9304 Ind. Eng. Chem. Res.

2008, 47, 9304–9313

A New Coated Catalyst for the Production of Diacetone Alcohol via Catalytic
Distillation
Greg P. Dechaine† and Flora T. T. Ng*
Department of Chemical Engineering, UniVersity of Waterloo, 200 UniVersity AVenue West,
Waterloo, Ontario, Canada N2L 3G1

A method has been developed for the production of catalytically active coated ceramic distillation saddles for
use in catalytic distillation (CD) columns. A thin layer of magnesium acetate was applied to ceramic Norton
saddles using a sol-gel dip-coating method. The magnesium acetate coating was converted to the catalytically
active magnesium oxide (MgO) via a temperature-ramped calcination program. The kinetic performance of
the MgO-coated saddles for the aldol condensation of acetone was determined in a batch reactor and a batch
CD column. Although the coated saddles provided lower yields to DAA than Amberlite IRA-900 ion exchange
resins in a batch reactor, their improved mass transfer characteristics provided higher yields than the same
ion exchange resins held inside fiberglass bags in a CD column at low flow rates. The coated saddles also
showed significant improvements in selectivity to DAA compared to the resin catalysts for the aldol
condensation reaction carried out both in the batch reactor and in the CD column.

1. Introduction a coated catalyst, the temperature limit can be much higher

1 (depending on the coating) so that CD can be applied to a greater
Catalytic distillation (CD) is a green reactor technology
which combines a liquid phase reaction over a solid phase
catalyst with simultaneous, countercurrent vapor flow. The
potential benefits of carrying out a reaction under distillation
conditions include reduced capital cost, higher than equilibrium
conversion,increasedselectivity,andimprovedenergyefficiency.1,2
However, CD technology does not present a viable solution to
all reaction systems, and each specific application must be
evaluated independently to determine the suitability of CD.
One of the primary challenges of combining heterogeneous
catalysis and distillation is devising methods for loading the
catalyst in the column. Special support structures are required
to contain the catalyst while maintaining a high void fraction
to facilitate countercurrent vapor and liquid flow within the
reaction zone. Taylor and Krishna2 did a thorough review of
the different methods available for this purpose. Unfortunately,
the packing structures currently available tend to separate the
vapor and liquid into separate streams, with the liquid flowing
through a zone filled with catalyst and the vapor flowing in
separate channels surrounding these catalyst zones. Separating
the liquid and vapor streams in this fashion decreases the
efficiency of the distillation occurring in the reaction zone and
reduces the impact of simultaneous separation on selectivity and
productivity.
The separation efficiency in a catalytic distillation process
can be improved by making traditional distillation packings
catalytically active. According to Taylor and Krishna,2 coated
distillation packings have not been used in practice because of
high cost and low catalyst loadings per unit volume. Despite
these roadblocks, incentives exist for using such coated distil-
lation packings. According to Oudshoorn et al.,3 coated catalysts
have much higher effectiveness factors. As well, the most
common catalysts used for CD are ion exchange resins which
generally have temperature limits of 60-120 °C. In the case of
* To whom correspondence should be addressed. E-mail: fttng@
cape.uwaterloo.ca.
†
Current address: Department of Chemical and Materials Engineer-
ing, University of Alberta, 114 St-89 Ave, Edmonton, Alberta, Canada
T6G 2G6.
10.1021/ie800009u CCC: $40.75  2008 American Chemical Society
Published on Web 11/05/2008
number of reactions. Finally, the use of coated distillation
packings will provide much more efficient distillation within
the reaction zone of the CD column, possibly leading to
improvements in conversion and selectivity for systems limited
by mass transfer. Attempts have been made by various
investigators to coat structured packings with a catalytically
active layer. Oudshoorn et al.3 coated a structured packing with
a zeolite coating, Mehrabani et al.4 coated a structured distil-
lation packing with cation-exchange resin, and Beers et al.5
coated monoliths and metal gauze packings with a BEA zeolitic
coating. Unfortunately, none of these investigators reported data
regarding the performance of these catalysts in a distillation
column.
A system that stands to benefit from the application of CD is
the production of the solvent diacetone alcohol (DAA) via the
aldol condensation of acetone1 (Ac), as shown in eq 1.
2Ac T DAA T MO + H2O (1)
6,7
In addition to being equilibrium limited, DAA is susceptible
to dehydration to form the byproduct mesityl oxide (MO) (eq
1). The DAA and MO products can also be further condensed
to higher molecular weight nonvolatile products such as
isophorone and mesitylene which lead to deactivation of solid
catalysts.8,9
Podrebarac et al.10,11 applied CD to the production of DAA
using the hydroxide form of a macroporous anionic exchange
resin (Amberlite IRA-900). The resin beads were contained
within a fiberglass bag surrounded by wire mesh (a catalyst
bale), resulting in severe mass transfer limitations within the
reaction zone. These mass transfer limitations were due to both
external resistances (the catalyst bale) and intraparticle resistance
(the catalyst pores), resulting in reduced reaction rates, rapid
deactivation of the catalyst, and poor selectivity to DAA. On
the basis of these results, it appears that the production of DAA
via CD could benefit greatly from the use of a coated distillation
packing instead of packing ion exchange resins in fiberglass
bags.
Many solid base catalysts for the aldol condensation of
acetone have been studied in the literature. Zhang et al.12 studied

Figure 1. Photographs of the alligator clips used for suspending the saddles for dip-coating.
the performance of alkaline earth metal oxides (including MgO)
and showed that these basic solids are active for the aldol
condensation reaction. Hydrotalcites and layered double hy-
droxides in various forms have also been shown to be active
for this reaction.13-17 MgO was chosen to be the catalytic
material in this study since several methods for applying thin
films of magnesium oxide (MgO) to ceramic and/or glass
substrates18-22 were reported although none of these studies
were of a catalytic nature. Ceramic distillation saddles should
have similar surface properties as the glass and ceramic
substrates, and therefore these methods were chosen to coat the
saddles.
This paper reports a new method for the preparation of a
coated ceramic saddle catalyst for use as a packing in a CD
process. Particular attention is given to the methods necessary
for applying the precursor coating to the saddle as well as the
successful conversion of this precursor coating to a catalytically
active form. The performance of these coated catalytic saddles
for the aldol condensation of acetone was determined in both a
batch reactor and a CD column. The results obtained in a CD
column are significant since this is first report on the use of a
coated catalytic distillation packing in an actual CD column.
These data provide insight into the performance of such a coated
catalyst in a CD column for the aldol condensation of acetone.
2. Experimental Section
2.1. Neutralization of Reagent Acetone. ACS grade acetone
contains up to 0.0003 mequiv/g of titratable acid,23 which is a
combination of dissolved carbon dioxide (0.000 23 mequiv/g)
and acetic acid (0.000 033 mequiv/g).24 Because the catalysts
used in this study are basic, this acidity must be removed from
the reagent acetone to avoid neutralization of the catalyst sites.
The reagent acetone was treated using Amberlite IRA-900 ion
exchange resin in the hydroxide form. The dried resin was added
to bottles of HPLC acetone (EMD Chemicals Inc. #AX0115-
1) and agitated for 45-60 min. The treated acetone was decanted
through a vacuum filter and distilled. The water content of the
neutralized and distilled acetone was 0.295 wt % measured using
Karl Fischer titration (Mitsubishi model CA-06 coulometric KF
titrator), and the DAA content was <0.02 wt %. Prior to use in
reactor studies, the neutralized acetone was degassed using
argon.
2.2. Production of Coated Catalytic Saddles. 2.2.1. Prepa-
ration of the Precursor Sol. A combination of the methods of
Menon and Bullard21 and of Shukla et al.19 was used because
of the relative simplicity of the method, and the resulting
precursor solutions are stable for several weeks following their
initial preparation. Magnesium ethoxide (Mg(OEt)2, Alfa Aesar
#14264) and glacial acetic acid (HOAc, Fisher Scientific #A38-
P212) were dissolved in ethanol (Commercial Alcohols Inc.,
maximum water content ) 0.1 vol %) in a 27:3:1 molar ratio
of ethanol:HOAc:Mg(OEt)2. The Mg(OEt)2 was handled and
dispensed in a glovebox to prevent reaction with atmospheric
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9305
moisture. This solution was stirred vigorously until all visible
solids dissolved and then refluxed for 24 h. The resulting
precursor solution is a colloidal suspension of magnesium
acetate (Mg(OAc)2) particles in an ethanol solvent and is referred
to as a precursor sol.
2.2.2. Preparation of the Saddles. Norton saddles provide
the highest specific area (984 m2/m3) and the highest void
fraction (0.65) of the three commercial packings available in a
1/4 in. nominal size and therefore were chosen for this project.
According to the manufacturer’s MSDS, Norton saddles are
composed of 65%-75% silica, 20%-27% alumina, and the
balance other metal oxides. Prior to being coated, the saddles
were cleaned and degreased using detergent and water, followed
by toluene and then acetone. The cleaned saddles were
thoroughly rinsed with demineralized water, dried in an oven
at 80 °C, and stored in a sealed glass container to prevent any
contamination.
2.2.3. Coating the Saddles. A thin layer of the precursor
sol was deposited onto the ceramic distillation saddles using a
dip-coating process. According to Brinker and Scherer,25 the
thickness of the film deposited by dip-coating is directly
proportional to the withdrawal speed of the substrate. Control
of the withdrawal rate of the saddles was accomplished using
a moving platform lowered by a threaded shaft and an electric
motor. For each revolution of the threaded shaft, the platform
is lowered by a distance equivalent to the distance between the
threads of the shaft. Since the distance between the threads
remains constant, the linear speed of the platform is directly
proportional to the rotational speed of the shaft and hence
proportional to the speed of the drive motor. The precursor sol
was placed in a stainless steel dish supported on the moving
platform.
For most applications of dip-coating, the substrate has a
relatively simple geometry (e.g., rectangular wafer) and is easily
held in place while being withdrawn from the coating solution.
Ceramic distillation saddles, however, have an irregular shape
that makes it difficult to suspend vertically for immersion and
withdrawal. This difficulty was overcome by using soldered
alligator clips (RadioShack #270-0380). To accommodate a
larger number of saddles, the clips were first mounted in strips
of 46 saddles (Figure 1a), and then five such strips were mounted
together onto a master bracket for a total of 230 saddles (Figure
1b). This master bracket was attached to a shaft for suspension
above the coating solution. With the saddles suspended above
the coating solution, the platform was raised until the saddles
were immersed 3-4 mm below the surface of the liquid to
ensure that the withdrawal rate was constant during the coating
deposition phase.
Once the saddles were withdrawn and the coating deposited,
the saddles were connected to a horizontally oriented motor and
rotated slowly at 45-75 rpm to prevent gravity drainage of the
coating while drying. A steady stream of ambient air was blown
over the rotating saddles to enhance evaporation of any residual
9306 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008

Table 1. Temperature Ramp Program for the Calcination of Coated

Catalyst Saddles in Flowing Air
temperature (°C)
ramp rate
step start end (°C/min) time
1 25 250 1 225 min
2 250 375 0.2 625 min
3 375 475 1 100 min
4 475 475 N/A 6h

solvent. The coating produced by a single dip was too thin so

the above process was repeated several times to obtain increased
catalyst mass.
2.2.4. Calcining the Coated Saddles. The precursor
Mg(OAc)2 coating was converted to catalytically active MgO
by calcination in flowing air. The saddles were calcined using
a tubular furnace/oven. A specially designed glass tube was
constructed to contain the coated saddles within the furnace and
allow for the introduction of air and cooling gas during various
stages of the calcination. The inlet and outlet gas connections
were equipped with Teflon stopcocks to allow for isolation of
the saddles following calcination. Helium was used as an inert
cooling gas, and the air and helium were metered using a
rotameter. The saddles were calcined according to the temper-
ature ramping program in Table 1 with an air flow of 1.5 L
(STP)/min. Once the calcination program was complete, the air
flow was switched to helium and the saddles were cooled to
ambient temperature at a rate of ∼2.5 °C/min.
2.3. Batch Reactor Testing of the Catalyst. The perfor-
mance of the catalyst saddles was determined in a batch reactor
consisting of a 250 mL, three-necked round-bottom flask. The
flask was equipped with a wire mesh screen to isolate the coated
saddles from the magnetic stirrer which kept the solution in
the reactor well mixed. The flask was immersed in a constant
temperature bath, and the temperature of the reactants was
monitored using a thermocouple. A gastight syringe was used
for taking samples of the reaction mixture at set time intervals.
The batch reactions were carried out using 100 mL of acetone.
In the cases where an air atmosphere was used, the amount of
acetone added to the flask was determined gravimetrically. In
the cases where an inert atmosphere was used, the amount of
acetone added was quantified using a graduated separatory
funnel. The acetone was degassed in a 100 mL separatory funnel
for 1 h with 0.4 L (STP)/min of argon. The acetone was brought
up to the reaction temperature (54 °C), and the calcined saddles
were quickly added to the flask. 0.5 mL samples were taken
from the reactor at varying time intervals and mixed with 0.5
mL of a 10 wt % 1-propanol solution in 2-propanol. 1-Propanol
was used as an internal standard for quantifying the concentra-
tion of the species present in the reactor sample. The samples
were placed in a freezer overnight prior to analysis to minimize Figure 2. Batch distillation apparatus for testing the coated saddle catalysts
sample deterioration due to the volatile nature of acetone. in CD experiments: (1) Glas-Col 115 V, 380 W heating mantle, (2) 1000
mL, three-necked boiling flask, (3) rubber septum and gastight syringe, (4)
The concentrations of DAA, MO, and isophorone in the inert gas connection, (5) 1/8 in. thermocouple, (6) 1 in. i.d. glass column,
reactor were determined using an Agilent Technologies model (7) Omega model HH501DK 4-channel type K thermometers, (8) overhead
6890N GC with an FID detector, a split/splitless inlet, and a manifold, (9) 200 mm long condenser, (10) Ametek Lo-Flo rotameter.
J&W scientific DB-WAX megabore capillary column. The
concentrations of DAA and MO were quantified directly from 2.4. Batch CD Column Testing of the Catalyst. The coated
the GC results with an accuracy of (3.0% and ( 1.1% of the saddles were tested in a batch CD column, illustrated in Figure
measured values, respectively. No isophorone was ever detected 2, which is identical in size and layout to the batch column
in any of the experiments conducted. The concentration of water used by Podrebarac et al.10 Argon gas connections were present
was determined on the basis of the initial water content of the at the bottom and top of the column to sweep the column free
reagent acetone (determined by Karl Fischer titration) and the of air and maintain an inert atmosphere in the column during
concentration of MO since the only source of water is via the the CD experiments. The column has an i.d. of 1 in. (25.4 mm)
production of MO. Finally, the acetone concentration was and a total packed length of 30 in. (762 mm). The first 16 in.
obtained by difference assuming it represented the remainder (406 mm) of the column was packed with ceramic Norton
of the solution. saddles and covered by a separator plate. The reaction zone

Figure 3. Comparison of the conversion of acetone (XAc), the selectivity to DAA (SDAA), and the initial rate of production of DAA for the coated saddles
with varying number of coats applied to the saddle (46 saddles in a batch reactor at 54 °C with un-neutralized acetone and an air atmosphere).
(indicated in Figure 2 by the X on the column) was loaded next,
covered by another separator plate, and the remainder of the
column was filled with more Norton saddles. The thermocouples
were equally spaced 6 in. apart along the height of the column.
The reboiler consisted of a boiling flask and heating mantle
controlled using a variable autotransformer and is the same
reboiler setup used by Podrebarac et al.10 The heat input of the
reboiler as a function of the input voltage and the reboiler
temperature was calibrated using pure water. Prior to starting
the batch CD experiment, the acetone was degassed in a 500
mL separatory funnel. The water content of the neutralized,
distilled acetone used in the CD experiments was 0.276 wt %
as measured using Karl Fischer titration. Approximately 600
mL of acetone was charged to the separatory funnel and
degassed using an argon flow of 1.3 L (STP)/min for ap-
proximately 11/2 h. Prior to loading the catalyst, the column
was swept with high flow rates of argon from the bottom inlet
(see item 4 in Figure 2). The overhead assembly was removed
from the column, and the coated ceramic saddles were quickly
added under argon flow. The remainder of the column was filled
with more Norton saddles and the overhead assembly reinstalled.
Throughout this process, argon gas was flowing from the bottom
inlet to ensure that the coated ceramic saddles were contained
within an inert atmosphere.
The column was further purged with argon and then the
degassed acetone was quickly added to the reboiler. Again, the
column was purged with argon from the bottom inlet, after
which the argon flow was switched to the top inlet (see item
10 in Figure 2). The flow of argon from this top inlet was 0.1
L (STP)/min. A 0.5 mL sample of the initial acetone in the
reboiler was taken, after which the power to the heating mantle
was turned on and the entire column was insulated. A stopwatch
was started once the temperature of the reaction zone began to
rise, indicating that the acetone vapor had reached the reaction
zone. The initial temperatures of the reboiler and the column
were recorded once reflux had been established. 0.5 mL samples
of the reboiler liquid were taken at regular time intervals and
analyzed using the GC methods previously described.
3. Results and Discussion
3.1. Calcination of Coated Ceramic Saddles. A final
calcination temperature of 475 °C was chosen since this was
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9307
reported to provide the optimum activity of the MgO catalyst
for the acetone condensation reaction.12 Preliminary attempts
to calcine Mg(OAc)2 using a muffle furnace resulted in the
formation of significant amounts of coke on the surface of the
precursor solids. Therefore, it was necessary to supply fresh
air to the solid surface during the calcination to ensure
conversion of acetate to carbon dioxide rather than to coke.
According to Menon and Bullard,21 two distinct transforma-
tions occur when Mg(OAc)2 is heated to 475 °C. At 200 °C
the form of Mg(OAc)2 changes from R-Mg(OAc)2 to β-M-
g(OAc)2, and any residual solvent is driven off. At 300 °C the
majority of the Mg(OAc)2 decomposes pyrolytically to MgO.
The majority of the decomposition occurs at ≈300 °C, although
it is not fully complete until ≈360 °C. In order to control the
decomposition and ensure adequate air supply, a means of
ramping the temperature slowly is necessary in order to properly
calcine Mg(OAc)2 to form MgO.
For preliminary trials using Mg(OAc)2 · 4H2O powder, the
same 0.1 °C/min ramping rate that Menon and Bullard21 used
was employed until a temperature of 475 °C was reached,
whereupon it was held for 1 h. Unfortunately, this ramping rate
is very slow and requires a prohibitively long time to complete.
Therefore, for the coated catalysts, the modified ramping
program shown in Table 1 was used. Since very little decom-
position occurs from ambient temperature to 250 °C, a higher
ramping rate of 1 °C/min was used through this region. In the
range between 250 and 375 °C where decomposition does occur,
a slower ramping rate of 0.2 °C/min was employed. Finally,
once the solids reach 375 °C and the Mg(OAc)2 has been
converted to MgO, the temperature can be ramped up to the
final temperature of 475 °C at a rate of 1 °C/min since coke
formation is no longer a concern. The final temperature is held
at 475 °C for an additional 6 h to ensure complete conversion
to MgO.
The coefficients of linear thermal expansion for pure mag-
nesium oxide and ceramic Norton Saddles are 6.01 × 10-6 °C-1
at 500 °C26 and 14.5 × 10-6 K-1 at 527 °C (800 K),
respectively. According to this data, at 500 °C, the MgO coating
will shrink by 141% more than the ceramic saddle substrate.
This effect will be magnified by the fact that the coating will
cool much more quickly than the substrate due to temperature
gradients present throughout the saddle during the rapid cooling
9308 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
process. Exposure of the coated saddles to extreme temperature
changes will cause the coating to crack and pull away from the
substrate. Therefore, once the calcination program was complete,
the catalyst saddles were cooled slowly at a rate of ≈2.5 °C/
min using inert helium gas. The use of an inert gas for cooling
also minimized the exposure of the catalytically active MgO
layer to air, thus preventing the poisoning of the basic catalyst
sites by atmospheric CO2.
3.2. Effect of Coating Mass on Performance. At the outset
of this work, it was unknown whether or not synthesizing a
thicker coating layer would result in increased yields of DAA.
The external surface area of the coating will be roughly the
same as that of the underlying support provided the thickness
of the coating is not large. If the coating layer has no porosity,
depositing additional layers of coating should not result in
improved catalytic performance. Therefore, varying the number
of coats applied to the saddles and testing the resulting
performance would provide information on whether the calcined
coating layer has any porosity.
The coating apparatus described earlier is capable of coating
230 saddles simultaneously in groups of 46 saddles. To test the
effect of additional coating layers on the performance, a batch
of 230 coated catalyst saddles was made using a single batch
of coating solution. The saddles were withdrawn at a speed of
1.25 mm/s and dried for 10 min on the rotating dryer between
each dip. Following the first 10 coats, 46 of the saddles were
removed. Following the next 10 coats (20 total coats) another
46 saddles were removed. This was repeated after every 10
coats, resulting in 5 batches of 46 saddles, each with 10 more
layers than the previous group. These 5 batches of catalyst were
calcined and tested in a batch reactor with the results shown in
Figure 3a. The conversion of acetone, XAc, and the selectivity
to DAA, SDAA, plotted in Figure 3a follow the standard IUPAC
nomenclature27 for conversion (X), yield (Y), and selectivity (S):
moles of acetone converted to product i
Yi ) (2)
initial moles of acetone
total moles of acetone reacted
Xi ) (3)
initial moles of acetone
Yi
Si ) (4)
XAc
From these results, it is evident that increasing the number of
coats does indeed lead to increased yield of DAA. This suggests
that there is some porosity in the coated layer following
calcination and that there is an incentive to deposit as much
coating as possible.
In an attempt to quantify the difference in performance
between the five different catalysts, the method of initial rates28
was used since basic catalysts applied to this reaction system
are susceptible to deactivation.8,9 A quadratic polynomial with
0 intercept was fit to the first 10 min of concentration vs time
data (5 data points), providing a smoothed functional relationship
for CDAA(t). This polynomial was then differentiated (to give
dCDAA/dt ) rDAA) and solved at t ) 0 to give the initial rate of
reaction before any potential deactivation and other detrimental
effects have occurred. Although the first data point, usually taken
after 2 min, could have been used to determine the initial rate
(i.e., dC/dt ≈ ∆C/∆t), using regression to smooth a curve over
multiple data points is preferred since inaccuracies in the first
data point are less likely to skew the results. Also, data points
at >10 min were not used in the regression analysis to avoid
incorporation of data with potential catalyst deactivation.
The initial rate of reaction for these five catalysts is plotted
as a function of the mass of catalyst coating in Figure 3b. The
mass of coating was determined after the batch reactor test was
completed. As a matter of reference, the mass of catalyst was
estimated from the mass of precalcined coating assuming that
the initial coating was either pure Mg(OAc)2 or pure
Mg(OAc)2 · 4H2O. This data is also included in Figure 3b. With
the exception of the value for 50 coats, the measured values
correspond very closely to those for Mg(OAc)2 · 4H2O, which
indicates that the original coating is reacting with atmospheric
moisture leading to the hydrate form. Also worth noting is that
the catalyst mass for the catalyst with 50 coats is higher than
both estimates (which is not possible) and therefore is question-
able. The specific activity of the magnesium oxide coating was
obtained by regressing the data (excluding the data point for
50 coats) to obtain a value of 178 mmol/(L min gMgO). The
regression line was extrapolated to illustrate that the estimated
mass of MgO (based on Mg(OAc)2 · 4H2O) for the catalyst with
50 coats lies very close to the line obtained for the other data.
Therefore, any further analysis will use this estimated value
rather than the (apparently erroneous) measured value for the
mass of MgO on the catalyst with 50 coats.
The drawback of a thicker catalyst layer is the potential for
increased diffusional resistance as a result of longer pores. The
impact of pore diffusion on the rate of reaction is usually
quantified using the effectiveness factor, η:
rate of reaction with pore diffusion limitations
η) (5)
intrinsic rate of reaction
In general, η for an nth-order irreversible reaction is a function
of the dimensionless Thiele modulus, φ:29

V n + 1 (kmcat)CA
n-1
φ) (6)
S 2 De
where V ) volume of catalyst (m3), S ) external surface area
of catalyst (m2), n ) the order of the reaction (2 in this case),
k ) the intrinsic rate constant for the reaction in the absence of
diffusion (mol1-n/m3(1-n) min gcat), mcat ) mass of catalyst (gcat),
CA ) external concentration of reactant A (mol/m3), and De )
the effective diffusivity of the reactant/product in the pores of
the catalyst (m2/min). Although the functional relationship
between η and φ is complex, particularly for the complex shape
of the distillation saddles used in the present work, it is still
possible to examine the rate data to determine whether or not
pore diffusion is significant. In the case where pore diffusional
resistance is negligible, η f 1 and the observed rate of reaction
should remain constant:29
η2 (robs)2 k2
) ) )1 (7)
η1 (robs)1 k1
On the other hand, when there is strong pore diffusion resistance,
η f 1/φ and the ratio of observed reaction rates is inversely
proportional to the ratio of the Thiele moduli:29
η2 φ1
) (8)
η1 φ2
The volume of MgO on the surface of the saddle is given by
mcat/FMgO, where mcat is the mass of MgO coating on the saddles.
For the thin coatings present on the saddles, the external surface
area, S, will remain relatively constant. Finally, since CA and

De are constant, then, for the case of strong pore diffusional
resistance, eqs 6 and 8 combine to give
η2
( )()
mcat,1 k1
φ1 3/2 1/2
) ) (9)
η1 φ2 mcat,2 k2
Therefore, if there is significant pore diffusion resistance, the
ratio of effectiveness factors should be inversely proportional
to the mass of catalyst coating on the saddles.
The aldol condensation of acetone (eq 1) is second order in
acetone concentration (CAc) while the reverse reaction is first
order in DAA concentration (CDAA), yielding the following rate
expression:6
1 dCDAA
rDAA ) ) k1CAc2 - k2CDAA (10)
mcat dt
where k1 ) the rate constant for the forward reaction (L/(mol
min gcat)), k2 ) rate constant for the reverse reaction (min-1
gcat-1), and mcat ) mass of catalyst (gcat). At the start of a batch
run (t ) 0), the concentration of DAA is zero, and therefore
the second term in eq 10 disappears. Therefore, using the initial
rate of reaction allows eq 6 to be used even though the aldol
condensation reaction is reversible. The initial rate and the mass
of catalyst can be used together with the initial acetone
concentration (12.91 mol/L at 54 °C) to calculate the initial rate
constant (k1,0) for the forward reaction. The values of k1,0, as
well values of η/η20 and φ20/φ (i.e., the values for 20 coats were
used as the baseline) are summarized in Table 2. Both η and φ
were referenced to the values for the catalyst with 20 coats since
the initial reaction rate for the catalyst with 10 coats seems
artificially low.
If there were significant diffusional resistances within the
pores of the MgO coating, then eq 9 would apply and the ratio
of the effectiveness factors would decline rapidly according to
the values calculated in the last column in Table 2. However,
the ratio of the effectiveness factors remains relatively constant
with a value around one, indicating that eq 7 applies and that
pore diffusion has very little effect on the rate of reaction with
the coated catalyst. This analysis was performed assuming an
irreversible reaction (eq 6) when it was stated earlier that the
aldol condensation reaction is reversible (eq 1). However, in
the case of a reversible reaction, diffusional resistances within
the pores would result in lower effectiveness factors than the
irreversible case, and therefore the effects would be even more
pronounced.
The analysis to this point does not give any indication about
the durability of the coating. Although the catalyst produced
with 50 coats had the highest yield, its integrity was question-
able. A large portion of the coating layer flaked off upon addition
to the reactor. A similar effect was seen for the catalyst produced
with 40 coats, although to a lesser degree. This effect was likely
due to aging of the coating solution as the coating process
proceeded. Toward the end of the coating process, the coating
solution became much thicker and more viscous due to
evaporation and general consumption of the coating solution.
This caused more coating to be deposited per dip, which in turn
led to a large excess of coating; particularly for the last batch
(i.e., 50 coats). The catalysts produced with 30 coats or less
did not exhibit this flaking behavior and remained intact even
after 7 h of use in the batch reactor. Therefore, the optimum
number of coats in the batch reactor was 30 coats at a
withdrawal speed of 1.25 mm/s. This recipe was used for the
remainder of this work to produce the coated saddles.
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9309
Table 2. Effect of Coating Mass on Catalyst Effectiveness Factor
no. of MgO mass k1,0 × 1000 η/η20 ) φ/φ20
coats (g) (L/(mol min gcat)) k/k20 (eq 9)
10 0.0190 0.273 0.32 1.61
20 0.0179 0.844 1.00 1.00
30 0.0318 0.803 0.95 0.43
40 0.0667 1.206 1.43 0.12
50 0.1907a 1.066 1.26 0.03
a
This is the catalyst mass estimated from the original mass of
coating, assuming that the coating was Mg(OAc)2 · 4H2O.
3.3. Catalytic Performance of Coated Saddles. Once the
procedure for producing the coated saddles (i.e., 30 coats) was
finalized, the catalytic performance of the saddles was studied
further. The performance of the coated saddles in a batch reactor
(92 saddles, 30 coats) is shown in Figure 4. The number of
saddles loaded to the batch reactor was doubled to 92 saddles
(vs 46 saddles in the previous section) in order to reduce the
time required for completing the experiment. Also, these
experiments were performed using neutralized acetone (see
section 2.1) to reduce the effects of deactivation. The data from
one of the batch reactor experiments of Podrebarac et al.6,30
for the strongly basic macroporous anion exchange resin
Amberlite IRA-900 is included in Figure 4 for comparison.
The resin catalyst used by Podrebarac et al.6,30 exhibits a
higher conversion of acetone, although the majority of the
increased conversion arises from the production of byproduct
MO rather than DAA. Since the dehydration of DAA to MO is
acid catalyzed, the use of un-neutralized acetone (i.e., acetone
containing trace acetic acid) could neutralize some of the basic
sites on the resin, and the trace acetic acid could potentially
increase the conversion of DAA to MO. In any case, the resin
catalyst does reach the equilibrium conversion to DAA much
faster than the coated saddles, implying a higher activity. In an
effort to compare the activities of these two catalysts, the initial
rates of the reaction are summarized in Table 3. The turnover
frequency (TOF) for each catalyst is also included in Table 3.
The number of basic sites present on the coated saddles was
estimated assuming a basic site density of 0.15 mequiv/g as
measured by Matsuda et al.31 for MgO derived from Mg(OAc)2.
This method of calculating TOF assumes that all sites present
on the catalyst are of equal activity for the aldol condensation
reaction. The TOF for the coated saddles are 2 orders of
magnitude higher than those for the resin catalyst, suggesting
stronger basic sites on the MgO coating than on the ion exchange
resins. The higher initial reaction rate of the resin catalysts is
therefore likely due to a much larger number of basic sites
present in the reactor. Since the ion exchange resins are not
stable beyond 60 °C, it is not possible to use temperature-
programmed desorption of CO2 to compare the distribution and
strength of the basic sites of the coated saddles and the resins.
Therefore, further discussions on the effect of basic site strength
and density on the relative rates of these two different types of
catalysts are not warranted.
In terms of the selectivity of the catalyst toward DAA, Figure
4b indicates that the coated saddles are significantly more
selective to DAA than the resin catalysts. The most likely reason
for this difference in selectivity is the difference in the porosity
of the two catalysts, although the acidity in the un-neutralized
acetone used by Podrebarac et al.6 may result in increased MO
production. According to Podrebarac et al.,6 diffusional limita-
tions cause the concentration of DAA within the pores of the
resin catalyst to remain at the equilibrium value even if the bulk
concentration is not. This leads to increased production of MO
since the active sites within the pore are exposed to a higher
concentration of DAA. The coated saddles, on the other hand,
9310 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008

Figure 4. Comparison of the acetone conversion and DAA selectivity of the coated saddles (92 coated saddles, 30 coats, neutralized acetone, Ar atmosphere)
and the resin catalyst of Podrebarac et al.6,30 (Amberlite IRA 900 macroporous resin, 2 mL resin, 0.49 mmol H+/mL Resin, un-neutralized acetone, air
atmosphere) at 54 °C.

Table 3. Comparison of the Initial Rate of DAA Production and the

Turnover Frequency (TOF) for the Coated Saddles and the Resin
Catalyst Used by Podrebarac et al.6,30 (Batch Reactor, 100 mL
Acetone at 54 °C)
initial rate
(mmol/ (mmol/ no. of sitesa TOFb
catalyst L · min) (L min gcat)) (mequiv) (min-1)
current work
(92 saddles, 30 coats)
23b (0.0640 g MgO) 17.5 273 0.0096 182
23c (0.0539 g MgO) 21.6 401 0.0081 268
24a (0.0940 g MgO) 28.5 303 0.0141 202
24b (0.0563 g MgO) 16.0 284 0.0084 189
resin catalyst6,30 (Amberlite IRA
900, 2 mL resin, 0.49 mmol/mL)
expt 5 61.7 0.98 6.29
expt 6 60.8 0.98 6.21
expt 7 60.0 0.98 6.12 Figure 5. Mass of DAA and MO in the reboiler as a function of time for
a CD run 1 (reboiler set at 85 V, 230 saddles with 30 coats, 500 mL of acetone
The number of base sites for the coated saddles was estimated charged to the reboiler).
assuming a basic site density of 0.15 mequiv/g as measured by Matsuda
et al.31 for Mg(OAc)2 derived MgO. b TOF ) turnover frequency based
on the initial rate. the results and operating conditions for each run are summarized
in Table 4. The productivity (in g/h) remained constant over
do not experience such a phenomenon since as previously the first 12 h of each experiment, and therefore these can be
discussed (section 3.2), there are essentially no diffusional taken as pseudo-steady-state values. These pseudo-steady-state
limitations within the pores of the coated saddles. Concentrations values were converted to conversion (X), yield (Y), and
of DAA within the pores will not likely increase to the same selectivity (S)27 per unit time (see eqs 2-4), and the results are
extent as in the resin catalyst resulting in improved selectivity shown in Figure 6.
toward DAA with the coated saddles. 3.4.1. DAA Productivity. According to the data in Table 4
3.4. Batch CD Column Experiments. The performance of and Figure 6, the coated saddles have higher absolute production
the coated saddles was measured in a batch CD column at three rates of DAA at lower flow rates within the column. It is only
different reboiler settings: 55, 70, and 85 V. For each experi- once the flow in the column exceeds 13 g/min that the yield of
ment, a fresh batch of coated saddles was produced. As DAA from the resin catalysts exceeds that produced from the
anticipated, the temperature in the reboiler rises steadily coated saddles. This is in stark contrast to the results observed
throughout the experiment as a result of increasing concentra- with the batch reactor, where the resin catalysts significantly
tions of DAA and MO. The temperatures within the reaction out produced the coated saddles.
zone did not vary with time by more than 0.2 °C for any of the In an attempt to understand the observed productivity of these
runs, indicating a pseudo-steady state within the column despite two catalysts in the CD column, the TOF obtained in the CD
the composition changes occurring in the reboiler. column was divided by the mean TOF obtained in the batch
The results of the first experiment at 85 V are shown in Figure reactor studies (see section 3.3), and these results are included
5. The mass of both DAA and MO in the reboiler increases in Table 4. Neither catalyst achieved the same TOF as was
linearly with time over the 12 h of the experiment. Both data observed in the batch reactor. This suggests external mass
sets were regressed (with a forced intercept of 0), and the results transfer is a limiting factor in the CD column at the flow rates
of the regressions are included in Figure 5. The slopes obtained used in the CD runs. This is not surprising since external mass
from these regressions give the productivity (in g/h) of each of transfer resistances were eliminated in the batch reactor experi-
the two products. This same analysis was repeated for all batch ments by providing adequate mixing. The effect of the external
CD experiments, including those of Podrebarac et al.,10,30 and mass transfer in the CD column is much more pronounced in
 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9311
Table 4. Summary of CD Operating Data and Productivities for the Coated Saddles and Ion Exchange Resin6,30 Catalysts
productivity (g/h)
reboiler reflux flow catalyst reaction zone no. of sitesa TOF TOFCD/
catalyst setting (V) (g/min) volume (mL) volume (mL) DAA MO (mequiv) (min-1) TOFbatchb (%)
coated catalyst 55 5.59 43.7 43.7 6.09 0.18 0.0211 41.4 19.7
(230 saddles, 30 coats)
70 9.01 43.7 43.7 12.3 0.23 0.0211 83.7 39.9
85 13.3 43.7 43.7 12.0 0.15 0.0211 81.7 38.9
85 13.3 43.7 43.7 11.4 0.24 0.0211 77.6 36.9
resin catalyst6,30 55 5.49 20.5 55.7 2.22 2.94 10.0 0.0317 0.5
65 8.76 21.8 55.7 5.05 4.01 10.7 0.0678 1.1
75 12.27 21.4 55.7 13.2 5.81 10.5 0.181 2.9
85 16.36 23.3 55.7 35.9 7.54 11.4 0.451 7.3
a
The number of sites for the coated saddles was estimated using the mean mass of catalyst/saddle from Table 3 as well as the assumed 0.15 mequiv/
g basic site density.31 b The mean value of the TOF values for the batch reactor was used to make this calculation.

proportion of the total flow were to contact the catalyst, then

Figure 6. Yield and selectivity of DAA for the coated saddles and ion
exchange resins6,30 in a batch CD column as a function of reflux flow.
the case of the resin catalysts as indicated by the much lower
yield of DAA and the lower percentage of the maximum TOF
obtained in the CD column. This effect is magnified at lower
flow rates in the CD column where the mass transfer rates are
reduced. The primary goal of synthesizing the coated saddles
was to improve external mass transfer within the reaction zone
of a CD column. These results indicate that indeed the coated
catalytic saddles improved the external mass transfer in the
reaction zone, leading to improved reaction rates.
It should also be noted that at higher flow rates the per-
formance of the coated saddles reaches a plateau. For flow rates
above 9.0 g/min, neither the yield of DAA nor the TOF
increases. This suggests that the external mass transfer has
reached its maximum and that the reaction rates are kinetically
limited rather than mass transfer limited. However, despite being
kinetically controlled, the TOF obtained within the CD column
is still much lower than that observed in the batch reactor.
Possible explanations for this phenomenon include liquid
distribution and the wall effect in the CD column in addition to
the differences in the hydrodynamics between the batch reactor
and the CD column. According to Porter and Templeman,32
for pilot and laboratory scale columns, a significant portion of
the total flow in the column will be along the wall region rather
than on the packing. In this study, the ratio of column diameter
(1 in.) to saddle size (1/4 in.) is 4:1, which according to Porter
and Templeman32 would result in >70% of the total flow along
the wall region (i.e., not flowing over the catalyst). If a larger
one would expect the productivity to increase, resulting in an
increase in the TOF. This could be one of the reasons for the
lower TOF observed for the coated saddles in the CD column
than those in the batch reactor despite being kinetically
controlled.
It should also be noted that the fiberglass bags used by
Podrebarac et al. are the first generation of physical structures
used for loading catalyst particles such as ion exchange resins
into a CD column. Newer packings such as structured catalytic
distillation packings overcome some of the external mass
transfer limitations presented by the fiberglass bags. Therefore,
such next generation packing structures would likely result in
increased production of DAA at lower flow rates, although to
what extent is unknown.
3.4.2. DAA Selectivity. The selectivity toward DAA for both
the resin catalysts and the coated saddles is also shown in Figure
6. Both catalysts show decreased selectivity to DAA in the CD
column relative to a batch reactor. In the case of the coated
saddles, the selectivity in the batch reactor exceeded 99.5% for
conversions below the equilibrium conversion to DAA. How-
ever, in the CD column the selectivity ranged from 96.6% to
98.5%. In the case of the resin catalysts the selectivity in the
CD column ranged from 38.9% to 80.1%, compared to
91.5%-94.4% in the batch reactor at equilibrium conversion
to DAA. Both catalysts showed increases in selectivity with
higher flow rates in the column, indicating that the selectivity
is sensitive to changes in mass transfer. Even for the coated
saddles, the selectivity increases as the flow rate in the column
increases albeit to a lesser degree. The improved mass transfer
characteristics of the coated saddles resulted in selectivities much
closer to those obtained in the batch reactor. Therefore, the
enhanced mass transfer characteristics of the coated saddles
compared to the resin catalyst held in fiberglass bags do lead
to significant improvements in selectivity to DAA in the CD
experiments.
3.4.3. Deactivation. As indicated previously, deactivation is
a major concern for any basic catalyst used for the aldol
condensation of acetone. Results of the batch CD experiments
for the coated saddles, however, showed very little sign of
deactivation over the first 12 h of operation as indicated by the
linearity of both the DAA and MO production data. In order to
assess the stability of the coated saddles, two of the four batch
CD experiments were carried out for 24 h (one run at 85 V and
the run at 55 V). The results of these extended runs are shown
in Figure 7. The regression lines obtained using the first 12 h
of data were extended to determine whether the productivity
remained constant after 24 h.
In both cases, the productivity of MO did not remain constant
over 24 h of operation, indicating some deactivation. As for
9312 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Figure 7. DAA and MO yield with coated saddles after 24 h in a batch CD column.
the productivity of DAA, the run at 55 V remained constant
while the run at 85 V showed a slight decline after 24 h.
Therefore, it appears slight deactivation is occurring in the CD
column based on the very limited data. Podrebarac et al.10 also
observed a similar decline in MO productivity with time, and
they attribute this to the formation of higher molecular weight
products due to further condensation reactions involving MO
on the catalyst surface.9 The fact that MO is a precursor to the
deactivation could explain why the effects of deactivation are
more prevalent in the formation of MO than DAA. However,
more experiments at much longer reaction time are required
before any conclusions could be made regarding the apparent
deactivation.
Another major concern when using the coated saddles is the
potential for the MgO coating to erode and leach from the saddle
substrate leading to catalyst in the reboiler. As mentioned
previously, the aldol condensation of acetone is an equilibrium-
limited reaction. At 54 °C, the equilibrium concentration of
DAA is 4.3 wt %.6 During the batch CD experiments, the
temperature in the reboiler ranged between 55.2 and 63.5 °C.
At these temperatures, the equilibrium concentration of DAA
should be less than 4.3 wt %. However, the concentration of
DAA in the reboiler exceeded this equilibrium value after only
2 h for experiments at 85 V and after 3 h at 55 V. At this point,
any possible MgO catalyst in the reboiler will catalyze the
reverse reaction (i.e., the decomposition of DAA to form
acetone). As the concentration of DAA in the reboiler increases,
the rate of this reverse reaction would increase. If there were
significant amounts of catalyst in the reboiler due to leaching
from the coated saddles, the decomposition of DAA would result
in a decrease in DAA productivity rather than the observed
increase in DAA concentration. The fact that the productivity
of DAA continued for 24 h indicates that very little (if any) of
the coating layer was removed from the saddles over the course
of the experiment. As well, no solids were observed in the
reboiler when the experiment was terminated, further supporting
the claim that the coating did not leach off during the course of
the experiment. Whether or not the coating could remain intact
under our CD experimental conditions for periods significantly
longer than 24 h is unknown.
4. Conclusions
A method has been developed for the production of catalyti-
cally active coated ceramic distillation saddles for use in CD.
Mg(OAc)2 was deposited onto ceramic Norton saddles using a
sol-gel dip coating method followed by calcination to produce
a catalytically active MgO layer. The initial rate of production
of DAA increases proportionally with the mass of coating, and
hence there is incentive to deposit as much coating mass as
possible. However, the durability of the coating degenerates with
an increase in the mass of coating, resulting in a tradeoff
between yield and durability. The durability of the coating is
also significantly affected by the calcination method used and
requires slow temperature ramping during both heating and
cooling to ensure adequate structural integrity of the catalytic
coating.
The initial rate of DAA production of the coated catalyst
saddles in a batch reactor was significantly lower than that for
the ion-exchange resin catalyst used by Podrebarac et al.6 but
with a much higher selectivity to DAA. The coated saddles are
much more active than the ion exchange resins based on
calculated TOF. The higher rates exhibited by the resins likely
resulted from the much higher concentrations of basic sites on
the resins. Despite having much lower concentrations of basic
sites, the coated saddles performed very well in a CD column.
The coated saddles do not experience the severe mass transfer
limitations that were encountered by the resin catalyst held in
fiberglass bags. At lower flow rates in the CD column, the coated
catalysts produce more DAA than the resin catalysts held in
the fiberglass bags. At higher column flow rates, however, the
resin catalysts held within fiberglass bags benefit from improved
mass transfer, resulting in a higher production of DAA than
the coated saddles. The coated saddles however provided a
higher selectivity to DAA than the resin catalysts in the CD
experiments due to the reduced external mass transfer resistance
and the intraparticle diffusional limitations of the resins.
Therefore, coated catalytic saddles would be particularly
advantageous for reaction systems where high selectivity is
required.
Slight deactivation of the coated saddles apparently occurred
in the CD experiments when operated for extended periods (i.e.,
24 h) while the productivity of both DAA and MO over a 12 h
period remained constant. Erosion of the coated catalyst did
not occur over the 24 h of CD experiments.
Acknowledgment
The authors acknowledge the financial support of the Natural
Sciences and Engineering Research Council of Canada (NSERC)
in the form of research grants and a scholarship for Greg
Dechaine.

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ReceiVed for reView January 2, 2008
ReVised manuscript receiVed September 14, 2008
Accepted September 23, 2008
IE800009U