Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
JohnJechura jjechura@mines.edu
Updated:August13,2015
Gases
Polymerization
Sulfur
Plant
Sat Gas
Plant
Gas
Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer
Fuel Gas
LPG
Alkylation
Polymerization
Naphtha
Isomerization
Light Naphtha
Alkylate
Isomerate
Aviation
Gasoline
Automotive
Gasoline
Reformate
Naphtha
Hydrotreating
Heavy
Naphtha
Sulfur
LPG
Naphtha
Reforming
Solvents
Naphtha
Atmospheric
Distillation
Crude
Oil
Jet Fuels
Kerosene
Desalter
Distillate
Hydrocracking
AGO
LVGO
Vacuum
Distillation
Kerosene
Gas Oil
Hydrotreating
Fluidized
Catalytic
Cracking
Cat
Naphtha
Solvents
Distillate
Hydrotreating
Cat
Distillates
Treating &
Blending
Heating Oils
Diesel
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting
Visbreaking
Vacuum
Residuum
Coker
Naphtha
Heavy
Coker
Gas
Oil
SDA
Bottoms
Asphalts
Naphtha
Distillates
Fuel Oil
Bottoms
Lube Oil
Lubricant
Greases
Solvent
Dewaxing
Waxes
Waxes
Coking
Light Coker
Gas Oil
Coke
JohnJechura jjechura@mines.edu
Updated:August13,2015
Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions
Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number
JohnJechura jjechura@mines.edu
Updated:August13,2015
CrudeOilasRefineryFeedstock
CrudeOil
Complexmixtureofhydrocarbons&heterocompounds
Dissolvedgasestononvolatiles(1000F+boilingmaterial)
C1 toC90+
Compositionsurprisinglyuniform
Element
Wt%
Carbon
84 87
Hydrogen
11 14
Sulfur
0 5
Nitrogen
0 0.2
Otherelements
0 0.1
JohnJechura jjechura@mines.edu
Updated:August13,2015
PrimaryHydrocarbonMolecularTypes
Paraffins
Carbonatomsinterconnectedbysinglebond
Otherbondssaturatedwithhydrogen
nHexane
iHexane
Naphthenes
Ringedparaffins (cycloparaffins)
Allotherbondssaturatedwithhydrogen
Methylcyclopentane
Cyclohexane
Aromatics
Decalin
Sixcarbonring(multiplebonding)
Bondsinring(s)areunsaturated
Olefins
Usuallynotincrudeoil
Benzene
Naphthalene
Formedduringprocessing
Atleasttwocarbonatomsinterconnectedby
(unsaturated)doublebond
DrawingsfromNISTChemistryWebBook
http://webbook.nist.gov/chemistry/
JohnJechura jjechura@mines.edu
Updated:August13,2015
1Hexene
cis3Hexene
trans3Hexene
ExampleHeterocompounds
Composition&AnalysisofHeavyPetroleumFractions
K.H.Altgelt &M.M.Boduszynski
MarcelDekker,Inc.,1994,pg.16
JohnJechura jjechura@mines.edu
Updated:August13,2015
ModelingandSimulationofCatalyticReactorsforPetroleumRefining.
byJorgeAncheyta,JohnWiley&Sons,2011
DistributionofCompounds
Carbon
Paraffin
Boiling Point
No.
Isomers
36
97
126
259
18
10
174
345
75
12
216
421
355
4347
15
271
520
20
344
651 3.66E+05
25
402
756 3.67E+07
30
449
840 4.11E+09
35
489
912 4.93E+11
40
522
972 6.24E+13
45
550
1022 8.22E+15
60
615
1139 2.21E+22
80
672
1242 1.06E+31
100
708
1306 5.92E+39
Examples
Gasoline
Vacuum residue
Nondistillable residue
Composition&AnalysisofHeavyPetroleumFractions
K.H.Altgelt &M.M.Boduszynski
MarcelDekker,Inc.,1994,pp.23&45
JohnJechura jjechura@mines.edu
Updated:August13,2015
CrudeOilAssay
Indicatesdistributionquantity &quality ofcrudeoilfeedstock
Definitionsbaseduponboilingpointtemperatureranges
Representsexpected productsfromcrude&vacuumdistillation
Completenessofdatadependsuponsource
Publicreportvs.inhouseanalyticallaboratory
Qualitymeasures
Specific/APIgravity
Sulfurcontent
Octanenumber
Cetanenumber
Viscosity
Carbonresidue
JohnJechura jjechura@mines.edu
Updated:August13,2015
100
90
80
97.8F
Temperaturesdefinethe
Propane
boundariesbetween fractions
70
Butanes
Pentanes
350F
400F
60
Barrels
180F
Light Naphtha
50
40
30
Heavy Naphtha
Mixedpropertyvaluesforthe
Distillate
650F
entirefraction
AGO
20
LVGO
850F
HVGO
10
1050F
Vacuum Resid
0
Total
JohnJechura jjechura@mines.edu
Updated:August13,2015
Continuum
Fractions
12
CrudeOilsAreNotCreatedEqual
JohnJechura jjechura@mines.edu
Updated:August13,2015
13
CrudeOilProperties
Distillationanalysis/Boilingpointrange
Amountcollectedfrombatchdistillationattheindicatedtemperature
Standardizedtests ASTMD86,D1160,
MostusefulisTBP(TrueBoilingPoint)
8.32828lb/gal
PureWater:
999.017kg/m=8.33720lb/gal
APIgravity.Higherdensity lowerAPI
API
141.5
141.5
131.5 o
o
131.5 API
Watsoncharacterizationfactor.12 13(paraffinic)to10(aromatic)
T
K b
W
o
3
JohnJechura jjechura@mines.edu
Updated:August13,2015
T inunitsofR
b
14
CrudeOilProperties
Sulfur,nitrogen,&metalscontent
Sulfur
Propertiesappropriateforcertainboiling
pointranges
Sourvs.sweet ~0.5wt%cutoff
Octanenumber
Restrictionsonsulfurinfinalproducts
Cetanenumber
Nitrogen
Canpoisoncatalysts
Viscosities
Carbonresidue
Usuallytolerateupto0.25wt%
Nickel,vanadium,copper
Canpoisoncatalysts
Tendtobeinthelargest
molecules/highestboilingfractions
JohnJechura jjechura@mines.edu
Updated:August13,2015
15
DistillationAnalysisTypes
TrueBoilingPoint(TBP) ASTMD2892
14to18theoreticalstages
Nearinfinitereflux(5:1refluxratiomin)
Nohotterthan650Ftominimizecracking
Maxvaportemperature410 F
Pressurelevels
760mmHg(1atm)
100mmHg
2mmHg(min)
ASTMD289213,StandardTestMethodforDistillationofCrudePetroleum
(15TheoreticalPlateColumn)
JohnJechura jjechura@mines.edu
Updated:August13,2015
16
DistillationAnalysisTypes
ASTMD86
Lowresolution nopacking,
refluxfromheatlosses
1atm;nohotterthan650F
minimizecracking
CorrelationstocorrecttoTBPbasis
600
500
TBPTemperature[F]
400
300
200
100
0
0
100
200
300
D86Temperature[F]
JohnJechura jjechura@mines.edu
Updated:August13,2015
400
500
http://www.koehlerinstrument.com/products/K45601.html
17
DistillationAnalysisTypes
ASTMD1160
Usedonresids (650F+)
Relativelylowresolution
Vacuumconditions 10
to40mmHg;nohotter
than1000FAEBP
Correlationstocorrectto
atmosphericpressure&
TBPbasis
http://www.lazarsci.com/d1160.htm
JohnJechura jjechura@mines.edu
Updated:August13,2015
18
DistillationAnalysisTypes
ShortPathDistillation
Singlestageflash
Extremelylowpressures
0.1mmHgorless
Characterizedeepcutresids
http://www.chemtechservicesinc.com/shortpathdistillation.html
JohnJechura jjechura@mines.edu
Updated:August13,2015
19
DistillationAnalysisTypes
SimulatedDistillation ASTM2887
Relativelylowresolutiongaschromatography
Severalthousandtheoreticalstages
EssentiallyTBPtemperatures wt%basis
Temperaturesinferredfromelutiontimes
Calibratedwithnparaffinmixture
JohnJechura jjechura@mines.edu
Updated:August13,2015
20
CrudeOilAssay Hibernia(fromChevronsite)
Whole
Light
Medium
Heavy
Crude
Naphtha
Naphtha
Naphtha
Kero
Atm
Light
Heavy
Vacuum
Atm
Gas Oil
VGO
VGO
Resid
Resid
Start
10
80
150
200
260
340
450
570
340
End
80
150
200
260
340
450
570
End
End
Start
55
175
300
400
500
650
850
1050
650
End
175
300
400
500
650
850
1050
End
End
2.3
8.0
20.8
30.0
39.5
54.0
73.2
85.8
54.0
8.0
20.8
30.0
39.5
54.0
73.2
85.8
100.0
100.0
4.4
11.5
8.5
9.1
14.6
20.0
13.7
16.7
50.4
5.6
12.9
9.2
9.5
14.6
19.1
12.6
14.2
46.0
Gravity, API
33.5
81.9
54.8
47.3
40.2
33.9
27.3
20.2
10.0
19.6
Specific Gravity
0.86
0.66
0.76
0.79
0.82
0.86
0.89
0.93
1.00
0.94
Sulfur, wt%
0.53
0.00
0.00
0.01
0.05
0.27
0.57
0.91
1.46
0.96
1
5860
2729
1384
Hydrogen, wt%
56
579
2050
16.2
13.9
14.2
13.7
13.2
12.9
12.5
6.73
0.48
0.67
1.04
1.72
4.10
19.04
3.05E+02
4.E+05
2.89E+02
5.17
0.45
0.61
0.92
1.48
3.33
13.42
1.64E+02
1.E+05
1.62E+02
1.93
0.34
0.43
0.58
0.83
1.49
3.92
1.97E+01
1.E+03
2.16E+01
1.21
0.30
0.37
0.47
0.64
1.01
2.20
7.95E+00
2.E+02
9.00E+00
Freeze Point, C
51
-122
-96
-68
-39
-2
30
53
78
63
Freeze Point, F
125
-188
-141
-90
-39
28
87
128
172
146
Pour Point, C
-128
-101
-71
-42
-7
26
48
35
36
Pour Point, F
44
-198
-151
-96
-43
20
79
119
95
96
35
32
27
22
17
11
Aniline Point, C
77
71
53
55
61
70
84
95
106
94
Aniline Point, F
171
160
127
131
142
159
183
204
222
201
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
40
47
56
57
131
70
62
57
54
50
41
22
39
12.0
12.6
11.7
11.8
11.8
11.8
12.0
12.0
12.1
12.0
71.8
64.1
37.3
70.3
62.5
Paraffins, vol%
84.9
48.8
45.4
38.6
Naphthenes, vol%
15.1
32.4
39.5
40.9
Aromatics, vol%
0.0
18.8
14.9
20.0
Simpleanalysis
Thiophenes, vol%
Molecular Weight
244
102
115
144
175
226
319
463
848
425
5.88
4.84
5.37
5.55
5.72
5.87
6.04
6.23
6.50
6.24
10894
11589
11212
11121
11009
10896
10765
10595
10310
10582
45.6
48.5
46.9
46.5
46.1
45.6
45.0
44.3
43.1
44.3
0.1
0.6
0.2
2.6
14.8
5.2
4.6
2.3
13.2
Vanadium, ppm
Nickel, ppm
Iron, ppm
http://crudemarketing.chevron.com/crude/north_american/hibernia.aspx
JohnJechura jjechura@mines.edu
Updated:August13,2015
21
CrudeOilAssay Hibernia(fromExxonMobilsite)
HIBER11Z
Cutvolume,%
APIGravity,
SpecificGravity(60/60F),
Carbon,wt%
Hydrogen,wt%
Pourpoint,F
Neutralizationnumber(TAN),MG/GM
Sulfur,wt%
Viscosityat20C/68F,cSt
Viscosityat40C/104F,cSt
Viscosityat50C/122F,cSt
Mercaptansulfur,ppm
Nitrogen,ppm
CCR,wt%
NHeptaneInsolubles(C7Asphaltenes),wt%
Nickel,ppm
Vanadium,ppm
Calcium,ppm
ReidVaporPressure(RVP)WholeCrude,psi
HeatofCombustion(Gross),BTU/lb
HeatofCombustion(Net),BTU/lb
HydrogenSulfide(dissolved),ppm
Saltcontent,ptb
Paraffins,vol%
Naphthenes,vol%
Aromatics(FIA),vol%
Distillationtype,D
ASTMIBP,F
5vol%,F
10vol%,F
20vol%,F
30vol%,F
40vol%,F
50vol%,F
60vol%,F
70vol%,F
80vol%,F
90vol%,F
95vol%,F
ASTMEP,F
Freezepoint,F
Smokepoint,mm
Naphthalenes(D1840),vol%
Viscosityat100C/212F,cSt
Viscosityat150C/302F,cSt
CetaneIndex1990(D4737),
Cloudpoint,F
Anilinept,F
Whole
crude
200to
1499
100
33.9
0.8555
37
0.095
0.54
12.49
6.21
4.7
1
1350
2.45
1.3
0.7
0.5
3.4
19429
18222
0
0.1
Butane
and
Lighter
200to60
1.51
121.42
0.5595
82.43
17.57
Lt.
Naphtha
C5165F
60to165
5.68
81.02
0.6658
83.95
16.05
0.35
0.3
0.28
0.41
0.35
0.32
Hvy
Naphtha
165
330F165
to330
14.83
54.91
0.7591
85.88
14.12
0.0011
0.75
0.62
0.56
1.5
0
Kerosene Diesel
330
480
480F330 650F480
to480
to650
14.76
17.03
43.1
34.04
0.8104
0.8548
86.21
86.51
13.77
13.23
62
17
0.054
0.0213
0.2431
1.79
6.88
1.31
3.96
1.15
3.16
2.1
0.2
88.5
0
19288
18852
18626
18567
100
0
84.28
14.13
1160
17.9
135.3
201.5
306.9
403.1
497.7
597
705
806.7
925.9
1082.4
1213.2
1401.5
86
127.8
94.6
52.1
10.5
29.8
35.9
35.8
38.8
43.7
47.3
46.1
46.1
47.2
86
95.9
101.4
106
110.9
114.6
117.1
121.9
129
134.1
139.3
141.8
144.4
147
51.64
31.88
16.48
86
208.1
213.7
216.6
223.6
231.7
240.8
249.1
258.8
269
279.9
291.1
297.4
302.5
1.81
1.03
33.1
0.21
0.17
152.4
0.23
0.18
44.1
0.38
0.28
29.4
47.08
32.71
16.9
86
363.8
368.2
370.4
375.5
381.8
389.1
396.4
405.1
414
423.8
434
439.8
444.5
48.2
21.3
4.4
0.69
0.47
43.8
54
138.2
Vacuum
GasOil
650
1000F
650to
1000
28.89
24.71
0.9058
86.39
12.81
103
0.116
0.6814
120.83
40.48
26.22
1196.1
0.26
Vacuum
Residue
1000F+
1000to
1499
17.29
12.65
0.9816
103
0.212
1.4428
472934.04
34316.32
11920.94
4868
11.9
0.3
6.5
3.5
0
0
0
0
41.83
34.07
26.36
37.12
86
506
510.8
512.9
518.9
526.3
535.3
543.8
553.8
564.5
576
587.8
594.4
605
29
1160
690.6
695.2
706.3
728.3
752.6
778.5
806.4
835.7
865.7
897.7
929
947.8
969.7
1160
1038.8
1043.4
1055.3
1081.3
1111.3
1145.4
1183.7
1228.7
1277.3
1330.3
1385.2
1419.1
1458
1.44
0.88
54.1
24
161.3
5.97
2.58
56.9
316.71
42.23
45.5
Simpleanalysis
&comparison
191.7
http://www.exxonmobil.com/crudeoil/about_crudes_hibernia.aspx
JohnJechura jjechura@mines.edu
Updated:August13,2015
22
Bakken
41
0.2
WTI
39
0.32
3.5
36.3
14.7
14.3
26.1
5.2
3.4
32.1
13.8
14.1
27.1
9.4
BottomsQualityVacuumResid1050+F
Yield,Vol.%
5.2
APIGravity
14
Sulfur,Wt.%
0.75
Vanadium,ppm
2
Nickel,ppm
7
Concarbon,Wt.%
11.3
9.4
11.4
1.09
87
41
18.2
http://www.turnermason.com/Publications/petroleum
publications_assets/BakkenCrude.pdf
JohnJechura jjechura@mines.edu
Updated:August13,2015
Hill,D.,et.al.
NorthDakotaRefiningCapacityStudy,FinalTechnicalReport
DOEAwardNo.DEFE0000516,January5,2011
23
CrudeOilAssay EagleFordvs.otherlightcrudes
METHODOLOGYANDSPECIFICATIONSGUIDE
TheEagleFordMarker:Rationaleandmethodology
Platts,McGrawHillFinancial
October2012
https://www.platts.com/IM.Platts.Content/MethodologyReferences/
MethodologySpecs/eaglefordmarker.pdf
JohnJechura jjechura@mines.edu
Updated:August13,2015
24
PetroleumProducts
Therearespecificationsforover
2,000individualrefineryproducts
Tookafullcenturytodevelopmarkets
forallfractionsofcrudeoil
Intermediatefeedstocks canbe
routedtovariousunitstoproduce
differentblendstocks
Dependsuponthelocaleconomics&
contractuallimitations
Ref:Unknownorigin.PossiblySoconyVacuumOilCompany,Inc.(1943)
JohnJechura jjechura@mines.edu
Updated:August13,2015
26
PetroleumProducts
RefineryFuelGas(StillGas)
Wax
LiquefiedPetroleumGas(LPG)
Asphalt&RoadOil
Ethane&EthaneRichStreams
PetroleumCoke
Propanes
Petrochemicals
Butanes
Sulfur
Gasoline
Naphtha
MiddleDistillates
Kerosene
JetFuel
Diesel,HomeHeating,&FuelOil
GasOil&TownGas
Lubricants
JohnJechura jjechura@mines.edu
Updated:August13,2015
27
SourcesofProductSpecifications
State&Federalregulatoryagencies
Industryassociations
Environmentallaws
AmericanPetroleumInstitute
Reflectneedtoreducepollutionin
manufacturing&useoffuels
GasProcessorsAssociation
ASTM(AmericanSocietyforTestingand
Materials)Specifications&associatedtest
procedures
Specificationsdraftedconsideringpositions
ofindustry®ulatoryagencies
JohnJechura jjechura@mines.edu
Updated:August13,2015
AsphaltInstitute
Betweencompaniesbasedontypical
specs
Negotiated
Deviationshavepredeterminedprice
adjustments
28
WhatMakesGasolineGasoline?
WhatMakesDieselDiesel?
Gasoline
Diesel
Mustbeagoodfuelinasparkignitedinternal
Mustbeagoodfuelinanonsparkignitedfuel
combustionengine
Properatomization&vaporizationwhenmixed
withcombustionair
Boilingpointsofchemicalspecies
injectedinternalcombustionengine
Properatomizationwheninjectedinto
compressedair
Boilingpointrangeofmixture
Boilingpointrangeofmixture
Abilitytocompress¬ignitepriortospark
ignition
Measuredasoctanenumber
Minimalcombustionbyproducts wantcomplete
combustion
Minimizeenvironmentalunfriendliness
Volatilityinstoragetanks
RVP ReidVaporPressure
Individualchemicalspecies
Sulfurcontent
Abilitytoignitewheninjectedintocompressed
air
Measuredascetane number
Minimalcombustionbyproducts wantcomplete
combustion
Minimizeenvironmentalunfriendliness
Volatilityinstoragetanks
Flashpoint
Individualchemicalspecies
Sulfurcontent
Benzene
JohnJechura jjechura@mines.edu
Updated:August13,2015
29
CharacteristicsofPetroleumProducts
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
JohnJechura jjechura@mines.edu
Updated:August13,2015
30
FuelGasSpecifications
Parameter
TemperatureRange
Pressure
GrossHeatingValue
HydrocarbonDewPoint1
Specification
40Fto120F
500to1,000psig
950 1050BTU/scf
10F 20F
Water
4or7lbs/millionscf
TotalSulfur
5to20grains/100scf
HydrogenSulfideH2S
Mercaptans
TotalNitrogen&CO2
CO2 (alsoTotalN2 +CO2)
Oxygen
4to16ppmv
1to5grains/100scf
4mol%
2to3mol%
0.1to0.4mole%
1Atpipelinepressure
JohnJechura jjechura@mines.edu
Updated:August13,2015
31
LiquefiedPetroleumGas(LPG)
Commercial
Propane
CommercialButane
ASTMTest
C3&C3=
C4&C4=
D126702
VaporPressure@100F
208
70
D126702
95vol%@maxF
37F
+36F
D183764
C4+max
2.5%
Characteristic
C5+max
D216377
2.0%
D216377
VaporpressurespecisactuallyanapproximateguidelinefordefiningthelightendscontentoftheLPGmixture.
JohnJechura jjechura@mines.edu
Updated:August13,2015
32
NaturalGasolineSpecifications
Characteristic
GPASpecifications
ASTMTest
ReidVaporPressure
10to34psig
D323
Evaporationat140F
25to85%
D216
Evaporationat275F
>90%
D216
EndPoint
JohnJechura jjechura@mines.edu
Updated:August13,2015
D216
33
AviationGasolineSpecifications
JohnJechura jjechura@mines.edu
Updated:August13,2015
34
MotorGasolineSpecifications
JohnJechura jjechura@mines.edu
Updated:August13,2015
35
MotorGasolineVolatilityClasses(ASTMD481413)
JohnJechura jjechura@mines.edu
Updated:August13,2015
36
OtherGasolineConsiderations
Reformulatedgasoline(RFG)blendedtoburncleanerbyreducingsmogformingandtoxicpollutants
CleanAirActrequiresRFGusedincitieswiththeworstsmogpollution
CleanAirActrequiredRFGtocontain2wt%oxygen
MTBEðanolwerethetwomostcommonlyusedsubstances
MTBElegislatedoutofusebecauseofhealthconcerns
Oxygenatecontentregulationsuperceeded bytheRenewableFuelStandard
Benzenecontent
Conventionalgasolinecouldhave1.0vol%benzene(max)pre2011
NewregulationsJan1,2011reducedbenzeneinall USgasolineto0.62vol%
HadbeenproposedbyEPAunderMobileSourcesAirToxics(MSAT)Phase2
Creditsystemforrefinersthatcouldnotmeetthe0.62%limit
Sulfurcontent
EPAcallingforultralowsulfurgasolineby2017 fromaverageof30ppm to10ppm
JohnJechura jjechura@mines.edu
Updated:August13,2015
37
WhatareOctaneNumbers?
References:
nheptane 0
isooctane 100(2,2,4trimethylpentane)
Tendencyforautoignitionuponcompression
Gasoline bad
Tendencyofgasolinetocausepinginginengine
Higheroctaneneededforhigher
compressionratios
Differenttypes(typicallyRON>MON)
RON ResearchOctaneNumber
Partthrottleknockproblems
MON MotorOctaneNumber
Moresevere highspeed&
highloadconditions
(R+M)/2 RoadOctaneNumber
AverageofMON&RON
Reportedatthepump
JohnJechura jjechura@mines.edu
Updated:August13,2015
38
WhatisReidVaporPressure(RVP)?
Specifictesttomeasurevolatilityat100F(37.8C)
Pressureat100Fwhenliquidisincontactwithairatavolumeratioof1:4
Relatedtothetruevaporpressure
Similartovaporformationinanautomobilesgasolinetank
Usuallyjustreportedaspsi
Actuallygaugepressuremeasured subtractoffthecontributionoftheatmosphericpressure
Relativelyeasytomeasure
Directpressuremeasurementinsteadofobservationofbubbleformation
ProcedurescontrolledbyASTMstandards(ASTMD323)
A:Lowvolatility(RVPlessthan26psi/180kPa)
B:Lowvolatility horizontalbath
C:Highvolatility(RVPgreaterthan26psi/180kPa)
D:Aviationgasoline(RVPapproximately7psi/50kPa)
JohnJechura jjechura@mines.edu
Updated:August13,2015
39
WhatarealternateRVPliketests?
ASTMD5191 StandardTestMethodforVaporPressureofPetroleumProducts(Mini
Method)
Expandliquidfrom32oFto5timesitsvolume(4:1volumeratio)at100oFwithoutadditionofair
ReferredtoastheDVPE(DryVaporPressureEquivalent)&calculatedfrommeasuredpressurevalue:
DVPE[psi]=0.965(MeasuredVaporPressure[psi]) 0.548[psi]
ASTMD6378 StandardTestMethodforDeterminationofVaporPressure(VPX)of
PetroleumProducts,Hydrocarbons,andHydrocarbonOxygenateMixtures(Triple
ExpansionMethod))
Expandliquidtothreedifferentvolumeratios
Nochillingofinitialsample sampleofknownvolumeintroducedtochamberat20oC(76oF)or
higher
Threeexpansionsatacontrolledtemperature 100oFequivalenttoASTMD5190
Allowsfortheremovalofthepartialpressureeffectsfromdissolvedair
RVPE(ReidVaporPressureEquivalent)calculatedfromcorrelationtomeasuredpressureminus
dissolvedaireffects
JohnJechura jjechura@mines.edu
Updated:August13,2015
40
MiddleDistillates
Generalclassifications
Properties
Kerosene
Flashpoint
Jetfuel
Cloudpoint/Pourpoint
Distillatefueloil
Anilinepoint
Diesel
Cetane number
Heatingoil
Viscosity
Water&sediment
JohnJechura jjechura@mines.edu
Updated:August13,2015
41
DieselCetaneNumber
Onekeytodieselquality
Measurestheabilityforautoignition
Essentiallytheoppositeofoctanenumber
Maybemeasuredbutfrequentlyapproximated
ASTMD976 StandardTestMethodsforCalculatedCetaneIndexofDistillateFuels
ASTMD4737 StandardTestMethodforCalculatedCetaneIndexbyFourVariableEquation
Trends
Cetanenumberhaddeclinedsincethemiddle1970s
Highdemand
Heaviercrudeswithnarrowdieselcuts
Blendingoflowercetane fractions
Trendstartingtoreverse
Morestringentemissionsrequirementsnecessitatehighercetane numbers
JohnJechura jjechura@mines.edu
Updated:August13,2015
42
WhatisFlashPoint?
Thelowesttemperaturecorrectedtoapressureof101.3kPa(760mmHg)at
whichapplicationofanignitionsourcecausesthevaporsofaspecimenofthe
sampletoigniteunderspecifiedconditions
ProcedurestrictlycontrolledbyASTMstandards
D56TagClosedTester
D92ClevelandOpenCup
D93PenskyMartensClosedCupTester
D1310 TagOpenCupApparatus4
D3143 CutbackAsphaltwithTagOpenCupApparatus
D3278ClosedCupApparatus
D3828 SmallScaleClosedTester
D3941 EquilibriumMethodwithClosedCupApparatus
JohnJechura jjechura@mines.edu
Updated:August13,2015
43
OSHAFlammableLiquidDefinitions
GHS
(GloballyHarmonizedSystem)
Category
Flammable1
Flammable2
Flammable3
Flammable4
None
FlammableandCombustibleLiquidsStandard
(29CFR1910.106)
FlashPoint
C(F)
<23(73.4)
<23(73.4)
BoilingPoint
Class
C(F)
35(95)
FlammableClassIA
>35(95)
FlammableClassIB
FlammableClassIC
23(73.4)&<60(140)
CombustileClassII
>60(140)&93(199.4)
CombustileClassIIIA
CombustileClassIIIB
FlashPoint
BoilingPoint
C(F)
C(F)
<22.8(73)
<37.8(100)
<22.8(73)
37.8(100)
22.8(73)&37.8(100)
37.8(100)&<60(140)
60(140)&<93.3(200)
93.3(200)
Source:OHSARIN1218AC20
https://www.federalregister.gov/articles/2012/03/26/20124826/hazardcommunication#t8
JohnJechura jjechura@mines.edu
Updated:August13,2015
44
WhatareCloud&PourPoints?
Indicatethetendencytoformsolidsatlowtemperatures thehigherthetemperaturethe
higherthecontentofsolidformingcompounds(usuallywaxes)
CloudPoint
Temperatureatwhichsolids
starttoprecipitate&givea
cloudyappearance
Tendencytoplugfiltersat
coldoperatingtemperatures
PourPoint
Temperatureatwhichtheoil
becomesagel&cannotflow
MeltingPointsofselectedlongchainnormal&iso paraffins
typicallyfoundinmiddledistillates
Solidificationofdieselfuelinafuelfilteringdeviceaftersuddentemperaturedrop
Considercatalyticdewaxing asatooltoimprovedieselcoldflowproperties,
Rakoczy &Morse,HydrocarbonProcessing,July2013
JohnJechura jjechura@mines.edu
Updated:August13,2015
45
AdditionalSpecifications
Sulfur
Controlofsulfuroxidesuponcombustion
Threelevels,reductionforthetraditionalfivecategories
AnilinePoint
Minimumtemperatureatwhichequalvolumesofaniline(C6H5NH2)andtheoilare
miscible
Thelowertheanilinepointthegreaterthearomaticcontent
Viscosity
Fluidityduringstorageatlowertemperatures
Sediment&watercontent
Controllingcontamination
JohnJechura jjechura@mines.edu
Updated:August13,2015
46
KeroseneSpecifications
Parameter
Specification
ASTMTestMethod
FlashPoint
100F
ASTMD56
10%distilled,max
401F
ASTMD86
FinalBoilingPoint
572F
ASTMD86
No.1sulfur,max
0.04%(No.1)
0.30%(No.2)
ASTMD1266
Burnquality
pass
ASTMD187
JohnJechura jjechura@mines.edu
Updated:August13,2015
47
JetFuelSpecifications
JohnJechura jjechura@mines.edu
Updated:August13,2015
48
StationaryTurbineFuel&DieselClasses
0GT
Includesnaphtha,jetfuelB&othervolatilehydrocarbons
1GT
ApproximatesNo.1FuelOil(D396)&1Ddiesel(D975)
2GT
ApproximatesNo.2FuelOil(D396)&2Ddiesel(D975)
3GT
ApproximatesNo.4&No.5fueloils
4GT
ApproximatesNo.4&No.5fueloils
No.1
Mostlyfromvirginstock.Superdiesel.Usedforautos&highspeed
engines.
No.2
Widerboiling&containscrackedstocks.Verysimilartohomeheatingfuel
(w/oadditives).
No.4
Traditionallylargestvolumeproduced.Usedformarine,railroads,&other
lowtomediumspeedpowerplants
JohnJechura jjechura@mines.edu
Updated:August13,2015
49
DieselSpecifications
JohnJechura jjechura@mines.edu
Updated:August13,2015
50
DieselSulfurContent
Sulfurlevelsdroppingbecauseofairqualityregulations
Since1993dieselfuelformulatedwith85%lesssulfur
LowSulfurDieselhadbeen500ppm sulfur
ULSD15ppm &requiredforonroadusagesinceJanuary2007
Worldwide,sulfurspecs
continuingtodropto
meetU.S.&European
standards
Globalstatusofmaximumallowablesulfurindieselfuel,partspermillion(June2012)
SaudiArabiasplanfornearzerosulfurfuels,HydrocarbonProcessing,March2013
JohnJechura jjechura@mines.edu
Updated:August13,2015
51
DistillateFuelOil
Onlygrades1and2havea(max)boilingrangespecs
No.1FuelOil similartokerosene(minorproduct)
No.2FuelOil domesticheatingoil
Similartomediumqualitydiesel2D
Madeinthewinterseasoninrefinerieswhen
automotivefueldemandislower.
No.3FuelOil nolongerproducedsince1948
Intendedtobealowerqualityspaceheatingoil
LittlepricedifferencebetweenNo.2&3
marketdisappeared
No.4FuelOil intendedforuseinindustrial
burnerinstallationswithnopreheatfacility
Sometimesamixtureofdistillate&residual
material
Lowerviscosityheatingoil
http://www.eia.gov/energyexplained/index.cfm?page=heating_oil_use
JohnJechura jjechura@mines.edu
Updated:August13,2015
52
ResidualFuelOils
No.5FuelOil premiumresidualfuel
oilofmediumviscosity,rarelyused
No.6FuelOil heavyresidualfueloil
Vacuumresid &cutterstockmix(to
decreaseviscosity)
Commonuse
Boilersforsteamturbinesofstationarypower
plants
Marineboilers variationofBunkerC
Industrial&commercialapplications
Leastvaluedofallrefineryproducts
Historicallyonlyliquidproductworthless
thanrawcrude
JohnJechura jjechura@mines.edu
Updated:August13,2015
53
ResidualFuelOils
No.6FuelOil Markethasbeendeclininginlast20years
Morepowerplantsusecoalornaturalgas
Shipsusedieselformarinedieselsorgasturbines
Environmentalreductionsinsulfurlevels
Emissioncontrolareas(ECAs)willshifttolowsulfur(0.1wt%)marinegasoil(MGO)or
marinedieseloil(MDO)
startingJanuary1,2015 U.S.,
Canada,Caribbean,&northern
Europe
Otheroptiononboard
emissionsscrubbingsystems
MethanoltakesonLNGforfuturemarinefuels,HydrocarbonProcessing,May2015
JohnJechura jjechura@mines.edu
Updated:August13,2015
54
ASTMFuelOilSpecs
JohnJechura jjechura@mines.edu
Updated:August13,2015
55
ComparisonKerosene/Jet/Diesel/HeatingOil
ASTMSpecificationsforMiddleDistillates
Property
CetaneNumber
Aromatics
[vol%]
Sulfur
[wt%]
FlashPoint
[C]
Distillation(D86)
T10 [C]
T20 [C]
T50 [C]
T90 [C]
[C]
EP [C]
DistillationResidue [vol%]
DistillationLoss
[vol%]
FreezingPoint
[C]
PourPoint
[C]
CarbonResidue
[wt%]
KinematicViscosity
@40C mm/s
mm/s
JohnJechura jjechura@mines.edu
Updated:August13,2015
No.2Kerosene
min
max
max
max
max
max
min
max
max
max
max
max
max
min
max
0.3
38
205
JetA
JetB
25
0.3
25
0.3
205
145
190
245
300
282
338
282
338
282
338
0.35
0.35
6
0.35
1.9
4.1
1.9
4.1
1.9
4.1
300
40
50
56
ComparisonofBoilingRanges
JohnJechura jjechura@mines.edu
Updated:August13,2015
57
GasOil&TownGas
Historicalusage
Gasoilsusedtomaketowngasforillumination
Decomposedoveraheatedcheckerwork
Composedofcarbonmonoxideandcarbondioxide
Lowheatingvalue
Burnedcleanly
Easilydistributedforilluminationfuel
Displacedkeroseneinthecities electricityultimatelyeliminateditsuse
Gasoilnolongeraconsumerproduct
Tradedbetweenrefineries
Feedstockforcatalyticcracking&hydrocracking
JohnJechura jjechura@mines.edu
Updated:August13,2015
58
LubricantTerminology
Phrase
Lubebasestock
Lubeslate
Meaning
Lubeproductthatmeetsallspecifications&is
suitableforblending
Setoflubebasestocks,usually3to5
Neutrallubes
Obtainedfromasidecutofthevacuumdistillation
tower
Brightstocklubes
Processedofvacuumresid fromthevacuumtower
bottoms
JohnJechura jjechura@mines.edu
Updated:August13,2015
59
Lubricants
TerminologybasedsolelyontheViscosityIndex independentofthecrude
sourceortypeofprocessing
Paraffiniclubricantsareallgrades,bothbrightstock&neutral,withafinishedviscosity
Indexmorethan75
NaphtheniclubricantsareallgradeswithaviscosityIndexlessthan75
Importantproperties
Kinematicviscosity(viscositydividedbymassdensity)
Color
Pourpointforcoldweatheroperation
Flashpoint
Volatilityforreducedevaporation
Oxidationstability
Thermalstability
JohnJechura jjechura@mines.edu
Updated:August13,2015
60
SAEViscositySpecifications
Kinematicviscosity
measuredincentistokes
butspecificationsare
labeledinSaybolt
Seconds(SUS)
Specificationsare
establishedbythe
SocietyofAutomotive
Engineers
SAEviscositywellknown
motoroilspecification
(e.g.,10W30)
JohnJechura jjechura@mines.edu
Updated:August13,2015
MaxViscosity
(SUS)@
210oF
Min
Viscosity
(SUS)@
210oF
20
58
45
30
70
58
40
86
70
50
110
85
Grade
Max
Viscosity
(SUS)@0oF
5W
6,000
10W
12,000
20W
48,000
61
Asphalt
Importantproductintheconstructionindustry
Comprise20%oftheOtherProductscategory
Asphaltcanonlybemadefromcrudescontainingasphaltenicmaterial
Numerousdetailedspecificationsonthemanyasphaltproducts
AsphaltInstitute,LexingtonKentucky
Industrytradegroupforasphaltproducers&affiliatedbusinesses
AmericanAssociationofStateHighwayandTransportationOfficials
SponsorstheAASHTOMaterialsReferenceLaboratory(AMRL)attheNationalInstitute
ofStandardsandTechnology(NIST)
AmericanSocietyofTestingandMaterials(ASTM)
JohnJechura jjechura@mines.edu
Updated:August13,2015
63
PetroleumCoke
GreenCoke
Calcined Coke
Fixedcarbon
86% 92%
99.5%
Moisture
6% 14%
0.1%
Volatilematter
8% 14%
0.5%
Sulfur
1% 6%
1% 6%
Ash
0.25%
0.40%
Silicon
0.02%
0.02%
Nickel
0.02%
0.03%
Vanadium
0.02%
0.03%
Iron
0.01%
0.02%
JohnJechura jjechura@mines.edu
Updated:August13,2015
64
SulfurSpecifications
Purity
Ash
Carbon
Color
H2S
State
99.8weight%sulfur,basedondryanalysis
500ppmwmaximum
1,000ppm(weight)maximum
"Brightyellow"whensolidified.
Sulfurrecoveredbyliquidreductionoxidationprocesseshavecolordueto
metals somepurchaserswillincludearequirementexcludingsulphur
recoveredfromtheseprocesses
10ppmw max(Importantforinternationaltransport&sales)
Shippedaseitherliquidorsolid.Internationaltransportspecifiessolid.
JohnJechura jjechura@mines.edu
Updated:August13,2015
65
Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions
Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number
JohnJechura jjechura@mines.edu
Updated:August13,2015
66
SupplementalSlides
Examplecrudeoilassay(withminimaldata)
Examplegasoline&gasolineblendstockanalyses
ASTMD323RVPProcedures
ASTMD56FlashPointbyTagClosedTesterFlash
Calculations
Linear&nonlinearblendingrules
Blendingrulesbasedonadditiveweight&additivevolumes
Blendingindices
Assaysoncommonbasis
Cumulativeyieldvs boilingpointtemperature
Fractionss averageyieldvs measuredproperty
Propertyestimationformulas
JohnJechura jjechura@mines.edu
Updated:August13,2015
67
CrudeOilAssay TenSectionField(Textpg.416)
Fraction
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Residuum
mm Hg
756
756
756
756
756
756
756
756
756
756
756
40
40
40
40
40
F
82
122
167
212
257
302
347
392
437
482
527
392
437
482
527
572
Total
Loss
Reported
IncrementCumulative
vol%
vol%
IBP
2.6
2.6
2.3
4.9
5.0
9.9
7.9
17.8
6.2
24.0
4.9
28.9
4.6
33.5
5.2
38.7
4.9
43.6
6.2
49.8
4.3
54.1
5.2
59.3
5.3
64.6
3.2
67.8
5.4
73.2
25.0
98.2
98.2
1.8
SpGr
0.644
0.683
0.725
0.751
0.772
0.791
0.808
0.825
0.837
0.852
0.867
0.872
0.890
0.897
0.915
0.984
Corrected Corrected
F
Cumulative
82.3
1.8
122.3
4.4
167.3
6.7
212.3
11.7
257.3
19.6
302.4
25.8
347.4
30.7
392.4
35.3
437.4
40.5
482.4
45.4
527.4
51.6
584.0
55.9
635.0
61.1
685.5
66.4
735.7
69.6
785.4
75.0
100.0
Mid-Cumulative
Amount
API
0.9
3.1
88.2
5.5
75.7
9.2
63.7
15.7
56.9
22.7
51.8
28.3
47.4
33.0
43.6
37.9
40.0
43.0
37.6
48.5
34.6
53.8
31.7
58.5
30.8
63.8
27.5
68.0
26.2
72.3
23.1
87.5
12.3
0.858
0.854
Stepsforthisexample
JohnJechura jjechura@mines.edu
Updated:August13,2015
68
CrudeOilAssay WTI(fromOGJarticle)
Steps
JohnJechura jjechura@mines.edu
Updated:August13,2015
69
SAE902098GasolineBlendStockAnalyses
Table 7 Analyses of Blending Components
Blending
Component
Light Cat
Cracked
Naptha
Light
Alkylate
Heavy
Alkylate
Full Range
Reformate
Light St
Run Naptha
C6
Isomerate
Light
Reformate
Mid Cut
Reformate
Heavy
Reformate
Gravity, API
52.1
51.9
66.8
72.3
55.8
44.2
81.8
83.0
72.0
32.8
29.8
Aromatics, vol%
Olefins, vol%
Saturates, vol%
35.2
32.6
32.2
35.9
25.4
38.8
17.6
44.9
37.4
0.5
0.2
99.3
1.0
0.9
98.1
61.1
1.0
37.9
2.2
0.9
96.9
1.6
0.1
98.3
4.8
1.5
93.7
94.2
0.6
5.1
93.8
1.9
4.2
Benzene, vol%
1.06
1.23
1.24
0.00
0.01
1.17
0.73
0.00
4.01
0.00
0.00
Bromine Number
57.1
41.7
91.4
2.3
0.3
1.2
0.5
3.8
3.1
0.6
0.9
RVP, psi
4.3
4.6
8.7
4.6
0.3
3.2
10.8
8.0
3.8
1.0
0.3
Distillation, F
IBP
T05
T10
T20
T30
T40
T50
T60
T70
T80
T90
EP
110
143
158
174
192
215
241
270
301
336
376
431
112
142
155
171
189
212
239
269
302
337
379
434
95
117
124
130
139
149
164
181
200
224
257
337
101
144
162
181
196
205
211
215
219
225
239
315
299
318
325
332
340
345
354
362
373
391
427
517
117
168
192
224
244
258
270
280
291
304
322
393
91
106
113
117
121
126
132
139
149
163
184
258
118
131
134
135
135
136
136
137
137
138
139
146
138
169
174
179
182
185
188
190
192
194
195
218
224
231
231
231
232
233
234
235
237
240
251
316
313
326
328
331
335
339
344
350
358
370
391
485
RON
MON
(R+M)/2
93.2
81.0
87.1
92.6
82.1
87.4
93.6
79.4
86.5
93.2
91.2
92.2
65.9
74.5
70.2
97.3
86.7
92.0
63.7
61.2
62.4
78.6
80.5
79.5
57.6
58.5
58.0
109.3
100.4
104.9
104.3
92.4
98.4
Carbon, wt%
Hydrogen, wt%
Nitrogen, ppmw
Sulfur, ppmw
86.94
13.00
46
321
85.88
13.56
37
522
85.60
14.20
27
0
84.00
16.09
0
15
84.39
15.54
0
15
88.11
11.60
0
9
83.58
16.29
0
325
83.44
16.49
0
10
84.41
15.54
0
7
90.87
9.32
0
10
89.62
10.34
0
8
Heating Value,
BTU/lb (net)
17300
17300
18700
18400
18100
16800
18400
18500
18200
15500
17300
JohnJechura jjechura@mines.edu
Updated:August13,2015
70
SAE902098GasolineAnalyses
Table 10 Blended Fuel Analyses
Fuel
Code
A
Avg
B
Cert
C
2211
D
1122
E
2222
F
1111
G
2121
H
1221
I
2112
J
1212
K
2111
L
2122
M
1222
N
1211
O
2221
P
1121
Q
1112
R
2212
A
M0
Z
M85
ZZ
M10
Gravity, API
57.4
58.8
50.2
59.2
50.2
64.1
53.4
62.2
51.9
58.2
53.4
50.6
59.1
62.6
51.7
64.2
59.6
49.1
57.4
47.9
56.8
Aromatics, vol%
Olefins, vol%
Saturates, vol%
32.0
9.2
58.8
29.9
4.6
65.5
43.8
3.3
37.5
20.7
22.3
57.0
43.7
17.2
24.3
20.0
3.2
76.8
44.3
17.4
38.3
20.2
20.2
45.0
42.9
4.1
53.0
21.4
4.0
59.7
45.7
4.9
49.4
47.8
17.7
34.5
18.0
21.8
45.7
21.4
5.7
59.0
46.7
19.3
19.4
20.3
18.3
61.4
21.5
4.8
73.7
46.0
4.0
34.8
32.0
9.2
58.8
5.0
1.0
8.4
28.0
6.8
55.5
MTBE, vol%
Methanol, vol%
0.00
0.00
0.00
0.00
15.40
0.00
0.00
0.00
14.80
0.00
0.00
0.00
0.00
0.00
14.60
0.00
0.00
0.00
14.90
0.00
0.00
0.00
0.00
0.00
14.50
0.00
13.90
0.00
14.60
0.00
0.00
0.00
0.00
0.00
15.20
0.00
0.00
0.00
0.00
85.60
0.00
9.70
Benzene, vol%
1.53
0.52
1.33
1.49
1.38
1.52
1.42
1.52
1.30
1.28
1.45
1.42
1.51
1.44
1.38
1.53
1.47
1.41
1.53
0.42
1.16
Bromine Number
21.3
12.2
9.2
44.3
32.5
10.0
35.7
41.1
11.5
10.0
13.3
38.7
42.6
16.2
35.0
38.9
12.2
10.8
21.3
3.0
18.6
RVP, psi
8.7
8.7
8.7
8.5
8.7
8.8
8.8
8.5
8.9
8.6
8.8
8.5
8.7
8.8
8.6
8.5
8.6
8.4
8.7
8.8
12.0
Distillation, F
IBP
T05
T10
T20
T30
T40
T50
T60
T70
T80
T90
EP
91
114
128
151
174
196
218
243
267
295
330
415
87
112
127
152
180
205
220
230
242
262
300
410
89
118
136
165
185
200
213
226
236
250
288
399
87
111
128
153
176
197
218
238
265
307
357
430
90
113
128
151
172
192
220
253
281
318
357
429
89
110
125
144
162
180
197
212
227
245
279
370
92
116
130
153
175
196
214
228
240
254
286
386
93
116
125
135
143
154
168
186
214
247
286
367
87
110
127
156
182
208
239
266
291
324
353
437
89
112
125
143
159
178
208
259
294
322
356
447
90
114
127
146
166
188
208
226
238
253
294
404
89
110
127
152
178
205
236
263
294
328
357
436
91
111
125
139
152
170
193
233
283
323
356
436
93
114
124
134
142
152
164
181
211
253
292
374
92
116
130
151
168
185
204
223
237
250
283
397
90
113
126
140
155
171
190
208
227
248
284
361
92
117
134
161
186
209
234
260
289
321
357
442
89
114
129
151
170
192
225
263
293
326
354
428
91
114
128
151
174
196
218
243
267
295
330
415
110
134
141
145
146
147
147
147
147
148
148
347
89
105
113
122
129
139
202
232
259
287
324
405
92.0
82.6
87.3
96.7
87.5
92.1
100.0
88.0
94.0
93.7
83.2
88.4
98.9
85.6
92.3
90.5
84.2
87.4
96.9
84.6
90.8
95.4
83.9
89.6
97.1
86.9
92.0
92.7
85.1
88.9
93.5
83.1
88.3
97.1
84.5
90.8
96.6
85.0
90.9
91.5
83.6
87.6
100.4
86.0
93.2
92.7
82.7
87.7
90.2
83.8
87.0
99.4
87.5
93.4
92.0
82.6
87.3
107.1
103.1
105.1
95.7
84.4
90.1
Carbon, wt%
Hydrogen, wt%
Nitrogen, ppmw
Sulfur, ppmw
Oxygen, wt%
86.74
13.22
29
339
0.00
86.64
13.35
12
119
0.00
85.34
11.92
1
284
2.72
86.29
13.73
46
316
0.00
85.09
12.20
31
267
2.69
85.05
14.12
4
290
0.00
87.79
12.17
15
317
0.00
83.53
13.56
10
312
2.88
87.71
12.26
3
261
0.00
83.51
13.70
12
297
2.76
87.88
12.10
1
318
0.00
87.87
12.07
26
266
0.00
83.65
13.60
16
301
2.67
83.36
13.92
6
294
2.68
85.44
11.94
9
288
2.60
86.11
13.82
13
333
0.00
85.85
14.08
8
310
0.00
85.50
11.84
11
279
2.63
86.74
13.22
29
339
0.00
44.25
12.61
2
27
43.13
81.48
13.17
25
242
5.33
Heating Value,
BTU/lb (net)
18300 18300 17500 18300 17800 18500 18100 17900 18200 17900 17500 17600 17700 18100 17100 18600 18100 17000 18300
RON
MON
(R+M)/2
JohnJechura jjechura@mines.edu
Updated:August13,2015
9600 17400
71
ASTMD323RVPProcedures
ProcedureA(AtmosphericallyStableLiquids)
Apparatus
LiquidPreparation
1Lsamplecontainerfilled7080%withtestliquidsample.Samplecontainercooledinacold
bathat0 1C(32 34F).Samplecontaineropened,allowingairtoentercontainer.
Containershakenvigorously(tosaturatetheliquidwithair)&returnedtocoldbath.
LiquidTransfer
Theliquidchambercooledinthesamecoldbath.Coldliquidsampletransferredtothecold
liquidchamber,entirelyfillingliquidchamber.
AirPreparation
Assembly
Vaporchamberremovedfromhotbath&coupledtoliquidchamber.Thecoupledapparatus
isinverted,shaken,&putintohotbath.
PressureMeasurement
Apparatusshouldremaininhotbathforatleast5minutesbeforetheapparatusisremoved
frombath,shaken,&returnedtohotbath.Shakingprocedureshouldberepeatedatleast5
timeswithnolessthan2minutesinbetween.Shakingprocedureshouldberepeateduntil2
consecutivepressurereadingsindicateequilibriumhasoccurred.Pressuremeasuredasgauge
butreportedwithreferencetogaugeorabsolute.
ProcedureC(VolatileLiquids)
LiquidPreparation
LiquidTransfer
Liquidchamberiscooledinthesamecoldbath.Coldliquidsampletransferredtothecold
liquidchamber,similartoProcedureA.However,sincethisliquidisunderpressure,extra
caremustbetakentoensurethatgasisnotflashedoffandlostandthattheliquidchamberis
actuallycompletelyfilledwiththeliquid.
JohnJechura jjechura@mines.edu
Updated:August13,2015
72
ASTMD56FlashPointbyTagClosedTesterFlash
PointsBelow60C(140F)
Apparatus
TagCloseTester testcup,lidwithignitionsource,&liquidbath.
Preparation
Transfersshouldnotbemadeunlesssampleisatleast10C(18F)belowthe
expectedflashpoint.Donotstoresamplesingaspermeablecontainerssincevolatile
materialsmaydiffusethroughthewallsoftheenclosure.Atleast50mLsample
requiredforeachtest.
ManualProcedure
1.Temperatureofliquidinbathshallbeatleast10C(18F)belowexpectedflash
pointatthetimeofintroductionofthesampleintotestcup.Measure50 0.5mL
sampleintocup,bothsample&graduatedcylinderbeingprecooled,whennecessary,
sothatspecimentemperatureattimeofmeasurementwillbe27 5C(80 10F)
oratleast10C(18F)belowtheexpectedflashpoint,whicheverislower.
2.Applytestflamesizeofthesmallbeadonthecover&operatebyintroducingthe
ignitionsourceintovaporspaceofcup&immediatelyupagain.Fulloperationshould
be1secwithequaltimeforintroduction&return.
3.Adjustheatsotemperaturerise1C(2F)/min 6s.Whentemperatureof
specimeninis5C(10F)belowitsexpectedflashpoint,applytheignitionsource.
Repeatapplicationofignitionsourceaftereach0.5C(1F)riseintemperatureofthe
specimen.
JohnJechura jjechura@mines.edu
Updated:August13,2015
73
LinearBlendingRules
Valuesforindividualblendstocksaveragedeitherwithvolumefractionsormass
fractions
Somepropertiesblendbestwithmolefractions,butmolaramountsnottypicallyknown
Unitsonthequalitymeasuremaygiveanindicationastovolumeormass
blending.
Volumeblending
X mix vi X i
Specificgravity(essentiallymassperunitvolume)
Aromaticscontent(vol%)
Olefinscontent(vol%)
V X
V
i
Massblending:
Sulfurcontent(wt%orppm)
Nitrogencontent(wt%orppm)
Nickel&vanadium(ppm)
JohnJechura jjechura@mines.edu
Updated:August13,2015
mix
w X
i i
v X
m X
i oi i
i
i
m
v
i
i oi
74
HowDoWeBlendSpecificGravities?
Assumeidealliquidmixing volumesareadditive
Shrinkagecorrelationsavailable,mostlyusedforcustodytransfer
Specificgravities/densitiesatfixedconditionsblendlinearlywithvolume
Mass&volumesareadditive
o ,mix
V
V
i o ,i
i o ,i
vi o ,i
Canalsoblendwithmass&molaramounts
Volumesareadditive
1
o ,mix
wi
o ,i
M
o ,mix
xi Mi
o ,i
Densityadjustments
Correctionsneededfortemperature&pressureeffects
JohnJechura jjechura@mines.edu
Updated:August13,2015
75
HowDoWeBlendAPIGravities?
Specificgravityisblended&APIgravityisbackcalculated.
MayhavetocalculateindividualspecificgravitiesfromgivenAPIgravities
Example
IncorrectvaluefromdirectvolumeblendingofAPIgravities
JohnJechura jjechura@mines.edu
Updated:August13,2015
76
TemperatureCorrectionstoSpecificGravity
ODonnellmethod1
T2 2o 0.000601 TF 60
APIVolumeCorrectionTables
T o exp 60 T F 60 1 0.8 60 TF 60
Different60 valuesdependingoncommoditytype
ATables CrudeOils
BTables RefinedProducts
DTables Lubricants
CTables Individual&SpecialApplications
1Reportedslopevalueis0.00108(g/cm3)2/oC,HydrocarbonProcessing,April1980,pp229231
JohnJechura jjechura@mines.edu
Updated:August13,2015
77
StandardConditions(Temperature&Pressure)
Standardconditionsmayvarybetweencountries,stateswithintheUS,&
betweendifferentorganizations
Standardtemperature 60F
Mostothercountriesuse15C(59F)
Russiauses20C(68F)
Normalconditions
Almostexclusivelyusedwithmetricunits(e.g.,Nm)
IUPAC:
0C&100kPa (32F&14.50psia)
NIST:
0C&1atm (32F&14.696psia)
JohnJechura jjechura@mines.edu
Updated:August13,2015
78
Whatifwewanttoestimatevolumetricshrinkage?
MethodinChapter12.3ofAPImeasurementmanual
S 4.86 10 8 C 100 C
0.819
GL GH
2.28
where C
VL
100
VH VL
Vmix VH VL 100,000bbl
mix
Gmix
Withshrinkage:
JohnJechura jjechura@mines.edu
Updated:August13,2015
LVL HVH
Vmix
141.5
mix
0.8612
131.5 32.8
5000
0.819
2.28
100 5 S 4.86 10 8 5 100 5
86.5 30.7 0.0972
5000 95000
100 S
100 0.0972
Vmix VH VL
100000
99,903bbl
100
100
79
HowDoWeBlendYieldCurves?
Onaconsistent
volume,mass,or
molebasis
Onanincrementalor
cumulativebasis
Temperatures
correctedto1atm
basis
Distillationtype
correctedtoTBP
forthesameTBP
temperatureranges
5.0
100
4.5
90
4.0
80
3.5
70
N'Kossa
Ratawi Crude Oil
3.0
Cumulative Amount
60
2.5
50
2.0
40
1.5
30
1.0
20
0.5
10
0.0
Amountsareadded
0
0
250
500
750
1000
1250
1500
1750
2000
Temperature [F]
JohnJechura jjechura@mines.edu
Updated:August13,2015
80
HowDoWeBlendPropertiesforIndividualFractions?
Blendbasedonpropertiesandamountsforthefraction ineachblendstock,not
theoverallamountofblendstock.
JohnJechura jjechura@mines.edu
Updated:August13,2015
81
HowDoWeCorrectBoilingPointforPressure?
EquationformofMaxwellBonnell charts(1955)
Pvap unitsofmmHg,temperaturesinunitsR
3000.538 X 6.761560
43 X 0.987672
2663.129 X 5.994296
log10 P vap
95.76 X 0.972546
2770.085 X 6.412631
36 X 0.989679
X 0.002184346
vap
1.7mmHg
0.001201343 X 0.002184346
1817mmHg P
vap
1.7mmHg
0.001201343 X
1817mmHg P
vap
1
0.0002867
P vap
T
760
1
748.1 0.0002867
TB
1
P vap 760mmHg
TB 659.67 vap
,0 P 760mmHg
Min 1,Max
200
JohnJechura jjechura@mines.edu
Updated:August13,2015
82
PressureCorrectionExample
Correcta437Fboilingpointmeasuredat40mmHgtothenormalboiling
point(at760mmHg).
Usingthe2nd of3equationsdetermineX=0.001767618
WithT=896.67oRdetermineTB=1094.98
IfweneglecttheWatsonKfactorcorrection(i.e.,assumeKW=12)thenTB=TB
Normalboilingpointis635oF
JohnJechura jjechura@mines.edu
Updated:August13,2015
83
HowDoWeInterconvertD86&TBPTemperatures?
Methodfrom1994APITechnicalDataBook
ConsistentwiththeAPI94optioninAspenPlus
1.0258
TTBP,50% 0.87180 TD86,50%
(TTBP,50% &TD86,50% inF)
TTBP A TD86
Vol%
100%to90%*
0.11798
1.6606
90%to70%
3.0419
0.75497
100
70%to50%
2.5282
0.82002
150
50%to30%
3.0305
0.80076
250
30%to10%
4.9004
0.71644
250
10%to0%*
7.4012
0.60244
100
*Reported100%&0%givebettertrendsas99%&1%.
JohnJechura jjechura@mines.edu
Updated:August13,2015
84
InterconvertD86&TBPTemperatures
120
90% to 100%
100
10% to 30%
0% to 10%
30% to 50%
80
50% to 70%
70% to 90%
60
40
20
0
0
10
20
30
40
50
60
70
JohnJechura jjechura@mines.edu
Updated:August13,2015
85
HowDoWeInterconvertD86&TBPTemperatures?
Methodfrom1987APITechnicalDataBook
TTBP a TD86
1/ b
T
TD86 TBP
a
Vol%
0%*
0.9167
1.0019
10%
0.5277
1.0900
30%
0.7429
1.0425
50%
0.8920
1.0176
70%
0.8705
1.0226
90%
0.9490
1.0110
95%
0.8008
1.0355
Usewithcare cangiveincorrecttemperaturevs.volumetrends
JohnJechura jjechura@mines.edu
Updated:August13,2015
86
HowDoWeInterconvertD1160&TBPTemperatures?
D1160temperaturesat10mmHgareconvertedtoTBPtemperaturesat10mm
Hg graphicalmethodtointerconvert
D1160temperaturesat50%&higherequaltotheTBPtemperatures
0%to10%,10%to30%,&30%to50%D1160temperaturedifferences convertedtoTBP
temperaturedifferences
Vol%
Distilled
Range
MaxT
0% 10%
2.23652561
1.39334703E2
3.6358409E5
1.433117E8
144F
10%30%
30%50%
1.35673984
5.4126509E3
2.9883895E5
6.007274E8
180F
JohnJechura jjechura@mines.edu
Updated:August13,2015
87
InterconvertD1160&TBPTemperatures
225
Note: ASTM D1160 & TBP 50% distillation
temperatures assumed equal at 10 mmHg
200
175
150
125
0% to 10%
100
75
50
25
0
0
25
50
75
100
125
150
175
200
225
JohnJechura jjechura@mines.edu
Updated:August13,2015
88
HowDoWeInterconvertD2887&TBPTemperatures?
Methodfrom1994APITechnicalDataBook
D2887essentiallyTBPonwt% basis,notvol%
TTBP,50% TD2887,50%
TTBP A TD2887
Vol%
100%to95%
0.02172
1.9733
95%to90%
0.97476
0.8723
90%to70%
0.31531
1.2938
70%to50%
0.19861
1.3975
50%to30%
0.05342
1.6988
30%to10%
0.011903
2.0253
10%to0%*
0.15779
1.4296
JohnJechura jjechura@mines.edu
Updated:August13,2015
89
D86ConversionExample 1994Correlation
Stepsforthisexample
Vol%
D86
IBP
91
D86T
79.5
155.6
218.4
279.9
JohnJechura jjechura@mines.edu
Updated:August13,2015
69.4
330
349.3
85
EP
61.5
267
63
90
62.7
218
49
70
76.1
174
44
50
65.2
128
46
30
415
TBP
14.3
37
10
TBPT
188.7
538.0
90
D86vsTBPTemperatures
600
500
600
300
500
200
DistillationTem perature[F]
TBPTemperature[F]
400
100
0
0
100
200
300
400
400
300
200
D86YieldCurve
500
D86Temperature[F]
TBPYield
100
0
0
10
20
30
40
50
60
70
80
90
100
CumulativeYield[vol%]
JohnJechura jjechura@mines.edu
Updated:August13,2015
91
HowDoWeCorrelateYieldtoBoilingPoint?
Neededforinterpolation,extrapolation,andsmoothingofdata
Typicalmethods
Electronicversionofplottingcumulativeyielddatavs.boilingpointtemperatureon
probabilitypaper
GuaranteesanSshapedcumulativeyieldcurve
Nospecific0%or100%points
Dhulesia smoothingmethod(1984)
1 T T
i
Y T 1 exp
Tf Ti
Whitsonmethod(1980)
GeneratesdistributionfromalimitedamountofC6+data
1 M Mi
p M
JohnJechura jjechura@mines.edu
Updated:August13,2015
92
HowDoWeUsetheProbabilityForm?
DistillationyieldcurvestypicallyhaveanSshape
Traditionaltolinearize onprobabilitygraphpaper
AxistransformedusingfunctionsrelatedtoGaussiandistributionfunction
FunctionsavailableinExcel
TransformedYield:
=NORMSINV( Pct_Yield/100 )
Frominterpolatedvalue:
Transformed0%&100%valuesundefined
TypicaltosetIBP&EPto1%&99%
JohnJechura jjechura@mines.edu
Updated:August13,2015
93
LinearizedDistillationYieldCurves
JohnJechura jjechura@mines.edu
Updated:August13,2015
94
Incrementalvs.CumulativeYield
Incrementalyieldcanbecalculatedasthe
differenceinthecumulativeyieldsatthe
final&initialboilingpoints
Y Ti ,Tf Y Tf Y Ti
Valuesimpactedbymethodchosento
interpolate/extrapolate
JohnJechura jjechura@mines.edu
Updated:August13,2015
95
HowDoWeBlendDistillationCurves?
Blendthedistillationcurvesforallblendstocks&extractthetemperaturesfrom
theresultingcurve
Steps
ConvertallofthestartingdistillationanalysestoTBPbasis(@1atm)
PickasetofTBPtemperaturesforwhichtheblendcalculationswillproceed.Extractthe
yieldvaluesforattheseselectedtemperaturevaluesforallblendstocks.
Usewhatevertemperaturesseemreasonabletocoverthespanofallinputvalues
Calculateayieldcurvefortheblendatthetemperatureschoseninthepreviousstep
Extractthetemperaturevaluesforthespecifiedyieldvalues
Converttooriginaldistillationbasis(ifrequired)
JohnJechura jjechura@mines.edu
Updated:August13,2015
96
DistillationCurveBlendExample
BlendStockData
API
IBP
T10
T30
T50
T70
T90
EP
Fraction
D86ConvertedtoTBP
LSR
MidCut
Reformate
81.8
91
113
121
132
149
184
258
50%
32.8
224
231
232
234
237
251
316
50%
Vol%
1
10
30
50
70
90
99
LSR
MidCut
Reformate
40.5
88.1
109.9
130.5
156.3
200.9
350.8
200.8
224.7
229.6
234.8
241.1
263.4
384.2
Steps
ConvertallD86analysestoTBP
ApproximateIBP&EPas1%&99%
PickasetofTBPtemperatures&interpolatefor
appropriateyieldvalues
BlendatSelectedTemperatures
F
LSR
MidCut
Reformate
Blend
25
50
75
100
125
150
175
200
225
250
275
300
325
350
375
400
81.8
0.4
1.7
5.8
19.3
44.4
65.4
80.0
89.7
92.6
94.8
96.4
97.6
98.4
99.0
99.4
99.6
32.8
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.9
11.0
79.6
91.7
94.5
96.5
97.9
98.8
99.3
54.1
0.2
0.9
2.9
9.6
22.2
32.7
40.0
45.3
51.8
87.2
94.0
96.0
97.5
98.4
99.1
99.5
BlendatSpecifiedYields
Vol%
TBP
D86
1
10
30
50
70
90
99
52.9
101.0
144.0
218.0
236.0
258.7
371.7
120.5
142.8
163.6
217.7
228.6
242.9
305.3
Volumetricallyblendateachtemperaturefor
combinedTBPcurve
InterpolateforappropriateTBPvaluesatthe
standardvolumetricyields
ConverttoD86analysis
JohnJechura jjechura@mines.edu
Updated:August13,2015
97
HowDoWeEstimateLightEndsfromYieldCurve?
Approximateincrementalamountfromthedifferenceincumulativeyields
betweenadjacentpurecomponentboilingpoints
Steps
Chooselightendscomponents
Typicallymethane,ethane,propane,iso &normalbutane,iso &normalpentane
Determineboilingpointrangesassociatedwithpurecomponentboilingpoints
Sometimesextendrangeto0.5Cabovethepurecomponentboilingpoint
Extrapolatedistillationyieldcurvetofindcumulativeyieldsattheboilingpointranges.
Finddifferencestodetermineincrementalamounts.
JohnJechura jjechura@mines.edu
Updated:August13,2015
98
LightEndsExample
TBP [F]
Init ial
Final
Yield [vol%]
TBP [F]
Cumulat iv e Cumulat iv e
@ Init ial
P ure
@ Final
Whole Crude
Component
Yield [vol%]
Init ial
Final
Methane
-258.73
N/A
-258.73
Cumulat iv e Cumulat iv e
@ Init ial
@ Final
0.0
0.02
Inc rement
0.02
Light Naphtha
55
175
1.7
5.6
Ethane
-127.49
-258.73
-127.49
0.02
0.17
0.15
Medium Naphtha
175
300
5.6
15.3
Propane
-43.75
-127.49
-43.75
0.17
0.53
0.36
Heavy Naphtha
300
400
15.3
21
i-Butane
10.78
-43.75
10.78
0.53
1.03
0.50
Kero
400
500
21
29.2
n-Butane
31.08
10.78
31.08
1.03
1.30
0.27
500
650
29.2
40.4
i-Pentane
82.12
31.08
82.12
1.30
2.27
0.97
Light VGO
650
850
40.4
57.3
n-Pentane
96.92
82.12
96.92
2.27
2.65
0.38
850
1050
57.3
71.5
1050
End
71.5
100
Heavy VGO
Vacuum Resid
250
Steps
Methane,ethane,propane,iso &normal
butane,iso &normalpentane
Determineboilingpointrangesassociatedwith
purecomponentboilingpoints.Useasthe
FinalBoilingPointforrange.
BoilingPoint(F)
Chooselightendscomponents
0
C3
C2
Extrapolatedistillationyieldcurvetofind
cumulativeyieldsattheboilingpointranges.
Finddifferencestodetermineincremental
amounts.
nC5
250
iC5
C1
iC4
nC4
500
0.01
0.10
1.00
10.00
100.00
CumulativeYield[vol%]
JohnJechura jjechura@mines.edu
Updated:August13,2015
99
HowDoWeEstimateOtherPropertiesofFractions?
Propertiesinferredfrommeasuredtrends
Relativedensity/specificgravity/APIgravity
Sulfurcontent
Carbonresidue
Propertiesfromcorrelations
Molecularweight/molarmass
JohnJechura jjechura@mines.edu
Updated:August13,2015
100
WhatHappensWhenWeChangeCutPoints?
Ingeneral
Theamountcanbecalculatedasthedifferenceincumulativeyieldsbetween
thenewinitial&finalboilingpoints
Interpolatewithintheyieldvs.temperaturecurveusingtheprobabilityform
Thepropertiescanbedeterminedbyinterpolatingthecurvefortheproperty
vs.themidincrementyield
Linearinterpolationusuallysufficient
Specialcases
Slightlysmallerthanagivencutintheassay findpropertiesofthe
excludedfraction&subtractcontributionfromthegivencut
Slightlylargerthanagivencutintheassay findpropertiesoftheincluded
fraction&addcontributiontothegivencut
Combinationoftwoormoregivencutsintheassay findpropertiesby
addingallcontributions
JohnJechura jjechura@mines.edu
Updated:August13,2015
101
RevisedCutPoints Example#1
Whatistheyieldofthetotalgasoil(500 1050oF)?Whataretheproperties?
AddcontributionsfortheAtm GasOil,LightVGO,&HeavyVGO
VGO Y 1050F Y 500F 85.8 39.5
46.3vol%
GO
46.3
VGO
0.8911
SGO
0.58wt%
JohnJechura jjechura@mines.edu
Updated:August13,2015
102
RevisedCutPoints Example#2
WhatistheyieldoftheHVGOifthecutrangeis850
1000oF?Whataretheproperties?
Determineamount&estimatepropertiesof
1000 1050oFcut.
RemovecontributionsfromtheHeavyVGOinthe
assay
VGO Y 1000F Y 500F 83.1 73.2
9.9vol%
Cumulativeyield@1000oFfrominterpolationof
yieldvs.temperature
Y 1000F 83.1vol% Ymid
83.1 85.8
84.4
2
Propertiesfromlinearinterpolationofmidincrement
yieldvs.property
GO
SGO
0.9262
9.9 0.9262
0.86wt%
S 84.4vol% 1.12wt%
JohnJechura jjechura@mines.edu
Updated:August13,2015
103
RevisedCutPoints Example#3
Determineamount&estimatepropertiesof
1000 1050oFcut.
Cumulativeyield@1000oFfrominterpolationof
yieldvs.temperature
Y 1000F 83.1vol% Ymid
83.1 85.8
84.4
2
Propertiesfromlinearinterpolationofmidincrement
yieldvs.property
GO
SGO
0.9931
S 84.4vol% 1.12wt%
JohnJechura jjechura@mines.edu
Updated:August13,2015
104
CanWeEstimateGravityCurveWhenNoneGiven?
AssumethatallfractionshavethesameWatsonKfactor
Kw
vi
TBi
1.20
Example EstimateRatawi
1.10
Specific Gravity
WatsonKfactor&gravity
curvebasedonoverall
gravity&distillation
analysis
1.00
0.90
0.80
0.70
0.60
0
10
20
30
40
50
60
70
80
90
100
JohnJechura jjechura@mines.edu
Updated:August13,2015
105
HowDoWeBlendWatsonKFactor?
Bestmethod
Blendspecificgravity
Determinenewaverageboilingpointfromblendedyieldcurve
Approximatemethod
BlendindividualWatsonKfactorsbyweight
K mix wi K i
v K
v
i oi
i oi
Impliesaverageboilingpointfromvolumetricblendofcuberootofboilingpoint
JohnJechura jjechura@mines.edu
Updated:August13,2015
106
WhatistheAverageBoilingPointforaFraction?
5typesaredefinedintheAPITechnicalDataBook
n
Volumeaverageboilingpoint
Tb v viTb ,i
i 1
Massaverageboilingpoint
Tb w wiTb ,i
i 1
Molaraverageboilingpoint
Tb M xiTb ,i
i 1
vi 3 Tb ,i
i 1
Cubicaverageboilingpoint
Tb cubic
Meanaverageboilingpoint
Tb mean
Tb M Tb cubic
2
WatsonKfactorusestheMeanAverageBoilingPoint
JohnJechura jjechura@mines.edu
Updated:August13,2015
107
HowDoWeBlendHeatingValues?
HeatingValue
Molarormassaverage(dependingonunits)
H mix xi H i or Hmix wi Hi
Lower/netheatingvalue(LHV) wateringasstate
JohnJechura jjechura@mines.edu
Updated:August13,2015
108
VaporPressureCalculations
BubblePoint TVP(TrueVaporPressure)
At1atm,coulduseidealgas&liquidassumptions molar blending
Pi vap T
yi xi K i 1 xi P 1
Vaporpressureapproximationusingaccentric factor
Pi vap 7
Tci
log10
1
i 1
P
T
3
ci
MaxwellBonnell relationshipforpetroleumfractions
EOS(equationofstate)calculationsmorerigorous
SoaveRedlichKwong orPengRobinson
JohnJechura jjechura@mines.edu
Updated:August13,2015
109
HowDoWeBlendRVPs?
RVPisnearlyequaltotheTrueVaporPressure(TVP)at100F
Foridealgas&liquidmixtures,TVPblendslinearlywithmolar fraction
P
vi
vap
yi i P xi i Pi exp
dP yi P xi Pi vap
Pvap RT
i
ApproximatevolumetriclinearblendingwithRVPBlendingIndices
JohnJechura jjechura@mines.edu
Updated:August13,2015
1.25
RVP mix
1.25
vi RVP i
1/1.25
110
RVP&TVP APITechnicalDataBookMethods
Intentistoestimate
truevaporpressures
(TVPs)froma
measuredRVP
CanalsoestimateRVP
fromanymeasured
vaporpressurevalue
TVPcouldbe
measuredatany
temperature could
useboilingpoint
SlopeisoftheASTM
D86distillationcurve
@T10
JohnJechura jjechura@mines.edu
Updated:August13,2015
111
Othercorrelations
GPSAFig.64makesuseof
Kremser relationship(1930)for
TVP@100oF:
TVP=1.07(RVP)+0.6
JohnJechura jjechura@mines.edu
Updated:August13,2015
112
Othercorrelations
SantaBarbaraCountyAPCDRule325,AttachmentB,equation25:
TVP=(RVP)exp(Co (IRTEMP ITEMP))+CF
where:
Co
ITEMP
IRTEMP
Ts
RVPdependentcoefficient
1/(559.69oR)
1/(Ts +559.69oR)
oF temperaturestoredfluid
BasedonAPIFigure5B1.2
JohnJechura jjechura@mines.edu
Updated:August13,2015
113
HowDoWeBlendOctaneNumbers?
Octanenumbersgenerallyblendnonlinearly
Interactionsbetweencomponentsinmixture
ApproximatelinearblendingwithOctaneBlendingIndices
Indicesarefairlycloselyguarded
Inthisclasswellgenerallyassumelinearblendingwithvolume
JohnJechura jjechura@mines.edu
Updated:August13,2015
114
NonLinearOctaneBlendingFormula
DevelopedbyEthylCorporationusingasetof75&135blends
R R a1 RJ R J a2 O2 O 2 a3 A2 A2
A2 A2
2
2
M M b1 MJ M J b2 O O b3
100
RM
"Road"Octane
75blends 135blends
2
0.03224
0.03324
a1
Sensitivity J R M
2
V X
VolumeAverage X
V
i
PetroleumRefineryProcessEconomics,2nd ed.,
byRobertE.Maples,PennWellCorp.,2000
JohnJechura jjechura@mines.edu
Updated:August13,2015
a2
a3
0.00101
0
0.00085
0
b1
b2
0.04450
0.00081
0.04285
0.00066
b3
0.00645
0.00632
115
GasolineBlendingSampleProblem
WhataretheAPIgravity,RVP,&averageoctanenumberfora33/67blendof
LightStraightRunGasoline&MidCutReformate?
Steps
for
thisexample
JohnJechura jjechura@mines.edu
Updated:August13,2015
116
WhatisDriveabilityIndex(DI)?
Orientedtowardstheautoindustry
Needenoughvolatilitytocompletelyvaporizefuelinthecylinder
LoweringRVPmakesthefuelhardertovaporize
Empiricalrelationshipbetweengasolinevolatility&engineperformance
(driveability &emissions)
DI 1.5 T10 3 T50 T90 2.4F EtOHvol%
ThelowertheDI,thebettertheperformance
AlkylatesraiseT50
EthanolraisesRVP&depressesT50,butnottheDI
JohnJechura jjechura@mines.edu
Updated:August13,2015
117
HowCanWeEstimateFlashPoint?
Relatedtovolatilityofmixture.
Assumeidealgassincetestsdoneat1atm.
MethodofLenoir
N
vap
x
M
P
i i i i 1.3
i 1
MethodofGmehling&Rasmussen
Relatedtolowerflammabilitylimit
T 25
xi i Pi vap
1
with
25
0.182
L
L
C
i
i
Li
H
i 1
c ,i
JohnJechura jjechura@mines.edu
Updated:August13,2015
118
HowCanWeEstimateFlashPoint?
APIProcedure2B7.1(ASTMD86T10)
1987Version(unitsofR)
1
2.84947
0.014568
0.001903ln T10
TF
T10
ModifiedbyChatterjee&Saraf
1
4.17015
0.076204
0.01043ln T10 0.000257ln o
TF
T10
1997Version(unitsofF)
OpenCupClosedCub
JohnJechura jjechura@mines.edu
Updated:August13,2015
119
HowDoWeEstimate&BlendCetaneIndex?
Cetaneindexisanestimateofthecetane numberbasedoncomposition.Itdoes
nottakeintoaccounteffectsofadditivestoimprovecetane number.
EstimationmethodoutlinedbyASTMD976
Index 420.34 0.016G 2 0.192G log T50 65.01 log T50 0.0001809T502
2
Cetaneindexcanbeapproximatelyblendedlinearlybyvolume
JohnJechura jjechura@mines.edu
Updated:August13,2015
120
HowAreOctane&Cetane NumbersRelated?
Ingeneralcompoundswithhighoctanenumbershavelowcetane numbers
Correlationdevelopedfromgasolinesamples
CN 60.96 0.56 MON
25
20
Cetane Number(CN)
RONExpression
MONExpression
15
10
5
0
70
80
90
OctaneNumber(MONorRON)
100
Bowden,Johnston,&Russell,OctaneCetane Relationship,
FinalReportAFLRLNo.33,March1974,
PreparedbyU.S.ArmyFuels&LubricantsResearchLab&SouthwestResearchInstitute
JohnJechura jjechura@mines.edu
Updated:August13,2015
121
HowDoWeConvertSUSviscosity?
1.0 0.03264
SUS 1.0 0.000061T 100 4.6324
2
3
5
3930.2
262.7
23.97
10
500
450
210F
400
0F
SUS Viscosity
350
300
250
200
150
100
50
0
0
20
40
60
80
100
JohnJechura jjechura@mines.edu
Updated:August13,2015
122
Howdoweadjustviscosityfortemperature?
Validforviscositiesabove0.21cSt
loglog Z A BlogT
Z 0.7 C D E F G H
C exp 1.14883 2.65868
D exp 0.0038138 12.5645
E exp 5.46491 37.6289
F exp13.0458 74.6851
G exp 37.4619 192.643
H exp 80.4945 400.468
2
3
Z 0.7 exp0.7487 3.295 Z 0.7 0.6119 Z 0.7 0.3193 Z 0.7
Forviscositiesabove2.0cSt theequationisessentially
log log 0.7 A B log T
JohnJechura jjechura@mines.edu
Updated:August13,2015
123
Viscosityvs.TemperatureExample
F
cSt
104
122
212
275
4,102
1,750
115
37.9
log(log(Z))
log(R)
0.5579
563.67
0.5110
581.67
0.3146
671.67
0.2005
734.67
Bylinearregression
A:
1.732
B: 0.002094
r:
0.997
Est
log(log(Z))
0.5514
0.5137
0.3253
0.1934
EstcSt
3,629
1,836
130
35.7
Relative
Deviation
12%
5%
13%
6%
10,000
Steps
CalculatetheZ &temperaturetermsfromthe
givendata
1,000
Thiscaseuseslinearregression&all4
points
UseA &B parameterstofindZ atother
temperatures
Viscosity[cSt]
Converttemperaturestoabsolutebasis
100
10
ConvertZ tocSt
Approximateformulausedhere
0
100
200
300
400
500
600
700
Temperature[F]
JohnJechura jjechura@mines.edu
Updated:August13,2015
124
HowDoWeBlendViscosities?
Viscosityblendingcomplicatedcompositioneffects
Simpleviscosityblendingequationsaremoreappropriateforgasphaseviscosity
shouldnotbeusedforblendingliquidphasepetroleumfractionvalues
Arrhenius
ln mix vi ln i
Bingham
1
v
i
mix
i
Kendall&Monroe
mix
xi ln 1/3
i
JohnJechura jjechura@mines.edu
Updated:August13,2015
125
HowDoWeBlendViscosities?
Desiretoblendviscositywitheithervolumeormassamounts
LinearblendingwithViscosityBlendingIndicesofkinematicviscosity
log log mix c vi log log i c where c 0.7
Mayseeanindexbasedonloglogtermswithextracoefficientsand/ornaturallog
terms.Giveidenticalresults.
Forheavyfractionsoftenmassblendingissuggestedwithc of0.8to1.0
Refutas equation massblending
ln mix
ln1000 mix
JohnJechura jjechura@mines.edu
Updated:August13,2015
vi
ln i
ln1000 i
S ln mix ln1000
S
1 S
126
ASTMD7152ViscosityBlending
ProcedureCwhenusingviscosityvaluesallatthesametemperature
ASTMBlendingMethod volumeblending
ModifiedASTMBlendingMethod massblending
Basedonloglog(MacCoullWaltherWright)transformationviscosity
Z i i 0.7 exp 1.47 1.84 i 0.512i
Wi log log Z i
WB viWi
WB
ZB 1010 0.7
B ZB exp 0.7487 3.295ZB 0.6119 ZB2 0.3193ZB3
Developedforvolumeblending&kinematicviscositybutcouldbeusedformass
blending
Forbasestockblends,nosignificantdifferencebetweenvolumetric&massblending
Forfuelblends(chemicallyconvertedblendstocks),massblendingmoreaccurate
Exponentialcorrectionterminsignificantabove2cSt
Extendstheuseofloglogtermsfromdownto0.2cSt.
JohnJechura jjechura@mines.edu
Updated:August13,2015
127
ViscosityBlendingExample
Determinetheamountofcutterstockneededtoblendwith5,000bpd80,000cSt
vacuumresid tomakeafueloilwith180cSt @122F.Thecutterstockhas8.0cSt
viscosity.
100,000
BlendViscosity[cSt]
10,000
VolumeAveragecSt
1,000
VolumeAveragelog(cSt)
100
LogLogBlendingRule
10
ASTMBlendingMethod&Chevron
Method2essentiallythesameresults
ChevronBlendingIndices
1
0.1
10
100
RatioCutter:Resid[vol/vol]
JohnJechura jjechura@mines.edu
Updated:August13,2015
128
HowaretheCarbonResiduesRelated?
Carbonresidue cokingtendency
ASTMD524 Ramsbottom (RCR)
ASTMD189 Conradson (CCR)
ASTMD4530 Microcarbon (MCRT)
CCR&MCRTessentiallythesame
129