NUMBER 101 Spring 2007

Hydroprocessing/FCC Synergy
A message from the editor...

Dear Refiner:

Recently, you have been demanding to know more

about the synergy between the fluid catalytic cracking
process and hydroprocessing. With the formation of
ART in 2001 and our long-standing premier position in
the FCC business, Grace Davison and ART have lead
the industry in these critical areas.

In light of clean fuels and ultra low sulfur diesel

requirements, you have expressed particular interest
in the dynamics between cat feed hydrotreating and
fluid catalytic cracking. Chuck Olsen, ART's Worldwide Manager of Technical
Service, has co-authored our lead article titled, " Balancing the Need for FCC
Product HDS and Opportunities for Improving FCC Performance," which
highlights the RT/ART efforts. Chuck was joined by Joanne Deady, George
Yaluris and Natalie Petti in preparing the paper, which will be presented at the
NPRA Annual Meeting in San Antonio in March 2007.

With our extensive experience in refining, Grace Davison and ART's Technical
Team are ready to assist you with optimizing your hydroprocessing and FCC
units to get the best yields possible. Please contact your technical team or go
to our website www.e-catalysts.com for more information. We are dedicated
to meeting your challenges.

Regards,

Robert H. Bullard
Vice-President and General Manager, Grace Davison
Managing Director, Advanced Refining Technologies

Catalagram 101 Spring 2007 1


NUMBER 101
Hydroprocessing/FCC Synergy
IN THIS ISSUE
Balancing the Need for FCC Product HDS 3
and Opportunities for Improving FCC Performance
Spring 2007
Chuck Olsen, Worldwide Technical Services Manager, Advanced Refining Technologies
Joanne Deady, Vice President Marketing and R&D, Grace Davison, Columbia, MD
George Yaluris, Marketing Manager, Grace Davison, Columbia, MD
Natalie Petti, Consultant
Clean fuels regulatory demands have brought a focus on the importance of optimized
FCC feed pretreating in efforts to facilitate compliance. The proper selection of FCC
Pretreater catalyst and severity integrated with the selection of the appropriate FCC
catalyst design and operating conditions offer a refiner the opportunity for an optimized
refining operation.

CATALAGRAM 101
Spring 2007 Catalytic FCC Gasoline Sulfur Reduction 16
Citgo's Corpus Christi refinery reduces FCC gasoline sulfur
by up to 31% using Grace Davison's GSR®-5 additive
Managing Editor: Lauren Blanchard, Strategic Business Marketing Manager,
Joanne Deady Advanced Refining Technologies, Columbia, MD
Michael Ziebarth, Research Manager, Grace Davison, Columbia, MD
Contributors: Timothy Dougan, Marketing Manager, Grace Davison, Columbia, MD
Lauren Blanchard Low gasoline sulfur is key to operating successfully in today's environment. In order to
Joanne Deady define an effective sulfur reduction strategy a good understanding of the sulfur
David A. Hunt species present in the gasoline streams is essential. Grace Davison Catalysts and
Additives are designed to remove specific compounds present at different boiling
Chuck Olsen
ranges in the gasoline. A Citgo Refinery successfully used an additive and reached
Craig Borchert gasoline sulfur reduction of 44% with undercutting (31% without undercutting).
Min Pu
Bill Minyard Clean Fuels: An Opportunity for Profitability Using
Jeff Koebel
23
Natalie Petti Gasoline Sulfur Reduction Technology
Timothy Dougan Lauren Blanchard, Strategic Business Marketing Manager,
Advanced Refining Technologies, Columbia, MD
George Yaluris
Craig Borchert, Valero Energy, Wilmington, CA
Michael Ziebarth Min Pu, Valero Energy, Wilmington, CA
FCC Gasoline Sulfur is an important operating parameter for a refinery operation in
efforts to meet strict regulations. Outages of processes upstream and downstream of
the FCC can impact continued compliance with these regulations. Grace Davison and
Please address Valero Wilmington worked closely together to develop a successful strategy involving
your comments to feed and catalyst selection to stay within gasoline sulfur compliance during an FCC Feed
betsy.mettee@grace.com Pretreater Outage.

W. R. Grace & Co.-Conn. Understanding and Minimizing FCC Slurry

7500 Grace Drive 30
Columbia, MD 21044 Exchanger Fouling
(410) 531-4000 David A. Hunt, Technical Service Manager, Grace Davison, Houston, TX
Bill Minyard, National Technical Sales Manager, Grace Davison, Houston, TX
www.e-catalysts.com
Jeff Koebel, Technical Service Manager, Grace Davison, Chicago, IL
Slurry Exchanger fouling can impact FCC operation by causing reduced feedrate, loss
conversion and increased maintenance costs. A good understanding of the fouling
mechanisms involved is important. The selection of appropriate operating conditions
and FCC catalyst selection can reduce the incidents of exchanger fouling and
improve unit profitability.

The information presented herein is derived from our testing and experience. It is offered, free of charge, for your
©2007 consideration, investigation and verification. Since operating conditions vary significantly, and since they are not under our
control, we disclaim any and all warranties on the results which might be obtained from the use of our products. You should
W. R. Grace & Co.-Conn. make no assumption that all safety or environmental protection measures are indicated or that other measures may not be
required.

2 www.e-catalysts.com
 Balancing the Need
for FCC Product HDS and Opportunities
for Improving FCC Performance
Chuck Olsen
Worldwide Technical Services Manager,
Advanced Refining Technologies,
Chicago, IL

Joanne Deady
Vice President Marketing and R&D,
Grace Davison, Columbia, MD

George Yaluris
Marketing Manager,
Grace Davison, Columbia, MD

Natalie Petti
Consultant

Introduction Catalyst SystemTM for FCC

pretreatment in 20015. This
he benefits of hydrotreating

T
FCC feed on product yields
and sulfur content were
recognized some time ago and
described in earlier publications1,2,3,4.
Recently, regulatory demands and
the drive towards clean fuels have
renewed interest in FCC feed
hydrotreating to facilitate compliance
and satisfy the need for improved
yields. To address these needs,
Advanced Refining Technologies
(ART) introduced the ApART
technology was developed to
provide increases in HDS
conversion while at the same time
providing significant upgrading of
FCC feeds. In essence, an ApART
Catalyst System is a staged bed of
high activity NiMo and CoMo
catalysts where the relative
quantities of each are optimized to
meet individual refiner goals and
constraints. The ApART technology
has been described in detail
previously6. ART has continued to

Catalagram 101 Spring 2007 3

develop a better understanding of
the reactions and kinetics involved
in FCC pretreating, and, through
our partnering with Grace Davison
Refining Technologies, a detailed
understanding of the effects of
hydrotreating on FCC unit
performance. The complexity of
combinations of catalyst design
and operating conditions for both
the FCC feed hydrotreater and the
FCC unit presents a significant
optimization oppor tunity for
refiners to drive the combined
operation to maximum product
value.
FCC Pretreating
There are numerous reactions that
occur during hydrotreating of heavy
gas oils making it a challenging
process to model. A partial list of
reactions includes sulfur and
nitrogen removal, aromatics
saturation, carbon (MCR) removal,
and contaminant metals removal.
The progression of several of these
reactions as a function of the
hydrotreater temperature is shown
in Figure 1. Each reactant in the
figure shows a unique response to
temperature which indicates that
different reaction kinetics are
involved for each species. A wide
range of conversion levels is
achieved, with some reactants at
50% conversion and others at
90%+ conversion. As shown in
Figure 1, the conversion of
Reactant Conversion in FCC Pretreat
55
Aromatics Conversion, wt.%
increasing LHSV
50
45
40
35
30
660 680
4 www.e-catalysts.com
0.60
0.50
Prod Conc / Feed Conc
0.40
0.30
0.20
0.10
0.00
660
polynuclear aromatics (PNA's) passes
through a maximum as temperature
increases, and begins to decrease as
temperature increases beyond that
point. The conversion of total
aromatics follows a similar profile with
increasing temperature.
The data in Figure 2 examines the
conversion of aromatics in more detail.
This figure shows how the aromatics’
conversion varies with temperature and
LHSV when hydrotreating a coker gas
oil feed blend. The existence of a
maximum in conversion is readily
apparent. At higher temperatures the
conversion begins to decrease, and
this is due to thermodynamic
equilibrium constraints. The
temperature where the conversion
becomes thermodynamically limited is
Figure 2
Equilib rium
conversion
f (T, H2 partial pressure)
700 720
Temperature, ˚F
Figure 1
Reactant Conversion in FCC Pretreat
Sulfur
Nitrogen
PNA
MCR
680 700 720 740 760 780
Temperature, ˚F
a strong function of feedstock,
hydrogen partial pressure and LHSV.
As indicated in Figure 2, the
temperature of maximum conversion
increases as LHSV increases and,
not surprisingly, the overall
conversion level decreases. A similar
trend is observed for the PNA
conversion although in that case the
conversion levels are higher
compared to total aromatics
conversion. It is important to note
that the aromatics conversion trends
observed with increasing LHSV are
similar to what is observed as the
hydrotreating catalyst ages. The
temperature for the maximum in PNA
conversion (and aromatics) gradually
increases as the catalyst ages from
start of run (SOR) to end of run
(EOR).
It is generally accepted that
removing PNA's and nitrogen from
the FCC feed will improve FCC
performance. As an example,
Figure 3 summarizes FCC pilot
plant data for several hydrotreated
FCC feeds. The left y-axis
represents the FCC conversion and
the right axis represents the FCC
feed quality, shown as a ratio of
either product nitrogen content to
feed nitrogen content or product
PNA content to feed PNA content.
Clearly, the PNA and nitrogen
content of the FCC feed have a
strong effect on FCC performance.
At the highest pretreater severity the
740 760 FCC conversion actually decreases
 Figure 3 summarized in Table I. The
Pretreater PNA and Nitrogen Conversion Effect FCC Conversion hydrotreating catalyst systems
78 0.8
included a NiMo catalyst (ART
AT575) and a CoMo catalyst (ART

Nitrogen or PNA Content (Prod/Feed)

PNA
0.7 AT775). Both catalysts have had
76
extensive use in FCC feed pretreat
FCC Conversion (wt.%)

Nitrogen 0.6 applications around the world.

74 Several hydrotreating severities
0.5
were investigated that cover the
72 0.4 typical range encountered in FCC
FCC
Conversion pretreating, and both catalysts were
0.3
70 tested across the same range of
0.2 severities. The resulting
68
hydrotreated products were then
0.1 used as FCC feed in subsequent
FCC pilot plant testing.
66 0.0
Increasing Pretreater Severity Figure 4 shows how the product
sulfur from the pretreater changes
with temperature for both catalysts.
by about 1 wt.% relative to the hydrotreating catalyst type, pretreater At the lowest severity, the CoMo
previous severity in the chart. The operating severity, and FCC catalyst catalyst removes more sulfur than
decrease in FCC conversion design on FCC yields. the NiMo catalyst, as expected. At
coincides with an increase in PNA
the higher severities the NiMo
content from 0.48 to 0.55. Notice I. FCC Pretreating Pilot Plant catalyst slightly outperforms the
also that the conversion decreases Results CoMo catalyst with this feed and
despite the fact that the FCC feed
these operating conditions. The
nitrogen content is at the lowest A VGO/coker gas oil blend was used product sulfur content spans the
level suggesting the PNA feed as the feedstock for the FCC range from 1000 ppm down to
content has the larger impact on pretreater in this case study. The around 50 ppm.
FCC conversion. properties for the feedstock, along
with the pilot plant test conditions are
It has been previously shown6 that
the type of hydrotreating catalyst or Table I
catalyst system used in the Test Conditions and Feed Properties
pretreater is critical for FCC unit
Operating Conditions
performance. However, it is not
enough to simply have the right FCC LHSV, hr-1 1.0
pretreat catalyst as there is also an Temperature, °F 675-750
operating window for the pretreater H2 Pressure, Psi 1300
which maximizes the performance
of the FCC. ART and Grace Feedstock SR/Coker
Davison Refining Technologies have
API 22.7
recently collaborated on a study
examining the synergy between the Sulfur, wt.% 1.40
FCC pretreater and the FCC unit. Nitrogen, ppm 1500
The scope of the study covered the Total Aromatics, wt.% 45.9
effects of catalyst type (both PNA, wt.% 25.1
pretreater and FCC catalysts) as Distillation, °F (ASTM D-1160)
well as pretreater operating severity.
IP 382
A typical FCC feed sample was
hydrotreated in the pilot plant with 10 595
both NiMo and CoMo hydrotreating 30 689
catalysts across a range of 50 751
operating severity levels, and the 70 816
hydrotreated product samples were 90 890
then catalytically cracked in the
95 960
FCC pilot plant. A variety of FCC
catalyst types were tested to EP 1060
evaluate the combined effects of

Catalagram 101 Spring 2007 5

 Figure 4 Figure 5 shows how the product
Comparison of HDS Activity in FCC Pretreat nitrogen varies with temperature for
both catalysts and, as expected, the
10000 NiMo catalyst significantly
outperforms the CoMo catalyst
throughout the temperature range
Product Sulfur, ppm

investigated. The product nitrogen

1000 NiMo covers the range from about 600
ppm down to <100 ppm. The wide
CoMo range in nitrogen content suggests
that clear differences might be
100 expected in the subsequent FCC
pilot plant testing.

Figure 6 shows how the PNA

conversion varies for both catalysts.
10
Again the NiMo catalyst significantly
660 680 700 720 740 760 outperforms the CoMo catalyst for
Temperature, ˚F saturation of PNA's. The range of
hydrotreater severity was chosen to
cover the range where PNA
Figure 5 conversion is thermodynamically
Comparison of HDN Activity in FCC Pretreat limited, and thus, PNA conversion
for both catalysts is seen to
700
decrease at the higher
temperatures in the study. The PNA
Product Nitrogen, ppm

600
conversion for the NiMo catalyst
500 varied from around 77% to 86%
compared to the CoMo catalyst
400 NiMo range of only 70% to 78%. Again,
CoMo these ranges suggest substantial
300 differences in FCC feed quality
which should result in differences in
200
FCC performance.
100
Figure 7 shows the HDS and PNA
0 data for the NiMo catalyst on one
660 680 700 720 740 760 chart. It is useful to view the data in
this way when discussing FCC
Temperature, ˚F pretreater operating modes. The
maximum PNA conversion is about
Figure 6 86%, and at that temperature the
Comparison of PNA Saturation in FCC Pretreat product sulfur (i.e. FCC feed sulfur)
is about 200 ppm. This represents
90
the FCC feed quality for a pretreater
running in maximum PNA saturation
PNA Conversion, wt.%

85 mode. Another common way to

operate the FCC pretreater is
constant HDS mode. Assuming the
80 NiMo
target sulfur is 0.1 wt.%, the sulfur
CoMo target is met at significantly lower
75 temperature than required for the
maximum PNA saturation mode. At
that temperature the corresponding
70 PNA conversion is nearly 10 wt.%
lower than that obtained in PNA
65 saturation mode.
660 680 700 720 740 760
Temperature, ˚F
6 www.e-catalysts.com
Given the lower nitrogen and PNA Figure 7
contents achieved from operating in Comparison of HDS and PNA Activities
PNA mode it is expected that the
FCC feed will result in significantly 1400 88
higher FCC conversion and higher

PNA Conversion, wt.%

1200 86

Product Sulfur, ppm

gasoline yield compared to running
in HDS mode. This improvement, Sulfur
1000 84
however, does come with some PNA
additional operating costs for the 800 HDS mode 82
pretreater. The PNA mode of PNA mode
operation will result in higher 600 80
hydrogen consumption and a
shorter run length compared to the 400 78
HDS mode of operation.
200 76
The pretreater pilot plant data was 0 74
used to calibrate the ART FCC
pretreatment model for the feed 660 680 700 720 740 760
whose properties are summarized Temperature, ˚F
in Table I. The model was then used
to predict the hydrogen
consumption and FCC pretreater
cycle length for both the HDS and
PNA modes of operation shown in Table II
Figure 7. The results are listed in Comparison of FCC Pretreater Operating Modes
Table II.
Mode HDS PNA
Figure 8 shows the results of FCC Feed Quality
modeling the differences in FCC Sulfur, ppm 1000 260
pretreater temperature profiles for
Nitrogen, ppm 420 150
the two operating strategies. In
HDS mode, the reactor temperature PNA Conversion, wt.% 77 86
is increased to maintain a constant
product sulfur, 0.10 wt.% in this H2 Consumption, SCFB 395-415 470-490
example. The end of run (EOR) is Cycle Length, mos 36 24
typically determined by a maximum
outlet temperature, which is
reached in about 36 months in this
case. In PNA mode, the reactor
temperature is ramped up to the
conditions resulting in maximum
PNA conversion. The temperature Figure 8
is then adjusted to maintain FCC Pretreat Temperature Profiles
constant PNA conversion. PNA
saturation activity deactivates at a 780
slower rate relative to HDS activity, EOR Temperature for HDS mode
so the rate of temperature increase 760
Temperature, ˚F

in PNA mode is much slower than

for the HDS mode. 740
PNA
The EOR for the PNA mode of 720
operation is determined by the HDS
required sulfur level in the FCC 700
feed. Figure 9 shows how the sulfur
conversion changes throughout the 680
cycle for each mode of operation. Constant HDS vs.Optimum PNA
In HDS mode the conversion 660
remains constant throughout the
0 3 6 9 12 15 18 21 24 27 30 33 36
Cycle Length, Months

Catalagram 101 Spring 2007 7

run. In PNA mode the sulfur Figure 9
conversion at SOR is much higher HDS Conversion Changes with Operating Mode
than required due to the higher SOR
temperature, and because HDS 100
activity deactivates at a higher rate 99
Constant PNA operation
than PNA saturation activity, the 98

% HDS Conversion
HDS conversion decreases as the 97
cycle progresses. The EOR is
reached when HDS conversion has 96
decreased to the target sulfur level, 95 PNA
24 months in this case. 94 HDS
Constant HDS operation
93
Figure 10 shows how the PNA
92 PNA mode EOR
conversion changes through the due to sulfur
cycle for both modes of operation. 91
In PNA mode the conversion stays 90
nearly constant until close to EOR
0 3 6 9 12 15 18 21 24 27 30 33 36
when equilibrium constraints start to
limit conversion. In HDS mode, the Cycle Length, Months
PNA conversion starts out relatively
low, and increases as the cycle
progresses. The PNA conversion Figure 10
reaches a maximum and then
PNA Conversion Changes with Operating Mode
begins to decrease through the last
part of the cycle due to equilibrium 88
limits. In this mode of operation the 86
PNA Conversion, wt.%

Constant PNA operation

maximum PNA conversion (i.e.
maximum FCC feed upgrade) is 84
only achieved for a small fraction of 82
the total cycle. PNA
80
As Figure 11 shows, the nitrogen
HDS
78
conversion decreases from SOR to Constant HDS operation
EOR for either operating mode. 76
Under these operating conditions PNA mode EOR
74 due to sulfur
HDN activity deactivates at a higher
rate than HDS activity or PNA 72
saturation activity, so HDN 0 3 6 9 12 15 18 21 24 27 30 33 36
conversion is much lower at EOR
Cycle Length, Months
compared to SOR. For the HDS
operating mode HDN activity
decreases from around 72% to 45% Figure 11
from SOR to EOR, while for the PNA HDN Conversion Changes with Operating Mode
mode the HDN conversion declines
100
from 87% to about 57% from SOR to
EOR.
90 Constant PNA operation
%HDN Conversion

These data clearly show that there

are significant differences in FCC 80
feed quality as the cycle moves from PNA
SOR to EOR in either mode of 70
operation, and this indicates that HDS
FCC performance will change as 60 Constant HDS operation
the cycle progresses regardless of
the operating strategy. To 50 PNA mode EOR
due to sulfur
investigate this further, the ART
model was used to simulate the 40
FCC feed properties as the
0 3 6 9 12 15 18 21 24 27 30 33 36
pretreater cycle progressed from
Cycle Length, Months

8 www.e-catalysts.com
 Figure 12 SOR to EOR for both modes of
PNA vs. HDS Run Mode Comparison pretreater operation. The FCC feed
properties were then used to
78 estimate FCC conversion, the
Incremental FCC Yield PNA Mode results of which are shown in Figure
76 12. Operating the pretreater in PNA
HDS Mode
FCC Conversion (wt.%)

mode provides significantly higher

74 FCC conversion for most of the
cycle, but again it comes at the cost
72 of shorter pretreater run length and
increased hydrogen consumption.
70 These costs need to be weighed
against the benefits in FCC
68 performance to determine the best
Reduced Run Length
operating strategy.
66
0 10 20 30 40 There is the potential to extend the
Run Length (months) cycle length of the pretreater when
operating in PNA mode through the
use of sulfur reduction technologies
in the FCC unit. FCC gasoline sulfur
Figure 13 can be reduced by 20%-35%
Cycle Length with a Sulfur Reduction Product commercially7,8,9 which would
100 enable the pretreater to run to a
PNA
higher sulfur level. Figure 13 shows
99 HDS the impact of using a sulfur
Constant PNA operation
98 FCC Sulfur Reduction reduction product in the FCC unit
%HDS Conversion

97 that delivers 20% reduction in FCC

gasoline sulfur (such as D-PriSM® or
96 GSR®-5 additives, or SuRCA®
95 catalyst) while operating the
94 pretreater in PNA mode. The
Constant HDS operation pretreater product sulfur is allowed
93 to increase in months 24 through 28
92 EOR with while the FCC gasoline sulfur
PNA mode EOR
FCC Sulfur remains constant because the
91 due to sulfur
Reduction
sulfur reduction product is used to
90
control FCC gasoline sulfur during
0 3 6 9 12 15 18 21 24 27 30 33 36 those months.
Cycle Length, Months
The results of estimating the FCC
Figure 14 conversion for the FCC sulfur
Benefit for PNA mode with FCC Sulfur Reduction vs. HDS Run Mode reduction case are shown in Figure
14. This chart demonstrates that
78 the use of a sulfur reduction
Incremental FCC Yield
PNA Mode product in the FCC can extend the
76 pretreater cycle length in PNA mode
FCC Conversion (wt.%)

HDS Mode while at the same time maintain the

74 benefits of increased FCC
conversion.
72
Figures 9 through 14 show how
70 changes in pretreater operating
mode can influence FCC feed sulfur,
68 Increased Run Length from nitrogen and PNA content which
FCC Sulfur Reduction
directly effects FCC unit conversion.
66 As the pretreater progresses from
0 10 20 30 40 SOR to EOR in either mode of
Run Length (months) operation, the FCC feed properties

Catalagram 101 Spring 2007 9

 Figure 15 change, again directly influencing
FCC Yields for NiMo Treated Feed Reacted over Type 1 Ecat FCC unit conversion. The next
section will show how the FCC
80.0 catalyst formulation can potentially
77.4
be used to offset pretreater product
75.0 74.5 1.56 property shifts, as well as to
1.55
6.3 optimize the joint operation of the
70.0
6.0
pretreater and FCC units for
FCC Yields (wt.%)

maximum profitability.
65.0 Dry Gas
C3's
12.4 II. FCC Unit Pilot Plant Results
60.0 C4's
11.7 Gasoline

55.0 The next phase of the study

involved taking the hydrotreated
50.0 products and using them as FCC
55.1 feed in an FCC pilot plant. The FCC
53.1
45.0 feeds were cracked over three
different FCC equilibrium catalyst
40.0 types. The pilot unit was run at a
HDS Mode PNA Mode constant reactor temperature of 990
ºF, and each of the FCC e-cat
samples was tested at three
catalyst-to-oil ratios (4, 6, and 8) in
Table III the pilot unit.
Equilibrium Catalyst Properties - Type 1
The yields resulting from FCC
MAT (wt.%) 76 equilibrium catalyst Type 1 will be
Total Surface Area (m2/g) 152 discussed first. The properties of
the Type 1 Ecat are shown in Table
Zeolite Surface Area (m2/g) 120
III.
Matrix Surface Area (m2/g) 32
Nickel (ppm) 183 Type 1 catalyst is high rare earth,
Vanadium (ppm) 1527 high zeolite to matrix (Z/M) ratio,
Unit Cell Size (Å) 24.34 and high equilibrium unit cell size
Rare Earth (wt.%) 3.72 (UCS) designed for maximum
gasoline selectivity. Ecat metals
Alumina (wt.%) 42.4
levels are moderate, and the
catalyst has a relatively high Ecat
activity (MAT). The yields for the
Figure 16 FCC feeds from the NiMo catalyst in
HDS and PNA modes with Type 1
C3 & C4 Olefinicity of FCC Products from
Ecat are shown in Figure 15, and
NiMo Treated Feed Reacted over Type 1 Ecat are presented at constant coke
0.81 0.46 yield (2.0 wt.%).

C3 Olefinicity - NiMo The trends indicate that the PNA

0.80 mode of pretreater operation results
C4 Olefinicity - NiMo
0.45 in higher overall conversion (the
maximum value on the y-axis).
C3 Olefinicity

C4 Olefinicity

0.79 Selectivity of gasoline and LPG also

increase, while dry gas yield is
0.44
essentially unchanged. The lower
0.78 PNA and nitrogen contents of the
FCC feed generated by the PNA
0.43
mode of operation result in higher
0.77 FCC conversion, and production of
more valuable products.

0.76 0.42
HDS Mode PNA Mode
10 www.e-catalysts.com
Figure 16 shows that olefinicity of Figure 17
both C3's and C4's is lower in PNA FCC Yields for CoMo Pretreater Feed Reacted over Type 1 Ecat
mode than HDS mode, which 80.0
supports previously observed
trends for hydrotreated feeds10. 75.0 74.9
Hydrotreated FCC feeds are more 73.1
1.51
hydrogen rich, and the resulting 70.0 1.54
products are therefore more 6.0

FCC Yields (wt.%)

5.8
hydrogen rich. 65.0
Dry Gas
Comparing the performance of the 60.0 11.7 C3 's
FCC feed produced by the CoMo 11.3 C4 's
catalyst, shown in Figure 17, shows 55.0 Gasoline
lower overall conversion and lower
selectivities for gasoline, C3's and 50.0
C4's than the NiMo produced feed. 52.3 53.6
Again, operating the hydrotreater in 45.0
PNA mode (i.e. higher severity)
instead of HDS mode results in 40.0
HDS Mode PNA Mode
higher conversion and selectivities
for gasoline and LPG. This is due to
the increased HDN and PNA Figure 18
removal at higher temperature. C3 & C4 Olefinicity of FCC Products from NiMo and CoMo
Both NiMo and CoMo will remove Pretreater Feeds Reacted over Type 1 Ecat
more nitrogen and PNA's from the
0.81 0.46
FCC feed at the elevated C3 Olefinicity - CoMo
temperatures of the PNA mode, C3 Olefinicity - NiMo
although the NiMo catalyst removes C4 Olefinicity - CoMo
0.80 C4 Olefinicity - NiMo
significantly more compared to the 0.45
CoMo catalyst. This results in
C3 Olefinicity

C4 Olefinicity
significantly higher FCC conversion
0.79
(1.4 wt.% in either mode) for the
NiMo than the CoMo catalyst. 0.44

0.78
Similar trends showing reduced C3
and C4 olefinicity for the hydrotreater
in PNA operating mode are observed 0.43
0.77
for CoMo produced FCC feed (Figure
18). Overall the C3 and C4 olefins
produced by FCC feed from the two
0.76 0.42
hydrotreating catalyst types are
HDS Mode PNA Mode
essentially equal.
Figure 19
Applying typical Gulf Coast Delta Economics for FCC Products from NiMo and CoMo Pretreater
economics to the FCC yields allows Feeds Reacted over Type 1 Ecat
a comparison of the value $0.50
associated with each pretreater
Delta Product Value ($/BBL)

$0.40 NiMo
catalyst type and each operating
mode. In the following figures, the $0.30 CoMo
NiMo produced FCC feed in HDS
mode is used as the base case $0.20
assuming a 50,000 BPD FCC unit. $0.10
Figure 19 shows the observed
$-
trends in FCC product value for
Type 1 Ecat. $(0.10)
$(0.20)
The NiMo catalyst produces FCC
feed that results in $0.19 to $(0.30)
$0.23/BBL higher total product $(0.40)
HDS Mode PNA Mode
Catalagram 101 Spring 2007 11
value than the CoMo catalyst. In Figure 20
addition, the PNA operating mode Delta Economics for FCC Products from NiMo and CoMo
yields $0.37 to $0.41/BBL higher
product value than HDS mode.
Pretreater Feeds Reacted over Type 1 Ecat Adjusted for
Note that this excludes any value Pretreater Catalyst Hydrogen Consumption
associated with lower sulfur FCC
NiMo

Delta Product Value ($/BBL)

products which result from the lower $ 0.50
sulfur content of feeds treated in CoMo
$ 0.40
PNA operation. However, these Adjusted NiMo
$ 0.30 Adjusted CoMo
product value benefits of operating
in PNA mode must be considered $ 0.20
against the higher hydrogen $ 0.10
consumption cost and the
associated costs of the reduction in $-
the hydrotreater run length resulting $ (0.10)
from higher severity operation, as
$ (0.20)
discussed previously.
$ (0.30)
Even after adjusting these product $ (0.40)
values to account for increased HDS Mode PNA Mode
hydrogen consumption, the NiMo
produced FCC feed in PNA mode
still yields higher product values.
Figure 21
Accounting for the higher hydrogen
consumption cost for NiMo relative Economics for FCC Products and Hydrotreater Severity
to CoMo, the delta FCC product for NiMo Pretreater Feed Reacted over Type 1 Ecat
value for NiMo catalyst is $0.14/BBL Optimum
higher than the CoMo product value PNA
$0.40 $0.40
in PNA mode (Figure 20), and $0.16
to $0.39/BBL higher than either $0.20 $0.20
catalyst in HDS mode.
Delta FCC Product Value ($/BBL)

$- $-

Higher Severity Cost ($/BBL)

Base
To determine the point at which the HDS
$(0.20) $(0.20)
incremental conversion from
$(0.40) $(0.40)
increasing pretreater severity
diminishes from reduced PNA $(0.60) $(0.60)
conversion and/or unfavorable Delta Product Value ($/BBL)
$(0.80) $(0.80)
hydrotreater operating costs for the Higher Severity Cost ($/BBL)
feed in Table I, additional modeling $(1.00) $(1.00)
Increasing
was conducted using the pilot plant Hydrotreater
$(1.20) $(1.20)
results. Starting with an FCC feed Severity
produced by a pretreater with NiMo $(1.40) $(1.40)
catalyst, assuming a 50,000 BPD
$(1.60) $(1.60)
pretreater with a catalyst change out
cost of $7 MM and a four-year FCC
unit shutdown cycle, running in
Table IV
higher severity mode would cause
additional pretreater outage and Equilibrium Catalyst Properties - Type 2
hydrogen consumption costs. As
shown in Figure 21, higher FCC MAT (wt.%) 73
product value can be obtained by Total Surface Area (m2/g) 175
running the hydrotreater at higher Zeolite Surface Area (m2/g) 116
severity. The HDS operating mode Matrix Surface Area (m2/g) 59
and Type 1 Ecat represents the base
Nickel (ppm) 231
operation. Increasing the severity of
the hydrotreater operation toward Vanadium (ppm) 953
optimum PNA mode results in higher Unit Cell Size (Å) 24.29
operating costs for the hydrotreater, Rare Earth (wt.%) 2.82
which are more than justified by the Alumina (wt.%) 48.5

12 www.e-catalysts.com
 Figure 22 higher FCC product value. At the
FCC Yields for NiMo Pretreater Feed Reacted over Type 2 Ecat optimum PNA point, $0.10/BBL
higher profit would be realized after
80.0 79.2
77.2 accounting for the higher cost of
1.58
75.0 1.69
running the hydrotreater in that mode.
7.0 Beyond the optimum PNA point,
70.0 7.1 however, the incremental FCC
product value begins to level off, and
FCC Yields (wt.%)

65.0
Dry Gas eventually begins to decline due to
13.2
60.0 13.2
C3 's the higher PNA levels in the feed (as
C4 's was observed in Figure 3). The
Gasoline
55.0 increasing cost of higher severity
operation of the hydrotreater is not
50.0
justified as it more than offsets the
55.5
53.1 FCC product value realized.
45.0

40.0 FCC catalyst can also be designed

HDS Mode PNA Mode to further enhance yield advantages
of hydroprocessing catalyst type or
hydrotreater mode/severity of
Figure 23 operation. As an example, the
Delta Economics for FCC Products from NiMo Pretreater Feed resulting yields for FCC feed
Reacted over Type 2 vs. Type 1 Ecata produced by NiMo catalyst in HDS
$1.20 and PNA operating modes over
Type 2
FCC equilibrium catalyst Type 2
Delta Product Value ($/BBL)

$1.00 were investigated. The properties

Type 1
of the Type 2 Ecat are shown in
$0.80
Table IV.
$0.60
Type 2 catalyst has moderate rare
$0.40 earth, with a lower zeolite to matrix
(Z/M) ratio and lower unit cell size
$0.20
than Type 1 catalyst. Shifts in Z/M
$- Delta Product Value over and UCS will result in a yield slate
Type #1 HDS Mode.
with more olefins and octane than
$(0.20) Type 1. For some hydrotreated feeds,
$(0.40) Type 2 catalyst will yield higher
HDS Mode PNA Mode overall conversion (see Figure 22), as
the matrix contribution from the
catalyst will crack more of the heavier
Figure 24 feed molecules.
Economics for FCC Products and Hydrotreater Severity
for NiMo Pretreater Feed Reacted over Type 2 Ecat Comparing Figure 22 to Figure 15,
switching to Type 2 FCC catalyst
$0.40 Optimum $0.40
PNA boosts conversion by 1.9 wt.% in
$0.20 $0.20 HDS mode and 2.7 wt.% in PNA
Base mode. Compared to Type 1 catalyst
Delta FCC Product Value ($/BBL)

$- $-
in HDS mode, the higher conversion
Higher Severity Cost ($/BBL)

HDS
$(0.20) $(0.20) for Type 2 results in $0.66/BBL
higher product value, and that
$(0.40) $(0.40) increases to $0.89/BBL higher
$(0.60) $(0.60)
product value in PNA mode (Figure
Delta Product Value ($/BBL) 23).
$(0.80) Higher Severity Cost ($/BBL)
$(0.80)
Figure 24 shows the product value
$(1.00) $(1.00)
Increasing increase along with the costs
Hydrotreater associated with the higher severity
$(1.20) $(1.20)
Severity
pretreater operation with Type 2
$(1.40) $(1.40) catalyst. In this case, there
$(1.60) $(1.60)
Catalagram 101 Spring 2007 13
 Table V appears to be a smaller window of
Equilibrium Catalyst Properties - Type 3 pretreater operation where the gain
in product value exceeds the
increasing operating costs. The
MAT (wt.%) 78
point at which the cost of higher
Total Surface Area (m2/g) 164 severity operation for the pretreater
Zeolite Surface Area (m2/g) 134 overwhelms the incremental FCC
Matrix Surface Area (m2/g) 30 product value is closer to the base
Nickel (ppm) 110 HDS operating mode, so the refiner
Vanadium (ppm) 235 running Type 2 FCC catalyst could
make up to $0.12/BBL more profit at
Unit Cell Size (Å) 24.32
the optimum PNA point, but the
Rare Earth (wt.%) 3.88 operating window is much narrower
Alumina (wt.%) 43.2 than it was for Type 1 catalyst.
Obviously the economics of each
combination of FCC catalyst,
pretreater catalyst, and hydrotreater
Figure 25 severity are unique to each refinery.
FCC Yields for NiMo Pretreater Feed Reacted over Type 3 Ecat For the last comparison case, the
80.0 79.7 resulting yields for an FCC feed
77.5
1.61 produced by NiMo hydrotreating
75.0 1.67 catalyst in HDS and PNA operating
7.1 modes over FCC equilibrium
FCC Yields (wt.%)

70.0 6.9
catalyst Type 3 are presented. The
properties of the Type 3 Ecat are
65.0
shown in Table V.
13.5
60.0 13.1 Dry Gas
Type 3 catalyst properties look similar
C3 's
55.0 C4 's
to Type 1, but Type 3 has a higher
Gasoline
Z/M ratio. Type 3 also has slightly
50.0 higher rare earth levels and a UCS
53.8 55.5 that favor gasoline selectivity. The
45.0 metals levels are appreciably lower
than Type 1 and the MAT activity is
40.0 higher. For the feed produced by the
HDS Mode PNA Mode NiMo catalyst in PNA or HDS mode,
Type 3 catalyst yields significantly
higher conversion than Type 1 (2.7
Figure 26 wt.% on average over yields
presented in Figure 18), and slightly
Delta Economics for FCC Products from NiMo Pretreater Feed
higher conversion than Type 2 (0.4
Reacted over Type 1, Type 2 and Type 3 Ecat wt.% on average over yields
$1.00 presented in Figure 22). However, as
Type #2 Figure 26 shows, the delta product
values for Type 2 catalyst are higher
Delta Product Value ($/BBL)

$0.90 Type #3
due to the higher olefins yield for this
type of catalyst.
$0.80
Modeling Type 3 catalyst yields and
selectivities for increasing severity
$0.70 of pretreater operation shows that
Type 3 will increase in delta product
$0.60 value and then level off across the
range of severity analyzed (Figure
Delta Product Value over 26). The benefits of increased
$0.50 Type #1 HDS Mode. severity level off sooner for Type 2
than Type 3 catalyst, and then Type
$0.40
HDS Mode PNA Mode Increasing Hydrotreater Severity
14 www.e-catalysts.com
2 catalyst product value actually
declines with the further increase in
severity while Type 3 catalyst
product value levels off. The higher
matrix surface area of Type 2
catalyst creates diminishing returns
on FCC conversion as the pretreater
severity increases (simulating the
pretreating catalyst progressing
toward EOR). This is because the
declining pretreater product quality
at end of run causes higher FCC
coke yield and Type 3 catalyst
designed with the higher Z/M ratio
will be more coke selective with this
feed trend.
Figure 26 indicates that there are
significant opportunities to adjust
FCC catalyst formulations as
pretreater cycles move from start of
run to end of run, however, the data
presented are specific to the feed in
Table I, the FCC catalyst types
tested, and the range of severities
tested. Each refinery operation
requires individual analysis of
candidate catalysts and operating
conditions of both FCC feed
pretreater and FCC units to
determine the optimum combination
which maximizes profitability.
Conclusion
FCC feed pretreating offers the
potential to significantly improve
refinery economics. Both the
hydrotreating catalyst system and
the operating strategy for the
pretreater are critical to providing
the highest quality feed for the FCC.
In general, NiMo based catalysts
produce better FCC feed, with both
lower nitrogen and PNA content.
The operating mode of the
hydrotreater can be used to further
improve the FCC feed. Driving the
hydrotreater to remove nitrogen and
PNA's improves FCC product value,
but this needs to be balanced
against the increased costs of
higher hydrogen consumption and
shorter cycle length that result from
this mode of operation.
The shorter run lengths from
operating in PNA mode can be
extended with the use of a sulfur
reduction catalyst or additive in the
downstream FCC unit. FCC gasoline
sulfur reduction of 20% or higher from
a product such as D-PriSM® or GSR®-5
additives, or SuRCA® catalyst would
enable the pretreater to run beyond the
point when product sulfur levels exceed
target levels, while FCC gasoline
product sulfur remains within the limits
needed for gasoline pool sulfur
compliance. Extending operation in
PNA mode closes the gap in run length
versus a hydrotreater in the HDS mode
of operation, while continuing to
provide FCC feed of higher quality than
HDS mode.
FCC catalyst formulation can also be
included as one of the variables that can
be adjusted to maximize profitability.
With constant hydrotreater product
properties, FCC catalyst formulation can
provide up to $0.90/BBL higher product
value. Pushing hydrotreater severity to
an optimum with constant FCC
catalyst can yield in excess of
$0.10/BBL net product value, which
includes the cost of higher severity
operation of the hydrotreater. Finally,
adjusting FCC catalyst formulation as
the hydrotreater moves from start of
run to end of run can significantly
offset decline in product quality, and
preserve product value.
All of the combinations presented
show the need for refiners to follow an
integrated approach to managing the
catalysts and operation of the FCC
pretreater and FCC units. FCC and
hydroprocessing operation can be
continuously optimized throughout the
course of the hydrotreater run, to
significantly increase refiner revenue.
Catalagram 101 Spring 2007 15
References
1. Wollaston, E. G., Forsythe, W. L.,
and Vasalos, I. A., Oil & Gas
Journal, August 2, 1971, pp. 64-69.
2. Huling, G. P., McKinney, J. D., and
Readal, T. C., Oil & Gas Journal,
May 19, 1975, pp. 73-79.
3. Campagna, R. J., Krishna, A. S.,
and Yanik, S. J., Oil & Gas Journal,
October 31, 1983, pp. 129-134.
4. Krenzke, L. D., and Baron, K., 1995
NPRA Annual Meeting, Paper AM-
95-67.
5. Shiflett, W. K., Krenzke, L. D., and
Wear, C. C., Davison Catalagram 89,
October, 2001, pp. 11-17.
6. Shiflett, W. K., Olsen, C. W, Watkins,
B. R., Krishnamoorthy, S., and Wear,
C. C., 2002 NPRA Annual Meeting
Paper, Paper AM-02-39.
7. Blanchard, L., Borchert, C., Pu, M.,
2007 NPRA Annual Meeting Paper,
Paper AM-07-06.
8. Blanchard, L., Oishi, T., Teo, B.,
Haley, J., Davison Catalagram 98,
Fall 2005, pp. 5-10.
9. Blanchard, L., Davison Catalagram
100, Fall 2006, pp. 8-13.
10. Salazar-Sotelo, D., Maya-Yescas, R.,
Mariaca-Dominguez, E., Rodriguez-
Salomon, S., Aguilera-Lopez, M.,
Catalysis Today 98, 2004, pp. 273-
280.
Catalytic FCC Gasoline Sulfur Reduction
Citgo's Corpus Christi refinery reduces FCC gasoline sulfur by
up to 31% using Grace Davison's GSR®-5 additive
ncreasingly stringent gasoline
Lauren Blanchard
I sulfur regulations such as the 30
ppm sulfur limit imposed on
most U.S. refiners in 2006 present yet
Strategic Business another challenge to the refining
industry. Refiners not only have to
Marketing Manager,
comply with the new specifications but
Grace Davison, they need to determine the most
Columbia, MD economical method to reduce gasoline
sulfur while preserving as much
operating flexibility as possible. The
Michael Ziebarth
fluid catalytic cracking (FCC) unit is a
Research Manager, significant contributor to the gasoline
Grace Davison, pool and one of largest sources of
Columbia, MD gasoline sulfur. Therefore, reducing
FCC gasoline sulfur is a key component
of a refiner's overall compliance
Timothy Dougan strategy. While pre-treating the feed or
Marketing Manager, post-treating the FCC gasoline are
Grace Davison, popular approaches, the use of
catalysts and additives for sulfur
Columbia, MD
reduction can provide increased
flexibility and improved profitability.
Grace Davison first commercialized
gasoline sulfur reduction catalysts and
additives in 1996 and has been
successful in introducing new
products to the market. These
products have been used in 85
commercial applications and have
demonstrated the ability to reduce
FCC gasoline sulfur by up to 46%.
16 www.e-catalysts.com
When combined with undercutting,
gasoline sulfur reduction approaches
60%. Refiners have found numerous
ways to incorporate these products
into their short-term and long-term
strategies to:
• Improve profitability
• Extend feed hydrotreater
run-life
• Manage FCC feed
hydrotreater outages
• Process higher sulfur
opportunity feeds
• Increase FCC feed
hydrotreater throughput
• Minimize undercutting
• Comply with pipeline
specifications
• Minimize octane loss from
post treatment
• Reduce hydrotreater
hydrogen consumption
Grace Davison's, SuRCA® catalyst,
which is designed to replace
conventional FCC catalyst, has
been Grace Davison's most
successful gasoline sulfur reduction
product. SuRCA catalyst has been
used in over 45 applications
worldwide. In addition to reducing
 Figure 27
Gasoline Sulfur Speciation Determined by Simulated Distillation
122 167 212 257
Temperature, (˚F)
gasoline sulfur, it has, in some
instances, reduced LCO sulfur by
10-15%. Grace Davison also offers
GSR-5® gasoline sulfur reduction
additive, which is based on similar
technology embodied in SuRCA
catalyst. This product provides
comparable performance with the
increased flexibility and the
convenience of an additive.
Typically, GSR-5 additive is used in
place of 25% of catalyst additions.
Grace Davison has had seven
commercial applications of GSR-5.
Citgo Petroleum Corporation's
Corpus Christi, TX refinery
successfully used the additive for
over a year and was able to reduce
gasoline sulfur by up to 31%.
Results from this application are
summarized in this paper.
The Origin of FCC Gasoline
Sulfur
The proper application of existing
products, as well as the
development of new technologies,
requires an understanding of
gasoline sulfur formation pathways,
the species that are formed and the
effect of FCC feed sulfur speciation
on the resulting gasoline sulfur.
Sulfur compounds in FCC feed
include mercaptans, sulfides, alkyl
substituted thiophenes, thiophenols,
benzothiophenes and multi-ring
aromatic thiophenes. The amount
302 347
and relative quantity of each of these
species is dependent on a wide range
of factors. These factors include feed
source, type of feed pretreatment
(hydrotreating, etc.), and whether or
not other refinery streams such as
coker gas oil have been blended into
the FCC feed.
In the FCC unit, typically 35-45% of
the feed sulfur is converted into H2S,
45-55% ends up in the light cycle oil
(LCO) and bottoms and 5% in the
coke. Only about 5% ends up in the
gasoline. Gasoline sulfur species can
be determined by using a Gas
Chromatograph (GC) equipped with
an Atomic Emission Detector (AED).
The typical sulfur compounds found in
FCC gasoline are presented in Figure
27 as a function of their boiling point.
The gasoline range sulfur species
1400
Cumulative Sulfur (ppm)
1200
1000
800
600
400
200
0
100
include mercaptans, sulfides, alkyl
substituted thiophenes, thiophenols,
and, depending on the gasoline cut
point, benzothiophene and
alkylbenzothiophenes.
The importance of the feed sulfur
type on the amount of gasoline
sulfur produced is shown in Figure
28. Two FCC gas oil feeds with
similar sulfur levels were cracked in
an FCC pilot plant and the resulting
gasoline analyzed for sulfur. The
gasoline produced from Gas Oil B
has about 75% higher sulfur than
the gasoline produced from Gas Oil
A, despite the fact that both starting
392 437 482 527
gas oils had similar sulfur levels.
The two gas oils were analyzed by
High Resolution Mass Spectrometry
(HRMS) and X-ray Photoelectron
Spectroscopy (XPS) to determine
the types of sulfur species present.
The HRMS determines the type and
amount of aromatic thiophenes
present by measuring the quantity
and mass of the molecular species.
XPS measures the binding energy
of the feed sulfur species and
allows quantification of the amount
of aromatic and aliphatic sulfur
species. An analysis of the two
feeds by these methods shows the
differences in the types of sulfur
species present in each feed (Table
VI). Gas Oil B has about twice the
level of alkylthiophenes, twice the
level of aliphatic sulfur species and
about 10% higher alkyl-
benzothiophenes, compared to Gas
Oil A. Gas Oil A has more multi-ring
benzothiophenes.
Figure 28
Sulfur Species From Two Cracked Gas Oils
Gas Oil A 2.8 wt.% S
Gas Oil B 2.6 wt.% S
150 200 250 300 350 400 450 500
Boiling Point ˚F
Catalagram 101 Spring 2007 17
 Table VI
Sulfur Characteristics of Gas Oil A and B
Sulfur Compounds by
High Resolution Mass Spec (ppm)
C(N)H(2N-4)S THIOPHENES
C(N)H(2N-10)S BENZOTHIOPHENES
C(N)H(2N-16)S DIBENZOTHIOPHENES
C(N)H(2N-22)S NAPHTHOBENZOTHIOPHENES
Total Sulfur XPS Analysis (wt.%)
ALIPHATIC SULFUR
AROMATIC SULFUR
Based on the feed sulfur analysis,
experiments were designed to
determine if feed alkylthiophenes,
alkylbenzothiophenes and
saturated sulfur compounds are
more likely to end up in the gasoline
as compared to multi-ring alkyl-
benzothiophenes. A hydrotreated,
low sulfur gas oil was spiked with
one of four model sulfur
compounds; a mercaptan, an alkyl-
thiophene, an alkylbenzothiophene
and an alkyldibenzothiophene.
These feeds were cracked in an
FCC pilot plant and the resulting
gasoline was analyzed for sulfur.
The results are shown in Figure 29.
The data shows that the
alkylthiophenes in the feed
contribute significantly to gasoline
range sulfur species. The alkyl
chains on the thiophene are
cracked and isomerized to produce
a range of alkylated thiophene
species. The alkyl group can also
cyclize and dehydrogenate to form
benzothiophene. The mercaptans
are cracked mainly to H2S and only
a small quantity ends up as
gasoline range sulfur. The alkyl-
benzothiophene and alkyl-
dibenzothiophene produce some
benzothiophene but essentially no
gasoline range alkylthiophenes.
In summary, this data shows that
(C5+)-alkylthiophenes in the feed are
18 www.e-catalysts.com
Catalytic Gasoline Sulfur
Reduction Options
Gas Oil A Gas Oil B D-PriSM® sulfur reduction additive,
another product from Grace
Davison, is effective at removing an
526 980
intermediate that converts to
alkylthiophene and therefore is
13918 12702 more effective at reducing light
gasoline sulfur. This product has
9439 7317
been used in more than 25
1517 0 refineries worldwide. The SuRCA®
catalyst family, GSR-5 additive and
the recently commercialized
0.23% 0.50%
NEPTUNETM catalyst are designed
to reduce a broader range of
2.54% 2.09% gasoline sulfur species (Figure 30).
When formulating a solution for a
the biggest contributors to gasoline customer, we consider the FCC
range alkylthiophenes, while the other gasoline speciation, the desired
feed sulfur molecules are more modest level of gasoline sulfur reduction,
contributors. The alkylbenzothiophene and whether a catalyst or an
and multi-ring thiophenes are the main additive is preferred. Careful
source of benzothiophene which may selection of the appropriate
not appear in the FCC gasoline, technology for each application has
depending on the end-point. resulted in consistent product
performance that has met or
Understanding the mechanisms by exceeded customer expectations.
which gasoline sulfur is formed has As a result, these technologies tend
allowed Grace Davison to develop a to be used on a long-term,
range of different products that target continuous basis. The average
the different sulfur producing length for all 85 commercial
pathways. applications is 388 days, with one
user at 6 years. Over one-half of
the applications have lasted 100
Figure 29
Gasoline Range Sulfur Distribution from Feedstock
Spiked with Model S Compounds
1200
Mercaptan
1000 Alkylthiophene
Alkylbenzothiophene
Alkyldibenzothiophene
Sulfur, ppm
800
600
400
200
0
C2-Thiophenes C3-,C4- Benzo-Thiophene
and Lighter Thiophenes
days and over one-quarter used the Figure 30
technologies for more than a year. Grace Davison's Portfolio of Gasoline Sulfur Reduction Products
Grace Davison currently has 25
gasoline sulfur reduction
applications worldwide.
Preferred Solution
Citgo Corpus Christi Technology Light & Intermediate
gasoline

® 10-35%
Citgo, Corpus Christi needed to D-PriSM reduction
reduce FCC gasoline sulfur to keep Light or ADDITIVE
their overall refinery gasoline pool in Intermediate
Gasoline
compliance. Citgo and Grace GSR ® -5 20-35%
Davison worked together to SuRCA® reduction
determine if catalytic sulfur Full Range
reduction technologies could Gasoline CATALYST TM
35%
NEPTUNE reduction
achieve the necessary reduction on or more

their 67,000 barrel per day UOP Light, Intermediate

High-Efficiency unit. The unit and Full range gasoline
processes 100% hydrotreated
vacuum gas oil and operates in full
combustion. After careful
evaluation of their unit operation
and objectives, and Citgo's
preference for an additive Figure 31
approach, GSR-5 additive was Normalized FCC Gasoline Sulfur for Citgo Corpus Christi
recommended. Citgo began
baseloading the product to achieve Base
1800
25% in the circulating inventory.
Gasoline Sulfur Normalized for Feed S

GSR-5
21% Reduction
Maintenance dosage was also at
the recommended level of 25% 1600
44% Reduction observed when
additions in place of normal GSR-5 & undercutting combined
1400
catalyst additions.

1200
Unit data, including feed quality, 31%
operating conditions, yields and Reduction
1000
yield quality was collected for eight
months that encompassed both the
base period, prior to additive 800

additions and the GSR-5 additive 600

period. Sulfur reduction on the
heavy gasoline stream is shown in 425˚F D86EP 445˚F D86EP

Figure 31. The data was normalized

for changes in feed sulfur and
endpoint. Sulfur reduction ranged Figure 32
from 21-31% depending on Gasoline Sulfur Reduction by Boiling Point
endpoint with an average reduction 1000
of 26%. Combining the effect of 900 Average Distillation ˚F GSR-5
undercutting with the GSR-5 T95 FBP Base
800
additive reduced gasoline sulfur by Base 414 456
44%. 700 GSR-5 413 460

600
To supplement the data generated A Thiophenes
500
by the refinery, FCC feed and heavy E B C2 Thiophenes
400 C C3Thiophenes
gasoline samples were collected by D C4Thiophenes
Citgo and sent to Grace Davison 300 E Benzothiophenes

both before and during the trial. 200

D
C
The samples were analyzed by Gas B
100
Chromatograph (GC) to determine A
the sulfur species present. 0
100 150 200 250 300 350 400 450 500 550
Sulfur Compound Boiling Point (˚F)

Catalagram 101 Spring 2007 19

 Table VII
The performance of the GSR-5 Commercial Users of GSR-5 Additive Technology
additive on individual sulfur species
is shown in Figure 32. Both sets of Feed S, wt.%
Unit % Sulfur Days
samples were normalized to account Refiner Region Type Reduction Used Min Max Avg
for variation in feed sulfur. The base
A* NA UOP HIGH EFF 26 382 0.2 0.5 0.3
line is steeper at the points A through
E than the GSR-5 additive line B* NA TEXACO DESIGN 23 398 0.2 0.4 0.3
illustrating the performance across C* NA UOP HIGH EFF 23 368 0.3 0.5 0.3
the entire range of sulfur species
present in the heavy gasoline. Total D* NA UOP SBS 15 96 0.8 1.6 1.4
gasoline sulfur reduction as E* NA UOP MOD V 29 231 0.2 0.4 0.3
measured by speciation is 30%. F* NA EXXON FLEXI 50 196 0.4 1.2 0.8
There were no adverse yield shifts
with the GSR-5 additive when G* NA EXXON FLEXI 8 196 0.9 2.3 1.3
incorporated into Citgo's operation at
25% of the unit inventory. The
product was baseloaded into the unit
allowing for quick results. This is
achievable because the GSR-5 Summary
additive contains catalytic cracking
functionality, which for Citgo resulted Gasoline sulfur regulations are
in a conversion increase of 0.7 lv% becoming increasingly stringent
and slurry decrease of 0.5 lv%. worldwide. Since the FCC unit is such a
large contributor of sulfur to the gasoline
Citgo will use the GSR-5 additive for pool, effective means of reducing FCC
about a year to help cost effectively gasoline sulfur can significantly improve
meet pool gasoline sulfur limits until refinery profitability and flexibility.
alternative technologies can be Catalysts and additives for FCC gasoline
commissioned. Then they will sulfur reduction have been commercially
evaluate using GSR-5 on a long- proven in 85 units worldwide.
term basis in conjunction with the Understanding the pathways of FCC
hardware that is installed. gasoline sulfur formation as well as the
species present is crucial in selecting
Citgo's experience with GSR-5 the most appropriate technology. Proper
additive technology is representative application leads to successful results
of other commercial applications. like those achieved at Citgo's Corpus
Table VII contains a list of refiners Christi refinery.
that have employed the product.
With this additive, refiners can take
advantage of FCC gasoline sulfur
reduction on either a short or a long-
term opportunity basis. Because the
product is an additive, the application
is independent of the base catalyst
technology used by the refiner.

20 www.e-catalysts.com
 Grace Davison:
Your proven FCCU emissions solution.
Grace Davison environmental technologies
have helped refiners reduce FCCU emissions
for over a quarter of a century.

The FCCU is often the largest point source within the refinery for SOx
and NOx emissions. The use of innovative catalytic technologies
reduces emissions from the FCCU regenerator, without the need for
capital intensive “end-of-pipe” hardware solutions.

Super DESOX® provides industry leading SOx removal

effectiveness. More and more refiners are finding that Super DESOX
can cost effectively control SOx emissions below 25 vppm from a
wide range of uncontrolled SOx baseline emissions.

Grace Davison researchers have studied the complex

formation of NOx and developed two additives to reduce NOx.
XNOx® is a low NOx combustion promoter designed to
replace conventional promoters, which often cause
increased NOx formation. For units not using a promoter,
or requiring additional NOx reduction, DENOX® is the
additive of choice. NOx reductions in excess of 50%
have been observed commercially with both products.
With more than 50 commercial applications of NOx
additives, Davison has more experience than the rest
of the industry combined and would be happy to
assist you in reducing FCCU NOx emissions.

Extensive customer-driven research efforts at Grace are providing new insights into improving
SOx and NOx removal. Want to find out more about our environmental technologies?
Contact us at www.e-catalysts.com or call us at (410) 531-8226.
Let Grace Davison help you meet your FCCU emission challenges.
 Your Clean Fuels Solutions
When it comes to commercially proven technology to meet increasingly stringent
Clean Fuels regulations, make Grace Davison and Advanced Refining Technologies
your one-stop shop for FCC catalysts, additives and hydroprocessing catalysts.

For gasoline sulfur reduction, today's refiners are challenged more

than ever before to blend various refinery streams to meet stringent
product specifications and government regulations for clean air.
Proven in over 75 commercial units, Grace Davison's portfolio of
FCC gasoline sulfur reduction technologies includes the D-PriSM®
and GSR®-5 additives and the SuRCA®, SATURN® and
Neptune™ catalyst families.

>Recently commercialized, NEPTUNE catalyst further expands

our sulfur reduction technologies to continuously improve both
performance and cost effectiveness. This next generation
technology is a step out improvement over earlier technologies,
providing 35-50% full range gasoline sulfur reduction
commercially with full catalyst formulation flexibility.

>For refiners with FCC pretreaters, the ApART Catalyst System™

utilizing combinations of ART AT575, AT775 and AT792 offers the
opportunity to significantly increase sulfur removal in the
hydrotreater while at the same time maximizing FCC feed quality. The
improved performance of the pretreater results in higher gasoline
potential in addition to decreasing FCC gasoline sulfur.

>For ULSD processing, the SmART Catalyst System™ utilizes

state-of-the-art catalyst technology which is staged in the proper
proportions to provide the best performance, while at the same
time meeting individual refiner requirements. The catalyst staging
is designed to selectively take advantage of the different reaction
mechanisms for sulfur removal with efficient hydrogen usage.
ART CDXi, our newest generation of high activity CoMo catalyst,
efficiently removes the unhindered, easy sulfur via the direct
abstraction route, while ART NDXi, our high activity NiMo
catalyst, then attacks the remaining sterically hindered, hard
sulfur. The SmART system provides higher activity than either the
traditional CoMo or NiMo catalyst alone while effectively helping
the refiner manage hydrogen utilization.

Have questions about our clean fuels technology?

Contact us at www.e-catalysts.com or call us at (410) 531-8226.
Let Grace Davison and Advanced Refining Technologies
give you the custom catalytic solution to your clean fuels challenges.
22 www.e-catalysts.com
 Clean Fuels:
An Opportunity for Profitability Using
Gasoline Sulfur Reduction Technology
Introduction
n most refineries, FCC gasoline
Lauren Blanchard
Strategic Business
Marketing Manager,
I is one of the largest, if not the
largest contributor of sulfur to
the overall gasoline pool. Regulations
Advanced Refining limiting the amount of sulfur in gasoline
Technologies, have highlighted the importance of
reducing sulfur in the FCC gasoline
Columbia, MD
stream. Grace Davison has been
providing catalysts and additives to the
Craig Borchert industry that reduce FCC gasoline
sulfur by 35% or more, for over ten
Valero Energy,
years. These technologies have been
Wilmington, CA proven in 80 units worldwide. Another
popular alternative to reduce gasoline
sulfur is the installation of hardware.
Min Pu Increasingly stringent regulations have
Valero Energy, forced refiners to install FCC feed
Wilmington, CA hydrotreaters and gasoline post-
treaters to meet ultra-low sulfur gasoline
regulations. Interestingly, the phase-in
of hardware has not eliminated the
benefit of sulfur reducing catalysts and
additives. Grace Davison's gasoline
sulfur reduction technologies are
complementary to hardware solutions.
They are being used at numerous
refineries around the world in
conjunction with hardware to drive
refinery profitability by providing
feedstock flexibility, minimizing octane
loss and providing operational
flexibility during hydrotreater outages.
Proper management of FCC feed
hydrotreater outages is becoming
increasingly important as more and
more refiners rely on hydrotreating
to meet their per-gallon gasoline
sulfur limits. About half of all FCC
units now have feed hydrotreaters.
Some are run at higher severity than
in the past to achieve these new
ultra-low gasoline sulfur targets.
Running at higher severity increases
the frequency of turnarounds.
Conventional methods of ensuring
that the gasoline pool stays below
Catalagram 101 Spring 2007 23
 Figure 33
Grace Davison's Portfolio of Gasoline Sulfur Reduction Products
Preferred
Technology
Light or ADDITIVE
Intermediate
Gasoline
Full Range
Gasoline CATALYST
the sulfur limit during the
hydrotreater turnaround are
purchasing low sulfur feed or
reducing FCC throughput. Either
approach can significantly reduce
refinery profitability. Another option
is to use one of Grace Davison's
sulfur reducing technologies during
the outage to provide feedstock
flexibility while maintaining sulfur
compliance.
This paper presents a case study in
which Grace Davison and Valero
Energy’s, Wilmington, California, USA
refinery worked closely together to
minimize the impact of a FCC feed
hydrotreater outage. Significant
planning and preparation took place,
including selecting the best
purchased feeds to run during the
outage as well as the best sulfur
reduction technology to use to meet
their objectives given the sulfur
species in the FCC gasoline. The use
of Grace Davison's GSR®-5 sulfur
reduction additive allowed Valero to
process feed that was higher in sulfur
than their routine feed yet remain in
gasoline pool sulfur compliance.
Valero estimates that the use of GSR-
5 additive saved them $1.7 million
during the hydrotreater outage. The
results were so encouraging that
Valero has elected to use GSR-5
additive on an on-going basis and
24 www.e-catalysts.com
technologies that evolved from over
14 years of continuous R&D include
D-PriSM® additive, SuRCA® catalyst,
GSR-5 additive, and NeptuneTM
catalyst.
Solution
Light & Intermediate A road map for product selection is
gasoline
shown in Figure 33. When
D-PriSM
® 10-35%
formulating a solution for a
reduction
customer, Grace Davison experts
consider the FCC gasoline stream
targeted for sulfur reduction, the
GSR ® -5 20-35% desired level of gasoline sulfur
SuRCA® reduction
reduction, and whether a catalyst or
an additive is preferred. Careful
35% selection of the appropriately
TM
Neptune reduction
or more
engineered solution for each
application has resulted in
Light, Intermediate consistent product performance
and Full range gasoline
and meeting or exceeding customer
expectations. Twenty-three refiners
are currently using Grace Davison
estimates increased profits of over $8 gasoline sulfur reduction products
million annually. worldwide, making Grace Davison
the leading supplier of gasoline
Evolution of Sulfur Reduction sulfur reduction catalysts and
Technologies additives. Many of these refiners
have been using these products on
In 1992, well before the industry a continuous basis as part of their
realized the need to reduce FCC overall sulfur reduction strategy.
gasoline sulfur, Grace Davison (Figure 34).
anticipated this requirement and
began a research and development For refiners who desire FCC
effort for catalytic reduction of FCC additives for maximum operating
gasoline sulfur. The objective was to flexibility, Grace Davison's D-PriSM
develop a family of FCC catalysts and additive is effective at reducing
additives to help refiners meet clean sulfur species in light and
fuels specifications. Established intermediate FCC gasoline. It has
Figure 34
Grace Davison Experience in Sulfur Reduction Applications
TIME
Average Length for
Length of
Applications all 85 Sulfur Reduction 388
Days
Applications Worldwide
Longest Application 5.9
(ongoing) Years
>365
days 27
>100 days 51
0 10 20 30 40 50 60
# of Applications
85 Total Applications WW to Date => 25 Current Users
been used in more than 25 Figure 35
refineries worldwide. D-PriSM Feed Distillation Profile
additive has provided up to 35% 1200
sulfur reduction on light FCC Routine Feed
gasoline with no FCC yield 1100 Sample A

deterioration. Sample B
1000
Sample C

Grace Davison's SuRCA catalyst
family is designed to completely
replace the conventional FCC
catalyst in the circulating inventory.
This product provides gasoline
sulfur reduction of up to 35% on full
range gasoline while maintaining or
even enhancing existing yields and
selectivities. Additionally, reductions
of 10-15% in LCO sulfur have been
observed in some applications.
Over 45 SuRCA catalyst ap-
plications have occurred worldwide,
with 10 current users having
employed the technology for an
average of more than three years.
These refiners have incorporated
SuRCA catalyst into their operating
strategies for long-term profitability
and operating flexibility.
Appreciating refiners’ desire for a
product that provides the
performance of SuRCA catalyst but
can be used as an additive for
maximum operating flexibility, Grace
Davison commercialized the GSR-5
additive in 2004. It is based on the
SuRCA catalyst chemistry and
provides similar gasoline sulfur
reduction with base cracking
catalyst functionality. There are
currently five refiners benefiting
from the use of GSR-5 additive.
Figure 36
Feed Properties
60 Routine Feed
Sample A
55
Sample B
50 Sample C
45
40
35
30
25
20
15
10
°API Aromatic Carbons,
Ca (wt.%)
Boiling Pt (°F)
900
800
700
600
500
400
300
0 10 20
To further expand the sulfur reduction
portfolio for continuous improvements
in both performance and cost
effectiveness, Grace Davison has
recently commercialized a new
gasoline sulfur reduction catalyst
family. This next generation
technology, Neptune, is a step out
improvement, providing 35-50% full
range gasoline sulfur reduction
commercially with full catalyst
formulation flexibility.
Pre Turnaround Preparation
The Valero, Wilmington refinery
approached Grace Davison four
months prior to their scheduled FCC
feed hydrotreater shutdown to help
them get a better understanding of
their options during the outage. Valero
Napthenic Paraffinic Carbons,
Carbons, Cn (wt.%) Cp (wt.%)
30 40 50 60 70 80 90 100
Percentage
and Grace Davison worked together
to determine if the use of a gasoline
sulfur reducing technology would
enable Valero to improve their
economics and remain within their
FCC gasoline sulfur limit during the
shutdown.
During the outage, the refinery
planned to purchase several
hydrotreated feeds. These would
be different than the pretreated feed
normally charged to the FCC unit.
The refinery planned to blend
purchased feeds with their routine
feed. The candidate feeds were
sent to Grace Davison for testing to
compare the potential effects of the
feeds on the refinery's FCC yields
and gasoline sulfur.
Analysis of the candidate feeds and
Valero, Wilmington's pretreated
Routine Feed is shown in Figures
35-37. Candidate feeds (Samples
A, B, and C) were heavier and more
aromatic than the Valero Wilmington
Routine Feed (Figure 36) making
them more difficult to crack (Figure
3). Additionally, the three sample
feeds contained significantly more
sulfur and nitrogen species, while
concarbon levels were similar to the
Routine Feed (Figure 37).
The four feeds were tested using a
representative Valero, Wilmington
equilibrium catalyst (Ecat) sample in
the pilot plant. The results

Catalagram 101 Spring 2007 25

 Figure 37 suggested that all of the candidate
Feed Properties feeds would suppress conversion
by at least 4 wt.% (Figure 38). Yields
0.25 interpolated at constant coke are
Routine Feed shown in Table VIII. All feeds
Sample A
showed the potential for increased
0.20 Sample B
Sample C
LCO and bottoms. These feeds also
yielded significantly less gasoline
0.15 with slightly lower octane.

0.10 In addition to shifting yields toward

less favorable products, the feeds
0.05 also increased gasoline sulfur.
Samples B and C increased sulfur
by 200%, while Sample A more than
0.00
Sulfur (wt.%) Basic Nitrogen Total Nitrogen Conradson tripled FCC gasoline sulfur relative
(wt.%) (wt.%) Carbon (wt.%) to the Routine Feed (Figure 39).

The gasoline sulfur concentration

Table VIII for the Routine Feed produced in
Interpolation at Constant Coke (3 wt.%) the pilot plant is significantly lower
than what is sent to blending from
the Wilmington FCC unit. A number
of “tramp” gasoline streams
generated at other process units
are currently processed in the FCC
gas plant. These streams elevate
the apparent “FCC gasoline sulfur”
as it is received in blending.

To help align the estimated FCC

gasoline sulfur that would result
from processing the candidate
feeds with predicted commercial
performance, the gasoline sulfur
species produced in the pilot plant
using the Routine Feed were
compared to the commercially
produced gasoline samples. The
commercial gasoline samples were
produced in the Valero Wilmington
FCC unit while processing two
different feeds (Figure 8). There is
good agreement for both individual
Figure 38
sulfur species, and the relative
Feed Study Conversion vs. Coke amount of each species present
84 when comparing the two sets of
82 samples. Therefore, we can
80 reasonably replicate the sulfur
Conversion (wt.%)

78 distribution of the commercially

76 produced gasolines in the pilot
74 plant. Cut gasoline sulfur is the sum
72 of the species (mercaptans through
70 Routine Feed C4 thiophenes) and is higher for the
68
Sample A commercially produced gasoline,
Sample B
66
suggesting the presence of
Sample C
additional sulfur from the “tramp”
64
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
streams.
Coke (wt.% Feed)

26 www.e-catalysts.com
 Figure 39
Another potential reason for Total Gasoline Sulfur vs. Coke
differences between the pilot plant 70
generated gasoline sulfur and that

Total Gasoline Sulfur (ppm)

produced commercially is the 60
method used to measure the sulfur
50
concentration. Refiners typically
measure gasoline sulfur by the bulk 40
x-ray gasoline sulfur method. The
30
measurement of gasoline sulfur
Routine Feed
produced in the pilot plant utilizes a 20
Sample A
gas chromatograph to identify the Sample B
10
individual sulfur species and total Sample C
sulfur concentration. 0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Sulfur species in the gasolines Coke (wt.% Feed)
produced by the candidate feeds
were compared to species present
in gasoline generated by the
Routine Feed. The candidate feeds
all produced the same gasoline Figure 40
species as the gasoline generated Comparison of Commercially Produced and Pilot Plant Gasolines
from the Routine Feed except in 16

higher concentrations (Figure 41).

1 - FCC Commercial Sample Includes Tramp Streams
2 - FCC Commercial Sample
Gasoline samples for each 12
1 - Pilot Plant
candidate feed in Figure 41 were 2 - Pilot Plant
Sulfur (ppm)

normalized to account for the delta

between FCC-produced and pilot 8

plant-produced methods (from

Figure 40). Additionally, data was
normalized to an x-ray basis to 4

reflect the levels of sulfur that would

be observed on the FCC unit.
Finally, gasoline sulfur for each 0
s

es

es

es

r
candidate feed was adjusted to
ol
s

l
an

lfu
en

no
ne

en

en
en

en

en
pt

ph

Su
he
he

ph

ph
ph

ph

ph
ca

io

op
op

io

e
io
io

io

io
maintain the same gasoline sulfur to
er

Th

in
Th

hi
Th
hi

Th

Th

Th
M

ol
lT
lT

ro

2-

3-

4-

as
hy
hy

yd

G
et

feed sulfur ratio observed on the

et

ah

ut
M
M

tr

C
Te

Wilmington FCC unit - resulting in

the data in Figure 42.

The results from the pilot plant Figure 41

study, along with information on the Pilot Plant Produced Gasolines
Valero, Wilmington FCC unit 40
operation (both routine and during a
35 Routine Feed
previous pretreater outage) were
Sample A
then used by Grace Davison to 30
Sample B
evaluate the performance of various 25 Sample C
Sulfur (ppm)

gasoline sulfur reduction

20
technology options. The GSR-5
additive, which contains base 15

cracking functionality, was 10

determined to be the best solution.
Based on the normalized species in 5

the gasoline produced by Samples 0

A through C, Grace Davison

r
e
s

es

es

es
l
e

ol

lfu
no
en
an

ne
en

en
en

en

en

Su
he
ph
he
pt

ph

ph
ph

ph

ph
ca

op
op

io

estimated that the GSR-5 additive

io

e
io
io

io

io

in
Th
er

Th

hi
hi

Th
Th

Th

Th

ol
M

lT
lT

ro

as
2-

3-

4-
hy
hy

yd

would reduce gasoline sulfur by 19-

C

G
et
et

ah

ut
M
M

tr

C
Te

Catalagram 101 Spring 2007 27

23%. This narrow range reflects Figure 42
extensive understanding of the Normalized Pilot Plant Produced Gasolines
customer's operation and the up-
70
front pilot plant work.
Routine Feed
60
Sample A
The Valero, Wilmington refinery pool Sample B
gasoline sulfur limit is 30 ppm. The 50
Sample C

refinery also must produce gasoline

Sulfur (ppm)
40
below California NOx emissions
limits, which are influenced heavily 30

by the sulfur and olefins content of

20
the gasoline streams blended into
the pool. The results of the pilot 10
plant testing confirmed that the
refinery would need to store Routine 0

Feed to blend with candidate feeds

es

es

es
s
e

r
s

l
ol
ne

no

lfu
en

ne
an

en
en

en

en
he

he

Su
ph

he
pt

ph
ph

ph

ph
op
ca

op
op
io

e
io
io

io

io
i

in
Th
er

hi
Th
hi

Th
during the pretreater outage to keep

Th

Th

Th

ol
M

lT
lT

ro

as
2-

3-

4-
hy
hy

yd

G
et
et

ah

ut
M
M
FCC feed sulfur levels low enough

tr

C
Te
to remain below their limits. Based the FCC gasoline prior to the inclusion depicts a year's worth of
on the pilot plant results, Valero of the “tramp” streams. The presence normalized gasoline data vs
concluded that Feed A was too risky of these streams in the gasoline endpoint. The three periods
in both gasoline sulfur and FCC samples used to evaluate GSR-5 represented are typical operation
yields/selectivities. The decision additive performance reduces the (Base Period), GSR-5 additive
was made to purchase the other apparent performance by reducing before and during the outage, and
feeds and blend them at various the calculated percentage sulfur finally GSR-5 additive following the
ratios with available Routine Feed reduction. outage. Throughout the outage,
during the outage. Valero remained within their FCC
Valero began use of GSR-5 additive gasoline sulfur limits while
GSR-5 Additive Application two months prior to the 45-day feed processing all candidate feeds.
hydrotreater outage. Coordinated After the outage, continued addition
As is common in many refineries, efforts with Grace Davison allowed of GSR-5 additive allowed them to
the FCC gas plant at Valero's Valero to receive material and run 10-15% higher feed sulfur.
Wilmington facility processes baseload their inventory in 14 days. A
streams from outside the FCC unit. blend of the candidate feeds along Economics
These streams contain sulfur that is with the Routine Feed was fed to the
not affected by the GSR-5 additive FCC prior to the outage, which The candidate feeds also increased
since the additive works by increased feed sulfur by 20-35%. the FCC gasoline olefins content,
participating in the cracking Additive additions proceeded which combined with the increase
reactions that take place in the FCC smoothly and the projected in the projected gasoline sulfur
unit. Unfortunately, the Wilmington performance was exceeded in less would have forced Valero to
refinery sampling configuration than 30 days with gasoline sulfur hydrotreat approximately five MBPD
does not allow for direct sampling of reduction of 20-25%. Figure 43 of FCC gasoline to comply with
California NOx emission
Figure 43 specifications. The loss of octane
Normalized FCC Gasoline Sulfur vs. T95 from hydrotreating the FCC gasoline
Base Period (Days 1-71) would have reduced the amount of
GSR-5 & Outage (Days 90-115) low octane streams, such as Light
550
GSR-5 After Outage (Days 116-375) Straight Run (LSR) and Heavy Cat
Gasoline Sulfur / Feed Sulfur (ppm/wt%)

GSR-5 provides 20-25%

500 reduction Naphtha (HCN), that could be
blended into the pool. The sulfur
450
reduction provided by the GSR-5
400 additive allowed Valero to avoid
hydrotreating the five MBPD FCC
350
gasoline stream, the value of which
300 was calculated to be $0.25/BBL or
$1.7 million over the three month
250
period surrounding the outage.
200
310 315 320 325 330 335
D86 T95 (°F)

28 www.e-catalysts.com
After the pretreater was back on-
line, Valero evaluated the
economics of continued GSR-5
additive usage. They determined
that by continuing to use it, they
could consistently feed high sulfur
VGO to their FCC feed hydrotreater
instead of medium sulfur VGO and
remain under the refinery pool
gasoline sulfur limit of 30 ppm.
Valero estimates the incremental
profit for processing high sulfur
VGO is $4.4 million per year (using
a conservative 3 cents per gallon
differential between high and
medium sulfur VGO). Accounting
for the cost of the GSR-5 additive
and incremental SOx additive
required to remain in SOx emission
compliance (higher FCC feed sulfur
yields higher SOx emissions) the
net profit is $3.8 million.
The Wilmington refinery targets a
two-year cycle on the FCC feed
hydrotreater. The cycle length is
determined by the catalyst activity,
which is influenced by operating
severity and throughput. Valero
determined that by using the GSR-5
additive to control FCC gasoline
sulfur, they could reduce
hydrotreater severity (even with
higher sulfur VGO feed to the
hydrotreater), which allowed them
to process more VGO through the
unit. Valero was able to increase
hydrotreater throughput by 4%. The
excess hydrotreated FCC feed is
periodically sold at a premium over
regular gasoil (using a seven cents
per gallon differential between
hydrotreated and regular gasoil) for
an estimated annual profit of $4.5
million.
The total benefit from the GSR-5
additive for the Wilmington refinery
is calculated to be $8.3 million per
year - a return of over 18 times the
incremental cost of the GSR
additive technology.
The refinery has also determined
that managing the tramp gasoline
streams using a different process,
rather than processing them in the
FCC gas plant, will allow them to
achieve significant flexibility in their
gasoline pool blending operation.
They plan to revamp an existing tower
into an LSR splitter, which will remove
C3's and C4's before sending gasoline
material directly to blending. The
operation of the FCC unit is expected
to shift in favor of more light olefins
with the new equipment in service.
The impact of the change in FCC
operation on FCC gasoline sulfur and
olefins will be evaluated to determine
if GSR-5 economics remain favorable
with the new process configuration.
Conclusion
Proper management of hydrotreater
outages is becoming increasingly
important as more and more refiners
rely on hydrotreating to meet gasoline
sulfur limits. Outages of either FCC
feed hydrotreaters or gasoline post-
hydrotreaters create opportunities for
refiners to incorporate Grace
Davison's sulfur reduction catalysts
and additives into their planning. This
would allow for significant savings in
purchased feeds or mitigation of the
cost of constraints caused by non-
routine operation leading up to and
during the outage. With hydrotreating
equipment in service, these
technologies can generate significant
revenue for refiners who want to
optimize operations to drive
profitability. Reduction of FCC
gasoline sulfur allows for higher feed
sulfur to the FCC unit or to an
upstream FCC feed hydrotreating unit
without risking gasoline sulfur non-
compliance. Lower FCC gasoline
sulfur can also allow for reduced
severity operation on either the FCC
feed hydrotreater or the gasoline
treating units, creating revenue in the
form of octane recovery, higher
throughput, or extended cycle life.
The Valero, Wilmington case study
presented here was made possible by
incorporating discussions between
Valero & Grace Davison into the
planning stages of the FCC feed
hydrotreater outage. Based on those
discussions, pilot plant testing was
completed which assisted Valero in
selecting the purchased feeds they
would run during the outage.
Estimates provided by Grace Davison
showed that the GSR-5 additive
would allow Valero to achieve their
shutdown objective of keeping their
gasoline sulfur in compliance while
running the higher sulfur purchased
feeds. The use of GSR-5 additive
during the outage resulted in $1.7
million in savings.
With the proven product
performance of the GSR-5 additive,
Valero was then able to optimize
their operation once the FCC feed
hydrotreater was put back in
service. The FCC feed hydrotreater
unit severity was reduced, allowing
for higher throughput, and the
incremental hydrotreated gasoil
was sold at a premium over regular
gasoil. Additionally, Valero was also
able to feed high sulfur VGO in
place of medium sulfur VGO to the
FCC feed hydrotreater without
exceeding the FCC gasoline sulfur
limits. Both operating changes
resulted in a combined profit of over
$8 million per year for the refinery.
While each refinery configuration is
unique, and the economics
presented here are specific to the
Valero Wilmington refinery, this
example demonstrates that Grace
Davison's gasoline sulfur reduction
products can provide enhanced
operating flexibility in any operation
and significantly improve refinery
profitability.
Acknowledgements: The authors wish to
thank Valero Petroleum Company and Grace
Davison for permission to release this
information. Natalie Petti (consultant), is
gratefully acknowledged for her contribution
of data evaluation and critique.
Catalagram 101 Spring 2007 29
Understanding and Minimizing FCC Slurry
Exchanger Fouling
Figure 44
Typical Main Fractionator Slurry Circuit
lurry exchanger fouling is often
David A. Hunt
S considered the worst fouling
service in the FCC process. (1)
The primary problem that results from
slurry exchanger fouling is reduced
Technical Service Manager, heat exchanger duty in the slurry/FCC
Grace Davison, feed preheat exchanger or the steam
Houston, TX generators. The reduction in feed
preheat temperature that can result
from just mild fouling of the FCC
Bill Minyard slurry/feedstock exchangers can
National Technical Sales result in reduced unit feed rate or
Manager, Grace Davison, conversion.* Additionally, excessive
Houston, TX pressure drop or inability to cool the
slurry to the necessary rundown
temperature can also require
Jeff Koebel reducing the feed rate. Certainly
Technical Service Manager, excessive slurry exchanger fouling
can be very costly to the refinery in
Grace Davison, terms of lost feed rate, lower
Chicago, IL conversion and higher maintenance
expenses.
The purpose of this article is to
present potential sources of slurry
exchanger fouling and suggestions on
how to prevent or minimize fouling. We
30 www.e-catalysts.com
will draw on industry experience from
several sources to present a broad
review of the subject. Our readers
may consider this information and
case study experience as they work to
understand and minimize slurry
exchanger fouling at their refinery.
Figure 44 illustrates a typical FCC
Main Fractionator Slurry circuit.
Superheated FCC product vapor is
quenched as it enters the main
fractionator using the reflux from the
slurry pumparound circuit. Slurry
exchangers, which recover this
energy by heating the feedstock
and generating steam, are often
subject to fouling through a number
of mechanisms. When slurry
exchangers foul, feed rate or
reactor temperature must often be
reduced.
*For those FCC units that do not have
a fired feed heater and are air blower
limited.
Figure 45 shows how quickly a Figure 45
slurry/feed exchanger heat transfer FCC Slurry Exchanger Heat Transfer Coefficient Deterioration
coefficient can deteriorate. Over a
ten-week period, this refiner needed 45
Exchanger Exchanger Exchanger
to clean their FCC slurry exchanger Cleaned Cleaned Cleaned

Heat Transfer Coefficient, BTU/hr - ft2 - F

three times. During each cleaning 40
cycle they were forced to
significantly reduce feed rate.
35

Potential causes of FCC slurry

exchanger fouling are shown in 30
Figure 46. Fouling can be generally
classified as either “organic” or
“inorganic” based. Several organic 25
or inorganic slurry fouling
mechanisms are possible. Each of 20
these possible fouling sources will
be discussed and suggestions to
prevent or reduce each type will be 15
6/1 7/21 9/9 10/29 12/18 2/6
presented.

ORGANIC BASED FOULING

Organic based fouling is the most Figure 46

common fouling type. The potential Root Causes of Slurry Exchanger Fouling
causes of organic based fouling
are very broad. It is helpful to Slurry
classify organic fouling into two Exchanger
general sub-types: “hard” and “soft” Fouling

coke fouling.
Inorganic Organic
Hard Coke Fouling

Solid coke fragments circulating to

Catalyst
the slurry exchanger tubes that Corrosion
Metals Particulates
Coke Precipitated
Products Deposits Asphaltenes
restrict the flow through the Al & Si
exchanger is an example of hard
coke fouling. This type of fouling
results in excessive pressure drop Polymerization

and a loss of heat transfer duty.

These shiny coke fragments
generally accumulate on the
exchanger tube sheets at the inlet to
the tubes. Figure 47 shows how
Figure 47
pieces of coke can block the
exchanger tubes, increasing Hard Coke Deposits
exchanger pressure drop.

These coke fragments can originate

in the reactor overhead line or the
main fractionator. The coke often
becomes dislodged following an
FCC shutdown because of the
thermal cycling of the surface that
the coke is adhered to. If the coke
fragments are small enough to pass
through the suction strainers on the
slurry pumparound pumps, they Photo Courtesy of:
Photo Courtesy of: GE Water and Process Technologies
GE Water and Process Technologies

Catalagram 101 Spring 2007 31

can eventually foul the first slurry
exchanger in the pumparound loop.
Another scenario that can result is
excessive hard coke accumulation
in the bottom head of the main
column that restricts the suction of
the circulating slurry pumps.
Smaller coke fragments that pass
through the exchanger tubes can
still be problematic. These coke
particles are either smaller coke
particles from the main fractionator
or are formed by polymerization
reactions in the slurry pumparound
circuit at high main fractionator
bottoms temperatures. Small coke
fragments can settle onto the tube
surface and further polymerize,
resulting in a barrier to heat transfer
and slurry flow.
In some cases, formation of a very
thin, hard layer of deposit has been
observed on the tube walls. This
type of deposit has a hard, shiny
appearance similar to varnish.
These deposits are formed by
polymerization reactions on the
tube surface. This type of fouling
can reduce the heat transfer
coefficient.
Preventing Hard Coke Fouling
Poor feed/catalyst contacting can
be a significant source of hard coke
formation in the vapor line. This is
particularly true in units that
process resid feeds. Feed /catalyst
contacting can be improved in
several ways:
• Improve feed atomization;
• Increase feed dispersion
steam within the limits of the
feed distributor design;
• Repair damaged feed
distributors or replace with a
more modern design;
• Increase the feed temperature
to avoid high feed viscosity at
the injection distributors. This
is particularly applicable to
resid operations.
32 www.e-catalysts.com
Figure 48
Slurry Quench and Coke Trap in the slurry circuit
Quench
Coke
Trap
• Increase the catalyst/oil mix
zone temperature. This is
most critical in resid or low
reactor temperature
operations where incomplete
vaporization of the feed is more
likely. Mix zone temperature
can be increased using Mix
Zone Temperature Control
(MTC) (2) and/or higher reactor
and regenerator temperatures;
• Optimal catalyst matrix design
can improve feedstock
vaporization. (3)
A hot wall reactor vapor line must be
properly insulated to reduce the
likelihood of liquid condensation at
cool spots. Insulation must be
properly anchored and should be
watertight. Once oil droplets form,
they eventually dehydrogenate to form
coke. The reactor vapor line blind
flange and all the vapor line pipe
supports should also be insulated if
the designs allow, as coke can
accumulate at these locations. Do not
insulate the bolts of the blind flange,
however, as this can result in the
flange opening due to bolt creep.
Reactor vapor line vapor velocities
less than 100 fps should be avoided to
minimize coke formation. The
exception to this is the velocity right at
the inlet nozzle to the main column,
where lower velocities are permitted.(4)
Higher velocities will reduce the
likelihood of un-vaporized oil
accumulating along the wall of the
vapor line and eventually forming
coke. Vapor line velocities between
100 to 120 fps are a good
compromise to minimize both coke
formation and pressure drop. (4)
Self-draining reactor overhead lines
are a design feature often used to
minimize coke formation and
subsequent slurry exchanger
fouling.
The maximum main fractionator
bottoms temperature is typically
between 680˚F and 700˚F to avoid
coke formation and slurry
exchanger fouling. The maximum
safe bottoms temperature for any
unit is unit and feedstock specific. It
is also important to note that the
bottoms temperature is often based
a single temperature indicator (TI)
at the outlet line of the main
fractionator. Poor pumparound
distribution and liquid mixing may
result in locally hotter temperatures
than what is actually measured in
the bottoms outlet line, increasing
the likelihood of coking. This can
be particularly true in operations
where quench is used to cool the
bottom of the main column.
Long liquid residence time in the
slurry circuit will also influence
coking. Reducing bottoms liquid
level can minimize slurry residence
time. Also note that increasing main
fractionator bottoms temperature
 Figure 49
Soft Coke Precipitation Fouling
5
and slurry pumparound rate both
increase the liquid residence time.(5)
FCC feedstock, particularly feed
containing resid, can form coke at
typical main fractionator bottom
temperatures. As a result, refiners
should ensure that no feedstock is
leaking into the slurry pumparound
circuit through an emergency feed
by-pass valve or slurry/feed
exchanger.(5)
The slurry pumparound return
should be properly distributed to
minimize hot spots. The
pumparound rate should be
sufficient to ensure the grid zone is
well wetted. Local areas devoid of
liquid flow will allow hard coke to
form. A minimum flux rate of 6
gpm/ft2 has been recommended.(6)
A slurry pumparound rate of 1.2 to
1.5 times the feed rate is a rule of
thumb that has also been
suggested to ensure good liquid
distribution in the bottom of the
main fractionator.(7)
Slurry quench, as shown in Figure
48, can be used to sub-cool the
main fractionator bottoms
temperature and reduce hard coke
formulation.(6) A quench distributor
should be used to minimize hot
spots. Slurry quench, however, is
commonly injected from a nozzle
that terminates near the wall of the
fractionator. As a result, the
returning quench liquid is often not
well distributed. Therefore, do not
rely on perfect mixing of the slurry
Photo Courtesy of:
GE Water and Process Technologies
quench, as zones of high temperature
could still be present. The refiner may
consider monitoring bottoms
temperature on a quench-free basis to
account for potential high temperature
zones.(6)
Maintaining slurry exchanger tube
velocities greater than 6 fps will help
minimize any settling of small coke
fragments or FCC catalyst onto the
tube service.(8) Units often have
spillback valves on the slurry product
exchangers to help maintain minimum
slurry flows during times of turndown
operation. Tube velocities should be
less than 10 fps to avoid erosion.(8)
Using an elevated slurry exit nozzle
can reduce the likelihood of coke
being entrained into the slurry
pumparound loop.(8) However, this
results in the bottom head of the main
column filling with accumulated coke
Figure 50
Soft Coke Precipitation Fouling
and catalyst. On units where the
liquid draw is on the bottom head, a
coke trap should be employed in
the bottoms suction nozzle on the
column and/or upstream of the
slurry exchanger as shown in Figure
48 to trap any entrained coke
particles before they can foul the
exchanger. G. Walker discussed
application of a coke trap and
resulting reduction in slurry
exchanger fouling.(9)
Soft Coke Fouling
Soft coke fouling is organically
based where commonly an
insulating barrier is deposited
inside the exchanger tubes,
reducing the exchanger heat
transfer coefficient. The insulating
barrier can be found throughout the
tube service.(10) Figures 49 and 50
show examples of soft coke fouling.
Just a thin layer of material can
result in a costly reduction of the
exchanger heat transfer coefficient.
In some cases, soft coke fouling can
also result in increased exchanger
pressure drop.(10) Generally,
however, reduced heat transfer is
apparent before excessive pressure
drop with this type of fouling.
Precipitated asphaltenes are a
common source of soft coke
fouling. Asphaltenes are highly
condensed polyaromatics typically
insoluble in a saturated
hydrocarbon such as heptane.(11)
The concentration of these multi-
ring aromatics in the slurry can be
Photo Courtesy of:
GE Water and Process Technologies
Catalagram 101 Spring 2007 33
 Figure 51
Catalyst and Coke Interaction with Precipitated Asphaltenes
Slurry
Exchanger
Fouling
Inorganic
Catalyst
Particulates
Al & Si
increased by thermal condensation
reactions in the slurry circuit.
Asphaltenes can become insoluble
in the slurry oil and begin to
precipitate onto the tube surface.
The tar-like layer on the tube service
can also trap coke and catalyst
particles that are present in the
slurry.(12) Figure 51, an abbreviated
version of Figure 46, illustrates the
sequence. Analyzing such tube
deposits and slurry for fused
aromatics can be insightful. Higher
amounts of fused aromatics in the
deposit relative to the slurry can
confirm asphaltene precipitation.(13)
Slurry viscosities increase at the
tube wall due to the locally cooler
temperature. The higher viscosity
can cause material to adhere to the
tubes, resulting in exchanger
fouling.(12) Slurry with a higher
paraffinic content may be more
prone to fouling due to the
inherently higher viscosity.
Preventing Soft Coke Fouling
Two sources suggest minimizing
asphaltene content of the slurry in
order to minimize fouling.(5,14) ASTM
D3279 can be used to determine
asphaltene content. The
asphaltene content is defined as
those components in the sample
that are not soluble in n-heptane.
This procedure gives the combined
34 www.e-catalysts.com
Organic
Coke
Precipitated
Deposits Asphaltenes
Polymerization
amount of asphaltenes and
particulate matter.
Maintaining asphaltenes in solution is
key to preventing soft coke fouling.
The composition of the slurry will
affect the solubility of the asphaltenes.
Generally higher aromatic content of
the slurry tends to keep asphaltenes
in solution. As such, changing the
slurry composition by dropping some
LCO down the tower can increase the
solubility of asphaltenes in the
bottoms material. This also has the
benefit of reducing the temperature at
the bottom of the main column.
It is often necessary to adjust the
bottoms composition and temperature
in this manner during changes in feed
composition. For example, slurry
produced from paraffinic feedstocks
tends to be more prone to fouling and
requires lower main fractionator
bottoms temperature to minimize
fouling.
Many refiners will also adjust bottoms
temperature with conversion shifts to
minimize fouling. A drop in conversion
could result in higher slurry exchanger
fouling. Slurry with higher API gravity,
generally due to lower conversion,
contains more saturated compounds,
which can reduce asphaltene
solubility and increase soft coke
fouling. Slurry with a high API gravity
is also more viscous and more prone
to fouling.
Feedstock leaking into the slurry
circuit can cause asphaltene
precipitation. This occurs because
the feedstock is more paraffinic
than the slurry and reduces the
solubility of the slurry asphaltenes.
The refiner should take all
precautions necessary to ensure
that the feed emergency by-pass
valve and the slurry/feed preheat
exchangers do not leak feedstock
into the slurry circuit.
The FCC catalyst can be formulated
with features to minimize fouling.
Catalyst matrix design can be
optimized to improve slurry
exchanger fouling by increasing
Type III cracking as described by
Zhoa.(3) Minimizing naphtheno-
aromatics and paraffinic content of
the slurry by increased Type III
cracking may improve asphaltene
solubility and reduce slurry
exchanger fouling. Using a catalyst
with proper tolerance to
contaminant metals will help avoid
fouling as well. Increased catalyst
contaminants that result in a loss of
FCC conversion can increase the
likelihood of fouling as discussed
above.
Hot Cycle Oil Flush at the inlet of the
slurry exchangers can help keep
asphaltenes in solution and
increase tube velocity, both of
which will help reduce slurry
exchanger fouling.(5)
INORGANIC BASED FOULING
Inorganic fouling can include
fouling prompted from corrosion or
iron scale, catalyst or precipitated
metals. Catalyst is often found in
tube deposits and can be identified
by the presence of alumina, silica,
and rare earth. Catalyst in the
deposits is often a result of organic
based fouling, since catalyst
generally accumulates onto viscous
precipitated asphaltenes or other
hydrocarbons already present on
the tubes.
Another inorganic foulant in FCC
slurry service is antimony. Antimony
present in the slurry has been found
on tube deposits. In one instance,
20 wt.% antimony was found in a
deposit.(15) The antimony source was
from antimony injection into the FCC
feedstock to passivate equilibrium
catalyst nickel.
Preventing Inorganic Based
Fouling
Catalyst losses to the main
fractionator should be minimized by
proper reactor cyclone operation
and good reactor cyclone
mechanical integrity. The catalyst
itself can also be designed to
minimize losses to the main
fractionator. To maximize catalyst
retention, the following catalyst
design parameters should be
considered:
• Low Attrition Index (Low DI);
• Low 0 to 40 micron content;
• High Particle Density.
Antimony levels in the slurry should
be closely monitored to minimize
the possibility of antimony
depositing onto the tube service.
FCC equilibrium catalyst antimony
to nickel ratio is generally between
0.10 and 0.60 by weight. The
antimony chemical should be
injected to maintain the target level
on the equilibrium catalyst without
significant overfeed.
Proper metallurgy in the main
fractionator, slurry piping and slurry
exchanger should be used to
minimize corrosion. Below is a
summary of suggested materials:(6)
• Main fractionator internals
TP 410 SS ;
• Exchanger tubes
TP 405 or TP 410SS ;
• Slurry Lines 5 Cr -
1/2 Mo with 1/4” CA.
Antifoulants
Antifoulants have been successfully
used to prevent FCC slurry
exchanger fouling. Antifoulants can
be generally classified as follows:
• Organic dispersants -
prevent the agglomeration
and deposition of
asphaltenes;
• Inorganic dispersants -
prevent the deposition of
catalyst fines or other
inorganic foulants such as
Fe compounds;
• Coke suppressants -
inhibit condensation
reactions, which lead to hard
coke-like deposits in
exchangers.
A combination of antifoulants can be
used. However, the likely source of
the fouling should be identified before
a specific antifoulant is applied.
Note that there can be some
downstream effects when using an
antifoulant. For example, in some
cases catalyst fines settling in slurry
tanks can be impacted if an inorganic
dispersant is used.
Additional Design and Operation
Considerations
There are many design considerations
for exchanges in slurry service that
can help to minimize the potential for
exchanger fouling.
Slurry exchanger tube velocities
should be 6 to 10 fps.(8) Velocities
below six fps can result in catalyst,
coke or other particulates settling onto
the tube surface, resulting in fouling.
The minimum slurry exchanger tube
diameter should be one inch.(5)
Smaller tubes can be subject to
excessive fouling and are difficult to
clean.
Spill back control can be used on net
product exchangers in turndown
conditions to keep tube velocities
above minimum values.
Slurry should be present only on the
exchanger tube side. With slurry on
the shell side, it is impossible to
prevent catalyst settling in the
exchanger because of low local
velocities.
Vertical and Spiral slurry
pumparound exchanger designs
tend to be less prone to slurry
exchanger fouling.
Finally, having spare slurry
exchangers should be considered
to minimize turndown during
exchanger cleaning.
Case Study
An FCC unit began observing severe
fouling of their Slurry Steam
Generator exchangers. The fouling
began suddenly and continued for
approximately two weeks and then
stopped. During that time, it was
necessary to clean the exchangers
several times. The exchangers
exhibited a reduction in heat transfer
coefficient. Exchanger pressure
drop was not affected.
The FCC was a modern design
employing a modern riser termination
device and state-of-the-art feed
injection nozzles. The reactor
temperature operated at 980˚F and
main fractionator bottoms
temperature was typically 690˚F.
Conversion normally was ~78 vol.%
with a slurry API gravity of -2 API.
The feedstock was a vacuum gas oil
and resid blend with the following
nominal feedstock properties:
• API 22˚ to 24˚;
• K Factor 11.7 to 11.8;
• Conradson Carbon ~1.0 wt.%;
• 10% Greater than 1050˚F.
A deposit was taken from the fouled
exchanger. Analysis of the deposit
showed the following:
• 87% Carbon, 94% Organic
Based (C, H, N);
• <1% Alumina;
• 1 wt.% Antimony;
• <1 wt.% Iron;
• 52% of the sample was
Asphaltenes.
Catalagram 101 Spring 2007 35
 Figure 52
Feed Shift Property Shift Impacts Slurry Exchange Fouling
26
Severe Slurry Exchanger
25 Fouling began suddenly
24
23
22
21
20
1-JAN 21-JAN 10-FEB
API Gravity
The refinery does use antimony to
passivate nickel. However, antimony
had been used for several years
without any previous issues. No
recent change in antimony injection
was made and consequently
antimony was likely not the cause of
the fouling.
The deposit itself did not contain
catalyst, as evident by the low
amount of alumina.
The high amount of asphaltenes in
the deposit confirmed asphaltene
precipitation as the likely fouling
mechanism.
A review of feedstock properties
showed the feedstock had recently
become more paraffinic, as evident
by the higher API gravity and K
Factor during the same time as the
exchanger fouling. Figure 52 shows
how feedstock API and K factor
shifted. When the refinery changed
the feed source the feedstock
properties returned to typical values
and the fouling stopped.
Many refineries recognize that some
feed and crude sources can result
in increased FCC slurry exchanger
fouling. Those sources are either
avoided, the main fractionator
temperature is reduced, and/or
antifoulants are used to minimize
fouling while those feedstocks are
processed.
36 www.e-catalysts.com
References
11.95
11.90
11.85
11.80
11.75
11.70
11.65
11.60
Fouling Stopped
11.55
1-MAR 21-MAR 10-APR 30-APR
K Factor
Final Remarks
Continuous monitoring of the overall
heat transfer coefficients is critical to
catch a slurry exchanger fouling
problem early. Monitoring slurry
properties such as API gravity, ash
content, asphaltene content, and
viscosity can also alert the refiner
when the FCC unit may be more
susceptible to slurry exchanger
fouling. A shift of feedstock
properties or unit conversion may also
increase slurry exchanger fouling.
Slurry exchanger fouling often occurs
during start-up or at turndown
conditions when feedstock and
operating conditions may be atypical.
Special precautions may be considered
during these unusual operations.
Reducing slurry exchanger fouling by
lower main fractionator bottoms
temperature and higher slurry product
rate can be costly in terms of lower
product value. Grace Davison can
work with the refiner to adjust catalyst
properties and operating strategy to
minimize fouling and any subsequent
yield loss.
1. Barlow, R., Reduce FCC Fouling,
Hydrocarbon Processing, July 1986
pg 37-39
2. Meyers, R., Handbook of Petroleum
Refining Processes 2nd Edition,
McGraw Hill 1996, pg 3.95
3. Zhao, X. FCC Bottoms Cracking
Mechanisms and Implications for
Catalyst Design, 2002 NPRA Annual
Meeting, San Antonio, TX, AM 02-53
4. Wilson, J., Fluid Catalytic Cracking
Technology and Operation, Penwell
Publishing 1997, pg 225
5. Sadeghbeigi, R., Fluid Catalytic
Cracking Handbook 2nd Edition,
Gulf Publishing Co. 2000, pg 251 to
253
6. Walker, P. , NPRA FCC Principles
and Practices, 2004 NPRA Q&A,
Anaheim CA
7. Wilson, J., Fluid Catalytic Cracking
Technology and Operation, Penwell
Publishing 1997, pg 257
8. Wilson, J., Fluid Catalytic Cracking
Technology and Operation, Penwell
Publishing 1997, pg 229-230
9. Walker, G, A Case Study in Slurry
Fouling, 2003 NPRA Annual
Meeting, San Antonio TX, AM 03-63
10. Fouling in FCC Units & Purification
Trains, GE Infrastructure Water and
Process Technologies Presentation
11. Dickakian, G., Asphaltene
Precipitation in Primary Crude
Exchanger Fouling Mechanism, Oil
and Gas Journal, Mar. 7, 1988, pg
47-50
12. Falker T. et al., Modeling of FCC unit
Main Fractionator Bottoms
Pumparound Fouling, 1995 NPRA
Annual Meeting, San Francisco CA,
AM-95-71
13. Shawney, K et al., The FCCU Slurry
Loop Fouling Mitigation, 2002
AIChE Spring Meeting, New
Orleans LA
14. NPRA Q&A Transcripts 1989, pg 68
15. NPRA Q&A Transcripts 1986, pg 54
 Dav i s o n Re fi n i n g Te c h no l o g ie s
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