advances in fcc catalyst development low/no rare earth fcc

Advances in FCC Catalyst Development

Low/No Rare Earth FCC Catalysts

Joanne Deady

Vice President – Global Marketing, RT

[email protected]

2

Outline

Rare-Earth Market: Supply and Demand

Use of Rare Earth in FCC catalyst

Davison‟s Low/No Rare Earth FCC Portfolio

Case Study

– Catalyst options with lower rare earth

– Impacts on operation

Conclusions

3

1950 1960 1980 1990P

rod

uc

tio

n K

mT

20001970

0

140

20

100

160

120

80

60

40

Credit: ACS, Du and Graedel.

Major Rare Earth Supplier is China

97% of world output

Dominant supplier since the 90‟s

Export quotas restrict supply

– Decreased 50% since 2009

– Quota needed for every pound

of material

Consolidation reduces suppliers

Environmental compliance

investment adds cost

Limited short term options for supply outside of China

Development of new sources will take 5-10 years

oxid

e

ca

rbo

na

te

nitra

te

oxa

late

ch

lori

de

hyd

roxyca

rbo

na

te

TREO

4

“Green” technologies (hybrid cars, wind turbines, energy-efficient lighting)

Military applications (guidance systems)

Lightweight electronic components (cell phones, music devices, flat panels)

Automotive (catalytic convertors, glass, motors)

FCC catalysts (activity and metals trapping), FCC environmental additives

Substitutes do not exist for many applications

Rare Earth Metals are Key Raw Materials in Many Industries

Credit: ACS, Du and Graedel

5

Future Rare Earth Metals Demand

Source: Lanthanide Resources and Alternatives, Oakdene Hollins Research & Consulting – May, 2010

La and Ce are forecasted to be in oversupply

China could become a net importer by 2015?

End users are actively searching for alternatives which may

ease some demand in the near future.

6

Use of Rare Earth in FCC

Rare earth discovered to enhance activity of

zeolites in 1960‟s

– Control the activity, selectivity and hydrogen

transfer of the zeolite

– Protect zeolite from metals deactivation

In the 80‟s and 90‟s, rare earth free catalysts

maximized FCC gasoline octane

Environmental additives rely upon rare earth

for SOx and NOx reduction

In 90‟s, FCC rare earth levels increased

– Improved coke selectivity

– Metals trapping

Rare earth is the primary driver for activity and can provide unique

functionalities to the FCC operation

Grace Davison-A History of FCC Innovation

1942 – 1st FCC catalyst

1948 – Microspheroidal catalyst

1955 – High alumina catalyst

1966 – Awarded patent for USY process

1985 – SOx transfer additives

1987 – Increased use of coke selective REUSY

1990 – RE free zeolites dominate market

1998 – NOx reduction additives

2003 – IMPACT® catalyst platform

2008 – MIDAS ® catalyst for max LCO

2011 – New zero rare earth FCC catalysts &

additives

7

low unit cell size 24.25 Å

Si/Al = 27

7 Al atoms/unit cell

Rare Earth Increases the Zeolite Active Site Density

Moderate unit cell size 24.32 Å

Si/Al = 12

15 Al atoms/unit cell

catalyst

wt% Re2O3

on catalyst

Unit Cell Size

(Å)

Conversion, wt%

at constant C/O

A 1.1 24.24 53

B 1.8 24.27 65

C 2.2 24.31 69

D 3.3 24.34 73

E 3.7 24.36 76

F 5.7 24.41 80

8

Industry Equilibrium Catalyst Trends 2000-2010

201020082006200420022000

2.8

2.6

2.4

2.2

2.0

E-cat RE2O3, wt %

201020082006200420022000

24.32

24.31

24.30

24.29

24.28

E-cat Unit Cell Size, Å

201020082006200420022000

72

71

70

69

68

E-cat Activity (MAT), wt %

24.24 24.30 24.40 24.48

Histogram of E-cat UCS (2010)

9

“Sweet Spot” Exists for Catalytic Performance

47.0

47.5

48.0

48.5

49.0

49.5

3.0

3.4

3.8

4.2

4.6

24.20 24.25 24.30 24.35 24.40 24.45

Gaso

line, w

t%Co

ke, w

t%

Unit Cell Size, Å

10

Olefins and RON Decrease with Increasing UCS

28.0

30.0

32.0

34.0

36.0

38.0

40.0

42.0

44.0

91.0

91.5

92.0

92.5

93.0

93.5

94.0

94.5

24.20 24.25 24.30 24.35 24.40 24.45

Gaso

line O

lefin

s, w

t%G

aso

lin

e R

ON

Unit Cell Size, Å

11

0

1000

2000

3000

4000

5000

6000

1980 1985 1990 1995 2000 2005 2010

FC

C f

ee

d b

arr

els

pro

ce

ss

ed

, k

bp

d

0

20

40

60

80

100

120

140

160

180

#u

nits

in U

SFCC barrels # units

Historical Trends in US FCC Unit Throughput

Capacity grew fastest in the late 80’s, early 90’s, while use of REUSY also increased

12

Davison Low/No Rare Earth FCC Catalyst Solutions

Company Confidential - INTERNAL ONLY

High Zeolite Activity Low Zeolite Activity

MIDAS®

Max Bottoms Reduction

RESID-MX

Max Metals Tolerance

ALCYON M™

High activity high MSA

REBEL®

Z-21 Technology for bottoms reduction

GENESIS®

Ultimate formulationflexibility for resid feeds

GENESIS®-LX

Ultimate formulationflexibility for VGO/HT feeds

REDUCER™

Low RE Technology for resid feeds

GENESIS®-XT

Next generation -flexibility for medium to high metal feeds

REMEDY™

Low RE Technology for VGO/HT feeds

ALCYON™

Ultra High Activity

IMPACT™

Minimum Coke & Gas

ResidUltra™

Next generation metals trap

RESULT™

Next generation low to moderate metals

REACTOR™

Z-22 Technology for higher olefins

13

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

1964

Grace invents USY

1976

Introduction of REUSY

1990

Z-14G RE free zeolite

1991

XP-L RE free

catalyst series

1997

Z-21 RE free

zeolite in Nexus

2008 -2010

Significant R&D effort

begins on RE replacement

2010

Z-22 RE free zeolite

Grace launches REpLaCeR, RE free catalysts

The addition of RE for stabilization of USY was revolutionary in cat cracking, delivering

coke selectivity and activity improvement

Several RE free catalysts were available in the 1990‟s, with a primary focus on increasing

gasoline octane

REACTOR™ is one of the new REpLaCeR™ family of RE free catalysts

It is built upon Grace Davison‟s alumina-sol technology platform and incorporates the

new rare-earth free Z-22 zeolite

Investigations continue, combining past experience and current material science to

discover the next innovation for catalyst activity and stability

Future

Grace Davison - Company Confidential

14

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

Non Rare Earth Zeolite Stabilization

24.20

24.24

24.28

24.32

Fully exchanged

Low RE exchange

No stabilization

Z-21 Z-22

Eq

uilib

rate

d U

CS

Proprietary Grace non-RE Stabilization

Z-21 and Z-22 have higher UCS after

deactivation than zeolite without stabilization

Z-2

2 T

ech

no

log

y

REACTOR™

Z-22 technology – new improvement over the Z-14G zeolites used at over 125 refineries in the 1990‟s.

Matches activity and selectivity of RE containing catalysts formulations without rare earth.

Z-2

1 T

ech

no

log

y

REBEL™

Z-21 technology launched in late‟90‟s as Nexus (10 commercial applications)

Matches activity and selectivity of RE containing high matrix MIDAS® catalyst without rare earth.

REACTOR™ - RE-free Catalyst

Catalysts with rare earth alternatives

March, 2011


16

Catalyst Properties – REACTOR™


REACTOR™ Aurora

Fresh Properties

Al2O3, wt.% 42.2 44.2

RE2O3, wt.% 0 1.5

DI 4 5

SA, m2/g 393 418

ZSA, m2/g 323 352

MSA, m2/g 70 66

CPS-1 / No Metals

SA, m2/g 252 262

ZSA, m2/g 194 203

MSA, m2/g 57 59

UCS 24.22 24.25

SA Retention 64% 63%

ZSA Retention 60% 58%

17

Performance of REACTOR™ vs. Aurora™


Similar activity Improved C4= olefins yield

Slightly lower gasoline yield Similar bottoms conversion

1

3

5

7

50 55 60 65 70 75 80

C/O

Ra

tio

Conversion (wt%)

Aurora™

REACTOR™

4

5

6

7

8

50 55 60 65 70 75 80

To

tal C

4=

s (

wt%

)

Conversion (wt%)

Aurora™

REACTOR™

40

44

48

52

56

60

50 55 60 65 70 75 80

C5

+ G

as

oli

ne

(w

t%)

Conversion (wt%)

Aurora™

REACTOR™

2

6

10

14

18

50 55 60 65 70 75 80

Bo

tto

ms

(w

t%)

Conversion (wt%)

Aurora™

REACTOR™

18

Yields at Constant Conversion of 74% - No metals

REACTOR™, has similar

performance to

RE-catalyst (Aurora™)

• Similar activity

• Higher LPG olefins

• Similar bottoms

conversion

• Similar coke selectivity

• Slightly lower gasoline

Designed for low to

moderate metal feeds


REACTOR™ Aurora™

Catalyst to Oil Ratio 6.0 6.0

Hydrogen, wt.% 0.05 0.04

Tot C1+C2, wt.% 1.4 1.4

Dry Gas, wt.% 1.5 1.4

C3=„s, wt.% 5.0 4.5

Total C3's, wt.% 5.8 5.2

Total C4=„s, wt.% 7.4 6.8

Total C4‟s, wt.% 11.8 10.9

Gasoline, wt.% 52.1 53.7

RON 91.8 90.9

MON 79.9 79.3

LCO, wt.% 19.1 19.4

Bottoms, wt.% 7.4 7.1

Coke, wt.% 2.4 2.3

REBEL™

Catalysts with rare earth alternatives for

maximum bottoms upgrading

May, 2011


20

Catalyst Properties – REBEL™ vs. MIDAS®


REBEL™ MIDAS®

Fresh Properties

RE2O3, wt.% 0.02 1.38

SA, m2/g 240 250

ZSA, m2/g 120 140

MSA, m2/g 120 110

CPS Deactivation w/ 1000ppm Ni / 2000ppm V

SA, m2/g 145 155

ZSA, m2/g 60 75

MSA, m2/g 85 80

Unit Cell 24.29 24.31

SA Retention, % 61% 62%

ZSA Retention, % 50% 54%

21

DCR Testing - REBEL™ vs. MIDAS®

Slightly lower activity Lower Hydrogen yield

Similar bottoms conversion Better coke selectivity


4

5

6

7

8

9

60 65 70 75 80

Cat/

Oil

Ratio

Conversion (wt%)

REBEL™

MIDAS®

0.1

0.15

0.2

0.25

0.3

0.35

60 65 70 75 80

Hyd

rogen

(w

t%)

Conversion (wt %)

REBEL™

MIDAS®

4

6

8

10

12

14

16

60 65 70 75 80

Bott

om

s (

wt%

)

Conversion (wt%)

REBEL™

MIDAS®

2

3

4

5

6

60 65 70 75 80

Coke (

wt%

)

Conversion (wt%)

REBEL™

MIDAS®

22

Constant Conversion Yields

REBEL™ provides

relative to base:

Slightly less

activity

Lower H2 yield

Similar gasoline

selectivity

Similar bottoms

conversion

Similar coke


REBEL™ MIDAS™

Cat-to-Oil 7.2 6.5

Hydrogen, wt% 0.21 0.26

C1 + C2's, wt% 2.0 2.0

Total C3, wt% 4.3 4.2

C3= wt% 3.8 3.7

Total C4, wt% 8.5 8.4

Total C4='s, wt% 6.5 6.4

Gasoline, wt% 51.4 51.6

LCO, wt% 21.1 21.4

Bottoms, wt% 8.9 8.6

Coke, wt% 3.6 3.8

REMEDY™ - Low RE Catalyst System

Catalysts with rare earth alternatives for coke

selective bottoms cracking

March, 2011


24

Case Study – Reduced Rare Earth vs REMEDY Option

Operating Objectives

Minimize catalyst costs due to rare earth hyperinflation

Maintain or improve total profitability

Total liquid yield and LCO are important

UOP Side by Side

Modern RTD and FIT

Full burn

Fired Feed Heater

Operating constraints

Air Blower

Catalyst Circulation

Wet gas at 98% of volume capacity

Feedstock Properties

Vacuum Gas Oil

24.1 API

11.7 UOP K

1.3 wt% Sulfur

0.2 wt% ConCarbon

Equilibrium Catalyst Properties

74 wt% Activity

110 m2/gm ZSA

2.6 wt% Rare Earth

Unit Cell Size 24.32 Å

470 ppm Nickel

1700 ppm Vanadium

Catalyst Additions 5 tpd

25

Fresh Catalyst Properties, Additions and ECAT Activity

Catalyst BASE

Re2O3, Wt.% 2.6

Zeolite SA, m2/gm 220

Total SA, m2/gm 290

Catalyst Additions, tpd 5

ECAT Activity 74

26

Base Yield and Operating Conditions

Feed Temp, F 600

Reactor Temp, F 992

Regenerator Temp, F 1325

Cat/Oil 6.2

Air Blower Base

Wet Gas Compressor Base

Dry Gas, scfb 214

C3=, Vol% 6.3

iC4, Vol% 3.1

C4=, Vol% 7.3

Gasoline, Vol% 54.9

RON/MON 92.5/80.5

LCO, Vol% 28.8

27

Economics

Moderate LCO incentive

C4= attractive due to volume

expansion

Product Value $/B

Dry Gas 55 ($/FOE)

C3= 85

C4= 105

iC4 80

Gasoline 109

Road Octane

Barrel Credit0.5 (Base 88)

LCO 115

Slurry 65

28

Base Fresh Catalyst Properties, Additions and ECAT Activity

Catalyst BASE Low Rare Earth

Re2O3, Wt.% 2.6 0.7

Zeolite SA, m2/gm 220 260

Total SA, m2/gm 290 330

Catalyst Additions, tpd 5 10

ECAT Activity 74 74

ECAT activity must be maintained due to catalyst circulation constraint

29

Low Rare Earth Yields and Operating Conditions

Catalyst BASE Low Rare Earth

Reactor Temp, F 992 983

Feed Temp, F 600 590

Regenerator Temp, F 1325 1317

Cat/Oil 6.2 6.2

Air Blower Base Base

Wet Gas Compressor Base 1.02 Base

Dry Gas, scfb 214 216

C3=, Vol% 6.3 7.0

iC4, Vol% 3.1 2.7

C4=, Vol% 7.3 7.7

Gasoline, Vol% 54.9 53.1

RON/MON 92.5/80.5 93.3/80.8

LCO, Vol% 28.8 29.7

Product value , $/B (1) Base -0.2 $/b

(1) Product Value includes total catalyst cost

30

Lowering Rare Earth Can Result in Higher Daily Costs

Base Lower RE

Daily Cost Cat adds, tpd

Reduce Re2O3

by 75%

Catalyst $/ton

is lower

Catalyst

additions

double

Daily cost

increases by

30%

+30%

31

REMEDY™ FCC Catalyst

Formulated with new RE free zeolites from

Grace Davison

– Proprietary stabilization process

– Unique treatment step to boost activity

– Foundation for new family of catalysts

Delivers similar activity and stability as

traditional RE based catalysts

Performance verified in multiple commercial

applications around the globe

32

Fresh Catalyst Properties, Additions and ECAT Activity

Catalyst BASE Low Rare Earth REMEDY™

catalyst

Re2O3, Wt.% 2.6 0.7 0.2

Zeolite SA, m2/gm 220 260 250

Total SA, m2/gm 290 330 320

Catalyst Additions, tpd 5 10 5

ECAT Activity 74 74 74

New FCC technology delivers required activity without rare earth

33

RE-Free Innovations Save Cost and Maintain Performance

Reduce Re2O3

by 90%

Maintain

activity and

catalyst

additions

Daily cost

decreases by

30%

Base Lower RE REMEDY™

Daily Cost Cat adds, tpd

-30%

34

Optimized Yields and Operating Conditions

Catalyst BASE Low Rare Earth REMEDY™

catalyst

Reactor Temp, F 992 983 988

Feed Temp, F 600 590 595

Regenerator Temp, F 1325 1317 1321

Cat/Oil 6.2 6.2 6.2

Air Blower Base Base Base

Wet Gas Compressor Base 1.02 Base 1.02 Base

Dry Gas, scfb 214 216 207

C3=, Vol% 6.3 7.0 6.9

iC4, Vol% 3.1 2.7 3.0

C4=, Vol% 7.3 7.7 7.8

Gasoline, Vol% 54.9 53.1 53.6

RON/MON 92.5/80.5 93.3/80.8 93.3/80.9

LCO, Vol% 28.8 29.7 29.2

Product value , $/B (1) Base -0.2 $/b +0.4

(1) Product Value includes total catalyst cost

REMEDY™

ECONOMICS

Reduce

daily costs

by 30%

Increased

profitability

by $7 mm/yr

for a 50,000

bpd FCCU–Lower dry

gas

–Higher C4=

& gasoline

35

Conclusions

Rare earth market prices are likely to remain elevated

– Restricted supply

– High demand

– Few viable alternatives exist for most applications

Activity and stability are critical for economic FCC operations

Consider all shifts when reformulating to lower Re2O3 on

catalyst

– Total daily cost, not just $/ton

– Operational impacts

Technology innovations alleviate the pressure and offer

alternatives for rare-earth based FCC catalyst

36

Thank you

GRACE®, GRACE DAVISON®, ENRICHING LIVES, EVERYWHERE.®, IMPACT® and MIDAS® are trademarks,

registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. ResidUltra™, REACTOR™,

REBEL™, REMEDY™ and REplaceR™ are trademarks of W. R. Grace & Co.-Conn. This trademark list has been

compiled using available published information as of the publication date of this presentation and may not accurately

reflect current trademark ownership or status. © Copyright 2011 W. R. Grace & Co.-Conn. All rights reserved.

advances in fcc catalyst development low/no rare earth fcc

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