Biodiesel Process Simulation: 1.

Computational Implementation of
Chemical and Physical Properties

F. RODRIGUES1 e A. J. de ASSIS1
1
Universidade Federal de Uberlândia, Faculdade de Engenharia Química, Núcleo de Modelagem,
Controle e Otimização de Processos
E-mails para contato: [email protected]; [email protected]

ABSTRACT – Process and product design are perhaps the chemical engineering
quintessential activity mainly due to the many different aspects involved such as
synthesis, design, optimization, control and the most recent trend of intensification.
Biodiesel is a very attractive alternative to fossil fuels regarding sustainability, but it
requires economic efficient process in order to be widely implemented. Therefore, the
application of systematic methods for process and product design is of special interest for
biodiesel. However, the success of most systematic approaches for process and product
design is based on reliable physical and chemical properties values. This work reports the
computational implementation of property estimation methods specially developed and
selected for biodiesel process related compounds into ChemSep™. The main advantage in
this implementation is brought by the CAPE-OPEN capabilities of ChemSep™ that
enables the use of reliable physical and chemical properties of more than 200 compounds
in any process simulator that is CAPE-OPEN compliant.

1. INTRODUCTION
Biodiesel is a very attractive alternative to fossil fuels regarding sustainability, but requires
economic efficient process in order to be widely implemented (Hill et al., 2006). Systematic
approaches for process and product design activities have been proposed in the literature (Biegler et
al., 1998; Grossman and Gani, 2007) and its application is of special interest for biodiesel. However,
the methods and tool for process and product design are most often based on a set of physical and
chemical properties values. Therefore, properties (pure compound and mixture) play a very important
role in process and product design, and the availability and reliability of these properties are important
limiting factors in the involved activities. Property estimation methods are the most practical way to
fulfill this gap (Poiling et al., 2001).
A very large number of property estimation methods have been reported in the literature, such
as those found in Poiling et al. (2001); Konteorgis and Gani (2004), and Su et al. (2011). A recent
assessment of most of these methods for biodiesel systems was proposed by Rodrigues and Assis
(2013) resulting in a property estimation framework for the simulation of biodiesel process systems.
However, the selected property estimation methods are of almost no use if these are not
computationally available to be used in a process simulator or other related tool.

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 Modern computational Chemical Engineering tools (software) are much influenced by the
CAPE-OPEN interoperability standard, which has proposed a component (piece of software)
architecture and clear interface standards. The authors developed a software presented in a previous
work (Rodrigues and Assis, 2013), called BioPES (BIOdiesel Property Estimation System), which
was able to calculate most of the important physical properties of 232 compounds involved in general
biodiesel process and, initially, the idea was to make BioPES CAPE-OPEN compliant. Nevertheless,
the simulator used in our research group is COCO (CAPE-OPEN to CAPE-OPEN), whose
thermophysical property package is that of ChemSep™ (van Baten, 2010). So, we decided to integrate
BioPES to ChemSep™, resulting in an easiest work path. ChemSep™ already has an efficient
software architecture that enables the addition of its own compounds database and property package
with the compounds involved in biodiesel and the property estimation methods selected by Rodrigues
and Assis (2013).

2. COMPUTATIONAL IMPLEMENTATION1
The framework for property estimation proposed by Rodrigues and Assis (2013) has the
structure shown in Figure 1 and provides appropriate models for the estimation of several properties
for 232 compounds.

Define Compound and

Conditions (T, P, x)

Step 3: Step 2: Step 4:

Estimate Primary Properties Define Compound Type Estimate Secondary Properties

ρ
Fatty Acid
Halvordensen et al. (1993)

Pvap
Tc, Pc, Vc, Gf, Hf, Tb, Tm Acylglyceride Ceriani et al. (2013)
Constantinou and Gani (1996)
Cp
Ceriani et al. (2009)
Vegetable Oil
µ
Ceriani et al. (2011)

Fatty Acid Alkyl Ester ΔHvap

Ceriani et al. (2013)

Database: Model parameters and other required data

Figure 1 – State-of-art property estimation methods for biodiesel process systems

(Rodrigues and Assis, 2013).

1Before any discussions, the authors want to clarify that here the words compound and component are used with
very different meanings. The word compound is used for chemical species, whereas component is a piece of software
usually connected to other components through middleware (usually COM or CORBA).

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 To increment the framework shown in Figure 1 into ChemSep™ was only possible due to some
of its features.
2.1. ChemSep™ Important Features
ChemSep™ has a component that manages the information regarding pure compounds, called
PCDmanager, in which the user can perform several tasks such as access pure compound properties,
add a new compound, insert and update correlation parameters for temperature dependent properties.
Among these tasks, some are of critical importance for the accomplishment of this work: export
compound to file and import compound from file. ChemSep-Lite™ has 432 compounds in
PCDmanager and by choosing one of these compounds and exporting it to a file one encounters a
simple text file that can be divided in:
1. Compound Identifiers (Name, Formula, CAS, Smiles 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, to
name a few).
Therefore, to add compounds to ChemSep™ systematically, all that is required is to create such
text file holding all the required information and then add the compounds through PCDmanager using
this text file. The process to increment ChemSep™ with the property estimation framework is also
explained by Figure 2.

BioPES

Property Estimation Framework Compound Text File PCDmanager

Create Import
(Rodrigues and Assis, 2013) (ChemSep can export such files) (ChemSep pure compound manager)

Figure 2 – Process to implement the property estimation framework on ChemSep™.

An additional difficulty to the process explained in Figure 2 is that the temperature dependent
correlations are based on a set of 35 defined model forms2. Unfortunately, no estimations methods in
the framework have the defined model forms, for instance some of the methods are based on group
contribution plus a correction term. To overcome this issue a parameter estimation procedure was
developed on MS Excel.

2The model forms are the same used in the DIPPR databank and a complete list can be found at
http://www.chemsep.com/downloads/docs/ChemSepTutorial_PCDManager.pdf

Área temática: Simulação, Otimização e Controle de Processos 3

2.1. Parameter Estimation Procedure
Even though the estimation methods/models were not directly constructed in any of the defined
equation forms shown in Appendix 1, all of them do follow at least one of the 35 defined model forms
as shown in the Figure 3 and 4 for the liquid density and heat of vaporization, respectively.

Figure 3 – Pamitoleic acid liquid density values generated using Halvordensen et al. (1993) and a
nonlinear regression using the model form number 105 ( 𝑦 = 𝐴/𝐵^[1 + (1 − 𝑇/𝐶)^𝐷] ).

Figure 4 – Pamitoleic acid heat of vaporization values generated using Ceriani et al. (2013) and a
nonlinear regression using the model form number 106 – (𝑦 = 𝐴(1 − 𝑇𝑟)^[𝐵 + 𝐶. 𝑇𝑟 + 𝐷. 𝑇𝑟 2 +
𝐸. 𝑇𝑟 3 ] ).

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 Therefore, all that is necessary is to obtain the parameters for 6 temperature dependent
properties for all the 232 compounds that means to perform at least 1362 nonlinear regressions. All
the necessary data can be generated on BioPES and the nonlinear regressions are easily done on Excel
through the development and application of an appropriate macro that systematically calls Excel
Solver. The process to obtain the property estimation model parameters in a model form compatible
with ChemSep™ is summarized in Figure 5 with a few more details.

BioPES

Property Estimation Framework Data Points

(Rodrigues and Assis, 2013)
1 (At least 35 data points generated for each
temperature dependent model for each compound)

4
MS Excel

Parameters
Macro to Perform 1362 Nonlinear
(Framework property estimation 3 Regressions Systematically
models in appropriate form)

Figure 5 – Process to obtain the property estimation model parameters in an model form compatible
with ChemSep™ in four steps.

The nonlinear regression was only accepted when the coefficient of correlation was higher than
0.99 resulting in 227 compounds with all the correlation parameters determined. An example of the
results for Trimyristin is given in Table 1.

2.2. Compound Text Files Generation and Compounds Addition to ChemSep™

After obtaining the property estimation model parameters in an model form compatible with
ChemSep™ all the requirements to accomplish the task defined in Figure 2 (create the compound text
files and import them on PCDmanager) are met. The compound text file generation was done through
BioPES using the .NET Framework and, using these files, the compounds were finally add to
ChemSep™ using the “Import from File” feature. At this point, the only step to be accomplished was
to save the work. The file generated contains 660 compounds (432 originally included and 228 add in
this work) with several reliable, constant and temperature dependent, physical property values ready
to be used in a distillation column simulation using ChemSep™ or an entire plant simulation using
COCO simulator or any other simulator that is CAPE-OPEN compliant such as Aspen Plus™. The
final file containing all the information can be obtained via email contact to the authors.

Área temática: Simulação, Otimização e Controle de Processos 5

 Table 1 – Nonlinear Estimation Results for Trimyristin.

Equation
Equation Form 𝐴 𝐵 𝐶 𝐷 𝐸
Number
Liquid
105 𝑦 = 𝐴/𝐵^[1 + (1 − 𝑥/𝐶)^𝐷 0.289 0.4443 808.40 0.5848 -
Density
Vapor 𝐵 𝐸 -
Pressure
101 𝑦 = 𝑒 𝐴+ 𝑇 +𝐶.ln⁡(𝑇)+𝐷.𝑇 194.2 -29241
22.028
0.0002 -0.375

𝑦 = 𝐴(1 − 𝑇𝑟)^[𝐵 + 𝐶. 𝑇𝑟
Heat of + 𝐷. 𝑇𝑟 2
106 4.27.107 -9.468 25.448 -25.98 9.857
Vaporization + 𝐸. 𝑇𝑟 3 ]

Heat
2 𝑦 = 𝐴 + 𝐵. 𝑇 1.01.106 1530.5 - - -
Capacity
Liquid 𝐵
101 𝑦 = 𝑒 𝐴+ 𝑇 +𝐶.ln⁡(𝑇)+𝐷.𝑇
𝐸
-32.186 4813.2 4.756 0.0005 -2
Viscosity
Surface 𝐵
101 𝑦 = 𝑒 𝐴+ 𝑇 +𝐶.ln⁡(𝑇)+𝐷.𝑇
𝐸
0.0281 -3.01.10-5 - - -
Tension

3. RESULTS
The implementation was successfully loaded on COCO simulator as shown in Figure 6 and, as
an initial validation, the biodiesel production process from waste cooking oil (triolein) proposed by
Zang et al. (2003) simulated on HYSYS™ was reproduced as represented in Figure 7.

Figure 6 – COCO flowsheet configuration GUI showing some of the Compounds added in this work.

Área temática: Simulação, Otimização e Controle de Processos 6

 Figure 7 – Simulation of the biodiesel production process from Canola oil (Triolein) proposed by
Zhang et al. (2003) using COCO simulator and the framework implemented in this work.

The simulation results were exact the same as those reported by Zhang et al. (2003). It should
be mentioned that triolein (the compound representing the waste cooking oil) is usually the only
triglyceride found in most of the commercial simulators and the advantage in using the
implementation 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 by the 228 compounds included in the framework can be
approached using the reliable property estimation methods.

4. CONCLUSIONS
The successful computational implementation described in this work shows the capabilities of
integrating several different methods and tools towards a common objective. One may realize that the
computational implementation developed here has a considerable resemblance to the CAPE-OPEN
standard, even though the former is not as elegant as the later, each of the tools used are specialized in
a certain task and the communication between the different tools were carefully controlled by the
author’s strategy.

The contribution of this work applied for biodiesel process synthesis and design is presented in
a subsequent article (Rodrigues and Assis, submitted for publication).

Área temática: Simulação, Otimização e Controle de Processos 7

5. NOMENCLATURE
𝐴, 𝐵, 𝐶, 𝐷 and 𝐸 – Correlation Parameters [-].
Cp – Heat Capacity [J/kmol.K].
Pc – Critical Pressure [Pa].
Pvap – Vapor Pressure [Pa].
Vc – Critical Volume [m3/kmol].
𝑇 – Temperature [K].
Tb – Normal Boiling Point [K].
Tc – Critical Temperature [K].
Tm – Melting Point [K].
𝑇𝑟 – Reduced Temperature [-].
𝑦 – Property Calculated by the Correlation [-].
𝜇 – Liquid Viscosity [kmol/m3].
∆𝐻𝑓 – Standard Heat of Formation [J/kmol].
∆𝐻𝑣𝑎𝑝 –Heat of Vaporization [J/kmol].
∆𝐺𝑓 – Standard Gibbs Energy of Formation [J/kmol].
𝜌 – Liquid Density [kmol/m3].

6. REFERENCES
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ed. New York: McGraw-Hill, 2001. Cap. 1, p. 1-3.
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CERIANI, R.; GONCALVES, C. B.; COUTINHO, J. A. P. Prediction of Viscosities of Fatty
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7. ACKNOWLEDGEMENT
The authors would like to thank the Brazilian National Council for Scientific and Technological
Development for scholarship and the Research Foundation of the State of Minas Gerais (FAPEMIG)
for funding this work.

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