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Biomass to Olefins: Steam Cracking of · PDF fileBiomass to Olefins: Steam Cracking of RenewableFeedstocks. Outline 2 ... Renewable Naphtha Steam Cracking 15 Methusalem Advisory Board

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  • Laboratory for Chemical Technology, Ghent University

    http://www.lct.UGent.be

    Steven P. Pyl

    1

    Methusalem Advisory Board Meeting, June 19, 2012

    Biomass to Olefins:

    Steam Cracking of Renewable Feedstocks

  • Outline

    2

    Methusalem Advisory Board Meeting, June 19, 2012

    Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass

    Feedstock analyses

    Effect of feedstock on product yields

    Effect of feedstock on run-length

    Introduction: Green Olefins

    Conclusions

    Reactor and Kinetic modeling

    Effect of Coil Outlet Temperature on product yields

  • Poultry Fat to Olefins

    3

    Methusalem Advisory Board Meeting, June 19, 2012

    Hydrocracking

    + FractionationGREEN

    OLEFINS

    Steam Cracking

    Steam Cracking

    LPG (C3-C4)Jet Fuel (C10-C15)

    HDO FAT(C14-C26 n-Paraffins)

    Renewable Naphtha(C4-C10)

    CO, CO2, H2O

    Hydro-deoxygenation

    Poultry Fat & YellowGrease

  • Tall Oil to Olefins

    4

    Methusalem Advisory Board Meeting, June 19, 2012

    TOFA

    DTO

    Heads

    Pitch

    Crude Tall Oil Refining

    Pine Wood

    Kraft PulpingProcess

    Wood Pulp

    CrudeTall Oil

    TOFA

    GREEN OLEFINS

    HDO TOFA(C14-C26 n-Paraffins)

    Hydro-deoxygenationTOFA

    SteamCracking

  • Outline

    5

    Methusalem Advisory Board Meeting, June 19, 2012

    Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass

    Feedstock analyses

    Effect of feedstock on product yields

    Effect of feedstock on run-length

    Introduction: Green Olefins

    Conclusions

    Reactor and Kinetic modeling

    Effect of Coil Outlet Temperature on product yields

  • Detailed Feedstock Analyses

    6

    Methusalem Advisory Board Meeting, June 19, 2012

    Using comprehensive 2D gas chromatography

    Hydrodeoxygenated Tall Oil Fatty Acids (TOFA) HDO-TOFA

    GC GC-FID

  • Fossil vs. Renewable Feedstocks

    7

    Methusalem Advisory Board Meeting, June 19, 2012

    HDO-FAT HDO-TOFARenewable Naphtha

    Gas Oil Natural Gas CondensateNaphtha

  • Steam Cracking Pilot Plant

    8

    Methusalem Advisory Board Meeting, June 19, 2012

    Gas-Fired Furnace + Reactor

    Online Analysis Section

    Control Room

    High temperaturesampling system

    HCFeed

    H2O

    CH4 PAHs

  • Effect of feedstock on product yields

    9

    Methusalem Advisory Board Meeting, June 19, 2012

    Yields [wt%] = 0.45kg/kg

    Full-range Naphtha

    RenewableNaphtha

    HDO-FAT HDO-TOFA

    Methane 16.9 17.6 11.0 10.4

    CO 0.08 0.17 0.15 0.11

    CO2 0.01 0.02 0.07 0.08

    P/E = 0.50

    COT 870C 865C 835C 820C

    Fuel Oil 1.54 0.56 0.27 8.57

    ReferenceFeedstock

    Renewable Feedstocks

    Benzene 9.74 6.11 5.23 4.35

    Toluene 4.59 2.50 1.49 1.42

    Xylenes 1.35 0.54 0.18 0.26

    Ethylene 26.5 32.0 38.4 35.4

    Propylene 13.1 16.4 19.5 18.2

    1,3-butadiene 5.41 5.03 7.77 6.41

  • 3.5

    5.55

    2.5

    4.4

    5.8

    0

    1

    2

    3

    4

    5

    6

    7

    RenewableNaphtha

    HDO-FAT HDO-TOFA Ethane PetroleumNaphtha

    Natural GasCondensate

    g co

    kes

    / 6 h

    Effect of feedstock on run-length

    10

    Methusalem Advisory Board Meeting, June 19, 2012

    COT = 850C

    ReferenceFeedstocks

    Pilot plant cokes test Cokes formation during 6-h steady state operation

    RenewableFeedstocks

    To d

    o

  • Outline

    11

    Methusalem Advisory Board Meeting, June 19, 2012

    Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass

    Feedstock analyses

    Effect of feedstock on product yields

    Effect of feedstock on run-length

    Introduction: Green Olefins

    Conclusions

    Reactor and Kinetic modeling

    Effect of Coil Outlet Temperature on product yields

  • Reactor and Kinetic Modeling

    12

    Methusalem Advisory Board Meeting, June 19, 2012

    Concentration Profiles & Product YieldsTemperature and Pressure Profile

    System of Differential Equations

    Microkinetic Model

    Feedstock Composition

    Reactor Geometry

    Operating Conditions

    Free RadicalMechanism

    + 2121 RRRR

    HRRRHR 2121 ++

    321321 RRRRRR +=

    numericalintegration

    = =

    k

    n

    1kkj

    j rdz

    dF r

    ( ) +=j k

    krkV,pjj Hrq dzdT

    c F

    zu

    u u r d

    f 2zdpd

    g2

    g

    bt

    t

    +

    +=

    Plug flow

    Reactor Model

  • Single-event Microkinetic Model

    13

    Methusalem Advisory Board Meeting, June 19, 2012

    Microkinetic Model1. Automatic reaction network generation

    2. Group-additive calculation of rate coefficients

    3. Quasi steady state approximation for radicals

    4. In situ lumping of primary products

    5. A posteriori lumping of feed molecules

    51 paraffins168 olefins14 aromatics43 radicals

    276 species

    C0 C26C2 C26C6 C14C0 C70

    C0 C26

  • 0

    1

    2

    3

    4

    5

    6

    7

    8

    9

    740 760 780 800 820 840 860 880

    Yie

    ld [w

    t%]

    benzene

    toluene

    naphthalene

    0

    2

    4

    6

    8

    10

    12

    14

    16

    740 760 780 800 820 840 860 880

    Yie

    ld [w

    t%]

    Coil Outlet Temperature [ C]

    methane

    ethane

    propane

    HDO-FAT Steam Craking

    14

    Methusalem Advisory Board Meeting, June 19, 2012

    simulated yields (lines) vs.pilot plant yields (symbols)

    = 0.45 kg/kg

    Coil Outlet Temperature (COT)755C 865C

    0

    5

    10

    15

    20

    25

    30

    35

    40

    45

    740 760 780 800 820 840 860

    Yie

    ld [w

    t%]

    ethene

    propene

    1.3-butadiene

    Coil Outlet Temperature [ C]

  • 0

    1

    2

    3

    4

    5

    6

    7

    8

    760 780 800 820 840 860 880 900

    Yie

    ld [w

    t%]

    benzene

    naphthalene

    toluene

    0

    5

    10

    15

    20

    25

    30

    35

    40

    760 780 800 820 840 860 880 900

    Yie

    ld [w

    t%]

    ethene

    propene

    1,3-butadiene

    Renewable Naphtha Steam Cracking

    15

    Methusalem Advisory Board Meeting, June 19, 2012

    simulated yields (lines) vs.pilot plant yields (symbols)

    = 0.45 kg/kg

    Coil Outlet Temperature (COT)820C 860C

    0.0

    0.5

    1.0

    1.5

    2.0

    2.5

    3.0

    3.5

    4.0

    4.5

    5.0

    760 780 800 820 840 860 880 900

    Coil Outlet Temperature [ C]

    1-pentene

    1-butene

  • Outline

    16

    Methusalem Advisory Board Meeting, June 19, 2012

    Pilot Plant Steam Cracking of Hydrodeoxygenated Biomass

    Feedstock analyses

    Effect of feedstock on product yields

    Effect of feedstock on run-length

    Introduction: Green Olefins

    Conclusions

    Reactor and Kinetic modeling

    Effect of Coil Outlet Temperature on product yields

  • Conclusions

    Biowaste is a promising starting material for the production of green olefins

    Hydrodeoxygenation of waste fats as well as tall oilsproduces highly paraffinic liquids

    Steam cracking of these liquids results in high light olefin yields

    Microkinetic modeling provides a rigorous fundamental basis for industrial reactor models

    17

    Methusalem Advisory Board Meeting, June 19, 2012

  • 18

    Methusalem Advisory Board Meeting, June 19, 2012

    Thank you foryour attention!

  • Glossary

    19

    Methusalem Advisory Board Meeting, June 19, 2012

    Biowaste A variety of renewable animal and vegetal waste streamsarising from households, commerce and the foodmanufacturing industry.

    Comprehensive two-dimensional gas chromatography

    Advanced analytical technique that provides two-dimensional separation by combining two differentanalytical columns connected with an interface, calledthe modulator, that ensures that the entire sample iscomprehensively subjected to both separations.

    Group additive framework Framework that enables automated calculation ofthermodynamic or kinetic data from the structure of themolecule or transition state respectively by summation ofgroup-additive values.

    Hydrodeoxygenation A catalytic process which, in the presence of hydrogen,removes oxygen from organic components in the form ofwater. Common side-reactions are decarboxylation anddecarbonylation producing carbon dioxide and carbonmonoxide respectively.

    Tall oil A viscous yellow-black odorous liquid obtained as a by-product of the Kraft process of wood pulp manufacturewhen pulping mainly coniferous trees. The nameoriginated as an Anglicization of the Swedish "tallolja"("pine oil"). Crude tall oil can be fractionated into severalfractions, including so-called tall oil fatty acids (TOFA)and distilled tall oil (DTO).