S. Koso et al. / Journal of Catalysis 280 (2011) 221–229
229
The overall rate of the hydrogenolysis of THFA is expressed
using Eqs. (18), (29), and (30):
and THFA concentration, respectively. Combined with the cata-
lyst characterization results showing that Rh–ReO /SiO has the
Rh metal particles modified with ReO clusters, it is suggested
x
2
x
r ¼ k
1
THFA;Re
h h
H ;Rh
ꢁ
that the hydride species formed at the interface between Rh
metal surface and ReOx cluster can attack the carbon atom
neighboring the ACH OH group adsorbed on ReO clusters. In
¼
k
1
fKTHFA
C
THFA=ðKTHFA
C
THFA þ 2KTHFA
C
1;5ꢁPeD þ 1Þg
ꢂ fK0
H2 =ðK0
P
P
H2 þ 1Þg
ð31Þ
2
x
H
2
H
2
addition, the presence of 1,5-pentanediol decreased the activity
of the THFA hydrogenolysis because of the strong interaction
between OH groups and the catalyst surface. Based on the
regioselective hydride attack mechanism of Rh–ReO /SiO -
where k
1
is the rate constant of Eq (18).
0
The first-order kinetics on PH2 (Table 5) indicates K
P
2
H2 ꢃ 1,
H
and the zero-order kinetics on THFA concentration (Table 4)
indicates KTHFA(CTHFA + 2C1,5-PeD) ꢄ 1. These can give the reaction
rate as below.
x
2
catalyzed hydrogenolysis, the Langmuir–Hinshelwood type
(L–H) kinetic modeling agreed with the reaction time depen-
dence very well.
0
r ¼ k
1
K
P
H2
C
THFA=ðCTHFA þ 2C1;5ꢁPeD
Þ
ð32Þ
H2
Fig. 2 shows the reaction time dependence of the THFA hydrogen-
olysis over Rh–ReO /SiO (Re/Rh = 0.5). The THFA conversion
x
2
Acknowledgment
increased almost linearly at the initial stage; however, the increase
became smaller at longer reaction time. Based on the results at 2 h,
This work was in part supported by Grant-in-Aid for JSPS
0
ꢁ1 ꢁ1
the rate constant k
1
K
was determined to be 0.025 MPa
h
Fellows. The measurement of NH -TPD was kindly performed by
H
2
3
ꢁ1
g-cat . It is possible to calculate the conversion curve using this
obtained reaction rate constant and the Eq. (32). The reaction time
dependence of the calculated conversion is also plotted in Fig. 2
Prof. Naonobu Katada, Department of Chemistry and Biotechnol-
ogy, Tottori University.
(
Closed circles). The decrease in H
2
pressure during the reaction
Appendix A. Supplementary material
(
initial 8.0 MPa ? 6.5 MPa at 94% conv.) was also considered in
the calculation. The agreement indicates the validity of the Eq.
32) and the reaction step including the adsorbed THFA on Re spe-
cies attached by the hydride species. In addition, Fig. 1b shows the
reaction scheme of ethylene glycol ethers, which is similar to the
(
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