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Departamento de Procesos y Tecnologa, Universidad Autnoma MetropolitanaCuajimalapa, Artificios 40, 01120 Mexico D.F., Mexico, E-mail:
asales@correo.cua.uam.mx, mtlopez@correo.cua.uam.mx
b
Colegio de Ingeniera de Alimentos, Facultad de Ingeniera Qumica, Benemrita
Universidad Autnoma de Puebla, Ciudad Universitaria, 72570 Puebla Pue., Mexico,
E-mail: gloryaca@yahoo.com.mx
c
Colegio de Ingeniera Qumica, Facultad de Ingeniera Qumica, Benemrita
Universidad Autnoma de Puebla, Ciudad Universitaria, 72570 Puebla Pue., Mexico,
E-mail: oosdaza@yahoo.com
Abstract
The knowledge of critical properties, densities and viscosities (in function of
temperature) of the main fatty compounds involved in the biodiesel production are
essential for process engineering. Even though several studies have reported properties
for some compounds (mainly for fatty acids), there are still a necessity of expanding the
databank gathered from literature. In contrast to traditional methods based on
temperature-dependence correlations, in this work, methodologies for property
prediction based on group contribution methods are presented.
Keywords: Group contribution, thermodynamic property estimation, oil compounds,
biodiesel compounds.
1. Introduction
Biodiesel fuels derived from vegetable oils or animal fats, which are used as substitutes
for conventional petroleum fuel in diesel engines, have recently received increased
attention. This interest is based on a number of properties of biodiesel including its
biodegradability and the fact that it is produced from a renewable resource. While the
high density and viscosity of vegetable oils and animal fats tends to cause problems
when used directly in diesel engines, if oils and fats are transesterified using short-chain
alcohols, the resulting methyl esters (biodiesel) have viscosities that are closer to
petroleum-based diesel fuel. So that the knowledge of their physical properties as a
function of temperature and reliable predictive models is of great practical interest for
process engineering, considering the demand of computational tools for process design,
evaluation, simulation, optimization, control, etc.
Recently much work has been done on measuring and estimating density and viscosity
of fatty compounds, vegetable oils and biodiesel fuels as a function of temperature. In
most cases, polynomial correlations or specific equations (like Rackett equation for
density and Vogel equation for viscosity) were generated by adjusting each set of
experimental data to a specific compound. More generalized models were developed for
M. Sales-cruz et al.
fatty acids, triacylglycerols, fatty esters and their mixtures. But few of them used the
widely concept of group contribution, e.g. for viscosity of fatty acids (Yinghua et al.,
2002; Ceriani et al., 2007), for melting points and fusion enthalpies of triglycerides
(Zeberg-Mikkelsen and Stenby, 1999), and for vapor pressure of fatty acids (Ceriani and
Mirelles, 2004).
In particular, the Rackett method as modified by Spencer and Danner (1972) was
recommended for density prediction of pure hydrocarbons, organic liquids and
mixtures. However, this method requires the critical temperature and pressure of the
liquid, and also an experimentally regressed parameter (ZRA), which is reported for fatty
acids (Halvorsen et al., 1993) but is unknown for triacylglycerols and methyl esters.
The objective of this work is the prediction of critical properties, density and viscosity
of the main compounds involved in vegetable oils, animal fats and biodiesel fuels
(namely, fatty acids, triacylglycerols and methyl esters), by means of predictive
methods based on group contribution. Three contribution-group methods were tested for
critical property prediction, which are available in commercial simulators (like Aspen
Plus and ICAS). Rackett method was employed for density prediction, based on the
previous critical property estimation. Ceriani et al. (2007) method was applied for
viscosity prediction. All properties are evaluated as a function of temperature, and the
results are in very good agreement with experimental data obtained in this work and
other studies reported. The main contribution of this work is the generation of a pure
component databank for several fatty acids (FA), triacylglycerols (TAG) and fatty acid
methyl esters (FAME), together with a group contribution methodology that can be
applied to other no reported compounds. In addition, the pure component data can be
used to ascertain mixture property values and to estimate oil and biodiesel properties.
Predicting critical properties, density and viscosity of fatty acids, triacylglycerols and
methyl esters by group contribution methods
RT 1+(1Tr ) 7
,
Vs = c Z RA
Pc
2
Vs =
(1)
Where Vs, R, M, Vc, Tc and Pc are the molar volume of saturated liquids, the gas ideal
constant, the molecular weight, and the (estimated) critical volume, temperature and
pressure, respectively. ZRA is the Rackett parameter, a correlating parameter unique to
each compound determined experimentally. Values of ZRA for FA were reported in
Halvorsen et al. (1993), which were calculated by solving the modified Rackett equation
(1) directly for ZRA with a reference density at a given temperature. However, there are
no values reported for TAG and FAME. In this work, values of parameter ZRA for all
compounds were estimated by a least-squares fitting of available experimental values
(from this research and other reported studies) of density as a function of temperature.
2.3. Viscosity prediction
The viscosity prediction is based on the group contribution model, proposed by Ceriani
et al. (2007), for fatty compounds (such as FA, FAME and TAG):
B
B
k
k
Q = 1q + 2 ,
q = +
ln T T ,
1 = f 0 + N c f1 ,
(2)
2 = s0 + N cs s1
M. Sales-cruz et al.
OOO; trilinolein, LiLiLi; trilinolenin, LnLnLn; and triricinolein, RRR. The names of
FAME are the methyl esters of the aforementioned FA.
For the validation of predicted values for all properties, experimental data available
from this work and other reported studies were used to evaluate the average relative
deviation (ARD) according to the relationship:
ARD ( % ) =
100,
Di =
exp calc
exp
( N : number of points )
(3)
MG1
6.83
10.97
3.64
CG1
1.21
4.12
3.82
FA
JR1
4.99
5.71
4.10
TAG
CG2
1.27
5.74
4.01
JR2
3.91
6.42
4.60
MG1
0.77
0.00
3.49
CG1
6.93
2.71
3.22
FAME
JR1
1.45
2.41
3.95
CG2
6.93
2.71
3.22
JR2
0.39
2.39
4.09
C10:0
C12:0
C14:0
C16:0
C18:0
C18:1
C18:2
C18:3 C18:1(OH)
811.21
12.79
1061.2
0.20
793.40
7.43
1609.7
0.18
CCC
LLL
MMM
PPP
SSS
OOO
LiLiLi LnLnLn
939.25
3.11
3188.1
0.13
RRR
964.18
3.36
3271.9
0.14
Predicting critical properties, density and viscosity of fatty acids, triacylglycerols and
methyl esters by group contribution methods
Table 4. Estimated properties for FAME: CG method (Tc in K, Pc in bar, Vc in cm3/mol)
C9:0
C11:0
C13:0
C15:0
C17:0
C19:0
C19:1
C19:2
C19:3 C19:1(OH)
759.83
11.41
1115.1
0.20
FA
ZRA
TAG
ZRA
FAME
ZRA
C8:0
C10:0
C12:0
C14:0
C16:0
C18:0
C18:1
C18:2
C18:3
C18:1(OH)
0.24920
0.24426
0.23983
0.23466
0.22953
0.22467
0.21939
0.22550
0.22840
0.22429
CCC
CaCaCa
LLL
MMM
PPP
SSS
OOO
LiLiLi
LnLnLn
RRR
0.21412
0.20990
0.19336
0.19308
0.18554
0.18332
0.18168
0.17860
0.17432
0.18951
C9:0
C11:0
C13:0
C15:0
C17:0
C19:0
C19:1
C19:2
C19:3
C19:1(OH)
0.25938
0.25124
0.24397
0.23757
0.23154
0.22559
0.22134
0.21606
0.21261
0.22413
FA (mPa.s)
0.88
-3
0.86
C10:0
C12:0
C14:0
C18:0
0.84
-3
TAG (g cm )
0.82
C10:0
C12:0
C14:0
C18:0
10
100
0.96
LLL
CCC
PPP
SSS
0.94
0.92
0.90
TAG (mPa.s)
FA (g cm )
CCC
LiLiLi
PPP
SSS
10
FAME (mPa.s)
-3
FAME (g cm )
0.88
0.86
0.84
C11:0
C13:0
C15:0
C19:0
0.82
0.80
20
40
60
T (C)
80
100
120
C11:0
C13:0
C15:0
C19:0
10
1
20
40
60
T (C)
80
100
120
M. Sales-cruz et al.
It is worth of mention that although only pure compounds properties have been
predicted, they can be used to predict mixture properties by mixing rules. For instance,
Rackett mixture density (Spencer and Danner, 1973) (Eq. 4a, b) and the modified Kays
rule for viscosity (Eq. 4c) can be applied (xi is the mole fraction of each compound):
m =
1
Vm
1+ (1T ) 2 7
r
xi M i , Vm = A R Z RA ,m
i =1
lnm = xi lni
(4a, b, c)
i =1
5. Acknowledgements
We acknowledge to Prof. Rafiqul Gani for the use of ICAS software. This work has
been supported by CONACyT research grants (Projects 84535 and 91222).
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