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Glycerol dehydration to acrolein in the context of new uses of glycerol

Benjamin Katryniok,a,b Sébastien Paul,a,b,c Virginie Bellière-Baca,d Patrick Reye and Franck Dumeignil*a,b
Received 9th July 2010, Accepted 5th October 2010
DOI: 10.1039/c0gc00307g
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Catalytic dehydration of glycerol to acrolein has the potential to valorise the glut of crude glycerol
issuing from biodiesel production. This reaction requires catalysts with appropriate acidity, and
intensive research activities have been focused on the application of families of catalysts including
zeolites, heteropolyacids, mixed metal oxides and (oxo)-pyrophosphates, as their acidic properties
are well-known. Nevertheless, their deactivation by coking remains the main obstacle in the way of
large-scale industrial applications. Considering this important issue, various technologies have been
proposed for regenerating the catalysts. This review shows that a well-balanced combination of an
appropriate catalytic system together with an adapted regeneration process could put large-scale
industrial applications within reach.

1 Introduction The capacity of biodiesel production is expanding all over

The finite reserves of fossil-fuel feedstocks have encouraged
intensive research activities for developing substitutes/additives
for fuels such as biodiesel, bioethanol or biokerosene. Due to
their origin from biomass, they have the strong advantage of
a lower carbon footprint than fuels derived from fossil-fuel
resources. However, from an economic point of view, it is not
yet possible to produce any of these biofuels competitively.
Nevertheless, political decisions have pushed the production of
fuels from bioresources in order to be able to fulfill the CO2
reduction objectives fixed by the Kyoto climate protocol.1 For
example, the European Union has planned a progressive increase
in the mandatory proportion of bioethanol blended in gasoline,
and of biodiesel blended in diesel fuel. The blended amounts
must reach 10% and 7% by 2015, respectively.2
The alternative gasoline production route using vegetable
oils and fats has attracted the attention of many academic
and industrial researchers.3 The raw materials for biodiesel
production are vegetable oils and fats – from canola, soy, corn,
etc. – and a mono-alcohol (usually methanol), which is used to
cleave the fatty acids from their glycerol backbone to yield the
desired fatty acid esters (Scheme 1). These esters can be directly
used as biodiesels, but they are commonly blended with diesels
derived from fossil-fuels to meet the regulations.
Scheme 1 Transesterification reaction of vegetable oils to yield
biodiesel.
a
Univ. Lille Nord de France, F-59000, Lille, France.
E-mail: Franck.Dumeignil@univ-lille1.fr; Fax: +33 (0)3.20.43.65.61;
Tel: +33 (0)3.20.43.45.38
b
CNRS UMR8181, Unité de Catalyse et Chimie du Solide, UCCS,
F-59655, Villeneuve d’Ascq, France
c
ECLille, F-59655, Villeneuve d’Ascq, France
d
RHODIA France, 52 Rue de la Haie Coq, 93308, Aubervilliers, France
e
ADISSEO France SAS, Antony Parc 2-10, 92160, Antony, France
the world. For example, in 2008, the USA produced 2.3 million
tonnes of biodiesel, while the EU produced 7.8 million tonnes
(Fig. 1), and these values are expected these to double by 2012.4,5
This growth is accompanied by a significant increase in glycerol
production, as this a significant by-product (~10 wt%) of the
biodiesel process (Scheme 1). Simple projections enable one to
forecast that 1.54 million tonnes of glycerol will be generated
worldwide in 2015,6 all of which will have to be efficiently
processed in order to achieve a sustainable business.
Fig. 1 Comparative evolution of the quantities of biodiesel produced
in the EU and the US.5,7
Depending on the process used for the cleavage of the fatty
acids, the purity of the crude glycerol can vary greatly. The
crude glycerol obtained from most of the conventional biodiesel
processes contains ca. 80 wt% of glycerol, but it also contains
water, methanol, traces of fatty acids as well as various inorganic
and organic compounds (called ‘MONG’, denoting ‘Matter
Organic Non-Glycerol’) (Table 1).
As a consequence, in most of the cases, crude glycerol must
be purified by an expensive distillation step prior to further
use, to meet the requirements of the downstream processes.
The proportion of glycerol that is refined is actually steadily
decreasing, due to the high cost of the distillation step, together
with a rapid growth of the quantity of crude glycerol produced,
and also (primarily) because of the absence of any market
able to absorb the massive overproduction (Fig. 2). In fact, an
increase in the price of glycerol – together with a sustainable and
significant demand – would automatically result in a decrease in

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Table 1 Examples of qualities of glycerol derived from some biodiesel

production processes.8 Compositions are given in wt%

Company production site

Robbe/Diester Saipol/Diester Diester/Bioenergy

Compiègne (France) Rouen (France) Marl (Germany)

Glycerol 65 93 85
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Water 31 4 10
MONGa <1 <1 <0.5
Salts 3 (Na2 SO4 ) 2.5 (NaCl) 4.5 (NaCl)
Methanol 0.3 0.2 <0.01
Fig. 3 Distribution of the glycerol consumption by sector/
a
MONG = Matter Organic Non-Glycerol.
application.10

such when the amount of water has to be controlled, namely in

Fig. 2 Global crude glycerol production compared to the amount
distilled. ‘Delta’ is the amount of glycerol that is not upgraded, and
usually burned.6,7
the production costs of the transesterification process, which
up to now had to be entirely compensated for by the sales
of biodiesel.9 New economical ways of using glycerol must
therefore be developed in order to substantially increase the
demand and the price of crude glycerol, and therefore to ensure
the sustainability of the biodiesel sector.10
More than 1500 direct applications of glycerol are already
known, especially in cosmetics, pharmaceuticals and food
industries.11 The large versatility of glycerol use is based on
both its chemical and physical properties (Fig. 3). Due to the
presence of three hydroxyl groups, glycerol is completely soluble
in water and alcohols, whereas it is completely insoluble in
hydrocarbons. It is a very hydrophilic species, and is employed as
glue or other adhesives. Further, the presence of hydroxyl groups
leads to the formation of intra- and inter-molecular hydrogen
networks, which explains its high boiling point (290 ◦ C at
atmospheric pressure) and high viscosity. This latter rheological
property is at the origin of the use of glycerol as a softener
in resins and plastics but also as a lubricant, for instance in
pharmaceutical applications. In addition, glycerol is non-toxic
and has a sweet taste. It can thus be incorporated in food,
medicines and cosmetics. However, as mentioned earlier, the
crude glycerol from the biodiesel processes contains impurities,
and is therefore not suitable for such applications without a
preliminary purification stage. In addition, the size of the existing
market is not sufficient to absorb the huge amount of glycerol
currently produced, and the gap between the absorption capacity
of the market and the amount of glycerol produced will increase
in the near future if no new applications are found.
Today, the crude glycerol that is not refined is generally
burned (Fig. 2), which must be considered as a tragic waste
of a potentially very useful organic raw material. Glycerol is
a molecule with a large functionalisation potential that offers
numerous opportunities for chemical or biochemical conver-
sions for producing value-added chemicals. A non-exhaustive
selection of these possibilities is shown in Scheme 2, and is
further discussed below.
For the moment, only a few applications utilise glycerol on a
large scale. One of them is the halogenation to epichlorhydrin,

Scheme 2 Selected glycerol valorisation target molecules.

2080 | Green Chem., 2010, 12, 2079–2098 This journal is © The Royal Society of Chemistry 2010

which is an important intermediate for epoxy resins. The process
uses hydrochloric acid in the presence of organic acids (caprylic
acid – Solvay/acetic acid – Dow)12 as catalysts working in the
gaseous phase at 180–220 ◦ C under a pressure of 1–5 bar.13
This technology was commercialised in 2007 by Solvay, which
operates an existing production facility in France that was
formerly used to produce glycerol from epichlorhydrin. Another
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commercialised process for large-scale consumption of glycerol
is the reforming over Pt–Rh catalysts to yield syngas. This
latter can either be used in the Fischer–Tropsch process for
the synthesis of alkanes (Biomass to Liquid, BtL) or for the
synthesis of methanol as performed by BioMCN in Delfzijl
(Netherlands) with a capacity of 200 kt/year.14–16 From this
technology is derived the sustainable production of hydrogen
– an energy vector with an expected high potential in the near
future – through the water-gas shift process. As another option,
the etherification to glycerol tert-butyl ether (GTBE) targets
the classical petrol-based economy. Indeed, this compound
is an environmentally friendly additive in gasoline, and can
beneficially substitute for the problematic methyl tert-butyl ether
(MTBE). Nevertheless, the associated process is still far from
reaching industrial applications.17
The selective reduction and esterification of glycerol are
two processes with potential impacts on glycerol consumption
at a medium scale. The former can be used to yield either
propylene glycol (MPG) or 1,3-propanediol (PD), which are
valuable intermediates in the polymer industry. The latter targets
the esters of glycerol – namely, monoacylglycerol (MAG) and
diacylglycerol (DAG) – that find applications as emulsifiers,
e.g., in food (margarines and sauces) or in cosmetics. This
process can either be catalysed by a conventional catalyst or by
enzymes (lipase-type).18 Recently, the production of MPG has
been commercialised by Synergy Chemicals with a production
capacity of 30 kt/year.10,19
A small-scale application, but aiming at the synthesis of
high-value fine chemicals, consists on the partial oxidation of
glycerol to carboxylic acids (i.e., glyceric acid, tartronic acid and
ketomalonic acid), aldehydes (i.e., glyceraldehyde) or ketones
(i.e., dihydroxyacetone). The main challenge is to find oxidation
catalysts that are highly selective to the target molecule, among
a large quantity of possible reaction products. One example is
the selective oxidation to dihydroxyacetone over Bi/Pt catalysts,
giving 37% yield at 70% conversion of glycerol.20 Oxidation
can also be performed using genetically modified bacteria or
electrochemical reactions.21,22
However, one of the most promising routes to glycerol
valorisation lies in its catalytic dehydration to acrolein, which
is an important industrial intermediate for the chemical and the
agro-industries. The synthesis of acrolein is currently based on
the selective oxidation of propene over complex multicomponent
BiMoOx -based catalysts (Scheme 3). The selectivity reached in
this process is close to 85% at 95% conversion.23 New approaches
with propane as a starting material are currently being explored
at the laboratory scale, but they suffer from insufficient yields,
which are incompatible with further commercialisation.24 Con-
Scheme 3 Catalytically-assisted selective oxidation of propene.
This journal is © The Royal Society of Chemistry 2010
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sidering the petrochemical feedstock depletion issues, sustain-
able resources will become more and more competitive, not to
mention their positive effect in terms of impact on the climate.
Within this context, a massive bioresourced and sustainable
acrolein production is an important challenge, which has been
accepted by academic and industrial researchers. An economics
study has shown that competitive production of acrolein from
glycerol could be possible if the price of glycerol became less
than ca. 300 US$/t.25 In January 2010, refined glycerol still cost
500–550 US$/t, but crude glycerol was only around 100 US$/t.
This makes this latter a potentially very competitive raw material
for acrolein production, even though some technical difficulties
in the application of crude glycerol have still to be solved, in
particular avoiding catalyst poisoning by the impurities.26
Due to its toxicity, acrolein is usually directly converted to
the desired high value-added derivatives. Most acrolein is used
for the synthesis of acrylic acid, which is used, for example, as a
starting material for synthesising sodium polyacrylate (Scheme
4). According to its physical properties, this polymer, classified as
a superabsorbent, finds uses in hygiene products, such as diapers.
The annual worldwide market for this superabsorbent polymer
(SAP) is estimated at 1.9 million tonnes for 2010.27
Scheme 4 Industrial synthesis of sodium polyacrylate, a superab-
sorbent polymer.
The second largest consumer of acrolein is represented by the
synthesis of DL-methionine via 3-methylthio-propionaldehyde
as an intermediate (Scheme 5).28 DL-Methionine is an essential
amino-acid, which cannot be synthesised by living organisms,
and is widely used in meat production to accelerate animal
growth. The annual worldwide production capacity of DL-
methionine is about 500 000 tonnes.29 As natural methionine
sources like plants and microorganisms provide concentrations
that are too low, it has to be synthesised on the industrial scale.
It is estimated that the global demand will increase by 3–7% in
the near future.30
Scheme 5 Chemical pathways for the industrial manufacture of DL-
methionine.
In the following sections, we will present the state-of-the-
art on the sustainable production of acrolein by gas-phase
dehydration of glycerol. In fact, since our last review on the
dehydration of glycerol,31 the number of publications in this
Green Chem., 2010, 12, 2079–2098 | 2081

field has greatly increased (Fig. 4). In particular, the funda-
mental scientific aspects of the reaction have been illuminated.
Therefore, we will first discuss the general properties needed to
give high catalytic performances, and then we will describe in
detail the three most common types of catalytic systems used
in this reaction. The possibility of catalyst regeneration, such
as the dehydration of glycerol in the presence of oxygen, will
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also be commented upon. After a short look at liquid-phase
dehydration, the fundamentals of the reaction will be discussed
in a section devoted to the insights in the understanding of the
mechanism. Finally, the possibility of using crude glycerol will
be discussed, before concluding the discussion and giving an
outlook on the possible directions for further research efforts.
Fig. 4 Evolution of the number of publications dealing with glycerol
dehydration to acrolein (plotted using data collected using ScopusTM by
performing a search with “glycerol, dehydration, acrolein” as keywords).
2 Historical context
It has been well known for a long time that heating glycerol
induces its decomposition to acrolein and water, with a certain
amount of by-products. However, an acid catalyst is needed to
provide good control of the reaction and to obtain a significant
yield of the unsaturated aldehyde at a moderate temperature.
The first patent on this subject was published by Schering in
1930 in France.32 The reaction was carried out in the gaseous
phase over supported lithium phosphate as a catalyst, with the
yield of acrolein being close to 75%. Later, in 1934, Groll and
Hearne from the Shell company applied for a patent for the
dehydration of an aqueous glycerol solution in the presence of
sulfuric acid at 190 ◦ C (supposedly the boiling point of the
solution).33 The product was recovered in the gas phase with a
yield of nearly 50%. Dehydration in the liquid phase was further
studied and patented by Hoyt and Manninen, this time using
a heterogeneous catalyst based on phosphorous acid supported
on clay.34 It is interesting to note that these authors even at that
time preferred petroleum oil as a reaction medium, due to its
high boiling point of more than 300 ◦ C. Thereby, they could use
higher reaction temperatures than Groll and Hearne,33 who were
limited to 190 ◦ C, as the reaction was performed in the aqueous
phase. This combination of a heterogeneous catalyst and a high
boiling point reaction medium allowed them to obtain a yield of
72.3%. However, these early works – in both the gaseous and the
liquid phases – remained undeveloped until the end of the 20th
century, when cheaper glycerol from the biodiesel production
process became available.
In 1994 and 1995, Neher et al. published two patents35,36 as
a follow-up of the pioneering work of Schering-Kahlbaum.32
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They reproduced the experiments over the lithium phosphate
catalyst and compared its performance to those of a set of acid
catalysts with well defined Hammett acidities (HAs) ranging
from +3 to -8.2. They claimed that aqueous solutions from 10
to 40 wt% of glycerol could be converted at 300 ◦ C over alumina-
supported phosphorous acid, to yield acrolein with a selectivity
up to 75% at full glycerol conversion. The main by-product was
acetol (hydroxyacetone), with a selectivity close to 10%. Neher
et al. also pursued research on alumina-supported phosphorous
acid, but with a view to producing 1,2- and 1,3-propanediol.37
The yield of acrolein formed as an intermediate was, however, a
little lower (70.5%).
3 Acidity of the catalysts
Clearly, the acidity of the active phase is a crucial parameter
that influences the catalytic performance and stability. The first
quantitative studies on this effect were published by Dubois
et al. in 2006.38,39 They carried out several tests with zeolites,
NafionR , heteropolyacids (HPAs) and also with different types
of acid-impregnated metal oxides. All these catalysts have a well
defined HA ranging from -9 to -18. The selectivity for acrolein
depended on the catalyst: For NafionR catalysts (HA = -12)
and for tungsten oxide on zirconium oxide (HA = -14.5), the
selectivity for acrolein was close to 70% at full conversion, while
the selectivity over zeolitic catalysts (HA < +2) did not exceed
60%. The authors concluded that catalysts with an HA of -10
to -16 were the best candidates for the selective dehydration of
glycerol to acrolein.
Inspired by these first results, a second research group focused
its activities on the influence of catalyst acidity. In 2007, Chai
et al. published two papers on the sustainable production
of acrolein from glycerol. Whereas the first paper focused
on niobium oxide as a catalyst,40 the second compared the
catalytic performances of different types of acid catalysts.41
As the acidity of niobium oxide is inversely related to the
calcination temperature of the hydrous niobium oxide precursor
(as previously described by Chen et al.42 and Lizuka et al.43 ),
this compound is particularly suitable as a model catalyst for
studying the influence of acidity on a given reaction. The best
results were obtained for catalysts calcined at low temperature
(250–300 ◦ C). In addition to their high acidity, these catalysts are
also advantageous as they have higher specific surface area than
the catalysts calcined at higher temperatures. Nevertheless, the
selectivity for acrolein barely exceeded 50% at 90% of glycerol
conversion. In addition, the catalysts calcined at low temperature
showed high carbon deposition, and were therefore subject to
quick deactivation. From these observations, it was already
possible to conclude that the strength of the acid catalyst must
be carefully kept in a narrow range, because acids that are too
weak give low selectivity, whereas acids that are too strong result
in accelerated deactivation.
Therefore, Chai’s team screened numerous catalysts, which
were classified into four different groups according to their
acidity.41 Group 1 contained basic catalysts with an HA higher
than +7, like magnesium oxide. These catalysts showed no
selectivity for acrolein at all. Group 2 contained catalysts with
an HA between -3 and +7, like zirconium oxide. According to
the work of Neher,35 these catalysts should give high acrolein
This journal is © The Royal Society of Chemistry 2010

selectivities, but, in practice, the selectivity did not exceed 30%,
while the performances remained quite stable for 10 h on stream.
Group 3, which was more promising, contained catalysts with an
HA between -8 and -3. In this group, we find alumina-supported
phosphorous acid next to alumina-supported HPAs, niobium
oxide (calcined at 400–500 ◦ C), as well as HZSM zeolite and
pure alumina. In good agreement with previous results,38,39 the
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selectivity was generally higher than that observed for Group 2
catalysts, with the exception of pure alumina and niobium oxide
calcined at 500 ◦ C. Interesting results were also observed over
the alumina-supported phosphotungstic HPA and over a mixed
phase of tungsten oxide/zirconium oxide, with approximately
70% selectivity at 70% conversion in both cases after 2 h on-
stream. Unfortunately, these catalysts showed poor stability,
and their performance significantly decreased during time on-
stream (for both catalysts, the glycerol conversion dropped from
68–69% after 1 h under reactant flow to 23–25% at 10 h, the
selectivity being more-or-less unaffected at roughly 66–70%).
The other catalysts were on the whole less efficient, and gave
selectivities of 35–55% at conversions of 55–100% after 10 h on-
stream. In Group 4 were included catalysts with a HA less than
-8, like Hb-zeolite, niobium oxide calcined at 350 ◦ C, and also
alumina-silicate as well as sulfonated zirconium oxide. These
catalysts were less selective to acrolein than those of Group 3,
but their performances were less altered with time on-stream.
As an example, the glycerol conversion over an aluminosilicate
dropped only from 94% after 1 h under reactant flow to 75%
after 10 h, the acrolein selectivity being more-or-less unchanged
at roughly 43–46%. Nevertheless, like niobium oxide, Group 4
catalysts were also subject to detrimental coke formation, with
a carbon deposit of 100–400 mg per gram of catalyst after ten
hours on-stream.
In addition to the acidic strength of the catalyst, the type of the
acid sites present at their surfaces has an important influence on
their catalytic performance. When Chai et al. classified the cata-
lysts according to their strength,41 they mixed up Brønsted and
Lewis acid catalysts without differentiation. Whereas Brønsted
acids donate a proton (as for the aforementioned silicotungstic
acid, protonated zeolites or phosphorous acid), Lewis acids
are acceptors for electron pairs (as for niobium oxide or pure
alumina). From the catalytic results obtained by Chai et al.
over these two different types of acids, one can conclude that
they do not obey the same reaction pathway, as the authors
systematically obtained rather low selectivities for acrolein over
Lewis acids.41 A more detailed study on the different catalytic
behaviors of Brønsted and Lewis acids in this reaction was
proposed by Alhanash et al.,44 who compared a pure Brønsted
acid catalyst (acidic caesium salts of phosphotungstic acid) to
a pure Lewis acid catalyst (tin-chromium mixed oxide). They
showed that:
∑ Lewis acid catalysts need a higher reaction temperature to
be activated, due to a higher activation energy compared to
Brønsted acid catalysts;
∑ Lewis acid catalysts give a larger selectivity for ace-
tol, which is the major by-product observed during glycerol
dehydration.
These results were confirmed by Kim et al., who compared
HZSM-5 aluminosilicates with different ratios of alumina and
silica.45
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According to Alhanash et al.44 the reaction over Brønsted-
type acid catalysts starts with the protonation of the secondary
hydroxyl group of glycerol by a proton from a Brønsted site, as
postulated by Bühler for homogenous reaction media (Scheme
6a).87 The resulting intermediate is transformed by release of a
hydronium ion (H3 O+ ) followed by a keto–enol rearrangement to
give 3-hydroxypropionaldehyde and – after a second dehydration
step – acrolein. The reacted Brønsted acid site can be regenerated
(re-protonated) by the aforementioned released hydronium ion.
The reaction over Lewis acid sites proceeds in a completely
different way (Scheme 6b), as the glycerol interacts via concerted
transfer of a terminal hydroxyl group on one of the metal centers
and migration of the secondary proton to the other metal center.
Consequently, 2,3-dihydroxypropene and pseudo-Brønsted sites
are formed. The enol will tautomerise to acetol, whereas
the pseudo-Brønsted site can either catalyse the dehydration
reaction, as in the case of the aforementioned Brønsted sites,
or can regenerate the initial Lewis site by thermal dehydration.
Thereby, one can explain why Lewis acid sites generally show
higher selectivity for acetol than Brønsted acid sites.
Scheme 6 Reaction mechanism over basic catalysts, as proposed by
Kinage et al.44
As catalysts usually contain both acidic and basic sites,
the influence of the basicity must also be considered. Kinage
et al. investigated the selective dehydration of glycerol to acetol
and proposed a reaction mechanism over basic catalysts.46 In
contrast to the mechanisms proposed over acid catalysts, the
reaction over basic catalysts does not begin with a dehydration
step but with a dehydrogenation step (Scheme 7). The resulting
2,3-dihydroxypropanal can either further react via consecutive
dehydration and hydrogenation to yield acetol, or can form – via
a retro-aldol reaction – formaldehyde and hydroxyacetaldehyde,
which can be subsequently hydrogenated to ethylene glycol. With
this reaction mechanism, one can explain the high selectivity for
acetol observed by Chai et al. over basic catalysts.41
In this section, we have seen that the strength and the type of
the catalyst acidity are of utmost importance for obtaining high
catalytic performances. In the following sections, we will further
discuss in detail the three most widely used catalytic systems for
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Scheme 7 Reaction mechanism over protonated zeolite (H-MFI) catalyst as proposed by Yoda et al.46

the dehydration of glycerol: supported HPAs, zeolites, and the
family of metal oxides, phosphates and pyrophosphates.
4 Supported heteropolyacids
The use of supported inorganic acids such as phosphorous
acid or HPAs is one possibility to reach high performances
in the dehydration of glycerol to acrolein, as shown by Neher
and Chai.35,36,41 However, when using supported catalysts, new
parameters in addition to acidity must be taken into account,
namely the influence of the support on the active-phase prop-
erties, the dispersion extent of the active phase on the support,
and the distribution of the pore size of the support.
In 2008 and 2009, Chai et al. published two papers dealing
with zirconia- and silica-supported HPA catalysts.47,48 These
studies showed that the nature of the catalyst support has a
significant effect on the thermal stability and on the dispersion
of the Keggin-type active phase. The use of zirconia as a support
led to better results, as far as the deactivation of the catalyst
is concerned. The Keggin-anion density at the surface of the
support was identified as being key for tuning the activity and
the selectivity of the HPA for acrolein production, which is
in good agreement with the conclusions of Ning et al., who
used activated carbon-supported silicotungstic acid catalysts.49
The latter claimed that a 10 wt% silicotungstic acid-supported
catalyst gives the best acrolein space-time yield ever reported
in the literature (namely 68.5 mmol acrolein h-1 g-1 ), but this
value is misleading, as the calculation is based on the mass of
active phase and not on the mass of catalyst. This promising
performance is attributed to the good dispersion of the HPA
on the support surface and also to the relative quantities of
strong acid sites. Our team also recently used silica-supported
silicotungstic acid as a catalyst, but on supports that were
grafted with zirconia before impregnation of the active phase.50
We showed that the strong electronic interaction between the
zirconia and the heteropolyanion results in a decreased strength
of the Brønsted acid sites, whereby the long-term catalytic
performances were increased in comparison to bare silica (69%
acrolein vs. 24% respectively, after 24 h on-stream) due to less
coking. Nevertheless, it is worth mentioning that the quantity of
grafted zirconia and active phase necessitates careful balancing
in order to avoid the introduction of undesired Lewis-acid
character into the catalyst, which results in decreased selectivity
for acrolein as shown by Alhanash et al.44
The influence of the pore size distribution of the support was
discussed for the first time in 2007 by Tsukuda and coworkers,51
who worked with silica-supported acids. They focused their
study on the influence of the textural properties of the porous
support on the selectivity, and used three commercial silicas
with pore sizes of 3, 6 and 10 nm, namely CARiACT Q3, Q6
and Q10. The active phase was either a HPA or a conventional
inorganic acid like phosphorous or boric acid. Good results
were obtained using Keggin-type HPAs such as phosphotungstic
acid (H3 PW12 O40 ) or silicotungstic acid (H4 SiW12 O40 ) deposited
on the 6 nm silica support. At full conversion, the selectivity
for acrolein was 65% and 74%, respectively, whereas the
molybdenum-based homologous HPA (i.e., H3 PMo12 O40 ) did
not yield high selectivity (34%) (Table 2). When a catalyst based
on silicotungstic acid over silica with 10 nm pore diameter was
used, the selectivity could be further increased to 86%, whereas
for a support with smaller pores (namely 3 nm) the selectivity
slightly decreased to 67%. Furthermore, it was observed that
the small pore size of 3 nm resulted in a decreased catalytic
activity (55% conversion), which most probably originates from
enhanced coking resulting from steric limitations within the
catalyst framework. The influence of temperature was also

Table 2 Catalytic results obtained over various supported heteropolyacidsa

Catalyst T react (◦ C) mcat (g) TOS (h) C (%) Sacrolein (%) Sacetol (%) Y acrolein (%) STY (mmol g-1 h-1 ) Ref.

15 wt% PW/SiO2 315 0.3 10 18 57 7 10 0.6 47

15 wt% PW/ZrO2 315 0.63 10 76 76 12 58 1.6 47
10 wt% SiW/AC 330 0.38 5 93 67 8 62 11.1 49
20 wt% PW/Al2 O3 275 0.3 5 99 52 8 51 5.1 52
20 wt% SiW/Al2 O3 275 0.3 5 98 64 8 63 6.3 52
30 wt% PMo/Q6 325 0.3 5 98 65 7 64 3.8 51
30 wt% PW/Q6 325 0.3 5 100 33 5 33 2.0 51
30 wt% SiW/Q6 325 0.3 5 100 74 7 74 4.4 51
30 wt% SiW/Q10 275 0.3 5 98 86 7 84 5.1 51
CsPW 275 0.3 1 100 98 nc 98 49.0 44
a
T react = reaction temperature; mcat = mass of catalyst; TOS = time on stream; C = conversion of glycerol; Sacrolein = selectivity for acrolein; Sacetol =
selectivity for acetol; Y acrolein = yield of acrolein; STY = space-time yield; nc = not communicated; PW = H3 PW12 O40 ; SiW = H4 SiW12 O40 ; CsPW =
Cs2.5 H0.5 PW12 O40 ; AC = active carbon; Q6 = CARiACT-Q6; Q10 = CARiACT-Q10.

2084 | Green Chem., 2010, 12, 2079–2098 This journal is © The Royal Society of Chemistry 2010

studied, 275 ◦ C being optimal in terms of acrolein yield, which
is consistent with earlier studies on Brønsted acid catalysts.
Similar results were obtained by Atia et al., who investigated
the catalytic performance of the silicotungstic acid supported
on alumina with 5 nm and 12 nm pore sizes.52 The reaction
conditions for the catalytic tests were chosen such as to match
those used by Tsukuda et al.,51 for the sake of easier comparison.
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The selectivity for acrolein increased from 65% for the alumina
support with a 5 nm pore size to over 85% for the alumina
support with a 12 nm pore size, both at full conversion and
for catalysts loaded with 20 wt% of active phase (Table 2).
Furthermore, Atia et al. found the same optimum reaction
temperature as Tsukuda, since the alumina-based catalysts also
showed complete conversion for a temperature higher than
275 ◦ C.
These results show that the size of the pores has a direct
influence on the selectivity of the catalysts. If steric limitations –
like pores that are too narrow – hinder the rapid desorption
and diffusion of the reactants and of the products in the
porous network of the catalyst, then condensation is more likely
to occur, which results in lower selectivity for acrolein and
deactivation of the catalyst due to carbon deposition (coke).
From the aforementioned studies, one can identify two
important parameters that govern the catalytic performances
of supported inorganic acids: (i) the dispersion of the active
phase and (ii) the textural properties of the support. These two
parameters were further investigated by Chai et al. and Sato
et al., who focused on supported HPAs and on their catalytic
performances with regard to the textural properties of the porous
support.53–55 They carried out a huge number of performance
tests, by varying both the loading of active phases and the
nature of the supports. Here also, phosphomolybdic acid was
unselective compared to phosphotungstic acid and silicotungstic
acid.51 With 20–30 wt% silicotungstic acid deposited on two
porous silicas with pore sizes of 6 and 10 nm, respectively, they
obtained a selectivity for acrolein up to ca. 87% at 275 ◦ C in
both cases. Smaller pore diameters (3 nm) or a higher reaction
temperature (300 ◦ C) always led to a decrease in the catalytic
performance. It is worth mentioning that the influence of the
BET specific surface area of the support was also studied, but
this proved to have only a small effect.
Whereas Chai and Tsukuda51,53 showed that silicotungstic
acid and phosphotungstic acid gave the best performances,
due to their higher acidities, the group of Brückner et al.56
recently decided to focus their investigations on supported phos-
phomolybdic (H3 PMo12 O40 ) and the vanado-phosphomolybdic
(H4 PMo11 VO40 ) acids. Using electron paramagnetic resonance
spectroscopy (EPR), they showed that the Keggin structure
of the molybdenum compounds was partially destroyed upon
impregnation on silica-alumina supports and that further
calcination at 350 ◦ C led to total decomposition to simple
metal oxides. These catalysts were then tested in the glycerol
dehydration reaction, and the oxidation state of the metal atoms
was followed by Operando EPR. The catalytic performance was
close to that already observed for these compounds by Chai
et al.,53 that is to say quite poor (the selectivity for acrolein did
not exceed 25%). On the other hand, the Operando analysis
of the catalyst revealed that the oxidation state of the metals
was 3+ for vanadium and 4+ for molybdenum, which indicates
This journal is © The Royal Society of Chemistry 2010
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that they were reduced during the reaction. When oxygen was
co-fed, the reduction degree of vanadium was limited to 4+
and that of molybdenum to 5+. Furthermore, the coking was
slowed down, and the authors claimed that the carbon was
preferentially deposited on the vanadium centers. The carbon
species constituting the coke layer was also analysed. According
to the EPR signal, the carbon was mainly in the sp3 hybridisation
state, which corresponds to non-double-bonded C–C chains, like
from the radical polymerisation of the C C bond in acrolein.
Furthermore, if oxygen was present in the feed, the formation
of C O carbonyl groups was observed.
Another idea for using heteropolycompounds was inves-
tigated by Dubois et al., who used salts of HPAs ob-
tained by complete or partial substitution of the protons
of HPAs by metal cations.57 They used silicotungstic or
phosphotungstic acid as bases, and prepared their respec-
tive salts using elements such as caesium, rubidium, calcium
or bismuth, or transition metals like zirconium, lanthanum,
iron or hafnium. The partially neutralised caesium-containing
HPAs (Cs2.5 H0.5 PW12 O40 and Cs2.5 H1.5 SiW12 O40 ) and rubidium-
containing HPAs (Rb2.5 H0.5 PW12 O40 ) required significantly lower
reaction temperatures (260–280 ◦ C vs. 300–350 ◦ C) than the
totally proton-free compounds, and further showed higher
selectivity for acrolein in oxydehydration (90% vs. 50–70%). The
best result was reported for Cs2.5 H1.5 SiW12 O40 , with a 93.1% yield
of acrolein. Nevertheless, when this catalyst was used without
co-feeding of oxygen the catalytic performance was much lower,
with an acrolein yield of no more than 40%. Comparable results
with caesium salts of phosphotungstic acid were reported by
Alhanash et al., who also obtained acrolein yields of up to
98% during the first hour of reaction, which is the highest
performance ever reported, with a productivity up to 49 mmol
g-1 h-1 (Table 2).44 Nevertheless, these authors admit that the
catalyst deactivates rapidly, and that excellent performances
claimed were observed only for the first few hours of reaction.
In conclusion, all these results suggest that the use of
Keggin-type heteropolycompounds is a highly promising means
of obtaining high catalytic performances. They offer many
possibilities for tuning their acidity due to the possible variations
in their composition, which can be adjusted by modifying the
central atom, the addenda atoms and the counter-ions. When
these compounds are deposited on a support, it is also possible
to adjust an additional parameter, as one can even control the
pore size of the catalyst, and thus reduce diffusion limitations.
5 Zeolites
The use of supported heteropolycompounds is not the only way
of obtaining good catalytic performances. Zeolitic structures are
promising, and have been well studied since the work of Dubois
et al.39
In addition to ZSM-5 and b-zeolite (already patented by
Dubois et al.39 ), Li and Zhuang et al. studied other zeolite
structures such as MCM-49, MCM-22, MCM-56 and ZSM-
11.58,59 The obtained acrolein yields were in the range of 70–85%
for all the catalysts, with nearly no decrease in the catalytic
performance during 400 h of reaction.
In 2007, Okuno and coworkers patented metallosilicate
catalysts with an MFI structure, a typical structure of zeolites
Green Chem., 2010, 12, 2079–2098 | 2085
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Table 3 Catalytic performances observed over various zeolitesa

Catalyst T react (◦ C) mcat (g) TOS (h) C (%) Sacrolein (%) Sacetol (%) Y acrolein (%) STY (mmol g-1 h-1 ) Ref.

b-Zeolite 300 4.2 1.5 100 57 10 57 5.8 39

HZSM-5 300 6.4 1 79 49 6 39 2.6 39
MFI+Ga 360 9 nc 96 62 nc 59 4.6 60
MFI (28)b 360 9 nc 92 69 nc 63 4.8 61
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MFI (200)b 360 9 nc 100 61 nc 61 4.6 61

ZSM-5 (30)b 315 0.3 2 52 42 7 22 17.0 45
ZSM-5 (150)b 315 0.3 2 76 64 5 49 37.9 45
ZSM-5 (500)b 315 0.3 2 39 44 4 17 13.4 45
HZSM-5 without Na 320 1.2 10 100 60 5 60 0.3 63
a
T react = reaction temperature; mcat = mass of catalyst; TOS = time on stream; C = conversion of glycerol; Sacrolein = selectivity for acrolein; Sacetol =
selectivity for acetol; Y acrolein = yield of acrolein; STY = space-time yield; nc = not communicated. b Si/Al ratio.

with a 3D porous network.60 In addition to aluminosilicates, they
also prepared gallosilicates and ferrosilicates. Nevertheless, good
catalytic performances were only obtained over the aluminosili-
cates and gallosilicates, whereas ferrosilicates were less selective
due to their higher redox-character. The aluminosilicates offered
the most stable performances without any ion exchange, with a
selectivity for acrolein around 65%. In this patent, the results
claimed over zeolitic catalysts were quite similar to those
reported in Dubois et al.’s work (i.e., 70% selectivity for acrolein
at full glycerol conversion).39 In further publications, the same
Japanese team reported the tuning of the acidity by modifying
the Si/Al ratio of the zeolite. The best results were achieved
using a ratio of 28, which resulted in yield of acrolein of 63%
(Table 3).61,62
Kim et al. studied the influence of the silica/alumina ratio in
zeolites of the HZSM-5 type.45 They chose commercial HZSM-
5 catalysts with Si/Al atomic ratios ranging from 23 to 1000.
A detailed characterisation of the acid properties using am-
monia temperature-programmed desorption revealed an inverse
relationship between the total acidity and the silica/alumina
ratio. In fact, the catalyst with a silica/alumina ratio of 30
had ca. 9 times more acid sites (66 mmol NH3 g-1 ) than the
catalyst with a ratio of 500 (7 mmol NH3 g-1 ). According to the
observed desorption temperature, Kim et al. also showed that
low silica/alumina ratios result in a higher number of strong acid
sites. Nevertheless, these very strong acid catalysts showed only
poor selectivity for acrolein (no more than 41.6% for the catalyst
with a silica/alumina ratio of 30, for instance). Therefore, Kim
et al. investigated the type of the acid sites and found that
these low silica/alumina ratios lead to Lewis acid catalysts,
whereas higher ratios give Brønsted acid catalysts, as already
postulated by Alhanash et al.44 They concluded that a Brønsted
acid catalyst with a high number of sites was more effective for
obtaining a high acrolein yield. These two favorable conditions
were gathered in a HZSM-5 with a silica/alumina ratio of 150,
which gave 63.8% selectivity at 75.8% conversion at 315 ◦ C
(Table 3). Furthermore, the influence of the reaction temperature
on the last mentioned catalyst was studied, showing that a
reaction temperature below 315 ◦ C gave only low conversion (no
more than 50.3%), whereas reaction temperatures above 315 ◦ C
resulted in poor acrolein selectivity (no more than 57.4%).
The idea of tuning the number of Brønsted acid sites by
adjusting the silica/alumina ratio is one possible means of
optimisation. An alternative was proposed by Schüth’s research
group, consisting of the replacement of the Brønsted protons
at the catalyst surface by sodium cations through an ion-
exchange step.63 They used a commercial HZSM-5 catalyst with
a silica/alumina ratio of 65 and varied the number of surface
protons between 0.5 and 1. Unsurprisingly, the sodium-free
catalyst exhibited the best performance in glycerol dehydration,
with a selectivity for acrolein of 60% at full conversion (Table
3), which was explained by a higher number of acid sites, which
were not replaced by sodium.
Further, Zhou and co-workers proposed a synthesis of micro-
and mesoporous ZSM-5 composites using dual templates,
subsequently used as catalysts in the dehydration of glycerol
to acrolein.64 The best result achieved with these catalysts was
73.6% acrolein selectivity at 98.3% glycerol conversion, which is
quite a good performance. The influence of the textural parame-
ters is not clear for the zeolite compounds used, but the authors
claim that mesopores are more favorable than micropores, as the
latter are likely to induce diffusional limitations. A more detailed
analysis of the impact of the pore size of ZSM-5 zeolites on the
selectivity was performed by Pathak et al.65 They showed that the
selectivity for acrolein increases with the pore size, whereas the
selectivities to acetaldehyde, formaldehyde and acetol decrease
in the same time. Nevertheless, an optimum pore size could not
be reliably determined, as only four different pore sizes, namely
0.54, 0.74, 3.15 and 11.2 nm, were investigated.
The use of zeolites as catalysts for the dehydration of glycerol
offers another attractive means of accomplishing this reaction,
linked with the possibility of tailoring the acid properties
by tuning the bulk composition (silica/alumina ratio), by
incorporation of transition-metal oxides (like gallium oxide or
iron oxide) or by modification of the surface (ion-exchange).
Furthermore, the structure and the mean pore diameter of the
porous network of zeolites can be tuned, whereby – as in the
case of supported inorganic acids – the diffusion limitations can
be avoided.
6 Mixed metal oxides, phosphates and
pyrophosphates
As a final group of catalysts used for the dehydration of glycerol,
we summarise in this section the results of various studies
concerning metal oxides, phosphates and pyrophosphates.
In addition to the aforementioned niobium oxide,40 the group
of Chai studied binary mixtures of zinc oxide, tin oxide, zirconia,

2086 | Green Chem., 2010, 12, 2079–2098 This journal is © The Royal Society of Chemistry 2010
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Table 4 Catalytic performances observed over metal oxides, phosphates and oxophosphates, with and without co-feedinga

Catalyst T react (◦ C) mcat (g) Co-feed TOS (h) C (%) Sacrolein (%) Sacetol (%) Y acrolein (%) STY (mmol g-1 h-1 ) Ref.

Nb2 O5 -350 315 0.56 — 10 75 47 10 35 1.3 40

Nb2 O5 -400 315 0.57 — 10 88 51 12 45 1.6 40
Nb2 O5 -500 315 0.61 — 10 91 35 14 32 1.2 40
TiAl-600 315 0.6 — 2 86 43 17 37 1.1 66
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SAPO-11 280 0.2 — 1 66 62 10 41 0.9 67

SAPO-34 280 0.2 — 1 59 72 7 42 0.9 67
VPO-700 300 0.2 O2 10 81 95 9 77 6.9 68
VPO-800 300 0.2 O2 10 100 80 6 80 7.1 68
VPO-900 300 0.2 O2 10 97 58 15 56 5.0 68
Fex (PO4 )y 280 0.8 — 5 100 92 0 92 4.1 72
9 wt% WO3 /ZrO2 300 17 — 5 100 74 11 74 1.9 38
19 wt% WO3 /ZrO2 280 5 — nc 83 69 10 57 9.3 79
a
T react = reaction temperature; mcat = mass of catalyst; co-feed = nature of the co-feeding gas; TOS = time on stream; C = conversion of glycerol;
Sacrolein = selectivity for acrolein; Sacetol = selectivity for acetol; Y acrolein = yield of acrolein; STY = space-time yield; nc = not communicated; Mx Oy -***
indicates the calcination temperature (in ◦ C); TiAl = TiO2 /Al2 O3 binary mixture; SAPO = silica-alumina phosphate; VPO = vanadium oxophosphate.

titania, alumina and silica.66 Whereas the catalytic performances
of these mixed oxides remained rather low, with acrolein yields
not exceeding 36%, the study of the acidity and of the textural
parameters clearly showed that the less acid catalysts have
increased selectivity for acetol, and that small pore diameters
induce a decrease in the selectivity for acrolein.
Suprun et al. published a paper on phosphate-modified
titania, alumina and silica/alumina (SAPO),67 and found a
strong influence of the acidic and textural parameters on the
catalytic performances. As in the case of supported inorganic
acids and of zeolites, a relationship between the total acidity and
the selectivity for acrolein was observed. In fact, the most acidic
catalyst, a silica-alumina phosphate, showed a selectivity for
acrolein up to 72% (Table 4). Furthermore, Suprun et al. pointed
out that microporous materials (5–6 Å) are less active due
to internal diffusion limitations, and tend to induce increased
carbon deposition, as observed on SAPO-34.
A similar catalytic system, namely vanadium oxophosphates
and oxo-pyrophosphates, was studied by Wang et al.68,69 As
in the case of niobium oxide, the acidity of these compounds
can be tuned by modifying their calcination temperature, but
in an inverse relationship, as high calcination temperatures
result in a larger number of acid sites. The catalysts were
tested in the glycerol dehydration reaction, with co-feeding
of oxygen. The best result was obtained using a vanadium
pyrophosphate calcined at 800 ◦ C, which gave a selectivity
for acrolein of 66% at full conversion (Table 4). Nevertheless,
this result was not obtained over the catalyst with the largest
number of acid sites. Actually, as the specific surface decreased
for high calcination temperatures due to sintering of the solid,
the selectivity consequently dropped drastically in this case.
Dubois extended the study of pyrophosphates using boron and
aluminium as cations, and observed that the boron-containing
compounds give the highest acrolein yields, with a maximum of
77.8%.70
Other metal pyrophosphates were studied by Liu and cowork-
ers, who used rare earth metals such as lanthanum, neodymium
and cerium.71 All the considered pyrophosphates exhibited
quite similar catalytic performances, with the best results being
achieved over Nd4 (P2 O7 )3 . As in the case of the aforementioned
vanadium pyrophosphates, the acidity of the neodymium com-
pounds increases with the calcination temperature, whereby the
optimum in the catalytic performance (80% yield of acrolein)
was found for a calcination temperature of 500 ◦ C.
The use of phosphates instead of pyrophosphates was studied
by Deleplanque et al.72 They prepared iron phosphates using
different preparation techniques, such as hydrothermal reaction
or precipitation. The highest acrolein yield without oxygen co-
feeding was 92.1% (Table 4). In the so-called ‘oxy-dehydration’
reaction, i.e., with co-feeding of molecular oxygen, the selectivity
for acrolein decreased to 62.5% at full conversion, due to the total
oxidation to carbon oxide species (COx ) as an important side
reaction. Therefore, Dubois investigated the addition of group 1
and group 2 metal cations to these catalytic formulations, such
as caesium, strontium and potassium.73 Doping with caesium in-
creased the acrolein yield to 72.2%, which was thus significantly
higher than that observed over the undoped iron phosphate
(62.5%), but still lower than the yield obtained without oxygen
co-feeding (92.1%). The idea of doping the phosphate species
was also investigated by Matsunami et al., who used phosphate-
modified silica with alkali salts. Nevertheless, in this latter case,
the yield of acrolein did not exceed 67%.74,75
In 2006, Dubois et al. proposed the use of tungsten oxide on
zirconia as a catalyst for glycerol dehydration. Total conversion
of glycerol was achieved at 300 ◦ C with a catalyst containing
9 wt% of tungsten oxide, with a yield of acrolein of 74%.38
Redlingshofer et al. further studied this binary metal oxide
system.76,77 The reaction was carried out at a lower temperature
(260 ◦ C). Good performances were observed with an acrolein
yield between 77 and 79%. Nevertheless, the catalysts tended
to deactivate on-stream, with the acrolein yield decreasing at a
rate of 5% every 10 h. Additionally, these authors described
the possibility of regenerating the catalysts by oxygen post-
treatment at 350 ◦ C for 5 h. Bythis treatment, they claimed
that the initial catalytic performances could be recovered.78
This well-known combination of tungsten oxide on zirconia
was further studied by Ulgen et al.79 They showed that the acidity
of the solid increases with the amount of tungsten oxide. For the
catalyst containing 19 wt% of tungsten oxide, an acrolein yield
of 57% was observed (Table 4).
Furthermore, they studied the influence of the calcination
temperature on the physical properties of the catalysts. Whereas

This journal is © The Royal Society of Chemistry 2010 Green Chem., 2010, 12, 2079–2098 | 2087

the temperature treatment had only a low impact on the acidic
properties, the number of basic sites significantly decreased when
the calcination temperature increased. Moreover, the textural
parameters were quite dramatically modified, as the sintering
led to larger pores but reduced specific surface areas. For these
two reasons, the thermal treatment had in any case a positive
impact on the catalytic performance, as the decrease in basicity
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led to the suppression of acetol formation, and the larger pore
size reduced the deactivation extent due to coking, as internal
diffusion limitations were lower.
The above-described family of mixed metal oxides, phosphates
and pyrophosphates is rather heterogeneous. Some compounds,
like niobium oxide, tungsten oxide and pyrophosphates, offer the
possibility of controlling their acid strength via the calcination
step. This thermal treatment generally also has an influence on
the specific surface area and the pore size due to sintering.
In comparison to the aforementioned zeolites and supported
HPAs, the control of the physical properties of the mixed metal
oxides and phosphates seems nevertheless less straightforward.
7 Regeneration of spent catalyst
From the studies reported above, it is clear that very efficient
catalysts for the dehydration of glycerol to acrolein can be
prepared. Unfortunately, these catalysts quickly deactivate, most
probably because of the formation of coke, which makes it
difficult to straightforwardly use them in industrial plants at
the current time. Up to now, only a few studies have been
devoted to the characterisation of carbon deposits and to the
sites responsible in these catalytic systems. Erfle et al. used FTIR
spectroscopy to characterise the spent catalyst and observed
C O and C C signals.56 They attributed these signals to cyclic
anhydride species and claimed that the Brønsted acid sites were
the centers of coke formation. Suprun and coworkers confirmed
that the acid sites were responsible for the formation of carbon
deposits on phosphate catalysts.67 They further found that the
quantity of coke increased with higher reaction temperatures
and also with decreasing the pore diameter of the catalyst (Table
5). For example, the coke loading on SAPO-11 increased from
4.6 wt% at 280 ◦ C to 9.5 wt% at 320 ◦ C. From the ammonia
desorption experiments, one can also see that the acid strength
increases in the order Al2 O3 -PO4 ª TiO2 -PO4 < SAPO-11 
SAPO-34, which correlates well with the amount of carbon
deposit found over these catalysts. Indeed, the quantity of
deposited carbon increased for all the reaction temperatures
in the same order.
Table 5 Correlation between acidity and the carbon deposit for phosphate catalystsa
Catalyst Ac (mmol NH3 g-1 ) Dp (Å) SBET (m2 g-1 )
Al2 O3 -PO4 295 111 118
TiO2 -PO4 258 101 38
SAPO-11 1330 6 172
SAPO-34 498 5 49
a
Ac = total acidity; Dp = pore diameter; SBET = specific surface area; T react = reaction temperature; SAPO = silica-alumina-phosphate.
2088 | Green Chem., 2010, 12, 2079–2098
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Furthermore, the hydrogen-to-carbon (H/C) ratio for the
carbon species was determined by elementary analysis. All the
catalysts showed a decrease in the H/C ratio at higher reaction
temperatures, meaning that the carbon deposit became more
deficient in hydrogen (Table 5). For example, the H/C ratio over
SAPO-34 decreased from 0.62 at 280 ◦ C to 0.47 at 320 ◦ C.
This can be ascribed to the formation of highly condensed,
unsaturated carbonaceous aromatic species. Solutions still have
to be found to avoid or to limit the coke deposit on the catalyst
surface or at least to optimise the regeneration of the catalysts.
Although a fundamental approach is still needed for studying
efficient means for limiting the coke deposition during the
reaction, at least three kinds of solutions have been proposed so
far for continuously regenerating the catalysts: (i) co-injection
(co-feeding) of oxygen or hydrogen with the gas feed to yield
in situ regeneration;39 (ii) cyclic regeneration of the used catalyst
by injection of a flow or of pulses of air or oxygen;83 and
(iii) circulation of the catalyst in a moving-bed reactor with
regeneration in a separate parallel vessel (as for the FCC
process).25 Whereas the first option is associated with the risk of
generating explosive conditions and/or to oxidise the various
reaction products, the second alternative is accompanied by
the disadvantage of a loss in productivity. The third option
does not suffer from these drawbacks, but the construction
and the operation of a circulating bed reactor implies serious
technological difficulties that can only be overtaken by skilled
persons through fine process control.
The idea of working with air in the reactant mixture was first
proposed by Dubois for catalysts of the zeolite type.39 To avoid
the explosivity range, the oxygen fraction must never overpass
7 vol%. Therefore, the composition of the reaction feed was
adjusted to 6% of oxygen for 4.5% of glycerol, the remaining
89.5% being steam. Thereby, the authors claim to reduce catalyst
deactivation and even to inhibit the formation of by-products
such as acetol in these conditions.
The same process was further used for vanadium
pyrophosphates,69 boron phosphates,70 iron phosphates,72 tung-
sten oxide on zirconia79 and caesium salts of phosphotungstic
acid.57 As a general trend, the selectivity for by-products such
as acetol, acetaldehyde and formaldehyde decreased, whereas
the formation of organic acids, like acrylic acid, acetic acid
and formic acid, increased, due to subsequent oxidation of the
aldehydes formed. For some catalysts, like zeolites, vanadium
oxophosphates, and tungsten oxide on zirconia, the selectivity
for acrolein was not or only slightly affected. In the case of
the caesium salt of phosphotungstic acid, an increase in the
selectivity for acrolein by a factor of two was even observed (93%
T react = 280 ◦ C T react = 300 ◦ C T react = 320 ◦ C
Coke loading H/C Coke loading H/C Coke loading H/C
(wt%) ratio (wt%) ratio (wt%) ratio
2.4 0.54 3.9 0.52 5.8 0.49
3.1 0.55 6.8 0.50 8.9 0.48
4.6 0.68 7.4 0.55 9.5 0.40
9.6 0.62 12.7 0.54 16.2 0.47
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Table 6 Comparison of catalytic performance observed in glycerol dehydration, with and without co-feedinga

Catalyst T react (◦ C) mcat (g) Co-feed TOS (h) C (%) Sacrolein (%) Sacetol (%) Y acrolein (%) STY (mmol g-1 h-1 ) Ref.

b-Zeolite 300 4.2 O2 3 100 57 0 57 5.8 39

b-Zeolite 300 4.2 — 1.5 100 57 10 57 5.8 39
HZSM-5 300 6.4 O2 1 88 46 2 40 2.7 39
HZSM-5 300 6.4 — 1 79 49 6 39 2.6 39
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VPO-800 300 0.2 O2 nc 100 65 6 65 5.8 68

VPO-800 300 0.2 — nc 95 60 12 57 5.1 68
BPO 280 0.3 O2 nc 100 65 8 65 0.8 70
BPO 280 0.3 — nc 96 81 6 78 0.9 70
Fex (PO4 )y 280 1.3 O2 5 100 63 0 63 1.7 72
Fex (PO4 )y 280 0.8 — 5 100 92 0 92 4.1 72
19 wt% WO3 /ZrO3 280 5 O2 nc 73 74 8 54 8.9 79
19 wt% WO3 /ZrO2 280 5 — nc 83 69 10 57 9.3 79
CsPW 260 23 O2 nc 100 93 nc 93 3.0 57
CsPW nc 23 — 1 83 47 3 39 0.7 57
0.5% Pd-CsPW 275 0.3 H2 5 79 96 1 76 37.9 44
CsPW 275 0.3 — 1 100 98 nc 98 49.0 44
WO3 /ZrO2 275 9.2 SO2 24 87 69 7 60 1.2 81
WO3 /ZrO2 275 9.2 — 24 69 71 9 49 1.0 81
a
T react = reaction temperature; mcat = mass of catalyst; Co-feed = nature of the eventual co-feeding gas; TOS = time on stream; C = conversion of
glycerol; Sacrolein = selectivity for acrolein; Sacetol = selectivity for acetol; Y acrolein = yield of acrolein; STY = space-time-yield; nc = not communicated;
VPO = vanadium oxophosphate calcined at 800 ◦ C; BPO = boron phosphate; CsPW = Cs2.5 H0.5 PW12 O40.

vs. 47%; Table 6). On the other hand, for boron phosphates and
iron phosphates, the co-feeding of oxygen led to a significant
decrease in the selectivity for acrolein, which was ascribed to
the over-oxidation to carbon oxides (CO/CO2 ). To facilitate the
activation of molecular oxygen, doping with metal cations like
caesium, potassium, strontium, silver and platinum was probed
by Dubois, which led to an acrolein selectivity of around 70%.73
A comparable approach was followed by Kasuga et al., who
used protonated MFIs as catalysts.80 When they injected air in
the gas reactant feed, the selectivity for acrolein on unmodified
catalysts was rather low and did not exceed 45% after 24 h
under reactant flow. To optimise the regeneration, Kasuga et al.
thus also proposed to modify the MFI protonated-zeolite with
a small amount of metal (Pt, Pd, Ru, Cu, Ir or Au). By this
mean of doping, they claimed that it is possible to accelerate the
splitting of the dioxygen used during regeneration.80 The best
results were obtained with 0.1 wt% Pt and 1 wt% Au (80.7 and
79.7% of acrolein yield, respectively, at full glycerol conversion
after 150 min under reaction conditions).
The same concept to reduce the carbon deposit, but this time
by co-feeding hydrogen, was investigated by Alhanash et al.,
who used caesium salts of HPAs.44 Following a similar principle
as that proposed by Kasuga et al.,80 they probed the doping with
small quantities of noble metals such as ruthenium, palladium
and platinum. Thereby, they could increase the catalyst activity
by a factor of two after 5 h of reaction (conversion of 79% vs.
41%; Table 6) without any significant impact on the selectivity
for acrolein (96% vs. 98%). The best results were obtained with
palladium on the caesium salt of phosphotungstic acid, over
which a productivity of 37.9 mmol g-1 h-1 was achieved.
Dubois proposed a third kind of feed additive for enhancing
the long-lasting performances of tungsten oxide on zirconia.
Instead of oxygen or hydrogen, he injected 250 ppm of sulfur
dioxide into the feed in order to slow down the deactivation.81 In
fact, the addition of SO2 even induced a slight positive impact
on the selectivity for acrolein (73% vs. 72% without SO2 ) and
significantly inhibited the formation of acetol (selectivity of
0.2% vs. 2.4% without SO2 ). After 24 h on-stream, the catalytic
performance observed when co-feeding SO2 were significantly
improved, still with an excellent conversion of 87% (initially
100%), whereas it was 69% in the absence of SO2 (Table 6).
The results obtained using co-feeding of oxygen are quite
different and strongly depend on the studied catalytic system. As
mentioned earlier, the oxygen concentration must be kept below
7 mol% in order to stay out of the explosion limits. Wang et al.
studied the influence of the oxygen concentration on the catalytic
performance of vanadium phosphate catalysts. They observed
that too little (as well as too much) oxygen has a negative impact
on the selectivity for acrolein.69 In fact, low quantities of oxygen
led to larger amounts of acetol, whereas high concentrations
induced an increase in the selectivity for acetaldehyde, acetic
acid, acrylic acid and – of course – to carbon oxides, which
is explained by the successive over-oxidation of the products.
The exceptions where the co-feeding process is unfavorable to
the selectivity for acrolein – as over iron phosphate and boron
phosphate – can be easily explained by the redox character of
the catalysts, which promotes oxidation processes. In these cases,
co-feeding with hydrogen might be a good way to overcome this
problem. The process using co-feeding of sulfur dioxide might
also be an interesting approach, even if one should keep in mind
its toxicity, which is certainly the most important drawback of
this method. Furthermore, this reagent may be incompatible
with some catalytic systems, due to some possible poisoning
issues.
The second process for regenerating the spent catalyst –
namely, periodic regeneration – was studied by Arita et al., who
regenerated a used H-ZSM5 catalyst under an air flow. They
evidenced the possibility of recovering the initial performances.82
However, the exothermicity of the regeneration led to the
formation of hot-spots. Consequently, the temperature during
regeneration exceeded the reaction temperature by more than
100 ◦ C, at which the catalyst risks thermal decomposition.

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 View Article Online

Therefore, this technique is not applicable for temperature-
sensitive catalytic systems.
A more academic approach was followed by Atia et al.
Their preliminary work involved long-term runs (up to 300 h),
and they found that over alumina-supported heteropolyacid
catalysts the selectivity for acrolein remained quite stable,
whereas glycerol conversion more-or-less linearly decreased.
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pretreatments induced higher acrolein selectivity in the first
few minutes after switching to the reactant flow. However,
after 150 min on-stream, the catalytic performances returned
to values similar to those obtained without any preliminary
pretreatment, which means that this effect is only effective in the
early stages of the reaction. Despite this, the authors pointed
out the possibility of recovering the initial performance by

This effect is typically observed for deactivation by deposition
of coke on the catalyst surface, and is linked with the progressive
decrease in the number of accessible active sites. To verify this
hypothesis, spent catalysts were regenerated under a flow of 1%
of oxygen in nitrogen at 325 ◦ C for 24 h. After this treatment, the
regenerated catalyst showed performances identical to those of
the fresh catalyst. To quantify the coking effect, the spent catalyst
was also analysed by thermogravimetry, which straightforwardly
confirmed the hypothesis of carbon deposition.52
Meanwhile, Corma et al. adopted the idea of a circulating
bed reactor,25,83 which was previously disclosed in a Dubois
patent.38,39 These authors studied the opportunity of injecting
crude glycerol directly into FCC plants. An advantage would
be the use of existing facilities and therefore avoiding having
to invest in building specific infrastructures. Note that this idea
was already proposed, but under another form, by Dubois, who
pointed out the possibility of injecting glycerol into propylene
oxidation plants to concomitantly yield acrolein from both
sources.84 In the FCC plants, the heat recovered by the burning
of coke could be used to provide the energy necessary for
the evaporation of glycerol. Corma et al. concluded that an
autothermal process is possible in that case. Nevertheless, the
authors did not limit their view to the dehydration reaction, but
also investigated the possibilities for reforming glycerol at 500–
600 ◦ C to produce ethylene and propylene. In this approach,
the glycerol feedstock may be an alternative or a complement to
naphtha cracking.
An original approach was followed by Kasuga et al., who
focused their investigations on various possibilities for pre-
treating catalysts (protonated MFI zeolite or Alox alumina).85
Three types of pretreatments were tested: (i) a flow of acetol,
water and nitrogen; (ii) a flow of acrolein, water and nitrogen;
and (iii) a flow of acetol, water and air. Irrespective of the
pretreatment method, the Alox catalyst always led to very
poor acrolein yields, while over the MFI catalyst all these
regenerating the catalysts at 500 ◦ C under a flow of air.
8 Dehydration of glycerol in the liquid phase
As mentioned in the introduction, the first experimental results
on dehydration of glycerol in the liquid phase were reported
by Groll in 1936,33 and by Hoyt and Manninen in 1951,34 in the
presence of either homogenous or heterogeneous catalysts. Since
these studies, less than a dozen articles and patents have been
published on liquid-phase dehydration, while there has been a
boom in the number of publications dealing with the gas-phase
reaction. In the following section, we give a brief overview of
the dehydration reaction in the liquid phase, and point out the
major drawbacks of this process.
Ramayya et al. studied the dehydration of glycerol in batch
experiments using an aqueous solution of sulfuric acid, and
conditions close to the critical point of water (namely P = 22.1
MPa, and T = 374 ◦ C).86 (Near) supercritical water offers the
advantage that its physical properties, like the dielectric constant
or the ion product, can be adjusted by varying temperature and
pressure. The mixture was heated in a batch reactor at 350 ◦ C,
pressurised to 34.5 MPa and acidified with 5 mM sulfuric acid.
In these conditions, and at a residence time of 25 s, the conversion
of glycerol and the selectivity for acrolein were 55% and 86%,
respectively (Table 7). Considering the fact that sulfuric acid is
soluble in supercritical water, this process can be classified as
homogeneous catalysis with, the consequent catalyst–reaction
mixture separation issues. Furthermore, a batch process is not
applicable for large-scale production of acrolein.
Nevertheless, the idea of using supercritical water as a reaction
medium was a new aspect, and Bühler et al. decided to study it
in more detail in 2001.87 Instead of working in a batch reactor,
they built a flow-type reactor and used supercritical water both
as a solvent and a catalytic system. They observed various
decomposition products such as acetaldehyde, formaldehyde,

Table 7 Catalytic performances observed for glycerol dehydration in the liquid phasea

Catalyst T react (◦ C) P (MPa) Solvent Reactor type C (%) S (%) Y (%) Ref.

H2 SO4 190 0.1 Water Batch nc nc 49 33

H3 PO3 /clay 300 0.1 Paraffin Batch nc nc 72 34
H2 SO4 350 34.5 Water Batch 55 86 47 86
No catalyst 356 45 Water Continuous 71 38 27 87
ZnSO4 360 25 Water Continuous 50 75 38 88
ZnSO4 360 34 Water Continuous 62 59 37 89
H2 SO4 400 34.5 Water Continuous 92 81 74 90
KHSO4 280 0.1 Paraffin Continuous 97 82 80 91
MgSO4 280 0.1 Paraffin Continuous 92 56 52 91
5 wt% H3 PO4 /Al2 O3 280 0.1 Paraffin Continuous 89 57 51 91
FePO4 320 0.1 Xylene Continuous 87 78 68 93
CuPO4 280 0.1 Sulfolane Continuous 98 85 84 93
a
T react = reaction temperature; P = pressure; C = conversion of glycerol; S = selectivity for acrolein; Y = yield of acrolein; nc = not communicated.

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allylic alcohol and propionaldehyde, as well as acrolein. The
acrolein yield varied between 10 and 27% depending on the
reaction conditions, with the best result (27%) obtained at a
reaction temperature of 350 ◦ C under 45 MPa pressure (Table 7).
As mentioned earlier, these tests were carried out in the absence
of any catalyst or acid component, which explains the poor yields
in acrolein.
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Recently, a combination of the ideas of Hoyt and Manninen34
and of Ramaya et al.,86 namely using a supported catalyst in
supercritical water as a reaction medium, was proposed by Ott
and coworkers.88 They investigated the dehydration of glycerol in
a batch reactor under supercritical conditions using zinc sulfate
as a catalyst. The choice of zinc sulfate as a catalyst is quite
surprising, as this compound is not known as a strong acid
catalyst, which is typically needed for this reaction. However,
they justified their choice considering material stress issues:
water in its supercritical form is very corrosive, and therefore
requires the use of special and expensive steel grades for reactors;
this corrosive power would become even stronger if acidic
compounds were subsequently added to the medium, leading
to unacceptable reactor material stress. In these conditions, the
authors showed that supercritical conditions are not necessarily
the optimal ones. Actually, the best catalytic performance,
namely 75% selectivity at 50% conversion, was obtained in the
near-critical region of water (310 ◦ C at 25 MPa) (Table 7). This
might be explained by the degradation of acrolein when it is
subjected to temperatures that are too high. In 2007, Lehr et al.
also published results on the dehydration of biomass-derived
polyols in sub- and super-critical water.89 As far as glycerol is
concerned, they reported 59% glycerol conversion with almost
60% selectivity for acrolein over zinc sulfate as a catalyst under
subcritical water conditions, like Ott et al. (Table 7).88
To determine if the dehydration of glycerol in the liquid phase
might offer a sustainable source of acrolein at an industrial scale,
Watanabe et al. attempted to optimise the acrolein yield.90 They
combined the supercritical conditions in a flow-type reactor with
sulfuric acid as a catalyst. Several blank tests performed in the
absence of a catalyst gave low glycerol conversions, but high
acrolein selectivities with a yield up to 16%. The best results
were obtained at 400 ◦ C under 34.5 MPa with a sulfuric acid
concentration of 5 mM. In these conditions, the yield of acrolein
was 74% at a glycerol conversion around 92% (Table 7). One of
the main issues in this work was to increase the formation rate
of acrolein without modifying its decomposition rate, which was
achieved by adding acid in supercritical conditions.
In 2007, Suzuki et al. and Yoshimi et al. revamped the idea
of Hoyt and Manninen,34 using a liquid reaction medium with
high boiling point at atmospheric pressure.91,92 Potassium sulfate
and bisulfate were used as catalysts in a batch reactor, where
the glycerol solution was added dropwise in a paraffin solution
maintained at 280 ◦ C. The produced acrolein was continuously
evaporated from the reaction mixture and was recovered in an
aqueous solution, and yields close to 80% were achieved. This
technique was further adapted by Takanori et al., who used iron
or copper phosphate as catalysts in high-boiling organic solvents
(e.g. n-octane, m-xylene or sulfolane) as reaction media.93,94 They
obtained (to our knowledge) the highest ever reported acrolein
yield in the liquid phase, over copper sulfate in sulfolane (84%;
Table 7).
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Thus, we have seen that the dehydration of glycerol in the
liquid phase (at atmospheric pressure or in near-critical or
supercritical conditions) leads to the formation of acrolein. The
application of supercritical conditions is an especially interesting
concept – the change in the physical properties of water inducing
dehydration of glycerol even in the absence of a catalyst –
but, unfortunately, the yield of acrolein remains rather low in
this case. On the other hand, the combination of acids and
near-critical or supercritical conditions results in much better
performances, but also in the generation of an extremely corro-
sive medium. Therefore, the reaction vessel, which must resist
high temperature and pressure, must be specifically designed,
implying important investment/maintenance costs, which is a
major drawback for industrial applications.
Recent results show that the initial idea of using high-boiling
liquids as reaction media at atmospheric pressure seems more
preferable. Furthermore, the proposed process in this latter case,
where the reactant is constantly fed into the reaction mixture
and the acrolein is separated by evaporation upon formation,
can be classified as a continuous process. Nevertheless, the
accumulation of heavier by-products in the reaction mixture
seems quite probable in this case. Moreover, the adaptation of
this kind of process for industrial application is a real challenge,
as the results from laboratory scale (300 mL) cannot easily be
transferred to plant size. In conclusion, one can state that a more
practical process seems to still be a topical issue of research
before commercial applications of liquid-phase dehydration of
glycerol to acrolein can be reliably envisaged.
9 Reaction mechanism
Whereas the research for an efficient catalyst can follow (at least
in an initial screening step) a more-or-less applied approach,
a more fundamental aspect lies in the understanding of the
reaction mechanism, which further enables back-optimisation
of the catalytic formulations. This requires the identification of
the intermediate steps and the explanation of the formation of
the by-products. A first proposal was made by Bühler et al. for
the glycerol activation in the liquid phase.87 Two pathways were
claimed, either via an ionic or a radical mechanism (Scheme
8). The ionic reaction (Scheme 8a) begins with the protonation
of glycerol either on one primary hydroxyl group or on the
secondary hydroxyl group. Consequently, the elimination of a
water molecule leads to the formation of a carbocation. In the
case of the secondary carbocation, the only possible product
after release of H3 O+ is acrolein, whereas either acrolein or
acetaldehyde + formaldehyde can be formed starting from the
primary carbocation. The radical pathway (Scheme 8b) starts
with the abstraction of a hydrogen atom from a primary carbon
using an OH∑ radical. The resulting radical species further loses
an hydroxyl radical (OH∑ ), which leads to the formation of
acrolein.
Tsukuda et al. – who performed the dehydration in the gaseous
phase – developed a more formal reaction framework (Scheme
9).51 The first dehydration step leads to the formation of two
enols, which are in tautomeric equilibrium with the correspond-
ing ketone (acetol) and aldehyde (3-hydroxypropionaldehyde).
The latter may subsequently react in a second dehydration
reaction to yield acrolein, or undergoes a retroaldol reaction to
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Scheme 8 Reaction pathways to the formation of acrolein considering
(a) an ionic pathway and (b) a radical pathway.87
liberate formaldehyde + acetaldehyde, which – in the presence of
oxygen – can easily be oxidised to acetic acid. In agreement with
the previous proposal of Bühler et al.,87 Tsukuda et al. confirmed
that the key to obtain high acrolein selectivity lies in the control
of the first dehydration step, whereby the formation of 3-
hydroxypropionaldehyde must be favored over the formation of
acetol, which is identified as the main by-product of the process.
The same mechanism has been further amended by Chai
et al. (Scheme 9),41 who added two possible hydrogenation
steps, one starting from acrolein and the other from acetol
to yield allylic alcohol and 1,2-propanediol, respectively. In
the catalytic system studied, these by-products can indeed be
observed. Furthermore, the hydrogenation of formaldehyde to
methanol or its decomposition to CO + H2 are mentioned.
Scheme 9 Mechanism proposed by Tsukuda et al. and further com-
pleted by Chai et al.41,51
These two first proposals were the first approaches for
explaining the observed by-products from glycerol dehydration.
Successively, Corma et al.25 postulated a more complex interwo-
ven reaction framework (Scheme 10), where the main reaction
steps are the same as those previously described by Tsukuda and
Chai. In order to achieve a deeper understanding and specifically
investigate the secondary reactions, the authors used acetol as
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Scheme 10 Reaction network proposed by Corma et al.25
a reactant at 350 ◦ C. The products were classified into three
groups: acids (9.4%), other aldehydes (52.0%) and coke (27.7%).
Furthermore, the formation of low amounts of acetone (4.0%),
acetaldehyde (1.4%) and carbon monoxide (1.2%) was observed.
Nevertheless, the conversion of acetol did not exceed 25%, which
means that this compound is quite stable and does not easily
undergo consecutive reactions. This explains why it is usually
identified as the major by-product in the reaction of dehydration
of glycerol to acrolein.
Even though only small amounts of acetone were observed,
Corma et al. investigated the consecutive reactions starting from
this compound by repeating their method. The resulting product
distribution was dominated by unsaturated hydrocarbons like
butene (27.9%), propylene (1.7%), C5 + C6–8 aromatics (6.6%)
and – as a product of these compounds – coke (31.9%). Other
identified products were various acids (20.2%) and aldehydes
(7.3%), but, as in the case of hydroxylacetone, the conversion
of acetone remained low and did not exceed 14%. Nevertheless,
with their findings, they enlarged the reaction scheme proposed
by Chai and Tsukuda by adding further side-reactions ema-
nating from acetol. Thereby, they explained the formation of
oligomers and coke by consecutive reactions starting from acetol
via acetone and acetaldehyde.
The idea of investigating the consecutive reactions starting
from a by-product was picked up by Suprun et al. for 3-
hydroxypropionaldehyde and acetol.67 They could thus confirm
the retroaldol reaction previously postulated by Tsukuda,51
which leads to the formation of formaldehyde and acetaldehyde
issuing from 3-hydroxypropionaldehyde. Additionally, signifi-
cant amounts of coke were found, which was ascribed to the
formation of cyclic C6 compounds identified by GC–MS analysis
(Scheme 11a). The authors further identified numerous furan
derivatives as products from acetol (Scheme 11b).
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Scheme 11 Products derived from (a) 3-hydroxypropionaldehyde and
(b) acetol.67
In the previous section, we have seen that the co-feeding of
oxygen has a positive impact on the long-term performances
of the catalysts. Nevertheless, the presence of oxygen also
Scheme 12 Reaction scheme proposed for dehydration of glycerol in the presence of oxygen.72
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results in a new type of product distribution. Indeed, new
by-products, such as organic acids, are observed, and a new
reaction scheme has thus been very recently proposed by
Deleplanque et al. (Scheme 12).72 In addition to dehydration,
which yields the already known products like acetol and
acrolein, or their reductions to acetone and allylic alcohol, the
authors postulate some new oxidation reactions. Starting from
formaldehyde, originating from the aforementioned retroaldol
reaction, oxidation leads to the formation of formic acid, which
is easily over-oxidised to CO or CO2 . When acrolein is oxidised,
acrylic acid is observed, which may further react to give acetic
acid by decarbonylation. Alternatively, the latter can also be
formed by oxidation of acetaldehyde. On the other hand, the
formation of propanoic acid is explained by the reduction of
allylic alcohol in a first step and subsequent oxidation of the
formed 1-propanol. In addition to these oxidation reactions, the
authors also describe the formation of acetals from condensation
of glycerol with formaldehyde. This may be possible when the
glycerol concentration is rather high compared to the oxygen
concentration, whereby the oxidation of formaldehyde to formic
acid becomes limited. Nevertheless, one can conclude that
the presence of oxygen results in a much higher number of
by-products, which explains the lower selectivity for acrolein
observed in the case of the dehydration reaction conducted in
the presence of oxygen.
All these reaction mechanisms are mostly formal and actually
do not explain the real interactions with the surface of the solid
catalysts. Therefore, Yoda et al. developed a mechanism for the
dehydration over H-MFI zeolites inspired by the results of in situ
infrared observations.95 The mechanism is similar to the afore-
mentioned ones, whereby glycerol interacts with the bridging
hydroxyl-group of the zeolite to give alkoxy species (Scheme
13). When glycerol is bound by a terminal OH-group, acetol
is formed by the known keto–enol tautomerism. On the other
hand, the interaction with the secondary OH-group leads to
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Scheme 13 Reaction mechanisms over (a) Brønsted and (b) Lewis acid sites as proposed by Alhanash et al.95

the formation of an intermediate of 3-hydroxypropionaldehyde,
and, after a second dehydration step, to the formation of
acrolein.
Based on these proposed reaction mechanisms, two research
groups calculated the energy states for the different reaction
pathways. Nimlos et al. concentrated on the calculations of the
neutral and the protonated reaction pathways using the Gaus-
sian 03 algorithm with B3LYP/6-311G sets for the molecular
orbitals.96 For the so-called ‘neutral glycerol’, they found a very
high activation barrier of 70.9 kcal mol-1 for the dehydration
of the secondary hydroxyl-group (Fig. 5). In contrast, the
second dehydration step – starting from the intermediate 3-
hydroxy-propionaldehyde – required only 29.7 kcal mol-1 . The
dehydration of the primary OH-group, leading to the formation
of acetol, was found to be energetically even more unfavorable,
with an activation energy of 73.2 kcal mol-1 . Nevertheless, the
formation of acetol is exothermic and liberates 4.0 kcal mol-1 ,
whereas acrolein requires +9.3 kcal mol-1 .
The calculations for the protonated glycerol – as proposed by
Bühler et al.87 – show that the activation energies are much lower

Fig. 5 Calculation for neutral and protonated reaction pathway to acrolein and acetol.96

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Fig. 6 Calculated energies for the glycerol dehydration over MFI-zeolite.97
than for the non-protonated one. Starting from the protonated
secondary hydroxyl group of glycerol, the activation energy of
the transition state of the first dehydration is only 22.4 kcal mol-1
vs. 70.9 kcal mol-1 without proton. The second dehydration
step, which is calculated to 24.6 kcal mol-1 in the presence
of a proton, is also 5.1 kcal mol-1 lower than without (29.7
kcal mol-1 ). Furthermore, the reaction pathway for protonated
glycerol leads to the exothermic formation of acrolein with an
energy release of 18.0 kcal mol-1 . As in the case of the non-
protonated reaction, the formation of acetol requires a higher
activation energy of 24.9 kcal mol-1 compared to that required
for the formation of acrolein (22.4 kcal mol-1 ). Moreover, the
differences in the final energy states of the two products are quite
low (acetol: -18.3 kcal mol-1 ; acrolein: -18.0 kcal mol-1 ). From
these results, one can conclude that the formation of acetol is
thermodynamically less favored than the formation of acrolein,
due to the associated higher barrier of activation energy.
Nevertheless, the difference is rather small, which suggests
that it might be difficult to entirely suppress the formation of
acetol.
The calculations based on the results obtained for the reaction
over ZSM-5 zeolite catalysts– as proposed by Yoda et al.95 – were
performed by Kongpatpanich et al., who used Gaussion 03 with
M06-2X/6-31G set for the zeolite 12T cluster model.97 For the
first dehydration step, they found an activation energy slightly
higher than that obtained by Nimlos et al. for the protonated
glycerol (41.4 kcal mol-1 vs. 22.4 kcal mol-1 (Fig. 6).96 The
activation energy of the second dehydration was calculated at
38.5 kcal mol-1 and the final energy state was +19.5 kcal mol-1 .
It is difficult to explain these differing results and, unfortunately,
Kongpatpanich has not yet calculated the reaction pathway
leading to the formation of acetol.
The mechanisms described give quite good explanations for
the observed products in the glycerol dehydration reaction, such
as acrolein, acetol, formaldehyde, acetaldehyde, 1,2-propanediol
and coke. The recently published mechanisms over basic cata-
lysts and over the different types of acid catalysts are the first
attempts to explain the different product selectivities observed
over these types of catalysts.
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View Article Online
10 Direct use of crude glycerol as a reactant: an
important economic issue
As mentioned in the introduction, the price of glycerol drasti-
cally depends on the required technical grade. Whereas refined
glycerol cost between 500 and 600 US$ t-1 in January 2010, crude
glycerol could be obtained at the same time for only 200 US$
t-1 .26 Nevertheless, the glycerol market has previously proven to
be highly volatile, with costs up to 1800 US$ t-1 for refined glyc-
erol and up to 500 US$ t-1 for crude glycerol in 2007–2008.26 It
should also be mentioned that glycerol availability and price also
depend on political decisions concerning biodiesel production
and agricultural subsidies. Therefore, making possible the use
of crude glycerol is a crucial issue for achieving a sustainable
and economically viable process for the production of acrolein.
However, as previously mentioned, crude glycerol is generally
contaminated with by-products issued from biodiesel process
(inorganic traces like salts and organic traces like water, esters,
fatty acids and alcohols). The use of crude glycerol as a feedstock
may therefore induce serious difficulties, either by poisoning of
the catalysts or by causing plugs due to deposition of high-
boiling organic materials or inorganic salts. To our knowledge,
at this time no catalytic test using this type of feedstock has
been reported in the literature – all the disclosed studies were
carried out using diluted aqueous solutions prepared from
refined glycerol. Furthermore, it has been found that the yield
of acrolein strongly depends on the glycerol concentration in
the reactor feed, with a decrease in the yield with increasing
concentration.35,36 However, the use of crude glycerol is of prime
economical importance, and different ideas have already been
proposed to avoid the costly distillation of crude glycerol and to
overcome the obstacles raised by its use as a feedstock. Kijenski
et al. proposed a modified evaporation system, where the crude
glycerol is brought into contact with an inert liquid at high
temperature.98 The glycerol is evaporated and fed to the reactor
diluted in an inert carrier gas, whereas the impurities remain in
the inert liquid. The authors describe an example of a process
in which a solution of 75 wt% of glycerol with up to 3 wt%
impurities is added to silicon-oil heated to 330 ◦ C.
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To facilitate the use of crude glycerol, Dubois and Sereshiki
et al. instead suggest a fluidised inert solid heated to high
temperature.99,100 This leads to the evaporation of glycerol,
whereas the impurities remain inside the fluidised bed, which
can be continuously regenerated. The regeneration may consist
in a flushing step with water to dissolve inorganic salts followed
by a thermal treatment to burn off the organic deposits. As
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an example, the authors describe a process whereby a solution
of 18 wt% glycerol with 2 wt% sodium chloride is put into
contact with a fluidised bed of silica particles. The fluidisation
is performed using nitrogen at 310 ◦ C. The author claims
a separation/recovery of 99.9% of the introduced sodium
chloride.
Another process enabling the use of crude glycerol was also
proposed by Dubois.101 As the evaporation of crude glycerol
at high temperature induces reactions between glycerol and
MONGs, this author proposed the possibility of forming acetals
by reacting glycerol with the acrolein in a first step (Scheme
14). These acetals have lower boiling points than glycerol (185–
240 ◦ C vs. 290 ◦ C), and thus the aforementioned undesired side-
reactions are said to be reduced. The formed acetals are then
evaporated in the second step and subsequently dehydrated over
an acid catalyst in the third step, to finally obtain acrolein. The
acrolein formed is partially recycled for the acetalisation in the
first step.
Scheme 14 Process based on an intermediate acetalisation step to
purify crude glycerol.
In conclusion, one can see that the use of crude glycerol
necessitates a supplementary upstream step at the level of
the reactant evaporation. All the proposed concepts have in
common the fact that inorganic impurities like salts are retained,
whereby the poisoning of the catalyst is inhibited. Nevertheless,
we have to mention that important progress has been made
concerning the improvement of the quality of the glycerol issuing
from biodiesel production processes.102 The early processes were
based on homogenous catalytic cleavage of the vegetable oils
and fats in the presence of a base – for example, one of the
new processes developed by the French company Axens uses
a heterogeneous catalyst.103 This ‘Esterfip-H’ process provides
exceptionally high glycerol purities close to 98%, with only a
few traces of inorganic salts.104 Furthermore, the costs generated
2096 | Green Chem., 2010, 12, 2079–2098
View Article Online
by the use of heterogeneous catalytic systems are claimed to be
lower than those from the conventional homogeneous process,
as the leaching of the catalyst is negligible in this case. This
process is planned or already in application in six units in Europe,
and North & South America, with a total capacity of nearly
1 million tonnes per year. Nevertheless, for the near future,
both homogenous and heterogeneous processes will still have
to deal with the availability of different grades of crude glycerol
on the global market. Therefore, the question concerning the
economic sense of investing (or not) in a supplementary unit for
the evaporation of crude glycerol is difficult to answer at this
stage.
11 Conclusion
The depletion of the petrol feedstock and the global warming
caused by CO2 emission have led to a change in the energy
policies. Biofuels have been proposed as an alternative to fossil
fuels for reducing the impact of greenhouse gases. Due to
political directives, the production of bioethanol for blending
with gasoline and the production of biodiesel have drastically
increased. As a consequence, the market has been flooded with
crude glycerol co-produced in the biodiesel production process.
As glycerol is a highly functionalisable molecule, many processes
for its valorisation have been recently published. In particular,
the catalytic dehydration to acrolein – a precursor of sodium
polyacrylate used as a superabsorbent polymer and of DL-
methionine used for cattle feeding – is of high economic interest.
This reaction is catalysed over Brønsted and Lewis acid sites
according to two different mechanisms, which are still a matter
of debate and will undoubtedly be refined in the near future.
Furthermore, the picture of the influence of the acidity on the
catalytic performances has become clearer, showing that optimal
acidic strength is needed for high and constant performance.
As far as gas-phase dehydration is concerned, a large variety of
highly efficient catalysts has been proposed, which can be divided
into three different categories: (i) supported HPAs; (ii) zeolites;
and (iii) mixed-metal oxide type catalysts, including phosphates.
The best catalytic performance has, up to now, been achieved
with caesium salts of HPAs, yielding up to 98% acrolein in the
very early stages of the reaction. On zeolitic and mixed oxide
catalysts, the acrolein yield is generally slightly lower (around 70
to 80%) and the temperature needed to reach high conversions
is higher (around 300 ◦ C vs. 275 ◦ C for HPAs). Nevertheless, the
family of zeolites and supported HPAs offers many possibilities
for tuning acidity and textural parameters, which makes possible
fine-tuning to yield tailor-made catalysts.
However, the main problem remains rapid catalyst deactiva-
tion due to carbon deposition. Up to now, no catalyst has had a
half-life of more than a few days, which is of course not sufficient
for commercial applications. Therefore, various approaches have
been published to regenerate the coked catalysts. These are: the
use of a fluidised circulating catalyst, which is continuously
regenerated in a parallel reactor; the introduction of oxygen,
hydrogen or sulfur dioxide into the reaction feed for continuous
regeneration of the catalyst inside the reactor; and discontinuous
regeneration by alternating the glycerol feed and the oxygen feed.
It was even proposed to dope the catalysts with noble metals for
facilitating the splitting of the dioxygen used for regeneration. At
This journal is © The Royal Society of Chemistry 2010

this time, the co-feeding of oxygen seems to be the most practical
way for extending catalyst life-time, as this technique requires
relatively low investment and is easy compared to pulse-wise
regeneration or to a fluidised process. Nevertheless, this method
is not applicable for all kinds of catalysts, as redox properties
may lead to significant decrease in the selectivity for acrolein.
Liquid-phase dehydration was well studied with the rise of
Published on 12 November 2010. Downloaded by Pennsylvania State University on 17/09/2016 04:41:30.
research into supercritical fluids. Nevertheless, a dead-end has
been reached, as dehydration just in supercritical water without
acid catalyst results in low acrolein yields, while the combination
of supercritical conditions with acids is problematic in terms
of material stress on the reaction vessel, which would lead to
significant investment costs. The second – and more promising
– route is the use of high-boiling solvents containing solid
catalysts. With this technology, a quasi-continuous process can
be achieved, even if scale-up to the industrial scale remains risky.
As a consequence, the dehydration of glycerol in the liquid phase
appears to be a rather uneconomic process.
Finally, we have shown the need for the use of crude glycerol
as a feedstock in regard to economic aspects. We have not
come across any attempt to directly use crude glycerol over
catalytic formulations, but two promising upstream technologies
have been presented, which aim to eliminate the impurities
of the crude glycerol during evaporation and thus avoid the
costly crude glycerol distillation. As the number of publications
concerning this kind of technology is still very limited, it is
difficult at the moment to foresee which of them is the most
promising. Furthermore, the quality of crude glycerol from
biodiesel production is constantly increasing, reaching a purity
up to 98% without any inorganic salts, which makes industrial
applications of the proposed purification techniques rather
improbable, at least in the long-term.
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