Download pdf - 02 Feedstocks & Products

8/9/2019 02 Feedstocks & Products

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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







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

9


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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

13


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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

15


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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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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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ASTMD1160

Usedonresids (650F+)

Relativelylowresolution

Vacuumconditions 10

to40mmHg;nohotter

than1000FAEBP

Correlationstocorrectto

atmosphericpressure&

TBPbasis

18

http://www.lazarsci.com/d1160.htm


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ShortPathDistillation

Singlestageflash

Extremelylowpressures

0.1mmHg

or

less

Characterizedeepcutresids

19

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


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SimulatedDistillation ASTM2887

Relativelylowresolutiongaschromatography

Severalthousandtheoreticalstages

EssentiallyTBPtemperatures wt%basis

Temperaturesinferredfromelutiontimes

Calibratedwithnparaffinmixture

20


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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




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



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







25


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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

27


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SourcesofProductSpecifications

State&Federalregulatoryagencies

Environmentallaws

Reflectneedtoreducepollutionin

manufacturing&useoffuels

ASTM(AmericanSocietyforTestingandMaterials)Specifications&associatedtest

procedures

Specifications

drafted

considering

positions

ofindustry&regulatoryagencies

Industryassociations

AmericanPetroleumInstitute

GasProcessorsAssociation

AsphaltInstitute

Betweencompanies basedontypicalspecs

Negotiated

Deviationshavepredeterminedprice

adjustments

28


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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


32/124


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MotorGasolineSpecifications

35


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MotorGasolineVolatilityClasses(ASTMD481413)

36


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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


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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


38/124

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

40


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MiddleDistillates

Generalclassifications

Kerosene

Jetfuel

Distillatefueloil

Diesel

Heatingoil

Properties

Flashpoint

Cloudpoint/Pourpoint

Anilinepoint

Cetane number

Viscosity

Water&sediment

41


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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

42


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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

43


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OSHAFlammableLiquidDefinitions

44

Category FlashPoint

C(F)

BoilingPoint

C(F) Class

FlashPoint

C(F)

BoilingPoint

C(F)

Flammable1


43/124


44/124

AdditionalSpecifications

Sulfur

Controlofsulfuroxidesuponcombustion

Threelevels,reductionforthetraditionalfivecategories

AnilinePoint

Minimumtemperatureatwhichequalvolumesofaniline(C6H5NH2)andtheoilare

miscible

Thelowertheanilinepoint thegreaterthearomaticcontent

Viscosity

Fluidityduringstorageatlowertemperatures

Sediment&watercontent

Controllingcontamination

46


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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


46/124

JetFuelSpecifications

48


47/124

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


48/124

DieselSpecifications

50


49/124

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


50/124

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


51/124

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

53


52/124

ASTMFuelOilSpecs

54


53/124

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


54/124

ComparisonofBoilingRanges

56


55/124

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


56/124

LubricantTerminology

58

Phrase Meaning

Lubebasestock Lubeproductthatmeetsallspecifications

&issuitableforblending

Lubeslate Setoflubebasestocks,usually3to5

Neutrallubes Obtainedfromasidecutofthevacuum

distillationtower

Brightstocklubes Processedofvacuumresidfromthe

vacuumtowerbottoms

L b i t


57/124

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


58/124

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


59/124

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


60/124

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


61/124

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


62/124

Topics

Quantity&Quality

Chemicalcomposition



Productsas

defined

by

their

properties

&

specifications




65

Supplemental Slides


63/124

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

66


64/124


65/124

SAE 902098 Gasoline Blend Stock Analyses


66/124

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


67/124

ASTMD323RVPProcedures


68/124

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)


69/124

( )

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


70/124

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?


71/124

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?


72/124

Specificgravityisblended&APIgravityisbackcalculated.

MayhavetocalculateindividualspecificgravitiesfromgivenAPIgravities

Example

Incorrectvalue

from

direct

volume

blending

of

API

gravities

75

TemperatureCorrectionstoSpecificGravity


73/124

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)


74/124

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?


75/124

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?


76/124

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?


77/124

Blendbasedonpropertiesandamountsforthefractionineachblendstock,nottheoverallamountofblendstock.

80

HowDoWeCorrectBoilingPointforPressure?


78/124

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


79/124

Correcta437Fboilingpointmeasuredat40mmHgtothenormalboilingpoint(at760mmHg).

Usingthe2nd of3equationsdetermineX=0.001767618

WithT=896.67oRdetermineTB=1094.98

IfweneglecttheWatsonKfactorcorrection(i.e.,assumeKW=12)thenTB=TB

Normalboilingpointis635oF

82

HowDoWeInterconvertD86&TBPTemperatures?


80/124

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


81/124

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



82/124

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


83/124

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



84/124

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


85/124

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


86/124

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


87/124

HowDoWeUsetheProbabilityForm?


88/124

DistillationyieldcurvestypicallyhaveanSshape

Traditionaltolinearize onprobabilitygraphpaper

AxistransformedusingfunctionsrelatedtoGaussiandistributionfunction

Functionsavailable

in

Excel

TransformedYield: =NORMSINV( Pct_Yield/100 )

Frominterpolatedvalue: =NORMSDIST( Value ) * 100

Transformed0%&100%valuesundefined

TypicaltosetIBP&EPto1%&99%

91

LinearizedDistillationYieldCurves


89/124

92

Incrementalvs.CumulativeYield


90/124

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


91/124

Blendthedistillationcurvesforallblendstocks&extractthetemperaturesfromtheresultingcurve

Steps

ConvertallofthestartingdistillationanalysestoTBPbasis(@1atm)

PickasetofTBPtemperaturesforwhichtheblendcalculationswillproceed.Extractthe

yieldvaluesforattheseselectedtemperaturevaluesforallblendstocks.

Usewhatevertemperaturesseemreasonabletocoverthespanofallinputvalues

Calculateayieldcurvefortheblendatthetemperatureschoseninthepreviousstep

Extractthetemperaturevaluesforthespecifiedyieldvalues

Converttooriginaldistillationbasis(ifrequired)

94

DistillationCurveBlendExampleBlendStockData D86ConvertedtoTBP BlendatSpecifiedYieldsBlendatSelectedTemperatures


92/124

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


93/124

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%]


94/124

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


95/124

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


96/124

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


97/124

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



98/124

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



99/124

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


100/124

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


101/124

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


102/124

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


103/124

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)


104/124

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


105/124


106/124

Othercorrelations

GPSA

Fig.

6

4

makes

use

of

Kremser relationship(1930)for


107/124

TVP@100oF:

TVP=1.07(RVP)+0.6

110

Othercorrelations

SantaBarbara

County

APCD

Rule

325,

Attachment

B,

equation

25:


108/124

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


109/124

NonLinearOctaneBlendingFormula

Developedby

Ethyl

Corporation

using

aset

of

75

&

135

blends


110/124

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?


111/124

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


112/124

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


113/124

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)


114/124

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.


115/124

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


116/124

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


117/124

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


118/124

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%


119/124

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


120/124

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


121/124

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


122/124

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


123/124

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


124/124