02 Feedstocks & Products

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    JohnJechura jjechura@mines.edu

    Updated:August9,2014

    RefineryFeedstocks &Products Properties&Specifications

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    Light Naphtha

    CrudeOil

    Desalter

    AtmosphericDistillation

    VacuumDistillation

    GasSeparation &

    Stabilizer

    SolventDeasphalting

    Coking

    Visbreaking

    FluidizedCatalyticCracking

    Hydro-cracking

    NaphthaReforming

    Isom-erization

    Sat GasPlant

    Polymer-ization

    Alkylation

    NaphthaHydro-treating

    Treating &

    Blending

    Coke

    Fuel Gas

    LPG

    AviationGasoline

    AutomotiveGasoline

    Solvents

    Jet Fuels

    Kerosene

    Solvents

    Heating Oils

    Diesel

    ResidualFuel Oils

    Lubricant

    Greases

    Waxes

    Asphalts

    HeavyNaphtha

    Kerosene

    Distillate

    AGO

    LVGO

    HVGO

    VacuumResiduum

    CatDistillates

    Gas OilHydro-treating

    DAO

    Isomerate

    Gas

    AlkylFeed

    Alkylate

    PolymerizationNaphtha

    Gases

    Butanes

    LPG

    Reformate

    Naphtha

    Fuel OilBottoms

    Distillates

    Distillate

    Hydro-treating

    CatNaphtha

    Cycle Oils

    SDABottoms

    CokerNaphtha

    Heavy

    CokerGasOil

    Light CokerGas Oil

    SulfurPlant

    Sulfur

    Naphtha

    Fuel Oil

    SolventDewaxing

    Lube Oil

    Waxes

    2

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    Topics

    Quantity&Quality

    Chemicalcomposition

    Distillationanalyses

    Propertiesofdistillationfractions

    Productsasdefinedbytheirproperties&specifications

    Composition,boilingpointranges,and/orvolatility

    Propertiesspecificforcertaindistillationfractions

    Autoignition tendency octane&cetane number

    3

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    Topics

    Quantity&Quality

    Chemicalcomposition

    Distillationanalyses

    Propertiesofdistillationfractions

    Productsasdefinedbytheirproperties&specifications

    Composition,boilingpointranges,and/orvolatility

    Propertiesspecificforcertaindistillationfractions

    Autoignition tendency octane&cetane number

    4

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    CrudeOilasRefineryFeedstock

    CrudeOil

    Complexmixtureofhydrocarbons&heterocompounds

    Dissolvedgasestononvolatiles(1000F+boilingmaterial)

    C1toC90+

    Compositionsurprisinglyuniform

    5

    Element Wt%

    Carbon 8487

    Hydrogen 1114

    Sulfur 0

    5

    Nitrogen 00.2

    Otherelements 00.1

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    PrimaryHydrocarbonMolecularTypes

    Paraffins

    Carbonatomsinterconnectedbysinglebond

    Otherbondssaturatedwithhydrogen

    Naphthenes

    Ringedparaffins (cycloparaffins)

    Allotherbondssaturatedwithhydrogen

    Aromatics

    Sixcarbon

    ring

    (multiple

    bonding)

    Bondsinring(s)areunsaturated

    Olefins

    Usuallynotincrudeoil

    Formed

    during

    processing

    Atleasttwocarbonatomsinterconnectedby(unsaturated)doublebond

    6

    DrawingsfromNISTChemistryWebBook

    http://webbook.nist.gov/chemistry/

    nHexane iHexane

    Cyclohexane Methylcyclopentane Decalin

    Benzene Naphthalene

    1Hexene cis3Hexene trans3Hexene

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    ExampleHeterocompounds

    7

    Composition&AnalysisofHeavyPetroleumFractions

    K.H.Altgelt &M.M.Boduszynski

    MarcelDekker,Inc.,1994,pg.16

    ModelingandSimulationofCatalyticReactorsforPetroleumRefining.

    byJorgeAncheyta,JohnWiley&Sons,2011

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    DistributionofCompounds

    8

    Carbon Paraffin

    No. C F Isomers

    5 36 97 3 Gasoline

    8 126 259 18

    10 174 345 75

    12 216 421 355

    15 271 520 4347 Diesel & jet fuels, middle distillates

    20 344 651 3.66E+05 Vacuum gas oil

    25 402 756 3.67E+07 Atmospheric residue

    30 449 840 4.11E+09

    35 489 912 4.93E+1140 522 972 6.24E+13

    45 550 1022 8.22E+15

    60 615 1139 2.21E+22 Vacuum residue

    80 672 1242 1.06E+31

    100 708 1306 5.92E+39 Nondistillable residue

    Boiling Point

    Examples

    Composition&AnalysisofHeavyPetroleumFractions

    K.H.Altgelt &M.M.Boduszynski

    MarcelDekker,Inc.,1994,pp.23&45

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    CrudeOilAssay

    Indicatesdistributionquantity&qualityofcrudeoilfeedstock

    Definitionsbaseduponboilingpointtemperatureranges

    Representsexpectedproductsfromcrude&vacuumdistillation

    Completenessofdatadependsuponsource

    Publicreportvs.inhouseanalyticallaboratory

    Qualitymeasures

    Specific/API

    gravity

    Sulfurcontent

    Octanenumber

    Cetanenumber

    Viscosity

    Carbonresidue

    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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    DistillationAnalysisTypes

    ASTMD86

    Lowresolution nopacking,

    refluxfromheatlosses

    1atm;

    no

    hotter

    than

    650F

    minimizecracking

    CorrelationstocorrecttoTBPbasis

    17

    http://www.koehlerinstrument.com/products/K45601.html

    0

    100

    200

    300

    400

    500

    600

    0 100 200 300 400 500

    D86Temperature[F]

    TBPTemperature[F]

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    DistillationAnalysisTypes

    ASTMD1160

    Usedonresids (650F+)

    Relativelylowresolution

    Vacuumconditions 10

    to40mmHg;nohotter

    than1000FAEBP

    Correlationstocorrectto

    atmosphericpressure&

    TBPbasis

    18

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

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    DistillationAnalysisTypes

    ShortPathDistillation

    Singlestageflash

    Extremelylowpressures

    0.1mmHg

    or

    less

    Characterizedeepcutresids

    19

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

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    DistillationAnalysisTypes

    SimulatedDistillation ASTM2887

    Relativelylowresolutiongaschromatography

    Severalthousandtheoreticalstages

    EssentiallyTBPtemperatures wt%basis

    Temperaturesinferredfromelutiontimes

    Calibratedwithnparaffinmixture

    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

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