Strategies for Managing Contaminant

Metals in the FCC Unit

RefComm Galveston – May 2017
Rebecca Kuo, Technical Service Engineer

1
Agenda

Feedstock variations

Contaminant metals and their effects

Case studies

Mitigation strategies

Advanced passivation technologies

2
Diverse FCC Feeds

Residue-containing and
tight oil feeds have Feed Global Global Global
become much more Property Average Minimum Maximum
prevalent in FCC API 24.0 10.4 31.7

Resids typically contain CCR, wt% 1.5 0.02 8.87
high Ni, V, CCR, N
Ni, ppm 2.3 0 13

Tight oils typically V, ppm 2.7 0 15
contain high Fe, Ca, Na
Fe, ppm 4.8 0 35
Na, ppm 1.3 0 6
Basic N, ppm 377 5 1058
Oil Quality Variability
from One Field
3
Gasoil-Resid Unit Split
100
% OF TOTAL

80 41 38 40 38 38 37 39 38 43 48 45 51 52 50 49
Chart Legend
60 Resid
40 Gasoil
59 62 60 62 62 63 61 62 57 52 55 49 48 50 51
20
0

Resid >3000 ppm ecat Ni + V; Gasoil <3000 ppm ecat Ni + V

Globally, more units are processing resid with the average moving from ~40%
resid in the early 2000s, to today ~50% 4
Feedstock Contaminant Effects

Why do we care about metal contaminants?

Metal contaminants are harmful to the catalyst and can cause unwanted reactions
in the FCCU

The metals deposit on the circulating catalyst and cause competing chemistries to
the desired reactions

Salts (Na, Ca, Mg) act as a base and attack the acid sites on the catalyst, lowering
activity and conversion

5
Elements of Concern
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

6
Elements of Concern: Nickel
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

7
Nickel Sources & Effects

Ni comes in with the feed and deposits
Catalyst activity is not significantly
on catalyst particles affected

Undergoes redox cycles
Ni acts as a dehydrogenation catalyst

Nickel oxides do not migrate
Feed Ni Histogram
60 100%
Frequency, %

40
50%
20
0 0%
0-1 1-2 2-3 3-4 4-5 5-6 >6
Ni, ppm
8
Nickel Effects
Case Study
Ecat Ni
11000
10000
Ni, ppm
9000
8000
7000
6000

Fluidized Dry Gas Factor Fluidized Coke Factor

1.70
1.80
FDGF, v/v

1.50 1.60

FCF, wt/wt 1.40

1.30
1.20
1.10 1.00
9
Nickel Mitigation Strategies

Typically, Ni becomes a concern >800
ppm on the ecat
7000 0.3

Some refiners use antimony (Sb)

Ecat Ni and Sb(x10), ppm

6000 0.25
injection to passivate Ni
5000

ACE H2, wt%

Can increase NOx emissions 0.2
4000

Can increase bottoms fouling 0.15
3000

A more permanent solution is to use 0.1
catalyst with specialty alumina (such as 2000 Ni
Flex-Tec) 1000 Sb 0.05

Ni deposits on alumina and becomes H2

0 0
passivated Time

10
Elements of Concern
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

11
Elements of Concern: Vanadium
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

12
Vanadium Sources & Effects

Vanadium comes in with the feed and
deposits on the catalyst particle
Feed V Histogram

V is converted into an oxide
30 100%

Frequency, %

V is very mobile – can migrate from 25 80%
20 60%
particle to particle & within the 15
10 40%
particle 20%
5
0 0%

Destroys zeolite, especially in the
presence of high Na
V, ppm

V causes significant reduction in activity
and has some dehydrogenation activity
13
Vanadium Effects
Case Study
Ecat Vanadium Content Ecat FACT
9,000 81
8,000 79

FACT, wt%
77
7,000 75
V, ppm

73
6,000 71
5,000 69
67
4,000 65

Ecat FACT vs V + Na
90
FACT, wt%

80
70
60
0 2000 4000 6000 8000 10000 12000

V+Na, ppm 14
Vanadium Mitigation Strategies

Typically, V becomes a concern >1500 ppm on ecat

Refiners can use a V-trap additive to passivate

Can be REO, Ca, or Ca/Mg based

Can be added separately or blended into the catalyst
formulation

Because the effect of V is exaggerated with high Na, use a low-Na fresh catalyst

Increase catalyst additions or use purchased catalyst to flush out the V in the
circulating inventory

15
Elements of Concern
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

16
Elements of Concern: Sodium
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

17
Sodium Sources

Sodium comes from various sources: Feed Na Histogram

Fresh catalyst – typically between 50 100%

Frequency, %
40 80%
0.15-0.3 wt%
30 60%

Feed – deposits on the surface of 20 40%
catalyst particle 10 20%

– Does not migrate within the 0 0%

particle or to other particles

Na, ppm

18
Sodium Effects

Na acts as a permanent catalyst
poison

Neutralizes acid sites

Also forms a low melting point
eutectic with vanadium to lower
ecat activity and conversion

Activity loss exaggerated when
ecat V and regen temps are also
high

Ca and K have similar effects
19
Sodium Mitigation Strategies
Feed Na Catalyst Additions
12 18
16

Employ low-Na fresh catalyst 10

Feed Na, ppm

Cat Adds, tpd
14
8
12

Improve and optimize desalter operation – 6 10
8
remove Na from the feed 4
6
2
4

Increase catalyst additions or use purchased 0
Time
2

catalyst to flush Na out of circulating 0.45 76

inventory 0.4
75

FACT, wt%
74

Ecat Na, wt%

0.35 73

Increase fresh catalyst activity to combat 72
0.3
activity loss from Na 0.25
71
70
0.2 69
Time
Ecat Na FACT
20
Elements of Concern
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

21
Elements of Concern: Iron
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

22
Iron Sources

Fe comes from various sources:

Fresh catalyst – typically between 0.25-0.75 wt% Fe(Added)

– Incorporated within the silica/alumina Fe(Fresh)

framework  does NOT impact surface

accessibility or side chemical reactions Equilibrium Catalyst

Organic Fe from the feed Feed Fe Histogram

40 100%

Inorganic Fe from equipment corrosion

Frequency, %
20 50%

Refiners should focus on “Added Fe” which
0 0%
deposits on the catalyst surface 0-1 1-2 2-3 3-4 4-5 5-6 >6

Fe(Added) = Fe(Ecat) –Fe(Fresh) Fe, ppm
23
Iron Effects

Physical Effects

Surface nodule formation, which has been reported to

cause catalyst circulation issues

Vitrification on catalyst surface, loss in surface area

Severe poisoning leads to surface blockage and reduced conversion and

high slurry yield with non-BASF catalyst

Slurry density becomes unusually light due to uncracked feed

24
Iron Effects

Chemical Effects

Dehydrogenation: some refiners have reported increased H2 make

Transfers S from reactor to regenerator for increased SOx

Acts as a CO promoter: can be an issue in partial-burn units

25
Iron Imaging: Iron deposits on the surface of the catalyst
Added Fe: 0.93 wt%

Al Fe

old new

Fe deposits on the catalyst surface, with formation of very
old
clear surface nodules.

Old and new catalyst particles can be easily distinguished

Dissimilar iron coating on each catalyst  indicative of limited
mobility from one catalyst particle to another.
26
Fe Effects
Case Study #1

Resid unit in Middle East
Added Fe increased from 0.23 to
0.43 wt%

Using non-BASF catalyst

Feed API: 16 – 19
Resulted in a conversion loss of 4
vol%

Ecat Ni: 6200 ppm; Ecat V: 5100 ppm

Unit Conversion and Added Fe versus Time 0.90

Unit Conversion,

Conversion

Ecat Added Fe,

75 0.70
vol%

wt%
0.50
65
Added Fe 0.30

55 0.10
Time (7 months) 27
Fe Effects
Case Study #2

R2R unit in Asia Pacific
Refiner started processing high-Fe

Feed API: 21 – 26 feed

Ecat Ni: 2200 ppm
Ecat Fe increased up to 1.3 wt%

(or Added Fe of 0.7 wt%)

Ecat V: 2000 ppm

Noticed change in color of the ecat

Long history of using BASF catalyst since around ~0.2 wt% added Fe
2002

28
Fe Effects
Case Study #2

Added iron increase from 0.15 to 0.70 wt% with no loss in unit conversion

During the same period, other contaminants (Ni, V) decreased / stayed same

85
Unit Conversion and Added Fe versus Time 0.8

Added Fe (wt%)
0.7
Unit Conversion

80 Added Fe
0.6
75 0.5
(wt%)

70 0.4
65 0.3
Conversion 0.2
60 0.1
55 0
Time (7 months)

Result: No detrimental impact on unit conversion and yields at significantly high

Added Fe 29
Iron Mitigation Strategies

Employ fresh catalyst with optimized surface porosity

Increase catalyst additions or use purchased catalyst to flush Na out of circulating
inventory

Added Fe

Surface Pores Minimal Optimized

Diffusion of feed poor excellent
Threshold to added Fe Low (e.g. 0.3 wt%) High (e.g. >1.5 wt%)
Resulting liquid yield low high
30
Mitigation strategies should make sense!

Design of the catalyst passivation technology: passivator mobility should complement metal’s
mobility
Metal Passivator Passivator
Metal
mobility mobility technology
REO or
separate
Mobile Immobile particle
V

Specialty
Immobile Alumina
Immobile
Mobile Boron Based
Ni Technology

31
Mitigation Strategies – Boron-Based Technology (BBT)

New BASF catalyst technology designed to passivate Ni

Boron is mobile under FCC conditions and migrates to Ni on the catalyst

B deters Ni from being

reduced to a more
detrimental state in the riser

Ni B

32
BOROCAT™ Reduces Hydrogen and Coke in the FCCU
Ecat H2/C1 vs. Eq. Ni Ecat Coke Factor vs. Eq. Ni

BoroCat™: lower hydrogen, lower coke, higher liquid products

Catalyst architecture modifications allow for dramatic alleviation of constraints
33
Mitigation Strategies Summary
Nickel

Iron
Vanadium

Sodium
• Employ • Employ • Employ low- • Employ
catalyst catalyst Na fresh catalyst with
incorporated designed for catalyst optimized
with high V – • Efficient and surface
specialty high REO, optimized porosity
alumina stable desalter • Use of
• Boron- zeolite operation purchased
based • Employ low- catalyst to
technology Na fresh lower ecat
• Antimony catalyst Fe
(Sb) • Incorporate
injection V-trap
additive

34
 Mitigation Strategies Summary
Feed Metal Deposition Method Primary Effect Secondary Effect What to Watch for in the Solutions
Unit
Vanadium Deposits evenly and Permanent catalyst Dehydrogenation • Increased H2 and coke • V-trap additive
migrates in the poison agent production • Flush catalyst
regenerator • Decreased catalyst
activity
Sodium Deposits evenly and Permanent catalyst Forms eutectic with • Decreased catalyst • Flush catalyst
does not migrate poison V activity • Catalyst change
• Optimize desalter
operation
Nickel Deposits and binds Dehydrogenation -- • Increased H2 and coke • Antimony injection
on the outside of the agent (creates coke production • Catalyst change
particle. Does not and H2) • Flush catalyst
migrate
Iron Deposits and binds Creates nodules on Dehydrogenation • Circulation issues and • Flush catalyst
on the outside of the the surface of the agent lower ABD • Catalyst change
particle. Low mobility particle at very high CO promotion • Over-promotion in partial
between particles levels Transfers S from burn units
reactor to • Slightly increased SOx
regenerator emissions 35
Additional Feed Contaminants
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

36
Additional Feed Contaminants
Elements of high concern to be discussed in this presentation
Elements of concern to be mentioned briefly in this presentation

37
Additional Feed Contaminants

Calcium Sulfur Barium Arsenic

Used in some V-
Comes in with
Comes in with traps or chemicals Comes in with
feed or some V-
feed for tight oil feed
trap additives
extraction

Neutralizes acid
sites (less active No negative Has no effect on Volatile at FCC
than Na); can also effects on catalyst activity or conditions and
plug pores in conversion or yields when REO does not stay on
combination with yields is present the FCC catalyst
high added Fe
Use hydrotreating
Arsine (AsH3)
Use flush catalyst or gasoline sulfur
does go out with
or employ catalyst additives to
the C3= stream
with optimized remove for
which must be
surface porosity environmental
treated
purposes

38
Additional Feed Contaminants

(Basic)
Chlorine Phosphorus Copper
Nitrogen Comes in with
Used to stabilize
Comes with feed Comes in with feed and
zeolite – typically
and poor desalter feed or NOx neutralizes acid
an indicator of
operation reduction additives sites, lowering
ZSM-5 additive
conversion

Re-disperses and Can also be used

Temporary poison
reactivates “old” in chemicals for Has 5x more
– burns off in the
metals on the tight oil extraction dehydrogenation
regenerator as
catalyst, especially – no effect on activity than Ni
coke
Ni activity

Use low-Cl
Use low-Cu
catalyst or flush
promoter such as
catalyst to remove
CONQUERNOX
from inventory

39
Summary: Metals Contamination in FCC

Metals are continuing to rise as we see increased resid

processing as a global trend

Ni, V, Fe, and Na among the most detrimental, with Ca, K,
Cu also of concern

Catalytically: employ catalyst designed for high metal
applications including metal passivators, REO, and
optimized surface porosity

Proper operational and catalytic mitigation strategies
enable stable operation and profitability at the refinery

40