ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. 2015; 10: 598–606

Published online 9 June 2015 in Wiley Online Library
(wileyonlinelibrary.com) DOI: 10.1002/apj.1909

Special theme research article

Enhancing allyl alcohol selectivity in the catalytic conversion
of glycerol; influence of product distribution on the
subsequent epoxidation step
Luke Harvey, Gizelle Sánchez, Eric M. Kennedy and Michael Stockenhuber*
PRCfE, Chemical Engineering, School of Engineering, The University of Newcastle, Callaghan, New South Wales 2308, Australia

Received 30 November 2014; Revised 22 April 2015; Accepted 24 April 2015

ABSTRACT: Conversion of glycerol to allyl alcohol in a flow reactor and subsequent conversion to glycidol in a batch
reactor are discussed in this paper. To increase reaction selectivity in the glycerol to allyl alcohol reaction, the catalyst
was modified with alkali metal salts. The treatment of the catalyst (Fe/Al2O3) with potassium, caesium and rubidium salts
enhanced the allyl alcohol yield when a 35 wt% glycerol solution was used as feed. Furthermore, the addition of organic
reductants or hydrogen to the glycerol feed increased the allyl alcohol yield. Optimisation of allyl alcohol selectivity was
achieved by a combination of alkali metal cation modifiers and the addition of reductants. The influence of acid, base and
redox properties on selectivity is presented, focusing on the effect of these properties on product distribution. The effect
of by-products from the conversion of glycerol to allyl alcohol on the epoxidation reaction was examined to identify the ideal
reaction conditions for maximising the glycidol yield. Epoxidation of allyl alcohol by 30 wt% hydrogen peroxide was
conducted in a batch reactor at 333K using titanium silicate-1 catalyst. Conversion of allyl alcohol was high for all
conditions; however, hydrolysis of glycidol to glycerol reduces selectivity. © 2015 Curtin University of Technology and
John Wiley & Sons, Ltd.

KEYWORDS: glycerol conversion; allyl alcohol; glycidol; iron oxide; acrolein; acid-base properties

INTRODUCTION Mechanisms where glycerol is dehydrated to

Carbon dioxide emissions and depleting fossil fuel
resources have been major drivers for the successful
industrial scale-up of the transesterification process
for the manufacture of fatty acid methyl esters. One
of the primary concerns with respect to this alternative
route to synthetic fuels is the generation of reaction side
products.[1–3] In spite of the various applications of
glycerol in other industries, the enormous production
rates and high cost of purification[4] threaten the financial
viability of biodiesel manufacture. For every 10 kg of
biodiesel being produced, roughly 1 kg of crude glycerol
is generated.[5] Conversion of glycerol to high-value
products like allyl alcohol, acrolein or glycidol is seen
as a viable option for using glycerol as a raw product.
In this paper, we report how various methods of
improving the selectivity from glycerol to allyl alcohol
impact the subsequent epoxidation reaction to glycidol.
*Correspondence to: Michael Stockenhuber, PRCfE, Chemical
Engineering, School of Engineering, The University of Newcastle,
Callaghan, New South Wales 2308, Australia. E-mail: michael.
stockenhuber@newcastle.edu.au
acrolein, which is subsequently hydrogenated to allyl
alcohol, have been reported over iron oxide catalysts
with high surface areas,[6] while alternative pathways
also leading to the selective formation of allyl alcohol
have been proposed to occur over catalysts with low
strength acid sites as zirconia–iron oxide.[7] In contrast,
production of acrolein at yields of up to 70% is usually
catalysed by solid acids.[8] This suggests that the
product distribution of the reaction depends on the
acid–base properties of the catalyst, which can be
modified by, for example, the deposition of alkali metal
salts on the catalyst.[9] A multitude of basic compounds
has been used to modify the nature of the catalyst
support. Nevertheless, under certain conditions,
treatment can even increase the acidity of the surface,
depending on the concentration of the metal cations
deposited on the support.[10] Konaka et al. deposited
alkali metals on zirconia–iron oxide catalysts for
glycerol conversion,[11] while we previously reported
correlations between acidity/basicity and allyl alcohol
production.[12] In this contribution, the focus is to link
the effects produced by alkali catalyst modification in
the first reaction to the epoxidation of glycidol, because
the formation of certain impurities (promoted/impeded

© 2015 Curtin University of Technology and John Wiley & Sons, Ltd.
Curtin University is a trademark of Curtin University of Technology
Asia-Pacific Journal of Chemical Engineering INFLUENCE OF GLYCEROL CONVERSION ON GLYCIDOL EPOXIDATION
by changes in acidity/basicity) has found to influence
the epoxidation reaction.[13] The unsaturated alcohol
produced from glycerol may be epoxidised to produce
glycidol. Traditionally, organic hydroperoxides were
used as the oxygen source for this reaction in an aprotic
organic solvent such as benzene, catalysed by a range
of transition metal oxides with or without supports, in
particular silica-supported molybdenum or tungsten
oxides.[14] The catalytic activity of many of these
transition metal catalysts was, however, attributed to
rapid leaching of metal ions from the catalyst surface,
essentially producing a homogeneous catalyst, the
parent catalyst being unable to be reactivated.[15] The
first truly heterogeneous catalyst for the selective
epoxidation of unsaturated alcohols was silica-
supported titania, initially developed by Shell[16] and
was found to not exhibit the same leaching problems
as with earlier transition metal catalysts.[17] All silica-
supported metal oxide catalysts were hindered severely
by water, because of competition with peroxide for the
active sites and as such, oxidising agents were limited
to hazardous organic hydroperoxides, in particular
tert-butyl hydroperoxide. The development of titanium
silicate with MFI structure (TS-1) in 1983 by Taramasso
et al.[18] led to the development of a heterogeneous
catalyst that was substantially less adversely affected by
water,[19–21] and as such, safer and more cost-effective
hydrogen peroxide could be used as an oxygen source.
In recent years, a variety of titanium-substituted
zeolites applicable to the epoxidation of unsaturated
alcohols have been developed. Zeolite topologies
containing titanium such as Ti-MWW,[22] Ti-BEA[23]
or Ti-SBA-15[24] have since been synthesised to
address the limitation of TS-1 in that the MFI
accommodates only smaller substrates such as linear
olefins. Ti-MWW in particular has been shown to be,
under certain conditions, superior to TS-1 in the
epoxidation of allyl alcohol[25,26] although has attracted
less attention industrially. This study focuses upon
catalytic systems with a view specifically to large-scale
application, and as such, TS-1 has been used in this
case because of its higher commercial significance.
Other zeolite topologies such as Ti-MWW are to be
the subject of future work.
Selectivity of the epoxidation reaction over TS-1 is
highly influenced by the acidity of the catalyst. Post-
synthetic treatment of the catalyst with base enhances
the selectivity to glycidol. Conversely, the Brønsted
acid sites have been shown to enhance subsequent
ring-opening reactions (solvolysis and/or hydrolysis)
on the epoxide ring.[27]
Reaction parameters optimising the epoxide yield (in
this case for 2-methyl-2-propen-1-ol methallyl alcohol)
are lower reaction temperatures (~293 K), equimolar
substrate/H2O2 ratio, 70 wt% solvent concentration and
3 wt% catalyst concentration, as found by Wróblewska
et al.[28] TS-2 reaches optimum performance under very
© 2015 Curtin University of Technology and John Wiley & Sons, Ltd.
599
similar conditions, with 100 mol% selectivity to glycidol
and 87.7 mol% conversion of allyl alcohol at 293 K,
equimolar allyl alcohol/H2O2 ratio.[29]
Ally alcohol in particular has shown to be a
challenging substrate for epoxidation reactions.
Substitution of the allyl alcohol pi bond by electron
withdrawing groups significantly decreases the
susceptibility of the bond to attack by an electrophilic
oxidising agent (in this case, hydrogen peroxide).[20,30]
This is most effectively illustrated by the relative
reactivity of allyl compounds featuring various
substituents alpha to the allyl group, in the order of
methyl > chloro > hydroxyl;[30] however, steric factors
have also shown to be key, in the case of cis-
enantiomers and trans-enantiomers of crotyl alcohol.[31]
In addition, the epoxide thus formed is highly
vulnerable to ring-opening reactions and nucleophilic
attack to yield glycerol or ether diols in the case of attack
by water or alcohol solvents, respectively.
In this study, the effects of catalyst modification on
product distribution in the production of allyl alcohol
from glycerol are examined. Then, the direct effect of
those product distributions on the epoxidation of allyl
alcohol by TS-1 is studied.
MATERIALS AND METHODS
A 13% iron oxide on alumina catalyst was synthesised
adopting the widely used solid impregnation
technique.[12] Alumina spheres (Sasol) were added to
a solution of Fe(NO3)3 (Sigma-Aldrich) in methanol.
The catalyst was calcined for 4 h at 673 K in air. This
was followed by alkali treatment, which consisted of
washing the catalyst with a 0.1-M solution of
potassium hydroxide in methanol, caesium nitrate in
water and rubidium nitrate in water (each solution for
a fresh batch of the iron catalyst as prepared).
Following modification, the resultant catalysts were
dried at 383 K for 2 h and then calcined for 4 h at
673 K in air flow. Changes in the preparation of the
standard iron oxide catalyst were implemented in order
to reduce the water content in the iron nitrate alcoholic
solution. Catalytic reactions were carried out in a
vertical stainless steel plug flow reactor at atmospheric
pressure and 613 K with nitrogen as carrier gas. The
reactor was of cylindrical shape (60 × 1.5 cm internal
diameter × 1.9 cm outer diameter) using 10 g of catalyst
for every set of experiments. In experiments where
hydrogen (Coregas 99.99%) was employed as reducing
agent, the gas was introduced at 20 mL min
1 using of
a Brooks 5850E mass flow controller. The feed
(glycerol 35 wt% aqueous solution) was pumped at
0.5 mL min
1 and varying concentrations of reductant
additives (ammonia propanoic acid, acetic acid, formic
acid and oxalic acid). Liquid samples were taken every
30 min, and after dilution, product analysis was carried
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600 L. HARVEY ET AL. Asia-Pacific Journal of Chemical Engineering

out using a Hewlett Packard 5890A gas chromatograph
equipped with a flame ionisation detector. Catalysts
were analysed by nitrogen adsorption at 77 K.
Isopropanol decomposition took place in a custom-
made apparatus,[32] where products of the reaction
between 303 and 1073 K were monitored using ion
currents at m/z = 58 (acetone) and m/z = 42 (propene).
Peak fitting was performed assuming Gaussian
distribution. Isopropanol conversion was estimated
using m/z = 60. Calculations for the heat of adsorption
of ammonia were based on Eqn (1), assuming first-
order kinetics:[33]
T 2p E 1
In ¼ (1)
β R TP
where Tp is the temperature at which the desorption is
maximum and β is the heating rate. The ion current
used for ammonia desorption was m/z = 16, while
m/z = 44 was used for carbon dioxide desorption.
Titanium silicate-1 catalyst was synthesised as per
Taramasso et al.[18] and reported previously by us[13]
where 37.99 g (0.182 mol) of tetraethylorthosilicate
(Merck) and 0.61 g (0.003 mol) tetratethylorthotitanate
(Merck) were mixed at 35 °C. The mixture was then
cooled in an ice bath, and 39.54 g (0.194 mol) of
tetraethylammonium hydroxide template (40 wt% in
water, Merck) was added dropwise using a burette.
The mixture was then heated to 353 K to evaporate
ethanol formed by hydrolysis of tetraethylorthosilicate,
and the volume returned to its initial level using
distilled water. The mixture was added to a 300-mL
Teflon-lined autoclave and heated to 175 °C for 2 days
with gentle stirring. The fine, white product was
recovered and washed by centrifugation and dried
overnight at 393 K before being calcined in air at
823 K for 4 h and heated with a ramp rate of 2 K per
minute. X-ray diffraction using a Philips X’pert Pro
diffractometer with Cu Kα incident radiation
(λ = 1.5406 Å) and that diffraction pattern have been
compared with samples synthesised by others[18] and
have been published elsewhere.[13]
The epoxidation reaction was conducted in a 25-mL
three necked round-bottomed flask fitted with a
condenser, thermocouple and septum. Feed solutions
representative of the product streams obtained from
the glycerol conversion reaction with a range of
modified iron oxide catalysts were reproduced from
neat chemicals (reactant compositions and suppliers in
Table 1).
All epoxidation reactions were carried out at 333 K
in ethyl acetate solvent for 4 h, as per previous
experiments,[13] with equimolar amounts of allyl
alcohol and hydrogen peroxide (30 wt%, aqueous).
The quantity of TS-1 catalyst was kept constant relative
to total reaction volume. First, TS-1 was added to the
reaction flask, followed by ethyl acetate solvent and
the feed mixture. Hydrogen peroxide was added last.
Seventy-five microlitres of aliquots were taken at zero
and 10 min after the addition of hydrogen peroxide,
then every hour following, until a total reaction time
of 4 h.
The progress of the reaction was monitored using a
Shimadzu 2014 gas chromatograph, fitted with an Rtx
wax column (30 m, with 1-m guard column) and flame
ionisation detector. Samples (1 μL) were injected at
308 K with a split ratio of 10 : 1 and a carrier gas (He)
flow rate of 13 cm min
1.[3] The injection temperature
was held for 5 min, followed by a ramp of 10 K min
1
to 473 K and held for 6 min.
The fractional conversion of allyl alcohol, XAA, was
calculated according to Eqn (2):

Table 1. Reaction feed composition and total allyl alcohol conversion for different catalyst treatments over 4 h
reaction time.

Iron oxide catalyst modification

Oxalic acid Formic acid Rb Ammonia Hydrogen Nil
Concentration (wt%)
Allyl alcohol (Sigma-Aldrich) 2.66 2.74 1.76 1.23 1.72 1.91
Acrolein (Sigma-Aldrich) 0.51 0.34 0.45 0.36 0.10 0.50
Ethanal (Merck) 1.28 0.73 0.20 1.18 0.61 0.50
Hydroxyacetone (Sigma-Aldrich) 1.07 0.88 2.27 1.43 0.45 0.90
Acetic acid (Univar) 1.13 1.08 0.40 1.13 0.81 0.40
Propanoic acid (Ajax Finechem) 1.69 1.32 0.81 1.28 1.01 1.31
Glycerol (Univar) 0.05 0.49 1.66 0.87 0.30 0.15
Watera 42.8 41.3 45.3 43.8 45.4 45.2
Solvent (EtOAc) (Fisher Scientific) 0.52 0.53 0.35 0.24 0.33 0.37
H2O2 (30 wt%)b (Chem Supply) 4.28 4.50 4.53 4.55 4.54 4.52
Titanium silicate-1 0.09 0.09 0.09 0.09 0.09 0.09
XAA 0.67 0.70 0.73 0.76 0.81 0.88
a
Does not include water contributed by hydrogen peroxide solution.
b
Total percentage of 30 wt% hydrogen peroxide solution added.
© 2015 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2015; 10: 598–606
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering INFLUENCE OF GLYCEROL CONVERSION ON GLYCIDOL EPOXIDATION
½AA0
½AAt
X AA ¼ (2)
½AA0
where [AA] is the concentration of allyl alcohol and
glycidol (µg μL
1) initially and at a given time
(indicated by subscripts 0 and t, respectively).
RESULTS AND DISCUSSION
Preliminary catalytic measurements using the alumina
support were conducted at 613 K at 1 atm for reaction
times as long as 5 h. Following 3 h of catalytic tests,
acrolein is produced in moderate yields, while allyl
alcohol production is low (Table 2). Similar molar
carbon selectivities to acrolein and allyl alcohol have
been reported previously at low conversions (17%).[34]
Glycerol conversion was close to 100% and remained
constant as a function on time on stream for 5 h.
Figure 1 shows allyl alcohol and acrolein yields
following 3 h of catalytic measurements for the alkali
metal-treated and alkali metal-unmodified 13% iron
oxide catalysts. Details on physicochemical properties
of the iron catalyst have been provided elsewhere.[12]
The presence of iron resulted in a product distribution
distinctly different to that listed on Table 2, obtained
operating at the same conditions over alumina. The
increase in the rate of formation of allyl alcohol over
the iron catalyst suggests that redox active sites are a
requirement for the formation of the desired product.
The decrease in the rate of formation of acrolein could
be explained by a reduction in the number of acid sites
due to iron deposition. If the catalyst is modified by an
alkali salt, a further increase in the yield of allyl alcohol
is observed (30–60%), presumably because of an
increase in the surface basicity of alumina, as observed
by other authors.[35] The acid sites of the alumina are
poisoned by the alkali metal cation; therefore,
selectivity towards acrolein is reduced, which is also
evident in Figure.
To test the hypothesis-proposed importance of
acidic and basic sites on the catalyst, the modified
catalysts were characterised using temperature-
programmed desorption of ammonia, carbon dioxide
and isopropanol.[12] There is a relationship between
the number of acid sites (determined by ammonia
Table 2. Product distribution from the conversion of glycerol over alumina at 613 K.
Time on Allyl alcohol Acrolein
stream (min) yield (%) yield (%)
120 2.5 19.1
180 1.4 14.4
300 1.5 15.3
Reactant: 35 wt% glycerol. Gas hourly space velocity (GHSV) = 1190 h
1.
© 2015 Curtin University of Technology and John Wiley & Sons, Ltd.
601
12
Allyl alcohol
Acrolein
10
Yield (%)
6
4
0
Rb K Cs Fe
Figure 1. Effect of alkali metal catalyst treatment on allyl
alcohol and acrolein yield at 613 K. Reactant: 35 wt%
glycerol. GHSV = 1190 h
1. This figure is available in
colour online at www.apjChemEng.com.
adsorption) and base sites (determined by CO2
adsorption) that directly correlates with selectivity
towards allyl alcohol and acrolein.[12] In accordance
with the literature, isopropanol can be used for both
acid and base site characterisation.[36] Over acid sites,
dehydration to propene is observed, whereas base sites
dehydrogenate i-propanol to acetone.
The addition of alkali metal cations to the catalysts
resulted in reduced acidity as evident by the decreased
propene yields (Table 3). A drop in the heat of
desorption for the ammonia experiment over modified
catalysts (Table 4) suggests that less energy is
required in the desorption process, implying that the
surface is less acidic than unmodified iron and
alumina. Moreover, an increase in basicity was found
in the modified catalyst as observed by increased
acetone yields when desorbing i-propanol (Table 3)
as well as increased CO2 desorption rate (not shown).
We also observed variations of the acid site strength
with the type of countercation, but the correlations are
not straightforward. Enhanced catalyst activities appear
to be related to the larger atomic radius of the metal
used to modify the support. While we observed a
general trend of increasing allyl alcohol yield with the
size and thus the polarisability of the countercation,
the highest allyl alcohol yield was observed with Rb
and not Cs. The acid site density and concentration
were also affected in a similar manner, whereas the
base site concentration was highest in K-modified
materials.[12] Thus, it is suggested that the optimum
Ethanal Hydroxyacetone Conversion
yield (%) yield (%) (%)
10.1 5.2 99.9
4.5 6.6 99.9
4.6 8.6 99.8
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602 L. HARVEY ET AL.
Table 3. Isopropanol temperature-programmed
desorption between 298 and 1073 K.
i-propanol
conversion
Catalyst
Iron oxide on alumina
Rb-modified iron oxide
on alumina
Table 4. Heat of desorption of ammonia.
Catalyst
Alumina
Iron oxide on alumina
Cs-modified iron oxide on alumina
acid and base site concentration and strength subtly
influence the selectivity and yield to allyl alcohol and
acrolein.
In addition to the chemical effects, alkali treatment
influenced surface area of the catalyst. Figure 2
discloses the nitrogen adsorption isotherms of alumina,
unmodified iron catalyst and caesium-treated iron
catalyst. In the absence of iron, an enhanced uptake
of nitrogen was observed, particularly in the range
P/Po = 0.6–0.95. It is generally accepted that metal
cation deposition on a support decreases its surface
area, which was observed following impregnation of
the alumina with the iron salt. Other authors found a
reduction on surface area when doping alumina with
400
Cs modified iron oxide on alumina
Iron oxide on alumina
350 -alumina
Volume adsorbed (cm3/g)
Asia-Pacific Journal of Chemical Engineering
salts of Li+, Na+ and K+.[37] However, with the
deposition of the alkali metal, an increase in surface
Propene Acetone area was observed, which was attributed to the removal
yield yield of pore blocking material on the alumina. Differences
(%) (%) (%) between the current findings and those from others[37]
98.5 97.8 0.7 were explained by differences in catalyst preparation.
89.3 86.1 3.2 While Perrichon et al. deposited the alkali metal salts
through impregnation, the current catalysts were
modified by washing. Even though there is a
substantial surface loss after reaction using the
modified catalyst, this value is still 4% higher in
modified used catalysts than untreated used iron oxide
alumina catalysts.
Energy of desorption
of ammonia (kJ mol) Deactivation of the iron on alumina catalyst was
observed, and conversion dropped to 76% following
28.8 3 h of time on stream with an untreated catalyst. In
28.0
27.9 contrast, for each of the three treated catalysts,
conversion levels remained at 87% following 3 h of
catalytic measurements (Fig. 3). This suggests that
acidity influences not only product distribution but also
catalyst stability. It is well known that coke can be
formed by interaction with acid sites, which affects the
dehydrogenation route of glycerol to form acrolein.
Consequently, deactivation reduces the rate of acrolein
formation (yield decreased significantly with time on
stream for the untreated catalysts, from approximately
5% in the first hour of catalytic measurements to 3% in
the following 2 h of test).
A further increase in the selectivity and yield of allyl
alcohol was achieved following the addition of a
reductant to the reaction. From a purely stoichiometric
perspective, the reaction of glycerol formally requires
two hydrogen atoms (under the assumption of water
formation) to be able to form allyl alcohol (Figure 4).
It is suggested that hydrogen is generated in situ, via
the dehydrogenation of intermediates formed at high
temperatures. Indeed, some hydrogen was detected in
the gas phase, in concentrations of approximately
0.8% v/v. We have thus investigated the addition of

300 100
90
250 80
Conversion (%)

70
200
60
150 50
40
100
30
20
50
10
0 0
0 0.2 0.4 0.6 0.8 1 Rb K Cs Fe
P/Po
Figure 3. Glycerol conversion at 613 K over different
Figure 2. Nitrogen adsorption isotherms of alumina, catalysts following 3 h of catalytic measurements.
unmodified iron catalysts and caesium-treated iron Reactant: 35 wt% glycerol in water. GHSV = 1190 h
1.
catalysts. This figure is available in colour online at This figure is available in colour online at www.
www.apjChemEng.com. apjChemEng.com.
© 2015 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2015; 10: 598–606
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering INFLUENCE OF GLYCEROL CONVERSION ON GLYCIDOL EPOXIDATION
Figure 4. Reaction mechanism for the transformation of glycerol to allyl alcohol. This figure is
available in colour online at www.apjChemEng.com.
reductants to the reaction and were able to increase
selectivity to allyl alcohol.[38] The addition of oxalic
acid, a known reductant, doubled the yield of allyl
alcohol over an unmodified iron catalyst. Formic acid
had a similar effect, although propanoic and acetic acid
did not have any effect on allyl alcohol yield.
Furthermore, the addition of ammonia, known for its
reductive properties, had a positive effect on the yield
of allyl alcohol (a 35% increment).
When molecular hydrogen is co-fed over bimetallic
(nickel–copper) catalysts supported on alumina, as
well as over palladium, rhodium and copper-based
catalysts supported on alumina, zinc oxide and carbon[39]
can produce 1,2-propanediol and 1,3-propanediol,
respectively, from glycerol at high pressures. Noble
metals are required for hydrogen activation in the
hydrogenolysis reactions of glycerol.[40] In some cases,
noble metals are employed in combination with an
acid, or base or as promoters of metal oxide
catalysts.[40] Iron oxide has been reported to catalyse
© 2015 Curtin University of Technology and John Wiley & Sons, Ltd.
603
hydrogen transfer reactions that led to the development
of a single-step reaction leading to the formation of
allyl alcohol from glycerol.[6] The effect of added
hydrogen on both allyl alcohol yield and glycerol
conversion was studied in a molar ratio of the additive
with respect to glycerol of 0.14 : 1. As evident in
Table 4, in the presence of hydrogen, conversion
remained constant following 3 h on stream. Moreover,
selectivity to coke decreased from 6.77 wt% over the
alumina-supported iron catalyst in the absence of
additives to 0.42 wt% when hydrogen was added.
Gandarias et al. reported previously lower rates of
catalyst deactivation for glycerol conversion in the
presence of hydrogen.[41] A significant enhancement
in the yield of allyl alcohol is also observed when
compared with the absence of additives. The product
distribution is summarised in terms of a product carbon
yield basis (Table 5). Hydroxyacetone and 3-
hydroxyprop-2-enal, which are formed by dehydration
of glycerol, were hydrogenated to 1,2-propanediol and
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604 L. HARVEY ET AL. Asia-Pacific Journal of Chemical Engineering
Table 5. Product distribution for glycerol conversion little, if any, distinguishable effect. Similarly, acetic
in the presence of hydrogen over the alumina- acid and ethanal were found to enhance the conversion
supported iron catalyst, carbon yield basis.
and reaction rate; however, this effect was not observed
Allyl alcohol 12.45 here. The low concentration of reactants and impurities
Acrolein 4.42 most likely diminishes the effect additives that may
Acetaldehyde 4.25 have on allyl alcohol conversion.
Hydroxyacetone 6.50 In line with that observation, the concentration of
Acetic acid 3.72
Propanoic acid 6.91 glycidol, in all cases, decreases substantially after
Acrolein (gas phase) 0.91 60–120 min reaction time as hydrolysis kinetics begin
Acetaldehyde (gas phase) 0.78 to dominate the reaction and the glycerol concentration
Carbon dioxide 3.85 increases (Figs 5 and 6, respectively).
Carbon monoxide 0.89 No other by-products, most notably the ethers and
Unconverted glycerol 0.61
Coke 0.15 ether diols, were formed during the reaction, and this
Other compoundsa 45.45 has been explained previously by surmising that aprotic
solvents do not readily engage in ring-opening
a
Other compounds include 1,2-propanediol and 1,3-propanediol. reactions with glycidol.[13] The water, present in the
feed stream in high concentrations, does engage in
1,3-propanediol, and its contribution to the carbon ring-opening reactions on either of the highly strained
balance is accounted together with other compounds epoxide carbon atoms.
in Table 5. It is evidence that allyl alcohol yield can
be improved by the inclusion of reductants in the feed
and that the redox activity of the catalyst appears to
be responsible for the increase in yield. At the same
time, the addition of some reductants such as ammonia
reduces acrolein yield, which is important for the
subsequent reaction to glycidol (see the following
discussions). Without iron in the catalyst, very little
selectivity to allyl alcohol was observed, which
suggests that the redox activity of the transition metal
is responsible for the generation and/or reaction of
hydrogen with the intermediates. The combination of
the suitable acid and base sites as well as the redox
properties of the catalysts significantly alters the Figure 5. Glycidol concentration over course of
selectivity to allyl alcohol, and the yield can be reaction for reaction mixtures as produced by each
optimised by variation of these parameters. glycerol conversion catalyst modification. This figure
Previous work has shown that certain by-product is available in colour online at www.apjChemEng.
functionalities (such as aldehydes), including those com.
produced as by-products in the glycerol conversion
reaction, are detrimental to the epoxidation reaction,
whereas others may act as reaction promoters,[13] and
a possible mechanism to explain these observations
was developed. The effect of selected product
distributions, as obtained directly from the glycerol
conversion reaction, on the epoxidation of allyl alcohol
has been examined (Table 1).
The conversion of allyl alcohol was uniformly
relatively high, with the reaction feed mixture produced
by the unmodified catalyst being the most favourable,
at 88%. The total amount of allyl alcohol obtained from
the unmodified glycerol conversion catalyst, however,
is slightly less than half of that obtained from the
formic acid-modified catalyst. The total yield of
glycidol therefore is higher for the formic acid catalyst
feed mixture, despite the lower allyl alcohol Figure 6. Glycerol concentration over course of
reaction for reaction mixtures as produced by each
conversion. In our previous work,[13] acrolein was glycerol conversion catalyst modification. This figure
found to be exceptionally detrimental to allyl alcohol is available in colour online at www.apjChemEng.
conversion; however, in this case, there appears to be com.
© 2015 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2015; 10: 598–606
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering INFLUENCE OF GLYCEROL CONVERSION ON GLYCIDOL EPOXIDATION
CONCLUSIONS
Catalyst acidity and basicity subtly influence allyl
alcohol and acrolein yields from glycerol. K, Rb and
Cs poison the catalyst acid sites and increase catalyst
basicity, improving selectivity towards allyl alcohol.
The same treatment reduces catalyst deactivation and
increases surface area by 8%. Furthermore, the addition
of reductants can double the yield of allyl alcohol.
Catalysing the reaction of the precursors with added
reductants is the main function of the redox site in these
multifunctional oxide-based catalysts.
The epoxidation of allyl alcohol to glycidol using
feed directly obtained from the conversion of glycerol
is feasible; however, the high water concentration leads
to rapid hydrolysis of the target product once the
glycidol concentration is sufficiently high. It is
recommended that allyl alcohol be removed from the
feed via distillation in order to mitigate glycidol
hydrolysis.
Acknowledgements
Financial support by AEL and the ARC is gratefully
acknowledged. Luke Harvey and Gizelle Sanchez
would like to thank the University of Newcastle for
their postgraduate research scholarships.
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