Applied Catalysis A: General 498 (2015) 8898

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Metalacid bifunctional catalysts for selective hydrogenolysis of

glycerol under atmospheric pressure: A highly selective route to
produce propanols
Samudrala Shanthi Priya a,b , Vanama Pavan Kumar a , Mannepalli Lakshmi Kantam a ,
Suresh K. Bhargava b , Selvakannan Periasamy b , Komandur V.R. Chary a,
a
b

Catalysis Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
School of Applied Sciences, RMIT University, GPO Box 2476V, Melbourne, VIC 3001, Australia

a r t i c l e

i n f o

Article history:
Received 9 December 2014
Received in revised form 13 March 2015
Accepted 19 March 2015
Available online 28 March 2015
Keywords:
Glycerol
Hydrogenolysis
Platinum
HPA
1-Propanol
2-Propanol

a b s t r a c t
Metalacid bifunctional catalysts containing platinum and heteropolyacids (HPA) in supported on
zirconia have been employed for the selective vapor phase hydrogenolysis of glycerol to propanols (1propanol + 2-propanol) under normal atmospheric pressure. The PtHPA/ZrO2 catalysts (HPAs such as
silicotungstic acid (STA), phosphotungstic acid (PTA), phosphomolybdic acid (PMA) and silicomolybdic
acid (SMA)) were prepared by impregnation method and the calcined catalysts were characterized by
means of X-ray powder diffraction, FTIR, Raman spectroscopy, BET surface area, CO chemisorption and
NH3 -Temperature-programmed desorption methods. The characterization results reveal the presence
of well dispersed Pt metallic phase and Keggin structure of HPAs on support. The catalytic performance
during glycerol hydrogenolysis is well correlated with Pt dispersion and the acidic properties of catalysts.
Among the tested catalysts, it was found that PtPTA/ZrO2 exhibited excellent selectivity to propanols
(98%) with total glycerol conversion at 230 C. A detailed study was made on the effect of various reaction
parameters such as the inuence of reaction temperature, reduction temperature, glycerol concentration,
hydrogen ow rate, feed ow rate and HPA loading to unveil the optimized reaction conditions. Reaction
temperature was observed to have a signicant effect on the glycerol conversion and product selectivity. The spent catalysts were also characterized by the X-ray diffraction, NH3 -TPD and SEM analysis to
investigate the changes in catalytic performance and causes of catalyst deactivation.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel production by transesterication of oils affords huge
amounts of glycerol as a byproduct [1]. Since utilization or safe
disposal of byproducts is a prime objective from the viewpoint of
sustainable development, researchers focused on various transformations of bioglycerol, a renewable feedstock, into value added
compounds and ne chemicals via oxidation, reduction, dehydration, hydrogenolysis, esterication, fermentation, pyrolysis,
etherication and so on [24]. Production of 1,2-propanediol (PDO),
1,3-propanediol (1,3-PDO) and propanols by hydrogenolysis of
bioglycerol over supported noble metal catalysts is one of such
potential routes which has been extensively studied by several
authors [58].

Corresponding author. Tel.: +91 40 27193162; fax: +91 40 27160921.

E-mail addresses: charykvr@gmail.com, kvrchary@iict.res.in (K.V.R. Chary).
http://dx.doi.org/10.1016/j.apcata.2015.03.025
0926-860X/ 2015 Elsevier B.V. All rights reserved.

Propanediols, both 1,2-propanediol and 1,3-propanediol, are

used as solvents and additives in many elds such as polymer, cosmetics and pharmaceuticals [9]. In comparison, propanols are also
expensive commodity chemicals widely employed as industrial
solvents and attracted much attention in recent years. Currently,
1-propanol is produced by hydroformylation of ethylene and is
mainly used as printing ink or in production of n-propyl acetate
[10]. 2-Propanol can be produced by the hydration of propylene and
nds application in pharmaceuticals, as a disinfectant and a deicer
[11]. However, routes to biopropanols [1214] such as 1-propanol
[7,15] and 2-propanol have been less discussed while abundant literature is available on conversion of glycerol to 1,2-PDO [1624]
and 1,3-PDO [2535].
Tomishige and coworkers [36] conducted the hydrogenolysis of
glycerol at 120 C and 8.0 MPa in which the optimized Ru-added IrReOx/SiO2 catalyst gave high yields of propanols (84%). Previously
reported processes describe a method of one step hydrogenolysis of
glycerol to biopropanols over PtHSiW/ZrO2 catalyst at a pressure

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

89

Scheme 1. Hydrogenolysis of glycerol to various products.

of 5 MPa and 200 C and achieved a combined selectivity of 90.9%

toward propanols [12].
In spite of these research efforts, a major drawback is the fact
that most research efforts to date have employed the use of high
reaction pressure carried out in batch reactors, although few operated in continuous xed bed reactors. Consequently, the energy
consumption of the process is increased and in turn a decrease
in the protability of the process. Above all, the selectivities to
propanols are still low and did not go beyond 91%. Therefore, there
is tremendous interest to selectively convert glycerol to propanols
under mild and most economical conditions.
In this context, developing proper xed bed continuous ow
reactors operated at desired temperature and atmospheric pressure for selective conversion of glycerol to propanols still remains
an open challenge. The present investigation was undertaken
considering the aforesaid background, evaluating metalacid
bifunctional catalysts for the vapor phase conversion of glycerol
to propanols at normal atmospheric pressure. To the best of our
knowledge, there is no report for the utilization of continuous xed
bed process under atmospheric pressure for the conversion of glycerol into propanols which is economically attractive.
The glycerol hydrogenolysis reaction involves dissociation of
C C and C O with simultaneous addition of hydrogen. Since glycerol is rich in oxygen content, C O hydrogenolysis is the most
promising method in view point of biomass conversion to chemicals. The glycerol hydrogenolysis is generally believed to take
place via the dehydrationhydrogenation mechanism [29,32,35].
In this view, acidmetal bifunctional catalysts are most effective
for the hydrogenolysis of glycerol wherein the acid sites are responsible for the dehydration step and the metallic sites are responsible
for the hydrogenation step, respectively (Scheme 1).
Noble metal based catalysts present good selectivity to
propanols for hydrogenolysis of glycerol [12,13]. Heteropolyacids
(HPAs) have high potential as catalyst. These materials offer the
unique opportunity to replace the corrosive liquid acids currently
used in many chemical conversion steps to provide greener
processes. HPAs are typical strong Bronsted acids compared to
conventional solid acid catalysts and catalyze a wide variety of
homogeneous and heterogeneous reactions [37] offering a strong
option for efcient and cleaner processing. Supported HPAs have
been used in a variety of organic transformations such as acylation,
alkylation, esterication, oxidation and hydrogenation. Zirconia
based materials have attracted considerable interest in recent years
for their potential use as catalyst supports [38] and often used to
immobilize HPAs [39] as they present special characteristics such
as high thermal stability, extreme hardness, and stability under
reducing conditions.
In the present investigation, several zirconia supported PtHPAs
(STA, PTA, PMA and SMA) bi-functional catalysts were prepared,
characterized, and tested for glycerol hydrogenolysis. The main
focus of this work was the evaluation of supported PtHPA catalysts

for the vapor phase hydrogenolysis of glycerol (Scheme 2) under

atmospheric pressure with the aim to produce alcohols, in particular 1-propanol (1-PrOH) and 2-propanol (2-PrOH) with highest
selectivities.
2. Experimental
2.1. Catalyst preparation
ZrO2 support was obtained by hydrolyzing ZrOCl2 with aqueous ammonia added until the solution reached pH 8.0, followed
by washing and then drying at 110 C for 24 h. The support was
calcined at 500 C for 3 h in air. The heteropolyacids (HPAs) such
as phosphotungstic acid (PTA), phosphomolybdic acid (PMA), silicotungstic acid (STA), silicomolybdic acid (SMA) were used. The
PtHPA/ZrO2 catalysts employed in this investigation were prepared by sequential or step by step wet impregnation method.
Initially, HPA/ZrO2 was prepared by impregnation of ZrO2 support
with an aqueous solution of HPA. The impregnated sample was
dried overnight at 110 C and then calcined at 300 C in static air
for 3 h. The PtHPA/ZrO2 catalysts were prepared by impregnation
of HPA/ZrO2 with aqueous solution of H2 PtCl6 6H2 O. After impregnation, the sample was dried overnight at 110 C and then calcined
at 350 C for 4 h. The optimum weight loadings of Pt metal and
acid components (STA, PTA, PMA and SMA) in all the catalysts were
conned to 2 wt% and 15 wt%, respectively. The catalysts will be
hereinafter referred to as PtPTA/ZrO2 , PtSTA/ZrO2 , PtPMA/ZrO2
and PtSMA/ZrO2 .
2.2. Catalyst characterization
The calcined forms of catalysts were characterized by powder X-ray diffraction (XRD) analysis using a Rigaku miniex X-ray
diffractometer using Ni ltered Cu K radiation ( = 0.15406 nm)

Biodiesel

Vapour phase
hydrogenolysis

OH

HO
OH

Pt-HPA/ZrO 2

Glycerol

Green Synthesis
High Selectivities

230 oC

atmospheric pressure
OH
OH

1-propanol

2-propanol

HPA = PTA, STA, PMA, SMA

Scheme 2. Hydrogenolysis of glycerol to propanols over PtHPA/ZrO2 catalysts.

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S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

from 2 = 2 to 65 , at a scan rate of 2 min1 with the beam voltage

and a beam current of 30 kV and 15 mA respectively.
FTIR spectra of the catalysts were taken on the IR (Model: GCFT-IR Nicolet 670) spectrometer by KBr disk method under ambient
condition.
Raman spectra of the catalyst samples were acquired with the
micro-Raman attachment of a Horiba-Jobin Yvon Raman spectrometer equipped with a confocal microscope, 2400/900 grooves/mm
gratings, and a notch lter. Visible Laser excitation 50 at 532 nm
(visible/green) is supplied by a Yag doubled diode pumped Laser
(20 mW). Scattered photons were dried and focused on to a
single-stage monochromator and measured with a UV sensitive
LN2-cooled CCD detector (Horiba-Jobin Yvon CCD-3000 V).
The surface area of the calcined catalysts were analyzed using
N2 adsorption at 196 C by the multipoint BET method taking
0.0162 nm2 as its cross-sectional area using Autosorb 1 (Quantachrome instruments, USA).
TPD experiments were conducted on AutoChem 2910
(Micromeritics, USA) instrument. In a typical experiment, 100 mg
of oven dried sample was pretreated by passage of high purity
(99.995%) helium (50 mL/min) at 200 C for 1 h. After pretreatment, the sample was saturated with highly pure anhydrous
ammonia (50 mL/min) with a mixture of 10% NH3 He at 80 C for
1 h and subsequently ushed with He ow (50 mL/min) at 80 C
for 30 min to remove physisorbed ammonia. TPD analysis was
carried out from ambient temperature to 600 C at a heating rate
of 10 C min1 . Ammonia concentration in the efuent stream
was monitored with thermal conductivity detector (TCD), and the
area underneath the peak was integrated using the software 70
GRAMS/32, to determine the desorbed amount of ammonia.
CO-chemisorption measurements were also carried out on
AutoChem 2910 (Micromeritics, USA) instrument. Prior to adsorption measurements, ca. 100 mg of the sample was reduced in a ow
of hydrogen (50 mL/min) at 400 C for 3 h and ushed out subsequently in a pure helium gas ow for an hour at 400 C. The sample
was subsequently cooled to ambient temperature in the same He
stream. CO uptake was determined by injecting pulses of 9.96% CO
balanced helium from a calibrated on-line sampling valve into the
helium stream passing over the reduced samples at 400 C. Platinum surface area, percentage dispersion and Pt average particle
size were calculated assuming the stoichiometric factor (CO/Pt) as
1. Adsorption was deemed to be complete after three successive
runs showed similar peak areas.

2.3. Catalyst testing

The gas phase hydrogenolysis of glycerol was carried out
under atmospheric pressure in a vertical xed bed quartz reactor (40 cm length, 9 mm i.d.) using 0.5 g of catalyst. Prior to the
reaction, the catalysts were pretreated at 350 C for 2 h in owing
H2 (60 mL/min). After cooling down to the reaction temperature
(230 C), hydrogen (100 mL/min) and an aqueous solution of 10 wt%
glycerol were introduced into the reactor through a heated evaporator. The reaction products were condensed in an icewater trap
and collected hourly for analysis. The liquid products were analyzed on a gas chromatograph GC-2014 (Shimadzu) equipped with
a DB-wax 123-7033 (Agilent) capillary column (0.32 mm i.d., 30 m
long) and ame ionization detector.
The gas products were collected in a gas trap and analyzed
ofine using a gas chromatograph equipped with a POROPAQ
packed column and FID. The identied products were 1-propanol,
2-propanol, hydroxyacetone, ethanol, ethylene glycol, methanol,
acetone and propane. Quantication of product mixture has been
achieved by comparing the weight composition in the input and
output. The conversion of glycerol and selectivity of products

obtained during glycerol hydrogenolysis were calculated on the

basis of the following equations:
Conversion (%)
=

moles of glycerol (in) moles of glycerol (out)

100
moles of glycerol (in)

Selectivity (%) =

moles of one product

100
moles of all product

3. Results and discussion

3.1. Characterization techniques
3.1.1. X-ray diffraction (XRD)
XRD patterns of pure ZrO2 , Pt/ZrO2 and PtHPA/ZrO2 catalysts
are shown in the Fig. S1 (Supporting information). In all the samples, ZrO2 mainly exhibited diffraction peaks corresponding to
monoclinic ZrO2 at 2 = 24.1 , 28.3 , 31.5 , 34.3 and 49.4 [40]. The
peaks related to HPAs (Keggin molecules) were not detected on the
catalysts and appear to be overlapped with that of ZrO2 . This might
be possibly due to the interaction of HPAs with ZrO2 or well dispersion of species on the surface of support. Meanwhile, a less intense
diffraction peak at 2 = 39.7 corresponding to Pt crystalline plane
(1 1 1) reveals the occurrence of small crystals of Pt on the support
surface of Pt/ZrO2 , PtSTA/ZrO2 , PtPMA/ZrO2 and PtSMA/ZrO2
catalysts. However, the intensity of Pt peak in case of PtPTA/ZrO2
catalyst was found to be very less which suggests that the Pt particles were highly dispersed on the support surface compared to
other PtHPA/ZrO2 catalysts.
3.1.2. Fourier transform infrared spectroscopy (FTIR)
Fig. S2 (Supporting information) shows the FTIR spectra of various platinum and heteropolyacid catalysts supported on zirconia.
The strong peaks in the wave number region 740,505 cm1 are
associated with Zr O Zr asymmetric stretching mode of zirconia. A series of peaks observed between 7001100 cm1 reveals
the presence of characteristic bands of Keggin structure of various
HPAs. The characteristic bands of PTA molecule at 1080, 985, 890
and 839 cm1 are assigned to the stretching modes of oxygen atom
bond to tungsten and phosphorous, P O, W O, W O W in corner
shared octahedral and W O W in edge shared octahedral, respectively. The bands at 1010, 975, 880 and 742 cm1 are attributed
to Si O, W O, W O W (inter octahedral) and W O W (intra
octahedral) phases of STA molecule respectively. The four characteristic bands for the Keggin structure of PMA molecule appeared
at 1031 (P O), 960 (Mo O) and 783 (Mo O Mo) cm1 . The peak at
956 cm1 has been assigned to the terminal Mo O bond of SMA. In
addition, the bands observed at 16221627 cm1 are due to the
bending vibrations of OH of water and an adsorption band in
between 3600 and 3000 cm1 corresponded to the stretching vibration of OH group of physically adsorbed water. Similar results
were also observed by Jadhav et al. [41] and Ferreira et al. [42].
These results indicate that the Keggin structure of heteropolyacids
remained intact in the supported catalysts.
3.1.3. Raman spectroscopy
Raman spectroscopy was further used to conrm the state of
primary structure of Keggin ion in the heteropolyacid catalysts.
Raman spectra of pure ZrO2 and as prepared catalysts are shown
in Fig. S3 of supporting information. Raman bands at 310, 382,
474, 499, 559, 620 and 636 cm1 corresponds to monoclinic zirconia as evidenced by XRD results. The bands appeared in the range
9001010 cm1 were assigned to W O symmetric and asymmetric stretching vibrations of HPAs Keggin structure. In addition, a

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

91

Table 1
Results of Temperature-Programmed Desorption and BET surface area of Pt/ZrO2 and PtHPA/ZrO2 catalysts.
Catalyst

Pt/ZrO2
PtPTA/ZrO2
PtSTA/ZrO2
PtPMA/ZrO2
PtSMA/ZrO2

BET surface area (m2 /g)

NH3 uptake (mol/g)

85
72
69
68
57

Total acidities (mol/g)

Weak

Moderate

Strong

83.2
21.1
53.9
42.6
18.8

193.2
226.1
199.0
267.8
184.5

31.0
28.5
23.0
15.6

276.4
278.2
280.9
333.4
218.9

Table 2
Results of CO uptake, dispersion, metal area and average particle size of Pt/ZrO2 and PtHPA/ZrO2 catalysts.
Catalyst

Dispersion (%)

CO uptake (mol/g)

Metal surface area (m2 /g)cat

Particle size (nm)

Pt/ZrO2
PtPTA/ZrO2
PtSTA/ZrO2
PtPMA/ZrO2
PtSMA/ZrO2

13.7
13.3
11.6
9.0
8.7

14.0
13.6
11.9
9.2
8.9

0.55
0.65
0.57
0.44
0.43

10.1
8.4
9.7
12.5
12.9

broad band in the range 980750 cm1 is observed in case of PMA

and SMA catalysts ascribed to the stretching vibrations of MoO3
Keggin structure [43]. These ndings are in good agreement with
the studies of Zhu et al. [31].

3.1.4. Temperature programmed desorption of ammonia

(NH3 -TPD)
The ammonia adsorptiondesorption technique usually enables
determination of the strength of acid sites present on the catalyst
surface together with total acidity. Generally the strength of solid
acid sites with TPD proles can be classied into three types by
the temperature of desorption NH3 weak (180250 C), moderate
(260330 C) and strong (340500 C) [44]. The NH3 -TPD proles
of Pt/ZrO2 and catalysts with different HPAs are shown in Fig.
S4 (Supporting information), and the amounts of NH3 desorbed
(mol/g) are presented in Table 1. Three types of acid sites are
observed in these catalysts. The low temperature desorption peak
(Tmax in the range 180360 C) is related to the zirconia support
corresponding to weak and moderate acidic sites. The peaks due
to strong acidic sites generated by the heteropolyacid interacting
with support are observed at Tmax 350480 C. However, the acidity of the catalyst depends on the type of HPA on zirconia. It is
evident from Table 1, that PtPTA/ZrO2 catalyst possesses more
number of strong acid sites compared with others. Therefore, the
results indicate that the acid strength of HPAs follows the order:
PTA > STA > PMA > SMA, consistent with the previous reports [45].
In addition, it is evident from NH3 -TPD results that the PtHPA/ZrO2
catalysts possess stronger acidity when compared to the Pt/ZrO2
catalyst signicantly affecting the catalytic performance in glycerol
hydrogenolysis.

3.1.5. BET surface area

The catalytic activity is signicantly increased by using a high
surface area catalyst since the catalytic action occurs on specic
sites on the surface of catalyst, called active sites. Therefore, measurement of the surface area is most important study, as it is
generally believed that higher the surface area, higher will be the
catalytic activity. The surface areas of the catalysts determined by
using BET method are listed in Table 1. It was observed that the
immobilization of HPAs on zirconia leads to a decrease in the surface area of the catalysts. The reduction in surface area may be due
to the blockage of pores by active species. A similar observation
was made by Malliek et al. [46].

3.1.6. CO-chemisorption
The CO chemisorption on the catalysts was used to estimate
Pt dispersion, metal surface area and active particle diameter. The
trends of activity observed for different catalysts can be explained
based on metal dispersion and active particle diameter of Pt. As
compiled in Table 2, the incorporation of HPAs did not affect Pt
particle size and Pt dispersion notably compared with Pt/ZrO2 catalyst. However, the results demonstrate that PtPTA/ZrO2 catalyst
exhibited high dispersion over other catalysts and simultaneously
improved catalytic performance of glycerol hydrogenolysis significantly. Zhu et al. [31] also reported that HPAs have little effect on
the dispersion of Pt. The obtained results are well in agreement
with the ndings of XRD studies.
3.2. Catalytic performance of the catalysts
3.2.1. Effect of HPAs on the glycerol hydrogenolysis
Glycerol hydrogenolysis is known to proceed through several sequential hydrogenolysis reactions and C C bond cleavage
reactions and therefore it is an important task to control the product distribution selectively. The catalytic performance of glycerol
hydrogenolysis over Pt/ZrO2 and PtHPA/ZrO2 catalysts with various HPAs was investigated in a continuous xed-bed reactor at
230 C under atmospheric pressure. The optimum loadings of Pt and
HPAs used in the present study are conned to 2 wt% and 15 wt%.
The major products obtained include propanols (1-PrOH + 2-PrOH)
whereas hydroxyacetone and other degradative products such
as ethanol, ethylene glycol, methanol, acetone and propane are
obtained as byproducts. This research work was aimed at analyzing and optimizing the sequential process in order to improve
conversion and selectivity of glycerol hydrogenolysis to propanols.
In general, propanols can be produced from glycerol by two
pathways (Scheme 3). Hydrogenolysis of glycerol to 1-propanol and
2-propanol via 1,2-propanediol is one signicant route whereas
hydrogenolysis of glycerol to 1-propanol via 1,3-propanediol is

Scheme 3. Glycerol hydrogenolysis to propanols.

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S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

Table 3
Catalytic performance of Pt/ZrO2 and PtHPA/ZrO2 catalysts for the production of propanols from glycerola .
Catalyst

Conversion (%)

Pt/ZrO2
PtPTA/ZrO2
PtSTA/ZrO2
PtPMA/ZrO2
PtSMA/ZrO2

85
99.9
99.7
98.4
98.1

Selectivity in liquid products (%)

Total propanols

1-PrOH

2-PrOH

1,3-PDO

1,2-PDO

HA

Others

62
98
96
90.7
80.9

33
52
62
62
53

29
46
34
28.7
27.9

6.0

27

5.0

2.5
5.3
13.4

2.0
1.5
4.0
5.7

a
Reaction conditions: 0.5 g catalyst; Reaction temperature: 230 C, 0.1 MPa H2 ; H2 ow rate: 100 mL/min; WHSV-1.02 h1 ; 1-PrOH: 1-propanol, 2-PrOH: 2-propanol, HA:
Hydroxyacetone, Others include ethanol, ethylene glycol, methanol and acetone.

Table 4
Performance of glycerol hydrogenolysis over PtHPA/ZrO2 catalystsa .
Catalyst

Conversion (%)

PtPTA/ZrO2
PtSTA/ZrO2
PtPMA/ZrO2
PtSMA/ZrO2

99.9
99.7
98.4
98.1

Selectivity in liquid and gas products (%)

Total propanols

1-PrOH

2-PrOH

Propane

HA

Others

88
84.5
79
70

47 (46.9)
54.5 (54.3)
54 (53.1)
46 (45.1)

41 (40.9)
30 (29.9)
25 (24.6)
24 (23.5)

10.2 (10.1)
12.5 (12.4)
14 (13.7)
15 (14.7)

1.8
4.0
11

1.8
1.2
3.0
4.0

a
Reaction conditions: 0.5 g catalyst; Reaction temperature: 230 C, 0.1 MPa H2 ; H2 ow rate: 100 mL/min; WHSV-1.02 h1 ; 1-PrOH: 1-propanol, 2-PrOH: 2-propanol, HA:
Hydroxyacetone, Others include ethanol, ethylene glycol, methanol and acetone. In parentheses, the yield (%) of the respective products is mentioned.

another possible route. Nevertheless, it is evident that the reaction route that leads 1,2-propanediol, 1,3-propanediol and ethylene
glycol should be suppressed in order to obtain propanols with high
selectivities. However it is important task to perform both the glycerol hydrogenolysis to propanediols and the hydrogenolysis of the
propanediols to propanols by using a single catalyst. Therefore, a
one-step transformation of glycerol to propanols over PtHPA/ZrO2
catalysts in vapor phase was attempted in the present investigation
for making the process more reliable and economic viable.
At rst, we examined the effect of HPAs on glycerol hydrogenolysis for the selective production of propanols in comparison with
Pt/ZrO2 catalyst. As it is obvious in Table 3, all the PtHPA/ZrO2
catalysts presented higher glycerol conversion and high selectivity
to 1-PrOH and 2-PrOH than that of Pt/ZrO2 sample. It is interesting
to note that propanediols have not been detected during the reaction which implies that the complete sequential hydrogenolysis of
propanediols to propanols occurred leading to higher selectivities
toward propanols. The promoting effect of the HPA was clear when
compared to the experiment carried out under same reaction conditions in the absence of HPA (85% conversion and 62% selectivity to
total propanols). This result suggests that the acidic component of
the catalyst have signicant inuence on the catalytic performance.
It is worth noting that, the PtPTA/ZrO2 catalyst reached
the excellent performance, 99.9% glycerol conversion with 98%
selectivity to total propanols, which appeared to be more superior and contrast to the previous PtH4 SiW12 O40 /ZrO2 [12]. The
PtSTA/ZrO2 catalyst also exhibited best catalytic activity in terms
of glycerol conversion and propanols selectivity. The superior performance of PtPTA/ZrO2 catalyst can be explained based on the
dispersion of active metal and acidity of catalyst which play a key

role in the bi-functional hydrogenolysis mechanism of glycerol. To

our knowledge, this is the best selectivity ever achieved for the
transformation of glycerol into propanols under atmospheric pressure. Table 4 presents the performance of glycerol hydrogenolysis
over various PtHPA/ZrO2 catalysts including both liquid and gas
product distribution. The result showed that propane is formed by
sequential hydrogenolysis of propanols and the yield of propane
varied with the type of HPA present in the catalyst.
Considering the remarkable higher activity of PtPTA/ZrO2 catalyst than that of other HPA supported catalysts, PtPTA/ZrO2
catalyst was chosen as the catalytic system for further optimization
in the hydrogenolysis of glycerol.
3.2.2. Effect of reaction temperature
The effect of temperature over PtPTA/ZrO2 catalyst on vapor
phase glycerol hydrogenolysis was investigated in detail. The
experiments were performed at different temperatures in the range
150270 C under atmospheric pressure and the results are presented in Table 5. As revealed in Table 5, the glycerol conversion
increased rapidly from 10 to 99.9% as the temperature elevated
from 150 to 230 C and then decreased to about 89% at 270 C,
whereas the total selectivity of propanols reached 98% at 230 C followed by a slight decrease at higher temperature. It is noteworthy
that, low temperatures promoted signicant formation of 1-PrOH
with little amounts of degradation products in spite of low glycerol conversion. Interestingly, 2-PrOH is observed only at moderate
temperatures which did not appear under low or high temperatures.
It is clear that, the 1-PrOH/2-PrOH relative ratio was signicantly affected by the temperature and excellent selectivity

Table 5
Effect of Reaction temperature on glycerol hydrogenolysis over PtPTA/ZrO2 catalyst under atmospheric pressurea Selectivity in liquid products (%).

Conversion
Total PrOHs
1-PrOH
2-PrOH
HA
Others

150 C

170 C

190 C

210 C

230 C

250 C

270 C

10
65
65

22
13

25
84
84

11
5.0

42
92
49
43
6.0
2.0

74
92
50
42
3.0
5.0

99.9
98
52
46
1.3
0.7

98.6
97
97

1.2
1.8

89
95.9
95.9

2.1
2.0

a
Reaction conditions: 0.5 g catalyst, Reduction temperature: 350 C, H2 ow rate: 100 mL/min, WHSV-1.02 h1 ; 1-PrOH: 1-propanol, 2-PrOH: 2-propanol, HA: Hydroxyacetone, Others include ethanol, ethylene glycol, methanol and acetone.

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

Conversion
1-PrOH
2-PrOH

100

80

80

60

60

40

40

20

20

Selectivity (%)

100

Conversion (%)

93

0
0

10

15

20

PTA loading (wt%)

Fig. 1. Effect of PTA loading on glycerol hydrogenolysis reaction to propanols. Reaction conditions: Reaction temperature = 230 C; H2 ow rate = 100 mL/min, WHSV
1.02 h1 .

to total propanols can be achieved at appropriate temperature.

Moreover, the increasing temperature could accelerate the glycerol hydrogenolysis to 1-PrOH with promoted dehydration and
hydrogenation of propanediols. Taking into account that selectivity
of 1-propanol is comparatively high (97%), indicates that overhydrogenolysis of propanediols to 1-propanol will be accelerated
at high temperatures. Based on these results, it is evident that
temperature is one such key parameter that has strongly inuenced glycerol conversion and propanols selectivity. This was also
observed by van Ryneveld and co-workers [14] where at higher
reaction temperatures, the glycerol conversion over Ni/SiO2 catalysts was increased signicantly. Further studies were performed

3.2.3. Effect of PTA loading

Fig. 1 shows the inuence of PTA loading on the catalytic performance of glycerol hydrogenolysis over the PtPTA/ZrO2 catalyst. In
the absence of PTA, the sequential hydrogenolysis capability was
comparatively low with a total selectivity of 62% to propanols. For
the catalysts with acidic component (520 wt% PTA), both glycerol
conversion and selectivity to propanols elevated and reached maximum at 15 wt% PTA loading (99.9% conversion with 98% selectivity
to propanols). Further increase in the loading of PTA dropped the

Conversion
1-PrOH
2-PrOH

100

80

80

60

60

40

40

20

20

Selectivity (%)

Conversion (%)

100

at 230 C, the conversion and selectivity being both signicant at

this temperature.

0
200

250

300

350
o

Effect of Reduction temperature ( C)

Fig. 2. Effect of Reduction temperature on hydrogenolysis of glycerol to propanols. Reaction conditions: Reduction temperature = 200350 C, Reaction temperature = 230 C;
H2 ow rate = 100 mL/min; WHSV 1.02 h1 .

94

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

Fig. 3. Effect of Glycerol concentration on hydrogenolysis of glycerol to propanols. Reaction conditions: Reaction temperature = 230 C; H2 ow rate = 100 mL/min, WHSV
1.01 h1 , 1.02 h1 , 1.03 h1 and 1.04 h1 .

glycerol conversion to 92% and propanols selectivity to 84%. From

the results, it is well-established that the cooperative effect of active
metal and acid sites appears to play a predominant role in the
catalytic performance of glycerol hydrogenolysis and a balanced
distribution of metal and acid sites favors to reach outstanding
reaction performance. Zhu et al. [12] also reported that the optimal
concentration of acid component was 15 wt%.
3.2.4. Effect of catalyst reduction temperature
The results of glycerol hydrogenolysis using PtPTA/ZrO2 catalyst reduced at different temperatures are presented in Fig. 2.
The sample was reduced in owing hydrogen at 200, 250, 300

100

Conversion
1-PrOH
2-PrOH

80

80

60

60

40

40

20

20

Selectivity (%)

Conversion (%)

100

and 350 C, respectively. As can be seen from Fig. 2, the catalyst

reduction temperature has a signicant effect on the selectivity
of propanols. As the reduction temperature elevated from 200 to
350 C, there was a uniform increase in the conversion of glycerol
from 70 to 99.9%. The selectivity to propanols (1-PrOH + 2-PrOH)
also gradually increased with increasing catalyst reduction temperature indicating that the reduction temperature can inuence
the catalytic performance promoting active hydrogen species on
the metal sites. Feng et al. [47] studied the effect of catalyst reduction temperature for the hydrogenolysis of glycerol to glycols over
ruthenium catalysts and concluded that reduction method has signicant inuence on the catalytic performance.

0
60

80

100

120

Effect of hydrogen flow rate (mL/min)

Fig. 4. Effect of H2 ow rate on hydrogenolysis of glycerol to propanols. Reaction conditions: Reaction temperature = 230 C; H2 ow rate =60 mL/min, 100 mL/min, 120 mL/min
and 140 mL/min, WHSV 1.02 h1 .

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

95

100

100

Conversion (%)

Conversion
1-PrOH
2-PrOH

60

60

40

40

20

20

Selectivity (%)

80

80

0
8

10

11

12

13

Effect of Partial Pressure of Glycerol (mm.Hg)

Fig. 5. Effect of partial pressure of glycerol on hydrogenolysis of glycerol to propanols. Reaction conditions: Reaction temperature = 230 C; H2 ow rate = 100 mL/min, WHSV
1.02 h1 , 2.04 h1 , 3.06 h1 and 4.08 h1

3.2.5. Effect of glycerol concentration

Previous studies by Chary et al. [48] showed that higher glycerol
conversion is favorable at low glycerol concentration. However, this
tendency was found to be the same over the PtPTA/ZrO2 catalyst
in the present work. Fig. 3 provides the effect of glycerol concentration on the glycerol hydrogenolysis investigated in the range
520 wt% glycerol feed. As the glycerol content increased, the glycerol conversion and the selectivity toward propanols decreased
considerably. At 5 wt% glycerol, the selectivity of propanols was
80% with conversion of 99.9%. The same conversion was obtained
at 10 wt%, but the selectivity of propanols increased to 98% which
indicates the over hydrogenolysis of propanediols to propanols is

Conversion (%)

80

3.2.6. Effect of hydrogen ow rate

The hydrogen pressure also inuenced the conversion of glycerol and the selectivities of propanols, and the results are shown
in Fig. 4. The conversion of the glycerol increased with the increase
of the hydrogen ow rate from 60 mL/min to 120 mL/min. When
hydrogen ow rate was low, only 54% of glycerol was converted

Conversion
1-PrOH
2-PrOH
HA
EG
Others

100

80

60

60

40

40

20

20

Selectivity (%)

100

accelerated. Further increase in the glycerol concentration caused

a rapid decline in the conversion and selectivity of propanols which
attributes to a lowered reaction rate due to higher viscosity. Therefore 10 wt% glycerol was found to be the optimal concentration to
obtain maximum conversion of glycerol and propanols selectivity.

0
0.4

0.6

0.8

1.0

-1

Effect of W/F (g ml h)
Fig. 6. Effect of contact time (W/F) on glycerol hydrogenolysis. Reaction conditions: Reaction temperature = 230 C; H2 ow rate = 100 mL/min; Glycerol feed: 0.5 mL/h;
W/F = 0.4, 0.6, 0.8, 1.0 g mL1 h.

96

100

100

95

95

Conversion of glycerol
Selectivity of 1-PrOH+2-PrOH

90

90

85

Selectivity (%)

Conversion (%)

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

85

10

Time (h)
Fig. 7. TOS on hydrogenolysis of glycerol to propanols over PtPTA/ZrO2 catalyst. Reaction conditions: Reaction temperature = 230 C; H2 Flow rate = 100 mL/min, WHSV
1.02 h1 .

with 84% propanols selectivity. While when hydrogen pressure

was 100 mL/min, the increment of glycerol conversion was as distinct as it reached maximum with an excellent selectivity of 98%
to propanols. Chary et al. [49] also reported a similar result that
the conversion of glycerol increased with the increase of hydrogen
ow rate.
3.2.7. Effect of partial pressure of glycerol
Reactions were carried out at 0.5, 1.0, 1.5 and 2.0 mL/h ow rate
of glycerol feed (8.3, 10.9, 12.2 and 13.0 mm. Hg partial pressure
of glycerol respectively) at a constant temperature of 230 C over
the PtPTA/ZrO2 catalyst to determine the effect of partial pressure of glycerol on the reaction. Fig. 5 provides the summary of the
propanols selectivity and conversions of 10 wt% glycerol solution
under different partial pressures of glycerol. As shown in Fig. 5, glycerol conversion decreased from 99.9% to 85% and the selectivities
of propanols (1-PrOH + 2-PrOH) decreased greatly from 98% to 40%
when partial pressure of glycerol increased from 8.3 to 13.0 mm.
Hg. The low conversion and selectivities at high glycerol feed ow
rate is as expected, due to limited availability of active sites on the
catalysts [50,51].
3.2.8. Effect of contact time (W/F)
The W/F was varied from 0.4 to 1.0 g mL1 h by changing the
weight of catalyst over a xed feed rate of glycerol. The effects
of contact time on glycerol conversion and product distribution
on PtPTA/ZrO2 catalyst are shown in Fig. 6. As expected, it was
found that glycerol conversion increased with prolonging contact
time. As the value of W/F increased from 0.4 to 1.0 g mL1 h, glycerol conversion increased from 74% to 99.9%. The selectivity of
over hydrogenolysis products, i.e. 1-propanol and 2-propanol also
increased to 52% and 46% from 30% and 23%, respectively, while
HA and EG selectivity decreased from 17% to 0.4% and 18% to

1.3%, respectively by increasing contact time. This suggests that

higher contact time tends to increase selectivity of propanols which
might be caused by the enhancement further hydrogenolysis, and
decreases the selectivity of undesired products such as methanol,
ethanol and acetone.
3.2.9. Time on stream studies
As a representative example, a time-on-stream behavior of
vapor phase hydrogenolysis of glycerol over PtPTA/ZrO2 catalyst
was examined for a period of 10 h at 230 C under atmospheric
pressure, and the results are shown in Fig. 7. The catalyst shows
a large increase in glycerol conversion and in the selectivities of
1-PrOH and 2-PrOH with increase in the reaction time up to 3 h.
At the reaction time of 3 h, the glycerol conversion reached maximum to 99.9%, with selectivity toward propanols increasing to
98%. Till the end of 7 h, the glycerol conversion remained almost
stable, even though there is a slight decrease in the selectivities of 1PrOH and 2-PrOH. Upon further increasing the reaction time to 10 h,
the glycerol conversion dropped to 86% while the decline in total
selectivity to propanols (94%) is not so obvious. These maximum
glycerol conversion and selectivities of propanols (1-propanol + 2propanol) in the vapor phase glycerol hydrogenolysis were higher
than those of the previously reported catalysts PtHSiW/ZrO2 [12]
and Rh-ReOx/SiO2 [15] (propanols (1-PrOH + 2-PrOH): 91% and 92%
respectively).
3.3. Studies on the spent catalyst
To verify the stability of the catalyst, the PtPTA/ZrO2 catalyst
was reused, and the results are shown in Table 6. The conversion
and the selectivity were almost reproduced over the used catalyst. Further, the stability of the catalyst was conrmed by various
characterization techniques. The XRD, SEM and TPD patterns of

Table 6
Studies of the spent catalyst PtPTA/ZrO2 .
Catalyst

Conversion (%)

Selectivity of Total PrOHs (%)

BET surface area (m2 /g)

Total acidity (NH3 mol/g)

Fresh
Spent

99.9
98.4

98
96.7

72
69

278.2
274.0

S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

97

Fig. 8. XRD, NH3 -TPD and SEM images of spent PtPTA/ZrO2 catalyst.

the spent PtPTA/ZrO2 catalyst were similar to those of the fresh

PtPTA/ZrO2 catalyst as shown in Fig. 8, indicating that the structure of PtPTA/ZrO2 was maintained during the catalytic reaction.
4. Conclusions
A single step vapor phase hydrogenolysis of glycerol to
propanols under atmospheric pressure, based on metalacid
bifunctional catalysts is presented as a new and efcient method.
Highly active platinum and heteropolyacid catalysts supported
on zirconia were prepared by a simple and convenient step by
step impregnation method. Different characterization methods
including XRD, FT-IR, Raman, NH3 -TPD, BET surface area and CO
chemisorption were used to evaluate the structural properties
of PtHPA/ZrO2 catalysts. The efciency of PtHPA/ZrO2 catalysts
employed for the vapor phase glycerol hydrogenolysis for the selective production of propanols was much higher than that of Pt/ZrO2
catalyst under the same conditions. These catalysts displayed excellent glycerol conversion (99.9%) and propanols selectivities (98%)
in the industrially relevant conditions, as they clearly outcompete the previously reported methods. Decisively, among various
PtHPA/ZrO2 catalysts, PtPTA/ZrO2 catalyst featured with high

dispersion of active species and strong acidity based on the results

from CO chemisorption and NH3 -TPD methods, correlates well
with the catalytic activity. A detailed study on reaction parameters
reveals the optimized reaction conditions and further conrms that
the reaction temperature had a signicant impact on the glycerol
hydrogenolysis. Further, the used catalyst was found to be relatively stable without considerable drop in the catalytic activity, as
evidenced from XRD, SEM and NH3 -TPD of spent catalyst.

Acknowledgements
SSP thanks CSIR-IICT & RMIT for the award of Junior Research
Fellowship. The authors gratefully acknowledge RMIT University
for supporting the catalyst characterization work.

Appendix A. Supplementary data

Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.apcata.
2015.03.025.

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S.S. Priya et al. / Applied Catalysis A: General 498 (2015) 8898

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