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0 Fluid Catalytic Cracking
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In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
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In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
375
ACS SYMPOSIUM SERIES
Fluid Catalytic Cracking
Role in Modern Refining
Mario L. Occelli, EDITOR
Unocal Corporation
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98 Developed from a symposium sponsored by
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bk- the Division of Petroleum Chemistry, Inc.,
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02 at the 194th Meeting
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10. of the American Chemical Society,
doi: New Orleans, Louisiana,
88 | August 30-September 4, 1987
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American Chemical Society, Washington, DC 1988
In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
Library of Congress Cataloging-in-Publication Data
Fluid catalytic cracking: role in modern refining
Mario L. Occelli, editor
Developed from a symposium sponsored by the Division
of Petroleum Chemistry, Inc., at the 194th Meeting of the
American Chemical Society, New Orleans, Louisiana,
August 30-September 4, 1987.
1
00 p. cm.—(ACS symposium series, ISSN 0097-6156;
w 375).
5.f
7 Papers presented at the Symposium on Advances in
03 FCC, held in New Orleans, La., Aug. 30-Sept. 4, 1987.
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98 Bibliography: p.
1
bk- Includes index.
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2 ISBN 0-8412-1534-0
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0. 1. Catalytic cracking—Congresses.
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oi: I. Occelli, Mario L., 1942- . II. American Chemical
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8 | SIIoI.c ieStyym. pDoisviuismio no no fA Pdevtarnocleesu min CFhCeCm i(s1t9ry8.7 : New Orleans,
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9 La.) IV. Series.
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12, TP690.4.F57 1988
ber 665.5'33—dc19 88-221C5IP1
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Dat Copyright © 1988
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In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
ACS Symposium Series
M. Joan Comstock, Series Editor
1988 ACS Books Advisory Board
Paul S. Anderson Vincent D. McGinniss
1 Merck Sharp & Dohme Research Battelle Columbus Laboratories
0
0 Laboratories
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5.f Daniel M. Quinn
7 Harvey W. Blanch
03 University of Iowa
8- University of California—Berkeley
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9
k-1 Malcolm H. Chisholm James C. Randall
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1/ Indiana University Exxon Chemical Company
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10. Alan Elzerman E. Reichmanis
oi: Clemson University AT&T Bell Laboratories
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8 John W. Finley
19 C. M. Roland
12, Nabisco Brands, Inc. U.S. Naval Research Laboratory
ber Natalie Foster
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pte Lehigh University W. D. Shults
e Oak Ridge National Laboratory
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e: Marye Anne Fox
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D The University of Texas—Austin Geoffrey K. Smith
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atio Roland F. Hirsch Rohm & Haas Co.
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bli U.S. Department of Energy
u Douglas B. Walters
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G. Wayne Ivie National Institute of
Environmental Health
USDA, Agricultural Research Service
Michael R. Ladisch Wendy A. Warr
Purdue University Imperial Chemical Industries
In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
Foreword
The ACS SYMPOSIUM SERIES was founded in 1974 to provide a
medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that, in order to save time, the
papers are not typeset but are reproduced as they are submitted
by the authors in camera-ready form. Papers are reviewed under
the supervision of the Editors with the assistance of the Series
01 Advisory Board and are selected to maintain the integrity of the
0
w symposia; however, verbatim reproductions of previously pub
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7 lished papers are not accepted. Both reviews and reports of
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8- research are acceptable, because symposia may embrace both
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In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
Preface
FÎUIDIZED CRACKING OF PETROLEUM FRACTIONS is still the main
process for large-scale gasoline production even 40 years after its
introduction. Worldwide cracking-catalyst sales in 1987 amounted to
about $457 million and represented 48% of the total catalyst sales to the
1
00 petroleum industry.
pr
5. In response to recent federal and local environmental concerns (e.g.,
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03 industrial emission controls and lead phase-out) and to the growing
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8 interest of refiners in cracking residual fuels, researchers have generated
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k- new families of cracking catalysts. There is now a need to review the
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1/ merits of these newly developed materials. This volume contains
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10 contributions from researchers involved in the preparation and
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1 characterization of cracking catalysts. Other important aspects of fluid
doi: catalytic cracking, such as feedstocks and process hardware effects in
8 | refining, have been intentionally omitted because of time limitations and
8
9
1 should be treated separately in future volumes.
2,
er 1 This volume focuses on the use of novel materials (zeolite beta,
mb pillared clays, or S scavengers) and novel compositions (e.g., those
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pt containing lanthanide-free faujasite crystals, shape-selective zeolite, or
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e: S metal scavengers) in meeting the challenges of lead-free gasoline
at production, the increasingly stringent S-emission regulations, and the
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n cracking of residual and metal-contaminated oils. Modern spectroscopic
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ati techniques, such as nuclear magnetic resonance spectroscopy, X-ray
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bli absorption and X-ray photoelectron spectroscopy, laser Raman
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spectroscopy, and electron microprobe measurements, have been used to
characterize extraframework Al in zeolites and to elucidate
metal-surface interactions in cracking catalysts. The applied aspects of
cracking are discussed in chapters dealing with heavy oils, hydrotreated
feedstocks, catalyst demetalation, and catalyst development for resid
upgrading.
In concluding, I would like to acknowledge the help received from
D. L. Hilfman in chairing the symposium from which this volume was
developed and to express my gratitude to colleagues at Unocal
Corporation and elsewhere for acting as technical referees. I am also
particularly grateful to Unocal for permission to participate in and
xi
In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
complete this project and to G. Smith for her invaluable secretarial
help. The views and conclusions expressed herein are those of the
authors, whom I sincerely thank for their time and effort in presenting
their research at the symposium and in preparing the camera-ready
manuscripts for this book.
MARIO L. OCCELLI
Unocal Science & Technology Division
P.O. Box 76
Brea, CA 92621
March 9, 1988
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xii
In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
Chapter 1
Recent Trends in Fluid Catalytic
Cracking Technology
Mario L. Occelli
Unocal Science & Technology Division, Unocal Corporation,
01 P.O. Box 76, Brea, CA 92621
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7 In the United States, approximately one-third of all
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8-0 processed crude oil, amounting to about 5 X 106
8 bbl/day, is catalytically converted over fluidized
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k-1 catalysts. Over 500 tons of catalyst are required
1/b daily, yielding sales that in 1987 were estimated at
2 ~250 million dollars (1). Thus, in terms of catalyst
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0.1 usage and product value, catalytic cracking is still
doi: 1 t-hreef inminogs t iinmdpuosrttrayn. t uTnhiits yoepaerr,a ttihoen woofr ltdhweid ep estarolelesu mof
8 | catalysts to the petroleum, petrochemical, and
98 chemical industry are expected to exceed 2.4 billion
1
2, dollars, and catalyst producers are preparing
ber 1 tahree mpserolvjeesc tefdo r ttoh eb ectuomrne oaf 5th eb ilcleinotnu ryd owllhaerns cpaetra lyyesatrs
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n In the United States, the catalytic cracking of petroleum fractions
o
ati is believed to have begun in 1936 with the Houdry fixed-bed process
blic employing a solid regenerable catalyst. E. Houdry observed that
u the performance of racing cars could be improved by using
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high-octane gasoline obtained from cracking heavy petroleum
fractions over acid-treated montmorillonites or halloysites (3).
Today, catalytic cracking is still the major process for gasoline
manufacture.
Prior to 1938, gasoline was obtained from thermal-cracking
plants; then the Houdry fixed-bed catalytic cracking process led to
the development of a fluidized-bed process by Standard Oil for the
catalytic production of motor fuels (4-8). Acid-treated clays of
the montmorillonite type were the first fluid-cracking catalysts
widely employed by the industry. However, the ever greater demand
for aviation fuels during the 1939-1945 period prompted the search
for more active and selective catalysts. Research on novel catalyst
0097-6156/88/0375-0001$06.00/0
© 1988 American Chemical Society
In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
2 FLUID CATALYTIC CRACKING: ROLE IN MODERN REFINING
formulations thus began, and by the end of World War II, clays were
abandoned in favor of synthetic silica-alumina, silica-magnesia,
alumina, or even phosphate catalysts (9). The beginnings and early
developments of the (FCC) process have been reviewed in detail by
Marshall (9).
Amorphous aluminosilicates were used as cracking catalysts for
over twenty years; then, in the early sixties, the catalytic
properties of synthetic faujasite were discovered, and zeolites
rapidly came to dominate the petroleum-refining industry (10,11).
The introduction of rare earth-exchanged zeolites X or Y in cracking
catalyst preparations was a most important breakthrough because
zeolitic catalysts afforded a large increase in cracking activity
and gasoline make while minimizing light gases and coke generation.
As a result, these new types of catalysts were quickly accepted by
refiners.
1 In 1976, the first African fluid cracking unit became
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5.c cracking units in North America and the USSR employed zeolites. In
37 the years that followed, catalyst manufacturers dedicated a large
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98 catalysts for processing sweet U.S. and Middle-Eastern crudes.
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k- Aluminosilicate matrices, clay minerals (kaolin), and zeolites (with
1/b the faujasite structure) were manipulated to yield cracking
02 catalysts capable of satisfying the refiner's special needs (12,13).
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0. Research work was then directed mainly toward the generation of FCC
1
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8 | selectivity.
8
9 In 1973, the Arab oil embargo and the sudden escalation in
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2, crude oil prices (Figures 1,2) and availability placed refiners
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er under great economic pressures to process more abundant, less
b expensive, metals-contaminated crude oils and residuum feedstocks.
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e The need for metals-resistant FCC became apparent, and work on
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e understanding metal-catalyst interactions became an area of intense
S
e: research in industrial laboratories and in the academic community.
Dat When in 1984 the Environmental Protection Agency (EPA) proposed
n the lead phaseout from gasoline, the emphasis on FCC research
o
ati shifted toward the generation of octane-selective catalysts.
blic Environmental concerns have also proposed limits on sulfur emissions
u from FCC units, thus initiating research on on catalysts capable of
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sorbing S-impurities in the regenerator and releasing them as r^S in
the reactor side from where they can be easily adsorbed.
Political events, oil supply and costs, technological
breakthroughs, and environmental concerns have influenced, and will
probably continue to influence, the petroleum and, therefore, the
catalyst manufacturing industry. Thus efforts to understand
possible trends in future catalyst activities and research
directions must proceed with the understanding of the aforementioned
factors.
In Fluid Catalytic Cracking; Occelli, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
