TABLE OF CONTENTS

CHAPTER
PAGE
TABLE OF CONTENTS .............................................................................................................. 1
1a. PROCESS FLOW DIAGRAM ............................................................................................... 2
1b. STREAM TABLE ................................................................................................................... 3
1c. OVERALL UTILITY FLOW RATES AND DUTIES ................................................................. 4
1d. EQUIPMENT LIST ................................................................................................................ 5
2. DISCUSSION OF THERMODYNAMIC PROPERTIES AVAILABLE IN ASPEN ...................... 6
3. VALIDATING THE SELECTED THERMODYNAMIC MODEL ............................................7-10
4. LIST OF ASPEN MODEL LIBRARY COMPONENTS ......................................................11-13
5. APPENDICES ..................................................................................................................14-24
6. REFERENCES ..................................................................................................................... 25

1a. PROCESS FLOW DIAGRAM

A

P-101 A/B
C-101
E-102 P-105 A/B H-108
H-102
H-101
P-105 A/B
R-101
D-101 A/B
F-101
H-103
E-101
P-102 A/B P-103 A/B
H-104
H-107
DISTILLATIONCONDENSOR REFLUX REBOILER REFLUX
PREACETIC ACID
REACTOR PRE-FURNACE FURNACE CONDENSOR SEPARATOR
HEAT
HEAT CONDENSOR REFLUX REFLUX
1
PUMP
DRUM
DISTILLATION COLUMN
HEAT
TO
STORAGE
PUMP EXCHANGER
DRUM
PUMP
PUMP EXCHANGER
COLUMN
EXCHANGER
HEAT
Exhaust
EXCHANGER

2
ACO

F-101

1
3

From storage tank

3 T=80C
P=100 kpa

P-101 A/B

NG

H-103

CW

H-107

CW

E-102
To storage
T=30C
P=300 kpa

E-101
5

CW

MPS

R-101
P-103 A/B

MPS

P-105 A/B

12

10

P-109 A/B To storage

T=30C
P=300 kpa

H-108
8

6
7

C-101

H-102

P-108 A/B
CW

D-101
Dowtherm A

H-101

P-102 A/B

15

P-104 A/B
H-105

P-102 A/B

Dowtherm A

K-102

K-101

11

21

20
P-106 A/B

22
H-106

K-101
KETTLE
REBOILER

H-105
HEAT
EXCHANGER

KEY
AA: ACETIC ACID
ACO: ACETYLATED CASTOR OIL
DO: DRYING OIL
GM: GUM
PG: PURGE
A
B

P-106 A/B
GUM TO
WASTE
DISPOSAL

P-107 A/B
PURGE
PUMP

H-106
HEAT
EXCHANGER

C-102
DISTILLATION
COLUMN

II

GM

16

19
CW

24

To waste disposal
T=150C
P=100 kpa 7

H-109

MPS

18

DO

17

CW
7

C-102

H-104

14

13

AA

To storage
T=80C
P=100 kpa

PG

23

P-107 A/B
P-104 A/B
REBOILER
PUMP

K-102
KETTLE
REBOILER

H-109
HEAT
EXCHANGER

P-108 A/B
DO
TO STORAGE

P-109 A/B
DO
TO STORAGE

Sheet: 01/01

PFD- DRYING OIL PROCESS

Date: 14/03/16

Student Number: 50

Project: P2

CHE4049F

1b. STREAM TABLE

1
T C
80.0
P bar
1.000
Vapor Frac 0
Mole Flow 5.85
kmol/hr
Mass Flow 1500
kg/hr
ACETI-01
0
1-TET-01
0
1-OCT-01
0
N-HEX-01 1500
WATER
0
DOWTH-01 0
Mass Frac
ACETI-01
0
1-TET-01
0
1-OCT-01
0
N-HEX-01
1
WATER
0
DOWTH-01 0
Mole Flow
kmol/hr
ACETI-01
0
1-TET-01
0
1-OCT-01
0
N-HEX-01 5.85
WATER
0
DOWTH-01 0
Mole Frac
ACETI-01
0
1-TET-01
0
1-OCT-01
0
N-HEX-01
1
WATER
0
DOWTH-01 0

2
3
4
80.0 227.3 340.0
1.013 1.013 1.013
0
0
0
5.85 11.96 11.96

5
6
7
8
9
10
11
258.8 105.0 105.0 150.0 120.2 141.0 350.0
1.013 1.013 1.013 1.068 1.013 1.786 1.013
0.49
0
0
0
0
0
0
17.11 17.11 17.11 17.11 10.32 10.32 6.79

1500 3067 3067

3067

3067 3067 3067 1326 1326

0
0
0
0
0
0
0
0
0
1500 3067 3067
0
0
0
0
0
0
0
0
0
1
0
0

0
0
0
1
0
0

0
0
0
0
0
0
5.85 12.0
0
0
0
0
0
0
0
1
0
0

0
0
0
1
0
0

0
0
0
1
0
0

0
0
0
12.0
0
0
0
0
0
1
0
0

12
118.0
1.013
0
5.12

13
30.0
0.027
0
5.12

AA
30.6
3
0
5.12

15
16
DO
18
19 GM 21
22
PRG
242.3 30.0 30.5 105.0 150.0 150.2 350.0 80.0
80.1
1.013 0.001 3.000 1.013 0.000 1.000 1.013 <0.0001
1
0
0
0
0
0
0
0
0
0
5.20 5.20 5.20 0.001 0.001 0.001 0.68 0.68
0.68

RCY
350.0
1.013
0
6.11

1741

308

308

308

1018

1018

1018 0.265 0.265 0.265 174

174

174

1567

309
309 309 309 309 309
1011 1011 1011 1011 1011 1011
0.265 0.265 0
0
0
0
1746 1746 1746 1746 5.00 5.00
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
1741
0
0

307
0.412
0
0
0
0

307
307 1.97
0.412 0.412 1011
0
0
0
0
0
5.00
0
0
0
0
0
0

1.97
1011
0
5.00
0
0

1.97
0
0
0
0
1011
0
0
0
0
0 0.265 0.265 0.265 0
5.00
0
0
0
174
0
0
0
0
0
0
0
0
0
0

0
0
0
174
0
0

0
0
0
174
0
0

0
0
0
1567
0
0

0.101 0.101 0.101 0.101 0.233 0.233

0.330 0.330 0.330 0.330 0.763 0.763
0
0
0
0
0
0
0.569 0.569 0.569 0.569 0.004 0.004
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
1
0
0

0.999
0.001
0
0
0
0

0.999 0.999 0.002 0.002 0.002

0.001 0.001 0.993 0.993 0.993
0
0
0
0
0
0
0
0.005 0.005 0.005
0
0
0
0
0
0
0
0
0
0

0
0
0
1
0
0

0
0
0
1
0
0

0
0
0
1
0
0

0
0
0
6.79
0
0

5.12
0.002
0
0
0
0

5.12 5.12 0.03 0.03 0.03

0
0
0
0
0
0.002 0.002 5.15 5.15 5.15
0
0
0
0
0
0
0
0
0
0 0.001 0.001 0.001 0
0
0
0
0.019 0.019 0.019 0
0
0 0.679 0.679
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
0.679
0
0

0
0
0
6.11
0
0

0
0
0
1
0
0

1
0
0
0
0
0

0
0
0
1
0
0

0
0
0
1
0
0

5.15 5.15 5.15

5.15 5.15 5.15
0.001 0.001 0
6.81 6.81 6.81
0
0
0
0
0
0

5.15 5.15 5.15

5.15 5.15 5.15
0
0
0
6.81 0.019 0.019
0
0
0
0
0
0

0.301 0.301 0.301 0.301 0.499 0.499

0.301 0.301 0.301 0.301 0.499 0.499
0
0
0
0
0
0
0.398 0.398 0.398 0.398 0.002 0.002
0
0
0
0
0
0
0
0
0
0
0
0

III

1
0
0
0
0
0

1
0
0
0
0
0

0.006 0.006 0.006

0.99 0.99 0.99
0
0
0
0.004 0.004 0.004
0
0
0
0
0
0

0
0
1
0
0
0

0
0
1
0
0
0

0
0
1
0
0
0

0
0
1
0
0
0

0
0
1
0
0
0

0
0
1
0
0
0

0
0
0
1
0
0

0
0
0
1
0
0

0
0
0
1
0
0

1c. OVERALL UTILITY FLOW RATES 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

HEATER (H-105)

MPS

175

174

8.76

8E-06

0.0142

0.1100

198

TOTAL

OVERALL UTILITY FLOWRATE

169300

IV

1d. EQUIPMENT LIST

PUMPS
HEAT
EXCHANGERS

DISTILLATION
COLUMNS

FURNACE
REACTOR
REFLUX DRUM
REBOILER

SEPARATION COLUMN

PFD Code
P-101 - 9 A/B
H-101
H-102
H-103
H-104
H-105
H-106
H-107
H-108
H-109
C-101

Equipment Type
Centrifugal/electric drive/API
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
1-2 Heat exchanger/Process Shell side
Total Condenser and Kettle Reboiler
Sieve trays and Stainless steel shell

C-102

Total Condenser/Kettle Reboiler

Sieve tray and Stainless steel shell

F-101
R--101
E-101
E-102
K-101

Carbon steel tubes, Refractory lining

Stainless steel PFR/ Adiabatic
Stainless steel vessel
Stainless steel vessel
Kettle type/ Dowtherm A

K-102

Kettle type/ Dowtherm A

D-101

Vertical vessel

Equipment Specifications
Stainless steel/corrosion resistance & and high T
Q=-0.42MW, Stainless Steel, 0.625 -1.5 tubes
Q=0.093MW, Stainless Steel, 0.625 -1.5 tubes
Q<0.0001MW, Stainless Steel, 0.625 -1.5 tubes
Q=0.017MW, Stainless Steel, 0.625 -1.5 tubes
Q<0.0001MW, Stainless Steel, 0.625 -1.5 tubes
Q=-0.0.037MW,Stainless Steel, 0.625 -1.5 tubes
Q<0.0001MW, Stainless Steel, 0.625 -1.5 tubes
Q=-0.0099MW, Stainless Steel, 0.625 -1.5 tubes
Q=-0.15MW, Stainless Steel, 0.625 -1.5 tubes
Reflux Ratio=0.9, Boil up Ratio=5.17, FS=11
Column pressure=1 ATM
Column diameter=2.1m, Column height=15.2m
Number of stages=22
RR=2, BR=1.02, FS=9
Column pressure=1 ATM
Column diameter=1.9m, Column height=12.8m
Number of stages=18
Q=1.05E+0.6KJ/hr, Texit=340C
L=9m, D=10m, X=0.42
Hold up time=5min whilst half full
Hold up time=5min whilst half full
Boil up Ratio=5.17; T=400C, P=5bar
Boil up rate= 35.1kmol/h
Boil up Ratio=1.02; T=400C, P=5bar
Boil up rate = 5.3kmol/hr
L/D=5, V=3m3 (Bailie & Whiting 2012)

2. DISCUSSION OF THERMODYNAMIC PROPERTY METHODS AVAILABLE IN ASPEN

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 most important decision when
carrying out a chemical process simulation(Hill & Justice 2011). 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 (Sandler, 2006).
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 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).

VI

3. JUSTIFYING THE SELECTED THERMODYNMIC 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. Appendix A shows the molecular structures of
acetic acid, drying oil (1-tetradecene), acetylated castor oil (N-hexadecanoic acid) and gum (1Octacosene). 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 known 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 dimers by means
of hydrogen bonds. This often occurs in the vapour phase. In conclusion, the mixture is highly
polar because of the hydrogen bond interactions between the carboxylic acid molecules and
dimerization that occurs to some extent. This is a highly non ideal and polar mixture. There is
no random distribution of molecules in polar solutions (Sandler, 2006)
With this knowledge in mind it is important to find thermos-physical properties of the
compounds involved and generate several T-X-Y and P-X-Y diagrams to validate the
thermodynamic model(Hill & Justice 2011). These diagrams can be found in APPENDIX B and
APPENDIX C.
Figure 2, Figure 4 and Figure 7 in APPENDIX B depict how the UNIFAC, WILSON AND UNIFHOC models are good approximations of vapour equilibrium data by (Matricarde Falleiro et al.
2010). 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.

FIGURE 1: EXPERIMENTAL DATA (Matricarde Falleiro et al, 2010)

COMPARED TO ASPEN MODELS
Y-N-TETRADECANOIC ACID

1
0.9
0.8
0.7

EXPERIMENTAL DATA

0.6

Equilibrium Line

0.5

UNIFAC

0.4

PENG ROBINSON

0.3

PRSK

0.2

NRTL

0.1

UNIF-HOC

0
0

0.2

0.4

0.6

0.8

X-TETRA DECA NOIC ACID

VII

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 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
( See APPENDIX A).
Similar compounds are used to model reactants in the drying oil process in the situation where
plant data, pilot plant data and laboratory 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 APPENDIX A.
In order to understand the absolute fit of ASPEN models to VLE data provided by (Matricarde
Falleiro et al. 2010), Table 1 shows the results of a root mean square error analysis.

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

The result from Table 1 shows how UNIFAC, UNIF-HOC, UNIQUAC, WILSON AND NRTL
models are a good fit to the vapour liquid equilibria data of palmitic acid and myristic acid.
The P-X-Y diagrams were generated from data for hexene and acetic acid. This data was
obtained from the NIST database provided by 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 APPENDIX C (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 (APPENDIX D) showing
that no azeotropes are formed at 1 atmosphere.

VIII

T-XY AND P-XY diagrams are plotted to understand the nature of the process mixture and the
ease of separation (Sandler 2006). 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 plant. 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
literature was sought to fill in the gap. 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 to find. Plant
data, pilot plant data, laboratory data and even literature data for the drying oil process could
not be easily accessed or found. As a result a predictive model was chosen.
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. Figure 9 below shows a comparison of activity coefficient data from a solubility data set
by (Ralston & Hoerr 1942) and ASPEN thermodynamic models(see calculation in APPENDIX
D). UNIFAC is a good approximation of the experimental data. Figure 2 also validates that
UNIFAC is an appropriate model to simulate the drying oil process.

IX

4. MODEL LIBRARY COMPONENTS

MODEL LIBRARY COMPONENTS
PUMPS

HEAT
EXCHANGERS

DISTILLATION
COLUMNS

FURNACE
REACTOR
REFLUX DRUM
REBOILER

SEPARATION COLUMN

PFD Code
P-101 A/B
P-102A/B
P-103A/B
P-104A/B
P-105A/B
P-106A/B
P-107A/B
P-108A/B
P-109A/B

Equipment Type
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API
Centrifugal/electric drive/API

H-101
H-102
H-103
H-104
H-105
H-106
H-107
H-108
H-109

Cooler
Heater
Condenser
Heater
Heater
Cooler
Condenser
Cooler
Cooler

C-101

Distillation column

C-102

Distillation column

F-101
R--101
E-101
E-102
K-101

Natural gas furnace

Plug flow reactor
Reflux drum
Reflux drum
Kettle type

K-102

Kettle type

D-101

XI

MODEL LIBRARY
COMPONENTS
PUMPS
P-101 A/B
P-102A/B
P-103A/B
P-104A/B
P-105A/B
P-106A/B
P-107A/B
P-108A/B
P-109A/B
HEAT EXCHANGERS
H-101
H-102
H-103
H-104
H-105
H-106
H-107
H-108
H-109
DISTILLATION
COLUMNS
C-101
C-102
FURNACE
F-101
REACTOR

FUNCTION
Pump liquid ACO from storage tanks and charge it into the process.
Pumping of the columns bottoms liquid to the kettle reboiler.
Condensers are not located at the top of columns, reflux and distillate is pumped up.
Pumping of the columns bottoms liquid to the kettle reboiler.
Condensers are not located at the top of columns, reflux and distillate is pumped up.
Gum needs to be pumped to storage. Gum exits process as a liquid at a pressure of 100kpa.
0.1 percent of recycled ACO with trace products is purged and pumped out to storage at 100kpa.
The product DO needs to be pumped from the second columns bottoms stream to storage at 300kpa.
The distillate AA has to be pumped from the distillate stream to storage at 300kpa.
Reactor products exit extremely hot. Energy from this stream can be used to generate lps from bfw.
Stream entering C-101 needs to be heat to get to the bubble point of the liquid mixture.
This is a total condenser.
Stream entering C-102 needs to be heat to get to the bubble point of the liquid mixture.
This is a heater used to melt the accumulated gum before it is pumped to waste disposal.
Recycled ACO coming from the bottoms of C-101 is hot liquid and needs to be cooled before purging.
This is a total condenser.
The distillate stream needs to cooled to a temperature of 30C before AA is pumped to storage.
The bottoms stream needs to be cooled before DO is pumped to storage at 30C.

Radfrac columns can handle highly non ideal components. Radfrac is more rigorous than DISTWU.
Radfrac columns can handle highly non ideal components. Radfrac is more rigorous than DISTWU.
Reactor inlet temperature T=340C is higher than the temperature of HPS at 4237kpa (253.794K).

XII

R--101
REFLUX DRUM
E-101
E-102
REBOILER
K101-102

PFRs are adequate for high throughput and short residence time reactions. Adiabatic reactor used.
Hold up time of 5 minutes when half full and these are good for limiting phase entrainment.
Hold up time of 5 minutes when half full and these are good for limiting phase entrainment.
More volatile components in the bottoms product need to be stripped.

XIII

APPENDIX A
MOLECULAR STRUCTURE

ACETIC ACID

1 TETRADECENE (DRYING OIL)

MYRISTIC ACID (1 TETRADECANOIC ACID)

XIV

1 OCTACOSENE (GUM)

N-HEXADECANOIC ACID (ACETYLATED CASTOR OIL)

PALMITIC ACID (HEXADECANOIC ACID)

HEXENE

XV

APPENDIX B
T-XY DIAGRAMS

XVI

XVII

XVIII

XIX

APPENDIX C
P-XY DIAGRAMS

XX

XXI

APPENDIX D
CALCULATING THE ACTIVITY COEFFICIENT
T (K)

T C

C/L (mol/mol)

293.15
20
0.0049866
303.15
30
0.0186385
313.15
40
0.107998
323.15
50
0.422967
333.15
60
0.842257
Table 2: Solubility of hexadecanoic acid as a function of temperature (Ralston & Hoerr 1942)
In order to calculate the activity coefficient (gamma) the following equation from (Sandler, 2006)
was used:

Notice the above equation has three terms on the RHS. Each term will be calculated using CP
and temperature data from (Ralston & Hoerr 1942). This data is shown in Table 1 above.
The following steps were taken to calculate gamma in EXCEL:
T (K)
CpL (J/g.K)
CpL (J/mol.K)
343
2.18
559
348
2.21
567
353
2.25
577
358
2.33
597
363
2.38
610
368
2.45
628
373
2.49
638
378
2.55
654
383
2.62
672
388
2.7
692
393
2.71
695
398
2.77
710
403
2.83
726
408
2.88
738
413
2.95
756
418
3.04
780
423
3.1
795
428
3.17
813
Table 3: Heat capacity data for hexadecanoic acid (source: http://webbook.nist.gov)

The following graph was then generated in order to obtain the gradient and intercept values.

XXII

Obtaining the gradient and intercept from the relationship between Cp(l) and temperature.
The following information necessary for the calculation was also obtained from
(http://webbook.nist.gov/cgi/cbook.cgi?ID=C57103&Mask=2)
Data: N-hexadecanoic acid
Value
Units
Molecular weight
256.42
g/mol
Ideal gas constant: R
8.314
J/mol.k
Heat of fusion
53642.3
J/mol
T(melting)
335.64
K
Table 4: Properties of N-hexadecanoic acid.
The following information was then used to appreciate the change in heat capacity.
Which is the difference between the heat capacity of the liquid and that of the solid
Cp= Cp(l) Cp(s)
Cp= gradient*T + constant
The gradient and constant are displayed by Figure 19.
This information was then used to compute the right hand side of the equation from (Sandler,
2006)
The second and third terms required integration.

XXIII

RIGHT HAND SIDE

OF EQUATION
1ST TERM
2ND TERM
3RD TERM
TOTAL
-2.786
-0.757
0.708
-2.835
-2.060
-0.551
0.524
-2.087
-1.381
-0.364
0.352
-1.393
-0.743
-0.193
0.189
-0.747
-0.144
-0.037
0.037
-0.144
Table 5: Calculating the the right handside of ln(xi*gamma) equation from (Sandler, 2006)
Once these values were obtained the gamma was made the subject of the formula and the following data was computed:

T (K)
293.15
303.15
313.15
323.15
333.15

T C
20
30
40
50
60

C/L (mol/mol)
0.005
0.019
0.108
0.423
0.842

EXPERIMENTAL
11.8
6.65
2.30
1.12
1.03

UNIQUAC
UNIQ-HOC
0.47
0.47
0.47
0.47
0.47
0.47
0.47
0.47
0.47
0.47
PEN
EXPERIMENTA
WIL
G
T (K)
T C
C/L (mol/mol)
L
SON
NRTL
ROBINSON
SRK
293.15
20
0.005
11.8
1
1
71.6
42.0
303.15
30
0.019
6.65
1
1
49.2
29.6
313.15
40
0.108
2.30
1
1
34.9
21.4
323.15
50
0.423
1.12
1
1
25.4
15.9
333.15
60
0.842
1.03
1
1
18.9
12.1
Table 5: EXPERIMENTAL VALUES OF GAMMA COMPUTED FROM USING EQUATION 1 FROM (SANDLER, 2006) AND
SOLUBILITY DATA FROM (Ralston & Hoerr, 1942)
Table 5 shows the experimental values of gamma obtained from solubility data from (Ralston & Hoerr, 1942).
These experimental values were then compared to different models from ASPEN.

XXIV

UNIFAC
2.42
2.34
2.27
2.20
2.13

UNIF-HOC
2.53
2.45
2.37
2.30
2.22

6. 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.70
77. 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.
SANDLER, S. I., & SANDLER, S. I. (2006). Chemical, biochemical, and engineering
thermodynamics. Hoboken, N.J., John Wiley

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XXVII