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    Haldor Topsoe PDF

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    Slamet Purwadi S.T

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    © All Rights Reserved
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    Haldor Topsoe PDF

    Uploaded by

    Slamet Purwadi S.T
    232 views28 pages

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    Haldor-Topsoe.pdf

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    232 views28 pages

    Haldor Topsoe PDF

    Uploaded by

    Slamet Purwadi S.T

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 28

    Challenges in Steam Reforming

    Steam Reforming Technology User Conference


    5-7 March 2007
    Bo Hartvigsen, Sales Manager, Haldor Topsoe
    A/S
    Challenges in Steam Reforming
    Agenda:
    1. Carbon formation
    2. Poisoning of catalyst (sulphur)
    3. Sintering of catalyst
    4. Loading
    Carbon Formation

    +H2O
    C2H6 2 CO + 5 H2
    Reforming

    2 C + 3 H2
    Carbon
    CARBON FORMATION
    Two types of carbon formation:

    • Catalytic cracking • Thermal cracking


    (on Ni crystals) (on hot surfaces)

    Carbon whiskers, physical Hot bands, NO physical


    damage of catalyst damage of catalyst
    Pyrolytic carbon (thermal cracking)
    Catalyst deactivation and
    carbon formation
    Carbon formation from higher hydrocarbons

    Actual (high activity) Actual (low activity)


    14
    Critical
    12
    hydrocarbon radio
    Steam to higher

    10
    8
    Carbon formation
    6
    4
    2
    0
    0 1 2 3 4 5
    m from inlet
    Formation of hot bands
    CnHm CnHm

    C 500°C C
    nH nH
    m m

    C nH m
    C nH m
    C nH m C nH m

    C nH m
    Cn
    Hm
    C nH m

    850°C
    High Low
    activity activity
    Hot Bands in top fired reformer
    Hot spots in a side-fired reformer
    Reformer design

    Radiant Wall Top Fired Bottom Fired Terrace Wall


    Topsøe MW Kellogg Chemico Foster Wheeler
    Selas KTI Girdler
    UHDE
    Risk for carbon formation is higher in a top fired reformer
    How to Prevent Carbon Formation

    1. High activity: reform higher hydrocarbons


    at low temperatures

    2. Use less acidic carrier

    3. Promote with alkali

    4. (Prereforming)
    Impact of Alkali
    Alkali lower catalyst activity, especially at low temperatures

    Relative Activity

    0
    400 500 600 700
    Catalyst Temperature
    Sulphur Poisoning

    Sulphur blocks the Nickel surface area

    Nisurface + H2S ↔ S-Nisurface + H2


    Temperature dependence

    Sulphur Coverage
    1 ppbv=10
    ppbv=50
    ppbv=100
    0.8

    0.6

    0.4
    500 550 600 650 700 750 800 850 900
    Temperature, °C
    Dynamics of poisoning

    Sulphur Coverage
    Year 1
    1
    Year 2
    0.9 Year 3
    0.8 Equilibrium
    0.7
    0.6
    0.5
    0.4
    0.3
    0.2
    0.1
    0
    0 20 40 60 80 100
    Tube Length, %
    Desorption of sulphur
    S-Nisurface + H2 ↔ Nisurface + H2S

    Sulphur Coverage

    1.0

    0.8

    0.6

    0.4

    0.2

    0.0
    1 10 100 1000 10000
    Time, hr

    700 °C 800 °C
    Sulphur Regeneration
    S-Nisurface + H2O → NiO + H2S
    H2S + 2 H2O → SO2 + 2 H2

    Steam SV : 4000 and T(exit): 800


    1000 TWT's 400
    Temperature °C

    980 300

    PPM SO2
    Before
    960 After
    200
    940
    920 SO2 100
    900 0
    0 2 4 6 8 10
    Time
    Regeneration for Carbon
    C + O2 → CO2

    Steam SV : 4000 and T(exit): 800


    6
    O2
    4 CO2
    %
    2

    0
    8 9 10 11 12
    Time
    Sintering

    • Decreased C tolerance
    • Decreased S tolerance
    • Decreased activity
    Fresh Used

    Fresh
    Sintering of Nickel Surface
    (Ceramic Reforming Catalyst)

    1.0
    after sinteri ng s/s0
    Relative N i area

    0.8 550°C

    0.6
    700°C
    0.4

    0.2
    800°C
    0
    1 10 100 1000
    Time/hours
    Triple Decker

    900 Sulphur Carbon Sintering

    850
    Temperature

    TWT
    800 Catalyst

    750
    RK-211 RK-201 R-67-7H

    700
    0 2 4 6 8 10
    Distance from Inlet, m
    Properties of Topsoe Reforming Catalyst

    R-67-7H : Carrier: MgAl2O4 (spinel)


    Ni content: 14 %
    RK-201: Carrier: CaAl2O4 + MgAl2O4
    Ni content: 12 %
    K content: 0.4 %
    RK211: As RK-201 except :
    Doped with noble metal
    Prereduced
    Reformer loading techniques
    • Sock loading
    • Unidense™
    • SpiraLoad™
    SpiraLoad loading tube
    The SpiraLoad™ technique
    Comparison of reformer loading
    techniques

    Sock loading Unidense™ SpiraLoad™

    Time pr. tube, min 30-40 15-20 15-20

    Tubes unloaded, % ~2 ~2 0.01

    Manpower Demanding Normal Normal

    Automised Low Low High


    END
    CHALLENGES IN STEAM REFORMING

    QUESTIONS?

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