RefineryFeedstocks &Products Properties&Specifications

JohnJechura jjechura@mines.edu
Updated:August9,2014

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

Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions

Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number

Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions

Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number

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

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/

1Hexene

cis3Hexene

trans3Hexene

ExampleHeterocompounds

Composition&AnalysisofHeavyPetroleumFractions
K.H.Altgelt &M.M.Boduszynski
MarcelDekker,Inc.,1994,pg.16

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

Diesel & jet fuels, middle distillates

Vacuum gas oil
Atmospheric residue

Vacuum residue
Nondistillable residue

Composition&AnalysisofHeavyPetroleumFractions
K.H.Altgelt &M.M.Boduszynski
MarcelDekker,Inc.,1994,pp.23&45

CrudeOilAssay
Indicatesdistributionquantity &quality ofcrudeoilfeedstock
Definitionsbaseduponboilingpointtemperatureranges
Representsexpected productsfromcrude&vacuumdistillation

Completenessofdatadependsuponsource
Publicreportvs.inhouseanalyticallaboratory

Qualitymeasures
Specific/APIgravity
Sulfurcontent
Octanenumber
Cetanenumber
Viscosity
Carbonresidue

100
90
80

97.8F

Temperaturesdefinethe

Propane

boundariesbetween fractions

70

Butanes
Pentanes

350F
400F

60
Barrels

Ethane & Lighter

180F

Light Naphtha

50
40
30

Heavy Naphtha

Mixedpropertyvaluesforthe

Distillate

650F

entirefraction

AGO

20

LVGO

850F

HVGO

10

1050F
Vacuum Resid

0
Total

Continuum

Fractions

12

CrudeOilsAreNotCreatedEqual

13

CrudeOilProperties
Distillationanalysis/Boilingpointrange
Amountcollectedfrombatchdistillationattheindicatedtemperature
Standardizedtests ASTMD86,D1160,
MostusefulisTBP(TrueBoilingPoint)

Specificgravity,o ratioliquiddensity@60F&1atm tothatofwater@60F&1atm

Airsaturated:

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

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

15

DistillationAnalysisTypes
TrueBoilingPoint(TBP) ASTMD2892
14to18theoreticalstages
Nearinfinitereflux(5:1refluxratiomin)
Nohotterthan650Ftominimizecracking
Maxvaportemperature410 F

Pressurelevels
760mmHg(1atm)
100mmHg
2mmHg(min)

ASTMD289213,StandardTestMethodforDistillationofCrudePetroleum
(15TheoreticalPlateColumn)

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]

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

18

DistillationAnalysisTypes
ShortPathDistillation
Singlestageflash
Extremelylowpressures
0.1mmHgorless
Characterizedeepcutresids

http://www.chemtechservicesinc.com/shortpathdistillation.html

19

DistillationAnalysisTypes
SimulatedDistillation ASTM2887
Relativelylowresolutiongaschromatography
Severalthousandtheoreticalstages

EssentiallyTBPtemperatures wt%basis
Temperaturesinferredfromelutiontimes
Calibratedwithnparaffinmixture

20

CrudeOilAssay Hibernia(fromChevronsite)
Whole

Light

Medium

Heavy

Crude

Naphtha

Naphtha

Naphtha

Kero

Atm

Light

Heavy

Vacuum

Atm

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

1
5860

2729

Mercaptan Sulfur, ppm

Nitrogen, ppm

1384

Hydrogen, wt%

56

579

2050

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

-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)

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

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

40

47

56

Cetane Index, ASTM D4737

Diesel Index

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

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

Characterization Factor (K Factor)

Simpleanalysis

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%

4.6

2.3

13.2

Vanadium, ppm

Nickel, ppm

Iron, ppm

http://crudemarketing.chevron.com/crude/north_american/hibernia.aspx
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
22

CrudeOilAssay Bakken vs.otherlightcrudes

Property
APIGravity
Sulfur,wt%
DistillationYield,volume%
LtEndsC1C4
NaphthaC5360F
Kerosene360500F
Diesel500650F
VacuumGasOil6501050F
VacuumResidue1050+F

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

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

24

Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions

Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number

25

PetroleumProducts
Therearespecificationsforover
2,000individualrefineryproducts
Tookafullcenturytodevelopmarkets
forallfractionsofcrudeoil

Intermediatefeedstocks canbe
routedtovariousunitstoproduce
differentblendstocks
Dependsuponthelocaleconomics&
contractuallimitations

Ref:Unknownorigin.PossiblySoconyVacuumOilCompany,Inc.(1943)

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

27

SourcesofProductSpecifications
State&Federalregulatoryagencies

Industryassociations

Environmentallaws

AmericanPetroleumInstitute

Reflectneedtoreducepollutionin
manufacturing&useoffuels

GasProcessorsAssociation

ASTM(AmericanSocietyforTestingand
Materials)Specifications&associatedtest
procedures
Specificationsdraftedconsideringpositions
ofindustry&regulatoryagencies

AsphaltInstitute

Betweencompaniesbasedontypical
specs
Negotiated
Deviationshavepredeterminedprice
adjustments

28

WhatMakesGasolineGasoline?
WhatMakesDieselDiesel?
Gasoline

Diesel

Mustbeagoodfuelinasparkignitedinternal

Mustbeagoodfuelinanonsparkignitedfuel

combustionengine
Properatomization&vaporizationwhenmixed
withcombustionair
Boilingpointsofchemicalspecies

injectedinternalcombustionengine
Properatomizationwheninjectedinto
compressedair
Boilingpointrangeofmixture

Boilingpointrangeofmixture

Abilitytocompress&notignitepriortospark
ignition
Measuredasoctanenumber

Minimalcombustionbyproducts wantcomplete
combustion

Minimizeenvironmentalunfriendliness
Volatilityinstoragetanks
RVP ReidVaporPressure

Individualchemicalspecies
Sulfurcontent

Abilitytoignitewheninjectedintocompressed
air
Measuredascetane number

Minimalcombustionbyproducts wantcomplete
combustion

Minimizeenvironmentalunfriendliness
Volatilityinstoragetanks
Flashpoint

Individualchemicalspecies
Sulfurcontent

Benzene

29

CharacteristicsofPetroleumProducts

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000

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

31

LiquefiedPetroleumGas(LPG)
Commercial
Propane

Commercial
Butane

ASTMTest

C3&C3=

C4&C4=

D126702

VaporPressure@100F

208

70

D126702

95vol%@maxF

37F

+36F

D183764

C4+max

2.5%

C5+max

D216377
2.0%

D216377

VaporpressurespecisactuallyanapproximateguidelinefordefiningthelightendscontentoftheLPGmixture.

32

NaturalGasolineSpecifications
Characteristic

GPASpecifications

ASTMTest

ReidVaporPressure

10to34psig

D323

Evaporationat140F

25to85%

D216

Evaporationat275F

>90%

D216

EndPoint

D216

33

AviationGasolineSpecifications

34

MotorGasolineSpecifications

35

MotorGasolineVolatilityClasses(ASTMD481413)

36

OtherGasolineConsiderations
Reformulatedgasoline(RFG)blendedtoburncleanerbyreducingsmogformingandtoxicpollutants
CleanAirActrequiresRFGusedincitieswiththeworstsmogpollution
CleanAirActrequiredRFGtocontain2wt%oxygen
MTBE&ethanolwerethetwomostcommonlyusedsubstances
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

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

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)

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

40

MiddleDistillates
Generalclassifications

Properties

Kerosene

Flashpoint

Jetfuel

Cloudpoint/Pourpoint

Distillatefueloil

Anilinepoint

Diesel

Cetane number

Heatingoil

Viscosity
Water&sediment

41

DieselCetaneNumber
Onekeytodieselquality
Measurestheabilityforautoignition
Essentiallytheoppositeofoctanenumber

Maybemeasuredbutfrequentlyapproximated
ASTMD976 StandardTestMethodsforCalculatedCetaneIndexofDistillateFuels
ASTMD4737 StandardTestMethodforCalculatedCetaneIndexbyFourVariableEquation

Trends
Cetanenumberhaddeclinedsincethemiddle1970s
Highdemand
Heaviercrudeswithnarrowdieselcuts
Blendingoflowercetane fractions

Trendstartingtoreverse
Morestringentemissionsrequirementsnecessitatehighercetane numbers

42

WhatisFlashPoint?
Thelowesttemperaturecorrectedtoapressureof101.3kPa(760mmHg)at
whichapplicationofanignitionsourcecausesthevaporsofaspecimenofthe
sampletoigniteunderspecifiedconditions

ProcedurestrictlycontrolledbyASTMstandards
D56TagClosedTester
D92ClevelandOpenCup
D93PenskyMartensClosedCupTester
D1310 TagOpenCupApparatus4
D3143 CutbackAsphaltwithTagOpenCupApparatus
D3278ClosedCupApparatus
D3828 SmallScaleClosedTester
D3941 EquilibriumMethodwithClosedCupApparatus

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

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

45

AdditionalSpecifications
Sulfur
Controlofsulfuroxidesuponcombustion
Threelevels,reductionforthetraditionalfivecategories

AnilinePoint
Minimumtemperatureatwhichequalvolumesofaniline(C6H5NH2)andtheoilare
miscible
Thelowertheanilinepointthegreaterthearomaticcontent

Viscosity
Fluidityduringstorageatlowertemperatures

Sediment&watercontent
Controllingcontamination

46

KeroseneSpecifications
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

47

JetFuelSpecifications

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

49

DieselSpecifications

50

DieselSulfurContent
Sulfurlevelsdroppingbecauseofairqualityregulations
Since1993dieselfuelformulatedwith85%lesssulfur
LowSulfurDieselhadbeen500ppm sulfur
ULSD15ppm &requiredforonroadusagesinceJanuary2007

Worldwide,sulfurspecs
continuingtodropto
meetU.S.&European
standards

Globalstatusofmaximumallowablesulfurindieselfuel,partspermillion(June2012)
SaudiArabiasplanfornearzerosulfurfuels,HydrocarbonProcessing,March2013
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

52

ResidualFuelOils(cont.)
No.5FuelOil premiumresidualfueloilofmediumviscosity
Atonetimeusedinthesteelindustrybutnowrarelyused

No.6FuelOil heavyresidualfueloil
Vacuumresid &cutterstockmix(todecreaseviscosity)
Commonuse
Boilersforsteamturbinesofstationarypowerplants
Marineboilers variationofBunkerC
Industrial&commercialapplications

Markethasbeendeclininginlast20years
Morepowerplantsusecoalornaturalgas
Shipsusedieselformarinedieselsorgasturbines
Environmentalreductionsinsulfurlevels

Leastvaluedofallrefineryproducts
Historicallyonlyliquidproductworthlessthanrawcrude

53

ASTMFuelOilSpecs

54

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

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

No.2DS15 No.2DS500 No.2HOS500

40
40
35
35
0.0015
0.05
0.05
52
52
38

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

55

ComparisonofBoilingRanges

56

GasOil&TownGas
Historicalusage
Gasoilsusedtomaketowngasforillumination
Decomposedoveraheatedcheckerwork
Composedofcarbonmonoxideandcarbondioxide
o

Lowheatingvalue

Burnedcleanly

Easilydistributedforilluminationfuel

Displacedkeroseneinthecities electricityultimatelyeliminateditsuse

Gasoilnolongeraconsumerproduct
Tradedbetweenrefineries
Feedstockforcatalyticcracking&hydrocracking

57

LubricantTerminology
Phrase

Meaning

Lubebasestock

Lubeproductthatmeetsallspecifications
&issuitableforblending

Lubeslate
Neutrallubes
Brightstocklubes

Setoflubebasestocks,usually3to5
Obtainedfromasidecutofthevacuum
distillationtower
Processedofvacuumresidfromthe
vacuumtowerbottoms

58

Lubricants
TerminologybasedsolelyontheViscosityIndex independentofthecrude
sourceortypeofprocessing
Paraffiniclubricantsareallgrades,bothbrightstock&neutral,withafinishedviscosity
Indexmorethan75
NaphtheniclubricantsareallgradeswithaviscosityIndexlessthan75

Importantproperties
Kinematicviscosity(viscositydividedbymassdensity)
Color
Pourpointforcoldweatheroperation
Flashpoint
Volatilityforreducedevaporation
Oxidationstability
Thermalstability

59

SAEViscositySpecifications
Kinematicviscosity
measuredincentistokes
butspecificationsare
labeledinSaybolt
Seconds(SUS)

Specificationsare
establishedbythe
SocietyofAutomotive
Engineers
SAEviscositywellknown
motoroilspecification
(e.g.,10W30)

Grade

MaxViscosity
(SUS)@0F

MaxViscosity
(SUS)@210F

MinViscosity
(SUS)@210F

5W

6,000

10W

12,000

20W

48,000

20

58

45

30

70

58

40

86

70

50

110

85

60

Asphalt
Importantproductintheconstructionindustry
Comprise20%oftheOtherProductscategory

Asphaltcanonlybemadefromcrudescontainingasphaltenicmaterial
Numerousdetailedspecificationsonthemanyasphaltproducts
AsphaltInstitute,LexingtonKentucky
Industrytradegroupforasphaltproducers&affiliatedbusinesses

AmericanAssociationofStateHighwayandTransportationOfficials
SponsorstheAASHTOMaterialsReferenceLaboratory(AMRL)attheNationalInstitute
ofStandardsandTechnology(NIST)

AmericanSocietyofTestingandMaterials(ASTM)

62

PetroleumCoke
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%

63

SulfurSpecifications
Purity
Ash
Carbon

99.8weight%sulfur,basedondryanalysis
500ppmwmaximum
1,000ppm(weight)maximum

Color

"Brightyellow"whensolidified.
Sulfurrecoveredbyliquidreductionoxidationprocesseshave
colorduetometals somepurchaserswillincludea
requirementexcludingsulphurrecoveredfromthese
processes

H2S

10ppmwmax(Importantforinternationaltransport&sales)

State

Shippedaseitherliquidorsolid.Internationaltransport
specifiessolid.

64

Topics
Quantity&Quality
Chemicalcomposition
Distillationanalyses
Propertiesofdistillationfractions

Productsasdefinedbytheirproperties&specifications
Composition,boilingpointranges,and/orvolatility
Propertiesspecificforcertaindistillationfractions
Autoignition tendency octane&cetane number

65

SupplementalSlides
Examplecrudeoilassay(withminimaldata)
Examplegasoline&gasolineblendstockanalyses
ASTMD323RVPProcedures
ASTMD56FlashPointbyTagClosedTesterFlash
Calculations
Linear&nonlinearblendingrules
Blendingrulesbasedonadditiveweight&additivevolumes
Blendingindices

Assaysoncommonbasis
Cumulativeyieldvs boilingpointtemperature
Fractionss averageyieldvs measuredproperty

Propertyestimationformulas

66

CrudeOilAssay TenSectionField(Textpg.416)
Fraction
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Residuum
Total
Loss
Reported

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

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

67

CrudeOilAssay WTI(fromOGJarticle)

Steps
68

SAE902098GasolineBlendStockAnalyses
Table 7 Analyses of Blending Components
Blending
Component

Cat Cracked Cat Cracked

Naptha #1 Naptha #2

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

69

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

9600 17400

70

ASTMD323RVPProcedures
ProcedureA(AtmosphericallyStableLiquids)
Apparatus

Liquid&vaporchambers.Vaporchamber4.0 0.2 timessizeofliquidchamber

LiquidPreparation

1Lsamplecontainerfilled7080%withtestliquidsample.Samplecontainercooledinacold
bathat0 1C(32 34F).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
timeswithnolessthan2minutesinbetween.Shakingprocedureshouldberepeateduntil2
consecutivepressurereadingsindicateequilibriumhasoccurred.Pressuremeasuredasgauge
butreportedwithreferencetogaugeorabsolute.

ProcedureC(VolatileLiquids)
LiquidPreparation

Samplecontainerofabout0.5Lcapacitycooledinacoldbathat0 4.5C(32 40F).This

samplecontainerisnotopened&contactedwithair.

LiquidTransfer

Liquidchamberiscooledinthesamecoldbath.Coldliquidsampletransferredtothecold
liquidchamber,similartoProcedureA.However,sincethisliquidisunderpressure,extra
caremustbetakentoensurethatgasisnotflashedoffandlostandthattheliquidchamberis
actuallycompletelyfilledwiththeliquid.

71

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.

72

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)

mix

w X
i i
v X
m X
i oi i
i
i

m
v
i
i oi
73

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

74

HowDoWeBlendAPIGravities?
Specificgravityisblended&APIgravityisbackcalculated.
MayhavetocalculateindividualspecificgravitiesfromgivenAPIgravities

Example
IncorrectvaluefromdirectvolumeblendingofAPIgravities

75

TemperatureCorrectionstoSpecificGravity
ODonnel (Chevron)method
T2 2o 0.000601TF 60

APIVolumeCorrectionTables

T o exp 60 TF 60 1 0.8 60 TF 60
Different60 valuesdependingoncommoditytype
ATables CrudeOils
BTables RefinedProducts
DTables Lubricants
CTables Individual&SpecialApplications

76

StandardConditions(Temperature&Pressure)
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?
MethodinChapter12.3ofAPImeasurementmanual
S 4.86 10 8 C 100 C

0.819

GL GH

2.28

where C

VL
100
VH VL

Example: Blend95,000bbl of30.7oAPI(0.8724specificgravity)crudeoilwith5,000bbl of

86.5oAPI(0.6491specificgravity)naturalgasoline
Byidealmixing:

Vmix VH VL 100,000bbl
mix
Gmix

Withshrinkage:

LVL HVH
Vmix
141.5
mix

0.6491 5000 0.8724 95000

100000

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

V V 0.6491 5000 0.8724 95000

mix L L H H
0.8621
99903
Vmix
141.5
Gmix
131.5 32.6
mix
C

78

HowDoWeBlendYieldCurves?

Onaconsistent
volume,mass,or
molebasis
Onanincremental
orcumulativebasis
Temperatures
correctedto1atm
basis
Distillationtype
correctedtoTBP

Incremental Amount [vol%]

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

Cumulative Amount [vol%]

Amountsareadded

0
0

250

500

750

1000

1250

1500

1750

2000

Temperature [F]

79

HowDoWeBlendPropertiesforIndividualFractions?
Blendbasedonpropertiesandamountsforthefraction ineachblendstock,not
theoverallamountofblendstock.

80

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

& TB TB 2.5 f KW 12 log10

X

760
1

748.1 0.0002867
TB

1
P vap 760mmHg

TB 659.67 vap
,0 P 760mmHg
Min 1,Max
200

81

PressureCorrectionExample
Correcta437Fboilingpointmeasuredat40mmHgtothenormalboiling
point(at760mmHg).
Usingthe2nd of3equationsdetermineX=0.001767618
WithT=896.67oRdetermineTB=1094.98
IfweneglecttheWatsonKfactorcorrection(i.e.,assumeKW=12)thenTB=TB

Normalboilingpointis635oF

82

HowDoWeInterconvertD86&TBPTemperatures?
Methodfrom1994APITechnicalDataBook
ConsistentwiththeAPI94optioninAspenPlus
1.0258
TTBP,50% 0.87180 TD86,50%
(TTBP,50% &TD86,50% inF)

TTBP A TD86

(TTBP &TD86 inF)

Vol%

100%to90%*

0.11798

1.6606

90%to70%

3.0419

0.75497

70%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%.
83

InterconvertD86&TBPTemperatures
120

90% to 100%

100
10% to 30%

TBP Temperature Difference [F]

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

D86 Temperature Difference [F]

84

HowDoWeInterconvertD1160&TBPTemperatures?
D1160temperaturesat10mmHgareconvertedtoTBPtemperaturesat10mm
Hg graphicalmethodtointerconvert
D1160temperaturesat50%&higherequaltotheTBPtemperatures
0%to10%,10%to30%,&30%to50%D1160temperaturedifferences convertedtoTBP
temperaturedifferences

TTBP a TD1160 b TD1160 c TD1160 d TD1160

2

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

85

InterconvertD1160&TBPTemperatures
225
Note: ASTM D1160 & TBP 50% distillation
temperatures assumed equal at 10 mmHg

200

TBP Temperature Difference [F]

175

10% to 30% & 30% to 50%

150

50% to 70% & 70% to 90%

125
0% to 10%

100

75

50

Based on API Figure 3A2.1

Subatmospheric Distillation &
True Boiling Point Distillation
Relationship

25

0
0

25

50

75

100

125

150

175

200

225

D1160 Temperature Difference [F]

86

HowDoWeInterconvertD2887&TBPTemperatures?
Methodfrom1994APITechnicalDataBook
D2887essentiallyTBPonwt% basis,notvol%

TTBP,50% TD2887,50%
TTBP A TD2887

(TTBP &TD2887 inF)

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
87

D86ConversionExample
Stepsforthisexample
Vol%

D86

IBP

91

D86T

79.5
155.6
218.4
279.9
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

88

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%]

89

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

90

HowDoWeUsetheProbabilityForm?
DistillationyieldcurvestypicallyhaveanSshape
Traditionaltolinearize onprobabilitygraphpaper
AxistransformedusingfunctionsrelatedtoGaussiandistributionfunction

FunctionsavailableinExcel
TransformedYield:

=NORMSINV( Pct_Yield/100 )

Frominterpolatedvalue:

=NORMSDIST( Value ) * 100

Transformed0%&100%valuesundefined
TypicaltosetIBP&EPto1%&99%

91

LinearizedDistillationYieldCurves

92

Incrementalvs.CumulativeYield
Incrementalyieldcanbecalculatedasthe
differenceinthecumulativeyieldsatthe
final&initialboilingpoints
Y Ti ,Tf Y Tf Y Ti
Valuesimpactedbymethodchosento
interpolate/extrapolate

93

HowDoWeBlendDistillationCurves?
Blendthedistillationcurvesforallblendstocks&extractthetemperaturesfrom
theresultingcurve

Steps
ConvertallofthestartingdistillationanalysestoTBPbasis(@1atm)
PickasetofTBPtemperaturesforwhichtheblendcalculationswillproceed.Extractthe
yieldvaluesforattheseselectedtemperaturevaluesforallblendstocks.
Usewhatevertemperaturesseemreasonabletocoverthespanofallinputvalues

Calculateayieldcurvefortheblendatthetemperatureschoseninthepreviousstep
Extractthetemperaturevaluesforthespecifiedyieldvalues
Converttooriginaldistillationbasis(ifrequired)

94

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

95

HowDoWeEstimateLightEndsfromYieldCurve?
Approximateincrementalamountfromthedifferenceincumulativeyields
betweenadjacentpurecomponentboilingpoints

Steps
Chooselightendscomponents
Typicallymethane,ethane,propane,iso &normalbutane,iso &normalpentane

Determineboilingpointrangesassociatedwithpurecomponentboilingpoints
Sometimesextendrangeto0.5Cabovethepurecomponentboilingpoint

Extrapolatedistillationyieldcurvetofindcumulativeyieldsattheboilingpointranges.
Finddifferencestodetermineincrementalamounts.

96

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

Cumulat iv e Cumulat iv e
@ Init ial

@ Final

Inc rement

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

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%]

97

HowDoWeEstimateOtherPropertiesofFractions?
Propertiesinferredfrommeasuredtrends
Relativedensity/specificgravity/APIgravity
Sulfurcontent
Carbonresidue

Propertiesfromcorrelations
Molecularweight/molarmass

M 20.486TB1.26007 o4.98308 exp 0.0001165TB 7.78712 o 0.0011582TB o

Criticalproperties&accentricfactor
Heatofcombustion

HLHV 16792 54.5G 0.217G 2 0.0019G 3

HHHV 17672 66.6G 0.316G 2 0.0014G 3

98

WhatHappensWhenWeChangeCutPoints?
Ingeneral
Theamountcanbecalculatedasthedifferenceincumulativeyieldsbetween
thenewinitial&finalboilingpoints
Interpolatewithintheyieldvs.temperaturecurveusingtheprobabilityform

Thepropertiescanbedeterminedbyinterpolatingthecurvefortheproperty
vs.themidincrementyield
Linearinterpolationusuallysufficient

Specialcases
Slightlysmallerthanagivencutintheassay findpropertiesofthe
excludedfraction&subtractcontributionfromthegivencut
Slightlylargerthanagivencutintheassay findpropertiesoftheincluded
fraction&addcontributiontothegivencut
Combinationoftwoormoregivencutsintheassay findpropertiesby
addingallcontributions

99

RevisedCutPoints Example#1

Whatistheyieldofthetotalgasoil(500 1050oF)?Whataretheproperties?

AddcontributionsfortheAtm GasOil,LightVGO,&HeavyVGO
VGO Y 1050F Y 500F 85.8 39.5
46.3vol%
GO

V 14.6 0.8554 19.1 0.8909 12.6 0.9327

i

46.3

VGO

0.8911
SGO

V Si 14.6 0.8554 0.27 19.1 0.8909 0.57 12.6 0.9327 0.91

14.6 0.8554 19.1 0.8909 12.6 0.9327
V
i

0.58wt%

100

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

V 85.8 83.1 2.7vol%

83.1 85.8

84.4
2

Propertiesfromlinearinterpolationofmidincrement
yieldvs.property

GO

SGO

12.6 0.9327 2.7 0.9564

9.9

0.9262

12.6 0.9327 0.91 2.7 0.9564 1.12

9.9 0.9262

0.86wt%

G 84.4vol% 16.5 0.9564

S 84.4vol% 1.12wt%

101

RevisedCutPoints Example#3

WhatistheyieldoftheVac Resid ifthecutpointis

1000oF+?Whataretheproperties?

Determineamount&estimatepropertiesof
1000 1050oFcut.

AddcontributionstotheVac Resid intheassay

VGO 100 Y 1000F 100 83.1
16.9vol%

Cumulativeyield@1000oFfrominterpolationof
yieldvs.temperature
Y 1000F 83.1vol% Ymid

V 85.8 83.1 2.7vol%

83.1 85.8

84.4
2

Propertiesfromlinearinterpolationofmidincrement
yieldvs.property

GO

SGO

14.2 1.0001 2.7 0.9564

16.9

0.9931

14.2 1.0001 1.46 2.7 0.9564 1.12

1.41wt%
16.9 0.9931

G 84.4vol% 16.5 0.9564

S 84.4vol% 1.12wt%

102

CanWeEstimateGravityCurveWhenNoneGiven?
AssumethatallfractionshavethesameWatsonKfactor
Kw

vi

TBi

from o vi oi vi Kwi 3 TBi

Ratawi Crude Oil

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

Mid-Increment Yield [vol%]

103

HowDoWeBlendWatsonKFactor?
Bestmethod
Blendspecificgravity
Determinenewaverageboilingpointfromblendedyieldcurve

Approximatemethod
BlendindividualWatsonKfactorsbyweight
K mix wi K i

v K
v
i oi

i oi

Impliesaverageboilingpointfromvolumetricblendofcuberootofboilingpoint

104

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

105

HowDoWeBlendHeatingValues?
HeatingValue
Molarormassaverage(dependingonunits)

H mix xi H i or Hmix wi Hi
Lower/netheatingvalue(LHV) wateringasstate

Fuel + O2 CO2 g +H2O g +N2 g +SO2 g

Higher/grossheatingvalue(HHV) waterinliquidstate

Fuel + O2 CO2 g +H2O +N2 g +SO2 g

H HHV H LHV nH2O HHvap
Tref
2O

106

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

107

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

TVP mix xi Pi vap

ApproximatevolumetriclinearblendingwithRVPBlendingIndices

RVP mix vi RVP i

1.25

1.25

RVP mix

1.25
vi RVP i

1/1.25

108

RVP&TVP APITechnicalDataBookMethods
Intentistoestimate
truevaporpressures
(TVPs)froma
measuredRVP

CanalsoestimateRVP
fromanymeasured
vaporpressurevalue
TVPcouldbe
measuredatany
temperature could
useboilingpoint
SlopeisoftheASTM
D86distillationcurve
@T10

109

Othercorrelations
GPSAFig.64makesuseof
Kremser relationship(1930)for
TVP@100oF:
TVP=1.07(RVP)+0.6

110

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

111

HowDoWeBlendOctaneNumbers?
Octanenumbersgenerallyblendnonlinearly
Interactionsbetweencomponentsinmixture

ApproximatelinearblendingwithOctaneBlendingIndices
Indicesarefairlycloselyguarded

Inthisclasswellgenerallyassumelinearblendingwithvolume

RON mix vi RON i

MON mix vi MON i

112

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

a2
a3

0.00101
0

0.00085
0

b1
b2

0.04450
0.00081

0.04285
0.00066

b3

0.00645

0.00632
113

GasolineBlendingSampleProblem
WhataretheAPIgravity,RVP,&averageoctanenumberfora33/67blendof
LightStraightRunGasoline&MidCutReformate?

Steps
for
thisexample

114

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

115

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

116

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

TF 0.68 T10 109.6

TF 0.69 T10 118.2

117

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

whereT50 is50%pointasdeterminedbyD86distillation&G istheAPIgravity

FourVariablemethodsoutlinedinASTMD4737
Differentcorrelationsfor15ppmw &500ppmw diesels

Cetaneindexcanbeapproximatelyblendedlinearlybyvolume

118

HowAreOctane&Cetane NumbersRelated?
Ingeneralcompoundswithhighoctanenumbershavelowcetane numbers
Correlationdevelopedfromgasolinesamples
CN 60.96 0.56 MON

25

CN 68.54 0.61 RON

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
119

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

Kinematic Viscosity [cSt]

120

Howdoweadjustviscosityfortemperature?
ASTMD341givesproceduretoadjustviscositywithtemperaturestartingwithatleast2
measuredvalues

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

Onlyvalidforviscositiesabove0.21cSt

121

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

DetermineA &B parametersfromdata

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]

122

HowDoWeBlendViscosities?
Viscosityblendingcomplicatedcompositioneffects
Simpleviscosityblendingequationsaremoreappropriateforgasphaseviscosity
shouldnotbeusedforblendingliquidphasepetroleumfractionvalues
Arrhenius
Bingham

ln mix vi ln i
v
1
i
mix
i

Kendall&Monroe

mix

xi ln 1/3
i

123

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

VBNblend wi VBNi where VBNi 14.534 lnln i 0.8 10.975

Othertypesofblendingindices
ChevronMethod2

ln mix

ln1000 mix

vi

ln i

ln1000 i

S ln mix ln1000

S
1 S
124

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.
125

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]

126

HowaretheCarbonResiduesRelated?
Carbonresidue cokingtendency
ASTMD524 Ramsbottom (RCR)
ASTMD189 Conradson (CCR)
ASTMD4530 Microcarbon (MCRT)
CCR&MCRTessentiallythesame

RCR exp 0.236 0.883ln CCR 0.0657ln2 CCR

127