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MEETING REPORT

April 2003 The Arabian Journal for Science and Engineering, Volume 28, Number 1B
115
MEETING REPORT
Catalysts in Petroleum Refining & Petrochemicals
12
th
Annual SaudiJapanese Symposium
Held at King Fahd University of Petroleum & Minerals (KFUPM)
Dhahran, Saudi Arabia,
On December 15-16, 2002.
A. M. Aitani
Center for Refining & Petrochemicals, The Research Institute
KFUPM, Dhahran, Saudi Arabia
Fax +966 38604509
Email: maitani@kfupm.edu.sa
More than 120 scientists, engineers, catalyst experts, and
researchers from Saudi Arabia, Japan, USA, Germany,
Denmark, France, the Netherlands, and South Africa
participated in the two-day symposium on refining and
petrochemical catalysts held on December 1516, 2002.
This annual symposium is jointly organized by KFUPM
and the Japan Petroleum Institute to discuss latest
developments and advances in refining and petrochemical
catalysts and processes. The emphasis was on ultra-deep
desulfurization of diesel and gasoline, hydroprocessing,
sulfur removal and analysis, catalyst characterization,
polymerization, and petrochemical applications. The
following is a brief report on the papers presented at the
symposium.
Ultra-Deep Desulfurization
Dr. Koichi Segawa of Sophia University, Japan, discussed
ultra-deep HDS of dimethyl dibenzothiophene over Mo
sulfide catalysts supported on TiO
2
Al
2
O
3
composites.
The composites were prepared by chemical vapor
deposition technique using TiCl
4
as precursor. A high
dispersion of titania over Al
2
O
3
has been elucidated using
nitrogen adsorption at 77K, X-ray photoelectron
spectroscopy and X-ray fluorescence measurements.
Mo/TiO
2
Al
2
O
3
catalysts exhibit much higher
hydrodesulfurization activity for 4,6-
dimethyldibenzothiophene compared to those supported on
alumina or titania under mild operating conditions. XPS
investigations indicated that molybdenum phases
supported on TiO
2
Al
2
O
3
composites present higher
reducibility/sulfidability properties compared to those
supported on alumina.
Dr. Kim G. Knudsen of Haldor Topsoe, Denmark,
presented a paper on ultra-deep desulfurization of diesel:
understanding of underlying kinetics. The paper covered
critical factors governing the production of ultra low sulfur
diesel (ULSD) i.e. diesel fuel with less than 50 ppm sulfur.
To produce ULSD, it is necessary to remove the most
refractory sulfur compounds such as alkyl-substituted
dibenzothiophenes. These compounds are desulfurized via
one of two routes: by direct extraction of the sulfur atom,
or by hydrogenation of one of the aromatic rings followed
by sulfur extraction. Factors affecting the relative rates of
reaction for the two routes were discussed, in particular the
inhibiting effect of certain nitrogencontaining
components of diesel oils on the hydrogenation route.
CoMo catalysts are generally more active for the direct
desulfurization route, whereas NiMoP catalysts show
relatively higher activity for the hydrogenation route.
Mr. Yasuhito Goto of Japan Energy Corporation discussed
CoMo/NiMo catalyst relay system for clean diesel
production. The catalyst system was able to achieve ultra
low-sulfur diesel production (less than 50 ppm sulfur)
without major revamp of conventional deep
hydrodesulfurization units. The relay system has been
developed, taking into consideration reaction conditions in
detail for each part in a desulfurization unit, particularly
the sulfur-containing compound types to be desulfurized
and catalyst poisoning by produced H
2
S and NH
3
.
Fundamental experimental results for the catalyst systems
were reported.
Dr. W. J. Stork of Shell Research & Technology Center,
presented Centinel technology catalysts for distillate
desulfurization. For improvement of the hydroprocesses, in
addition to the development of better catalysts, based on
mechanistic research, attention is being given to
technology improvements as well. In September 2000,
Criterion Catalysts introduced its new catalyst technology,
Centinel, for refinery hydroprocess applications. Both
CoMo and NiMo type catalysts were launched
MEETING REPORT
The Arabian Journal for Science and Engineering, Volume 28, Number 1B April 2003
116
simultaneously in distillate HDS, First-Stage
hydrocracking, and catalytic feed hydrotreating. The paper
focused on the novel catalyst technologies and on a better
understanding of the chemistry involved. In order to derive
the maximum benefits out of high performance catalysts,
the reactor designs and process conditions should also be
optimized. It is essential to use an optimized combination
of catalysis and reactor/process technology to arrive at
optimum results in demanding applications such as ultra-
deep HDS.
Dr. Shigeto Hatanaka of Nippon Oil Corporation,
discussed selective hydrodesulfurization of catalytic
cracked gasoline. The possibility of improving the
desulfurization selectivity of catalytic cracked gasoline
was investigated using CoMo/Al
2
O
3
catalyst. The
difference of the active sites was studied and three
different active sites were proposed (i.e. HDS active site,
iso-olefin hydrogenation active site, and n-olefin active
site). Coke pretreatment and pyridine modification
improve HDS selectivity by the selective deactivation of
olefin hydrogenation active sites. The study also suggested
the possible direction for commercial HDS catalyst
through the improvement of Co distribution and the
decrease of acidic sites.
Hydroprocessi ng
Dr. Takeshige Takahashi of Kagoshima University,
studied the effect of mean pore diameter of -alumina and
effective metal content on HDS activity and catalyst
deactivation. The HDS reaction of atmospheric residue
over NiCoMo catalysts supported on alumina with
different mean pore diameter was carried out to examine
the effect of pore size on catalyst deactivation at deep
desulfurization conditions. The catalyst deactivation of
HDS catalyst supported on large pore was larger than that
of the catalyst supported on medium pore size. Although
the hydrometallation activity increased with the pore size,
the HDS activity decreased with the pore size due to the
decrease in the surface area of the support. The
deactivation of the large pore supported catalyst is larger
than that of medium pore catalyst. The combination of
large pore HDS catalyst (40%) and medium pore HDS
catalyst (60%) could not improve the life of the catalyst.
The results suggest that the best catalyst for deep HDS
operation was the one with medium pore size support.
Mr. Hirofumi Aizono of Japan Cooperation Center,
Petroleum (JCCP) reviewed the development of NiMo
zeolite-based catalyst for the hydrocracking of
atmospheric residue. Catalyst production in industrial scale
was successfully accomplished and its high and stable
performance as residue hydrocracking catalyst was
confirmed in bench scale plant using Kuwait atmospheric
residue as feed. Namely, toward 2500 hours of duration,
residue conversion, and middle distillates yield was stable
at 47% and 30wt%, respectively. Product quality was
excellent, such as cetane index of diesel fraction which
reached 56, and sulfur content was 30ppm, which was by
far the lower compared to conventional ARDS unit.
Dr. Suheil Abdo of UOP discussed the advances in
Unicracking catalyst technology. An increased demand for
clean transportation fuels has made hydrocracking one of
the key processes in modern refineries. In order to meet
this increased demand, hydrocracking catalyst
development must continue at a rapid pace and catalyst
performance must be precisely tailored to deliver the
desired product slate and yield characteristics. Application
of catalyst science and technology which involves not only
materials synthesis and modification but also an intimate
understanding of catalyst-feed interactions under the
conditions of the process, is critical to accomplishing this
objective. Examples of successful catalyst design and
development at UOP were cited in the paper to illustrate
the performance achieved with-state-of-the-art catalysts
and identify needs for future performance improvements.
Dr. Shakeel Ahmed of KFUPMResearch Institute
reviewed the phenomena of hydrogen spillover in
hydrocracking catalyst using temperature-programmed
reduction (TPR) study. The phenomenon is defined as the
dissociative chemisorption or adsorption of hydrogen on
the metal and migration of atomic hydrogen to the surface
of the support such as alumina, silica, and zeolites. A
novel method has been established to incorporate a very
small amount of precious metal directly on the base metals
supported catalyst to enhance the hydrogenation
functionality. NiW supported on alumina reduced at
around 586 C. Similar catalysts with Rh incorporated by a
novel method produced a large reduction peak at 380 C.
This substantial reduction in peak temperature is a clear
indication of the hydrogen spillover effect.
Dr. Yuzo Sanada of Hokkaido University discussed the
catalytic transformations of petroleum derived asphaltenes
with Co loaded smectite and CoMo loaded alumina-based
catalysts in a temperature range from 40420C were
studied using proton magnetic resonance thermal analysis.
Residual hydrogen as a qualitative measure of the
hydrogen remaining in the sample was obtained as a
function of temperature. Metal oxides in the Co-porous
saponite and CoMoalumina based catalysts were reduced
to ferromagnetic metals at about 350C. Moderate
interaction of the metal oxide with the support material
resulted in an intermediate reduction state with high HDS
performance. It was concluded that the magnetic resonance
technique can be used to investigate the catalytic reactions
of heavy hydrocarbons and to characterize the catalyst
behavior.
MEETING REPORT
April 2003 The Arabian Journal for Science and Engineering, Volume 28, Number 1B
117
Dr. Hartmut Weyda of Sud-Chemie, discussed modern
refining concepts: no oil refining without hydroprocessing.
The paper provided an overview of the range of
hydroprocessing applications especially for middle
distillate range feedstocks, based on Sud-Chemie's
catalysts. Key process is catalytic hydrodewaxing. It is
gaining increasing importance in terms of producing high
quality diesel fuels and improving refining economics.
Sud-Chemie provides the refining industry various
hydroprocessing catalyst packages, including catalytic
hydrodewaxing, dearomatization, deep desulfurization,
and MHC-catalysts. These catalyst packages mainly focus
on the economic benefits of implementing these catalysts
into existing hydrotreating units.
Sulfur Recovery and Analysis
Dr. Joe Allison of Conoco Gas Solutions Technology
reviewed partial oxidation of hydrogen sulfide to
elemental sulfur: a Claus alternative.
The trend toward processing more sour crude oil and gas
necessitates a greater need for additional sulfur handling
capacity in refineries and gas plants. The H
2
S that is
generated from refining processes, or removed from gas
streams, is typically converted to elemental sulfur via the
Claus process, or some variation thereof. Conoco has
developed a novel catalytic partial oxidation system that
will convert H
2
S to elemental sulfur in a compact reactor
using air as the oxidant. Performance of this system rivals
that of the Claus process, while saving on capital
investment. Hydrogen sulfide concentrations of between
3% and 100% in a gas stream can be converted to
elemental sulfur in the same reactor set up. Laboratory
studies and early results from a 1 LTPD pilot plant were
presented. The use of this process in refinery, mid-stream,
and upstream applications was also discussed.
Dr. Franck Baco of the Institut Franais du Ptrole (IFP)
discussed the analysis of total sulfur: speciation of sulfur
compounds by hyphenated techniques. The paper
described the state of the art for the analysis of sulfur in
petroleum products and what kind of techniques and
normalized methods that could be used. The reduction of
total sulfur in gasoline and diesel has necessitated the
introduction of techniques and methods able to analyze
sulfur for levels less than 10ppm. These techniques
possess good sensibilities and good reproducibility. The
paper presented hyphenated techniques in gas
chromatography able to analyze sulfur such as GCAED,
SCD, PFPD in gasoline and diesel. One of the best
methods is UV fluorescence, which can be installed in a
laboratory or directly on-line on industrial unit.
Characterization of Zeolites and Catalysts
Mr. Kazuhiko Hagiwara of Cosmo Oil Company,
discussed the deactivation of USY zeolite with residue
cracking in FCC process. The effect of sodium ion and
vanadium on the deactivation of USY FCC catalyst under
hydrothermal conditions deactivation was investigated by
solid state NMR and XRD. By treating USY in 100%
steam and increasing sodium ion content, the crystallinity
decreased remarkably. Dealumination was more
obstructive in the crystal region as the sodium content was
increased. The effect of deposited vanadium on the
framework destruction was remarkable only when a
certain number of sodium ions were present in the USY
zeolite. The study concluded that vanadium and sodium
ions have a synergistic effect on the zeolite framework
destruction. A super-cage of USY containing vanadium
and sodium ions was plugged after heat treatment in 100%
steam.
Dr. Mohammad Khadim, Saudi Aramco R&D Center,
Dhahran, discussed solid state NMR spectroscopy of
selected refinery catalysts. During the last two decades
high resolution solid state NMR spectroscopy has emerged
as a powerful tool for the investigation of zeolitic
structures. This is due to NMR sensitivity to local
orderings and geometries of zeolite structures. The paper
presented applications of solid state NMR spectroscopy on
zeolites and other catalysts used in a refinery. Some of the
examples include changes in structures of zeolites during a
catalytic process, status and structural changes in
deactivation and reactivation of catalysts, characterization
of coke and organic deposits on spent catalysts, thermal
and hydrothermal stability of zeolites, dealumination of
catalysts, and quantitative determination of aluminum in
zeolites. Supporting data from the scanning electron
microscope were also presented.
Dr. Gert-Jan Gruter of Avantium Technologies, The
Netherlands, discussed high throughput R&D through high
throughput experimentation. Various methods have been
developed such as impregnation, zeolites synthesis, and
precipitation that not only lead to fast lead generation by
screening but also will assist scale-up of the catalyst or
process leads. This is done by using realistic catalyst
preparation methods as well as applying realistic testing
conditions. Moreover, by using the obtained data to
generate kinetic models, it was possible to assist in the
scale-up process by using kinetic modeling and reactor &
process simulation. By combining micro-reactor
technology with high speed performance analysis,
informatics, simulation, and also library synthesis, a
virtuous circle of technology is created, reducing the scale,
increasing the speed of execution and broadening the
knowledge base of R&D.
Production of Hydrogen
Dr. Gene Yeh of Saudi Aramco, Dhahran, presented a
computer model for steam reforming of natural gas. The
paper discussed how this computer program was
MEETING REPORT
The Arabian Journal for Science and Engineering, Volume 28, Number 1B April 2003
118
developed, validated and applied the steam reformer is an
essential part of a hydrogen plant. It converts steam and
light hydrocarbon, methane, LPG , or naphtha, to
hydrogen and carbon oxides. There are many types of
steam reforming catalysts and which type of catalyst is
selected for a particular steam reformer normally depends
on the feed type. In order to ensure a good hydrogen plant
operation, the selection of a suitable steam reforming
catalyst and monitoring its activity is a must.
Dr. Koichi Eguchi of Kyoto University reviewed the
catalytic production of hydrogen from hydrocarbon fuel
for fuel cell applications. Processes and methods of
hydrogen production have been investigated for the
application to polymer electrolyte fuel cells. Methanol
reforming and partial oxidation and/or steam reforming of
hydrocarbons were considered as possible methods for
hydrogen production. For the processed fuels after these
reactions, CO removal by water gas shift reaction and/or
preferential oxidation CO should be carried out to reduce
CO level to avoid poisoning of the electrode by CO. The
paper concluded that the development of active catalysts
for reforming, shift reaction, preferential oxidation, and
electrode reaction has been increasingly requested for the
realization of the fuel cell technology. The use of purified
hydrogen, methanol, or hydrocarbon is still controversial
and the selection may depend on the application field.
However, catalytic fuel conversion processes should be
developed for the effective use of fossil fuels in the near
future.
Petrochemical Catalysis
Dr. Mike Scurrell of the University of Witwatersrand,
South Africa, reviewed the aromatization of propane to
BTX over ZnZSM5 catalysts. BTX selectivity increased
from about 7580 % to over 91% in the case of catalysts
where cations of iron (or another second transition metal,
such as chromium or manganese) have been separately
introduced by means of solid state ion exchange
procedures. So far all selectivity improvements seen are
associated with the use of transition metals having more
than one readily accessible oxidation state and so redox
processes may be of importance. However, an additional
factor is a modification of acidity, as evidenced by changes
in ammonia desorption behavior of the iron-promoted
catalysts. A further factor appears to be associated with
changes in hydrogen mediated reduction characteristics of
the second transition metal cations, as observed in TPR
studies.
Dr. Chris Nicolaides of Sasol Technology, South Africa,
discussed the dehydration of 1-hexanol, which is produced
industrially via the Ziegler alcohol synthesis route (Alfol
process), to co-monomer grade hexene-1. Various -
aluminas were tested as catalysts for the dehydration
reaction, in short runs up to 8 hours. At a fixed
WHSV=25h
-1
, the conversion increased with temperature,
with dihexyl ether being the major product for
temperatures up to about 275

C. From the experiments


conducted under different reaction conditions (temperature
varied from 250 to 350
o
C, and WHSV from 3 to 25h
-1
), it
was observed there was a distinct conversionselectivity
relationship, viz. that the selectivity to the ether decreased
whilst that to the hexenes increased with increasing
conversion, irrespective of the -alumina type and reaction
conditions. For conversions up to 80%, the purity of the
1-hexene was between 9597%.
Mr. Katsumi Nakashiro, of Mitsubishi Chemical
Corporation reviewed the progress in catalysts for
ethylene oxide production and epoxidation mechanism.
The reactivity of adsorbed O
2
molecule and O atom
adsorbed on Ag surface for ethylene oxide formation and
complete oxidation were examined with the density
functional method. In order to understand the complete
oxidation route, H-migration and H-abstraction leading to
acetaldehyde and radical intermediate were examined. It
has been proven that energy of transition state for the H-
migration is lower than that for the H-abstraction in
oxidation by both the O species, suggesting that the H-
migration route as complete oxidation. An upper limit of
ethylene oxide selectivity (85.7% on ethylene basis,
corresponding to 50% on oxygen basis) under a
mechanism in which adsorbed O
2
molecule and O atom
lead to epoxidation and combustion, respectively, is
supposed to be invalid even by either oxygen species.
Polymerization Catalysis
Dr. Syriac Palackal of Sabic R&D, Riyadh reviewed
metallocene catalysts for ethylene polymerization
Metallocene catalysts are the latest addition to the olefin
polymerization catalyst family. Some chiral metallocenes
are also capable of stereospecific polymerization, where
isotactic and syndiotactic polymers can be produced.
Although it was proven that metallocene catalysts can
polymerize ethylene in the late fifties, it took more than 20
years before technology was developed that could provide
an economically viable catalyst. In the mid-eighties,
Kaminsky and Sinn developed methylaluminoxane based
co-catalysts that substantially increased the activity of the
metallocene catalysts. After this breakthrough, many
academics and most of the industrial polyolefin research
organizations began focusing on the metallocene catalysts.
The paper addressed some of the major reasons why
metallocene catalyst research is given a high priority.
Mr. Thorsten Merz of Basell Polyolefins, Italy discussed
polyolefin innovations and new catalyst systems. Current
state-of-the-art Ziegler-Natta catalysts were summarized
and the driving forces for catalyst changes were
highlighted. The phthalate family of polyolefin catalysts
have evolved into a high yield-high selectivity fourth
MEETING REPORT
April 2003 The Arabian Journal for Science and Engineering, Volume 28, Number 1B
119
generation catalyst. To tailor-make a desired resin property
profile, a new diether and succinate catalysts were
discussed. A brief coverage on how to select the best
polypropylene catalyst depending on resin requirements
was presented. The paper was concluded by a description
of the new Z501 Ziegler HDPE catalyst, which is used in
the production of PE 100 pipe grades in Basell's Hostalen
process.
Dr. Atieh Abu-Raqabah of Sabic R&D, Riyadh, addressed
recent advances in ZieglerNatta catalysts. The
development of ZieglerNatta catalysts in the 1950s is
without doubt considered one of the most remarkable
discoveries in polymer science. Based on these catalyst
systems, an enormous number of publications was
disclosed, and many technologies were developed and
commercialized. Despite that, we still believe that these
important catalyst systems can be further improved. In this
paper an overview was given on areas where
improvements can take place with practical examples on
their applications in industry.
Dr. Roger Ceustermans, Engelhard Corporation, Belgium,
presented Lynx

technology for advanced polypropylene
performance. Engelhard's highly successful Lynx catalyst
system technology for advanced polypropylene
performance was explained, drawing upon specific
examples of technical success in process and product
superiority in both catalyst and donor technology. The
crucial role of polymer science was highlighted, taking
into consideration the future direction and the fundamental
role that catalyst and donor technology will play in the
development of advanced polypropylene capabilities.
Specific examples were made of superior film
development utilizing Lynx technology.


















Dr. Mohammed Bahattab of the King Abdulaziz City for
Science and Technology (KACST), Riyadh, discussed
ultrasonic energy applications for driving emulsion as a
means of changing the reactivity ratio, and of driving
emulsion polymerization of methyl methacrylate (MMA)
and butyl acrylate (BA) to completion at different
temperatures, composition, and polymerization conditions.
A faster rate of polymer production was achieved by using
ultrasonic energy at 70
o
C, where the ultrasonic
polymerization was completed in half the time as
compared with the normal thermal polymerization at 70
o
C.
The conversion to polymer was about 100% when the Ar
flow rate was 1.0 ml/min. The molecular weight of the
copolymer produced by ultrasonic process at 25
o
C and
70
o
C was half the molecular weight of copolymer that was
produced by the thermal process at 70
o
C. The reactivity
ratios for both MMA and BA are higher for the copolymer
produced by ultrasonic energy at 25
o
C and 70
o
C than the
one that was produced by thermal process at 70
o
C.
Next Annual Symposium
The 13
th
annual symposium on Catalysts in Petroleum
Refining and Petrochemicals will be held at KFUPM,
Dhahran, on December 1415, 2003. The Call for Papers
emphasizes areas such as: fuels processing for fuel cell
applications; gas-to-liquids; catalyst development;
hydroprocessing; FCC catalyst additives; ultra-low sulfur
diesel; paraffin oxidation; polymerization; and
petrochemicals.