Article

pubs.acs.org/IECR

Successful Scale-up of an Industrial Trickle Bed Hydrogenation Using

Laboratory Reactor Data
Daniel A. Hickman,*,† Michael T. Holbrook,‡,§ Samuel Mistretta,‡ and Steven J. Rozeveld†
†
The Dow Chemical Company, Midland, Michigan 48674, United States
‡
The Dow Chemical Company, Plaquemine, Louisiana 70765, United States

ABSTRACT: This work validates the appropriate application of chemical reaction engineering principles in the successful design
of a full-scale industrial trickle bed reactor for a proprietary hydrogenation reaction over a palladium catalyst. After identifying an
effective catalyst formulation in a continuous laboratory scale trickle bed reactor, the project team used the same small-scale
reactor to generate kinetic data for scale-up. The scale factor from the laboratory to the final design was about 3 × 106. The
development effort identified and resolved three important problems: (1) incomplete catalyst wetting of the small catalyst bed,
even though the catalyst was diluted with inert fines; (2) lower than economically attractive catalyst productivity; and (3) catalyst
deactivation.

■ INTRODUCTION
An important objective for the industrial reaction engineer is to
design a commercial scale reactor that achieves the target
performance parameters, including production rate and product
yield, while minimizing the investment of resources and the
time elapsed. The scale-up risks encountered by the engineer
vary depending on the nature of the chemistry and the reactor
system. In practice, no single work process can be universally
applied to all reactor scale-up projects. However, certain classes
of problems provide opportunities to apply reaction engineer-
ing fundamentals to enable an efficient scale-up program while
sufficiently mitigating risk factors associated with the scale-up
process. In this paper, we describe a specific program in which a
new trickle bed hydrogenation process was scaled directly from
the laboratory to the commercial scale reactor without building
and operating intermediate scale reactors. This program
succeeded by properly accounting for the relevant interactions
between transport phenomena and kinetics1 while scaling by a
factor of about 3 × 106.
Many previous authors have highlighted the importance of
properly designing a continuous laboratory scale fixed bed
reactor to avoid axial dispersion,2−7 wall effects,7,8 incomplete
catalyst wetting,8−10 and nonisothermal bed temperatures.11 In
this work, we applied those principles to enable generation of
apparent kinetic data, or reaction kinetics that lump the effects
of pore diffusion and the intrinsic rates, in an integral reactor
with fines.12 During this scale-up program we encountered and
resolved three particular problems, resolutions of which are
summarized in this paper. While we do not discuss the
proprietary chemistry, we offer this case study to illustrate the
application of basic reaction engineering principles to the scale-
up process and to provide insights into the nature of some of
the typical problems encountered in the scale-up of an
industrial trickle bed reactor. We also use this case study to
defend our assertion that an intermediate-scale pilot plant is not
always necessary to achieve successful scale-up and commerci-
alization of new trickle bed reactor technology.
■ EXPERIMENTAL METHODS
Reactor System. The integral laboratory reactor operated
in cocurrent downflow (trickle flow) or cocurrent upflow
depending on the configuration of multiple feed delivery and
product collection valves. An excess volume of silicon carbide
(100−140 mesh, or about 0.2 mm diameter) or glass beads
(60−80 mesh, or about 0.4 mm in diameter) diluted the
catalyst (0.4−4.1 g of extrudates with a nominal diameter of 1/
16 in. or 1/8 in., or about 1.6 or 3.2 mm) and filled the empty
space in the reactor above the catalyst bed. The reactor
consisted of a 1/2-in. or 1/4-in. nominal outer diameter metal
tube inside an oil jacket constructed of 1-in. tubing. An oil bath
with circulation pump circulated thermostatically controlled oil
through the jacket to ensure a uniform reactor wall temper-
ature. A positive displacement pump delivered the liquid feed
mixture to the reactor from a feed reservoir on a balance. A
mass flow controller continually delivered hydrogen. A cooled
vapor−liquid separator provided the means to separate the
vapor and liquid effluent from the reactor. A control valve
maintained the liquid level in the phase separator, and a second
control valve on the vapor effluent controlled the system
pressure. Online gas chromatography provided separate
analyses of the vapor and liquid products, enabling closure of
the system mass balance for each atomic species.
For both reactors, the feed mixture was representative of the
composition expected in the commercial scale reactor. We
varied the reactor pressure and temperature systematically to
cover the entire range expected in the full-scale reactor, and we
varied the liquid and hydrogen feed rates from 0.35 to 7.0 mL/
min and 100 to 400 sccm, respectively.
Special Issue: NASCRE 3
Received: February 18, 2013
Revised: March 22, 2013
Accepted: March 27, 2013

© XXXX American Chemical Society A dx.doi.org/10.1021/ie4005354 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Catalyst Deactivation Experiments. Following an
extended (3600 h) lab reactor run, the catalyst was unloaded
and separated into two samples based on color: a tan sample
from the beginning (top) of the catalyst bed and a black sample
from the end (bottom) of the bed. We also collected samples of
fresh catalyst and catalyst used in a different experiment for 600
h for analysis by various analytical techniques. The goal of the
analyses was to understand the deactivation mechanisms and
the extent that each played in the observed catalyst deactivation
process. We label the samples as follows: (1) fresh, (2) 600 h,
(3) 3600 h bottom, and (4) 3600 h top. Portions of both 3600
h samples were subsequently separately loaded and rerun in the
lab reactor to determine the activity of each type of catalyst and
compared with fresh catalyst. The fresh sample, the bottom
sample, and the top sample gave relative rates of 1.3, 1.0, and
0.5, respectively.
X-ray Photoelectron Spectroscopy. Catalyst extrudates
were affixed onto a metal plate using carbon tape for each
sample and spectra were recorded from three different areas for
statistical analysis. Samples were examined in the as-received
state, and it was necessary to solvent extract the residual
reaction liquids prior to the analysis.
Samples were initially examined by low-resolution survey
scans followed by high-resolution spectra of specific elements in
order to determine the binding energy (chemical state) and
concentration of the elements detected in the survey scans. The
quantification of the elements was accomplished by using the
atomic sensitivity factors for a Kratos model HSi XPS
spectrometer, using monochromatic Al−Kα as the X-ray
source. Charge compensation was used for all spectra.
The carbon (1s) photoline was used as the calibration
reference for the binding energy axis of all high-resolution
spectra. Intensity due to aromatic carbon−carbon bonding was
shifted to 284.8 eV. The resulting offset was measured and
applied to the other high-resolution spectra for the same point
of analysis. Each point of analysis was energy corrected
independent of the others.
Microprobe Sample Preparation. Cross-section samples
of the fresh and used catalysts were prepared by embedding the
catalysts in acrylic resin followed by microtoming the samples.
These samples were used for both electron microprobe and
TEM (transmission electron microscopy) experiments.
The procedure for embedding the catalyst samples was as
follows: First, several of the fresh extrudates were placed “edge-
on” into gelatin capsules, filled with LR White acrylic resin, and
placed under house vacuum (∼1 Torr) for 20 min to remove
trapped air from the catalyst pores. The capsules were then
dried at room temperature for 7 days. The samples were cured
at room temperature to eliminate any artificial sintering by
heating the samples during the curing process.
The used catalysts were prepared using a slightly different
method from the fresh catalyst. Several pieces (0.5 in. long) of
the used catalysts were soaked overnight in acetone to extract
the excess oligomers that were trapped in the porous catalyst
that would inhibit the acrylic resin from curing. The acetone-
soaked catalysts were then cured at room temperature and
embedded in the LR White acrylic resin. The samples were
microtomed (dry) using a diamond knife to prepare cross-
section blocks.
Electron Microprobe Experiments. The microtomed
blocks were carbon coated and examined in a Cameca SX50
electron microprobe (serial no. SX401) run by SAMx software.
Quantitative microanalysis was done at 15 keV and 50 nA. The
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concentrations of iron (Fe) and palladium (Pd) were measured
using wavelength dispersive spectrometers (WDS) using the
Fe−Kα and Pd−Lα peaks. Element maps were collected at 15
keV, 50 nA, and 50 μs/pixel using WDS. The standard map size
was 800 μm × 200 μm, although higher resolution maps of 100
μm × 100 μm were also recorded at the pellet rim.
Quantitative line scans were used to determine the weight
percent of iron and palladium as a function of distance from the
pellet exterior. This was done by collecting WDS peaks for each
element (and background) at discrete positions along a line
(∼200 μm long) starting at the rim of the pellet and traversing
into the pellet interior. The distance between data points was
10 μm in the bulk and reduced to 2 μm closer to the acrylic
resin/catalyst surface.
Aberration-Corrected High-Resolution TEM. Aberration
corrected (AC) TEM experiments were conducted at Oak
Ridge National Laboratory (ORNL) using the JEOL AC-
2200FS. The JEOL 2200FS-AC was equipped with a CEOS
GmbH aberration corrector. The AC-TEM formed extremely
small probe sizes of less than 1.2 Å diameter and was optimized
for scanning-TEM experiments on catalyst materials.
We captured images at a resolution of 1024 × 1024 pixels
using a 100 μs/pixel dwell time. At a magnification of 200kx,
the resolution was 6.9 Å/pixel and at 500kx, the resolution was
2.8 Å/pixel. The probe size for the ORNL AC-TEM instrument
was 1.2 Å diameter using a 35-μm aperture (25 pA probe
current). Before the scanning-TEM analysis, the area of interest
was exposed to an electron dose (“beam shower”) by removing
the condenser aperture and defocusing the probe over a ∼100-
μm area for several minutes.
The catalysts for the TEM analysis were prepared using the
same procedure as for the microprobe experiments. Thin
sections ∼70 nm thick were cut using a Riechart Ultracut
microtome at room temperature using a diamond knife, floated
onto DI water, and collected onto Cu grids with a lacey carbon
support. Note that the samples that were prepared for electron
microprobe studies were cut dry with a diamond knife as only a
polished block face was needed.
Before the TEM analysis, the area of interest was exposed to
an electron dose (“beam shower”) by removing the condenser
aperture and defocusing the probe over a ∼100-μm area for
several minutes. This step minimized carbon contamination
from the acrylic resin and did not introduce artifacts into the
TEM analysis.
■ RESULTS AND DISCUSSION
Catalyst Wetting. The earliest experiments in our research
used the 1/2-in. reactor tube. In preliminary experiments to
generate kinetic data, we found that the reaction order was first
order with respect to the organic reactant. We determined this
by varying the reactant concentration in the feed by a factor of
2 at a fixed space time (liquid volumetric feed rate),
temperature, and pressure; the fractional conversion was the
same in both cases. However, when we varied the space time at
several different temperatures with a fixed feed composition,
the apparent reaction order with respect to the reactant was
near 1.5.
These contradictory results (reaction order of 1.55 instead of
first order) led to the hypothesis that the experiments gave
fractional wetting efficiencies that increased with increasing
flow rates. In support of this hypothesis, a report in the open
literature shows that complete wetting is not guaranteed when
the catalyst is diluted with small, inert particles.13 We tested this
Industrial & Engineering Chemistry Research
hypothesis by loading a similar quantity of catalyst and silicon
carbide diluent into the 1/4-in. tube and repeating the variable
space time experiments using the same range of volumetric flow
rates and, thus, higher superficial velocities. In this case, the
results fit very nicely to a first order model over the entire range
of flow rates (Figure 2). This result supported the hypothesis
that the higher apparent reaction order in the experiments in
the 1/2-in. tube was the consequence of incomplete catalyst
wetting, with the fractional wetting efficiency increasing with
increasing flow rate. All subsequent experiments for catalyst
testing and kinetic model development used the 1/4-in. tube
reactor, where the superficial velocities were high enough to
give complete catalyst wetting for range of flow rates employed
in the experimental program.
For the experiments in Figures 1 and 2, the total mass of
catalyst loaded for each of these experiments was the same
Figure 1. Fit of 1.55 order model (curves) to fractional conversion
data (symbols) for 1/8-in. extrudates in 1/2-in. tube at five different
temperatures (T1−T5) and various total volumetric flow rates (F).
Each temperature curve was fit separately assuming a reaction order of
1.55 with respect to the reactant.
Figure 2. Fit of 1.0 order model (curves) to fractional conversion data
(symbols) for 1/8-in. extrudates in 1/4-in. tube at two different
temperatures (T1 and T2) and various total volumetric flow rates (F).
Each temperature curve was fit separately assuming a reaction order of
1.0 with respect to the reactant.
(2.05 g). In the 1/2-in. tube experiments, we observed 60%
conversion at temperature T2, a flow rate of 1.24 mL/min, and
763 h on stream. In the 1/4-in. tube, we obtained 62%
conversion at the same temperature, a flow rate of 2.95 mL/
min, and 145 h on stream. This corresponds to a productivity
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increase of about 140% (a factor of 2.4), although some of that
difference could be attributed to catalyst deactivation since the
data point from the 1/2-tube was for a catalyst with significantly
more time on stream.
We also performed experiments comparing the effect of the
flow direction with the 1/4-in. reactor. According to the
literature, a lab reactor in which the catalyst bed is diluted with
fines should give identical results regardless of the flow
direction (cocurrent upflow or cocurrent downflow) if the
fines have effectively decoupled the hydrodynamic effects from
the reaction kinetics and intraparticle effects.14,15 In other
words, since complete wetting of the catalyst surface is ensured
during upflow because the continuous fluid phase is the liquid
phase, then achieving identical results in both upflow and
downflow implies that essentially complete wetting of the
catalyst surface is obtained during downflow.
These experiments used 0.82 g of supported Pd, 1/16-in.
extrudates, diluted with 60/80 mesh glass balls. These
experiments were conducted after the catalyst had been in
operation for about 4000 h. The conversion was 53.6% with
downflow and 52.6% with upflow under otherwise identical
conditions, supporting our assumption that the catalyst was
fully wetted during downflow experiments. With confidence
that these data were not compromised by incomplete catalyst
wetting, we used this same catalyst load to generate data for
development of models of reaction kinetics and deactivation
kinetics.
Catalyst Productivity. Early catalyst development work
used catalyst extrudates with a diameter of 1/8-in. Calculations
predicted that pore diffusion significantly limited the rate of
reaction, even in smaller catalyst particles. For example, for
extrudates 1/16-in. in diameter and 1/8-in. long, based on the
observed reaction rate and assuming a first-order reaction,
calculations gave an estimated Thiele modulus of 2.5. For a
Thiele modulus above 2.0, the effectiveness factor is inversely
proportional to the Thiele modulus and is therefore inversely
proportional to the characteristic pore length. Consequently,
for particles approximately 1/16 in. and larger, we predicted
and observed experimentally (Table 1) that the activity per
Table 1. Comparison of Apparent Activity of 1/16-in. and 1/
8-in. Extrudates
1/8-in. 1/16-in.
extrudates extrudates
mass of catalyst (g) 2.05 2.00
time on stream (h) 6.2 8.2
liquid feed rate (mL/min) 3.04 3.27
hydrogen feed rate (sccm) 400 400
first-order rate constant (mL/g-min) 2.46 4.85
mass of catalyst was inversely related to the particle diameter.
This motivated the use of catalyst particles as small as possible
within the limits of reactor pressure drop constraints and the
limitations of the catalyst production process. By switching
from 1/8-in. to 1/16-in. extrudates, we effectively doubled the
reactor productivity, providing a positive boost to the economic
attractiveness of the process.
Catalyst Deactivation. Our conceptual model of the
deactivation of the supported Pd catalyst in this reaction system
involved four distinct mechanisms: (1) sintering of the initially
highly dispersed Pd particles, (2) iron poisoning of the catalyst,
which results in the formation of Fe−Pd alloy particles with
Industrial & Engineering Chemistry Research Article

lower or perhaps no activity for hydrogenation, (3) Pd loss near

the surface, and (4) fouling. We observed these modes of
deactivation by comparing fresh and spent catalyst using XPS,
electron microprobe, and TEM.
Following extended (3600 h) lab reactor runs, we discovered
that a portion of the catalyst extrudates from the inlet (top) of
the reactor bed were discolored on the outer surfaces (with a
distinct “tan” color) compared to the fresh, 600-h, and the
3600-h bottom samples, which were all black. The interior of
the discolored “tan” extrudates was still black. XPS revealed a
substantial increase in the concentration of surface carbon with
time on stream, strong evidence for significant catalyst fouling
(Figure 3). A second notable difference identified by the XPS

Figure 4. Line scan of fresh catalyst.

Figure 3. XPS surface concentration (atom %) of C and Fe in fresh

and used catalysts.
Figure 5. Line scan of 3600-h bottom sample.
analyses was a sharp increase in the concentration of iron in the
3600-h top sample. Iron was not expected or detected in the
fresh catalyst material.
Among the most informative electron microprobe experi-
ments in this study were quantitative line scans of the fresh and
used catalysts in cross-section. The line scans provided a more
accurate measurement of the Pd and Fe concentration
compared to the element maps since a longer dwell time/
pixel could be used. Line scans were generated by collecting a
spectrum at discrete points (for example, every 2 μm) on the
cross-sectional sample from the edge of the pellet to ∼200 μm
into the pellet interior.
Line scans from the fresh sample, shown in Figure 4,
indicated that the Pd loading was uniform across the pellet
(∼2.2 wt % Pd) with no depletion near the rim. The Fe
concentration was below the detection limit (0.05 wt %) in the
fresh catalyst.
Similar line scans were done for two different 3600-h bottom Figure 6. Line scan of 3600-h top sample.
pellets, and a representative profile is shown in Figure 5. The
Pd concentration (∼2.0 wt %) was uniform across most of the
cross-section, although a small decrease in the Pd concentration the areas with high Fe contamination. The line profiles clearly
was observed near the pellet edge. The Fe concentration was show Pd depletion in the outer ∼30 μm of the pellet to as low
near or below the detection limit (0.05 wt %). as ∼0.3 wt % Pd (data not shown). In the pellet interior, the Fe
Line scans from the 3600-h top sample were recorded from concentration was low, ∼0.1 wt %. The line profiles clearly
two different pellets (Figure 6). The maximum Pd concen- showed Pd depletion in the outer 30 μm of the pellet, with Fe
tration of the first pellet was ∼1.7 wt % Pd (as shown in the preferentially depositing onto Pd rich areas near the surface,
figure) but only ∼1 wt % Pd for the other pellet. In both cases, giving local Fe concentrations approaching 20 wt %. Fuentes
the Pd concentration was highest away from the pellet surface. and Figueras previously reported similar iron poisoning of
The Pd concentration in the 3600-h top sample decreased supported Pd catalysts.16 Based on further analyses of the fresh
toward the rim of the pellet but with spikes to ∼1−2 wt % at catalyst samples, the Pd-rich areas appear to be the
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Industrial & Engineering Chemistry Research Article

consequence of the catalyst preparation process rather than a
result of Pd migration with time on stream.
Scanning TEM (dark field) experiments of the used catalysts
were conducted at ORNL to determine the Pd particle size and
distribution. Surprisingly, after 600 h, the average Pd size
distribution had decreased (near the pellet surface), and many
small Pd particles were observed. The median particle size for
the 600-h sample was ∼17 Å, compared to ∼34 Å in the fresh
sample (Table 2). The downward trend in Pd particle size
Table 2. Palladium Particle Size near the Pellet Surface
median average (±1 SD)
fresh 34 Å 45 ± 32 Å
600-h 17 Å 23 ± 16 Å
3600-h bottom 17 Å 18 ± 9 Å
3600-h top little Pd detected little Pd detected
continued with the 3600-h bottom catalyst, and few Pd particles
were observed near the surface of the 3600-h top sample. From
these observations, the leaching of Pd into the liquid reaction
mixture likely drives the loss of Pd near the surface.
Scanning TEM (dark field) images were also recorded ∼100
μm away from the pellet surface to determine the Pd particle
size and distribution as a function of time on stream. The
median Pd particle size was 14 Å for the fresh catalyst (Table 3)
and increased linearly over time on stream (Figure 7),
providing clear evidence of Pd sintering.
due to sintering, leaching, and fouling in the absence of iron
poisoning was determined to be sufficiently slow to provide an
economically viable catalyst lifetime.
■ CONCLUSIONS
By increasing the aspect ratio of the catalyst bed in order to
increase the liquid superficial velocity, the development team
overcame the catalyst wetting problem in the laboratory
reactor. Furthermore, decreasing the characteristic diffusion
length by choosing smaller catalyst particles increased the
productivity to an economically attractive conversion rate. By
using raw materials representative of the expected commercial
plant feed stream rather than synthetic feeds from the
beginning of the experimental program, the team identified
catalyst deactivation as an important problem. The team then
managed this problem using state-of-the-art analytical techni-
ques to identify several parallel modes of catalyst deactivation,
followed by the identification of appropriate steps to minimize
the rate of catalyst deactivation to an economically viable rate.
Then, using the appropriately sized and loaded lab reactor, the
team generated data for development of models of reaction
kinetics and deactivation kinetics. The team used these models
to design the commercial-scale reactor, successfully scaling the
reactor by a factor of about 3 × 106 from these laboratory scale
experiments to the full-scale reactor design. Finally, effective
technology transfer from the development team to the process
design and construction team, coupled with implementation of
a strict operating discipline in the plant, resulted in the
successful startup and operation of the hydrogenation plant.

■
Table 3. Palladium Particle Size in the Pellet Interior (∼100
μm from the Pellet Surface)
AUTHOR INFORMATION
median average (±1 SD) Corresponding Author
fresh 14 Å 18 ± 12 Å *E-mail: dahickman@dow.com; phone: 989-636-2165.
600-h 21 Å 26 ± 18 Å
Notes
3600-h bottom 62 Å 58 ± 40 Å
The authors declare no competing financial interest.
3600-h top 21 Å 30 ± 26 Å §
Retired.

■ ACKNOWLEDGMENTS
We thank Timm Richardson and Cliff Todd of Analytical
Sciences, Dow Chemical, for their expertise in conducting the
electron microprobe and XPS experiments. We also thank
Doug Blom and Larry Allard at ORNL for assistance with the
AC-TEM experiments (High Temperature Materials Labo-
ratory, Microscopy, Microanalysis, Microstructures Group, Oak
Ridge National Laboratory, PO Box 2008, 1 Bethel Valley
Road, Oak Ridge, TN 37831-6064). This portion of the
research was sponsored by the Asst. Sec. for Energy Efficiency
and Renewable Energy, Office of FreedomCAR and Vehicle
Technologies, as part of the High Temperature Materials
Laboratory User Program, ORNL, managed by UT-Battelle
LLC for the U.S. DOE.

Figure 7. Pd median and average particle size versus time on stream in

the pellet interior (100 μm from catalyst surface).
These efforts to understand the likely mechanisms for
catalyst deactivation led the scale-up team to focus on
controlling the one mechanism that could be controlled: iron
poisoning. To prevent or minimize this poisoning, we designed
the process and operating discipline to prevent introduction of
an iron-contaminated feed to the catalyst bed. The deactivation
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