Ultra Low Sulfur Gasoline

via Commercially Proven

Catalytic Distillation
Gasoline Desulfurization Requirements
- Pool sulfur specification
- Europe
European Union
50 ppm max - 2005
10 ppm max
- available 2005
- standard 2008
- US, Canada
30 ppm avg - 2002 to 2008
- Future
15 -10 -5 ppm? - 2005+
- México
300 / 500 ppm max (150 avg) - 2004
80 ppm max (30 avg) - 2006 / 2008
Modern Refinery Requirements

• Maximize refinery margin

• Minimize refinery downtime/shutdown costs
• Minimum FCC turnaround cycle – 5 years
• Avoid any FCC downstream shutdowns
- Choose FCC gasoline HDS technology wisely
FCC Gasoline Feed Composition

12000 40
10000
30
Sulfur, ppm

Olefins, %
8000
6000 20
4000
10
2000
0 0
50 100 150 200 250
Temperature, C

Sulfur Olefins
 Optimized FCC Gasoline HDS

Mild HDS
LCN

Medium
MCN
HDS
FCC C5+
GASOLINE

MCN/HCN

HCN
Severe
HDS
 Conventional FCC LCN Treating

FRESH CAUSTIC • Fractionate LCN from FCC

LCN
Mercaptan Gasoline
Removal
• Caustic wash for mercaptan
Selective
TREATED
LCN removal
Hydrogenation - ~90% effective

FCC C5+
Hydrogen • Selective hydrogenation of
GASOLINE
Compression
HYDROGEN dienes for alky/ethers
SPENT CAUSTIC
• Compression of makeup
MCN/HCN
hydrogen
Hydrogenation/Distillation

CDHydro® Process
• Replace trays with CW
Vent
structured distillation Gas

packing containing
catalyst
• Add Hydrogen Feed Hydrogen Treated
Distillate

• Vent excess Hydrogen Hydrocarbon

Steam
Feed

Bottoms
Catalytic Distillation

Catalyst Section
Drawing

Reflux LCN

Catalyst
Wire
Mesh

LCN
RSH
Sulfides
Dienes
Hydrogen

RSH + Diene ⇒ Sulfide⇓

 Improved LCN Treating

• Replace upper section with FRESH CAUSTIC

CDHydro (5-7 barg) CDHydro
Mercaptan
Removal
• Eliminate fresh caustic and
TREATED
caustic wash LCN
Selective
- < 1 ppm RSH HYDROGEN Hydrogenation

• Eliminate separate
FCC C5+
hydrogenation unit GASOLINE
Hydrogen
Compression
HYDROGEN
• Eliminate hydrogen SPENT CAUSTIC

compression MCN/HCN

• Boost octane via

hydroisomerization
 Conventional Optimized FCC Gasoline HDS

Mild HDS
LCN

Medium
MCN
HDS
FCC C5+
GASOLINE

MCN/HCN

HCN
Severe
HDS
 Optimized FCC Gasoline HDS

LCN

CDHydro® Medium
Hydrogen
MCN
HDS
FCC C5+
GASOLINE

MCN/HCN

HCN
Severe
HDS
 MCN/HCN Desulfurization

CDHDS®
Conditions milder than conventional fixed
CW Off Gas
bed (17 barg vs 28+)
> 99.5% HDS
Heavy sulfur to bottom
Light olefins to top FCC C7+
Gasoline
Min octane loss
Low H2 consumption
Low sulfur bottoms product good for
gasoline or diesel Hydrogen

No yield loss due to cracking

No makeup compressor Desulfurized
No mid-cycle shutdown for catalyst regen FCC C7+ Gasoline

No feed storage required

 CD Optimized FCC Gasoline HDS

LCN

CDHydro®
Hydrogen
MCN
FCC C5+
GASOLINE
MCN/HCN
CDHDS®
Hydrogen
HCN
 CDTECH FCC Gasoline Desulfurization Operating Experience

Shell Martinez, California Depentanizer LCN CDHydro September-95

Pennzoil Shrevesport, Louisiana Depentanizer LCN CDHydro April-97
Shell Port Arthur, Texas Dehexanizer HCN CDHDS May-00
Irving Oil St. John, New Brunswick, Can. Dehexanizer LCN CDHydro November-00
Irving Oil St. John, New Brunswick, Can. Splitter HCN CDHDS November-00
Veba Oel Gelsenkirchen, Germany Dehexanizer LCN CDHydro October-00
ChevronTexaco Pembroke, UK Dehexanizer LCN CDHydro January-00
ChevronTexaco Pembroke, UK Splitter HCN CDHDS January-00
PetroChina Nanchong, China Dehexanizer LCN CDHydro January-00
Motiva Port Arthur, Texas Dehexanizer LCN CDHydro February-03
Motiva Port Arthur, Texas Splitter HCN CDHDS February-03
Hellenic Aspropyrgos, Greece Dehexanizer LCN CDHydro September-03
Motiva Convent, Louisiana Dehexanizer LCN CDHydro October-03
Motiva Convent, Louisiana Splitter HCN CDHDS October-03
Valero Texas City, Texas Dehexanizer LCN CDHydro November-03
Valero Texas City, Texas Splitter HCN CDHDS November-03
Equilon Puget Sound, WA Dehexanizer LCN CDHydro November-03
Equilon Puget Sound, WA Splitter HCN CDHDS November-03
Motiva Norco, Louisiana Dehexanizer LCN CDHydro January-04
Motiva Norco, Louisiana Splitter HCN CDHDS January-04

21 Units with greater than 45 years total operation

Why does CDTECH have less octane
loss for a given olefin reduction?
 CDHDS Selectivity Comparison
MCN/HCN Feed

1
Conversion, Fraction

0.8

0.6
0.4

0.2

0
200 250 300 350 400 450 500
Temperature, F

Sulfur reduction Olefin reduction

Olefin saturation is higher for heavy olefins

 Conventional Fixed Bed Reactor
Selectivity Comparison

100.00%
Conversion, Fraction

80.00%

60.00%
40.00%

20.00%

0.00%
200 250 300 350 400 450 500
Temperature, F

Sulfur reduction Olefin reduction

Olefin saturation is higher for light olefins

Heavy Olefins Have Less Octane loss

RON Linear Olefin - RON Linear Saturate

120

100
80
RON

60

40

20
0
5 6 7 8 9 10 11
Carbon Number
Why is CDTECH’s octane loss lower?
Answer:

• Conventional fixed bed hydrotreaters

- Saturate primarily light olefins
- Light olefin saturation causes high octane loss
• CDHDS
- Higher saturation of heavy olefins
- Less octane to lose in heavy olefins
- Lower octane loss at a given olefin reduction
 Why Does CDTECH Claim Longer
Catalyst Life?
• Conventional fixed bed hydrotreaters
- Olefins form oligomers
- Oligomers form coke that fouls catalyst
- Catalyst activity reduced
- Regenerate or replace catalyst
• CDHydro/CDHDS
- Olefins form oligomers
- Oligomers removed by distillation
- Catalyst stays clean
- Replace catalyst at end of FCC cycle (5 years)
- No mid FCC cycle shutdown required
 Commercial Catalyst Activity for FCC Gasoline HDS

Conventional
Fixed Bed
Technology
SOR

0 EOR 365 730

Days on Oil
Fixed Bed HDS
 Catalyst Activity Tracker for the Motiva, Port Arthur CDHDS Units
CD TECH - Confidential

1.8
1.6 ate !!
Observed Rate Const.

1.4 Upd
1.2
1
0.8
0.6
0.4
0.2
0
3/15/00 10/1/00 4/19/01 11/5/01 5/24/02 12/10/02 6/28/03 1/14/04 8/1/04
Date
K pod CDHDS1 K pod CDHDS2
An approach used by others
Wet
treatment
LCN

FCC

HCN Diene Fixed-bed

Wet
Treater treatment
An approach used by others
Wet
treatment
LCN

FCC

HCN Diene Fixed-bed

Wet
Treater treatment

CDTECH has lower capital cost

 Long CDTECH Catalyst Cycle
Reduces Capex
• Conventional Fixed Bed HDS
- Feed diene removal required
- Mid FCC cycle catalyst regeneration/replacement
- Shutdown FCC or store HDS feed
• CDHydro/CDHDS
- No feed diene removal required
- No shutdown during FCC cycle
- No FCC shutdown
- No additional storage tanks
- No additional capex required
FCC Gasoline HDS Commercial Status
• CDHydro
- 12 commercial units in operation
- 5 years guaranteed catalyst life
• CDHDS
- 7 commercial units in operation
- Motiva, Port Arthur (expanded)
- Irving Oil, Saint John, NB
- ChevronTexaco, Pembroke, UK
- Motiva, Convent
- SOPUS, Puget Sound
- Valero
- 5 years guaranteed catalyst life
Motiva Port Arthur CDHDS
Phase 1
12,000 BPD HCN
90% HDS
Phase 2
- Tier II - 30 ppm S
- ~50,000 BPD FRCN
- New CDHydro
- Additional CDHDS
- Future 10 ppm S
capability
- Demo 1400 ppm
to <8ppm
Irving Oil Limited CDHydro/CDHDS

• Saint John, New Brunswick

Canada
• 58,000 BPD RFCC gasoline
• November 2000 start up
- < 1 month to acceptance
- 150 ppm pool
- 2 years ahead of regulations
• 2002
- 30 ppm pool
- 3 years ahead of regulations
Texaco

• Pembroke, UK
• 50,000 BPD full range
FCC gasoline
• 1st CDHydro/CDHDS
in Europe
• 1Q02 start up
- UK ULSG supported
by tax incentive
Equilon/Motiva/Deer Park Refining

• 7 refineries
• 275,000 bpd FCC gasoline capacity
• CDHydro and/or CDHDS
• Start-up 2002 - 2004
Valero Refining

• 5(+2) refineries
• World Fuels Today statement by Valero V.P.
- For grassroots units, CDTECH has:
- Lowest capital cost
- Lowest octane loss
- Lowest hydrogen consumption
 PetroChina Announcement – 05/03/2003

• 2002 World Oil Industry Top Ten Technology

Breakthroughs
- 9 upstream technologies
- 1 downstream technology
- CDTECH’s CDHydro/CDHDS
FCC gasoline desulfurization
 Conclusions
• CDHydro
- Lowest sulfur and diolefins in LCN
- Eliminates separate mercaptan and diolefin removal units
- Boosts octane
• CDHDS
- Lowest olefin loss via HDS
- No diene pretreatment required
- No regeneration/feed storage required
• CDHydro/CDHDS
- Commercially proven
- Most cost effective HDS in FR FCC CN
- Long catalyst life via catalytic distillation
- Only HDS technology to provide 5 year life
- Low capital cost
Q&A