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    Desulphurzation of Hydrocarbon Final MDF

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    Muhammad Abuzar Siddiqi
    This document discusses desulphurization of hydrocarbon feedstocks using hydrogenation and zinc oxide catalysts. It summarizes the reactions that take place to remove sulfur, the characteristics of Topsøe hydroprocessing catalysts TK-550/250 and zinc oxide catalyst HTZ-3/5, common problems in hydrodesulphurization units, and safety precautions when handling the spent catalysts.

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    Desulphurzation of Hydrocarbon Final MDF

    Uploaded by

    Muhammad Abuzar Siddiqi
    246 views26 pages
    This document discusses desulphurization of hydrocarbon feedstocks using hydrogenation and zinc oxide catalysts. It summarizes the reactions that take place to remove sulfur, the characteristics of Topsøe hydroprocessing catalysts TK-550/250 and zinc oxide catalyst HTZ-3/5, common problems in hydrodesulphurization units, and safety precautions when handling the spent catalysts.

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    desulfphurization

    Original Title

    Desulphurzation of Hydrocarbon Final Mdf

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    This document discusses desulphurization of hydrocarbon feedstocks using hydrogenation and zinc oxide catalysts. It summarizes the reactions that take place to remove sulfur, the characteristics of Topsøe hydroprocessing catalysts TK-550/250 and zinc oxide catalyst HTZ-3/5, common problems in hydrodesulphurization units, and safety precautions when handling the spent catalysts.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    246 views26 pages

    Desulphurzation of Hydrocarbon Final MDF

    Uploaded by

    Muhammad Abuzar Siddiqi
    This document discusses desulphurization of hydrocarbon feedstocks using hydrogenation and zinc oxide catalysts. It summarizes the reactions that take place to remove sulfur, the characteristics of Topsøe hydroprocessing catalysts TK-550/250 and zinc oxide catalyst HTZ-3/5, common problems in hydrodesulphurization units, and safety precautions when handling the spent catalysts.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 26
    At a glance
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    The key takeaways are that desulphurization involves hydrogenation and zinc oxide catalysts to remove sulfur from hydrocarbon feedstocks. Various hydrogenation reactions are used to convert organic sulfur to H2S and the zinc oxide acts as an absorbent for the H2S.

    The main hydrogenation reactions involved in desulphurization are the conversion of thiols, thiophenes, carbonyl sulfide, and other organic sulfur compounds to hydrogen sulfide and desulfurized hydrocarbons. Other reactions also occur such as the water-gas shift reaction.

    Catalyst activity is dependent on operating temperature and sulfur content in the feedstock. Activity generally increases with temperature up to around 350-400°C but can decrease at higher temperatures due to carbon laydown. Activity also increases with sulfur content up to around 10-15 ppm sulfur before declining.

    Desulphurisation of Hydrocarbon

    Feedstocks
    Using
    Hydrogenation & Zinc Oxide Catalysts
    Desulphurisation System Lay-outs
    Feed

    H2 HDS ZnO ZnO


    TK HTZ HTZ
    Hydrogenation Reactions
    Organic Sulphur
    RSH + H2  H2S + RH
    COS + H2  H2S + CO
    R1SR2+ 2H2  H2S + R1H + R2H
    R1SSR2 + 3H2  2H2S + R1H + R2H
    Thiophenes + 4H2  H2S + Hydrocarbons
    Other Reactions
    CO2 + H2  CO+H2O
    RCl +H2  HCL + RH
    Topsøe Hydrogenation Catalyst
    Physical and Chemical Characteristics

    Catalyst TK-550
    TK-250

    Shape Rings
    Dimensions OD x ID, mm 4.8 x 2.4
    Active Component CoMoSx
    Carrier Al2O3
    CoMoSx Phase
    Sulphur

    Molybdenum

    Catalyst pore Cobalt

    H2 + CH3SH H2S+ CH4


    CoMo Catalyst Activity as a Function
    of Sulphur Content in Natural Gas
    Catalyst Activity

    0 5 10 15 20 25
    Sulphur in Feed, ppm
    CoMo Catalyst Activity as a Function
    of Operating Temperature
    HDS Activity

    250 300 350 400


    Operating Temperature, C
    Catalyst Deactivation
    Reduction of Unsulphided Catalyst

    H2 + MoO3  MoO2 + H2O

    • Operation with low sulphur feedstock and


    high hydrogen during initial start-up
    Catalyst Deactivation - Carbon
    CH4  C + 2H2

    H2 + CH3SH H2 + CH3SH
    Catalyst Deactivation
    Pore Mouth Plugging
    New catalyst Plugged catalyst
    CH3SH

    Catalyst pore
    The Sulphur Absorption Reaction

    ZnO + H2S  ZnS + H2O

    Other Reactions

    CO2 + H2  CO + H2O

    2 HCl + ZnO  ZnCl2 + H2O


    Equilibrium H2S Outlet ZnO
    Vessel
    5% CO2 in Natural Gas
    100 5 % H2

    80 3 % H2

    2 % H2
    H2S eq. ppb

    60

    40

    20

    0
    300 320 340 360 380 400 420 440
    Temperature C
    Sulphur Profile in a Zinc Oxide Bed
    Zone 1: Bulk Saturation

    Zone 2: Main Absorption Front


    Sulphur Uptake

    Zone 3: Chemisorption Front

    Zone 1 Zone 2 Zone 3

    Top Bed Bottom Bed

    Direction of Gas Flow


    Typical Sulphur Uptake for HTZ-3
    40
    Sulphur Uptake, wt%

    35
    30
    25
    20
    15
    10
    5
    0
    100 200 300 400
    Operating Temperature, C
    Absorption Front - Zone 2
    Pore Diffusion

    H2S

    H2O
    Absorption Front - Zone 2
    Solid Diffusion

    H2S
    Chemisorption Front - Zone 3

    H2S
    ZnO
    Topsøe Zinc Oxide Catalyst
    Physical & Chemical Characteristics

    Catalyst HTZ-3 HTZ-5


    Shape Cylinders Cylinders
    Dimensions OD, mm 4 4
    Active Component ZnO ZnO
    Other Compounds Traces Traces
    Bulk Density, kg/l 1.3 1.0
    Common Problems Experienced
    in the HDS Section
    • Too low operating temperature
    • Too high operating temperature
    • No hydrogen recycle to HDS
    • Operation with fluctuating sulphur
    content in feedstock
    • CO2 in feedstock
    Low Operating Temperature
    in HDS Section

    • Risk of organic sulphur breakthrough due


    to insufficient catalyst activity
    • Decreased lifetime of zinc oxide due to
    less sulphur pick-up capacity
    High Operating Temperature
    in HDS Section
    CH4  C + 2H2

    • Potential risk of carbon lay-down from


    cracking of hydrocarbons resulting in
    reduced catalyst activity
    No Hydrogen Recycle to HDS

    • Risk of organic sulphur breakthrough as


    no hydrogenation takes place
    • The affinity for carbon lay-down on the
    catalyst is increased
    Fluctuating Sulphur Levels

    3
    H2S-in
    ppm Sulphur

    org-S-in
    2 org-S-exit

    0
    Time
    Monitoring the Performance of
    the HDS Section
    • Measure
    - Organic sulphur & H2S in the feedstock
    - Organic sulphur slip from hydrogenator
    - H2S concentration exit both desulphurisers

    • Check the pressure drop across the


    hydrogenator & desulphurisers and evaluate
    the trend
    Normal Operation of HDS Section
    • Maintain an operating temperature of
    360-380°C
    • Ensure an hydrogen recycle which is
    close to the recommended (design)
    value
    • Replace ZnO in lead vessel when H2S
    slip increases from this reactor
    Safety Precautions for
    TK-550/250 & HTZ-3

    • Catalyst which has been in operation may


    be pyrophoric and could heat up when
    getting in contact with air
    • Catalyst should be cooled down before
    opening the reactor manholes

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