A Presentation on

Reforming Process –Catalyst Advancement

Guided by Submitted by
Prof.V.G.Lade Chemosapiens
VII Sem B. Tech CE

Department of Chemical Engineering

Laxminarayan Institute of Technology
RTM Nagpur University, Nagpur
Group members:

1.Aniket Kalambe(Group Leader)

2.Atharv Themdeo
3.Gauri Dalwankar
4.Vaibhavi Ramteke
5 Nishat Qureshi
6.Bhushan Belkhede
7.Raj masram
8.Prajwal Lohakare
9.Musaib Ahmed
10Gaurav Raut
11.Sufiyan Ahmad
 Definition
• In catalytic reforming, the change in the boiling point of the
stock passed through the unit is relatively small as the
hydrocarbon molecular structures are rearranged to form
higher-octane aromatics with only a minor amount of
cracking.

• Catalytic reforming primarily increases the octane of motor

gasoline rather than increasing its yield; in fact, there is a
decrease in yield because of hydrocracking reactions which
take place in the reforming operation
 Catalytic reforming mainly in
4 stages

Hydrocracking

Dehydrocyclization Dehydrogenation
Isomerization of paraffins to of naphthenes to
aromatics, aromatics
Catalytic Reforming Semi Regenerative Process
 CASE STUDY-1

Progress in catalytic naphtha

reforming process
 Reforming Catalyst
 Reforming catalyst activity is a function of surface area, pore volume,
and active platinum and chlorine content.
 Catalyst activity is reduced during operation by coke deposition and
chloride loss.
 In a high pressure process, up to 200 barrels of charge can be processed
per pound of catalyst before regeneration is needed. The activity of the
catalyst can be restored by high temperature oxidation of the carbon
followed by chlorination. This type of process is referred to as semi-
regenerative and is able to operate for 6- to 24-month periods between
regenerations.
 The activity of the catalyst decreases during the on-stream period and
the reaction temperature is increased as the catalyst ages to maintain
the desired operating severity. Normally the catalyst can be regenerated
in situ at least three times before it has to be replaced and returned to
the manufacturer for reclamation.
1.Continuous catalyst regeneration (CCR
Platforming) catalytic reformer.
• CCR is the most modern type of the catalytic reformers. The
continuous process represents a step change in reforming. In this
unit the catalyst regenerates continuously in a special regenerator
and adds to the operating reactors. The advantages of CCR process
against traditional methods are
• – Production of higher octane reformate even working with a low
feed quality.
• – Long time working of the process for hydrogen demand.
• – Using catalyst with less stability but higher selectivity and yield.
• – Lower required recycle ratio and the lower operational pressure
with high yield of hydrogen.
• The used catalyst in CCR process is mainly of the platinum/tin
alumina type because addition of tin enhances the selectivity to
aromatics, stability, and regeneration ability of Pt/Al2O3. It should
mentioned that in CCR unit, catalyst regenerates continuously, thus,
selectivity to aromatics of the catalyst is more important than its
resistance to deactivation, while in SRR unit, despite the ability to
increase the yield of the process, catalyst should be able to tolerates
high coke levels.
2.Semi-regenerative catalytic reformer(SRR)
Semi-regenerative catalytic reformer(SRR)

• The most commonly used type of the catalytic reforming unit is SRR.
• This process is characterized by continuous operation over long
periods, with decreasing catalyst activity due to coke deposition.
• By decreasing the activity of the catalyst, the yield of aromatics and
the purity of the byproduct hydrogen decrease.
• In order to maintain the conversion nearly constant, the reactor
temperature is raised as catalyst activity decline.
• When the reactors reach end-of-cycle levels, the reformer is shut
down to regenerate the catalyst in situ.
• Different criteria may be used to determine the end-of-cycle levels
such as the reactor metallurgy temperature limit, prescribed
weighted average inlet temperature (WAIT) increase, specified
amount of C5+ yield decline, specified amount of hydrogen decline,
and refinery and reformer economics.
• To maximize the length of time (cycle) between regenerations, these
early units were operated at high pressures because high reactor
pressure minimizes deactivation by coking.
• The shutdown of this unit occurs approximately once each 6–24
months. Research octane number (RON) that can be achieved in this
process is usually in the range of 85–100, depending on an
optimization between feedstock quality, gasoline qualities, and
quantities required as well as the operating conditions required to
achieve a certain planned cycle length.
• The Pt–Re catalyst is usually used in SRR units because it tolerates
high coke levels and regenerates easily. These catalysts enable a
lower pressure and higher severity operation.
• Semi-regenerative reformers are generally built with three to four
catalyst beds in series. The fourth reactor could be added to allow
an increase in either severity or throughput while maintaining the
same cycle length. A schematic diagram of SRR unit and all of the
aforementioned reactor configurations have been proposed for this
process.
• The following procedure is used:
1. Calculate the characterization factor (KW) of the feed.
2. Determine C5 gasoline volume yield .
3. Determine weight or volume yields of H2, C1 C2, C3,
iC4, and nC
4. Calculate weight yield of all product streams except C5
gasoline. 5. Determine weight yield of C
5 gasoline by difference.
6. Calculate API gravity of C5 gasoline.
7. Make sulfur and/or nitrogen balance if needed to
determine H2S and NH3 made and net hydrogen
produced.
8. Estimate utility requirements
Conclusion
• Catalytic naphtha reforming is one of the backbone processes in refining
industries. This process is used widely for production of high-octane
gasoline and aromatic components.
• Various investigators have been studied different aspects of the naphtha
reforming process due to the importance of this industrial process.
Finding a suitable catalyst with higher selectivity and stability and lower
coking and deactivation comprise an extensive part of these studies.
• To achieve this purpose, various components have been added to the
metal and acid function of the catalyst. Presenting a proper kinetic
model with appropriate amount of components and reactions, and
deactivation model involving the affecting parameters attracts much
attention too.
• Different modes of operations are presented for a catalytic naphtha
reforming unit including semi-regenerative catalytic reformer (SRR), and
continuous catalyst regeneration reformer. SRR is the most commonly
used type of the catalytic reforming unit, but due to the better
performance of CCR, all new units are designed based on this
technology and old units are revamped to the continuous process or
combination of both.
 CASE-STUDY PROBLEM: NAPHTHA
HYDROTREATER, CATALYTIC REFORMER, AND
ISOMERIZATION UNIT
• In this case, the feed to the catalytic reformer consists of the heavy
straight-run (HSR) gasoline (190 to 380°F) from the crude unit and
the coker gasoline.
• In practice the coker gasoline would probably be separated into a
C5-180°F fraction, which would not be reformed, and a 180 to 380°F
fraction which would be used as reformer feed.
• As sufficient information is not available to estimate the quantities
and properties of these fractions, it is necessary for the purposes of
this calculation to send all of the coker gasoline to the reformer.
• The C5-180°F fraction will undergo little octane improvement but its
gasoline quality will be helped by saturation of the olefins. The
required severity of reforming is not known until after the gasoline
blending calculations are made. Therefore it is necessary to assume
a value for the first time through.
• A severity of 94 RON clear is used for this calculation.
Characterization
XRD spectra of
(A) the Ni/TiO 2 catalyst after reduction at 773 K,
(B) the Ni/SiO 2 catalyst after 5.5 h on stream,
(D) the Ni/C catalyst after 6 h on stream, and
(C) the Ni/MgO catalyst after reduction at 1123 K.
TEM micrograph of a used Ni/TiO 2 catalyst illustrating lattice fringes
 1. 2.

1.TEM micrograph of a used Ni/SiO 2 catalyst illustrating well-faceted nickel particles and
filamentous carbon whiskers.

2.TEM micrograph of a used Ni/MgO catalyst illustrating supported nickel particles.

TPO spectra for Ni/TiO 2, Ni/SiO 2 and Ni/MgO.
References:
• Mohammad Reza Rahimpour , Mitra Jafari , Davood
Iranshahi, Progress in catalytic naphtha reforming process: A
review, Applied Energy 109 (2013) 79–93.
• Michael C.J. Bradford, M. Albert Vannice , Catalytic reforming
of methane with carbon dioxide over nickel catalysts I. Catalyst
characterization and activity, Applied Catalysis A: General 142
(1996) 73-96 .
• Petroleum Refining Technology and Economics , James H. Gary
and Glenn E. Handwerk, Eastern Hemisphere Distribution
THANK YOU!!