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OVERALL UTILITY FLOWRATES AND DUTIES

Equipment

Utility type

Tin utility

Tout utility

Pressure (bar)

Duty

Usage

MW

kg/hr

FURNACE (F-101)

DOWTHERM-A

400

370

0.292

16700

RADFRAC1(C-101)

DOWTHERM-A

400

370

0.629

36000

RADFRAC2(C-102)

DOWTHERM-A

400

370

0.171

9790

1.09

62500

Duty

Usage

MW

kg/hr

TOTAL
Equipment

Utility type

COOLER (H-106)

COOLING WATER

20

25

0.037

6380

COOLER (H-108)

COOLING WATER

20

25

0.010

1720

COOLER (H-109)

COOLING WATER

20

25

0.150

25900

COOLER (H-101)

COOLING WATER

20

25

0.421

72600

0.618

106600

Duty

Usage

MW

kg/hr

TOTAL
Equipment

Utility type

HEATER (H-102)

MPS

175

174

8.76

0.0928

167

HEATER (H-104)

MPS

175

174

8.76

0.0172

30.9

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HEATER (H-105)

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MPS

TOTAL

OVERALL UTILITY FLOWRATE

175

174

8.76

8E-06

0.0142

0.1100

198

169300

THERMODYNAMIC PROPERTY METHODS IN ASPEN PLUS

Aspen Plus Version 8.8 has a wide range of physical Property Methods to choose from. Selecting the right thermodynamic model is the first
step and the most important decision when carrying out a chemical process simulation. The main model categories are Equations of State
models (EOS), Activity Coefficient Models, Predictive Activity Models and Electrolyte models.
Equation of state models are based on the specification of pure substances such as boiling point, critical conditions, and acentric factors.
Frequently used EOS models are Soave Redlich Kwong and Peng Robinson. These are great for modelling light gases, similar hydrocarbons
and petroleum pseudo-components (Hill & Justice 2011). Equation of state models can compute information on compressibility of gases. EOS
models are used for real gases and ideal liquid systems.
Activity Coefficient Models are also known as Binary Interaction Parameter (BIP) models. NRTL and Wilson are examples of Activity Coefficient
models, and are most commonly used for water and different hydrocarbon compounds like alkanes and alkenes (Hill & Justice 2011).
Furthermore, different organic molecules like ester and alcohols are modelled well by activity coefficient models. These models calculate
activity from binary interaction parameters gleaned from empirical data. The parameters are extracted from experimental data by regression
methods. In situations where an activity coefficient model does not have Binary Interaction Parameters, a predictive activity coefficient model is
required.
UNIFAC and UNIQUAC also fall under the Activity coefficient category. However, they are set apart as Predictive Activity Coefficient models.
They require group interaction parameters obtained from sub groups on the molecule. The notion behind a predictive approach is that a
molecule is the sum of its smaller parts whose interactions are known (Hill & Justice 2011). Further developments to these models in Aspen

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are UNIF-HOC and UNIQ-HOC. UNIF-HOC and UNIQ-HOC were developed to handle dimerization(Liu et al. 2015). (Sandler, 2006) advises
the use of UNIFAC when there is no experimental data is available.
Another model category found in Aspen is for electrolytes. The most commonly used model for electrolyte based systems is NRTL(Hill & Justice
2011). Examples of aqueous electrolyte type systems are: water and acid systems, and base or salt systems.
Most applications involve liquid solvents. Henrys Law makes comes with the assumption of infinite dilution, even though most systems never
get to that state. The non-linear temperature dependence of Henrys constant must be taken into account for accurate process design (Smith &
Harvey 2007).

VALIDATION OF THE CHOSEN THERMODYNAMIC MODEL

In order to choose the right thermodynamic model for the drying oil process simulation, the first step is to understand the nature of the mixture
in the process. Part A of the appendix shows the molecular structures of acetic acid, drying oil (1-tetradecene), acetylated castor oil (Nhexadecanoic acid) and gum (1-Octacosene). Drying oil and gum are alkenes whilst acetic acid and acetylated castor oil are carboxylic acids.
It is understood that drying oil has a tendency to dimerize and form gum(Bailie & Whiting 2012). Furthermore it is also know that acetic acid has
a tendency to dimerize as well (Fujii et al. 1988). Basic chemistry knowledge points to the fact that carboxylic acids form hydrogen bonds. In
conclusion, our mixture is a highly polar because of the hydrogen bond interactions and dimerization that occur in the mixture. There this is a
highly non ideal and polar mixture. There is no random distribution of molecule in polar solutions (Sandler 2006)
With this knowledge in mind it is important to find thermophysical properties of the compounds involved and generate T-X-Y and P-X-Y
diagrams to validate the thermodynamic model(Hill & Justice 2011). These diagrams can be found in Part B and Part C of the appendix.
Furthermore, an X-Y plot can also be used to determine if ASPEN can identify the formation of an Azeotrope at the operating conditions of the
system(Hill & Justice 2011).

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EXPERIMENTAL DATA COMPARED TO ASPEN MODELS

1
0.9
0.8

EXPERIMENTAL DATA
Equilibrium Line
UNIFAC
PENG ROBINSON
PRSK
NRTL
UNIF-HOC

0.7
0.6

Y--TETRADECANOIC ACID

0.5
0.4
0.3
0.2
0.1
0

0 0.2 0.4 0.6 0.8 1

X-TETRADECANOIC ACID

Figure 1: X-Y diagram using Tetradecanoic acid data from (Matricarde Falleiro et al. 2010)

The experimental data from the (Matricarde Falleiro et al. 2010) was plotted against thermodynamic models from ASPEN and Figure 1 was the
result. The experimental data was obtained by (Matricarde Falleiro et al. 2010) using differential scanning calorimetry. The experiment involved
palmitic acid (hexadecanoic acid), which is what we are using as a model for acetylated castor oil, and myristic acid (tetradecanoic acid) which
can be modelled as a similar molecule to drying oil.
(Hill & Justice 2011) encourages the use of similar components in the situation where plant data, pilot plant data and lab data may not be
readily available. Therefore palmitic acid is used to model acetylated castor oil while myristic acid is used as a model to drying oil. Their
similarities are shown in Part A of the appendix.

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In order to understand the difference between experimental data provided by (Matricarde Falleiro et al. 2010) and the thermodynamic models
on ASPEN the following table show the results of a root mean square error analysis.

Thermodynamic Model
RMSE Value
UNIFAC
0.00639
UNIF-HOC
0.00671
UNIQUAC
0.00570
WILSON
0.00540
NRTL
0.00547
PENG ROBINSON
0.01151
PRSK
0.00587
Table 1: Root mean square error analysis.

The results from this analysis give insight to Figure 1s result.

The result from Table 1 shows how UNIFAC, UNIF-HOC, UNIQUAC, WILSON AND NRTL are potential thermodynamic models.
The T-X-Y diagrams in Part B of the appendix show that UNIFAC, UNIF-HOC and WILSON seem to correlate well with experimental data. The
T-X-Y diagrams where compiled by using the same data from (Matricarde Falleiro et al. 2010).
The P-X-Y diagrams were generated from data for hexane and acetic acid. This data was obtained from the NIST database from ASPEN.
Hexene is used to model drying oil. Hexene is a shorter chain alkene to 1-tetradecene (drying oil) therefore it can be argued that they have
similar properties to a certain extent. The P-X-Y diagrams in Part C of the appendix (data at 224 degrees Celsius; Pressure range 12 to 31 bar))
alert us to the possibility of an azeotrope at those conditions. However, granted that the simulation of the drying oil process in this project is
done at 1 atmosphere this maybe unlikely. ASPEN generated a report (PART D of the appendix) showing that no azeotropes are formed at 1
atmosphere.
T-XY AND P-XY diagrams are plotted to understand the nature of the process mixture and the ease of separation (Sandler 2006). (Hill &
Justice 2011) highly recommend the plotting of ternary, bimodal and residue curve maps when dealing with highly non ideal systems. These
have been included in Part D of the appendix and they were generated by ASPEN.
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In selecting the thermodynamic model for this project recommendations from literature were considered. An attempt was made to find a
simulation model that has been used for an actual drying oil process. The search for this was unsuccessful. The next step was to find
thermodynamic models that have been frequently used for the simulation of the drying oil process. This information was also not found.
Therefore (Sandler 2006) and (Hill & Justice 2011), were consulted. It was clear that Wilson and NRTL are the obvious choice for mixtures
containing strongly polar compounds and alkenes. It is mentioned in literature that a mixture containing components from more than one
class exhibits greater non-ideality (Sandler 2006). Therefore the use of Wilson is highly recommended. However, vapor equilibrium data for the
compounds used in the drying oil process was difficult or almost impossible to find. Plant data, pilot plant data, laboratory data and even
literature data for the drying oil process could not be found. As a result a predictive model was needed.
This was something that could not be taken lightly, therefore experienced process engineers and proffessors were consulted. They agreed with
( Sandler 2006) who recommends that when no experimental data is available UNIFAC should be used. The notion behind a predictive
approach is that a molecule is the sum of its smaller parts whose interactions are known (Hill & Justice 2011). Therefore UNIFAC was the
chosen model for this project.
Aspen recommends UNIFAC-HOC which may have the added advantage of accounting for dimerization. However, it is good to take advice
from experienced process simulation engineers and that is why UNIFAC was used. Literature upholds this prudent reasoning. UNIFAC may be
an older version than UNIFAC-HOC, but it is great as an initial iteration.
How can UNIFAC be validated for the drying oil process? A simple flash separation performed can verify that the vapour liquid separation that
occurs with the mixture from the reactor is in line with expectations from experienced engineers (Hill & Justice 2011). An inappropriate model
will yield wrong results. Part D of the appendix shows a comparison of activity coefficient data from a solubility data set by (Ralston & Hoerr
1942) and ASPEN thermodynamic models. UNIFAC is a good approximation of the experimental data. The T-XY diagram in Part B of the
appendices also validates that UNIFAC as an appropriate model.

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REFERENCES

Aspen Technology, 2010. Aspen Physical Property System. , pp.6970.

Bailie, R.C. & Whiting, W.B., 2012. Analysis , Synthesis , and Design of Chemical Processes Fourth Edition,
Benziane, M. et al., 2013. Isothermal vapor-liquid equilibria of n-tetradecane + ethyl hexanoate, ethyl decanoate, and ethyl tetradecanoate.
Journal of Chemical and Engineering Data, 58(2), pp.492498.
Fujii, Y., Yamada, H. & Mizuta, M., 1988. Self-association of acetic acid in some organic solvents. The Journal of Physical Chemistry, 92(23),
pp.67686772. Available at: http://pubs.acs.org/doi/abs/10.1021/j100334a054.
Hill, D. & Justice, F.C., 2011. Understand thermodynamics to improve process simulations. Chemical Engineering Progress, 107(12), pp.2025.
Liu, L. et al., 2015. Isobaric Vapor-Liquid-Liquid Equilibrium for Water + Cyclohexane + Acrylic Acid at 200 mmHg. Journal of Chemical and
Engineering Data, 60(11), pp.32683271.
Mahapatra, N., 2010. Design and Simulation of Cumene Plant Using Aspen Plus. Chemical Engineering.
Matricarde Falleiro, R.M., Meirelles, A.J.A. & Krhenbhl, M.A., 2010. Experimental determination of the (vapor+liquid) equilibrium data of
binary mixtures of fatty acids by differential scanning calorimetry. The Journal of Chemical Thermodynamics, 42(1), pp.7077. Available at:
http://dx.doi.org/10.1016/j.jct.2009.07.008.
Ralston, A.W. & Hoerr, C.W., 1942. The solubilities of the normal saturated fatty acids. The Journal of Organic Chemistry, 7(6), pp.546555.
Available at: http://pubs.acs.org/doi/abs/10.1021/jo01200a013.
Report, D., Compounds: Literature: , pp.910.
Smith, F.L. & Harvey, A.H., 2007. Avoid common pitfalls when using Henry s law. Chemical Engineering Progress, (September), pp.3339.

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