CATALYTIC REFORMING

CONTENTS

INTRODUCTION
FEED STOCK
REACTIONS
PROCESS VARIABLES
REFORMING CATALYST
CATALYST CHEMISTRY
VARIOUS CATALYTIC REFORMING PROCESSES
CLASSIFICATION OF C.R PROCESSES
UOP PLATFORMING PROCESS
CATALYST REGENERATION
REACTOR DESIGN
Conclusion
Q&A

INTRODUCTION
Demand of high-octane gasoline.
30-40 % of gasoline production is by C.R.
The production might decrease by the
implementation on the aromatic content of
gasoline.
Only change in molecular structure so B.P
of the feedstock after the process is small.
C.R increases the octane of motor gasoline
rather than increasing its yield. (in fact due
to cracking there is a decrease in yield).

FEED STOCK
Feed consists of

Heavy straight run gasoline (HSR)

Naphtha
Heavy hydrocracker naphtha
Naphtha containing (C6-C11) chain paraffins,
olefins, naphthenes & aromatics.
Aromatics in feed remains unchanged

COMPOSITION OF FEED
STOCK
Major hydrocarbon groups (PONA)

Paraffin
Olefin

Aromatics
Naphthenes

PONA ANALYSIS (VOL%)

Paraffins
Olefins
Naphthenes
Aromatics

FEED

PRODUCT

30-70

30-50

0-2

0-2

20-60

0-3

7-20

45-60

Basics of Catalytic Reforming

Catalytic reforming uses catalytic reactions to process
primarily low octane heavy straight run (from the crude
distillation unit) gasoline and naphtha into high octane
aromatics (including benzene).
Major types of reactions which occur during reforming
processes : 1) dehydrogenation of naphthenes to aromatics;
2) dehydrocyclization
of paffins to aromatics; 3)
isomerization; and 4) hydrocracking.
Feedstocks to catalytic reforming processes are usually
hydrotreated first to remove sulfur, nitrogen and metallic
contaminants.
In continuous reforming processes, catalysts can be
regenerated one reactor at a time, once or twice per day;
without disrupting the operation of the unit.

REACTIONS
4 major reactions are categorized as

Desirable
Dehydrogenation of naphthenes to
aromatics
Dehydocyclization of paraffins to aromatics
Isomerization

Undesirable
Hydrocracking

Dehydrogenation &
Dehydrocyclization

Highly endothermic
Cause decrease in
temperatures
Highest reaction rates
Aromatics formed
have high B.P so end
point of gasoline rises
Favourable conditions
High temperature
Low pressure
Low space velocity
Low H2/HC ratio

+ H2

n-C7H16

+ H2

Isomerization
Branched isomers
increase octane
rating
Small heat effect
Fairly rapid reactions
Favourable conditions
High temperature
Low pressure
Low space velocity
H2/HC ratio no
significant effect

+ H2

Hydrocracking

Exothermic reactions
Slow reactions
Consume hydrogen
Produce light gases
Lead to coking
Causes are high
paraffin conc feed

Favourable conditions
High temperature
High pressure
Low space velocity

PROCESS VARIABLES
Catalyst type

Chosen to meet refiners yield, activity and stability need

Temperature

Primary control of changing conditions or qualities in reactor.

High temp increase octane rating but decrease run length.
High temp reduce catalyst stability but may be increased for
declining catalyst activity. Measured in WAIT or WABT.

Pressure

Pressure effects the reformer yield & catalyst stability.

Low pressure increases yield & octane but also increases coke
make.
Low pressure decreases the temperature requirement for the given
product quality

PROCESS VARIABLES
Space velocity

Amount of Naphtha processed over a given amount of catalyst.

Low space velocity favors aromatic formation but also promote
cracking.
Higher space velocity allows less reaction time.

H2 / HC ratio

Moles of recycle hydrogen / mole of naphtha charge

Recycle H2 plays a sweeping effect on the catalyst surface supplying
catalyst with readily available hydrogen
Increase H2 partial pressure or increasing the ratio suppresses coke
formation but promotes hydrocracking.

Catalytic reforming (Axens)

Application: Upgrade various types of naphtha to
produce high-octane reformate, BTX and LPG.
Description: Two different designs are offered. One
design is conventional where the catalyst is
regenerated in place at the end of each cycle.
Operating normally in a pressure range of 12 to 25 kg
/cm2 (170 to 350 psig) and with low pressure drop in
the hydrogen loop, the product is 90 to 100 RONC.
With its higher selectivity, trimetallic catalysts RG582
and RG682 make an excellent catalyst replacement
for semi-regenerative reformers.

The second, the advanced Octanizing process, uses continuous

catalyst regeneration allowing operating pressures as low as 3.5
kg /cm2 (50 psig).
This is made possible by smooth-flowing moving bed reactors
(13) which use a highly stable and selective catalyst suitable for
continuous regeneration (4).
Main features of Axens regenerative technology are:
Side-by-side reactor arrangement, which is very easy to erect
and consequently leads to low investment cost.
The Regen C2 catalyst regeneration system featuring the dry
burn loop, completely restores the catalyst activity while
maintaining its specific area for more than 600 cycles.

Finally, with the new CR401 (gasoline mode) and

AR501 (aromatics production) catalysts specifically
developed for ultra-low operating pressure and the
very effective catalyst regeneration system, refiners
operating Octanizing or Aromizing processes can
obtain the highest hydrogen, C5+ and aromatics
yields over the entire catalyst life.

Installation: Of 111 units licensed, 64 units are designed with

continuous regeneration technology capability.
Reference: Continuing Innovation In Cat Reforming, NPRA
Annual Meeting, March 15 17, 1998, San Antonio.
Fixed Bed Reformer Revamp Solutions for Gasoline Pool
Improvement, Petroleum Technology Quarterly, Summer 2000.
Increase reformer performance through catalytic solutions,
Seventh ERTC, November 2002, Paris.
Squeezing the most out of fi xed-bed reactors, Hart Show
Special, NPRA 2003 Annual.
Licensor: Axens.

Catalytic reforming (Howe Baker)

Application: Increase the octane of straight-run or
cracked naphtha's for gasoline production.
Products: High-octane gasoline and hydrogen-rich
gas. Byproducts may be LPG, fuel gas and steam.
Description: Semi-regenerative multibed reforming
over platinum or bimetallic catalysts.
Hydrogen recycled to reactors at the rate of 3 mols /
mol to 7 mols /mol of feed.
Straight-run and /or cracked feeds are typically
hydrotreated, but low-sulfur feeds (<10 ppm) may be
reformed without hydrotreatment.
Operating conditions: 875F to 1,000F and 150 psig
to 400 psig reactor conditions.

Yields: Depend on feed characteristics, product octane

and reactor pressure.
The following yields are one example. The feed
contains 51.4% paraffins, 41.5% naphthenes and 7.1%
aromatics, and boils from 208F to 375F (ASTM D86).
Product octane is 99.7 RONC and average reactor
pressure is 200 psig.

Economics:
Utilities, (per bbl feed)
Fuel, 103 Btu release
Electricity, kWh
Water, cooling (20F rise), gal
Steam produced (175 psig sat), lb
Licensor:CB&I
Technology.

Howe-Baker

275
7.2
216
100
Process

and

Catalytic reforming (UOP LLC)

Application: The CCR Platforming process is used
throughout the world in the petroleum and
petrochemical industries. It produces feed for an
aromatics complex or a high-octane gasoline
blending product and a significant amount of
hydrogen.
Description:
Hydrotreated
naphtha
feed
is
combined with recycle hydrogen gas and heat
exchanged against reactor effluent. The combined
feed is then raised to reaction temperature in the
charge heater and sent to the reactor section.

Radial-flow reactors are arranged in a vertical stack.

The predominant reactions are endothermic; so an
interheater is used between each reactor to reheat the
charge to reaction temperature.
The effluent from the last reactor is heat exchanged
against combined feed, cooled and split into vapor
and liquid products in a separator.
The vapor phase is hydrogen-rich. A portion of the
gas is compressed and recycled back to the reactors.
The net hydrogen-rich gas is compressed and
charged together

with the separator liquid phase to the product

recovery section.
This section is engineered to provide optimum
performance.
Catalyst flows vertically by gravity down the
reactor stack.
Over time, coke builds up on the catalyst at
reaction conditions.
Partially deactivated catalyst is continually
withdrawn from the bottom of the reactor
stack and transferred to the CCR regenerator.

Installation: UOP commercialized the CCR

Platforming process in 1971 and now has
commissioned more than 180 units (more than 3.9
million bpd of capacity) with another 30 in various
stages
of
design,
construction
and
commissioning.
Efficiency/product quality: Commercial on stream
efficiencies of more than 95% are routinely
achieved in CCR Platforming units.
Licensor: UOP LLC.

REFORMING
CATALYST
Catalyst used now a days is platinum on alumina base.
For lower pressure stability is increased by combining
rhenium with platinum.
Pt serve as a catalytic site for hydrogenation and
dehydrogenation reactions
Chlorinated alumina provides acid site for isomerization,
cyclization & hydrocracking reactions.
Catalyst activity reduced by coke deposition and
chlorine loss.
As catalyst ages activity of the catalyst decreases so
temperature is increased as to maintain the desired
severity.

CATALYST CHEMISTRY
Properly balanced catalyst
Metal-Acid balance
Cl Acid function
Cracking

Metal- Pt function
Demethylation
Dehydrogenation
Dehydrocyclization
Isomerization

VARIOUS C.R. PROCESSES

Platforming (UOP)
Powerforming (Exxon)
Ultraforming (Amoco)
Magnaforming (ARCO)
Rheniforming (Cheveron)

Classification of processes
Continuous

Semi Regenerative

Cyclic

CATAYST REGENERATION
Performance of the catalyst decreases wrt
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.

CATAYST REGENERATION
Objective of regeneration
Surface area should be high
Metal Pt should be highly dispersed
Acidity must be at a proper level
Regeneration changes by the severity of the
operating conditions
Coke formation can be offset for a time by
increasing reaction temperatures.

CONCLUSIONS
Purpose of reforming process is to improve RONC.
The basic and fastest reaction is naphthene
conversion to aromatic so the feed rich in
naphthene that is rich naphtha is preferred as a
feed.
Useful operating condition is at low pressure, low
space velocity & high temperatures.
The platinum is thought to serve as a catalytic site
for hydrogenation & dehydrogenation reactions
While chlorinated alumina as an acid site for
isomerization & hydrocracking reactions.
The activity of the catalyst decreases during the on
stream period hence leading to regeneration.