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Ind. Eng. Chem. Res. 2010, 49, 1082610835

Kinetic Modeling of Aqueous-Phase Glycerol Hydrogenolysis in a Batch Slurry

Reactor
Arely Torres, Debdut Roy, Bala Subramaniam, and Raghunath V. Chaudhari*
Center for EnVironmentally Beneficial Catalysis, Department of Chemical and Petroleum Engineering,
UniVersity of Kansas, 1501 Wakarusa Dr., Lawrence, Kansas 66047

The kinetics of the aqueous-phase hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) was studied using
a bimetallic Ru-Re/C catalyst in a slurry reactor in a temperature range of 493-513 K and a hydrogen
pressure of 2.4-9.6 MPa. Glycerol hydrogenolysis to produce 1,2-PDO via C-O cleavage (i) proceeds with
parallel C-C cleavage, reforming, water-gas shift, and Fischer-Tropsch reactions, (ii) results in a very complex
reaction network with several gaseous- and liquid-phase products, and (iii) poses a challenge to design selective
catalysts. It is observed that Ru-Re bimetallic catalyst shows higher hydrogenolysis activity (glycerol
conversion of X ) 57.7%) and 1,2-PDO selectivity (S ) 36.6%), compared to the monometallic Ru catalyst
(X ) 52.1%; S ) 18.9%) but the monometallic Re catalyst showed no catalytic activity for the reaction.
Stirred-batch reactor data on the transient concentrations of reactants and products in both the gas and liquid
phases were obtained using a bimetallic Ru-Re/C catalyst under different conditions to understand the reaction
pathways, selectivity behavior, and intrinsic kinetics of the different reaction steps. For kinetic modeling,
several experiments were performed at different initial pressures of hydrogen, catalyst concentration, and
temperatures. The proposed rate equations, along with the regressed kinetic and activation energy parameters,
were found to represent the experimental data for the multistep hydrogenolysis reaction very satisfactorily.
Introduction
In the search for renewable sources for fuels and chemicals,
the conversions of lignocellulosic biomass and vegetable oils
to such products have been receiving increased attention.1,2 In
this context, biodiesel production via the transesterification of
fatty acid methyl esters (FAME) has attained some success and
the process is at an advanced stage of commercialization.3
However, the sustainability of this process and its commercial
viability depend on utilization of the large quantities of glycerol
byproduct produced (10% by weight) in this process.4 Among
many possibilities,5 the hydrogenolysis of glycerol to 1,2propanediol (1,2-PDO) and ethylene glycol (EG) provides a
practical solution to glycerol utilization, because this route is
not only expected to be less expensive for the commodities (1,2PDO and EG), compared to the petroleum-based routes, but
also uses abundantly available renewable feedstocks. The
transformation of glycerol to 1,2-PDO involves catalytic C-O
bond cleavage, commonly known as hydrogenolysis, and
represents a class of reactions useful in conversion of many
other polyhydroxy compounds to lower oxygenated industrial
chemicals.6 However, the challenge is to achieve selective
conversion of glycerol to 1,2-PDO and EG, and to understand
the underlying kinetics and mechanism of the catalytic
hydrogenolysis.
In previous reports, several supported transition-metal catalysts consisting of Ru,79 Pt,1012 Rh,13 Cu,1416 and Ni17,18 have
been investigated and the activity of different supported metal
catalysts for glycerol hydrogenolysis generally follows the
order19
Ru Cu Ni > Pt > Pd
Although Ru is known to be one of the best catalysts for this
reaction, it is also known to promote unwanted C-C cleavage
to produce gaseous products (mainly methane).20 A few
* To whom correspondence should be addressed. Tel.: +1 785 864
1634. Fax: +1 785 864 6051. E-mail address: rvc1948@ku.edu.

bimetallic catalysts consisting of Ru-Cu,21 Pt-Ru, Au-Ru,22

Ni-Re,23 and Ru-Re24 are also reported. In a recent study,
different Ru-Cu catalyst compositions were tested for glycerol
hydrogenolysis, and it was observed that a Ru:Cu ratio of 3:1
gave the optimum conversion (70%) of glycerol and 1,2-PDO
(71% of the liquid-phase products).21 However, the study reflects
that, more than the synergy of the two components in the
bimetallic catalyst, the metals work independently. Maris et al.
studied the bimetallic effect using Pt-Ru and Au-Ru catalysts
and reported that, although the individual metals showed
different activities, the bimetallic catalysts showed the activity
similar to that with only an Ru catalyst.22 Marincean et al.
studied the pH and solvent effects on 1,2-PDO selectivity
behavior using a Ni-Re catalyst.23 However, the bimetallic
catalyst was not compared with the monometallic Ni or Re
catalysts under identical conditions to evaluate the advantage
of the bimetallic catalyst. In another study with Ru-Re
bimetallic catalysts, it was reported that the conversion of
glycerol increased, compared to monometallic Ru, without
changing the 1,2-PDO and propanol selectivity.24
Lahr et al. studied the kinetics of glycerol hydrogenolysis
using 5% Ru/C under basic conditions (at pH 8 and 11.7).25
This work proposed a Langmuir-Hinshelwood-type rate model,
considering the formations of EG and 1,2-PDO, as well as the
effect of competitive adsorption of these products and glycerol
on the catalyst surface. In a later study, Lahr et al. investigated
temperature effects on glycerol hydrogenolysis with sulfurpromoted Ru catalyst.26 However, a limitation of these works
is that the authors considered only 1,2-PDO and EG as products
for model predictions and the side reactions that lead to the
formation of gaseous products are not considered. Furthermore,
there have been no other published reports on the kinetics of
glycerol hydrogenolysis, on either mono or bimetallic catalysts
that employ a comprehensive reaction network that accounts
for the formation of both liquid- and gas-phase products.
Therefore, the objective of this work is a detailed understanding
of the reaction pathways associated with the hydrogenolysis of

10.1021/ie100553b 2010 American Chemical Society

Published on Web 05/21/2010

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

10827

Figure 1. Possible reactions during glycerol hydrogenolysis.

glycerol to 1,2-PDO and the development of appropriate kinetic

models that will aid in catalyst development and process
optimization.
Based on the literature reports and experiments in our
laboratory, the possible reactions involved in glycerol hydrogenolysis are shown in Figure 1.27 It is evident that a series of
reactions occur during glycerol hydrogenolysis, which lead to
several gas- and liquid-phase products. This clearly poses a
significant challenge to achieve high selectivity to the desired
products such as 1,2-PDO.
In our recent report,28 we have shown that a supported
Ru-Re bimetallic catalyst gives improved activity (glycerol
conversion of X ) 57.7%) and 1,2-PDO selectivity (S ) 36.6%)
over the supported Ru catalyst (X ) 52.1%; S ) 18.9%) for
glycerol hydrogenolysis. In particular, the Ru-Re catalyst
reduced the gaseous product formation (methane, ethane, etc.)
and improved the liquid-phase product selectivity, compared
to the monometallic Ru catalyst. Therefore, it was thought
worthwhile to investigate the intrinsic kinetics of glycerol
hydrogenolysis using the Ru-Re bimetallic catalyst. For the
kinetic study, the effects of H2 partial pressure, catalyst concentration, and temperature on concentration-versus-time profiles
were determined experimentally in a batch-slurry reactor. The
integral batch-reactor data were used to determine rate and
activation energy parameters. The results from this study will
be useful in understanding the kinetics of the competing
reactions and selectivity behavior during hydrogenolysis of
glycerol and guide the rational design of catalysts as well as
the modeling of slurry- and fixed-bed reactors.
Experimental Section
Materials. Glycerol (g99.5%, spectrophotometric grade),
activated carbon, ruthenium trichloride hydrate (RuCl3 xH2O),
and perrhenic acid (HReO4) were purchased from Sigma-Aldrich
and used without further purification. Hydrogen (>99.5% pure,

from Air Gas, Inc.) and nitrogen (>99% pure, from Linweld)
were purchased and used as received.
Catalyst Synthesis. The bimetallic Ru-Re and the monometallic Ru and Re catalysts were prepared in the laboratory
via precipitation techniques.29 The required amount of activated
carbon (Sigma-Aldrich) was charged in distilled water and
stirred for 2 h in a round-bottomed flask, using a magnetic stirrer
and a condenser in an oil bath (368 K). Required amounts of
ruthenium trichloride hydrate (Sigma-Aldrich) and perrhenic
acid (Sigma-Aldrich) then were dissolved in water and added
dropwise to the stirred suspension. After stirring for 3 h, a dilute
aqueous ammonia solution was added dropwise until the solution
became strongly alkaline (pH 10). The solution was then
stirred for 3 h, after which point the contents were filtered,
washed using hot distilled water, and dried in an oven at 363 K
under vacuum overnight. The catalyst was reduced for 6 h at
493 K in a slurry reactor under 80 bar of H2 pressure using
water as a solvent. The resulting activated catalyst was filtered,
dried, and stored under dry conditions.
The supported Ru and Ru-Re catalysts were characterized
by inductively coupled plasma-optical emission spectroscopy
(ICP-OES) and surface area analysis. The surface areas of the
activated carbon and 1% Ru/C, as well as fresh and spent 1%
Ru-1% Re/C catalysts, were measured using a Gemini Model
2360 surface area analyzer (Micromeritics) and the values were
983.2, 987.1, 978.8, and 794.5 m2/g. The materials were
degassed for 2 h under N2 flow at 363 K before analysis. Other
specifications of the powdered 1% Ru-1% Re/C catalyst are
as follows: Ru content, 0.97% (w/w); Re content, 0.98% (w/
w); average particle size, 125 m; particle density, 413.5 kg/
m3; and surface area, 978.8 m2/g.
Reactor Setup and Procedures. The kinetic experiments of
hydrogenolysis of glycerol were conducted in a high-pressure,
high-temperature multiple slurry reactor system supplied by Parr
Instrument Co. (Moline, AL).27 The reactor system consists of
a parallel array of six autoclave reactors that can be operated

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Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

Table 1. Typical Material Balance Calculations for Glycerol Hydrogenolysisa

1% Ru-1% Re/C

1% Ru/C

concentration (kmol/m3) C ( 103 mol) conversion, X (%) concentration (kmol/m3) C ( 103 mol) conversion, X (%)
Initial Concentration
glycerol

1.104

99.36

1.086

97.74

Final Sample Concentration

concentration (kmol/m3) C ( 103 mol) conversion, X (%) concentration (kmol/m3) C ( 103 mol) conversion, X (%)
Liquid-phase components
glycerol

0.467

42.03
3

concentration (kmol/m ) C ( 10 mol)

Liquid-phase components
ethylene glycol
1,2-propanediol
lactic acid
methanol
ethanol
1-propanol
2-propanol
Gas-phase components
methane
ethane
propane
n-butane
n-pentane
CO
CO2
totals
Carbon deficit

57.70
selectivity, X (%)

0.521

46.87
3

concentration (kmol/m ) C ( 10 mol)

52.05
selectivity, X (%)

0.070
0.233
0.000
0.013
0.034
0.011
0.060

4.20
20.97
0.00
0.390
2.04
0.990
5.40

7.33
36.58
0.00
0.68
3.56
1.73
9.42

0.156
0.107
0.000
0.019
0.011
0.000
0.000

9.39
9.62
0.00
0.56
0.65
0.00
0.00

18.45
18.92
0.00
1.11
1.28
0.00
0.00

0.005
0.001
0.001
0.000
0.000
0.000
6.4 10-4

10.62
4.92
5.22
0.00
0.00
0.00
0.15

18.52
8.58
9.11
0.00
0.00
0.00
0.26

0.011
0.001
1.4 10-4
0.00
0.00
0.00
6.6 10-4

26.27
3.01
1.06
0.00
0.00
0.00
0.16

51.63
5.91
2.09
0.00
0.00
0.00
0.32

96.93

95.77

97.59

99.71

2.4%

0.15%

Reaction conditions: glycerol concentration, 1.1 kmol/m (10 wt %); catalyst concentration, 16.66 kg/m3; temperature, 493 K; PH2 ) 6.9 MPa;
solvent, H2O; initial liquid volume, 30 mL; and reaction time, 6 h. Gas-phase concentrations in this table represent values under atmospheric conditions.
a

Figure 2. Conversion and selectivity of supported monometallic Ru and

bimetallic Ru-Re catalysts. Reaction conditions: glycerol concentration,
1.1 kmol/m3; catalyst concentration, 16.66 kg/m3; PH2 ) 6.9 MPa;
temperature, 493 K; solvent, H2O; initial liquid volume, 30 mL; and reaction
time, 6 h. Re/C displays no activity.
Table 2. Range of Experimental Conditions for the Kinetic Study of
Glycerol Hydrogenolysis Using the 1% Ru-1% Re/C Catalyst
parameter

value

glycerol concentration
catalyst concentration
temperature
hydrogen partial pressure
solvent (water)
reaction time

1.1 kmol/m3
8.33-66.67 kg/m3
473-503 K
2.4-9.7 MPa
30 10-6 m3
1-6 h

simultaneously at different temperatures and pressures. Each

autoclave reactor is equipped with a thermowell, pressure
transducer, gas inlet, gas outlet, and a rupture disk. A magnetic
stirrer with maximum agitation speed of 30 Hz provides mixing
in each reactor. The temperatures and pressures in the individual
reactors are independently controlled and monitored with a

computer interfaced with the control module of the reactor

system. The agitation speeds of the reactors are controlled from
the computer interface or with the manual controller in the
reactor setup itself. The temperature and pressure of the reactors
are logged every 10 s through SpecView data acquisition
software.
In a typical reaction experiment, an aqueous glycerol
solution was charged in the autoclave with a measured
amount of catalyst. The reactor was sealed and loaded into
the multireactor setup with well-defined initial conditions.
Subsequently, the reaction mixture was purged with N2 gas
several times and then with H2 gas while stirring gently. The
reactor was then heated to the desired operating temperature,
and then the reactant gas (H2) was charged to the desired
pressure. Following the fixed-time batch run, the reactor was
cooled to room temperature. After noting the reactor pressure
at room temperature, and the reactor was depressurized by
releasing the gas-phase products to fill two external sampling
loops for offline gas chromatography (GC) analysis (Shimadzu, Model GC-2014). In one sampling loop, C2-C5
alkanes were separated with a RT-QPLOT column (15 m
long, inner diameter of ID ) 0.53 mm) and analyzed via
flame ionization detection (FID). In a second sampling loop,
methane, ethane, CO, CO2 were separated with a 60/80
Carboxane 1000 column (4.57 m long, ID ) 3.175 mm) and
analyzed using a thermal conductivity detection (TCD)
device. After the gas-phase analysis, the reactor was opened
to extract a liquid sample to identify the remaining products
in that phase. Glycerol, EG, 1,2-PDO, methanol (MeOH),
ethanol (EtOH), 1-propanol, and 2-propanol were analyzed
by high-performance liquid chromatography (HPLC) (Shimadzu Model LC-10A) using a Razex ROA-Organic Acid
H+ (8%) column (300 mm 7.8 mm), 0.005 N aqueous
H2SO4 as mobile phase at a flow rate of 0.5 mL/min and a

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

10829

Figure 3. Effect of H2 partial pressure on glycerol conversion and 1,2-PDO and propanol selectivities in glycerol hydrogenolysis using 1% Ru-1% Re/C
catalyst. Reaction conditions: glycerol concentration, 1.1 kmol/m3, 1% Ru-1% Re/C concentration, 16.66 kg/m3; temperature, 493 K; solvent, H2O; and
initial liquid volume, 30 mL.

Figure 4. Effect of H2 partial pressure on gas-phase product selectivity in glycerol hydrogenolysis using the 1% Ru-1% Re/C catalyst. Reaction conditions
are as described in Figure 3.

Figure 5. Effect of temperature on glycerol conversion and product

selectivities in glycerol hydrogenolysis using 1% Ru-1% Re/C catalyst.
Reaction conditions: glycerol concentration, 1.1 kmol/m3; 1% Ru-1% Re/C
concentration, 16.66 kg/m3; PH2 ) 6.9 MPa; solvent, H2O; initial liquid
volume, 30 mL; and reaction time, 6 h.

refractive index detector (RID). Based on calibrations with

standards, glycerol and all the products in the hydrogenolysis
reactions were quantified by GC and HPLC analyses to
estimate a material balance for the reaction. It is important
to mention that, as the glycerol hydrogenolysis reactions
produced gas-phase as well as liquid-phase products, intermediate sampling was not done in any of the batch runs. To
obtain concentration-time profiles, reactions under identical
conditions were followed in multiple reactors and the

Figure 6. Effect of catalyst concentration on glycerol conversion and product

selectivities in glycerol hydrogenolysis using the 1% Ru-1% Re/C catalyst.
Reaction conditions: glycerol concentration, 1.1 kmol/m3; PH2 ) 6.9 MPa;
temperature, 493 K; solvent, H2O; initial liquid volume, 30 mL; and reaction
time, 1 h.

reactions in the various reactors were stopped at various

predetermined times to conduct analyses of gas- and liquidphase products. The glycerol conversion, selectivity to a
particular product, and carbon deficit (to determine massbalance closure) are defined as follows:
conversion (%) )

Cmolinitial - Cmolunreacted glycerol

Cmolinitial

100

10830

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

Figure 7. Typical concentration-time profile for glycerol hydrogenolysis, using the 1% Ru-1% Re/C catalyst. Reaction conditions: glycerol concentration,
1.1 kmol/m3; 1% Ru-1% Re/C concentration, 16.66 kg/m3; temperature, 493 K; PH2 ) 6.9 MPa; solvent, H2O; and initial liquid volume, 30 mL.

in Table 2, in which concentration-time profiles, as well as

data regarding hydrogen consumption versus time, were obtained.
Results and Discussion

Figure 8. Glycerol hydrogenolysis reaction scheme considered for the kinetic

study.

selectivity (%) )

carbon deficit (%) )

Cmolproduct
Cmolinitial - Cmolunreacted glycerol

100

Cmolinitial - Cmolunreacted glycerol + products

Cmolinitial

100

where Cmol represents the number of moles of carbon. In other

words, the selectivity to a product is defined on a carbon
basis. The logic behind the definition was discussed in our
previous publication.27
As inferred from Table 1, typical material balance analysis
for 1% Ru/C and 1% Ru-1% Re/C catalysts shows very good
mass balance closure. In all the reactions, the material balance
of glycerol reacted and the products formed was >95%. It is
important to mention that the gas-phase hydrogen concentration
could not be measured directly, because of the similar thermal
conductivities of H2 and He, the carrier gas in the TCD analysis;
however, the hydrogen concentration was calculated by difference from the gas-phase analysis. For the kinetic study, several
experiments were performed over the range of conditions given

Experiments To Delineate Reaction Pathways. In a few

preliminary experiments, carbon-supported catalysts consisting
of either Ru or Re were evaluated against the bimetallic Ru-Re
supported catalyst for hydrogenolysis of glycerol and the results
are shown in Figure 2. Re was found to have a prominent effect
as a promoter for the selectivity to 1,2-PDO (18.9% to 36.6%),
as well as the liquid-phase products, such as ethylene glycol
(EG), propanol, and ethanol (39.8% to 52.3%). This may be
due to improved dispersion of Ru in the presence of Re, as
reported earlier.24 Another important finding is that, by itself,
Re has no activity toward the hydrogenolysis of glycerol.
For a detailed comparison of the 1% Ru/C and 1% Ru-1%
Re/C catalysts for the hydrogenolysis of glycerol, the material
balance analyses are presented in Table 1. Note that 1-propanol
and 2-propanol (S ) 9.4% and 1.7%, respectively) are the other
major liquid-phase products with the Ru-Re bimetallic catalyst,
along with 1,2-PDO and ethylene glycol (S ) 7.3%). The Ru/C
catalyst showed relatively higher selectivity to EG and methane
with respect to Ru-Re bimetallic catalyst indicating its higher
activity for C-C bond breaking, compared to hydrogenolysis.
Based on its distinct edge in hydrogenolysis efficiency over the
monometallic catalyst, the Ru-Re bimetallic catalyst was
selected for further studies.
Glycerol conversion and 1,2-PDO and propanol selectivity
profiles with the bimetallic catalyst at 493 K under different
partial pressures of hydrogen are shown in Figure 3. Glycerol
conversion increases as the initial hydrogen pressure increases,
but the selectivity to 1,2-PDO follows an opposite trend.
However, the 1,2-PDO selectivity decreased only marginally
with time, except at a hydrogen partial pressure of 4.8 MPa.
Second, there is a substantial difference in selectivity of 1,2PDO at 2.4 MPa and at higher hydrogen partial pressures. This
is partly due to the higher hydrogenolysis activity of 1,2-PDO
to propanol (Figure 3b) and a possible increase in the formation
of gaseous products via the reforming of glycerol, as also
indicated by the results in Figure 4.
The effects of temperature on glycerol conversion and product
selectivity pattern were studied over a temperature range of
473-503 K, and the results are shown in Figure 5. Glycerol
conversion increased significantly with temperature, as expected,
but the 1,2-PDO and propanol selectivities decreased marginally.
The decreases in 1,2-PDO and propanol selectivities are

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

10831

Figure 9. Initial global rate of hydrogenation, as a function of temperature and pressure.

Table 3. Mass Balance Equationsa

dCgly
) rgly ) -r1 - r2 - r5
dt

dCPDO
) rPDO ) r1 - r3
dt

dCEG
) rEG ) r2 - r4
dt

dCPrOH
) rPrOH ) r3
dt

dCEtOH
) rEtOH ) r4
dt

dCMeOH
) rMeOH ) r2 - r6
dt

Vg d(CCO)g
) 3r5 - r7 - r8 - 2r9 - 3r10
Vl dt

Vg d(CCO2)g
) r7
Vl
dt

Vg d(CCH4)g
) r6 + r8
Vl
dt

Vg d(CC2H6)g
) r9
Vl
dt

Vg d(CC3H8)g
) r10
Vl
dt

Vg d(CH2)g
) -r1 - r2 - 2r3 - r4 + 4r5 - r6 + r7 - 3r8 - 5r9 - 7r10
Vl dt

The initial conditions are as follows: At t ) 0, Cgly ) Cgly,0; (CH2)g ) (CH2)g,0. The concentrations of the other components are zero.

Table 4. Rate Terms for Reaction Steps Shown in Figure 8

r1 ) wk1Cgly

(CH2)g
HH2

r3 ) wk3CPG1/2

(CH2)g
HH2

r5 ) wk5Cgly

r7 ) wk7

r9 ) wk9

(CCO)g
HCO
(CH2)3/2
g
HH2

r2 ) wk2Cgly

r4 ) wk4CEG

HH2

component

at 473 K

at 493 K

at 503 K

(CH2)g

H2
CH4
C2H6
C3H8
CO
CO2

24.757
25.637
17.007
14.634
29.030
3.717

20.488
19.906
11.827
9.138
22.489
3.277

18.612
17.408
9.758
7.128
19.663
3.050

HH2
(CH2)g
HH2

(CH2)g3/2

r10 ) wk10

Henrys Constant, Hi (m3(liq)/m3(gas))

(CH2)g

r6 ) wk6CMeOH

r8 ) wk8

Table 5. Henrys Constants for Different Gases in Water

HH2
(CH2)g3/2
HH2

attributed to higher reforming activity at higher temperatures,

which leads to more gaseous products such as methane, ethane,
and propane (see Figure 5). EG selectivity was almost constant
(S ) 6%-7%) at all temperatures.
Similar conversion and selectivity trends were observed with
catalyst concentration variation, as shown in Figure 6. The
glycerol conversion and product selectivity profiles shown in
Figures 3-6 indicate parallel and consecutive reaction networks
in glycerol hydrogenolysis, as shown in Figure 1. Furthermore,
higher temperature, H2 pressure, and catalyst concentration each
lead to more gaseous products, which adversely affects the 1,2PDO selectivity.

In summary, the various likely reactions in glycerol hydrogenolysis are shown in Figure 1, while the product distribution
and material balance data for a specific case with a Ru-Re
bimetallic catalyst are presented in Table 2. A typical
concentration-time profile for the reaction is also shown in
Figure 7 for 493 K and 6.9 MPa.
The main liquid-phase products were 1,2-PDO, EG, propanol,
ethanol, and methanol, whereas the gas-phase products included
methane, ethane, propane, and traces of carbon dioxide. Based
on these experimental observations, the reactions shown in
Figure 8 were considered for the kinetic modeling.
Analysis of Mass-Transfer Effects. To ensure that the batch
experiments were performed in a kinetic regime, the initial
global rates of hydrogenation were calculated for a wide range
of conditions (Table 2) from the hydrogen consumption-time
profiles observed in the batch reactions under conditions such
that glycerol conversion was <10%. The effects of different
parameters on initial global rates were evaluated, and typical
results, relative to the hydrogen partial pressure and temperature,

10832

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

Figure 10. Concentration-time profile at 473 K. Reaction conditions: glycerol concentration, 1.1 kmol/m3; catalyst concentration, 16.66 kg/m3; PH2 ) 6.9
MPa; solvent, H2O; and initial liquid volume, 30 mL.

Figure 11. Concentration-time profile at 493 K. Reaction conditions: glycerol concentration, 1.1 kmol/m3; catalyst concentration, 16.66 kg/m3; PH2 ) 6.9
MPa; solvent, H2O; and initial liquid volume, 30 mL.

Figure 12. Concentration-time profile at 503 K. Reaction conditions: glycerol concentration, 1.1 kmol/m3; catalyst concentration, 16.66 kg/m3; PH2 ) 6.9
MPa; solvent, H2O; and initial liquid volume, 30 mL.

are shown in Figure 9. These data were used to assess the

significance of mass-transfer resistances, viz. gas-liquid (R1),
liquid-solid (R2), and intraparticle (exp), using the criteria
described by Ramachandran and Chaudhari.30 The required
mass-transfer and diffusion parameters for this analysis were
similar to those reported previously,31 and the solubility data
used are given later in Table 5. The calculated values of the
factors R1 (R1 ) [RH2/(kla)CH*2], R2 (R2 ) [RH2/(ksap)CH*2], and
exp (exp ) (dp/6)[FpRH2/(Dew)CH*2]0.5) were determined to be
in the ranges of R1 ) 0.004-0.011, R2 ) 1 10-5 - 5
10-5, and exp ) 0.07-0.09, respectively, which clearly indicate
that mass-transfer limitations are insignificant in our experiments.
Kinetic Modeling. For the purpose of kinetic modeling,
experiments were conducted at different initial pressures, catalyst
concentrations, and temperatures, in which all the liquid- and

gas-phase products were analyzed as a function of time. Since

the presence of gas-phase products is not convenient for
sampling in batch reactors, a series of batch-slurry reactors were
used in this study, in which the experiments with the same initial
conditions were conducted for different time durations. A typical
result is shown in Figure 7 for 493 K. In these batch
experiments, the variations of gas- and liquid-phase concentrations with time in the isothermal, constant-volume batch reactor
are described by the mass balance equations given in Table 3.
The rate terms, ri, representing the different reaction steps
are defined in Table 4.
To simulate the experimental concentration-time data, equations presented in Table 3 were solved numerically, using a
modified Rosenbrock algorithm for stiff systems, coupled with
the Levenberg-Marquardt method in Matlab, and the optimized

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

10833

Figure 13. Concentration-time profile at 493 K. Reaction conditions: glycerol concentration, 1.1 kmol/m3; catalyst concentration, 16.66 kg/m3; PH2 ) 4.8
MPa; solvent, H2O; and initial liquid volume, 30 mL.

Figure 14. Concentration-time profile at 493 K. Reaction conditions: glycerol concentration, 1.1 kmol/m3; catalyst concentration, 16.66 kg/m3; PH2 ) 9.7
MPa; solvent, H2O; and initial liquid volume, 30 mL.
Table 6. Rate Constants and Activation Energies
temperature (K)

k1 ( 102)

k2 ( 102)

k3 ( 102)

k4

k5 ( 103)

473
493
503

4.43
7.08
10.3

1.22
2.15
3.28

3.17
3.44
4.86

0.103
0.135
0.179

k6

k7

k8 ( 10)

k9 ( 10)

k10 ( 102)

Rate Constants
1.31
2.48
4.99

101.3
254.1
359.9

0.214
0.766
1.575

0.409
1.268
3.291

0.174
0.415
1.012

1.98
3.08
6.43

Activation Energy (kJ/mol)

54.19

63.85

25.11

34.78

83.99

84.51

130.30

133.26

111.26

72.27

rate parameter values were obtained. The solubility data for

hydrogen and other gaseous components in the aqueous phase
were used from the literature sources with appropriate extrapolation, and the relevant data are presented in Table 5 as Henrys
constants.32

more-rigorous rate models, following a systematic model

discrimination procedure, are underway in our laboratory.

Typical results of experimental and predicted concentrationversus-time profiles for both gas- and liquid-phase components
at different pressures and temperatures are shown in Figures
10-14. The optimized values of the rate parameters are
presented in Table 6 and are shown as an Arrhenius plot in
Figure 15. The agreement between the predicted and experimental data was observed to be well within the experimental
error for most components. The parity plot in Figure 16 shows
the goodness of fit for all the data observed at different
temperatures and pressures. The activation energy values (see
Table 6) also support the assumption of kinetic regime in
analysis of the batch reactor data.

The detailed kinetics of glycerol hydrogenolysis using a

bimetallic Ru-Re/C catalyst was studied in a batch-slurry
reactor. The hydrogenolysis occurs with several parallel and
consecutive reaction pathways, leading to 1,2-PDO, EG, propanol, ethanol, and methanol, along with gas-phase products
such as methane, ethane, propane, and CO2. Experimental
concentration-time data at different temperatures and H2
pressures were obtained, and, based on a detailed reaction
scheme, kinetic parameters were evaluated. The hydrogenolysis
was determined to be kinetically controlled, as indicated by the
criteria for insignificant mass-transfer effects and also supported
by the activation energy values obtained for various reactions.
Although the results presented here showed improved selectivity
for 1,2-PDO and propanol with Ru-Re bimetallic catalysts, the
gas-phase products such as methane and higher alkanes are still

As a first step, only the power-law-type kinetics was

considered for fitting the experimental data, considering the
complexity of the reaction scheme; however, efforts to develop

Conclusions

10834

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

k6 ) rate constant for r6 as in Table 4 [(m3)2/(kg kmol/h)]

k7 ) rate constant for r7 as in Table 4 [(m3)/(kg/h)]
k8 ) rate constant for r8 as in Table 4 [(m3)3/2/(kg kmol1/2/h)]
k9 ) rate constant for r9 as in Table 4 [(m3)3/2/(kg kmol1/2/h)]
k10 ) rate constant for r10 as in Table 4 [(m3)3/2/(kg kmol1/2/h)]
kla ) overall gas-liquid mass-transfer coefficient [s-1]
ksap ) overall liquid-solid mass-transfer coefficient [s-1]
RH2 ) initial global rate of hydrogenation [kmol/(m3/s)]
ri ) rate of the ith reaction [kmol/(m3/h)]
S ) selectivity [%]
Vg ) volume of gas in the reactor [m3]
Vl ) volume of liquid in the reactor [m3]
w ) catalyst concentration [kg/m3(liq)]
X ) conversion [%]

Figure 15. Temperature dependence of selected rate constants.

Greek Letters
R1 ) [RH2/(kla)]CH*2
R2 ) [RH2/(ksap)]CH*2
) porosity of catalyst particles
exp ) (dp/6)[(FpRH2/Dew)CH*2]0.5
Fp ) catalyst particle density [kg/m3]
) tortuosity factor
Acknowledgment
A.T. acknowledges a graduate research assistant fellowship,
and D.R. acknowledges a postdoctoral fellowship from the
Center for Environmentally Beneficial Catalysis (CEBC) at The
University of Kansas.
Literature Cited

Figure 16. Comparison of fitted data versus experimental data, showing

the extent of fit.

significant. The kinetic study reported here will be a useful guide

to further develop catalysts for the hydrogenolysis of polyols.
Notations
CH*2 ) saturation solubility of H2 in the liquid phase [kmol/m3]
Cgly,0 ) glycerol concentration at time zero [kmol/m3]
(CH2)g,0 ) H2 concentration in the gas phase at time zero
[kmol/m3]
Ci ) concentration of a liquid component in the liquid phase
[kmol/m3]
(Ci)l ) concentration of a gaseous component in the liquid
phase [kmol/m3]
(Ci)g ) concentration of a gaseous component in the gas phase
[kmol/m3]
Cmol ) number of moles of carbon
dp ) catalyst particle diameter [m]
De ) effective diffusivity; De ) D/ [m2/s]
H ) Henrys constant [m3(liq)/m3(gas)]
k1 ) rate constant for r1 as in Table 4 [(m3)2/(kg kmol/h)]
k2 ) rate constant for r2 as in Table 4 [(m3)2/(kg kmol/h)]
k3 ) rate constant for r3 as in Table 4 [(m3)3/2/(kg kmol1/2/h)]
k4 ) rate constant for r4 as in Table 4 [(m3)2/(kg kmol/h)]
k5 ) rate constant for r5 as in Table 4 [(m3)/(kg/h)]

(1) Corma, A.; Huber, G. W.; Sauvanaud, L.; OConnor, P. Biomass to

chemicals: Catalytic conversion of glycerol/water mixtures into acrolein,
reaction network. J. Catal. 2008, 257 (1), 163171.
(2) Huber, G. W.; Iborra, S.; Corma, A. Synthesis of transportation fuels
from biomass: Chemistry, catalysts, and engineering. Chem. ReV. 2006, 106,
40444098.
(3) Fukuda, H.; Kondob, A.; Noda, H. Biodiesel fuel production by
transesterification of oils. J. Biosci. Bioeng. 2001, 92 (5), 405416.
(4) Pagliaro, M.; Ciriminna, R.; Kimura, H.; Rossi, M.; Pina, C. D. From
glycerol to value-added products. Angew. Chem., Int. Ed. 2007, 46, 4434
4440.
(5) Zhou, C.-H. C.; Beltramini, J. N.; Fan, Y.-X.; Lu, G. Q. M.
Chemoselective catalytic conversion of glycerol as a biorenewable source
to valuable commodity chemicals. Chem. Soc. ReV. 2008, 37, 527549.
(6) Blanc, B.; Bourrel, A.; Gallezot, P.; T., H.; Taylor, P. Starch-derived
polyols for polymer technologies: Preparation by hydrogenolysis on metal
catalysts. Green Chem. 2000, 8, 991.
(7) Miyazawa, T.; Koso, S.; Kunimori, K.; Tomishige, K. Glycerol
hydrogenolysis to 1,2-propanediol catalyzed by a heat-resistant ion-exchange
resin combined with Ru/C. Appl. Catal., A 2007, 329, 3035.
(8) Wang, J.; Shen, S.; Li, B.; Lin, H.; Yuan, Y. Ruthenium nanoparticles
supported on carbon nanotubes for selective hydrogenolysis of glycerol to
glycols. Chem. Lett. 2009, 38 (6), 572573.
(9) Feng, J.; Fu, H.; Wang, J.; Li, R.; Chen, H.; Li, X. Hydrogenolysis
of glycerol to glycols over ruthenium catalysts: Effect of support and catalyst
reduction temperature. Catal. Lett. 2008, 9 (6), 14581464.
(10) DHondt, E.; Van de Vyver, S.; Sels, B. F.; Jacobs, P. A. Catalytic
glycerol conversion into 1,2-propanediol in absence of added hydrogen.
Chem. Commun. 2008, 45, 60116012.
(11) Kurosaka, T.; Maruyama, H.; Naribayashi, I.; Sasaki, Y. Production
of 1,3-propanediol by hydrogenolysis of glycerol catalyzed by Pt/WO3/
ZrO2. Catal. Commun. 2008, 9, 13601363.
(12) Wawrzetz, A.; Peng, B.; Hrabar, A.; Jentys, A.; Lemonidou, A. A.;
Lercher, J. A. Towards understanding the bifunctional hydrodeoxygenation
and aqueous phase reforming of glycerol. J. Catal. 2010, 269, 411420.
(13) Furikado, I.; Miyazawa, T.; Koso, S.; Shimao, A.; Kunimori, K.;
Tomishige, K. Catalytic performance of Rh/SiO2 in glycerol reaction under
hydrogen. Green Chem. 2007, 9 (6), 582588.
(14) Dasari, M. A.; Kiatsimkul, P.-P.; Sutterlin, W. R.; Suppes, G. J.
Low-pressure hydrogenolysis of glycerol to propylene glycol. Appl. Catal.,
A 2005, 281, 225231.

Ind. Eng. Chem. Res., Vol. 49, No. 21, 2010

(15) Bienholz, A.; Schwab, F.; Claus, P. Hydrogenolysis of glycerol
over a highly active CuO/ZnO catalyst prepared by an oxalate gel method:
Influence of solvent and reaction temperature on catalyst deactivation. Green
Chem. 2010, 12, 290295.
(16) Guo, L.; Zhou, J.; Mao, J.; Guo, X.; Zhang, S. Supported Cu
catalysts for the selective hydrogenolysis of glycerol to propanediols. Appl.
Catal., A 2009, 367, 9398.
(17) Perosa, A.; Tundo, P. Selective hydrogenolysis of glycerol with
raney nickel. Ind. Eng. Chem. Res. 2005, 44, 85358537.
(18) Yin, A.-Y.; Guo, X.-Y.; Dai, W.-L.; Fan, K.-N. The synthesis of
propylene glycol and ethylene glycol from glycerol using Raney Ni as a
versatile catalyst. Green Chem. 2009, 11, 15141516.
(19) Chheda, J. N.; Huber, G. W.; Dumesic, J. A. Liquid-phase catalytic
processing of biomass-derived oxygenated hydrocarbons to fuels and
chemicals. Angew. Chem., Int. Ed. 2007, 46, 71647183.
(20) Montassier, C.; Menezo, J. C.; Hoang, L. C.; Renaud, C.; Barbier,
J. Aqueous polyol conversions on ruthenium and on sulfur-modified
ruthenium. J. Mol. Catal. 1991, 70 (1), 99110.
(21) Jiang, T.; Zhou, Y.; Liang, S.; Liu, H.; Han, B. Hydrogenolysis of
glycerol catalyzed by Ru-Cu bimetallic catalysts supported on clay with
the aid of ionic liquids. Green Chem. 2009, 11, 10001006.
(22) Maris, E. P.; Ketchie, W. C.; Murayama, M.; Davis, R. J. Glycerol
hydrogenolysis on carbon-supported PtRu and AuRu bimetallic catalysts.
J. Catal. 2007, 251, 281294.
(23) Marincean, S.; Peereboom, L.; Xi, Y.; Miller, D. J.; Jackson, J. E.
Hydrogenolysis to propylene glycol under heterogeneous conditions. Chem.
Ind. 2007, 115, 427436.
(24) Ma, L.; He, D. Hydrogenolysis of glycerol to propanediols over
highly active Ru-Re bimetallic catalysts. Top. Catal. 2009, 52, 834844.

10835

(25) Lahr, D. G.; Shanks, B. H. Kinetic analysis of the hydrogenolysis

of lower polyhydric alcohols: Glycerol to glycols. Ind. Eng. Chem. Res.
2003, 42, 54675472.
(26) Lahr, D. G.; Shanks, B. H. Effect of sulfur and temperature on
ruthenium-catalyzed glycerol hydrogenolysis to glycols. J. Catal. 2005, 232,
386394.
(27) Roy, D.; Subramaniam, B.; Chaudhari, R. V., Aqueous phase
hydrogenolysis of glycerol to 1,2-propanediol without external hydrogen
addition. Catal. Today 2010, DOI: 10.1016/j.cattod.2010.01.007.
(28) Subramaniam, B.; Roy, D.; Chaudhari, R. V. Hydrogenolysis of
biomass-derived polyols. Presented at the 238th ACS National Meeting,
American Chemical Society, Washington, DC, 2009.
(29) Roy, D.; Chaudhari, R. V. Analysis of a gas-liquid-liquid-solid
catalytic reaction: Kinetics and modeling of a semibatch slurry reactor. Ind.
Eng. Chem. Res. 2005, 44, 95869593.
(30) Ramachandran, P. A.; Chaudhari, R. V. Three Phase Catalytic
Reactors; Gordon & Breach: New York, 1983.
(31) Patil, N. G.; Roy, D.; Chaudhari, A. S.; Chaudhari, R. V. Kinetics
of reductive alkylation of p-phenylenediamine with methyl ethyl ketone
using 3% Pt/Al2O3 catalyst in a slurry reactor. Ind. Eng. Chem. Res. 2007,
46, 32433254.
(32) Wilhelm, E.; Battino, R.; Wilcock, R. J. Low-pressure solubility
of gases in liquid water. Chem. ReV. 1977, 77 (2), 219262.

ReceiVed for reView March 8, 2010

ReVised manuscript receiVed May 4, 2010
Accepted May 5, 2010
IE100553B