Bioresource Technology 101 (2010) 6225–6229

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Glycerol acetals as anti-freezing additives for biodiesel

Paulo H.R. Silva, Valter L.C. Gonçalves, Claudio J.A. Mota *
Universidade Federal do Rio de Janeiro, Instituto de Química. Av. Athos da Silveira Ramos, 149, CT Bloco A, Cidade Universitária, 21941-909, Rio de Janeiro,
Brazil and INCT de Energia e Ambiente, UFRJ, 21941-909, RJ, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Glycerol acetals from butanal, pentanal, hexanal, octanal and decanal were prepared with the use of
Received 15 October 2009 Amberlyst-15 acid resin as catalyst. The glycerol conversion decreases with the size of the hydrocarbon
Received in revised form 14 January 2010 chain. This fact has been associated with formation of micelles and aggregates of the aldehyde to mini-
Accepted 25 February 2010
mize the interaction between the polar glycerol molecule with the hydrocarbon chain. The Z + E mixture
Available online 20 March 2010
of the acetals with five and six-member rings were produced in all cases. The distribution of the acetal
isomers varied with the reaction time, especially for the long chain aldehydes. Addition of 5 vol.% of
Keywords:
the butanal–glycerol acetal reduced the pour point of animal fat biodiesel (methyl ester) from 18 to
Biodiesel
Glycerin
13 °C. The decrease in the pour point of the glycerol acetals-biodiesel mixtures were dependent on the
Acetals size of the hydrocarbon chain and the percent blended.
Catalysis Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Biofuels are growing in importance due to global warming and
decrease of the fossil fuel reserves. Among these new energy
sources, the biodiesel (Hill et al., 2006; Ma and Hanna, 1999) ap-
pears as one of the most promising and feasible at short term. Its
production and use has been stimulated in many countries, espe-
cially in Europe. Biodiesel is generally produced by transesterifica-
tion of vegetable oils with methanol or ethanol, under base
catalysis conditions (Meher et al., 2006). In Brazil, the Federal
Government has established a mandatory blending of 4 vol.% of
biodiesel in the petrodiesel (B4), starting in 2009. Nevertheless,
this amount will increase to 5 vol.% (B5) in 2010. Together with
ethanol, used in Otto cycle motor vehicles to substitute gasoline,
the increasing use of biodiesel in Brazil places the country as one
of the major producer and user of biofuels in the world.
Biodiesel is normally produced from the transesterification of
vegetable oil. However, in Brazil, about 20% of the biodiesel pro-
duced comes from animal fat. The production of biodiesel involves
the transesterification of a triglyceride molecule with three mole-
cules of methanol or ethanol to afford three molecules of fatty acid
methyl or ethyl esters, the biodiesel themselves, and a molecule of
glycerol or glycerin, produced as byproduct. The world forecast of
glycerol production form biodiesel points to an increasing supply,
with net global production around 1.2 million tons by 2012 (Zhou
et al., 2008). In Brazil, the estimated amount of glycerin production
with the implementation of B4 is 260 thousand tons per year, but
* Corresponding author.
E-mail address: cmota@iq.ufrj.br (C.J.A. Mota).
this production will increase in 2010 with the introduction of B5.
By contrast, the present glycerin consumption in Brazil, mostly
for personal care, cosmetics and food usage, is about 30 thousand
tons per year. Therefore, it is imperative to find new applications
for the excess of glycerin produced from biodiesel.
The chemical transformation of glycerol into more economic
valuable products has attracted the attention of the scientific com-
munity in recent years (Behr et al., 2008; Jérôme et al., 2008; Pagli-
aro et al., 2007). Among the possible glycerol derivatives, which
find applications in fuel, plastic and fine chemical industries, we
may quote ethers, esters, diols and acetals compounds.
The treatment of glycerol with isobutene under acid catalysis
conditions affords glycerol-tert-butyl ethers, which can be used
as fuel additives (Karinen and Krause, 2006). Etherification of glyc-
erol with alcohols was also reported in the literature (Gu et al.,
2008; da Silva et al., 2009a; Klepacova et al., 2005). Esterification
of glycerol with fatty acids and a proper heterogeneous catalysts
affords monoacylglycerides in high selectivity, which are used as
surfactants and in the food industry (Cho et al., 2006; Kharchafi
et al., 2006). Gonçalves et al. (2008) reported the acetylation of
glycerol over various heterogeneous acid catalysts to produce
mono, di and triacetin. These esters may find applications that go
from monomer for polyester production to fuel additives. Hydroge-
nation of glycerol to propylene glycol over metal supported cata-
lysts is a reaction widely studied in the literature (Dasari et al.,
2005; Kusunoki et al., 2005; Miyazawa et al., 2006). It may become
an important industrial process for production of propylene glycol
from a renewable feedstock. Yet, hydrogen and hydrocarbons of
gasoline and diesel range may be produced from glycerol through
reforming (Simonetti et al., 2007; Soares et al., 2006).

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.02.101
6226 P.H.R. Silva et al. / Bioresource Technology 101 (2010) 6225–6229
R R
OH
"H+" O O
HO OH + RCHO O O
+ + H2O
OH
OH
Scheme 1. Acid-catalyzed acetalization of glycerol with aldehydes of different
chain length (R = n-C3H7; n-C4H9; n-C5H11; n-C7H15; n-C9H19).
Glycerol acetals may find applications as fuel additives (Garcia
et al., 2008), surfactants (Piasecki et al., 1997), flavours (Climent
et al., 2002, 2004) and disinfectants (Sari et al., 2004), among oth-
ers. We recently reported the use of water-resistant heterogeneous
acid catalysts for the acetalization of glycerol with formaldehyde
solution and acetone (da Silva et al., 2009b). We wish to report
now, a study of the acetalization of glycerol with aldehydes of dif-
ferent hydrocarbon chain (Scheme 1) and its use as anti-freezing
agents for biodiesel.
2. Experimental
A round bottom flask was loaded with 0.36 g of Amberlyst-15
acid resin, corresponding to 1.5 mmol of acid sites. The flask was
then transferred to an oven and the catalyst was activated for 2 h
at 120 °C. After cooling to room temperature in an empty glass
box kept under vacuum, 2.0 g (21.7 mmol) of glycerol and
22.8 mmol of the aldehyde (butanal, pentanal, hexanal, octanal
and decanal) were added to the flask containing the pre-activated
catalyst, together with 5 mL of dimethylsulfoxide (DMSO) as sol-
vent and dimethylformamide (DMF) used as internal standard.
The molar ratio of glycerol to aldehyde was 1:1.05. The system
was then stirred with a magnetic bar and heated to 85 °C. Samples
were removed from the reaction medium to obtain the kinetics
from the data of gas chromatography analysis.
The glycerol acetals were also produced in higher amounts
using 40 g of glycerol and the same molar ratio of aldehydes used
in the kinetic experiments. In this case, the reactions were carried
out without solvent at 85 °C for 48 h. The products were distilled
under reduced pressure and characterized by gas chromatography
coupled with mass spectrometry. No separation of the four acetal
isomers (five and six-member rings, Z + E isomers) was attempted.
The mixture of the acetals were used, as such, in the preparation of
the mixtures containing 1 and 5 vol.% of the acetals with animal fat
biodiesel (methyl esters). The pour point determinations of the
acetals, pure biodiesel and of the mixtures were performed accord-
ing to the ASTM D6749 method (2007).
3. Results and discussion
The acetals formed were (Z + E)-(2-propyl-1,3-dioxolan-4-yl)
methanol and (Z + E)-2-propyl-1,3-dioxan-5-ol in the reaction with
butanal, (Z + E)-(2-butyl-1,3-dioxolan-4-yl)methanol and (Z + E)-
2-butyl-1,3-dioxan-5-ol in the reaction with pentanal, (Z + E)-2-
(pentyl-1,3-dioxolan-4-yl)methanol and (Z + E)-2-pentyl-1,3-diox-
an-5-ol, in the reaction with hexanal, (Z + E)-2-(heptyl-1,3-dioxo-
lan-4-yl)methanol and (Z + E)-2-heptyl-1,3-dioxan-5-ol, in the
reaction with octanal. Finally, the acetals (Z + E)-2-(nonyl-1,3-
dioxolan-4-yl)methanol and (Z + E)-2-nonyl-1,3-dioxan-5-ol were
formed in the reaction with decanal. In all cases, four isomeric ace-
tals were observed, the Z + E isomers of the five-member ring and
six-member ring acetals. In addition, there are the enantiomers,
but we were unable to separate them in the conditions used in
the gas chromatography analysis. For simplicity, we will refer to
glycerol/aldehyde acetals for the mixture containing the four
isomers.
Fig. 1 shows the glycerol conversion against reaction time for
the acetalization of butanal, pentanal, hexanal, octanal and decanal
over Amberlyst-15 acid resin. One can see that conversion de-
creases with the size of the aldehyde chain. The highest conversion
was achieved in the reaction with butanal after 120 min (around
75%), whereas the lowest conversion was observed in the reaction
with decanal (around 10%) after the same time period. Analysis of
the reaction medium after 24 h indicated a glycerol conversion of
85% in the reaction with butanal, 81% with pentanal, 77% for ace-
talization with hexanal, 53% with octanal and 17% for reaction with
decanal. These results indicated that most of the conversion takes
place within 2 h of reaction time. Fig. 2 shows the selectivity to the
Z + E isomers of the five and six-member ring acetals. One can see
that the distribution is not significantly affected by the structure of
the aldehyde at the beginning of the reaction, yielding about 80% of
the five-member ring acetal (Z + E) and 20% of the six-member ring
acetal (Z + E) in reactions of glycerol with butanal and pentanal.
This distribution is similar to what was found in other studies of
glycerol acetalization (Deusch et al., 2007; da Silva et al., 2009b)
and may reflect the kinetic control. For hexanal and octanal the
distribution approaches 60% of the five-member ring acetal
(Z + E) and 40% of the six-member ring acetal (Z + E), whereas for
acetalization with decanal, a 1:1 distribution of the acetal isomers
was observed after 120 min of reaction. The isomer distribution in
the reactions with aldehydes of higher hydrocarbon chains tends
to favor the thermodynamically more stable six-member ring ace-
tal, especially for longer reaction times. This might be due to the
lower conversion observed in these reactions. The formed acetal,
which is more polar than the aldehydes, may undergo acid-cata-
lyzed isomerization, affording a distribution with a higher content
of the six-member ring acetal.
We initially thought that diffusion problems inside the catalyst
pore structure might be affecting the glycerol conversion in the
acetalization with the aldehyde of longer hydrocarbon chains.
These aldehydes might diffuse slower inside the pores affecting
the overall conversion. To check this possibility we carried out
the reaction without catalyst. The results are presented in Fig. 3.
One can see that, although the conversions were significantly low-
er within the same reaction time, the same pattern of the catalyzed
reactions was observed. The glycerol conversion decreases as the
size of the aldehyde chain increases. Therefore, it is clear that the
catalyst pore network has little or no effect in the conversion.
The most plausible explanation is related with the aggregation of
80
60
Conversion %
40
20
0
0 20 40 60 80 100 120
Time (min)
Fig. 1. Conversion of glycerol in the acetalization with different aldehydes at 70 °C
catalyzed by Amberlyst-15: (j) butanal, ( ) pentanal, ( ) hexanal, ( ) octanal, ()
decanal.
 P.H.R. Silva et al. / Bioresource Technology 101 (2010) 6225–6229 6227

100 100
A
B
80 80
Selectivity %

Selectivity %
60 60

40 40

20 20

0 0

0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)

80 80
C D
70 70

60 60

50 50
Selectivity %
Selectivity %

40 40

30 30

20 20

10 10

0 0

-10 -10
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)

70
E
60

50
Selectivity %

40

30

20

10

-10
0 20 40 60 80 100 120
Time (min)

Fig. 2. Selectivity to the Z + E five-member acetal (j) and Z + E six-member acetal ( ) in the reaction of glycerol with butanal (A), pentanal (B), hexanal (C), octanal (D) and
decanal (E) over Amberlyst-15 as catalyst at 70 °C.

the aldehyde in the reaction medium. Glycerol and DMSO are polar
molecules and together with the water released upon acetalization
make the reaction medium not so effective for the dissolution of
the aldehydes. Thus, we suggest that the aldehyde molecules
aggregate or form micelles, to minimize the repulsive interactions
between the apolar hydrocarbon chain and the polar reaction med-
ium. This behavior would be more pronounced with the aldehydes
of longer hydrocarbon chains, explaining the reactivity pattern.
This aggregation decreases the conversion because the interaction
between the glycerol and the aldehyde is minimized.
Table 1 shows the pour point temperature of the glycerol ace-
tals and their mixtures with animal fat biodiesel. One can see that
6228 P.H.R. Silva et al. / Bioresource Technology 101 (2010) 6225–6229

perature, being a good alternative for absorbing the glycerin

formed in biodiesel production.
20

4. Conclusions
15
Conversion %

Glycerol acetals of different hydrocarbon chains can be effi-

ciently produced by reaction of glycerol with butanal, pentanal,
hexanal, octanal and decanal, with use of Amberlyst-15 acid resin.
10 The conversion decreases with the size of the aldehyde chain, pos-
sibly due to aggregation of the hydrocarbon chain to minimize
repulsive interactions with the polar environment.
5 The glycerol acetals were blended with animal fat biodiesel to
study its performance as anti-freezing agents. The results indicated
that addition of 5 vol.% of butanal/glycerol acetal reduces the pour
point of animal fat biodiesel in 5 °C.
0
0 20 40 60 80 100 120
Acknowledgements
Time (min)

Fig. 3. Conversion of glycerol in the acetalization without catalyst at 70 °C: (j) Authors thank FINEP, CNPq and FAPERJ for financial support.
butanal, ( ) pentanal ( ) hexanal, ( ) octanal, () decanal. Authors also thank Mr. L.G. Marques, from the biodiesel pilot plant
of COPPE/UFRJ for providing the animal fat biodiesel sample used
in the experiments.

Table 1
Pour point temperature of the glycerol acetals animal fat biodiesel blends.
a
Product Pour point (°C)
Glycerol/butanal acetal 66
Glycerol/pentanal acetal 66
Glycerol/hexanal acetal 63
Glycerol/octanal acetal 39
Glycerol/decanal acetal 12
Animal fat biodiesel 18
Animal fat biodiesel-glycerol/butanal acetal (1 vol.%) 18
Animal fat biodiesel-glycerol/butanal acetal (5 vol.%) 13
Animal fat biodiesel-glycerol/pentanal acetal (1 vol.%) 18
Animal fat biodiesel-glycerol/pentanal acetal (5 vol.%) 14
Animal fat biodiesel-glycerol/hexanal acetal (1 vol.%) 18
Animal fat biodiesel-glycerol/hexanal acetal (5 vol.%) 15
Animal fat biodiesel-glycerol/octanal acetal (1 vol.%) 18
Animal fat biodiesel-glycerol/octanal acetal (5 vol.%) 15
Animal fat biodiesel-glycerol/decanal acetal (1 vol.%) 18
Animal fat biodiesel-glycerol/decanal acetal (5 vol.%) 18
a
Brackets stands for the volume percent of the glycerol acetal blended in the
biodiesel.
all acetals have pour point temperatures below 0 °C. The animal fat
biodiesel (methyl esters) has one of the highest pour point temper-
ature (Knothe et al., 2006). The reduction in pour point tempera-
ture is proportional to the size of the hydrocarbon chain of the
acetal. The butanal/glycerol and pentanal/glycerol acetals showed
the largest reduction in pour point among the blends tested. How-
ever, this effect is only noticed with 5 vol.% of the acetals. Addition
of 1 vol.% did not lead to noticeable reductions in pour point.
In Brazil, about 20% of the biodiesel used comes from animal fat
and freezing problems may occur during winter, especially in the
southern part of the country. Therefore, additives for reducing
the pour point are necessary. The results indicated that 1 vol.%
mixture of glycerol acetals with animal fat biodiesel did not pro-
duce significant changes in the pour point temperature, but a
5 vol.% blend leads to a significant reduction of the pour point.
The addition of 5 vol.% butanal/glycerol acetal in the animal fat bio-
diesel led to a reduction of 5 °C in the pour point temperature,
whereas the decanal/glycerol acetal was ineffective for reducing
the pour point. In general, the reduction in pour point temperature
was more pronounced as the size of the aldehyde chain was re-
duced. These results indicated that the butanal/glycerol acetal
might be blended with the biodiesel to reduce the pour point tem-
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