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DOI 10.1007/s11244-010-9464-1
ORIGINAL PAPER
1 Introduction
Nowadays, the synthesis of biodiesel has been receiving
more attention all over the world since the raw materials
(vegetable oils and animal fats) are often locally available,
renewable, and environmental friendly. In addition, biodiesel can be used without modification of diesel engines
[1, 2]. The transesterification of triglycerides (TGs) and
esterification of free fatty acids (FFAs) contained in vegetable oils and animal fats are the two main reactions for
converting vegetable oils and animal fats into biodiesel. To
make biodiesel economically competitive with diesel fuel
derived from crude oil, low cost feedstocks (feedstocks
with high FFAs) such as animal fats, yellow grease (used
cooking oil) (FFAs less than 15%), and brown grease (trap/
sewer grease) (FFAs more than 15%) are attracting attention to replace costly refined vegetable oil as the raw
material for biodiesel synthesis [36]. Use of solid acid
catalysts can also greatly improve the economics of biodiesel synthesis because of their ability to be reused and the
decreased need for many separation steps. In particular,
solid acid catalysts can carry out transesterification and
esterification simultaneously using low cost feedstocks
without multiple reaction and post-treatment steps, greatly
improving the economics of biodiesel production [712].
This is an advantage of the use of solid acid catalysts for
biodiesel synthesis over that of solid base catalysts. However, solid base catalysts are more active and can be used at
lower temperatures. Lopez et al. [13]. reported that sulfated
zirconia (SZ) and Nafion resin catalysts catalyzed biodiesel
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784
123
2 Experimental
2.1 Materials
Commercial amorphous tungstated zirconium hydroxide
precursor (XZ01251) containing 16 wt% WO3 was kindly
provided by Magnesium Electron, Inc. (MEI, Manchester,
UK). The WZ precursor was activated by calcination under
static air (zero grade) at 800 C for 2 h [17]. The activated
WZ catalyst was placed inside sealed containers and stored
in a desiccator until use.
Tricaprylin (TCp) (glyceryl trioctanoate, 99%) and
anhydrous methanol (99.8%) were obtained from SigmaAldrich. Dicaprylin (DCp) (97%, Sigma-Aldrich), monocaprylin (MCp) (99%, Sigma-Aldrich), glycerol (GL)
(99%, Acros), caprylic acid (HCp) (99%, MP Biomedicals
Inc.) and methyl caprylate (MeCp) (99%, Sigma-Aldrich)
were employed as reference compounds for gas chromatography (GC) calibration. All reference chemicals were
chromatographically pure and used as received without
further purification. Double distillation and deionization
were used to obtain high purity water for hydrolysis. A
mixture of hexane (99.9%, Fisher Scientific) and dodecanoic acid (HLa) (lauric acid, 98% from Sigma-Aldrich) and
hexane were utilized as a solvent to carry out the kinetic
measurements for hydrolysis and transesterification,
respectively. Methyl valerate (99%, Sigma-Aldrich) and
2-isopropanol (99.9%, Fisher Scientific) HPLC grade were
used for GC analysis as an internal standard and a solvent,
respectively.
785
123
786
(a)
12
% TCp conversion
123
8
6
4
2
1790 rpm
2140 rpm
2385 rpm
10
20
30
40
50
60
Time (min)
14
(b)
12
% TCp conversion
10
10
8
6
4
non sieved
0.178-0.251 mm
0.104-0.152 mm
2
0
0
10
20
30
40
50
60
Time (min)
787
18
(a)
16
% TCp conversion
14
12
10
8
6
4
1790 rpm
2140 rpm
2385 rpm
2
0
0
10
20
30
40
50
60
Time (min)
18
(b)
16
% TCp conversion
14
12
10
8
6
non sieved
0.178-0.251 mm
0.104-0.152 mm
4
2
0
0
10
20
30
40
50
60
Time (min)
conversion after 1 h) was observed in all cases. The maximum % TCp conversions obtained with WZ in place at
time zero (at the end of the start-up period) were 0.5 and
2% for hydrolysis and for transesterification, respectively.
Table 1 Comparison of WZ catalyzed hydrolysis of TCp (H2O:TCp = 1:1)a and transesterification of TCp with methanol (MeOH:TCp = 1:1)a
Reaction
Reactivity
% TCp conv.b
Initial ratec
(mmol/L-min)
Initial ratec,d
(mmol/g cat-min)
Initial TOFc,e
(min-1)
@10 min
@1 h
@10 min
Hydrolysis
4.9
12.6
2.6
7.9
5.7
0.10
0.61
Transesterification
5.9
15.5
3.6
10.0
5.25
0.09
0.56
Initial rates were calculated using data below 10% TCp conversion and represent the rate of TCp conversion, experimental error = 0.1
Initial rate per gram of catalyst (mmol/g cat-min) was calculated by dividing the initial rate by catalyst loading (mg/mL)
Initial TOF was calculated by dividing the initial rate per gram of catalyst by the acid site concentration of the catalyst per gram
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788
(a)
R2 = 0.9996
-5.5
-6.0
ln (r0 )
-6.5
-7.0
data
linear regression
-7.5
2.45
-4.0
% Selectivity
2.60
2.65
2.70
(b)
R2 = 0.9987
-4.5
70
60
MCp
ln (r0)
-5.0
DCp
-5.5
GL
50
40
-6.0
data
linear regression
30
20
-6.5
2.45
10
2.50
2.55
2.60
2.65
2.70
1/T x 10 3 (1/K)
hydrolysis
transesterification
123
2.55
1/T x 10 3 (1/K)
80
2.50
789
Table 2 Orders of reaction for WZ catalyzed hydrolysis of TCp and transesterification of TCp with methanol at 130 C for various reactant
molar ratios
ac
Apparent order
Water or MeOH:TCp ratio
a
Hydrolysis rinitail
b
a
CTCp
CW
b
a
Transesterificationb rinitail CTCp
CM
bg
0.30.8d
0.81.2e
1.21.7f
0.60.8h
1.34
1.13
0.98
0.85
0.66
e
F
0.81.2i
1.27.0j
1.15
0.17
-0.72
123
790
(a)
-4.0
R2 = 0.9891
-4.8
0.50
0.33
-3.8
-4.6
(a)
-4.2
-4.4
-5.0
ln (r0)
ln (r0)
-4.6
-5.2
-5.4
-4.8
-5.0
-5.2
-5.6
R2 = 0.9947
-5.4
-5.6
data
linear regression
-5.8
-6.0
-0.6
-6.0
0.0
0.1
data
linear regression
-5.8
0.2
0.3
0.4
-0.4
-0.2
0.0
0.8
1.2
0.4
0.6
0.8
1.0
1.2
1.4
0.8
2.0
3.0
5.0
6.0
7.0
-4.8
-4.0
(b)
(b)
R2 = 0.9908
ln (r0)
-5.2
-5.0
-5.4
-5.6
-5.8
-5.5
data
linear regression
-6.0
-0.4
data
-5.0
-4.5
ln (r0)
0.2
ln [TCp]
ln [TCp]
-0.2
0.0
-6.0
0.2
0.4
0.6
0.8
ln [H 2O]
-6.2
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
ln [MeOH]
the apparent reaction orders for hydrolysis for TCp (A) and
water (B) based on slopes of the plots in Fig. 5a, b were
a = 1.34 and b = -1.15 for water-to-TCp molar ratios of
0.81.2.
The reaction orders for non-catalytic reaction in the
temperature range of 100250 C [24, 33, 36] and for
123
0.10
R2 = 0.9977
791
hydrolysis
transesterification
0.08
0.06
0.04
0.02
0.00
0
50
100
150
200
TCp S $ TCp S
KM
M S$ M S
KR
TCp S M $ E S DCp
KE
E S$ E S
T1
T2
T3
T4
123
792
kR KTCp CTCp CM
1 KM CM KTCp CTCp
123
TCp S $ TCp S
KW
W S$ W S
KR
FFA S $ FFA S
793
H1
H2
H3
H4
kTCp CTCp
1 KW CW
4 Conclusions
The fundamental aspects of both liquid-phase hydrolysis
and transesterification with low molar ratios of water (or
methanol)-to-TCp catalyzed by WZ have been investigated
at 100130 C and 120180 psi. The kinetic measurements
were obtained under conditions where external and internal
mass transport limitations were able to be ruled out. The
catalytic activities of both hydrolysis and transesterification
were comparable based on the initial TOFs with 100%
selectivity to predicted products. Transesterification tended
to produce more final products (GL and methyl esters) than
hydrolysis did in the same time period. The apparent
activation energy of transesterification was 2-fold higher
than that of hydrolysis in the temperature range of 100
130 C. For hydrolysis at low water-to-TCp ratios (0.8
1.2) necessary to maintain single phase behavior, the
reaction was positive order in TCp and negative order in
water. For transesterification, at similar methanol-to-TCp
ratios, the apparent order of reaction for TCp was also
positive, as was that for methanol as well (slightly positive). The apparent order of reaction of methanol transitioned to negative order only for methanol-to-TCp ratios
[1.2. The mechanism for both reactions seem to be similar
and best described as EleyRideal single site mechanisms.
Reaction seems to occur between the adsorbed protonated
TCp and methanol (water) from the liquid phase. Water,
being more strongly adsorbed than methanol, impacts the
reaction negatively at a lower concentration (methanol or
water-to-TCp ratio). Methanol, on the contrary, seems to
inhibit by blocking of active sites only at a higher concentration. As the results for transesterification suggest, as
the concentration of the polar reactant increases, the RDS
shifts from surface reaction limited to being TCp adsorption limited. The same probably happens for hydrolysis as
well although at much lower reactant ratios.
Acknowledgements
on Higher Education
Animal Co-Products
Clemson University.
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