Annual Meeting

March 23-25, 2003

Marriott Rivercenter Hotel
San Antonio, TX

AM-04-45 Controlling FCC Yields and Emissions

UOP Technology for a Changing
Environment

Presented By:

Keith A. Couch
FCC Process Specialist
UOP LLC
Des Plaines, IL

Kelly D. Seibert
FCC Technology
Manager
UOP LLC
Des Plaines, IL

Pete Van Opdorp

Senior FCC Specialist
UOP LLC
Des Plaines, IL

National Petrochemical & Refiners Association 1899 L Street, NW 202.457.0480 voice

Suite 1000 202.429.7726 fax
Washington, DC www.npra.org
20036.3896
This paper has been reproduced for the author or authors as a courtesy by the National
Petrochemical & Refiners Association. Publication of this paper does not signify that the
contents necessarily reflect the opinions of the NPRA, its officers, directors, members, or staff.
Requests for authorization to quote or use the contents should be addressed directly to the
author(s)
 CONTROLLING FCC YIELDS AND EMISSIONS
UOP TECHNOLOGY FOR A CHANGING ENVIRONMENT

Keith A. Couch, Kelly D. Seibert and Pete J. Van Opdorp

UOP LLC
Des Plaines, Illinois, USA

INTRODUCTION
Optimizing a fluid catalytic cracking (FCC) unit requires the balancing of many operating
variables. However, the refiner is required to operate within certain limits when it comes to
process manipulation. These limits can include feedstock quality, equipment capacity, system
design, and environmental constraints. Over the past 20 years, FCC technology has seen
significant improvement in catalyst, equipment, and process design. Catalyst companies have not
only advanced basic catalyst design, but have developed emission and yield selective additives.
Technology licensors have continued to make advancements in feed distribution systems, riser
termination devices, and spent catalyst stripping. Each has contributed to improved operability
and product selectivity through essentially the same objective: lowering the delta coke (weight
percentage of coke on catalyst per pass through the regenerator) to achieve better yields and
higher throughput.

In practical application, lower delta coke (∆Coke) in the FCC unit manifests itself as a cooler
regenerator dense-bed temperature. Traditionally, a lower regenerator temperature has permitted
greater flexibility to increase unit conversion, and thereby improve unit profitability. Refiners
have progressively revamped their FCC units toward this goal. As improved equipment

© 2004 UOP LLC. All rights reserved.

AM-04-45
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technology and catalyst offerings result in compounded decreases in ∆Coke, hydraulic limits can
be reached in the catalyst circulation between the reactor and regenerator. While it can be
tempting to relieve one aspect of a hydraulic constraint through a slide valve or standpipe
modification, not paying attention to the overall “system” design can result in moving a problem
to another location and effectively accepting greater reliability risk. With the on-set of clean
fuels initiatives, these issues can be further strained by an increase in the percentage of
hydrotreated feed to the FCC unit. While this presents problems that the refiner must overcome,
it also presents some excellent financial and environmental opportunities.

This paper will highlight the UOP technology improvements that provide for higher conversion,
better product selectivity, and lower flue gas emissions from the FCC unit, while providing the
refiner with greater reliability and flexibility to maximize margins in a competitive marketplace.

REACTOR HARDWARE FOR IMPROVED PERFORMANCE

The path for improved FCC performance typically begins with the reactor side of the unit. The
feed distributor system, riser termination device, and spent catalyst stripper are the three
common areas where substantial improvements can be achieved.

FEED INJECTION SYSTEMS

When a refiner decides to upgrade equipment technology on an FCC unit, quite often they start
with the reactor riser and feed distribution system. The reasons for this selection are straight
forward:

„ Well defined and commercially proven yield and process benefits

„ High return on investment
„ Lowest CAPEX project possible for a major technology upgrade

With each generation of feed distributor technology, the catalyst and oil contacting has been
improved to achieve lower coke and dry gas yields with improved product selectivities. This is a
progression that started in the early 1970s and continues today.

The benefit that a refiner can realize through an upgrade in FCC feed distribution technology is
mostly dependent on the vintage of the existing feed injection system. The older the existing
technology, the greater the benefit will be. Significant benefit can also be realized through
technology upgrades within each vintage of feed injection. A review of the history behind
modern feed distributor systems is useful to understanding the current state of the technology.

AM-04-45
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Feed Injection History

In early FCC units, raw oil feed was injected into a moving catalyst stream that disengaged into a
fairly dense bed reactor. Long contact times were required due to low activity amorphous
catalysts. In the 1960s, high-activity zeolitic catalysts became the standard and greatly increased
the conversion potential of the FCC unit. To improve product selectivities, modifications to the
reactor were made to decrease the contact time between the catalyst and the oil. At that point,
existing reactor systems started to be revamped to include a riser termination device through
which the catalyst and hydrocarbon were disengaged and separated at the top of the riser.

Within the original dense-bed reactor systems, riser feed injection was through an open ended
pipe “bayonet” inserted into the base of the catalyst riser. “Bayonet” feed distributors were
quickly replaced with “showerhead” distributors that incorporated multiple nozzle jets to achieve
better oil distribution across the diameter of the riser.

In the late 1970s and throughout the 1980s, UOP focused its effort on improved oil and steam
mixing inside the distributor for better dispersion into the flowing catalyst stream. The result of
this effort was the “Wye Premix” distributor in which the steam and oil passed through a
tortuous path of mechanical internals to create a pseudo-emulsion phase for better distribution
into the flowing catalyst.

It was recognized that optimal feed injection in the area around the Wye section of the riser was
hindered by the large mass flux of catalyst changing direction to move up the riser. This
turbulent environment included significant back-mixing and density gradients, which contributed
to uneven oil–catalyst contacting. The single feed distributor at the base of the riser was
eventually replaced with multiple, elevated distributors spaced around the circumference of the
riser. During the late 1980s and early 1990s, elevated feed injection became the norm throughout
the FCC industry.

To optimize the elevated feed injection into an FCC unit, UOP considered the entire feed
distribution system, not just a single piece of equipment. UOP accomplished this by expanding
its vision beyond just the feed distributor toward the dynamic balance between the physical
properties of the oil, steam, and flowing solids in the riser. This led to the concept of properly
conditioning the catalyst phase prior to feed injection.

The acceleration zone is the vertical section between the base of the Wye and the elevated feed
distributors (Figure 1). Proper riser design and operation of the acceleration zone result in a more
even catalyst flow distribution and lower slip factor. “Slip” is defined as the ratio between the
gas-phase velocity and the catalyst-particle velocity. A riser operating with a high slip factor has
the gas rising significantly faster than the catalyst. Uneven catalyst flow, back-mixing, and high

AM-04-45
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slip in the riser can lead to localized areas of high temperature and feed over-cracking which
result in higher coke and dry gas yield, and reduced selectivity to desired products.

Figure 1
Reactor Riser Dynamics

Reaction Zone
Riser (Minimum Slip /
Plug Flow)

Initial Contacting
Zone

Riser Length
Regenerated Elevated
Catalyst Feed
Injection Acceleration
(High Slip/Back
Mixing)
Acceleration
Zone

Riser Density

Wye Injection

With the functionality of the lower riser better understood, efforts were shifted to the feed
distributor. The first task with the feed distributors was to optimize the degree of feed
atomization and dispersion to achieve an even distribution and penetration into the riser. One
problem associated with atomizing oil with steam is the inherent nature of these materials to
separate. Steam injection into the oil phase is ineffectual if the oil is allowed to re-coalesce prior
to exiting the feed distributor tip. This could be overcome in large part through higher steam
injection. However, over-atomizing the oil to alleviate this problem not only increases operating
cost through increased steam consumption and sour water production, but can also force unit
operations above recommended or hydraulic constraints. The objective should be to develop an
atomized spray of uniform droplet size, with proper mass and velocity to achieve controlled
penetration into the flowing catalyst phase.

OPTIMIX™ FEED DISTRIBUTION SYSTEM

The primary result of all this work was the Optimix feed distribution system. The Optimix
system incorporates the feed distributor (Figure 2), the riser acceleration zone, and the feed
preheat process. In this system, the riser section below the feed distributor is designed to achieve
a moderate and uniform catalyst density for optimum feed dispersion into the riser. The feed
distributors are designed with three stages of atomization to achieve efficient use of energy with
minimized oil re-coalescing.

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 Figure 2
Optimix Feed Distibutor

Steam
Inlet

DUR O LOK™
Couplings

U P N
O
NO

PR

GG A
I A
D

IN S

CU
SS

TA

AT
B

T
Oil
Feed
Inlet

1 2 3

Riser Nozzle Atomizing Stages

Flange

The Optimix feed distributor was introduced to the market in 1994. Since that time the
distributors have gone through several stages of mechanical design improvements. The
distributor tip design has been improved to control erosion and meet the demands of refiners
wanting to achieve turnaround cycles greater than five years. Today’s Optimix feed distributors
are designed to achieve two operating cycles, or 10 year service life, without replacement.

Another major mechanical advancement to Optimix feed distributor designs is the inclusion of
DUR O LOK couplings on both the inner oil gun assembly, and the outer distributor barrel
assembly (Figure 2). In previous generations of feed distributors, if the refiner wanted to either
significantly change throughput capacity, optimize performance with a dramatically different
feed slate (VGO vs. resid), or plan for 10 year maintenance spares, complete replacement of the
feed distributors would have been recommended. Through application of the DUR O LOK
couplings, UOP has lowered the cost to the refiner by limiting the maintenance requirement to
periodic replacement of only the outer tip assembly. In applications of throughput increase or
feed slate change, both the internal oil gun and outer tip assembly can be easily changed-out.

AM-04-45
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UOP offers several variations of the Optimix feed distributor in diameters from 3 to 8 inches that
include:

„ Standard Optimix
„ Optimix LS – for low steam consumption
„ Optimix RF – for primarily residue feed processing

The results of these efforts are a feed distribution system that can be optimized for any FCC
application.

Optimix feed distributor experience as of February 2004:

„ 80 unit installations world wide

„ Complete application range
─ Hydrotreated VGO through 100% residue operation
─ Conradson Carbon up to 7.5 wt-%
─ Riser diameter application range: 1.9 ft ⇒ 9.0 ft
„ Typical revamp benefit: elevated distributors to elevated Optimix distributors
─ Conversion: 1.0 – 2.0 lv-% increase
─ Gasoline yield: 0.7 – 1.5 lv-% increase

REACTOR RISER TERMINATION DEVICES

Replacement of the riser termination device (RTD) with modern technology typically involves
removal of the reactor head, and replacement with a new head, plenum chamber, and cyclone
assembly. As such, upgrading the RTD is often associated with a throughput increase or
maintenance turn-around in which the reactor cyclones have been identified for replacement.

RTD History
UOP riser termination devices have included:

„ Tee Disengager
„ Down-Turned Arm
„ Vented Riser: 16 placed into operation, 6 since modified to VSS RTD
„ Direct-Connected Cyclones: 7 placed into operation, 2 since revamped to VSS RTD
„ Vortex Separation Technology (VSS and VDS): 36 placed into operation

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 Figure 3
Progression of Riser Termination Technology

“Tee” “Down-Turned “Vented Riser” “DCC-SCSS”

Arm”

With the introduction of riser cracking, modern reactors could more properly be called a
disengaging vessel. Down-turned arms replaced tee disengagers starting in the 1980’s. This
provided improved separation efficiency and a reduction in catalyst loss from the reactor.
Additional benefits of this technology upgrade were reduced catalyst fines generation and
reduced mechanical erosion to the disengager as a result of less abrupt directional change in
catalyst flow.

The vented riser termination system was commercialized in 1983 and represented a step-change
advancement in RTD technology. It was the first UOP RTD system to offer “hydrocarbon
containment.”

The next significant improvement in riser termination devices was the direct-connected cyclone
(DCC) system. UOP in conjunction with Mobil Oil commissioned the first DCC in 1988. The
DCC RTD further increased hydrocarbon containment and improved yield selectivities. It did,
however, suffer from sensitivity to pressure upsets which made it a bit “temperamental,”
especially during startups.

Because DCC represented a major reduction in post-riser cracking, it was it was also very
sensitive to riser residence time. Conversion loss had to be compensated with higher severity in
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the other process variables (reactor temperature, catalyst activity, catalyst-to-oil ratio). Although
the DCC pushed yield selectivity to the highest level achieved, it suffered from some serious
operating issues that needed to be addressed.

In the early 1990s UOP commercialized the Suspended Catalyst Separation System (SCSS).
While it was similar to the DCC, it incorporated a pressure relief system at the top of the riser
that made it much less sensitive to pressure upsets. In both the DCC and the SCSS, the cyclones
are connected directly to the riser which provided for 100% of the catalyst circulation and
reaction products to flow directly into the cyclones.

With the high primary cyclone catalyst loading associated with DCC systems, the downward
velocity of catalyst through the dipleg entrains hydrocarbon with the catalyst circulation and
discharges the mixture into the reactor vessel where it is subject to post riser cracking. The flow
rate is actually high enough to account for an effective 6% loss in hydrocarbon containment.

VSS and VDS Riser Termination Devices

To address the hydrocarbon entrainment in the catalyst discharge from the diplegs, for improved
yield selectivities, and make the RTD more operator friendly, UOP developed vortex separation
technology (Figure 4). This includes the vortex separation system (VSS) RTD for internal risers
and the vortex disengager stripper (VDS) RTD for external risers. Since its first installation in
1991, 30 VSS RTD’s and 6 VDS RTD’s have been placed into operation. Applications range
from 8,000 BPSD to 184,000 BPSD.

In VSS / VDS RTD’s, catalyst is centrifugally discharged from the top of the reactor riser in the
horizontal plane, swirls downward along the wall of the vortex chamber, and accumulates in the
pre-stripping section. The small portion of catalyst that is carried to the cyclones exits into the
reactor vapor space and accumulates as a bed on the outside of the vortex chamber, thus sealing
the stripper from the reactor vapor space. The level in the system is controlled so that the catalyst
entering the stripper from outside the vortex chamber does not drop below the top of the
“window” openings into the stripper. The catalyst in the pre-stripping section counter-currently
contacts stripping steam and hydrocarbon rising out the top of the integral stripper. The net
superficial velocity of the catalyst as it flows into the stripper is well below the hydrocarbon
bubble rise velocity, allowing the hydrocarbon to be “pre-stripped” from the catalyst. This
minimizes hydrocarbon entrainment into the stripper and resultant bed cracking reactions that
preferentially form dry gas and coke. The vapor outlet from the RTD is directly connected to a
single stage of conventional cyclones. The swirl arm/chamber configuration effectively separates
95% of the catalyst from the hydrocarbon stream. Since only 5% of the catalyst enters the
cyclone, the hydrocarbon underflow to the reactor vessel is essentially 5% of the DCC system.
The net result is an improvement in hydrocarbon containment from 94 to 99.7%; meaning very
little hydrocarbon is allowed to over-crack to dry gas and coke.
AM-04-45
Page 8
 Figure 4
Vortex Separation Technology

“VDS” “VSS”
1991 1995

VSS
Disengager

Swirl
Arms

VSS
Chamber

To help quantify the potential benefits of increased hydrocarbon containment, UOP

commissioned an independent laboratory to sample a reactor equipped with a DCC riser
termination device (see Figure 5). The reaction mix sampling was conducted on the vapor line
(Point 1) and the annular area (Point 2). The results are presented in Figure 5. The sampling of
the cyclone outlets (Point 1) shows the more desirable products of a highly contained system.
The sampling of the reactor vessel open area (Point 2) represents the effects of post-riser
cracking of un-contained hydrocarbon and high residence time. Although the high LPG yield
associated with the un-contained sample might appear attractive to some refiners, the olefinicty
of the LPG is decreased by ~80% due to hydrogen transfer reactions. The long residence time
also produces significant increases in dry gas and coke. The net effect is that whatever
hydrocarbon escapes from a highly contained RTD will be dramatically changed to a lower
economic value before it finally exits the system.

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 Figure 5
Hydrocarbon Containment

Point 1
Effect on FCC Reaction Products

Cyclone Outlet Reactor Vessel

Yields (Point 1) (Point 2)

C2-, wt-% 2.7 15.6 Point 2

C3, lv-% 8.9 17.2
C4, lv-% 14.9 20.4
Gasoline, lv-% 54.2 46.6
LCO, lv-% 20.9 10.0
Slurry, lv-% 8.1 5.8

In addition to “best of class” hydrocarbon containment, with only a single stage of cyclones
required, VSS / VDS RTD’s excel in de-bottlenecking existing reactor vessels by making the
most efficient use of reactor cross-sectional area of any high containment RTD available. A
recent VSS RTD revamp design accommodated an increase of >50% in throughput while
accommodating a higher conversion than the original design and maintaining the existing reactor
shell.

Even with the excellent performance already achieved, UOP continues to optimize the VSS /
VDS RTD’s for improved operability, reliability, and higher containment. While some
hydrocarbon will always flow down the cyclone diplegs with the catalyst discharge, UOP has
recently designed an improvement that reduces the volume into which the cyclone diplegs
discharge by 50% to further “contain” the hydrocarbon. This improvement also provides a 10%
reduction in active catalyst inventory and fresh catalyst make-up requirements.

SPENT CATALYST STRIPPING

The primary objective of the FCC stripper is to remove the “strippable” hydrocarbon from the
spent catalyst. Early stripper designs incorporated anywhere from one to nine stripping stages.
As catalyst and hardware changes achieved lower ∆Coke operations, catalyst circulation rates
were pushed progressively higher and a decline in stripper efficiency was observed. Refiners lost
valuable products to the regenerator and had to increase stripping steam rates, or reached a
hydraulic bottleneck in the unit. The loss of stripper efficiency offset a portion of the benefit

AM-04-45
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gained from the lower ∆Coke operations achieved through the previous revamps, i.e., upgraded
feed distribution system and/or riser termination device.

Improved stripping of hydrocarbon from the spent catalyst can provide significant processing
and yield advantages. To maintain the unit heat balance, the coke component that is removed
from the regenerator by more efficient stripping can be shifted to catalytic coke to produce
higher conversion.

AF Stripper Technology

In early 1997, UOP launched an intensive review of FCC stripper technology in which we
challenged much of what the industry thought to be true about hydrocarbon displacement in the
FCC stripper. The bulk of the work focused on an extensive cold flow modeling program in
which 15 different styles of stripper internals (both UOP and competitive) were tested. UOP
constructed two large scale models, one “wedge” and one “cylinder”, which would accurately
simulate commercial sized stripper hydraulics.

The “wedge” model was developed to simulate the actual spatial conditions of a commercial 8 ft
diameter annular stripper. The model could generate commercial tray pressure drops across an
eight-tray configuration, and allowed for jet and bubble dynamics and catalyst flow to fully
develop. The model was able to support studies up to a catalyst flux of 140,000 lb/ft2/hr (2,333
lb/ft2/min). Within this model, UOP tested various historical and developmental tray
configurations, including high flux bypass tubes. The “cylinder” model was constructed to test
non-annular tray configurations, including various types of full cross-section trays, gratings, and
structured packing.

The first development from the stripper improvement program was the AF tray technology. The
AF tray was commissioned in 1998 and as of February 2004, there are 27 applications. An
additional 21 AF tray strippers are in various stages of design and construction. These stripper
installations have resulted in an average ∆Coke reduction of 0.04 wt-% at a typical steam
consumption of 2 lbsteam / 1000 lbCatCirc. The 0.04 wt-% ∆Coke reduction equates to an average
22°F reduction in regenerator temperature, a 6% increase in catalyst-to-oil ratio, and all of the
associated conversion, yield, and selectivity benefits.

The benefits of the AF stripper technology are realized through more efficient contacting
between steam and catalyst with improved hydrocarbon displacement. For a given unit design
capacity, the dimensions of an AF stripper are ~10 ft shorter in length with equivalent diameters
to those of an equal capacity FCC unit designed in the 1990s.

In addition to improved stripping efficiency, a primary objective of the improvement program

was to increase the catalyst flux capacity of stripper designs. The success in this area has been
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tremendous. One particular application of AF stripper technology has been operating routinely at
a catalyst flux rate of 120,000 lb/ft2/hr (2,000 lb/ft2/min) with stable operations. This represents a
20% capacity increase over the pre-revamp operation without any changes in stripper cross-
sectional area.

The second and third developments from the stripper improvement program were the AF grid
and AF packing designs. The first unit with grid style stripper internals was commissioned in
2002. As of February 2004, five grid style AF strippers have been placed into operation. This
brings UOP’s commercial experience with AF stripper technology to 32 operating units. The first
AF packing design has been awarded and is currently in engineering.

THE ∆COKE CHALLENGE

As improved equipment technology and catalyst offerings have resulted in progressive decreases
in ∆Coke, many refiners have continued to de-bottleneck unit constraints within the capacity of
existing major equipment, often with the constraint of not replacing main vessels or large
rotating equipment, i.e., main air blower (MAB), wet gas compressor (WGC), regenerator shell,
reactor shell, stripper shell, and catalyst circulation standpipes. Maintaining this philosophy
through several technology upgrades can result in several operational and reliability concerns.

1. Excessive catalyst loading to regenerator cyclones

– Cyclone erosion, fines generation
2. High catalyst circulation and catalyst flux
– Insufficient regenerator & stripper residence time
– Hydraulic instability or limitation in the catalyst standpipes
3. Excessive catalyst fines to the flue gas system
– Increased particulate matter (PM) emissions

Improvements in FCC technology to achieve lower ∆Coke operations, not only present the
concerns listed above, but also cause refiners to face several dilemmas between “wants” and
often conflicting “also wants” (see Table 1). Optimum product selectivities, conversion, and
throughput are traditionally opposite to lower coke yield, optimum coke combustion, and
retaining existing equipment.

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 Table 1
Conflicting “Wants”

“WANTS” “ALSO WANTS”

Optimum Product Selectivities BUT Sufficient regenerator temperature for
„ Improved coke burn kinetics
Higher Conversion BUT Lower coke yield for
„ Improved selectivity and
„ Lower CO2
Less Dry Gas BUT Sufficient regenerated catalyst
Temperature for
„ Improved coke burn kinetics

Higher Throughput BUT Retain existing equipment – Min CAPEX

„ MAB, WGC, standpipes

COMBINED TECHNOLOGY EFFECTS

Figure 6 shows the expected benefits to be obtained from a stew-wise improvement in FCC
reactor technology. The individual steps include:

1) Replaced elevated Premix distributor with elevated Optimix feed distribution system
2) Replaced reactor stripper with an AF stripper technology
3) Replaced a tee RTD with a VSS RTD

With each progression, the refiner gains the yield and selectivity benefits inherent of increased
catalyst-to-oil and lower ∆Coke. The combined technology improvements result in a 23%
increase in catalyst circulation and a regenerator dense-bed temperature reduction to 1260°F. The
technology benefits are summarized in Table 2.

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 Figure 6
Technology Upgrade Effects

Regenerator Dense Bed, °F 1330 16

Regen Temp
(0) 14
1310
12

Cat/Oil
(1)
1290
10
Cat/Oil
1270 (2)
8
(3)
1250 6
Elevated Elevated + AF + VSS
Premix Optimix Stripper RTD

Table 2
Technology Upgrade Effects
Base Case
Premix Feed Plus
Distributor VSS
(Point 0) (Point 3)

Cat-to-Oil 8.27 10.14

Regen Temp, °F 1324 1260
Conversion, lv-% Base +0.7
(90% at 380°F)

Gasoline, lv-% Base +1.8

(90% at 380°F)

Coke, wt-% 5.6 5.6

∆Coke 0.68 0.55

As hydraulic limits are reached in the catalyst circulation between the reactor and regenerator it
can be tempting to relieve one aspect of a hydraulic constraint through a slide valve or standpipe
modification. However, not paying attention to the overall design can simply result in the
relocation of the constraint and the introduction of greater risk to the system reliability. With the
on-set of clean fuels initiatives, these issues can be further strained by increasing the percentage

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of hydrotreated feed to the unit and further decreasing the ∆Coke and regenerator temperature.
Refiners moving towards more hydrotreated feeds are often placed in the position of opting for
less coke selective catalyst, firing the air heater, or firing torch oil to add heat to the regenerator.
The use of less coke selective catalyst (more coke produced) negates yield and selectivity
benefits previously gained from equipment upgrades. Firing the direct fired air heater for long
durations can lead to erosion and failure of the air distributor as the distributor jets are pushed
beyond design exit velocities. These high exit velocities can also lead to excessive catalyst fines
generation. Firing torch oil to keep the regenerator hot essentially burns high value feedstock as
fuel, while at the same time damaging the catalyst activity. The burning of any fuel in the
regenerator apart from coke on the circulating catalyst inventory is an economic loss.

While the above issues present problems that the refiner must overcome, they also presents some
excellent operational, financial, and environmental opportunities.

THE RXCAT SOLUTION

The problems of low ∆Coke operations (low regenerator temperature) have created an
opportunity that UOP has uniquely addressed. Traditionally the catalyst from the bottom of the
reactor stripper has commonly been referred to as “spent”. However, modern catalyst systems
can accumulate appreciable quantities of coke and still maintain a significant amount of activity.
UOP has adopted the term “carbonized” to describe this catalyst. The activity characteristics of
carbonized catalyst are not only usable, but in certain cases preferred. Coke deposition
preferentially attenuates the strongest catalytic sites providing for more selective cracking with
carbonized catalyst. To take advantage of the selectivity benefits of conditioned catalyst, UOP
developed RxCat technology.

In a traditional FCC unit, increasing the catalyst-to-oil ratio to increase conversion also increases
the coke yield and catalyst circulation to the regenerator. RxCat technology provides the ability
to increase both conversion and selectivity by recycling a portion of the carbonized catalyst back
to the base of the reactor riser (Figure 7). The carbonized catalyst circulated from the stripper
back to the base of the riser is effectively at the same temperature as the reactor. Since the
recycle catalyst adds no heat to the system, the recycle is heat-balance neutral. For the first time,
the catalyst circulation up the riser can be varied independently from the catalyst circulation rate
to the regenerator and is de-coupled form the unit heat balance.

With RxCat technology, a portion of the stripped catalyst (~1000°F) is directed through the
recycle catalyst standpipe to the MxR chamber where it is combined with the hot regenerated
catalyst (~1300°F). The lower contact temperature between the combined catalyst and raw oil
feed results in higher product selectivity with less dry gas and coke production, and a substantial
increase in conversion due to the higher riser catalyst-to-oil ratio. Similar to a conventional FCC
unit, the balance of the carbonized catalyst that is not recycled travels through the stripper to the
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regenerator where the coke is burned off before it returns to the base of the riser. The catalyst
flowing to the regenerator carries a higher coke content, which in turn raises the regenerator
temperature and enables the easing of constraints in the system.

Figure 7
RxCat Technology

Combustor Style
High-Efficiency
Regenerator
VSS Riser
Termination
Device

Carbonized
Catalyst
Recycle

Spent Catalyst
Standpipe

Carbonized
Catalyst
Slide Valve

Regenerated MxR Chamber

Catalyst Standpipe

The ability to control the catalyst flow up the riser independently of the heat-balance adds
increased flexibility to the FCC unit to more easily handle changes in feed quality and shifting
product slates. This aspect of the technology is particularly useful in units that periodically
switch from gasoline to olefin or distillate mode, throughout the year. In a conventional FCC unit
a shift in operating mode is accomplished by a change in reactor temperature and a change in the
rate or activity of the catalyst make-up. With RxCat technology, a change in catalyst activity in
the riser can be accomplished by merely changing the amount of carbonized-catalyst recycle and
as such, the change from gasoline mode to/from olefin mode can be rapid. This application has
an even greater impact for refiners that use LPG olefins additives, i.e., ZSM-5 or Supra ST-5,

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and have traditionally had to shift their catalyst inventory over several weeks to reap the full
financial benefits of a change in product slate.

As of February 2004, three RxCat designs have been delivered to customers. Two of these units
are now under construction, and the first unit is expected to go on-stream in mid-2004.

Integration of RxCat technology provides numerous benefits in both revamp and new unit
applications, providing the refiner with the ability to accomplish many of the following:

„ Increased conversion
„ Increased gasoline yield
„ Decreased dry gas yield
„ Increased propylene yield with additive use
„ Decreased coke yield at constant conversion
„ Increased regenerator dense bed temperature
„ Increased regenerator residence time
„ Lower regenerated and spent catalyst standpipe flux
„ Lower regenerator emissions

Two of the largest benefits listed above are described briefly below.

Increased conversion - The substantial increase in riser catalyst-to-oil ratio results in a

significant increase in conversion. At a 1:1 blend of carbonized to regenerated catalyst, the
catalyst-to-oil ratio in the riser will typically increase 3 to 4 numbers. At a constant reactor
temperature and catalyst activity, conversion can be increased 3 to 5 lv-%. Alternatively, the
large increase in the catalyst-to-oil ratio with its corresponding increase in conversion allows the
reactor temperature (and hence thermal cracking) to be reduced while still maintaining or
exceeding the original conversion level. Depending on the severity of the operation and the
catalyst quality, most of this conversion would be directed towards increased gasoline yield.

Decreased dry gas yield – A major portion of the thermally cracked (dry gas) products formed
in conventional FCC units occurs at the initial point of catalyst-feed contact due to the hot
catalyst temperature. The catalyst blend from the MxR chamber results in a mix-zone
temperature typically 150°F lower compared to a conventional FCC unit. This large reduction in
catalyst temperature results in a large reduction in C2- yield which could be very valuable in units
limited by dry gas production.

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In addition to the yield and selectivity benefits, RxCat technology can be used to effectively de-
bottleneck unit constraints. Approximately half of the catalyst that would traditionally circulate
from the reactor to the regenerator is recycled to the base of the riser. As such, the catalyst
circulation through the spent and regenerated catalyst standpipes is actually less than the “base
case” operations before any technology upgrades were initiated. As opposed to a purely
mechanical modification which utilizes CAPEX (new reactor, stripper, standpipes, etc.) for only
capacity benefits, RxCat technology pays back with both increased throughput and product
yields.

The expected benefits for the previously presented case study with the implementation of RxCat
technology is shown below in Figure 8 and Table 3.

Figure 8
Effect of RxCat Technology on Unit Performance
Riser Cat/Oil
1330 16
(0) (4)
Regenerator Dense Bed, °F

Regen Temp
14
1310
12

Cat/Oil
Base
1290
10
Cat/Oil
1270
8
Regen S. P.
Cat/Oil 6
1250
Elevated Elevated + AF + VSS + RxCat
Premix Optimix Stripper RDT

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 Table 3
Effects of RxCat Technology on Unit Performance

Base Case Cumulative

Premix Feed to RxCat
Distributor Technology
(Point 0) (Point 4)
Riser Regen. Standpipe
Cat-to-Oil 8.27 15.6 7.8
Regen Temp, °F 1324 1312
Conversion, lv-% Base +3.8
(90% at 380°F)

Gasoline, lv-% Base +4.9

(90% at 380°F)

Coke, wt-% 5.6 5.4

∆Coke 0.68 0.35 0.70

The ability of RxCat technology to improve conversion and selectivity provides the refiner with
a tool to achieve improved yield targets with less coke make. The reduced coke make translates
to reduced air blower demand as well as a reduction in CO2 emissions.

EMISSIONS CONTROL
In addition to the desires for increased throughput, better yields and product selectivities, refiners
are facing increasing demands to reduce environmental emissions. Proper definition of specific
emission limits, today and future, and identifying the proper engineering controls to best address
these emissions can be a daunting task. UOP has some very effective solutions to meet refiner’s
needs.

PARTICULATE MATTER CONTROL WITH THE UOP THIRD STAGE SEPARATOR

Since the advent of the FCC third stage separator (TSS), the primary focus of the TSS was to
protect downstream power recovery system turbo-expanders. While power recovery system
applications have been in use for decades, UOP wanted to improve TSS technology to a point
where it could be used to effectively meet FCC flue gas stack PM emission standards.

UOP has been designing power recovery systems since 1973. Since that time, UOP has licensed
31 TSS’s with 20 placed into operation. The original units were designed by UOP under license

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from Shell. Over the years, UOP improved upon the original design by implementing several
modifications. Even with these modifications incorporated into the base design, very little had
actually changed in the overall design of the TSS in 25 years. These TSS designs still suffered
from the limitations imposed by radial flow gas distribution and reverse flow in the cyclone
elements.

In 1996, UOP launched a development program to design and offer a smaller, more economic,
high efficiency TSS that could not only be utilized in power recovery installations, but also be a
viable alternative to electrostatic precipitators and wet gas scrubbers for environmental
applications.

The cold flow modeling (CFM) test program extended over 2 years, during which both
dimensional variables and process flow variables were studied. Based on a thorough
understanding of cyclone theory, and drawing on other sources of cyclone expertise, the UOP
program investigated the contribution of many variables on catalyst separation efficiency. These
variables included:

„ Cyclone diameter and geometry

„ Inlet velocity
„ Length to diameter ratio
„ Outlet velocity
„ Catalyst loading
„ Gas distribution

Over 200 individual tests were conducted on single and multiple cyclone models to determine
the highest efficiency and highest capacity design cyclone. The tests were conducted with
commercial FCC catalyst fines. Computational fluid dynamic (CFD) computer modeling was
used to validate and benchmark the CFM work, and to quickly investigate potential
improvements and guide the physical modeling program.

The development work culminated in the new UOP TSS design (see Figure 9). The most
significant improvement in the design is that the UOP TSS utilizes axial flow for catalyst/gas
separation. The flue gas flow is maintained essentially in one direction - in the top and out the
bottom of the unit. Axial flow distribution minimizes the potential for solids re-entrainment
resulting from gas flow direction change and resultant eddy current formation. The older style
TSS utilizes radial flow distribution in which the flue gas is distributed from the centerline of the
TSS, radially outward between the two tube-sheets. As such, the inner tubes see a higher gas and
dust loading than the outer tubes. The mal-distribution of flue gas and fines inherent in this
design results in varying efficiency across the older style TSS.
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The new UOP TSS is about 40% smaller than other TSS offerings for the same capacity; making
it less expensive to fabricate, easier to install, and better suited where plot space is a premium.

Figure 9
Third Stage Separator Equal Capacity Comparison

Old Style TSS New Style TSS

29' 11' 6" OD

48 Tubes
23'

70 Tubes 19' 3" OD

The first UOP TSS was commercialized in April 2002. Performance testing on the unit was
performed twice in 2002, following the unit startup in April and again in December. The initial
test showed that the UOP TSS discharged between 36-50 mg/Nm3 of particulates, depending on
flue gas rate. The NSPS compliance testing resulted in a particulate matter emission of 0.6
lbs/1000 lbs of coke burn, only 67% of that allowed by NSPS standards. After nearly two years of
continuous operations no performance degradation has been observed (Table 4).

Table 4
Commercial Unit Stack Data
PM lb/M lb
Date PM lb/hr mg/Nm3 Coke

Sept. 2002 3.54 38 0.69

Dec. 2002 5.12 47 0.60
Oct. 2003 4.79 41 0.57

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This performance shows that the UOP TSS can replace more traditional and costly means
(electrostatic precipitators and wet gas scrubbers) of controlling particulates exiting the flue gas
stack.

In addition to the on-stream UOP TSS, there are currently four more in various stages of
engineering and construction with the second unit scheduled for startup in 2004.

COMBUSTION KINETICS
In the RxCat technology analysis (Table 3), we showed how coke yield could be decreased
coincident with increased conversion and improved yields through the advantages of decoupling
the catalyst circulation up the riser from the FCC heat balance. The benefit of lower coke
production can be utilized by the refiner either through increased capacity, increased severity, or
lower CO2 emissions.

Catalyst regeneration, as a carbon removal process, is widely accepted as being first order with
respect to carbon concentration and oxygen partial pressure. The change in coke concentration
on a catalyst particle with respect to time fits the following equation:

–∆E
– dC / dt = K0e CPo2
RT

Where:
K0 = Frequency constant, (hr-1atm-1)
C = Carbon on Catalyst, wt-fraction
Po2 = Oxygen Partial Pressure, (atm)
∆E = Activation Energy, BTU/lb-mol
R = Gas Constant, BTU/lb-mol/°R
T = Temperature, °R

Given a higher regenerator temperature, the coke burn rate is accelerated due to the increasing
rate constant. This relationship for the rate of carbon burning from FCC catalysts holds over a
wide range of temperatures with diffusional limitation not controlling. The important
relationships to note are that the rate of coke combustion increases with:

„ Higher coke content of catalyst

„ Higher oxygen partial pressure
„ Higher regenerator temperature

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The application of RxCat technology to the FCC unit can effectively increase all three variables.
Being able to manipulate each of these coke combustion drivers provides significant flexibility to
the FCC operator.

NOx Control and UOP’s High Efficiency Regenerator

In an effort to better understand the chemistry and variables that affect NOx production in an
FCC regenerator, UOP has embarked on a thorough investigative and development effort.
Feedstock characteristics and quality, excess O2 in the regenerator, use of CO promoter,
regenerated catalyst temperature, and regenerator design are among many variables evaluated.

While the industry has not observed a model-predictable relationship between feed nitrogen and
NOx, one particular FCC unit data set did show a substantial NOx response to a shift in the type
of feed processed. The unit response is closely related to two feed characteristics:

„ Degree of residue processing

„ Degree of feed pre-treating

In a refinery with a fixed infrastructure, (for example, always processing virgin gas oil with no
residue in the FCC), different feeds with varying amounts of basic or total nitrogen have shown
no strong correlation with NOx. However, when residue is blended into the feed, or if the feed is
hydrotreated, then a noticeable change in NOx may be observed. Depending on simultaneous
changes in other operating variables; e.g., regenerated catalyst temperature, flue gas excess
oxygen, and use of CO promoter to name a few, the magnitude or actual direction of the shift
may change from unit to unit. Figure 10 shows a noticeable effect on regenerator NOx emissions
when 10-20% residue is blended into the feed, and also the relationship of lower NOx formation
with lower O2 in the regenerator. This data set is from a single FCC unit equipped with a
bubbling bed regenerator that processes both clean VGO and residue blended feedstocks. This
data set is also consistent with those from other units, showing the relationship of lower NOx
formation with lower excess oxygen in the flue gas.

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 Figure 10
Unit “F” - NOx Response on Feed Composition and Excess O2
800
Flue Gas NOx, ppmv 700 NOx with Resid Feed
600
500
Increasing
400 Air Dilution
300
200
100 NOx without Resid Feed
0
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Flue Gas Excess Oxygen, mol-%

One of the challenges in minimizing excess oxygen in the flue gas to achieve lower NOx
emissions is the apparent effect of CO promoter to increase the formation of NOx (Figure 11).
In this graph, NOx emissions are plotted against platinum in the circulating catalyst inventory.
The relationship is quite clear: as platinum increases with higher CO promoter use, NOx
emissions increase. This same relationship has been observed through pilot plant studies and in
many commercial FCC operations. This reproducible response is strong evidence that CO
combines with NO to form N2 by the reaction: 2CO + 2 NO ⇒ N2 + 2 CO2. It is believed that
when the CO combustion rate is increased by the CO promoter (2CO + O2 ⇒ 2CO2), the
reduction of NOx to diatomic nitrogen is suppressed, promoting the release of NOx from the
regenerator. While a hotter catalyst temperature kinetically provides the capability for lower
excess O2 operation in the regenerator, tending towards lower NOx formation, achieving a hotter
regenerator through the use of CO promoter can negate the benefits and drive NOx emissions
higher.

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 Figure 11
Unit “A” – Impact of CO Promoter on NOx

160
Flue Gas NOx, ppmv

140
120
100
80
60
Increasing CO Promoter
40
20
0
0.3 0.4 0.5 0.6 0.7 0.8 0.9
E-Cat Platinum, ppmw

Simultaneous control of CO and NOx in a complete combustion regenerator poses a challenge as

CO is eliminated through oxidation while NO is eliminated through reduction. UOP’s high-
efficiency combustor style regenerator excels in controlling these simultaneous reactions with
typical emissions of CO less than 100 ppmvd and NOx less than 40 ppmvd. The differences
between bubbling bed (turbulent regime) regenerators and combustor regenerators are shown in
Figure 12. In the bubbling bed regenerator, the combustion air flows from the grid up through a
dense bed of catalyst where the carbon is burned off. The catalyst enters the vessel from the
spent catalyst standpipe, and is ideally distributed evenly across the bed.

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 Figure 12
Bubbling Bed Regenerator Combustor Regenerator
Flue Gas Flue Gas

Dilute
Dilute Phase
Phase
Spent
Catalyst

Dense
Phase
T

Regenerated
Dense
Catalyst
Phase

Recirc. Spent
Catalyst Catalyst

Regenerated
Catalyst

Main Air

Main Air

The high-efficiency combustor regenerator approximates a plug flow burning profile for the
catalyst as opposed to the back-mix regime of the standard bubbling bed design. The spent
catalyst from the reactor mixes with the blower air and roughly an equal amount of recirculation
catalyst at the bottom of the regenerator (combustor). The coke burns off the catalyst as it travels
up the combustor vessel with the air. There is a rough separation at the top of the combustor riser
through a “tee” shaped outlet. The flue gas enters a two-stage cyclone before leaving the
regenerator vessel. The catalyst discharge from the cyclone diplegs is returned to a dense phase
catalyst bed. From there, the flow splits, part of the catalyst going to the base of the reactor riser,
and the rest back to the combustor.

To validate the superior performance of UOP’s combustor regenerators on NOx emissions, data
was collected from many operating units. The effects of feedstock quality, type of feed being
processed, presence or absence of CO promoter, O2 concentration, catalyst bed temperature, etc.,
can all drive NOx emissions and need to be screened for proper data validation. However, when

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we plot a comparison of eight different combustor style regenerators against fifteen bubbling bed
regenerators, the data are very clear: at any given excess oxygen level, combustors result in
much lower NOx emissions (see Figure 13).

Figure 13
Comparative Regenerator Performance Analysis
200
15 Bubbling Bed Regenerators
Flue Gas NOx, ppmv

160

120

80

40
8 Combustor Regenerators
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Excess Oxygen, mol-%

SUMMARY
Proper control and optimization of an FCC unit requires careful balancing of many variables.
This is particularly challenging in the changing refinery environment, where profitability
revamps and the environmental control revamps compete for capital investment. UOP has a
growing “toolbox” of process improvements in Optimix feed distributor systems, VSS and VDS
riser termination devices, AF stripper technology, and RxCat technology to help refiners
maximize profitability from their FCC unit. The cumulative benefits of these yield-improving
technologies together with the new UOP third stage separator and UOP’s high-efficiency
combustor regenerator are available to help refiners meet the challenges of maximizing return on
investment while simultaneously providing a cleaner environment.

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 REFERENCES

1. L. L. Upson, and E. Cole Nelson, “RxCat Technology for More FCC Gasoline,” 1998

2. B. W. Hedrick, J. P. Koebel, and I. Cetinkaya, “Improved Catalyst Stripping from Cold Flow
Modeling,” 2001

3. D. A. Kauff, and B. W. Hedrick, “FCC Process Technology for the 1990s,” AM-92-06,
NPRA 1992 Annual Meeting

4. L. L. Upson, and D. A. Wegerer, “Rapid Disengager Techniques in Riser Design,” 1993

5. L. A. Lacijan, and M. W. Schnaith, “Refinery Profitability Drives FCC Revamps,” 2003

6. M. W. Schnaith, A. T. Gilbert, D. A. Lomas and D. N. Myers, “Advances in FCC Reactor

Technology,” AM-95-36, NPRA 1995 Annual Meeting

7. V. J. Memmott, and B. Dodds, “Innovative Technology Meets Processing and Environmental

Goals: Flying J Commissions New MSCC and TSS,” AM-03-13, NPRA 2003 Annual
Meeting

8. J. A. Montgomery, “Guide to Fluid Catalytic Cracking Part One,” W.R. Grace & Co., CT,
1993

9. S. B. Reddy Karri, T. Balteau and T.M. Knowlton, “PSRI Desktop Design Manual – Edition
1,” June 1994

uop
UOP LLC
25 East Algonquin Road
Des Plaines, IL 60017-5017
© 2004 UOP LLC. All rights reserved.
UOP 4285B

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