Resid Cracking

Technology Review

Integral Catalyst Metals Traps

Grace Davison
Refining Technologies

July
July 2006
2006
Overview

Integral Catalyst Metals Trapping Technology

ƒIntroduction
ƒNickel Tolerance
ƒVanadium Tolerance
ƒBottoms Cracking & the Effect of Pore Structure
ƒPutting it all together
 Comparison of Two Typical Gas Oils
to Average FCC Resid Feedstock Properties
Industry Resid Cracking Survey
Gas Oil A Gas Oil B Resid Total FCC Feed
API Gravity 22.7 22.5 19 25

K Factor 12.01 11.57 12 11.9

Sulfur, wt% 0.62 2.59 0.8 0.6

Ni, ppm 0.2 0.8 7.5 1.5

V, ppm 0.3 0.6 4 1.3

CCR, wt% 0.89 0.25 5.7 1.1

Catalyst Deactivation by Metals

ƒNi and V deposited on FCC catalyst from high

boiling metal organics in feed
ƒOrganics burned off, metals oxidized in
regenerator
ƒOxidized V is mobile within and between
particles
ƒFCC Unit conditions affect activity of metals
deposited on catalyst
 Nickel Tolerance

ƒNi is a strong dehydrogenation catalyst and Ni

contamination increases H2 and Coke

ƒNi is relatively immobile and does not transfer

from particle to particle

ƒNi can be passivated by reaction with certain

forms of alumina, to form low surface area bulk
nickel aluminate
 Oxygen Chemisorption
Principle For Ni Reactivity
Ni Al2O4
Surface
Spinel Ni
NiO Ni Hydroxy Sulfate Ni Ni Ni NiO NiO
Silicate Ni NiO NiO

Ni SiO3 Ni SiO3
Ni SiO3 Ni Al2O4 Ni Al2O4
Ni Al2O4

Encapsulated Ni
Reduction O2 @
(collapsed pores in H2 500 deg C
and zeolites)

Oxygen uptake is related to amount of reducible nickel.

 LCM Matrix Passivates Nickel

O2 Chemisorption Isotherms @ 3000 ppm Ni

0.20
Standard Catalyst
O2 Uptake (cc/g)

25% Active Nickel

0.15

0.10

0.05 LCM Technology

0% Active Nickel
0.00

-0.05
0 100 200 300 400 500
Pressure (torr)
Uptake is Difference between 3000 ppm Ni and 0 ppm Ni
 LCM Matrix Reduces H2 Yield at Higher Ecat Ni

120
100
H2 Yield, SCFB

Base
80
60
40
LCM Matrix
20
0
200 400 600 800 1000
Ecat Ni, ppm
 LCM Technology Reduces
Ecat Hydrogen and Coke Factors
Refiner Nickel Ecat H2 Ecat Coke
Equivalents % Reduction Factor
ppm % Reduction

A 2500 38 38

B 1650 50 27

C 950 33 21

D 1100 27 26
Vanadium Deactivation

ƒ V has larger effect than Ni

ƒ V migrates to and attacks zeolite
ƒ affects both yields and activity
ƒ more mobile under FCC conditions
ƒ FCC conditions strongly affect V
ƒ oxidized V more mobile
ƒ oxidized V more destructive
ƒ oxidized V has higher dehydrogenation activity
Vanadium is a Significant Contributor to
Catalyst Deactivation
75
Regen Bed Temps: 1330 - 1345 °F (721 - 729 °C)
Microactivity (vol.%)

Catalyst: Same Family

70
Re203: 1.6 - 1.8%

65

60

55
1000 1500 2000 2500 3000 3500 4000 4500 5000
Vanadium (ppm)
 Vanadium is More Destructive in Oxidized State

70
68
MAT Activity

66
64 full burn
62 partial burn
60
58
56
0 1000 2000 3000 4000 5000
Vanadium, ppm
Vanadium Produces more Coke and Hydrogen in its Oxidized State

5
Yield, Wt. %

4
Coke
3
Hydrogen
2

0
Oxidized Reduced
 RV Trap Technology
z Lanthanum-based vanadium
passivation technology.
z Not affected by sulfur competition.
z Can be incorporated as a separate
particle or as an integral catalyst
component (preferred).
z Commercially proven.
Electron Microprobe Image
of Commercial ECAT

Silicon La-Based V Trap Vanadium

La-based material preferentially traps vanadium

 V Traps Show Excellent Activity Retention

75
With V Trap
70

With Out V Trap

MAT Activity

65
(Curve fit from multiple samples)

60

55

50
0 2000 4000 6000 8000 10000 12000
Metals Level (Ni + V ppm)
V Trap shows Better Coke Selectivity with Higher Metals

5.5

No V Trap and 3000 ppm V

5

4.5
Coke wt%

4 w/ V Trap and 4500 ppm V

3.5

3
60 61 62 63 64 65 66 67 68 69

Conversion wt%
V Trap Technology Improves Activity Retention
Commercial FCC Unit

72
70
68
Ecat MA

66
64
62 V Trap Technology
Base Case
60
58
1,000 2,000 3,000 4,000
Ecat V (ppm)
V trap Improves Zeolite Surface Area Retention
Commercial FCC Unit

70
% ZSA Retention

65 V Trap Technology

Base Case
60

55

50
1,000 2,000 3,000 4,000
Vanadium (ppm)
Selective Bottoms Cracking - the Effect of Pore Structure

ƒMatrix sites must pre-crack large molecules

ƒActive sites must be accessible
ƒSufficient pore volume to adsorb the
unvaporized portion of the feed
Hg PSD of Commercial FCC Catalysts

0.6

0.5

0.4
dV/d(logPD)

0.3

0.2

0.1

0
4
10 100 1000 10
Pore Diameter, Angstroms
Mesopore Volume Improves Bottoms Cracking

700 °F+ (371° C+) Kinetic Conversion 7

6.5
6
5.5
5
4.5
Constant 67% conversion to
4
430 °F (221 °C) and lighter
3.5
3
0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2
100 to 1000 Angstrom Mesopore Volume (cc/g)
Properties of Catalysts with Varying PSD

Cat A Cat B Cat C Cat D Cat E Cat F

Catalyst Analyses
NA2O 0.28 0.22 0.21 0.17 0.23 0.23
AL2O3 55.3 57.8 56.3 57.2 55.9 56.6
RE2O3 2.0 1.7 1.8 1.9 2.0 1.8
ZSA 131 105 99 113 120 93
MSA 89 93 97 81 92 108
5000 ppm Metals CPS
Hg PSD
<100A 0.043 0.049 0.055 0.055 0.06 0.073
100-1000A 0.271 0.247 0.228 0.255 0.243 0.225
>1000A 0.011 0.019 0.028 0.017 0.044 0.028

ZSA 83 58 43 47 54 50
MSA 62 61 67 65 68 71
Ni 2037 2024 2012 1965 2023 2028
V 2830 2700 2700 2740 2790 2750
Coke Yield Increases with Hg PV < 100 Å

DCR testing, resid feed, 5000 ppm metals/CPS

10.0

9.5
Coke, wt%

9.0

8.5

8.0
0.04 0.05 0.06 0.07 0.08
PV < 100 Å
Hydrogen Yield Increases with Hg PV < 100 Å

DCR testing, resid feed, 5000 ppm metals/CPS

0.300

0.250
H2, wt%

0.200

0.150

0.100
0.04 0.05 0.06 0.07 0.08
PV < 100 Å
Putting it Together

ƒGrace FCC Catalysts can be designed

specifically for use with Resid feedstocks
ƒ optimized pore structure to crack large molecules
to useful products
ƒ Ni-tolerant matrix component
ƒ La-based V passivator - integral or separate
particle
Hg PSD of a Commercial Grace Resid FCC
(RFCC) Catalyst
0.60

0.48
Steam Deactivated for
4 hrs at 1500 °F (816 °C)
dV/d(logPD)
DV/DLOGD

0.36

0.24

0.12

0.00
10000 1000 100 10
PorePORE
Diameter,
SIZE ( ) Å

Grace Resid FCC catalyst has high pore volume

in the desired 100-1000 Å range.
Bottoms Cracking Advantage of Grace RFCC Versus Feed Heaviness

Grace RFCC - Base Catalyst 5

Ramcat vs Low
Grace RFCC Matrix
vs Low Catalyst
Matrix FCC
Grace RFCC
Ramcat vs High
vs High Matrix
Matrix FCC
Catalyst
4

0
0 5 10 15 20 25 30 35
Feedstock 1070
Feed°F+ (577 °C+)
1070F+ wt%Content, wt%
Commercial Grace RFCC Ecat Shows Improved Yields with Resid Feed

Ecat Ecat/w 50% Grace RFCC

Conversion : wt% 75 75
C/O 8.0 7.6

H2 : wt% 0.08 0.06

Total C1 + C2 : wt% 3.2 3.1
C3= : wt% 5.7 5.6
Total C3 : wt% 6.9 6.6
Total C4= : wt% 7.0 7.4
Total C4 : wt% 11.2 11.0

C5 + Gasoline : wt% 48.5 49.1

LCO : wt% 18.3 18.9
Bottoms : wt% 6.7 6.1
Coke : wt% 5. 3 4.7

Ecat contains 1300 ppm Ni, 3000 ppm V, Feed - 2 % CCR