IPS Confidential

Handling Assays in PRO/II

Mike Donahue
NA Technical Support
August19
th
,2009
2 IPS Confidential
Outline
Background
What they are
Why theyre used
Pseudo-components
Laboratory Methods
TBP
D86
D1160
D2887 et al
Pro/II Data Entry
Stream
Characterization
Cut-points
Assay Processing
Steps
Light Ends
Blending
Common Pitfalls
IPS Confidential 3
Background
Handling Assays in Pro/II
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Petroleum Assay Background
The chemical evaluation of crude oil feedstocks by petroleum testing
laboratories. The test consists of the recording the temperature and
corresponding volume or weight % recovered.
Whattheyare:
T
% Dist illed
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Petroleum Assay Background
API Project 6
Isolated over 16,000 distinct hydrocarbon compounds
from a single sample of Oklahoma crude.
C40 has 62,491,178,805,831 isomers
Petroleum assays were utilized to reduce the
dimensionality of the calculations.
Whyweusethem
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Crude Oil Assay Data
There is a large amount of crude assay data available for crude oils of the world
Some are proprietary / some are available in open literature
Typically the data contained in a crude assay includes:
Yields generated from the physical or simulated distillation
Specific gravity
Gas chromatographic components
Sulfur
Nitrogen
Viscosity
Cold flow (pour point, cloud point, freeze point)
Heavy Metals
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Petroleum Assay Background
Pseudo-components are developed to represent the unknown components in the stream
Petroleum assay is divided into predetermined cut-point ranges
Each pseudo-component corresponds to several unknown actual components
Doing this introduces a degree of uncertainty
DevelopingPetroleumPseudocomponents
Pseudo-component Properties (FCC Gasoline)
Cut-point range on TBP 150-175 F
Average NBP 164F
Average API 63.4
Average MW 84.4
Component Class NBP API MW Octane
Hexane paraffin 155.7 81.6 86.2 24.8
2,2 dimethylpentane paraffin 174.6 77.1 100.2 92.8
MCP naphtene 161.3 56.2 84.2 91.3
Hexene olefin 146.3 72.2 84.2 83.0
1-M-cyclopentene olefin 158.4 48.7 82.1 >100
4-M-cyclopentene olefin 167.4 48.8 82.1 >100
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Petroleum Assay Background
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LaboratoryMethods
Handling Assays in Pro/II
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Laboratory Methods - TBP
True Boiling Point (TBP)
Thebestrepresentationofthetruecompositionofthepetroleum

stream
Unfortunately,time(minimumof8hours)andexpenseusuallylimititsusetocrude

samples
Fractionatingstillwithreflux
Thereisnostandard(ASTM289215trays&5:1refluxratio)
Separatescomponentbycomponent(sharpcuts)
Upperlimitisapproximately650For900950FNBP
Typicallythepressureisreducedto40mmHg

950F
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TBP Equipment
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ASTM D86
TheD86isanonfractionatingtestrunatroom

temperatureandpressure
Condenseriscooledwithicewaterspecifiedtobe

between32and40F
Mostcommonlaboratorydistillation
Mostwidelyusedforfinishedproductspecifications
Reproducibilityisreportedtobe+/

6degrees
Careshouldbetakentoinsuredataiscorrectedfor

labpressure
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Distillations ASTM D1160
Designedforhighboilingpointsamples(heavyheating

oil,gasoils,residualoils)
Commonlyconductedat10mmHg
Upperlimitisapproximately1000F
Mostlabsapplypressurecorrectionsandreportat760

mmHg
InitialpointishigherthanTBP,from50%toendpoint

testisnearlyidenticaltoTBPdistillation
Thepressureconversionbackto1ATMisprescribedby

theASTMmethod
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ASTM D2887
G.C. simulated distillation approximates TBP distillation
There are four standard tests
Replacing TBP distillations (time and cost are much less)
Aromatic limitations aromatic compounds have lower retention times
than normal paraffins
ASTMD2887
ASTMD3710
ASTMD5307
ASTMD6352
ASTMD6417
ASTMD7096
ASTMD7169
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ASTM D2887
REFERENCE RUN 1 RUN 2
0.5% (IBP) 115 112 112
5% 151 148 147
10% 176 173 175
15% 201 197 198
20% 224 221 220
25% 243 241 240
30% 259 255 256
35% 275 271 272
40% 289 287 288
45% 302 298 299
50% 312 309 308
55% 321 318 318
60% 332 329 330
65% 343 339 340
70% 354 350 352
75% 365 362 363
80% 378 374 376
85% 391 388 387
90% 407 404 404
95% 428 426 425
99.5% 475 474 475
Highlyreproducible
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AssayDataEntry/Characterization/Cutpoints
Handling Assays in Pro/II
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Distillation Data Entry in Pro/II
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Distillation Data Entry in Pro/II
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Distillation Data Entry in Pro/II
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Characterization Options
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Characterization Options
PropertyGeneration
AllthecharacterizationmethodsexceptHeavyoil

apply

predominantlytoparaffinicfluidshavingAPIgravities

greaterthan20andWatsonKfactorsinthe12.5to

13.5range.
TheyareprogressivelylessaccurateastheAPIgravity

dropsto10orless,andastheWatsonKfactor

approaches9or10.
TheHEAVYextensionoftheSIMSCImethodexhibits

betterextrapolationqualitiesforheavier,more

naphthenicandaromaticmaterialstypicallypresentin

heavyoilsandbitumens.
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Characterization Options
PropertyGeneration
AllthecharacterizationmethodsexceptHeavyoil

apply

predominantlytoparaffinicfluidshavingAPIgravities

greaterthan20andWatsonKfactorsinthe12.5to

13.5range.
TheyareprogressivelylessaccurateastheAPIgravity

dropsto10orless,andastheWatsonKfactor

approaches9or10.
TheHEAVYextensionoftheSIMSCImethodexhibits

betterextrapolationqualitiesforheavier,more

naphthenicandaromaticmaterialstypicallypresentin

heavyoilsandbitumens.
AssayCurveFittingProcedures
Thecurvefittingproceduresareusedtoextrapolateand

interpolatethedistillationdatasuppliedforanassay.
CubicSpline

(defaultorSPLINEmethod)
Thismethodusuallyresultsinthebestpossiblefitfor

nearlyalllaboratorycurves.Curveswithstepfunctions

maycausefittingproblemsandshouldthisoccurthe

validityofthedatashouldbechecked.
QuadraticPolynomials
ThismethodisnotaselegantastheCubicSpline

method,

butdoesexhibitmorestabilityforcurveswithstep

functions.
ProbabilityDensityFunction(PDF)
PDFisaleastsquaresprobabilitydensityfunctionwhichis

fittoallpointsonthecurvethataresupplied.Thismethod

isrecommendedwhenerrorsaresuspectedinthe

distillationdata.
AlternateCubicSpline
Incertainsituations,whenpartitioninganassay,the

SPLINEoptionselectsanintegrationblockthatis

inappropriatelylarge,resultingininaccuratecutranges.
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Characterization Options
DistillationCurveInterconversions
API1994
DevelopedbyDaubert,T.E..Thismethodusesanapproach

similiar

tothatoftheAPI1963procedure,whichalways

producesamonotonicD86curve.
API1987
DevelopedbyRiazi

andDaubert.
Thismethodisreputedtobemoreaccuratethanolder

methodsbystatisticalcomparisons.Becarefulofnarrow

boilers anonmonotoniccurvemayresult.
API1963
ProceduredevelopedbyW.C.Edmister,et.al.
ThismethodwasusedexclusivelyintheSimSciProcess

programandalwaysproducesamonotonicD86curve.
EdmisterOkamoto
ThisisanearlierversionoftheAPI1963method.

ApplicationisidenticaltothatdescribedaboveforAPI

1963.
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Characterization Options
CurveFit
VER6
SelectsthetraditionalPRO/IImethod(defaultpriortover

7.0)
Generatesaquadraticusingthefirst3(forIP)orlast3(forEP)supplieddatapoints.It

usestheslopeofthiscurvetolinearlyextrapolatetotheappropriateendpoint(0%)or

100%).Thismayartificiallyintroduceaninflectionpointinthedatacurve.
VER8(Improved7.08.1)
Usesaquadraticspline

forlocatingtheendpoints.ThisfirstappearedinPRO/IIv7.0,and

becamethedefaultstartingwithv8.0.
CURRENT
SamemethodastheVER8option,butnowignoresallcomponentshavingzeroflow

rates.
Addingacomponenttothecomponentlistwithoutchangingcompositionofastream

couldchangetheassaycurvefitperformedusingVER8.ThisisbecausetheVER8curve

fittingalgorithmattemptstofitthemidpointofallcomponents,evencomponents

havingazerorate.
Startingwithversion8.2,PRO/IInolongersupportsadefaultmethodforCURVEFIT.
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Characterization Options
KinematicViscosityReconciliation(KVRECONCILE)
Selectsamethodforadjustingsuppliedkinematicviscositydata

toagreewithsupplied

averageKVISvalue.
Thisoptionappliesonlywhencalculatingkinematicviscosityusinganindexmethodfora

streamcontainingassaycomponents.
ItapplieswhenKVIScalculationsarerequested,butthesuppliedkinematicviscositydata

areincompleteanddonotincludevaluesabovethe95%distillationcut.
TAIL
Thedefaultoption(andtheonlyoptionavailableinPRO/IIpriortoversion8.1).
Itextrapolatesthekinematicviscositycurvetomatchthecalculatedaveragekinematic

viscositytothesuppliedaverageKVISvalue(requiredinputdataontheKVISstatement).
CURVE
FirstavailableinPRO/IIversion8.1.
InsteadofextrapolatingtheKVIScurve,itshiftstheentirecurveuntiltheaverage

calculatedvaluematchesthesuppliedaverageKVISvalue.
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Assay Cutpoints
IPS Confidential 27
AssayProcessing
StepstakeninPro/II
LightEnds
Blending
Handling Assays in Pro/II
28 IPS Confidential
Assay Processing Steps
Light Ends
in Stream
Light Ends
in Stream

Determine Average NBP,

SPGR and MW for
Pseudocomponents
Determine Average NBP,
SPGR and MW for
Pseudocomponents
Process Light Ends
Process Light Ends
Characterize Other
Thermophysical Properties
for Pseudocomponents
Characterize Other
Thermophysical Properties
for Pseudocomponents
Determine Moles, Mass and
Volume for Each Cut
Determine Moles, Mass and
Volume for Each Cut
Convert Data to Equivalent
TBP Curve @ 760mm Hg
Convert Data to Equivalent
TBP Curve @ 760mm Hg

Distribute Assay Curve

into Cuts
Distribute Assay Curve
into Cuts
Set of Petroleum
Components
Distillation Data
Distillation Data
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Light Ends
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Light Ends Matching
Volume % Distilled
T
e
m
p
e
r
a
t
u
r
e

F

i
C
4
n
C
4
i
C
5
n
C
5
N
B
P
1
2
0
N
B
P
1
3
7
N
B
P
1
6
3
N
B
P
1
8
8
N
B
P
2
1
2
N
B
P
2
3
7
0
N
B
P
2
6
2
N
B
P
2
8
7
TBP Data
Match Lightends
to TBP Curve
010203040

506070
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Assay Blending
Specific Gravity cut weight cut volume
blend i
i
i
i

i blend
mole cut weight cut Weight Molecular

i blend
Volume NBP NBP
A blend is a set of cutpoints (petrocomponents)
The properties of a given cut are averaged from every assay containing that cut:
The blend properties are used everywhere in the simulation for that component
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Assay Blending
Blending
NBP = 212
SPGR = 0.85
Sulfur wt% = 0.012
Rate = 30
NBP = 211
SPGR = 0.83
Sulfur wt% = 0.010
Rate = 60
NBP = 213
SPGR = 0.85
Sulfur wt% = 0.011
Rate = 10
205
215
TBP
% Distilled
NBP = 211.5
SPGR = 0.838
Sulfur wt% = 0.0107
Feed 1, Rate=150 Feed 2, Rate=400 Feed 3, Rate=100
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Assay Blending
Property Differentiation
Overhead
Light Oil
LSFO
Low Sulfur
Assay
HSFO
High Sulfur
Assay
Economic Analysis
Product A (X$/BBL) Assay 1
Assay 2 Product B (Y$/BBL)
Processing
34 IPS Confidential
Assay Blending
Multiple blends:
Use to preserve stream differences
(e.g. Virgin & Cracked stocks)
Any number of assays can be combined into a blend
Any number of blends can be defined
Default: Combine all streams that use the same cutpoint set
XBLEND (exclude from blending):
Use when you wish to characterize a stream using a certain blend but do not want the
properties of that stream to be included in the blending operation
IPS Confidential 35
CommonPitfalls
Handling Assays in Pro/II
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Common Pitfalls
Cut-Point ranges
Accuracy
TBP Percent Distilled
T
e
m
p
e
r
a
t
u
r
e
Light Product
Heavy Product
Overlapping
Components
Needed
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Common Pitfalls
Cut-Point ranges
Accuracy
100
150
200
250
300
350
400
450
500
0 10 20 30 40 50 60 70 80 90 100
Percent Di stil led
T
e
m
p
e
r
a
t
u
r
e

(
F
)
NBP-288
NBP-311
NBP-262
Only two petrocomponents
in overlap region
Only 2 pseudo-components
in overlap region
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100
150
200
250
300
350
400
450
500
0 10 20 30 40 50 60 70 80 90 100
Percent Distilled
T
e
m
p
e
r
a
t
u
r
e

(
F
)
Many petrocomponents
in overlap region
Many pseudocomponents
in overlap region
Common Pitfalls
Accuracy
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Pseudo Components
Do you have enough?
Crude Distillation Example
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Common Pitfalls
Production
Wells on line
The general rule of thumb is to be wary of assays more than 2 years old for simulation work
Assays change over time
41
Feed Characterization
When product data is available
Supply the product and back blend together to produce the feed for:
Crude and Vacuum Units
FCC Main Fractionators
Coker Fractionators
Be careful to enter the data as a mid-point /cumulative basis
42
-100
100
300
500
700
900
1100
1300
1500
1700
0 10 20 30 40 50 60 70 80 90 100
Percent Distilled
T
e
m
p
e
r
a
t
u
r
e

(

F
)
0
10
20
30
40
50
60
70
80
90
100
A
P
I

G
r
a
v
i
t
y
L
i
g
h
t

E
n
d
s
L
i
g
h
t

N
a
p
h
t
h
a
H
e
a
v
y

N
a
p
h
t
h
a
K
e
r
o
s
e
n
e
D
i
e
s
e
l
L
i
g
h
t

G
a
s

O
i
l
H
e
a
v
y

G
a
s

O
i
l
B
o
t
t
o
m
s
10%
7.2%
15.3%
9.3% 13.5%
24%
8%
12.7%
Enter Gravity at Midpoint
of Product Cut
Feed Characterization
43 IPS Confidential
Average Gravity assumes a constant (or nearly constant) UOP K.
The slope tends to be too flat.
Average Gravity
First, Integrate
to Get NBPs . . . .
Volume % Di stilled
T
e
m
p
e
r
a
t
u
r
e
A
P
I

G
r
a
v
i
t
y
L
i
g
h
t

E
n
d
s
1
s
t

C
u
t
2
n
d

C
u
t
3
r
d

C
u
t
. . . Then Use Watson K
Factor to Compute Gravity
Percent Di stilled
"K" = NBP
SPGR
3
"K" = NBP
SPGR
3
Common Pitfalls
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Molecular weight is the most difficult property to predict
Molecular weight is the most difficult property to predict accurately, especially for cracked stocks
such as FCC and coker cycle oils, FCC slurry, etc. Therefore, this property should always be
supplied when possible for the most accurate characterization of a petroleum component.
Correlations biased towards paraffins
Common Pitfalls
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API 1987 Interconversion by Riazi and Daubert (default for Pro/II 7.0 - 8.1)
TBP curves with narrow boiling range or flat sections in curve can result in negative slopes
when converted back to D86. PRO/II will generate Non-monotonic curve message.
API 1994 is more widely recognized
Recent versions of the API data book no longer include this correction
Pro/II still provides this functionality
Better results from adjusting the cracking portion of the curve with probability
paper
ASTM D86 Distillations
Common Pitfalls
Interconversion
CrackingCorrection
46
Assay Conversion - Tips
20 50 80 99.9
700
800
900
1500
F
Percent Distilled
Crude Oil Data
FCC Slurry E.P. = 1200F
Crude Oil E.P. = 1600F
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Applicabletofractionswithafinalboilingpointof1000Forless.
API1987Interconversion

usesatwostepprocessandisnotrecommended
API1994correctedthistoasingleconversionwherethe50%pointsareequal
API1994hadstrictlimitationsontheboilingpointgapsandis

notrecommendedforbroadboiling

mixturessuchascrudeunits.Forexample,thelimitforD2887(100)

D2887(95)is30F.Becauseof

theexponentialformoftheconversion,broaderboilinghighendsresultsinwildTBP(100)points.
PerASTM:Boilingrangedistributionsobtainedbythistestmethodareessentiallyequivalentto

thoseobtainedbytrueboilingpoint(TBP)distillation.
ForbroadboilingmixturesitsbesttoentertheD2887asaTBPwtbasis
ModifytheTBPtoaccountforthearomatics
Aromaticboilingpointcorrectionestimatedthroughcomparisonwithaphysicaldistillation
Probabilitypaper
Usediscretion thereisnosinglesolution
D2887 (SimDist)
Common Pitfalls
Suggestions
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Assay Blending
Pro/IIsdefaultistoblendallassaysintoonecutpoint

set
UseXBlend

tolimitthisdataaveraging
Usemultiplecutpoint

setstopreserveassaydata
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SimSci Technical Support
Manuals:
C:\SimSci\ProII83\Manuals
Help while running program
Searchable
Content sensitive
Technical Support
Phone: (800) SIMSCI-1 (746-7241)
E-mail: [email protected]
Training
Public
Private
Seminars/Webinars
IPS Confidential 50
Thank You!
Michael Donahue
Lake Forest, CA
W (909) 593-1999
C (949) 632-5976
[email protected]