FACULTY OF ENGINEERING AND BUILT ENVIRONMENT

DEPARTMENT OF CHEMICAL ENGINEERING

ADVANCED DIPLOMA
PROJECT II: MODELLING AND SIMULATION

Subject: PROCESS DESIGN 4

Subject code: PQD470S
Lecturer: Mr T. Madzimbamuto
Name: Denilson
Surname: Marcos
Student number: 219180962
Due date: 4 September 2022

I certify that this document is my own unaided work, except for the
assistance received from the teaching stuff. I undertake not to pass this
report onto any other student.

04 September 2022

______________ __________________

Signature Date submitted

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Summary

In this report, different streams were cleaned, with one not cleaning so well (wastewater
stream 2). In the air stream there was a removal of 95% of acetaldehyde and basically all the
methanol. As will be shown on Table 20 in the Appendix A. In the extractor in the wastewater
stream 1, dichloromethane removes 96% of acetaldehyde, achieving the main objectives of
the task.

The pressure and the temperature in the absorption column is high and low respectively, and
in the extraction column the temperature is as high as possible, and the pressure is kept low.

All the simulations were performed at using Aspen Plus, which as is very satisfactory. The
manually designed PFD’s were the base models for the particular plant simulation. No
significant energy was lost because this process is mostly about the author shied the book.

Most streams are working perfectly well, except the wastewater stream 2. At the end of the
day the streams become cleaned and purified.

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Table of Contents
Summary.............................................................................................................................................ii
I. Introduction................................................................................................................................1
CHAPTER 1: PROCESS TOPOLOGY...........................................................................................1
II. PROCESS FLOWSHEET......................................................................................................2
1.1. PROCESS DESCRIPTION............................................................................................2
1.1.2. Air Stream...................................................................................................................2
1.1.2.1. Material requirements..........................................................................................2
1.1.3. Wastewater stream 1................................................................................................6
1.1.3.1. Material requirements..........................................................................................6
1.1.4. Wastewater stream 2................................................................................................9
1.1.4.1. Material requirements..........................................................................................9
III. PROCESS MODELLING.................................................................................................13
1.2. Overview.......................................................................................................................13
1.2.2. Units specified in process models.....................................................................14
1.2.3. Discussion of results.............................................................................................14
1.2.3.1. Air stream..............................................................................................................14
1.2.3.2. Wastewater stream 1..........................................................................................16
1.2.3.3. Wastewater stream 2..........................................................................................17
1.2.3.4. Thermodynamic considerations/Physical properties................................18
1.2.3.5. Sensitivity analysis.............................................................................................24
I. Reference..............................................................................................................................25
Appendix A – Important data.......................................................................................................26
Appendix B – Preliminary models and results........................................................................30
Appendix C – Preliminary models..............................................................................................32
Aspen Plus simulation links:................................................................................................................36

Figure 1: Process flow diagram: Absorption of methanol and acetaldehyde from air,
and stripping of methanol and acetaldehyde from water.......................................................3
Figure 2:Process flow diagram: Solvent-solvent extraction of acetaldehyde from
water, using dichloromethane.......................................................................................................6
Figure 3:Process flow diagram: Solvent-solvent extraction of ethylene glycol from
water, using 2 ethylhexanol.........................................................................................................10
Figure 4:Aspen Plus PFD model to purify a contaminated air stream..............................14
Figure 5:Aspen Plus PFD model to purify a contaminated wastewater stream 1...........16
Figure 6:Aspen Plus PFD model to purify a contaminated wastewater stream 2:.........17

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Figure 7: Approach to select best thermodynamic model...................................................20
Figure 8: Property package selection........................................................................................21
Figure 9: Sensitivity test on liquid-liquid extractor unit for the wastewater stream 1...24
Figure 10:Sensitivity test on liquid-liquid extractor unit for the wastewater stream 1
with recycling stream....................................................................................................................24
Figure 11:Sensitivity test on liquid-liquid extractor unit for the air stream 1 with
recycling stream.............................................................................................................................26
Figure 12: Recycling stream energy balance..........................................................................28
Figure 13:Stripper feed energy balance....................................................................................28
Figure 14: Absorber split fraction...............................................................................................28
Figure 15:Absorber pressure.......................................................................................................29
Figure 16:Absorber configurations............................................................................................29
Figure 17:Stripper configuration.................................................................................................30
Figure 18:Stripper pressure.........................................................................................................30
Figure 19:Extractor from wastewater 1 split fraction............................................................30
Figure 20:Specs for extractor 1...................................................................................................31
Figure 21: Extractor for wastewater stream 2..........................................................................31
Figure 22:Stripper Streams..........................................................................................................31
Figure 23:Sensitivity analysis using the pressure.................................................................33

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 I. Introduction

When representing a physical, chemical, biological or any other technical process as well as
unit operations, a process simulation has become the go to software for different industries
such as petro-chemicals process industries. This is because by using a process simulation
software industries are able to design a technical process, improve it, evaluate it, and
enhance it according the desired specifications. Material and energy balances are performed
thanks to the optimal algorithm that best suits the process at hand. All thermodynamics and
transport characteristics are also taken into consideration, through the use of property
methods that come in the program (Khan and Hassan, 2016). This prevents unnecessary
costs as a process simulation software also accounts for the economics involved in each unit
operation and in the process as a whole, leading to a more effective design, efficient
process, and feasible operation, given that a preliminary gross profit calculation was done in
Chapter 1. Material and energy balances were manually performed in Chapter 2, as well as
the utilities and equipment choices. In Chapter 3 the main unit operations would be designed
individually.

On the other hand, this report’s main focus is to optimize the unit operations chosen to purify
an air stream and two water streams respectively, though the modification of certain
parameters such as operational conditions, columns internals and hydraulics involved in the
process. At the end of this report a clear view and more realistic results can be expected.

CHAPTER 1: PROCESS TOPOLOGY

This section highlights a purification process performed in three different major waste
streams which originated from a polymer-processing facility, using the most adequate
approaches to promote an environmentally friendly image of the company.

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 II. PROCESS FLOWSHEET

1.1. PROCESS DESCRIPTION

1.1.2. Air Stream

Compressed air mixture (stream-1), containing acetaldehyde and methanol, flows through a
cooler (HX-101) reducing its temperature to the operational conditions (stream 2)
when it enter an absorption column (C-101) from the bottom.

Pumped water (stream 3&4) is fed to the same column (C-101) from the top. The, now
cleaner, air (stream 5) is released into the environment through the top of the column (C-
101). The contaminants are absorbed by the water leaving the column (C-101) from the
bottom (stream 6) to enter the stripping column (C-102) from the top where the contaminants
are stripped off from the water (stream-10) to be further separated in the distillation column
(D-101). Steam (stream 7) is fed into the stripper(C-102) while the rest of the water (stream
8) is cooled (HX-102) to be recycled (stream 9) to the absorption column (C-101).

1.1.2.1. Material requirements

Here, the necessary feedstock material to purify the AIR-STREAM by removing more than
90% of methanol (0,3%) and acetaldehyde (0,3%) respectively is found in Table 1. These
materials have already been brought to light on Chapter 1, and their values had been
calculated on Chapter 2.

Table 1:Material Requirements per year

Feedstock Quantity (kg/year)

Water 7280524,2

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 1.1.2.2. PFD model

Figure 1: Process flow diagram: Absorption of methanol and acetaldehyde from air,
and stripping of methanol and acetaldehyde from water.

Table 2:Equipment List

Displayed Text Description

Pump P-101
Heat Exchanger HX-101

Absorption Column C-101

Compressor P-102
Stripper Column C-102
Distillation Column D-101
Condenser E-101
Reflux Drum RD-101
Storage Tank S-101
Reboiler E-102
Storage Tank S-102
Heat Exchanger HX-102

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Table 3:Stream Table

MASS FLOW RATES [kg/h]

STREAM 1,2 4 5 6
Component        
Acetaldehyde 8,71 0,00 0,44 8,28
Methanol 8,71 0,00 0,44 8,28
Air 2886,80 0,00 2886,80 0,00
Water 0,00 902,70 0,00 902,70
Total 2904,23 902,704 2887,68 919,26

1.1.2.3. Unit summary of each unit

The operation units used in this process of air purification, includes the following units shown in
table 4.

Table 4:Summary of basic unit operations

Momentum Mass Transfer Unit Heat Transfer Unit

Transport Unit Operations Operations
Operations
Piping system Absorber Condenser
Pumps Stripper Heat-exchanger
Compressor Cooler

Momentum Transport Unit Operations

They certify the transport of the fluids in the whole system.
The piping system is what allows the fluids to flow throughout the whole process while the
pumps and the compressors set the operating conditions of the fluids.
Mass Transfer Unit Operations
These are also known as the major equipment’s. In the absorber the contaminants,
acetaldehyde and methanol, are absorbed by cold water, thus, purifying the air stream. The
stripper strips off the contaminants from the solvent used, water, purifying it.
Heat Transfer Unit Operations
These are very important for the operation as they regulate the operating conditions of the
streams flowing in the treatment plant.

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 1.1.2.4. Summary of basic unit operations

Absorption Column (C-101)

Column type Plate column
Operating temperature 6℃

Operating pressure 1 bar

Number of Stages 7
Stripper Column(C-102)
Column type Tray column
Operating temperature 81℃
Operating pressure 0,5 bar
Number of Stages 10
Condenser type Partial-vapor
Reboiler type Kettle
Bottoms rate 72 kmol
Boilup ratio 0,5

Table 5: Basic unit operations

1.1.2.5. Utilities

Utilities were chosen based on the available services of in the process.

Utility type

Cooling water max T. 24oC.

Steam at 1400 kN/m2
Electricity at at 440 V

Table 6: Utility specifications

1.1.3. Wastewater stream 1

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A feed of contaminated solution, water and acetaldehyde, is pumped into an extractor (C-
103) from the top (stream 18). A solvent, dichloromethane, enters the column from the
bottom (stream 19&20), then the extract (stream 22), dichloromethane and acetaldehyde,
exits the column to become the feed of a distillation column (D-102) to be further separated
from the dichloromethane and create a recycling stream (stream 20) with the rest of the
dichloromethane. Meanwhile the, now purified, raffinate exits the column from the bottom to
be disposed of (stream 21)

1.1.3.1. Material requirements

Table 7:Material Requirements per year

Quantity
Feedstock (kg/year)
Dichlorometha
6544849,5
ne

Here, the necessary feedstock material to purify the water-stream 1 by removing more than
90% of acetaldehyde (2%) is found in Table 8. These materials have already been brought
to light on Chapter 1, and their values had been calculated on Chapter 2. However, a more
accurate list of the materials required per year should be given once we reach the economic
analysis where all sorts of relevant costs shall be calculated and analyzed

1.1.3.2. PFD model

Figure 2:Process flow diagram: Solvent-solvent extraction of acetaldehyde from

water, using dichloromethane.

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 Displayed Text Description
Pump P-103
Pump P-104

Liquid-liquid Extraction Column C-103

Distillation Column D-102

Reboiler E-103

Condenser E-104

Reflux Drum RD-102

Reflux Drum RD-101
Storage Tank S-103
MASS FLOW RATES [kg/min]

STREAM 18 19+20 21 22 28

Component          

Acetaldehyde 19,83 0,00 0,99 18,84 18,84

Water 971,81 0,00 971,81 0,00 0,00

Dichloromethane 0,00 15,57 0,00 15,57 0,00

Total 991,64 15,57 972,80 34,41 18,84

Table 8:Equipment List and Stream Table

1.1.3.3. Unit summary of each unit

The operation units used in this process of air purification, includes the following units shown
in table 9.

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Table 9:Summary of basic unit operations

Momentum Mass Transfer Unit Heat Transfer Unit

Transport Unit Operations Operations
Operations
Piping system Liquid-liquid extractor Condenser
Pumps Distillation column Heat-exchanger
Compressor Cooler

Momentum Transport Unit Operations

They certify the transport of the fluids in the whole system.

The piping system is what allows the fluids to flow throughout the whole process while the
pumps and the compressors set the operating conditions of the fluids.

Mass Transfer Unit Operations

These are also known as the major equipment’s. In the absorber the contaminants,
acetaldehyde and methanol, are absorbed by cold water, thus, purifying the air stream. The
stripper strips off the contaminants from the solvent used, water, purifying it.

Heat Transfer Unit Operations

These are very important for the operation as they regulate the operating conditions of the
streams flowing in the treatment plant.

1.1.3.4. Summary of basic unit operations

Liquid-liquid extractor(C-103)
Column type Pulsed Sieve Tray
Operating temperature 20

Operating pressure 1 bar

Number of Stages 8
Distillation column (D-102)
Column type continuous

Table 10:: Basic unit operations

8
The unit operations for the water stream will be better described based on the ASPEN
simulated model of the process by focusing on the main results.

1.1.3.5. Utilities

Utilities were chosen based on the available services of in the process.

Utility type

Cooling water max T. 24oC.

Steam at 1400 kN/m2
Electricity at at 440 V
Table 11: Utility specifications

1.1.4. Wastewater stream 2

A feed of contaminated solution, water and ethylene glycol, is pumped into an extractor (C-
104) from the top (stream 29). A solvent, 2-ethylhexanol, enters the column from the bottom
(stream 30+31), then the extract (stream 33), 2-ethylhexanol and ethylene glycol, exits the
column to become the feed of a distillation column (D-103) to be further separated from the
2-ethylhexanol and create a recycling stream (stream 31) with the rest of the
dichloromethane. Meanwhile the, now purified, raffinate exits the column from the bottom to
be disposed of (stream32).

1.1.4.1. Material requirements

Table 12:Material Requirements per year

Feedstock Quantity (kg/year)

2-ethylhexanol 158408553,6

Here, the necessary feedstock material to purify the water-stream 2 by removing more than
90% of ethylene glycol (3%) is found in Table 12. These materials have already been
brought to light on Chapter 1, and their values had been calculated on Chapter 2.

9
However, a more accurate list of the materials required per year should be given once we
reach the economic analysis where all sorts of relevant costs shall be calculated and
analyzed.

1.1.4.2. PFD model

Figure 3:Process flow diagram: Solvent-solvent extraction of ethylene glycol from

water, using 2 ethylhexanol.

Table 13:Equipment List

Displayed Text Description

Pump P-105
Pump P-106
Liquid-liquid Extraction
Column C-104
Distillation Column D-103
Reboiler E-105
Condenser E-106
Reflux Drum RD-103
Storage Tank S-104

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Table 14:Stream Table

MASS FLOW RATES [kg/min]

STREAM 29 30+31 32 33 39
Component          
Ethylene glycol 30,00 0,00 1,50 28,50 28,50
Water 970,05 0,00 970,05 0,00 0
2-ethylhexanol 0,00 12,21 0,00 12,21 0
Total 1000,05 12,21 971,55 40,72 28,50

Note that for simulation purposes the entering feed was based on the conversion of the
provided specifications, as the material balance for the wastewater-stream 2 showed on
Table 14 might be faulty.

1.1.4.3. Unit summary of each unit

The operation units used in this process of air purification, includes the following units shown
in table 15.

Table 15:Summary of basic unit operations

Momentum Mass Transfer Unit Heat Transfer Unit

Transport Unit Operations Operations
Operations
Piping system Liquid-liquid extractor Condenser
Pumps Distillation column Heat-exchanger
Compressor Cooler

Momentum Transport Unit Operations

They certify the transport of the fluids in the whole system.

The piping system is what allows the fluids to flow throughout the whole process while the
pumps and the compressors set the operating conditions of the fluids.

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Mass Transfer Unit Operations

These are also known as the major equipment’s. In the absorber the contaminants,
acetaldehyde and methanol, are absorbed by cold water, thus, purifying the air stream. The
stripper strips off the contaminants from the solvent used, water, purifying it.

Heat Transfer Unit Operations

These are very important for the operation as they regulate the operating conditions of the
streams flowing in the treatment plant.

1.1.4.4. Summary of basic unit operations

Liquid-liquid extractor(C-103)
Column type Pulsed Sieve Tray
Operating temperature 20

Operating pressure 1 bar

Number of Stages 8
Distillation column (D-102)
Column type continuous

Table 16:: Basic unit operations

The unit operations for the water stream will be better described based on the ASPEN
simulated model of the process by focusing on the main results.

1.1.4.5. Utilities

Utilities were chosen based on the available services of in the process.

Utility type

Cooling water max T. 24oC.

Steam at 1400 kN/m2
Electricity at at 440 V
Table 17: Utility specifications

12
However, a more accurate list of the materials required per year should be given once we
reach the economic analysis where all sorts of relevant costs shall be calculated and
analyzed.

III. PROCESS MODELLING

1.2. Overview

Aspen Plus was the chosen software to model the PFD’s presented in the figures bellow.
These processes were simulated bearing in mind thermodynamics and transport properties
through the application of the most suitable property method, NRTL, which we will dive more
into, later in this report. The bellow figures present the models which now have been
optimized so that it can complete the tasks for which it has been designed.

A careful approach was used when selecting the equipment for these operations, since we
are dealing with dilute solutions, meaning, very small concentrations of solute present in the
air and in the two wastewater streams, so that the best option would also be the most
feasible, economical, and environmentally friendly as possible.

These processes are based on mass transfer, with very little to negligible energy transfers.
Thus the main focused was on how to deal with the amount of materials used, and how to
optimize the streams in such ways that the processes are affected positively, with an
increased rate of success.

Now lets us dive more into the designed models.

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 1.2.2. Units specified in process models

1.2.3. Discussion of results

1.2.3.1. Air stream

Figure 4:Aspen Plus PFD model to purify a contaminated air stream

Now, Figure 4 shows a PFD considerably different from the preliminary design shown in
Figure 1. In terms of physical structure, the skeleton is kept the same with a mixer
connecting the recycling stream with the feed stream. Nonetheless, it can be noticed the
absence of a distillation column in this model. It has been done so to improve the feasibility
of the of the treatment operation by reducing the costs of acquiring a distillation column,
while still successfully achieving the end goal, which was to purity the air stream, a more
than 90% removal of all the contaminants present in this stream. This is thanks to the
intelligent design which took into consideration the operating conditions which favour the
success of the operation. Such as the streams’ temperature and pressure.

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 WATER-IN FLUE-OUT WAT-OUT FLU-RICH RECY PURGE RECYC FEED-MIX
Temperature (C) 6 6,230 6,294 4,722 81,211 81,342 6 6
Pressure (bar) 1,000 5,000 1,000 1,000 0,500 0,500 5,000 5,000
Mass Flows (kg/hr) 2700,000 3867,390 2895,119 3876,501 2579,401 1297,100 129,710 1167,390
AIR 0,000 0,000 2877,511 9,294 9,294 0,000 0,000 0,000
METHA-01 0,000 0,000 0,000 8,713 8,713 0,000 0,000 0,000
ACETA-01 0,000 0,000 0,393 8,319 8,319 0,000 0,000 0,000
WATER 2700,000 3867,390 17,214 3850,176 2553,076 1297,100 129,710 1167,390

Mole Fractions
AIR 0,000 0,000 0,990 0,001 0,002 0,000 0,000 0,000
METHA-01 0,000 0,000 0,000 0,001 0,002 0,000 0,000 0,000
ACETA-01 0,000 0,000 0,000 0,001 0,001 0,000 0,000 0,000
WATER 1,000 1,000 0,010 0,996 0,995 1,000 1,000 1,000

Table 18:Stream table of the major units for the modelled air stream operation.

Unfortunately, Table 18 does not show neither the mass flow nor the mole fraction of the air
stream entering the column (Absorber) for a good comparison of the results, however, in the
Appendix … we can see the final split fraction of the absorption column after the sensitivity
analysis, which will be covered later, was performed. The absorber was run with cold
temperatures and high pressure to increase the solubility of the solutes with the removing
solvent, (Madzimbamuto, 2022). Because of the high operating pressure of the column, the
number of stages was small, 7, decreasing the construction costs and overcoming any
significant pressure drop. After the sensitivity analysis the flow rate of the inlet solvent
increased so that the air could reach the set purification standards. After absorbing methanol
and acetaldehyde from the air stream, the air was completely clean with more than 90%
removal of the contaminants. The water stream entered a stripping column (Stripper) where
the contaminants were successfully removed from the solvent. It was also thanks to the
stripper operating condition and good understanding of fluid properties such as the solubility
relation with temperature and pressure. With that being said, the pressure in the stripper was
reduced, and because of the high water flowrate, there was no need to implement a pump or
turbine in the solvent stream entering the stripper. The temperature was increased to
facilitate the stripping of the contaminants from the water. After it had been successfully
done, an energy balance was performed to check whether the outlet stream from the stripper
has enough power to heat up the stripper inlet stream in order to make good use of any left
out heat, but it was observed that it would not be possible because the inlet stream (Wat-out)
had a higher power than the outlet stream (Recy). Therefore, to account for the lack of
energy integration, a material integration was done instead. Thus, the birth of the recycling
stream (Recyc) which made the sure that no solvent is wasted. A split of the water from the
recycling stream was purged, but according the heuristics no violation was done because

15
the stream is clean and has been cooled down to 6 degrees Celsius. Therefore, this plant is
environmentally friendly.

1.2.3.2. Wastewater stream 1

Figure 5:Aspen Plus PFD model to purify a contaminated wastewater stream 1

The simulation model brought forth has been considered a success in the treatment of a
stream containing water and acetaldehyde. The solvent feed flowrate was based on the
value obtained from the conversion of the given data. This process is pretty much similar to
the one showed in Figure 2. However, what makes this operation different is that it works.
The column had 8 stages and operates adiabatically. Dichloromethane has proven to be the
ideal solute extractor by achieving more than 90% removal of the acetaldehyde just like
water in the air stream. The streams entered the extraction column (Extract) at 20 degrees
Celsius and 1 bar as can be observed from Figure 5, from the literature we want to keep the
fluids’ temperature not above standard conditions, as it has been shown before in ternary
graphs that solubility is decreased with increase in temperature. Basically, the desired
compounds do not dissolve as expected. An optimal solvent flowrate was also estimated
thanks to the graph generated from the sensitivity test, will be shown as we go deeper in this
report. In overall, this design has been successful, and is ready for the next stage of the
project which takes into consideration other relevant parameters of this operation.

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 MAIN-FD WATERMIX SOL-OUT WAT-OUT ACE-OUT RECY SOLVENT
Temperature (C) 20 20 19 18 37 39 20
Pressure (bar) 1 1 1 1 1 1 1
Mass Flows (kg/hr) 50000,000 103666,210 104707,949 58456,861 51041,897 53666,053 53666,210
WATER 0,000 0,077 434,511 57874,194 434,434 0,078 0,077
ACETA-01 0,000 55,399 1199,989 45,383 1144,587 55,401 55,399
DICHL-01 50000,000 103610,734 103073,449 537,284 49462,875 53610,574 53610,734
Mass Fractions
WATER 0,000 0,000 0,004 0,990 0,009 0,000 0,000
ACETA-01 0,000 0,001 0,011 0,001 0,022 0,001 0,001
DICHL-01 1,000 0,999 0,984 0,009 0,969 0,999 0,999

Table 19:Stream table of the major units for the modelled wastewater stream
operation

Keeping in mind that the results displayed on Table 19 were generated by Aspen Plus after
the sensitivity test had been done and the operating conditions or unit operations had been
improved. Thus, it is seen that about fifty thousand kilograms per hour of dichloromethane is
enough for the percentage removal that we are seeking for. It might appear like that a lot,
but given the initial specifications it is safe to say that the process is feasible. The absence of
pumps or turbines is due to the high flowing rates of the fluids throughout the plant.
Information on the split fraction of the extraction column can be observed in the Appendix A
figure 19.

1.2.3.3. Wastewater stream 2

20
1

WAT ERMIX 20
1

EXTRACT

EXTCOLUM
20
20
1
1

SOLVENT
RAFFINAT

Temperature (C )

Pressure (bar)

17
Figure 6:Aspen Plus PFD model to purify a contaminated wastewater stream 2:

This process went so south that nothing could bring it back north. Ethylene glycol is a
component almost impossible to extract from water unless an adsorption column is used
instead. The Appendix A shows the split balance of this column (Extcolum) with little to
almost no quantity of ethylene glycol leaving in the solvent stream, and this is purely
because, naturally ethylene glycol has high hydrophilic properties making it almost
impossible to be separated from water. Due to its impracticality, the table of results for the
streams will not be displayed.

1.2.3.4. Thermodynamic considerations/Physical properties

The different streams contain different functional groups that form polar molecules, such as
alcohol. When deciding on the correct property method to use is it something that is kept in
mind and overlooked, due to its importance. Aspen Plus is the ideal simulation program for
this task because when working with polar molecules it generates data far from ideal
conditions, thus, results considerably close to reality.

Aspen Plus uses different estimation methods contained in the property methods, to make
considerations for thermodynamics and transport properties. Mixtures’ physical and chemical
characteristics are determined through a combination of store interaction parameters,
(Thermodynamic Models & Physical Properties, n.d.).

Important property models

Different mixtures contain different components; thus different property models are
respectively required for each process.

Ideal conditions
For ideal conditions it is best to use the ideal model which makes use of the ideal gas law for
gases and makes other assumptions for liquids, these include a fugacity of 1 for gases and
an activity coefficient of 1 for liquids. Generally, when dealing with operations under
extremely high temperatures and/or under vacuum pressure, ideal behaviour is assumed,
and the property method that models these ideal behaviour is the IDEAL property method,
(Thermodynamic Models & Physical Properties, n.d.).

Equations of state

To predict thermodynamic properties, equations of state (EOS), are the go to model. For
different applications Aspen makes use of equations of state derived from statistical

18
thermodynamics such as the SAFT and the Sanchez-Lacombe, as well as cubic equations
of state such as the Peng-Robinson EOS (including its variations) and the Soave-Redlich-
Kwong. Not to mention that even steam tables are also EOS models., (Thermodynamic
Models & Physical Properties, n.d.)

Activity coefficient models

When dealing with non-ideal solutions the components in mixtures have different fugacity.
Activity is the name attributed to the ratio of fugacity in dilution to that of a pure component.
The higher the fugacity the slimmer the likelihood of a component to vaporize in its pure
state, indicating that the activity is greater than unity. It is believed that it happens due to the
levels of repulsion among molecules with mixture, (Thermodynamic Models & Physical
Properties, n.d.).

There is a variety of activity coefficient model available in Aspen Plus, they include the
following:

 NRTL
 Van Laar
 Wilson
 UNIFAC
 UNIQUAC
 Flory Huggins
 Electrolyte NRTL; and
 Scatchard Hildebrand

What happens is that Aspen Plus makes use of the EOS to calculate the vapour phase
properties, while the activity coefficient calculates the liquid properties, (Thermodynamic
Models & Physical Properties, n.d.)

Thermodynamic model choosing criteria

Engineers are well known for using mount up experience to make decisions regarding
productions processes, or any technical operations. Therefore, the same approach applies
when choosing a thermodynamic property. Different guidelines for selecting the most

19
suitable property method for different operations under different operating conditions have
been made available, such as Figure 7 and Figure 8 however the rule of thumb would be to
check whether the compounds are polar (acids, water, alcohol) or not. Given that they are
polar then we can anticipate a case of non-ideality. Thus refer to the activity coefficient
models, such as the most frequently used NRTL. In case of CO2, N2 or any other
component that is non-condensable then a special approach must be used, such as the
implementation of Henry’s law, (Thermodynamic Models & Physical Properties, n.d.).

According to the information under this topic, and considering the nature of the contaminants
present in the air and in both wastewater streams it was easy to decide to use the NRTL
thermodynamic model as we are looking for non-ideal results which can give as a real
approximation of the parameters we need as well as the structure of our plant, that will allow
for the removal of more than 90% of the contaminants.

Figure 7: Approach to select best thermodynamic model

20
Figure 8: Property package selection

The different streams contain different functional groups that form polar molecules, such as
alcohol. When deciding on the correct property method to use is it something that is kept in
mind and overlooked, due to its importance. Aspen Plus is the ideal simulation program for
this task because when working with polar molecules it generates data far from ideal
conditions, thus, results considerably close to reality.

Aspen Plus uses different estimation methods contained in the property methods, to make
considerations for thermodynamics and transport properties. Mixtures’ physical and chemical
characteristics are determined through a combination of store interaction parameters,
(Thermodynamic Models & Physical Properties, n.d.).

Important property models

Different mixtures contain different components; thus different property models are
respectively required for each process.

21
Ideal conditions

For ideal conditions it is best to use the ideal model which makes use of the ideal gas law for
gases and makes other assumptions for liquids, these include a fugacity of 1 for gases and
an activity coefficient of 1 for liquids. Generally, when dealing with operations under
extremely high temperatures and/or under vacuum pressure, ideal behaviour is assumed,
and the property method that models these ideal behaviour is the IDEAL property method,
(Thermodynamic Models & Physical Properties, n.d.).

Equations of state

To predict thermodynamic properties, equations of state (EOS), are the go to model. For
different applications Aspen makes use of equations of state derived from statistical
thermodynamics such as the SAFT and the Sanchez-Lacombe, as well as cubic equations
of state such as the Peng-Robinson EOS (including its variations) and the Soave-Redlich-
Kwong. Not to mention that even steam tables are also EOS models., (Thermodynamic
Models & Physical Properties, n.d.).

Activity coefficient models

When dealing with non-ideal solutions the components in mixtures have different fugacity.
Activity is the name attributed to the ratio of fugacity in dilution to that of a pure component.
The higher the fugacity the slimmer the likelihood of a component to vaporize in its pure
state, indicating that the activity is greater than unity. It is believed that it happens due to the
levels of repulsion among molecules with mixture, (Thermodynamic Models & Physical
Properties, n.d.).

There is a variety of activity coefficient model available in Aspen Plus, they include the
following:

 NRTL
 Van Laar
 Wilson

22
  UNIFAC
 UNIQUAC
 Flory Huggins
 Electrolyte NRTL; and
 Scatchard Hildebrand

What happens is that Aspen Plus makes use of the EOS to calculate the vapour phase
properties, while the activity coefficient calculates the liquid properties, (Thermodynamic
Models & Physical Properties, n.d.).

Thermodynamic model choosing criteria

Engineers are well known for using mount up experience to make decisions regarding
productions processes, or any technical operations. Therefore, the same approach applies
when choosing a thermodynamic property. Different guidelines for selecting the most
suitable property method for different operations under different operating conditions have
been made available, such as figure… and figure…, however the rule of thumb would be to
check whether the compounds are polar (acids, water, alcohol) or not. Given that they are
polar then we can anticipate a case of non-ideality. Thus refer to the activity coefficient
models, such as the most frequently used NRTL. In case of CO2, N2 or any other
component that is non-condensable then a special approach must be used, such as the
implementation of Henry’s law, (Thermodynamic Models & Physical Properties, n.d.).

According to the information under this topic, and considering the nature of the contaminants
present in the air and in both wastewater streams it was easy to decide to use the NRTL
thermodynamic model as we are looking for non-ideal results which can give as a real
approximation of the parameters we need as well as the structure of our plant, that will allow
for the removal of more than 90% of the contaminants.

23
 1.2.3.5. Sensitivity analysis

The sensitivity analysis is being done so that the process can be optimized to become more
feasible and the objective becomes more achievable thanks to Aspen Plus which can create
various simulations based on the conditions set.

Figure 9: Sensitivity test on liquid-liquid extractor unit for the wastewater stream 1

The sensitivity test shown in Figure 9 was done before the implementation of the recycling
stream in the system, and from it the solvent flowrate necessary to remove about 90 percent
of the contaminants is approximately 90000 kg/hr. To reduce this flowrate to something more
economically friendly the recycling stream was added and figure 10 shows us the new
sensitivity test done for the wastewater stream 1.

Figure 10:Sensitivity test on liquid-liquid extractor unit for the wastewater stream 1
with recycling stream

24
Figure 10 shows how the necessary solvent flowrate reduced drastically from 90000 to 50000kg/hr,
while reducing the solvent quantity needed. Based on the sensitivity performed a flowrate of 100
000kg/hr was chosen as the range.

Water is cleaned from a mass fraction of 0.98 to 0.99, by using he 50000kg/hr.

This is one set of process conditions that has been decided up.

Figure 11:Sensitivity test on liquid-liquid extractor unit for the air stream 1 with
recycling stream

Sensitivity test with recycling stream

Flow rate was initially 1380kg/h, Based on the sensitivity test it was optimized to 2700kg/h/

I. Reference

 What are Unit Operations? - (Lec003) - YouTube unit operations

 Chemical Engineering Guy (2018). What are Unit Operations? - (Lec003). YouTube.

Available at: https://www.youtube.com/watch?v=ntjyr9kXuCs.

 Chemical Engineering World. (2021). Unit Operation and Unit Process. [online]

Available at: https://chemicalengineeringworld.com/unit-operation-and-unit-process/.

25
  Anon, (n.d.). Material Requirements Planning - Input, Output, Objectives,
Advantages. [online] Available at: https://learnmech.com/introduction-to-material-
requirements/

 www.bing.com. (2022). microsoft - Search. [online] Available at:

https://www.bing.com/ck/a?.

 www.echemi.com. (n.d.). Acetaldehyde for Sale from Quality Suppliers - ECHEMI.

[online] Available at: https://www.echemi.com/searchGoods/pid_Rock16660-
acetaldehyde.html.

 www.echemi.com. (n.d.). Product Search for dichloromethane on ECHEMI. [online]

Available at: https://www.echemi.com/searchGoods.html?
keywords=dichloromethane.

 Water Purification Systems. (n.d.). Activated Carbon Media. [online] Available at:

https://www.vontron.co.za/product/activated-carbon-filter-media/?
attribute_type=Activated+Carbon+-+Coal+Based+25+KG&gclid=CjwKCAjwo8-
SBhAlEiwAopc9W8tNdvFLe-
N6O0WHJPLa4tFScQ97AF_AJapcuf1p2vCGAfczAP4LwxoCM7gQAvD_BwE.

 Khan, M.M.K. and Hassan, N.M.S. (2016). Thermofluid modeling for energy

efficiency applications. London, UK: Academic Press

Appendix A – Important data

Figure 12: Recycling stream energy balance

26
Figure 13:Stripper feed energy balance

Table 20:Absorber split fraction

27
Figure 14:Absorber pressure

Figure 15:Absorber configurations

28
Figure 16:Stripper configuration

Figure 17:Stripper pressure

Figure 18:Extractor from wastewater 1 split fraction

29
Figure 19:Specs for extractor 1

Figure 20: Extractor for wastewater stream 2

Figure 21:Stripper Streams

Appendix B – Preliminary models and results

On the first run using an inlet water flow rate of 3500kg/h we managed to extract almost
`100% of the methanol from the air stream, however it was not the case with acetaldehyde.
Thus the need for an optimization in the operating conditions to achieve a removal of more

30
than 90% of each contaminant from the air stream. To maintain the process feasible, it was
decided that not a lot of water should we used.

Table 21: Preliminary data for the air stream

31
Figure 22:Sensitivity analysis using the pressure

Appendix C – Preliminary models

32
33
 6 6 90
1 1 1
1380 2902 85

WATER FLUE-OUT FLU- RICH

6
1 -2 94
STRIPPER
2904 ABSORBER 1 1

1382 1297
-2
FLUE 1
COMPR RECYCLED
2904 WATR- OUT

FLUE-IN

Temperature (C)

Pressure (bar)

Mass Flow Rate (kg/hr)

34
 6
1

B1
WATER

39 93
1 1

FLUE-OUT FLU-RICH
94
RECYC-2 1

ABSO RBER
6
1 ST RIPPER
8
1

-2
1 WATR-OUT
CO MPR

FLUE-IN
Te mpe ratu re ( C)
FLUE
Pr essu re (b a r)

94
1

RECYCLED

6 39
1 1

B1
WATER FL UE- OUT

93
1

FL U-R ICH
94
RECYC -2 1

FL UE
ABSOR BER
6
1 STRIPPER

-2 8
1 1

COMPR

FL UE- IN WATR -OU T

Te mpe ratu re ( C)

Pr essu re (b ar)

94
1

RECYC LED

35
Aspen Plus simulation links:

AIR STREAM

https://mail.google.com/mail/u/0?ui=2&ik=135ce95c21&attid=0.5&permmsgid=msg-
a:r3156794080127700017&th=18304a1899b092f9&view=att&disp=safe&realattid=f_l7m8u4yv4

WASTEWATER STREAM 1 LINK

https://mail.google.com/mail/u/0?ui=2&ik=135ce95c21&attid=0.3&permmsgid=msg-
a:r3156794080127700017&th=18304a1899b092f9&view=att&disp=safe&realattid=f_l7m8nxxx3

WASTEWATER STREAM 2 LINK

https://mail.google.com/mail/u/0?ui=2&ik=135ce95c21&attid=0.1&permmsgid=msg-
a:r3156794080127700017&th=18304a1899b092f9&view=att&disp=inline&realattid=f_l7m8nxuf1

36