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FRACTIONSANDCRUDEOILS
3.1Introduction
Table3.1
ThermopysicalPropertyPrediction
___________________________________________________
ThermodynamicProperties:
Enthalpy
HeatCapacity
CompressibilityFactors
EquilibriumKvalues
FlashCurves
TransportProperties:
Viscosity
ThermalConductivity
Diffusivity
PhysicalProperties:
Densities
Volumes
3.2BasicInputData
3.2.1Gravity:
Specificgravityforliquidoilsisdefinedas:
S liq =
liq
water
3.1
Both densities of oil and water are at some standard temperature and
pressure.Thesestandardconditionsforspecificgravityofpetroleumliquids
are1atmand60F.Sinceunderthesameconditions,mostpetroleumfractions
arelighterthanwater, liq 1 .
AnotherparameterforoildensityisAPIgravitydefinedas:
141.5
API =
131.5
S
HeavyoilshavelowAPIandlightoilshighAPIgravities.
3.2
Density measurement of petroleum fractions and crude oils are carried out
usingeitherapycnometeroraMettler/Parrdensitometer.Thelattermethod
is based on densitydependent frequency changes of an oscillating glass U
tube.
3.2.2BoilingPointCurves
3.3.3ASTMDistillation:
Thetemperatureatwhichthefirstdropofcondensateiscollectediscalledthe
initial boiling point (IBP). The end point (EP) is the maximum vapor
temperaturewhenalmosttheentiresampleisdistilled(above95%).
Boilingtemperaturesatsubatmosphericpressures(lessthan760mmHg)can
beconvertedtonormalboilingpoints(at760mmHg)usingprocedure5A1.13
ofAPITDB.
SinceminimumfractionationoccursinASTMdistillation,componentsinthe
mixture do not distill one by one in the order of their boiling points, but as
mixtures of successively higher boiling points. Thus, components boiling
below the IBP and above the EP are present in the sample. Nevertheless,
becauseASTMdistillationsarequicklyconductedandhavebeensuccessfully
automated,requireonlyasmallsample,andarequitereproducible,theyare
widelyusedforcomparisonandspecificationofpetroleumfractions.
3.2.3TrueBoilingPointDistillation:
3.2.4ConversionbetweenASTMandTBPdistillation:
SinceTBPdistillationisbothtediousandtimeconsumingvisvistheASTM
method,therehasbeenanincentivetodevelopcorrelationtoconvertASTM
toTBPdistillationandachievingthebenefitofthedetailedseparationofTBP
withthelittleeffortinASTMdistillation.Thefollowingequationssuggested
by Riazi and Duabert and published by the API(1) are used for the
interconversion:
a,b=constantsvaryingwithpercentofliquidsampledistilledasgivenin
Table3.2.
TBP=trueboilingpointtemperaturesat0,10,30,50,70,90,and95volume
percentdistilled,indegreesRankine.
ASTMD86=observedASTMD86temperaturesatcorrespondingvolume
percentdistilled,indegreesRankine.
AverageerrorbetweenthecalculatedandmeasuredTBPisintherangeof5
C.
Table3.2
Constantsforequation3.3
Volume%
distilled
0
10
30
50
70
90
95
0.9167
0.5277
0.7429
0.8920
0.8705
0.9490
0.8008
1.0019
1.0900
1.0425
1.0176
1.0226
1.0110
1.0355
Morerecently,Daubert(2)publishedanewmethodfordistillationcurves
interconversionusingthefollowingequations:
T50' = A4 (T50 ) B 4
T30' = T50' T3'
T10' = T30' T2'
Ti = Ai (Ti )
T2 = T30 T10
T6 = T90 T70
'
Bi
T1 = T10 T0
T3 = T50 T30
T7 = T f T90
3.4
T2 = T30 T10
T5 = T70 T50
The symbol T and T stands for ASTM D86 and TBP temperatures
respectively, both in F. The subscript 0 and f stands for the initial andfinal
temperaturesrespectively.AiandBiareconstantsgiveninTable3.3
Table3.3
ConstantsforDaubertsDistillationCurvesInterconversion
Method
Index
Ai
Bi
numberi
1
7.4012
0.6024
2
4.9004
0.7164
3
3.0305
0.8008
4
0.8718
1.0258
5
2.5282
0.8200
6
3.0419
0.7750
7
0.1180
1.6606
Thereportedaverageerrorforthismethodisabout3C
Example3.1:
ApetroleumcuthasthefollowingASTMD86Distillationdata:
Volume%
0
10
30
50
70
90
95
distilled
Temperature,
36.5
54
77
101.5
131
171
186.5
C
ConvertthesedatatoTBPdatausingtheAPImethodofRiaziandDaubert
andDaubertsmethod.Plottheresultsandcompare.
Solution:
ApplicationofAPImethodisstraightforwardusingtheconstantsinTable3.2.
FortheDaubersmethod,theconstantsinTable3.3areusedtocalculateTBP
at50vol%.the TarecalculatedfromtheASTMdata,theTfortheTBPare
calculated.ThenTforTBParecalculatedusingtheformulasinequation3.2.
TheresultsareshowninTable3.4
Table3.4:Example3.1
250.0
200.0
Temperature,C
APITBPCurve
ASTMD86
150.0
DuabertTBP
100.0
50.0
0.0
0
10
20
30
40
50
60
70
80
90
100
50.0
Volume%Distilled
Figure3.1ConversionofASTMD86intoTBP(Example3.1)
AscanbeseenfromFigure3.1,TheTBPdistillationcurveisbelowtheASTM
curveatvolumedistilledbelow50%andaboveitforvolumedistilledabove
50%.TheAPIandDuabertsmethodsgivecomparableresultsexceptforthe
lowrange,lessthan10%distilled.
Based on the distillation curve, five different average boiling points can be
estimated. Among these, the volume average boiling point (VABP) and the
mean average boiling points (MeABP) are the most widely used in property
estimation and design. The mean average boiling point is utilized in the
definition of an important parameter, the Watson characterization factor K
givenby:
( MeABP) 3
3.5
K =
S
WhereMeABPisindegreesRankine.
Thefollowingistheprocedureforestimatingtheaverageboilingpointwhen
theASTMD86distillationdataisavailable.TheVABPiscalculatedfromthe
boilingtemperaturesateachofthe10,30,50,70,and90percentdistilled:
3.6
5
WherealltemperaturesareindegreesF.
TheMeABPiscalculatedusingthefollowingequation:
MeABP = VABP
3.7
Where isgivenby:
T T10
SL = 90
90 10
AsmentionedbeforeASTMandTBPdistillationcanbeperformedoncrude
oils and petroleum products. The petroleum fractions are cuts from the
crude oil with specific boiling point range and with special specification of
propertiessuchasAPIgravityandviscosity.Eachofthesecutscanbefurther
defined by dividing them into narrow boiling fractions, called pseudo (not
real) components. For these pseudocomponents, the average boiling point
canbeestimatedaseithermidboilingpointormidpercentageboilingpoint.
TheTBPcurveisdividedintoanarbitrarynumberofpseudocomponentsor
narrowboilingcuts.Theaverageboilingpointiseithertheaveragebetween
the IBP and the EP of that pseudocomponent. The midvolume percentage
point is the temperature at the arithmetic average of the volume distilled at
theIBPandEPofthatpseudocomponent.Sinceboilingrangeissmall,both
averages are close to each other and can be considered the VABP or the
MeABPforthatpseudocomponent.
Example3.2:
Calculatethemeanaverageboilingpointofthepetroleumfractionofexample
3.1. If the API gravity of this fraction is 66, calculate the Watsons
characterizationfactor.
Solution:
MeBP=224.418.3=206.1For96.8C
Fromequation3.2
141.4
S=
= 0.7313
62 + 131.5
(206.1 + 459.6)
K =
0.7313
= 11.94
3.3PseudoComponents
3.3.1BreakupofTBPcurveintoPseudocomponents
TheTBPforthecrudeoilorthepetroleumfractionhastobeavailable,either
by direct laboratory measurements through ASTM D1160 distillation or
throughtheconversionofASTMD86distillationintoTBPdistillationcurve.
TBP cut point ranges are used to define pseudocomponents , with the
averagetemperatureofthecutorthemidpointnormalboilingpoint(NBP).If
the petroleum fraction contains components lighter than pentanes, the
composition of the lighter ends has to be available experimentally through
chromatographic analysis of the vapors. Otherwise the lighter ends are
lumped with lightest pseudo component. The number of such pseudo
components depends on the boiling point range of the whole petroleum
Ageneralguidelinefordeterminingthenumberofpseudocomponentsisas
follows:
10Cforlightfractionswithboilingpointslessthan200C
15Cforfractionswithboilingpointsbetween200to400C
20Cforfractionswithboilingpointsbetween400to600C
30Cforfractionswithboilingpointsbeyond600C
Thenumberofpseudocomponentdependsontheapplication.Indistillation
calculations, more NBP cuts might be needed to represent narrow boiling
products.Figure3.2showshowtheTBPcurveiscutintoseveralpseudo
components.
Figure3.2RepresentationofTBPcurvebyPseudoComponents
_____________________________________________________________________
Example3.3
Using the TBP curve of the petroleum cut of example 1, divide it into 20
pseudocomponents. Calculate the volume percentage of each pseudo
component.
10
Solution:
TheTBPcurveobtainedextendsto95volumepercentdistilledonly.Inorder
to obtain the average boiling point of the last fractions, the curve is
extrapolated to the final point of the distillation (100%) by using fitting the
curve a suitable polynomial function and extrapolating the results. In this
chapter Excel spreadsheet program was used with a fifth order polynomial
functionwasused.Theresultsareshownbelow.
TBP Curve
300
y = 0.0000001x5 - 0.0000287x4 + 0.0027144x3 -
250
TBP, C
200
150
100
TBP Curve
ASTM D86
50
0
-50
10
20
30
40
50
60
70
80
90
100
Vol%
Figure3.3ExtrapolationofTBPcurve
The end point of the cut is 218.2 C and the IBP is 5.4 C. Therefore each
pseudocomponent has a temperature interval of (218.2+5.4)/2 or 11.2 C
.Thenthecurvecanbecutasfollows.TheEBPofthefirstcutisIBP+11.2 C
or 5.8 C. The average boiling point for the first pseudocomponent is (
5.4+5.8)/2or0.2C.Thevol%is2.84asreadfromtheTBPcurve.Thesecond
cut has an end boiling point of 17 C and end volume percent of 6.19.
Therefore the volume % of this cut is 6.19 2.84 or 3.36 vol%. The average
boiling point for the second cut is (17+5.8)/2 or 11.2 C . For the subsequent
cuttheresultsareshowninTable3.4
11
EBPofcut,C
5.8
17.0
28.2
39.4
50.5
61.7
72.9
84.1
95.3
106.4
117.6
128.8
140.0
151.1
162.3
173.5
184.7
195.9
207.0
218.2
Table3.5Pseudocomponentstable
Vol%atendof
NBPofcut,C
cut
0.2
2.84
11.4
6.19
22.6
10.22
33.8
15.09
44.9
20.82
56.1
27.15
67.3
33.68
78.5
40.10
89.7
46.36
100.8
52.53
112.0
58.69
123.2
64.89
134.4
71.09
145.6
77.07
156.7
82.53
167.9
87.25
179.1
91.25
190.3
94.63
201.5
97.51
212.6
100.00
Cutvol%
2.84
3.36
4.03
4.87
5.73
6.34
6.52
6.42
6.26
6.17
6.16
6.21
6.20
5.98
5.45
4.73
4.00
3.37
2.88
2.49
3.3.2CalculationofpseudocomponentsSpecificGravities
12
the above definition of the K factor is used to calculate the gravity of each
pseudocomponentgivenitsaveragenormalboilingpoint.
Example3.4
Table3.6SpecificgravityofPseudocomponents
NBPofcut,C
S
0.2
0.6615
11.4
0.6704
22.6
0.6790
33.8
0.6875
44.9
0.6957
56.1
0.7038
67.3
0.7117
78.5
0.7194
89.7
0.7269
100.8
0.7343
112.0
0.7416
123.2
0.7487
134.4
0.7556
145.6
0.7625
156.7
0.7692
167.9
0.7758
0.7823
179.1
190.3
0.7887
201.5
0.7950
212.6
0.8012
13
3.4ThermophysicalPropertiesCalculation
3.4.1MolecularWeight
1.26007 4.98308
M = 42.965 exp(2.097 10 4 Tb 7.78712 S + 2.08476 10 3 Tb S ) Tb
S
3.8
Where:
M=molecularweightofpetroleumfraction.
Tb =MeanaverageboilingpointofpetroleumfractionindegreesK.
S=specificgravity,60F/60F.
Example3.6
CalculatethemolecularweightforthecutwithNBPof216.4C.
Solution:
This cut has a NBP of 216.4 C or 489.55 K and a specific gravity of 0.6718
from table 3.6. Using equation 3.8, the molecular weight is calculated to be
170.8.
3.4.2Viscosity:
14
3.9
3.10
Where 100 and 210 are the kinematic viscosities at 100 F and 210 F, in
centistockes.
3.4.3RefractiveIndex:
1/ 2
1 + 2I
n=
1 I
ValuesofImaybecalculatedfrom:
e
I = a exp(bTb + cS + dTb S )Tb S f
3.11
3.12
Where:
a,b,c...f=constantsvaryingwithmolecularweightrangeasgivenbelow.
ConstantsLightFractionsHeavyFractions
Molecularweightrange70300
300600
Boilingpointrange,F 90650
6501000
2
a
2.266x10 2.341x102
b
3.905x104 6.464x104
c
2.468
5.144
4
d
5.704x10 3.289x104
e
0.0572
0.407
f
0.720
3.333
15
n=refractiveindexat68F.
I=Huangcharacterizationparameterat68F.
Tb=meanaverageboilingpoint,indegreesRankine.
M=molecularweightofpetroleumfractions.
S = specific gravity of petroleum fraction, 60 F/60 F.
____________________________________________________________________
Example3.7
Calculate the kinematic viscosities and the refractive index for an oil which
hasameanaverageboilingpointof320Cand34APIgravity.
Solution:
The boiling point is 593.15 K or 1067.7 R. Using equations 3.2 and 3.5, The
specificgravityis0.855andtheWatsonKfactoris11.95.Fromequations3.9
and3.10:
100=5.823CSt,and210=1.196CSt.
From equation 3.11 and 3.12, the refractive index n is calculated to be 1.481
(Mis257.1ascalculatedfromequation3.8).
3.4.4MolecularTypeCompositionofPetroleumfractions
xp=a+bRI+c(VG)
xn=d+e(RI)+f(VG)
3.13
xa=g+h(RI)+i(VG)
Where:
a,b,c,...,i=constantsvaryingwithmolecularweightrangeas
givenbelow.
16
Constants
Molecularweight
range
a
b
c
d
e
f
g
h
i
LightFraction
70200
HeavyFractions
200600
13.359
+14.4591
1.41344
+23.9825
23.333
+0.81517
9.6235
+8.8739
+0.59827
2.5737
+1.0133
3.573
+2.464
3.6701
+1.96312
4.0377
+2.6568
+1.60988
d
RI = n
2
Where:
n=refractiveindexat68Fand1atmosphere.
d = liquid density at 68 F and1 atomosphere in
gramspercubiccentimeter.
VGC =
or
VGC =
Where:
S=specificgravityat60F160F
V=Sayboltuniversalviscosityat100or210F,inSayboltuniversal
seconds.
or
17
3.4.5PseudoCriticalConstantsandAcentricFactors
Almost all the methods which are used to calculate the thermodynamic
properties and transport properties rely on the principle of corresponding
states and an equation of state. In order to use these methods the critical
temperature and pressure and the acentric factor are required as input
constants.Whiletheseconstantsaretabulatedfordefinedcomponents,these
have to be estimated for narrow boiling petroleum cuts or pseudo
components.Thegeneraladoptedmethodinthisregardistocalculatethese
constantsfromtwocharacteristicproperties;theaverageboilingpointandthe
specific gravity or API gravity. While there several equations are available
suchasthoseofRiaziandDaubert,LeeandKesler,Winn,andCavett(3),we
willusethoseofLeeandKesler(4)becausetheyareusedasdefaultmethods
inprocesssimulators.
3.4.5.1PseudoCriticalTemperature:
(14,410 100,688S )
Tc = 189.8 + 450.6S + (0.422 + 0.1174S ) +
3.14
Tb
wherepseudocriticaltemperatureTcandtheaveragenormalboilingpointTb
areindegreesK.
3.4.5.2PseudoCriticalPressure
0.0566
4.12164 0.213426
ln Pc = 5.689S
10 3 Tb 0.436392 +
+
S
S
S2
3.15
11.819 1.53015
9.901
7 2
10 3
+ 10 Tb 4.75794 +
+
10 Tb 2.45055 + 2
S
S2
S
wherePcisinbars.
3.4.5.3AcentricFactor
The equation for calculating the acentric factor depends on the value of the
reducedaveragenormalpointTbr=Tb/Tcasfollows:
= (ln Pbr 5.92714 + 6.09648 / Tbr + 1.28862 ln Tbr 0.169347Tbr6 ) /(15.2518 15.6875 / Tbr
13.4721 ln Tbr + 0.43577Tbr6 )
forTbr<0.8 3.16
where Pbr = Pb /Pc and Pb is the pressure at which Tb is measured which is
atmosphericpressure.ForTbr>0.8theequationtouseis:
18
Example3.8
Calculatethecriticaltemperatureandpressureandtheacentricfactorforan
oilwhichhasameanaverageboilingpointof320Cand34APIgravity.
Solution:
Theboilingpointis593.15Kandthespecificgravityis0.855.Usingequations
3.14and3.15:
Tc =765.5KandPc =15.26bar.Theacentricfactoris0.777(Tbr =0.755souse
equation3.16).
_____________________________________________________________________
3.4.6GeneralisedEquationforThermophysicalProperties
Riazi and AlSahhaf (5) presented a method for the calculation of different
propertiessuchasthenormalboilingpoint,density,refractiveindex,critical
temperature, pressure and density, acentric factor, solubility parameter and
surface tension given only the molecular weight and using the following
generalequation
= exp(a bM C )
3.18
where can be any one of the properties mentioned above. M is the
molecular weight and is the limiting value for any property as M .
This generalized equation can be used to calculate the following properties
giventhemolecularweight.Thepropertiesare:
ThemeanaverageboilingpointTb,K
ThespecificgravityS.
Theliquiddensityat20Cor68F.d20
TheHuangcharacterizationparameterI.
The reduced boiling point which is used to calculate the critical
temperatureindegreesK.Tbr=Tb/Tc
ThecriticalpressureinbarsPc
Thecriticaldensitydc
Theacentricfactor.
Thesurfacetensionindynes/cm.
Thesolubilityparameter,in(cal/cm3)2,
Theconstantsa,bandcforeachpropertyaregivenintable3.8.Giventhe
Table3.8ConstantsfortheRiaziAlSahhafequation
19
Tb
S
d20
I
Tbr
Pc
dc
1080
1.07
1.05
0.34
1.2
0
0.22
0.3
30.3
8.6
a
b
c
6.97996 0.01964 0.666667
3.56073 2.93886
0.1
3.80258 3.12287
0.1
2.30884 2.96508
0.1
0.34742 0.02327
0.55
6.34492 0.7239
0.3
3.2201
0.0009
1
6.252 3.64457
0.1
17.45018 9.70188
0.1
2.29195 0.54907
0.3
The application of this correlation is simple. You only need to know the
average normal boiling point of the petroleum fraction. First the molecular
weight is calculated from the correlation using the constants for the boiling
point.Oncethemolecularweightisknownotherpropertiescanbecalculated
usingequation3.18withtheappropriateconstantsfromtable3.8.
Example3.9
UsetheRiaziAlSahhafequationtocalculatethepropertiesforanoilwhich
hasameanaverageboilingpointof320Cand34APIgravity.
Solution:
From the boiling point the molecular weight is calculated as 256. Using this
valueotherpropertiesarecalculatedandthevaluesareshownbelow
S
0.859
0.855
d20
I
0.2824
773
Tc
Pc
12.5
dc
0.252
0.798
28.55
8.055
20
3.5CalculationofenthalpyofPetroleumFractions
Z = Z 0 + Z 1
3.19
RT
Equation 3.19 can be used to calculate the molar volume as: V =
or the
P
M
massdensityas =
.
V
Misthemolecularweight.
ThedeparturefunctionsHHigisgivenby
H H ig H H ig
H H ig
=
+
3.20
RT
RT
RT
c
c
c
The superscript 0 and 1 denotes the value for the simple fluid and the
dcorrection terms respectively. These values are obtained from published
tables which can be founds in standard chemical engineering
thermodynamics textbooks as functions of the reduced temperature and
pressure(6)andaretabulatedintheEXCELspreadsheetLeeKesler.xlswhich
willbediscussedinsection3.7.Thecriticaltemperature,criticalpressureand
the acentric factor for the petroleum fraction can be obtained from the
equations in section 3.4.5. If the fraction is treated as being made up of
pseudocomponents, the critical temperature, critical pressure and the
acentric factor can be calculated using the following simple mixing rule
equations:
Tc = yi Tci
i
Pc = y i Pci
3.21
= yii
i
Theenthalpychangeofafluidfromstate1atT1andP1tostate2atT2andP2
isgivenby:
21
Tocalculatetheenthalpywithrespecttoareferencestateset
H 1 = H ref = 0
Ifthereferencestateisatlowpressure(idealgas),then
( H 1 H 1ig ) = 0
Theenthalpyequationbecomes
ig
H = ( H H ig ) + ( H ig H ref
)
3.22
3.23
T2
3.24
T1
Theidealgasheatcapacityforpetroleumfractionsisgivenby
C igp = A + BT + CT 2
3.25
Integrationofequation3.23yields:
B
C
H 2ig H 1ig = A(T2 T1 ) + (T22 T12 ) + (T23 T13 )
3.26
2
3
3.29
22
Example3.10
Calculatethemolarvolumeandenthalpyofanoilat450Cand3.45bar.The
oil has a mean average boiling point of 320 C and 34 API gravity. The
referencestateisidealgasat298K.
Solution:
Thespecificgravityis0.855andtheKfactoris11.95.Usingequations3.14and
3.15:Tc=765.5KandPc=15.26bar.Theacentricfactoris0.777.Themolecular
weightfromequation3.8is257.12.
Tr = 0.9447 and Pr = 0.2261 .
FromtheLeeKeslertables:
Z 0 = 0.9029 , Z 1 = 0.0325
Z = 0.9029 + (.777)(0.0325) = 0.8776
(0.8776)(8.3143)(450 + 273.15)
V =
= 15294.5 cm3/mol
0.345
Fromequation3.23
ig
H = ( H H ig ) + ( H ig H ref
)
FromtheLeeKeslertrables:
o
H H ig
= 0.1487 ,
= 0.2882
RTc
ig
( H H ) = 2371.9 kJ/kgmol
H H ig
RTc
H H ig
RTc
Fortheidealheatcapacityandfromequations3.273.29
A = 8.74721 , B = 1.44929 ,and C = 0.000581
Fromequation3.26andfortemperaturesbetween298and723.15K;
ig
( H ig H ref
) = 312088.8 kJ/kgmol
Therefore
H = 314460.8 kJ/kgmolor1223kJ/kg
23
3.6EstimationofPropertiesRelatedtoPhasechanges
In petroleum refining crude oil and petroleum fractions are separated into
narrower fractions by chemical engineering unit operations that utilizes the
phase equilibria between the hydrocarbons in the liquid and vapor phases
suchasdistillation,adsorption,condensationandevaporation.Whenwateris
present such as the case in the atmospheric column of crude distillation,
liquidliquidvaporequilibriumisencountered.
Equilibrium K values, i.e. (yi/xi ) are the fundamental building blocks of all
unit operations involving phase change. Traditional older methods for
calculations of K values rely on methods or charts which were based on
temperatureandpressureonlywithnocompositiondependence.
3.6.1CubicEquationsofState
With the development of more accurate equations of state and with the
widespreaduseofcomputersimulationinprocessdesignthesemethodsare
replacedwithcomputerpackageswhichrelyonequationsofstateforphase
equilibria calculations. Equations of based on the RedlichKwong equation
have proven to be most successful for petroleum systems. The most widely
used modifications of the RedlichKwong equations are the modifications of
Soave and PengRobinson. In this chapter we will concentrate on the latter
equation.
ThePengRobinson(PR)equation(7)isacubicequationinvolumewiththe
form:
V
a (T )
Z=
V b V (V + b) + b(V b)
a = xi x j aij
and b = xi bi
i
thecombiningruleforaijisgivenby
aij = ( ai a j ) 2 (1 k ij )
24
3.6.2VaporLiquidEquilibrium
Ki =
il
il
iv
and iv arecalledthefugacitycoefficientofcomponentiintheliquidand
Afterenteringthecomponentsorpseudocomponentsnumbers,theprogram
asksforthebinaryinteractioncoefficients.Asmentionedearlier,thesevalues
canbesettozeroforhydrocarbonhydrocarboninteractions.
Amenuofdifferenttypesofphaseequilibriumcalculationappears.Perform
the desired calculations. For multicomponent mixtures such as the case of
petroleum fractions made up of several pseudocomponents, the program
might not converge or gives a warning. This might be a problem with the
initial guesses which the program takes as it is caked shortcut Ki which
basically the Raoults law values. In such cases, try to get convergence at
25
Example3.11
Anoilmixturecanberepresentedbythefollowingpseudocomponents
Pseudo
Pc,MPa
Mol%
Tc,K
component
1
50.0
190.6
4.60
0.008
2
11.0
338.2
4.56
0.126
3
7.00
464.5
3.36
0.242
4
20.0
619.4
2.56
0.581
5
8.0
760.2
1.52
1.046
5
4.0
925.6
1.14
1.585
Ifisoilisflashedat500Kand3MPa,whatisthefractionofvapor.Whatare
thecompositionsoftheexitingvaporandliquidphases?
Solution:
Firstenterthecriticaltemperatureandpressureandtheacentricfactorforthe
pseudocomponents in CRITPARM.TXT. Start with the number 2001 at
bottomofthelistto2006.UsingtheprogramPRMIX.EXE,thevaporfraction
and the liquid and vapor compositions are shown in the output file ( figure
3.4)
3.7UsingSpreadsheetsforThermophysicalProperties
Calculations
SpreadsheetsprogramssuchasMicrosoftEXCELhavebeenshowntobevery
usefulinsolvingengineeringproblemsandasasubstitutefortedioushand
calculations.Wehavedevelopedspreadsheetsforcalculatingthethermo
physicalpropertiesdiscussedinsections3.2to3.5.Thesespreadsheetsare
PetProp.xlsandLeeKeslerProp.xls.
26
ID NAME
Tc(K)
Pc(MPa)
2001 NBP_1
190.6000
4.6000
2002 NBP_2
338.2000
4.5600
2003 NBP_3
464.5000
3.3600
2004 NBP_4
619.4000
2.5600
2005 NBP_5
760.2000
1.5200
2006 NBP_6
925.6000
1.1400
THE DEFAULT Kij MATRIX IS
2001 2002 2003 2004 2005 2006
2002 .0000
2003 .0000 .0000
2004 .0000 .0000 .0000
2005 .0000 .0000 .0000 .0000
2006 .0000 .0000 .0000 .0000 .0000
vl
REQUIRED NUMBER OF ITERATIONS WAS:
COMPONENT IS NBP_1
ID NO. IS
COMPONENT IS NBP_2
ID NO. IS
COMPONENT IS NBP_3
ID NO. IS
COMPONENT IS NBP_4
ID NO. IS
COMPONENT IS NBP_5
ID NO. IS
COMPONENT IS NBP_6
ID NO. IS
T(K)= 500.00 P(MPa)= 3.000
ZL= .2080
ID
LIQUID X VAPOR Y Yi/Xi
2001
.0604 .6935
11.49
2002
.0313 .1446
4.617
2003
.0527 .0776
1.471
2004
.4659 .0830
.1781
2005
.2588 .0013
.4970E-02
2006
.1309 .0000
.1225E-04
7
2001
2002
2003
2004
2005
2006
ZV= .9544
Figure3.4OUTPUT.TXTfileforPRMIX.EXE
ThespreadsheetPetProp.xlscontainsthefollowingworksheets:
Distil_conv: Distillation conversion from D86 to TBP as shown in
section3.2.4
Prop_calc: Calculation of thermophysical properties given the mean
averageboilingpointandtheAPIgravity.
Pseudo_comp: Given the TBP distillation curve and the API gravity,
this worksheet splits the petroleum fraction into pseudocomponents.
The results for splitting the oil into 20, 10 and 5 pseudocomponents
are tabulated. The specific gravity of each pseudocomponent is
calculated assuming that the whole fraction has the same Watson K
factor (see section 3.3.2). The volume percent of each pseudo
component is converted to weight percent and to mole percent with
thecalculationofthemolecularweight.Thepropertiesofeachpseudo
component is then calculated from the average normal boiling point
andthespecificgravity.
RiaziAlSahhaf: this worksheet utilizes the equation of Riazi and Al
Sahhaf. From the mean average boiling point the molecular weight is
calculated.Fromthemolecularweight,otherpropertiesareobtainted.
27
28
Figure3.5Distil_convWorksheet
Conversion between ASTM and TBP distillation:
Method of Riazi and Duabert 1987
TBP= a(D86)b
Volume %
distilled
D86 T, C
D86 T, F
TBP, F
TBP, C
0
10
30
50
70
90
95
0.9167
0.5277
0.7429
0.892
0.8705
0.949
0.8008
1.0019
1.09
1.0425
1.0176
1.0226
1.011
1.0355
36.5
54
77
101.5
131
171
186.5
97.7
129.2
170.6
214.7
267.8
339.8
367.7
57.4
92.0
156.1
214.9
275.3
356.9
381.4
14.1
33.4
69.0
101.6
135.2
180.5
194.1
224.42
206.14
F or
F or
106.90
96.75
C
C
29
Constant
a
7.4012
4.9004
3.0305
0.8718
2.5282
3.0419
0.118
Constant
b
0.6024
0.7164
0.8008
1.0258
0.82
0.755
1.6606
D86 T, C
D86 T, F
Ti
Ti', F
TBP, F
TBP,C
36.5
54
77
101.5
131
171
186.5
97.7
129.2
170.6
214.7
267.8
339.8
367.7
31.5
41.4
44.1
59.14
70.57
62.86
0.00
65.67
76.81
29.68
22.4
81.6
152.1
215.0
280.7
357.5
387.2
-5.3
27.5
66.7
101.7
138.1
180.8
197.3
53.1
72
27.9
The TBP curve is extrapolated to 100% volume distilled using a 5th order polynomial fit.
Calculation
of average
boiling
points
VABP
MeABP
30
224.42
206.14
F or
F or
106.9
96.75
C
C
Figure3.6Prop_CalcWorksheet
34.00
0.8550
320.00
11.95
257.12
593.15
494.59
5.823
1.916
K
765.49
Critical Pressure,
Pc
R
1377.87
bar
15.26
Density Calculation at T =
Tr =
density at 60 F, g/cm3
Tr at 60
F
Zra
molar volume, cm3/gmole
density,g/cm3
Tbr
0.774867
0.7770
20
0.3830
0.8542
0.3772
0.2458
302.0074
0.8514
Refractive Index
Light Fractions MW=70-300
Huang Characterization parameter,
Refrective index
Density at 68 F, g/cm3
Refractivity
intercept
I=
n=
d=
0.284
1.481
0.8514
RI =
1.055
I=
n=
d=
0.308
1.528
0.8514
Density at 68 F, g/cm3
31
Constants for I
0.02266
a
0.02341
b
c
d
0.000391
2.468
-0.00057
0.000646
5.144
-0.00033
e
f
0.0572
-0.72
-0.407
-3.333
Refractivity intercept
RI =
1.102
VGR =
0.9591
53.83
15.03
31.14
100.00
45.01
0.8346
70.80
5.86
23.33
100.00
Flash Point
ASTM 10% temperature, F
Flash point, F
454
196.35
913.67
Pour Point
Pour point , F
31.57
32
3.8 QuestionsandExercises
1) AnaphthafractionhasthefollowingASTMD86distillationdata:
Vol%
Temperature,C
0.0
138.8
10.0
149.6
30.0
158.8
50.0
165.8
70.0
169.9
90.0
178.1
95.0
180.4
ObtaintheTBPcurveusingtheDaubertsmethod.Extrapolatethecurveto
100%volumedistilled.
2) Ifthespecificgravityofthisnaphthacutis0.801,Drawthevolume
percentversusspecificgravitycurve.
3) UsethespreadsheetprogramPetProp.xlstosplittheabovenaphtha
cutintopseudocomponents.Use10pseudocomponents.
4) AgasoilhasthefollowingTBPdistillationdata
Vol%
0
10
30
50
70
90
95
100
TBP,C
216
243
268
284
304
318
327
334
Andhasanaverageboilingpointof280Candanaveragedensityof
0.850g/cm3:
a) Splitthisgasoilfractionintofivepseudocomponents.CalculateTc,
PcandforeachpseudocomponentusingtheRiaziAlSahhaf
equation.
b) CalculateTc,Pcandforthewholefractionusingequations3.21.
c) Calculatetheenthalpyofthisgasoilfractionat400Cusingthe
LeeKeslercorrelationwithareferencestateofidealgasat273.15K.
33
5) Anaturalgasstreamhasthefollowingcomposition:
Component
Mol%
C1
80
5
C2
C3
4
3
nC4
iC4
2
nC5
3
iC5
2
C6
0.5
0.5
C7+
IftheaverageboilingpointandspecificgravityofC7+are174Cand0.79,
calculatethedewpointpressure.
References
1) American Petroleum Institute, Technical data bookPetroleum
Refining,1993
2) Duabert,HydrocarbonProcessing,p.75,1994.
3) PedersenK.S.,Aa.FredenslundandP.Rasmussen,PropertiesofOils
andNaturalGases,GulfPublishingCompany,1989,Chapter7.
4) Kesler, M.G. and B.I. Lee, Improve Prediction of Enthalpy of
FractionsHydrocarbonProcessing,55,1976,pp.153158.
5) Riazi, M.R. and T.A. AlSahhaf, Physical Properties of Heavy
Petroleum Fractions and Crude Oils, Fluid Phase Equilibria, 117,
1996,pp.217224.
6) Smith, J.M, Van Ness, and Abbott, Chemical Engineering
Thermodynamics,9thedition,McGrawHill,1999.
7) Elliot, J.R. and C.T. Lira, Introductory Chemical Engineering
Thermodynamics,PrenticeHall,1999.
34