Prime-G+TM

Commercial Performance of Desulfurization Technology

Quentin Debuisschert Axens
1 NPRA 2003 Annual Meeting

Agenda

Gasoline Sulfur Control Prime-G+ Technology Update Prime-G+ Commercial Update The European Experience The North American Experience
2 NPRA 2003 Annual Meeting

Fully Integrated Services

RSI

Axens

July 1, 2001
Procatalyse

Eurecat

IFP

Licensing

IFP School

Prosernat

Axens Core Business: Licensing, Catalysts, Services

3 NPRA 2003 Annual Meeting

Agenda

Gasoline Sulfur Control Prime-G+ Technology Update Prime-G+ Commercial Update The European Experience The North American Experience
4 NPRA 2003 Annual Meeting

FCC Gasoline HDS Requirements

Maximize Octane Retention Minimize H2 Consumption Reliability - Key Unit in the Refinery Cycle Length equivalent to FCC Turn-around Maximize Gasoline Yield without RVP Increase Possibility to Control Olefins Content Ability to Co-Process other S containing Streams Ability to Meet Potential Future Specs.
5 NPRA 2003 Annual Meeting

Agenda

Gasoline Sulfur Control Prime-G+ Technology Update Prime-G+ Commercial Update The European Experience The North American Experience
6 NPRA 2003 Annual Meeting

Prime-G+ - 10-50 ppm Sulfur Selective HDS

IBP-140F to Pool after Sweetening Splitter Full Range Cracked Naphtha Prime-G+ Dual Catalytic System

Low Sulfur Heavy Gasoline 10 - 50 ppm S

140F+

H2 Make-up
7 NPRA 2003 Annual Meeting

HDO vs. HDS: Conventional and Prime-G+

Extent of HDO 4-8 Point Road Octane Difference
al nvention Co

1st

catalyst

2nd catalyst

Prime-G+

Extent of HDS
8 NPRA 2003 Annual Meeting

Prime-G+ HDS Benefits

High performance

Deep HDS (less than 10 wppm product S) Low Octane Loss, Low product mercaptan Well suited for idle units reutilization Easy operation Excellent stability

Low Cost and Utilities Simple and Reliable Process

Industrially proven at Ultra Low Product Sulfur Ability to Co-process other Streams than FCC
9 NPRA 2003 Annual Meeting

Prime-G+ Process 10-50 ppm Sulfur Spec

Prime-G+ Selective Hydrogenation

Ultra Low S LCN to Pool, TAME or Alky Unit Splitter

FRCN

Prime-G+ Dual Catalyst Reactor System HCN 140F +

10

H2 Make-up

Ultra-Low Sulfur Gasoline

NPRA 2003 Annual Meeting

Prime-G+ 1st Step - SHU + Splitter

Removes Diolefins from HCN

Minimizes pressure drop in selective HDS Allows to achieve long cycles on selective HDS Feed preparation for alkylation or etherification Very low sulfur LCN product No need for extractive sweetening Moderate octane gain on LCN
11 NPRA 2003 Annual Meeting

Removes Diolefins from LCN Converts Lt. Mercaptans/Sulfides to Heavy Sulfur

Isomerizes External Olefins into Internal Olefins

SHU Performance & Mercaptans Conversion

LCN (145F-)
25.5 % vol S = 261 ppm RSH = 239 ppm

LCN (145F-)

Prime-G+ SHU

25.5 % vol S = 14 ppm RSH = 1 ppm

S = 587 ppm RSH = 54 ppm MAV=10 BrNo=60 (R+M)/2=86.0

MAV < 2 BrNo=59 (R+M)/2=86.2

FRCN+LSRN HCN (145F+)

HCN (145C+) H2
74.5 % vol S = 775 ppm
NPRA 2003 Annual Meeting

FRCN

74.5 % vol S = 703 ppm

12

Agenda

Gasoline Sulfur Control Prime-G+ Technology Update Prime-G+ Commercial Update The European Experience The North American Experience
13 NPRA 2003 Annual Meeting

Prime-G+ Commercial Success Starting Point: August 1999

NPRA 2001
Prime-G References Prime-G+ References Total Prime-G/Prime-G+ Designs at 10 ppm S Prime-G+ Units Running Capacity (million BPSD)
14

NPRA 2002
6 37 43 25 2 1.1

NPRA 2003
7 63 70 48 7 1.9

6 15 21 10 No 0.7

NPRA 2003 Annual Meeting

Prime-G+ Flexibility Licensed Units - Design Range

Unit Capacity 2,500 - 115,000 BPD Feed Sulfur 30 - 4,100 ppm Olefins Content 15 - 55 vol. % Feeds FCC Naphtha, light Coker Naphtha, LSR, Steam-Cracking Naphtha Product S < 10 ppm
15 NPRA 2003 Annual Meeting

Prime-G+ Industrial Success

7 Prime-G+ units in operation at Ultra Low Sulfur Technology Selection after Pilot Testing Fast Track Projects

Less than 2 years between BEDP and Oil In Basic Engineering Catalyst Supply Assistance for Start-up Follow-up of the unit

Full Set of Axens services

All Axens guarantees met

16 NPRA 2003 Annual Meeting

Agenda

Gasoline Sulfur Control Prime-G+ Technology Update Prime-G+ Commercial Update The European Experience The North American Experience
17 NPRA 2003 Annual Meeting

European Gasoline Sulfur Regulations

EU 2000 spec. EU 2005 spec. U.K., October 2000 Germany, End 2001 Germany 2003 EU 2009 spec.?

150 ppm sulfur 50 ppm sulfur Tax incentive for 50 ppm S Tax Incentive for 50 ppm S Tax Incentive for 10 ppm S 100% of Mogas pool at 10 ppm S

EU 2003 +

10 ppm S driven by marketing

18 NPRA 2003 Annual Meeting

Prime-G+ First Unit Germany

19

NPRA 2003 Annual Meeting

Prime-G+ Commercial Achievements

SHU performance HDS Octane Retention Permanent On-spec Sulfur Production SHU/HDS Mercaptan Control Prime-G+ Unit Reliability

Unit response to feed upsets Catalysts stability Pressure Drop management

20 NPRA 2003 Annual Meeting

Prime-G+ SHU Performance Mercaptans Removal

SHU Feed RSH Sulfur 100 2100 LCN Product <2 < 10

Almost complete mercaptans removal Doctor Test negative LCN

21 NPRA 2003 Annual Meeting

Prime-G+ SHU Performance Octane Balance

Performance Test Results
SHU Feed RON MON 94.0 82.0 SHU Product 94.3 82.2

Slight Octane Boost on SHU Octane boost mostly concentrated on LCN

22 NPRA 2003 Annual Meeting

Prime-G+ HDS Octane Retention

Octane Loss 3.0 2.5 2.0 1.5 1.0 0.5 0 95 96 97 98 99 Extent of HDS for Typical European Unit Per Cent Sulfur in Feed to Prime-G+ Unit
23

Delta MON Delta (MON + RON) / 2

100

NPRA 2003 Annual Meeting

On-Spec Product Produced At All Times

Feed S, ppm
600 400 200 0

Product S, ppm
60 40 20

100

200

300

400

0 500

Days on Stream
24 NPRA 2003 Annual Meeting

Product Mercaptan Control

Sulfur & Mercaptans in Product, wt ppm 100 80 60 40 20 0 0 50 100 150 200
25

Total sulfur in product Mercaptans in product

250

300

350

400

450

Days on Stream
NPRA 2003 Annual Meeting

Reliability - Response to Feed Upsets

Feed and Product Sulfur Contents, ppm 1600 1200 800 400 0 0 5 10 15 20 Days of Operation
26

Sulfur in Feed Sulfur in Product

25

30

NPRA 2003 Annual Meeting

Reliability: Stability of HDS Catalysts

HDS Catalyst WABT 0 100 200 300 400 500

Days on Stream

27

NPRA 2003 Annual Meeting

Reliability: Pressure Drop Management

Normalized Pressure Drop, P (Flow Rate)2

In SHU Reactor In HDS Reactor

100

200
28

300

400

500

Days on Stream
NPRA 2003 Annual Meeting

Agenda

Gasoline Sulfur Control Prime-G+ Technology Update Prime-G+ Commercial Update The European Experience The North American Experience
29 NPRA 2003 Annual Meeting

The North American Experience

US RFG 2000 US RFG 2004-2006 Canada 06/2002 to 12/2004 Canada 01/2005 December 2002 March 2003

150 ppm sulfur 30 ppm sulfur 150 ppm sulfur average 30 ppm sulfur 2 Prime-G+ Start-up in Canada Successful operation 2 additional Start-up in US
30 NPRA 2003 Annual Meeting

Ultra Low Sulfur Production Unit A

Feed S, ppm 1300 1100 900 700 500 300 Run Days
31 NPRA 2003 Annual Meeting

Feed S Product S

Product S, ppm 100 80 60 40 20 0

Octane Retention Coupled with ULS Unit B

Overall Octane Loss 4.0 3.0 2.0 1.0 0.0 0 10 20
32

30

40

50

Recombined Product Sulfur, ppm

NPRA 2003 Annual Meeting

Conclusion

Worldwide Trend towards ULS Fuels

10 ppm S today effective in Europe 70 References worldwide 14 units in operation Industrially Proven at ULS (10 ppm S) Schemes with or without splitter Flexible HDS Section SHU upstream splitter / OATS NPRA 2003 Annual Meeting 33

Prime-G+ Leading Technology

Technology showing High Flexibility

Thank You For Being So Patient

34

NPRA 2003 Annual Meeting