction Parameter point
(values of kij for around 100 pairs are r Reduced Value
available) pc Pseudo-critical value
aij Cross-parameter • Superscripts
0 property of a standard state, e.g. f0
Ltd
Accentric Factor
• The acentric factor describes the Compound Acentric Factor
change in the intermolecular attraction Nitrogen 0.039
component, a with temperature Carbon Dioxide 0.239
• In the S-R-K equation of state, the Methane 0.011
variation of factor a of the component i Ethane 0.099
with temperature is given by: Butane 0.119
– ai = aci i (T) Hexane 0.299
– where aci is the value of a derived Octane 0.398
from the critical values Decane 0.489
– aci = 0.427 R2 Tci2 / Pci
– and i (T) = (1+mi (1-Tri0.5))2
• The table shows typical acentric factors,
– The variable mi is a function of the
the value increases with the size of the
acentric factor i
molecule and polarity
– i = 0.480 + 1.574 i - 0.172 i2
Ltd
Binary Interaction Coefficients
• The cubic Equations of State were originally developed for pure substances
and have been subsequently adapted for mixtures
• This adaptation introduced a measure of the polar and other interactions
between pairs of dissimilar molecules
• For a component in a mixture:
a   i  jzizjaij
– where zi and zj are mol fractions of components i and j respectfully
– and
aij  ( aiaj ) (1  kij )
– where kij is the binary interaction coefficient
• Binary Interaction Coefficients represent a flexible way of modelling the ideal
EOS to match the non-ideal reality of many mixtures
Ltd
EOS Bubble Pressure Routine
Input feed
composition, guess
vapour composition
and bubble pressure.
Use mixing rules
to calculate Iterate on the vapour phase
mixed P-R composition until the vapour
parameters. phase species fugacity is
equal to the liquid phase
species fugacity.
Use critical and
accentric values to Calculate Z for
calculate P-R vapour and
parameters for liquid.
single components.
Check vapour and liquid

mole fractions sum to 1. If
not iterate on pressure.
Initialise Calculate
interaction fugacity.
parameters.
Ltd
EOS Flash Calculation
Given
zj, p, T
Assume
Kj
yj,nv Perform Flash X n

j, L
Calculations
Calculate Calculate Calculate

vj Kj ØL j
No Test for
Convergence
Yes
Solution
Ltd
Example
Calculation of the saturation pressure of n-Pentane at 100 ºC using an Equation of State
• At equilibrium, the fugacity of the liquid and vapour phases is equal
• The experimentally determined vapour pressure is 5.86 atm
• Critical properties of n-Pentane are:
Tc = 469.7 K, Pc = 33.25 atm,  = 0.251
• Using S-R-K :
  1  m (1  Tr ) where m  0.48  1.574  0.172 2
 373 
  1   0.48  1.574  0.251   0.172  0.2512  1    1.094

 469.6 
• Calculate A & B
A  0.42747  P / Pc  Tc / T   0.0224P
2
B  0.08664 P / Pc  Tc / T   0.0033P
• Substitute values of A & B into the polynomial compressibility equation:
Z 3  Z 2  ( A  B  B 2 ) Z  AB  0 z f
• Solve to find Z for liquid and vapour phases P Vapour Liquid Vapour Liquid Ratio
4 0.8943 0.0184 3.665 5.196
• Calculate the fugacity of the vapour and liquid phases: 5 0.8647 0.0229 4.4774 5.2287 0.8563
ln z - 1 - ln (z - B) - A/B ln (1 + B/z) 6 0.831 0.0275 5.2482 5.2512 0.9994
VfV/PV and LfL/PV 7  0.0321 5.9775 5.2807
0.7955 1.132
• At equilibrium, fV = fL therefore V = L
By interpolation of the above table, the predicted vapour pressure is 6.01 atm
Ltd
E.o.S Comparison: Peng Robinson v
Zudkevitch Joffee
PR ZJ
GOR PR ZJ
MW 18.53 18.43
1st Stage (scf/bbl) 299 292
Q (mmscfd) 15.0 14.6
2nd Stage (scf/bbl) 19 24
C1 (mol%) 88.57 88.94
Overall (scf/bbl) 318 316
C2 (mol%) 7.17 6.87
C3 (mol%) 0.13 0.12
PR ZJ
MW 22.09 21.54
Q (mmscfd) 0.9 1.2
C1 (mol%) 74.75 76.34
C2 (mol%) 16.33 15.80
Reservoir 9 barg C3 (mol%) 0.45 0.41
Fluids
54 C
1.1 barg
53 C
50 mbd stabilised crude
Ltd
Phase Behaviour – Pipeline Gas
Gullfaks Fluid from SOW
Components Gas A Application of BWRS erroneous – Pipeline two-phase
C1 86.5473 130
C2 7.30256
C3 2.01471 120
Minimum
IC4 0.475166 110 Pipeline
NC4 0.566198 Operating
100
IC5 0.213075 Pressure
NC5 0.230081 90
C6 0.120042 80
C7 0.100035 BWRS
Pressure (bar)
70 PR
C8 0.060021 RKS
N2 0.880308 60 Cricondentherm
CO2 1.49052 50
Cricondenbar
SUM 100
40
Molar weight 19.1
HC dewpoint 23.5 °C @ 30
(Cricondentherm) 40.1 bara
20
HC dewpoint 101.2 bara 10
0
(Cricondenbar) @ -16.4 -40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35
°C Temperature (C)
Ltd
High Pressure Compressor Simulation
• At pressure above ca 250 Bar P-R and SRK

may not accurately represent the system
thermodynamics
• Other EOS options should be considered –
– Lee Kessler Plocker - LKP
– P-R with Lee Kessler Plocker Enthalpy – PR-LK
– Corresponding States Method - Infochem
Ltd
Limitations of Phase Behaviour Prediction
• All phase behaviour methods assume an equilibrium is reached, this is an idealised

situation and in reality equilibrium is not always achieved.
• EOS can not be used to predict water/hydrocarbon separation
• Phase behaviour prediction deals with mass transfer effects and therefore does not take
into account bulk fluid flow. In practice there is almost inevitably some bulk transfer of
fluids between the phases: emulsions may be formed due to high shear rates across
control valves and the addition of corrosion inhibitor which holds water in the oil phase,
oil will carry over into the oil phase, liquid droplets carry over into the gas phase.
• Prediction methods are generally only valid over a particular range of conditions and for
particular components.
• EOS do not accurately predict phase behaviour at the critical point.
Ltd
Polar Fluids
• For the majority of calculations, simple treatment of hydrocarbon/water behaviour is
sufficient, however for systems containing large amounts of polar fluids (water,
methanol or glycol) more rigorous treatment is required.
• For polar systems it is generally recommended to use an activity model to predict liquid
phase behaviour. Although work is being undertaken to extent the validity of EOS
methods into the liquid phase (e.g. Peng-Robinson-Stryjek-Vera [PRSV])
• For water/oil mixtures the accuracy of calculations depends on the availability and
accuracy of the binary interaction data available, at low pressures NRTL will give
accurate results providing all the data required is available.
• For methanol/water mixtures, NRTL provides accurate results at pressures below 1000
kPa.
• Many of the commercially available simulators provide methods for such systems.
Expert advice is usually available from their technical support.
Ltd
Activity Models
• The most common liquid activity methods are:
– NRTL - Non-random two liquid method
– Useful for highly non-ideal systems where very sharp separations are required
– Valid for both liquid-liquid and vapour-liquid-liquid systems, excellent for aezotropic column
– Accurate liquid density data is essential
– Should not be used if the temperature of any component is above the critical temperature
– Should not be used for pressures above 1500 kPa
– UNIQUAC
– This method utilises phase equilibrium data to predict phase data for systems where no such
information is available
– Activity coefficients for mixtures are related to interactions between structural groups and
corrections are then applied to take into account differences in molecular size and molecular
interactions
– UNIQUAC is an approximate method and should not be used for detailed design
– Works best at pressures below 500 kPa and temperatures between 300 K and 425 K
Ltd
PVT Matching
• The Equation of State model is generally accurate for predicting phase behaviour for
‘normal’ oil systems. Physical property estimates such as density require careful
evaluation. For example, the P-R EOS underpredicts by 5-10% the density of light
hydrocarbons (C1 to C5) and overpredicts the heavier ones
• Since all volumetric oil properties, FVF and GOR for example are derived from specific
gravity, it is important that density is modelled accurately. Also many items of equipment
will require accurate prediction of physical properties - pumps, heat exchangers,
compressors etc.
• The liquid density derived from EOS methods is very sensitive to property and
compositional changes hence matching to experimentally determined results is often
undertaken
• PVT matching involves manipulating the boiling point and associated Tc, Pc and Acentric
Factor of the pseudo-components. Matching requires great care and guidance should be
sought if unfamiliar with the techniques
• Condensates can be much more difficult to match than oils as the use of Binary Interaction
Parameters is not as effective in this area
Ltd
SPR CRUDE OIL COMPREHENSIVE ANALYSIS
Sample ID BAYOU CHOCTAW SWEET Date of Assay 18/09/2000
Crude Assays
Crude
Specific Gravity, 60/60° F 0.8447 Ni, ppm 3.50 RVP, psi @ 100° F 4.62
API Gravity 36.0 V, ppm 5.49 Acid number, mg KOH/g 0.084
Sulfur, Wt. % 0.36 Fe, ppm 0.844 Mercaptan Sulfur, ppm 7.021
Nitrogen, Wt. % 0.114 H2S Sulfur, ppm 0
Micro Car. Res., Wt. % 2.22 Org. Cl, ppm 0.3 Viscosity: 77° F 6.874 cSt
Pour Point, °F 31 UOP "K" 11.94 100° F 4.623 cSt
Fraction Gas 1 2 3 4 5 6 Residuum Residuum

C2 - C5 - 175° - 250° - 375° - 530° - 650° -
Cut Temp. C4 175° F 250° F 375° F 530° F 650° F 1050° F 650° F+ 1050° F+
Vol. % 1.7 7.3 8.1 14.2 16.3 10.0 31.8 42.4 10.7
• An Assay is a detailed fluid analysis of Vol. Sum %

Wt. %
1.7
1.2
9.0
5.8
17.1
7.1
31.3
13.1
47.6
15.9
57.6
10.1
89.3
34.3
100.0
47.0
100.0
12.7
crude oil, sampled under strictly

Wt. Sum % 1.2 7.0 14.1 27.1 43.0 53.1 87.4 100.0 100.0
Specific Gravity, 60/60° F 0.6730 0.7396 0.7763 0.8240 0.8526 0.9116 0.9349 1.004
API Gravity 78.8 59.8 50.8 40.2 34.5 23.7 19.9 9.4
controlled conditions Sulfur, Wt. %
Molecular Weight
0.0043
97
0.0040
111
0.0123
136
0.07
184
0.21
246
0.57
425
0.69 1.04
• Assay reports include the quantities and

Hydrogen, Wt. %
Mercaptan Sulfur, ppm
15.89
14.6
14.65
10.1
na
22.5 17.4
12.99 10.61
H2S Sulfur, ppm 0.03 0.8 0.7 0.02

properties of distillates used for crude Organic Cl, ppm
Research Octane Number*
2.1
68.4
0.5
61.1
0.5
42.3
0.6
valuation purposes, the quantity of Motor Octane Number*

Flash Point, ° F
66.5 58.6 40.0
77 171 246 303
waxes, heavy metals, salt and sulphur Aniline Point, ° F

Acid Number, mg KOH/g
122.4 144.1
0.03
164.3
0.10
193.3
and physical properties of the fluid such

Cetane Index 47.1 53.2
Diesel Index 62.2 58.0 56.6
Naphthalenes, Vol. % 4.42 8.20
as viscosity Smoke point, mm

Nitrogen, Wt. %
20.3
0.0015
16.8
0.006 0.108 0.240 0.603
• Assay samples are taken monthly for the

Viscosity, cSt 77° F 2.473
100° F 1.951 4.795
130° F 3.312 37.03 95.3
purposes of crude valuation purposes 180° F

210° F
14.22 28.28 5671
1722
and annually for crudes being exported Freezing Point, °F

275° F
-28.54
249.3
via a pipeline shared with other fields Cloud Point, °F

Pour Point, °F
24.0
19.9
106
102 75
Ni, ppm 7.539 26.2
V, ppm 11.81 41.0
Fe, ppm 3.856 13.87
Micro Car. Res., Wt. % 5.07 18.17
* = calculated from gas chromatographic data
Ltd

Upstream Process Engineering Course: 1. Hydrocarbon Phase Behaviour

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Upstream Process Engineering Course: 1. Hydrocarbon Phase Behaviour

Загружено:

Авторское право:

Доступные форматы

Upstream Process

gasoline Petrol for vehicles

kerosene Jet fuel and paraffin

diesel oils Diesel fuel

Fuel oil Fuel for ships and central heating

Typical P-T diagrams showing the position of

Total Distillate Wt%

to take in distillation test data directly and to

43 Components – simplify for

Component Pseudo Component Simplification

C7 C8 C9 C13 C17 C19 C23 C27 C31 C37 C45 C62

b = bRTc/Pc = 0.08664RTc/Pc b = yibi

α  1  m(1  Tr 0.5 ) where A = yiyjAij

z3 - (1- B)z2 + (A - 3B2 - 2B)z - (AB - B2 - B3) = 0

Check vapour and liquid

yj,nv Perform Flash X n

Calculate Calculate Calculate

50 mbd stabilised crude

HC dewpoint 101.2 bara 10

• At pressure above ca 250 Bar P-R and SRK

• All phase behaviour methods assume an equilibrium is reached, this is an idealised

Sample ID BAYOU CHOCTAW SWEET Date of Assay 18/09/2000

Fraction Gas 1 2 3 4 5 6 Residuum Residuum

• An Assay is a detailed fluid analysis of Vol. Sum %

crude oil, sampled under strictly

• Assay reports include the quantities and

H2S Sulfur, ppm 0.03 0.8 0.7 0.02

valuation purposes, the quantity of Motor Octane Number*

waxes, heavy metals, salt and sulphur Aniline Point, ° F

and physical properties of the fluid such

as viscosity Smoke point, mm

• Assay samples are taken monthly for the

purposes of crude valuation purposes 180° F

and annually for crudes being exported Freezing Point, °F

via a pipeline shared with other fields Cloud Point, °F

* = calculated from gas chromatographic data

Вам также может понравиться