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JohnJechura [email protected]
Updated:August9,2014
RefineryFeedstocks &Products Properties&Specifications
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Light Naphtha
CrudeOil
Desalter
AtmosphericDistillation
VacuumDistillation
GasSeparation &
Stabilizer
SolventDeasphalting
Coking
Visbreaking
FluidizedCatalyticCracking
Hydro-cracking
NaphthaReforming
Isom-erization
Sat GasPlant
Polymer-ization
Alkylation
NaphthaHydro-treating
Treating &
Blending
Coke
Fuel Gas
LPG
AviationGasoline
AutomotiveGasoline
Solvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
ResidualFuel Oils
Lubricant
Greases
Waxes
Asphalts
HeavyNaphtha
Kerosene
Distillate
AGO
LVGO
HVGO
VacuumResiduum
CatDistillates
Gas OilHydro-treating
DAO
Isomerate
Gas
AlkylFeed
Alkylate
PolymerizationNaphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel OilBottoms
Distillates
Distillate
Hydro-treating
CatNaphtha
Cycle Oils
SDABottoms
CokerNaphtha
Heavy
CokerGasOil
Light CokerGas Oil
SulfurPlant
Sulfur
Naphtha
Fuel Oil
SolventDewaxing
Lube Oil
Waxes
2
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Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions
Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number
3
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Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions
Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number
4
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CrudeOilasRefineryFeedstock
CrudeOil
Complexmixtureofhydrocarbons&heterocompounds
Dissolvedgasestononvolatiles(1000F+boilingmaterial)
C1toC90+
Compositionsurprisinglyuniform
5
Element Wt%
Carbon 8487
Hydrogen 1114
Sulfur 0
5
Nitrogen 00.2
Otherelements 00.1
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PrimaryHydrocarbonMolecularTypes
Paraffins
Carbonatomsinterconnectedbysinglebond
Otherbondssaturatedwithhydrogen
Naphthenes
Ringedparaffins (cycloparaffins)
Allotherbondssaturatedwithhydrogen
Aromatics
Sixcarbon
ring
(multiple
bonding)
Bondsinring(s)areunsaturated
Olefins
Usuallynotincrudeoil
Formed
during
processing
Atleasttwocarbonatomsinterconnectedby(unsaturated)doublebond
6
DrawingsfromNISTChemistryWebBook
http://webbook.nist.gov/chemistry/
nHexane iHexane
Cyclohexane Methylcyclopentane Decalin
Benzene Naphthalene
1Hexene cis3Hexene trans3Hexene
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ExampleHeterocompounds
7
Composition&AnalysisofHeavyPetroleumFractions
K.H.Altgelt &M.M.Boduszynski
MarcelDekker,Inc.,1994,pg.16
ModelingandSimulationofCatalyticReactorsforPetroleumRefining.
byJorgeAncheyta,JohnWiley&Sons,2011
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DistributionofCompounds
8
Carbon Paraffin
No. C F Isomers
5 36 97 3 Gasoline
8 126 259 18
10 174 345 75
12 216 421 355
15 271 520 4347 Diesel & jet fuels, middle distillates
20 344 651 3.66E+05 Vacuum gas oil
25 402 756 3.67E+07 Atmospheric residue
30 449 840 4.11E+09
35 489 912 4.93E+1140 522 972 6.24E+13
45 550 1022 8.22E+15
60 615 1139 2.21E+22 Vacuum residue
80 672 1242 1.06E+31
100 708 1306 5.92E+39 Nondistillable residue
Boiling Point
Examples
Composition&AnalysisofHeavyPetroleumFractions
K.H.Altgelt &M.M.Boduszynski
MarcelDekker,Inc.,1994,pp.23&45
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CrudeOilAssay
Indicatesdistributionquantity&qualityofcrudeoilfeedstock
Definitionsbaseduponboilingpointtemperatureranges
Representsexpectedproductsfromcrude&vacuumdistillation
Completenessofdatadependsuponsource
Publicreportvs.inhouseanalyticallaboratory
Qualitymeasures
Specific/API
gravity
Sulfurcontent
Octanenumber
Cetanenumber
Viscosity
Carbonresidue
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0
10
20
30
40
50
60
70
80
90
100
Total Continuum Fractions
Barrels
Ethane & Lighter
Propane
Butanes
Pentanes
Light Naphtha
Heavy Naphtha
Distillate
AGO
LVGO
HVGO
Vacuum Resid
12
97.8F
180F
350F
400F
650F
1050F
850F
Temperaturesdefinethe
boundariesbetween fractions
Mixedproperty
values
for
the
entirefraction
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CrudeOilsAreNotCreatedEqual
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CrudeOilProperties
Distillationanalysis/Boilingpointrange
Amountcollectedfrombatchdistillationattheindicatedtemperature
Standardizedtests ASTMD86,D1160,
Mostuseful
is
TBP
(True
Boiling
Point)
Specificgravity,o ratioliquiddensity@60F&1atm tothatofwater@60F&1atm
Airsaturated: 8.32828lb/gal
PureWater: 999.017kg/m=8.33720lb/gal
APIgravity.
Higher
density
lowerAPI
Watsoncharacterizationfactor.12 13(paraffinic)to10(aromatic)
14
3
inunitsofRb
TK T
W bo
141.5 141.5API 131.5
131.5 APIo
o
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CrudeOilProperties
Sulfur,nitrogen,&metalscontent
Sulfur
Sourvs.sweet ~0.5wt%cutoff
Restrictionsonsulfurinfinalproducts
Nitrogen
Canpoisoncatalysts
Usuallytolerateupto0.25wt%
Nickel,vanadium,copper
Canpoisoncatalysts
Tendtobeinthelargest
molecules/highestboilingfractions
Propertiesappropriateforcertainboilingpointranges
Octanenumber
Cetanenumber
Viscosities
Carbonresidue
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DistillationAnalysisTypes
TrueBoilingPoint(TBP) ASTMD2892
14to18theoreticalstages
Nearinfinitereflux(5:1refluxratiomin)
Nohotterthan650Ftominimizecracking
Maxvaportemperature410F
Pressurelevels
760mmHg(1atm)
100mmHg
2mmHg(min)
16
ASTMD289213,StandardTestMethodfor DistillationofCrudePetroleum
(15TheoreticalPlateColumn)
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DistillationAnalysisTypes
ASTMD86
Lowresolution nopacking,
refluxfromheatlosses
1atm;
no
hotter
than
650F
minimizecracking
CorrelationstocorrecttoTBPbasis
17
http://www.koehlerinstrument.com/products/K45601.html
0
100
200
300
400
500
600
0 100 200 300 400 500
D86Temperature[F]
TBPTemperature[F]
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DistillationAnalysisTypes
ASTMD1160
Usedonresids (650F+)
Relativelylowresolution
Vacuumconditions 10
to40mmHg;nohotter
than1000FAEBP
Correlationstocorrectto
atmosphericpressure&
TBPbasis
18
http://www.lazarsci.com/d1160.htm
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DistillationAnalysisTypes
ShortPathDistillation
Singlestageflash
Extremelylowpressures
0.1mmHg
or
less
Characterizedeepcutresids
19
http://www.chemtechservicesinc.com/shortpathdistillation.html
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DistillationAnalysisTypes
SimulatedDistillation ASTM2887
Relativelylowresolutiongaschromatography
Severalthousandtheoreticalstages
EssentiallyTBPtemperatures wt%basis
Temperaturesinferredfromelutiontimes
Calibratedwithnparaffinmixture
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CrudeOilAssay Hibernia(fromChevronsite)
21
http://crudemarketing.chevron.com/crude/north_american/hibernia.aspx
Whole Light Medium Heavy Kero Atm Light Heavy Vacuum Atm
Crude Naphtha Naphtha Naphtha Gas Oil VGO VGO Resid Resid
TBP Temp At Start, C Start 10 80 150 200 260 340 450 570 340
TBP Temp At End, C End 80 150 200 260 340 450 570 End End
TBP Temp At Start, F Start 55 175 300 400 500 650 850 1050 650
TBP Temp At End, F End 175 300 400 500 650 850 1050 End End
Yield at Start, vol% 2.3 8.0 20.8 30.0 39.5 54.0 73.2 85.8 54.0
Yield at End, vol% 8.0 20.8 30.0 39.5 54.0 73.2 85.8 100.0 100.0
Yield of Cut (wt% of Crude) 4.4 11.5 8.5 9.1 14.6 20.0 13.7 16.7 50.4
Yield of Cut (vol% of Crude) 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
Mercaptan Sulfur, ppm 0 0 0 1
Nitrogen, ppm 1384 0 0 0 1 56 579 2050 5860 2729
Hydrogen, wt% 16.2 13.9 14.2 13.7 13.2 12.9 12.5
Viscosity @ 40 C (104 F), cSt 6.73 0.48 0.67 1.04 1.72 4.10 19.04 3.05E+02 4.E+05 2.89E+02
Viscosity @ 50 C (122 F), cSt 5.17 0.45 0.61 0.92 1.48 3.33 13.42 1.64E+02 1.E+05 1.62E+02
Viscosity @ 100 C (212 F), cSt 1.93 0.34 0.43 0.58 0.83 1.49 3.92 1.97E+01 1.E+03 2.16E+01
Viscosity @ 135 C (275 F), cSt 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 7 -128 -101 -71 -42 -7 26 48 35 36
Pour Point, F 44 -198 -151 -96 -43 20 79 119 95 96
Smoke Point, mm (ASTM) 7 35 32 27 22 17 11 5 2 4
Aniline Point, C 77 71 53 55 61 70 84 95 106 94Aniline Point, F 171 160 127 131 142 159 183 204 222 201
Total Acid Number, mg KOH/g 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Cetane Index, ASTM D4737 40 47 56
Diesel Index 57 131 70 62 57 54 50 41 22 39
Characterization Factor (K Factor) 12.0 12.6 11.7 11.8 11.8 11.8 12.0 12.0 12.1 12.0
Research Octane Number, Clear 71.8 64.1 37.3
Motor Octane Number, Clear 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
Thiophenes, vol%
Molecular Weight 244 102 115 144 175 226 319 463 848 425
Gross Heating Value, MM BTU/bbl 5.88 4.84 5.37 5.55 5.72 5.87 6.04 6.23 6.50 6.24
Gross Heating Value, kcal/kg 10894 11589 11212 11121 11009 10896 10765 10595 10310 10582
Gross Heating Value, MJ/kg 45.6 48.5 46.9 46.5 46.1 45.6 45.0 44.3 43.1 44.3
Heptane Asphaltenes, wt% 0.1 0.6 0.2
Micro Carbon Residue, wt% 2.6 14.8 5.2
Ramsbottom Carbon, wt% 2.3 13.2 4.6
Vanadium, ppm 1 5 2
Nickel, ppm 1 4 1
Iron, ppm 1 3 1
Simpleanalysis
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CrudeOilAssay Hibernia(fromExxonMobilsite)
22
HIBER11Z Whole
crude
200to
1499
Butane
and
Lighter
200to60
Lt.
Naphtha
C5 165F
60to165
Hvy
Naphtha
165
330F165
to330
Kerosene
330
480F330
to480
Diesel
480
650F480
to650
Vacuum
GasOil
650
1000F
650to
1000
Vacuum
Residue
1000F+
1000to
1499
Cutvolume,% 100 1.51 5.68 14.83 14.76 17.03 28.89 17.29
APIGravity, 33.9 121.42 81.02 54.91 43.1 34.04 24.71 12.65
SpecificGravity(60/60F), 0 .8 55 5 0 .5 59 5 0 .6 65 8 0 .7 59 1 0 .8 10 4 0 .8 54 8 0 .9 05 8 0 .9 81 6
Carbon,wt% 82.43 83.95 85.88 86.21 86.51 86.39
Hydrogen,wt% 17.57 16.05 14.12 13.77 13.23 12.81
Pourpoint,F 37 62 17 103 103
Neutralizationnumber(TAN),MG/GM 0.095 0.054 0.116 0.212
Sulfur,wt% 0.54 0.0011 0.0213 0.2431 0.6814 1.4428
Viscosityat20C/68F,cSt 12.49 0.35 0.41 0.75 1.79 6.88 120.83 472934.04Viscosityat40C/104F,cSt 6.21 0.3 0.35 0.62 1.31 3.96 40.48 34316.32
Viscosityat50C/122F,cSt 4.7 0.28 0.32 0.56 1.15 3.16 26.22 11920.94
Mercaptansulfur,ppm 1 1.5 2.1
Nitrogen,ppm 1350 0 0 0 0.2 88.5 1196.1 4868
CCR,wt% 2.45 0 0.26 11.9
NHeptaneInsolubles(C7Asphaltenes),wt% 0.3
Nickel,ppm 1.3 0 0 6.5
Vanadium,ppm 0.7 0 0 3.5
Calcium,ppm 0.5
ReidVaporPressure(RVP)WholeCrude,psi 3.4
HeatofCombustion(Gross),BTU/lb 19429
HeatofCombustion(Net),BTU/lb 18222 19288 18852 18626 18567
HydrogenSulfide(dissolved),ppm 0
Saltcontent,ptb 0.1
Paraffins,vol% 100 84.28 51.64 47.08 41.83 26.36Naphthenes,vol% 0 14.13 31.88 32.71 34.07 37.12
Aromatics(FIA),vol% 16.48 16.9
Distillationtype,D 1160 86 86 86 86 86 1160 1160
ASTMIBP,F 17.9 127.8 95.9 208.1 363.8 506 690.6 1038.8
5vol%,F 135.3 94.6 101.4 213.7 368.2 510.8 695.2 1043.4
10vol%,F 201.5 52.1 106 216.6 370.4 512.9 706.3 1055.3
20vol%,F 306.9 10.5 110.9 223.6 375.5 518.9 728.3 1081.3
30vol%,F 403.1 29.8 114.6 231.7 381.8 526.3 752.6 1111.3
40vol%,F 497.7 35.9 117.1 240.8 389.1 535.3 778.5 1145.4
50vol%,F 597 35.8 121.9 249.1 396.4 543.8 806.4 1183.7
60vol%,F 705 38.8 129 258.8 405.1 553.8 835.7 1228.7
70vol%,F 806.7 43.7 134.1 269 414 564.5 865.7 1277.3
80vol%,F 925.9 47.3 139.3 279.9 423.8 576 897.7 1330.3
90vol%,F 1082.4 46.1 141.8 291.1 4 34 587.8 929 1385.2
95vol%,F 1213.2 46.1 144.4 297.4 439.8 594.4 947.8 1419.1ASTMEP,F 1401.5 47.2 147 302.5 444.5 605 969.7 1458
Freezepoint,F 48.2 29
Smokepoint,mm 21.3
Naphthalenes(D1840),vol% 4.4
Viscosityat100C/212F,cSt 1.81 0.21 0.23 0.38 0.69 1.44 5.97 316.71
Viscosityat150C/302F,cSt 1.03 0.17 0.18 0.28 0.47 0.88 2.58 42.23
CetaneIndex1990(D4737), 33.1 152.4 44.1 29.4 43.8 54.1 56.9 45.5
Cloudpoint,F 54 24
Anilinept,F 138.2 161.3 191.7
http://www.exxonmobil.com/crudeoil/about_crudes_hibernia.aspx
Simpleanalysis
&comparison
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CrudeOilAssay Bakken vs.otherlightcrudes
23
Property Bakken WTI
APIGravity 41 39
Sulfur,wt% 0.2 0.32
DistillationYield,volume%
LtEnds C1C4 3.5 3.4
Naphtha C5360F 36.3 32.1
Kerosene 360500F 14.7 13.8
Diesel 500650F 14.3 14.1
VacuumGasOil 6501050F 26.1 27.1
VacuumResidue 1050+F 5.2 9.4
BottomsQuality VacuumResid1050+F
Yield,Vol.% 5.2 9.4
APIGravity 14 11.4Sulfur,Wt.% 0.75 1.09
Vanadium,ppm 2 87
Nickel,ppm 7 41
Concarbon,Wt.% 11.3 18.2
http://www.turnermason.com/Publications/petroleum
publications_assets/BakkenCrude.pdf
Hill,D.,et.al.
NorthDakota
Refining
Capacity
Study,
Final
Technical
Report
DOEAwardNo.DEFE0000516,January5,2011
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CrudeOilAssay EagleFordvs.otherlightcrudes
24
METHODOLOGYANDSPECIFICATIONSGUIDE
TheEagleFordMarker:Rationaleandmethodology
Platts,McGrawHillFinancial
October2012
https://www.platts.com/IM.Platts.Content/MethodologyReferences/
MethodologySpecs/eaglefordmarker.pdf
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Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions
Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number
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PetroleumProducts
Therearespecificationsforover2,000individualrefineryproducts
Tookafullcenturytodevelopmarkets
for
all
fractions
of
crude
oil
Intermediatefeedstocks canberoutedtovariousunitstoproduce
differentblendstocks
Dependsuponthelocaleconomics&
contractuallimitations
26
Ref:Unknownorigin. PossiblySoconyVacuumOilCompany,Inc.(1943)
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PetroleumProducts
RefineryFuelGas(StillGas)
LiquefiedPetroleumGas(LPG)
Ethane&EthaneRichStreams
Propanes
Butanes
Gasoline
Naphtha
MiddleDistillates
Kerosene
JetFuel
Diesel,HomeHeating,&FuelOil
GasOil&TownGas
Lubricants
Wax
Asphalt&RoadOil
PetroleumCoke
Petrochemicals
Sulfur
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SourcesofProductSpecifications
State&Federalregulatoryagencies
Environmentallaws
Reflectneedtoreducepollutionin
manufacturing&useoffuels
ASTM(AmericanSocietyforTestingandMaterials)Specifications&associatedtest
procedures
Specifications
drafted
considering
positions
ofindustry®ulatoryagencies
Industryassociations
AmericanPetroleumInstitute
GasProcessorsAssociation
AsphaltInstitute
Betweencompanies basedontypicalspecs
Negotiated
Deviationshavepredeterminedprice
adjustments
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CharacteristicsofPetroleumProducts
30
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
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FuelGasSpecifications
31
Parameter Specification
TemperatureRange 40Fto120F
Pressure 500to
1,000
psig
GrossHeatingValue 950 1050BTU/scf
HydrocarbonDewPoint1 10F 20F
Water 4or7lbs/millionscf
TotalSulfur 5
to
20
grains/100
scf
HydrogenSulfideH2S 4to16ppmv
Mercaptans 1to5grains/100scf
TotalNitrogen&CO2 4mol%
CO2(alsoTotal
N2+
CO2) 2
to
3mol%
Oxygen 0.1to0.4mole%
1Atpipelinepressure
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LiquefiedPetroleumGas(LPG)
32
Commercial
Propane
Commercial
Butane ASTMTest
C3
&
C3= C4
&
C4= D1267
02
VaporPressure@100F 208 70 D126702
95vol%@maxF 37F +36F D183764
C4+max 2.5% D216377
C5+max 2.0% D216377
VaporpressurespecisactuallyanapproximateguidelinefordefiningthelightendscontentoftheLPGmixture.
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NaturalGasolineSpecifications
33
Characteristic GPASpecifications ASTMTest
ReidVaporPressure 10to34psig D323
Evaporationat140F 25to85% D216
Evaporationat275F >90% D216
EndPoint D216
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MotorGasolineSpecifications
35
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MotorGasolineVolatilityClasses(ASTMD481413)
36
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OtherGasolineConsiderations
Reformulatedgasoline(RFG)blendedtoburncleanerbyreducingsmogformingandtoxicpollutants
CleanAirActrequiresRFGusedincitieswiththeworstsmogpollution
CleanAirActrequiredRFGtocontain2wt%oxygen
MTBEðanolwerethetwomostcommonlyusedsubstances
MTBElegislatedoutofusebecauseofhealthconcerns
Oxygenatecontentregulationsuperceeded bytheRenewableFuelStandard
RBOB ReformulatedBlendstock forOxygenateBlending
LowerRVPtoaccountfor1.5psiincreasedueto10vol%ethanol
Benzenecontent
Conventionalgasolinecouldhave1.0vol%benzene(max)pre2011
NewregulationsJan1,2011reducedbenzeneinall USgasolineto0.62vol%
HadbeenproposedbyEPAunderMobileSourcesAirToxics(MSAT)Phase2
Creditsystemforrefinersthatcouldnotmeetthe0.62%limit
Sulfurcontent
EPAcallingforultralowsulfurgasolineby2017 fromaverageof30ppm to10ppm
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WhatareOctaneNumbers?
References:
nheptane0
isooctane100(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
38
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WhatisReidVaporPressure(RVP)?
Specifictesttomeasurevolatilityat100F(37.8C)
Pressureat100Fwhenliquidisincontactwithairatavolumeratioof1:4
Relatedtothetruevaporpressure
Similarto
vapor
formation
in
an
automobiles
gasoline
tank
Usuallyjustreportedaspsi
Actuallygaugepressuremeasured subtractoffthecontributionoftheatmosphericpressure
Relativelyeasytomeasure
Directpressure
measurement
instead
of
observation
of
bubble
formation
ProcedurescontrolledbyASTMstandards(ASTMD323)
A:Lowvolatility(RVPlessthan26psi/180kPa)
B:Lowvolatility horizontalbath
C:High
volatility
(RVP
greater
than
26
psi
/180
kPa)
D:Aviationgasoline(RVPapproximately7psi/50kPa)
39
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WhatarealternateRVPliketests?
ASTMD5191StandardTestMethodforVaporPressureofPetroleumProducts(MiniMethod)
Expandliquidfrom32oFto5timesitsvolume(4:1volumeratio)at100oFwithoutadditionofair
ReferredtoastheDVPE(DryVaporPressureEquivalent)&calculatedfrommeasuredpressurevalue:
DVPE[psi]=0.965(MeasuredVaporPressure[psi]) 0.548[psi]
ASTMD6378StandardTestMethodforDeterminationofVaporPressure(VPX)ofPetroleumProducts,Hydrocarbons,andHydrocarbonOxygenateMixtures(Triple
ExpansionMethod))
Expandliquidtothreedifferentvolumeratios
Nochillingofinitialsample sampleofknownvolumeintroducedtochamberat20oC(76oF)or
higher
Threeexpansionsatacontrolledtemperature 100oFequivalenttoASTMD5190
Allowsfortheremovalofthepartialpressureeffectsfromdissolvedair
RVPE(ReidVaporPressureEquivalent)calculatedfromcorrelationtomeasuredpressureminus
dissolvedaireffects
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MiddleDistillates
Generalclassifications
Kerosene
Jetfuel
Distillatefueloil
Diesel
Heatingoil
Properties
Flashpoint
Cloudpoint/Pourpoint
Anilinepoint
Cetane number
Viscosity
Water&sediment
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DieselCetaneNumber
Onekeytodieselquality
Measurestheabilityforautoignition
Essentiallytheoppositeofoctanenumber
Maybe
measured
but
frequently
approximated
ASTMD976 StandardTestMethodsforCalculatedCetaneIndexofDistillateFuels
ASTMD4737 StandardTestMethodforCalculatedCetaneIndexbyFourVariableEquation
Trends
Cetanenumber
had
declined
since
the
middle
1970s
Highdemand
Heaviercrudeswithnarrowdieselcuts
Blendingoflowercetane fractions
Trend
starting
to
reverse
Morestringentemissionsrequirementsnecessitatehighercetane numbers
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WhatisFlashPoint?
Thelowesttemperaturecorrectedtoapressureof101.3kPa(760mmHg)at
whichapplicationofanignitionsourcecausesthevaporsofaspecimenofthe
sampletoigniteunderspecifiedconditions
Procedure
strictly
controlled
by
ASTM
standards
D56TagClosedTester
D92ClevelandOpenCup
D93PenskyMartensClosedCupTester
D1310
Tag
Open
Cup
Apparatus4
D3143 CutbackAsphaltwithTagOpenCupApparatus
D3278ClosedCupApparatus
D3828 SmallScaleClosedTester
D3941
Equilibrium
Method
with
Closed
Cup
Apparatus
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OSHAFlammableLiquidDefinitions
44
Category FlashPoint
C(F)
BoilingPoint
C(F) Class
FlashPoint
C(F)
BoilingPoint
C(F)
Flammable1
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AdditionalSpecifications
Sulfur
Controlofsulfuroxidesuponcombustion
Threelevels,reductionforthetraditionalfivecategories
AnilinePoint
Minimumtemperatureatwhichequalvolumesofaniline(C6H5NH2)andtheoilare
miscible
Thelowertheanilinepoint thegreaterthearomaticcontent
Viscosity
Fluidityduringstorageatlowertemperatures
Sediment&watercontent
Controllingcontamination
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KeroseneSpecifications
47
Parameter Specification ASTMTestMethod
FlashPoint 100F ASTMD56
10%distilled,max 401F ASTMD86
FinalBoilingPoint 572F ASTMD86
No.1sulfur,max 0.04% ASTMD1266
No.2sulfur,max 0.30% ASTMD1266
Burnquality pass ASTMD187
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JetFuelSpecifications
48
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StationaryTurbineFuel&DieselClasses
49
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
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DieselSpecifications
50
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DieselSulfurContent
Sulfurlevelsdroppingbecauseofairqualityregulations
Since1993dieselfuelformulatedwith85%lesssulfur
LowSulfurDieselhadbeen500ppm sulfur
ULSD15
ppm &
required
for
on
road
usage
since
January
2007
Worldwide,sulfurspecscontinuingtodropto
meetU.S.&European
standards
51
Globalstatusofmaximumallowablesulfurindieselfuel, partspermillion(June2012)
SaudiArabiasplanfornearzerosulfurfuels,HydrocarbonProcessing,March2013
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DistillateFuelOil
Onlygrades1and2havea(max)boilingrangespecs
No.1FuelOil similartokerosene(minorproduct)
No.2FuelOil domesticheatingoil
Similartomediumqualitydiesel2D
Madeinthewinterseasoninrefinerieswhenautomotivefueldemandislower.
No.3FuelOil nolongerproducedsince1948
Intendedtobealowerqualityspaceheatingoil
Little
price
difference
between
No.
2&
3marketdisappeared
No.4FuelOil intendedforuseinindustrialburnerinstallationswithnopreheatfacility
Sometimesamixtureofdistillate&residualmaterial
Lowerviscosityheatingoil
52
http://www.eia.gov/energyexplained/index.cfm?page=heating_oil_use
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ResidualFuelOils(cont.)
No.5FuelOil premiumresidualfueloilofmediumviscosity
Atonetimeusedinthesteelindustrybutnowrarelyused
No.6FuelOil heavyresidualfueloil
Vacuum
resid &
cutter
stock
mix
(to
decrease
viscosity)
Commonuse
Boilersforsteamturbinesofstationarypowerplants
Marineboilers variationofBunkerC
Industrial
&
commercial
applications Markethasbeendeclininginlast20years
Morepowerplantsusecoalornaturalgas
Shipsusedieselformarinedieselsorgasturbines
Environmentalreductionsinsulfurlevels
Leastvaluedofallrefineryproducts
Historicallyonlyliquidproductworthlessthanrawcrude
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ASTMFuelOilSpecs
54
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ComparisonKerosene/Jet/Diesel/HeatingOil
55
Property No.2Ke rose ne Je tA JetB No.2DS15 No.2DS500 No.2HOS500
CetaneNumber min 40 40
Aromatics [vol%] max 25 25 35 35
Sulfur [wt%] max 0.3 0.3 0.3 0.0015 0.05 0.05FlashPoint [C] 38 52 52 38
Distillation(D86)
T10 [C] max 205 205
T20 [C] max 145
T50 [C] max 190
T90 [C] min 282 282 282
[C] max 245 338 338 338
EP [C] max 300 300
DistillationResidue [vol%] max
DistillationLoss [vol%] max
FreezingPoint [C] max 40 50
PourPoint [C] max 6
CarbonResidue [wt%] 0.35 0.35 0.35
KinematicViscosity
@40C mm/s min 1.9 1.9 1.9
mm/s max 4.1 4.1 4.1
ASTMSpecificationsforMiddleDistillates
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ComparisonofBoilingRanges
56
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GasOil&TownGas
Historicalusage
Gasoilsusedtomaketowngasforillumination
Decomposedoveraheatedcheckerwork
Composedof
carbon
monoxide
and
carbon
dioxide
o Lowheatingvalue
o Burnedcleanly
o Easilydistributedforilluminationfuel
Displacedkerosene
in
the
cities
electricity
ultimately
eliminated
its
use
Gasoilnolongeraconsumerproduct
Tradedbetweenrefineries
Feedstockforcatalyticcracking&hydrocracking
57
L b i T i l
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LubricantTerminology
58
Phrase Meaning
Lubebasestock Lubeproductthatmeetsallspecifications
&issuitableforblending
Lubeslate Setoflubebasestocks,usually3to5
Neutrallubes Obtainedfromasidecutofthevacuum
distillationtower
Brightstocklubes Processedofvacuumresidfromthe
vacuumtowerbottoms
L b i t
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Lubricants
TerminologybasedsolelyontheViscosityIndex independentofthecrudesourceortypeofprocessing
Paraffiniclubricantsareallgrades,bothbrightstock&neutral,withafinishedviscosity
Indexmorethan75
NaphtheniclubricantsareallgradeswithaviscosityIndexlessthan75
Importantproperties
Kinematicviscosity(viscositydividedbymassdensity)
Color Pourpointforcoldweatheroperation
Flashpoint
Volatilityforreducedevaporation
Oxidationstability
Thermalstability
59
SAE Vi it S ifi ti
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SAEViscositySpecifications
Kinematicviscositymeasuredincentistokes
butspecificationsare
labeledinSaybolt
Seconds(SUS)
Specificationsareestablishedbythe
SocietyofAutomotive
Engineers
SAEviscositywellknown
motoroilspecification
(e.g.,10W30)
60
Grade MaxViscosity
(SUS)@0FMaxViscosity
(SUS)@210FMinViscosity
(SUS)@210F
5W 6,000
10W 12,000
20W 48,000
20 58 45
30 70 58
40 86 70
50 110 85
Asphalt
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Asphalt
Importantproductintheconstructionindustry
Comprise20%oftheOtherProductscategory
Asphaltcanonlybemadefromcrudescontainingasphaltenicmaterial
Numerousdetailed
specifications
on
the
many
asphalt
products
AsphaltInstitute,LexingtonKentucky
Industrytradegroupforasphaltproducers&affiliatedbusinesses
AmericanAssociationofStateHighwayandTransportationOfficials
SponsorstheAASHTOMaterialsReferenceLaboratory(AMRL)attheNationalInstitute
ofStandardsandTechnology(NIST)
AmericanSocietyofTestingandMaterials(ASTM)
62
Petroleum Coke
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PetroleumCoke
63
GreenCoke CalcinedCoke
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%
Sulfur Specifications
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SulfurSpecifications
64
Purity 99.8weight%sulfur,basedondryanalysis
Ash 500ppmwmaximum
Carbon 1,000ppm(weight)maximum
Color
"Brightyellow"whensolidified.
Sulfurrecoveredbyliquidreductionoxidationprocesseshave
colordue
to
metals
some
purchasers
will
include
a
requirementexcludingsulphurrecoveredfromthese
processes
H2S 10ppmwmax(Importantforinternationaltransport&sales)
State Shippedaseitherliquidorsolid.Internationaltransport
specifiessolid.
Topics
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Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions
Productsas
defined
by
their
properties
&
specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number
65
Supplemental Slides
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SupplementalSlides
Examplecrudeoilassay(withminimaldata)
Examplegasoline&gasolineblendstockanalyses
ASTMD323RVPProcedures
ASTMD
56
Flash
Point
by
Tag
Closed
Tester
Flash
Calculations
Linear&nonlinearblendingrules
Blendingrulesbasedonadditiveweight&additivevolumes
Blendingindices
Assaysoncommonbasis
Cumulativeyieldvs boilingpointtemperature
Fractionss averageyieldvs measuredproperty
Propertyestimation
formulas
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SAE 902098 Gasoline Blend Stock Analyses
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SAE902098GasolineBlendStockAnalyses
69
Light Cat
Blending Cat Cracked Cat Cracked Cracked Light Heavy Full Range Light St C6 Light Mid Cut Heavy
Component Naptha #1 Naptha #2 Naptha Alkylate Alkylate Reformate Run Naptha Isomerate Reformate Reformate 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% 35.2 35.9 17.6 0.5 1.0 61.1 2.2 1.6 4.8 94.2 93.8
Olefins, vol% 32.6 25.4 44.9 0.2 0.9 1.0 0.9 0.1 1.5 0.6 1.9
Saturates, vol% 32.2 38.8 37.4 99.3 98.1 37.9 96.9 98.3 93.7 5.1 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 110 112 95 101 299 117 91 118 138 224 313
T05 143 142 117 144 318 168 106 131 169 231 326
T10 158 155 124 162 325 192 113 134 174 231 328
T20 174 171 130 181 332 224 117 135 179 231 331
T30 192 189 139 196 340 244 121 135 182 232 335
T40 215 212 149 205 345 258 126 136 185 233 339
T50 241 239 164 211 354 270 132 136 188 234 344
T60 270 269 181 215 362 280 139 137 190 235 350
T70 301 302 200 219 373 291 149 137 192 237 358
T80 336 337 224 225 391 304 163 138 194 240 370
T90 376 379 257 239 427 322 184 139 195 251 391
EP 431 434 337 315 517 393 258 146 218 316 485
RON 93.2 92.6 93.6 93.2 65.9 97.3 63.7 78.6 57.6 109.3 104.3
MON 81.0 82.1 79.4 91.2 74.5 86.7 61.2 80.5 58.5 100.4 92.4
(R+M)/2 87.1 87.4 86.5 92.2 70.2 92.0 62.4 79.5 58.0 104.9 98.4
Carbon, wt% 86.94 85.88 85.60 84.00 84.39 88.11 83.58 83.44 84.41 90.87 89.62Hydrogen, wt% 13.00 13.56 14.20 16.09 15.54 11.60 16.29 16.49 15.54 9.32 10.34
Nitrogen, ppmw 46 37 27 0 0 0 0 0 0 0 0
Sulfur, ppmw 321 522 0 15 15 9 325 10 7 10 8
Heating Value,
BTU/lb (net) 17300 17300 18700 18400 18100 16800 18400 18500 18200 15500 17300
Table 7 Analyses of Blending Components
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ASTMD323RVPProcedures
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ProcedureA(AtmosphericallyStableLiquids)
ProcedureC(VolatileLiquids)
71
Apparatus Liquid&vaporchambers. Vaporchamber4.0 0.2 timessizeofliquidchamber
LiquidPreparation 1Lsamplecontainerfilled7080%withtestliquidsample.Samplecontainercooledinacold
bathat01C(3234F).Samplecontaineropened,allowingairtoentercontainer.Containershakenvigorously(tosaturatetheliquidwithair)&returnedtocoldbath.
LiquidTransfer Theliquidchambercooledinthesamecoldbath.Coldliquidsampletransferredtothecold
liquidchamber,entirelyfillingliquidchamber.
AirPreparation Vaporchamberfullofairisplacedinahotbathat37.8 0.1C(100 0.2F).
Assembly Vaporchamberremovedfromhotbath&coupledtoliquidchamber. Thecoupledapparatus
isinverted,shaken,&putintohotbath.
PressureMeasurement Apparatusshouldremaininhotbathforatleast5minutesbeforetheapparatusisremoved
frombath,shaken,&returnedtohotbath.Shakingprocedureshouldberepeatedatleast5
timeswith
no
less
than
2minutes
in
between.
Shaking
procedure
should
be
repeated
until
2
consecutivepressurereadingsindicateequilibriumhasoccurred.Pressuremeasuredasgauge
butreportedwithreferencetogaugeorabsolute.
LiquidPreparation Samplecontainerofabout0.5Lcapacitycooledinacoldbathat04.5C(3240F). Thissamplecontainerisnotopened&contactedwithair.
LiquidTransfer Liquidchamberiscooledinthesamecoldbath. Coldliquidsampletransferredtothecold
liquidchamber,similartoProcedureA. However,sincethisliquidisunderpressure,extra
caremustbetakentoensurethatgasisnotflashedoffandlostandthattheliquidchamberis
actuallycompletelyfilledwiththeliquid.
ASTMD56FlashPointbyTagClosedTesterFlashPointsBelow60C(140F)
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( )
Apparatus TagCloseTester testcup,lidwithignitionsource,&liquidbath.
Preparation Transfersshouldnotbemadeunlesssampleisatleast10C(18F)belowtheexpectedflashpoint.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
ignitionsource
into
vapor
space
of
cup
&
immediately
up
again.
Full
operation
should
be1secwithequaltimeforintroduction&return.
3.Adjustheatsotemperaturerise1C(2F)/min 6s.Whentemperatureofspecimeninis5C(10F)belowitsexpectedflashpoint,applytheignitionsource.Repeatapplicationofignitionsourceaftereach0.5C(1F)riseintemperatureofthespecimen.
72
LinearBlendingRules
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Valuesforindividualblendstocksaveragedeitherwithvolumefractionsormassfractions
Somepropertiesblendbestwithmolefractions,butmolaramountsnottypicallyknown
Units
on
the
quality
measure
may
give
an
indication
as
to
volume
or
mass
blending.
Volumeblending
Specificgravity(essentiallymassperunitvolume)
Aromaticscontent(vol%)
Olefinscontent(vol%)
Massblending:
Sulfurcontent(wt%orppm)
Nitrogen
content
(wt%
or
ppm)Nickel&vanadium(ppm)
73
mix i i
i i
i
X v X
V XV
X w Xmix i i
v Xm Xi oi i i i
m vi i oi
HowDoWeBlendSpecificGravities?
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Assumeidealliquidmixing volumesareadditive
Shrinkagecorrelationsavailable,mostlyusedforcustodytransfer
Specificgravities/densitiesatfixedconditionsblendlinearlywithvolume
Mass&volumesareadditive
Canalsoblendwithmass&molaramounts
Volumesare
additive
Densityadjustments
Correctionsneededfortemperature&pressureeffects
74
, ,
, ,
i o i i o i
o mix i o i
i
V Vv
V V
, , , ,
1i i i
o mix o i o mix o i
w x MM
HowDoWeBlendAPIGravities?
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Specificgravityisblended&APIgravityisbackcalculated.
MayhavetocalculateindividualspecificgravitiesfromgivenAPIgravities
Example
Incorrectvalue
from
direct
volume
blending
of
API
gravities
75
TemperatureCorrectionstoSpecificGravity
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ODonnel (Chevron)method
APIVolume
Correction
Tables
Different60valuesdependingoncommoditytype
ATables CrudeOils
BTables RefinedProducts
DTables Lubricants
CTables Individual&SpecialApplications
76
2 2 0.000601 60T o F
T
60 60exp 60 1 0.8 60T o F F T T
StandardConditions(Temperature&Pressure)
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Standardconditionsmayvarybetweencountries,stateswithintheUS,&betweendifferentorganizations
Standardtemperature 60F
Mostothercountriesuse15C(59F)
Russiauses20C(68F)
Standardpressure 1atm (14.696psia)
Othertypicalvaluesare14.73psia (ANSIZ132.1)&14.503psia
Normalconditions
Almostexclusivelyusedwithmetricunits(e.g.,Nm)
IUPAC: 0C&100kPa (32F&14.50psia)
NIST: 0C&1atm (32F&14.696psia)
77
Whatifwewanttoestimatevolumetricshrinkage?
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MethodinChapter12.3ofAPImeasurementmanual
Example: Blend
95,000
bbl of
30.7o
API
(0.8724
specific
gravity)
crude
oil
with
5,000
bbl of
86.5oAPI(0.6491specificgravity)naturalgasoline
Byidealmixing:
Withshrinkage:
78
0.819 2.2884.86 10 100 where 100LL H
H L
VS C C G G C
V V
100,000bbl
0.6491 5000 0.8724 950000.8612
100000
141.5131.5 32.8
mix H L
L L H H
mix
mix
mix
mix
V V V
V V
V
G
0.819 2.2885000 100 5 4.86 10 5 100 5 86.5 30.7 0.09725000 95000
100 100 0.0972100000 99,903bbl
100 100
0.6491 5000 0.8724 950000.8621
99903
141.513
mix H L
L L H H
mixmix
mix
mix
C S
SV V V
V V
V
G 1.5 32.6
HowDoWeBlendYieldCurves?
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AmountsareaddedforthesameTBP
temperatureranges
Onaconsistent
volume,mass,
or
molebasis
Onanincremental
orcumulativebasis
Temperatures
correctedto
1atm
basis
Distillationtype
correctedtoTBP
79
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 250 500 750 1000 1250 1500 1750 2000
Temperature [F]
Incremen
talAmount[vol%
]
0
10
20
30
40
50
60
70
80
90
100
CumulativeAmount[vol%
]
N'Kossa
Ratawi Crude Oil
Cumulative Amount
HowDoWeBlendPropertiesforIndividualFractions?
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Blendbasedonpropertiesandamountsforthefractionineachblendstock,nottheoverallamountofblendstock.
80
HowDoWeCorrectBoilingPointforPressure?
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Equationform
of
Maxwell
Bonnell charts
(1955)
Pvap unitsofmmHg,temperaturesinunitsR
81
10
0.0021843463000.538 6.761560
1.7mmHg43 0.987672
0.001201343 0.0021843462663.129 5.994296log
1817mmHg 1.7mmHg95.76 0.972546
0.0012013432770.085 6.412631
1817mmHg36 0.989679
vap
vap
vap
XX
PX
XXP
PX
XX
X
vapP
10
10.0002867
& 2.5 12 log7601
748.1 0.0002867
vap
B B W
B
PTX T T f K
T
1 760mmHg
659.67Min 1,Max ,0 760mmHg
200
vap
vapB
Pf T
P
PressureCorrectionExample
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Correcta437Fboilingpointmeasuredat40mmHgtothenormalboilingpoint(at760mmHg).
Usingthe2nd of3equationsdetermineX=0.001767618
WithT=896.67oRdetermineTB=1094.98
IfweneglecttheWatsonKfactorcorrection(i.e.,assumeKW=12)thenTB=TB
Normalboilingpointis635oF
82
HowDoWeInterconvertD86&TBPTemperatures?
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Methodfrom
1994
API
Technical
Data
Book
ConsistentwiththeAPI94optioninAspenPlus
83
1.0258
TBP,50% D86,50% TBP,50% D86,50%
TBP D86 TBP D86
0.87180 ( & inF)
( & inF)B
T T T T
T A T T T
Vol% A B
100%to90%* 0.11798 1.6606
90%
to
70% 3.0419 0.7549770%to50% 2.5282 0.82002
50%to30% 3.0305 0.80076
30%to10% 4.9004 0.71644
10%to0%* 7.4012 0.60244
*Reported100%&0%givebettertrendsas99%&1%.
InterconvertD86&TBPTemperatures120
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84
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70
D86 Temperature Difference [ F]
T
T
m
p
a
u
e
D
e
e
F
0 to 10
10 to 30
90 to 100
30 to 50
50 to 70
70 to 90
HowDoWeInterconvertD1160&TBPTemperatures?
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D1160temperaturesat10mmHgareconvertedtoTBPtemperaturesat10mmHg graphicalmethodtointerconvert
D1160temperaturesat50%&higherequaltotheTBPtemperatures
0%to10%,10%to30%,&30%to50%D1160temperaturedifferences convertedtoTBP
temperaturedifferences
85
2 3 4
1160 1160 1160 1160TBP D D D DT a T b T c T d T
Vol%Distilled
Range
a B c d Max T
0%10% 2.23652561 1.39334703E2 3.6358409E5 1.433117E8 144F
10%30%
30%
50%
1.35673984 5.4126509E3 2.9883895E5 6.007274E8 180F
InterconvertD1160&TBPTemperatures225
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86
0
25
50
75
100
125
150
175
200
0 25 50 75 100 125 150 175 200 225
D1160 Temperature Difference [ F]
T
T
m
p
a
u
e
D
e
e
F
Note: ASTM D1160 & TBP 50% distillation
temperatures assumed equal at 10 mmHg
Based on API Figure 3A2.1
Subatmospheric Distillation &
True Boiling Point Distillation
Relationship
0 to 10
10 to 30 & 30 to 50
50 to 70 & 70 to 90
HowDoWeInterconvertD2887&TBPTemperatures?
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Methodfrom
1994
API
Technical
Data
Book
D2887essentiallyTBPonwt%basis,notvol%
87
TBP,50% D2887,50%
TBP D2887 TBP D2887
( & inF)B
T T
T A T T T
Vol% A B
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%to
10% 0.011903 2.0253
10%to0%* 0.15779 1.4296
D86ConversionExample
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Vol% D86 D86 T TBP T TBP
IBP 91 14.3
37 65.210 128 79.5
46 76.1
30 174 155.6
44 62.7
50 218 218.449 61.5
70 267 279.9
63 69.4
90 330 349.3
85 188.7
EP 415 538.0
88
Steps
for
this
example
D86vsTBPTemperatures
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89
0
100
200
300
400
500
600
0 100 200 300 400 500
D86Temperature[F]
TBPTemperature
[F]
0
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90 100
Cumulative
Yield
[vol%]
DistillationTem
perature[F]
D86YieldCurve
TBP
Yield
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HowDoWeUsetheProbabilityForm?
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DistillationyieldcurvestypicallyhaveanSshape
Traditionaltolinearize onprobabilitygraphpaper
AxistransformedusingfunctionsrelatedtoGaussiandistributionfunction
Functionsavailable
in
Excel
TransformedYield: =NORMSINV( Pct_Yield/100 )
Frominterpolatedvalue: =NORMSDIST( Value ) * 100
Transformed0%&100%valuesundefined
TypicaltosetIBP&EPto1%&99%
91
LinearizedDistillationYieldCurves
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92
Incrementalvs.CumulativeYield
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Incrementalyieldcanbecalculatedasthedifferenceinthecumulativeyieldsatthe
final&initialboilingpoints
Values
impacted
by
method
chosen
tointerpolate/extrapolate
93
,i f f i Y T T Y T Y T
HowDoWeBlendDistillationCurves?
l d h di ill i f ll bl d k & h f
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Blendthedistillationcurvesforallblendstocks&extractthetemperaturesfromtheresultingcurve
Steps
ConvertallofthestartingdistillationanalysestoTBPbasis(@1atm)
PickasetofTBPtemperaturesforwhichtheblendcalculationswillproceed.Extractthe
yieldvaluesforattheseselectedtemperaturevaluesforallblendstocks.
Usewhatevertemperaturesseemreasonabletocoverthespanofallinputvalues
Calculateayieldcurvefortheblendatthetemperatureschoseninthepreviousstep
Extractthetemperaturevaluesforthespecifiedyieldvalues
Converttooriginaldistillationbasis(ifrequired)
94
DistillationCurveBlendExampleBlendStockData D86ConvertedtoTBP BlendatSpecifiedYieldsBlendatSelectedTemperatures
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LSR MidCut
Reformate Vol% LSR
MidCut
Reformate F LSR
MidCut
Reformate Blend Vol% TBP D86
API 81.8 32.8 81.8 32.8 54.1
IBP 91 224 1 40.5 200.8 25 0.4 0.0 0.2 1 52.9 120.5
T10 113 231 10 88.1 224.7 50 1.7 0.0 0.9 10 101.0 142.8
T30 121 232 30 109.9 229.6 75 5.8 0.0 2.9 30 144.0 163.6
T50 132 234 50 130.5 234.8 100 19.3 0.0 9.6 50 218.0 217.7
T70 149 237 70 156.3 241.1 125 44.4 0.0 22.2 70 236.0 228.6
T90 184 251 90 200.9 263.4 150 65.4 0.0 32.7 90 258.7 242.9
EP 258 316 99 350.8 384.2 175 80.0 0.0 40.0 99 371.7 305.3
Fraction 50% 50% 200 89.7 0.9 45.3
225 92.6 11.0 51.8
250 94.8 79.6 87.2
275 96.4 91.7 94.0
300 97.6 94.5 96.0
325 98.4 96.5 97.5350 99.0 97.9 98.4
375 99.4 98.8 99.1
400 99.6 99.3 99.5
Steps
ConvertallD86analysestoTBP
ApproximateIBP
&
EP
as
1%
&
99%
PickasetofTBPtemperatures&interpolatefor
appropriateyieldvalues
Volumetricallyblendateachtemperaturefor
combinedTBPcurve
InterpolateforappropriateTBPvaluesatthe
standardvolumetric
yields
ConverttoD86analysis
95
HowDoWeEstimateLightEndsfromYieldCurve?
Appro imate in remental amo nt from the differen e in m lati e ields
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Approximateincrementalamountfromthedifferenceincumulativeyieldsbetweenadjacentpurecomponentboilingpoints
Steps
Chooselightendscomponents
Typicallymethane,ethane,propane,iso &normalbutane,iso &normalpentane
Determineboilingpointrangesassociatedwithpurecomponentboilingpoints
Sometimesextendrangeto0.5Cabovethepurecomponentboilingpoint
Extrapolate
distillation
yield
curve
to
find
cumulative
yields
at
the
boiling
point
ranges.
Finddifferencestodetermineincrementalamounts.
96
LightEndsExample
Cumulative Cumulative Pure Cumulative Cumulative
Yield [vol%]TBP [F] TBP [F]Yield [vol%]
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97
Steps
Chooselightendscomponents
Methane,ethane,propane,iso &normalbutane,iso &normalpentane
Determineboilingpointrangesassociatedwithpurecomponentboilingpoints.UseastheFinalBoilingPointforrange.
Extrapolatedistillationyieldcurvetofindcumulativeyieldsattheboilingpointranges.
Finddifferencestodetermineincrementalamounts.
Init ial Final
@ Initial @ Final Component
Init ial Final
@ Initial @ Final
Increment
Whole Crude Methane -258.73 N/A -258.73 0.0 0.02 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
Atm Gas Oil 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
Heavy VGO 850 1050 57.3 71.5
Vacuum Resid 1050 End 71.5 100
500
250
0
250
0.01 0.10 1.00 10.00 100.00
CumulativeYield[vol%]
BoilingPoint(F)
C1
C2
C3
iC4nC4
iC5
nC5
HowDoWeEstimateOtherPropertiesofFractions?
Properties inferred from measured trends
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Propertiesinferredfrommeasuredtrends
Relativedensity/specificgravity/APIgravity
Sulfurcontent
Carbonresidue
Propertiesfromcorrelations
Molecularweight/molarmass
Criticalproperties
&
accentric
factor
Heatofcombustion
98
2 3
LHV
2 3
HHV
16792 54.5 0.217 0.0019
17672 66.6 0.316 0.0014
H G G G
H G G G
1.26007 4.9830820.486 exp 0.0001165 7.78712 0.0011582B o B o B oM T T T
WhatHappensWhenWeChangeCutPoints?
In general
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Ingeneral
Theamountcanbecalculatedasthedifferenceincumulativeyieldsbetween
thenewinitial&finalboilingpoints
Interpolatewithintheyieldvs.temperaturecurveusingtheprobabilityform
Theproperties
can
be
determined
by
interpolating
the
curve
for
the
property
vs.themidincrementyield
Linearinterpolationusuallysufficient
Specialcases
Slightlysmaller
than
agiven
cut
in
the
assay
find
properties
of
the
excludedfraction&subtractcontributionfromthegivencut
Slightlylargerthanagivencutintheassay findpropertiesoftheincluded
fraction&addcontributiontothegivencut
Combinationoftwoormoregivencutsintheassay findpropertiesby
addingall
contributions
99
RevisedCutPoints Example#1
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Whatistheyieldofthetotalgasoil(500 1050oF)?Whataretheproperties?
AddcontributionsfortheAtm GasOil,LightVGO,&HeavyVGO
100
1050 500 85.8 39.5
46.3vol%
GOV Y F Y F
14.6 0.8554 19.1 0.8909 12.6 0.932746.3
0.8911
ii
GO
GO
V
V
14.6 0.8554 19.1 0.8909 12.6 0.9327
14.6 0.8554 19.1 0.8909 12.6 0.9327
0.58wt%
0.27 0.57 0.91ii
GOii
iV
SV
S
RevisedCutPoints Example#2
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WhatistheyieldoftheHVGOifthecutrangeis850
1000oF?Whataretheproperties?
Determineamount&estimatepropertiesof1000 1050oFcut.
Cumulativeyield@1000oFfrominterpolationof
yieldvs.
temperature
Propertiesfromlinearinterpolationofmidincrement
yieldvs.
property
RemovecontributionsfromtheHeavyVGOintheassay
101
1000 500 83.1 73.2
9.9vol%
GOV Y F Y F
12.6 0.9327
9.9
2.7 0.95640.9262
GO
12.6 0.93270.86wt%
0.91 2.7 0.9564 1.12
9.9 0.9262GO
S
1000 83.1vol% 83.1 85.8
84.42
85.8 83.1 2.7vol%
midY F Y
V
84.4vol% 16.5 0.9564
84.4vol% 1.12wt%
G
S
RevisedCutPoints Example#3
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WhatistheyieldoftheVac Resid ifthecutpointis
1000oF+?Whataretheproperties?
Determineamount&estimatepropertiesof1000 1050oFcut.
Cumulativeyield@1000oFfrominterpolationof
yieldvs.
temperature
Propertiesfromlinearinterpolationofmidincrement
yieldvs.
property
AddcontributionstotheVac Resid intheassay
102
100 1000 100 83.1
16.9vol%
GOV Y F
14.2 1.0001
16.9
2.7 0.95640.9931
GO
14.2 1.0001
1.41wt%16.9 0.9931
1.46 2.7 0.9564 1.12GO
S
1000 83.1vol% 83.1 85.8
84.42
85.8 83.1 2.7vol%
midY F Y
V
84.4vol% 16.5 0.9564
84.4vol% 1.12wt%
G
S
CanWeEstimateGravityCurveWhenNoneGiven?
Assume that all fractions have the same Watson K factor
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Example EstimateRatawiWatsonKfactor&gravity
curvebasedonoverall
gravity&distillation
analysis
103
Ratawi Crude Oil
0.60
0.70
0.80
0.90
1.00
1.10
1.20
0 10 20 30 40 50 60 70 80 90 100
Mid-Increment Yield [vol%]
SpecificGrav
ity
3
3
fromow o i oi i wi Bi
i Bi
K v v K T v T
HowDoWeBlendWatsonKFactor?
Bestmethod
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Blendspecificgravity
Determinenewaverageboilingpointfromblendedyieldcurve
Approximate
method BlendindividualWatsonKfactorsbyweight
Impliesaverage
boiling
point
from
volumetric
blend
of
cube
root
of
boiling
point
104
i oi i
mix i i
i oi
v KK w K
v
WhatistheAverageBoilingPointforaFraction?
5types
are
defined
in
the
API
Technical
Data
Book
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Volumeaverageboilingpoint
Massaverageboilingpoint
Molaraverageboilingpoint
Cubicaverageboilingpoint
Meanaverageboilingpoint
WatsonKfactorusestheMeanAverageBoilingPoint
105
,1
n
b i b i vi
T v T
,1
n
b i b i wi
T w T
,1
n
b i b i Mi
T x T
3
3,
1
n
b i b i cubici
T v T
2
b bM cubic
b mean
T TT
HowDoWeBlendHeatingValues?
HeatingValue
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Molarormassaverage(dependingonunits)
Lower/netheatingvalue(LHV) wateringasstate
Higher/gross
heating
value
(HHV)
water
in
liquid
state
106
ormix i i mix i i H x H H w H
2 2 2 2 2Fuel + O CO g +H O g +N g +SO g
2 2
2 2 2 2 2
HHV LHV H O H O
Fuel + O CO g +H O +N g +SO g
vap
refH H n H T
VaporPressureCalculations
BubblePoint
TVP
(True
Vapor
Pressure)
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At1atm,coulduseidealgas&liquidassumptions molar blending
Vaporpressureapproximationusingaccentric factor
Maxwell
Bonnell relationship
for
petroleum
fractions
EOS(equationofstate)calculationsmorerigorous
SoaveRedlichKwong orPengRobinson
107
1 1
vap
i
i i i i
P Ty x K x
P
10
7log 1 1
3
vap
cii
i
ci
TP
P T
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Othercorrelations
GPSA
Fig.
6
4
makes
use
of
Kremser relationship(1930)for
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TVP@100oF:
TVP=1.07(RVP)+0.6
110
Othercorrelations
SantaBarbara
County
APCD
Rule
325,
Attachment
B,
equation
25:
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TVP=(RVP)exp(Co(IRTEMP ITEMP))+CF
where: Co RVPdependentcoefficient
ITEMP 1/(559.69
o
R)IRTEMP 1/(Ts+559.69oR)
TsoF temperaturestoredfluid
BasedonAPIFigure5B1.2
111
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NonLinearOctaneBlendingFormula
Developedby
Ethyl
Corporation
using
aset
of
75
&
135
blends
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113
2 2 2 2
1 2 3
2
2 22 2
1 2 3100
"Road"Octane2
Sensitivity
VolumeAverage i i
i
R R a RJ R J a O O a A A
A AM M b MJ M J b O O b
R M
J R M
V XX
V
PetroleumRefineryProcessEconomics,2nd ed.,
byRobertE.Maples,PennWellCorp.,2000
75blends 135blends
a 1 0.03224 0.03324
a 2 0.00101 0.00085
a 3 0 0
b 1 0.04450 0.04285
b 2 0.00081 0.00066
b 3 0.00645 0.00632
GasolineBlendingSampleProblem
Whatare
the
API
gravity,
RVP,
&
average
octane
number
for
a33/67
blend
of
Light Straight Run Gasoline & MidCut Reformate?
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LightStraightRunGasoline&Mid CutReformate?
114
Steps
for
thisexample
WhatisDriveabilityIndex(DI)?
Orientedtowards
the
auto
industry
d h l ili l l i f l i h li d
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Needenoughvolatilitytocompletelyvaporizefuelinthecylinder
LoweringRVPmakesthefuelhardertovaporize
Empirical
relationship
between
gasoline
volatility
&
engine
performance
(driveability &emissions)
The
lower
the
DI,
the
better
the
performanceAlkylatesraiseT50
EthanolraisesRVP&depressesT50,butnottheDI
115
10 50 90DI 1.5 3 2.4F EtOHvol%T T T
HowCanWeEstimateFlashPoint?
Relatedto
volatility
of
mixture.
Assume ideal gas since tests done at 1 atm
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Assumeidealgassincetestsdoneat1atm.
MethodofLenoir
MethodofGmehling&Rasmussen
Relatedtolowerflammabilitylimit
116
1 1.3
N
vapi i i i
i
x M P
1 ,
251 with 25 0.182
vapN
i i ii i
i i c i
x P TL L C
L H
HowCanWeEstimateFlashPoint?
APIProcedure
2B7.1
(ASTM
D86
T10)
1987 Version (units of R)
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1987Version(unitsof R)
ModifiedbyChatterjee&Saraf
1997Version(unitsofF)
OpenCup ClosedCub
117
100.68 109.6FT T
1010
1 2.849470.014568 0.001903ln
F
T
T T
100.69 118.2FT T
1010
1 4.17015
0.076204 0.01043ln 0.000257ln oF TT T
HowDoWeEstimate&BlendCetaneIndex?
Cetaneindex
is
an
estimate
of
the
cetane number
based
on
composition.
It
does
nottakeintoaccounteffectsofadditivestoimprovecetane number.
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EstimationmethodoutlinedbyASTMD976
whereT50is50%pointasdeterminedbyD86distillation&GistheAPIgravity
FourVariablemethodsoutlinedinASTMD4737
Differentcorrelations
for
15
ppmw &
500
ppmw diesels
Cetaneindexcanbeapproximatelyblendedlinearlybyvolume
118
22 2
50 50 50Index 420.34 0.016 0.192 log 65.01 log 0.0001809G G T T T
HowAreOctane&Cetane NumbersRelated?
Ingeneral
compounds
with
high
octane
numbers
have
low
cetane numbers
Correlation developed from gasoline samples
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Correlationdevelopedfromgasolinesamples
119
CN 60.96 0.56 MON
CN 68.54 0.61 RON
Bowden,Johnston,&Russell,OctaneCetane Relationship,
FinalReportAFLRLNo.33,March1974,
PreparedbyU.S.ArmyFuels&LubricantsResearchLab&SouthwestResearchInstitute
0
5
10
15
20
25
70 80 90 100
Cetan
eNumber(CN)
OctaneNumber
(MON
or
RON)
RON
ExpressionMONExpression
HowDoWeConvertSUSviscosity?
2 3 5
1.0 0.032641.0 0.000061 100 4.63243930.2 262.7 23.97 10
SUS T
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120
0
50
100
150
200
250
300
350
400
450
500
0 20 40 60 80 100
Kinematic Viscosity [cSt]
SUS
Viscosity
210F
0F
Howdoweadjustviscosityfortemperature?
ASTMD
341
gives
procedure
to
adjust
viscosity
with
temperature
starting
with
at
least
2
measuredvalues
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Forviscositiesabove2.0cSt theequationisessentially
Onlyvalidforviscositiesabove0.21cSt
121
log log log
0.7
exp 1.14883 2.65868
exp 0.0038138 12.5645
exp 5.46491 37.6289
exp 13.0458 74.6851
exp 37.4619 192.643
exp 80.4945 400.468
0.7 exp 0.7487 3.295 0.7 0.611
Z A B T
Z C D E F G H
C
D
E
F
G
H
Z Z
2 3
9 0.7 0.3193 0.7Z Z
log log 0.7 logA B T
Viscosityvs.TemperatureExample
F cSt log(log(Z)) log(R) Est
log(log(Z)) EstcSt
Relative
Deviation104 4,102 0.5579 563.67 0.5514 3,629 12%
122 1,750 0.5110 581.67 0.5137 1,836 5%
212 115 0.3146 671.67 0.3253 130 13%
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122
Steps
CalculatetheZ&temperaturetermsfromthegivendata
Converttemperaturestoabsolutebasis
DetermineA&Bparametersfromdata
Thiscase
uses
linear
regression
&
all
4
points
UseA&BparameterstofindZatothertemperatures
ConvertZtocSt
Approximateformulausedhere
212 115 0.3146 671.67 0.3253 130 13%
275 37.9 0.2005 734.67 0.1934 35.7 6%
A: 1.732
B: 0.002094
r: 0.997
Bylinearregression
0
1
10
100
1,000
10,000
100 200 300 400 500 600 700
Temperature[F]
Viscosit
y[cSt]
HowDoWeBlendViscosities?
Viscosityblending
complicated
composition
effects
Simpleviscosityblendingequationsaremoreappropriateforgasphaseviscosity
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p y g q pp p g p y
shouldnotbeusedforblendingliquidphasepetroleumfractionvalues
Arrhenius
Bingham
Kendall&Monroe
123
ln lnmix i i v
1 i
mix i
v
31/3ln
mix i i x
HowDoWeBlendViscosities?
Desireto
blend
viscosity
with
either
volume
or
mass
amounts
LinearblendingwithViscosityBlendingIndicesofkinematicviscosity
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g y g y
Mayseeanindexbasedonloglogtermswithextracoefficientsand/ornaturallog
terms.Giveidenticalresults.
Forheavyfractionsoftenmassblendingissuggestedwithcof0.8to1.0
Refutas equation massblending
Othertypesofblendingindices
ChevronMethod2
124
log log log log where 0.7mix c i i c cv
VBN VBN where VBN 14.534 ln ln 0.8 10.975i iblend i i w
ln lnln ln 1000
ln 1000 ln 1000 1
mix i
i mix
mix i
Sv S
S
ASTMD7152ViscosityBlending
ProcedureCwhenusingviscosityvaluesallatthesametemperature
ASTMBlendingMethod volumeblending
ModifiedASTMBlendingMethod massblending
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g g
Basedonloglog(MacCoullWaltherWright)transformationviscosity
Developedforvolumeblending&kinematicviscositybutcouldbeusedformass
blending
Forbasestockblends,nosignificantdifferencebetweenvolumetric&massblending
Forfuelblends(chemicallyconvertedblendstocks),massblendingmoreaccurate
Exponentialcorrectionterminsignificantabove2cSt
Extendstheuseofloglogtermsfromdownto0.2cSt.
125
2
10
2 3
0.7 exp 1.47 1.84 0.51log log
10 0.7
exp 0.7487 3.295 0.6119 0.3193
WB
i i i i
i i
B i i
B
B B B B B
ZW Z
W v W
Z
Z Z Z Z
ViscosityBlendingExample
Determinethe
amount
of
cutter
stock
needed
to
blend
with
5,000
bpd
80,000
cSt
vacuumresid tomakeafueloilwith180cSt @122F.Thecutterstockhas8.0cStviscosity
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viscosity.
ASTMBlendingMethod&Chevron
Method2essentiallythesameresults
126
1
10
100
1,000
10,000
100,000
0.1 1 10 100
RatioCutter:Resid
[vol/vol]
Ble
nd
Viscosity[cSt]
VolumeAveragecSt
LogLog
Blending
Rule
VolumeAveragelog(cSt)
ChevronBlendingIndices
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