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
Development of RE-Free and Low RE Catalysts
for HT/Low-Metal Feed Applications
for Resid Feed Applications
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
Development of RE-Free and Low RE Catalysts
for HT/Low-Metal Feed Applications
for Resid Feed Applications
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
commercialised in 2010
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
Development of RE-Free and Low RE Catalysts
for HT/Low-Metal Feed Applications
for Resid Feed Applications
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
commercialised in 2011
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
Refinery B – FCC Unit Data (100% Change Out)
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
Refinery B – FCC Unit Data (100% Change Out)
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
Refinery B – FCC Unit Data (100% Change Out)
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