Applied Catalysis A: General 221 (2001) 389–396

New developments in FCC catalyst technology

R.H. Harding a,∗ , A.W. Peters b , J.R.D. Nee a
aGrace GmbH and Co. KG, In der Hollerhecke 1, 67547 Worms, Germany
b Grace Davison, Washington Research Center, 7500 Grace Drive, Columbia, MD 21044, USA

Abstract
Fluid catalytic cracking (FCC) is a central technology in refining. The present paper will focus on recent progress in FCC
catalyst and process technology and will analyze the driving forces for such improvements. Thereby, the direct response
to environmental regulations will become obvious. Another target of new developments has been to process heavier crude
sources with higher levels of contaminants. Short contact time (SCT) cracking will also be discussed, reflecting significant
developments in the reactor hardware. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Fluid catalytic cracking; Zeolite; Catalyst

1. Introduction
Fluid catalytic cracking (FCC) is a central technol-
ogy in modern refining [1,2]. The FCC unit is used
to upgrade heavy gas oils and resid fuels to gasoline,
diesel fuel, and light gases. An extension of the Houdry
process, the unit was first implemented in the early
1940s. A brief history of the important events in the
development of FCC catalysts is shown in Table 1. In
the 1960s, the introduction of zeolite Y revolutionized
the process by increasing gasoline selectivity, adding
almost US$ 2 of value per barrel of feed processed [3].
In the 1980s, the introduction of zeolite ZSM-5 dra-
matically improved the ability of refiners to increase
both gasoline octane number and the yields of light
olefins. In the early 1990s, the introduction of new
alumina technologies further increased the flexibility
of the FCC unit to process heavier crude sources with
a higher tolerance to the contaminant metals Ni and V.
In this paper, we focus on recent improvements in
FCC catalyst technology and the driving forces be-
∗ Corresponding author. Tel.: +49-6241-403-685;
fax: 49-6241-403-630.
E-mail address: robert.h.harding@grace.com (R.H. Harding).
hind them. Although the FCC process has been used
for more than half a century, new and important devel-
opments continue to be made in several areas. Some
of these new developments are a direct response to
environmental regulation. Another important driving
force is the goal to process heavier crude sources with
higher levels of contaminants. Changes in hardware,
such as the increasing use of advanced riser termina-
tion technology to further reduce catalyst/oil contact
time have also resulted in significant changes in FCC
catalyst technology. With the increasing integration
of petroleum refining and chemicals production, the
value of specific molecules in the product spectrum
are driving FCC catalysts towards specific selectivi-
ties. Each of these trends has long term implications
for the development of future catalysts and hardware
for the FCC unit.
2. Environmental
One of the most influential drivers for new FCC
catalysts has been the changing objective function
that refiners must meet in order to satisfy even more

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PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 8 1 4 - 6
390 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396

Table 1
Important dates in FCC catalyst development [4]
Development Date

Aluminum chloride catalyst 1915

Activated clay catalysts (Houdry) 1928
Silica/alumina catalyst (Houdry) 1940
First commercial production of FCC catalyst (Davison) 1942
Commercial production of microspheroidal catalysts (Davison) 1948
Last run of powdered catalyst 1956
Commercial production of zeolite Y (Union Carbide) 1959
Introduction of zeolitic FCC catalyst (Mobil) 1962
Introduction of USY and REUSY (Davison) 1964
Introduction of combustion promotion (Mobil) 1974
Feed-added Ni passivation technology (Phillips) 1975
Introduction of ZSM-5 (Mobil) 1986
Introduction of Ni-tolerant matrix technologies (Davison) 1990
Introduction of SOx reduction technology (Amoco) 1992
Introduction of additives for gasoline sulfur reduction (Davison) 1995
Introduction of CSSN zeolite (Davison) 1996

stringent environmental regulations. The regulations 2.1. Particulates

that influence refinery operation include air and water
quality emission standards and clean fuels initiatives
[5]. Air quality emission standards require lower par-
ticulate emissions and lower emission of pollutants
such as CO, NOx and SOx . Clean fuels initiatives are
reducing the amount of sulfur, olefins, and aromatics in
transportation fuels. In Europe, the regulations phases
over time are with the following schedule of Table 2.
Some of these regulations are local (California
Air Resources Board), some are national (EU gaso-
line quality standards), and some reflect international
agreements (e.g., the Kyoto Protocol to the United
Nations Framework Convention on Climate). The
wide variation in environmental standards, implemen-
tation measures and enforcement translates to very
different results for each refinery. The current EU
standards for air quality are listed in Table 3.
During normal operation, an average FCC unit may
replace approximately 1% of its catalyst inventory to
make up for particle attrition. The physical properties
of FCC catalysts are designed for optimum fluidiza-
tion and low attrition. A trade-off exists between the
mechanical strength of the catalyst and the desire to
limit erosion of FCC hardware [7–9].
Catalyst manufacturers have recently developed
methods of limiting the losses due to attrition. There
are also trade-offs between the hardness of the par-
ticle (which is related to the amount of binder in
the formulation) and the catalyst selectivity. Too
much binder, which increases attrition resistance, can
Table 3
Emissions standards for EU countries [6]

Table 2 New plants (authorized or built after 1 July 1987)a

European gasoline specifications SO2 (mg/N m3 ) 800
NOx (mg/N m3 ) 350
1997a 2000 2005 Particulates (mg/N m3 ) 100
Sulfur (mg/kg) 300 150 50 Old plants (authorized or built before 1 July 1987)
Olefins (%v/v) 18 18 10–14b SO2 Reduce by 40–70% from
Benzene (%v/v) 2.3 1 –b 1980 levels by 2003
Aromatics (%v/v) 45 42 35 Nox Reduce by 24–40% from
Oxygen 0.6 2.7 –b 1980 levels by 1998
a Particulates N/A (to be issued later)
Typical values.
b To be determined. a FCC emission limits.
 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396
increase the ratio of matrix to zeolite activity, leading
to higher coke and gas production.
Particulate emissions are expected to be further re-
duced as catalyst research focuses on this area.
2.2. SOx
Sulfur oxides (SOx ) are a major atmospheric pol-
lutant and precursors for acid rain. The majority of
SOx produced from the FCC unit comes from the
sulfur in coke that is burned off during hydrother-
mal regeneration of the catalyst in the FCC regener-
ator. In the 1990s additive technology was developed
in order to adsorb the SOx in the regenerator and
carry it over to the riser side of the FCC unit where
it can be released as H2 S [10]. H2 S is conveniently
treated with the Claus process to convert it to elemental
sulfur.
A successful SOx transfer additive must have three
primary components. The first step in the mechanism
of SOx transfer additives is the oxidation of SO2 . Un-
der FCC regenerator conditions, SO2 is favored over
SO3 . Thus, SOx transfer additives contain catalytic in-
gredients that promote the oxidation of SO2 . A metal
oxide component, such as magnesium alumina spinel
is also included to strongly chemisorb the SO3 in the
regenerator. A metal with multiple valence states such
as vanadium should be included to catalyze the release
of sulfur as H2 S in the riser [11].
Use of SOx additive technology will be an impor-
tant tool, in addition to scrubbing hardware, to help
Fig. 1. Expanded reaction mechanism of NOx formation in FCC.
391
refiners meet increasingly stringent specifications for
SOx emissions.
2.3. CO and NOx
Regulations limiting the release of nitrogen oxides
from stationary sources affect the FCC regenerator and
are expected to phase in within the next decade. As
NOx reduction becomes more important, the relation-
ship between NO and CO production in the regen-
erator is becoming better understood [12,13]. Carbon
monoxide can be readily converted to carbon dioxide
with the introduction of a combustion promoter based
on platinum or other noble metals. When the level of
CO in the regenerator is reduced through the use of
combustion promoter, nitrogen oxides have been ob-
served to increase. The simplest explanation for this
observation is that the direct reaction of NO and CO
to form N2 and CO2 . As CO is eliminated from the
system by the combustion promoter, there is less CO
to reduce NO to N2 .
Recent experiments have shown that this reac-
tion, while it exists, is not the dominant one under
FCC regenerator conditions. A reaction mechanism
adapted from Yaluris et al. is shown in Fig. 1 [14].
Nitrogen-containing species in coke are one of the
last species burned off the catalyst due to the strong
acid-base interaction between nitrogen and the acidic
catalyst. A significant proportion of the nitrogen is
burned to nitrogen gas, some is burned to NOx and
some is burned to hydrocarbon species such as HCN.
392 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396
Pt-based combustion promoters have been found to
catalyze the reaction of HCN to NO. Non-platinum
combustion (such as X-NOx ® ) catalyze the reaction
of HCN-type species to nitrogen. Thus, a non-Pt-based
combustion promoter is desired for the combined ob-
jective of reducing CO and NO from the regenerator
flue gas.The importance of nitrogen oxide removal
technology is expected to increase as environmental
regulations become more stringent.
2.4. Gasoline sulfur control
The class of environmental regulations with the
most far-reaching implications is the reduction of sul-
fur in transportation fuels. The reduction is motivated
by studies, such as the Auto Oil II study, which have
shown that sulfur in gasoline reversibly deactivates
automobile catalytic converters, and thus has a large
impact on a broad range of environmental pollutants.
The most recent European Union legislation on gaso-
line requires a reduction in gasoline sulfur to 50 ppm.
A number of European Union countries are currently
producing gasoline with <50 ppm sulfur to bene-
fit from tax concessions. Germany, for example, is
planning to produce 30 ppm gasoline from 2001 and
10 ppm from 2003 to make full use of tax incentives.
The U.S. EPA has recently recommended a reduction
to 30 ppm S to be phased in between 2004-2008.
Additionally, California’s CARB Phase 3 gasoline
(2003) will have 15 ppm S.
In order to achieve these low levels, refiners have
a number of choices including gas oil hydrotreating,
FCC feed hydrotreating, gasoline sulfur adsorption
processes, and gasoline hydrofinishing. Each of these
techniques has debits associated with it. Some, like
gasoline hydrofinishing, lead to a reduction in gasoline
olefins and thereby reduce gasoline octane. Some, like
feed hydrotreating, have a high demand for molec-
ular hydrogen, which is often in short supply in the
refinery.
Several strategies have been shown to reduce the
level of sulfur in gasoline. While several basic FCC
catalyst properties such as zeolite unit cell size, matrix
activity and alumina content can be adjusted to pro-
vide sulfur reduction of about 10%, these adjustments
also produce yield selectivity changes which may or
may not be desirable. As a more targeted approach,
catalysts have also been designed specifically for the
removal of gasoline sulfur. These catalysts; GSR-1,
SuRCA (with GSR-4 technology) and GFS-2000 have
provided commercial gasoline sulfur reductions in the
15–35% range.
While we expect these catalytic technologies to im-
prove significantly over time, it is not likely that they
will provide the very high reductions required by leg-
islation. However, we expect that catalysts designed to
reduce sulfur in gasoline and diesel fuel will work in
concert with the hardware solutions to provide more
cost effective clean fuels. The sulfur reduction cata-
lysts introduce another degree of freedom for the re-
finer, and allow less severe operation of the hardware
solutions or less capital investment. For example, low-
ering the level of sulfur in the gasoline stream input to
hydrotreaters would result in lowering the hydrotreat-
ing severity, which would reduce both hydrogen con-
sumption and octane loss.
2.5. Gasoline olefins
An upper limit of 18% olefins in the gasoline has
been set for the European Union, and levels as low
as 10–14% have been proposed. In the U.S., gasoline
olefin level is one of the variables used in the complex
model to predict emissions of volatile organic com-
pounds (VOCs), NOx and toxic air pollutants (TAPs).
RFG regulations mandating minimum levels of
VOC/NOx /TAP reduction have pushed refiners to pro-
duce gasoline with very low levels of olefins. Federal
U.S. RFG typically contains about 7% olefins while
California CARB gasoline contains about 5% olefins.
Catalyst manufacturers are meeting this challenge
by extending current technology to limit the formation
of gasoline olefins and increase their destruction rate.
One effective approach to the reduction of gasoline
olefins is the use of extremely high hydrogen transfer
catalysts combined with matrix technology that limits
the production of gasoline olefins and has strong met-
als trapping functionality. New technologies are also
being developed.
A particular challenge in this area is reducing these
gasoline range olefins while maintaining the yield of
light (C3 and C4) olefins and gasoline octane. Grace
Davison RFG Catalyst technology has provided com-
mercial gasoline olefins reduction of 15% (absolute)
while maintaining the yield of light olefins and gaso-
line octane.
 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396
2.6. Interaction with hydrotreated feeds
As refiners invest in new hardware to meet the low
gasoline sulfur requirements, a greater percentage of
FCC units will be treating hydrotreated feedstocks
with lower sulfur content, lower metals levels, and
lower nitrogen content. One significant technical chal-
lenge is the ability to maintain the heat balance of the
FCC reactor/regenerator as hydrotreated feeds are in-
cluded in the blend. With the intrinsically low coke
make of these feedstocks, catalysts with higher delta
coke may be required.
We believe these high delta coke catalysts will prob-
ably only be required in the transition period between
the installation of feed hydrotreating and the installa-
tion of additional hardware flexibility to take full ad-
vantage of the low coke production.
2.7. CO2 emission
One of the most difficult environmental challenges
for the refinery in the next century is the reduction
of CO2 emissions required by the Kyoto Protocol
to the United Nations Framework Convention on
Climate [15]. The solution to this problem is not
likely to be found in the FCC catalyst, but rather
from elimination of energy inefficiencies in the in-
tegrated refinery system. The primary reason is the
heat balance of reactor/regenerator combination. The
endothermic FCC process requires a predictable
amount of heat to convert a gas oil to gasoline and
other products. The amount of coke required per
unit of feedstock to supply this reaction energy is
constant.
3. Residual oil processing
In addition to environmental regulations, several
other driving forces are emerging to determine the di-
rection of new technologies for FCC catalysts. Feed
sources are expected to evolve towards heavy resids,
which contain higher metals levels, and higher levels
of polynuclear aromatics and heteroatom species [16].
In the 1990s, several new catalytic technologies were
introduced in response to these trends. We’ll focus on
the influential effects of metals tolerance and bottom
of the barrel processing.
393
3.1. Contaminant metals
In the 1990s, a wide range of technologies were
developed to improve the tolerance of FCC catalysts
to contaminant metals in the feed, primarily vana-
dium and nickel [17]. The dearomatization function
of nickel is responsible for an increase in coke yield
as the Ni level increases on the equilibrium catalyst.
Moreover, the dehydrogenation activity of the Ni
leads to the formation of molecular hydrogen. Since
hydrogen is the most difficult gas to compress, an
increase in the FCC unit can quickly limit the wet gas
compressor. In order to increase the tolerance of FCC
catalysts to Ni contamination, a set of aluminas based
on special selective active matrix aluminas were devel-
oped. Oxygen TPD measurements provide evidence
for the solid state diffusion of Ni into the alumina
away from the surface and therefore the reactants.
Vanadium forms vanadic acid in the regenerator,
which destroys the zeolitic component of the catalyst
[18]. Vanadium mobility varies from unit to unit, de-
pending on, among other things, the level of excess
oxygen in the regenerator [19]. Catalyst manufactur-
ers have developed more stable zeolites (for example:
CSSN and CSX) and a series of vanadium traps to in-
crease the ability of the zeolite to handle vanadium.
These traps are based on Ba, Ti, Rare Earth, and other
elements. Some are more effective than others, but the
basic idea is the same, i.e. to keep the vanadium away
from the zeolite by binding to the surface of an inac-
tive particle.
Catalyst manufacturers are continuously striving to
improve the stability of their catalysts to metals poi-
soning as resid processing becomes more important in
the future.
3.2. Catalyst connectivity and transport limitations
Another change in FCC catalysts in the 1990s was
the introduction of materials that have good bottoms
cracking performance. At constant conversion of
feed, these materials convert a greater percentage of
>370 ◦ C boiling range material to products. The abil-
ity of the feed molecules to reach the active sites of the
catalyst is important and for heavy resid molecules,
mass transport limitations play an important role [20].
In order to handle the challenges associated with
cracking of resid molecules, catalyst manufacturers
394 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396
have increased the use of high surface area alumina in
the catalyst. These aluminas have a small crystal size
and significant pore volume in the 50–600 Å range.
Very small pores 50–100 Å increase bottoms cracking,
but do so at the expense of coke formation. Catalysts
with the intermediate pores 100–300 Å have a lower
matrix surface area for the same pore volume, but tend
to convert resid molecules into more useful products.
There is increasing evidence that the external sur-
face area of the zeolite is responsible for a portion of
the bottoms cracking activity of the catalyst. There-
fore, it is important to construct the catalyst in such a
way as to ease mass transport limitations to the sur-
face of the zeolite.
New technologies are emerging in the area of bot-
toms cracking designed to reduce the mass transport
limitations of larger molecules. We expect this area to
grow significantly over time
4. Short contact time (SCT) cracking
In order to minimize non-selective post riser crack-
ing many refiners are revamping their units to operate
in the so-called “short contact time” mode. In the
FCC operation, catalyst and feed are contacted at the
bottom of the riser with cracking reactions proceed-
ing along the length of the riser as depicted in Fig. 2.
Fig. 2. Basic profiles of kinetic trajectories along the FCC riser. Schematic adapted from [2].
Contact time over the length of the riser is ca. 5–8 s.
At the end of the riser, the catalyst and products are
separated in the disengager. It is here that product
vapor can undergo non-selective (essentially thermal)
cracking as hydrocarbon vapors come into contact
with hot, coked catalyst.
In the early 1990s, a closed cyclone system was in-
troduced that featured cyclones directly coupled to the
end of the riser [21]. This allowed rapid separation of
the catalyst and products, reducing post riser cracking
in the disengager. Today, all major process licensors
offer advanced riser termination technologies of one
sort or another with one objective in common - reduc-
tion of non-selective post-riser cracking.
New processes are emerging where the catalyst/feed
contact time is reduced to less than 2 s. The so-called
millisecond catalytic cracking (MSCC) process was
introduced in the early 1990s in the U.S. [22]. The first
MSCC unit in Europe is expected to be on-stream in
2001.
5. FCC catalysts for SCT operations
Catalysts for SCT operations must be designed tak-
ing into account the following considerations [23]:
• catalyst/oil contact time is shorter—leading to lower
intrinsic conversion and bottoms cracking;
 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396
• reactor temperature is generally higher—leading to
increased conversion and light olefins yields (in-
cluding increased gasoline olefinicity);
• catalyst circulation rate is generally increased—
leading to an overall increase in selective conver-
sion;
• regenerator/regenerated catalyst temperatures are
generally lower—leading to cooler catalyst/oil mix
zone temperature, hence the need for improved
feed nozzles to ensure efficient feed vaporisation.
To compensate for the reduced catalyst/feed con-
tact time and consequently loss in conversion, high
activity catalysts are needed. The zeolite component
within the catalyst has the greatest effect on activity
and therefore, proper zeolite selection is very impor-
tant. In addition, it is very important to choose a matrix
with the right level of activity for a particular appli-
cation to address the reduction in bottoms upgrading
that occurs with shorter contact time. Excess matrix
activity is undesirable because it leads to poorer coke
and gas selectivities. In addition to providing bottoms
cracking activity, the matrix should be selected to pro-
vide low coke and gas selectivities, particularly in the
presence of contaminant metals.
6. Product and selectivity control
Petroleum refiners that have close connection to
chemical plants have a strong economic incentive to
produce chemical feed stocks. This area has a par-
ticular application in the production of light olefins
(propylene and butylene) which have driven the recent
growth of ZSM-5 usage in FCC units worldwide.
6.1. Light olefin production
The market for propenes and butenes is cyclical, and
depends on the local demand for plastics precursors
and alkylate feed [24]. In 1998, 45% of U.S. propylene
was produced by the FCC unit [25]. The production of
MTBE has declined due to environmental concerns,
but is still a strong driver for isobutylene. There are
several key determinants of light olefin selectivity. In
addition to increasing reactor temperature and using
ZSM-5, catalysts can be designed with lower hydrogen
transfer (to reduce the conversion of isobutylene to
395
isobutane) and moderate matrix activity (to increase
the C4-olefinicity of the product) [26].
The addition of ZSM-5 is the single most important
method to increase the yields of light olefins at the ex-
pense of gasoline. Catalyst producers have developed
methods to increase the concentration of the ZSM-5 in
their additives in order to avoid dilution effects at high
levels of additive. The breakthrough technologies in
this area involve the stabilization of the ZSM-5 to hy-
drothermal deactivation at higher concentrations in the
additive. Current commercial technologies range from
10–25% ZSM-5, although techniques are expected to
allow much higher levels in an additive particle. Sev-
eral recent efforts have also been made to change the
selectivity of ZSM-5 by increasing the Si/Al ratio to in-
crease the ratio of butene to propene. However, this ap-
proach reduces the overall activity quite significantly.
In addition to C3 and C4 olefins, FCC catalysts can
also be designed to increase ethylene yield. World-
wide demand for ethylene is expected to increase by
50% between 1998 and 2010 [27]. With the correct
application of current catalyst technologies, increases
of 6 wt.% ethylene can be observed.
6.2. Production of chemical precursors
In addition to light olefins, the FCC catalyst can be
designed to enhance the production of several other
chemical precursors. The yields of xylenes and BTX,
for example, can be selectively increased in the FCC
gasoline range [28]. Effective use of these technolo-
gies depends on efficient separation technologies.
7. Conclusions
Over the last decade, the field of fluid catalytic
cracking has advanced considerably in the areas of alu-
mina technology (for improved binding and improved
cracking of heavy resid molecules), zeolite stability
(for improved activity and surface area retentions), and
tolerance to catalytic poisons (for improved process-
ing of heavy feeds containing high levels of Ni, Fe,
and V). Current developments are improving the cat-
alyst technology in response to environmental regula-
tions on emissions (particulates, NOx , SOx , and CO)
and the composition of transportation fuels (e.g., sul-
fur in diesel fuel, gasoline sulfur, benzene and olefins
396 R.H. Harding et al. / Applied Catalysis A: General 221 (2001) 389–396
content). In addition, breakthroughs in the stabiliza-
tion and composition of ZSM-5-based additives have
given more control over light olefins selectivity.
Future catalyst developments in the area in FCC
are likely to continue to be driven by response to en-
vironmental regulation, changes in feed quality, and
advances in reactor hardware.
Acknowledgements
The authors thank Grace GmbH and Co. KG for
permission to publish this work.
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