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Refinery and Petrochemical Processing

Catalytic Reforming

Dr. Philip Holmes


Department for Chemical and Process Engineering
University of Surrey
Specification for Gasoline
Performance based specification, rather than composition or purity based.
Set by combustion, volatility, cleanliness and others criteria:

Octane ratings Knock performance


Vapour pressure Cold start, emissions
Volatility Drivability
Cleanliness Deposits, catalyst
Benzene (aromatics) Health (not clear)
Olefins Smog (C4= to C6=)
Oxygenates (ethanol, ether) Old cars, environmental

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Gasoline Specification for Unleaded Premium
(from BS EN 228:2004)

Research Octane Number 95.0 min


Motor Octane Number 85.0 min
Lead content 5 mg/l max
Density 720 – 775 kg/m3
Sulphur 10.0 mg/kg max
Oxidation stability, existent gum content, copper strip corrosion
Appearance clear and bright
Hydrocarbon content 18 vol % max olefins, 35 vol % max aromatics
Benzene content 1.00 vol % max
Oxygenates content 5.0 vol % max ethanol, 15.0 vol % max ethers (C5+)
Volatility requirements
vapour pressure depends upon summer/winter
% evaporated at 100 degC 46.0 – 71.0 vol %
% evaporated at 150 degC 75.0 vol % min
Final Boiling Point 210 degC
Distillation residue 2 vol % max
Vapour Lock Index depends upon summer/winter

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Significance of Octane Number
• Octane number is a measure of the “knocking” tendency of gasoline.

• Ignition of vaporised fuel for petrol engine:


- Normal: spark plug initiates flame in combustion chamber that travels at steady
rate until fuel-air mixture is consumed.
- Abnormal: spontaneous ignition ahead of the flame front results in noise (“knock”),
power loss, damage.

• For gasoline internal combustion engine:


+ octane number  + compression ratio  + performance

• Measured in special single-cylinder laboratory engine at fixed operating


conditions:
- Motor Octane Number (MON) ASTM D 2700 at 900 rpm i.e. simulated driving
under load or accelerating conditions.
- Research Octane Number (RON) ASTM D 2699 at 600 rpm i.e. simulated driving
under mild conditions.

• UK gasoline octane number reported as RON; US as (RON+MON)/2.

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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).

• Aim is to increase octane by reforming of :


naphthenes to aromatics
paraffins to aromatics
normal paraffins to iso-paraffin
Without significantly reducing carbon number (cracking).

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Chemistry of Catalytic Reforming - Dehydrogenation

CH3 CH3
+ 3H2
Methyl Toluene
Cyclohexane

• Unsaturated molecules formed with large production of hydrogen.

• Metal catalyst required.

• Highly endothermic reaction. Causes large drop in temperature that requires


interstage heating.

• Extremely rapid reaction. Equilibrium favours aromatics at:


low pressure, high temperature, low space velocity, low H2/oil ratio

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Chemistry of Catalytic Reforming - Dehydrocyclisation

C H3C CH3
+ H2
C-C-C-C-C-C
Isoheptane
Dimethylcyclopentane

• Conversion of C6+ paraffin to a 5 or 6 member saturated ring (naphthene).

• A difficult reaction that requires both acid and metal function catalyst.

• Endothermic reaction favoured by high temperature/low pressure.

• Cyclohexanes dehydrogenate immediately to aromatics.


Cyclopentanes undergo ring isomerisation to yield an aromatic.

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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

• Geometric rearrangement of molecular structure.

• Acidic function catalyst reqiured.

• Very rapid, slightly exothermic reaction. Yield increased by:


high temperature, low space velocity, low pressure.

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Chemistry of Catalytic Reforming - Hydrocracking

C-C-C-C-C-C-C C-C-C + C-C-C-C


+ H2
Heptane Propane Butane

• Cracking and saturation of paraffins, particularly high carbon number.

• Exothermic, relatively slow reactions. Yields increased by:


high temperature, high pressure, low space velocity.

• Undesirable since loss of H2 and liquid yield.

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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

• Catalyst structure and physical properties also important.

• Catalyst activity is reduced by coke deposition and chloride loss.


Yields maintained by increasing reactor temperature.
Activity restored by high temperature oxidation of carbon followed by chlorination.

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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 fixed bed reformers, e.g. ExxonMobil semiregenerative reformers with three


reactors, catalyst regeneration required every 3 to 24 months with unit shutdown.
Cyclic reformers typically have four reactors i.e. three operating with fourth (swing
reactor) on regeneration with unit maintained in operation.
Normally the catalyst can be regenerated three times or more before it is replaced
(precious metals reclaimed).

• 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

Reactors at 495 to 525 °C; 6.5 to 25 barg

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Typical Fixed Bed Catalytic Reactor

Source: Gary and Handwerk, 1984


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Continuous Catalytic Reforming

Source: UOP, 2007

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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

Source: Criterion Catalysts, 2009

• 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.

• Recycle gas ratio.


- Typically 4000 to 8000 scf/bbl (700 to 1400 sm3/m3).
- Decrease gives + yields and – runlength.

• Reactor pressure.
- Typically 100 to 350 psig (6.5 to 25 barg).
- Similar effect to recycle gas ratio.
- Decrease gives + yields and – runlength.

• Liquid hourly space velocity.


- Typically 2 to 3 v/h/v (feedrate/catalyst volume).
- Usually set at design stage.
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Catalytic Reforming Yield Correlations - 1
• Main products are high octane gasoline (Reformate) (RON from 95 to 100+);
benzene, toluene and xylene (BTX) (chemicals feedstocks); and
H2 (for hydrotreating).

• Important by-products are:


- C2- for refinery fuel gas
- C3/C4 for LPG and gasoline.

• 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).

• For a given feed quality:

[ MABP (F) + 460 ] 1/3 K = low for naphthenic


K = ________________________ high for paraffinic feeds
Spec. Gravity 15°C / 15°C

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Catalytic Reforming Yield Correlations – 2

Source: Gary and Handwerk, 1984


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Catalytic Reforming Yield Correlations – 3

Source: Gary and Handwerk, 1984


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Effect of Reduced Catalyst Activity Over the Cycle

PR-30 from Criterion


Catalysts is improved
skewed metal, Pt/Re
catalyst with modified
alumina technology.

Source: Edgar and Phansalkar, 2007 24


References
BS EN 228, 2004: Automotive fuels – Unleaded petrol – Requirements and test methods. British Standards Institute,
London.
Criterion Catalysts, 2009: Photograph taken from Criterion Catalysts and Technologies website.
Edgar, M.D. and S.S. Phansalkar, 2007: New Reforming Catalysts Help Refiners Cope with Greater Demand for Gasoline.
Criterion Catalysts and Technologies. Paper presented at NPRA Annual 2007, San Antonio, Texas, USA.
Gary, J.H. and G.E. Handwerk, 1984: Petroleum Refining Technology and Economics, 2nd Edition. Marcel Dekker Inc., New
York, USA.
UOP, 2007: CCR Platforming Process for Motor Fuel Production. Available from website.

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