Lec 18 PDF

Petroleum Refining Fourth Year Dr.Aysar T.
Jarullah
Catalytic Reforming
Catalytic reforming is the process of transforming C7 –C10 hydrocarbons with low octane
numbers to aromatics and iso-paraffins which have high octane numbers. It is a highly
endothermic process requiring large amounts of energy. A schematic presentation of the
feedstock, products and process condition is shown in Figure below. The process can be
operated in two modes: a high severity mode to produce mainly aromatics (80–90 vol%) and
a middle severity mode to produce high octane gasoline (70% aromatics content).
Role of Reformer in the Refinery and Feed Preparation

The catalytic reformer is one of the major units for gasoline production in refineries. It can
produce 37 wt% of the total gasoline pool. Other units such as the fluid catalytic cracker
(FCC), the methyl ter-butyl ether (MTBE) production unit, alkylation unit and isomerization
unit, also contribute to this pool. These units will be covered in other chapters of the book.
The straight run naphtha from the crude distillation unit is hydrotreated to remove sulphur,
nitrogen and oxygen which can all deactivate the reforming catalyst. The hydrotreated
naphtha (HTN) is fractionated into light naphtha (LN), which is mainly C5 –C6, and heavy
naphtha (HN) which is mainly C7 –C10 hydrocarbons. It is important to remove C6 from the
reformer feed because it will form benzene which is considered carcinogenic upon
combustion. Light naphtha (LN) is isomerized in the isomerization unit (I). Light naphtha can
be cracked if introduced to the reformer. The role of the heavy naphtha (HN) reformer in the
refinery is shown in Figure below. Hydrogen, produced in the reformer can be recycled to the
naphtha hydrotreater, and the rest is sent to other units demanding hydrogen.
Research Octane Number

The research octane number (RON) is defined as the percentage by volume of iso-
octane in a mixture of iso-octane and n-heptane that knocks with some intensity as the fuel is
being tested. A list of the RON of pure hydrocarbon is given in Appendix D. It is seen from
this appendix that the RON of paraffins, iso-paraffins and naphthenes decrease as the carbon
number of the molecule increases. Aromatics have the opposite trend.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Reforming Reactions
Coke Deposition
Coke can also deposit during hydrocracking resulting in the deactivation of the catalyst. The
catalyst in this case has to be re-activated by burning off the deposited coke. The catalyst is
selected to produce a slow hydrocracking reaction. Coke formation is favoured at low partial
pressures of hydrogen. Hydrocracking is controlled by operating the eaction at low pressure
between 5–25 atm (74–368 psia), not too low for coke deposition and not too high in order to
avoid cracking and loss of reformate yield.
Catalytic Reforming Catalysts

Catalytic reforming catalysts contain highly dispersed platinum (Pt), the activity of which is
inhibited by sulfur. Therefore, an upstream hydrotreater lowers the sulfur content of reformer
feeds to <1 wppm. In addition to Pt, modern multi-metallic catalysts contain highly dispersed
rhenium (Re) and in some cases tin (Sn).
Process Technology
There are several commercial processes available for reforming. These include Platforming
(UOP), Powerforming (Exxon), Magna forming (Engelhard), Catalytic reforming (IFP),
Rheniforming (Chevron) and Ultra forming (Amoco). The old technologies are fixed bed
configuration. Moving bed technology has also recently been introduced.
Semi-regenerative Fixed Bed Process

The schematic flow diagram of this process is shown in Figure below. The name semi-
regenerative comes from regeneration of the catalyst in the fixed bed reactors after shut down
by burning off the carbon formed on the catalyst surface. Reactions such as dehydrogenation
of paraffins and naphthenes which are very rapid and highly endothermic occur in the first
reactor, with high temperature drop. Reactions that are considered rapid, such as paraffin
isomerization and naphthens dehydroisomerization, give moderate temperature decline in the
second reactor. Furthermore, slow reactions such as dehydrocyclization and hydrocracking
give low temperature decline in the third reactor.
To prevent catalyst coking, the hydrogen partial pressure is maintained at a level such that the
H2-to-hydrocarbon ratio by weight (H2/HC) is greater than 25 for monometallic catalyst. This
is done by recycling some of the hydrogen produced. Some light hydrocarbons (C1 –C4) are
separated from the reformate in the stabilizer. At the top of the stabilizer residual hydrogen
and C1 to C4 are withdrawn as condenser products, which are then sent to gas processing, and
part of the liquid product (C3 and C4) is returned from the reflux drum back to the stabilizer.
The main product of the column is stabilized reformate, which is sent to the gasoline blending
plant. A slight modification to the semi-regenerative process is to add an extrareactor to avoid
shutting down the whole unit during regeneration. Three reactors can be running while the
forth is being regenerated. This modified process is called the ‘‘cyclic fixed bed’’ process.

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Petroleum Refining Fourth Year Dr.Aysar T.

Role of Reformer in the Refinery and Feed Preparation

Research Octane Number

Catalytic Reforming Catalysts

Semi-regenerative Fixed Bed Process

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