CatalysisToday 18 (1993) 509428 Elsevier Science Publishers B.V.

, Amsterdam CATTOD 233

509

Fluid catalytic cracking: some recent developments in catalyst particle design and unit hardware
R. Mann*
Department of Chemical Engineering, UMIST, Manchester M60 IQD (UK)

Abstract

Catalytic cracking is an old process, but is still subject to new pressures for change and improvement. In the 199Os,these pressures arise from the need to crack components drawn from deeper down the barrel as well as to reformulate fuel products which can meet more stringent environmental requirements. Recent efforts at correlating catalyst formulation and cracking performance still rely on largely empirical understanding of the role of catalyst composition and zeolite/matrix pore architecture. However, new tests measuring cracking performance at constant surface area as the zeolite/ matrix ratio varies have indicated that the pore architecture should be designed to facilitate a staged cracking. The whole range of pore sizes from micro-pores ( < 20 A) to giant macro-pores ( > 1000 A ) are now known to be influential in determining cracking yield and activity and these pores should be assembled into an optimal architecture. Unfortunately, the configuration of pores in a typical spray dried FCC catalyst is usually far from such an optimal design. The use of stochastic pore networks to characterise macro-pore structures is described in conjunction with some experimental results employing a visualised porosimetry based on low melting point alloy impregnation. Improved designs of catalyst will impose new requirements on the fluid&d bed hardware. Some recent improvements in the chemical engineering of riser reactor/regenerator units are described which centre on atom&d injection, segregated feeding, closed cyclones, staged stripping and catalyst cooling.

INTRODUCTION

Fluid catalytic cracking is now more than fifty years old. Despite this maturity, there continues to be significant pressures to upgrade the performance of existing units. Some of this pressure is quite longstanding and related to the need to deal with still heavier feedstocks drawn from deeper down the barrel. These heavier feeds will often present additional difficulties because of higher sulphur contents. Improved performance can usually be registered by increases in olefins yield. Other pressures for better performance are more recent and are being driven by environmental issues in two main ways. Firstly there is a need to re*Corresponding author.

0920-586 l/93/$06.00

0 1993 Elsevier Science Publishers B.V. All rights reserved.

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R. Mann / Catal. Today 18 (1993) 509-528

formulate liquid fuels to give a reduced environmental impact. This reformulation requires a reduction in aromatics and an increase in oxygenates. Secondly, emissions from units themselves need to contain less SO,, NO, and particulates to satisfy tightening legislation. Improvements however continue to be mostly piecemeal and empirical. This reflects the lack of any comprehensive understanding of the fundamentals of the catalytic cracking event as it takes place within typical fluidisable particles. These particles are configured with a zeolite component dispersed in a silica-alumina support matrix. Unusually for a supported catalyst, both the zeolite and support show catalytic activity. The additional complexities of multicomponent cracking and intra-particle diffusion and mass transport present a formidable difficulty in uncovering a fundamental understanding sufficient to guide process innovations.
CORRELATING CATALYST PROPERTIES AND PERFORMANCE

The empirical basis for the understanding of the performance of an individual unit has, not surprisingly, led to very few general insights into the problem of relating the intricacies of the design of the fluidised particles to the overall performance of cracking units themselves. It has already been indicated that the processes inside the particles are complicated. This is no less true for a typical cracker, which has twin fluid beds connected by a riser around which the solid catalyst particles are moved by transported flow with intermittent fluidisation. This intrinsic process complexity is compounded because units are invariably feedstock specific and their operational policies are affected by local economic factors. Even so, the establishment of some correlation between catalyst characteristics and performance under relevant realistic conditions is of practical importance to refineries seeking guidance for catalyst selection. Also, such correlations should help to develop more fundamental understanding capable of leading to improved catalyst particle design. Improved catalyst designs need to optimise the complex and conflicting interactions of multi-species cracking reactions, diffusion and coke deposition. To this end, extensive testing has been reported [ 1 ] using a riser pilot plant designed to simulate a commercial FCC unit riser temperature profile and achieve vapour residence times from 2 to 5 seconds. Results from 12 commercial catalysts available from 5 reactors, as indicated in Table 1, were examined in great detail. Some measure of the empirically determined variety of property/performance achievable from the variety of formulations tested can be gauged from Fig. 1. This shows how a basic measure of conversion varies with the total specific surface area of the catalyst. This correlation appears to be random. In respect of other property/performance aspects, some underlying features could be discerned, although no correlation could be found

R. Mann / Catd. T&y TABLE 1

18 (1993) 509428

511

Catalyststestedin minatm riser unit (Hsing and Pratt [ 1] ) Vendor

AlUO Ah0 AkZO

Catalyst Vision 49A Advance 407B Octaboost 627-3 Super Nova-D LRE Super Octacat RN+ Astra-278 XP-750+ Dynasiv 850+ Precision-R HRO-600 FX-500 Alpha-550

Davison Davison Davison Davison Engelhard Engelhard Filtrol Filtrol Katalistiks

Conversion

vs total at cat/oil

fresh =

surface 6.0

area

75 74 &f r 6G I ? s v 73. 72. 71. 70 69 68. 67 66 65

* .

*
l

.
w

.
l

.
l

. . -! 200 215 230 245 260 275

.

290

305

320

335

350

Surface

areo,

m2/g

Fig. 1. Conversion vs. surface area for 12 commercial catalysts.

between overall working activity and unit (zeolite) cell size. A key factor is the so-called zeolite/ (support) matrix ratio and features of performance could be more clearly identified with yield rather than conversion performance. Thus dry gas yield decreased with increasing z~lite/mat~x ratio as shown in Fig. 2. Other clear correlations were established between: coke yield - increased with increasing unit cell size; bottoms cracking - increased when the zeolite/ matrix ratio decreased, and CJC, olefms - increased with increasing zeolitefmatrix ratio. However, it is obvious from Fig 2 that even a clear correlation between empirical performance measures leaves a degree of uncertainty in the quality of the correlation. A more fundamental approach requires a rational framework which incorporates the architecture or physical geome-

512
Dry gas ot
4.5

R. Mann / Catal. Today 18 (1993) 509-528

vs 69 Zeolite/Matrix wt% conversion ratio

1 ,
. .

K r . : cl ,x n

4.3 -

4.1.

39 3.7 . . . 35 _I 05 0.6 1 1 1.4 1.7 2.0 2 3 2 6 2.9 3.2 3.5

Fig. 2. Dry gas yield vs. zeolite/matrix

4

ratio.

kiko

r ko = Cracking rate 01 hexadecane 0

0

1 12

2 Naphlhenic 13

3 rungs 14

4 16

16

Carbon number

Fig. 3. Catalytic cracking with molecular sieving.

try of the zeolite/matrix assembly. New developments in this direction promise a degree of understanding that is for the first time giving a genuine impetus to radical improvements in catalytic cracking performance.
FCC CATALYST PORE ARCHITECTURE AND PERFORMANCE

The importance of pore architecture in determining cracking performance was initially limited to the internal pore structure of zeolite crystallites. The results for several model compounds compared to the cracking rate for hexadecane are shown in Fig. 3 [ 2 1, from which it is clear that there is an accessibility limitation due to the zeolite portal areas which is effectively molecular

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513

sieving with/without reaction. As the number of naphthenic rings increases (beyond 1 ), the crackability increases, but the cracking rate (relative to the potential activity of the zeolite cages) falls off due to the increasingly limited accessibility of the intra-zeolite acid sites. This shape-selecting concept has now been recognised as being important for the larger pores, exterior to the zeolite, which arise from the amorphous support matrix and possibly also from the exterior surfaces of zeolite crystallites. As an idealised simplification, three possible stages of the cracking process can be envisaged [ 3 1. Firstly, large asphaltenes crack and metals are deposited. Secondly, products of the primary cracking pre-crack further in mesopores. Thirdly, final cracking of the smaller molecules takes place inside zeolite cages. This concept of an architecture for the catalyst which promotes staged cracking is clearly important for the design of FCC resid catalyst that will be simultaneously efficient/effective/selective and resistant to deactivation. Moreover, as Fig. 4 shows schematically, size, shape, acidity and accessibility have to be designed for and particles have to be fabricated and assembled accordingly. In practise, the pore size distribution formation ought to be manipulated into a continuous form similar to that shown in Fig. 5. The micro-pores ( < 20 ) promote the cracking of the smallest hydrocarbon fragments, the mesopores (between 30 and 1000 ) accommodate the intermediate second stage of cracking. The large pores ( > 1000 ) serve as liquid catching pores and give preliminary cracking of asphaltenes as well as accommodating metals deposition. Extensive experimental results relating to this theoretical concept have explored the cracking performance of a set of test catalysts for which the ratio of silica matrix material relative to an active selective alumina was varied [ 41. This study used catalysts with low rare earth (RE) content comprising dealuminated Y zeolites. These have reduced unit cell size with fewer but
PORE
LOW ACIDITY I

ACIDITY
MEDIUM

DISTRIBUTION
ACIDITY HIGH ACIDITY

NICKEL-ORGANIC MOLECULE ,,, RE?; \\\,

LCOIHCO ,, ,, ;..-4;.LpG

-----,

BULK

Fig. 4. Schematics of staged cracking.

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R. Mann / Catal. Today 18 (1993) 509-528

SMALL PORES SURFACE AREA _ c 20 A

EFFECT OF ACTIVE MATRIX AT CONSTANT Z/M

11 MESO PORES

RELATIVE ACTIVITY ._I

30.

IOOOA

LIQUID CATCHING LARGE PORES >

roooA

.---

PORE DIAMETER
THE

c DESIGN CONCEPT

PORE ARCHITECTURE

Fig. 5. Pore size distributions for catalytic cracking.

EFFECT
350 ,

OF ACTIVE

MATRIX

AT CONSTANT
MATRIX

Z/M

FRESH !?.AVS ZEOJTE/Am

;
s
w
0

;_.3,- --- -y
280 270 260 250 FA/S 0.84 + 0 2101 2.0 4.0 6.0 6.0 10.0 12.0 14.0 16.0

cc ii

Fig. 6. Overall surface area vs. alumina( FS) /silica( S ) ratio.

more active sites, typically applied in fluid catalytic cracking units (FCCUs) for producing higher octane gasolines. The results reported explore the effect of the active matrix at a fixed zeolite/matrix or z/m ratio. Fig. 6 shows how the overall surface area of the fresh catalysts varied with the selective alumina

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515

EFFECT OF ACTIVE MATRIX AT CONSTANT Z/M NIT. PORE SIZE DISTRIBUTIONS BY ADS.
0.2 0 18 0.16 0.14 0 12 0.1 0 08 0.06 0.04 0.02 0

ORE VOLUME:CC/G _ .__~--.__---~~-

-----

FA/S=2.67

PORE DIAMETEFkA

Fig. 7. Pore volume distributions

and zeolite/matrix

ratios.

EFFECT
4.8 4.6 4.4 4.2 43.8 3.6 f 3.4 3.2 S2.1 2.6 2.4 2.2 H -

OF ACTIVE

MATRIX

AT CONSTANT

Z/M

w
H

+\NL
H 92 WlRIX 96 AERACE too 104 108 112 116 PORE DWElER(OESORPllON)A u:FA/S-0.84 LFA/S-0.23 H:fA/S-2.67

2 88

Fig. 8. Coke yield vs. matrix average pore diameter.

(FA) /silica (S ) ratio. In effect the total area is held constant whilst the zeolite/active matrix surface area is varied. Results for a micro-activity test (MAT) unit were reported for a hydrotreated, aromatic west coast VGO. The lower hydrogen transfer activity of the reactive matrix was evident from the higher olefinicity gained at the ex-

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R. Mann / Catal. Today 18 (1993) 509-528

pense of aromaticity. The zeolite hydrogen transfer activity was much lower than for a corresponding high rare earth (RE) formulation, although still much greater than for the active matrix component. Fig. 7 shows how the pore volume distribution was modified for two values of the zeolite/matrix ratio. At a high value of 2.67, the catalyst has a larger proportion of the smaller intermediate cracking matrix pores. Fig. 8 then shows one of the very many results reported [ 41 which indicates how the coke yield falls as the matrix average pore diameter increases. All the results reported by Yanik et al. [ 41, comprising some 40 figures, ranging through many measures of activity, selectivity and yield, confirmed the validity of the staged cracking concept in Fig. 4. However, it is clear that whilst the concept of staged cracking is important in understanding general issues relating to quantitative design of cracking catalyst particles, a more precise quantification of the complex multi-species cracking and diffusional processes is needed. This in turn requires better definition of the pore architectures themselves.
MODELLING FCC CATALYST PORE STRUCTURES

The simplest approach to modelling the pore spaces inside FCC particles is to envisage that the zeolite pores are uniformly distributed amongst support pores represented by a parallel bundle. This is a mathematically highly convenient formulation, which is depicted in Fig. 9. This model has already been developed to analyse the relative activities of the zeolite and matrix in the face of coke laydown [ 5,6 1.

Idealized catalyst pore structure

of an FCC catalyst

Fig. 9. Simple parallel bundle model for a supported zeolite catalyst.

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517

However, scanning electron micropscopy (SEM) studies of typical commercial FCC particles, show, in common with most porous materials, that the pore spaces are an evident tangled mass of widely varying sizes. Pores are thus expected to be randomly jumbled together, but to be interconnected thoroughly amongst one another. Fig. 10 shows how an FCC particle of about 70 m in diameter appears when viewed by an SEM. So called stochastic pore networks are a suitable model concept for representing randomness and interconnectively in porous catalysts. A simple 2-D example of size 30x 30 is depicted in Fig. 11. Large and small pores can be randomly allocated within such a simple square network, providing a reasonably realistic and yet still tractable description of the pore structure. Such simple pore networks can be analysed for diffusion, reaction and coke laydown. Some results for the cracking of cumene over a commercial catalyst (SUPER-D) showed how coke deposition within the zeolite could be separated from coke laydown on the support. Moreover, the model clearly indicated how interior accessibility could be affected as the support pores became plugged with coke [ 7 1. In the longer

Fig. 10. SEM view of a FCC particle.

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R. Mann / Catal. To&y 18 (1993) 509-528

Fig. 11. A simple 30 x 30 2-D stochastic pore network.

Fig. 12. A 10 x 10 x 10 3-D stochastic pore network.

term, it will eventually be desirable to apply 3-D pore networks to represent the support/matrix pore structure. An example of a stochastic pore network in 3-D is visualised in Fig. 12.

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519

The use of 3-D networks is obviously more realistic for calculating multispecies cracking, diffusion and coke laydown. Furthermore, the linking of a theoretical 3-D network structure to the matrix/support pores in typical cracking catalyst particles can now be linked to techniques which can visualise the pore spaces exposed by a plane section through a particle. One experimental method for achieving this uses the pressurised penetration of a fluid low melting point alloy (LMPA) into the pore spaces. On lowering the temperature, the alloy is solidified within the pores and thereby comprises a measure of the accessible pore volume at the penetrating pressure. This is a kind of visualised porosimetry. Assemblies of particles subjected to this technique can then be sectioned and polished to provide an image of the pore spaces. This has been done for a sample of an (unused) industrial cracking catalyst (SUPER-D) and the results are shown in Fig. 13 [ 8 1. This section is of size 500 p x 600 e, which exposed cross-sections of some 200 (or so) cracking catalyst particles. Several features of this result are worth noting. Firstly, although the exposed sections appear to show particles of variable diameter, this is because the sections pass randomly through approximately spherical particles of roughly equal size. In this case the catalyst particles are some 70 pm in diameter. Secondly, and perhaps most significantly, there is a startling non-uniformity of penetrated internal matrix/support pore structure as indicated by the extent of invasion of the low melting point alloy. The individual particles internal pore spaces are much more widely variable than they are similar. This variability ranges from the total non-penetration of some 50 particles (about 25%) to the largest exposed section which contains giant sized pore voids. In between these two extremes, there appears to be a continuous variation in the indicated porosity and associated pore space dimensions. Thirdly, all the particles show a significant skin effect, so that interior access can be expected to be restricted by smaller exterior pores. This outer skin is also probably the explanation for the large fraction of totally unpenetrated particles which appear completely black in Fig. 13. The major conclusion from Fig. 13 is that whatever the optimal pore structure of the matrix/support should be in terms of meso-pores linked to precracking pores as staged pathways to the zeolite micro-pores, the assembly of particles in Fig. 13 could hardly be expected to begin to approximate it. Because of the intrinsic wide variation from particle to particle, each one would have different flux/permeation/diffusivity characteristics. Moreover, each one would behave quite differently with respect to coke laydown and buildup. Finally, each one would then have quite different burn-off behaviour at the regeneration stage. The subsidiary conclusion from Fig. 13 is then that the procedures used to fabricate cracking catalyst particles need to be examined and revised so as to be able to control individual pore structures much more precisely. Only in this way will it become possible to fabricate particles which have optimally tailored pore structural characteristics.

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R. Mann / Catal. Today 18 (1993) 509428

Fig. 13. Low melting point alloy (LMPA) impregnation of cracking catalyst.

As a post-script to Fig. 13, it ought to be possible to draw some inferences as to the average particle structure. This should serve as some guide to improvements, since it is reasonable to assume that the disparate set of particles in Fig. 13 on average delivers reasonable performance. Thus, Fig. 14 shows the particle which is subjectively judged to represent a pore structure average. This detailed view of an individual particle clearly shows an outer skin, which has been penetrated by alloy through three closely adjacent large peripheral pores (upper right particle periphery). Fig. 15 then shows a computer generated random section through a 3-D stochastic pore network by low melting point alloy (LMPA) impregnation. The computer image has been generated from a so-called regular 3-D network extended to accommodate 5 degrees of randomness. These 5 degrees of ran-

R. Mann / Catal. Today 18 (1993) 509-528

521

Fig. 14. Alloy penetration of an average FCC particle.

domness are: pore diameter, pore length, pore direction, pore cross-section and wall roughness. The computer generated regeneration in Fig. 15 is consistent with mercury porosimetry results. The random 3-D network of Fig. 15 contains pore elements up to 3~ in diameter. The computer image however shows pore features up to 9p in (equivalent ) diameter. The imaged representation exhibits these large pore features due to overlapping of pores as the plane section passes close by pore junctions (nodes). A feature may thus contain elements of several pores and thereby appear enlarged in the plane of the section. This aggregation of pore sections is readily discernible in Fig. 15. The foregoing assessment of the pore structures of actual cracking catalyst particles has indicated the need for catalyst manufacturing and preparation techniques to recognise the importance of dovetailed pore structures that could optimise architectures so as to deliver staged cracking of the heavier resid feedstocks. Techniques developed for imaging stochastic pore networks [ 91 can be readily adapted to construct pore assemblies with any geometrical properties. In this respect, Fig. 16 shows a concept network in which pore sizes are controlled from the interior (smallest) to the exterior (largest). The diffusional and reaction performance of such networks can be readily calculated, so that candidate pore structures can be screened by a modelling stage. The spiralled network of Fig. 16 would appear to have a desirable geometry

R. Mann / Catal. Today 18 (1993) 509-528

real

image

computer generated

image

Fig. 15. Average FCC particle modelled by a slice through a 3-D network.

for a staged cracking reaction which requires pre-cracking pores capable of taking up metals deposits. Other workers have also developed pore network modelling for catalytic reaction applications [ 101, allowing for variable connectivity of 3-D networks within a spherical envelope and extended their approach to nested networks, of the type shown in Fig. 17 [ 111. Calculations of the effect of coke laydown on particle deactivation behaviour have also been carried out in regular 3-D lattice networks [ 121. Attention has also recently been focused in parallel on the impact of coke deposition in uniform lattice models of the zeolite cage/channel structure [ 13 1, although this problem is itself further complicated by the fact that site occupation by molecules in typical configurational diffusion itself causes ac-

Ii. Mann I Cati. T&y

18 (1993) 509-528

523

smaestpoxw

on interior/lqt

pores on csterior

Fig. 16. A concept 2-D network for optimising staged cracking.

Micro.Pbrc I

Mscro-Pore

Prriodlc Buuodrrr

bw

Fig. 17. Nested stochastic pore networks in 2-D.

cess blocking and reduced activity [ 141. The problem of effectively jointing the diffision and reaction behaviour of zeolites to the transport and cracking performance of the support matrix obviously requires fiuther work, which

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R. Mann / Catal. Toalay 18 (1993) 509-528

will ultimately be necessary for the complete modelling of modem cracking catalysts.
NEW DEVELOPMENTS IN FCCU HARDWARE

Since fluid catalytic cracking is the dominant upgrading process in a refinery, the fluid catalytic cracking unit (FCCU) has a key role to play in meeting new fuel based challenges for the 1990s. These challenges are summarised schematically in Table 2. The US Clean Air Act amendments of November 1990 require reductions in vehicle exhaust gas emissions, which could be met by greater use of alkylates and ethers. These have high octane values with zero aromatics and in addition the ethers have a beneficially high oxygen content. Light olefins are precursors to these particular gasoline components, so that increasing the olefin potential from FCCUs is highly desirable. Emissions from the regenerator itself are also becoming more tightly controlled by US State and Federal regulatory bodies. This requires regenerators to reduce SO, and NO, emissions as well as particulates. These environmental requirements for the product balance and the process have to be achieved in the face of continuing pressures to process heavier higher sulphur crudes (in the jargon of the industry, to improve the uplift from a barrel of crude). As Johnson et al. [ 151 have so succinctly stated ... the FCC (unit) will be called upon to process poorer quality feeds while meeting strict environmental laws and increase the yield of lighter olefins for cleaner fuels. New technology is required to upgrade FCCUs which are generally already running at capacity limits. Table 3 then lists a summary of six key innovations in unit hardware, which progress the three challenges of Table 2. These hardware changes have all been implemented in the recent Orthoflow and Resid FCC design depicted in Fig. 18, which resulted from collaborative development between Mobil and Kellogg [ 151.
TABLE 2 FCC: Major challenges for 1990s (Johnson et al. [ 171) Producing reformulated fuels Reduce aromatics Increase oxygenates SO, NO, Particulates Higher S Increased olefms

Meeting environmental limits

Uplifting heavier feedstocks

R. Mann / Catal. Today 18 (1993) 509-528 TABLE 3 FCC units: new hardwaredevelopments (Johnson et al. [ 17 1) Feed atomisation - improves liquid products Segregatedinjection - increases light oleflns Closed cyclones - reduces thermal cracking Staged stripping-lowers regeneratortemperature Catalyst di~~bution - reduces after burning Catalyst cooling - better conversion for heavier feeds

525

DISEHGAGER

REGENERATOR SPENT c*T*l.vs,

Fig. 18. Mobil/Kellog orthoflow and resid FCC unit (Johnson et al. [ 171).

The changes in atomisingfeed injection improve the contacting in the zone where liquid feed and hot, active (regenerated) catalyst are brought together. Podr Ontario increases coke and dry gas which adversely affects both conversion and selectivity. The new nozzle designs, jointly developed by Kellogg and Mobil, produce a flat, fan shaped spray which gives a tighter droplet size distribution. Performance has also been improved by co-injecting steam with

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R. Mann / Catal. Today 18 (1993) 509-528

the feedstock and using an improved geometrical distribution in the riser. The consequent improvement in mixing reduces thermal cracking at the riser base. Incorporation of segregatedfeed injection separates the riser into two zones. A high nitrogen feed is introduced at the base and a low nitrogen feed partway up the riser. This helps to increase the conversion of heavy ends, particularly when the maximum riser top temperature is acting as a constraint. CIosed cyclones reduce any thermal cracking after exit from the top of the riser. Yield losses from earlier designs were attributable to post-riser non-selective thermal cracking. Mobil made use of a plexiglass scale model to deduce a closed cyclone design which reduced the spread of hold-up times of vapour in the reaction vessel, thereby giving substantial improvements in yields. Steam stripping of spent catalyst is a basic operation in FCC. Any underflow of hydrogen rich hydrocarbons is detrimental because it gives higher than desirable regenerator bed temperatures and higher individual catalyst particle temperatures, which acts in turn to decrease the conversion. These effects are shown in Fig. 19. In the Orthoflow design a more efficient staged catalyst stripping is achieved by two stages which produces a lower 6% hydrogen in coke at 2 to 2.5 kg steam per 1000 kg of recirculating catalyst. Spent catalyst, especially when fresh (and tending therefore to be more heavily coked), when it contacts combustion air close to the inlet, can experience a temperature rise sufficiently high to provoke sintering. This has been known for a long time [ 16 ] and causes undue deactivation. Regenerator performance can be improved by dispersing the spent catalyst well away from the incoming combustion air. This is also an important factor when working heavier feedstocks which tend to give higher coke on catalyst. A more uniform catalyst distribution thereby enables heavier feeds to be more effectively accommodated. Kellogg has developed and commercialised a spent catalyst distributor which achieves this more effective uniform dispersal (US Patent No. 4 150 090). This improved contacting also reduces NO, formation and therefore NO, emissions. Table 4 shows typical improvements obtained. These improvements are claimed to be due to the initial burning-off taking place in
TABLE 4 Improved air/catalyst contacting (Johnson et al. [ 17 ] ) Before Excess O2 vol.% AfterbumOc Feed rate Feed N,-tNO, 2.5 23 Base Base After 1.0 19 +5% -45%

zones of tower oxygen ~n~en~tion, in turn resulting in a lower parti& temperature rise. As Table 4 shows, not only have NO, emissions reduced, but more feed can be processed without reaching detrimental& high temperatures. Reduced emissions are therefore achieved at gre&er ~rou~put. The use of dense phase ~~~~~~~ coding restricts the r~e~emtor temperature rise when processing feedstocks that produce heavier coke laydown. Temperatures which are too high reduce the conversion to more desirable produets and ~~es~n~~y give a high dry gas yield. Early unit designs used tube flow of the dense phase in a shell and tube heat exchanger, which caused u~a~ptabIe erosion rates and gave poor availability in service, Later improvement used regenerator in-bed coils, which improved pliability but proved insufficiently flexible. New imp~vements now make use of tow velocity flow of the dense phase on the shell-side, with steam on the tube-side [ 17 1, In the new designs, the tubes are freely suspended from the tube sheet as a bayonet-TV future. This design gives lower thermaI stresses peskily on start-up) ) which improves ~~ab~ity by reducing tube f&lwes. This approach also gives a high heat transfer capability similar to that achieved by regenerator bed coils, so that smaller shell sizes are needed. Heat removal rates in excess of 29 mW are being achieved using this approach.
REFERENCE I L.H. Hsing and R.E. Pratt, carrelations between FCC Catalyst Properties and Performance in a Riser Pilot Plant, Paper 126f, AIChE Annual Meeting, Los Angeles,CA ( 1991). 2 D.M. Nate, Catalytic Cracking over Crystalline ~~nosi~~te~ Ind. Eng. Chem. Prod, Res. Develop_., 9 (2) ( 1970) 203-209. 3 P. Hettinger, ~velopment of a Reduced Crude Cracking Crttalyst, ACS S~rn~si~~ Series, 375 ( 1989) 308. 4 S.J. Yanik, P. OConner, M.F. Rrady, D.K. Abner and MC. Friedrich, FCC Catalyst Pore Architecture and Performance, AIChE Symposium Series No. 291,88 ( 1992) 9-20, S R, Mann and I.R. Moore, ~~~~tion of a Supine Zeolite Cracking ~t~yst: A Pore Structural Approach, I. Chem. E. Symposium Series, 87 (1984) 25-33. 6 R. Mann and G. Thomson, variation of a Supported Zeolite Catalyst: Simulation of Diffusion, Reaction and Coke Laydown in a Parallei Bundle, Chem. Eng. Sci., 42 ( 1987) 555-563. 7 R. Mann, G. Thomson and P.N. Sharratt, Deactivation of a Supported Zeolite Catalyst: Diffusion, Reaction and Coke Deposition in Stochastic Pore Networks, Chem. Eng. Sci,, 41(1986)711-719. 8 K Khalaf, Appli~~on of Stochastic Pore Network Models to Craekiug Catalyst, Ph.D, Thesis, UMIST ( 1987). 9 R. Mann and H.N.S. Yousef, Q~ti~cati~n of Random Pore Structures of Porous Adsorbents, Adsorption Science and Technology, 8 (4) ( 1991) 196-2 16. 10 R.L. Portsmouth and L.F. Gladden, Determination of Pore Connectivitiy by Mercury Porosimetry, Chem. Eng. f&i., 46 ( 1991) 3023-3036. 11 M.P. Hollewand and L.F. Gladden, Repres~~~ou of Porous Catalysts using Random Pore Networks, Chem. Eng. Sci., 47 ( 1992) 2757-2762.

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R. Mann / Catal. Today 18 (1993) 509-528

12 S. Arabi and M. Sahimi, Computer Simulations of Catalyst Deactivation. II: Effect of Morphological, Transport and Kinetic Parameters on the Performance of a Catalyst, Chem. Eng. Sci., 46 (1991) 1749-1755. 13 A.O.E. Beyne and G.F. Froment, A Percolation Approach for the Modelling of Deactivation of Zeolite Catalysts by Coke Formation: Diffusional Limitations and Finite Rate of Coke Growth, Chem. Eng. Sci., 48( 3) (1993) 503-511. 14 J.G. Tsilcoyiannis and J. Wei, Diffusion and Reaction in High-Occupancy Zeolite Catalysts. I: A Stochastic Theory Chem. Eng Sci., 46 ( 1991) 233-253. 15 T.E. Johnson, Catalyst Coolers for Fluid Catalytic Cracking: Past and Present, Int. Conf. on Circulating Fluid Bed 4, Nagoya, Japan ( 1990). 16 A. Bondi and R.S. Miller, Rapid Deactivation of Fresh Cracking Catalyst, I and EC Proc. Des. and Develop., 1 (3) ( 1962). 17 T.E. Johnson, P.R. Niccum, M.F. Raterman and P.H. Schipper, FCC for the 90s: New Hardware Developments, AIChE Symposium Series No. 29 1,88 ( 1992) 9-20.