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Catalytic Reforming

1 Introduction:
Catalytic reforming is a major conversion process in petroleum refinery and petrochemical
industries. The reforming process is a catalytic process which converts low octane naphthas into
higher octane reformate products for gasoline blending and aromatic rich reformate aromatic
production.

Basically, the process re-arranges or re-structures the hydrocarbon molecules in the naphtha
feedstocks as well as breaking some of the molecules into smaller molecules.
Naphtha feeds to catalytic reforming include heavy straight run naphtha. It transforms low
octane naphtha into high octane motor gasoline blending stock and aromatics rich in benzene,
toluene and xylene with hydrogen and liquified petroleum gas as a byproduct.
Feeds consists of heavy straight run gasoline, naphtha, heavy hydrocracker naphtha and naphtha
containing (C6-C11) chain paraffins, olefins, naphthenes and aromatics.

2 Process steps in catalytic reforming:

• Basis steps in catalytic reforming involves:


a. Feed preparation: Naphtha hydrotreatment.
b. Preheating: Temperature control.
c. Catalytic reforming: The occurrence of the reaction.
d. Product separation: Removal of gases and reformate by fractional distillation.
e. Separation of aromatics: In case of aromatic production.

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3 Classification of processes:
a. Semi-Regenerative catalytic reforming.
b. Cyclic catalytic Reforming.
c. Continuous catalytic reforming. (CCR)

4 Reactions in catalytic reforming:

• Desirable Reactions:
✓ Dehydrogenation of naphthenes to aromatics.
✓ Isomerization of paraffins and naphthenes.
✓ Dehydrocyclization of paraffins to aromatics.
• Undesirable Reactions:
✓ Hydrocracking of paraffins to lower molecular weight compounds.

5 Process Variables:

• The following variables affect the reformate yield and quality of the product. Favorable
conditions for different reforming reactions is mention in Table (1).

✓ Reaction temperature.
✓ Space velocity.
✓ Reaction pressure.
✓ H2/HC ratio.
✓ Feedstock characteristics.
• These variables would affect:
✓ Product yields.
✓ Product quality (PON).
✓ Catalyst stability (coke deposit).
Table 1 Favorable Conditions for Different Reforming Reactions

Reaction Pressure Temperature


Dehydrogenation of
Low Pressure High Temperature
naphthenes to aromatics
Isomerization of naphthenes Indeterminate Indeterminate
Dehydrocyclization of
Low Pressure High Temperature
paraffins to aromatics
Hydrocracking High Pressure High Temperature

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5.1 Reaction Pressure:

• Decreasing pressure will:


✓ Increase dehydrogenation of naphthenes and dehydrocyclization of paraffins which
favors an increase in production of aromatics and hydrogen (increase catalyst
coking and shorter cycle life).
• Higher pressure causes:
✓ Higher rates of hydrocracking reducing reformate yield.
✓ Decrease in coking of catalyst resulting in longer life cycle.

5.2 Reaction Temperature:

• Temperature is the most important operating parameter. By simply raising or lowering


reactor inlet temperature, operators can raise or lower the octane number of the product.

5.3 Space Velocity:

• The lower the space velocity (i.e., higher contact time), the higher the severity assuming
all other conditions unchanged.
• Lowering the space velocity has the same effect as increasing temperature:
✓ Increase the octane number.
✓ Decrease the product yield.
✓ Decrease hydrogen purity.
✓ Increase coke deposition.

5.4 Hydrogen to Hydrocarbon Ratio:

• Main purpose of hydrogen is to react with coke precursors removing them from the catalyst
reforming polycyclic aromatics.
• Higher the H2/HC ratio, higher the cyclic length.
• Two main reasons for reducing H2/HC ratio:
✓ Reduction in energy costs for compressing and circulating H2.
✓ Favors naphthene dehydrogenations and dehydrocyclization reaction.

5.5 Feed Quality:

• Lighter fractions have a poor naphthene and aromatic content, therefore poor feed for
reforming. Low initial boiling point feed results in lower aromatics and hydrogen yield.
• Heavy fractions have naphthene and aromatic hydrocarbon content. Therefore, good
reforming feed but tendency of coke formation is high.

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Table 2 The Theoretical effect on the unit performance of each independent process
variable taken separately.

Increased ON Reformate Coke Deposit


Yield

Pressure

Temperature

Space Velocity

H2/HC

End Boiling
Point
Naphtha
Quality
Initial Boiling
Point

6 Catalyst Regeneration:

• Performance of the catalyst decreases with respect to 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.