Escolar Documentos
Profissional Documentos
Cultura Documentos
200900134
action. The processes developed in both the liquid and the gas
phases are detailed and the best catalytic results obtained so
far are reported as a benchmark for future developments. The
advances on the understanding of the reaction mechanism are
also discussed and we further focus particularly on the main
obstacles for an immediate industrial application of this technology, namely catalyst coking and crude glycerol direct-use
issues.
1. Introduction
The exhaustion of nonrenewable fossil fuels is foreseen in the
next several decades. During the last years, the production of
alternative gasolines by making use of vegetable oils and fats
has attracted the attention of many academic and industrial researchers. In addition to renewability, the resulting biodiesels
have the advantage of providing a neutral CO2 balance with a
much lower environmental impact than petrodiesels. The raw
materials for biodiesel production are vegetable oils and fats
from canola, soy, corn, or othersand a mono-alcohol (usually
methanol), which is used to cleave the fatty acids from the
glycerol backbone to finally yield the fatty-acid-esters
(Scheme 1). These acid-esters can be used as biodiesels either
directly or after blending with fossil-fuel-derived diesels.
The use of biodiesels as substitutes or additives for petrolbased diesels can be seen as a political choice, rather than a
decision driven socio-economic reasons. Recently, this choice
has even been criticized owing to the concurrent use of the
same raw materials for food production. Nevertheless, the European Union has planned to progressively increase the biodiesel proportion in commercial fuels to reach a target of 10 %
in 2015.[1] This is a general trend, and the capacity for biodiesel
production is continuously increasing all over the world. For
example, in 2007 the USA and the EU produced 1.2 and 5.7
million tonnes (Figure 1) of biodiesel, respectively, and these
quantities are expected to double by 2012.[2]
ChemSusChem 2009, 2, 719 730
This growth is accompanied by a significant increase in glycerol production, as this compound is a major byproduct of biodiesel production (ca. 10 wt %; Scheme 1). A projection of the
global production forecasts that world-wide 1.2 million tonnes
of glycerol will be generated in 2010,[3] which has to be processed to achieve a sustainable industry. Crude glycerol obtained from the biodiesel process contains 80 wt % of glycerol
but, as a drawback, also contains water, methanol, traces of
fatty acids, and various inorganic and organic compounds (re-
719
F. Dumeignil et al.
ferred to as MONG: matter organic non-glycerol). As a consequence, crude glycerol must in most cases be purified by an
expensive distillation step prior to further use. The proportion
of glycerol that is actually refined is now decreasing owing to
the high cost of the distillation step accompanied by a toorapid growth of the quantity of produced crude glycerol, but
mostly because of the absence of any market able to absorb
the overproduction (Figure 2). In contrast, a model based on
tion, as noted earlier the size of the existing markets is not sufficient to absorb the huge amounts of glycerol currently being
produced, and the gap between the absorption capacity of
the market and the glycerol production will steadily increase in
the near future. Today, crude glycerol that is not refined is generally burned (Figure 2), which must be considered as a dramatic waste of a potentially very interesting organic raw material. Glycerol is a molecule with a large potential for functionalization that offers many opportunities of chemical or biochemical conversions to produce value-added chemicals. A selection
of these possibilities is shown in Scheme 2 and briefly further
720
www.chemsuschem.org
In this context, obtaining acrolein from bioresources in substantial yields is an important challenge. An economical study
has shown that a competitive production of acrolein from glycerol would be possible at a glycerol price lower than ca.
US$ 300 t 1.[25] Currently (June 2009), refined glycerol still costs
US$ 400500 t 1 but crude glycerin is around US$ 100200 t 1,
which makes it a potentially very competitive raw material for
acrolein production.[26]
In this Minireview, we draw the state-of-the-art of the sustainable production of acrolein by dehydration of glycerol. Processes developed in the liquid and the gas phase are detailed,
and the best catalytic results obtained up to now are reported
and commented. The fundamentals of the reaction are also
discussed in a section devoted to its mechanism. Finally, the
main obstacles to an immediate industrial development of the
process are discussed in order to outline new insights for
future research efforts.
2. Historical Context
It has been well-known for a long time that heating glycerol
induces its decomposition into acrolein and water, with the
production of byproducts. However, an acid catalyst is needed
to have better control over the reaction and to obtain a significant yield of the unsaturated aldehyde at a moderate temperature. The first patent on this subject was published in France
in 1930.[27] The reaction was carried out in the gaseous phase
over a supported lithium phosphate catalyst, which already
provided an acrolein yield close to 75 %. Later, in 1934, Groll
and Hearne claimed a patent for the Shell company for the dehydration of an aqueous glycerol solution in the presence of
sulfuric acid at 463 K, which was supposedly the boiling point
of the solution.[28] The resulting acrolein stream was a condensed vapor with a yield of nearly 50 %. Hoyt and Manninen,
17 years later, patented the dehydration of glycerol using supported H3PO4.[29] This heterogeneous catalyst was prepared by
impregnation of a clay with 25 wt % of acid. The authors chose
petroleum oil with a boiling point higher than 573 K as a reaction medium, which enabled the use of higher reaction temperatures compared to those used by Groll and Hearne,[28] who
worked in the aqueous phase. Even when the glycerol was
used at a larger concentration (95 wt %) a high yield in acrolein
(72.3 %) could be reached. However, these early works, in both
gaseous and liquid phases, remained without further follow-up
until the end of the 20th century and the upcoming of the
massive production of cheap glycerol resulting from biodiesel
production processes.
www.chemsuschem.org
721
F. Dumeignil et al.
acrolein following its formation when it is subjected to too
high temperatures. In 2007, Lehr et al. also published on the
dehydration of biomass-derived polyols in sub- and supercritical water. As far as glycerol is concerned, they reported 59 %
glycerol conversion with almost
60 % acrolein selectivity, using
Table 1. Selection of the best catalytic performances reported for the dehydration of glycerol in the liquid
ZnSO4 as a catalyst in subcritical
phase.
water conditions (see Table 1).[32]
To determine if the dehydration
T [K] P [MPa] Catalyst
Glycerol
Acrolein
Acrolein yield [%] Reactor type Ref.
of glycerol in the liquid phase
conversion [%] selectivity [%]
might offer a sustainable source
97
82
79.5
Batch
[34]
553
0.1
KHSO4
of acrolein at an industrial scale,
553
99
76
75.2
Batch
[34]
72.3
Batch
[29]
573
0.1
H3PO4/Clay
Watanabe et al. attempted to
92
81
74.0
Continuous [33]
673 34.5
H2SO4
optimize the acrolein yield.[33]
75
86
64.5
Batch
[34]
473
0.1
KHSO4
They combined the supercritical
71
87
61.8
Batch
[34]
553
0.1
KHSO4
conditions in a flow-type reactor
92
56
51.5
Batch
[34]
553
0.1
MgSO4
57
50.7
Batch
[34]
553
0.1
H3PO4 (5 wt %)/Al2O3 89
with sulfuric acid as a catalyst. It
49.0
Batch
[28]
463
0.1
H2SO4
should be noted that they con55
86
47.3
Batch
[30]
623 34.5
H2SO4
firmed the results of Bhler
50
75
37.5
Continuous [3]
633 25
ZnSO4
et al.[31] Several blank tests per40
38.0
Batch
[34]
553
0.1
H3PO4 (20 wt %)/Al2O3 95
633 34
ZnSO4
62
59
37.0
Continuous [32]
formed in the absence of a cata52
64
33.3
Batch
[34]
553
0.1
Al2ACHTUNGRE(SO4)3
lyst gave low glycerol conversions but high acrolein selectivities, with a yield up to 16 %. The
Considering the fact that sulfuric acid is soluble in supercritical
best results were obtained at 673 K under 34.5 MPa, with a sulwater, this process can be classified as homogeneous catalysis
furic acid concentration of 5 mm. In these conditions, the yield
with, as a consequence, catalyst/reaction mixture separation
of acrolein was 74 % with a glycerol conversion of around
issues. Nevertheless, the idea of using supercritical water as a
92 %. One of the main issues in this work was to sufficiently
reaction medium was a new aspect, and Bhler et al. decided
promote the acrolein formation rate to make it much larger
to deepen the subject in 2001.[31] Instead of working in a batch
than the decomposition rate, which was achieved by adding
acid in supercritical conditions.
reactor, they built a flow-type reactor and used supercritical
However, to our knowledge, the largest acrolein yield reportwater as both solvent and catalyst. They observed various deed in the liquid phase was observed at atmospheric pressure
composition products, such as acetaldehyde, formaldehyde, aland a low temperature by Suzuki et al.[34] Potassium sulfate
lylic alcohol, propionaldehyde, and, of course, acrolein. The
acrolein yield varied between 10 and 23 % depending on the
and hydrogenosulfate were used as catalysts in a batch reacreaction conditions, with the best result (23 %) obtained at a
tor, into which the glycerol solution was added dropwise to a
reaction temperature of 623 K at a pressure of 45 MPa. As
paraffin solution maintained at 553 K. The produced acrolein
aforementioned, the tests were in the absence of any catalyst
was then evaporated and recovered in an aqueous solution
or acid component, which explains the poor yields in acrolein.
containing 0.25 % of hydroquinone as stabilizer. The best yield
Recently, a combination of the ideas of Hoyt and Manniwas close to 80 %, but the described process seems difficult to
nen[29] and Ramaya et al.[30] , that is, using a supported catalyst
scale-up to an industrial level owing to its complex set-up and
and using supercritical water as a reaction medium, respectivediscontinuous processing mode.
ly, was proposed by Ott and co-workers.[3] These authors invesThus, we have seen that the dehydration of glycerol in the
tigated the dehydration of glycerol in supercritical water with
liquid phase (at atmospheric pressure or in near- or supercritizinc sulfate as a catalyst, which is surprising because this catacal conditions) leads to the formation of acrolein. However, in
lyst is supposedly not acidic enough to efficiently promote the
the absence of a catalyst, the glycerol conversion and the acroreaction. However, they justified their choice considering matelein selectivity remain very low. The reaction is efficiently catarial stress issues: water in its supercritical form is a highly corlyzed by acids, but near- or supercritical conditions induce the
rosive agent and therefore requires special and expensive steel
presence of an extremely corrosive medium, and the vessel,
grades for reactors; this corrosive power would become even
which must also resist high temperatures and pressures, must
stronger if acidic compounds were subsequently added in the
be specifically designed, resulting in high investment/maintemedium, leading to unacceptable reactor material stress. In
nance costs. The best yield claimed in these conditions is close
these conditions, the authors showed that supercritical condito 80 % for homogeneous catalysis, compared to ca. 50 % in
tions are not necessarily the optimal ones. Actually, near-critical
the best case under heterogeneous conditions. As mentioned,
water (633 K at 25 MPa) showed better conversion and selechowever, the application of homogenous catalysis on an industivity than supercritical water, that is, 75 % selectivity at 50 %
trial scale is often hampered by awkward separation issues.
conversion. This might be explained by the degradation of
Therefore, the development of a high-performance heterogein a batch reactor at 623 K, pressurized to 34.5 MPa, and acidified with 5 mm of sulfuric acid. In these conditions, and at a
residence time of 25 s, the conversion of glycerol and the selectivity towards acrolein were 55 % and 86 %, respectively.
722
www.chemsuschem.org
633
100.0
82.8
n.a.
n.a.
[54]
their acidity.[41] Group 1 included
H-MFI+1 % Au
633
100.0
82.8
6.3
1
[66]
ZSM-11
633
99.0
81.3
n.a.
n.a.
[54]
basic catalysts with HA values
633
100.0
80.7
6.2
3
[66]
H-MFI+0.1 % Pt
higher than 7, such as magnesib-zeolite
633
100.0
80.3
n.a.
n.a.
[54]
um oxide. These catalysts
MCM-22
633
100.0
80.1
n.a.
n.a.
[54]
showed no selectivity to acrolein
Pumice stone
673693
n.a.
80.0
n.a.
n.a.
[27]
Fe2ACHTUNGRE(PO4)3
Nd4ACHTUNGRE(P2O7)3
593
96.4
79.7
n.a.
7
[57]
at all. Group 2 contained cataMFI + Ba
633
100.0
79.0
6.2
2.5
[51]
lysts with a HA value ranging be
533
100.0
79.0
1.2
5
[60]
H2WO4
tween 3 and 7, such as zirconiZrO2/montmorillonite 533
100.0
79.0
1.2
5
[63]
WO3
um oxide. According to the work
533
100.0
77.0
1.2
5
[62]
H2WO4+1 wt % Pd
MCM-56
633
100.0
76.8
n.a.
n.a.
[54]
of Neher,[35] these catalysts
Nafion
SiO
573
100.0
76.0
19.8
7
[38]
should give high acrolein seleca-Al2O3
573
n.a.
75.0
0.3
n.a.
[35]
H3PO4
tivities but, in practice, the selecPumice stone
673693
n.a.
75.0
n.a.
n.a.
[27]
Li3PO4
tivity did not exceed 30 % al
593
98.2
74.3
n.a.
1
[57]
Gd4ACHTUNGRE(P2O7)3
593
99.6
73.9
n.a.
1
[57]
Sm4ACHTUNGRE(P2O7)3
though the performances reZSM-5
588
98.3
73.6
n.a.
n.a.
[56]
mained rather stable for 10 h
ZrO2
573
100.0
73.5
19.2
7
[38]
WO3
on-stream. Group 3, which was
ZrO2
588
100.0
70.0
12.6
4
[55]
H3PW12O40
more promising, comprised cata[a] n.a. = data not available in the publication; STY = Space-time yield of acrolein.
lysts with a HA value between
ChemSusChem 2009, 2, 719 730
www.chemsuschem.org
723
F. Dumeignil et al.
8 and 3. In this group, alumina-supported phosphorous
acid could be found, and also alumina-supported heteropolyacids and niobium oxide (calcined at temperatures between
673 K and 773 K). The group also contained a HZSM zeolite
and pure alumina. In good agreement with previous results,[38, 39] the selectivity was generally higher than that observed for Group 2 catalysts, with the exception of pure alumina and niobium oxide calcined at 773 K. Interesting results
were observed with the alumina-supported phosphotungstic
heteropolyacid and a mixed phase of tungsten oxide/zirconium oxide with approximately 70 % selectivity at a conversion
of 70 %, in both cases after 2 h on-stream. Unfortunately, these
catalysts showed poor stability, and their performance significantly decreased during time-on-stream. Actually, for both catalysts, the glycerol conversion dropped from 6869 % to 23
25 % between 1 and 10 h under reactant flow; the selectivity
being rather constant at roughly 6670 %. The other catalysts
were overall less efficient, and gave selectivities between 35 %
and 55 % at conversions between 55 % and 100 % after 10 h
on-stream. Group 4 contained catalysts with a HA value of less
than 8, such as Hb-zeolite, niobium oxide calcined at 623 K,
and also alumina-silicate as well as sulfonated zirconium oxide.
These catalysts were less selective to acrolein than those of
Group 3 but they showed increasing performances during
time-on-stream. For example, the glycerol conversion on an
alumina-silicate dropped from 94 to 75 % between 1 to 10 h
under reactant flow, the selectivity being rather unchanged at
roughly 4346 %. Nevertheless, similar to niobium oxide,
Group 4 catalysts were also subjected to a detrimental carbonization, with a carbon deposit that represented between
100 mg and 400 mg of carbon per gram of catalyst after 10 h
on-stream.
The same team further published two other papers in 2008
and 2009 dealing with zirconia- and silica-supported 12-tungstophosphoric acid catalysts.[44, 45] 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 ZrO2 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 a key parameter 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.[46] The latter
claimed that a 10 wt % H4SiW12O40 supported catalyst gives the
best acrolein space-time yield ever reported in the literature
(i.e., 68.5 10 3 molacrolein h 1 gactive phase 1). This promising performance was attributed to the good dispersion of the HPA on
the support surface and also to the relative quantities of
strong acid sites.
In this section we have seen that the tuning of the acidity of
the active phase is of prime importance for getting a good catalytic performance. However, this characteristic alone is not
sufficient to also get a sufficient stability of the active phase
and a good selectivity to acrolein. It seems that the properties
of the support and the way the active phase is dispersed on
724
www.chemsuschem.org
www.chemsuschem.org
725
F. Dumeignil et al.
the catalyst are also of prime importance to achieve good performances. Here, the supports can play a major role through
modifying the textural properties of the catalyst, which has a
dramatic effect on the selectivity probably because of steric
and diffusion issues. The best results published so far were obtained at a relatively low temperature (523548 K) using silicasupported HPAs. These catalysts, however, tend to deactivate
quite rapidly with time-on-stream. The zeolite family is also
promising but needs higher working temperatures (more than
623 K) to achieve high yields.
When the necessary data were available in the papers, we
calculated the acrolein space-time yield (STY) taking the total
catalyst mass as a reference. The obtained values are reported
in Table 2. Accordingly, the best result obtained up to now
were achieved by Dubois et al. on a SiO2-supported Nafion catalyst.[38] The STY was 20 10 3 molacrolein h 1 gcatalyst 1. However,
another method to calculate the STY takes into account only
the active phase mass, and when using this method the best
result was achieved by Ning et al. with an activated carbonsupported silicotungstic acid catalyst (10 wt % H4SiW12O40).[64]
The STY was 68.5 10 3 molacrolein h 1 gactive phase 1.
5. Reaction Mechanism
Whereas the research for an efficient catalyst can follow a
more or less purely applied approach, an understanding of the
reaction mechanism is a more fundamental aspect. This implies
the identification of the intermediate steps and the explanation of formation of the byproducts. A first proposal for the
glycerol activation in near- or supercritical conditions was
made by Bhler et al.[31] Two pathways were claimed, via either
an ionic or a radical mechanism. The ionic reaction
(Scheme 4 a) begins with the protonation of glycerol on either
one primary hydroxyl group or the secondary hydroxyl group.
Afterwards, the elimination of a water molecule leads to the
formation of a carbocation. In the case of the secondary carbo-
726
www.chemsuschem.org
meric equilibrium with the corresponding ketone (hydroxyacetone) and aldehyde (3-hydroxypropionaldehyde). The latter
subsequently reacts in a second step either via dehydration to
acrolein or via a retroaldol reaction to give formaldehyde and
acetaldehyde, which may be easily oxidized to acetic acid (in
the presence of O2). As an important conclusion, Tsukuda, in
agreement with Bhlers previous proposal,[31] pointed out that
the key to obtaining a high selectivity for acrolein lies in the
control of the first dehydration step to favor the formation of
3-hydroxypropionaldehyde while suppressing the formation of
hydroxyacetone, which is identified as the main byproduct of
the process.
The same mechanism has been further completed by Chai
et al. (Scheme 5),[41] who added the two hydrogenation steps
that can occur starting from acrolein and hydroxyacetone to
form allylic alcohol and 1,2-propanediol, respectively, which are
sometimes actually observed. The hydrogenation of the formaldehyde to methanol or its decomposition into CO+H2 is also
mentioned.
These schemes are interesting for a first approach, but an
even deeper analysis is needed to explain the formation of all
the observed byproducts. Corma postulated a more complex
were found, which is explained by the formation of cyclic C6compounds identified by GC-MS analysis (Scheme 7 a). The authors further identified various furan derivates (Scheme 7 b),
which must be thus taken into account when one specifically
seeks for fine information on the minor reaction byproducts.
www.chemsuschem.org
727
F. Dumeignil et al.
or oxidizing the various reaction products, the second alternative is accompanied by the disadvantage of a loss of 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 personnel and fine process control.
The idea of working with air in the reaction gas was first
proposed by Dubois.[38] To stay out of the explosivity range,
the oxygen fraction must never exceed 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 author claimed to reduce catalyst deactivation and even to inhibit the formation of byproducts such as
hydroxyacetone in these conditions. Kasuga et al. injected air
into the gas feed to have a feed ratio of 7 % of oxygen for
27 % of glycerol, the remaining 66 % being steam and nitrogen
from air. Nevertheless, the selectivity towards acrolein was
then rather low and did not exceed 45 % after 24 h under reactant flow.[67] To optimize the regeneration, Kasuga et al. also
proposed to modify their MFI protonated-zeolite with a small
amount of metal (Pt, Pd, Ru, Cu, Ir, or Au). By this doping, they
claimed to accelerate the split of the dioxygen used for the regeneration.[66] 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 possibility of periodic regeneration was studied by Arita
et al., who regenerated a used H-ZSM5 catalyst under air flow
and showed the possibility of recovering the initial performance. However, the hot-spot temperature during regeneration surpassed the regeneration temperature by more than
100 K.[67] Atia et al. carried out long-term runs (up to 300 h)
and observed that the selectivity to acrolein remained stable
whereas glycerol conversion decreased more or less linearly.
This effect could be well explained by the deposit of coke
onto the catalyst surface and the concomitant decrease of the
number of accessible active sites. To verify this hypothesis,
coked catalysts were regenerated under a flow of 1 % oxygen
in nitrogen at 598 K during 24 h. After this treatment, the catalyst performed identical to the fresh catalyst. To quantify this
effect, the used catalyst was also analyzed by thermogravimetry, which confirmed the carbon deposit hypothesis.[50]
Meanwhile, Corma et al. adopted the idea of a circulating
bed reactor.[25, 68] The authors studied the opportunity of injecting crude glycerol directly into FCC plants. An advantage
would be the use of existing facilities and, therefore, no need
for investments for building specific infrastructures. It is worth
noting that this idea has already been proposed in a different
form by Dubois, who pointed out the opportunity of injecting
glycerol into propylene oxidation plants to concomitantly yield
acrolein from both sources.[69] 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 on the dehydration but also investigated the possibilities for reforming the
glycerol at 773 K to 873 K to produce ethylene and propylene.
728
www.chemsuschem.org
8. Conclusions
The finite nature of the fossil fuel supply and the global warming problem have led to a change in energy policies. In this
context, biofuels have received increased attention as CO2-neutral alternatives to crude oils. Beside bioethanol as a substitute
for gasoline, the use of biodiesel has drastically progressed
especially in the European Union. The increase in biodiesel
production has also led to an oversupply of glycerol as a coproduct. Because glycerol is a highly functionalizable molecule,
many processes for its valorization have been recently published. In particular the catalytic dehydration to acroleina
precursor of DL-methionine used for cattle feedingis of economic interest.
This reaction can proceed in either the gas or the liquid
phase. The reaction conditions in the liquid phase include the
possibility to use supercritical solvents. In terms of economical
interest, the use of heterogeneous catalysis is usually preferred
rather than the use of homogenous catalysis, as the separation
of the catalyst from the reaction medium is simplified. Therefore, the possibility of using supported acids instead of dissolved ones is preferable, even if it has been demonstrated
that both technologies show comparable catalytic performances. A second important step on the road to commercialization
is demonstrating the feasibility of working in continuous
mode. Experimental results have already been published, and
show only slightly decreased performances when compared
with discontinuous experiments.[33] At last, the use of supercritical water as a reaction medium has been proven to be adaptable to the reaction. Nevertheless, the combination of supercritical and acid conditions leads to high demands on the materials used for the reaction vessel and all peripherals. For all
these reasons, and even if an acrolein yield of 80 % has already
been achieved in the liquid phase, the possibility of a commercial application seems questionable at this date.
Concerning the gas-phase reaction, this Minireview has outlined a great variety of efficient catalysts. We can classify them
according to three different categories: (1) supported inorganic
acids, with a subcategory for supported heteropolyacids;
(2) protonated zeolites; and (3) mixed-oxide type catalysts. The
best acrolein yields are, up to now, achieved with supported
ChemSusChem 2009, 2, 719 730
Acknowledgements
The authors would like to thank the French Research Network
No. 1 (RDR1) of the CPDD program as well as CE (through contract number MIRG-CT-2007-046 383) for their financial support
for realizing this bibliographic study.
Keywords: acrolein biomass catalysis dehydration
glycerol
[1] Directive 2003/30/EC of the European Parliament and of the council of
05/08/2003 on the promotion of the use of biofuels or other renewable
fuels for transport.
[2] Eurostat European Commission, http://epp.eurostat.ec.europa.eusion.
[3] L. Ott, M. Bicker, H. Vogel, Green Chem. 2006, 8, 214.
[4] M. J. Haas, A. J. Mc Aloon, W. C. Yee, T. A. Foglia, Bioresour. Technol.
2006, 97, 671.
[5] M. Pagliaro, M. Rossi, The Future of Glycerol: New Uses of a Versatile Raw
Material, RSC Green Chemistry Book Series, 2008.
[6] http://theglycerolchallenge.org/index.htm.
[7] Data sources: European Biodiesel Board and HB I.
www.chemsuschem.org
729
F. Dumeignil et al.
[8] C. S. Callam, S. J. Singer, T. L. Lowary, C. M. Hadad. , J. Am. Chem. Soc.
2001, 123, 11743.
[9] G. Paulo da Silva, M. Mack, J. Contiero, Biotechnol. Adv. 2009, 27, 30.
[10] Y. Zheng, X. Chen and Y. Shen, Chem. Rev. 2008, 108, 5253.
[11] M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, C. Della Pina, Angew.
Chem. 2007, 119, 4516; Angew. Chem. Int. Ed. 2007, 46, 4434.
[12] D. A. Simonetti, J. Ross-Hansen, E. L. Kunkes, R. R. Soares, J. A. Dumesic,
Green Chem. 2007, 9, 1073.
[13] R. R. Soares, D. A. Simonetti, J. A. Dumesic, Angew. Chem. 2006, 118,
4086; Angew. Chem. Int. Ed. 2006, 45, 3982.
[14] D. Siano, E. Santacesaria, V. Fiandra, R. Tesser, G. Di Nuzzi, M. Di Serio, M.
Nastasi (ASER), WO2006111 810, 2006.
[15] D. Schreck, W. Kruper, F. Varjian, M. Jones, R. Campbell, K. Kearns, B.
Hook, J. Briggs, J. Hippler (DOW Chemicals), WO2006020 234, 2006.
[16] N. O. V. Sonntag, J. Am. Ceram. Soc. 1992, 75, 795.
[17] H. Kimura, Appl. Catal. A: Gen. 1993, 105, 147; H. Kimura, K. Tsuto, T. Wakisaka, Y. Kazumi, Y. Inaya, Appl. Catal. A 1993, 96, 217.
[18] K. Nabe, N. Izuo, S. Yamada, I. Chibata, Appl. Environ. Microbiol. 1979,
38, 1056.
[19] R. Ciriminna, G. Palmisano, C. Della Pina, M. Rossi, M. Pagliaro, Tetrahedron Lett. 2006, 47, 6993.
[20] A. Yamamoto, Encyclopedia of Chemical Technology 3rd ed., 1978, Vol. 2,
403.
[21] M. P. Malveda, H. Janshekar, K. Yokose, CEH Marketing Research Report
SRI Consulting, Major Amino Acids, June 2006.
[22] M. P. Malveda, H. Janshekar, K. Yokose, Chemical Economics HandbookSRI Consulting, June 2006, 502.5000 B.
[23] G. W. Keulks, L. D. Krenzke, T. M. Notermann, Adv. Catal. 1978, 27, 183.
[24] M. M. Lin, Appl. Catal. A: Gen. 2001, 207, 1.
[25] A. Corma, G. W. Huber, L. Sauvanaud, P. OConnor, J. Catal. 2008, 257,
163.
[26] Petrosil Glycerine Report, June 12, 2009, www.glycerinereport.com.
[27] Schering-Kahlbaum AG, FR 695931, 1930.
[28] H. Groll, G. Hearne (Shell), US 2042224, 1936.
[29] H. Hoyt, T. Manninen (US Ind. Chemicals. Inc.), US 2558520, 1951.
[30] S. Ramayya, A. Brittain, C. DeAlmeida, W. Mok, M. J. Antal, Fuel 1987, 66,
1364.
[31] W. Bhler, E. Dinjus, H. J. Ederer, A. Kruse, C. Mas, J. Supercrit. Fluids
2002, 22, 37.
[32] V. Lehr, M. Sarlea, L. Ott, H. Vogel, Catal. Today 2007, 121, 121.
[33] M. Watanabe, T. Iida, Y. Aizawa, T. M. Aida, H. Inomata, Bioresour. Technol.
2007, 98, 1285.
[34] N. Suzuki, M. Takahashi (KAO Corp.), JP 2006290815, 2006.
[35] A. Neher, T. Haas, A. Dietrich, H. Klenk, W. Girke (Degussa), DE 4238493,
1994.
[36] A. Neher, T. Haas, A. Dietrich, H. Klenk, W. Girke (Degussa), US 5387720,
1995.
[37] A. Neher, T. Haas (Degussa), US 5426249, 1995.
[38] J.-L. Dubois, C. Duquenne, W. Hoelderich, J. Kervennal (Arkema), WO
2006087084, 2006.
[39] J.-L. Dubois, C. Duquenne (Arkema), WO 2006087083, 2006.
[40] S.-H. Chai, H.-P. Wang, Y. Liang, B.-Q. Xu, J. Catal. 2007, 250, 342.
[41] S.-H. Chai, H.-P. Wang, Y. Liang, B.-Q. Xu, Green Chem. 2007, 9, 1130.
[42] Z. H. Chen, T. Lizuka, K. Tanabe, Chem. Lett. 1984, 13, 1085.
730
www.chemsuschem.org
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
T. Lizuka, K. Ogasawara, K. Tanabe, Bull. Chem. Soc. Jpn. 1983, 56, 2927.
S-H. Chai, H-P. Wang, Y. Liang, B-Q. Xu, Green Chem. 2008, 10, 1087.
S.-H. Chai, H.-P. Wang, Y. Liang, B.-Q. Xu, Appl. Catal. A 2009, 353, 213.
L. Ning, Y. Ding, W. Chen, L. Gong, R. Lin, Y. L, Q. Xin, Chin. J. Catal.
2008, 29, 212.
E. Tsukuda, S. Sato, R. Takahashi, T. Sodesawa, Catal. Commun. 2007, 8,
1349.
B.-Q. Xu, S-H. Chai, T. Takahashi, M. Shima, S. Sato, R. Takahashi (Nippon
Catalytic Chem. Ind.), WO 2007058221, 2007.
T. Sato, R. Takahashi (Nippon Catalytic Chem. Ind.), JP 2008088149,
2008.
H. Atia, U. Armbruster, A. Martin, J. Catal. 2008, 258, 71.
M. Okuno, E. Matsunami, T. Takahashi, H. Kasuga, M. Okada, M. Kirishik
(Nippon Catalytic Chem. Ind.), WO 2007132926, 2007.
M. Okuno, E. Matsunami, T. Takahashi, H. Kasuga (Nippon Catalytic
Chem. Ind.), JP 2007301505, 2007.
M. Okuno, E. Matsunami, T. Takahashi, H. Kasuga (Nippon Catalytic
Chem. Ind.), JP 2007301506, 2007.
X.-Z. Li (Shanghai Huayi Acrylic Acid Co), CN 101070276, 2007.
H. Jo, S.-H. Chai, T. Takahashi, M. Shima (Nippon Catalytic Chem. Ind.),
JP 2007137785, 2007.
C.-J. Zhou, C.-J. Huang, W.-G. Zhang, H.-S. Zhai, H.-L. Wu, Z. S. Chao,
Stud. Surf. Sci. Catal. 2007, 165, 527.
Q. Liu, Z. Zhang, Y. Du, J. Li, X. Yang, Catal. Lett. 2009, 127, 419.
E. Matsunami, T. Takahashi, H. Kasuga (Nippon Catalytic Chem. Ind.), JP
2007268363, 2007.
E. Matsunami, T. Takahashi, H. Kasuga (Nippon Catalytic Chem. Ind.), JP
2007268364, 2007.
H. Redlingshoefer, C. Weckbecker, K. Huthmacher, A. Doerflein (Evonik
Degussa), WO 2008092533, 2008.
H. Redlingshoefer, C. Weckbecker, K. Huthmacher, A. Doerflein (Evonik
Degussa), DE 102007004351, 2007.
H. Redlingshoefer, C. Weckbecker, K. Huthmacher, A. Doerflein (Evonik
Degussa), WO 2008092534, 2008.
H. Redlingshoefer, C. Weckbecker, K. Huthmacher, A. Doerflein (Evonik
Degussa), DE 102007004350, 2007.
L. Ning, Y. Ding, W. Chen, L. Gong, R. Lin, Y. L, Q. Xin, Chin. J. Catal.
2008, 29, 212.
W. Suprun, M. Lutecki, T. Haber, H. Papp, J. Mol. Cat. A: Chem. 2009,
309, 71.
H. Kasuga, M. Okada (Nippon Catalytic Chem. Ind.), JP 2008137950,
2008.
Y. Arita, H. Kasuga, M. Kirishiki (Nippon Catalytic Chem. Ind.), JP
2008110298, 2008.
P. OConnor, A. Corma, G. W. Huber, L. Savanaud (Bioecon. Internat.
Holding), WO 2008052993, 2008.
J.-L. Dubois (Arkema), FR 2897058, 2007.
H. Kasuga (Nippon Catalytic Chem. Ind.), JP 2008137952, 2008.
J. Kijenski, A. Migdal, O. Osawaru, E. Smigiera (Inst. Chemii Przemyslowe), EP 1860090, 2007.
J.-L. Dubois (Arkema), WO 2008129208, 2008.