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Ind. Eng. Chem. Res.

2003, 42, 3881-3885 3881

KINETICS, CATALYSIS, AND REACTION ENGINEERING

Kinetics of Liquid-Phase Hydrogenation of Furfuraldehyde to


Furfuryl Alcohol over a Pt/C Catalyst
Prakash D. Vaidya and Vijaykumar V. Mahajani*
Chemical Engineering Department, Institute of Chemical Technology, University of Mumbai,
Matunga, Mumbai-400019. India

The kinetics of the liquid-phase hydrogenation of furfuraldehyde to furfuryl alcohol over a 5%


Pt/C catalyst was studied in a slurry reactor. The solvent used was a mixture of 2-propanol and
water (12.4% w/w). At the temperatures (403-448 K) and pressures (1.03-2.06 MPa) studied,
all mass-transfer resistances (gas-liquid, liquid-solid, and intraparticle diffusion) were absent.
The initial rate data were analyzed using a power-law model. The initial rates increased almost
linearly with hydrogen concentration at all temperatures. The reaction showed a zeroth-order
dependence with respect to furfuraldehyde above a feed concentration of 0.13 kmol m-3. Below
this value, the order was found to be 0.86. Therefore, a Langmuir-Hinshelwood-type model for
a dual-site mechanism with molecular adsorption of all species was proposed, and this model
provided the best fit of the experimental data. Catalyst reusability studies showed that the
catalyst could be reused without any adverse effects.

Introduction economic advantage. Further, conducting exothermic


reactions using water as the medium or one of the media
Furan chemicals will assume importance in the future
enhances the intrinsic safety of the process. We have
because they can be manufactured from renewable
addressed this issue in the present investigation.
sources. For example, furfuryl alcohol (FA) is an im-
portant chemical of furan class. It is mainly used in
the manufacture of resins. Furfuryl alcohol resins find Experimental Section
wide application in chemical resistance construction as
foundry binders in foundries and as adhesives in the Materials. The furfuraldehyde used in all experi-
manufacture of plywoods and furniture.1 FA is also the ments was of analytical reagent grade and was pur-
starting material for the manufacture of tetrahydro- chased from S.D. Fine Chemicals, Mumbai, India. The
furfuryl alcohol (THFA). Furfuryl alcohol is prepared 5% Pt/C supported catalyst was obtained from Arora
industrially by the catalytic reduction of furfuraldehyde Matthey Ltd., Kolkata, India, and was used as such.
using Ni and Cu/CrO catalysts. The liquid-phase cata- Hydrogen from a cylinder with a minimum stated purity
lytic hydrogenation of furfuraldehyde has been widely of 99.9% was obtained from Industrial Oxygen Company
studied using Raney Ni catalyst either alone or pro- Ltd., Mysore, India. Analytical reagent-grade 2-propanol
moted by Ru, Pd, and Pt.2,3 Supported noble metal was obtained from a local vendor and used as the
catalysts, especially Ru and Pd, also seem to be promis- reaction medium.
ing.4,5 Merat et al.4 also studied furfural hydrogenation The catalyst had a BET surface area of 948 m2 g-1, a
over Pt supported catalysts under mild operating condi- pore volume of 0.43 cm3 g-1, and an average pore
tions and reported that no reaction takes place at a diameter of 6.5 nm. The particle size range was 23-69
temperature of 50 C. In general, studies on Pt-based m, and the mean diameter was 36.6 m. Catalyst
catalysts have been fewer.6-8 Little information is characterization was done using a Micromeritics ASAP
available in the published literature on insights into the 2010 analyzer by nitrogen adsorption. The particle size
hydrogenation of furfuraldehyde to furfuryl alcohol range was determined using a particle size analyzer
using Pt as the catalyst. It was therefore thought (Coulter LS 230).
desirable to study the hydrogenation of furfuraldehyde Experimental Setup. A schematic diagram of the
over Pt/C as the catalyst. During the manufacture of experimental setup is shown in Figure 1. All experi-
furfural, the product containing 6% water is first ments were conducted in a SS-316 Parr high-pressure
obtained. Pure furfural is obtained by breaking this reactor of capacity 0.1 dm3. The reactor was equipped
azeotrope. In the present investigation, attention was with an electrically heated jacket, a turbine agitator,
focused on using furfural containing water as the and a variable-speed magnetic drive. The temperature
feedstock. This approach would eliminate one unit and the speed of agitation were controlled by means of
operation of breaking the azeotrope, thereby gaining a Parr 4842 controller. The gas inlet, gas release valve,
cooling water feed line, pressure gauge, and rupture
* To whom correspondence should be addressed. Tel.: 91- disk were situated on top of the reaction vessel. The
22-24145616. Fax: 91-22-24145614. E-mail: vvm@udct.ernet.in. liquid sample line and the thermocouple well were
10.1021/ie030055k CCC: $25.00 2003 American Chemical Society
Published on Web 07/19/2003
3882 Ind. Eng. Chem. Res., Vol. 42, No. 17, 2003

Figure 1. Schematic diagram of experimental setup for hydrogenation (PI, pressure indicator; TI, temperature indicator; SI speed indicator;
R, reaction vessel/autoclave; T, thermocouple; H, electric heater; RD rupture disk; I, impeller; GS, gas sparger; SC, sample condenser;
CY, gas cylinder).

immersed in the reaction mixture. A chilled water THFA was formed and furfuryl alcohol was the major
condenser was fitted on the sample valve exit line to product. A high-boiling byproduct was formed in minor
avoid flashing of the sample. The entire assembly was amounts (4%). However, it could not be identified. The
leak proof. reproducibility of the results was checked, and the error
Experimental Procedure. The reactor was first in all experimental measurements was less than 2%.
charged with 0.05 dm3 of the reaction mixture and the General Considerations. In all experiments, fur-
catalyst. It was purged with nitrogen to ensure that the fural containing water (6%) was used as the feedstock.
entire assembly was leak-proof under nitrogen pressure. A few experiments were carried out at 423 K and 2.06
The residual nitrogen left over near atmospheric pres- MPa hydrogen pressure to study product distribution.
sure also ensured an inert atmosphere. Then, hydrogen The results showed that, for a furfural feed concentra-
was used to purge the nitrogen. All lines were closed, tion of 0.17 kmol m-3, the conversion was 58% after 1.5
the speed of agitation was adjusted to a predetermined h, and the selectivity to furfuryl alcohol was 96%. The
value, and the reaction temperature was set. The only byproduct formed, which remained unknown,
contents were heated to the desired temperature, and might be acetal between aldehyde and alcohol. The
a sample was withdrawn. This was considered zero active acidic site on the catalyst might lead to the
time for the reaction. Hydrogen from the cylinder was formation of acetal. Merat et al.4 observed the formation
then sparged into the liquid phase directly beneath the of furfural dimethyl acetal during hydrogenation in the
impeller at the desired partial pressure of hydrogen. The presence of Ni supported catalyst using methanol as the
amount of hydrogen charged was far in excess of that reaction medium. Broekhuis et al.9 also reported cyclic
theoretically required. Samples were withdrawn peri- acetalization of diols with aldehydes in the presence of
odically after sufficient flushing of the sample line. The an acid catalyst. The addition of small quantities of
decrease in pressure was monitored by a pressure monoethanolamine (base) at 500 ppm almost eliminated
gauge. Additional hydrogen was charged from the this product (selectivity > 99%), thereby indirectly
cylinder through a manually operated control valve to confirming the possible formation of acetal.
make up for the hydrogen consumed during the re- 2-Propanol forms an azeotrope with water. If this
action, thus maintaining a constant total pressure. azeotropic mixture could be used as the reaction me-
(The entire system was in semi-batch mode.) The dium, an economic advantage would be gained. Our
reaction was allowed to proceed for a prescribed time, results showed an increase in the selectivity to furfuryl
after which the autoclave was allowed to cool. Samples alcohol (>98.5%) in the presence of water. Although no
of the remaining reaction mixture were analyzed there- remarkable difference in conversion was observed, this
after. approach would also increase furfuryl alcohol yields and
Product Analysis. Analysis of the reaction mixture hence prove profitable. All further experiments were
was carried out using gas chromatography. A GC 1000 conducted using 2-propanol containing water (12.4%
unit (Chemito Instruments) equipped with a flame w/w) as the reaction medium. It is assumed that the
ionization detector was used for this purpose. Furfur- conversions and yields are the same for all practical
aldehyde, furfuryl alcohol, and other byproducts formed, purposes.
if any, were separated using a 2.5-m-long SE 30 column. At these reaction conditions, experiments were carried
The samples of the reaction mixture showed that no out to test the suitability of this catalyst for reuse.
Ind. Eng. Chem. Res., Vol. 42, No. 17, 2003 3883

Figure 2. Effect of catalyst loading on initial rates (423 K, 2.06


MPa H2 pressure, feed furfural concentration 0.17 kmol m-3). Figure 3. Effect of hydrogen pressure on initial rates at various
temperatures (feed furfural concentration ) 0.17 kmol m-3,
catalyst loading ) 0.96 kg m-3): [, 403 K; 9, 423 K; 2, 448 K.
Starting with the fresh catalyst, the same catalyst was
reused three times after separation from the reaction
medium. The catalyst activity remained the same
throughout, thus indicating the high stability of the
catalyst under these conditions.
In all experiments, reactant concentrations were
measured at different time intervals. From these data,
initial rates were calculated by the well-known proce-
dure of fitting a polynomial followed by differentiation
at time t ) 0 to obtain initial rates.

Results and Discussion


The catalytic hydrogenation of furfuraldehyde is a
heterogeneous gas-liquid-solid catalyzed reaction in-
volving the following transfer processes:10 transfer of
hydrogen from the gas phase to the gas-liquid interface;
instantaneous saturation of the interface; diffusion of
hydrogen through the interface to the bulk liquid;
transfer of dissolved hydrogen and furfuraldehyde
present in the liquid phase to the catalyst surface
through the solid-liquid interface; intraparticle diffu- Figure 4. Effect of initial furfural concentration on initial rates
sion followed by chemical reaction at the active centers at various temperatures (H2 pressure ) 2.06 MPa, catalyst loading
and diffusion of the products. Any of these mass-transfer ) 0.96 kg m-3): [, 403 K; 9, 423 K; 2, 448 K.
processes (gas-liquid, liquid-solid, and intraparticle
diffusion) can influence the rates of reaction. Thus, to the ranges 25-60 and 120-180 m. It was observed
study the true kinetics, these diffusional resistances that the catalyst particle size had no effect on the rate
should be absent. of reaction, and hence, pore diffusion was deemed to be
The partial pressure of hydrogen was 2.06 MPa, absent. From this result, it is seen that various diffu-
whereas the total system pressure was 3.45 MPa. At sional resistances associated with the transfer of hy-
this pressure of hydrogen, gas-side mass-transfer re- drogen and furfural were absent, and true kinetics could
sistance could be ignored. The liquid-side mass-transfer be inferred from experimental data.
coefficient and liquid-solid mass-transfer coefficient Initial Rate Data. The kinetics of this reaction was
depend on the intensity of turbulence in the liquid studied between 403 and 448 K with initial concentra-
phase. By varying the speed of agitation, we effectively tions of furfural in the range 0.04-0.17 kmol m-3 and
varied the intensity of turbulence and hence the mass- a hydrogen partial pressure range of 1.03-2.06 MPa.
transfer coefficients. Experiments performed at 448 K The initial rate was found to vary linearly with the
and 2.06 MPa hydrogen pressure using a furfural feed catalyst loading in the range of 0.19-0.96 kg m-3
concentration of 0.17 kmol m-3 showed that the rate of (Figure 2). The effect of the hydrogen partial pressure
reaction was independent of the speed of agitation above on the initial rates at various temperatures is shown
an impeller speed of 15 rps, thus indicating the absence in Figure 3. These results indicate an approximately
of these resistances. All experiments were conducted at linear dependence on the hydrogen concentration at all
lesser temperatures and speeds equal to 20 rps. The temperatures. The dependence of the rate on the fur-
catalyst particle size was varied to test the significance fural feed concentration at various temperatures is
of intraparticle mass-transfer resistance. Two experi- shown in Figure 4. The reaction is zeroth-order with
ments were carried out at 448 K using particle sizes in respect to furfural at feed concentrations higher than
3884 Ind. Eng. Chem. Res., Vol. 42, No. 17, 2003

Table 1. Estimated Orders of the Hydrogenation Table 2. Residual Sum of Squares and Variance for the
Reaction: Initial Rate Data Model Proposed (Eq 3)
temperature temperature residual sum
(K) k na m (K) of squares variance
403 0.063 ( 0.02 0.82 ( 0.02 1.12 ( 0.02 403 2.57 10-7 6.42 10-8
403b 0.069 ( 0.02 0.81 ( 0.02 1.12 ( 0.02 423 4.21 10-7 1.05 10-7
423 0.101 ( 0.05 0.86 ( 0.03 1.15 ( 0.02 448 5.10 10-7 1.27 10-7
448 0.140 ( 0.07 0.91 ( 0.07 1.16 ( 0.03
Table 3. Rate Parameters with 95% Confidence Intervals
Valid up to a furfuraldehyde concentration of 0.13 kmol m-3.
a
for the L-H Model
bKinetic parameters based on rates at different times from
concentration vs time profile. temperature k2 (m6 kmol-1
(K) kgcat-1 min-1) KA KB
403 0.13 ( 0.07 7.30 ( 5.10 0.19 ( 0.09
423 0.24 ( 0.13 4.51 ( 2.40 0.14 ( 0.04
448 0.40 ( 0.28 2.20 ( 1.27 0.10 ( 0.02

Because the order with respect to furfuraldehyde is


fractional, it is desirable to obtain insight into the
kinetics via Langmuir-Hinshelwood models.
Langmuir-Hinshelwood Models. Various Lang-
muir-Hinshelwood-type models were proposed to gain
further insight into the reaction mechanism. Two single-
site mechanisms with and without dissociation of hy-
drogen were proposed. Further, in each of these models,
rate expressions were developed for the case in which
either the adsorption of furfuraldehyde or hydrogen or
the surface reaction was the rate-controlling step. All
these models gave negative parameters and hence were
rejected. Another dual-site mechanism was also pro-
posed in which hydrogen was molecularly adsorbed on
active sites different from those involved in the adsorp-
Figure 5. Temperature dependence of the reaction rate constant. tion of furfuraldehyde and furfuryl alcohol and surface
reaction between adsorbed furfuraldehyde and adsorbed
0.13 kmol m-3. Below this value, the order with respect
hydrogen was assumed to be rate-controlling. This
to furfural is slightly less than unity. This observation
model was found to give positive parameters. The rate
is very important from a process development point of
expression derived for this case is
view.
A power-law model was used to fit the initial rate data k2KAKB[A][B]
for furfural concentrations less than 0.13 kmol m-3. The r) (3)
initial rate of reaction could be expressed as (1 + kA[A])(1 + kB[B])

r0 ) k[A]0m[B]0n (1) The influence of the product furfuryl alcohol on the


rate of reaction was studied at 423 K and 2.06 MPa
The orders of the reaction, m and n, with respect to hydrogen partial pressure to ascertain any deactivation
hydrogen and furfuraldehyde at different temperatures of the catalyst. For this purpose, furfuryl alcohol (10%
were obtained by linear regression analysis. Although w/w of the reactant furfuraldehyde) was added initially
the reaction mixture is 2-propanol containing water before the reaction started. It was observed that, under
(12.4%), the solubility of hydrogen in 2-propanol at the these conditions, the presence of furfuryl alcohol had
given partial pressure was used.11 The error due to this no effect on the rate of reaction. This finding was also
approximation can be neglected. The values of kinetic indirectly confirmed by the kinetic analysis using power-
parameters with 95% confidence intervals are reported law model, as stated earlier. Hence, the product term
in Table 1. in the denominator of eq 3 was omitted. The kinetic data
To investigate the effect of deactivation by the prod- at various temperatures were correlated to this rate
uct, it was thought desirable to obtain kinetic param- expression using MathCad. Table 2 shows the values
eters by having rates at different times from concen- of the residual sum of squares and the variance at
tration vs time profile various temperatures for this model. It was found that
the initial rate data, as well as the kinetic data at all
-d[B] reactant concentrations in the range studied, could be
r) ) k[A]m[B]n (2) fitted well by this model. The various parameters and
dt
the 95% confidence intervals for this model are given
The data were correlated with eq 2 via linear regression in Table 3.
analysis. The parameters obtained (Table 1) indicate A comparison of the rates predicted by this model and
that their values are similar to those obtained via initial the experimentally observed rates is shown in Figure
rates, thereby confirming the hypothesis of no deactiva- 6. The predicted values are in fair agreement with each
tion of the catalyst by the product formed. other. The energy of activation for the surface reaction
The variation of k with temperature is shown in was found to be 60.5 kJ mol-1. From the vant Hoff
Figure 5. The energy of activation for this reaction was equation, the heats of adsorption of furfuraldehyde and
found to be 28 kJ mol-1, which indirectly confirms the hydrogen were found to be 39.8 and 21.3 kJ mol-1,
observation of the absence of diffusional resistances. respectively.
Ind. Eng. Chem. Res., Vol. 42, No. 17, 2003 3885

Nomenclature
A ) hydrogen
B ) furfuraldehyde
[A] ) concentration of hydrogen in the bulk liquid phase,
kmol m-3
[B] ) concentration of furfuraldehyde in the liquid phase,
kmol m-3
[A]0 ) initial hydrogen concentration, kmol m-3
[B]0 ) initial furfuraldehyde concentration, kmol m-3
k ) reaction rate constant in eq 1, (m3)m+n kmol1-m-n kgcat-1
min-1
k2 ) surface reaction rate constant in eq 3, m6 kmol-1
kgcat-1 min-1
KA ) adsorption equilibrium constant for A
KB ) adsorption equilibrium constant for B
m ) order with respect to hydrogen
n ) order with respect to furfuraldehyde
r ) overall rate of reaction, kmol kgcat-1 min-1
r0 ) initial rate of reaction, kmol kgcat-1 min-1
t ) time, min
Figure 6. Comparison of predicted rates (eq 3) to experimental
rates at various temperatures and reactant concentrations (feed Literature Cited
furfural concentration ) 0.043-0.17 kmol m-3, 95% confidence
intervals for slope ) 1.02 ( 0.08). (1) McKetta, J. J.; Cunningham, W. A. Encyclopedia of Chemi-
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24, p 63.
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University of Mumbai, Mumbai, India, 1978.
(3) Erzhanova, M. S.; Beisekov, T.; Sokolskii, D. V. Hydrogena-
The kinetics of the liquid-phase hydrogenation of tion of furfural in mixed solvents on Raney nickel catalysts
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catalyst was studied in the range of temperatures from 11, 122; cf Chem. Abstr. 1971, 78, 84151w.
403 to 448 K and in the range of pressures from 1.03 to (4) Merat, N.; Godawa, C.; Gaset, A. High Selective Production
2.06 MPa. The solvent used was 2-propanol containing of Tetrahydrofurfuryl Alcohol: Catalytic Hydrogenation of Fur-
12.4 % (w/w) water. The initial rate of reaction varied fural and Furfuryl Alcohol. J. Chem. Technol. Biotechnol. 1990,
48, 145.
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rps, thus indicating the absence of gas-liquid and hydrogen pressure. Zh. Prikl. Khim. 1994, 67 (6), 1041; cf Chem.
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the conditions employed, the catalyst particle size has (6) Kijenski, J.; Winiarek, P. Selective hydrogenation of R,-
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monolayer supports. Appl. Catal. A 2000, 193 (1, 2), L1-L4.
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were analyzed using a simple power-law model. The rate MonolayersNew Concept of Selective Catalyst for R,-Unsaturated
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(9) Broekhuis, R. R.; Lynn, S.; King, C. J. Recovery of Propylene
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Acknowledgment
Received for review January 21, 2003
P.D.V. is grateful to the University Grants Commis- Revised manuscript received June 9, 2003
Accepted June 11, 2003
sion, New Delhi, Government of India, for financial
support. IE030055K

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