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

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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.

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At that point. To improve product selectivities. high-activity zeolitic catalysts became the standard and greatly increased the conversion potential of the FCC unit. “Slip” is defined as the ratio between the gas-phase velocity and the catalyst-particle velocity. The acceleration zone is the vertical section between the base of the Wye and the elevated feed distributors (Figure 1). UOP considered the entire feed distribution system. During the late 1980s and early 1990s. and flowing solids in the riser. In the late 1970s and throughout the 1980s. back-mixing. Long contact times were required due to low activity amorphous catalysts. The single feed distributor at the base of the riser was eventually replaced with multiple. Proper riser design and operation of the acceleration zone result in a more even catalyst flow distribution and lower slip factor. 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. Uneven catalyst flow. which contributed to uneven oil–catalyst contacting. A riser operating with a high slip factor has the gas rising significantly faster than the catalyst. Within the original dense-bed reactor systems. UOP focused its effort on improved oil and steam mixing inside the distributor for better dispersion into the flowing catalyst stream. In the 1960s. 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. This led to the concept of properly conditioning the catalyst phase prior to feed injection. and high AM-04-45 Page 3 . “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. UOP accomplished this by expanding its vision beyond just the feed distributor toward the dynamic balance between the physical properties of the oil. not just a single piece of equipment. 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. elevated feed injection became the norm throughout the FCC industry. modifications to the reactor were made to decrease the contact time between the catalyst and the oil. elevated distributors spaced around the circumference of the riser. This turbulent environment included significant back-mixing and density gradients.Feed Injection History In early FCC units. To optimize the elevated feed injection into an FCC unit. riser feed injection was through an open ended pipe “bayonet” inserted into the base of the catalyst riser. raw oil feed was injected into a moving catalyst stream that disengaged into a fairly dense bed reactor. steam.

OPTIMIX™ FEED DISTRIBUTION SYSTEM The primary result of all this work was the Optimix feed distribution system. In this system. with proper mass and velocity to achieve controlled penetration into the flowing catalyst phase. The Optimix system incorporates the feed distributor (Figure 2). Figure 1 Reactor Riser Dynamics Riser Reaction Zone (Minimum Slip / Plug Flow) Initial Contacting Zone Regenerated Catalyst Elevated Feed Injection Acceleration Zone Riser Length Acceleration (High Slip/Back Mixing) Riser Density Wye Injection With the functionality of the lower riser better understood. over-atomizing the oil to alleviate this problem not only increases operating cost through increased steam consumption and sour water production. the riser acceleration zone. However. and reduced selectivity to desired products. and the feed preheat process. 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. This could be overcome in large part through higher steam injection. Steam injection into the oil phase is ineffectual if the oil is allowed to re-coalesce prior to exiting the feed distributor tip. One problem associated with atomizing oil with steam is the inherent nature of these materials to separate.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. the riser section below the feed distributor is designed to achieve a moderate and uniform catalyst density for optimum feed dispersion into the riser. but can also force unit operations above recommended or hydraulic constraints. The feed distributors are designed with three stages of atomization to achieve efficient use of energy with minimized oil re-coalescing. efforts were shifted to the feed distributor. AM-04-45 Page 4 . The objective should be to develop an atomized spray of uniform droplet size.

without replacement. Since that time the distributors have gone through several stages of mechanical design improvements. resid). In previous generations of feed distributors. In applications of throughput increase or feed slate change. UOP has lowered the cost to the refiner by limiting the maintenance requirement to periodic replacement of only the outer tip assembly. or plan for 10 year maintenance spares. and the outer distributor barrel assembly (Figure 2). Through application of the DUR O LOK couplings. complete replacement of the feed distributors would have been recommended. both the internal oil gun and outer tip assembly can be easily changed-out. AM-04-45 Page 5 . 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.Figure 2 Optimix Feed Distibutor Steam Inlet DUR O LOK™ Couplings U P N O GG A NO I A D SS B PR I NS TA CU AT T Oil Feed Inlet 1 2 3 Riser Nozzle Flange Atomizing Stages The Optimix feed distributor was introduced to the market in 1994. Another major mechanical advancement to Optimix feed distributor designs is the inclusion of DUR O LOK couplings on both the inner oil gun assembly. optimize performance with a dramatically different feed slate (VGO vs. if the refiner wanted to either significantly change throughput capacity. or 10 year service life. Today’s Optimix feed distributors are designed to achieve two operating cycles.

and replacement with a new head.9 ft ⇒ 9. plenum chamber.0 lv-% increase ─ Gasoline yield: 0. 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.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.5 wt-% ─ Riser diameter application range: 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. upgrading the RTD is often associated with a throughput increase or maintenance turn-around in which the reactor cyclones have been identified for replacement. 6 since modified to VSS RTD Direct-Connected Cyclones: 7 placed into operation.7 – 1.0 – 2. and cyclone assembly. RTD History UOP riser termination devices have included: Tee Disengager Down-Turned Arm Vented Riser: 16 placed into operation. 2 since revamped to VSS RTD Vortex Separation Technology (VSS and VDS): 36 placed into operation AM-04-45 Page 6 . As such.0 ft Typical revamp benefit: elevated distributors to elevated Optimix distributors ─ Conversion: 1.

it was it was also very sensitive to riser residence time.Figure 3 Progression of Riser Termination Technology “Tee” “Down-Turned Arm” “Vented Riser” “DCC-SCSS” With the introduction of riser cracking. modern reactors could more properly be called a disengaging vessel. It was the first UOP RTD system to offer “hydrocarbon containment. suffer from sensitivity to pressure upsets which made it a bit “temperamental. The DCC RTD further increased hydrocarbon containment and improved yield selectivities. however. It did. Because DCC represented a major reduction in post-riser cracking.” The next significant improvement in riser termination devices was the direct-connected cyclone (DCC) system. 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. Down-turned arms replaced tee disengagers starting in the 1980’s. The vented riser termination system was commercialized in 1983 and represented a step-change advancement in RTD technology. This provided improved separation efficiency and a reduction in catalyst loss from the reactor. Conversion loss had to be compensated with higher severity in AM-04-45 Page 7 .” especially during startups. UOP in conjunction with Mobil Oil commissioned the first DCC in 1988.

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.000 BPSD to 184. VSS and VDS Riser Termination Devices To address the hydrocarbon entrainment in the catalyst discharge from the diplegs. Since its first installation in 1991. meaning very little hydrocarbon is allowed to over-crack to dry gas and coke.the other process variables (reactor temperature. Although the DCC pushed yield selectivity to the highest level achieved. 30 VSS RTD’s and 6 VDS RTD’s have been placed into operation.000 BPSD. catalyst is centrifugally discharged from the top of the reactor riser in the horizontal plane. The flow rate is actually high enough to account for an effective 6% loss in hydrocarbon containment. 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. thus sealing the stripper from the reactor vapor space. catalyst-to-oil ratio). swirls downward along the wall of the vortex chamber. UOP developed vortex separation technology (Figure 4). the hydrocarbon underflow to the reactor vessel is essentially 5% of the DCC system. Since only 5% of the catalyst enters the cyclone. The net superficial velocity of the catalyst as it flows into the stripper is well below the hydrocarbon bubble rise velocity. AM-04-45 Page 8 . 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. This includes the vortex separation system (VSS) RTD for internal risers and the vortex disengager stripper (VDS) RTD for external risers. The net result is an improvement in hydrocarbon containment from 94 to 99. Applications range from 8. This minimizes hydrocarbon entrainment into the stripper and resultant bed cracking reactions that preferentially form dry gas and coke. catalyst activity. The vapor outlet from the RTD is directly connected to a single stage of conventional cyclones. In VSS / VDS RTD’s. While it was similar to the DCC.7%. for improved yield selectivities. The catalyst in the pre-stripping section counter-currently contacts stripping steam and hydrocarbon rising out the top of the integral stripper. In the early 1990s UOP commercialized the Suspended Catalyst Separation System (SCSS). 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. The swirl arm/chamber configuration effectively separates 95% of the catalyst from the hydrocarbon stream. it suffered from some serious operating issues that needed to be addressed. In both the DCC and the SCSS. allowing the hydrocarbon to be “pre-stripped” from the catalyst. With the high primary cyclone catalyst loading associated with DCC systems. and make the RTD more operator friendly. it incorporated a pressure relief system at the top of the riser that made it much less sensitive to pressure upsets. and accumulates in the pre-stripping section.

The reaction mix sampling was conducted on the vapor line (Point 1) and the annular area (Point 2). 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. 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. AM-04-45 Page 9 . 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.Figure 4 Vortex Separation Technology “VDS” 1991 “VSS” 1995 VSS Disengager Swirl Arms VSS Chamber To help quantify the potential benefits of increased hydrocarbon containment. The long residence time also produces significant increases in dry gas and coke. UOP commissioned an independent laboratory to sample a reactor equipped with a DCC riser termination device (see Figure 5).

4 46. Refiners lost valuable products to the regenerator and had to increase stripping steam rates. and higher containment.9 8. 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. lv-% Gasoline.0 5.2 20. reliability. catalyst circulation rates were pushed progressively higher and a decline in stripper efficiency was observed.9 54.8 Point 2 Yields C2-. 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. The loss of stripper efficiency offset a portion of the benefit AM-04-45 Page 10 . lv-% C4. lv-% Slurry.9 14. UOP has recently designed an improvement that reduces the volume into which the cyclone diplegs discharge by 50% to further “contain” the hydrocarbon. UOP continues to optimize the VSS / VDS RTD’s for improved operability.1 Reactor Vessel (Point 2) 15.Figure 5 Hydrocarbon Containment Point 1 Effect on FCC Reaction Products Cyclone Outlet (Point 1) 2.7 8. SPENT CATALYST STRIPPING The primary objective of the FCC stripper is to remove the “strippable” hydrocarbon from the spent catalyst. or reached a hydraulic bottleneck in the unit. Early stripper designs incorporated anywhere from one to nine stripping stages. While some hydrocarbon will always flow down the cyclone diplegs with the catalyst discharge.6 10.6 17. wt-% C3. lv-% In addition to “best of class” hydrocarbon containment.2 20. with only a single stage of cyclones required. lv-% LCO. Even with the excellent performance already achieved. This improvement also provides a 10% reduction in active catalyst inventory and fresh catalyst make-up requirements. As catalyst and hardware changes achieved lower ∆Coke operations.

and allowed for jet and bubble dynamics and catalyst flow to fully develop. The first development from the stripper improvement program was the AF tray technology.000 lb/ft2/hr (2. upgraded feed distribution system and/or riser termination device. For a given unit design capacity..04 wt-% at a typical steam consumption of 2 lbsteam / 1000 lbCatCirc. The “cylinder” model was constructed to test non-annular tray configurations. 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. 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. To maintain the unit heat balance. and all of the associated conversion. AF Stripper Technology In early 1997. An additional 21 AF tray strippers are in various stages of design and construction. The 0. UOP constructed two large scale models. i. the coke component that is removed from the regenerator by more efficient stripping can be shifted to catalytic coke to produce higher conversion. The AF tray was commissioned in 1998 and as of February 2004.333 lb/ft2/min). 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. Within this model. In addition to improved stripping efficiency. The model was able to support studies up to a catalyst flux of 140. one “wedge” and one “cylinder”. and structured packing. including high flux bypass tubes. a primary objective of the improvement program was to increase the catalyst flux capacity of stripper designs. The success in this area has been AM-04-45 Page 11 . including various types of full cross-section trays. UOP tested various historical and developmental tray configurations. These stripper installations have resulted in an average ∆Coke reduction of 0.04 wt-% ∆Coke reduction equates to an average 22°F reduction in regenerator temperature. there are 27 applications. The model could generate commercial tray pressure drops across an eight-tray configuration.e. The benefits of the AF stripper technology are realized through more efficient contacting between steam and catalyst with improved hydrocarbon displacement. and selectivity benefits. yield. a 6% increase in catalyst-to-oil ratio. gratings. Improved stripping of hydrocarbon from the spent catalyst can provide significant processing and yield advantages. 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.gained from the lower ∆Coke operations achieved through the previous revamps.

reactor shell. conversion. The first unit with grid style stripper internals was commissioned in 2002. many refiners have continued to de-bottleneck unit constraints within the capacity of existing major equipment. Excessive catalyst loading to regenerator cyclones – Cyclone erosion. AM-04-45 Page 12 . One particular application of AF stripper technology has been operating routinely at a catalyst flux rate of 120. not only present the concerns listed above. The second and third developments from the stripper improvement program were the AF grid and AF packing designs. wet gas compressor (WGC). and catalyst circulation standpipes. Maintaining this philosophy through several technology upgrades can result in several operational and reliability concerns.tremendous. Optimum product selectivities. fines generation 2. but also cause refiners to face several dilemmas between “wants” and often conflicting “also wants” (see Table 1). This represents a 20% capacity increase over the pre-revamp operation without any changes in stripper crosssectional area. often with the constraint of not replacing main vessels or large rotating equipment.. The first AF packing design has been awarded and is currently in engineering. and retaining existing equipment. regenerator shell. i. optimum coke combustion.000 lb/ft2/hr (2. THE ∆COKE CHALLENGE As improved equipment technology and catalyst offerings have resulted in progressive decreases in ∆Coke.000 lb/ft2/min) with stable operations. and throughput are traditionally opposite to lower coke yield. As of February 2004. High catalyst circulation and catalyst flux – Insufficient regenerator & stripper residence time – Hydraulic instability or limitation in the catalyst standpipes 3.e. This brings UOP’s commercial experience with AF stripper technology to 32 operating units. five grid style AF strippers have been placed into operation. Excessive catalyst fines to the flue gas system – Increased particulate matter (PM) emissions Improvements in FCC technology to achieve lower ∆Coke operations. stripper shell. main air blower (MAB). 1.

AM-04-45 Page 13 . 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.Table 1 Conflicting “Wants” “WANTS” Optimum Product Selectivities BUT Higher Conversion “ALSO WANTS” Sufficient regenerator temperature for Improved coke burn kinetics Lower coke yield for Improved selectivity and Lower CO2 Sufficient regenerated catalyst Temperature for Improved coke burn kinetics Retain existing equipment – Min CAPEX MAB. WGC. The technology benefits are summarized in Table 2. The combined technology improvements result in a 23% increase in catalyst circulation and a regenerator dense-bed temperature reduction to 1260°F. the refiner gains the yield and selectivity benefits inherent of increased catalyst-to-oil and lower ∆Coke. standpipes BUT Less Dry Gas BUT Higher Throughput BUT COMBINED TECHNOLOGY EFFECTS Figure 6 shows the expected benefits to be obtained from a stew-wise improvement in FCC reactor technology.

14 1260 +0. 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.6 0.27 1324 Base Base 5.8 5. lv-% (90% at 380°F) Plus VSS (Point 3) 10. With the on-set of clean fuels initiatives.55 8.6 0. lv-% (90% at 380°F) Coke. °F 1310 1290 Cat/Oil (0) Regen Temp 16 14 (1) 10 (2) (3) 1270 1250 8 + VSS RTD 6 Elevated Premix Elevated Optimix + AF Stripper Table 2 Technology Upgrade Effects Base Case Premix Feed Distributor (Point 0) Cat-to-Oil Regen Temp. wt-% ∆Coke 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.7 +1.68 Gasoline. these issues can be further strained by increasing the percentage AM-04-45 Page 14 Cat/Oil 12 . °F Conversion. However.Figure 6 Technology Upgrade Effects 1330 Regenerator Dense Bed.

financial. 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. and a substantial increase in conversion due to the higher riser catalyst-to-oil ratio. 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). they also presents some excellent operational. the balance of the carbonized catalyst that is not recycled travels through the stripper to the AM-04-45 Page 15 . Firing torch oil to keep the regenerator hot essentially burns high value feedstock as fuel. In a traditional FCC unit. Similar to a conventional FCC unit. While the above issues present problems that the refiner must overcome. For the first time. increasing the catalyst-to-oil ratio to increase conversion also increases the coke yield and catalyst circulation to the regenerator. firing the air heater. UOP developed RxCat technology. However. and environmental opportunities. Traditionally the catalyst from the bottom of the reactor stripper has commonly been referred to as “spent”. Since the recycle catalyst adds no heat to the system. The burning of any fuel in the regenerator apart from coke on the circulating catalyst inventory is an economic loss. but in certain cases preferred. 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. Coke deposition preferentially attenuates the strongest catalytic sites providing for more selective cracking with carbonized catalyst. UOP has adopted the term “carbonized” to describe this catalyst. Refiners moving towards more hydrotreated feeds are often placed in the position of opting for less coke selective catalyst. The use of less coke selective catalyst (more coke produced) negates yield and selectivity benefits previously gained from equipment upgrades. the recycle is heat-balance neutral. These high exit velocities can also lead to excessive catalyst fines generation. THE RXCAT SOLUTION The problems of low ∆Coke operations (low regenerator temperature) have created an opportunity that UOP has uniquely addressed. With RxCat technology. modern catalyst systems can accumulate appreciable quantities of coke and still maintain a significant amount of activity. The carbonized catalyst circulated from the stripper back to the base of the riser is effectively at the same temperature as the reactor. The activity characteristics of carbonized catalyst are not only usable. The lower contact temperature between the combined catalyst and raw oil feed results in higher product selectivity with less dry gas and coke production.of hydrotreated feed to the unit and further decreasing the ∆Coke and regenerator temperature. or firing torch oil to add heat to the regenerator. To take advantage of the selectivity benefits of conditioned catalyst. while at the same time damaging the catalyst activity. 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).

This aspect of the technology is particularly useful in units that periodically switch from gasoline to olefin or distillate mode.regenerator where the coke is burned off before it returns to the base of the riser. This application has an even greater impact for refiners that use LPG olefins additives. which in turn raises the regenerator temperature and enables the easing of constraints in the system. i. throughout the year. AM-04-45 Page 16 . the change from gasoline mode to/from olefin mode can be rapid. The catalyst flowing to the regenerator carries a higher coke content.e. ZSM-5 or Supra ST-5. Figure 7 RxCat Technology Combustor Style High-Efficiency Regenerator VSS Riser Termination Device Carbonized Catalyst Recycle Spent Catalyst Standpipe Carbonized Catalyst Slide Valve Regenerated Catalyst Standpipe MxR Chamber 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.. a change in catalyst activity in the riser can be accomplished by merely changing the amount of carbonized-catalyst recycle and as such. 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.

Depending on the severity of the operation and the catalyst quality. conversion can be increased 3 to 5 lv-%. Increased conversion . the catalyst-to-oil ratio in the riser will typically increase 3 to 4 numbers. Two of these units are now under construction.yield which could be very valuable in units limited by dry gas production. Integration of RxCat technology provides numerous benefits in both revamp and new unit applications. Alternatively. 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. 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. 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. AM-04-45 Page 17 . The catalyst blend from the MxR chamber results in a mix-zone temperature typically 150°F lower compared to a conventional FCC unit. As of February 2004. three RxCat designs have been delivered to customers. At a 1:1 blend of carbonized to regenerated catalyst.The substantial increase in riser catalyst-to-oil ratio results in a significant increase in conversion. and the first unit is expected to go on-stream in mid-2004. This large reduction in catalyst temperature results in a large reduction in C2. most of this conversion would be directed towards increased gasoline yield.and have traditionally had to shift their catalyst inventory over several weeks to reap the full financial benefits of a change in product slate. At a constant reactor temperature and catalyst activity.

RxCat technology pays back with both increased throughput and product yields. Approximately half of the catalyst that would traditionally circulate from the reactor to the regenerator is recycled to the base of the riser. P. stripper. Figure 8 Effect of RxCat Technology on Unit Performance 1330 Regenerator Dense Bed. RxCat technology can be used to effectively debottleneck unit constraints. etc. 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.In addition to the yield and selectivity benefits. The expected benefits for the previously presented case study with the implementation of RxCat technology is shown below in Figure 8 and Table 3. standpipes.) for only capacity benefits. Cat/Oil 6 + RxCat AM-04-45 Page 18 . As such. °F 1310 1290 1270 1250 Base Cat/Oil Riser Cat/Oil (0) Regen Temp (4) 16 14 Cat/Oil 12 10 8 Elevated Elevated Premix Optimix + AF Stripper + VSS RDT Regen S.

6 0. EMISSIONS CONTROL In addition to the desires for increased throughput. refiners are facing increasing demands to reduce environmental emissions. lv-% (90% at 380°F) Coke. UOP has been designing power recovery systems since 1973. Standpipe 7. The reduced coke make translates to reduced air blower demand as well as a reduction in CO2 emissions. The original units were designed by UOP under license AM-04-45 Page 19 .8 +4. Since that time.68 15. °F Conversion.Table 3 Effects of RxCat Technology on Unit Performance Base Case Premix Feed Distributor (Point 0) Riser Cat-to-Oil Regen Temp. the primary focus of the TSS was to protect downstream power recovery system turbo-expanders. Proper definition of specific emission limits. While power recovery system applications have been in use for decades.27 1324 Base Base 5. UOP has some very effective solutions to meet refiner’s needs.8 1312 +3. UOP has licensed 31 TSS’s with 20 placed into operation. better yields and product selectivities. today and future. and identifying the proper engineering controls to best address these emissions can be a daunting task.9 5. lv-% (90% at 380°F) Cumulative to RxCat Technology (Point 4) Regen.4 0. PARTICULATE MATTER CONTROL WITH THE UOP THIRD STAGE SEPARATOR Since the advent of the FCC third stage separator (TSS).6 Gasoline. UOP wanted to improve TSS technology to a point where it could be used to effectively meet FCC flue gas stack PM emission standards.70 8. wt-% ∆Coke 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.35 0.

These TSS designs still suffered from the limitations imposed by radial flow gas distribution and reverse flow in the cyclone elements. the inner tubes see a higher gas and dust loading than the outer tubes. 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. Over the years. The cold flow modeling (CFM) test program extended over 2 years. Computational fluid dynamic (CFD) computer modeling was used to validate and benchmark the CFM work. The flue gas flow is maintained essentially in one direction . UOP improved upon the original design by implementing several modifications. As such. UOP launched a development program to design and offer a smaller. but also be a viable alternative to electrostatic precipitators and wet gas scrubbers for environmental applications. and to quickly investigate potential improvements and guide the physical modeling program. In 1996. The mal-distribution of flue gas and fines inherent in this design results in varying efficiency across the older style TSS.in the top and out the bottom of the unit. very little had actually changed in the overall design of the TSS in 25 years. The tests were conducted with commercial FCC catalyst fines. Even with these modifications incorporated into the base design. during which both dimensional variables and process flow variables were studied. 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. The development work culminated in the new UOP TSS design (see Figure 9). the UOP program investigated the contribution of many variables on catalyst separation efficiency. more economic.from Shell. high efficiency TSS that could not only be utilized in power recovery installations. radially outward between the two tube-sheets. and drawing on other sources of cyclone expertise. Based on a thorough understanding of cyclone theory. The most significant improvement in the design is that the UOP TSS utilizes axial flow for catalyst/gas separation. AM-04-45 Page 20 .

After nearly two years of continuous operations no performance degradation has been observed (Table 4).60 0.The new UOP TSS is about 40% smaller than other TSS offerings for the same capacity. following the unit startup in April and again in December. Table 4 Commercial Unit Stack Data Date Sept.54 5. 2003 PM lb/hr mg/Nm3 3. making it less expensive to fabricate. Performance testing on the unit was performed twice in 2002. The initial test showed that the UOP TSS discharged between 36-50 mg/Nm3 of particulates. 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. 2002 Oct. depending on flue gas rate. easier to install. 2002 Dec. and better suited where plot space is a premium.6 lbs/1000 lbs of coke burn. only 67% of that allowed by NSPS standards.57 AM-04-45 Page 21 .69 0. The NSPS compliance testing resulted in a particulate matter emission of 0.79 38 47 41 PM lb/M lb Coke 0.12 4.

COMBUSTION KINETICS In the RxCat technology analysis (Table 3). as a carbon removal process. The change in coke concentration on a catalyst particle with respect to time fits the following equation: – dC / dt = K0e Where: K0 C Po2 ∆E R T = = = = = = –∆E CPo2 RT Frequency constant. °R Given a higher regenerator temperature. BTU/lb-mol Gas Constant.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. there are currently four more in various stages of engineering and construction with the second unit scheduled for startup in 2004. This relationship for the rate of carbon burning from FCC catalysts holds over a wide range of temperatures with diffusional limitation not controlling. In addition to the on-stream UOP TSS. BTU/lb-mol/°R Temperature. 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 AM-04-45 Page 22 . the coke burn rate is accelerated due to the increasing rate constant. or lower CO2 emissions. 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. wt-fraction Oxygen Partial Pressure. increased severity. The benefit of lower coke production can be utilized by the refiner either through increased capacity. is widely accepted as being first order with respect to carbon concentration and oxygen partial pressure. (atm) Activation Energy. Catalyst regeneration. (hr-1atm-1) Carbon on Catalyst.

The application of RxCat technology to the FCC unit can effectively increase all three variables. AM-04-45 Page 23 . the magnitude or actual direction of the shift may change from unit to unit. Feedstock characteristics and quality.. one particular FCC unit data set did show a substantial NOx response to a shift in the type of feed processed. flue gas excess oxygen. and also the relationship of lower NOx formation with lower O2 in the regenerator. excess O2 in the regenerator. and regenerator design are among many variables evaluated. showing the relationship of lower NOx formation with lower excess oxygen in the flue gas. Depending on simultaneous changes in other operating variables. This data set is also consistent with those from other units.g. However. While the industry has not observed a model-predictable relationship between feed nitrogen and NOx. different feeds with varying amounts of basic or total nitrogen have shown no strong correlation with NOx. then a noticeable change in NOx may be observed. 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. Figure 10 shows a noticeable effect on regenerator NOx emissions when 10-20% residue is blended into the feed. regenerated catalyst temperature. use of CO promoter. and use of CO promoter to name a few. always processing virgin gas oil with no residue in the FCC). or if the feed is hydrotreated. Being able to manipulate each of these coke combustion drivers provides significant flexibility to the FCC operator. when residue is blended into the feed. e. 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. regenerated catalyst temperature. This data set is from a single FCC unit equipped with a bubbling bed regenerator that processes both clean VGO and residue blended feedstocks. (for example. UOP has embarked on a thorough investigative and development effort.

0 3. tending towards lower NOx formation. While a hotter catalyst temperature kinetically provides the capability for lower excess O2 operation in the regenerator. promoting the release of NOx from the regenerator. In this graph. NOx emissions increase. mol-% 6. achieving a hotter regenerator through the use of CO promoter can negate the benefits and drive NOx emissions higher.0 NOx without Resid Feed Increasing Air Dilution NOx with Resid Feed 2. AM-04-45 Page 24 .Figure 10 Unit “F” .NOx Response on Feed Composition and Excess O2 800 Flue Gas NOx.0 1. This same relationship has been observed through pilot plant studies and in many commercial FCC operations. ppmv 700 600 500 400 300 200 100 0 0. The relationship is quite clear: as platinum increases with higher CO promoter use.0 4. 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).0 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).0 Flue Gas Excess Oxygen.0 5. NOx emissions are plotted against platinum in the circulating catalyst inventory. the reduction of NOx to diatomic nitrogen is suppressed.

4 0. In the bubbling bed regenerator.8 0. The catalyst enters the vessel from the spent catalyst standpipe. UOP’s highefficiency combustor style regenerator excels in controlling these simultaneous reactions with typical emissions of CO less than 100 ppmvd and NOx less than 40 ppmvd.3 Flue Gas NOx. AM-04-45 Page 25 . the combustion air flows from the grid up through a dense bed of catalyst where the carbon is burned off.7 0.6 0.5 0. ppmv Increasing CO Promoter 0.Figure 11 Unit “A” – Impact of CO Promoter on NOx 160 140 120 100 80 60 40 20 0 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. and is ideally distributed evenly across the bed. The differences between bubbling bed (turbulent regime) regenerators and combustor regenerators are shown in Figure 12.

Catalyst Spent Catalyst Dense Phase 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 effects of feedstock quality. the flow splits. 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). can all drive NOx emissions and need to be screened for proper data validation. catalyst bed temperature.. when AM-04-45 Page 26 . presence or absence of CO promoter. The catalyst discharge from the cyclone diplegs is returned to a dense phase catalyst bed. type of feed being processed. part of the catalyst going to the base of the reactor riser. To validate the superior performance of UOP’s combustor regenerators on NOx emissions. etc. and the rest back to the combustor. The flue gas enters a two-stage cyclone before leaving the regenerator vessel.Figure 12 Bubbling Bed Regenerator Flue Gas Combustor Regenerator Flue Gas Dilute Phase Spent Catalyst T Dilute Phase Dense Phase Regenerated Catalyst Recirc. data was collected from many operating units. However. The coke burns off the catalyst as it travels up the combustor vessel with the air. O2 concentration. From there. There is a rough separation at the top of the combustor riser through a “tee” shaped outlet.

This is particularly challenging in the changing refinery environment.0 0.0 Excess Oxygen.5 2.0 SUMMARY Proper control and optimization of an FCC unit requires careful balancing of many variables. VSS and VDS riser termination devices. ppmv 160 120 80 40 0 0. the data are very clear: at any given excess oxygen level. combustors result in much lower NOx emissions (see Figure 13). 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. AF stripper technology. Figure 13 Comparative Regenerator Performance Analysis 200 15 Bubbling Bed Regenerators Flue Gas NOx.5 4. UOP has a growing “toolbox” of process improvements in Optimix feed distributor systems.5 3.we plot a comparison of eight different combustor style regenerators against fifteen bubbling bed regenerators. AM-04-45 Page 27 . mol-% 3. and RxCat technology to help refiners maximize profitability from their FCC unit. where profitability revamps and the environmental control revamps compete for capital investment.5 1.0 8 Combustor Regenerators 1.0 2.

Knowlton. W. P. Kauff. W. All rights reserved. J. L. D. 1993 9. Wegerer. Koebel. J. CT. A.” 2003 6. “RxCat Technology for More FCC Gasoline. NPRA 2003 Annual Meeting 8. and I. and M. L.REFERENCES 1. A. Cetinkaya. Cole Nelson. J. S. “FCC Process Technology for the 1990s. Grace & Co. NPRA 1995 Annual Meeting 7.” 1993 5.” AM-92-06. Reddy Karri. L. A. and B. L. IL 60017-5017 © 2004 UOP LLC. V. M. Gilbert. “Refinery Profitability Drives FCC Revamps. Montgomery.” AM-95-36.” AM-03-13. Hedrick. Dodds. NPRA 1992 Annual Meeting 4. D. B. UOP 4285B AM-04-45 Page 28 . “PSRI Desktop Design Manual – Edition 1. T. and B. “Innovative Technology Meets Processing and Environmental Goals: Flying J Commissions New MSCC and TSS.R. “Advances in FCC Reactor Technology. Upson. Memmott. W. Hedrick. A. and E. A.M. and D. Myers. Lomas and D. “Improved Catalyst Stripping from Cold Flow Modeling. N.. A.” June 1994 uop UOP LLC 25 East Algonquin Road Des Plaines.” W. “Rapid Disengager Techniques in Riser Design. B. W. “Guide to Fluid Catalytic Cracking Part One.” 2001 3. T.” 1998 2. Schnaith. Schnaith. L. Balteau and T. Lacijan. Upson.

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