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Reactions and Separations

Succeed at

Catalyst SCALE-UP
Uday T. Turaga
Donald R. Engelbert
William H. Beever
ConocoPhillips Co.

Follow these principles to reduce the time


required for scale-up and commercialization and
to improve the resource effectiveness of the effort.

J. Todd Osbourne
Ben Wagner
Richard Allen
Jeff Braden
Sd-Chemie Inc.

Polymers and
Polyolefins
21%

Petroleum
Refining
24%

atalysts are of vital importance to the global chemical, petrochemical, petroleum refining and transportation sectors. By some estimates, catalysts
have enabled worldwide value of trillions of dollars. In
2004, the global catalyst market was estimated to be worth
$10.5 billion (1). The figure shows the major catalyst
applications and their relative share of the global catalyst
market (13).
Catalysts have been a subject of vigorous research and
development in the last 50 years. Catalysts have helped
produce new and important chemicals, fuels and materials.
As a science, catalyst development has evolved from a
point where the catalyst was merely a serendipitously discovered and valuable black box, to the situation today
where modern synthesis, characterization, reaction and
kinetic modeling techniques have led researchers to confidently boast of their ability to design catalysts for whatever application they desire.
Most of these important advances have focused on
characterizing catalysts, discovering new catalysts, or
unraveling reaction schemes and kinetics occurring on catalytic surfaces. Little research has focused on understanding and improving the scale-up and commercialization of
laboratory-scale catalyst discoveries. Scale-up and commercialization continues to be mostly a trial-and-error
process. It is generally governed by empirical and experiential insights, and can take a long time.
Even so, the last decade has witnessed another wave of

Chemical
Industry
26%

Environmental
Control
29%

Figure. Catalyst applications and their relative share of the global


catalyst market. Sources: (13).

exciting scientific developments and innovations in catalysis. Some of the factors contributing to these developments
are: new methods and approaches to catalyst development
and testing (e.g., combinatorial catalysis); new problems
where catalysts play an important role (e.g., hydrogen production); the increasing interdisciplinary nature of catalysis
(e.g., catalysis through polyfunctional materials); an intensifying focus on continued process improvements (e.g.,
next-generation hydrotreating catalysts); identification of
appropriate catalyst systems for specific applications and
reactors (Table 1); and creation of new processes (e.g., catalytic processing of renewable feedstocks).
Clearly, the relative importance of scale-up and comCEP

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Reactions and Separations

Table 1. Types of catalyst particles (6).

Shape

Dimension

Reactor Application

Microsphere

Dia = 20100 mm

Fluid bed, slurry phase

Spheres

Dia = 110 mm

Fixed bed, moving bed

Granules

Dia = 120 mm

Fixed bed

Beads

Dia = 15 mm

Moving bed, fixed bed

Pellets

Dia = 315 mm,


Fixed bed
Height = 315 mm

Extrudates

Dia = 150 mm,


Fixed bed
Length = 330 mm

mercialization of laboratory-scale catalyst discoveries is


growing. However, most catalyst scale-up, commercialization and manufacturing innovations are made in industry,
and they are frequently neither published nor patented and
instead kept as trade secrets. While academic interest is
growing (for example, in 2002, the Rutgers State Univ. of
New Jersey created the Consortium of Catalyst
Manufacturing Science and Technology, the first of its
kind in the U.S., to address the technical needs of the catalyst manufacturing industry at both a fundamental and
applied level) little understanding of the scale-up and
commercialization process is publicly available.
This article seeks to change that by presenting five
important principles that can greatly reduce scaleup/commercialization time, improve the resource efficiency of this important segment of the innovation
process, and enhance the odds of success. These principles are based on the authors collective experience with
S Zorb sulfur removal technology sorbent, including the
recent successful scale-up and commercialization of different sorbent generations and the delivery of commercial quantities of sorbents. While the S Zorb sorbent is
not a conventional catalyst, it does have physical properties similar to many catalysts and is made via processes typically used for manufacturing catalysts. Thus, the
principles learned in scaling up and commercializing
these sorbents should be applicable to catalyst development in general.

Involve the catalyst vendor early


Scale-up is about understanding and overcoming the
problems associated with making tens of thousands of
pounds of a catalyst using a procedure that has so far
been used to make no more than a few pounds. Industrial
manufacture is substantially different from a laboratoryscale procedure. Laboratory studies provide (at best)
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Table 2. Some leading catalyst vendors.

Albemarle
Alcoa
Axens/Procatalyse
BASF
Criterion Catalysts
Engelhard
Grace Davison
Haldor Topsoe, Inc.
Intercat
PQ Corporation
Sd-Chemie, Inc.
Tricat
Zeochem

www.akzonobel-catalysts.com
www.adcats.alcoa.com
www.axens.net
www.basf.com
www.criterioncatalysts.com/
www.engelhard.com
www.gracedavison.com
www.topsoe.dk
www.intercatinc.com/
www.pqcorp.com
www.sud-chemie.com
www.tricatgroup.com
www.zeochem.com

directional guidance, but they cannot accurately forecast


scale-up and commercialization problems.
Catalyst vendors can identify such problems by virtue
of the breadth and depth of their professional experience.
Therefore, the vendor should be brought into the project at
an early stage. Table 2 lists major catalyst vendors.
Bringing vendors into the project early is particularly
important in catalyst manufacturing because innovations
and developments are closely guarded and are rarely
patented or published. Vendors are better able to effectively assess the applicability of new innovations, equipment
and methods. They can also accurately identify the
strengths and pitfalls of a process, objectively assess its
commercial feasibility, and focus future research.

Accelerate scale-up
using statistically designed experiments
Once researchers identify a promising lead, it often has to
be optimized for product properties and process parameters.
Because time and budgets are frequently limited, optimization efforts must be speedy, cost-effective and focused,
which can be accomplished using statistically designed
experiments and other Six Sigma techniques. In addition to
reducing time and work, such tools identify the effects of,
relationships between, and relative importance of multiple
variables. In designing the optimization studies, it is important to include all of the relevant scale-up variables.
Catalyst discovery programs focus on improving one or
two major properties, typically activity or selectivity. As a
result, during discovery, limited attention is paid to characterizing other properties, such as particle strength, particle size
distribution, density, flow properties, pore volume, surface
area, metal dispersion, crystallinity and morphology. Nevertheless, scale-up requires careful attention to all of the resulting products physical and chemical properties, since each
plays an important role and cannot be compromised. Often,

Table 3. Important unit operations in catalyst scale-up and manufacturing (6, 7).

Unit Operation

Description

Applications and Equipment Types

Precipitation /
Co-precipitation

Separating catalytic materials Steam-hydrocarbon reforming catalysts,


by altering solution conditions, high-temperature carbon monoxide
e.g., pH
shift catalysts

Reagent purity, control of pH,


temperature and concentration

Solution/Slurry
Transfer

Vessel-to-vessel transfer of
solutions and slurries

Centrifugal, reciprocating, diaphragm


or screw pumps

Clogged lines, contamination

Filtration

Powder separation from gels


and slurries

Funnels, settlers, centrifuges, rotary


vacuum, line, disc and
pressure-leaf filters

Mixing problems, concentration


gradients

Drying

Elimination of water and


moisture from slurries, gels,
particles and pellets

Ovens, and belt, tunnel, drum, rotary,


flash, freeze and spray dryers

Temperature gradients, residence


time control

Calcination

High-temperature-assisted
solid-state reactions to
complete product activation,
impart strength and eliminate
templates and salts

Muffle, split-tube, tunnel, belt and


rotary calciners

Temperature gradients, residence


time control, sintering

Washing /
Ion-Exchange

Elimination of foreign species / Zeolites, hydrocracking catalysts


Replacement of framework
ions with protons or other
preferred ions

Mixing, atmosphere control

Compaction /
Densification

Improving density of the


catalyst powder/granules by
either creating finer particles
or eliminating gaps

Ball mills, grinders and kneaders

Residence time control

Particle Formation Shaping catalytic materials


into uniform particles,
including extrudates, spheres,
tablets and pellets

Pillers, extruders, granulators,


pelletizers and spherudizers (which
convert highly viscous paste into
spherical particles)

Control of pH and concentration,


particle strength

Spray Drying

Shaping catalytic materials


into microspherical particles

Fluidized catalytic cracking catalysts,


Fischer-Tropsch catalysts

Control of temperature, feed rates,


slurry viscosity

Crushing and
Screening

Altering particle size


distribution of catalysts

Jaw and cone crushers, air classifiers


and sieves

Residence time control, separation


quality

Coating

Loading active components


on the outer periphery of
the support

Three-way catalysts

Support residence time, solution


concentration and viscosity

Impregnation

Loading active components


in the supports pore system

Hydrogenation, hydrotreating and


reforming catalysts

Support residence time, solution


concentration and viscosity

the product and process optimization studies are a good time


in the scale-up program to look for such effects.
A more sophisticated approach integrates Six Sigma principles during both catalyst development and scale-up. Six
Sigma is a widely practiced business process that dramatically reduces manufacturing defects and improves process reliability, product quality and customer satisfaction.
Rajagopalan et al. make a persuasive case for using Six
Sigma to develop catalysts. They identify benefits such as:
reduction of scale-up time and costs; earlier identification of
product properties critical to meeting customer needs;

Examples of Scale-up Problems

improved understanding of the effects of manufacturing variations on critical product properties; and the development of
a commercial manufacturing process with Six Sigma capability, i.e., less then four defects per million opportunities (4).

Characterize unit operations


for effects on product properties
An effective strategy to improve the probability of
scale-up and manufacturing success is to carefully characterize the main manufacturing unit operations for
effects on product quality and/or properties. Every manuCEP

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facturing unit operation has at least one important effect


on the resulting product. A good understanding of such
effects is critical in isolating equipment failures or suboptimal operations.
For example, understanding the effect of residence
time in an impregnator on the distribution of the active
components on the catalyst can provide valuable insight
in both designing optimum impregnation conditions as
well as troubleshooting during commercial manufacturing. Similarly, the relationship between classification systems and the products particle size distribution will
enable later operations at optimal conditions. Table 3 outlines some important manufacturing unit operations and
their potential effects on product properties as well as
related scale-up issues.

Use pilot plants to validate laboratory


studies and simulate industrial conditions
Pilot plant trials are important for the successful scaleup of catalysts and are a critical step toward commercial
manufacturing. Pilot plants can be complex, require experienced personnel, are always overbooked, and are both
expensive and time-consuming. Therefore, careful and
detailed planning must precede their use for scaling up
catalysts and developing a commercial manufacturing
process. The pilot-scale studies must always include
experiments to validate the directional guidance obtained
in the laboratory-scale studies and to simulate commercial

manufacturing conditions, with the objective of


unearthing scale-related problems that are not apparent
when working in the laboratory.
Pilot-scale studies should also be used to confirm
changes made to the process, e.g., the use of less-expensive
precursors, recycling waste product, processing additives,
etc. Careful process monitoring and product characterization should be conducted during pilot-scale studies to generate data that will eventually help in monitoring a commercial trial. Pilot-scale studies are also opportunities to
develop alternative processes that could be used in case
insurmountable problems arise during the commercial trial.

Carefully plan, monitor and analyze


the first commercial trial
The first attempt to commercially produce the catalyst
will likely be the most taxing step in the scale-up and
commercialization process. While a substantial number of
laboratory- and pilot-scale tests will have been completed,
working with commercial equipment and large amounts of
raw materials, intermediate slurries, and products involves
a unique set of challenges and issues. These could include
problems associated with the process, equipment, personnel or product characterization. Therefore, it is of vital
importance that the first commercial trial be preceded by
sufficient planning.
A process flow diagram along with specific details of the
commercial equipment to be used during the manufacturing

PUTTING THE PRINCIPLES INTO PRACTICE


ConocoPhillips Co. and Sd-Chemie Inc. recently scaled up a new
sorbent for ConocoPhillips proprietary S Zorb sulfur removal technology. The new sorbent costs less, is manufactured in less time,
utilizes unusual chemistry, and has at least one improved property,
while it retains the advantages offered by previous sorbent formulations. The scale-up effort was completed in six months.
Since the new sorbent candidate utilized a drastically different manufacturing procedure, catalyst vendors were involved early
in the scale-up effort. Details of the laboratory-scale studies (e.g.,
synthesis steps, composition, ingredients and their manufacturers,
viscosity, temperature, and resulting product properties) were documented and shared with the vendors.
Following the discussions, a statistically designed experimental
program comprising only 13 experiments was developed. In addition to compositional variables affecting key product properties,
the experiments also characterized and optimized operational and
scale-up variables that would be important for commercial sorbent
manufacturing. Based on these laboratory-scale studies, a sorbent
composition and the synthesis procedure were frozen for further
scale-up studies.
The first round of studies using pilot-scale equipment confirmed and validated the laboratory work. Even so, the pilot studies

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identified new scale-up concerns that were critical to the sorbents


continued competitiveness, and these had to be overcome. Further
laboratory experimentation addressed and overcame these issues.
These results were validated and improved upon in further rounds
of pilot studies.
The insights gained from these studies were integrated, and
10,000 lb of the new sorbent was successfully produced. This sorbent load met all specifications and was delivered to a commercial
S Zorb sulfur removal technology unit for installation.
Chronology of key scale-up and commercialization steps:
Month 1: Laboratory-scale optimization using statistically
designed experiments
Month 2: First round of scale-up studies at vendors pilot plant
Month 3: Laboratory-scale process development based on
feedback from first round of scale-up work
Month 4: Second round of scale-up studies using pilot-scale
equipment
Month 5: Third round of scale-up studies using pilot-scale
equipment
Month 6: Commercial manufacture of 10,000 lb of sorbent
Month 7: Delivered sorbent load to commercial unit

campaign, as well as a detailed, step-wise description of the


catalyst formulation process, must be carefully documented
and reviewed. Such reviews should be used to stress to the
vendor the need to utilize standard, widely used, and wellcharacterized manufacturing equipment to minimize equipment-related upsets. If new equipment or unit operations are
to be included at later stages, efforts to characterize them
for effects on product properties must be made.
Early commercial campaigns are typically completed in
short periods of time and produce large amounts of product. Thus, the ability to predict or estimate final product
properties based on the properties of intermediate products
is invaluable in optimizing unit operations to afford products that meet specifications.
Laboratory- and pilot-scale data must be mined to
obtain process and product quality-control indicators and
correlations for process intermediates. Round-robin studies
are often conducted to validate analytical and test equipment used by the vendor and the customer. Round-robin
studies involve multiple analyses or characterizations of a
single set of samples performed at different locations or
using different equipment. Comprehensive sampling programs must be developed and implemented in collaboration with the vendor.
The sampling program along with corresponding

Literature Cited
1.
2.
3.
4.
5.
6.
7.

Silvy, R. P., Future Trends in the Refining Catalyst


Market, Applied Catalysis A: General, 261, pp. 247252
(2004).
Silvy, R. P., Global Refining Catalyst Industry Will Achieve
Strong Recovery in 2005, Oil & Gas Journal, pp. 4856
(Sept. 2, 2002).
The Catalyst Industry: Dynamic Technology in Rapidly
Changing Industries, Chemical Week, Todays Refinery
Supplement, pp. S3S5 (Sept. 1999).
Rajagopalan, R., et al., Developing Novel Catalysts with
Six Sigma, Research-Technology Management, pp. 1316
(Jan-Feb 2004).
Tullo, A., Quick Discovery, Chemical & Engineering
News, 81, pp. 1417 (July 21, 2003).
Campanati, M., et al., Fundamentals in the Preparation
of Heterogeneous Catalysts, Catalysis Today, 77, pp.
299314 (2003).
Stiles, A. B., Catalyst Manufacture: Laboratory and Commercial Preparations, Marcel Dekker, New York, NY (1983).

Acknowledgements
The authors acknowledge several useful discussions with current and past
colleagues, including Jim Scinta, Dennis Kidd, Ed Sughrue, Jason
Gislason, Ryan Zarnitz, Gary Hatfield and Debbie Just. In addition,
Richard Allen, Jeff Braden, Todd Osbourne, Ben Wagner, Eric Lowenthal,
Raj Rajagopalan, Marius Vaarkamp, John Macoay and John Henderson,
technical personnel from various catalyst vendors with whom the
authors have collaborated, are also acknowledged. The authors are
grateful to ConocoPhillips for permission to publish this paper.

process parameter measurements must yield samples capable of providing a diagnostic fingerprint of the commercial
campaign so that problems can be isolated and identified
should the product not meet specifications.

Closing thoughts
Catalysts will continue to play a vital role in improving the quality of modern life through the production of
chemicals, fuels and materials, in addition to having
important environmental applications. Scale-up is the critical link that will bring laboratory-scale innovations into
the commercial marketplace. While new tools and techniques will improve and accelerate the scale-up process
(7), the five principles identified here provide a generic
framework for enhancing the success rate of this
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vital link in the innovation chain.
UDAY T. TURAGA is an associate scientist in the Advanced Technology
Division, Downstream Technology, at ConocoPhillips Co.s Bartlesville
Technology Center (Bartlesville, OK 74006; Phone: (918) 661-0113; Email: Uday.T.Turaga@ConocoPhillips.com), where he has been involved
with the development, scale-up and commercialization of sorbents for
the proprietary S Zorb sulfur removal technology for gasoline
desulfurization since May 2002. He holds Bachelors and Masters
degrees in chemistry from the Univ. of Delhi in India and a doctorate in
fuel science from Pennsylvania State Univ.
DONALD R. ENGELBERT is a senior technologist at ConocoPhillips with 16
years experience in catalyst and sorbent synthesis, characterization,
scale-up and manufacturing. He has been involved with a suite of
proprietary catalysts and sorbents, including the sorbents used for the
S Zorb sulfur removal technology.
WILLIAM H. BEEVER leads the sorbent development group for the S Zorb
sulfur removal technology at ConocoPhillips. During his 25 years with
the company, his responsibilities have included managerial positions
leading several innovation projects in plastics, composite materials,
polyolefins and catalysts. He received Bachelors, Masters, and
doctoral degrees in chemistry from Missouri Western State College, the
Univ. of Iowa, and Colorado State Univ., respectively.
JOSEPH TODD OSBOURNE is the manager of the South Pilot Plant at SdChemie Inc. (Louisville, KY), where he has worked in refinery zeolite
catalyst R&D and led one of SCIs pilot plants. He has served as a team
member, project leader and technical resource on several custom
catalyst development projects, including sorbents used for the S Zorb
sulfur removal technology. He holds a Bachelors degree in chemistry
and mathematics from Campbellsville Univ.
BEN WAGNER has worked as an engineer in one of the pilot plants at SdChemie Inc. since May 2003. He holds a BS in chemical engineering
from the Univ. of Cincinnati.
RICHARD ALLEN has been employed by Sd-Chemie Inc. for 25 years in
various manufacturing managerial positions, which now involves the
scaling up of products from the pilot plant to commercial production,
including the sorbents for the S Zorb sulfur removal technology. He
received a Bachelors degree in chemical engineering from Eastern
Kentucky Univ. and an MBA from Bellarmine College.
JEFF BRADEN is currently director of sales and marketing for Sd-Chemie
Inc.s refinery catalysts, having worked for the firm for 22 years as an
R&D group leader, process control and product development manager,
and production manager. He received a BS in chemistry from the Univ.
of Louisville and an MBA from Indiana Univ.

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