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M.Seitz | Catalytic Cracking of Lignites 23/06/16 | page 1 Methods for predicting the hydrocarbon yield in the catalytic cracking of lignite 8 th International Freiberg Conference on IGCC & XtL Technologies Innovative Coal Value Chains 12-16 June 2016, Cologne, Germany Mathias Seitz* , Armin Engelhardt*, Jens Zimmermann*, Timo Stam-Creutz*, Thomas Hahn** * University of Applied Science, Merseburg, Germany, **MLU Halle-Wittenberg, Halle, Germany
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Methods for predicting the hydrocarbon yield in the ... · Methods for predicting the hydrocarbon yield in the catalytic cracking of lignite 8th International Freiberg Conference

Oct 23, 2020

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  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 1

    Methods for predicting the

    hydrocarbon yield in the catalytic

    cracking of lignite

    8th International Freiberg Conference on IGCC & XtL Technologies

    Innovative Coal Value Chains

    12-16 June 2016, Cologne, Germany

    Mathias Seitz*, Armin Engelhardt*, Jens Zimmermann*, Timo Stam-Creutz*, Thomas Hahn**

    * University of Applied Science, Merseburg, Germany, **MLU Halle-Wittenberg, Halle, Germany

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 2

    BGR 2008

    reserves

    In Gt

    assumed

    accumulated

    production

    since 1950

    resources reserves production

    Introduction (1) Lignite: reserves, resources and production

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 3

    Introduction (2): different types of lignites

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 4

    oil

    lignite

    H rich

    yellow lignite:

    - high content of liptinite

    high content of aliphatic molecules

    Introduction (3): different types of lignites

    1872 Riebeck‘schen Montanwerke am Standort Oberröblingen;

    Quelle: LMBV

    Historical oil and paraffin production

    by low-temperature carbonisation

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 5

    Batch Concept of Catalytic Cracking

    cracking in situ

    at 400 – 600°C no use of hydrogen

    no heavy tar formation

    catalyst regeneration

    catalyst coated beads

    inert gas

    solids

    (char/catalyst separation)

    vapor

    (gas/liquid separation)

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 6

    meth

    an

    e

    eth

    an

    e

    eth

    en

    e

    pro

    pan

    e

    pro

    pen

    e

    bu

    tan

    e

    bu

    ten

    e

    pen

    tan

    e

    pen

    ten

    e

    hexan

    e

    hexen

    e

    C7

    C8

    ben

    zen

    e

    tolu

    en

    e

    eth

    ylb

    en

    zen

    e

    xyle

    ne

    meb

    0,0

    0,5

    1,0

    1,5

    2,0

    yie

    ld [

    %m

    af]

    without catalyst

    catalyst powder

    beads

    excess powder

    Typical products

    Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst ratio = 20 : 1; MFI

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 7

    mining

    NIR-

    analysis

    prediction

    H/C ratio

    prediction

    HC yield

    batch

    prediction

    HC yield

    continuous

    Three steps of modeling - from mining to hydrocarbons -

    H/C ratio as a light

    measurable factor

    to predict the

    hydrocarbon yield.

    Easy statements

    about the

    achievable

    products.

    Prompt information

    about the potential of

    the lignite.

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 8

    Characterization of molar H/C ratio

    NIR spectrum of lignite to determine the molar H/C-ratio Cepus, V., et. al. IR Spectroscopic Characterization of Lignite as a Tool to Predict the Product Range of Catalytic Decomposition, International Journal of Clean Coal and Energy (2016) 5, pp. 13-22

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 9

    Characterization of molar H/C ratio

    Cepus, V., et. al. Journal of Clean Coal and Energy (2016) 5, pp. 13-22

    Assumption:

    - molar O/C ratio

    has no influence

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 10

    Influence of the molar H/C ratio

    Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst ratio = 20 : 1; MFI

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 11

    0.00 0.02 0.04 0.06 0.08 0.100

    5

    10

    15

    20

    different CTC; H/C 1.3

    variation modulus H/C; 1.3

    different CTC; H/C 1.02

    variation modulus H/C; 1.02yie

    ld p

    er

    lig

    nit

    e (

    ma

    f) i

    n M

    a-%

    amount of acid sites (maf) in mmol/g

    Influence of the amount of acid sites

    Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst ratio = 20 : 1; MFI

    CTC: catalyst to

    coal ratio (mass)

    modulus: molar

    Al2O3/SiO2 ratio

    of the catalyst

    modulus > 60 because of less

    contact of catalyst and lignite

    and coking

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 12

    Influence of the amount of …

    Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst ratio = 20 : 1; MFI

    - different catalysts

    - different catalyst properties

    - H/C ratio; O/C ratio

    - temperature

    - catalyst to coal ratio

    - gas residence time

    - solid residence time

    - inert gas/solid ratio

    - reactor operation mode; flash behaviour

    - coal/catalyst contact

    - water content of the lignite

    Nearly all measurements

    of the batch process

    (except some catalyst

    types) were used to find a

    an as easy as possible

    model !

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 13

    Batch model

    4

    6

    8

    10

    12

    14

    16

    18

    20

    22

    24

    ad

    jus

    ted

    hy

    dro

    ca

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    n y

    ield

    C1

    -C9

    [%

    ma

    f]

    0,8 0,9 1 1,1 1,2 1,3 1,4molar H/C-ratio [-]

    0,2 0,4 0,6 0,8modificated acidic centre ratio [-]

    450 500 550temperature [°C]

    Adjusted Response Graph - Hydrocarbon yield C1-C9 (86 experiments)

    a -1,13E+02 9,91%

    b 4,14E-01 11,52%

    c 3,13E+01 4,95%

    d -5,37E-02 8,52%

    e -3,16E-04 15,71%

    R2 = 0,9827

    𝒀𝑪𝟏−𝟗 = 𝒂 + 𝒃 ∙ 𝑻 °𝑪 + 𝒄 ∙𝒏𝑯𝒍𝒊𝒈𝒏𝑪𝒍𝒊𝒈

    ∙𝒏𝑨𝒄𝒎𝒐𝒅𝒎𝒍𝒊𝒈

    + 𝒅 ∙ 𝑻 ∙𝒏𝑨𝒄𝒎𝒐𝒅𝒎𝒍𝒊𝒈

    + 𝒆 ∙ 𝑻𝟐

    HC yield

    parity plot

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 14

    Continuous concept of catalytic cracking

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 15

    batch reactor conti reactor

    From batch to a continuous reactor

    carrier

    gas

    carrier

    gas

    Reaction parameters:

    gas residence time: 1 sec

    lignite residence time 40 sec

    Reaction parameters:

    gas residence time: 100 sec

    lignite residence time 40 min

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 16

    0

    2

    4

    6

    8

    oil

    ph

    as

    e

    me

    b

    xy

    len

    e

    C7

    eth

    ylb

    en

    ze

    ne

    he

    xe

    ne

    tolu

    en

    e

    be

    nze

    ne

    C8

    he

    xa

    ne

    yie

    ld [

    % m

    af]

    batch H/C 1.1

    batch H/C 1.3

    continuous H/C 1.3

    pe

    nte

    ne

    pe

    nta

    ne

    bu

    ten

    e

    bu

    tan

    e

    pro

    pe

    ne

    pro

    pa

    ne

    eth

    en

    e

    eth

    an

    e

    me

    tha

    ne

    Batch and continuous reactor

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 17

    Continuous model:

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 18

    Continuous model: parameter value error

    3.207 ± 18 %

    0.929 ± 18 %

    2.284 ± 7,4 %

    HC yield

    parity plot

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 19

    Continuous model vs batch

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 20

    Continuous model vs batch

    more

    catalyst

    activity has to be

    adjusted to the

    amount of volatile

    matter and the gas

    residence time

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 21

    H/C 1.3 (with transfer of the linear batch relation to the continuous model)

    CTC 1:10; T 600°C

    batch model: YHC = 27.7%

    continuous model: YHC = 27.0%

    continuous measured: YHC = 28.7%

    Continuous model vs batch –

    extrapolation/validation

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 22

    Summary

    lignite is an interesting feedstock

    - cheap, - available, - can obtain paraffins

    catalytic conversion in situ without hydrogen to

    olefins (about 11 % maf) and aromatics is possible

    model for

    - rapid prediction of molar H/C ratio is possible

    - prediction of HC yield of batch process is possible

    - prediction of HC yield of continuous process is possible

    but work is to be done.

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 23

    - physico-chemical based models

    - models to describe the single products

    - extension to different lignites with higher O/C

    - improvement of the continuous model in

    consideration of the residence time

    - catalyst and its properties

    Outlook

  • M.Seitz | Catalytic Cracking of Lignites

    23/06/16 | page 24

    Acknowledgement

    for financial support

    for cooperation

    03WKBZ05