COLLEGE OF ENGINEERING

DEPARTMENT OF PETROLEUM AND CHEMICAL

ENGINEERING
COURSE NAME: PETROLEUM REFINING OPERATIONS
FALL SEMESTER

Reforming
PRESENTED BY ENG. JAMIL MAHFOUD
 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 for 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 liquefied petroleum gas as a
byproduct.
With the fast growing demand in aromatics and demand of high
octane numbers, catalytic reforming is likely to remain one of the most
important unit processes in the petroleum and petrochemical industry.
 Chemistry
Hydrocarbons exist in different shapes and sizes. They range from small
simple molecules to large complex compounds. The characteristics of
hydrocarbons such as:
• Boiling point  Determined by the size and structure of the molecules in crude oil
• Flash point  These characteristics determine what types of products can be
• Color used for reforming

Four main groups of hydrocarbons:

1. Paraffins
2. Olefins
3. Naphthenes
4. Aromatics
In terms of gasoline blending the characteristic we are mostly concerned
of is octane number. Aromatics class of hydrocarbons has the highest
octane numbers.
 RON
Octane number is a measurement of antiknock characteristics of fuels
• Among the same carbon number compounds, the order of RONC is
(Research Octane Number ) Paraffins < Naphthenes < Aromatics
• Branched paraffins also have high octane. It increases with degree of
branching. Therefore, octane number of naphtha can be improved by
reforming the hydrocarbon molecule (Molecular rearrangement).
Octane number of various hyrdrocarbons is mentioned in the table. Such
rearrangement takes place in reforming reactors in presence of catalyst by
way of numerous complex reactions.
Table 1: RON of various HC
 Purpose
Main purpose of catalytic reforming is to convert paraffins and naphthenes
into high octane aromatic compounds. How is that accomplished?
Catalytic reforming uses:
• Heat
• Pressure
• Catalyst to rearrange or reform the structure of HC molecules
The feed is basically a low octane Naphtha (mainly composed of paraffins and
naphthenes). Reforming occurs in a series of reactors where the feed is in
contact with a catalyst that promotes several chemical reactions that lead to
high octane reformate.

Chemical feedstock Some by products along with

reformate are hydrogen and some
Gasoline blending component light hydrocarbons.
 Steps
Basic steps in catalytic reforming involve:
Prevent the deposition of
• Feed preparation: Naphtha Hydrotreatment
impurities and catalyst damage
• Preheating: Temperature Control,
• Catalytic Reforming and Catalyst Circulation and Regeneration in
case of continuous reforming process
• Product separation: Removal of gases and Reformate by fractional
Distillation
• Separation of aromatics in case of Aromatic production

A typical reformer consists of:

• 3 or more reactors
• Furnace
• Separator
• Stabilizer
• Recycle compressor
 Chemical reactions
1. Dehydrogenation of paraffins and naphthenes:
n-paraffins = alkenes + hydrogen CnH2n+2 = CnH2n + H2
naphthenes = aromatics + hydrogen CnH2n = CnH2n-2 + H2
These reactions are endothermic.
2. Dehydrocyclisation of paraffins:
n-paraffins = naphthenes + hydrogen CnH2n+2 = CnH2n + H2
This reaction is also endothermic.
3. Isomerisation of paraffins:
n-paraffins = i-paraffins
This reaction is nearly thermo-neutral.
4. Hydrocracking:
n-paraffins + hydrogen = hydrocarbon gases + lighter paraffins
and
naphthenes + hydrogen = hydrocarbon gases + lighter naphthenes
These reactions are exothermic.
5. Hydrogenation
alkenes + hydrogen = alkanes
aromatics + hydrogen = naphthenes Deposition of coke on catalyst result in
These reactions are exothermic. decreasing the reactivity of the catalyst
6. Coking reactions: and the temperature has to be raised to
hydrocarbons = carbon or cokes maintain the uniform reactivity.
Process

Vapor form

Flashing

Example 5.1 (fundamentals of

Final products petroleum refining)
 Coke
During reforming process coke or carbon is
gradually deposited on the catalyst, as a result the
catalyst ability to reform the feed declines
→ coke must be removed or regenerated by
Spent catalyst
burning the coke off its surface.

Reforming units are classified based on the

method used to regenerate the catalyst. We
basically have three ways:
1. Semi-regenerative reformer: In this type of Regenerated catalyst
reformers the catalyst generally has a life of one or more years between
regeneration. The time between two regeneration is called a cycle. The
catalyst retains its usefulness over multiple regeneration.
2. Cyclic reformer: Cyclic reformers run under more severe operating
conditions for improved octane number and yields. Individual
reactors are taken offline by a special valving and manifold system
and regenerated while the other reformer unit continues to operate.
 Classification
3. Continuous reformer: In these reformers the catalyst is in moving
bed and regenerated frequently. This allows operation at much
lower pressure with a resulting higher product octane, C5+, and
hydrogen yield.

This chart shows the relationship that exists between octane number
and yields:
As the octane number goes up, the
volume of reformate produced goes
down which means the higher the
octane specifications, the less
reformation.
This means that if the unit is
producing reformate that is above
octane specifications, products is
being wasted.
Semi-regenerative
Cyclic
Continuous
 Operating variables 1/3
1. Reactor temperature:
Treactor is a key operating variable where the desired operating
temperature is maintained by passing the feed through a furnace
prior to each reactor.
In general we have a set value for T, however if the octane number
of the reformate decreases, it can be raised back to the desired
value by increasing the reactor temperature for 3-5oF for one
octane number.
Add to that, as the catalyst deactivates during reforming, the
octane number of the reformate will fall below specifications
which push the operator to increase T in order to bring the octane
back to the desired value.
Last but not least, there is an operating temperature limit that
should not be exceeded in order to prevent catalyst damage like
hot spots formation and feed channeling.
 Operating variables 2/3
2. Pressure is usually controlled by regulating the amount of
hydrogen that is allowed to leave the system. A constant
pressure should be remained throughout the reforming
process because if P increases (severe conditions), more light
hydrocarbons are produced (hydrocracking) with less hydrogen
and reformate. If P decreases, the greater hydrogen and
reformate yields (less cracking) but more coke will be
deposited on the catalyst (high concentration of heavy
compounds). In addition, the vapor pressure of the reformate
should also be controlled in a stabilizer (removal of light HC).
3. Feed rate:
Normally, a constant amount of feed is charged into the reactor all
the time but if any mechanical problems forced to decrease the
feed rate, reforming process will be negatively affected unless
other operating variables are adjusted (↓ reactor temperature).
 Operating variables 3/3
4. Feed composition also affect products yields. For example, if
the feed contains too many heavy high boiling point
hydrocarbons, coke production will increase at the expense of
reformate yields and octane number.
5. Hydrogen recycle ratio: It is simply defined as the amount of
hydrogen in the recycled gas compared to the amount of
hydrocarbons being charged to the reactor. For low hydrogen
recycle ratio, coke deposition occurs faster which lead to early
shut down.
6. Catalyst activity: So far we learned that coke deposition
decreases the activity of the catalyst, what increase that
activity?
A certain level of chlorides should be maintained on the catalyst
surface by adding chloride injection to the feed or hydrogen
stream.
Thanks for your attention