Microporous and Mesoporous Materials 3536 (2000) 245252 www.elsevier.

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History of ZSM-5 uid catalytic cracking additive development at Mobil

T.F. Degnan *, G.K. Chitnis, P.H. Schipper
Mobil Technology Company, Paulsboro, NJ, 08066, USA Received 31 March 1999; received in revised form 24 August 1999; accepted for publication 26 August 1999 Dedicated to the late Werner O. Haag in appreciation of his outstanding contributions to heterogeneous catalysis and zeolite science

Abstract ZSM-5 has found widespread application as a uid catalytic cracking additive for both propylene production and gasoline octane improvement. This paper traces its development by Mobil from the laboratory evaluation stage through its full-scale commercialization. Correct laboratory testing and an elucidation of reaction chemistry were critical to the successful commercialization of this catalyst. This review focuses not only on the historical development and renement of the ZSM-5 additive concept within Mobil, but also on lessons learned in the eective evaluation of this catalyst in progressing it from laboratory- to commercial-scale catalytic cracking units. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Additives; Cracking; Fluid catalytic cracking; History; ZSM-5

1. Introduction Nearly 18 years passed between the initial discovery of ZSM-5 in 1965 and its rst scale commercial trial in a cracking unit in 1983. That rst commercial trial in the Neste Oy renery, Naantali, Finland, was the culmination of many years of painstaking testing and analysis of ZSM-5 activity, selectivity, and stability in laboratory- and pilotscale catalytic cracking units. In the course of this commercialization of new technology, seven major technical hurdles were overcome. These were: 1. development of laboratory tests for measuring ZSM-5 stability, selectivity, and metals resistance; 2. development of a Thermofor catalytic cracking
* Corresponding author. Fax: +1-609-224-3608.

( TCC moving bed catalytic cracking technology commercialized in 1941) bead catalyst containing ZSM-5; 3. migration from a single TCC composite particle to a separate particle uid catalytic cracking (FCC circulating technology rst commercialized in 1940) additive; 4. migration of uid catalyst testing from xed uidized bed to riser reactors; 5. scale-up of ZSM-5 crystal to production quantities; 6. commercial evaluation of ZSM-5 additive catalysts in a catalytic cracking unit; 7. development of a process model for how ZSM-5 works in a riser. At the same time, the market place provided three major incentives for developing ZSM-5 including: 1. the elimination of lead from gasoline in the

1387-1811/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S1 3 8 7 -1 8 1 1 ( 9 9 ) 0 0 22 5 - 5

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early 1980s, which prompted a search for a means to increase octane from non-traditional sources; 2. the need for cleaner gasoline depleted in sulfur, olens, and aromatics that produced more favorable economics for alkylation; 3. a robust market for propylene that developed in the 1990s. This paper describes how ZSM-5 FCC additive technology development overcame these hurdles and managed to achieve the goals established by the marketplace for a new, selective cracking technology. Heavy emphasis is placed on the experience gained in learning how to test these materials properly.

2. Discovery of ZSM-5 and early cracking catalyst trials ZSM-5 was rst synthesized in 1965 by Landolt and Argauer [1]. Their discovery was a direct result of Mobils investigation of quaternary amines as directing agents in zeolite synthesis. Because it was only synthesized in very small quantities (<5 g), ZSM-5 remained a laboratory curiosity until 1967 when it was rst evaluated for processing waxy gas oils. It was soon determined to be a very shape-selective material that cracked only normal or slightly branched parans. For much of the late 1960s most of the ZSM-5 that was synthesized was directed toward the development of new dewaxing catalysts [2]. Zeolite Y-based cracking catalysts were commercially introduced in 1964 [3]. During the 1960s a signicant fraction of Mobils catalytic cracking research and development eort was directed at improving the stability and eectiveness of these new Y-based catalysts, including detailed studies of ion exchange with rare earth cations. Additional eorts were directed toward the development and commercialization of CO promoters as FCC additives [4]. It was not surprising, therefore, that eorts to assess the potential of ZSM-5 were delayed. When ZSM-5 was rst evaluated as a cracking catalyst in the Mobil laboratories, its initial evaluation was quite unremarkable. A blend of 10% rare

earth (e.g. La, Ce) exchanged zeolite Y (REY ) and unsteamed 5% ZSM-5 evaluated in a xed uid bed gave the same octane improvement as REY alone. Separate experiments aimed at evaluating the eect of processing wide cut FCC gasoline over ZSM-5 also showed that gasoline research octane was not aected. However, additional experiments showed that the heavier fraction of FCC gasoline (boiling above 355 K ) could be separately upgraded over ZSM-5 and that octane did increase when this was blended back with the lighter gasoline. Eorts to evaluate ZSM-5 in cracking applications began to gain momentum in the early 1970s. By then, several studies with small quantities of ZSM-5 showed that mildly steam-deactivated ZSM-5 did, in fact, improve gasoline octane, but the mechanism by which this was occurring was not yet understood. Nevertheless, several key properties of ZSM-5 had to be evaluated prior to even considering it for service in TCC and FCC units. These included steam stability, metals resistance, and selectivity maintenance.

3. ZSM-5 steam stability The stability of ZSM-5 to steam was examined in the late 1960s. It was soon found that the highly siliceous nature and the structure of ZSM-5 provided both a very thermally and a very hydrothermally stable zeolite. The zeolite could be treated at temperatures as high as 1260 K before encountering any crystallinity loss. Yet, identifying what steaming conditions to use in simulating FCC and TCC regeneration conditions remained a challenge. The steaming conditions used to simulate commercial regeneration conditions for Y zeolite had been studied for several years. Initial evidence showed that these same models did not apply to ZSM-5. Later attempts to match ZSM-5 loading and performance in laboratory and commercial trials showed that ZSM-5, when used in commercial trials, was less active than projected when the predictions were based on laboratory steaming under the same conditions as zeolite Y. In other words, ZSM-5 had to be steamed more

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severely than Y in laboratory simulations in order to provide estimates for commercial performance.

ZSM-5 produced far less light gas and hydrogen than comparable amounts of nickel on zeolite Y cracking catalysts. This is shown in Table 2, which is taken from Ref. [6 ].

4. ZSM-5 metals resistance Vanadium, which accumulates on cracking catalysts from vanadium in the gas oil feed, is known to cause zeolite crystallinity loss. This loss is apparently the result of vanadic acid attack on the Y zeolite. The vanadic acid is produced in the regeneration [5]. In a series of experiments, ZSM-5 was doped with larger and larger concentrations of vanadium and then steamed under simulated FCC conditions to test metals tolerance [6 ]. As shown in Table 1, these experiments demonstrated that ZSM-5 had a much higher tolerance for vanadium than USY (ultrastable Y zeolite Y that has been steamed while in the ammonium form to selectively reduce framework aluminum content). For ZSM-5, crystallinity losses were far less than for Y at equivalent vanadium levels and steaming conditions. This trait was subsequently borne out in later commercial trials. The ability of ZSM-5 to resist attack from vanadium likely stems from its highly siliceous composition. Mobils studies in the early 1980s also examined the nickel and sodium tolerance of ZSM-5 [6 ]. Nickel-doped
Table 1 Eect of vanadium on Y and ZSM-5 product selectivity after steaming ZSM-5a Vanadium content of catalyst (wt-ppm) Surface area (m2 /g) X-ray crystallinity (%) D yieldsb C1+C2 (wt%) C3 (vol.%) C4 (vol.%) gasoline (vol.%) coke (wt%) 0 87 100 +3 +1 3 10 000 68 85 +2 +2 3 USY a 0 240 100 10 000 110 55 +1 2 4 8 Nickel (ppm) on base REY catalyst on ZSM-5 additive D yieldsb hydrogen (wt%) C1+C2 (wt%) C3 (vol.%) C4 (vol.%) gasoline (vol.%) coke (wt%) 0 0 +2 +1 2 0 2000 +4 +2 4 2000 2000 +0.7 +0.4 +3 +1 11 +6.5

5. Laboratory catalytic cracking tests Although laboratory studies of ZSM-5 continued to bear out the octane-enhancing and light olen producing attributes of ZSM-5, scale-up studies began to show dramatic eects on catalyst contact time. It was soon realized that ZSM-5 accumulated coke much more slowly than the base Y zeolite cracking catalyst with which it was combined [7]. This meant that ZSM-5 continued to operate long after the Y zeolite became deactivated by coke. Coke deactivation is generally accepted to follow the Voorhies relationship: Fraction of initial activity=exp(at ), where a is an empirical coking factor and t is the time exposed to the gas oil [8]. For ZSM-5, a is much less than it is for Y. Thus, in experiments where gas oil was fed over a period of several minutes, the ZSM-5 remained very active whereas the base catalyst deactivated almost completely. The eects are not immediately obvious, since the cracked products from the Y
Table 2 Eect of nickel addition on ZSM-5 product selectivitya Case 1 Case 2 Case 3

a Steaming conditions: 1060 K, 50% steam, 1 bar, 20 h. b Fixed uidized bed cracking test, 783 K, 1 min, Arabian Light vacuum gas oil ( VGO distillate obtained by rectication under vacuum of the residue from the atmospheric rectication of crude oil ) feed; % on fresh feed at constant conversion relative to base without ZSM-5.

a Steaming conditions: 20 h, 1060 K, 50% steam, atmospheric pressure. b Fixed uidized bed cracking test, 783 K, 1 min, Arabian Light VGO feed; % fresh feed at constant conversion relative to base REY catalyst without ZSM-5 or Ni.

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zeolite are the primary reactants for ZSM-5. However, for longer residence time experiments the eects are to drive the product distribution toward much lighter products. Tests like the ASTM microactivity test (MAT xed bed test used to characterize activity and selectivity of uid cracking catalysts; ASTM D 3907-02), which are designed for evaluating conventional Y-based cracking catalysts, fail to approximate ZSM-5 performance very well because ZSM-5 cracking and isomerization activity decays via coking at a much lower rate than Y. In tests that use long contact times (e.g. 1 to 5 min) the eects are to overstate the eects of ZSM-5, since the average activity of ZSM-5 is much greater as contact time is extended. Nor is it straightforward to translate the results of small transient reactors to steady-state riser performance. Early work by Mobil showed that both xed bed (e.g. MAT ) and xed uidized bed (FFB well-mixed ebullating bed cracking test unit used to evaluate uid cracking catalysts) tests, conventionally used for evaluation of small batches of catalyst, suered from deciencies that were especially pronounced when two catalysts decayed at dierent rates. Problems associated with nonisothermality, axial dispersion, and poor gas-phase hydrodynamic characteristics all resulted in improper ranking of catalysts. Catalytic evaluation in FFBs has long been considered as an improvement compared with the more conventional xed bed MAT. This was also borne out in the testing of ZSM-5 catalysts. The back-mixing and improved heat transfer intrinsic to the xed uid bed provided a more accurate assessment of ZSM-5s yield shifts. In testing the ZSM-5 additives at the laboratory scale, it is important in equilibrium catalyst simulation to steam the ZSM-5 under more severe conditions than the base cracking catalysts. The steamed base cracking catalyst and the ZSM-5 additive can then be blended together prior to evaluation. When using deactivation techniques such as the Modied Mitchell Method [method of simulating the deactivation of uid cracking catalysts via the accumulation of metals (Ni and V ) by impregnating fresh catalysts with nickel and vanadium naphthenates prior and then severely steaming the catalysts] or

programmed cyclic cracking and steam deactivation, it is normally sucient to steam the ZSM-5 additive at temperatures that are 25 to 40 K higher than the base catalyst for an equivalent length of time. The added severity reduces the overall eect of an average higher activity ZSM-5 over the length of the longer cycle FFB or MAT test.

6. ZSM-5 TCC bead catalyst development As manufacturers of TCC bead catalysts, it was logical for Mobil to attempt to incorporate ZSM-5 into its Durabead formulations. The initial development in the early and mid-1970s focused on combining ZSM-5 and REY in a single silica alumina bead. Beads with the requisite hardness were successfully produced in laboratory bead towers, but commercial certication had to await the successful scale-up of ZSM-5 to tonnage quantities. Still, there were economic barriers to overcome. When Mobil assessed the benets of adding ZSM-5 TCC beads at its Ferndale, WA, renery in 1972, it found that the net eect of ZSM-5 addition was a $1000/day reduction in earnings even in the case where the light olens were alkylated. Commercialization was determined to be attractive only if catalyst or isobutane costs could be substantially reduced.

7. ZSM-5 zeolite manufacture The commercial manufacture of ZSM-5 was another major hurdle along the path to achieving an FCC additive. Prior to the commercialization of ZSM-5, all zeolites were manufactured by lowtemperature, atmospheric pressure synthesis. Higher-pressure syntheses using organic directing agents were mainly the province of scientists working in academic and industrial laboratories. So-called templated zeolites were rst synthesized in 1960 by Barrer and Kerr, see Ref. [9], and the scale-up of these materials remained a challenge. Thus, there were no precedents to draw upon when Mobil decided to construct its own pilot-scale zeolite synthesis and catalyst manufacturing plant in Beaumont, TX, in 1973.

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The incentive for constructing this plant was not ZSM-5 crystals for FCC. Rather, it was a paran dehydrocyclization and aromatic alkylation process that Mobil termed M-forming that provided the economic motivation. In fact, the Beaumont Chemical Specialty Plant ultimately produced very little M-forming catalyst since it was soon determined that xylene isomerization processes were more attractive commercial applications for ZSM-5. Over the next 5 years, the initial demand for xylene isomerization and, soon after, distillate dewaxing (MDDW ) catalysts transformed the plant from a pilot-scale facility to a small catalyst manufacturing plant. Still, the capacity of the plant was not sucient to supply the needs of a process as large as FCC. The economies of scale achieved through several plant expansions, and the experience gained in synthesizing ZSM-5 in larger and larger volumes, decreased the manufacturing costs to the point where cracking applications could at least be considered.

product octane and yields would revert to pre-test levels soon after the ZSM-5 addition stopped. However, although gasoline yield did return to the original values fairly quickly, the three to ve number RON and two number MON shifts were sustained through nearly the entire trial. This results from the relatively long-lived isomerization activity of ZSM-5 compared with the shorter-lived cracking activity, which is responsible for gasoline yield loss. The TCC catalyst was commercialized by Mobil as Durabead 11. Further renements were commercialized as Durabead 12 and 14 [11].

9. Riser evaluations Pilot-scale riser testing at the 80 to 160 l/day scale provided much better estimates of ZSM-5 performance than other tests. However, scale-up from the FFB to the riser reactors presented new challenges. Early riser studies by Mobil showed that ZSM-5 was much less eective than anticipated from xed uid bed studies. A thorough analysis showed that the initial ZSM-5 uid catalyst had a signicantly lower density than the base cracking catalyst, which caused the ZSM-5 to have a much lower residence time. Once the catalyst was reformulated to incorporate a heavier matrix, the riser predictions more closely approximated those of the xed uid bed systems. However, as Grace Davison cautions in its excellent monograph on FCC catalysts [12], in pilot-scale riser reactors there may still be a tendency to overestimate the gasoline yield losses if the actual reactor residence times are longer than what is found in commercial units.

8. ZSM-5 TCC catalyst commercialization The rst full-scale commercial trial of ZSM-5 was in the TCC unit of the Neste Oy renery in Naantali, Finland, in 1983 [10]. The bead catalyst contained both REY and ZSM-5. A TCC rather than an FCC was used because of Mobils experience with TCC catalyst formulation and TCC unit operation. The renewed emphasis on octane prompted by the phasing out of tetraethyl lead had transformed the economics of ZSM-5 addition. As expected, the gasoline research octane number (RON measurement of the knocking characteristics of a gasoline measured in a standardized engine at 600 rpm) and motor octane number (MON measurement of the knocking characteristics of a gasoline measured in a standardized engine at 900 rpm) both showed steady increases that paralleled the ZSM-5 addition rate. Gasoline yield declined, but this was oset by increases in propylene and butylene. The ZSM-5/REY catalyst was added over the course of 92 days. The surprising aspect of this test was the stability of the gasoline octane uplifts. It had been anticipated, based on laboratory testing, that

10. Evolution of the additive concept The concept of using small amounts of ZSM-5 as an additive derived from three factors: $ determination that ZSM-5 was eective in increasing RON and MON at even small concentrations; $ Mobils previous experience in commercializing Pt-based FCC carbon monoxide oxidation promoters; $ the cost of manufacturing the novel zeolite. One of the critical questions in the development of a ZSM-5 catalyst was whether ZSM-5 could be

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incorporated into a separate additive or whether it was most eective when incorporated in the same particle as the Y zeolite. Mobils testing showed that there was no synergism between Y and ZSM-5 and, therefore, the separate additive case was attractive. The main reason for combining ZSM-5 and Y in the same particle was to reduce the eect of dilution attributable to the additional binder used in the additive. The attractive feature of the separate particle approach was that it allowed much greater exibility in ZSM-5 addition and make-up rate.

11. Development of ZSM-5 FCC additives Shortly after the successful TCC evaluations, ZSM-5 FCC additives were developed by a number of companies, including Filtrol, Akzo, and Grace Davison. In 1984, Filtrol became the rst to demonstrate successfully a commercial ZSM-5 FCC catalyst [13]. As in the case of Neste Oy, the catalyst was a composite ZSM-5/REY catalyst. Grace Davison and Intercat were the rst companies to produce a ZSM-5-only additive in 1986. ZSM-5 additives are now marketed by Grace Davison, Intercat, Akzo, Engelhard, and CCIC.

bility and shape-selectivity of ZSM-5 [14]. Table 3, for example, compares the steam stability of phosphorus-doped ZSM-5 with undoped ZSM-5 for the cracking of n-hexane. The benet of adding phosphorus appears to be due to its ability to retard aluminum from leaving the zeolite framework. Phosphorus reduces the initial acidity of the zeolite but, after severe steaming, produces a zeolite that retains a larger fraction of its acidity. MAS NMR analyses have shown that the stabilization of cracking activity is entirely due to the improved retention of framework aluminum in ZSM-5. Phosphorus has also been used as a marker for the ZSM-5 additive that allows reners to track the amount of ZSM-5 in the catalyst FCC inventory. Beginning in 1987, ZSM-5 additive manufacturers began to add phosphorus to their formulations. The eects were dramatic in improving the eectiveness of ZSM-5 and reducing the amount of additive required to achieve the desired eect on octane and light olen yield. The increased eectiveness translated into reduced additive costs for reners and ultimately led to a much wider use of the ZSM-5 additive. 13. Development of selective ZSM-5 additives Many reners make use of the additional propylene and butylene for alkylate feed. The resulting alkylate more than osets the gasoline loss produced by ZSM-5. Nevertheless, a demand developed in the late 1980s for an additive that produced octane shifts similar to ZSM-5 but without the gasoline losses obtained with the conventional ZSM-5. Mobil began work on such an additive in 1986 and by 1988 had commercially demonstrated a selective version that provided similar shifts in RON and MON at roughly half the gasoline yield loss [15]. Although some FCC operators still use this type of additive, the current focus on propylene maximization has driven most reners to use high activity versions of ZSM-5. 14. Process modeling ZSM-5 yield predictions Extensive laboratory work on the chemistry of ZSM-5-catalyzed cracking, together with large

12. Phosphorus stabilization of ZSM-5 Researchers at Mobil were among the rst to recognize the benets of phosphorus on the staTable 3 Eect of phosphorus doping on the steam stability of ZSM-5 Relative rate constant k for n-hexane n-C6 cracking at 811 K ZSM-5, unsteamed ZSM-5, steamed a ZSM-5, unsteamed; doped with 1 wt% phosphorus ZSM-5, steamed a after doping with 1 wt% phosphorus 100 1 80 6

a Steaming conditions: 5 h 1033 K, 100% steam, atmospheric pressure.

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riser pilot-scale and commercial evaluations, allowed Mobil to construct a process model that it uses for both development and for support of its ZSM-5 sales [6,16 ]. The model is capable of predicting yield shifts and octane changes as a function of ZSM-5 loading, feed properties, riser operating conditions, riser conguration and base cracking catalyst properties. It has been updated over the past 10 years to incorporate the results of more recent Mobil work on FCC conventional and selective additives [17,18]. The model includes a decay function for ZSM-5 coking along with kinetics and associated rate constants for the primary reactions. This model permits a tailoring of the ZSM-5 addition rate for particular applications. Mobil has also adapted its Structured Oriented Lumping (SOL mathematical modeling methodology that calculates cracked product composition through the discrete lumping of hydrocarbon species of similar structure) modeling strategy to the FCC process, and has developed an improved SOL-based model for predicting the eect of ZSM-5 additives.

15. Recent ZSM-5 additive developments Additives with high levels of ZSM-5 have only become commercially available in the last 2 years [19]. These new ZSM-5 additives produce high levels of light olens with minimal dilution of the base cracking catalyst. In 1992, Mobil conducted its own trial of this high ZSM-5 additive at its Joliet renery. The results of that trial veried the value of high levels of highly active ZSM-5 in the inventory for the production of propylene and butylenes. If coupled with improved hardware modications, such as closed cyclones, improved atomizing nozzles and second risers of lift zones for recracking FCC naphtha, the impact of this new ZSM-5 additive on propylene and butylene makes can be magnied even further.

FCC additive. The development of ZSM-5 technology for FCC was unique in the signicant number of hurdles that the technology had to traverse on the path to commercialization. Competing developments in the catalytic cracking process and catalyst technology slowed ZSM-5 development for the FCC, as did the need to nd ways to produce the zeolite crystal economically and in quantities sucient for commercial evaluations. Underlying this were complications in using conventional testing methods to evaluate the eectiveness of ZSM-5. Unexpected results were obtained at virtually every stage of test scale-up, which pointed to shortcomings in the smaller-scale tests. This continued even into commercial testing. The signicant incentives provided by the need for additional gasoline octane in the early 1980s, combined with more recent favorable economics for producing light olens, provided the momentum to overcome these hurdles. This examination of the history of the development of ZSM-5 FCC additives has provided insight into the considerations that should be taken into account in the introduction of new FCC catalysts involving unique process chemistries. Hopefully, past experience will provide a basis for streamlining this process in the future.

Appendix: Glossary of terms FCC Fluid Catalytic Cracking circulating uid bed cracking technology rst commercialized in 1940. Fluid Catalytic Cracking Unit combination reactor and regenerator for hydrocarbon molecular weight reduction. Fixed Fluidized Bed well-mixed ebullating bed cracking test unit used to evaluate uid cracking catalysts. Microactivity Test xed bed test used to characterize activity and selectivity of uid cracking catalysts. Method of simulating the deactivation of uid cracking catalysts via the accumulation of metals (Ni and V ) by impregnating fresh catalysts with nickel

FCCU

FFB

MAT

16. Conclusions Nearly two decades passed between the discovery of ZSM-5 and its widespread acceptance as a

Modied Mitchell Method

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MON

REY RON

SOL

TCC

USY

VGO

and vanadium naphthenates prior and then severely steaming the catalysts. Motor Octane Number measurement of the knocking characteristics of a gasoline measured in a standarized engine at 900 rpm. Rare earth (e.g., La, Ce) exchanged zeolite Y Research Octane Number measurement of the knocking characteristics of a gasoline measured in a standardized engine at 600 rpm. Structured Oriented Lumping mathematical modeling methodology that calculates cracked product composition through the discrete lumping of hydrocarbon species of similar structure. Thermofor Catalytic Cracking moving bed catalytic cracking technology commercialized in 1941. Ultrastable YZeolite Y which has been steamed while in the ammonium form to selectively reduce framework aluminum content. Vacuum Gas Oil distillate obtained by rectication under vacuum of the residue from the atmospheric rectication of crude oil.

References
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Catalysis in Industrial Applications, second ed.Marcel Dekker, New York, 1996. [3] C.J. Plank, in: B.H. Davis, W.P. Hettuler ( Eds.), ACS Monograph No. 222 ACS, Washington, DC, 1983. [4] A.W. Chester, A.B. Schwartz, W.A. Stover, J.P. McWilliams, Chemtech (1981) 50. [5] R.F. Wormsbecker, A.W. Peters, J.M. Maselli, J. Catal. 100 (1986) 130. [6 ] S.P. Donnelly, S. Mizrahi, P.T. Sparrell, A. Huss, P.H. Schipper, J.A. Herbst, Division Of Petroleum Chemistry, ACS Meeting, New Orleans, August 30September 4, 1987. [7] L.D. Rollmann, D.E. Walsh, J. Catal. 56 (1979) 139. [8] B.C. Gates, J.R. Katzer, G.C.A. Schuit, in: Chemistry of Catalytic Processes, McGraw Hill, New York, 1979, p. 91. [9] D.A. Breck, Zeolite Molecular Sieves, Wiley Interscience, New York, 1973. [10] C.D. Anderson, F.G. Dwyer, G. Koch, P. Niiranen, Proceedings of the Ninth Iberoamerican Symposium on Catalysis, Lisbon, Portugal, 1984. [11] C.D. Anderson, L.L. Breckenridge, R.G. Bundens, F.G. Dwyer, J.A. Herbst, National Petroleum Reners Association Annual Meeting, San Antonio, TX, March 2931, 1987. [12] J.A. Montgomery, The Grace Davison Guide to Fluid Catalytic Cracking Part Two, Grace Davison Conn. & Co., Baltimore, MD, 1996. [13] S.J. Yanik, E.J. Demmel, A.P. Humphries, R.J. Campagna, Oil Gas J. 83 (19) (1985) 108. [14] W.W. Kaeding, J. Catal. 61 (1981) 240. [15] R.P.L. Absil, R.J. Cimini, G.W. Kirker, D.A. Pappal, J.A. Herbst, D.J. Klocke, RPS Seminar on Advances in Fluid Catalytic Cracking Technology, Houston, TX, November 1214, 1991. [16 ] P.H. Schipper, F.G. Dwyer, P.T. Sparrell, S. Mizrahi, J.A. Herbst, S.P. Donnelly, A. Huss Jr,, ACS Symp. Ser. 375 (1988) 64. [17] J.S. Buchanan, Appl. Catal. 74 (1991) 83. [18] J.S. Buchanan, Appl. Catal. A: Gen. 171 (1998) 57. [19] P.K. Niccum, R.B. Miller, A.M. Claude, M.A. Silverman, N.A. Bhore, K. Liu, G.K. Chitnis, S.J. McCarthy, NPRA Annual Meeting, San Francisco, 1998.