1. Finding Gems in the Rough
Soni O. Oyekan
Reforming & Isom Technologist
Marathon Oil
AIChE MAC William Grimes Award
November 17, 2008

2. A Simplified Refinery Flow Diagram
NHT Reformer
Gas
Recovery
Sulfur
Plant
FCCU
HC
Coker
Unit
Gasoline
Blending
DHT
Distillate
Fuels
Atm
Unit
Vac
Unit
Coke
Asphalt
Fuels
Gasoline
Sulfur
LPG, C3=
Crude
Oil
LSRN

3. Naphtha Reforming Basics
• Operating Goals
– Produce high octane gasoline blending component from low
octane naphtha
– Produce hydrogen
– Produce aromatics
• Platinum and Bimetallic Catalysts
– Pt/Al2O3/Cl, Pt/Re/Al2O3/Cl, Pt/Sn/Al2O3/Cl
– Dual functional (hydrogenation/dehydro, acid)
• Hydrotreated Naphtha Feed
– paraffins, naphthenes and aromatics
– carbon range of C6 to C11
• Typical Process Conditions
– 100 to 300 psig, 900 to 1000 F, LHSV 1.0 to 4.0, H2/HC molar
ratio of 3 to 8
• Hundreds of Reactions:
– dehydrogenation, isomerization, dehydrocyclization,
hydrocracking, hydogenolysis, dehydroalkylation

4. 1977 Assignment & Plan
• First assignment in Exxon was to determine the mode of
promotion of Re in Pt/Re catalysis
• Immersed myself as much in understanding fundamental
Pt, Pt/Re catalysis and the naphtha reforming process
• Worked on cleaning a Hydrotreating catalyst sulfiding
unit for “clean sulfur” platinum/rhenium naphtha
reforming studies
• Cleaning with Isopropyl alcohol took about 10 weeks!
• Developed a working network with fundamental
researchers and surface characterization specialists,
sought out mentors and worked diligently
• Was highly driven, challenged and wanted to succeed

5. Experimental Program
• Varied rhenium content on a constant Pt catalyst and used Pt and
Re only catalysts
– 0.3 % Pt, 0.3 % Re, 0.3 %Pt/0.3 %Re, O.3 % Pt/0.6 % Re
• Activated the catalysts in a dedicated unit and characterized
catalysts for coke, chloride and sulfur
• Conducted test runs in the a common heater using four separate
reactor and product separation systems
• Used same operating conditions and same naphtha feed
– 950 F, 175 psig, H2/HC molar ratio of 5
• Completed data work up and compared product yields of C5+, H2
and light gases (C1 – C4)
• Characterized spent catalysts for coke, chloride and sulfur
• Conducted necessary catalyst surface characterizations
• Conducted model compound reforming studies with Heptane and
methyl cyclopentane.

6. A Sample Set of Test Data
Catalyst
(wt. %)
Low Rhenium
0.3 Pt/0.3 Re (A)
High Rhenium
0.3 Pt/0.6 Re (B)
Activity, No 72.0 96.0
C5+ yield, vol. %) 72.0 69.3
• Data indicated 2.7 vol. % lower C5+ yield for B
• Lower H2 yield
• Higher C1 to C4 gas
• Lower coke make
• Different C/H ratios for catalyst coke
• Sulfur was retained in proportion to Re content
• Overall negative catalyst performance data for B
• However, data and other factors provided valuable
information for developing a mechanism for rhenium
promotion effects

7. Combo Catalyst Data
Catalyst Low Rhenium
0.3 Pt/0.3 Re (A)
Combo
A Catalyst / B Catalyst
Activity 77.0 92.0
H2 yield, wt. % 2.26 2.31
C1 – C4, wt. % 18.82 17.86
C5+ yield, vol. % 74.3 75.5
• Achieved greater than 1 vol % C5+ yield
• About $3+ MM dollars a year for a 40 MBPD Platformer
• Introduced new combination Pt/Re catalyst systems
• Equi-molar, balanced, skewed, high rhenium terms introduced
• Determined that rhenium promoted platinum catalysis via
minimization of steric hindrance for intermediate compounds
• Combination Pt/Re catalyst systems now used worldwide
• Studies led to 1 US and 9 patents from other countries

8. Continuous Catalyst Reforming Process
A Major Technology Advancement
• Key objective was getting longer cycle
• Note performances of Pt/Sn and Pt were poor
• Numerous oil and technology R&D centers discarded poor data
Platinum Catalysis in Naphtha Reforming
72.00
76.00
80.00
84.00
88.00
92.00
96.00
Time
C5+,Vol.%
Pt/Re
Pt
Pt/Sn

9. UOP & IFP Found Gems In Effective Utilization of
Pt/Sn Catalysts
• UOP decided to capture the high C5+ yield edge of
Pt/Sn over Pt and Pt/Re catalyst systems
• UOP introduced Platforming with continuous catalyst
regeneration system – CCR Platforming in 1971
• Continuous catalyst regeneration systems required
– Spherical catalysts for facile circulation
– A regenerator for coke burn and catalyst activation
• IFP later introduced its version of continuous catalyst
regeneration reforming system
• UOP has about 225 units in commercial operations and
Axens (IFP) has 60 units.
• Principal catalytic reforming technology in use for
petroleum refining

10. CCRTM Platforming Unit
at Marathon Detroit.

11. Summary
• Soni Oyekan and George Swan of Exxon used
“negative” Pt/Re test data to advantage in fixed bed
reforming
• I acknowledge the work of George Swan, Bill Baird,
Harry Drushel, Chuck Mauldin, Ken Riley and many
others for the Exxon work
• UOP used what many oil and technology companies
considered “negative” Pt/Sn data to advantage to
develop a major CCR reforming technology process
• Axens and UOP have capitalized on licensing CCR
technologies to generate hundreds of millions of dollars
for their companies.
• In your research studies, critically analyze and look for
gems in “negative” data