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 Fluid Catalytic Cracking V

Materials and Technological Innovations

by Occelli M. L. Occelli, P. O'Connor

• ISBN: 0444504753

• Publisher: Elsevier Science

• Pub. Date: April 2001

 vii

List of Contributors

S. A1-Khattaf H. de Lasa
Chemical Reactor Engineering Centre Chemical Reactor Engineering Centre
Faculty of Engineering Faculty of Engineering
University of Western Ontario University of Western Ontario
London, Ontario London, Ontario
CANADA N6A 5B9 CANADA N6A 5B9

S.-I. Andersson M.A. den Hollander

Chalmers University of Technology Industrial Catalysis
Department of Applied Surface Chemistry Department of Chemical Technology
SE-41296 Gothenburg Faculty of Applied Sciences
SWEDEN Delft University of Technology
Julianalaan 136
A. Auroux 2628 BL Delft
Institut de Recherches sur la Catalyse THE NETHERLANDS
CNRS
2 Av. A. Einstein H. Eckert
69626 Villeurbanne Institut ftir Physikalische Chemie
FRANCE Westf~ilische Wilhelms-Universit~it Miinster
Schlossplatz 7
R.A. Beyerlein D-48149 Miinster
National Institute of Standards and Technology GERMANY
Gaithersburg, MD 20899-4730
USA I. Eilos
Fortum Oyj
L.T. Boock P.O. Box 310
Grace Davision 06101 Porvoo
7500 Grace Drive FINLAND
Columbia, MD 21044
USA A.E. Fallick
Scottish Universities Research & Reactor
M. Castro Diaz Centre
University of Strathclyde East Kilbride
Department of Pure and Applied Chemistry Glasgow G75 0QU
Glasgow G1 1XL UK
Scotland
UK J. Frasch
Laboratoire de Matrriaux Minrraux (CNRS-
A. Corma ENSCMu)
Instituto de Tecnologfa Qufmica 3 rue Alfred Wemer
UPV-CSIC F-68093 Mulhouse
Avda. de los Naranjos, s/n FRANCE
46022 Valencia
SPAIN
viii

R. Garcia-de-Le6n P.J. Hall

Programa de Investigaci6n en Tratiamento de University of Strathclyde
Crudo Maya Department of Pure and Applied Chemistry
Instituto Mexicano del Petr61eo Glasgow G1 1XL
Ejo Central L~aro C&denas 152 Scotland
C.P. 07730 UK
M6xico, D.F.
MEXICO M. He
Research Institute of Petroleum Processing
W.R. Gilbert China Petrochemical Corporation
PETROBAS R & D Center Beijing 100083
Process Division P.R. CHINA
Rio de Janeiro, 21949-900
BRAZIL F. Hern~dez-Belmin
Programa de Investigaci6n en Tratiamento
R. Gonz~ilez-Serrano de Crudo Maya
Programa de Investigaci6n en Tratiamento de Instituto Mexicano del Petr61eo
Crudo Maya Ejo Central L~aro C~denas 152
Instituto Mexicano del Petr61eo C.P. 07730
Ejo Central L~aro C&denas 152 M6xico, D.F.
C.P. 07730 MEXICO
M6xico, D.F.
MEXICO J. Hiltunen
Fortum Oyj
M.-Y. Gu P.O. Box 310
Research Institute of Petroleum Processing 06101 Porvoo
(RIPP) FINLAND
SINOPEC
Beijing R. Hughes
CHINA University of Salford
Chemical Engineering Unit
N.J. Gudde Salford M5 4WT
BP, Oil Technology Centre UK
Chertsey Road
Sunbury-on-Thames A. Humphries
Middlesex TW16 7LN Akzo Nobel Catalysts Inc.
UK 2625 Bay Area Blvd., Suite 250
Houston, TX 77058
P. Gullbrand USA
Instituto de Tecnologfa Qufmica
UPV-CSIC P. Imhof
Avda. de los Naranjos, sin Akzo Nobel Catalysts
46022 Valencia Research Center Catalysts
SPAIN Amsterdam
THE NETHERLANDS
P. Hagelberg
Fortum Oyj K. J/i/iskel/iinen
P.O. Box 310 Fortum Oyj
06101 Porvoo P.O. Box 20
FINLAND 00048 Fortum
FINLAND
R. Jonker B. Lebeau
Akzo Nobel Catalysts Laboratoire de Mat6riaux Min6raux
Research Center Catalysts (CNRS-ENSCMu)
Amsterdam 3 rue Alfred Werner
THE NETHERLANDS F-68093 Mulhouse
FRANCE
M. Kalwei
Institut fiir Physikalische Chemie M.I. Levinbuk
Westf~ilische Wilhelms-Universit~it Miinster Gubkin Moscow Oil and Gas University
Schlossplatz 7 65 Leninsky prosp.
D-48149 Miinster Moscow 117917
GERMANY THE RUSSIAN FEDERATION

S. Katoh C.-Y. Li
Kashima Oil Company Research Institute of Petroleum Processing
Kashima (RIPP)
JAPAN SINOPEC
Beijing
G.W. Ketley CHINA
BP, Oil Technology Centre
Chertsey Road K. Lipiainen
Sunbury-on-Thames Fortum Oyj
Middlesex TW16 7LN P.O. Box 310
UK 06101 Porvoo
FINLAND
P. Knuuttila
Fortum Oyj F. L6pez-Isunza
P.O. Box 310 Departamento de Ingenierfa de Procesos e
06101 Porvoo Hidrfiulica
FINLAND Universidad Aut6noma Metropolitana-
Iztapalapa
C.L. (Arthur) Koon Av. Michoacfin y La Purisima sin
University of Salford Col. Vicentina
Chemical Engineering Unit Iztapalapa
Salford M5 4WT M6xico 09340, D.F.
UK MEXICO

C.W. Kuehler E. L6pez-Salinas

Akzo Nobel Catalysts Programa de Investigaci6n en Tratiamento de
Houston, Texas Crudo Maya
USA Instituto Mexicano del Petr61eo
Ejo Central Lfizaro Cfirdenas 152
A.A. Lappas C.P. 07730
Chemical Process Engineering Research M6xico, D.F.
Institut (CPERI) MEXICO
Department of Chemical Engineering
University of Thessaloniki Y. Lu
P.O. Box 361 Research Institute of Petroleum Processing
57001 Thermi, Thessaloniki China Petrochemical Corporation
GREECE Beijing 100083
P.R. CHINA
J. Majander J.C. Moreno-Mayorga
Fortum Oyj Programa de Investigaci6n en Tratiamento de
P.O. Box 20 Crudo Maya
00048 Fortum Instituto Mexicano del Petr61eo
FINLAND Ejo Central L~aro C~irdenas 152
C.P. 07730
M. Makkee M6xico, D.F.
Industrial Catalysis MEXICO
Department of Chemical Technology
Faculty of Applied Sciences J.A. Moulijn
Delft University of Technology Industrial Catalysis
Julianalaan 136 Department of Chemical Technology
2628 BL Delft Faculty of Applied Sciences
THE NETHERLANDS Delft University of Technology
Julianalaan 136
S.C. Martin 2628 BL Delft
University of Strathclyde THE NETHERLANDS
Department of Pure and Applied Chemistry
Glasgow G1 1XL T. Myrstad
Scotland Statoil's Research Centre
UK N-7005 Trondheim
NORWAY
C. Martfnez
Instituto de Tecnologfa Quimica M. Nakamura
UPV-CSIC Nippon Ketjen
Avda. de los Naranjos, s/n Tokyo
46022 Valencia JAPAN
SPAIN
V.M. Niemi
G.B. McVicker Fortum Oyj
ExxonMobil Research & Engineering Co. P.O. Box 310
Annandale, NJ 08801 06101 Porvoo
USA FINLAND

V.B. Melnikov S. Numan

Gubkin Moscow Oil and Gas University Gubkin Moscow Oil and Gas University
65 Leninsky prosp. 65 Leninsky prosp.
Moscow 117917 Moscow 117917
THE RUSSIAN FEDERATION THE RUSSIAN FEDERATION

E. Mogica-Martfnez M.L. Occelli

Programa de Investigaci6n en Tratiamento de MLO Consulting
Crudo Maya Atlanta, GA 30328
Instituto Mexicano del Petr61eo USA
Ejo Central L~aro C~denas 152
C.P. 07730 P. O'Connor
M6xico, D.F. Akzo Nobel Catalysts
MEXICO Amersfoort
THE NETHERLANDS
J. Patarin X. Shu
Laboratoire de Mat6riaux Min6raux Research Institute of Petroleum Processing
(CNRS-ENSCMu) China Petrochemical Corporation
3 rue Alfred Wemer Beijing 100083
F-68093 Mulhouse P.R. CHINA
FRANCE
B. Skocpol
V.A. Patrikeev Akzo Nobel Catalysts
Salavat Catalyst Factory Amersfoort
Salavat 453206 THE NETHERLANDS
THE RUSSIAN FEDERATION
C.E. Snape
M.L. Pavlov University of Strathclyde
Ishimbai Catalyst Factory Department of Pure and Applied Chemistry
Ishimbai 453210 Glasgow G1 1XL
THE RUSSIAN FEDERATION Scotland
UK
A. Petre
Institut de Recherches sur la Catalyse J. Song
CNRS Research Institute of Petroleum Processing
2 Av. A. Einstein China Petrochemical Corporation
69626 Villeurbanne Beijing 100083
FRANCE P.R. CHINA

T.F. Petti M. Soulard

Grace Davision Laboratoire de Mat6riaux Min6raux
7500 Grace Drive (CNRS-ENSCMu)
Columbia, MD 21044 3 rue Alfred Werner
USA F-68093 Mulhouse
FRANCE
Z.-H. Qiu
Research Institute of Petroleum Processing L.-W. Tang
(RIPP) Research Institute of Petroleum Processing
SINOPEC (RIPP)
Beijing SINOPEC
CHINA Beijing
CHINA
J. R6pp~inen
Fortum Oyj Z.A. Tsagrasouli
P.O. Box 20 Chemical Process Engineering Research
00048 Fortum Institut (CPERI)
FINLAND Department of Chemical Engineering
University of Thessaloniki
W.L. Schuette (deceased) P.O. Box 361
57001 Thermi, Thessaloniki
A.E. Schweizer GREECE
ExxonMobil Refining and Supply Company
Process Research Laboratories Y.R. Tyagi
P.O. Box 2226 University of Strathclyde
Baton Rouge, LA 70821-2226 Department of Pure and Applied Chemistry
USA Glasgow G1 1XL, Scotland
xii

I.A. Vasalos
Chemical Process Engineering Research
Institute (CPERI)
Department of Chemical Engineering
University of Thessaloniki
P.O. Box 361
57001 Thermi, Thessaloniki
GREECE

C.L. Wallace
University of Strathclyde
Department of Pure and Applied Chemistry
Glasgow G1 1XL
Scotland
UK

A. Wrlker
Institut fiir Physikalische Chemie
Westf/ilische Wilhelms-Universi~t Miinster
Schlossplatz 7
D-48149 Miinster
GERMANY

S.-H. Yan
Research Institute of Petroleum Processing
(RIPP)
SINOPEC
Beijing
CHINA

S.J. Yanik
Akzo Nobel Catalysts
Singapore
 Preface

Catalyst production for the transformation of crudes into gasoline and other fuel products is a
$2.1 billion/year business and fluid cracking catalysts (FCCs) represent almost half of the
refinery catalyst market (M. MacCoy, Chemical and Engineering News, p. 17, September 20
(1999)). During the cracking reactions, the FCC surface is contaminated by metals (Ni, V, Fe,
Cu, Na) and by coke deposition. As a result, the catalyst activity and product selectivity is
reduced to unacceptable levels thus forcing refiners to replace part of the recirculating
equilibrium FCC inventory with fresh FCC to compensate for losses in catalyst performance.
About 1,100 tons/day of FCC are used worldwide in over 200 fluid cracking catalyst units
(FCCUs). Today, the worldwide capacity to produce gasoline exceeds the 460 million
gal/day. In addition, FCCs are used in the commercial synthesis of acrylonitrile, phthalic
anhydride and maleic anhydridie and in the production of 45% of the world propylene
(Chemical and Engineering News, p. 51, November 23, 1998). In recognition of the great
technological importance of the FCC process, on November 3, 1998 the first commercial fluid
bed reactor using catalytic cracking constructed at the Exxon Baton Rouge refinery, was
designated a National Historic Chemical Landmark by the American Chemical Society.
It is for these reasons that refiners' interest in FCC research has remained high through
the years and almost independent of crude oil prices. However, recent oil company mergers
and the dissolution of research laboratory, has drastically decreased the number of researchers
involved in petroleum refining research projects. As a results the emphasis has shifted from
new materials research to process improvements and this trend is clearly reflected in the type
of papers contained in this volume.
Modem spectroscopic techniques continue to be essential to the understanding of
catalysts performance and several chapters in the book describe the use of 27A1, 29Si and ~3C
NMR to study variation in FCC acidity during aging and coke deposition. In addition several
chapters have been dedicated to the modeling of FCC deactivation, and to the understanding
of contact times on FCC performance. Refiners efforts to conform with environmental
regulations are reflected in chapters dealing with sulfur removal, metals contaminants and
olefins generation
In conclusion, as before we would like to express our gratitude to our colleagues for
acting as technical referees. The views and conclusion expressed herein are those of the
chapter authors whom we sincerely thanks for their time and effort in presenting their research
at the Symposium and in preparing the camera ready manuscripts for this Volume.

Mario L. Occelli and Paul O'Connor

November 2000
 Table of Contents

List of Contributors

Preface 1

Defect structure and acid catalysis of high silica, FAU-framework

1 zeolites: effects of aluminum removal and of basic metal oxide 3

addition

The use of microcalorimetry and solid state nuclear magnetic

resonance (NMR) to study the effects of post-synthesis treatments

2 41
on the acidity and framework composition of several HY-types

zeolites

The effects of steam aging temperature on the properties of an HY

3 59
zeolite of the type used in FCC perparations

Effect of catalyst properties and feedstock composition on the

4 71
evaluation of cracking catalysts

Study on the deactivation-aging patterns of fluid cracking

5 87
catalysts in industrial units
 The improvement of catalytic cracking process through the
6 107
utilization of new catalytic materials

7 NExCC-Novel short contact time catalytic cracking technology 111

8 Effect of vanadium on light olefins selectivity 133

9 Reduction of olefins in FCC gasoline 141

Gasoline sulfur removal: kinetics of S compounds in FCC

10 153
conditions

Development of a kinetic model for FCC valid from ultra-short

11 167
residence times

Deactivation of fluid catalytic cracking catalysts: a modelling

12 187
approach

Catalyst design for resin cracking operation: benefits of metal

13 201
tolerant technologies

14 Active site accessibility of resid cracking catalysts 209

Catalyst evaluation for atmospheric residue cracking, the effect of

15 219
catalyst deactivation on selectivity
16 Optimum properties of RFCC catalysts 227

An experimental protocol to evaluate FCC stripper performance in

17 239
terms of coke yield and composition

Use of [superscript 13]C-labelled compounds to probe catalytic

18 251
coke formation in fluid catalytic cracking

19 Bifunctionality in catalytic cracking catalysis 263

Catalytic cracking of alkylbenzenes. Y-zeolites with different

20 279
crystal sizes

On the mechanism of formation of organized mesoporous silica

21 293
that may be used as catalysts for FCC

Catalyst assembly technology in FCC. Part I: A review of the

22 299
concept, history and developments

Catalyst assembly technology in FCC. Part II: The influence of

23 fresh and contaminant-affected catalyst structure on FCC 311

performance

Keyword Index 333

Studies in Surface Science and Catalysis 134
M.L. Occelli and P. O'Conner (Editors)
9 2001 Elsevier Science B.V. All rights reserved

Defect Structure and Acid Catalysis of High Silica, F A U - F r a m e w o r k

Zeolites: Effects of A l u m i n u m R e m o v a l and of Basic Metal Oxide Addition

Robert A. Beyerlein* and Gary B. McVicker*

*National Institute of Standards and Technology, Gaithersburg, MD 20899-4730
*ExxonMobil Research & Engineering Co., Annandale, NJ 08801

The catalytic properties of ultrastable Y (USY) are directly influenced by the zeolite
destruction that occurs during formation of USY and during subsequent hydrothermal
treatment. Mildly steamed USY materials exhibit a secondary pore system (mesopores) of 5-
50 nm dimensions, which are evident as light amorphous zones in Transmission Electron
Microscopy (TEM). Combined high resolution electron microscopy (HREM) and analytical
electron microscopy (AEM) investigations on hydrothermally deaiuminated USY materials
have shown that, in regions of high defect concentration, mesopores "coalesce" to form
channels and cracks, which, upon extended hydrothermal treatment, define the boundaries of
fractured crystallite fragments. The predominant fate of aluminum ejected from lattice sites
appears to be closely associated with dark bands, which decorate the newly formed fracture
boundaries. A smaller proportion of ejected aluminum exists as "nonframework AI" within
the zeolite cages. High silica Y materials, having little or no nonframework A1 exhibit poor
catalytic activity for a large variety of acidity-dependent reactions. Investigations on mildly
dealuminated zeolites suggest that the origin of the enhanced catalytic activity is a synergistic
interaction between Br0nsted (framework) and highly dispersed Lewis (nonframework) acid
sites. The enhanced cracking, isomerization activity associated with the presence of highly
dispersed nonframework A1 species i) is not reflected in direct measures of solid acidity
obtained, for example, by calorimetry or by NMR spectroscopy, and ii) is not consistent with
a major increase in average acid site strength.
Numerous structure/function studies indicate that the critical nonframework A1 species
may exist as cationic species in the small cages of dealuminated H-Y. By contrast, partial
exchange of high silica Y materials with monovalent cations, such as Na or K, leads to
significant reduction in activity, presumably by poisoning acid sites. In prior studies of
isobutane conversion over dealuminated H-Y, it was shown that the addition of sodium
equivalent to 1/3 of the total framework A1 atoms completely eliminates catalyst activity.
Extensions of these poisoning studies show that addition of potassium produces a much
stronger poisoning effect, with one K + ion giving an activity suppression roughly equivalent
to that produced by two Na § ions. Calcium addition gives rise to a poisoning effect
intermediate between those of Na + and K + at low levels of exchange, ca. 10%, but is more
mild than that of sodium as Ca ++ exchange levels exceed 20%.
Previous correlations of isobutane conversion activity with framework composition
support a direct dependence of carbocation-facilitated processes on framework aluminum
(A1F), with a linear dependence of carbonium ion rates on A1F content. The observed linear
dependencies exhibited for Na or K addition show that the primary effect of poisoning, or of
A1F removal, is a decrease in the number of active sites. Measured selectivities for carbocation
products indicate a limiting site density of about A1F/ucell - 8 (out of a maximum 56 A1
among 192 tetrahedral framework sites for a starting zeolite Y), below which carbocation
activity diminishes rapidly. Consistent with previous discussion of dual mechanisms, the
results for formation of methane, a stable reaction product marker, show that the initiation
step and the secondary carbocation processes are intimately linked over the entire range of
acid site content, whether manipulated by dealumination or by permanent poisoning by basic
alkali or alkaline metal oxides.

1. INTRODUCTION
The importance of acid catalysis for the production of fuel and petrochemicals is
underscored by recent environmental mandates calling for reformulated motor fuel that
contains greater proportions of high octane, branched paraffins and oxygenates.
Environmental concerns about the catalysts themselves, particularly the highly corrosive and
toxic liquid acids, such as sulfuric and hydrofluoric acids, have created a need for stable,
strongly acidic solid acids. Combined theoretical and experimental studies of the last decade
have substantially improved our level of understanding of solid acidity in zeolites. The
prospect for obtaining a detailed molecular level understanding of heterogeneous catalysts that
could better guide the search for improved catalysts appears to be optimum for crystalline
solid acids. It is the object of this paper to review our current understanding of the
predominant solid acid catalyst, the family of protonated FAU-framework materials stabilized
by hydrothermal treatment, originally designated ultrastable Y (USY) [1, 2] and commonly
referred to as dealuminated H-Y (H-ultrastable Y).
The catalytic properties of ultrastable Y are directly influenced by the zeolite destruction
attending its formation and further modification by subsequent hydrothermal treatment. For
ultrastable, high silica, FAU framework materials prepared by steam dealumination,
interpretation of catalytic data is complicated by the presence of entrained, nonframework
aluminum (NFA) species. Although the individual and collective roles of framework and
nonframework aluminum species are not well understood, it is clear that the presence of some
nonframework A1, presumably highly dispersed, is essential for the strong solid acidity
exhibited by high silica H-Y [3-5]. While the critical nonframework species are not easily
subject to direct observation, the existence of isolated, intracrystalline NFA species in
dealuminated H-Y materials is not in doubt.
The importance of certain nonframework A1 species for the ability of zeolitic solid acids
to catalyze acidity-demanding reactions [6], such as alkane skeletal isomerization or cracking,
is not limited to H-Y. An abundant literature shows a consensus that the development of
"enhanced carbocation activity" in mildly steamed HZSM-5 is also critically dependent on
the presence of nonframework A1 [6-9]. Enhancement of carbocation activity, generally
associated with BrCnsted acidity, has also been observed in mildly steamed mordenite [10]
and in HZSM-20 [ 11 ].
Knowledge of framework geometry is essential for understanding overall reactivity
patterns for hydrocarbon conversions over these open framework solid acids. The well-known
features of "molecular traffic management" exhibited by these materials are not always
limited to molecular sieving, that is reactant or product size exclusion effects. For example,
at reaction temperatures of 400 ~ to 500~ dealuminated H-USY and dealuminated mordenite
(large pore zeolites)each catalyze the isomerization of isobutane to n-butane [12, 13]. Under
similar conditions, the medium pore system HZSM-5 produces relatively little n-butane, but
instead yields much methane and propylene [13, 14]. The dramatically different product
selectivities in the latter case are attributed to the more severe spatial restrictions of the
medium pore ZSM-5, which tend to inhibit hydride transfer and oligomerization/back-
cracking processes involving bulky reaction intermediates.
Ever since the rapid commercialization in the early 1960's of a zeolite-catalyzed process
for gas oil cracking [15, 16], zeolites have comprised the predominant usage of solid acid
catalysts. The characterization and application of high silica, protonated zeolites in fluid
catalytic cracking has been reviewed by Scherzer [17]. A broader overview of the use of
zeolites in hydrocarbon processing is found in Maxwell and Stork [ 18]. A large number of
potential zeolite catalyst applications in the synthesis of intermediates and fine chemicals have
been discussed by Hoelderich et al. [19-21].
An outstanding attribute of the acidic FAU H-Y materials is their ability to catalyze
intermolecular hydride transfer reactions in numerous hydrocarbon conversions, which are all
but missing in less strongly acidic amorphous solid acids. Despite high industrial and
academic interest, the nature of the active site in solid acids remains largely unresolved. In
systems of wide interest such as a protonated zeolite, a chlorided or fluorided alumina, or
sulfated zirconia, we are unable to quantify the distribution or relative importance of BrCnsted
and/or Lewis sites, the surface acid strength, or the concentration of acid sites [22]. Recent
advances in physical characterization of sites have substantially improved our understanding
of these issues. Both 1H MASNMR [8, 23-25] and 13C MASNMR [26] have been effective
in formalizing the structure/function relationships for BrCnsted acid sites in HZSM-5, an
especially favorable system for analysis owing to its low BrCnsted acid site density and high
crystallinity. So far, only "clean framework" ZSM-5 has been reasonably well characterized.
The extension of these and related spectroscopic studies to the more complex systems
represented by mildly steamed, carbocation activity enhanced HZSM-5 or dealuminated H-Y
comprises a significant experimental and data interpretation challenge.
 In the following sections, we review advances in the understanding of (i) the evolution
of defect formation in dealuminated H-Y, (ii) the critical role played by nonframework
aluminum in the acid catalysis exhibited by these materials and (iii) the dual effects of
aluminum removal and of basic metal oxide addition on catalyst activity and selectivity. The
discussion of acid catalysis is cast primarily in terms of kinetic methods for classifying solid
acidity. As noted in a recent review by Haag [27], the question of acid strength is much more
problematic and complicated. Theoretical efforts to elucidate structure-acidity relationships
have made great progress, but are primarily limited to the "clean framework" case. Direct
measures of solid acid strength within a homologous series of solid acids, e.g., ZSM-5 or
dealuminated H-Y, including "in situ" calorimetric and/or spectroscopic methods, will often,
but not always correlate with catalytic properties.

2. D E F E C T S P R O D U C E D BY H Y D R O T H E R M A L T R E A T M E N T
2.1. B a c k g r o u n d - F o r m a t i o n of Ultrastable Y
The formation of Ultrastable FAU materials may be viewed as a two-step process in
which steam-calcination of the ammonium (or H) form of the Y-zeolite at the approximate
conditions T=500~ Pa2o = 1 atm, for 2 hours, leads to the expulsion of A1 atoms from
framework T-sites as indicated in Figure 1. Following aluminum expulsion from framework
positions, the resulting vacancies are to a great extent, refilled by silicon atoms migrating from

Two-step process:
1 Calcination of the ammonium (or H) form of the
Y-zeolite at T > 500~ PH20< 1 atm
==~>Expulsion of AI atoms from framework T-sites
Si Si
I I
0 H+ 0 0
I I H
Si--O-AI- O-Si-O + 3H20 b,- Si-OH HO-SI + AI(OH)3
I I H
0 0 0
I I
Si Si
G.T: Kerr, 1979

2 Healing / Si replacement- Resulting vacancies

are refilled to a large extent with Si atoms
Limited concensus on this m e c h o n i s m

Figure 1. Schematic representation of formation of ultrastable Y materials

the collapsed portions of the crystal. If this "healing" did not occur, the entire zeolite crystal
would transform into a predominantly x-ray amorphous phase. The resulting restructured FAU
material, originally designated Ultrastable Y or USY [1, 2], displays a contracted unit cell size
and increasing hydrothermal stability as framework Si/A1 increases. A typical reduction in
unit cell dimension is from 2.470 nm for the starting zeolite Y to 2.456 nm for the product
USY. Increasingly more severe steam treatments result in a higher level of dealumination, a
more contracted unit cell, and an increasing fraction of crystalline zeolite destruction.
In certain chemical methods of dealumination, notably the ammonium hexafluorosilicate
(AHF) method of Skeels and Breck [28], the silicon for "healing" of vacancies resulting from
framework A1 removal originates from an external source. In contrast, during the formation
of USY, the inserted silicon originates from an internal source (the zeolite itself) that results
from damage to the zeolite framework with the concomitant formation of mesopores. The
mechanism of silica transport and insertion into vacancies was first suggested by Maher,
Hunter and Scherzer [29]. According to this mechanism, the silica required to fill the
framework vacancies originates in those parts of the zeolite crystal which collapse during the
hydrothermal treatment. The silica freed from the collapsed framework migrates under high
temperature steam toward the tetrahedral vacancies of the remaining framework and, by filling
them, increases framework stability [30]. Prior sorption studies tend to support this
interpretation. Based on sorption studies on USY zeolites, Lohse et al. concluded that entire
sodalite units, or [3-cages, are destroyed during hydrothermal dealumination [31, 32], leading
to the formation of a secondary pore system [30] or mesoporosity in the range of 5 to 50 nm.
As shown schematically in Figure 2, the collapse of sodalite units, or even ensembles of them,
generates mesoporosity and simultaneously provides the source of Si atoms for healing the
framework sites vacated by A1. Lattice destruction of hydrothermally dealuminated (or
thermochemically treated) FAU materials, leading to the formation of an amorphous silica
phase, may be identified in the 29Si MASNMR spectra by a broadened peak or shoulder at
about-110 ppm (TMS) [33]. Recent 29Si and 27A1 MASNMR and microcalorimetry
investigations of the aging and regeneration of Fluid Cracking Catalysts (FCC) have shed new
light on mechanisms of healing and on overall silica losses [34a]. Results of these studies
indicate that the products of hydrothermal transformation of the kaolin clay and the
alumina/silica gel (components of the catalyst matrix of the composite FCC particle) represent
possible sources of silica. Upon aging, each of these components generate penta-,
tetrahedrally- and octahedrally-coordinated A1 species, and at the same time, Si compounds,
which can contribute both to healing and to net silica losses from the FCC particle [34a,b].
Measurements of silica/alumina composition for a fresh catalyst and for the corresponding
equilibrium catalyst from a commercial Fluid Cracking Unit show a dramatic drop in the bulk
Figure 2. Schematic model for mechanisms of dealumination in FAU, showing Si for
"healing," and the source of mesoporosity.

SIO2/A1203 ratio from 3.6 for fresh to 2.5 for the used or "equilibrium" catalyst, indicating a
substantial silica loss from the FCC particle during use [34b].

2.2. Nonframework Aluminum- Local Environment

Nonframework aluminum (NFA) is a catchall description for a wide collection of defects
that are produced during the formation of USY and during subsequent hydrothermal
treatment. NFA species are themselves composed of several different types, some isolated,
some agglomerated, as outlined in Table 1. It has proven to be particularly difficult to
characterize the many different NFA species in dealuminated H-Y. Structural studies using
X-ray and neutron diffraction have indicated the presence of octahedrally coordihated
microcrystalline aluminum species in the supercages [35], and isolated tetrahedral aluminum
species in the small (sodalite) cages [36], but do not give much information about
agglomerated noncrystalline species. A systematic study of the reduction in micropore volume
[37] resulting from mild dealumination of H-Y, and of HZSM-5, indicated that the majority
of NFA species go to the micropores accessible to N2, the supercages (c~-cages) in the case
of H-Y, and to the channels or channel intersections in the case of HZSM-5. The combination
of high resolution 29Si and of 27A1 solid state NMR has been effectively applied to studies of
Table 1
Types of aluminum a in ultrastable Y

Types detect- Probable structure Isolated or Most abundant

able by NMR description clustered

TF T-site isolated mildly dealuminated

TNFA A1 in small cage and/or isolated mildly dealuminated
TNFA alumina species in S-C b clustered severely dealuminated
and/or surface enrichment
PNFA intermediate between unknown severely dealuminated
octahedral and tetrahedral
ONFA alumina species in s-c clustered always present

b
a T = tetrahedral, 0 = octahedral s-c = supercage [from Ref. 61]

hydrothermally dealuminated Y zeolites [38]. The former provides direct information on the
composition and Si, A1 distribution of the tetrahedral framework, independently of the
presence of non-framework A1 species, while the latter allows distinction between tetrahedral
framework A1 (-60 ppm) and octahedral non-framework A1 (-0 ppm). The interpretation of
27A1NMR in terms of A1 species location or state of agglomeration is often ambiguous. Even
at low levels of dealumination, the contribution of nonframework species to the tetrahedral
resonance cannot be ruled out. The fact that a wide range of transitional aluminas exhibit a
ratio of tetrahedrally coordinated A1 over total A1 content of about 0.4 [39] illustrates the need
for caution in attributing the tetrahedral resonance in zeolites to framework aluminum.
Extensively dealuminated samples typically show substantial broadening of the tetrahedral
resonance [40, 41], as shown in Figure 3, only a small portion of which can be attributed to
framework A1 [41, 42]. In addition, as higher magnetic fields and faster sample spinning have
become more routine, a new resonance has been observed at 30 ppm (Figure 3), which has
been attributed to either an aluminum in a highly distorted tetrahedral environment [41-44]
or a penta-coordinated aluminum species [44, 45]. Application of the novel double-rotation
(DOR) spinning technique [46, 47] to the study of 27A1in zeolites [48] has shown two
different tetrahedral A1 species for a commercial USY material, one framework and the other
nonframework [48]. On the basis of comparison of single pulse 27A1MASNMR and 27A1CP
MASNMR taken on a steamed Y zeolite, Fripiat and co-workers [49] concluded that a
substantial portion of the band near 60 ppm is contributed by tetrahedrally-coordinated NFA.
10

4X

T
Acid wash, 0.1 N HCI
. Steam 650~ 4 hr

5X

T
Acid wash x 2, 0.1 N
~, " Steam650~ 3 hr,
It NH4§ exch.,acid wash,
2X ]\ A o.o33..
A
Calcine 538~ 2 hr
l ~ j ~ Steam 600~ 3 hr
T
1X Parent USY (LZ-Y82)

9 A z~

=+0 ~5o ~oo"5'o . . . . o:sO-~'oo"-l'sOPp", ~

Figure 3. Evolution of deauluminated USY as tracked by 27A1

MAS NMR [42, 61 ]. 9 framework AI" •, nonframework A1.

2.3. Nonframework A l u m i n u m and Mesoporosity

Previous transmission electron microscope (TEM) studies of hydrothermal aging of neat USY
materials [50-54] and also of USY cracking catalysts [55-58] have shown 5 to 50 nm defect
domains, which were attributed to mesopores. Such features, more pronounced in the presence
of vanadium [55, 56], are characteristic of extended hydrothermal treatment. Typical porosity
analyses of mildly steamed USY materials show a distribution of mesopore dimensions in the
range 5 to 50 nm that is skewed toward the smaller sizes [5 l, 53], supporting the association
of the light amorphous zones observed by TEM with the secondary pore system characteristic
of USY materials [3 "., 32, 50-53].
A new understanding of the formation and evolution of mesopores has emerged from
combined high resolution electron microscopy (HREM) and analytical electron microscopy
(AEM) investigations on hydrothermally treated USY materials [42, 59]. In contrast with
 11

results of previous TEM investigations [50, 51, 54], HREM and AEM studies of a steam/acid
treated neat USY material, and of a high-temperature steam-treated USY cracking catalyst
[42, 59], gave clear evidence for an inhomogeneous distribution of mesopores (Figure 4),
which occurs concomitantly with further zeolite dealumination. Such inhomogeneities were
found to be more pronounced for the (high temperature) steam-deactivated USY cracking
catalyst than for the (moderate temperature) steam/acid-treated neat USY material. It was
concluded that the extent of inhomogeneity is driven by non-equilibrium processes
represented by accelerated steam-aging treatments in the laboratory.
In regions with high defect concentration, mesopores "coalesce" to form channels and
cracks (Figures 4, 5a, 6), which ultimately define the boundaries of fractured crystallite
fragments. At these boundaries, a dark band is often observed which is highly enriched in
aluminum (Figure 5), while within the mesopore, aluminum appears to be deficient (Figure
7) [59]. Such dark bands appear to have been observed in prior studies [53], but their presence
was not discussed. The predominant fate of aluminum ejected from lattice sites appears to be
closely associated with the dark bands, which often decorate these newly formed fracture

Figure 4. HREM image of several USY grains in the steamed USY catalyst showing an
inhomogeneous distribution of mesopores. A coalescence of mesopores indicating an
evolving fracture is indicated by an arrow [42].
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