Property estimation for design, simulation and analysis

of biodiesel process systems: Review and Plant

Simulation
Fabrcio Rodrigues, Adilson J. de Assis
a
Faculty of Chemical Engineering, Federal University of Uberl
andia, Av. Jo
ao Naves de

Avila,
2121, Bloco 1K, Campus Santa M
onica, CEP: 38400-901, Uberl
andia, MG, Brazil

Keywords: Biodiesel property estimation, Biodiesel process simulation,

CAPE-OPEN process simulators

Corresponding author. Tel.: +55 3291 4189

Email address: ajassis@ufu.br (Adilson J. de Assis)

Preprint submitted to Journal of Thermodynamics

July 14, 2015

Property estimation for design, simulation and

analysis of biodiesel process systems: Review and
Plant Simulation
Abstract:
Biodiesel is an attractive alternative to fossil fuels in several aspects (e.g.,
sustainability), but requires an economic and efficient production process to
be viable. Our objectives in this paper are to discuss, assess, select property
estimation methods, and develop a computational tool for biodiesel process
systems analysis and design. We show that appropriate analysis of the property models behaviors provides a powerful selection tool in the face of scarce
experimental data. We do an extensive review of the property estimation
methods for the compounds involved in biodiesel process systems and we
show the importance of consistency tests when constructing property models. Additionally, the identification of the best estimation methods is not
enough if the methods are not computationally available; thus, the generated
knowledge is implemented in a computational tool that is CAPE-OPEN compliant, thereby providing a reliable environment for the application of process
synthesis and design techniques to biodiesel process systems.
1. Introduction
Biodiesel has numerous advantages over fossil fuels: it yields much more
energy than it uses for its production (372% more than bioethanol) (Hill
et al., 2006), is easily transported because of its low volatility (Krawczyk,
1996), can be produced from numerous different renewable sources (Ma and
2

Hanna, 1999), and can be added, in small amounts (1-2w%), to regular diesel
fuel with poor lubricant properties to yield an acceptable fuel (Gerpen, 2005).
Nonetheless, numerous obstacles to its production and consumption exist;
the primary obstacle is its high cost, which stems from the fact that most
existing processes can only use high value raw materials (Ma and Hanna,
1999; Zhang et al., 2003b).
Although many governments offer subsidies to make the production of
biodiesel cost effective, there is a strong need to improve the process economics. The application of process synthesis and design techniques (Biegler
et al., 1997) can contribute to process profitability while simultaneously amplifying the social and environmental benefits of biodiesel. Energy savings
of approximately 50% and net present cost reductions of 35% have been
achieved in industries (Siirola, 1996), and several other examples of successful industrial applications and best practices of process synthesis and design
methods and tools have been reported (Harmsen, 2004). However, most, if
not all, of these techniques require knowledge of a set of physical and chemical properties that are currently not widely available for the compounds
involved in biodiesel processing.
The complex nature of some molecules (typical triglycerides contain more
than 50 carbons with numerous unsaturations present) and the experimental difficulties (and impossibilities) of obtaining experimental data for some
properties (e.g., critical temperature due to degradation) requires the application of more refined theories to capture the physicochemical behavior
of the involved molecules. Several estimation methods have been developed
and represent a practical way to fill this gap. Many authors have reviewed

this field (Su et al., 2011; Daz-Tovar et al., 2011; Chang and Liu, 2009);
however, none of these authors have appropriately discussed the behavior of
such property models. For example, some property models fit experimental
data very well for some compounds, but for others with no or little experimental data available, the models present inconsistencies (e.g., heat capacity
decreases with increasing temperature) that a purely statistical analysis is
not able to identify.
Therefore, our objectives in this paper are to discuss, assess, and select property estimation methods to demonstrate that consistency tests of
the property models provides a powerful selection tool in the face of scarce
experimental data. Finally, the identification of the best estimation methods is not enough if the selected methods are not computationally available;
thus, the generated knowledge is implemented in a computational tool that
is CAPE-OPEN compliant, thereby providing a reliable environment for the
application of process synthesis and design techniques to biodiesel process
systems.
2. Computer-aided tools developed for the analysis
The compounds present in biodiesel process systems can be categorized
into short-chain alcohols (e.g., methanol and ethanol), glycerol, acylglycerides (AG), fatty acids (FA), and alkyl esters (AE). The properties of shortchain alcohols and glycerol are usually included in common process simulators
and databases, and the first step toward the analysis was the identification of
220 relevant compounds (29 fatty acids, 69 triglycerides, 40 diglycerides, 15
monoglycerides, 29 fatty acid methyl esters and 29 fatty acid ethyl esters).
4

Figure 1: Concept of BioPES

The next and more time-consuming step was an extensive literature review
to gather information regarding compounds, important properties, and stateof-the-art estimation methods. To manage and organize the information, a
database was created in Microsoft Access and implemented in C#, resulting
in a software named BioPES (Biodiesel Property Estimation System) that
offers help as illustrated in Figure 1 (the software can be obtained by the
reader by contacting the authors).
3. Property estimation model analysis
To organize and simplify the literature review, we classified the properties
as primary (those that depend only on the molecular structure), secondary
(those that cannot be explicitly calculated just from the structural information and usually require knowledge of other properties), and temperaturedependent properties, as proposed by Gani and Constantinou (1996). Several state-of-the-art property estimation methods were identified for each of
5

Figure 2: General molecules of saturated (a) fatty acids, (b) simple triglycerides, (c) fatty
acid methyl esters and (d) fatty acid ethyl esters.

the properties analyzed. These methods can be also classified on the basis of
their approach to estimate the properties. Most of the considered methods
are based on the group-contribution approach; a complete classification of
the estimation methods is presented in Tables 2 and 10.
The compounds analyzed are also classified as FA, AG, fatty acid methyl
esters (FAME), or fatty acid ethyl esters (FAEE). The compounds in these
four classes can be divided into subclasses based on the number of unsaturations present in their molecular structure. A general structural form exists
for each of these subclasses for every property estimation approach. These
general structures allow the property estimation methods to be written in a
simplified manner that can substantially increase our understanding of the
model.
3.1. General Structure of the Compounds Involved in Biodiesel Process Systems
We derived a general structure for each subclass of the involved compounds as a basic way to understand and extrapolate the behavior of the
property estimation methods within that subclass. Some generalized sub6

Table 1: General structure of saturated FA, simple TG, FAME and FAEE for a first-order
group contribution method.

Class

Group Contribution

(Saturated)

Structure

FA

1.CCH3 + n.CCH2 + 1.CCOOH

TG

3.CCH3 + (3n + 2).CCH2 + 3.CCH 2 COO + CCH

FAME

2.CCH3 + n.CCH2 + 1.CCH 2 COO

FAEE

2.CCH3 + (n + 1).CCH2 + 1.CCH 2 COO

classes of molecules are presented in Figure 2, this representation allows us

to draw generalized structures for each of the approaches listed in Tables 2
and 10. For example, the generalized structures for the sub-classes of Figure 2 for a group-contribution method (based on the UNIFAC groups and
considering only first-order groups) are presented in Table 1. Other groupcontribution methods that use different groups can be easily converted into
the proposed general structure, as can other classes of compounds. More
information is given in Tables S1, S2, and S3 in the supplementary data.
3.2. Primary and Secondary Properties
Primary properties depend on the chemical structure of the molecule
considered. The primary properties considered are the critical temperature
(Tc ), critical pressure (Pc ), critical volume (Vc ), boiling point (Tb ), melting
point (Tm ), standard Gibbs energy of formation (Gf ), and the standard
enthalpy of formation (Hf ). Secondary properties cannot be explicitly
written only in terms of the chemical structure and are often a function of
7

other properties, the only secondary property analyzed in this work is the
acentric factor ().
Most of the estimation methods used in the literature for primary properties belong to the group contribution type. They all assume that the groups
have an additive contribution to the overall property value. Multi-level contributions are used as corrections for specific multigroup, conformational, or
resonance effects.
The methods in Table 2 represent selected methods for the estimation of
primary and secondary properties. The experimental data points gathered
for the evaluation of primary properties are presented in Table 3 in which
the lack of experimental data for acylglycerides in most properties is evident.
3.2.1. Critical Temperature
As presented in Table 2, five estimation methods were analyzed for critical temperature; the property model functions are presented in Table 4. The
generalized property model functions obtained by applying the general structure of saturated are shown in Table 5. The property model functions for
other classes of compounds are presented in Tables S3 and S4.
The estimation methods were checked against 22 experimental data points,
distributed within each class of compounds as presented in Table 3. The reP
sults in terms of the average absolute deviation (AAD = 1/n ni=1 |Pexp
P
Pcalc |) and the average relative deviation (ARD = 1/n ni=1 100|Pexp Pcalc |/Pexp )
are presented in Table 6. In the case of FA, a considerable amount of experimental evidence suggests that the CG method is the most accurate; similar
evidence exists for FAME, and FAEE, as shown in Figures S1 and S2. However, no experimental data are available for AG, and hence, further analysis
8

Table 2: Characteristics of the primary and secondary property estimation methods considered.

Property

Estimation Method

Approach

Fedors (1982)
Joback and Reid (1987) (JR)
Tc

Tu and Liu (1996) (TL)

Group-Contribution

Gani and Constantinou (1996) (CG)

Marrero and Gani (2001) (MG)
Vc , Pc , Tb ,
Tm ,

Joback and Reid (1987) (JR)

Gf , Gani and Constantinou (1996) (CG)

Hf

Group-Contribution

Marrero and Gani (2001) (MG)

Pitzer (1955)

Correlation

Pitzer (1955)

Definition

Lee and Kesler (1975)

Pitzer expansion/Corresponding-states

Ambrose and Walton (1989)

Pitzer expansion/Corresponding-states

Gani and Constantinou (1996) (CG)

Group-Contribution

Marrero and Gani (2001) (MG)

Group-Contribution

Table 3: Experimental data points per class of compounds for primary properties.

Number of data points

Tc

Vc

Pc

Tb

Tm

Hf

Gf

FA

18 19

24

71

18

AG

11

29

ME

16

43

11

EE

15

43

Total

22 19

66 186

32

is necessary.
Irrespective of the experimental data obtained, the generalized critical
temperature model functions for each compound class are a way to gain a
deeper understanding of the estimation method.
Figures 3 and 4 presents the Tc estimations vs the number of carbon atoms
(N C) for saturated FA and saturated simple TG, respectively. The Tc vs.
N C curve for each estimation method deviate considerably in both cases.
As evident from Figure 4 the JR method provides a completely different
curve compared with the other estimation methods, even when experimental
boiling points are used (see Figure S4). The JR method generalized Tc model
function for saturated simple triglycerides is

Tc =

311.0526Tb
(n + 11.67678)(n 20.202233)
10

(1)

Table 4: Property model functions for the critical temperature.

Method

Critical temperature model function

Fedors

P
Tc = 535log( i Ni Tc1i )

JR

Tc = Tb [0.584 + 0.965

P
Ni Tc1i ( i Ni Tc1i )2 ]1

1
+
Tc = [6.26897.106 + 2.56086.103 ( 2x

1 )]1
x

TL
where x = 0.160864 +
CG
MG

Tc = 181.28ln[

Ni Tc1i +

Ni Tc1i

Mj Tc2j ]

P
P
P
Tc = 181.6716ln[ i Ni Tc1i + j Mj Tc2j + k Mk Tc3k ]

11

Table 5: General property model functions for the critical temperature estimation of
saturated FAME.

Method

Generalized critical temperature model function for saturated FAME

Fedors

Tc = 232.3475ln(4.88 + 1.34N C)
Tc = 2799.4737Tb [(N C + 22.3266)(N C 73.31076)]1

JR

Tc = [6.26897.106 +

TL

0.00128
2.475+0.9172N C

0.00256
]1
2.475+0.9172N C

CG

Tc = 181.28ln[3.1998 + 3.492N C]

MG

Tc = 181.6716ln[3.9749 + 3.4607N C]

Table 6: Tc estimation methods experimental analysis.

Method

AAD

ARD

Fedors

14.41 (5.46 - 27.59) 2.05 (0.77 - 4.16)

JR

13.18 (1.92 - 28.68) 1.81 (0.28 - 3.57)

TL

13.74 (5.94 - 25.05) 1.95 (0.84 - 3.77)

CG

4.39 (0.25 - 11.31)

MG

18.09 (5.17 - 33.63) 2.57 (0.73 - 5.09)

12

0.64 (0.03 - 1.70)

Figure 3: Behavior of various Tc estimations with NC for saturated fatty acids.

In this case N CF A = n + 3; therefore the model will return a negative

value for Tc for TG formed from FA with a NC greater than 23, such as
Trilignocerin (C24:0, C24:0, C24:0). This result is the first example of a
useful property model consistency test.
As also evident in Figures 3 and 4 the CG and MG methods provide
almost the same estimations (the difference is always less than 8 K for AG,
FAME and FAEE; and approximately 25 K for low-N C FA; the difference decreases as N C increases). The TL and Fedors predictions were qualitatively
similar to the CG and MG predictions, but they overestimated the critical
temperatures by approximately 50 K. Similar results were also observed for
other groups of compounds, as shown in Figure S1.
On the basis of this analysis, we recommend the CG method for the estimation of Tc because of its confirmed usefulness as a correct thermodynamic
parameter for the calculation of acentric factors (see section 3.2.8 ).

13

Figure 4: Behavior of various Tc estimations with NC for saturated triglycerides.

3.2.2. Critical Pressure

Different from Tc , the Pc model functions of all methods have the following
form:
Pc = A +

1
P
(B + i Ni Pc1i )2

(2)

where A and B are additional adjustable parameters of the property estimation models. The generalized form for each of the subclasses of compound
has the following model form:
Pc = A +

1
(B1 + C.n)2

(3)

where n is a function of N C, B1 combines the adjustable parameter B and

the group-contributions that are independent of n and C are the groupcontributions dependent on n.
The AAD and ARD for JR, CG, and MG were calculated on the basis
of 19 experimental data points, describing only FA (see Tables 3 and 7). As
presented in Figure 5, the Pc estimation methods differ slightly for saturated
14

FA; similar results were obtained for FAME and FAEE (see Figure S2 and
Table S3).
The estimations differ significantly only in the case of AG, an example is
provided in Figure 6 for simple TGs. Equations 4, 5, and 6 are the generalized
model functions for JR, CG and MG, respectively, applied for saturated
simple triglycerides.

Pc =

1
(0.2347 + 0.0288.(N C 3))2

(4)

Pc = 1.3705 +

1
(0.24782 + 0.0318.(N C 3))2

(5)

Pc = 0.0519 +

1
(0.2325 + 0.0261.(N C 3))2

(6)

From these equations, two different regions:

if 10 N C 18 then Pc (M G) > Pc (JR) > Pc (CG)
if 19 N C 32 then Pc (M G) > Pc (CG) > Pc (JR)
else N CF A > 33 then Pc (CG) > Pc (M G) > Pc (JR)
The same analysis was applied for all other classes of compounds; the
identified regions are described in Table S4. Our final recommendation is to
use the CG method for FA, FAME, and FAEE because it performed slightly
better compared to the experimental data. A proper recommendation for
AG is highly dependent on the situation; the user must keep in mind the
regions defined previously and proceed knowing if the estimated value is a
high, a low, or an intermediate estimation.

15

Table 7: Critical pressure estimation methods analysis.

Method

Pc AAD

Pc ARD

JR

0.72 (0.21 - 1.32) 3.44 (0.91 - 8.80)

CG

0.66 (0.11 - 1.31) 3.09 (0.64 - 7.75)

MG

1.07 (0.17 - 2.13) 5.10 (0.96 - 9.88)

Table 8: Critical volume estimation methods analysis

Method

Vc AAD

Vc ARD

JR

10.71 (0.17 - 22.5)

1.81 (0.03 - 5.07)

CG

10.06 (0.32 - 21.85) 1.73 (0.06 - 5.08)

MG

12.73 (0.32 - 24.77) 2.04 (0.06 - 5.05)

Figure 5: Pc estimations behavior with NC for saturated fatty acids.

16

Figure 6: Pc estimations behavior with NC for saturated triglycerides.

3.2.3. Critical Volume

All of the critical volume model functions are linear, and essentially no
differences exist among the methods (see Figures 7, 8, and S3 as well as
Table 8).
3.2.4. Boiling Temperature
Substantially more experimental data are available for Tb and Tm than for
the other primary properties. The estimations for the CG and MG methods
are very good, except in the case of AG, as shown in Figures 9 and 10.
Table 9 gives the calculated AAD and ARD, which suggest that the MG
method is the most accurate among those investigated. However, it is clear
from Figure 10 that the methods overestimate the experimental data for TG.
The reasons for these deviations are difficult to determine from a theoretical
view point. The group-contribution models may be missing one or several
important groups definitions that are highly important for AG. However, the
17

Figure 7: Vc estimations behavior with NC for saturated FA.

Figure 8: Vc estimations behavior with NC for saturated TG.

18

Table 9: Boiling-point estimation methods analysis.

Method

Tb AAD

Tb ARD

JR

0.72 (0.21 - 1.32) 3.44 (0.91 - 8.80)

CG

0.66 (0.11 - 1.31) 3.09 (0.64 - 7.75)

MG

1.07 (0.17 - 2.13) 5.10 (0.96 - 9.88)

Figure 9: Tb estimations behavior with NC for saturated FA.

definition of many other groups would also increase the complexity of the
models, which also result in an undesirable situation. A proper correction
for the CG method was proposed using a second-order group specifically for
triglycerides:

Tb = 204.359ln

X
Ni Tb1i
+
Mj Tb2j
0.08891NC 0.77797
j
i

The improved estimations are presented in Figures 11 and S4.

19

(7)

Figure 10: Behavior of Tb with the NC for saturated triglycerides (JR estimations are
above 1000 K).

Figure 11: Improved Tb estimations for saturated triglycerides .

Figure 12: Behavior of Tm estimations with NC for saturated FA.

20

3.2.5. Melting Temperature

Similar to the case of Tb , a considerable amount of experimental data
exist for Tm , the JR method strongly overestimates the experimental values,
whereas the estimations obtained from the CG and MG methods fit the data
well, except in the case of TG (no data exists for di- and monoglycerides), as
presented in Figure 12 and 13. Here, we define two new second-order groups
for the MG method; one to account solely for the TG form and another
to incorporate a proper description of unsaturations present in triglycerides.
The modified MG-Tm for TGs is:

Tm = 143.5706 ln

X

Ni Tm1i +

X
k

Mj Tm2j

C2 NDB
Wk Tm3k + C1 +
3

(8)

where C1 and C2 are given by Equations 9 and 10 respectively, NC is

the number of carbons in the TG, and NDB is the number of double bonds
in the TG. The improved estimations are shown in Figures 14 and S5.

C1 =

0.643364 0.18376.NC , if N C is even

2.559501 0.2099.NC ,

C2 =

(9)

if N C is odd

5.21927, if NC is even

(10)

4.08173, if NC is odd
3.2.6. Standard Enthalpy of Formation
A considerably large amount of experimental data is available for Hf
regarding FA and FAME, and the estimation methods agree well with the
21

Figure 13: Tm estimations behavior with NC for saturated TG.

Figure 14: New MG-Tm estimations for triglycerides with up to three unsaturations.

22

Figure 15: Behavior of Hf estimations with NC for (a) saturated FA and (b) saturated
FAME.

experimental data (see Figures 15, 16 and S6). In the case of AG, the estimation methods deviate slightly and the extent of deviation increases with
the degree of unsaturation. The greatest deviation occurred between JR and
MG: approximately 80 K for trioctadecatrienoin (C18:3). Our recommendation is to use the CG method; however, one must consider Equation 11

Hf JR > Hf CG > Hf M G

(11)

3.2.7. Standard Gibbs Energy of Formation

No experimental data are available for Gf ; nevertheless, Figures 17, 18
and S7 demonstrate that all the methods exhibit precisely the same qualitative behavior. The JR method provides a considerably lower estimation, and
no significant difference is observed between the results of the CG and MG
methods (the largest difference encountered was approximately 27 kJ/mol,
which was observed for TGs with numerous degrees of unsaturation).

23

Figure 16: Behavior of Hf estimations with NC for (a) saturated FA and (b) saturated
FAME.

Figure 17: Behavior of Gf estimations with NC for saturated TG.

Figure 18: Behavior of Gf estimations with NC for triply unsaturated TGs.

24

3.2.8. Acentric Factor

The acentric factor is the only secondary property considered in this work.
It was originally defined by Pitzer (1955) as:

log 10


lim (Pvap /Pc ) 1

Tr 0.7

(12)

According to Poling et al. (2001) two useful procedures to estimate the

acentric factor have been developed: one approach is to use an accurate
equation for Pvap and obtain (or estimate) the critical properties; the second
approach is to use group-contribution methods such as CG and MG. On the
basis of experimental data points for Pvap , Tc and Vc , 12 true experimental
values can be derived for the acentric factor from Equation 12 (11 for FA and
1 for FAME). Figure 19 presents the estimation curves for FA, which clearly
show the accuracy of the acentric factor calculations derived directly from
Equation 12 using the model by Ceriani et al. (2013) for Pvap and CG for the
critical properties, respectively. As shown in Figure 20, the influence of the
estimation methods for Tc and Pc were investigated; the results demonstrate
that the chosen Tc method is crucial whereas changing the Pc method has
little effect on the acentric factor calculations.
On the basis of the experimental Pvap values available for all the classes
of compounds analyzed, the Pvap model by Ceriani et al. (2013) is considered
the most accurate model. Our recommendation is to use this method and
the CG to find the critical properties in Equation 12.
3.3. Temperature-dependent Properties
The temperature-dependent properties considered were vapor pressure
(P vap ), liquid density (L ), liquid heat capacity (CpL ), liquid viscosity (L ),
25

Figure 19: Acentric factor estimation curves for FA.

Figure 20: Effect of the critical properties estimation method on the acentric factor estimation curves for FA.

26

and the heat of vaporization (H vap ). The methods considered are listed in
Table 10.
An analysis regarding experimental data has already been reported by Su
et al. (2011) for all the temperature-dependent properties considered here.
Similar results from our database are provided in the supplementary data,
Table S6. We, therefore, focused our analysis on the generality and inconsistencies of the property models by taking advantage of the general structure
described in Section 3.1.
3.3.1. Heat Capacity
Four models were analyzed for cp and some critical inconsistencies were
observed.
The method by Kolska et al. (2008) is ultimately given by the following
quadratic function:

cp = a + b T + d T 2

(13)

where a, b, and d are given by the group contributions. This model equation must not have a negative value for the parameter d; otherwise, it will
lead to the unreal behavior of cp decreasing with an increase in temperature.
Applying the generalized structures, presented in 3.1, we obtained the generalized formulas for the parameter d, as presented in Table 11 for saturated
compounds.
As directly determined from the general formulas, the model by Kolska
et al. (2008) is inconsistent for:
simple saturated TG with N C smaller than 51.
27

Table 10: Secondary property estimation methods considered and their characteristics.

Property Estimation Method

Approach

Kolska et al. (2008)

Group-Contribution

Morad et al. (2000)

Rowlinson-Bondi Equation

Ceriani et al. (2009)

Group-Contribution

cp

Zong et al. (2009)

Fragment-based

Tu and Liu (1996)

Hvap

Basarova and Svoboda (1995)

Group-Contribution

Ceriani et al. (2013)

Halvorsen et al. (1993)

Rackett Equation + Correction Term

Ihmels and Gmehling (2003)

Zong et al. (2009)

Group-Contribution
Fragment-based

Ceriani et al. (2013)

Group-Contribution

Pvap
Zong et al. (2009)

Fragment-based

28

Table 11: Heat Capacity.

Classes of

Generalized formula for

Compounds

d from Eq. 13

Sat. FA

5.06 + 0.41 N C

Sat. TG

27.59 + 0.41 N C

Sat. FAME

5.39 + 0.41 N C

Sat. FAEE

4.98 + 0.41 N C

saturated FAME with N C smaller than 14.

saturated FAME with N C smaller than 15.
Examples of these inconsistencies are presented in Figures 21, 22, and 23.
The same inconsistencies occur for numerous other sub-classes of compounds,
especially when unsaturations are present.
The cp model by Morad et al. (2000) also presents inconsistencies. This
method is based on the Rowlinson-Bondi equation, that requires knowledge
of the critical properties and the acentric factor. The authors argue that to
apply this method to acylglycerols and vegetable oils one can use a simple
molar average of the required properties (Tc , Pc and ) to represent the mixture properties. For example, the critical temperature suggested by Morad
et al. (2000) for a triglyceride is

29

Figure 21: Heat capacity profile estimated for trioctanoin (N C = 27).

Tc,mix =

xi Tci

(14)

where Tci is the critical temperature of the compound i and xi is the

composition of the compound i in the mixture. This assumption does not
introduce any problems for moderate temperatures; however, the critical
temperature of a TG is not simply the molar average of the FA that composes
it. As evident in Figure 24, at approximately Tr = 0.8, the estimated value
for cp estimated using the method of Morad et al. (2000) is indeterminate
(at this point, Tr,mix = 1).
The methods that do not present inconsistencies have provide almost
identical estimations, and the method of Ceriani et al. (2009) is recommended
for use, because it can describe a larger number of molecules than the method
of Zong et al. (2009).
3.3.2. Density
Three models were analyzed for the density estimation (see Table 10).
The model of Ihmels and Gmehling (2003) (version GCVOL-OL-60) ex-

30

Figure 22: Heat capacity profile estimated for methyl octanoate (N C = 9).

Figure 23: Heat capacity profile estimated for methyl octanoate (N C = 10).

Figure 24: Estimated heat capacity profile for Trilaurin.

31

Table 12: Density inconsistency for the method of Ihmels and Gmehling (2003).

Classes of

Generalized value for

Compounds

c from Eq. 15

Sat. FA

1-Unsat. FA

-0.0002878

2-Unsat. FA

-0.0005756

3-Unsat. FA

-0.0008634

4-Unsat. FA

-0.0011512

hibits an inconsistency very similar to the one observed for the method
by Kolska et al. (2008). The density estimation model proposed by Ihmels
and Gmehling (2003) can be represented by the following model equation:

MW
A + B T + C T2

(15)

The quadratic function in the denominator of Equation 15 is the molar volume of the substance. Because the volume must increases with an
increase in temperature, an inconsistency appears if the parameter C is negative. Applying the general structure presented in Section 3.1, we obtained
c parameter values for the sub-classes of compounds. Some results shown in
Table 12, confirm that the model exhibits innacurate profiles (see Figures 25
and 26.

32

Figure 25: Estimated density profiles for Myristoleic acid.

Figure 26: Estimated liquid density profiles for Trioctanoin.

33

Another consistency test for molar volume estimation methods is:

lim (Vm ) = Vc

Tr 1

(16)

As evident in Figure 25, the method of Zong et al. (2009) does not return
a value for Vc similar to those predicted by the group-contribution methods;
thus, our final recommendation is to use the model of Halvorsen et al. (1993).
3.3.3. Vapor Pressure
Vapor pressure is one of the most important properties required for process simulation. Only two estimation models were analyzed in this work;
those of Zong et al. (2009) and Ceriani et al. (2013). Both these methods
provided estimations consistent with experimental data for all the classes
of compounds analyzed (see Figure S8). For TG, both the methods were in
good agreement in the reduced temperature range of 0.4-0.7; however, outside
this range, no experimental data are available and the models estimations
deviate strongly from each other, as shown in Figure 27 (in a representative
example for trioctanoin). Vapor pressure fundamentally behaves as an exponential function, and the extrapolation of theoretical or empirical models can
lead to very large deviations. The authors of both methods reported using
data from a similar reduced temperature range, and it can be said that both
methods can be used; however, we recommend the model of Ceriani et al.
(2013) because it can describe a larger number of molecules.
3.3.4. Heat of Vaporization
None of the analyzed methods exhibited inconsistencies. Su et al. (2011)
analyzed the methods of Basarova and Svoboda (1995) and Ceriani et al.
34

Figure 27: Estimated Pvap profile for Tricaprin

Figure 28: Heat of vaporization for octanoic acid.

(2009) and claimed that the method of Ceriani et al. (2009) provided profiles
in which Hvap increased with temperature. Recently, we used an updated
model proposed by Ceriani et al. (2013) and did not observe any inconsistencies, as shown in the profile of Figure 28. The estimations agreement with
experimental data are reported in Table S5, and the results suggest that the
model of Ceriani et al. (2013) is the best estimation method among those
investigated.

35

4. Computational Implementation of the Framework

The selected property estimation methods are not useful if they cannot
be computed in a process simulator or other related tools. Modern computational chemical engineering tools (i.e., softwares) are heavily influenced
by the CAPE-OPEN interoperability standard, which proposes a component
(piece of software) architecture and clear interface standards. Our initial idea
was to make BioPES CAPE-OPEN compliant. Nevertheless, the simulator
used in our research group is COCO (CAPE-OPEN to CAPE-OPEN) that
is based on ChemSep (van Baten, 2007), where the easiest work path was
encountered. ChemSep already has an efficient software architecture that
enables incrementation of custom databases.
4.1. ChemSep Important Features
ChemSepTM has a component1 named PCDmanager that manages the
information with regard to pure compounds; with this component, the user
can perform several tasks such as access pure compound properties, add a new
compound, and insert and update correlation parameters for temperature
dependent properties. Among these tasks, some are of critical importance
for the accomplishment of this work:
1. export compound to file
2. import compound from file
1

The word component in this context is not a synonym for compound; here, it

refers to a piece of software in the paradigm of component-based software engineering.

36

ChemSep-LiteTM has 432 compounds in PCDmanager; the selection of one of

these compounds and its export to a file results in a simple text file that can
be divided into the following sections:
1. Compound identifiers (name, formula, CAS number, smiles string and
family)
2. Pure compound primary properties (critical properties, molecular weight,
boiling point and melting point, to name a few).
3. Parameters for 17 pure compound temperature dependent properties
(solid density, liquid density, vapor pressure and heat of vaporization,
to name a few).
4. Additional pure compound parameters for calculation of mixture properties and molecular properties (UNIQUAC r and q, Chao-Seader acentric factor, Chao-Seader solubility parameter).
5. Group contribution data (UNIFAC, UNIFAC-LLE, ASOG and Modified UNIFAC, among others).
Therefore, all that is required for the systematic addition of compounds
to ChemSepTM is the creation of such text files that contain all the required
information and subsequent addition of the compounds through PCDmanager using the text file. The process used to implment our custom database
to ChemSepTM is further explained in Figure 29.
An additional difficulty in the process stems from the temperature-dependent
correlations being based on a set of 35 defined model forms2 . Unfortunately,
2

The model forms are the same as those used in the DIPPR databank; a com-

plete list is available at http://www.chemsep.com/downloads/docs/ChemSepTutorial_

37

Figure 29: Process to export a file compound from BioPES to ChemSep.

no estimation methods have the defined model forms; for instance, some of
the methods are based on group contribution plus a correction term. To
overcome this issue, we developed a parameter estimation procedure using
MS Excel.
4.2. Parameter Estimation Procedure
Even though the estimation methods/models were not directly constructed
in any of the defined equation forms available in ChemSep, all of them follow
at least one of the 35 defined model forms, as shown in Figures 30 and 31
for liquid density and heat of vaporization, respectively.
Therefore, all that is necessary is to obtain the parameters for 5 temperaturedependent properties for all of the 232 compounds is to perform at least 928
nonlinear regressions. All the necessary data can be generated using BioPES,
and the nonlinear regressions are easily performed using Excel through the
development and application of appropriate macros that systematically call
Excel Solver. The process to obtain the property estimation model parameters in a model form compatible with ChemSepTM is summarized in Figure 32
with a few additional details.
The nonlinear regression was only accepted when the coefficient of corPCDManager.pdf

38

Figure 30:

Palmitoleic acid liquid density values generated using the method of

Halvorsen
et al. (1993)
and a nonlinear regression using the model form number 105


A
y = B [1+(1T
/C)D] .

Figure 31: Pamitoleic acid heat of vaporization values generated using the method
 of
Ceriani et al. (2013) and a nonlinear regression using the model form number 106 y =

B+C Tr +D Tr2 +E Tr3
.
A(1 Tr )

39

Figure 32: Four-step process to obtain the property estimation model parameters in an
model form compatible with ChemSepTM .

relation was greater than 0.99, resulting in 227 compounds with all the correlation parameters determined. An example of the results for trimyristin is
given in Table 13.
4.3. Compound Text Files Generation and Addition of Compounds to ChemSep
After the property estimation model parameters in a model form compatible with ChemSepTM were obtained, all of the requirements to accomplish
the task defined in Figure 2 (create the compound text files and import them
via PCDmanager) were satisfied. We performed the compound text file generation through BioPES using the .NET Framework, and, using these files,
finally added the compounds to ChemSep using the import from file feature.
At this point, the only remaining step was to save the work. The file generated contains 660 compounds (432 originally included and 228 added in this
work) with several reliable, constant, and temperature-dependent physical
property values ready to be used in a distillation column simulation using
ChemSepTM or in entire plant simulation using the COCO simulator or any
40

Table 13: Nonlinear estimation results for trimyristin.

Eq.

Eq.

Number

Form

Property

105

0.289

0.443

808.4

0.5848

194.2

-29241

-22.028

0.0002

-0.375

0.289

0.443

808.4

0.5848

1.01.106

1530.5

y=


B

1+(1T /C)D


E

Pvap

101

Hvap

106

y = eA+ T +C ln(T )+D T



B+C Tr +D Tr2 +E Tr3
y = A(1 Tr )

y =A+BT

cp

other simulator that is CAPE-OPEN compliant, such as Aspen PlusTM . The

final file containing all the information can be obtained via email from the
authors.
4.4. Results and Discussion for the Computational Implementation of the
Framework
The implementation was successfully loaded into the COCO simulator, as
shown in Figure 33. As an initial validation, the biodiesel production process
from waste cooking oil (triolein) proposed by Zhang et al. (2003a) simulated
on HYSYS was reproduced as represented in Figure 34.
The simulation results were very similar to those reported by Zhang et al.
(2003a) for the alkali-catalyzed process (see Table 14). Notably, triolein (the
compound representing the waste cooking oil) is usually the only TG observed
in most commercial simulators; the advantage of using the implementation
41

Figure 33: COCO flowsheet configuration GUI showing some of the compounds added in
this work.

Figure 34: Simulation of the biodiesel production process from triolein proposed by Zhang
et al. (2003) using the COCO simulator and the framework implemented in this work.

42

Methanol recycle stream

Product stream

Zhang et al. (2003a)

This work

Zhang et al. (2003a)

This work

28.2

29.29

193.7

130.62

20

20

10

10

3.47

3.30

3.84

3.63

Methanol

0.001

TG (Oil)

FAME

0.997

0.995

Glycerol

Water

0.003

0.004

Temperature (o C)
Pressure
Molar flow (kmol/h)
Component Mass Fraction

Table 14: Comparison of key streams simulated in this work and in HYSYS by Zhang
et al. (2003a).

43

developed here is that other compounds present in the waste cooking oil
can be included in the analysis, resulting in a more detailed description of
the system. Furthermore, any other biodiesel production systems composed
of the 228 compounds included in the framework can be approached using
reliable property estimation methods.
5. Conclusions
Our extensive review of the property estimation methods for the compounds involved in biodiesel process systems shows the importance of consistency tests when constructing property models. Nevertheless, a robust
framework for the estimation of many properties was successfully built. Two
subjects of substantial importance not addressed in this work are phase equilibria and chemical reactions; however, these topics are addressed elsewhere
by Likozar and Levec (2014) and Coelho et al. (2011). The computational
implementation developed in this work strong resembles the CAPE-OPEN
standard, and, even though the former is not as elegant as the latter, each
of the tools used are specialized in a certain task, and the communication
between the different tools was carefully controlled via our method.
List of Symbols
Gf Standard Gibbs Energy of Formation (J/mol)
Hf Standard Enthalpy of Formation (J/mol)
Ci

Contribution of the group i in the property function

Pc

Critical Pressure (bar)

44

Tb

Boiling Temperature (K)

Tc

Critical Temperature (K)

Tm

Melting Temperature (K)

Vc

Critical Volume (cm3 /mol)

AAD Average Absolute Deviation

AE

Alkyl esters

AG

Acylglycerides

ARD Average Relative Deviation (%)

BioPES A software developed in this work (Biodiesel Property Estimation
System)
CG

Gani and Constantinou (1996) property estimation method

FA

Fatty acids

FAEE Fatty acid ethyl esters

FAME Fatty acid methyl esters
JR

Joback and Reid (1987) property estimation method

MG

Marrero and Gani (2001) property estimation method using the updated parameters by Hukkerikar et al. (2012).

TG

Triglycerides

TL

Tu and Liu (1996) method for critical temperature estimation

45

6. Acknowledgements
The authors acknowledge the financial support of the Brazilian government agency CNPq (grants 471054/2012-7 and 304865/2011-7).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online version, at https://dl.dropboxusercontent.com/u/8781257/artigos%
20proprios%20download/supplementary%20data.docx.
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