Recent Advances in Catalysis for

Catalytic Naphtha Reforming

Mark Lapinski, Mark Moser,

Steve Metro, Chris Polaniecki, and Manuela Serban*

2010 AIChE Regional Process Technology Conference

Galveston, Texas
October 8, 2010
© 2010 UOP LLC. All rights reserved.
 Agenda

• Reforming market drivers and objectives

• Reforming process, catalysts and reactions
• New UOP semiregenerative and CCR
reforming catalysts
• Taking advantage of new catalyst to meet
processing objectives
• Conclusions

2 File Number
 Refining Market Overview
TM unit TM
•Total US products demand
TM unit

TM unit
~ 19 MMBPSD
•Total US gasoline demand
~ 9 MMBPSD
• Reformate is an aromatic rich
high octane liquid blending
component making up ~1/3 of
gasoline pool
• Other desirable products from
the reformer include aromatics
and hydrogen
TM unit

Reforming Unit Types

Continuous
Semiregenerative
Cyclic
TM unit

3 File Number
 North American Refining Scenario

North American Reformer Refiner

Trends Impact Needs

y Lower gasoline y Octane long y Flexible Operation

consumption y Lower severity ops y Improved profitability
y Ethanol – Reduced throughput – H2 yields
y Renewables/ – Lower octane – C5+ liquid yields
Biofuels y Higher severity ops – Aromatic yields

y Shift to diesel – Feedstock changes – Catalyst stability

& longer cycles
y Excess gasoline – Increased throughput
U.S. Gasoline Demand
imports – Higher Octane / Aromatics
Forecast
9.5
– More H2
y Regulations 9.3
9.1

y Decreased 8.9

MMBPD
8.7

utilizations 8.5
8.3
8.1
y Lower 7.9
7.7
profitability 7.5

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Market Trends Impact Refinery and Reforming Unit UOP 5381F-03
File Number
4
 Semiregenerative Reforming Process

Desired products include C5+ for gasoline, aromatics for petrochemicals, and H2
5 File Number
Continuous Catalyst Regeneration (CCR)
Reforming Process

Simplified CCR PlatformingTM Unit Flow Scheme

Desired products include C5+ for gasoline, aromatics for petrochemicals, and H2
6 File Number
 Reforming Reactions
C1+C2+Cracked Products
promotes
M M
M A M A

M
M=Metal
+
A
A=Acid

Catalyst Temperature Pressure

Naphthene Dehydrogenation M High Low
Naphthene Isomerization A Low*
Paraffin Isomerization A Low*
Paraffin Dehydrocyclization M/A High Low
Hydrocracking A High High
Demethylation M High High
Aromatic Dealkylation M/A High High

*Low Temperatures Favor Higher Iso/Normal Ratios; Rate of

Isomerization Increases with Increasing Temperature
7 File Number
 Effect of Pressure on Yield Structure

Hydrogen
Product Yield, wt-%

C1 + C2 + C3 + C4

C5+ Reformate

0
Pressure kg/cm2 (psig)

Catalyst Deactivation Rate Increases

Low operating pressures favor naphthene dehydrogenation and

paraffin dehydrocyclization reactions
8 File Number
 Reforming Catalysts

Dual function catalyst

• Acid sites: Chloride
- Responsible for the formation of carbonium ions by
extraction of hydride ions or addition of protons to double
bonds
- Carbonium ions are intermediates in isomerization and
hydrocracking reaction
Desired
• Metal sites: Platinum Metal-Acid
Balance
- Responsible for the extraction of (Pt) (Cl)
hydrogen from HC, the splitting Increasing Metal Increasing Acid
of H2 molecule, and addition of H Function Function
atoms to unsaturated species
Demethylation Cracking

• Balance maintained by proper

Dehydrogenation
regenerator operation Dehydrocyclization
Isomerization

9 File Number
 Improving Catalyst Performance

Catalyst Function Variables

Metal Function Metal levels, metal ratio, promoter
Acid Function Cl level, promoter
Shape, density, pore size distribution,
Alumina Support
Cl retention

• Approach for new catalyst design

- Reduce cracking with addition of promoter
- Increase activity with new base composition and manufacturing
- Keep temperature lower over cycle in order to reduce cracking
reactions
- Less cracking maintains higher H2, C5 and aromatic production
- Accelerated coke precursor conversion with improved accessibility
to rhenium

Catalyst reformulation leads to improved performance

10 File Number
 Semiregenerative Reforming Catalysts

• Semiregenerative catalyst Comparison of Pt and Pt-Re Catalysts

composition 6

- Pt, Re, and Cl 5

Pt - Re
- Gamma alumina support

C5+ Yield, LV%

4

• Role of Re is to hydrogenate or 3

2 All Pt
crack coke precursors 1
- Keeps Pt metal free of coke 0

- Initial high hydrogenolysis activity 0 20 40 60 80 100

Æ must be sulfided 40
Catalyst Age, Days on Stream

- Increased stability makes ideal for

Reaction Temperature,
semi-regen long cycle operations 30
All Pt Pt - Re
- Unbalanced Re catalyst can provide 20
additional stability
10
• Sulfur upsets
- PtRe has poor resistance to sulfur 0
0 20 40 60 80 100
upsets (vs. Pt-only) C a ta ly s t Ag e , D a y s o n S tre a m
Š Strong bond between Re-S
Š With higher sulfur levels, S may not
desorb as readily

11 File Number
 UOP’s New R-500 Platforming Catalyst
TM

R-500
R-500 Catalyst
y Addresses needs for increased
R-98 flexibility
y Highest activity and stability of any
commercially available catalyst
R-86 y Superior stability leads to increased
average yield per cycle
y Several ways to take advantage of
improved yield stability
R-56

R-500 adds significant value over any

12
commercially available fixed-bed reforming catalystUOP 5381F-11
File Number
UOP’s R-500 Break-Through Performance

• Unique proprietary high-density base formulation and

proprietary manufacturing technique for increased
activity
• Optimized metals formulation (balanced metals) with
promoter in finished catalyst for increased selectivity
• Performance enhancing trilobed shaped extrudate for
improved stability

R-500 achieves breakthrough performance

with optimized base and finished catalyst

13 File Number
 UOP Catalyst Performance Comparison

R-86 R-98 R-500

C5+ Yield (SOR), LV% Base Base + Base +

C5+ Yield (Over Cycle), LV% Base Base + Base ++

H2 Yield (SOR), SCFB Base Base + Base +

H2 Yield (Over Cycle), SCFB Base Base + Base ++

Start Of Run (SOR)

Base -3 - 15
Temperature, °F
Stability, Relative Base Base Base ++

R-500 has 15ºF activity and increased stability advantage

UOP 5381F-14
14 File Number
 Operational Flexibility with Multiple Benefits

No Change in Operation
(severity of unit)
Longer Cycle:
>25% longer cycle length with
lower SOR and same EOR Temp;
one less shut down over a 3-5
years depending on cycle length
Change in Operation
(operating conditions and/or
change in feed source or
product spec requirements)
Higher C5+ and H2 Yields:
by lower pressure (higher
severity), same SOR

Higher C5+ and H2 Yields Higher Throughput:

over cycle by improved stability lower SOR and same EOR and
with lower WAIT same cycle length & yield decline

More Robust Higher Severity:

to feed and operational upsets Higher octane, higher aromatics,
(sulfur, water-chloride balance) or more paraffinic feed

R-500 has multiple benefits to meet shifting demands

of reforming units
15 File Number
 R-500 Yield Improvement Over Cycle

R-98 and R-500 have

the same SOR yield
benefit vs. R-86 UOP Pilot Plant Data

Red Line: R-86 (low density)

Green Line: R-98 (low density & promoter)
Blue Line: R-500 (high density & promoter)
C5+, Wt%

R-86
R-500

$1MM increased production/ yr

Area shaded
- 30,000 BBL/Dis the increase
Feed R-98
in barrels
- 94 RON of product vs. R-98
for same
- 12 month cycle length
cycle
- $2.23/ gallon 89 (R+M)/2

Constant Feed Rate and Octane

Time Same cycle length

Improved Stability Results in Higher C5+ and H2 Yields Over Cycle

UOP 5381F-16
16 File Number
 R-500 Cycle Length Advantage

UOP Pilot Plant Data

Longer cycle with same

yield decline and EOR
temp.
C5+, Wt%

R-86
R-500
Same yield decline
R-98

Constant Feed Rate and Octane

Time

Improved Stability Results in Longer Cycle Lengths

UOP 5381F-17
17 File Number
Continuous Catalyst Regeneration (CCR)
Reforming Catalysts
• CCR catalyst composition
- Pt, Sn, and Cl
- Gamma alumina support

• Sn attenuates Pt metal
- Sn reduces the Pt hydrogenolysis reactions
Š Reduction in cracked productsÆ higher yields
Š Sulfiding is not required
- Deactivation and coking are reduced
- Sn inhibits sintering of metal crystallites during
oxidation and reduction

• Commercial PtSn catalysts

- Good stability at low pressure operation

18 File Number
 UOP CCR Platforming Catalysts
• UOP has a broad product portfolio for many applications
- Meeting range of customer objectives
- Providing value and operational flexibility

Current Portfolio
• R-234 Catalyst
- High yields, lowest coke
- Low-density (low fill cost)
- Proven commercial experience in ~ 100 units
• R-274 Catalyst
- Highest yields, lowest coke
- Low-density, acidity modified base
- More than 15 units loaded
• R-264 Catalyst
- Highest activity, low coke, with flexibility to run in high yield mode
- High density maximizes throughput by alleviating pinning constraints
- Catalyst of choice for new CCR Platforming units

19 File Number
 UOP Continues to Innovate New Products
New low-density R-254 and high-density R-284 catalysts
y New catalysts have modified acid function to improve selectivity
of cyclization vs. cracking but with less activity loss
y Acidity modification of alumina bases with addition of promoter
y Higher activity than R-274 catalyst while maximizing yields

C1 + C2 Cracked Products

M M
M A M A

M
M = Metal A +
A= Acid H2 +

Improve selectivity
of cyclization over
cracking Rxs.
20 File Number
 Catalysts for Achieving Highest Yields
Yield-Activity Deltas for UOP CCR Catalysts
R-254 & R-284
1.8 UOP Pilot Plant Data
• Benefits vs. R-274
Aromatics Yield, Wt%

1.4 New R-284 New R-254

- Higher activity
Delta C5+ or Total

1.0 - Increased throughput

R-264HY
- Higher RON
0.6 R-274
R-264HA • Benefits vs. R-234
0.2 and R-264
R-234 - Higher C5+ yield
-0.2
Higher R-134
- Higher H2 yield
Yield
-0.6 Higher
Activity
-1.0
-6.0 -4.0 -2.0 0.0
Delta 2.0
Temperature,
4.0 °C
6.0 8.0 10.0

• New High Yield catalysts can be applied

- For product increases at constant feed rate
- To achieve maximum yield at reduced severity
- For more flexibility (more activity) vs. previous R-274
21 File Number
 New High Yield R-254 Catalyst

• R-254 Catalyst
Catalyst R-234 R-254 R-274
- C5+, H2 and aromatic yields
similar to R-274 catalyst Shape Sphere
- Low coke Pill Diameter 1.6 mm (1/16 inch)
- Higher activity vs. R-274
catalyst Surface Area 180 m2/g
- Low-density (low fill cost) Density, ABD 560 kg/m3 (35 lb/ft3 )
- Modified alumina base Pt Level 0.29 wt%
with promoter
- Builds on knowledge and Crush Strength 50+ N
experience of the R-234
Promoter No Yes Yes
and R-274 catalysts

Excellent application for reduced severity and flexibility

22 File Number
 New High Yield R-284 Catalyst

• R-284 Catalyst
Catalyst R-264 R-284
- Aromatics and motor fuels catalyst
Shape Sphere
- High yields, low coke
- Higher activity vs. R-274 catalyst Pill Diameter 1.6 mm (1/16 inch)
- High density can help maximize Surface Area 180 m2/g
throughput by alleviating pinning
constraints Density, ABD 670 kg/m3 (42 lb/ft3 )
- Modified alumina base with
Pt Level 0.25 wt%
promoter
- Builds on knowledge and Crush Strength 70+ N
experience of the R-264 and Promoter No Yes
R-274 catalysts

New R-284 CCR catalyst provides high yields and flexibility

UOP 5236B-18
23 File Number
 Conclusions
• North American refining market generally octane
long and under pressure to maximize efficiency of
existing assets
• Hydrogen remains primary objective for many
reforming units for hydrotreating and hydrocracking
• New high-activity, high-selectivity UOP R-500
semiregenerative catalyst provides flexibility to
produce more C5+ and H2
- High stability and longer cycle length
(less down time)
- Higher yields maintained over cycle
- More robust to contaminants and upsets
- Opportunity to lower pressure for higher
yields
- Opportunity to increase feedrate or run
at higher severity

24 File Number
 Conclusion (cont.)

• New high yield UOP R-254 and R-284 CCR catalysts

- R-254 low-density and R-284 high-density catalysts provide highest
C5+, H2 and aromatic yields with increased flexibility (activity) vs.
R-274
- Both new catalysts build upon proven technology
of R-234 (high yield, lowest coke) , R-274 (highest yield, lowest
coke) and R-264 (highest activity, low coke, flexible for
higher yields) catalysts
Š UOP CCR catalysts have been extensively proven
in 200+ units

Established and new CCR Platforming

catalysts meet a wide range of
customer objectives to provide
high value and flexibility

UOP 5236B-19
25 File Number
 UOP 4934C-52
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