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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a sample was withdrawn.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 Samples were withdrawn peri- acetalization of diols with aldehydes in the presence of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
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
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-
cal Processing and Design; Marcel Dekker: New York, 1986; Vol.
24, p 63.
Conclusions (2) Singh, P. Development of Furan Chemicals; Ph.D. Thesis,
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
furfuraldehyde to furfuryl alcohol over a 5 % Pt/C promoted by platinum group metals. Khim. Khim. Tekhnol. 1971,
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.
linearly with the catalyst loading, whereas the impeller (5) Beisekov, T. B.; Zhurkhabaeva, L. A.; Bitemirova, A. E.
speed had no influence on the rates above a speed of 15 Hydrogenation of furfural on supported Palladium catalysts under
rps, thus indicating the absence of gas-liquid and hydrogen pressure. Zh. Prikl. Khim. 1994, 67 (6), 1041; cf Chem.
liquid-solid mass-transfer resistances. Similarly, under Abstr. 1994, 122, 55836v.
the conditions employed, the catalyst particle size has (6) Kijenski, J.; Winiarek, P. Selective hydrogenation of R,-
no effect on the rates, and hence, the intraparticle mass- unsaturated aldehydes over platinum catalysts deposited on
monolayer supports. Appl. Catal. A 2000, 193 (1, 2), L1-L4.
transfer resistance was negligible. The initial rate data (7) Kijenski, J.; Winiarek, P.; Paryjczak, T. Metal on Oxide
were analyzed using a simple power-law model. The rate MonolayersNew Concept of Selective Catalyst for R,-Unsaturated
of reaction was almost linearly dependent on the Aldehydes Hydrogenation. Pol. J. Chem. Technol. 1999, 1, 16.
hydrogen concentration. Also, for concentrations less (8) Marinelli, T.; Ponec, V.; Raab, C. G.; Lercher, J. A. Fur-
than 0.13 kmol m-3, the order with respect to furfur- fural-Hydrogen Reactions, Manipulation of Activity and Selectiv-
ity of the Catalyst. Stud. Surf. Sci. Catal. 1993, 78, 195.
aldehyde was 0.86. However, the reaction was found to
(9) Broekhuis, R. R.; Lynn, S.; King, C. J. Recovery of Propylene
be of zeroth order with respect to furfuraldehyde above Glycol from Dilute Aqueous Solutions via Reversible Reaction with
this concentration. The experimental data could also be Aldehydes. Ind. Eng. Chem. Res. 1994, 33, 3230.
explained using Langmuir-Hinshelwood kinetics. A (10) Doraiswamy, L. K.; Sharma, M. M. Heterogeneous Reac-
dual-site mechanism with nondissociative adsorption of tions: Analysis, Examples and Reactor Design; John Wiley and
hydrogen and surface reaction as the rate-controlling Sons: New York, 1984; Vol. 2.
(11) Shaw, J. M. A Correlation for Hydrogen Solubility in
step provided the best fit of the experimental data. Aliphatic and Aromatic Solvents. Can. J. Chem. Eng. 1987, 65,
293.
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