9
Synthesis of methyl isobutyl ketone from acetone over metal-doped ion exchange resin catalyst Sandip Talwalkar, Sanjay Mahajani * Department of Chemical Engineering, Indian Institute of Technology Bombay, Powai, 400076 Mumbai, India Received 21 September 2005; received in revised form 29 December 2005; accepted 4 January 2006 Available online 14 February 2006 Abstract The kinetics of one-step synthesis of methyl isobutyl ketone from acetone was studied in the presence of the bifunctional commercial ion exchange resin, Amberlyst CH28 over a wide range of temperature, total pressure and catalyst loading in a batch reactor. An activity-based kinetic model is proposed to predict the observed results, with the non-idealities of the liquid phase being described using the UNIQUAC method. Formation of mesityl oxide was found to govern the overall rate of reaction. Low reaction rates were observed at higher conversion, possibly due to a pseudo-equilibrium caused by reversible deactivation of the catalyst as a result of formation of water in the reaction system. Simultaneous removal of water during the course of the reaction may result in an enhanced conversion. # 2006 Elsevier B.V. All rights reserved. Keywords: Methyl isobutyl ketone; Bifunctional catalyst; Hydrogenation; Ion exchange resin; Acetone; Mesityl oxide 1. Introduction Cation exchange resins are popular solid acid catalysts for liquid phase reactions conducted under relatively mild conditions. Some excellent reviews on catalysis by cation exchange resin have appeared in the past [1,2]. However, not much information is available on catalysis with a bifunctional ion exchange resin catalyst, as it is a relatively new field. Multiple reactions involving acid catalysts followed by hydrogenation or dehydrogenation and vice versa are com- monly encountered in many industrial processes. If the conditions for both the reactions are overlapping, one can advantageously perform them in a single step with a bifunctional catalyst. Aldol condensation followed by hydro- genation of dehydrated aldol is an important class of these reactions [3–5] for which such a bifunctional catalyst can be a potential candidate. An industrially important reaction of aldol condensation of acetone, followed by hydrogenation to methyl isobutyl ketone, has been studied in the present work. Methyl isobutyl ketone is a widely used solvent in the pharmaceutical, coating and mining industries. It is also used in the manufacture of rubber antiozonants. Its synthesis from acetone in the presence of acidic and hydrogenation catalyst consists of three reaction steps. They are as follows: Reaction 1: Reaction 2: Reaction 3: Several references in the form of communications, research articles and patents are available in the literature on the synthesis of methyl isobutyl ketone from acetone. www.elsevier.com/locate/apcata Applied Catalysis A: General 302 (2006) 140–148 * Corresponding author. Tel.: +91 22 25767246; fax: +91 22 25726895. E-mail address: [email protected] (S. Mahajani). 0926-860X/$ – see front matter # 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2006.01.004

Synthesis of methyl isobutyl ketone from acetone over metal-doped ion exchange resin catalyst

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Page 1: Synthesis of methyl isobutyl ketone from acetone over metal-doped ion exchange resin catalyst

www.elsevier.com/locate/apcata

Applied Catalysis A: General 302 (2006) 140–148

Synthesis of methyl isobutyl ketone from acetone over

metal-doped ion exchange resin catalyst

Sandip Talwalkar, Sanjay Mahajani *

Department of Chemical Engineering, Indian Institute of Technology Bombay, Powai, 400076 Mumbai, India

Received 21 September 2005; received in revised form 29 December 2005; accepted 4 January 2006

Available online 14 February 2006

Abstract

The kinetics of one-step synthesis of methyl isobutyl ketone from acetone was studied in the presence of the bifunctional commercial ion

exchange resin, Amberlyst CH28 over a wide range of temperature, total pressure and catalyst loading in a batch reactor. An activity-based kinetic

model is proposed to predict the observed results, with the non-idealities of the liquid phase being described using the UNIQUAC method.

Formation of mesityl oxide was found to govern the overall rate of reaction. Low reaction rates were observed at higher conversion, possibly due to

a pseudo-equilibrium caused by reversible deactivation of the catalyst as a result of formation of water in the reaction system. Simultaneous

removal of water during the course of the reaction may result in an enhanced conversion.

# 2006 Elsevier B.V. All rights reserved.

Keywords: Methyl isobutyl ketone; Bifunctional catalyst; Hydrogenation; Ion exchange resin; Acetone; Mesityl oxide

1. Introduction

Cation exchange resins are popular solid acid catalysts for

liquid phase reactions conducted under relatively mild

conditions. Some excellent reviews on catalysis by cation

exchange resin have appeared in the past [1,2]. However, not

much information is available on catalysis with a bifunctional

ion exchange resin catalyst, as it is a relatively new field.

Multiple reactions involving acid catalysts followed by

hydrogenation or dehydrogenation and vice versa are com-

monly encountered in many industrial processes. If the

conditions for both the reactions are overlapping, one can

advantageously perform them in a single step with a

bifunctional catalyst. Aldol condensation followed by hydro-

genation of dehydrated aldol is an important class of these

reactions [3–5] for which such a bifunctional catalyst can be a

potential candidate. An industrially important reaction of aldol

condensation of acetone, followed by hydrogenation to methyl

isobutyl ketone, has been studied in the present work.

Methyl isobutyl ketone is a widely used solvent in the

pharmaceutical, coating and mining industries. It is also used in

the manufacture of rubber antiozonants. Its synthesis from

* Corresponding author. Tel.: +91 22 25767246; fax: +91 22 25726895.

E-mail address: [email protected] (S. Mahajani).

0926-860X/$ – see front matter # 2006 Elsevier B.V. All rights reserved.

doi:10.1016/j.apcata.2006.01.004

acetone in the presence of acidic and hydrogenation catalyst

consists of three reaction steps. They are as follows:

� R

eaction 1:

Reaction 2:

Reaction 3:

Several references in the form of communications,

research articles and patents are available in the literature

on the synthesis of methyl isobutyl ketone from acetone.

Page 2: Synthesis of methyl isobutyl ketone from acetone over metal-doped ion exchange resin catalyst

S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148 141

Nomenclature

ai activity of component i

E8 activation energy for reaction (kJ/mol)

k8 rate constant for reaction (kmol/(s gcat))

kwtr adsorption coefficient of water

kact adsorption coefficient of acetone

MCAT mass of the catalyst (g)

ni number of moles of component i

nAc,0 initial number of moles of acetone

nAc,f number of moles of acetone at any time t

r rate of reaction (kmol/s)

S selectivity towards methyl isobutyl ketone

T Temperature (K)

xi liquid mole fraction of component i

X conversion of acetone

Greek letters

yi stoichiometric coefficient for component i

F objective function for optimisation

However, the use of bifunctional catalyst for one-step

synthesis is gaining importance and substantial work has

been reported with different metals from Groups VIII and

IB of the Periodic Table like Pd, Cu and Pt on acid supports.

Table 1 gives a review on the previous studies on this system

with bifunctional catalysts. It is clear from Table 1 that

Pd is the most widely used metal for this system with almost

all types of acid/base catalytic supports like alumiosi-

licates, zeolites, metal oxides and ion exchange resins.

Different catalysts, like Pd-ZSM-5 [24], Pd–C–Nb2O5

[12,13] and Pd–CuO/MgO/SrO [8] in liquid phase and Pd-

H-ZSM-5 [37], Cu–MgO [26] and Pd-CS-H-ZSM-5 [16] in

gas phase, have been studied. They show conversions of

acetone in the ranges 20–40% and 40–60% and selectivity

towards methyl isobutyl ketone of �90% and 30–80%,

respectively. It is reported that the catalyst used in the

present work gives a conversion as high as 50% with 90%

selectivity towards methyl isobutyl ketone in a liquid phase

reaction [45]. The supports other than ion exchange resins

need pre-treatment; indeed, the performance of these

supports is sensitive to the method and conditions of the

pre-treatment. Moreover, the reaction conditions are more

severe than those with ion exchange resins without much

improvement in conversions and selectivities. Ion exchange

resins are more popular than traditional supports for low

temperature operations due to the ease of separation, less

pre-treatment and high acid strength. A commercial

bifunctional ion exchange resin, Amberlyst CH28, has been

designed for such performance and has been investigated in

the present work.

Ion exchange resin can be loaded with desired metal ions by

contacting an aqueous solution of the metal ion with the

hydrogen form of the cation exchange resin in a batch or

continuous mode. Typically, the metal ion will be provided in

the form of a metal salt, such as chlorides, bromides, nitrates,

sulphates and acetates. The detailed procedure for preparation

for such catalysts can be found elsewhere [9].

In spite of a lot of literature on the present system, very little

work is reported on commercial metal-ion exchange resins as a

catalyst. Nicol and du Toit [45] have successfully performed

reactions with the same catalysts in a laboratory-scale trickle

bed reactor. A couple of patents from Catalytic Distillation

Technologies [50–53] claim the use of catalytic distillation for

enhanced conversion of acetone to methyl isobutyl ketone

preferably catalysed by metal-ion exchange resin as a catalyst.

Systematic kinetic studies and a reliable kinetic model are

necessary to design an industrial reactor; the present work is

undertaken to provide inputs in this regard.

2. Experimental

2.1. Materials

Acetone (99.5%), methyl isobutyl ketone (99%) and

methyl ethyl ketone (99.5%) were obtained from Merck Ltd.,

India. Rohm and Haas, France, supplied the catalyst

Amberlyst CH28. The properties of catalyst are given in

Table 2. Before its use, the catalyst was dried in an oven at

353 K for 3 h.

2.2. Apparatus and procedure

A stainless steel autoclave from Parr Instrument Company,

USA, with a capacity of 3 � 10�4 m3, equipped with an online

temperature monitoring and control facility was used for

conducting all the batch reactions. Before feeding to the

reactor, each catalyst was washed with acetone in order to

remove the moisture present, if any. The desired quantities of

the catalyst and reactants (100 g of acetone in all runs) were

charged to the reactor. The reactor and gas lines were flushed

with hydrogen in order to remove the air present in the empty

space in the reactor and lines. The reaction mixture was heated

up to the desired temperature with slow stirring. As the

reaction temperature was reached, the speed of agitation was

increased up to the desired level and the corresponding time

was regarded as the zero reaction time. The samples were

withdrawn at different time intervals to study the kinetics of

the reaction. In all the runs, the reaction volume was about

8 � 10�5 m3.

2.3. Analysis

The reactants and products were analysed using a gas

chromatograph (GC-MAK-911) equipped with a flame ionisa-

tion detector (FID). A 25 m long capillary column BP-1 (SGE,

Australia) was used to separate the different components in the

reaction mixture using methyl ethyl ketone as an external

standard. The column temperature was maintained at 373 K

isothermally. The various components in the reaction mixture

and the separated products were characterized by authentic

samples.

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S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148142

Table 1

Previous work for one-step synthesis of methyl isobutyl ketone from acetone

Catalyst Pressure (atm) T (K) Conversion (%) Selectivity (%) Reference

Pd-KUZ 20 393 50 94.5 [6]

Pd–CuO/Al2O3/SiO2 1 423–503 30 60 [7]

Pd–CuO/MgO/SrO 20 433 38.5 93.6 [8]

Pd–Nb2O5–Al2O3 – – 28 90 [9]

Pd-oxides of Ti, Zr, Cr 10 413 33.9 92.3 [10]

Pd-KUZFPP 30 353–388 – – [11]

Pd–C–Nb2O5 20 413 39.5 92.5 [12]

Pd–C–Nb2O5 10 413 30 91.7 [13]

Pd-oxides of Ce, Hf, Ta 10 413 33 90.2 [14]

Pd-IER 40 363–393 - – [15]

Pd-CS-H-ZSM-5 1 523 41.9 82.4 [16]

Pd–Nb2O5 – – 41.8 93.5 [17]

Pd-oxides of Zr – – 27 94.9 [18]

Pd-KS-IER 50 373–403 - 90 [19]

Pd-ZSM-5 50 443 40.25 95.36 [20]

Pd-IER – – – – [21]

Ni, Cu, Co-g-a-Al2O3 – 453 53.9 37.1 [22]

Ni–Al2O3 1 373 – 95 [23]

Pd-ZSM-5 SiO2/Al2O3 = 30 6–60 433 41.24 90.98 [24]

Ni–CaO – 473 70–80 60 [25]

Cu–MgO 1 653 60–80 60–75 [26]

Pt-HMF 1 433 – – [27]

Ni–CaO – – 60–80 50–60 [28]

Pd–AIPO4-II, SAPO4 – – – – [29]

Ni–Al phosphate – – – – [30]

Pd-(Zn)-H-ZSM-5 5 408–483 55 83–94 [31]

Pd–Nb2O5–SiO2 – – 30–35 88–92 [32]

Ni–CaO – – 60–70 70 [33]

Pd–Al2O3 40–90 413–473 – – [34]

Pt-H-ZSM-5 1 433 – – [35]

Pt-NaX – 713 – 70 [36]

Pd-H-ZSM-5 1 473 47.3 30.7 [37]

Pd-IER 40–70 353–373 – – [38]

Cu–MgO–Al2O3 – – 65.26 57.49 [39]

Pd-zeolite – – 70 87.5 [40]

Pd-IER – 403 43.2 98.2 [41]

Pt-Sn-H-ZSM-5 1 433 – – [42]

Pd–C 1-20 333 – – [43]

Pd–Ca–Al2O3 - - – – [44]

Amberlyst CH28 30 403–423 25–50 70–90 [45]

Pd-IER 5–15 373–453 – – [46]

Pd-MCM-56 – – 33.5 81.2 [47]

Pd-MCM-49 – – 35.6 85 [48]

Cu–MgO–Al2O3 1 513 71.7 50.1 [49]

Table 2

Physical properties of Amberlyst CH28 [59]

Property Value

Matrix Styrene DVB polymer

Physical form Spherical beads

Total capacity (mequiv./g dry basis) 4.8

Palladium loading (% dry basis) 0.7

Specific surface area (m2/gm) 36

Pore diameter (A) 260

Temperature stability (K) 403

Harmonic mean size (mm) 0.85–1.05

Moisture content in wet form (%) 52–58

2.4. Calculations for conversion and selectivity

The conversion of acetone was calculated as

X ¼ nAc;0 � nAc;fnAc;0

(1)

while the selectivity towards methyl isobutyl ketone was

calculated as

S ¼ 2nMIBK

nAc;0 � nAc;f(2)

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S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148 143

Fig. 2. Effect of speed of agitation on reaction kinetics. Temperature = 413 K;

catalyst loading: 5% w/w of acetone; pressure = 30 bar; speed in rpm.

3. Results and discussion

3.1. General course of the reaction

As mentioned earlier, we define the zero reaction time as the

time at which the desired temperature is attained. Hence, in all

the kinetic runs, we observe a small extent of reaction that

occurred before the desired temperature was reached. The

extent of reaction during this heat-up period was found to be

relatively higher at higher catalyst loadings and temperature.

Fig. 1 shows typical profiles of mole fractions of acetone and

methyl isobutyl ketone with respect to time. The concentration

of water is the same as the concentration of methyl isobutyl

ketone and is not shown in Fig. 1. It should be noted that the

concentrations of intermediates, diacetone alcohol and mesityl

oxide, were below the detectable limits.

3.2. Mass transfer effects

In order to ensure that there is no significant external mass

transfer resistance across the solid–liquid and gas–liquid

interfaces, the reactions were performed at different stirrer

speeds over a range 600–1700 rpm. It was observed that the

reaction kinetics is insensitive to agitation above 1000 rpm, as

shown in Fig. 2, and hence all the reactions were performed

above 1000 rpm.

3.3. Comparisons of the rates of individual steps

In all the experiments, we have observed very little or no

intermediate products, i.e., mesityl oxide and diacetone

alcohol. Therefore, it was assumed that rapid dehydration of

diacetone alcohol leads to formation of mesityl oxide, which in

turn instantaneously gets converted to methyl isobutyl ketone in

the presence of hydrogen. To compare the rates of mesityl oxide

Fig. 1. General course of the reaction. Temperature = 393 K; catalyst loading:

5% w/w of acetone; pressure = 30 bar.

and methyl isobutyl ketone formation, we performed a run in

the absence of hydrogen for 50 min. The samples were

collected up to 50 min and hydrogen was introduced to the

reactor at this time at 30 bar. Fig. 3 shows that, as soon as

hydrogen was fed to the reactor, the concentrations of mesityl

oxide and diacetone alcohol dropped instantaneously to almost

zero and the methyl isobutyl ketone concentration builds up

sharply. This suggests that the hydrogenation is much faster

than both the intermediate reactions and practically no or very

little intermediate components were observed in the range of

parameters for which the kinetics of methyl isobutyl ketone

formation from acetone was generated on the bifunctional

Amberlyst CH28.

Fig. 3. Speed of hydrogenation reaction. Temperature = 393 K; catalyst load-

ing: 5% w/w of acetone; hydrogen injection at 3000 s at 30 bar.

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S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148144

Therefore, the overall reaction with the present catalyst is

given by

Fig. 3 also indicates that the rate of mesityl oxide formation is

very low even at low conversion levels, indicating that the

reaction rates are highly affected by equilibrium. Thus, the

simultaneous hydrogenation of mesityl oxide may help in

shifting the reaction in the forward direction by keeping the

mesityl oxide concentration at low level at any given time in the

reactor. Thus, complete conversion of acetone was expected in

the present work because of the removal of mesityl oxide in

hydrogenation reaction to of methyl isobutyl ketone. However,

low reaction rates were observed at higher conversion levels.

This may imply that the hydrogenation reaction is equilibrium-

limited and only equilibrium conversions can be obtained. How-

ever, Winter et al. [43] showed that 100% conversion mesityl

oxide in liquid phase could be possible on Pd/CNF catalyst. This

confirms that the observed low reaction rates onAmberlyst CH28

at higher conversion level are due to catalyst deactivation and not

because of reaction equilibrium. The overall reaction is thus a

pseudo equilibrium type as a result of deactivation of catalyst by

the moisture formed. More evidence of the same can be found in

the literature [54]. We confirmed this through the catalyst

deactivation experiments described in the next section.

3.4. Cause of catalyst deactivation

As discussed above, the catalyst gets deactivated during the

course of reaction, as a result of which low rates were observed

Fig. 4. Cause of catalyst deactivation. Temperature = 393 K; catalyst loading:

5% w/w of acetone; pressure = 30 bar.

at higher conversion levels of acetone. To find out the cause of

catalyst deactivation, the catalyst was separated from the

reaction mixture and dried in an oven at 353 K for 3 h and the

same catalyst was reused in the next run. This procedure was

repeated for next few runs. As shown in Fig. 4, the performance

of the used catalyst was almost identical to that of the fresh

catalyst. This indicates that the deactivation of catalyst is

reversible and that is caused by the presence of polar

components like water [1,2,55], which is produced in the

dehydration of aldol. Polar compounds like water have strong

affinity towards catalytic sites. In a relatively non-polar

environment, water molecules are known to adsorb on the

resin surface and cover the catalytic sites, thereby causing an

‘‘inhibition effect’’. As mentioned before, it should be noted

that the reaction becomes very slow in this region and the

kinetics, as shown in Fig. 1, looks similar to that of a reversible

reaction approaching equilibrium. Since in this case, true

thermodynamic reaction equilibrium is not attained, we call

this state a ‘‘pseudo-equilibrium’’. A detailed investigation of

the same has been reported in the literature for the reaction of

acetone to mesityl oxide on a mono-functional ion exchange

resin [54].

3.5. Effect of moisture concentration

In order to ascertain the exact role of water in the kinetics,

we performed experiments with and without water. As shown in

Fig. 5, we found that the presence of water in the reaction

Fig. 5. Effect of water addition. Temperature = 413 K; catalyst loading: 5% w/

w of acetone; pressure = 30 bar water concentration in wt.%.

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S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148 145

Fig. 6. Effect of temperature on reaction kinetics. Temperature in K; catalyst

loading: 5% w/w of acetone; pressure = 30 bar.

Fig. 7. Effect of temperature on selectivity towards methyl isobutyl ketone.

Temperature in K; catalyst loading: 5% w/w of acetone; pressure = 30 bar.

system is the true cause of the observed reversible catalyst

deactivation; hence, low rates of reaction are observed for the

reaction with initial moisture. This implies that the rate of

formation of mesityl oxide is affected due to inhibition of

sulfonic acid groups by polar components like water. This

phenomenon is well known for many reactions on ion exchange

resins. However, mesityl oxide formation is still followed by its

instantaneous hydrogenation to methyl isobutyl ketone. In

short, the rate of formation of methyl isobutyl ketone is equal to

the rate of formation of mesityl oxide as in the case without

moisture. This suggests that simultaneous removal of mesityl

oxide along with the removal of water by some means is

necessary to enhance the reactor performance further. There-

fore, one can regard this system to be a good candidate for

multifunctional reactor system like reactive distillation or

reactive adsorption. As mentioned before, except for few

Fig. 8. Effect of catalyst loading on (a) reaction kinetics (b) initial rate. Tem

references [50–53] not much work has been reported in the

literature on this aspect.

3.6. Effect of temperature

The effect of temperature was studied over a range of

373–413 K. Fig. 6 shows the conversion of acetone at different

temperatures. As expected, the conversion of acetone increases

with an increase in temperature at the cost of reduced selectivity

towards methyl isobutyl ketone, as shown in Fig. 7. At

relatively high temperatures, mesityl oxide is likely to react

with acetone to form heavy components like isophorone

and other condensation products. Nicol and du Toit [45]

evaluated the thermal stability of the present catalyst for

the same reaction, and reported that the catalyst is stable

up to 423 K.

perature = 393 K; catalyst loading: in w/w of acetone; pressure = 30 bar.

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S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148146

3.7. Effect of catalyst loading

The reactions were performed at different catalyst loadings

(2–12% w/w of acetone) and it was observed that the rate of

reaction increases when the catalyst loading was increased from

2% to 5%w/w of acetone. However, the rate of reaction reaches

saturation above the catalyst loading of 5% w/w of acetone, as

shown in Fig. 8. Moreau et al. [56] have reported such non-liner

influence of catalyst loading on the rate of hydrolysis of acetals

over H-montmorillonite and strong cation exchange resin. It is

expected that the number of catalyst sites above a particular

catalyst loading becomes excessive and hence the rate becomes

insensitive to the further increase in the catalyst loading. We

believe this effect is not because of the diffusional limitations as

variables such as stirrer speed etc. do not influence the overall

rate of reaction under these conditions. In our opinion, such an

effect can be explained only through the rigorous thermo-

dynamic models of adsorption. A theoretical explanation for

the same is lacking in the literature though some evidences have

been reported [56].

3.8. Effect of hydrogen pressure

The solubility of hydrogen varies with pressure and hence

it may influence the reaction kinetics. In order to study the

effect of hydrogen pressure, we performed reactions over a

range of 15–45 bar. Interestingly, it was observed that there is

no effect of hydrogen pressure on the reaction kinetics, as

shown in Fig. 9. This finding again confirms that the catalyst

activity for hydrogenation is sufficient enough and that it is

the formation of mesityl oxide that governs the overall rate of

the reaction.

Fig. 9. Effect of hydrogen pressure on the reaction kinetics. Tempera-

ture = 393 K; catalyst loading 5% w/w of acetone; pressure in bar.

4. Kinetic modeling

O’Keefe et al. [57] proposed a mechanism for hydrogenation

of mesityl oxide to methyl isobutyl ketone. The mechanism

consists of five steps. In the first step, mesityl oxide adsorbs on

two adjacent sites to form a di-adsorbed species. In the second

step, hydrogen adsorbs dissociatively on two adjacent sites. The

adsorbed hydrogen atoms are then added stepwise to the di-

adsorbed mesityl oxide to give methyl isobutyl ketone, which

then desorbs from the catalyst surface to the bulk. The authors

have confirmed this mechanism by pulse adsorption of mesityl

oxide, which was monitored by diffuse reflectance infrared

spectroscopy and they proposed a model based on the

Langmuir–Hinshelwood approach. We assume that a similar

mechanism holds good for the present system. Acetone gets

adsorbed on two adjacent active acid sites and condenses to

give diadsorbed dimer, which then dehydrates to form di-

adsorbed mesityl oxide to give methyl isobutyl ketone in an

adsorbed state in a similar way to that discussed above. As

discussed before, we observed that the reaction is pseudo-zero

order with respect to the hydrogen concentration over the range

of pressure studied. The rate equation may be given by

r ¼ ka2actð1þ kwtrawtr þ kactaactÞ4

(3)

The adsorption term for the methyl isobutyl ketone was omitted

from the model, as O’Keefe et al. [57] found that there is no

effect on reaction kinetics when methyl isobutyl ketone was

added to the reaction mixture at time equal to zero. Also, the

parameter fitting with inclusion of this term gave us very low

values for the adsorption coefficient of methyl isobutyl ketone.

5. Parameter estimation

The mole balance for the batch reactor for all the

components can be written as

dnidt

¼ MCATyir (4)

The temperature dependency of the rate constant can be

expressed by the Arrhenius equation

k ¼ k0 exp

��E�

RT

�(5)

The objective function to be minimized is given as

minF ¼X

All samples

ðxi;calculated � xi;measuredÞ2 (6)

For optimisation, a SQP (Sequential Quadratic Programming)

approach from NAG library was used in the DIVA [58]

simulation environment. The non-idealities of liquid phase

were described using the UNIQUAC method and the thermo-

dynamic parameters were obtained from the data bank of the

commercial package ASPEN. Hydrogen solubility was pre-

dicted by using Henry’s law and interaction parameters to

calculate Henry’s constant were also taken from the commer-

cial package ASPEN. The estimated parameters for the kinetic

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S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148 147

Table 3

Kinetic parameters for proposed model

k8 (kmol/(g s)) 5.8714 � 107

E8 (kJ/mol) 97.60

Kwtr 4.22

Kact 2.58

f 2.3 � 10�3

Fig. 10. Comparison between modelled and measured conversion of acetone at

different temperatures. Temperature in K; catalyst loading: 5% w/w of acetone;

pressure = 30 bar.

Fig. 11. Comparison between modelled and measured conversion of acetone at

different values of catalyst loadings. Temperature = 393 K; catalyst loading: in

% w/w of acetone; pressure = 30 bar.

Fig. 12. Model predictions for effect of moisture conversion of acetone.

Temperature = 413 K; catalyst loading: 5% w/w of acetone; pressure = 30 bar,

moisture concentration in wt.%.

model are given in Table 3. As shown in Figs. 10 and 11, the

model captures the effect of parameters like temperature and

catalyst loading. It should be noted that the model is applicable

for catalyst loading up to 5% w/w of acetone, beyond which the

rate change is non-liner with catalyst loading (see Fig. 8). The

model was thus used to independently predict the performance

of a batch reactor with initial moisture present. The predicted

results are compared with the experimental ones in Fig. 12. The

model slightly over-predicts the rate in the presence of initial

moisture content. Another approach to capture the effect of

moisture by considering Freundlich adsorption of water [55]

was also applied. However, the fitting was worse by the latter

approach.

6. Conclusions

Kinetics of the one-pot synthesis of methyl isobutyl ketone

from acetone was studied. The effects of various parameters

like temperature and catalyst loading were investigated in

detail. It was observed that catalyst undergoes reversible

deactivation due to the formation of water in the condensation

reaction. As a result, lower rates are observed at higher

conversion levels of acetone, showing pseudo-equilibrium,

which was confirmed by independent reactions. About 45%

conversion of acetone with more than 95% selectivity towards

methyl isobutyl ketone was realised in about 3.5 h at 393 K.

This is promising, considering the performance of different

reported catalysts, like Pd-ZSM-5 [24], Pd–C–Nb2O5 [12,13],

Pd–CuO/MgO/SrO [8], Pd-H-ZSM-5 [37], Cu–MgO [26] and

Pd-CS-H-ZSM-5 [16] with 20–60% conversion of acetone and

30–90% selectivity towards methyl isobutyl ketone under

similar or even more harsh conditions. The pseudo-equilibrium

due to adsorption of water may be considered as a possible

Page 9: Synthesis of methyl isobutyl ketone from acetone over metal-doped ion exchange resin catalyst

S. Talwalkar, S. Mahajani / Applied Catalysis A: General 302 (2006) 140–148148

limitation of ion exchange resin catalyst. However, the

simultaneous removal of water during the course of reaction

will help to overcome this drawback. A kinetic model that

considers the adsorption of water on the catalyst is proposed

which satisfactorily explains the experimental observations.

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