1. Catalytic Applications for EnhancedCatalytic Applications for Enhanced
Production of Transportation FuelsProduction of Transportation Fuels
Soni O. OyekanSoni O. Oyekan
Reforming & Isom TechnologistReforming & Isom Technologist
Marathon OilMarathon Oil
2009 NOBCCHE Percy L. Julian2009 NOBCCHE Percy L. Julian
LectureLecture
April 14, 2009April 14, 2009

2. Lecture OutlineLecture Outline
• Introduction and Acknowledgement
• Overview of Oil Refining Processes
• Hydroprocessing and Hydrogen
• Catalytic Reforming Process
• Staged Platinum/Rhenium Catalysts
• Two Stage Reduction of Platinum Catalysts
• Summary

3. Introduction & AcknowledgementsIntroduction & Acknowledgements
• Dr. Percy L. Julian’s pioneering work that led to
foam, paint, hormones and cortisone
• ExxonMobil and Dr George Swan, co-inventor, on
US Patent 4,436,612 and for work on Pt/Re
studies in the late 1970s in Baton Rouge, LA
• Engelhard for catalytic reforming work in the
1980s in Edison, NJ
• Marathon for opportunities to apply my expertise
to oil refining processes in the past 10 years and
support of my professional organization activities
• The catalytic studies were conducted between
1977 and 1984 and the ideas have been
incorporated into hundreds of catalytic reformers

4. Overview of Oil Refining Processes

5. CRUDE OIL
GASOLINE
DIESEL
ASPHALT
Oil Refiners 6-3-2-1 Crack Spread
 A Crude Oil Crack Spread = {(Revenue from 3 barrels of
gasoline + 2 barrels of diesel + 1 barrel of asphalt) –
(Cost of 6 barrels of crude oil)}/6
 3-2-1 Crude Oil Crack Spreads are based on gasoline &
diesel only

6. A Simplified Refinery Flow DiagramA Simplified Refinery Flow Diagram
NHT
Catalytic
Reformer
Gas
Recovery
Sulfur
Plant
FCCU
H/C
Coker
Unit
Gasoline
Blending
DHT
Distillate
Fuels
Atm
Unit
Vac
Unit
Coke
Asphalt
Diesel
Fuels
Gasoline
Sulfur
LPG, C3=
Hydrogen
Crude
Oil

7. Marathon Garyville CCR Platformer

8. Hydroprocessing and Hydrogen

9. A Typical Hydrotreater Flow DiagramA Typical Hydrotreater Flow Diagram

10. Hydroprocessing ReactionsHydroprocessing Reactions
 Sulfur, Nitrogen and Oxygenates Removal
– Hydrodesulfurization is the major reaction in hydroprocessing
– Hydrodenitrogenation is essential in FCC and hydrocracker feed
pre-treatment
– Hydrodeoxygenation is not common, except in the processing of
synthetic (coal, shale) oils and with rerun streams (MTBE, EtOH)
 Olefins and Aromatics Saturation
– Olefin saturation for product stability and color
– Aromatic saturation for solvents, transportation fuels production
and FCC feed pretreatment.
 Hydrocracking like FCC is used for conversion of
gas oils to gasoline, diesel, heating oil and jet fuel
 Hydroprocessing reactions consume significant
amounts of hydrogen

11. Refinery Process HRefinery Process H22 ConsumptionConsumption
0
500
1000
1500
2000
2500
H2, SCF/B
LSR H/T
NHT
DHT LP
GO H/T
DHT HP
H/C
H2 consumption is a
function of:
 Process type
 Feed boiling range
 Composition
 Sulfur
 Nitrogen
 Metals
 Oxygenates
 Unit pressure
 Unit temperature
Avg. H2 price ~ $4/MSCF
H2 consumption for a 70 MBPD Hydrocracker ~ $220 MM/yr

12. Catalytic Reforming Processes

13. Catalytic Naphtha Reforming BasicsCatalytic Naphtha Reforming Basics
• Upgrade the octane of a naphtha feed to
produce
– High octane gasoline blending component
– Hydrogen
– Aromatics
• Platinum containing catalysts
– Pt/Al2O3/Cl, Pt/Re/Al2O3/Cl, Pt/Sn/Al2O3/Cl
– Dual functionality
• Hydrogenation/dehydrogenation
• Acidic/isomerization

14. Catalytic Naphtha Reforming BasicsCatalytic Naphtha Reforming Basics
• Hydrotreated Naphtha Feed
– Sulfur < 0.3 wppm
– Nitrogen < 0.2 wppm
– Metals < 10 ppb
– Paraffins, naphthenes and aromatics
– Carbon range of C6 to C11
• Typical Process Conditions
– 35 to 300 psig, 900 to 1000 F, LHSV 1.0 to 4.0,
– H2/HC molar ratio of 1.5 to 6
• Principal Reactions
– Naphthenes Dehydrogenation
– Naphthenes isomerization
– Paraffin dehydrocyclization
– Paraffin hydrocracking
– Hydrodealkylation of aromatics
– Hydogenolysis

15. Semi Regen & CCR ReformersSemi Regen & CCR Reformers

16. Platinum/Rhenium CatalysisPlatinum/Rhenium Catalysis
• First assignment in Exxon was to determine the
mode of promotion of Rhenium for Pt/Re catalysts
• Fundamental Pt/Re catalysis an naphtha reforming
process
• Cleaned a 4 reactor Hydrotreating catalyst sulfiding
unit for “clean sulfur” platinum/rhenium naphtha
reforming studies
• Isopropyl alcohol was used to clean the unit in 8
weeks!
• 4 reactors shared a common heater
• Developed close working relationship with other
Exxon researchers and surface characterization
specialists

17. Catalytic Reforming ReactionsCatalytic Reforming Reactions

18. Paraffin Dehydrocyclization
4H2
Adapted from G. A Mills, H. Heinemann, T. H. Milliken and A. G. Oblad, Ind. Eng. Chem.
45, 134 (1953)
C-C-C-C-C-C-C
+
C2H5
C2H5
CH3
Coke
M/A
M/A
A
M
A
M
CH3
M metal sites
A acid site
C2H5
Heptane, 0 RON
Toluene, 120 RON

19. Staged Platinum/Rhenium Catalysts

20. Catalyst Test ProgramCatalyst Test Program
• Assess rhenium effects at various rhenium concentrations
• Make catalysts with varying rhenium content on a constant
Pt catalyst
– 0.3 %Pt/0.3 %Re, O.3 % Pt/0.6 % Re, relative Re/Pt ratios
– 0.3 % Pt/Al2O3, 0.3 % Re/Al2O3,
• Activate catalysts and characterize for start of run (SOR)
coke, chloride and sulfur
• Conduct test runs in a common sand bath heater with four
separate reactor and product separation systems
• Use the same operating conditions and naphtha feed
– 935 F, 200 psig, 5000 SCF/B H2/HC
• Obtain C5+, H2 and light gases (C1 – C4) yields
• Characterize spent catalysts for coke, chloride and sulfur
• Conduct model compound reforming studies with Heptane
and methyl cyclopentane.

21. Isothermal Unit Evaluation of Pt/ReIsothermal Unit Evaluation of Pt/Re
CatalystsCatalysts
Rel
Re
C5+,
vol. %
Catalyst
Activity
EOR
Coke
EOR
Sulfur
1.0 70.8 85.0 8.4 0.03
1.5 71.2 83.0 9.2 0.05
2.0 70.7 81.0 8.5 0.07
2.7 70.3 95.0 7.3 0.12
3.9 69.9 109.0 7.3 0.14
Test Summary
 Lower coke make with higher Rhenium
 Lower C5+ and H2 yields
 Higher sulfur retention
 Higher activities with Rhenium content
 Different H/C ratios for the coke
 Shift in aromatics to BTX
Feed: P, 69.1 vol. %; N + A, 30.9, vol. %
Process Conditions;
935 F, 200 psig, H2 rate of 5000 SCF/B
Rel. Re = wt % Re/wt % Pt in catalyst

22. Commercial Simulation Unit DataCommercial Simulation Unit Data
Catalyst Cat A Cat B Delta
Activity,
No
72.0 96.0 +24
C5+, vol.
%
72.0 69.3 -2.7
Cat A 0.3 % Pt/0.3 % Re
Cat B 0.3 % Pt/0.6 % Re
Cat B = Rel 2
Feed: Light Arabian Naphtha
Process Conditions:
950 F, 175 psig, 3000 SCF/B, 102
RON
Test Summary
• 2.7 vol. % lower C5+ for B
• Lower H2 yield
• Higher C1 to C4 gas
• Lower coke make

23. Combination/Staged Catalyst DataCombination/Staged Catalyst Data
Catalyst Low Rhenium
0.3 Pt/0.3 Re (A)
Combination
Catalyst A &
Catalyst B
Delta
Activity 77.0 92.0 +15
H2 yield, wt. % 2.26 2.31 +0.05
C1 – C4, wt. % 18.82 17.86 -0.96
C5+ yield, vol. % 74.30 75.50 +1.2
• Production gains for C5+ (gasoline) and H2
• $5+ MM dollars a year for a 40 MBPD Platformer
• Introduced staged Pt/Re catalyst systems based on Rel. Re
• Combination Pt/Re catalyst systems are now used worldwide
• Determined that rhenium promoted platinum catalysis via
minimization of steric hindrance for intermediate compounds
• Studies led to KX-160, US Patent 4,436,612 & other 8 patents

24. Paraffin Dehydrocyclization
4H2
Rhenium modifies sterically hindered intermediate
compounds
C-C-C-C-C-C-C-C-C
+
C4H9
C4H9
C4H9
C3H7
COKE
M/A
M
A
M
A
M
, X
M metal sites
A acid site
Where X is CH3, or C2H5

25. Two Stage Reduction of Platinum Catalysts

26. Reforming Catalyst ReactivationReforming Catalyst Reactivation
• Burn coke off spent catalyst
– CXHy + (x+y/4) O2 xCO2 + (y/2)H20
• Re-disperse agglomerated platinum and
promoter metal sites
• Reduce platinum and promoter
– Manage water evolution
– Manage reactions with hydrocarbons
– Optimize reduction of platinum and promoter
– Manage catalyst chloride loss
• Sulfide Pt/Re catalysts to temper
hyperactive sites

27. Platinum & Rhenium ReductionPlatinum & Rhenium Reduction
Past work had shown the following:
• Platinum is reduced at 600 F
• Rhenium reduction is not facile and
requires temperatures > 1100 F
Scelza et. al: TPR work shown here
Hypothesis:
Use reduced Platinum to catalyze the
reduction of rhenium oxide or a promoter
metal oxide
PtO2 + 2H2 Pt + 2H2O
Re2O7 + 7H2 2Re + 7H2O

28. Two Stage ReductionTwo Stage Reduction
Enhances Gasoline and H2 YieldsEnhances Gasoline and H2 Yields
Standard
Red.
2 Stage
Red.
Delta
H2, wt. % 2.44 2.52 +0.08
C1, wt. % 1.27 1.18 -0.09
C2, wt. % 1.81 1.65 -0.16
C3+C4, wt.
%
6.87 5.63 -1.24
C5+, vol. % 82.54 83.77 +1.23
Novel activation involves:
US Patent 4,539,307
1)Reduction at a temp
between 600 F and 750 F
2)Nitrogen purge to remove
water
3)Another reduction at temp
between 900 F and 1000 F
eed: P/N/A 46.9/37.0/16.1
rocess conditions: WHSV 4
200 psig, H2/HC 3, 98
RON

29. SummarySummary
• Pt/Re catalysis work by Soni Oyekan and George Swan of
Exxon led to increased production of hydrogen and gasoline
blending components for oil refiners
• The Pt/Re studies led to use of terms such as equi-molar,
balanced, unbalanced and skewed by technology providers
and oil refiners
• Two stage reduction of platinum containing catalysts is now
used worldwide in over 120 high performance catalytic
reformers
• Platinum catalyst inventions have led to enhanced
economic benefits for oil refiners through increased
production of hydrogen, gasoline, diesel and jet fuel
• Other catalytic reforming process contributions led a better
assessment of the impact of feed sulfur for platinum
containing catalysts

30. Thank You For Your Time
2005 Marathon Garyville Refinery