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    Catalytic Reforming

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    Anonymous 1Faavt
    Catalytic reforming uses catalytic reactions to process primarily low octane heavy straight run gasoline and naphtha into high octane aromatics. Major types of reactions include dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics, isomerization, and hydrocracking. Feedstocks are usually hydrotreated first to remove contaminants. In continuous reforming processes, catalysts can be regenerated one reactor at a time without disrupting operations.

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    Catalytic Reforming

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    Anonymous 1Faavt
    485 views35 pages
    Catalytic reforming uses catalytic reactions to process primarily low octane heavy straight run gasoline and naphtha into high octane aromatics. Major types of reactions include dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics, isomerization, and hydrocracking. Feedstocks are usually hydrotreated first to remove contaminants. In continuous reforming processes, catalysts can be regenerated one reactor at a time without disrupting operations.

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    Catalytic reforming uses catalytic reactions to process primarily low octane heavy straight run gasoline and naphtha into high octane aromatics. Major types of reactions include dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics, isomerization, and hydrocracking. Feedstocks are usually hydrotreated first to remove contaminants. In continuous reforming processes, catalysts can be regenerated one reactor at a time without disrupting operations.

    Copyright:

    © All Rights Reserved
    485 views35 pages

    Catalytic Reforming

    Uploaded by

    Anonymous 1Faavt
    Catalytic reforming uses catalytic reactions to process primarily low octane heavy straight run gasoline and naphtha into high octane aromatics. Major types of reactions include dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics, isomerization, and hydrocracking. Feedstocks are usually hydrotreated first to remove contaminants. In continuous reforming processes, catalysts can be regenerated one reactor at a time without disrupting operations.

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    of 35

    CATALYTIC REFORMING

    CONTENTS
    • INTRODUCTION
    • FEED STOCK
    • REACTIONS
    • PROCESS VARIABLES
    • REFORMING CATALYST
    • CATALYST CHEMISTRY
    • VARIOUS CATALYTIC REFORMING PROCESSES
    • CLASSIFICATION OF C.R PROCESSES
    • UOP PLATFORMING PROCESS
    • CATALYST REGENERATION
    • REACTOR DESIGN
    • Conclusion
    • Q&A
    INTRODUCTION
    • Demand of high-octane gasoline.
    • 30-40 % of gasoline production is by C.R.
    • The production might decrease by the
    implementation on the aromatic content of
    gasoline.
    • Only change in molecular structure so B.P
    of the feedstock after the process is small.
    • C.R increases the octane of motor gasoline
    rather than increasing its yield. (in fact due
    to cracking there is a decrease in yield).
    FEED STOCK
    • Feed consists of
     Heavy straight run gasoline (HSR)
    Naphtha
     Heavy hydrocracker naphtha
    • Naphtha containing (C6-C11) chain paraffins,
    olefins, naphthenes & aromatics.
    • Aromatics in feed remains unchanged
    COMPOSITION OF FEED
    STOCK
    Major hydrocarbon groups (PONA)

    Paraffin

    Olefin Aromatics

    Naphthenes
    PONA ANALYSIS (VOL%)

    FEED PRODUCT

    Paraffins 30-70 30-50

    Olefins 0-2 0-2

    Naphthenes 20-60 0-3

    Aromatics 7-20 45-60


    Basics of Catalytic Reforming
    •Catalytic reforming uses catalytic reactions to process
    primarily low octane heavy straight run (from the crude
    distillation unit) gasoline and naphtha into high octane
    aromatics (including benzene).
    •Major types of reactions which occur during reforming
    processes : 1) dehydrogenation of naphthenes to aromatics;
    2) dehydrocyclization of paffins to aromatics; 3)
    isomerization; and 4) hydrocracking.
    •Feedstocks to catalytic reforming processes are usually
    hydrotreated first to remove sulfur, nitrogen and metallic
    contaminants.
    •In continuous reforming processes, catalysts can be
    regenerated one reactor at a time, once or twice per day;
    without disrupting the operation of the unit.
    REACTIONS
    4 major reactions are categorized as

    Desirable

    • Dehydrogenation of naphthenes to
    aromatics
    • Dehydocyclization of paraffins to aromatics
    • Isomerization

    Undesirable

    • Hydrocracking
    Dehydrogenation &
    Dehydrocyclization
    • Highly endothermic
    • Cause decrease in
    temperatures
    • Highest reaction rates + H2

    • Aromatics formed
    have high B.P so end
    point of gasoline rises
    n-C7H16 + H2
    Favourable conditions
    • High temperature
    • Low pressure
    • Low space velocity
    • Low H2/HC ratio
    Isomerization
    • Branched isomers
    increase octane
    rating
    • Small heat effect
    • Fairly rapid reactions

    Favourable conditions
    + H2
    • High temperature
    • Low pressure
    • Low space velocity
    • H2/HC ratio no
    significant effect
    Hydrocracking
    • Exothermic reactions
    • Slow reactions
    • Consume hydrogen +
    • Produce light gases
    • Lead to coking
    • Causes are high
    paraffin conc feed

    Favourable conditions
    • High temperature
    • High pressure
    • Low space velocity
    PROCESS VARIABLES
    Catalyst type
    • Chosen to meet refiners yield, activity and stability need

    Temperature
    • Primary control of changing conditions or qualities in reactor.
    • High temp increase octane rating but decrease run length.
    • High temp reduce catalyst stability but may be increased for
    declining catalyst activity. Measured in WAIT or WABT.

    Pressure
    • Pressure effects the reformer yield & catalyst stability.
    • Low pressure increases yield & octane but also increases coke
    make.
    • Low pressure decreases the temperature requirement for the given
    product quality
    PROCESS VARIABLES

    Space velocity
    • Amount of Naphtha processed over a given amount of catalyst.
    • Low space velocity favors aromatic formation but also promote
    cracking.
    • Higher space velocity allows less reaction time.
    H2 / HC ratio
    • Moles of recycle hydrogen / mole of naphtha charge
    • Recycle H2 plays a sweeping effect on the catalyst surface supplying
    catalyst with readily available hydrogen
    • Increase H2 partial pressure or increasing the ratio suppresses coke
    formation but promotes hydrocracking.
    Catalytic reforming (Axens)

    Application: Upgrade various types of naphtha to


    produce high-octane reformate, BTX and LPG.

    Description: Two different designs are offered. One


    design is conventional where the catalyst is
    regenerated in place at the end of each cycle.

    Operating normally in a pressure range of 12 to 25 kg


    /cm2 (170 to 350 psig) and with low pressure drop in
    the hydrogen loop, the product is 90 to 100 RONC.

    With its higher selectivity, trimetallic catalysts RG582


    and RG682 make an excellent catalyst replacement
    for semi-regenerative reformers.
    The second, the advanced Octanizing process, uses continuous
    catalyst regeneration allowing operating pressures as low as 3.5
    kg /cm2 (50 psig).

    This is made possible by smooth-flowing moving bed reactors


    (1–3) which use a highly stable and selective catalyst suitable for
    continuous regeneration (4).

    Main features of Axens’ regenerative technology are:

    Side-by-side reactor arrangement, which is very easy to erect


    and consequently leads to low investment cost.

    The Regen C2 catalyst regeneration system featuring the dry


    burn loop, completely restores the catalyst activity while
    maintaining its specific area for more than 600 cycles.
    Finally, with the new CR401 (gasoline mode) and
    AR501 (aromatics production) catalysts specifically
    developed for ultra-low operating pressure and the
    very effective catalyst regeneration system, refiners
    operating Octanizing or Aromizing processes can
    obtain the highest hydrogen, C5+ and aromatics
    yields over the entire catalyst life.
    Installation: Of 111 units licensed, 64 units are designed with
    continuous regeneration technology capability.

    Reference: “Continuing Innovation In Cat Reforming,” NPRA


    Annual Meeting, March 15 –17, 1998, San Antonio.

    “Fixed Bed Reformer Revamp Solutions for Gasoline Pool


    Improvement,” Petroleum Technology Quarterly, Summer 2000.

    “Increase reformer performance through catalytic solutions,”


    Seventh ERTC, November 2002, Paris.

    “Squeezing the most out of fi xed-bed reactors,” Hart Show


    Special, NPRA 2003 Annual.

    Licensor: Axens.
    Catalytic reforming (Howe Baker)
    Application: Increase the octane of straight-run or
    cracked naphtha's for gasoline production.
    Products: High-octane gasoline and hydrogen-rich
    gas. Byproducts may be LPG, fuel gas and steam.

    Description: Semi-regenerative multibed reforming


    over platinum or bimetallic catalysts.
    Hydrogen recycled to reactors at the rate of 3 mols /
    mol to 7 mols /mol of feed.
    Straight-run and /or cracked feeds are typically
    hydrotreated, but low-sulfur feeds (<10 ppm) may be
    reformed without hydrotreatment.
    Operating conditions: 875°F to 1,000°F and 150 psig
    to 400 psig reactor conditions.
    Yields: Depend on feed characteristics, product octane
    and reactor pressure.

    The following yields are one example. The feed


    contains 51.4% paraffins, 41.5% naphthenes and 7.1%
    aromatics, and boils from 208°F to 375°F (ASTM D86).
    Product octane is 99.7 RONC and average reactor
    pressure is 200 psig.
    Economics:

    Utilities, (per bbl feed)


    Fuel, 103 Btu release 275
    Electricity, kWh 7.2
    Water, cooling (20°F rise), gal 216
    Steam produced (175 psig sat), lb 100

    Licensor:CB&I Howe-Baker Process and


    Technology.
    Catalytic reforming (UOP LLC)

    Application: The CCR Platforming process is used


    throughout the world in the petroleum and
    petrochemical industries. It produces feed for an
    aromatics complex or a high-octane gasoline
    blending product and a significant amount of
    hydrogen.

    Description: Hydrotreated naphtha feed is


    combined with recycle hydrogen gas and heat
    exchanged against reactor effluent. The combined
    feed is then raised to reaction temperature in the
    charge heater and sent to the reactor section.
    Radial-flow reactors are arranged in a vertical stack.

    The predominant reactions are endothermic; so an


    interheater is used between each reactor to reheat the
    charge to reaction temperature.

    The effluent from the last reactor is heat exchanged


    against combined feed, cooled and split into vapor
    and liquid products in a separator.

    The vapor phase is hydrogen-rich. A portion of the


    gas is compressed and recycled back to the reactors.

    The net hydrogen-rich gas is compressed and


    charged together
    with the separator liquid phase to the product
    recovery section.

    This section is engineered to provide optimum


    performance.

    Catalyst flows vertically by gravity down the


    reactor stack.

    Over time, coke builds up on the catalyst at


    reaction conditions.

    Partially deactivated catalyst is continually


    withdrawn from the bottom of the reactor
    stack and transferred to the CCR regenerator.
    Installation: UOP commercialized the CCR
    Platforming process in 1971 and now has
    commissioned more than 180 units (more than 3.9
    million bpd of capacity) with another 30 in various
    stages of design, construction and
    commissioning.

    Efficiency/product quality: Commercial on stream


    efficiencies of more than 95% are routinely
    achieved in CCR Platforming units.

    Licensor: UOP LLC.


    REFORMING
    CATALYST
    • Catalyst used now a days is platinum on alumina base.
    • For lower pressure stability is increased by combining
    rhenium with platinum.
    • Pt serve as a catalytic site for hydrogenation and
    dehydrogenation reactions
    • Chlorinated alumina provides acid site for isomerization,
    cyclization & hydrocracking reactions.
    • Catalyst activity reduced by coke deposition and
    chlorine loss.
    • As catalyst age’s activity of the catalyst decreases so
    temperature is increased as to maintain the desired
    severity.
    CATALYST CHEMISTRY
    Properly balanced catalyst
    Metal-Acid balance

    Cl Acid function
    Cracking

    Metal- Pt function
    Demethylation
    Dehydrogenation
    Dehydrocyclization
    Isomerization
    VARIOUS C.R. PROCESSES
    • Platforming (UOP)
    • Powerforming (Exxon)
    • Ultraforming (Amoco)
    • Magnaforming (ARCO)
    • Rheniforming (Cheveron)

    Classification of processes

    Continuous Semi Regenerative Cyclic


    CATAYST REGENERATION

    • Performance of the catalyst decreases wrt


    time due to deactivation.
    • Reasons for deactivation
    Coke formation
    Contamination on active sites
    Agglomeration
    Catalyst poisoning
    • Activity could be restored if deactivation
    occurred because of coke formation or
    temporary poisons.
    CATAYST REGENERATION

    • Objective of regeneration
    Surface area should be high
    Metal Pt should be highly dispersed
    Acidity must be at a proper level
    • Regeneration changes by the severity of the
    operating conditions
    • Coke formation can be offset for a time by
    increasing reaction temperatures.
    CONCLUSIONS
    • Purpose of reforming process is to improve RONC.
    • The basic and fastest reaction is naphthene
    conversion to aromatic so the feed rich in
    naphthene that is rich naphtha is preferred as a
    feed.
    • Useful operating condition is at low pressure, low
    space velocity & high temperatures.
    • The platinum is thought to serve as a catalytic site
    for hydrogenation & dehydrogenation reactions
    • While chlorinated alumina as an acid site for
    isomerization & hydrocracking reactions.
    • The activity of the catalyst decreases during the on
    stream period hence leading to regeneration.

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