A REPORT

ON

ASPEN based Simulation, Analysis and Control of a Chemical

Process
By

Name of the student

K.Hemanth

ID No.
2009B4A1573H

AT
INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY
HYDERABAD

A Practice School II Station of

BIRLA INSTITUTE OF TECHNOLOGY & SCIENCE,
PILANI
(December, 2013)

A REPORT

ON

ASPEN based Simulation, Analysis and Control of a Chemical

Process
By
Name of the student
K.Hemanth

ID No.

Discipline

2009B4A1573H

B.E (Hons.) Chemical Engineering

Prepared in the partial fulfillment of the

Practice School II Course

AT
INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY
HYDERABAD

A Practice School II Station of

BIRLA INSTITUTE OF TECHNOLOGY & SCIENCE,
PILANI
(December, 2013)

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE

PILANI (RAJASTHAN)
Practice School Division
Station: Indian Institute of Chemical Technology

Centre: Hyderabad

Duration: 5.5 months

Date of Start: 4th July 2013

Date of Submission: 6th December, 2013

Title: ASPEN based simulation, analysis, and control of a chemical process
ID No./Name/:
Discipline of the
Student

2009B4A1573H / K.Hemanth / Chemical Engineering

Name and
Designation
of the expert

Dr. K. Yamuna Rani

Senior Principal Scientist

Name of the
PS Faculty

Keywords:

Dr. K. Vandana/ Mr. K. Srikanth

Nucleation,

magma

density,

recirculation,

anti-solvent,

cooling

crystallization, particle size distribution.

Project Areas: Modelling and simulation of process control and dynamics
Abstract:
Simulation of a chemical process which involves solids is done using Aspen Plus
software. The process chosen is synthesis of Aspirin (acetyl salicylic acid) as it involves
solids in the product. As the synthesis involves crystallization, the process is simulated
using the MSMPR crystallizer and a stoichiometric reactor. The simulated results showed
the crystal product flow rate from which the yield is calculated. The variation of the
crystal flow with various factors is analysed.
Signature of Student

Signature of PS Faculty

Date

Date

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE

PILANI (RAJASTHAN)
Response Option Sheet

Station: Indian Institute of Chemical Technology Center: Hyderabad

ID No. & Name: 2009B4A1573H / K.Hemanth
Title of the Project: ASPEN based simulation, analysis and control of a chemical
process

Code No.
1.
2.

3.

4.

5.

Response Option
A new course can be designed out of this
project.
The project can help modification of the
course content of some of the existing
Courses
The project can be used directly in some of
the existing Compulsory Discipline Courses
(CDC)/ Discipline Courses Other than
Compulsory (DCOC)/ Emerging Area (EA),
etc. Courses
The project can be used in preparatory
courses like Analysis and Application
Oriented Courses (AAOC)/ Engineering
Science (ES)/ Technical Art (TA) and Core
Courses.
This project cannot come under any of the
above mentioned options as it relates to the
professional work of the host organization.

Course No.(s) & Name

NA
NA

CHE C441-Process Control

AAOC C321- Control

Systems

NA

Signature of Student

Signature of Faculty

Date:

Date

Acknowledgements
A comprehensive report always requires the goodwill, encouragement, guidance and
support of many people. I am grateful to Mr. K.H.V. Prasad, HOD, Chemical
Engineering, IICT for providing me opportunity to work in IICT.
I am also deeply indebted to Dr. K. Yamuna Rani to give me the opportunity to work on
this project and prepare this report. Also I thank her for unflinching support and guidance
provided for completion of this report.
I am also grateful to Mr. Anjani Srikanth Koka and Dr. Vanadana K., Practice School
faculty, BITS Pilani for helping us out in working on this project.
I would also like to thank, Kamesh Reddi and Swapna Reddy for providing technical
guidance on this project and also acknowledge the consistent cooperation received during
my work.
It would be impossible to refer in detail to the many persons who have been consulted in
the compilation of this work. I may be excused for not naming them individually.
K Hemanth

Table of Contents

Acknowledgement
Abstract
Response Option Sheet
1. Introduction--------------------------------------------------------------------------------1
1.1. General Introduction------------------------------------------------------------ 2
1.2. Aspen---------------------------------------------------------------------------------3
1.3. Crystallization----------------------------------------------------------------------4
2. Methodology-------------------------------------------------------------------------------7
2.1 General Methodology--------------------------------------------------------------8
2.2 Objective and Approach----------------------------------------------------------17
3. Simulation of solid process using ASPEN Plus--------------------------------------18
3.1. Brief Introduction about Aspirin-----------------------------------------------19
3.2. Working conditions and assumptions of the process----------------------21
3.3 Simulation (compilation) of the process---------------------------------------22
4. Conclusions and Future work----------------------------------------------------------29
4.1 Conclusion---------------------------------------------------------------------------30
4.2 Future work-------------------------------------------------------------------------30
References-------------------------------------------------------------------------------------31

-1-

Chapter 1: Introduction

-2-

1.1. Basic Introduction

Due to rapid decline in the cost of computers and improvement in its quality and
speed (doubling every 18 months, according to Moores Law), the use of simulation
tool for dynamics prediction and control has become indispensable for industrial
plants. The future success of the chemical process industries mostly depends on the
ability to design and operate complex, highly interconnected plants that are profitable
and that meet quality, safety, environmental and other standards. To achieve this goal,
the software tools for process simulation and optimization are increasingly being used
in industry.
By developing a computer program, it may be manageable to solve a model structure
of a chemical process with a small number of equations. But as the complexity of a
plant integrated with several process units increase, the solution becomes challenge.
Under these circumstances , in recent years, the use of flow sheet simulator has been
increased considerably as it helps in solving the problems faster and in more reliable
manner. In this project, the AspenTM software package has been used for steady state
simulation, process optimization, dynamics and closed-loop control.
The process dynamics can be predicted in short time period quite accurately and
efficiently by using Aspen flow sheet simulator. This software tool is not only useful
for plant simulation but can also automatically generate several control structures,
suitable for the used process flow diagram. In addition the control parameters,
including the constraints imposed on the controlled as well as manipulated variables,
are also provided by Aspen to start the simulation run. However, we have the option
to modify or even replace them.

-3-

1.2. Aspen
By developing a computer program, it may be manageable to solve a model structure
of a chemical process with a small number of equations. However, as the complexity
of a plant integrated with a several process units increases we usually use the process
flowsheet simulator such as Aspen PlusTM (AspenTech), ChemCadTM, HYSYSTM and
PRO/IITM.
Process simulation allows us to predict the behaviour of a process by using basic
engineering relationships, such as mass and energy balances, and phase and chemical
equilibrium. Given reliable thermodynamic data, realistic operating conditions, and
rigorous equipment models, we can simulate actual plant behaviour.
Process simulation enables we to run many cases, conduct "what if" analyses, and
perform sensitivity studies and optimization runs. With simulation, we can design
better plants and increase profitability in existing plants. Process simulation is useful
throughout the entire lifecycle of a process, from research and development through
process design to production.
The sophisticated Aspen software tool can simulate large processes with a high
degree of accuracy. It has model library that includes mixers, splitters, phase
separators, heat exchangers, distillation columns, reactors, pressure changers,
manipulators. etc. Fortron codes are already built-in in the simulator to solve this
process flow diagram.
Aspen Plus The process simulation tool is mainly used for steady state simulation of
chemicals, petrochemicals, and petroleum industries. It is also used for performance
monitoring, design , optimization and business planning. It is extensively used used
both in the educational arena and industry to predict the behaviour of a process by
using material balance equations, equilibrium relationships, reaction kinetics, etc.

-4-

1.3. Crystallization
Mechanisms of crystallization that affects crystal size distribution are:
(i) Nucleation rate
(ii) Crystal growth rate
These both are affected by supersaturated solution. The phenomenon that occurs in the
solution with the formation of first small crystal is called nucleation. Nucleation is
different from crystal growth as it form solid from liquid and it sets the properties for
crystallization process whereas, crystal growth is the deposition of crystals on already
existing crystals in solution. Therefore, nucleation is very important in the design of
crystallizer.
The method for the separation of compounds by forming crystals from supersaturated
solution is termed crystallization. For inorganics, this process can be applied in chemical
industry especially, when salts are obtained usually from aqueous solutions. For the
production of organics, the purpose of crystallization is the recovery of product, for the
refinement of intermediate chemicals and the elimination of unwanted salts.
Crystallization has got high rank in industrial processes due to the purity of chemicals
produced by using crystallization. Beyond the fact that product obtained by
crystallization has an attractive and clear appearance, crystallization could be the easiest
and cheapest way to get pure product from an impure solution. Conventional distillation
techniques are unable to separate the close boiling liquid without using azeotropes but
crystallization can get the complete separation.
The major difference between crystallization and other unit operation is the obtaining of a
solid phase in crystallization process. In the creation of a solid phase, crystal size and size
distribution are very important.

-5-

The requirements for crystallization process are as follows,

(i) Product purity
(ii) Yield of product
(iii) Capacity of crystallizer system
(iv) Energy requirements
(v) Rate of nucleation and crystal growth
Crystallization has the following benefits,
(i) Separation for a pure product can be achieved in a single stage. It means, if a proper
care is taken in designing, purity of the product can be more than 99% in one step of
crystallization, separation and washing.
(ii) Large solid particles break into smaller particles. During this process, conditions are
monitored and controlled in order to get required physical size that can be used for direct
packaging.
(iii) With this packaging, it is easy and cheap to transport and sell solid products

Crystallization has disadvantages as well,

(i) In single stage process, it is hard to obtain the purification for more than one
component
(ii) It is also not possible to achieve full solute recovery in single step. So, it is often
necessary to use multistage process to get maximum recovery of solute from the
remaining solution.
Crystallization is usually preferable due to the simplicity of the process and this process
is normally considered as good option due to the formation and controlling of solids. But
crystallization offers some advantages over other unit operations. For example, it has the

-6-

following benefits over distillation and it can be applied in following processes where
distillation is not suitable:
(i) When the solute is heat sensitive and there is a danger that it will be decomposed at a
temperature required to distillate
(ii) When there is no or very low volatility between the solute and component
(iii) When the product is required in a special form
(iv) Unlike distillation, crystallization is more economic as it is not energy intensive
process and does not require high temperature

-7-

Chapter 2: Methodology

-8-

2.1 General Methodology

Using Aspen Plus, which is a part of Aspen software package, we will mainly perform
the steady state simulation and optimization. The simulation engine of Aspen Plus is
independent from its Graphical User Interference (GUI). We can create our simulations
using the GUI at one computer and run them connecting to the simulation engine at
another computer.
Crystallizer models a mixed suspension, mixed product removal (MSMPR) crystallizer. It
performs mass and energy balance calculations and optionally determines the crystal size
distribution. Crystallizer assumes that the product magma leaves the crystallizer in
equilibrium, so the mother liquor in the product magma is saturated. The feed to
Crystallizer mixes with recirculated magma and passes through a heat exchanger before it
enters the crystallizer. The product stream from Crystallizer contains liquids and solids.
We can pass this stream through a hydro cyclone, filter, or other fluid solid separator to
separate the phases. Crystallizer can have an outlet vapour stream. Using the following
forms to enter specifications and we can view results for Crystallizer:
Form

To do this

Setup

Specify operating parameters, crystal product and solubility

parameters, recirculation options and flash convergence
parameters

PSD

Specify PSD and crystal growth calculation parameters

Advanced

Specify component attributes, convergence parameters, and name

and parameters for user solubility subroutine

Block Options

Override global values for physical properties, simulation options,

diagnostic message levels, and report options for this block

-9-

Results

View summary of Crystallizer results, material and energy balance

results, and crystal size distribution results

Flowsheet Connectivity for Crystallizer

Material Streams
inlet

At least one material stream

outlet

One material stream for liquid and solid

One optional vapor stream
The outlet material stream should normally have at least one solid substream for

the crystals formed. If we select Calculate PSD from Growth Kinetics or User-Specified
Values on the PSD sheet, each substream must have a particle size distribution (PSD)
attribute.

If electrolyte salts are formed based on electrolyte chemistry calculations, a solid

substream is not required when we select Copy from Inlet Stream on the PSD sheet.

- 10 -

If we do not use the vapor outlet stream, vapor products will be placed in the liquid/solid
product stream.
Heat Streams
inlet

Any number of optional inlet heat streams

outlet

One optional outlet heat stream

If we give only one specification on the Setup Specifications sheet (temperature or

pressure), Crystallizer uses the sum of the inlet heat streams as a duty specification.
Otherwise, Crystallizer uses the inlet heat streams only to calculate the net heat duty. The
net heat duty is the sum of the inlet heat streams minus the actual (calculated) heat duty.
We can use an optional outlet heat stream for the net heat duty.
Crystallizer Specifications
Crystallizer calculates crystal product flow rate and/or vapor flow, based on solubility
data we supply. Or we can specify the chemistry for electrolyte systems instead of
specifying solubility data.
We must specify two of the following:
Crystallizer temperature
Pressure or pressure drop
Heat duty for the heat exchanger
Crystal product flow rate
Vapor flow

- 11 -

If we specify

Crystallizer calculates

Temperature and Pressure

Heat duty, crystal product flow rate, vapor

flow rate

Pressure and Heat Duty

Temperature, crystal product flow rate,

vapor flow rate

Temperature and Heat Duty

Pressure, crystal product flow rate, vapor

flow rate

Pressure and Crystal Product

Temperature, heat duty, vapor flow rate

Temperature and Crystal

Pressure, heat duty, vapor flow

Product

rate

Pressure and Vapor Flow Rate

Temperature, heat duty, crystal

product flow rate

Temperature and Vapor

Pressure, heat duty, crystal

Flow Rate

product flow rate

Recirculation Specifications
We can model crystallizer with or without magma recirculation.
To activate recirculation, specify one of the following on the Setup
Recirculation sheet:
Recirculation fraction
Recirculation flow rate
Temperature change across heat exchanger
If we want to model a different crystallization process flowsheet, we can use Crystallizer
without recirculation, and use other blocks in the flowsheet to model the recirculation.

- 12 -

Solubility
Crystallizer calculates the amount of crystal produced at its saturation (class II
crystallization). We can provide solubility data in one of these ways:
Enter solubility data on the Setup Solubility sheet
Reference an electrolyte chemistry (defined in the Reactions Chemistry forms) in which
the crystallizing component has been declared as a "salt"
Supply a subroutine to provide the saturation concentration or
Saturation Calculation Method
Choose the saturation calculation method from these options:

Solubility method: Identify the crystallizing component as solid product on the

Setup Crystallization sheet. Enter solubility data on the Setup Solubility sheet.
This data applies to the reactant species in the mixed substream.

Chemistry method: Create a new Chemistry on the Reactions Chemistry object

manager. Enter the crystallization as a salt reaction on the Reactions Chemistry
Stoichiometry sheet. On the Block Options Properties sheet of the crystallizer,
enter the Chemistry ID and select True Species for Simulation Approach. We
must specify the crystallizing component as a Salt Component ID on the Setup
Specifications sheet.

User Subroutine method: Identify the crystallizing component on the Setup

Crystallization sheet and the solubility data basis and solvent ID on the Setup
Solubility sheet. Specify a user subroutine to calculate saturation concentration or
crystallizer yield on the Advanced User Subroutine sheet.

In general, when using the Solubility method, we should blank out the Chemistry ID field
on the Block Options Properties sheet. If we specify chemistry when using the Solubility
method, the chemistry must not contain the crystallizing component.

- 13 -

Supersaturation
The degree of super saturation is the driving force for
Crystallization processes. Super saturation is defined as:
S=C- Cs
Where:
S = Super saturation (kg of solute/m3 of solution)
C = Solute concentration
Cs = Solute saturation concentration
Because the crystallizer model assumes that the product magma is in phase equilibrium,
this equation is not used. It is provided only for reference.
Crystal Growth Rate
The crystal growth rate can be expressed as a function of the degree of super
saturation(S):
Go = kgS n
Where:
Go = Growth rate dependence on supersaturation (m/s)
kg = Growth rate expression coefficient
n = Exponent
This expression is provided as background information only.
In Aspen Plus, Go is calculated implicitly from the third moment of the population
density.
For a size-dependent growth rate, the growth rate is a function of crystal length (L):
G = Go (1 + L)
Where:
= Constant

For 0 1

- 14 -

= Exponent
If the growth rate is independent of crystal size, then the values for and are set to zero.
Crystal Nucleation Rate
The overall nucleation rate can be expressed as the sum of specific contributing factors
(Bennett, 1984):
Bo= kb Gi MT iRk
Where:
Bo = Overall nucleation rate
i, j, k = Exponents
kb = Overall nucleation rate expression coefficient
MT = Magma density = P/q (kg/m3)
G = Crystal growth rate
R = Impeller rotation rate (revs/s)
P = Crystal mass flow rate (kg/s)
q = Volumetric flow rate of slurry in the discharge (m3/s)
Population Balance
If the feed stream contains no crystals, the population balance for a well-mixed
continuous crystallizer can be written as
(Randolph and Larson, 1988):
d(nG)/dL + qn/V =0
Where:
G = Crystal growth rate
n = Population density (no. /m3/m)
L = Crystal length (m)
V = Crystallizer volume (m3)

- 15 -

q = Volumetric flow rate of slurry in the discharge (m3/s)

The boundary condition is n = no at L = 0, where n o =B o /G is the population density of
nuclei. For a constant crystal growth rate, the population density is:
n(L)=no exp[-L/G ]
where = V / q is the crystal residence time.
PSD Statistics
Aspen Plus calculates the crystal size distribution statistics once we select the Calculate
PSD from Growth Kinetics option on the PSD PSD sheet. Properties of the distribution
may be evaluated from the moment equations. The j-th moment of the particle size
distribution is defined as:
mj=0Ljn(L)dL
The system reports several crystal size distribution statistics, measured on a volume or
mass basis, including:
Mean size
Standard deviation
Skewness
The coefficient of variation (expressed as a percentage)
The mean size is the mass-weighted average crystal size, as determined by the ratio of the
fourth moment to the third moment, as follows:
L = m4/m3
The skewness of a symmetric size distribution about the mean is zero. Negative values of
skewness indicate the distribution is skewed toward the presence of small crystals.
Positive values of skewness indicate the crystal distribution contains an excess of large
crystals.
Skewness is defined as f (xmean)3/ (standard deviation)3

- 16 -

The system uses the coefficient of variation to calculate variation related to the
cumulative volume (or mass) distribution.
Coeff Var(%) =100pd@(.86)-pd@(.16)/2pd@(.5)
where pd@ (x) is the particle diameter corresponding to fraction x of the cumulative
volume (or mass) distribution. The fraction can be entered as the Fractional Coefficient
on the PSD Crystal Growth sheet; otherwise, it defaults to .16.
Calculating PSD
The magma density, defined as total mass of crystals per unit volume of slurry, can be
obtained from the third moment:
MT=c kv 0 L3n(L)dL
Where:
c = Density of crystal (kg/m3)
kv = Volume shape factor of the crystal
Since:
n(L)=no exp[-L/G]
n o =B o/G
Bo= kb Gi MT iRk
these equations can be substituted into the third moment of population density, yielding:
MT=c kv 0 L3kb Gi/GoMT iRkdL
where G =Go(1 + L )
Because L is made discrete by the increments of the particle size distribution, the
equations can be solved for Go .

- 17 -

2.2 Objective and Approach

The purpose of this project is to

Get familiar with Aspen Plus software.

Learn how to simulate a process involving primarily a crystallizer which involves

mainly solids.

Investigate the applicability of the crystallisation process using the Aspen

software. Here the process which involved crystallization is taken to be Synthesis
of Acetylsalicylic acid.

Analyse, Simulate and Control the process with various variables using Aspen
Plus software.

The direction of approach taken in order to achieve this objective is as follows:

Surveyed relevant literature regarding the software and the process to be studied.
Flow sheeted the required process in the software.
Inserted data into the software wherever required from the sources surveyed.
Errors from the simulation are analyzed and solved by making technical
corrections in the inputs.
Results got from the simulation are analyzed.
Did sensitivity analysis i.e., control the yield (dependent variable) with various
factors (manipulated variable) and analyzed the resuults.

- 18 -

3. Simulation of solid process using

ASPEN Plus

- 19 -

3.1. Brief introduction about Aspirin (acetylsalicylic acid)

Aspirin (acetyl salicylic acid) is a salicylic acid derivative and is one of the most popular
and commonly used drugs. Analgesics are compounds used to reduce pain, antipyretics
are compounds used to reduce fever. One popular drug that does both is aspirin. It was
first synthesized in 1893 at the Bayer Chemical Company in Germany from salicylic acid

Properties:
Acetylsalicylic Acid (MW: 180.16)
Melting Point: 136o C
Boiling Point: 140o C

SYNTHESIS OF ASPIRIN (acetylsalicylic acid)

.
Formation of Aspirin from Salicylic acid is an esterification reaction. From
stoichiometry, the ratio of moles reacting is 1:1. Generally in the laboratory preparation,
salicylic acid is taken as limiting reagent and acetic anhydride as excess reagent due to
the fact that salicylic acid exists in solid state at room temperature. Moreover, excess
acetic anhydride can be converted to acetic acid (by-product) by addition of water.

- 20 -

Experimental procedure for the synthesis of Aspirin

Place 2.8 g of salicylic acid in a dry 125-mL Erlenmeyer flask, then add 5.0 mL acetic
anhydride and 3-4 drops concentrated sulphuric acid. Mix the resultant white slurry
thoroughly with a spatula, and place the flask in a warm water bath (45-50C) for 5-7 min.
Swirl or stir the mixture occasionally to dissolve all the solid material. Because the
reaction is slightly exothermic, a small temperature rise can be detected.
Allow the flask to cool. The aspirin begins to precipitate when the temperature of the
solution is about 35-40C, and the mixture becomes semisolid.

hen this occurs, add

50mL water and break up any lumps with a spatula. Allow the mixture to stand for an
additional 5 minutes, then chill the flask in an ice bath and remove the crystals by
vacuum filtration (stopping point). Crystallize the crude aspirin from 25 mL of warm
water not exceeding 0C (see Experimental Note). Allowing the mother liquor to sit
overnight may produce a second crop of crystals. Air-dry the crystals and determine the
percent yield and melting point.

- 21 -

3.2. Working conditions and assumptions of the process

Here we synthesized Aspirin using a stoichiometric reactor and crystallized it using a
MSMPR crystallizer.
The feed details are as follows:
Salicylic acid: 24kg/h~ 174mol/h
Acetic anhydride: 20kg/h~ 196mol/h
The reaction temperature is taken as 100oC and pressure as atmospheric pressure.
The percentage of conversion is assumed to be 96.7% as this was the mean conversion
rate resulted from various ratios of molar feed ratio.

Flow sheet for the cooling crystallization process by Aspen Plus

Due to the compatibility of acetylsalicylic acid with ethanol, it is added as a solvent in the
crystallization. This liquid product stream is reconnected to the source stream of MSMPR
crystallizer.

- 22 -

3.3 Simulation (compilation) of the process:

The simulated table of all the streams is as follows:
Synthesis of Aspirin
Stream ID

SA

Temperature

Pressure

bar

Vapor Frac
Mole Flow

kmol/hr

Mass Flow

kg/hr

Volume Flow

cum/hr

Enthalpy

MMkcal/hr

Mass Flow

kg/hr

SALIC-01

AA

INTER

25.0

25.0

100.0

10.0

1.013

1.013

1.013

1.013

0.000

0.000

0.000

0.000

0.174

0.196

0.370

0.403

24.000

20.000

44.000

23.099

0.019

0.023

0.038

0.025

-0.024

-0.029

-0.054

-0.037

0.720

0.720

30.365

0.250

2.793

2.793

10.122

10.122

24.000

ACETY-01
ACETI-01

20.000

ACETI-02
ETHAN-01
Mole Flow

ASP

9.214
kmol/hr

SALIC-01

0.174

ACETY-01
ACETI-01

0.196

ACETI-02

0.005

0.005

0.169

0.001

0.027

0.027

0.169

0.169

ETHAN-01

0.200

Mass Flow

kg/hr

24.000

20.000

44.000

53.214

Enthalpy

MMkcal/hr

-0.024

-0.029

-0.054

-0.037

Temperature

Pressure

bar

1.013

1.013

1.013

1.013

Mole Flow

kmol/hr

0.000

0.000

0.000

0.167

Mass Flow

kg/hr

0.000

0.000

0.000

30.115

Volume Flow

cum/hr

0.000

0.000

0.000

0.022

Enthalpy

MMkcal/hr

Mass Flow

kg/hr

10.0

Vapor Frac

0.000

> -0.001

SALIC-01
ACETY-01

30.115

ACETI-01
ACETI-02
ETHAN-01
Mole Flow

kmol/hr

SALIC-01
ACETY-01
ACETI-01
ACETI-02
ETHAN-01

0.167

- 23 -

Analysis:
The crystal product flow is 167mole/h. As the flow rate of limiting reagent taken is
174mole/h, the yield turns out to be 95.9% which is approximately 20 percentage points
greater than the experimental yield.
Variation of Crystal product flow rate with Ethanol (solvent) concentration:
When the solvent i.e., ethanol concentration is varied from 200mol/h to 800mol/h, the
resultant crystal product flow rate varied from 167mol/h to 163mol/h.
ETHANOL
mole/h
200

CRYSTAL FLOW
mole/h
167.15

300

166.46

400

165.76

500

165.07

600

164.38

700

163.68

800

162.90

Graph with x-axis as molar flow of Ethanol and y-axis as crystal product flow

- 24 -

Variation of Crystal product flow rate with the percentage of conversion in the
stoichiometric reactor:
The conversion of the limiting reagent i.e., salicylic acid in the stoichiometric reactor is
varied from 0.5 to 0.97 and the resultant variation observed is as follows.

CONVERSION
0.5

CRYSTAL FLOW
kmole/h
0.08549067

0.55333333

0.09475778

0.66

0.11329201

0.76666667

0.13182624

0.82

0.14109335

0.87333333

0.15036047

0.92666667

0.15962758

0.97

0.16715711

Graph with x-axis as conversion fraction and y-axis as crystal product flow

- 25 -

Variation of Crystal product flow rate with the crystallizer temperature:

When the temperature of the MSMPR crystallizer is varied from 10oC to 50oC, the
resultant crystal product flow rate varied from 167mole/h to 135mole/h.

TEMPERATURE oC
10

CRYSTAL FLOW
kmole/h
0.16715711

15.71

0.16305111

21.42

0.15894511

27.14

0.15483911

32.85

0.15073312

38.57

0.14590564

44.28

0.14064529

50

0.13538494

Graph with x-axis as temperature and y-axis as crystal product flow

- 26 -

Variation of Crystal product flow rate with the temperature of the reaction:
As the temperature of the reaction is varied from 50oC to 100oC there was no change in
the flow of the crystal product.
TEMPERATURE oC
50

CRYSTAL FLOW
kmole/h
0.16715711

60

0.16715711

70

0.16715711

80

0.16715711

90

0.16715711

100

0.16715711

Variation of Crystal product flow rate with the fraction of RECIRCULATION:

The reflux ratio is changed from 0.1 through 0.9 and the change observed in the product
flow rate was very minute, i.e., 10-4 kg/hr and around 30.115 kg/h.

- 27 -

Anti-solvent crystallization:
The combined cooling/anti-solvent crystallization process of acetylsalicylic acid
from ethanol-water solutions was designed and simulated. The technique of addition of a
second solvent (here water) to reduce the solubility of the solute is known as anti- solvent
or drown-out. Supersaturation may be generated by changing the solubility of the system
by the addition of an anti-solvent a liquid miscible with the solvent which reduces
solute solubility in this new mixed solvent. An advantage of the anti-solvent
crystallization is that the process can be carried out at temperatures near the ambient
temperature. It is quite convenient for heat-sensitive substances. Also, the process would
demand less energy than a solvent evaporation process. However, the solvent-anti-solvent
mixture must be separated in order to recover and recycle one or both solvents.
Another advantage of anti-solvent crystallization is that the change in solvent
composition may favour one crystalline structure in those cases where the solute may
crystallize in two or more crystalline phases (what is called polymorphism), and only
one of them is desired for product application. Because of these characteristics, antisolvent crystallization has been widely used to crystallize pharmaceutical products, which
are generally sensitive to degradation by heating and frequently have polymorphism
occurrence. Anti-solvent crystallization may be combined with cooling strategies to
enhance crystallization.
In combined cooling anti-solvent crystallization, it seems that when anti-solvent is added
before cooling, the results are better than the opposite. Studying crystallization of
paracetamol in isopropanol-water system in which water was added as anti-solvent; Knox
et al. (2009) increased the yield from 78.4% to 93.5% when anti-solvent was added
before cooling.

- 28 -

Variation of Crystal product flow rate with the concentration of anti-solvent(water):

In anti-solvent crystallization, acetylsalicylic acid was dissolved in ethanol and water is
used as anti-solvent. For different concentrations of anti-solvent (water) the process is
simulated. The solubility data of the solute is taken as reported by Christian Lindenberg,
2009.

The trend in the crystal product flow is tabulated for different concentrations of water
which is used as an anti-solvent.
CONCENTRATION OF H2O

CRYSTAL FLOW kg/h

(anti-solvent)
0%

30.115

10%

29.63

25%

29.69

40%

30.29

55%

30.35

75%

30.34

- 29 -

Chapter 4: Conclusions and Future work

- 30 -

4.1. Conclusions
In the pharmaceutical and chemical industry, precipitation and crystallization processes
are employed to produce crystalline particles with specific properties, e.g. particle size,
polymorphic form and purity. The model-based optimization required the knowledge of
solubility, nucleation and growth kinetics of acetylsalicylic acid, which were measured
using process analytical technologies, such as ATR-FTIR and FBRM, and by applying
previously developed experimental protocols (Christian Lindenberg, 2009).
Trends in in the crystal product flow with various factors is analysed and
presented in tabular and graphical formats. Some variations showed regular conventional
patterns but some manipulated variables such as anti-solvent concentration and reflux
ratio showed distinguished features.

4.2. Future work

As present work satiate only part of the problem, design of chemical plants using Aspen
can be done. The components in the flow sheet can be increased to the plant level and
simulated successfully. The simulation need to be checked with proper experimental
methods. Controlling and designing of chemical plants can be simulated if it is backed by
lab results and inputs which are required for simulation.

- 31 -

References
[1]. Bennett, R.C. "Crystallization from Solution", in Perrys Chemical Engineers
Handbook, 6th Ed., pp. 19.24-19.40, McGraw-Hill, 1984.

[2]. Randolph, A.D. and Larson, M.A., Theory of Particulate Processes,

2nd Ed.,

Academic Press, 1988

[4]. Process Simulation And Control Using Aspen By A K Jana

[5]. Solvent Reclaiming by Crystallization of Potassium Sulfate By Qing Xu, B. S.(2008)

Ind. Eng. Chem. Res. 2009, 48, 424429

[6]. Zhang Q., Mao Z.S., Yang C., Zhao C., "Numerical Simulation of Barium Sulfate
Precipitation Process in a Continuous Stirred Tank with Multiple-Time-Scale Turbulent
Mixer Model", Ind. Eng. Chem. Res., 2009, 48, 424429..
[7]. J. Koralewska, K. Piotrowski, B. Wierzbowska and A. Matynia Kinetics of barium
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[8]. Krzysztof Piotrowski1, Joanna Koralewska, Bogusawa Wierzbowska, Andrzej

Matynia2 Kinetics of the continuous reaction crystallization of barium sulphate in
BaCl2 (NH4)2SO4 NaCl H2O system neural network model Polish Journal of
Chemical Technology, 11, 4, 13, 2009
[9] Christian Lindenberg Optimizing the precipitation of organic compounds, June
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[10] Hafiz Muhammad Irfan Anwar, Simulation of Solid Processes by Aspen Plus
Lappeenranta University of Technology pp.46-68, 2011

- 32 -

[11] Marco Giulietti* and Andr Bernardo Crystallization by Antisolvent Addition and
Cooling Chemical Engineering Department Federal University of So Carlos UFSCar,
Brasil,2007
[12] H.W. Goh, A. Salmiation, N.Abdullah and A.Idris, Process Simulation of Twostage Evaporation and Crystallization Systems for Bis(2-hydroxyethyl terephthalate)
Recovery ,2010
[13] Nirlipt Mahapatra Design And Simulation Of Cumene Plant Using Aspen Plus
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[14] Hannu Alatalo Supersaturation-Controlled Crystallization Lappeenranta
University of Technology, Lappeenranta, 2010
[15] Luis A. Cisternas and Cristian M. Vasquez On the Design of Crystallization-Based
Separation Processes: Review and Extension Dept. of Chemical Engineering,
Universidad de Antofagasta, Antofagasta, Chile, 2006
[16] Magnus Lindberg, As ke C. Rasmuson* Supersaturation generation at the feed
point in reaction crystallization of a molecular compound,1999
[17] K.L. Choong, R. Smith Optimization of semi-batch reactive crystallization
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