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Catalytic hydrogenolysis of biodiesel derived glycerol to 1,2-propanediol
over Cu–MgO catalysts
M. Balaraju, K. Jagadeeswaraiah, P. S. Sai Prasad and N. Lingaiah*
Received 2nd February 2012, Accepted 3rd May 2012
DOI: 10.1039/c2cy20059g
Published on 03 May 2012. Downloaded on 11/4/2021 7:18:13 AM.

Selective hydrogenolysis of glycerol to 1,2-propanediol over Cu–MgO catalysts is reported.

A series of Cu–MgO catalysts with varying Cu content were prepared by a co-precipitation
method. The physico-chemical properties of the catalysts were derived from BET surface area,
X-ray diffraction, temperature programmed reduction of hydrogen, temperature programmed
desorption of carbon dioxide, X-ray photoelectron spectroscopy, transmission electron
microscopy and dissociative N2O adsorption techniques. The activity results showed that
Cu content on MgO has a significant role in glycerol conversion as well as formation of
1,2-propanediol. Well dispersed Cu species and accessible basic sites of MgO are the essential
requirements for high glycerol hydrogenolysis activity. 20 wt% of Cu content on MgO is
identified as an optimum Cu content. The catalyst is equally active even with crude glycerol and
glycerol containing alkali salts as impurity. Different reaction parameters were evaluated and
optimized reaction conditions were established.

1. Introduction renewable resources such as glycerol by conversion into useful

1,2-Propanediol (1,2-PDO), a three carbon diol with a sterio-
genic center at the central carbon atom, is an important
medium-value commodity chemical with annual production
of 1 billion pounds in the United States.1,2 It is used in the
preparation of polyester resins, liquid detergents, pharma-
ceuticals, cosmetics, tobacco humectants, flavors and fragrances,
personal care products, paints, animal feed, antifreeze etc.1,3–5
It can be used as an alternative to toxic ethylene glycol based
deicing agents.1 The present industrial method for the synth-
esis of 1,2-PDO is by hydrolysis of propylene oxide with water
at temperatures between 125 1C and 200 1C with a pressure of
20 bar.6,7 The propylene glycol market is under severe pressure
due to rapid increase in oil and natural gas costs. Propylene,
which is a precursor to propylene oxide used to make propylene
glycol, has seen significant rise in price.8 An alternative route
to synthesize 1,2-PDO is from renewable feedstocks through
hydrogenolysis of sugars, higher polyols or glycerol in the
presence of a metal catalyst.9–12
Glycerol is a by-product of the biodiesel industry, formed
during the transesterification of edible, non-edible oils or
animal fats.13 Now, additional glycerol from biodiesel production
is flooding the market and substantially influencing the glycerol
price in the global market.5,14 The effective utilization of
Catalysis Laboratory, I&PC Division, Indian Institute of Chemical
Technology, Hyderabad 500607, India.
E-mail: nakkalingaiah@iict.res.in; Fax: +91 40 2716 0921;
Tel: +91 40 2719 3163
chemicals is essential for development of the society.15 Many
researchers have focused on the catalytic conversion of bio-
glycerol into value-added chemicals by various reactions.14,16,17
One such method is the conversion of glycerol into 1,2-PDO by
hydrogenolysis. This approach overcomes the dependency on
fossil fuel and substantially alters the price of 1,2-PDO.18
Hydrogenolysis of glycerol leads to the formation of 1,2-
propanediol, 1,3 propanediol (1,3-PDO) as main products,
ethylene glycol (EG) as a degradative product and 1-propanol
(1-PO), 2-propanol (2-PO) as over hydrogenolysis products.
Glycerol hydrogenolysis is generally carried out in liquid phase
under elevated H2 pressure and temperature.11 Noble metal
catalysts such as supported Rh, Ru, Pt and Pd were studied
extensively for glycerol hydrogenolysis.19,20 Ru based catalysts
were identified as efficient catalysts for glycerol hydrogenolysis
and the main drawback with Ru based catalysts is that they also
cleave C–C bonds which leads to the formation of EG.7,19,20
Copper and nickel based catalysts are used as alternatives to
noble metal catalysts as they are cheap and active under mild
reaction conditions. Moreover, the Cu and Ni based catalysts
are known for their poor hydrogenolysis activity towards C–C
bonds and high selectivity for C–O bond hydro-dehydrogenation.
Y. Nakagawa and Tomishige described in detail about the
latest trends in catalyst development for hydrogenolysis of
glycerol to propylene glycol in a recent review.21
Copper based catalysts, particularly Cu–ZnO catalysts,
have been studied for glycerol hydrogenolysis.22,23 The cata-
lysts are active under mild reaction conditions and do not
require a separate solid acid catalyst. The ZnO present in the

This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1967–1976 1967

catalyst drives the dehydration step to yield acetol from
glycerol, which is further hydrogenated on Cu sites to yield
propylene glycol. A. Bienholz et al. reported 46% glycerol
conversion with 90% selectivity towards propylene glycol over
a Cu–ZnO catalyst.24 Wang and Liu obtained 23% glycerol
conversion with 83% selectivity to 1,2 propanediol at 200 1C
with 42 bar of H2 pressure for 12 h over a Cu–ZnO catalyst
prepared by a co-precipitation method.23 In our previous
study, Cu–ZnO catalysts with more than 90% 1,2-PDO
selectivity were reported.21 Even though all these catalysts
are selective for 1,2-PDO, the overall glycerol conversion is
limited and requires long reaction times.
High glycerol conversion and selectivity to 1,2-PDO was
achieved over catalytic systems containing precious metals
along with base, such as Pt/C + CaO, PtRu/C + NaOH
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and Ru/TiO2 + LiOH.25–27 When base is used instead of acid
as a co-catalyst the overall activity is high. They found that
glycerol hydrogenolysis activity depends on the alkaline
strength of the base material. The glycerol hydrogenolysis
proceeds in a three step mechanism in alkali solution. Initially,
glycerol dehydrogenates to glyceraldehyde, followed by the
dehydration of glyceraldehyde to 2-hydroxyacrolein which
subsequently hydrogenates to 1,2-PDO.28 In the case of
Cu–ZnO catalysts, it is proved that the reaction proceeds
through an acetol mechanism.22,23 If the acidic support for
Cu is replaced by a basic support, the reaction mechanism is
expected to be different leading to high glycerol conversion
and selectivity to 1,2-PDO. There are few reports where Cu is
supported on basic supports like MgO and hydrotalcites.
X. Zheng et al. prepared solid base supported Cu catalysts
and examined for glycerol hydrogenolysis activity. They
achieved high glycerol conversion with retaining of high 1,2-
PDO (495%) selectivity over Cu–MgO and Cu/Mg/Al hydro-
talcite catalysts.29,30 Most of the researchers studied glycerol
hydrogenolysis activity on pure and synthetic glycerol. There
are no detailed studies about the characterization of Cu–MgO
catalysts to understand the observed catalytic activities.
The present work is related to development of a highly
active non-noble Cu–MgO catalyst for the hydrogenolysis of
glycerol to 1,2-PDO under mild reaction conditions. The study
aims to understand the role of support, basicity in Cu–MgO
catalysts. The catalytic activity of the Cu–MgO catalyst is
studied using crude glycerol and alkali salts containing glycerol
to know the practical applicability. The catalysts are charac-
terized by various techniques and the relation between the
glycerol hydrogenolysis activity and surface and structural
characteristics of Cu–MgO catalysts is discussed.
2. Experimental
2.1 Catalyst preparation
A series of Cu–MgO catalysts were prepared by a co-precipitation
method. Calculated amounts of aqueous solutions of
Cu(NO3)23H2O and Mg(NO3)26H2O were taken and preci-
pitated with dropwise addition of 0.1 M aqueous potassium
carbonate solution. During the precipitation the solutions
were maintained at 70 1C. The precipitate was aged further
at the same temperature for 3 h. After cooling, the precipitate
1968 Catal. Sci. Technol., 2012, 2, 1967–1976
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was separated by filtration and washed thoroughly with
de-ionized water to remove traces of potassium ions. The thus
obtained precipitate was dried overnight at 120 1C. The
prepared catalysts are designated as 10CuMgO, 20CuMgO,
40CuMgO, 60CuMgO, 80CuMgO. The numbers indicate the
weight percentage of Cu on the MgO support.
Conventional Cu supported on SiO2, Al2O3, ZrO2 and ZnO
catalysts were prepared by a wet impregnation method using
aqueous solution of Cu(NO3)23H2O. In this method, a calcu-
lated amount of aqueous solution of copper precursor was
added dropwise to supports. After allowing overnight adsorp-
tion of the metal on the support, the excess solution was first
evaporated to near dryness on a water bath and then the
partially dried material was dried in an air oven at 120 1C for
12 h. All catalysts were calcined finally at 400 1C for 3 h.
2.2 Catalysts characterization
The BET surface areas of the catalyst samples were calculated
from N2 adsorption–desorption data acquired on an Autosorb-1
instrument (Quantachrome, USA) at liquid N2 temperature.
X-ray powder diffraction (XRD) patterns of the catalysts
were recorded on a Rigaku Miniflex (M/s. Rigaku Corporation,
Japan) X-ray diffractometer using Ni filtered Cu Ka radiation
(l = 1.5406 Å) with a scan speed of 21 min1 and a scan range
of 2–801 at 30 kV and 15 mA. Particle sizes of Cu and Mg
oxides were calculated by using the Debye–Scherrer equation.
Temperature programmed reduction (TPR) of the catalysts
was carried out in a flow of 10% H2–Ar mixture gas at a flow
rate of 30 ml min1 with a temperature ramp of 10 1C min1.
Before the TPR run the catalysts were pretreated with Ar gas
at 300 1C for 2 h. The hydrogen consumption was monitored
using a thermal conductivity detector.
XPS measurements were conducted on a KRATOS AXIS
165 with a DUAL anode (Mg and Al) apparatus using the
Mg Ka anode. The non-monochromatized Al-Ka X-ray source
(hn = 1486.6 eV) was operated at 12.5 kV and 16 mA. Before
acquisition of the data the sample was out-gassed for about 3 h
at 100 1C under a vacuum of 1.0  107 torr to minimize
surface contamination. The XPS instrument was calibrated
using Au as standard. For energy calibration, the carbon 1S
photoelectron line was used. The carbon 1S binding energy
was taken as 285 eV. Charge neutralization of 2 eV was used to
balance the charge up of the sample. The spectra were
deconvoluted using a Sun Solaris based Vision-2 curve resolver.
The location and the full width at half maximum (FWHM)
value for the species were first determined using the spectrum of
the pure sample. Symmetric Gaussian shapes were used in all
cases. Binding energies for identical samples were, in general,
reproducible within 0.1 eV.
The total basicity of the catalysts was measured by
temperature programmed desorption of CO2 (TPD-CO2). In
a typical experiment, 0.1 g of catalyst was loaded and
pretreated in He gas at 300 1C for 2 h. After pretreatment
the temperature was brought to 100 1C and the adsorption of
CO2 was carried out by passing a mixture of 10% CO2
balanced He gas over the catalyst for 1 h. The catalyst surface
was flushed with He gas at 100 1C for 2 h to flush off the
physisorbed CO2. The TPD of the catalysts was carried out in
This journal is c The Royal Society of Chemistry 2012

a He gas flow at a flow rate of 30 ml min1 with a temperature
ramp of 10 1C min1. The CO2 desorption was monitored
using a thermal conductivity detector (TCD) of a gas
chromatograph.
In order to determine the exposed copper surface area and
the dispersion of the catalysts, dissociative N2O adsorption–H2
TPR reverse titration experiments were carried out as
described in the literature.31 In a typical experiment, temperature
programmed reduction (TPRI) was carried out to reduce the
CuO phase to Cu(0) with a 5% H2–Ar mixture with a heating
rate of 10 1C min1. Then the sample which is in the form of
Cu(0) phase is exposed to N2O to oxidize Cu to Cu2O by
adsorptive decomposition of N2O at 80 1C by a continuous
N2O flow for 0.5 h. Then, again TPRII was carried out for the
second time on the re-oxidized Cu2O surface in order to reduce
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Cu2O to Cu. The thermal conductivity detector (TCD) was
used to measure the amount of H2-uptake in TPR experi-
ments. The Cu dispersions (D) and specific Cu surface area (S)
of the catalysts were calculated by the following equations.
2  H2 consumption in TPRII
DispersionðD%Þ ¼  100
H2 consumption in TPRI
Specific Cu surface area ðSÞ
2  H2 consumption in TPRII  N
¼ m2 g1
H2 consumption in TPRI  MCu  1:4  109
where N = Avogadro’s constant, MCu = atomic mass
(63.456 g mol1), 1.47  1019 is the number of surface Cu
atoms per unit surface area (0.0711 nm2).
The morphology features of the catalysts were characterized
by transmission electron microscopy (TEM). TEM investiga-
tions were carried out using a Philips CM20 (100 kV)
transmission electron microscope equipped with a NARON
energy-dispersive spectrometer with a germanium detector.
The specimens were prepared by dispersing the samples in
methanol using an ultrasonic bath and evaporating a drop of
resultant suspension onto the lacey carbon support grid. The
sizes of the catalyst particles were measured by digital micro-
graph software (version 3.6.5, Gatan Inc.).
2.3 Activity measurements
Hydrogenolysis of glycerol was carried out in a 100 ml haste
alloy PARR 4843 autoclave. Required quantity of glycerol
diluted in de-ionized water and catalysts were charged into the
autoclave. The reactor was purged with H2 three times to flush
off the air. After the purge, the reactor was heated to
Table 1 Physico-chemical properties of Cu–Mg catalysts
Catalyst Cu/Mg ratioa BET surface area (m2 g1)
10CuMgO 0.005 42.7
20CuMgO 0.12 39.5
40CuMgO 0.21 20.2
60CuMgO 0.58 11.8
80CuMgO 0.71 9.6
a
Atomic ratio determined by XPS analysis. b Cu metal surface area determined from N2O chemisorption. c Basicity of catalyst measured by CO2
desorption studies. d Crystal size of catalyst measured by an XRD technique.
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the reaction temperature while maintaining the required H2
pressure. During the reaction a decrease in hydrogen pressure
is observed. After the reaction, the gas phase products were
collected in a gas bag and the liquid phase products were
separated from the catalyst by filtration. Products in the liquid
phase and the gas phase were analyzed by a gas chromato-
graph (Shimadzu 2010) equipped with an FID and a TCD.
The liquid products were separated on a capillary INNOWax
(30 m  0.25 mm  0.25 mm) column. Products were
also identified by GC–MS (Shimadzu, GCMS-QP2010).
The gas products were analyzed by using a Porapak Q column
(4 m  3 mm) equipped with a thermal conductivity detector.
The products identified during glycerol hydrogenolysis are
1,2-propanediol (1,2-PDO), 1-propanol (1-PO), and 2-propanol
(2-PO) (hydrogenolysis products) and ethylene glycol (EG),
ethanol, methanol, ethane and methane.
Conversion of the glycerol was calculated on the basis of the
following equation:
Moles of glycerol consumed
Conversion ð%Þ ¼  100
Moles of glycerol initially charged
The selectivity of the products was calculated on carbon
basis.
Selectivity ð%Þ
Moles of carbon in a specific product
¼  100
Moles of carbon in all detected products
3. Results and discussion
3.1 Catalysts characterization
Table 1 summarizes the physico-chemical properties of Cu–MgO
catalysts. BET surface area of the catalysts decreased sharply
from 43 to 12 m2 g1, when copper loading increased from 10
to 60 wt%. This can be attributed to the formation of CuO
clusters on the MgO support which might be blocking the
pores of moderate surface area of MgO.
X-ray powder diffraction patterns of calcined Cu–MgO
catalysts are shown in Fig. 1. The diffraction peaks corres-
ponding to CuO phases were not observed for low copper
containing catalysts (10CuMgO and 20CuMgO) suggesting
the high dispersion of copper. The most intense reflections
corresponding to CuO at 2y of 35.51 and 38.81 were clearly
seen for the catalysts with high CuO content (60CuMgO and
80CuMgO). The presence of peaks at 2y values of 42.81 and
Crystal sized (nm)
Metal surface areab (m2 g1) Basicityc ( 106 mol g1) Cu MgO
115.6 321 12.1 33.8
120.4 290 13.7 31.7
102.2 250 14.3 30.5
70.9 180 25.9 28.9
30.9 90 29.9 27.6
Catal. Sci. Technol., 2012, 2, 1967–1976 1969

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Fig. 1 X-ray diffraction patterns of calcined Cu–Mg catalysts. (*)
CuO and (#) MgO phases.
Fig. 2 Temperature programmed reduction patterns of Cu–Mg catalysts.
62.21 suggests the crystalline phases of MgO in the all samples.
The crystallite sizes of Cu and MgO particles of the catalysts
were calculated using the X-ray line broadening technique and
are listed in Table 1.
The reducibility of the catalysts was studied using tempera-
ture programmed reduction of hydrogen (TPR). The TPR
profiles of the catalysts are shown in Fig. 2. As expected, the
hydrogen consumption increased with increase in the copper
content on the support. A sharp reduction peak was observed
at 240 1C for the 20CuMgO catalyst. This peak is due to the
reduction of CuO to Cu. The reduction peak was shifted
remarkably to high temperature with increased broadness, as
Cu content increased on the support. The high temperature
peak can be attributed to the reduction of the cluster or bulk
CuO particles.32 A broad reduction peak for the catalyst with
high Cu content might be due to merging of reduction peaks
related to dispersed and cluster CuO species. This indicates
that copper oxide species with different redox behavior were
present on the MgO support.
1970 Catal. Sci. Technol., 2012, 2, 1967–1976
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Table 2 Binding energies of Cu–MgO catalysts
Binding energy (eV)
Catalyst Cu 2p3/2 Cu 2p1/2 Mg 2p O 1s
10CuMgO 934.8, 943.1 954.6, 963.4 51.6 531.6, 533.6
20CuMgO 934.4, 943.3 954.1, 963.5 51.4 531.6, 533.4
40CuMgO 934.5, 943.4 954.4, 963.4 51.3 531.1, 533.8
80CuMgO 934.3, 943.6 954.5, 963.5 51.5 532.1, 534.0
The surface of the Cu–MgO catalysts was characterized by
an XPS technique. The binding energy values of Cu, Mg and
O are listed in Table 2. Fig. 3 shows the Cu 2p spectra of
calcined Cu–MgO catalysts. The catalysts show binding
energy values of 934 and 954 eV related to Cu 2p3/2 and
Cu 2p1/2 respectively. The binding energy corresponding to
Cu 2p1/2 was due to a spin–orbit coupling, with an energy gap
of more than 20 eV of Cu 2p3/2. The main peaks were followed
by strong satellite peaks around 944 and 964 eV confirming the
presence of Cu2+ species in the calcined catalysts.33,34 In fact,
transition metal ions with unfilled 3d orbitals are reported to
show prominent satellite peaks in the core level XPS spectra
due to electron shake-up transitions because of the ligand to
metal 3d charge transfer. The structure of the satellite peak,
i.e., the peak number, intensity and splitting reflect the nature
of chemical bonding of the transition metal ions.35,36 The peak
intensity of Cu 2p electrons in XP spectra significantly
increased with increase in Cu loading from 10 to 80%. The
shift in binding energies was not observed even for a high Cu
content catalyst. These results suggested a high homogeneity
of CuO sites on the support. The O 1s spectra showed two
bands in the binding range of 530–534 eV for all the catalysts.
The Mg 2p binding energy value of 51 eV is almost the same
for all the samples. The XPS results suggest the presence of
Cu2+ species on MgO in the calcined catalysts. The surface
Cu/Mg atomic ratio of Cu–MgO catalysts was determined by
using an XPS technique and results are listed in Table 1. The
surface Cu/Mg ratio increased with Cu content of catalysts. Very
low surface Cu to Mg ratio was observed for low Cu content
catalysts due to high Cu dispersion on the MgO support.
The copper surface area of Cu–MgO catalysts was deter-
mined by a dissociative N2O adsorption–H2 TPR reverse
titration method and the results are summarized in Table 1.
The Cu metal area of the catalysts was found to be 115.6, 120.4
and 102.2 m2 g1 for 10CuMgO, 20CuMgO, 40CuMgO catalysts
respectively. Surface area of Cu was drastically decreased for the
catalyst with high Cu loading (60CuMgO and 80CuMgO) due to
formation of cluster particles of CuO. XRD and TPR results are
in support of the formation of CuO clusters.
The TEM images of the catalysts are shown in Fig. 4. The
particle sizes of CuO in these catalysts were estimated by
TEM analysis. The calculated copper mean particle sizes of
10CuMgO, 20CuMgO, 40CuMgO, 60CuMgO and 80CuMgO
were 10.0, 12.0, 15.7, 24.5 and 30.5 nm, respectively. The
particle sizes of the catalysts obtained from TEM analysis were
comparable with those obtained from XRD results. It was
identified that the copper metal particles in Cu–MgO catalysts
were smaller than those of Cu–ZnO catalysts.22 The difference
in metal particle size on different supports can be related to the
intrinsic property of the support. Many previous studies have
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Fig. 3 XPS of calcined Cu–Mg catalysts. (a) 10CuMgO, (b) 20CuMgO, (c) 60CuMgO, (d) 80CuMgO.
shown that the support material can influence the metal particle
size and consequently influence the catalytic performance.37,38
3.2 Activity measurements
3.2.1 Influence of Cu loading on MgO on glycerol hydro-
genolysis. Table 3 reports glycerol hydrogenolysis activity of
Cu–MgO catalysts. About 30% glycerol conversion with 92%
selectivity to 1,2-PDO was achieved over the 10CuMgO
catalyst. As copper content on MgO increased from 10 to
20 wt%, the glycerol conversion also raised substantially from
30 to 50% with retaining of the similar selectivity to 1,2-PDO.
Conversion of glycerol is gradually decreased with further
increase in Cu content. The high copper containing catalysts
particularly 60CuMgO and 80CuMgO showed very low activ-
ity. From above results it is noticed that low Cu containing
catalysts showed high glycerol hydrogenolysis activity. It is
also reported that in the case of Cu/MgO high glycerol
conversion is achieved with low Cu content catalysts.29 The
present results are comparable with the results reported by
Yuan et al.29 However, they reported about 72% glycerol
conversion when the reaction was carried out for 20 h.
Consistent selectivity to 1,2-PDO was observed for all Cu–MgO
catalysts irrespective of glycerol conversion.
Previously, many authors reported Ru or Cu supported
on solid acid catalysts for glycerol hydrogenolysis.5,22,23,38,39
Glycerol hydrogenolysis was also carried out by adding
base as a co-catalyst over carbon supported noble metal
catalysts.25–27 The hydrogenolysis activity of the present
Cu–MgO catalyst is higher than that of reported Cu–ZnO
catalysts and comparable with that of hybrid Ru/C +
Amberlyst and Pt/C or Ru/C + NaOH. Montassier et al.
proposed a reaction mechanism for the conversion of glycerol
to 1,2-PDO under basic reaction conditions.28 According to
this reaction mechanism, dehydrogenation of glycerol leads to
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glyceraldehyde and it subsequently dehydrates to hydroxy-
acrolein on basic sites of catalyst. Further hydrogenation of
these reaction intermediates to 1,2-PDO took place over
metallic sites. A considerable amount (B5%) of acetol (inter-
mediate) was observed in our previous studies whereas acetol
is not identified in the present study.22 Therefore, it is con-
cluded that the reaction proceeds over the catalysts with acidic
supports as well as over those with basic supports through
different reaction mechanisms as shown in Scheme 1.
From the above reaction mechanism, it is known that basicity
and copper metal area are essential for glycerol hydrogenolysis.
During glycerol hydrogenolysis, Cu and MgO sites play an
important role in glycerol conversion and 1,2-PDO selectivity.
The observed glycerol hydrogenolysis activity is related to the
Cu metal area and basicity of the catalyst. The relation of Cu
metal surface area and basicity of the catalysts with glycerol
conversion is shown in Fig. 5. A linear correlation is observed
between Cu metal surface area and glycerol conversion as
shown in Fig. 5(A). The low Cu containing catalyst showed
maximum Cu metal area and exhibited high activity. Metal
surface area and dispersion rapidly decreased for the catalysts
with high Cu content such as 60CuMgO and 80CuMgO due to
formation of multi-layer CuO clusters on the support. The
TPR, XRD and TEM analyses are in support of these observa-
tions. The relation between glycerol conversion and catalyst
basicity shown in Fig. 5(B) suggests that the catalyst with high
basicity exhibits high glycerol conversion. The basicity of low
Cu content catalysts is also high. Basicity of the 10CuMgO
catalyst was found to be 321 mmol g1. As CuO content
increased from 10 to 80%, basicity of the Cu–MgO catalysts
gradually decreased from 321 to 90 mmol g1 due to blockage of
surface MgO sites by CuO clusters. As these catalysts contain
low amounts of MgO, their overall basicity is also minimum.30
These results indicate that the glycerol conversion depends on
the basicity and Cu metal area. As a whole a judicious amount
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Fig. 4 TEM images of Cu–Mg catalysts. (a) 10CuMgO, (b) 20CuMgO, (c) 40CuMgO, (d) 60CuMgO, (e) 80CuMgO.

Table 3 Influence of Cu content in Cu–Mg catalysts on glycerol temperature for glycerol hydrogenolysis, the reaction was
hydrogenolysis carried out from 160 to 220 1C. A significant influence of the
Selectivity (%) reaction temperature on glycerol conversion and selectivity to
1,2-PDO was observed. With increase in reaction temperature,
Catalyst Conv. (%) 1,2-PDO EG Others
a uniform increase in glycerol conversion was observed.
10CuMgO 30.2 92.4 5.4 2.8 Substantial increase in glycerol conversion was observed
20CuMgO 49.3 92.3 5.9 1.8 between reaction temperatures of 180 and 200 1C. The selectivity
40CuMgO 36.6 90.3 6.7 3.0
60CuMgO 18.0 90.0 6.9 3.1 to 1,2-PDO increased up to 200 1C and decreased with further
80CuMgO 6.1 87.6 5.6 6.8 increase in reaction temperature. This indicates that when
Reaction conditions: 20 wt% glycerol aqueous solution: 50 ml, H2 reaction temperature is more than 200 1C, excessive hydro-
pressure: 40 bar, reaction time: 8 h, catalyst weight: 0.6 g (6%), genolysis of glycerol and 1,2-PDO is taking place and that
reaction temperature: 200 1C. leads to formation of lower alcohols like methanol, ethanol
and other gaseous products. A reaction temperature of 200 1C
was identified as the optimum for selective hydrogenolysis of
of basicity and Cu metal surface area is required for the catalyst glycerol to propylene glycol over Cu–MgO catalysts.
to show better glycerol conversion and selectivity.
3.2.3 Effect of glycerol concentration on glycerol hydro-
3.2.2 Effect of reaction temperature on hydrogenolysis of genolysis. The effect of glycerol concentration on the hydro-
glycerol. Fig. 6 shows the influence of reaction temperature on genolysis of glycerol was studied and the results are shown in
hydrogenolysis of glycerol. In order to optimize the reaction Fig. 7. The conversion of glycerol decreased with increase in

1972 Catal. Sci. Technol., 2012, 2, 1967–1976 This journal is c The Royal Society of Chemistry 2012
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Scheme 1 Glycerol hydrogenolysis mechanism over acid or base catalysts.

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Fig. 5 Correlation of (A) Cu metal area and (B) basicity of Cu–MgO catalysts with glycerol conversion.

Fig. 6 Effect of reaction temperature on hydrogenolysis activity over Fig. 7 Effect of glycerol concentration on hydrogenolysis activity
20CuMgO catalyst. Reaction conditions: 20 wt% glycerol aqueous over 20CuMgO catalyst. Reaction conditions: glycerol aqueous
solution: 50 ml, H2 pressure: 40 bar, reaction time: 8 h, catalyst weight: solution: 50 ml, H2 pressure: 40 bar, reaction time: 8 h, catalyst
0.6 g (6%). weight: 0.6 g (6%), reaction temperature: 200 1C.

the concentration of glycerol. The decrease in conversion at
higher glycerol concentration may be due to the availability of
less number of Cu active sites for the large amount of glycerol
molecules present in the reaction medium. However, the
selectivity to 1,2-PDO was unaltered with glycerol concen-
tration, implying the high selectivity of the Cu–MgO catalysts.
The catalyst showed considerable glycerol conversion even at
high glycerol concentrations.
3.2.4 Effect of reaction time on glycerol hydrogenolysis.
Reaction time is an important parameter and long reaction
times (424 h) were adopted usually for glycerol hydrogeno-
lysis to obtain reasonable conversion.4,10 The conversion of
glycerol and selectivity to 1,2-PDO at different reaction times
were studied over the 20CuMgO catalyst. As shown in Fig. 8,
about 32% glycerol conversion and 86% selectivity towards
1,2-PDO were achieved within 4 h of reaction time. A considerable

This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1967–1976 1973
Published on 03 May 2012. Downloaded on 11/4/2021 7:18:13 AM.
Fig. 8 Effect of reaction time on hydrogenolysis activity over
20CuMgO catalyst. Reaction conditions: 20 wt% glycerol aqueous
solution: 50 ml, H2 pressure: 40 bar, catalyst weight: 0.6 g (6%),
reaction temperature: 200 1C.
change in glycerol conversion was observed up to a reaction
time of 6 h, thereafter the increase in conversion was marginal.
The Cu–MgO catalysts were very active compared to Cu–ZnO
catalysts which took longer reaction times to obtain reasonable
glycerol conversion.21 The catalyst was also selective in forming
1,2-PDO in more than 90% yield, irrespective of reaction time.
The higher selectivity to 1,2-PDO even at longer reaction times
reflects that the present catalyst was efficient to selectively
cleave only C–O bonds instead of C–C bonds.
3.2.5 Effect of hydrogen pressure on glycerol hydrogenolysis.
Reactions were carried out at different hydrogen pressures
from 20 to 80 bar at a constant reaction temperature of 200 1C
to determine the effect of hydrogen pressure on the overall
activity and the results are shown in Fig. 9. Generally, glycerol
hydrogenolysis at low hydrogen pressure is important to maximize
the utility of the existing equipment for performing hydrogenolysis.
Fig. 9 Effect of reaction pressure on hydrogenolysis activity over
20CuMgO catalyst. Reaction conditions: 20 wt% glycerol aqueous
solution: 50 ml, reaction time: 8 h, catalyst weight: 0.6 g (6%), reaction
temperature: 200 1C.
1974 Catal. Sci. Technol., 2012, 2, 1967–1976
View Article Online
Fig. 10 Effect of catalyst weight on hydrogenolysis activity over
20CuMgO catalyst. Reaction conditions: 20 wt% glycerol aqueous
solution: 50 ml, H2 pressure: 40 bar, reaction time: 8 h, reaction
temperature: 200 1C.
As expected the conversion of the glycerol marginally increased
as the hydrogen pressure increased from 20 to 60 bar. The
hydrogen atoms at higher pressure compete with the
re-adsorption of an intermediate on active catalyst sites
leading to the decrease in glycerol conversion. A similar
observation was reported by Rode et al. for a copper chromite
catalyst.40 The Cu based catalysts are highly active at moderate
hydrogen pressure unlike noble metal catalysts which are active at
elevated H2 pressure. Hydrogen pressure in the range of 40 to
80 bar resulted in a marginal decrease in the selectivity to 1,2-PDO
from 92 to 89% due to enhanced hydrogenation of 1,2-PDO to
2-propanol. It was interesting to note that an increase in H2
pressure did not affect the selectivity to the degradation product
EG because copper is selective for cleavage of C–O bonds.
3.2.6 Effect of catalyst weight on glycerol hydrogenolysis.
Fig. 10 shows the variation in the glycerol conversion with
increase in the catalyst weight during glycerol hydrogenolysis.
The glycerol conversion varied with change in catalyst loading.
As the catalyst weight increased from 4 to 10%, the glycerol
conversion increased from 32 to 60%. The increase in catalyst
weight results in more number of available active sites for
hydrogenolysis reaction to take place. A similar increase in
hydrogenolysis activity with increase in catalyst concentration
is also reported.2
3.2.7 Glycerol hydrogenolysis on crude glycerol. Hydro-
genolysis of glycerol was studied using 5% sodium sulphate
containing synthetic glycerol and crude glycerol obtained from
a biodiesel plant to know the practical applicability of the
present catalyst. These results are listed in Table 4. The
bioglycerol obtained from the biodiesel industry generally
contains alkali salts, as alkali is used as catalyst for biodiesel
synthesis. During the neutralization of alkali it leads to
formation of alkali salts. It is important to study glycerol hydro-
genolysis over Na2SO4 containing glycerol. The present catalyst
showed about 41% glycerol conversion with 92% 1,2-PDO
selectivity even with sodium sulphate containing glycerol.
This journal is c The Royal Society of Chemistry 2012
 View Article Online

Table 4 Hydrogenolysis of crude glycerol over 20CuMgO catalyst The Cu–MgO catalysts are highly active and selective to
1,2-PDO in glycerol hydrogenolysis under mild reaction
Selectivity (%)
conditions. The content of Cu and its dispersion, metal surface
Type of glycerol Conversion (%) 1,2-PDO EG Others area and the basicity of the catalyst are responsible for the
Pure glycerol 49.3 92.3 5.9 1.8 high glycerol hydrogenolysis activity. The catalyst with low Cu
5% Na2SO4 + pure glycerol 41.6 92.3 5.0 2.7 content (20 wt%) on MgO showed the highest activity with
Crude glycerol 44.5 92 4.9 3.1 50% glycerol conversion and 92% selectivity to 1,2-PDO. The
Pure glycerola 45.8 92.3 5.8 1.9
Pure glycerolb 39.7 92.2 4.5 3.3 glycerol conversion also depends on the reaction parameters,
and optimum reaction conditions were established. The
Reaction conditions: 20 wt% glycerol aqueous solution: 50 ml, H2
pressure: 40 bar, reaction time: 8 h, catalyst weight: 0.6 g (6%), reaction
present Cu–MgO catalyst tolerates even alkali salts and other
temperature: 200 1C. a Activity on 200 ml scale. b Activity on 500 ml scale. impurities present in crude glycerol.

Acknowledgements
Table 5 Comparison of conventional Cu catalysts with 20CuMgO
catalyst for the hydrogenolysis of glycerol The authors thank Department of Science & Technology,
Published on 03 May 2012. Downloaded on 11/4/2021 7:18:13 AM.

New Delhi, India, for financial support. MB and KJ thank

Catalyst Conversion (%) Selectivity to 1,2PDO (%)
20% Cu–SiO2 20.0 83.6
20% Cu–Al2O3 25.3 85.6
20% Cu–ZrO2 10.2 62.0
20% Cu–ZnO 37.0 92.0
20% Cu–MgO 49.3 92.3
Reaction conditions: 20 wt% glycerol aqueous solution: 50 ml, H2
pressure: 40 bar, reaction time: 8 h, catalyst weight: 0.6 g (6%),
reaction temperature: 200 1C.
The decrease in glycerol conversion is marginal when com-
pared to the results of pure glycerol.
Crude glycerol was obtained from a biodiesel plant where
sodium hydroxide is used as catalyst. Demethanolised crude
glycerol was used for glycerol hydrogenolysis under optimized
reaction conditions. A maximum glycerol conversion of about
44% with 92% selectivity toward 1,2-PDO was obtained. The
activity results show that the Cu–MgO catalyst is active even
for crude glycerol to synthesize 1,2-PDO. It is very important
to mention that the present catalyst is resistant towards the
salts and other impurities present in crude glycerol.
3.2.8 Comparison of present Cu/MgO catalyst with conven-
tional Cu catalysts. The conventional Cu based catalysts are
prepared by an impregnation method keeping the same weight
percentage of Cu as that of Cu/MgO catalysts. These catalysts
were studied for the glycerol hydrogenolysis under the optimum
reaction conditions and the results are shown in Table 5. The
Cu supported on supports such as alumina, silica, zirconia, zinc
oxide exhibited lower activity when compared to Cu/MgO
catalysts. The Cu supported on conventional supports (Al2O3,
SiO2, ZrO2) showed relatively less activity under the present
experimental conditions. The results suggest that the glycerol
hydrogenolysis activity depends on the nature of the catalysts
and their method of preparation. The commercial Cu catalysts
copper and copper chromite (Sud-Chemie) catalysts gave about
21.1 and 46.6% yield of 1,2PDO with 39.8 and 85% selectivity
respectively.2 These results suggest that the present catalyst is
highly active and selective for the hydrogenolysis of glycerol.
4. Conclusions
The use of a basic support like MgO for Cu based catalysts
alters the reaction mechanism of glycerol hydrogenolysis.
CSIR for the award of Senior Research Fellowships.
References
1 Chemical Marketing Reporter, 1092-0110, 260 (11) (September 24,
2001) 30.
2 M. A. Dasari, P. Kiatsimkul, W. R. Sutterlin and G. J. Suppes,
Appl. Catal., A, 2005, 281, 225–231.
3 A. Behr, J. Eilting, K. Irawadi, J. Leschinski and F. Lindner, Green
Chem., 2008, 10, 13–30.
4 J. Chaminand, L. Djakovitch, P. Gallezot, P. Marion, C. Pinel and
C. Rosier, Green Chem., 2004, 6, 359–361.
5 M. Balaraju, V. Rekha, B. L. A. P. Devi, R. B. N. Prasad, P. S. S.
Prasad and N. Lingaiah, Appl. Catal., A, 2010, 384, 107–114.
6 R. Perrin and J. P. Scharff, Chimie industrielle, ed. Masson, 1993.
7 M. Balaraju, V. Rekha, P. S. S. Prasad, B. L. A. P. Devi, R. B. N.
Prasad and N. Lingaiah, Appl. Catal., A, 2009, 354, 82–87.
8 A. Brandner, K. Lehnert, A. Bienholz, M. Lucas and P. Claus,
Top. Catal., 2009, 52, 278–287.
9 S. P. Chopade, D. J. Miller, J. E. Jackson, T. A. Werpy, J. G. Frye
Jr. and A. H. Zacher, US Pat., US 6291725 to Board of Trustees
operating Michigan State University, Battelle Memorial Institute,
Pacific Northwest Laboratory, 2001.
10 J. C. Chao and D. T. A. Huibers, US Pat., US 4366332 to
Hydrocarbon Research Inc, 1982.
11 B. Casale and A. M. Gomez, US Pat., US 5276181 to Novamont
S.p.A, 1994.
12 P. Bloom, US Pat., US 7928148 to Archer Daniels Midland
Company, 2008.
13 J. M. Marchetti, V. U. Miguel and A. F. Errazu, Renewable
Sustainable Energy Rev., 2007, 11, 1300–1311.
14 D. T. Johnson and K. A. Taconi, Environ. Prog., 2007, 26, 338–348.
15 R. D. Cortright, R. R. Davda and J. A. Dumesic, Nature, 2002,
418, 964–967.
16 M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi and C. D. Pina,
Eur. J. Lipid Sci. Technol., 2009, 111, 788–799.
17 N. R. Shiju, D. R. Brown, K. Wilson and G. Rothenberg, Top.
Catal., 2010, 53, 1217–1223.
18 L. C. Meher, R. Gopinath, S. N. Naik and A. K. Dalai, Ind. Eng.
Chem. Res., 2009, 48, 1840–1846.
19 T. Miyazawa, Y. Kusunoki, K. Kunimori and K. Tomishige,
J. Catal., 2006, 240, 213–221.
20 Y. Kusunoki, T. Miyazawa, K. Kunimori and K. Tomishige,
Catal. Commun., 2005, 6, 645–649.
21 Y. Nakagawa and K. Tomishige, Catal. Sci. Technol., 2011, 1,
179–190.
22 M. Balaraju, V. Rekha, P. S. S. Prasad, R. B. N. Prasad and
N. Lingaiah, Catal. Lett., 2008, 126, 119–124.
23 S. Wang and H. Liu, Catal. Lett., 2007, 117, 62–67.
24 A. Bienholz, F. Schwab and P. Claus, Green Chem., 2010, 12,
290–295.
25 E. P. Maris and R. J. Davis, J. Catal., 2007, 249, 328–337.
26 E. P. Maris, W. C. Ketchie, M. Murayama and R. J. Davis,
J. Catal., 2007, 251, 281–294.

This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1967–1976 1975

27 J. Feng, J. B. Wang, Y. F. Zhou, H. Y. Fu, H. Chen and X. J. Li,
Chem. Lett., 2007, 1274–1275.
28 C. Montassier, D. Giraud and J. Barbier, Heterogeneous Catalysis
and Fine Chemicals, 1988, pp. 165–170.
29 Z. Yuan, J. Wang, L. Wang, W. Xie, P. Chen, Z. Hou and
X. Zheng, Bioresour. Technol., 2010, 101, 7088–7092.
30 Z. Yuan, L. Wang, J. Wang, S. Xia, P. Chen, Z. Hou and
X. Zheng, Appl. Catal., B, 2011, 101, 431–440.
31 C. J. G. Van Der Grift, A. F. H. Wielers, B. P. J. Jogh, J. Van
Beunum, M. De Boer, M. Versluijs-Helder and J. W. Geus,
J. Catal., 1991, 131, 178–189.
32 S. Xu, C. Huang, J. Zhang and B. Chen, Korean J. Chem. Eng.,
2009, 26, 1568–1573.
33 R. Kam, C. Selomulya, R. Amal and J. Scott, J. Catal., 2010, 273,
73–81.
Published on 03 May 2012. Downloaded on 11/4/2021 7:18:13 AM.
1976 Catal. Sci. Technol., 2012, 2, 1967–1976
View Article Online
34 C. C. Chusuei, M. A. Brookshier and D. W. Goodman, Langmuir,
1999, 15, 2806–2808.
35 D. C. Frost, A. Ishitani and C. A. McDowell, Mol. Phys., 1972,
24, 861.
36 T. A. Carlson, Photoelectron and Auger Spectroscopy, Plenum
Press, New York, 1975.
37 J. Feng, H. Fu, J. Wang, R. Li, H. Chen and X. Li, Catal.
Commun., 2008, 9, 1458–1464.
38 E. S. Vasiliadou, E. Heracleous, I. A. Vasalos and
A. A. Lemonidou, Appl. Catal., B, 2009, 92, 90–99.
39 L. Guo, J. Zhou, J. Mao, X. Guo and S. Zhang, Appl. Catal., A,
2009, 367, 93–98.
40 C. V. Rode, A. A. Ghalwadkar, R. B. Mane, A. M. Hengne,
S. T. Jadkar and N. S. Biradar, Org. Process Res. Dev., 2010, 14,
1385–1392.
This journal is c The Royal Society of Chemistry 2012