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Advanced catalyst technology and applications for higher quality fuels and
lubes

Article · September 2004

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 Catalysis Today 104 (2005) 55–63
www.elsevier.com/locate/cattod

Advanced catalyst technology and applications for

high quality fuels and lubricants
Michael C. Kerby *, Thomas F. Degnan Jr., David O. Marler, Jeffrey S. Beck
ExxonMobil Research and Engineering, Annandale, NJ 08801, USA

Available online 7 April 2005

Abstract

Within the petroleum refining and petrochemical industries, catalysts provide the opportunity for drop-in solutions for addressing ever
more stringent product quality and environmental specifications. Improved catalysts have also been instrumental in debottlenecking many
refining and chemical processes. In order to stay competitive, many companies are focused on taking advantage of higher activity and more
selective catalysts to facilitate ‘‘capacity creep’’. Increasingly, these catalyst advances stem from the commitment to develop and nurture
active materials platforms. ExxonMobil has focused its platform efforts in several areas including micro- and mesoporous molecular sieves,
supported metals, and mixed metal oxides and sulfides. The recently announced alliance between ExxonMobil and Symyx Technologies, Inc.
(Santa Clara, CA) is a further step in the company’s commitment to strengthen its materials platforms.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Catalysis; Zeolites; Clean fuels

1. Introduction sort. The majority of major refining conversion processes

are catalytic, the exceptions being thermal conversion
The global refining and petrochemical industries face processes such as delayed or fluid coking and visbreaking.
increasingly more difficult technical challenges. Stricter While catalysts accelerate desired reactions they also
environmental mandates and more demanding product lower energy requirements. Catalysts provide a focal point
quality specifications contrast with an operational environ- for improving plant energy efficiency and debottlenecking
ment structured around processing heavier and more operations. The US refining industry has been exception-
contaminant-laden crudes on the refining side and ‘‘oppor- ally successful in using both catalysts and process
tunistic’’ feeds containing more byproducts on the chemicals engineering to expand refining capacity while minimizing
side. Frequently, the most cost effective and efficient way to capital investment. In fact, there have been no new
confront these challenges is through implementation of refineries constructed in the United States since 1978 [2].
newer catalyst technology [1]. This paper describes how Between 1980 and 2002, the industry shut down 160 of its
ExxonMobil is exploiting its catalyst technology ‘‘pipeline’’ 319 domestic petroleum refineries, yet refining capacity
as catalytic materials move from discovery to development remained constant at approximately 18 million barrels per
and ultimately to deployment. ExxonMobil is focused on day [3]. Increasingly, the refining and petrochemical
reducing the often lengthy interval between discovery to industries have come to rely on a steady record of catalytic
deployment by using a range of strategies, many of which advances to increase plant efficiency. Catalyst advances
are linked to high throughput experimentation and closely improve the flexibility for units to squeeze more value from
associated model development. existing hardware while meeting the tighter molecular
Nearly, 90% of all molecules in crude feedstocks specifications required of today’s fuels, lubricants, and
eventually find their way into contacting a catalyst of some petrochemicals. Catalysts are also a major operational
expense. ExxonMobil annually purchases more than 100
* Corresponding author. Tel.: +1 908 730 2116; fax: +1 908 730 3031. million lb of catalysts for its refineries and petrochemical
E-mail address: [email protected] (M.C. Kerby). plants.

0920-5861/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2005.03.028
56 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63

2. Catalytic challenges standing of how to discover new materials, develop them

into active materials, and commercialize them at a reason-
In transportation fuels, the focus is on improving both able cost. Zeolites, supported metals, and mixed metal
product yields and product quality. The term quality also oxides/sulfides are the three types of catalysts that have
extends to removal of nitrogen and sulfur compounds from been, over a sustained period, the source of most major
fuel products, mainly for environmental reasons. In advances in refining and petrochemical catalysts. The ability
lubricants, the market is demanding better viscometrics— to exploit these materials has increasingly relied upon a
improved viscosity retention (i.e., higher viscosity indices) better understanding of how molecular sieve, metals, and
and lower pour points. This translates into more highly mixed metal oxide/sulfide catalysts behave at the molecular
hydroprocessed stocks, which contain predominantly level.
branched paraffins. Finally, in the area of commodity
petrochemicals, the focus is on higher selectivity principally
in the production of aromatics and olefins. 3. ExxonMobil’s active materials platforms
Petroleum companies, and particularly ExxonMobil,
have been major innovators in the development and ExxonMobil is developing next generation catalyst
adaptation of new catalytic technologies (Fig. 1). In the ‘‘platforms’’ that will support future business needs. In
1930s and 1940s, the build-up to the war efforts provided the addition to zeolites and supported metals, the company’s
incentive for the development of fluid catalytic cracking other major heterogeneous catalyst platforms include mixed
catalysts and with them the production of higher perfor- metal oxides/sulfides and mesoporous materials (Fig. 2).
mance motor and aviation gasoline. In the 1960s, hydro- The company relies on these platforms for advanced catalyst
processing became viewed as a practical means of developments to maintain the operational flexibility it needs
improving fuel quality, and advanced supported metal to improve its products and often to provide ‘‘drop-in’’
catalysts began to emerge. The 1970s brought oil supply solutions to tighter environmental regulations. The cap-
disruptions and the phase-out of lead from gasoline. This abilities in these platforms extends throughout the technol-
spawned catalytic research in the areas of synthetic fuels, ogy pipeline (Fig. 3), from discovery through development
e.g., methanol to gasoline and Fischer Tropsch synthesis, as and into commercial deployment.
well as reforming and FCC catalysis oriented toward The discovery component includes the use of strong
producing more aromatic- and olefin-rich gasoline to fundamental science in identifying promising new structures
supplant the octane lost through the phase out of tetraethyl and compositions. Detailed screening involves analysis of
lead. Sulfur reduction in gasoline and specialty petrochem- intrinsic kinetics combined with kinetic modeling of model
icals were focal points in the1980s and 1990s, and the compound reactions, and advanced materials characteriza-
petroleum industry responded with a slate of highly tailored tion. A thorough understanding of catalytic hydrocarbon
and specific shape selective catalysts oriented toward higher chemistry is combined with a computational analysis of the
quality and lower operating cost. Advances in catalyst active site and the transition state to identify the best
design and development have required improved under- candidates.

Fig. 1. The petroleum industry has been a leader in the implementation of new catalyst technology.
 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63 57

Fig. 2. Developing materials platforms to support the future.

Development involves an iterative refinement of catalyst 4. Exxon and Mobil—a marriage of catalytic science
properties using carefully planned catalytic tests. Once the and material strengths
preferred formulation is identified, work starts on finding the
most cost effective means to manufacture the catalyst. Prior to the merger of Exxon and Mobil in December
Development is carried out at a scale that increases confidence 1999, both companies had strong, yet complementary
of successful commercialization. The development stage catalytic materials capabilities. Exxon brought a history of
normally takes the catalyst formulation from the gram scale to excellence in supported metal and mixed metal catalysts
the 10–100 kg scale. The decision whether to internally along with a strong effort in large pore, highly acidic
manufacture the catalyst, collaborate with another company molecular sieves. Just as importantly, Exxon scientists had
to co-develop the catalyst, or simply to toll manufacture the long studied and had developed a deep understanding of
catalyst involves the consideration of a large number of acidity in solids and metal-support interactions. Mobil
factors including cost, strength, and breadth of intellectual brought a rich heritage in the discovery of new materials,
property coverage, compatibility with internal manufacturing particularly micro- and mesoporous molecular sieves along
capabilities, and even geographical proximity to base research with a sound understanding of silica chemistry, shape-
and development operations. Once the commercial catalyst is selectivity, and an internal capability for materials scale-up
produced and a representative composite sample is obtained, and commercial manufacture.
the final steps in establishing the process yields and selectivity Today the focus is on strengthening all platform areas and
can be completed. Lastly, but most importantly, the catalyst is on exploiting opportunities at the interfaces to address a set
deployed as broadly as possible. The process data from the of technical challenges that include:
commercial units provide valuable information about catalyst
durability and longevity and ultimately validate the scale-up  lower targets for sulfur and nitrogen in gasoline and
work. In sum, designing a catalyst is just as complex as diesel;
designing a computer chip. Just as a computer chip  lower cost, higher performance lubricants;
manipulates information in its final form, a well-designed  heavier and more aromatic hydrocarbon feed streams;
catalyst transform molecules into their final form, rapidly,  greater versatility and process flexibility in producing
efficiently, and with high selectivity. olefins and aromatics;
58 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63

Fig. 3. The catalyst technology pipeline.

 new petrochemical opportunities; backbone. Over the past 15 years, ExxonMobil has utilized
 low energy separations that focus on efficient molecularly its capability to discover and develop novel microporous
specific segregation. materials along with its understanding of supported metals
and metal placement to innovate in this area. Today, it has
To avoid bottlenecks, emphasis has to be placed on developed several generations of lube and diesel dewaxing
developing capabilities throughout the materials pipeline catalysts that the company both uses internally and licenses
from discovery through development of new materials all to other refiners.
the way to commercial deployment. There is significant MSDW-2 represents the latest in the development of
value in reducing time and complexity of each part of the lubricant hydroisomerization technology. The technology
materials pipeline. Accelerating the pace of discovery pr- uses a special proprietary catalyst to very selectively place
ovides earlier and more comprehensive intellectual property side chains on the longer lube-range paraffins. Yields and
position for discovered materials. The need to reduce the viscometrics (e.g., viscosity index or VI) are significantly
time from discovery to deployment is driven, in part, by better than conventional solvent dewaxing and greatly
potential R&D cost savings for each successfully commer- improved over the first generation, MSDW-1 catalyst (Fig. 4).
cialized material. However, the major incentive for accel- The second example involves a class of supported metal
erating the pace of discovery to deployment is the ability to catalysts that are used for removing sulfur from catalytically
capitalize on the innovations at a much earlier date. cracked gasoline. SCANfining [4] is ExxonMobil’s pro-
prietary technology for the production of low-sulfur gasoline
The process uses a specially designed supported metal
5. Catalyst technology—examples catalyst, commercialized with Akzo Nobel Catalysts (now
Albemarle Catalysts) that selectively converts mercaptans
Three examples serve to demonstrate the process of and thiophenes with minimal saturation of the gasoline-
materials innovation, development, and commercialization range (mainly C5 and C6) olefins which contribute
to meet ExxonMobil’s needs for improved product quality. significantly to gasoline octane. The design basis for the
The first is the development of advanced dewaxing catalysts. catalyst emerged from the company’s firm understanding of
Catalytic hydroisomerization improves lubricant and dis- supported metals and control of the metal function.
tillate fuel viscometrics by selectively restructuring long Fig. 5 shows some of the performance data for
chain alkanes to have branches periodically along their SCANfining. The graph on the left plots product sulfur
 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63 59

Fig. 4. Hydroisomerization dewaxing technology; two generations of lubes hydroisomerization processes – MSDW-1 and MSDW-2 – comparison with solvent
dewaxing.

(in ppm) versus octane loss. For relatively low sulfur feed of the alkyl groups into positions where they have less of a
gasolines, the first generation SCANfining technology steric hindrance and selective hydrogenation of one of the
shows very low octane loss or hydrogenation of olefins aromatic rings to allow the molecule to flex more and
for product sulfur targets of less than 30 ppm. However, if therefore become non-planar. The objective of both of these
the feed sulfur is significantly higher, for example, approaches is to allow the molecule to have greater access to
3000 ppm, the octane loss increases because more olefins the active catalytic site. Recent studies have also shown that
are hydrogenated when the process is driven to achieve the nitrogen compounds, both basic and non-basic, can have a
same product sulfur level. significant effect on desulfurization of molecules such as
ExxonMobil has developed a second generation SCAN- DBT because they selectively adsorb on the same sites active
fining technology, SCANfining II that shows even greater for desulfurization. Thus, research has focused on the
improvement in limiting octane loss. For the same high investigation of structure–reactivity relationships of more
sulfur feed, the octane loss is very similar to the octane loss advanced catalysts to optimize sites that can attack not only
at very low sulfur levels. This technology is rapidly ‘hard sulfur’ species but ‘hard nitrogen’ species as well.
becoming the technology of choice for the production of The third example involves a truly breakthrough
low sulfur gasoline. Over 30 units are either announced or in hydroprocessing catalyst for removing sulfur from distillate
operation. SCANfining capacity is expected to exceed more stocks. Fig. 7 plots the relative activity of distillate
than 950,000 barrels per day over the next several years. hydrodesulfurization catalysts as a function of time. Until
As US sulfur requirements for on-road diesel move the last 4 years improvements have been relatively
toward 30 ppm by 2006, and 10 ppm by 2010, the removal of incremental. However, over the past several years there
so-called ‘‘hard sulfur’’ species such as di-beta substituted have been significant developments. A real breakthrough in
dibenzothiophenes will become essential. Because of the hydrodesulfurization catalyst technology has been the
steric hinderance of the alkyl groups adjacent to the sulfur development of Nebula catalysts. The technology was
atom, the desulfurization reaction rate is reduced. Kinetic discovered by ExxonMobil in the last decade and was
studies have demonstrated that the disubstituted diben- recently commercialized jointly with Albemarle Catalysts.
zothiophenes (DBT) are 30–50 times less reactive than Nebula is a unique composition that differs substantially
unsubstituted dibenzothiophene (Fig. 6). Some recent from traditional hydroprocessing catalysts based on combi-
approaches to addressing the problem include isomerization nations of metals deposited on a high surface area support.
60 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63

Fig. 5. SCANfining II enables deep HDS of high sulfur feeds with reduced octane loss.

The activity of Nebula is at least three times greater than that novel material from the discovery through the commercia-
of earlier hydroprocessing catalysts. Because of its unique lization stage is on the order of 5–10 years. Efforts to reduce
composition, producing a finished Nebula catalyst presented the time required to move new materials through the system
a challenge to developers. This challenge was successfully are now focused on accelerated discovery and development
overcome through the combined efforts of ExxonMobil work processes assisted by high throughput experimentation
researchers and scale-up and commercialization expertise (HTE).
brought by Albemarle. The Nebula catalyst has been
successfully commercialized for a number of applications
including ultra-low sulfur diesel fuels [5] and distillate 6. High throughput experimentation
hydrocracking [6]. Like the previous catalyst used in
SCANfining, ExxonMobil uses Nebula internally. The Attempts to conduct massively parallel or very rapid
significantly enhanced activity of the Nebula catalyst allows sequential experimentation to improve research productivity
a ‘‘drop-in’’ solution into existing units without having to initially started in the pharmaceutical area and then spread to
spend capital to build additional units or increase the the fine chemicals and polymers areas. Recently, high
operating pressure of hydrodesulfurization units. throughput experimentation capabilities have begun to
In each of these three examples, the development of step- appear in petrochemical and refining R&D laboratories.
out catalysts drew heavily from existing materials platforms. These capabilities constitute a suite of technologies that
Fundamental understanding of the material structure– accelerate not only the pace of discovery, but also the pace of
function relationships provided a strong base around which process and materials development by providing a broader
the catalysts were developed. An understanding of the and richer knowledge base which reduces the risk of
complexities associated with the scale-up steps allowed skipping steps along the process or materials development
developers to anticipate and adequately address manufac- pipeline. High throughput tools are integrated into ‘work-
turing problems. However, in all but one of the cases, the flows’, which comprise sequential materials synthesis,
time required to move from initial concept to full-scale characterization, and materials performance evaluation
manufacture was protracted. In fact, the norm in taking truly steps. Workflows are typically highly instrumented and
 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63 61

Fig. 6. Conversion of ‘‘hard sulfur’’ species.

Fig. 7. ‘‘Nebula’’: step-out catalyst for removing S & N from motor fuels.

are constructed around robotics and miniaturized experi- data is an informatics system, which allows the data to be
mentation. Conceptually, high throughput technologies may rapidly accessed and processed through advanced visualiza-
also link with process modeling so that the small-scale tion software and methods such as principal component
experiments can be effectively linked to larger pilot plants analysis. In essence, high throughput technologies provide
and eventually commercial units. A critical component in an ability to carry out a larger number of experiments with
the collection and interpretation of the massive amounts of correspondingly increased prospects for discovery. Used
62 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63

correctly, these techniques accelerate the identification of appropriate catalyst components. This is followed by a series
leads, reduce the cost per experiment, and progress of synthesis and formulation steps where the active materials
development programs more rapidly. are synthesized, binding and support materials are added,
In July of 2003, ExxonMobil and Symyx Technologies, and metals are impregnated onto supports. After the
Inc., a pioneer and leader in the development and application catalysts are prepared they are automatically transferred
of high-speed materials research methods, announced a to a primary screening test, shown here as a set of small
technology alliance focused on high throughput experi- wells. The objective of this step is to rapidly scan the
mentation. This alliance is representative of ExxonMobil’s materials in order to identify a single performance
commitment to innovation and technology and recognizes parameter, such as activity. As promising candidates are
the commercial value of HTE. identified, the focus turns to the use of secondary tools where
ExxonMobil’s agreement with Symyx marks a very catalysts can be evaluated in parallel on a larger scale for a
extensive and highly integrated commitment to apply HTE more extensive set of performance parameters. This step is
technology across its entire downstream and chemical geared toward obtaining information critical to the selection
portfolio. Under the terms of the agreement, the companies of the best material for the application. Scale-up of the
will work together over a 5-year period in a number of fields catalyst involves the addition of binders, various modifiers,
seeking faster paced development of chemicals, lubricants, or metal salts. Larger pilot plants are used to validate the
and fuels products and processes to continue to expand results derived from the smaller scale HT equipment, to
markets and meet customers’ changing needs. produce sufficient quantities of product for performance
The tools and techniques developed as part of this evaluation, and occasionally, to study the longer term
alliance will enable ExxonMobil to generate new products stability of the preferred catalyst. The data from all of the
and accelerate the commercialization of new technologies, evaluations are used to refine the catalyst formulation prior
broadening ExxonMobil’s intellectual property portfolio. to commercialization. An informatics system collects the
Fig. 8 shows an example of an integrated high throughput data, facilitates the design of further experiments, and aids in
workflow for catalyst synthesis, characterization and the visual interpretation of the data. Significant advantages
performance evaluation. The picture at top left shows an can be realized using an informatics suite that enables data
automated high-speed robotic device that combines the collection and analysis across each of the various research

Fig. 8. High throughput R&D workflow for catalysis.

 M.C. Kerby et al. / Catalysis Today 104 (2005) 55–63 63

stages for a particular project—primary synthesis and use of high throughput technologies to reduce the time
screening, secondary synthesis and screening, and pilot plant between discovery and commercialization.
synthesis and screening.

7. Conclusions References

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[2] Diesel World, October 31, 2004. p. 2.
refining and petrochemical industries have come to rely even [3] Department of Energy, Energy Information Administration, 2003.
more heavily on development of new catalytic technology. [4] K.L. Riley, J.L. Kaufman, S. Zaczepinski, P.H. Desai, S.W. Mayo, Akzo
ExxonMobil, a beneficiary of the merger of two strong and Nobel Catalyst Symposium, vol. G-3, 1998, p. 1.
complementary catalytic technology organizations, has [5] T. Reid, K. Kunz, S. Mayo, AM-04-55, off-setting the cost of ultra
low sulfur diesel, in: 2004 NPRA Annual Meeting, San Antonio,
focused developing materials platforms, which promote
2004.
innovation of new process technologies. Efforts to accelerate [6] G. Meijburg, E. Brevoord, F. Plantenga, S. Mayo, Y. Inoue, K. Fujita, W.
the development of new catalytic technology have been Lewis, A. Sapre, NEBULATM for Hydrocracker Pretreat Operations,
augmented by the establishment of an alliance aimed at the ERTC, London, 2003.

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