Catalytic Reforming
Catalytic Reforming
Catalytic Reforming
Catalytic Reforming
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Gasoline Specification for Unleaded Premium
(from BS EN 228:2004)
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Significance of Octane Number
• Octane number is a measure of the “knocking” tendency of gasoline.
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Molecular Structure Determines Octane Number
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Chemistry of Catalytic Reforming
• Feed is typically heavy straight-run naphtha 80 - 190 °C.
(Lighter material tends to crack; heavier material hydrocracks and deposits
coke on the catalyst).
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Chemistry of Catalytic Reforming - Dehydrogenation
CH3 CH3
+ 3H2
Methyl Toluene
Cyclohexane
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Chemistry of Catalytic Reforming - Dehydrocyclisation
C H3C CH3
+ H2
C-C-C-C-C-C
Isoheptane
Dimethylcyclopentane
• A difficult reaction that requires both acid and metal function catalyst.
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Chemistry of Catalytic Reforming - Isomerisation
C C C C
C-C-C-C-C-C-C C-C-C-C-C-C
n-Heptane i-Heptane
Dimethylcyclopentane Methylcyclohexane
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Chemistry of Catalytic Reforming - Hydrocracking
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Chemistry of Catalytic Reforming - Catalyst
• Catalyst is bifunctional with both metal and acid sites:
Metal: Platinum and optional promoter metals (Re, Ir, Sn)
Acid: Alumina (Al2O3) with chloride
• Desirable reactions:
Dehydrogenation - Metal
Isomerisation - Acid
Dehydrocyclisation - Metal + Acid
• Undesirable reactions:
Hydrocracking - Metal or Acid
Dealkylation - Metal
Polymerisation
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Catalyst Deactivation and Regeneration
• Catalyst is deactiviated by coke.
Voorhies defines coke formation is proportional to square root of time
C = (k1 * θ) ½
and fraction of initial activity (A/Ao) is proportional to coke
ln (A/Ao) = k 2 * C
where: C is coke on catalyst
A and A0 are catalyst activities at times θ and 0
θ is time on oil
k1and k2 are constants.
• In continuous catalytic refomers, e.g. UOP CCR design, a slip stream of catalyst is
continually regenerated that permits runlengths of up to six years.
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Catalytic Reforming
Feed Lead
Preheat Reactor
Hydrofined
Exchangers
Naphtha
Feed
(Low
Octane)
i.e. 40
Preheat Reheat
Furnace Furnace
Recycle Additional
Gas Reactors
Reactor
Effluent
H2 Rich Coolers
Make Gas to
Refinery
Treat Gas
System
Effluent
Recycle Gas Separators
Compressor
Reformate
(High Octane)
i.e. 95
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Typical Fixed Bed Catalytic Reactor
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Operating Variables
• Catalyst type and properties (fresh and in-situ):
- Surface area.
- Chloride content.
- Platinum dispersion.
- Deactivation.
• Feed quality:
- Chemical composition (PIONA).
- Distillation range.
- Impurities - sulphur, nitrogen, metals, etc.
• Process Conditions:
- Temperature.
- Space Velocity.
- Pressure.
- Recycle Gas Ratio.
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Catalyst Overview
• Catalysts designed for fixed and moving beds and particular process duties.
• Platinum content (0.3 – 0.6 wt %) means high price/value. Overall catalyst
management is an important aspect of operations.
• Criterion Catalysts an example of company providing range of catalysts and
technologies.
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Catalyst Features
• Molecular activities with catalyst:
- Migration of reactants from bulk fluid to external catalyst surface
- Diffusion of reactants into catalyst pores
- Adsorption of reactants on internal catalyst surface
- Reaction
- Desorption of products from internal surface
- Diffusion out of pores
- Migration of products into external bulk fluid
• Relative dimensions:
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Feed Quality
Reformate yield and operating severity for given octane are a strong function of
feed properties:
- Naphthenenes provide good yield of high octane aromatics and H2.
- Aromatics require no treatment (but contribute to coke).
- Paraffins are hard to reform to aromatics.
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Process Variables
• Reactor temperature.
- Typically 925 to 975 °F (495 to 525 °C).
- Increase gives + octane, - yields and + runlength.
- Temperature drop over catalyst bed due to endothermic reaction. Hence reheating
required between reactors.
- In semiregenerative units, generally increased to compensate for reduced catalyst
activity over the cycle.
- Good indicator of catalyst condition and flow through bed.
• Reactor pressure.
- Typically 100 to 350 psig (6.5 to 25 barg).
- Similar effect to recycle gas ratio.
- Decrease gives + yields and – runlength.
• Yield predictions:
- Empirical yield correlations from pilot plant and commercial operations.
- Kinetic models include operating conditions.
- Lump models based on first principles. (Complex and most advanced).
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Catalytic Reforming Yield Correlations – 2
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