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A message from the Editor: DA11\p1ATALYSTS
Sixty years ago, the pioneering work of a group of scientists and engineers led to the
start-up of the first commercial FCC unit (Standard Oil’s PCLA No. 1 Powdered
—
Catalyst Louisiana No. 1). This was a heroic effort to overcome many obstacles in a
short period of time, driven by the onset of World War II and the subsequent need for
motor fuels. This issue of the Catalagram is dedicated to the spirit of innovation that
led to the commercial success of FCC technology, which has provided people around
the globe enormous benefit over the last sixty years.
The FCC catalyst produced for PCLA No. 1 ‘s start-up was manufactured at Davison’s
Curtis Bay, Maryland facility in May of 1 942. Since that historic date, Davison has
developed better and better products for FCC operation in order to meet the needs of
refiners of the time. For example, Davison developed ultra-stable Y-zeolite containing
catalysts in the mid- 1 960 ‘s that enabled refiners to cost effectively meet increasing
demand for gasoline. Similarly, Davison introduced octane catalysts in the mid-1970’s
to help refiners deal with their octane crunch.
Although the FCC catalyst field is mature by many measures, I am continually amazed
at the pace of innovation and level of excitement evident throughout Davison’s Refining
Catalyst business. True to our history, we continue to dedicate our efforts to inventing
cost effective and flexible solutions for refiners’ toughest problems. And we continue to
be successful. In this issue of the Catalagram, we introduce a number of options to help
refiners deal with upcoming clean fuels regulations, including a truly breakthrough cat-
alytic solution, $aturnTM, that may allow some refiners to completely avoid capital
investment. I would not have believed that this was possible only a year ago.
We would like to thank our customers, whose loyalty and support have made our busi
ness exciting and rewarding over the last sixty years.
Tom Petti, Editor
—
-‘-
— I-’
In this issue....
Next Generation FCC Clean Fuels Technology Breaks Through 50% Gasoline
Sulfur Reduction page 3
By Scott K. Purnell, Marketing Specialist, Davison Catalysts, Columbia, MD;
David A. Hunt, Sr. Technical Service Rep., Davison Catalysts, Houston, TX;
and Dana Leach, Process Superintendent, Montana Refining Co., Great Falls, MT
The newest member of Davison’s FCC clean fuels line-up, $atuTnTM, has demonstrated
50% sulfur reduction in its first commercial application at Montana Refining Co.
Hydrotreating Coker Naphthas: Silicon Management with START Catalyst
Systems by ART page 5
By L. David Krenzke, Ph.D., Manager, Hydrotreating Technical Service;
Charles W. Olsen, Ph.D., Manager, New Product Development;
and Brian R. Watkins, Performance Testing Team Leader,
Advanced Refining Technologies
Hydrotreating coker naphtha poses some unique problems for the refiner and
ART has a strong position in naphtha hydrotreating technology. In addition to high HD$ and HDN activity
with 535 NiMo catalyst, ART now offers ATZ24G. ATZ24G is a new active silicon guard catalyst that eco
nomically supplements the silicon holding capacity and provides activity grading for coker naphtha applica
tions.
Optimizing your FCC Regenerator Operation and Catalyst Design can
Minimize Catalyst Losses page 11
By David A. Hunt, Senior Technical Service Representative, Davison Catalysts;
Gautham Krishnaiah, Davison Refining Services; and
Thomas F. Petti, Ph.D, Marketing Manager, Catalyst Technologies, Davison Catalysts
FCC operations in the United States are highly constrained with new challenges constantly
presenting themselves. One such challenge is operating below stringent flue gas particulate
emission limits. Common factors impacting catalyst losses from the FCC regenerator,
including FCC design, equipment mechanical integrity, regenerator and cyclone operation
and catalyst properties, are discussed.
Davison SBraneTM Technology for Sulfur Removal from FCC Gasoline page 22
By Jeffrey W. Balko, Marketing Manager, Clean Fuels Technology, Davison Catalysts
Davison is currently working towards commercialization of a sulfur separation process that
has the potential to substantially reduce refiner’s capital expenditures for compliance with
Tier 2 gasoline regulations.
1

Tier 2 gasoilne sulfur compliance is going to cost a lot of money. If
you’re a refiner that already spends miions of extra dollars per year
purchasing sweet crudes or running a big FCC feed pretreater, the last
thing you want to do is buy an expensive gasoilne post-treater.
Davison’s Saturn has demonstrated 50% sulfur reduction in its first corn-
rnercial application at Montana Refining Co. Based on this, a refiner with
an FCC gasoline sulfur level of 300 pprn, could reduce the sulfur level to
less than 1 50 pprn with Saturn. With additional operational changes such
as undercutting and/or increased feed hydrotreating severity, FCC can pro-
vide an ultimate reduction of greater than 80%. At 40% of the total gaso
line pool, this would result in a blended sulfur level of less than 30 ppm,
thereby achieving the 2005 Tier 2 regulations without any additional capital
investrnent. For a 40,000 bpd FCCU, this could result in a capital savings
of $30 MM and annual operating expense savings of $3 MM or rnore.
Next Generation
FCC Clean Fuels Technology
Breaks Through
50% Gasoline Sulfur Reduction
by
Scott K. Purnell, Ph.D., Marketing Specialist,
Davison Catalysts, Columbia, MD
David A. Hunt, Senior Technical Service Representative,
Davison Catalysts, Houston, TX
Dana Leach, Process Superintendent,
Montana Refining Co., Great Falls, MT
Davison Catalysts is pleased to introduce the newest
member ofits FCC clean fuels line-up. This FCC cat-
alyst, known as $atUrflTM, incorporates Davison’s lat
est developments in gasoline sulfur reduction func
tionality and is effective over the entire gasoline boil-
ing range. Saturn has exhibited gasoline sulfur
reductions as high as 50% in the laboratory.
Reductions in LCO sulfur from 10-30% have also
been observed. As with SuRCA, the Saturn catalyst
is custom-formulated with both cracking activity and
sulfur reduction functionality so that it can replace
the conventional FCC catalyst in the circulating
inventory with minimal impact on yields and selec
tivities. The magnitude of the sulfur reduction
observed with this product is such that select refin
ers may find that use of Saturn would allow them to
comply with upcoming clean fuels regulations while
avoiding the significant capital expense of an FCC
feed or naphtha hydrotreater.
Commercial Demonstration
Montana Refining Company (MRC) operates a 7,000-
bpd refinery with a 2,400-bpd FCCU in Great Falls,
Montana. The refinery processes a mix of Canadian
3
c
‘ 4
crudes. The VGO produced from this crude slate is
hydrotreated prior to the FCCU resulting in a typical
FCC feed sulfur content of 0.4-0.5 wt%. With a D-86
gasoline endpoint of about 400°F, this translates to
gasoline sulfur levels of approximately 300-400 ppm.
At the 300-ppm sulfur level in FCC gasoline, which
makes up about 40% of the total gasoline pool, it was
anticipated that a significant capital investment
would be required to meet upcoming Tier 2 gasoline
specifications. For planning purposes, MRC decided
to switch from their Davison XP® catalyst to Saturn,
thereby becoming the first commercial application of
this breakthrough technology in October 2001.
By late January 2002, changeout to Saturn had
reached approximately 65% and significant sulfur
reduction was clearly observable in the commercial
data. Figure 1 shows the trend of full-range FCC
gasoline sulfur over time. Absolute gasoline sulfur
levels had dropped to 120 ppm from the base case
range of 300-600 ppm. In order to eliminate the
effect of day-to-day feed sulfur variations, the gaso
line sulfur data were normalized by dividing through
by feed sulfur, indicating a sulfur reduction of 60%
over base case conditions. To the best of our knowl
 iI
L’ -
S
( .

Table I

Catalyst
MRC Test Run Results for Capital Avoidance Potential

Base Case
Base
Saturn
Saturn
Test 1
Saturn
Test 2
Saturn
Test 3
Saturn
(A9
(65% Change-out) (65% Change-out) (65% Change-out) (65% Change-out) Advanced Refining Technologies
-
Feed S 0.4-0.5 wt% 0.4-0.5 wt% 0.32 wt% 0.32 wt% 0.3 wt%
Gasoline EP 400F 400F 380-400F 360-370F
Gasoline S 300-600 ppm 120 ppm 90-100 ppm 70-90 ppm
350-360F
40-60 ppm Hydrotreating Coker Naphthas
edge, this is the highest gasoline sulfur reduction
ever observed in an FCCU where the sulfur is
line representing about 40% of the overall gasoline
pool, clearly sulfur levels <75 ppm, like those Silicon Management with
removed catalytically, not via dilution and/or observed here, would blend to <30 ppm, thereby
undercutting. meeting the requirements of Tier 2 gasoline specifi
cations without any capital investment. START Catalyst Systems by ART
Recently, MRC has conducted some test runs, adjust-
ing operating conditions in order to demonstrate the Saturn, a recently developed catalyst combining all
true potential of this catalyst technology for capital of Davison’s considerable expertise pertaining to cat- by
avoidance. Undercutting and increased FCC feed alytic sulfur reduction, has exhibited FCC gasoline L. David Krenzke, Ph.D.,
hydrotreater severity were combined with Saturn sulfur reduction in excess of 50% in its first commer Manager, Hydrotreating Technical Service
catalyst technology with truly extraordinary results cial application at Montana Refining Co. This
(summarized in Table I). remarkable performance may allow refiners like
MRC, who currently have FCC gasoline sulfur levels Charles W. Olsen, Ph.D.,
When FCC feed sulfur was lowered to about 0.32 of 300 ppm or less, to altogether avoid additional cap- Manager, New Product Development
wt% with a gasoline endpoint of 380-400°F, gasoline ital expenditures to meet Tier 2 gasoline specifica
sulfur levels were reduced to 90-100 ppm. Reducing tions. Please refer to our 2002 NPRA Annual Brian R. Watkins,
the endpoint further to 360-370°F led to gasoline sul Meeting paper (AM-02-37) for a more detailed Performance Testing Team Leader
fur levels of 70-90 ppm, and 40-60 ppm sulfur levels description of Saturn, along with recent commercial
have been observed with 0.3 wt% feed sulfur and experience on all Davison FCC Clean Fuels products.
gasoline endpoints of 350-360°F. With the FCC gaso
Introduction guard material to economically supplement the sili
1
Figure con holding capacity and provide activity grading.
Activity grading is an important aspect of coker
Montana Refining Saturn Trial Hydrotreating coker naphtha poses some unique
naphtha processing. The high heat release resulting
problems for the refiner. All coker naphthas contain
from olefin saturation can cause polymerization and
a high concentration of olefins/diolefins, and naph
800 a subsequent pressure drop problem. By grading
thas from delayed cokers also contain silicon. In
hydrogenation activity from low to high (active guard
addition, these stocks have a significantly higher
700 to catalyst) the temperature rise is spread out over a
concentration of sulfur and nitrogen than straight
larger portion of the catalyst bed and the potential
run naphthas. Even though the typical processing
600 for polymerization is mitigated.
scheme involves blending the coker stock with
500
straight run naphtha, issues of high exotherms, pres
‘I sure drop increase and silicon poisoning often control Silicon Deposition

400 the cycle length.

0 The source of most silicon contamination problems is
300 Advanced Refining Technologies has a strong posi the delayed coker. This is a common process in
tion in naphtha hydrotreating technology. ART 535 refineries because it is the lowest cost option for
0 200 NiMo catalyst combines high HD$ and HDN activity upgrading residual oils. The thermal cracking of the
U)
Cu with moderate density for excellent value. It has an heavy oil leads to some gas formation, which can
0 I 00 outstanding commercial track record with over 100 cause the coker drum to foam over. A foam over
Performance up to 65% turn-over to Saturn users worldwide, especially in coker naphtha service results in a very costly cleanup and possible safety
0 --
where silicon tolerance is a key factor. In addition to hazard. In order to suppress foaming, an anti-foam
9/1/01 10/1101 10/31/01 11/30/01 12/30/01 agent such as silicone oil (i.e. polydimethylsiloxane)
1/29/02 2/28/02 the active catalyst, ART supplies an active silicon

4 5

is added. Excess quantities of the silicone oil are usu
ally added to the coker as insurance to prevent any
possibility of a foam over. The silicone oil breaks
down during the coking process to lower molecular
weight fragments consisting of modified silica gels.
These remnants distill primarily in the naphtha
range although small quantities can also be found in
kero and diesel fractions.
In coker naphtha service, the rate of silica deposition
on the hydrotreating catalyst usually determines run
length instead of coke deactivation. In the absence of
silica contamination, naphtha hydrotreaters regular-
ly achieve three to five year cycles. In extreme cases
of contamination, cycle lengths can be as short as
three to six months.
Catalyst Deactivation
Silicon fragments in the form of modified silica gels
are deposited on the catalyst support and are dis
persed on the surface much like catalytic coke. These
modified gels adsorb strongly on the catalyst surface
and are associated primarily with the alumina sup-
port as opposed to the active metal sulfides. There
also appears to be a preference for adsorption on the
acidic sites of the alumina.
Figure 2
HT Catalyst in Coker Naphtha Service
Feed: 800 ppm sulfur, 12 ppm nitrogen product: <0.1 ppm sulfur & nitrogen
680
660
640
EOR due to silica poisoning
620 Spent catalyst contained 1 9.1 wt% 5i02
U-
600
I-
580
560
540
520
500
480
0 100 200
CataIt Life BbVIb
6 7
The silica does not appear to poison the active metal
sites directly, but rather restricts the pore structure
eventually blocking access to the active sites. This
phenomenon is referred to as pore mouth plugging
and is associated with a characteristic deactivation
pattern. First, there is a period of modest activity
loss followed by a very rapid deactivation. This
occurs because much of the internal surface area
becomes inaccessible to reactants. Figure 2 gives a
commercial example showing a rapid loss of activity
at about 19 wt% 5i02 pick-up.
As evidence of how detrimental silica deposition is to
catalyst activity, a series of spent catalyst samples
containing between 0 and 20 wt% 5i02 were careful-
ly regenerated in the laboratory. The coke-free sam-
ples were then activity tested and the results are
plotted in Figure 3. A sample containing about 20
wt% 5i02 has a 40T activity debit for HDS when
compared to a non-contaminated sample. A delta of
40T represents most of the temperature span in a
typical cycle.
An interesting aspect of catalyst deactivation by sili
ca contamination is the relative rates of deactivation
for HDS and HDN. The loss in HDN activity is more
rapid than for HDS activity even though pore mouth
300 400 500
I—I
---.
_, ii
Figure 3
Effect of Si02 on Regenerated Naphtha HT Catalyst
50
U-
0
0
0
0 40
-I
C.) 30
0
I 20
0
a)
a)
a) 10•
I
0•
0
wt% Si02 on Catalyst
plugging should affect them equally. This may be a amount of silicon captured depends upon the operat
reflection of the preference for silicon adsorption on ing environment and the silicon content of the feed.
acidic sites mentioned above. This phenomenon can The deposition of the modified silica gels on the alu
be useful to the refiner because nitrogen break- mina surface is a catalyzed reaction that has a tem
through typically precedes silica breakthrough. It is perature dependency. For example, a catalyst that
much easier to analyze for nitrogen in the product picks up about 10 wt% silicon in a typical coker
than it is to analyze for silicon. This gives the refin naphtha service (630T average bed temp.) will accu
er a way to anticipate silicon breakthrough and pre mulate only 2 to 3 wt% in a low temperature diolefin
vent contamination of the downstream noble metal saturation reactor (350 400T).
—
reforming catalyst.
A more meaningful measurement of silicon capacity
Analyzing the silicon content of spent catalysts as is pounds of silicon per cubic foot because catalysts
weight percent silicon would appear to be the most are loaded by volume. Frequently, fresh catalysts are
straightforward approach of comparing materials, “ranked” by surface area per unit volume (m2/cc).
but it can be misleading. For a given catalyst, the However, as Figure 4 depicts, silicon pickup can vary
 .
(*
J

-,i
‘I1-t
i1
-

widely. As shown in the figure, a given material does
not have a unique silicon capacity but a range of
capacities depending on the service environment.
The best way to directly compare materials is in a
basket test where all the catalysts see the same feed
and operating conditions.
ARTTechnology for Silicon
Management
As noted above, the deposition of silica is a catalyzed,
diffusion-controlled reaction. Therefore, to maximize
silica capacity, the chemistry and structure of the
support must be tailored to minimize “rinding’ on
the external surface and allow uniform penetration
and distribution of silica throughout the catalyst par-
tide. Figure 5 demonstrates this optimization with
cross-sectional silicon profiles of 535 naphtha cata
lyst with various levels of silicon contamination.
k I
mi
This catalyst design aspect is a key reason why ART Figure 5
535 is widely recognized as a leading, silica-tolerant
naphtha catalyst.
Silica Profile of Spent 535
Effective Si Trapping Shown: No Rinding, Uniform Penetration
In order to boost silica tolerance performance with
minimal activity dilution, ART has developed the
START (Silicon Tolerance by ART) catalyst system
that combines 535 with a newly developed silica
guard material, ART ATZ24G. The ATZ24G is spe
cially formulated with a novel support for both high
surface area and low density. Figure 6 compares
properties and Si pick-up for ATZ24G and 535 as sep
arate materials.
Owt%Si02 3wt%Si02 llwt%Si02
To avoid compromising catalyst activity and silicon
capacity, the combination of 535 and ATZ24G in the
START system results in high HDS and HDN activi
ty for extended run lengths, as well as activity grad-
ing needed for coker naphtha service. Figure 7 illus
trates the extended cycle length afforded by ATZ24G
and the START system.

Figure 4
Elemental Silicon Pick Up from Spent Catalyst Analyses 1 8 wt% S102 25 wt% Si02

Relative color scale indicates local concentration of Si02

1.0

Figure 6
AT724G Properties and Performance
0.
a)
6 ART 535 AT724G
0> I Service HDS Cat Si Guard
.— Lbs Si 5
00 0.5 per Ft3 Surface Area, m2/gm 250 355

11 11
Reactor
4
Volume Pore Volume, cc/gm 0.55 0.71
3 CBD, gm/cc 0.71 0.51

E
Active Metals NiMo CoNiMo
2
Sock Density, lb/ft3 40 29
1 HDS/HDN Activity High Moderate
SiCapacity Good High
0.0 k--- 1

CatA Cat B CatC CatD Cat E Cat F ART 535 A7724G

180 255 150 180 170 j95 Elemental Silicon Pickup

Basket Data from Coker Naphtha Unil
Numbers denote m cat SA per cc reactor volume based on fresh catalyst properties
-

8 9
 Figure 7
Projected System Improvement with AT724G Optimizing your
-

j -
START Catalyst System in Coker Naphtha Service
Feed: 800 ppm sulfur, 12 ppm nitrogen Product: <0.1 ppm sulfur & nitrogen
FCC Regenerator Operation
680 and Catalyst Design
660
Can Minimize Catalyst Losses
U-
I-
640

620

600

580

560
EOR due to silica poisoning extended with
AT724G in START catalyst system

I by
David A. Hunt,
Senior Technical Service Representative,
Davison Catalysts

Gautham Krishnaiah,
. S I S I S
540 Davison Refining Services
520
Thomas F. Petti, Ph.D,
500 Marketing Manager, Catalyst Technologies,
480 Davison Catalysts
.

0 I 00 200 300 400

Catalyst Life, Bbl/b
Summary
ART has a strong position in naphtha hydrotreating
technology, especially in coker naphtha service where
silicon tolerance is a key factor. Stand alone silicon
FCCU (Fluidized Catalytic Cracking Unit) charge units operating in the United States has fallen by
rates have risen steadily in the United States since approximately 10%. As a result, today’s average
1992. Energy Information Administration data, FCC unit is processing 20% more feedstock than it
shown in Figure $(1), illustrates that average FCC was ten years ago. Obviously, FCC operations in the
charge rates have climbed to 5,200,000 barrels per United States are highly constrained with new chal
day (bpd) during the year 2000 from 4,800,000 bpd in lenges constantly presenting themselves. One such
1992. Over the same time period, the number of FCC challenge is operating below stringent flue gas par-
ticulate emission limits.
ATZ24G, a new high-performance silica guard mate-
rial, has been developed to further extend cycle Figure 8
length under the most adverse conditions. The
resulting START catalyst system provides high United States FCC Throughput, 1922-2000
HDS/HDN activity with maximum silicon capacity.
5300

tolerant catalysts like 535 are widely used and high-
ly regarded.
To learn more about the START system, or any other
ART catalyst system, please contact your local 52OO
A
ART/Davison Catalysts sales representative or
catalystW?grace.com.

::
5100
.

Cu

5000
Li:.

I IJ
1992 7993 1994 1995
I_I LLIJ
Year
1996 1997 1998 1999 2000

11
10
 :i;* *:I;
r

FCC flue gas particulate emission requirements vary Table II Figure 9

from site to site. Depending on the location, these
limits are defined by the regenerator coke combus Example FCCU Regenerator Regenerator Pressure Survey
tion rate (ibm of particulates per 1000 lbms of coke Conditions
burn) or by opacity measurements. The most strin Regenerator Pressure, lbf/in2 gauge 25
gent particulate emission standards are achieved
Regenerator Temperature, T 1300
with downstream abatement equipment like a wet
Regenerator Gas Density, lbm/ft3 0.063
gas scrubber or an electrostatic precipitator (E$P).
Regenerator Inside Diameter. ft 32 25.0 Top Level Tap
Nevertheless, in order to ensure that a particular
FCC is always in compliance, the refiner has to mm- Regenerator Velocity, ft/s 2.8
imize catalyst losses from the regenerator. With
increased utilization, however, continuous operation Primary Cyclone Inlet Velocity. ft/s 70
below these emission limits is often difficult and $econdary Cyclone Inlet Velocity. ft/s 80 0
C
0 C
should the operation deteriorate, emission violations -

> -
0 QIbf/in

are possible. EQuilibrium Catalyst Size Distribution 0

0
> LI
0 to 40 microns, wt.% 8 0
0
Common factors impacting catalyst losses from the 0 to 80 microns, wt.% 65 C
0 E
0
FCC regenerator are listed below: 0 to l05microns, wt.% 87 a)
U)
D_

0 to 149 microns, wt.% 100 26.0 Top Density Tap

.
FCC design
Catalyst Particle Density, lbm/ft3 85 DI Bottom Level
.
equipment mechanical integrity 27 1
& Density Tap
.
regenerator and cyclone operation 5.l9ftE
.
catalyst properties understanding of the absolute physical level. In
order to give the operator a better understanding of
Proper regenerator bed level and cyclone operation the operation, the regenerator bed level should be
are important to ensure minimum catalyst losses reported in terms of an absolute level relative to a
from FCC units. Monitoring the regenerator bed convenient reference point such as the regenerator
level in relationship to the cyclone dipleg valves and bottom tangent line, catalyst withdrawal well nozzle Figure 10
the transport disengaging height (TDH) is key to cur- or cyclone dipleg valve.
tailing catalyst losses. Absolute catalyst level inside
Regenerator Bed Level, Cyclone Dipleg Levels and TDH
the cyclone diplegs should be periodically evaluated Regenerator bed level can be easily computed and
to ensure losses are minimized, particularly in units displayed on the operator control screen. A single
that operate at high regenerator superficial veloci gauge pressure survey, preferably a digital gauge
ties. illustrating pressure in terms of inches of water,
should be used to periodically verify bed level and
Catalyst properties are also critical to the successful density instrumentation.
operation of FCC units. The Davison Loss IndexTM
(DLI) is a better indicator of catalyst retention than
traditional attrition tests Davison’s AuroraT’LLI
The simple hydraulic relationship 1I
> 0
.
0
( Low Loss Index) catalysts balance particle density, _Ph (1) c
-
TDH
21ft
size distribution and attrition resistance to provide
the most retentive catalyst in the industry. Aurora
LLI catalysts also provide excellent coke selectivi
gc
0
C
0

c
.
l5Aft
ties, activity retention and bottoms conversion over a can be used for all bed level and density calculations 8.lft

wide range of activities and product selectivities. in the FCC.

4ft

Regenerator Operation For example purposes, we use a 50,000 bpd FCC tlOft
operating at the conditions listed in Table II.
Regenerator Catalyst Level and TDH
Figure 9 lists data collected during a pressure survey
Most refiners refer to the regenerator bed level in
along the regenerator. Measurements were taken at
terms of inches of water or percent of scale. Often
the bottom level instrument tap (also the bottom
the bed level range, which the regenerator operates
density tap), top density tap, top level tap and a pres
within, is based solely on experience with little

12 13

Figure 11 sure tap in the flue gas line just downstream of the
cyclones. From this data and unit operating data,
Splash Plate the regenerator bed level and cyclone dipleg levels
can all be estimated.
Before the bed level can be calculated, the bed densi
ty must be estimated from the differential pressure
measured beneath the catalyst bed. In our example,
a 30.5 lbm/ft3 bed density is calculated by the rela
tionship:
(2)
= feet below the inlet horn of the primary cyclones.
Pbd (27. 1 — 26.0) lbf/in2 144 in2
hdg Ift2/5.19 ft = 30.5 lbm/ft3.
( Density taps are often separated by a convenient
distance such that the bed density is the same num
ber as the differential pressure in inches of water.
The same holds true in this example.)
Figure 12 Using the actual bed density, the regenerator bed
Counterweighted Check Valve (Left) level relative to the bottom level instrument tap is
estimated to be ten feet:
and Partially Shrouded Flapper Valve (Right)
( 3)
Ag. =
hbd (27.1 — 25.0) lbf/in2 144 in2!
Pbd ft2 ! (30.5 lbm!ft3) 10 ft.
The bed level is shown in Figure 10 and is sufficient
to bury the cyclone dipleg valves by four feet. (The
burial height is determined by subtracting the dipleg
valve elevation from the bed elevation.) Dipleg valve
burial requirements, however, vary by valve type.
A splash plate, shown in Figure 11, should always be
buried by the regenerator catalyst bed during normal
operations. Counterweighted check valves shown in
Figure 12 should operate unburied.2 Flapper valves
also shown in Figure 12 can operate either buried or
unburied. Regenerator secondary cyclone flapper
valves, however, should be buried to minimize losses
by preventing re-entrainment of catalyst fines.3
Specific dipleg burial requirements should be con-
firmed with the FCC licensor or cyclone vendor. If
the operation or design requires that the cyclone
valve be buried, the valve should always terminate
in a well fluidized zone to ensure proper valve and
cyclone operation.
TDH is the distance above the fluidized bed where
the solid density (entrainment) becomes constant.
The FCC regenerator bed level must be such that the
14
L N
i.3
TDH does not extend into the primary cyclone inlet
horn. This will minimize the amount of catalyst
entrained into the regenerator cyclones and catalyst
losses from the FCCU regenerator.
TDH can be estimated by the equation:
Log10 TDH20 Log10 20.5+0.07 (V-3) (4)
TDH = TDH20 + O.1(D-20) (4)•
TDH is estimated to be 21 feet with data from Table
II. Figure 10 shows that the TDH terminates five
The height between the primary cyclone inlet horn
and the point where the TDH terminates should be
maximized within regenerator constraints.
Cyclone Operation
Combustion air rates and regenerator bed level sig
nificantly impact the operation of the cyclones. A
head of catalyst in the dipleg balances the pressure
drop across the cyclones. Increasing combustion air
rates will increase the cyclone pressure drop, which
in turn increases the necessary catalyst level inside
the dipleg. Cyclone diplegs must be long enough for
the catalyst inside to build the necessary static pres
sure head to overcome the cyclone gas pressure drop.
In some cases, high combustion air rates can cause
the catalyst level inside the dipleg to rise into the
cyclone body, causing dipleg “flooding,” significantly
increasing catalyst losses.
Regenerator bed level can also influence the catalyst
level inside the dipleg. An excessive regenerator bed
level can cause high losses by increasing the catalyst
dipleg level just as high combustion air rates do.
Estimating the catalyst level inside the cyclone dip-
leg requires a pressure balance be made around the
cyclone. Constructing this pressure balance requires
an estimation of the pressure inside the cyclone hop-
per just above the cyclone dipleg.
The total pressure drop across the cyclone system is
the sum of the acceleration pressure drop and the gas
pressure drop across the primary and secondary
cyclones (and in some cases, the tertiary cyclone). In
our example, “b c1 c2’ is equal to 1.5 psi.
Acceleration pressure drop into the primary cyclone
can be estimated by:
15

? L
Al? = V2 (P +)H /g (5)
The vapor pressure drop of the cyclones can be esti
mated by the relationship:
AP = VCflpgFI/C
(6)
Finally, vapor pressure drop from the cyclone inlet to
the top of the dipleg is:
APdfl= Vcnpg/c (7)
These equations are similar to those presented by
Tenney and Gardner2 except, in this case, the H
term is dimensionless.
of course, the challenge with using these simple
equations is determining the value for the velocity
head correction terms Hb, Hcn and Hdn. Since each
FCC operation and cyclone system is unique, the
velocity head correction terms are unique.
In an effort to estimate Hcn one may assume that the
pressure profile across the primary and secondary
cyclones is proportional to the respective velocity
squared term. This is equivalent to assuming that
HclHc2. It can also be assumed that Hb << than
Hcn due to the relatively large value for solid densi
ty in the ‘‘b term compared to gas density in cn
For the purpose of this example, we assume that Hb
is 0.5 and that HclHc2.
Estimating ‘‘b requires the calculation of the solids
density. Primary cyclone gas velocity and gas densi
ty, which are also required to compute APb, are list-
ed in Table II. The solids density, p5, represents cat-
alyst entrainment to the cyclone and can be approxi
mated by:
Log10Y = Log1060+O.69Log10X-O.445(Log10X)2
16
T::
4i_
Where: (8)
Y=w
VPg
x-v2 —
(4)
gd p2
This equation is valid for all elevations above the
TDH and must be used at discrete particle size
ranges. Wilson offers a thorough explanation of the
technique (5) .
The entrainment, W, is estimated to be 1.73 lbm/s/ft2
in our 50,000 bpd FCC example. The solids loading,
PS, 5 calculated from W by dividing by the regenera
tor superficial velocity. In our example, p5 is 0.61
lb/ft3. With a value for p5, APb can be calculated and
is equal to 0.35 psi. Since the total pressure drop of
the cyclones is 1.5 psi, this leaves 1.15 psi to be dis
tributed across the two cyclones.
With “c1 ‘c2 1.15 and HclHc2, the velocity
head correction terms and pressure drop can be esti
mated. In our example, Wc1 and c2 are estimat
ed to be 0.49 psi and 0.66 psi, respectively, and the
values for Hci and Hc2 are 7.5.
Assuming the H terms remain constant for a given
system, the total cyclone pressure drop can be esti
mated for other operating conditions.
The level in the primary and secondary diplegs can
be estimated by:
_(M+M1)g. +L
L p si (9)
L
+zi9g +L Pbd
2 s2
p (10)
For our example, we will assume a primary dipleg
catalyst density of 30 lbm/ft3 and a 22 lbm/ft3 catalyst
density inside the secondary dipleg. Tenney and
Gardner discuss catalyst dipleg densities.2 A pres
rl tt: :t
!J HC--
Table Ill
Cyclone Design Velocities and Dipleg Flux Rates6
Cyclone Type Inlet Velocity, ft/s Outlet Velocity, ft/s
Reactor, Single-Stage 65-75 100-120
Reactor or Regenerator Primary or First-Stage 60—70 65-75
Reactor, Secondary or Second-Stage 75-85 100-110
Regenerator, Secondary or Second-Stage 80-85 120-140
Minimum Cyclone Velocity 25-35
Single-Stage or Primary Dipleg Catalyst Flux, lbm/s/ft2 100 125
sure drop term for the dipleg valve can be included in body. The FCC operator can take the following
the two equations above if desired. actions to reduce the dipleg level if required:
The gas pressure drop from the top of the dipleg to .
lower regenerator bed level within unit
cyclone gas outlet is small compared to the vapor vor constraints
tex pressure drop along the cyclone barrel. By .
increase regenerator pressure
assuming that c’d and HcHd, allow a conser .
reduce combustion air rate
vative estimation of the two cyclone dipleg levels.
Cyclone velocities and dipleg mass flux rates should
The catalyst heights inside the primary and second- be reviewed to ensure that they are within accept-
ary diplegs in our example are estimated to be 8.1 able rates. Operating the cyclones within these con-
and 15.4 ft., respectively. as shown: ditions reduces the likelihood of catalyst losses by
attrition or equipment deterioration. Table III lists
L1 = (0.35+0.49)lbf/in2 144 in2/ft2 /(30 lbm/ft3) + 4 design cyclone vapor gas velocities and dipleg mass
flux rates.
ft (30.5 lbm/ft3)/(30 lbm/ft3) = 8.1 ft
L2 (0.35+0.49+ 0.66)lbf/in2 144 in2/ft2 /(22 Catalyst Design
lbm/ft3) + 4 ft (30.5 lbm/ft3)/(22 lbm/ft3)
15.4 ft Parameters Influencing Cyclone
The primary and secondary cyclone dipleg levels are Collection Efficiencies
depicted in Figure 10 and terminate well below the
cyclone hopper. Maximizing cyclone collection efficiency requires
that DpTH be minimized. DpTH is the smallest par-
The necessary catalyst level in the secondary dipleg tide diameter, which can theoretically reach the
is higher than the primary due to the additional cyclone barrel wall and hence be collected. DpTH is
pressure drop of the secondary cyclone and lower cat-
alyst density inside the secondary dipleg. The dipleg defined as:
burial depth will influence the catalyst level inside
the dipleg, particularly in the secondary dipleg
because of the lower density relative to the bed.
Dipleg levels can be easily computed at other operat
D
pTH
9LgLw (7)
(11)
icN4(p-p)
ing conditions by estimating regenerator bed density,
bed level and cyclone pressure drop using the values
and is a parameter used to model cyclone collection
for H.
efficiencies.
To ensure minimum cyclone losses, the cyclone dipleg
level should terminate comfortably below the cyclone
17
 “

I!I —‘- ‘,
I

Figure 13 More spirals, N, inside the cyclone favor efficiency performance. The Davison Loss Index (DLI) has
as it increases the chance of collecting a particle. (N been developed considering all of the catalyst van-
Commercial Examples Showing the Davison Loss Index ables that play a role in unit retention. Figure 13
is generally expressed as a function of cyclone gas
versus Relative Unit Losses velocity and design.) Higher gas inlet velocity, Vcn,
shows three commercial examples of relative unit
losses as a function of the catalyst DLI.
increases centrifugal force toward the outer wall and
40% increases cyclone efficiencies. A wider cyclone inlet, In conjunction with the development of DLI, Davison
0
0
0 30%• Lw, reduces collection efficiencies by increasing the also introduced the Aurora LU (Low Loss Index)
0
0 . Opacity spiral width in the cyclone, making it harder for the subfamily of catalysts. While most refiners do not
-I 20%
particles to reach the cyclone wall to be collected. require the level of unit retention these catalysts pro-
C x Losses
1 0% Efficiencies drop when viscosity of the gas increases. vide, it is beneficial to those refiners constrained by
o unit losses or opacity. Catalyst losses and opacity
Co 0%•
In fin fl9fl
Finally, a higher particle density, not necessarily were reduced in Figure 13 by changing catalyst to an
higher apparent bulk density, raises collection effi Aurora LLI grade.
00
0
ciencies by increasing centrifugal force. A high par-
C
0 -“no’ tnz tide density also favors a lower entrainment rate Aurora catalysts are available with Davison’s Z-14
0
I- \ ,‘)LI LU Catalyst h and losses as shown above in Equation (8). ( U$Y), Z-17 and other advanced zeolites over a wide
0 -40% range of activity and rare earth levels. Aurora LU
5O% Minimizing the amount of small particles, particu catalyst can also incorporate Davison’s proprietary
larly that smaller than DpTH in the FCC inventory Low Coke Martix (LCM) (for improved gas and coke
Davison Loss Index selectivities) and active matrix technologies.
is the most important catalyst factor for reducing
regenerator losses. This can be achieved by reducing
10% the amount of fines, less than 40 micron particles, in References
0
0 the fresh FCC catalyst and to an even larger extent
0 M’
0
0% i
by minimizing the amount of fines produced by cata 1. Data published by the Energy Information
0 0. 0 0.10 0.20 0.30 0.40 0.
-J lyst attrition during normal FCC operation. Administration, “Petroleum Supply Monthly” 1992-
C -10%
2001.
0
0) Aurora LU Catalyst and Davison Loss Index
C -20%
0
.C
2. Tenney, E. and Gardner, A., “Fluid Catalytic
0 -30% .
Traditionally the industry has focused on catalyst Cracking Cyclone Design and Modifications,” Today’s
0
0) attrition testing to judge the relative retentive qual Refinery, October 1998, pp. 23-32.
0
C
-40% ities of an FCC catalyst. While it is certainly true
0 ‘Losses that results from these attrition tests do offer an
0 3. Private Communication with Edwin Tenney
0 -50%• indication of fines generated in a particular testing of Mansulex Environmental Technologies LLC, April
0
Aurora LLI Catalyst apparatus, these results provide limited information 2001.
0
- 0 —--- ——
___nfl__-__ —-..--——- -— on unit losses at actual unit conditions. These tests
Davison Loss Index are normally carried out at very high severity and 4. Ewell, R. B. and Gadmer, G., “Design cat
are difficult to extrapolate the results to commercial crackers by computer, Hydrocarbon Processing,
“

10% conditions. This is evident from commercial data, April 1978, pp. 125-134.
0 which has shown that one catalyst type may exhibit
0
0
0 different retention characteristics than another cata 5. Wilson, J., “Fluid Catalytic Cracking
0 I0 0.’l 0 ;20 lyst type, yet has the same attrition test results. As Technology and Operation,” Tulsa, OK: Pennwell,
C discussed above, many catalyst properties play a role 1997, pp. 188-189.
0 in unit retention as they impact DPTH and the
0)
C
0 amount of catalyst entrained to the cyclones. While 6. Sadeghbeigi, R., “Fluid Catalytic Cracking
.C
0 catalyst attrition is a very critical catalyst property Handbook,” Houston, TX: Gulf Publishing Co. 2nd
0
0) impacting catalyst losses, other catalyst properties ed., 2000, p 229.
0
C
-40%• such as particle density and fresh catalyst particle
0 xLosj size distribution are also significant. 7. “Manual on Disposal of Refinery Wastes
0 Aurora LLI_Catalyst
0 -50% Volume on Atmospheric Emissions” American
0
By taking all of these factors into consideration, Petroleum Institute Publication 931 May 1975
-60% — --- --- .— -- .--.--.--
Davison Catalysts has developed the Davison Loss Chapter 11, p. 20.
Davison Loss Index Index to serve as a better indicator of unit retention

18 19
 I

cII1
Nomenclature

dp Catalyst Diameter, ft
Ms
D Regenerator Inside Diameter, ft
DI Density Indicator

DPTH Smallest particle diameter which can theoretically reach the cyclone barrel wall, ft 4
g Acceleration Constant, ft/s2
gc Conversion Constant lbm/lbf ft/s2
h Height, ft
hbd Regenerator Bed Height, ft
hdt Height between Bed Density Taps, ft
Hb
Hcn
Hdn
——
Primary Cyclone Inlet Bell Velocity Head Correction Term
Nt’ Cyclone Velocity Head Correction Term Cyclone Inlet to Gas Outlet
Nth Cyclone Velocity Head Correction Term Cyclone Inlet to Dipleg Top
LI Level Indicator
Catalyst Height inside the Nt’ Cyclone Dipleg, ft

e-Catalysts
n
‘sn Dipleg Valve Burial Depth of the Nth Cyclone, ft
Lw Cyclone inlet width, ft
Number of spirals in a cyclone
TDH
- Transport Disengagipgjeight, ft A

V Regenerator Superficial Gas Velocity, ft/s

Vcn Nth Cyclone Inlet Gas Velocity, ft/s
w Catalyst Entrainment Flux, lbm/ft2/s
Feedback
x Physical Property_Gropg
form
Y Catalyst Entrainment, lbm of Catalyst Entrained/lbm Fluidizing Medium

AP Pressure Differential, lbf/ft2

AP5 Pressure Differential across Primary Cyclone Inlet Bell, lbf/ft2
A
‘bd Pressure Differential across Regenerator Bed, lbf/ft2
A’cn Vapor Pressure Differential across the Nt Cyclone, lbf/ft2
Vapor Pressure Differential from the Inlet to the Dipleg Top of the Nth Cyclone, lbf/ft2
dn Industry
‘dt Pressure Differential across Bed Density Taps, lbf/ft2
p Density, mt3 News f
Pg Gas Density, lbm/ft3
Pbd Regenerator Bed Density, lbm/ft3
Pdn Catalyst Dipleg Density inside the Nt’ Cyclone, lbm/ft3
PD Catalyst Particle Density, lbm/ft3
Catalyst Solid Density (Catalyst Entrainment), lbm/ft3 Davison Catalysts announces the launch of www.e If you are interested in joining, we invite you to apply
s_
Catalysts.com. This customized portal is designed to at www.e-Catalvsts.com or contact Vassilis
ii- Gas Viscosity, lbm/ft/s
enhance the sales and service for all Davison Catalysts, Vergopoulos at (410) 53 1-4339; Phyl Strawley at (410)
including FCC catalysts and additives and ART 531-8257; or in Europe, Thalia Bruhin at (49) 6241-
hydroprocessing catalysts The free membership
. 403 700.
requires a pre-approval, as well as user identification,
password and user’s internet public IP address(es).

20 21

Davison SBraneTM Technology
for Sulfur Removal from FCC
Gasoline
by
Jeffrey W. Balko
Marketing Manager, Clean Fuels Technology
Davison Catalysts
Davison Catalysts has devoted substantial research
and development spending over the last several
years to developing technologies that can help refin-
ers comply with clean fuels regulations.
In addition to Davison catalysts and additives for
sulfur and olefins reduction, we are currently work-
ing towards commercialization of a sulfur separation
process that will substantially reduce refiner’s capi-
tal expenditures for compliance with Tier 2 gasoline
regulations. While most “selective” gasoline post-
treating technologies are expected to have capital
costs in the $1,200-i,600/bbl capacity range, $-Brane
is expected to require a capital investment of rough-
ly one-third this amount.
$-Brane is a gasoline sulfur separation membrane
process that can drastically reduce the amount of
light and intermediate boiling range FCC gasoline
that requires hydrotreating. We have done extensive
laboratory work on this technology and are now
working very closely with our technology engineering
partner (Sulzer Membrane Systems) on a commer-
22
cial demonstration plant design. Additionally, a two
BPD pilot plant is in operation at our Columbia facil-
ity. This pilot unit is being used to explore certain
design parameters, feed flexibility and operating con-
dition impact. A diagram illustrating typical separa-
tion performance for the $-Brane process is shown in
Figure 14. Note that the performance of the process
(i.e., the V2 to yV3 ratio) can improve substantially
and costs decrease as the feed sulfur level, $1, goes
down.
S-Brane operates as a pervaporation mode mem-
brane process. Gasoline containing sulfur is fed over
a specially formulated organic membrane that is
selective for sulfur containing hydrocarbon mole-
cules. As the gasoline passes over the membrane,
sulfur-containing molecules and some aromatic mol-
ecules enter into the membrane structure while
other molecules are kept out. In pervaporation mode
membrane processes, the driving force that moves
molecules through the membrane is a vacuum on the
back side (permeate side) of the membrane. The vac-
uum results in a vaporization of the molecules as
Figure 14
S-Brane Process
vi
s1= 500 ppm SBrane
Cl = Feed Gasoline
composition
I
Note: Vi is a light+intermediate cut FCC gasoline
stream (about 70% of total gasoline) C4-350°F
-
Note: C3 is enriched in aromatics and lighter olefins,
C4 is slightly enriched in C6 + olefins
they move through the membrane. Once through the
membrane, these molecules are then condensed and
passed along for further processing to remove the
now concentrated sulfur species. The gasoline that
does not pass through the membrane (retentate) has
a substantially reduced sulfur level and can be
blended directly into the ultra-low sulfur gasoline
pool.
Due to the fact that many refiners have selected, or
are already in the process of selecting, technologies
for gasoline sulfur reduction, Davison Catalysts is
working closely with our engineering partner ($ulzer
Membrane Systems) to fast-track this technology.
Fast tracking efforts include discussions with poten-
tial refinery commercialization partners and design
and construction of a demonstration plant.
While many refiners will clearly not be able to take
advantage of $-Brane due to their timeline con-
straints of meeting Tier 2 regulations, some refiners
have additional time. Refiners that fit into the fol-
lowing scenarios should be able to benefit from this
technology. Refiners that:
23
_
p v2
S2
= 70% of Vi
30 ppm
C2 Retenate
=
gasoline composition
V3 = 30% of Vi
) $3i600ppm
C3 Permeate
gasoline composition
--;-
1) Already have relatively low gasoline sulfur
levels and therefore have additional time to
comply.
2) Are currently treating their heavy FCC gaso
line and could modify this treatment unit to
handle some portion of the light/intermediate
FCC gasoline.
3) Have a priority of minimizing capital outlays
for Tier 2 compliance and are therefore open to
creative processing scenarios (such as building a
smaller capital intensive “selective post-treater”
to handle the heavy FCC gasoline and a portion
of the light/intermediate FCC gasoline, instead
of a larger “selective post-treater” to treat the
entire volume).
If you see $-Brane as a potential piece of your Tier 2
gasoline sulfur compliance strategy, please contact
your Davison representative today. Also, please refer
to our upcoming NPRA Annual Meeting paper (AM-
02-21) for a more detailed discussion of this new
technology. To request a copy of our paper, please
contact us at catalysts@grace.com.
 :
: S%3
u
Have you ever wished it were
this easy to remove suLfur?

With the products and expertise available

F
through Davison Catalysts and Advanced
Refining Technologies, our team now offers a
one-stop shop for clean fuels solutions. Davison
Catalysts pioneered technologies for gasoline
sulfur reduction in the FCCU over a decade ago.
Today, we offer the only commercially successful
products, D-PrISMTM and SuRCATM, which have
been used in over 30 units worldwide.

DAJ1\4p.ATALYSTS
Advanced Refining Technologies

To meet today’s low sulfur diesel needs, refiners

can improve performance and reduce operating
costs with products like AT405, ARTh newest
hydrotreating catalyst. Innovative applications like
the SMART Catalyst SystemlM have been
developed to meet ULSD regulations of the future.

If you have questions about dealing with gasoline

j S

or diesel regulations, the Davison Catalysts/ART

team has solutions.
DA11\pATA LYSTS

Davison Catalysts Davison Catalysts Asia Davison Catalysts Europe

W.R. Grace & Co. Pacific In der Hollerhecke 1
7500 Grace Drive 501 Orchard Road Postfach 1445
Columbia, MD 21044 #07-02A Wheelock Place D-67545 Worms, Germany
(41 0) 531-4000 Singapore 238880 49 (6241) 4030
(65) 6737-5488

I cata1ystW?grace.com
The information contained herein is based on our testing and experience and is offered for the user’s consideration, investiga
tion and verification. Since operating and use conditions vary and since we do not control such conditions, we must DISCLAIM
ANY WARRANTY, EXPRESSED OR IMPLIED, with regard to results to be obtained from the use of this product. Test meth
w E B www.gracedavison.com ods are available on request.
E M A I L cataLysts@grace.com
 . , . -
%_,..:?.
1
.
4-:;,,.L
, ‘ )
. -. :.
. :t* :
,