successful commercialisation of zero/low rare-earth...

Successful Commercialisationof Zero/Low Rare-Earth FCC Catalysts

Colin BaillieE il C li B illi @GEmail: [email protected]

CatCracking.com Seminar, 17-21 October, Düsseldorf

Overview

Development of RE-Free and Low RE Catalysts

for HT/Low-Metal Feed Applications

for Resid Feed Applications

2

Overview




3

Grace Davison has developed the REplaceR family of RE-free FCC catalysts

Grace Davison RE-free technologies include:

Z-21 a RE-free zeolite developed in 1997Z 21, a RE free zeolite developed in 1997

Z-22, a state-of-the-art RE-free zeolitedeveloped in 2010

These RE-free zeolites can be used with the following EnhanceR technologies

EAM, Acidity Modification

EMR, Metals Resistance

EPR, Pore Restructuring

ESS, Structure Stabilisation

4

Overview




5

NEXUS was the first RE-free catalyst family

NEXUS:

incorporates Z-21 zeolite

RE-free catalyst for low-metal feed applications

commercialised in 1997

successfully used in 10 applications

For example the following table showsthe use of NEXUS at a refinery wheremaximum gasoline yieldg ywas the key objective

6

NEXUS improved FCC product yields

NEXUS-346 Competitor Delta

Product Yields

H2 0.03 0.07 -0.04

Dry Gas 3.60 4.12 -0.52

LPG 16.25 18.19 -1.94

Gasoline 50 16 45 20 4 96Gasoline 50.16 45.20 4.96

LCO 15.62 18.72 -3.10

MCB 7.98 7.68 0.30

Coke 4 72 4 56 0 16

• Higher conversion

Coke 4.72 4.56 0.16

Conversion 76.39 73.60 2.79

• Lower hydrogen yield

• Lower dry gas yield

Economic analysis showed a benefit toRefinery A of ca.1 million €/year

• Higher gasoline yield7

Refinery A continued to use NEXUS

REsolution is the successor to NEXUS

REsolution:

combines Z-21 zeolite with new matrix

provides higher activity and bottoms upgradingcompared to NEXUS

RE-free catalyst for low-metal feed applications


successfully being used in 7 applications

for example…

8

REsolution provides similar activity

ACE E-Cat Pilot Plant Testing, Ni+V ca. 1000 ppm

77Standard Conversion (ASTM)

1 4

1.5

1.6Dry Gas

62

67

72

0 9

1.0

1.1

1.2

1.3

1.4

52

57

3.0 4.0 5.0 6.0 7.0 8.0Cat to Oil [-]NEKTOR REsolution

0.7

0.8

0.9

52 57 62 67 72 77Conversion

NEKTOR REsolution

6.57.07.58.0

Propylene

505254

Gasoline

4.04.55.05.56.06.5

4042444648

9

3.03.5

52 57 62 67 72 77Conversion

NEKTOR REsolution

3638

52 57 62 67 72 77Conversion

NEKTOR REsolution

REsolution provides similar dry gas

ACE E-Cat Pilot Plant Testing, Ni+V ca. 1000 ppm

16

16LCO

29

HCO

14

15

15

19

24

13

14

52 57 62 67 72 77Conversion

NEKTOR REsolution

9

14

52 57 62 67 72 77Conversion

NEKTOR REsolution

2.4

2.9

Coke

1.4

1.9

10

0.952 57 62 67 72 77

ConversionNEKTOR REsolution

To summarise the commercial trial of REsolution

REsolution:

The trial is taking place at a refinery inThe trial is taking place at a refinery incentral Europe

Rare earth was reduced from Rare earth was reduced from3.1 to 2.1 wt.% (30% change out)without affecting performance

Catalyst change out has since reached 70%(3.1 to 0.9 wt.% rare earth) with evenli htl i d f b dslightly improved performance observed

• Higher iC4 selectivity• Similar bottoms upgrading• Similar dry gas

11

• Similar dry gas• Lower delta coke

Overview




12

REduceR is a RE-free catalyst for resid feed applications

REduceR:

combines new RE-free Z-21 and Z-22 zeoliteswith EnhanceR Metals Resistance Technology

can be blended with RE-based resid catalystswithout performance deterioration


currently being used in over 10 applications

13

REduceR – Application in Blends

CPS-3 Deactivation Protocol, 2000 mg/kg Ni, 3000 mg/kg V

79

80

t. C

/O CPS-3

2000 mg/kg Ni3000 mg/kg V

76

77

78on

vers

ion

@ c

onst

FF]

g/ g

72

73

74

75

ated

Sta

ndar

d Co

[wt.

%

70

71

72

0 20 40 60 80 100

inte

rpol

a

REduceR content in blends with NEKTOR-ULCC [%]

REduceR blends show very good activity retention (even up to blends of 60%)(even up to blends of 60%)

REduceR – Metals Tolerance

CPS-3 Deactivation Protocol, 4000 mg/kg Ni, 6000 mg/kg V

300

150

200

250m

2 /g)

50

100

150

ZSA

(m

0

0 500 1000 1500 2000 2500 3000

CPS-3 deactivation duration

NEKTOR-ULCC NEKTOR-ULCC/REduceR 70/30

The REduceR blend shows very good ZSA retention even with a very severe extended metals deactivation protocolvery severe, extended metals deactivation protocol

REduceR Commercial Trial

In April 2011 Refinery B began to blend in 30%of the rare-earth free REduceR catalystywith the current NEKTOR catalyst

The objective of the trial was to maintainthe high performance whilst reducingcatalyst rare-earth requirementcatalyst rare-earth requirement(from 3.1 to 2.2 wt.%)

Upon a successul performance at a 30% level Upon a successul performance at a 30% levelthe REduceR catalyst would then be testedat 50%

16

Refinery B – E-Cat MAT Study (60% Change Out)

70% NEKTORNEKTOR 30% REduceR

ca. 60% change out

MAT, wt.% 67 70Gas Factor 5.1 3.2H2 Yield, wt.% 0.35 0.25Coke Factor 1.4 1.2

Ni, ppm 3532 3500V, ppm 4157 4034Na, wt.% 0.48 0.48Fe, wt.% 0.43 0.58Sb, ppm 138 469Cu, ppm 41 33

The REduceR blend provides high MAT, low GF, CF and H2 yields

, ppRE2O3, wt.% 3.1 2.6

Refinery B – E-Cat MAT Study (60% Change Out)

70% NEKTORNEKTOR 30% REduceR

ca. 60% change outCat-to Oil 2.2 2.3

Conversion, wt.% 64 69

Hydrogen, wt.% 0.31 0.28

Propylene, wt.% 4.1 4.5C4 olefins, wt.% 6.2 6.8LPG, wt.% 14.3 16.8

Gasoline, wt.% 42.6 44.5LCO, wt.% 17.2 15.6HCO, wt.% 18.3 15.4

Coke, wt.% 4.7 4.7Coke on catalyst, wt.% 2.13 2.04

RON 93 7 93 8

The REduceR blend provides improved product yields

RON 93.7 93.8MON 80.9 81.5

Refinery B – E-Cat Data (100% Change Out)

REduceR shows good activity retention at similar to lower CAR

19 19

REduceR shows good activity retention at similar to lower CAR

Refinery B – E-Cat Data (100% Change Out)CAR

1 5

2.0

2.5

3.0

R [k

g/t F

F]

spec. CAR

0.0

0.5

1.0

1.5

,000

,500

,000

,500

,000

,500

,000

,500

,000

,500

spez

. CAR

c

72.0

74.0

76.0

78.0

NEKTOR REduceR blend

2, 2, 3, 3, 4, 4, 5, 5, 6, 6,

V (mg/kg)

ResidMax-312E REduceR blend

62.0

64.0

66.0

68.0

70.0

72.0

0.0

0.0

0.0

0.0

0.0

0.0

0.0

0.0

0.0

0.0

MAT

wt.%

FF

ccc

2,00

0

2,50

0

3,00

0

3,50

0

4,00

0

4,50

0

5,00

0

5,50

0

6,00

0

6,50

0

V (mg/kg)

ResidMax-312E REduceR blendNEKTOR REduceR blend

SCAR and MAT remained similar after addition of REduceR

20 20

SCAR and MAT remained similar after addition of REduceRconfirming good vanadium tolerance of REduceR

Refinery B – E-Cat Data (100% Change Out)deact coefficient vs Reg temp

-0.006

-0.004

-0.002

0.000

ct. c

oeff

icie

nt

deact. coefficient vs Reg. temp

-0.012

-0.010

-0.008

680

690

700

710

720

730

740

deac

Regenerator dense temperature °C

c

Regenerator dense temperature C

NEKTOR REduceR blend

-0.0020000

0.0000000

deact. coefficient vs V

-0.0080000

-0.0060000

-0.0040000

deac

t. co

effic

ient

c

-0.0120000

-0.0100000

2,00

0

2,50

0

3,00

0

3,50

0

4,00

0

4,50

0

5,00

0

5,50

0

6,00

0

6,50

0

V (mg/kg)

ResidMax-312E REduceR blend NEKTOR REduceR blend

21 21

Intrinsic catalyst stability improved after addition of REduceR

Refinery B – E-Cat Data (100% Change Out)

Commercial equilibrium catalyst (e-cat), Coke/Gas Factor vs. Ni equivalents

Gas Factor vs. Ni Equiv. Coke Factor vs. Ni Equiv.

5 0

6.0

7.0

r

1.9

2.3

ctor

3.0

4.0

5.0

Gas

Fac

tor

1 1

1.5Cok

e Fa

2.03000 4000 5000 6000 7000

Ni Equivalents [mg/kg]

NEKTOR REduceR

1.1

3000 4000 5000 6000 7000Ni Equivalents [mg/kg]

NEKTOR REduceR

The good nickel tolerance of REduceR blends

NEKTOR REduceR NEKTOR REduceR

is confirmed at Refinery B

Refinery B – FCC Unit Data (100% Change Out)

40.0

Auswertung

25.0

30.0

35.0

.% F

F]

10.0

15.0

20.0

HC

O+S

lurry

[wt

0.0

5.0

60 62 64 66 68 70 72 74 76 78

Conversion [wt.%FF]

The REduceR blend showed similar bottoms cracking

ResidMax-312E ResidMax-312E+30%REduceRNEKTOR REduceR

Latest Developments in RE-free FCC Catalyst Technologies - June 2011 Confidential

The REduceR blend showed similar bottoms cracking

23


0 89

0.91

0.93

ced)

[wt.%

]

0 83

0.85

0.87

0.89

mas

s ba

lanc

0.77

0.79

0.81

0.83

lta C

oke

(non

0.75

0.77

60 62 64 66 68 70 72

Del

Apparent Conversion (non mass balanced) [wt.%FF]

The REduceR blend showed a significant

[ ]NEKTOR REduceR

improvement in delta coke


720

725Regenerator Bed Temperature

705

710

715

°C

695

700

705

690505 510 515 520 525

ROT (°C)

The REduceR blend reduced Regen Bed Temp

NEKTOR REduceR


69

71

63

65

67

69

n[w

t.% F

F]

57

59

61

63

Con

vers

ion

55

57

50 55 60 65 70 75 80 85 90AtRes in Feed [wt.%]

The REduceR blend showed higher conversion

NEKTOR REduceR

at const AtRes content

FCC Unit Data with 50% REduceRTo evaluate the catalyst performance the yields are calculated on the basis of constant

NEKTOR 50% NEKTOR50% REduceR

To evaluate the catalyst performance the yields are calculated on the basis of constant feed properties and independent operating conditions

Cat-to-Oil g/g 6.1 base + 0.4Conversion wt.% 74.5 base + 0.5Hydrogen wt.% 0.11 base + 0.02C1+C2's wt.% 2.2 base + 0.2Propylene wt.% 4.6 base + 0.4pyC4 Olefins wt.% 5.3 base + 0.6LPG wt.% 15.5 base + 2.0Gasoline wt.% 50 base - 1.6LCO wt.% 15.2 base - 0.2Slurry wt.% 10.3 base - 0.2Coke wt.% 6.4 base - 0.1Delta coke wt.% 1.05 base - 0.09

CAR MT/D base basee-cat Ni ppm base basee-cat V ppm base base

Regen Bed Temp °C base base - 15 °C

The key objectives of maintaining conversion and bottoms

27

y j gupgrading were clearly met, and were even increased

To summarise the commercial trial of REduceR at Refinery B

A 30% blend of REduceR was added to a NEKTOR catalyst with theobjective of maintaining performance whilst reducing catalyst rare-earth requirementj g p g y q

Rare earth was reduced from 3.1 to 2.2 wt.%, and despite the high Ni+V, theexcellent performance of NEKTOR was maintained and even improvedexcellent performance of NEKTOR was maintained and even improved

Refinery B subsequently moved to 50% REduceR, and reduced the overall catalystrare-earth content to 1 5 wt %rare-earth content to 1.5 wt.%

The key requirement of maintaining conversion and bottoms upgradingwas not only achieved they were even improvedwas not only achieved, they were even improved

28

Low/Zero Rare-Earth FCC Catalyst Reference List for EMEATypical E Cat Properties (June to August 2011)

Target RE Level Ni V CaO Fe Na MA CRCCatalyst (wt.%) (ppm) (ppm) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)

1 REsolution 0 237 403 0.03 0.30 0.30 66 0.022 REsolution 0 444 1171 0.03 0.37 0.27 72 0.073 REsolution 0 777 931 0.06 0.58 0.24 62 0.02

Typical E-Cat Properties (June to August 2011)

4 REsolution 0 409 836 0.10 0.67 0.10 61 0.145 REsolution 0 108 247 0.03 0.45 0.29 74 0.066 REsolution 0 na na na na na na na7 REsolution 0 na na na na na na na8 NADIUS + 50% REactoR 0.9 62 120 0.03 0.43 0.22 71 0.179 NADIUS + 80% NEXUS 0.5 356 1282 0.03 0.81 0.25 68 0.2110 NADIUS + 45% REsolution 1.7 na na na na na na na11 DieseliseR + 30% REduceR 2.4 2461 3273 0.06 0.55 0.32 71 0.1912 NEKTOR + 30% REduceR 2.5 na na na na na na na13 NEKTOR + 30% REduceR 2.5 2060 3632 0.07 0.37 0.34 71 0.2014 NEKTOR + 30% REduceR 2.2 1545 2476 0.20 0.48 0.38 71 0.0614 NEKTOR + 30% REduceR 2.2 1545 2476 0.20 0.48 0.38 71 0.0615 NEKTOR + 30% REduceR 2.2 2172 5003 0.07 0.40 0.49 70 0.1216 NEKTOR + 50% REduceR 1.5 3736 4528 0.16 0.58 0.50 71 0.1417 NEKTOR-ULCC + 30% REduceR 2.5 1813 2589 0.06 0.37 0.62 71 0.0718 NEKTOR-ULCC + 30% REduceR 2.5 2420 3637 0.04 0.38 0.32 73 0.3519 NEKTOR-ULCC + 50% REduceR 1.6 2550 1910 0.05 0.36 0.29 68 0.05

Rare earth free catalyst technologies have received excellent

20 NEKTOR-ULCC + 30% REduceR 2.5 2883 4300 0.09 0.39 0.48 69 0.0421 NEKTOR-ULCC + 50% REduceR 1.8 5321 2422 0.06 0.43 0.31 69 0.3822 ResidCrackeR + 30% REduceR 2.5 6044 4937 0.08 0.49 0.38 64 0.1123 ResidCrackeR + 50% REduceR 1.7 3547 4747 0.14 0.60 0.43 70 0.14

Rare-earth free catalyst technologies have received excellent market acceptance, and are performing well

successful commercialisation of zero/low rare-earth...

Documents