Catalytic Reforming Process

Introduction

● Catalytic reforming is a chemical process used to convert petroleum refinery naphthas distilled
from crude oil (typically having low octane ratings) into high-octane liquid products called
reformates which are premium blending stocks for high-octane gasoline.

● The process converts low-octane linear hydrocarbons (paraffins) into branched alkanes
(isoparaffins) and cyclic naphthenes, which are then partially dehydrogenated to produce high-
octane aromatic
Catalytic Reforming Unit
Catalytic Reforming Unit
Reforming Reactions
● Dehydrogenation
● Isomerization
● Hydrogenation of un-saturates
● Paraffin de-hydrocyclisation
● Naphthene isomerisation and dehydrogenation
● Cracking
● Hydrodesulfurization
● Denitrogenation
● Deoxidation
Reforming Reactions
The four major catalytic reforming reactions are:
1. The dehydrogenation of naphthenes to convert them into aromatics as exemplified in the conversion
methylcyclohexane (a naphthene) to toluene (an aromatic)

2. The isomerization of normal paraffins to isoparaffins as exemplified in the conversion of normal octane to 2,5-
Dimethylhexane (an isoparaffin)
Reforming reactions
3. The dehydrogenation and aromatization of paraffins to aromatics (commonly called dehydrocyclization) as
exemplified in the conversion of normal heptane to toluene:

4. The hydrocracking of paraffins into smaller molecules as exemplified by the cracking of normal heptane into
isopentane and ethane,
Purpose of Catalytic Reforming

Purpose of reforming process is to produce:

● high octane reformate, which is a main component of motor fuel,aviation gasoline blending or
aromatic rich feedstock.
● Hydrogen rich gas
● Due to the nature of reactions, reforming process produces also
○ LPG-FG-600 psig steam with waste heat reboilers.
Feed

Reformer feed:
● Low quality straight run naphtha.
● Or cracked naphtha, generally mixed with straight run naphtha.
● Feed should be free from impurities like sulfur, nitrogen and oxygen compounds
● For Pt based catalysts, sulfur and nitrogen content < 5 ppm.
Reaction conditions
Process Variables:
● Reactor Temperature
● Pressure
● Space Velocity
● Hydrogen/Hydrocarbon ratio
● Feedstock characteristics

Typical operating parameters (from economic operation):

• Low pressure (10 – 50 atm)
• High temperature ( 450 – 500 C)
• High H2 recirculation (H2/HC ratio)
• High catalyst to feed ratio (effects on space velocity)
Catalyst

● The catalyst affects reaction rates through its two different functions/type of sites:
○ Metallic
○ Acidic

● Different types of reactions are promoted by these sites as:

Catalyst

Some examples of catalysts used:

● ZSM – 5 (Zeolite Socony Mobil – 5)
● R-132 (UOP) (Pt based)
● Cr oxide and Mb oxide on alumina
● Bauxite and clay catalysts were used in earlier days
● Pt combination with other metals are also being used
Catalytic reforming technologies

Different commercial catalytic reforming processes:

● Platforming (UOP) – 1949

● Rheinforming (Chevron)
● Powerforming (Exxon)
● Ultraforming (Amoco)
● Catalytic reforming (Engelhard)
Platforming process

1)In the Platforming process, light petroleum distillates (naphtha) is contacted with a platinum-containing catalyst at
elevated temperatures and hydrogen pressures ranging from 345 to 3450 kPa.

2)Originally developed to upgrade low-octane-number straight-run naphtha to high-octane motor fuels

3)The process has since been applied to the production of LPG and high purity aromatics.

4)The first Platforming units were designed as semi regenerative (SR),Semi Regenerative Platforming units are periodically
shut down to regenerate the catalyst. This regeneration includes burning off catalyst coke and reconditioning the catalyst’s
active metals.

.
Platforming process
Platforming process
Uniqueness and specificness -

1. Reactions- dehydrogenation,isomerization,dehydrocyclization, and cracking.

The reactions are promoted by two kinds of active sites on the catalyst, acidic and metallic.
Platforming Process

2. Heat of reactions
Platforming process
3. Catalyst -
I) Platforming catalysts are heterogeneous and composed of a base support material (usually Al2O3) on which catalytically
active metals are placed. The first Platforming catalysts were monometallic and used platinum as the sole metal.

II) UOP introduced bimetallic catalysts in 1968. These catalysts contained platinum and a second metal, rhenium, to meet
increasing severity requirements. Catalyst metals are typically added at levels of less than 1 wt % of the catalyst

III) To develop the acid functionality of the catalyst, a promoter such as chloride or fluoride is added. Most catalyst
development for SR Platforming has followed the path of maximizing the efficiency and balance of the metal and acid
functionalities of the catalyst system.
CONTINUOUS PLATFORMING PROCESS
● Improvements in the catalyst and process could not keep up, and the need to regenerate catalyst at shorter and
shorter intervals became a serious limitation of the SR Platforming units. UOP developed the CCR Platforming
process to overcome this limitation.
● In the CCR Platforming unit, partially coked catalyst in the reactors is continuously replaced with catalyst that has
been freshly regenerated in an external regenerator (CCR section) to maintain a low average coke for the reactor
catalyst.
CONTINUOUS PLATFORMING PROCESS
CONTINUOUS PLATFORMING PROCESS
CONTINUOUS PLATFORMING PROCESS
Advantages of CCR Platforming-

1)The CCR Platforming unit has the highest possible yields because it is capable of the lowest possible pressure operation.
If operated at the same conditions, the SR Platforming catalyst is completely deactivated after only a few days of operation.

2)CCR Platforming units have higher on-stream efficiency and are able to handle upset scenarios without long-term
shutdown or significant decline in performance.

3)Since the catalyst is not regenerated in situ, the reactor section operates only in its primary function of providing the
catalytic environment for the reforming reactions.
CONTINUOUS PLATFORMING PROCESS
Rheinforming (Semi regenerative process)
Challenges
Platforming
CHALLENGES FACED:
1)Lots of fire heaters required as most of the reactions which occur are endothermic

2) The increased coking of the catalyst at the higher severity limits the operating run length and the ability to further reduce
pressure.
3) Fixed- bed catalyst stability was an issue in the first process due to coking of the catalyst.
4) The sensitivity of catalytic reforming to contamination by sulfur and nitrogen.
5) The platformate has a much higher content of benzene than is permissible by the current regulations in many countries.
Challenges
SOLUTIONS:

1)Heat Integration- Effluent from the last reactor exchanges heat with the feed for maximum heat recovery.
2) Catalyst development alone could not solve these problems; process innovations were needed. In the 1960s, cyclic
reforming was developed to sidestep this barrier. Cyclic reforming employs fixed-bed reforming, but the reactors can be
individually taken off-line, regenerated, and then put back into service without shutting down the unit and losing production.
3) The inception of CCR Platforming ( Continuous Catalyst Regeneration) was done in 1971. The process employs
continuous catalyst regeneration in which catalyst is continuously removed from the last reactor, regenerated in a
controlled environment, and then transferred back to the first reactor. With continuous regeneration, coke laydown is no
longer an issue because the coke is continuously burned off and the catalyst is reconditioned to its original performance.
The CCR Platforming process has enabled ultra low-pressure operations at 345 kPa (50 lb/in2 gage) and produced product
octane levels as high as 108.
Challenges
SOLUTIONS:

4) Hydrotreating the naphtha before it enters the reformer, adding to the cost and complexity of the
process.
5) The reformate should either be further processed in an aromatics extraction unit, or blended with
appropriate hydrocarbon streams with low content of aromatics.