Rare Earth Free Catalyst for FCC

16th – 17th April, 2012

New Delhi

International Conference On“Refining Challenges & Way Forward”

Vipan Goel

2

Agenda

� Rare Earth importance in FCC catalyst

� RE-free and Low RE Catalyst Technologies - family

� REMEDY™ Performance

� REDUCER™ Performance

� Reference List

� Summary

3

Rare Earth Increases the Zeolite Active Site Density

Moderate unit cell size 24.32 Å

Si/Al = 12

15 Al atoms/unit cell

catalystwt% Re2O3on catalyst

Unit Cell Size(Å)

Conversion, wt%at constant C/O

A 1.1 24.24 53B 1.8 24.27 65C 2.2 24.31 69D 3.3 24.34 73E 3.7 24.36 76F 5.7 24.41 80

low unit cell size 24.25 Å

Si/Al = 27

7 Al atoms/unit cell

4

Gasoline Yield and Octane Response to Unit Cell Size

91.0

91.5

92.0

92.5

93.0

93.5

94.0

94.5

95.0

24.2 24.25 24.3 24.35 24.4 24.45

Unit Cell Size, Angstroms

Gas

olin

e O

ctan

e N

umbe

r, R

ON

47.0

47.5

48.0

48.5

49.0G

asol

ine

Yie

ld, w

t%

5

Electron Microprobe Analysis of ResidUltra Ecat

� Microprobe analysis show vanadium to migrate to regions of high RE2O3.

� ResidUltra employs a RE oxide-based vanadium trap. RE oxides do not form stable compounds with silica and sulfate and thus remain available as a vanadium trap.

� ResidUltra is an integral catalyst. It is effective even in units with low vanadium mobility.

ResidUltra contain commercially proven, RE2O3-based vanadium traps.

Vanadium Rare Earth

6

Grace has a long history of RE-free innovation in FCC

1964

Grace invents

USY

1976Introduction of REUSY

1990RE free zeolite

1991XP-L RE

free catalyst series

1997RE free zeolite in NEXUS

2008 -2010 Significant R&D effort

begins on RE replacement

2010Grace launches

REpLaCeR, RE free catalysts

� Several RE free catalysts were available in the 1990’s, with a primary focus on increasing gasoline octane

� Introduced the first of Grace’s new REpLaCeR™ family of RE-free catalysts called REACTOR™ , which uses new Z-22 technology, early in 2011.

� REduceR™ is the recent addition to REpLaCeR™ series of RE free catalysts, designed for resid applications.

� REBEL™ is built upon Grace Davison’s high matrix catalyst technology and incorporates the new rare-earth free Z-21 zeolite.

Future

7

Zeolite Stabilization summary

� Rare Earth Impact on Zeolite

– Prevents dealumination

– Stabilizes the structure

� Rare earth controls zeolite

– Activity

– Selectivity

– Hydrogen transfer

� Prevents metals deactivation

– Very effective vanadium trap

� Alternate methods are used to stabilize the zeolites in Grace’s RE-free catalyst

– Proprietary stabilizing compounds

– Unique manufacturing processes

� Alternative materials provide activity and stability similar to RE containing catalysts

– Similar UCS as RE containing zeolites

– Truly RE-free, without stabilization, would yield a very low UCS and activity

Unit cell size 24.32 Å

Si/Al = 12

15 Al atoms/unit cell

24.20

24.24

24.28

24.32

Fully exchanged

Low RE exchange

No stabilization

Z-21 Z-22E

quili

brat

ed U

CS

Rare earth enhances activity of zeolites and increases gasoline yield

50

60

70

80

90

Cat

alys

t Act

ivity

Increasing Rare Earth on Catalyst

Stabilization with Rare Earth Proprietary Grace non-RE Stabilization

Z-21 and Z-22 have higher UCS after deactivation than zeolite without stabilization

8

Even without any RE stabilization, Z-21 and Z-22 te chnologies exhibit very good hydrothermal stability, comparable to REUSY catalys t

RE-Free Technology – After Extended Metals Free CPS Deactivation

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500 2000

ZS

A-r

ete

nti

on

[%

]

CPS-3 deactivation duration

REUSY Z-21 Z-22

Deactivation Duration, min

50%

55%

60%

65%

70%

0 1000/2000 2000/4000

ZS

A R

eten

tion

CPS Deactivation Metal Levels (Ni/V ppm)

Z-22RE-USY

30%

35%

40%

45%

50%

0 500/1000 1000/2000 2000/3000

ZS

A R

eten

tion

CPS Deactivation Metal Levels (Ni/V ppm)

Z-21

RE-USY

9

RE-Free Catalyst Technologies Maintain High Aciditi esAfter Metals-Free Deactivation

Acidity by NH3 Temperature Programmed Desorption (TPD)

0.E+00

1.E-06

2.E-06

3.E-06

4.E-06

5.E-06

6.E-06

7.E-06

8.E-06

9.E-06

REUSY Z-21 Z-22

tota

l aci

dit

y [

mo

l/g

]

CPS-3, metals free

After Metals Free CPS Deactivation

10

RE-free and Low RE Catalyst Technologies -

family

11

Low RE V-Trapping

family of RE-free catalysts

Z-2

2 T

echn

olog

y

REACTOR™

Z-2

1 T

echn

olog

y

REBEL™

• REBEL is formulated with proprietary Grace alumina and Z-21 zeolite• The activity and selectivity of REBEL™ is similar to RE containing high

matrix MIDAS® catalyst• Commercial production commenced early 2Q’11• Z-21 technology is in 25 commercial applications

• REBEL is formulated with proprietary Grace alumina and Z-21 zeolite• The activity and selectivity of REBEL™ is similar to RE containing high

matrix MIDAS® catalyst• Commercial production commenced early 2Q’11• Z-21 technology is in 25 commercial applications

• Z-22 zeolite in REACTOR™ is stabilized with a proprietary element• REACTOR™ matches activity and selectivity of equivalent RE containing

alumina sol formulations• Full scale production commenced in 2Q’11• 30 commercial applications and growing

• Z-22 zeolite in REACTOR™ is stabilized with a proprietary element• REACTOR™ matches activity and selectivity of equivalent RE containing

alumina sol formulations• Full scale production commenced in 2Q’11• 30 commercial applications and growing

Low RE Catalyst Systems

REDUCER™

Low RE Technology for resid feeds

REMEDY™

Low RE Technology for VGO/HT feeds

RE Free Catalysts

ResidUltra™Next generation metals

trap technology

12

REMEDY™ Performance

13

REMEDY™ for VGO Cracking: Unit Background

� UOP Stack, full burn, HT VGO cracking

� Base case: Genesis ®(Aurora/Midas)

� New blend: REMEDY™

– Replaced in Aurora with REACTOR ® and REBEL™

replaced Midas in 2 step.

– Z22 and Z21 technologies eliminated the need for RE2O3

� Super DESOX ® user (source of some RE fluctuation)

GENESIS® GSR® REMEDY™ 1 GSR® REMEDY™ 2 GSR®

Reformulation January 2011 August 2011Activity, Wt.% 80 80 80RE2O3, Wt.% 1.50 1.00 TraceAl2O3, Wt.% 51 51 47Zeolite Surface Area, m2/gm 200 200 220

0 to 40µ, % 13 13 13Gasoline Sulfur Reduction 30% 30% 30%

• Each REMEDY™ formulation was designed for similar yields and catalyst additions, but lower Rare Earth

REMEDY™ 2 GSR ® eliminated the Rare Earth Surcharge

14

REMEDY™ 2 GSR®GENESIS® GSR®

74

73

72

71

70

69

68

Catalyst

Activity, %

Box Plots Basics

� Represents the data distribution

� Allows a quick comparison between datasets

3rd Quartile

2nd Quartile

Median

5% Point

Mean

95% Point

15

FCC Conversion and Catalyst Additions

REMEDY™ 2 GSR®GENESIS® GSR®

84%

82%

80%

78%

76%

74%

72%

70%

REMEDY™ 2 GSR®GENESIS® GSR®

0.150

0.145

0.140

0.135

0.130

430F Conversion, Vol% Catalyst Additions, lb/b

Conversion was maintained without Rare Earth at sim ilar catalyst additions

16

REMEDY ™ Enhanced Selectivities and Profitability

20.0%

17.5%

15.0%

12.5%

10.0%

80%75%70%

69%

66%

63%

60%

80%75%70%

10%

8%

6%

4%

6.00

5.75

5.50

5.25

5.00

LCO to 650F, Vol%

430F Conversion, Vol%

Gasoline Vol% ( no ZSM-5)

Slurry 650F, Vol% COKE,WT %

GENESIS® GSR®

REMEDY™ 2 GSR®

Cat a lyst

REMEDY™ increased gasoline selectivity and bottoms conversi on at similar coke

17

Unit Activity and Dry Gas Production

8.58.07.57.06.5

84%

82%

80%

78%

76%

74%

72%

70%

940935930925

170

160

150

140

130

120

110

430F Conversion, Vol%*Cat/Oil DRY GAS,SCFB*REACTOR T,F

GENESIS® GSR®

REMEDY™ 2 GSR®

Cat alys t

REMEDY™ provided similar in-unit Activity and produced low Dry Gas rates

18

Equilibrium Catalyst Shifts with REMEDY™

74

72

70

REMEDY™ 2 GSR®

GENESIS® GSR®

120

115

110

105

100

REMEDY™ 2 GSR®

GENESIS® GSR®

24.29

24.28

24.27

24.26

REMEDY™ 2 GSR®

GENESIS® GSR®

3500

3250

3000

2750

2500

56.0%

54.0%

52.0%

50.0%

Activity, % Zeolite SA, m2/gm Unit Cell Size, Å

V plus Na, ppm ZSA Retention, %

� Similar Activity and Zeolite SA retention

� Additional V+Nalevels

� Lower UCS, but higher than an un-stabilized Zeolite

19

REMEDY™ Commercial Performance – Final Remark

�The performance of REMEDY™ was a successful

– Similar Conversion levels at the same catalyst addition rate

– Low Dry Gas and Slurry Yield

– High Gasoline Selectivity at similar Octane

– Coke Selectivity was maintained– Gasoline Sulfur reduction maintained– No increase in Flue Gas Opacity

�UCS is down from 24.29Å to 24.27Å but confirms the stabilization of zeolite even without rare earth

20

REDUCER™ Performance

21

REDUCER™ for Resid Cracking: Refinery Background

� UOP SBS, partial burn, resid cracking

� Base case : IMPACT® Family

� New REDUCER blend: 50/50 ResidUltra™/Hi-Ni Trap REACTOR™

� Based on the success, have since reformulated the REDUCER™ system to 70% Hi-Ni Trap REACTOR™

22

Ecat Data (100% Turnover)

Activity Remained Similar after Addition of REDUCER ™

Confirming Good Vanadium Tolerance of REDUCER ™

62.0

64.0

66.0

68.0

70.0

72.0

74.0

76.0

78.0

2,00

0.0

2,50

0.0

3,00

0.0

3,50

0.0

4,00

0.0

4,50

0.0

5,00

0.0

5,50

0.0

6,00

0.0

6,50

0.0

MA

T w

t.% F

F

V (mg/kg)

ccc

Resid Catalyst REDUCER™

23

REDUCER™ Demonstrated Good Nickel Tolerance

Ecat Data (100% Turnover)

2.0

3.0

4.0

5.0

6.0

7.0

3000 4000 5000 6000 7000

Gas

Fac

tor

Ni Equivalents [mg/kg]

Gas Factor vs. Ni Equiv.

1.1

1.5

1.9

2.3

3000 4000 5000 6000 7000

Co

ke F

acto

r

Ni Equivalents [mg/kg]

Coke Factor vs. Ni Equiv.

REDUCER™Resid Catalyst REDUCER™Resid Catalyst

24

Reduction in Regen Temp Allowed for an Increase in A tmospheric Resid by 15% abs

FCC Data of REDUCER™ (50/50 Blend)

REDUCER™

100% Turnover

100% Turnover

Catalyst to Oil Ratio Base + 0.4

Hydrogen, wt% Base + 0.02

Dry Gas, wt% Base + 0.2

Propylene, wt% Base + 0.4

Total C4=s, wt% Base + 0.6

LPG, wt% Base + 2.0

Gasoline, wt% Base – 1.6

LCO, wt% Base – 0.2

Bottoms, wt% Base – 0.2

Coke, wt% Base – 0.1

Delta coke Base – 0.09

CAR (mTPD) Base

Regen Temp Base -15°C

25

Conclusions of REDUCER™ Commercial Performance

� Rare earth was reduced from 3.1 to 2.2 wt.% (nearly 0.2m$/annum saving in RES

for refinery CAD @1MTD)

� Despite high Ni+V, the high performance was maintained and even improved

� Base on the yield trends at 50%, refiner increased the concentration to 70% RE free catalyst

� REDUCER™ has been successfully rolled out in EMEA region(18 resid applications)

26

Reference List

27

Low-and-No-RE Commercial Applications

ID Target RE(wt.%)

%RE Free Cat

Unit Type Region Ni(ppm)

V(ppm)

1 0 100 Texaco Design Europe 237 4032 0 100 UOP SBS Europe 444 1,1713 0 100 Shell Mod II Europe 777 9314 0 100 ICI/TPR Europe 409 8365 0 100 Exxon Mod III Europe 108 2476 0 100 UOP SBS Europe na na7 0 100 EXXON III Europe 108 2478 0 100 UOP SBS Europe 597 1,7769 0 100 K OF B Europe 129 16010 0 100 EXXON III Europe 40 12811 0 100 UOP SBS Europe 56 012 0 100 UOP C Europe 169 49013 0 100 UOP SBS Europe na na14 0 100 UOP Stack Europe 356 1,28215 2.2 30 KEL ORTHO Europe 50 12616 0 100 UOP HIGH EFF North America 72 18117 0.6 50 UOP SBS North America 210 55018 0.8 25 KEL MOD III North America 1,036 96619 1.0 50 EXXON MOD IV North America 838 3,01520 3.2 20 UOP HIGH EFF North America 9,085 2,11021 0 100 UOP Stack North America 394 50022 0 100 Texaco Design North America 3,077 1,66623 0 100 UOP Stack North America 50 2,32424 0 100 KEL MOD III 2RIS North America 705 1,23625 0 80 UOP SBS North America 584 1,214

• Demonstrating excellent performance across a wide r ange of metals levels Low metals VGO to high metals Resid applications

• Rare Earth Reduction 100% to 20%

28

Low-and-No-RE Commercial Applications

ID Target RE(wt.%)

%RE Free Cat

Unit Type Region Ni(ppm)

V(ppm)

26 0 100 UOP Stack Asia 1,483 2,26427 0 100 UOP SBS Asia 504 24328 0 100 SHELL DESIGN Asia 36 1,23529 0 100 UOP SBS Asia 1,116 19030 0 100 UOP VSS Europe 62 12031 0 100 UOP VSS Europe 175 56632 1.5 50 UOP Stack North America 492 1,25533 2.4 30 EXXON IV Europe 2,461 3,27334 2.5 ? UOP SBS Europe 1,018 1,05935 1.8 50 EXXON IV Europe 2,060 3,63236 2.5 30 UOP SBS Europe 3,170 5,05937 1.8 50 UOP RFCC Europe 14,806 1,32138 1.6 50 UOP C Europe 1,545 2,47639 2.2 30 SHELL 3 Europe 2,172 5,00340 1.0 70 UOP SBS Europe 3,736 4,52841 2.5 30 UOP C Europe 1,813 2,58942 2.5 30 UOP ST Europe 2,420 3,63743 1.6 50 K OF F Europe 2,550 1,91044 2.5 30 UOP RCC Europe 2,883 4,30045 2.5 30 UOP C Europe 5,321 2,42246 2.2 30 K III Europe 3,796 6,94047 2.5 30 K OF F Europe 2,228 2,81748 2.5 30 UOP SBS Europe 2,301 3,36749 2.5 30 EX FX Europe 6,044 4,93750 1.7 50 UOP ST Europe 3,547 4,747

• Demonstrating excellent performance across a wide r ange of metals levels Low metals VGO to high metals Resid applications

• Rare Earth Reduction 100% to 20%

29

Summary

� Grace has invested in R&D and capital to bring non-RE and low-RE catalysts to the market

� Successful launch of family globally– REACTOR™ - high ZSA, non-RE catalyst – Improve LPG olefinincity– REBEL™ - high MSA, non-RE catalyst– REMEDY™ - low RE catalyst systems for VGO/HT feed applications– REDUCER ™ - low RE catalyst systems for resid feed applications– DeSOX Products with reduced Cerium level to control SOX emission

� Performance is comparable to RE-catalysts� Producing on commercial scale for 50 units� Low to Zero RE product portfolio extended to special functionalities

– Resid Ultra™ designed for resid feed applications special technology with lower RE content metal trap with similar performance to our flagship IMPACT® technology.

– New low/no Super DESOX® formulations, on an equivalent Super DESOX®

performance basis, provide significant cost reductions over Super DESOX®

� Solution for Refiners during economic uncertainty

30

Thank you

GRACE®, GRACE DAVISON®, ENRICHING LIVES, EVERYWHERE .®, IMPACT®, MIDAS® , ResidUltra ™, REACTOR®, REBEL ™, REMEDY™, REDUCER® and REpLaCeR ® are trademarks, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. This trademark list has been compiled using availab le published information as of the publication date of this presentation and may not accurately reflect c urrent trademark ownership or status. © Copyright 2011 W. R. Grace & Co.-Conn. All rights reserved.