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Paper no: 1477

UNDERSTANDING SELECTIVITY AND ACTIVITY OF REDOX CATALYSTS FOR INDUSTRIAL


AND ENVIRONMENTAL APPLICATIONS

M. Stockenhuber
Priority Research Centre for Energy (PRCfE), The University of Newcastle, Callaghan NSW 2308, Australia
Email: michael.stockenhuber@newcastle.edu.au

Keywords : glycerol conversion, allyl alcohol, glycidol, iron oxide, acrolein acid base properties

Abstract

Conversion of glycerol to allyl alcohol which is converted to glycidol in a separate process step is
discussed in this paper. Microreactor studies were carried out over a number of catalysts and
operating conditions with the aim of improving the overall process yield to glycidol. To increase
the reaction selectivity of the first step (glycerol to allyl alcohol), the support was modified with
alkaline metal salts. It was found that the catalyst treatment with solutions of sodium,
potassium, caesium and rubidium significantly enhanced the allyl alcohol yield using a 35%wt.
glycerol aqueous feed. Furthermore the addition of organic reductants increased the yield of
conversion of glycerol to allyll alcohol. Optimisation towards high allyl alcohol selectivity was
achieved by variation of alkaline metal cation modifiers and addition of reducants. A model for
the influence of acid, base and redox properties on slecctivity and yield is presented.

Introduction

Carbon dioxide emissions and depleting fossil fuel resources have strongly promoted the
successful industrial scaling up of the transesterification process for the manufacture of Fatty
acid methyl esters (FAME). However, from a practical point of view, 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 the food, pharmaceutical, chemical
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and cosmetics industry the enormous production rates and costly purification threaten the
financial viability of biodiesel manufacture. For every 10 kg of product being produced, roughly
1 kg of crude glycerol is generated 5. Clearly 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 mainly on how to improve the first step of the conversion of glycerol to
Paper no: 1477

allyl alcohol but also give some insight on how byproducts influence the subsequent epoxidation
of allyl alcohol with H2O2 to glycidol over titanium containing microporous catalysts. Even
though iron oxide is generally not considered to be a catalyst for hydrogen transfer reactions,
the dehydration of glycerol to acrolein and its consequent hydrogenation to the selective
production of allyl alcohol has been reported over iron oxide catalysts with high surface areas.
In contrast the 1-2 dehydration of the central OH group in glycerol, producing acrolein at a yield
of up to 75% is usually catalysed by strong solid acids solids 6,7. Clearly the product distribution
of the converted glycerol is expected to depend on the acid base properties of the catalyst and/
or support. The acid-base nature of catalyst supports can be modified by the deposition of alkali
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metals and a multitude of basic compounds have been used to modify catalyst support
properties. The effect of alkali modification is not necessarily straightforward, as under certain
conditions treatment can increase the acidity of the surface, depending on the concentration of
the metal in the support 9. In this study, the effect of alkali treatment of an alumina-supported
catalyst and the addition of reductants to the feed for the selective conversion of glycerol into
allyl alcohol was examined. We also investigated the subsequent conversion of allyl alcohol to
glycidol in the presence of the byproducts and observed significant influence of some of the
oxygenates on the epoxidation reaction.

Experimental

A 15% iron oxide on alumina catalyst was synthesised from a recently developed non-aqueous
impregnation method. High purity alumina spheres (Sasol 1,8/210 in pellet form) were dried
prior to treatment for 1 hour at 120°C. Aluminium oxide pellets ( Sasol) were added to a
prepared solution of precursor salt: was and stirred overnight. The catalyst was calcined for 4
hours at 400°C with an air flow and a heating rate of 4°C·min-1. The alkali treatment was
accomplished after calcination, by impregnating the catalyst with a 0.1 M solution of sodium
hydroxide in methanol, potassium hydroxide in methanol, caesium nitrate in water and
rubidium nitrate in water. The spheres were filtered, washed and dried at room temperature.
Catalytic reactions were carried out in a packed bed reactor. The reaction temperature was
monitored by a thermocouple placed in the centre of the catalyst bed, maintaining a constant
temperature of 613 K. Nitrogen was used as a carrier gas and introduced at a volumetric flow of
226 cm3·min-1. The feed: a glycerol 35% wt. aqueous solution was pumped at 0.5 ml·min-1and
varying concentrations of reductant additives ( ammonium hydroxide, propanoic acid, acetic
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acid, formic acid oxalic acid. The setup was equipped with a condenser allowing liquid product
to accumulate and samples to be taken every 30 minutes using a syringe. After dilution, product
analysis was carried out using a HP 5890A gas chromatograph equipped with a flame ionization
detector. Used and fresh catalysts treated and not treated were analysed by nitrogen
adsorption at 77 K and surface areas were calculated using the BET equation. For the
epoxidation reaction, typically 0.25 g of TS-1, 2.90 g allyl alcohol and 22.5 mL solvent were
added in a batch reactor. The reactants were then heated to the required temperature and 5.67
g hydrogen peroxide (30 wt%, aqueous) and impurities (acrolein, glycerol, water) were added
and the reaction followed by gas chromatography.

Results and discussion

Fig. 1 shows the allyl alcohol and acrolein yield versus the reaction time for the treated and
unmodified 15% iron oxide catalyst. If the catalysts is modified by an alkali salt, the allyl alcohol
yield rises by 30% to 60% presumably due to an increase in the surface basicity of alumina and a
decrease in the acidity as a result of the impregnation method 10. The acid sites of the alumina
are be poisoned by the alkali metal cation and thus reduce the selectivity towards the acrolein
product which can be seen in Fig1b.

Table 1 Effect of catalyst type on allyl alcohol and acrolein yield. Reaction time is 3 hours.

Catalyst Conditions Allyl alcohol Acrolein Conversion (%)


yield (%) yield (%)

γ-alumina -1 1.5 14.5 99.8


340 °C, WHSV = 0.3 h, 35 wt %
glycerol

-1 4.3 4.3 78.6


340 °C, WHSV = 0.3 h, 35 wt %
γ-alumina/Fe
glycerol

-1
γ-alumina/Fe/Rb 340 °C, WHSV = 0.3 h, 35 wt % 11.6 3.2 89.8
glycerol
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a b

Fig. 1. Effect of alkali metal catalyst treatment on allyl alcohol (left) and acrolein yield (right) as a function
-1 11
of time on stream at 613K. Reactant: 35%wt. GHSV=6625 h .

Blank experiments were carried out over the alumina carrier without iron phase under the
same conditions as outlined above. Product distribution and conversion values obtained on this
surface (Table 1) are in agreement with previous studies over the same material, in which
complete conversion of glycerol was observed. Activity of the catalyst remained constant as a
function on time on stream for five hours. Due to the moderate acidity alumina exhibits,
problems with product desorption typical of strong acids are not observed even on the
unmodified alumina. 12. It is evident from Table 1, that iron is increasing allyl alcohol selectivity,
which is similar to what has been reported 13,14. In line with the literature 12, γ alumina is forming
acrolein with relatively high selectivity. Iron forms sites that can catalyse the conversion of
glycerol to allyl alcohol and simultaneously remove sites responsible for acrolein formation. To
further substantiate this hypothesis, the modified catalysts were characterised using TPD of
ammonia, carbon dioxide and also isopropanol 15. It was observed that there is a relationship
between the number of acid sites and base sites that correlates with the selectivity towards allyl
alcohol. The number of acid sites was determined by ammonia adsorption and the base sites by
CO2 adsorption15. In accordance with the literature, isopropanol can be used for both, acid and
base site characterisation 16. Over acid sites, dehydration to propene is observed whereas base
sites dehydrogenate i-propanol to acetone. Indeed, the addition of alkaline metal cations to the
catalysts resulted in reduced acidity (decreased ammonia desorption rate and decreased
selectivity towards propene and increased CO2 desorption rate and increased selectivity towards
acetone in the i-propanol desorption. We also observed variations of the acid site strength with
the type of contercation, 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
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support. While we observed a general trend of increasing allyl alcohol yield with the size and
thus the basicity and polarizability of the countercation the highest allyl alcohol yield was
observed with Rb and not Cs. The acid site density and concentration was also effected in a
similar manner, whereas the base site concentration was highest in K modified materials15. Thus,
it is suggested that the optimum acid and base site concentration and strength subtly influences
the selectivity and yield to allyl alcohol and acrolein.
In addition to the chemical effects, alkali treatment had an effect on the pore volume and
surface area of the catalyst. The increase in surface area is suggested to be enhanced by the
removal of pore blocking, extraneous material in the alumina and as such the alkali treatment
process increased the catalyst surface area by 8%. Even though there is a substantial surface loss
after reaction using the modified catalyst, this is still 4% lower than the untreated iron oxide
alumina catalysts (Table 2).

Table 2
Surface areas of iron oxide alumina supported catalysts as studied by glycerol conversion at
613K
Catalyst Surface Area (m2/g)
Blank (alumina spheres) 200.0
15% Fe2O3 on alumina spheres fresh 164.1
15% Fe2O3 on alumina spheres used 138.1
Alkali treated 15% Fe2O3 on alumina fresh 178.4
Alkali treated 15% Fe2O3 on alumina used 156.1

Significant deactivation of the Iron on alumina catalyst was observed. Conversion dropped by
approximately 20% after three hours of time-on-stream with an untreated catalyst. In contrast,
for the treated catalysts only a 10 % reduction in conversion was observed even after six hours
of time on stream (Fig. 2). This suggests that acidity influences not only selectivity of the catalyst,
but also the 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. As a consequence, deactivation reduces the
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rate of acrolein formation (yield exhibited a significant decrease as function on time on stream
for the untreated catalyst) (Fig. 1).

Fig. 2. Catalytic activity as a function of time on stream at 613 K over different catalysts.
Reactant: 35%wt. glycerol in water. GHSV=6625h-1. 15

A further increase in the selectivity and yield of allyl alcohol was possible by addition of a
reductant to the reaction17. From a pure stoichiometric point of view, the reaction of glycerol
formally needs hydrogen to be able to make allyl alcohol:

Scheme 1) Reaction scheme for the transformation of glycerol to allyl alcohol.

It is suggested that hydrogen is generated in situ by dehydrogenation of intermediates formed


at higher temperatures. Indeed some hydrogen is found in the gas phase. We have thus
investigated the addition of reductants ( or hydrogen sources) to the reaction and were able to
increase the selectivity towards the allyl alcohol.17 Addition of oxalic acid, a known reductant
doubled the yield of allyl alcohol over an unmodified catalyst from 8% to 18% yield. Formic acid
had a similar effect but propanoic and acetic acid, which do not act as a reductant did not have
any effect. Furthermore, addition of ammonia (a reductant) again had a significant effect on the
yield of allyl alcohol ( 15%). This is very clear evidence that allyl alcohol yield can be improved by
reductants and that the redox property is responsible for the increase in yield. At the same time
the addition of reductants reduces the acrolein yield which is important for the subsequent
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reaction to glycidol ( see below). Without iron in the catalyst very little selectivity to allyl alcohol
was observed which suggest the redox activity of the transition metal is responsible for the
generation and/or reaction of hydrogen with the intermediates.
The combination of the correct acid and base sites as well as the redox properties of the
catalysts significantly alter the selectivity to allyl alcohol and the yield can be optimised by
variation of these parameters.
It is important to note that acrolein and other impurities in the allyl alcohol reaction product
influence the activity in the consecutive reaction step to produce glycidol from allyl alcohol with
hydrogen peroxide over TS-1:

Scheme 2) Reaction of allyl alcohol to glycidol over TS1 with hydrogen peroxide

Selectivity and yield of the glycidol product from the epoxidation of allyl alcohol was negatively
influenced by acrolein and glycerol and thus the selectivity of the first step of the reaction
cascade is crucial for the overall feasibility of the over process of the conversion of glycerol to
glycidol. The reason for the selectivity change of the epxodation recation of allyl alcohol to
glycidol is the poisoning of the active titanium site in TS-1. This will be reported in a future
communication.

Conclusions

Catalyst acidity and basicity subtly influences the allyl alcohol and acrolein yields from glycerol.
Na+, K+, Rb+, Cs+ poison the catalyst acid sitesa dn increase catalys basicity, improving selectivity
towards allyl alcohol. The same treatment has the effect of doubling catalyst and increasing the
surface area by 8%. Furthermor, addition of reductants can again double the yield of allyl
alcohol. The reaction of the precursors with reductant and the formation of the active reduction
phase is the main function of the redox site in these multifunctional oxide based catalysts.

Acknowledgements

Financial support by AEL and the ARC is gratefully acknowledged.


Paper no: 1477

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