STATE OF LIBYA

Sabratha University
Faculty of Engineering - Sabratha
Chemical Engineering Department

Thermodynamic analysis of Isopropyl alcohol

production system

The Thesis was submitted in partial fulfillment of the

requirement for the Bachelor of science in chemical engineering

By
Ahmed Masoud Jmea
Mohammed Emhemmed Alssyh

Supervised by
Dr. Ruqaia A. Sheliq

Spring 2022
 ‫إهداء‬
‫ى‬
‫المصطف عليه أفضل صالة‬ ‫الحمد هلل والصالة والسالم عىل الحبيب‬
‫وسالم أما بعد‪:‬‬

‫مسيتنا الدراسية ى يف‬ ‫ى‬

‫الحمد هلل الذي وفقنا للوصول لهذه الخطوة يف ر‬
‫َّ‬
‫ومشقة‪.‬‬ ‫المرحلة الجامعية إىل نهايتها بعد تعب‬
‫همة ونشاط‪ ،‬ممت ىُّ‬
‫ني لكل من كان له‬ ‫تخرجنا بكل َّ‬
‫وها نحن نختم بحث ُّ‬
‫ر‬
‫المستني لمن كان معنا‬ ‫السية العطرة‪ ،‬والفكر‬ ‫ى‬
‫ر‬ ‫مسيتنا‪ ،‬ألصحاب ر‬
‫فضل يف ر‬
‫باليسي‪.‬‬
‫ر‬ ‫وساعدنا ولو‬

‫العاىل (والدينا األحبة)‪ ،‬أطال‬ ‫التعليم‬ ‫بلوغنا‬ ‫ف‬ ‫األول ى‬

‫لمن كان له الفضل َّ‬
‫ي‬ ‫ي‬
‫هللا ى يف ُعمرهم ورحم من فارقنا‪.‬‬

‫إىل من وضعتننا عىل طريق الحياة إىل من وضع الموىل ‪ -‬سبحانه وتعاىل ‪-‬‬
‫َّ‬
‫الجنة تحت قدميها‪ ،‬و وقرها ى يف كتابه العزيز (أمهاتنا الحبيبات)‪.‬‬

‫كثي من العقبات والصعاب‪.‬‬ ‫ى‬

‫إىل إخوتنا؛ من كان لهم بالغ األثر يف ر‬

‫صياتة؛ ممن لم يتوانوا‬ ‫ى‬

‫إىل جميع أساتذتنا الكرام يف كلية الهندسة بجامعة ر‬
‫ى يف مد يد العون‪.‬‬
‫ُّ‬
‫نجلهم ون ر‬
‫حيمهم‪.‬‬ ‫إىل كل األصدقاء والمعارف الذين‬

‫نهدي لكم بحثنا‬

 ‫الشكر والتقدير‬
‫األخية ى يف الحياة الجامعية من وقفة نعود‬
‫ر‬ ‫ال بد لنا ونحن نخطو خطواتنا‬

‫إىل أعوام قضيناها ى يف رحاب الجامعة مع أساتذتنا الكرام الذين قدموا لنا‬

‫كبية ى يف بناء جيل الغد‪.‬‬ ‫الكثي ر ى‬

‫باذلي جهود ر‬ ‫ر‬

‫نقدم أسىم آيات الشكر واالمتنان والتقدير والمحبة إىل الذين حملوا‬

‫أقدس رسالة ى يف الحياة إىل الذين أناروا لنا طريق العلم والمعرفة إىل جميع‬

‫صياتة‪.‬‬
‫أساتذتنا األفاضل بكلية الهندسة بجامعة ر‬

‫نتوجه بالشكر الجزيل إىل الذين تفضلوا ر‬

‫باإلشاف عىل هذا البحث جزاهم‬

‫الخي فلهم منا كل التقدير‪.‬‬

‫هللا عنا كل ر‬
 ABSTRACT

Abstract
Isopropyl alcohol (IPA) has been called the first modern synthetic petrochemical.
Because IPA has physical characteristics compatible with those of alcohol, water, and
hydrocarbons, it is a versatile and inexpensive solvent used widely in the chemical and
cosmetics industries. Unlike ethanol, IPA is subject to few government regulations, and
no special taxes are levied on consumption of IPA. IPA is used as feedstock for the
manufacture of acetone and other compounds. IPA is used widely as an antiseptic and
disinfectant for home, hospital, and industry application.

Several methods are available for manufacture of IPA. The methods used most widely
are direct hydration and indirect hydration of propylene. Both processes use propylene
and water as raw materials. There are three propylene direct hydration processes in
commercial operation: vapor phase hydration over a fixed-bed catalyst, mixed vapor
liquid phase hydration using strongly acidic proton -exchange resin catalyst, and liquid
phase hydration in the presence of a homogeneous catalyst.

Direct hydration of propylene is the preferred process for production of IPA because it
avoids some corrosion and environment problems.

In this work, the process design of almost pure IPA with a capacity of 25.000 tone/year
is performed, where a direct hydration process of pure propylene as feedstock is
considered. The work was divided parts, where in the first part a thermodynamic
analysis of the synthesis section was performed to estimate the equilibrium conversion
of propylene to IPA, moreover, the effect of some key parameters was investigated.

I
 Table of Content
Abstract I
Table of content II
List of Tables IV
List of Figures V
Acronyms VI
CHAPTER ONE
1.1 Introduction 1
1.2 Chemical and Physical Properties of Isopropyl Alcohol 2
1.2 Manufacturing Processes 3
1.3 Uses and Application of IPA 3
1.4 Problem Statement and Methodology 4
1.5 Objectives 5
CHAPTER TWO
2.1 Conventional Method for Isopropanol Production 6
2.1.1 indirect hydration of Propylene 6
2.1.2 Direct Hydration of Propylene 9
2.1.3 Acetone Hydrogenation 11
2.2 Catalytic Distillation for Isopropanol Production 12
2.2.1 Application of Catalytic Distillation 12
2.2.2 Catalytic Distillation Column 14
2.3 Azeotrope Phenomena 16
2.3.1 Distillation 16
2.32 Azeotrope Definition 16
2.3.3 IPA-Water Binary System 16
2.3.4 Phase diagram 17
2.4 Separation of Azeotropic Mixture 18
2.4.1 Azeotropic Distillation 18
2.4.2 Extractive Distillation 19
2.4.3 Salted-out Distillation 20
CHAPTER THREE
3.1 Introduction 21
3.2 Synthesis section 21
3.2.1 Thermodynamic analysis 22
3.3 Material balance 27
3.3.1 Material Balance around Reactor 27
3.3.2 Energy balance a round the reactor 29
3.4 Separation section 32
3.4.1 Thermodynamic analysis 32
3.4.2 Simulation setup 33
3.4.3 Material and energy balance 34

II
 CHAPTER FOUR
4.1 Project evaluation 38
4.1.1 Evaluation methodology 38
4.2 Result of cost estimation 39
CHAPTER FIVE
5.1 Conclusion 40
5.2 Recommendation 41
References
Appendix

III
 List of Tables
Table 1.1: Chemical and physical properties of isopropyl alcohol 2
Table 3.1: Free Gibbs Energy of Formation. 22
Table 3.2: Equilibrium constant at different temperatures 23
Table 3.2: Equilibrium conversion at different temperatures 24
Table 3.3: Equilibrium conversion at different pressures 25
Table 3.4: Equilibrium conversion at different feed ratio 25
Table 3.5: Operating condition of the reactor 27
Table 3.6: result of mole balance around the reactor 29
Table 3.7: Heat of formation data 30
Table 3.8: Feed specification for the separation section 34
Table 3.9: Column specification 34
Table 3.10: Result of mass balance for column T-100 35
Table 3.11: Result of energy balance for column T-100 35
Table 3.12: Result of mass balance for column T-101 35
Table 3.13: Result of energy balance for column T-101 36
Table 3.14: Result of energy balance for cooler E-100 36
Table 3.15: Result of energy balance for pump P-100 37
Table 4.2 Shown the assumptions of the equipments 38
Table 4.3: Shown the assumptions to estimate the NPC 39
Table 4.4: Result of cost estimation for each equipment 39
Table 4.5: Economic results of entire process 39

IV
 List of Figures
Figure 1.1: Uses of isopropanol 4
Figure 2.1: Isopropanol production routs. 6
Figure 2.2: Flowsheet of indirect hydration of propylene to isopropanol. 8
Figure 2.3: Flowsheet of direct hydration of propylene to isopropanol. 10
Figure 2.4: Flowsheet of acetone hydrogenation to isopropanol. 11
Figure 2.5: Flow diagram of CD isopropyl alcohol process 15
Figure 2.6: Phase diagram of IPA/Water/Entrainer mixture. 17
Figure 2.7: Azeotropic distillation process. [15] 19
Figure 2.8: Extractive distillation process. [16] 20
Figure 3.1: effect of temperature on the equilibrium constant 23
Figure 3.2: effect of temperature on the equilibrium conversion 24
Figure 3.3: effect of pressure on the equilibrium conversion 25
Figure 3.4: effect of feed molar ratio on the equilibrium conversion 26
Figure 3.5: Txy diagram for IPA / water mixture 32
Figure 3.6: Txy diagram for IPA / DIPE mixture 32
Figure 4.1: Describe the project evaluation methodology 38

V
 ACRONYMS

IPA Isopropyl Alcohol

VLE Vapor Liquid Equilibrium
MTO Methanol to Olefins
PDH Dehydrogenation of Propane
LP Low Pressure
DIPE Di-Isopropyl-Ether
DMSO dimethyl Sulfoxide
NRTL Non-Random Two-Liquid Model

VI
CHAPTER ONE
INTRODUCTION
CHAPTER ONE INTRODUCTION

1.1 Introduction

IPA is one of the most important chemicals for solvent applications, chemical derivatives
and cosmetics. Most of them are produced by hydration reaction using propylene and water
as raw materials. There are two representative processes for the synthesis of IPA. The first
method consists of indirect hydration, in which propylene reacts with highly concentrated
sulfuric acid to form sulfuric ester, followed by hydrolysis to form IPA. [1]

The second method involves direct hydration of propylene with an acid catalyst, such as
acidic ion-exchange resin or solid phosphorous acid. Although the bulk of IPA is
manufactured by indirect processes, direct processes are simpler and technically newer,
and have become of much interest in chemical industry. [1]

Isopropanol is an important derivative of propylene in petrochemical industry. It is used as

solvent, dehydrating agent and disinfectant as well as a base for the manufacture of acetone
and other compounds. [2]

Since the first commercial production of isopropanol in 1920, most methods for hydrating
propylene to isopropanol have been based on the use of concentrated sulfuric acid in a two
stage esterification-hydrolysis process. This process, although resulting in substantial
conversion of propylene, has the problems of severe corrosion and disposal or re-
concentration of dilute spent acid. [2]

Many processes of direct hydration of propylene in one step in the presence of catalyst
have been studied in order to avoid the disadvantages of the sulfuric acid process and to
obtain the rapid conversion of propylene to isopropanol with the lowest possible amount
of by-products. It is quite lately, however, that some economical direct hydration processes
for commercial isopropanol production have been developed. Now, with the rising market
of isopropanol, the economic importance of isopropanol production by direct hydration has
been well recognized. [3]

1
CHAPTER ONE INTRODUCTION

1.2 Chemical and physical properties of isopropyl alcohol

Properties of isopropyl alcohol are shown in table 1.1 including physical and chemical
properties. [3]

Table 1.1: Chemical and physical properties of isopropyl alcohol

Molecular Weight 60.09 g/mol
Empirical Formula C3H8O
Appearance Colorless Liquid
Boiling Point @ 760mm Hg 82.2°C(180.0°F)
Freezing Point -88.5°C (-123.7°F)
Flash Point – Closed Cup 12°C (53°F)
Autoignition Temperature 425°C
Specific Gravity @ 20/20°C 0.787
Vapor Pressure @ 20°C 4.1 kPa
Evaporation Rate (n-butyl acetate =1) 1.5
Solubility in Water @ 20°C Miscible
Surface Tension @ 20°C 23 mN/m
Refractive Index @ 20°C 1.376
Viscosity @ 20°C 2.4 mPa·s
Lower Explosive Limit 2 v/v%
Upper Explosive Limit 12 v/v%
Conductivity @ 20°C 6 μS/m
Dielectric Constant @ 20°C 18.6
Specific Heat @ 20°C 2.6 kJ/kg/°C
Odor Threshold 22 ppm
Heat of Vaporization @ Tboil 664 kJ/kg
Heat of Combustion (net) @ 25°C 31000

2
CHAPTER ONE INTRODUCTION

1.2 Manufacturing processes

Isopropyl alcohol has been called the first petrochemical (IARC, 1992). It can be prepared
via three different methods: indirect hydration of propylene, direct hydration of propylene,
and catalytic hydrogenation of acetone. Indirect hydration, also called the sulfuric-acid
process, was the only method used to produce isopropanol worldwide until the first
commercial direct-hydration process was introduced in 1951. Each method has its
advantages and disadvantages. For example, direct hydration is less corrosive than indirect
hydration mediated by sulfuric acid. However, the direct method requires a pure propylene
feed, in contrast to the indirect process, which can use a dilute, refinery stream In the
indirect-hydration process, propylene is reacted with sulfuric acid to produce mono- and
di-isopropyl sulfates, which are then hydrolysed to isopropanol. In the two-step strong-acid
process, separate reactors are used for the propylene-absorption phase and the hydrolysis
of the sulfate esters. The reaction occurs at high sulfuric acid concentration (> 80% wt)
and low temperature (e.g. 20–30 °C). The weak-acid process is conducted in a single step
at lower acid concentration (60–80% wt) and higher temperature (60–65 °C). [4]

1.3 Uses and application of IPA

Isopropyl alcohol is used in the manufacture of acetone, glycerol, isopropyl acetate,

shellacs, quick drying inks, and creosote. It is a solvent for essential and other oils,
alkaloids, gums, resins, coatings and cellulose, and a deicing agent for liquid fuels,
lacquers, and extraction processes. It is also used in antifreeze compositions and as an
antiseptic. [5]

Isopropyl alcohol is registered as an antimicrobial, bactericide, fungicide, and virucide. It

is used for sterilizing and disinfecting surfaces in hospitals, dairy farms, food processing
plants, eating establishments, and in household dwellings. Isopropyl alcohol is also
registered for use as a topical disinfectant in animal areas in and around the house, in
veterinary institutions, farm structures, poultry areas, and in hatcheries and zoo animal
premises. It is registered for use in barbershops for cleaning hair cutting and styling
instruments and equipment. Isopropyl alcohol is also registered as an adjuvant, used to

3
CHAPTER ONE INTRODUCTION

facilitate pesticide applications in agricultural settings, and as an adjuvant in industrial

water washer, cooler, and condenser systems. [5]

Figure 1.1: Uses of isopropanol

1.4 Problem statement and Methodology

Preliminary process design of isopropanol production at a rate of 50,000 ton/year has to be

made. The work was divided into two sections, synthesis section and separation /
purification section. The first section was performed manually based on thermodynamic
principles combined with a material and energy balance around the reactor. The second
section including the separation of unreacted propylene, and purification of IPA from water
and by-product, which performed using Aspen HYSYS software due to the azeotrope issue
in IPA/water system, which make the separation / purification process extremely
complicated and needs a special solution such as extractive distillation that have been used
in this study.

4
CHAPTER ONE INTRODUCTION

1.5 Objectives
1. Perform an intensive literature review and screening the IPA production and
purification routs.
2. Perform a thermodynamic analysis (hand calculation) of the reactor to estimate the
equilibrium constant, extent of reaction, and conversion.
3. Perform sensitivity analysis using MS excel to study the effect of some key
parameters on the reactor performance.
4. Generate a VLE data for the system to find the azeotrope point and select
appropriate purification method.
5. Perform a process simulation of the separation / purification section based on the
extractive distillation process to achieve high IPA purity.

5
CHAPTER TWO
LITERATURE REVIEW
CHAPTER TWO LITERATURE REVIEW

2.1 Conventional Method for Isopropanol Production

There are several pathways for isopropanol production as shown in figure 2.1, which
can be divided into two sections. The first section (Section I) includes different routes
to produce propylene. Those routes include hydro-deoxygenation of glycerol,
dehydrogenation of propane (PDH), and Methanol to Olefins (MTO) process. The
second section (Section II) includes different routes for isopropanol production. All of
these routes are commercial processes. They are indirect hydration of propylene, direct
hydration of propylene, and acetone hydrogenation. [6]

Figure 2.1: Isopropanol production routs.

2.1.1 Indirect Hydration of Propylene

Propylene gas (70 wt% propylene, 30 wt% propane) is fed to the bottom of the absorber
reactor to mix with weak sulfuric acid (80 wt% H2SO4) from the top of the absorber
reactor. In the absorber reactor, propylene is absorbed by the weak sulfuric acid and
forms sulfate solution by esterification at the condition of P = 6 bar and T = 363 K.
While spent gas is vented out of the process from the top of the absorber reactor, the
sulfate mixture from the bottom of the absorber reactor is depressurized and heated
before entering the top of the stripper reactor. To form a hydration reaction at streamed
pressure with T = 407 K, water and low-pressure stream (LP stream) are supplied to the
lower section of the stripper reactor. Unreacted sulfuric acid is removed from the
bottom of the stripper reactor and recycled back to the absorber reactor for a further
esterification reaction. Product from the top of the stripper reactor is fed to the scrubber
to neutralize the residual acid with caustic. While spent soda is discharged from the

6
CHAPTER TWO LITERATURE REVIEW

bottom of the scrubber, neutral product leaves the top of the scrubber as vapor stream.
The vapor stream is condensed and sent to the drum to separate propylene and propane
gases from product stream. The liquid product stream from the drum is pressurized and
fed to the first distillation column. The first distillation column operates with the partial
condenser. This column separates DIPE and the remaining gas from the product stream.
The distillate is sold as fuel. The product stream then enters the isopropanol-water
distillation column. As it is an azeotrope distillation, DMSO is used to separate
isopropanol from water. Isopropanol with a purity of 99 wt% concentrates in this
distillation column as the product stream. The heavy stream from the isopropanol-water
distillation column is sent to the last column for separation of water and DMSO. While
DMSO is recycled back to the azeotropic distillation column, water is removed from
the process as a wastewater. A flowsheet of the indirect hydration process is presented
in Figure 2.2. [6]

7
CHAPTER TWO LITERATURE REVIEW

Figure 2.2: Flowsheet of indirect hydration of propylene to isopropanol. [6]

8
CHAPTER TWO LITERATURE REVIEW

2.1.2 Direct Hydration of Propylene

Liquid propylene (95 wt% propylene, 5 wt% propane) is fed to the process and mixed
with recycled propylene. The combined propylene stream is pressurized to 15 bar and
preheated to 395 K before entering the reactor. Process water is pressurized to 15 bar
and preheated to 543 K. Then, propylene and process water react in the liquid phase.
The liquid effluent is cooled so that propylene and propane vaporize in a flash drum.
The vapor stream from the flash drum is condensed and sent to the propylene-propane
distillation column to purify unconverted propylene before recycling it back to the
process. Liquid from the flash drum is sent to the separation section to purify the
isopropanol product. The separation section consists of three distillation columns. The
first column is a partial distillation column, which separates DIPE from isopropanol.
Distillate stream from this column is discharged from the process as fuel. The second
column is an azeotropic distillation column, which separates water from isopropanol by
using DMSO as an extractive solvent. This column purifies the isopropanol product to
have 99 wt% purity. The last column is a water-DMSO distillation column, which
separates water from solvent in order to recycle water to the feed preparation section
and DMSO to the azeotropic distillation column. A flowsheet of the direct hydration
process is shown in Figure 2.3. [3,6]

9
CHAPTER TWO LITERATURE REVIEW

Figure 2.3: Flowsheet of direct hydration of propylene to isopropanol. [6]

10
CHAPTER TWO LITERATURE REVIEW

2.1.3 Acetone Hydrogenation

Hydrogen is fed to the process and pressurized to a pressure of 30 bar. Then, it is mixed
with recycled hydrogen and heated to a temperature of 373 K. Acetone is also
pressurized and preheated to a pressure of 30 bar and temperature of 373 K. Then,
hydrogen gas reacts with liquid acetone in the reactor and gives the vapor-liquid phase
product. The mixed-phase effluent is sent to drum to separate vapor from the liquid
product. The vapor mixture then enters a cooler to condense all the chemicals but
hydrogen. This condensed mixture enters the second drum in order to separate
unreacted hydrogen from the mixture. As the liquid mixture from this second drum
contains 98.5 wt% of isopropanol, it combines with the liquid product from the first
drum in the mixer and leaves the process as a 98.5 wt% isopropanol product. Unreacted
hydrogen that leaves the second drum is recycled back to the feed preparation section.
Figure 2.4 presents a flowsheet of the acetone hydrogenation process. [6]

Figure 2.4: Flowsheet of acetone hydrogenation to isopropanol. [6]

11
CHAPTER TWO LITERATURE REVIEW

2.2 Catalytic Distillation for Isopropanol Production

Reactive distillation comprises the processes of catalytic reaction and multistage
distillation carried out simultaneously in a single vessel. A reactive distillation column
replaces the reactor and a series of distillation columns, thereby reducing the number
of process vessels and materials transfer and control equipment required. Thus, capital
costs are reduced.

The concept of reactive distillation is not new. It was first applied to eaterification
process using homogeneous catalysts in 1920’s. The use of solid heterogeneous catalyst
for reactive distillation is a more recent development, first described by Sennewald et
al. (1971). The advantages of using solid catalysts over homogeneous catalysts are
obvious: they are easy to separate from reaction mixtures, easy to handle and less waste.
Solid catalysts also offer the potential for superior effectiveness and environmental
integrity. However the column internals are more complicated when using solid
catalysts.

Bubble-cap or sieve trays are common equipment used for homogenous reactive
distillation processes. With high weirs, they provide the necessary liquid hold up and
residence time needed for the reaction. Equipment for heterogeneous reactive
distillation consists primarily of catalyst containing packing, which allows for
simultaneous reaction and mass transfer between vapor and liquid phases. The
heterogeneous catalyst acts as distillation packing as well as catalyst, therefore,
heterogeneous reactive distillation is often termed as catalytic distillation (CD) to
differentiate between the two processes (homogeneous and heterogeneous).

2.2.1 Application of Catalytic Distillation

CD is a viable option when the temperature and pressure of a process are such that the
rate of reaction is sufficiently high under conditions for separation of products by
distillation. The catalyst life must be long in order to avoid frequent start-up and shut-
down. Equilibrium-limited reactions are excellent candidates for catalytic distillation;
by continuously separating products from reactants while the reaction is in progress,
the reaction can proceed to a much higher level of conversion than is attainable using a
conventional process.

12
CHAPTER TWO LITERATURE REVIEW

Propylene hydration to IPA is an excellent candidate for application of CD technology

for the following reasons:

1. Direct hydration of propylene is an equilibrium-limited reaction 2. Hydration

2. Takes place in the liquid phase; catalyst pellets remain completely wetted.

3. The reaction occurs at a temperature and pressure equivalent to the boiling point

of the liquid product; thus distillation and reaction can be carried out

simultaneously in the same column.

4. Hydration is exothermic; the heat of reaction provides a portion of energy

required for the separation of the reaction mixture by distillation.

5. Durable heterogeneous hydration catalysts with suitable physical properties are

commercially available

6. In a CD hydration process, water will be continuously consumed by fresh

propylene, and an IPA-rich stream will be continuously produced. Hence,

equilibrium limitations will be overcome, and the product stream will have a

higher IPA content than product streams from conventional processes.

A major advantage of catalytic distillation over conventional fixed-bed reactors is the

reduction in capital investment. In addition, operating costs for production of IPA are

reduced, as there is essentially no need to cool or heat the reactor. We will show that

other benefits accrue from use of CD technique, including substantially complete

consumption of water and improved selectivity to IPA. Safety and catalyst performance

are also enhanced by use of CD technology, as the risk of formation of hot spots is

lower in a CD system than in a conventional vapor phase hydration reactor.

13
CHAPTER TWO LITERATURE REVIEW

2.2.2 Catalytic Distillation Column

The core of the CD process is the catalytic distillation column (Figure 2.1). A column

in which propylene hydration is to be performed has three major sections. The reaction

occurs over one or more catalyst beds mounted in the middle section of the column.

Rectification of the volatile components of the reaction mixture occurs in the top

section. Liquid product is recovered from the bottom of a lower stripping section. We

investigated CD columns with up to three catalyst beds. Hydration of propylene to IPA

and IPA etherification to DIPE proceed over the catalyst simultaneously with

distillation on the separation plates of the column. Unreacted volatiles rise from the

reaction zone to the rectifying section where they are separated from heavier

components before being removed from the top of the column. Condensed materials

fall as liquid from the reaction zone into the stripping section. In the present model, an

azeotropic mixture of IPA, DIPE and water is concentrated at the top of the stripping

section, and enriched IPA having a very low water content is gathered at the bottom of

the stripping section. The azeotrope vapor works as a carrier to lift water and DIPE back

to the reaction zone for water to be further reacted with propylene and for DIPE to

equilibrate with IPA. The IPA concentration in the product stream thereby exceeds the

equilibrium limit for the propylene-water-IPA reaction by continuous removal of IPA

from the reaction zone.

14
CHAPTER TWO LITERATURE REVIEW

Figure 2.5: Flow diagram of CD isopropyl alcohol process

15
CHAPTER TWO LITERATURE REVIEW

2.3 Azeotrope Phenomena

2.3.1 Distillation
Distillation process is a method for separating the various components of a liquid
solution depending upon the distribution of these components between a vapour phase
and a liquid phase based on their boiling points. In the world of Chemical Engineering,
solvent recovery is important to reduce the number of hazardous waste and pollutions.
In the industries, IPA (Isopropyl Alcohol) is known as rubbing alcohol used as a cleaner
and solvent. It is miscible with water, thus forming azeotrope with water at certain
temperature. [10]

2.3.2 Azeotrope Definition

The term azeotrope means “nonboiling by any means” (Greek: a - non, zeo - boil, tropos
-way/mean), and denotes a mixture of two or more components where the equilibrium
vapor and liquid compositions are equal at a given pressure and temperature. More
specifically, the vapor has the same composition as the liquid and the mixture boils at
a temperature other than that of the pure components’ boiling points. Azeotropes have
sometimes been mistaken for single components because they boil at a constant
temperature. However, for an azeotrope a variation in pressure changes not only the
boiling temperature, but also the composition of the mixture, and this easily
distinguishes it from a pure component. [10]

2.3.3 IPA-Water Binary System

At atmospheric condition, a binary mixture of 2-propanol (isopropyl alcohol, IPA)–
water forms a homogeneous minimum-boiling azeotrope at 87.4 – 87.7 mass% and
80.3–80.4 ◦C. Some investigations have reported that IPA–water azeotrope can also be
broken with other azeotropic distillations to form heterogeneous azeotropic systems by
adding one of the following entrainers: isopropyl ether, benzene, methyl ethyl ketone,
and isopropyl acetate. Sometimes, ethyl ether is used as entrainer at pressures
substantially above atmospheric. [11]

16
CHAPTER TWO LITERATURE REVIEW

2.3.4 Phase Diagram

Figure 2.5 shows the residual diagram for tertiary mixture of IPA/water/entrainer.
Points A, B and C are the binary azeotrope compositions. Azeotropes A and B are
usually homogenous, single liquid phase, whereas azeotrope C, between one
component and the entrainer, is heterogeneous and splits into two liquid phases. Point
D is the ternary heterogeneous azeotrope with a boiling point lower than A, B or C (at
the same pressure). Curves AD, BD, and CD divide the composition diagram into three
regions, numbered with the Roman numerals I, II and III. The significance of these
regions is:

 that any mixture within region I can be separated by simple distillation into pure
entrainer as a bottom product and the ternary azeotrope as a top product
 a mixture in region III will separate into pure water and the ternary azeotrope
 only mixtures in region II will give the desired products of pure IPA and the
ternary azeotrope.

Figure 2.6: Phase diagram of IPA/Water/Entrainer mixture. [12]

The problem is that a typical feed to the column is in region III. If, however, sufficient
entrainer can be added to move the overall feed composition to some point G, within
region II, then the column can be operated to give pure IPA as the bottom product.
Moreover, if the overhead vapour composition, V, when condensed is the two liquid
phase region, bounded by the boiling surface and portions of the curves AD and BD,
the resulting entrainer rich phase, R, can be used as a reflux to the column and to create
the overall feed composition, G, on the line linking F and R. Point G must be at the
intersection of line FR and the line linking pure IPA, P and point V. Unfortunately,

17
CHAPTER TWO LITERATURE REVIEW

point V cannot be arbitrarily fixed. Its location depends on the combination of stages,
reflux and feed location in the column. The key to setting up and solving this type of
column is accurately determining the feasible region for the overhead composition, V,
by locating curves AD and BD. [12]

2.4 Separation of Azeotropic Mixture

An azeotrope cannot be separated by ordinary distillation since no enrichment of the
vapour phase occurs at this point. Therefore, in most cases, azeotropic mixtures require
special methods to facilitate their separation such as a mass separating agent like a
membrane-material for pervaporation or an entrainer /solvent for azeotropic and
extractive distillation. Extractive and heteroazeotropic distillation are the most common
methods to break this azeotrope behavior. [14]

2.4.1 Azeotropic Distillation

Azeotropic distillation is accomplished by adding to the liquid phase, a volatile third

component, which changes the volatility of one of the two components more than the other so
that the components are separated by distillation. The two components to be separated often are
close boiling point components which do or do not azeotrope in the binary mixture, but
sometimes they are components which do azeotrope although they aren't close boiling point
components It is likely that in some cases, one system can be separated either by azeotropic
distillation or by extractive distillation, for instance, alcohol/water, acid/water, etc.
The added third component, sometimes called the entrainer, may form a ternary azeotrope with
the two components being separated. However, it must be sufficiently volatile from the solution
so that it is taken overhead with one of the two components in the azeotropic distillation column.
If the entrainer and the component taken overhead separate into two liquid phases when the
vapor overhead is condensed, the entrainer phase is refluxed back to the column. The other
phase can be fractionated to remover the dissolved entrainer and the residual amount of the
other component before it is discarded in the solvent (entrainer) recovery column).
Alternatively, this second liquid phase is recycled to some appropriate
place in the main process scheme. [15]
Azeotropic distillation is usually divided into two types: homogeneous azeotropic distillation
and heterogeneous azeotropic distillation. They are illustrated in Figure 2.6, respectively. In
homogeneous azeotropic distillation, phase split doesn't appear in the liquid along the whole
column. Whereas, in heterogeneous azeotropic distillation, two liquid phases exist in some
regions of the composition space. Heterogeneous azeotropic distillation is more widely used
for separating the close boiling point components or azeotropes than homogeneous azeotropic

18
CHAPTER TWO LITERATURE REVIEW

distillation. In particular, the case of heterogeneous mixtures without decanter at the top of
azeotropic distillation column can be looked upon as the one of homogeneous mixtures, and at
the same time the liquid composition on a tray or a section of packing is replaced by the overall
liquid composition. [15]

Figure 2.7: Azeotropic distillation process. [15]

2.4.2 Extractive distillation

Extractive distillation is commonly used to separate mixtures which display minimum

boiling azeotropes. In the extractive column a heavy boiling entrainer is fed to a tray
above the main feed stream. The entrainer facilitates the separation by interacting with
the azeotropic mixture and altering the thermodynamic equilibrium in the extractive
section of the column. Figure 2.7 displays the column configuration for a binary process
feed. The heavy entrainer E preferably associates to component B and takes it down
the column. Therefore, a binary mixture of B and E is recovered in the bottom product
whereas high purity A is obtained in the distillate product. Separation feasibility and
process cost are characterized by two major parameters entrainer feed flow rate and
reflux ratio (or condenser and reboiler heat duties, see shaded degrees of freedom in
Figure 2.7. In addition to minimum reflux, which limits feasibility for all azeotropic
and azeotropic separations, there is a maximum reflux above which separation cannot
be achieved. These bounds for the reflux ratio depend on the entrainer feed flow rate.
The range of feasible choices for the reflux ratio decreases with decreasing entrainer
flow rates. Below a minimum entrainer flow rate the extractive effect is no longer
sufficient for separation and a feasible reflux policy cannot be found. [16]

19
CHAPTER TWO LITERATURE REVIEW

Figure 2.8: Extractive distillation process. [16]

2.4.3 Salted-out distillation

Instead of adding a solvent a non volatile salt could be used as a separating agent to
alter the VLE of a given mixture. It is envisioned that the ions of the added salt form
association complexes more with the molecules of one of the components to be
separated than with the other components. This association complex phenomenon
may result in altering the vapour and partial pressures, solubility , thermal
conductivity, density, surface tension etc. These changes may result in altering the
VLE of the system , thus altering the ease of separation and shifting or eliminating the
azeotropic point of a given mixture. [16]

There are many advantages of adding salts instead of liquids in an extractive

distillation process

 Lower energy consumption since salts are nonvolatile and do not evaporate or
condense in the distillation process
 Purity of the overhead product from the extracting agent is high since the salts
are non-volatile.
 Sometime a small amount of salt will facilitate required separation.

20
 CHAPTER THREE
MATERIAL & ENERGY BALANCE
CHAPTER THREE PROCESS CALCULATION

3.1 Introduction
The selected process for IPA production was a direct hydration of propylene, where the
calculation has been divided into two parts. The first part was focusing on the synthesis
section namely, the reactor, where thermodynamic analysis of the reaction was
performed followed by material and energy balance, while the second part was focusing
on the separation and purification section, where the firstly, the thermodynamic analysis
of the mixture was performed to investigate the solution behaviour, and then the
material and energy balance for the separation equipment were performed.

3.2 Synthesis Section

The synthesis section is limited to the reactor where the propene is hydrated to the IPA,
since the reaction is thermodynamically controlled and due to the lake of information
about the reaction kinetics and conversion, the thermodynamic analysis was performed
manually to estimate the equilibrium constant and conversion for the reaction,
moreover, the effect of some key parameters “such as operating temperature and
pressure, and water to propylene ratio in the feed” on the reactor performance. After
that the material & energy balance were performed around the reactor based on the
conversion data obtained from thermodynamic analysis, to estimate the reactor effluent
flowrate, composition, and stream temperature.

21
CHAPTER THREE PROCESS CALCULATION

3.2.1 Thermodynamic Analysis

Free energy calculations are a powerful tool that can be employed to predict the
equilibrium yield of a reaction. By definition the free energy of a reaction is the energy
change occurring when the reactants, in their standard states, are converted to the
products in their standard states

∆𝐺𝑟𝑥𝑛 = ∑ ∆𝐺𝑃 − ∑ ∆𝐺𝑅 (3.1)

Table 3.1: Free Gibbs Energy of Formation.

298 400 500 700 1000
Propene 14.99 17.62 22.45 30.6 43.43
water -54.64 -53.52 -52.36 -49.92 -46.04
IPA -41.49 -33.17 -24.66 -7.07 19.93

Using equation (3.1) and the values in Table 3.1 it is possible to calculate the free energy
change for the following reaction:

CH3-CH=CH2 + H2O  CH3CH(OH)CH3

Using these values for the free energy change of the reaction, and the following relation:

∆𝐺𝑟𝑥𝑛 = −𝑅𝑇 𝑙𝑛𝑘𝑝 (3.2)

the equilibrium constants can be calculated at 298°K

∆𝐺𝑟𝑥𝑛 = (∆𝐺𝐶3𝐻8 𝑂 ) − (∆𝐺𝐻2 𝑂 ) + (∆𝐺𝐶3𝐻6 )

= (-41,49)-(-54.64 + 14.99)

= -1.84 kcal/mole

∆𝐺𝑟𝑥𝑛 = −𝑅𝑇 𝑙𝑛𝑘𝑝

∆𝐺𝑟𝑒𝑥𝑛
log kP =
2.303·1.987 cal/mole/°K·298°K

kp = 22.36

The other values of the ∆𝐺𝑟𝑥𝑛 and kp were calculated in the same manner using MS
excel, where the results are shown in table 3.2

22
CHAPTER THREE PROCESS CALCULATION

Table 3.2: Equilibrium constant at different temperatures

298 400 500 700 1000
Propene 14.99 17.62 22.45 30.6 43.43
water -54.64 -53.52 -52.36 -49.92 -46.04
IPA -41.49 -33.17 -24.66 -7.07 19.93
∆𝐺𝑟𝑒𝑥𝑛 -1.84 2.73 5.25 12.25 22.54
k 22.36 0.0322 0.0051 0.00015 1.18E-05

The effect of temperature on the equilibrium constant has been investigated and shown
in the figure 3.1

Figure 3.1: effect of temperature on the equilibrium constant

It is noted in figure 3.1, that the equilibrium constant kp decreases rapidly as the
temperature increases to reach the equilibrium at about 400 K. These values of kP can
be used to calculate the equilibrium yield (conversion) of isopropanol at various
temperatures as follows:

𝑃𝐶3 𝐻8 𝑂
𝑘𝑃 = (3.3)
𝑃𝐶3 𝐻6 𝑃𝐻2 𝑂

𝑛𝐶3 𝐻8 𝑂
𝑘𝑛 = (3.4)
𝑛𝐶3 𝐻6 𝑛𝐻2 𝑂

𝑃
𝑘𝑃 = 𝑘𝑛 𝑛𝑡𝑜𝑡𝑎𝑙 ∗ ∆𝑣 (3.5)
𝑡𝑜𝑡𝑎𝑙

At 𝑃𝑡𝑜𝑡𝑎𝑙 = 1 atm

𝑛𝐶3 𝐻8 𝑂 1
𝑘𝑃 = ∗ (𝑛 )−1 (3.6)
𝑛𝐶3 𝐻6 𝑛𝐻2 𝑂 𝑡𝑜𝑡𝑎𝑙

23
CHAPTER THREE PROCESS CALCULATION

assuming an initial charge of 1 mole C3H5 and 1 mole H2O forming x moles of C3H8O
at 298°K

𝑥 2−𝑥
22.36 = ∗
(1−𝑥)(1−𝑥) 1

x = 0.793  conversion = 79.3 %

In a similar manner the theoretical equilibrium conversion at other temperatures can be

calculated. Also the effects of changes in total pressure and the mole ratio of water to
propylene in the feed can be determined. All calculations were done using MS Excel.

 Effect of temperature on equilibrium conversion

The effect of temperature on equilibrium conversion is investigated at 1 atm, and 1:1

mole ratio, and the results are tabulated in table 3.2, and shown in figure 3.2.

Table 3.2: Equilibrium conversion at different temperatures

T (K) T (𝐶 𝑜 ) conversion %
298 25 79.3
373 100 13.8
400 127 5.2
500 227 0.2

Figure 3.2: effect of temperature on the equilibrium conversion

24
CHAPTER THREE PROCESS CALCULATION

 Effect of pressure on equilibrium conversion

Effect of pressure on equilibrium conversion is investigated at 25 oC, and 1:1 molar

ratio of water to propylene in the feed, and the results are tabulated in table 3.3, and
shown in figure 3.3.

Table 3.3: Equilibrium conversion at different pressures

Pressure (atm) conversion %
1 79.3
2 85.2
5 90.6

Figure 3.3: effect of pressure on the equilibrium conversion

From the above result it can be seen clearly that the operating pressure has a positive
effect on the conversion.

 Effect of feed molar ratio on equilibrium conversion

𝐶3 𝐻6
Effect of feed molar ratio ( ) on equilibrium conversion is investigated a 100 oC, 1
𝐻2 𝑂

atm, and the results are tabulated in table 3.4, and shown in figure 3.4.

Table 3.4: Equilibrium conversion at different feed ratio

Feed molar ratio Yield %
1/1 13.8
1/10 24
1/100 25.6

25
CHAPTER THREE PROCESS CALCULATION

Figure 3.4: effect of feed molar ratio on the equilibrium conversion

26
CHAPTER THREE PROCESS CALCULATION

3.3 Material Balance

Material balances are the basis of process design. A material balance taken over
complete process will determine the quantities of raw materials required and products
produced. Balances over Individual process until set the process stream flows and
compositions and provide the basic equations for sizing equipment.

The general conservation equation for any process can be written as:

Material out = Material in + Generation - Consumption - Accumulation

For a steady state process, the accumulation term is zero. If a chemical reaction is taking
place a particular chemical species may be formed or consumed, the steady state
balance reduces to:

Material out = Material in+ Generation – Consumption (3.7)

In case of the is no chemical reaction taking place, the generation and consumption
terms are omitted, and the balance equation is reduced to the simplest form:

Material out = Material in (3.8)

3.3.1 Material Balance Around Reactor

Based on the thermodynamic analysis that have been made, the operating condition is
selected to have the maximum conversion at low temperature, high pressure, and high
molar ratio of water to propylene. The reactor operating condition will be as in table
3.5.

Table 3.5: Operating condition of the reactor

Temperature (oC) 25
Pressure (bar) 15
Feed ration (H2O/ C3H6) 10
Equilibrium conversions % 88

The following assumptions are made for calculations

 Take a 100 kgmol of propylene as a bases

 The conversion of propylene in the first reaction (Conv1) is 77% of equilibrium
conversion
 The conversion of IPA to DIPE is taken as 5%

27
CHAPTER THREE PROCESS CALCULATION

The following reactions taking place in Liquid-Phase

C3H6 + H2O ⇄ i- C3H7OH R1

2 i- C3H7OH ⇄ (i- C3H7)2O + H2O R2

S7
S5

S8

Mole balance around the reactor is performed using the extent of reaction method to
estimate the outlet flow of each component and the stream composition.

Extent of reaction for the main reaction R1, and side reaction R2 are calculated using
as following:

𝐹𝑖𝑛 − 𝐹𝑜𝑢𝑡
Conversion  Conv. = 𝐹𝑖𝑛

𝐹𝑖𝑛 − 𝐹𝑜𝑢𝑡 𝐶𝑜𝑛𝑣∗𝐹𝑖𝑛

Extent of reaction  𝜉 =  𝜉=
𝑣𝑖 𝑣𝑖

0.67∗100
ξ1 = = 67 kmol
1

0.05∗67
ξ2 = = 1.675 kmol
2

the outlet flowrate of each component from the reactor is calculated using the following
equation:

𝐹𝑜𝑢𝑡 = 𝐹𝑖𝑛 + ∑ 𝑣𝑖 ∗ 𝜉

28
CHAPTER THREE PROCESS CALCULATION

The mole fraction of each component is calculated using the following equation
𝑁𝑜. 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖
𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 =
𝑇𝑜𝑡𝑎𝑙 𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
All calculations are made using MS excel, the results are shown in table 3.6.
Table 3.6: result of mole balance around the reactor
Component Input (S5 + S7) kmol/hr Output (S8) kmol/hr
C3H6 100 FC3H6=100 - (100*0.67) = 33
H2O 1000 FH2O= 1000-(100*0.67)+(0.05*67)/2 = 931.325
IPA 0 FIPA= 67- (2*0.05*67) = 63.65
DIPA 0 FDIPA= (0.05*67)/2 = 1.675
Total 1100 1029.65

3.3.2 Energy balance a Round the Reactor

Energy balance around the reactor is made to find the outlet stream temperatura, sice
the reactor is operated adiabatically, where the Q = 0.

Reactor energy balance equation is given by:

Q = Hout – Hin + △HR

Hout,Hin: are the enthalpy of exit and feed stream respectively in kj /hr

∆HR: Heat of reaction in kj/hr

𝑇
Hout = 𝑆₈ ∫298𝐾 𝐶𝑝 𝑑𝑡

473𝐾
Hin = 𝑆₇ ∫298𝐾 𝐶𝑝₇ 𝑑𝑡 , S7 = S6 + S5

473 473
Hin = 𝑆₆ ∫298 𝐶𝑝₆ 𝑑𝑡 + S₅ ∫298 𝐶𝑝₅ 𝑑𝑡

△HR = [(△H0R1(298) +△Cp1 (T–298))*0.67*162.2) + (△H R2(298) + △Cp2 (T–

298))*0.05*162.2)]

△Cp1 = (c CpC + d CpD) – (a CpA + b CpB)

29
CHAPTER THREE PROCESS CALCULATION

Table 3.7: Heat of formation data

Component kJ/kmol
C3H6 2.043*104
H2O -2.018*104
IPA -272.6*103
DIPA -272.6*103

Reaction: R1

△H0R1 at (298) = (-272.6*103) – (-2.018*104 + 2.043*104) = -27285 KJ/Kmol

△Cp1 = CpIPA – (CpH2O + CpC3H6) = 228 – (75 + 113) = 40 KJ/Kmol

Reaction: R2

△Cp2 = (CpH2O + CpDIPA) – (2CpIPA) = (75 + 228) – (2*228) = -153 KJ/Kmol

△H0R2 at (298) = (-2.018*104 – 272.6*103) – (-272.6*103) = -2.018*104 KJ/Kmol

Substituting into the reactor energy balance equation to estimate the output stream
temperature. If the temperature is a reasonable value, then the adiabatic operation will
be considered, otherwise (very high output temperature), a cooling stream must be
considered.

𝑇
Hout = 𝑆₈ ∫298 𝐶𝑝8 𝑑𝑡

Hout = 1756.6*81.6791 (T-298) = 143477.5 T – 42756297.1

473 473
Hin = 𝑆₆ ∫298 𝐶𝑝₆ 𝑑𝑡 + 𝑆₅ ∫298 𝐶𝑝₅ 𝑑𝑡

Hin = 162.2 * (113 * (473 – 298)) + 1622 * (71.25 * (473 – 298)

Hin = 3207505 + 20224312.5 = 23431817.5 KJ/hr

△HR = [(△H0R + △Cp1 (T – 298))*0.67*162.2) + (△H0R + △Cp2 (T –

298))*0.05*162.2)]

Q = Hout – Hin + △HR

0 = 146583.63 T – 70242571.23

30
CHAPTER THREE PROCESS CALCULATION

70242571.23 = 146583.63 T

70242571.23
T = 146583.63 T = 479 K

Output reactor stream temperature is a reasonable value, then the adiabatic operation

(Q = 0) will be accepted.

31
CHAPTER THREE PROCESS CALCULATION

3.4 Separation Section

3.4.1 Thermodynamic Analysis

The idea here is to separate the desired product based on the difference in the boiling
point, where the distillation column was used. To ensure the smooth operation and easy
separation is possible, the VLE data was generated using aspen properties software and
shown in the figures 3.5 and 3.6.

From figure 3.5 it can be seen clearly that the IPA /water system exhibits an azeotrope
which limiting the separation process at maximum purity of 60% IPA.
T-xy diagram for ISOPR-01/WATER
102.5
x 1.0132 bar
100.0 y 1.0132 bar

97.5

95.0
Temperature, C

92.5

90.0

87.5

85.0

82.5

80.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00

Liquid/vapor mole fraction, ISOPR-01

Figure 3.5: Txy diagram for IPA / water mixture

From figure 3.6 it can be seen clearly that the mixture of IPA/DIPE has an azeotrope
point at 66 oC which liming the IPA purity to no more than 20%.

T-xy diagram for ISOPR-01/DIISO-01

84
x 1.013 bar
82 y 1.013 bar

80

78
Temperature, C

76

74

72

70

68

66

64
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00

Liquid/vapor mole fraction, ISOPR-01

Figure 3.6: Txy diagram for IPA / DIPE mixture

32
CHAPTER THREE PROCESS CALCULATION

From the VLE analysis of the IPA/WATER/DIPE system it is clearly that the separation and
purification process will be compacted due to the azeotrope issue, means that the hand
calculation will be difficult to be perfumed. Aspen HYSYS process simulation software has
been used to model the separation and purification section.

3.4.2 Simulation Setup

Due to the azeotrope problem in the system of IPA/water, the separation and
purification of the IPA using the traditional distillation will be impossible, to solve this
problem the extractive distillation is used where the dimethyl sulfoxide (DMSO) is used
as entrainer to break the azeotrope point. Due to the complicity of the system, material
and energy balance for the separation section is performed using Aspen HYSYS V11.

 Component list and Fluid package

The component list was selected directly from databank which including IPA, water,
water, and DMSO.

NRTL fluid package was selected due to its high capability of modelling the high
pressure system, and it can handle any combination of polar and non-polar compounds,
up to very strong non ideality.

33
CHAPTER THREE PROCESS CALCULATION

 Flowsheet construction

The column configuration is shown in Figure 3.7. There are two feed streams entering
this column: a fresh feed (mixture of IPA and water) is fed in 35th stage, and a solvent
entrainer stream (dimethyl sulfoxide) is fed in 7th stage. The column has total of 41
stages (including total condenser and reboiler). Other operating conditions are shown
in table 3.8 and 3.9.

Table 3.8: Feed specification for the separation section

Parameter F1 F2
Temperature (oC) 25 72
Pressure (kPa) 131.7 111.5
Molar flowrate 100 100
Composition (mole fraction)
Propylene 0 0
H2O 0.5 0
2-propanol 0.5 0
DIPE 0 0
DMSO 0 1

Table 3.9: Column specification

Parameter T-100 T-101
No. of trays 41 18
Top 101.3 101.3
Pressure (kPa)
Bottom 111.5 102
Reflux ratio 1.5 0.915
Distillate rate (kgmol/h) 50 50.05

3.4.3 Material and Energy Balance

Distillation column T-100

Mass balance around the distillation column T-100 is

performed so that the IPA is separated as a top product
with a purity of 100%, while the water is extracted and
separated with DMSO as a bottom product. The results of
mass balance are shown in table 3.10.

34
CHAPTER THREE PROCESS CALCULATION

Table 3.10: Result of mass balance for column T-100

F1 F2 D1 B1
Molar flowrate (kgmole/h) 100 99.95 50 150
Mass flowrate (kg/h) 3906 7810 3005 8711
Composition (mass fraction)
Propylene 0 0 0 0
H2O 0.2306 0 0 0.1034
2-propanol 0.7694 0 1 0
DIPE 0 0 0 0
DMSO 0 1 0 0.8966

The energy balance around the column T-100 is performed to estimate the condenser
and reboiler duties, and streams properties such as enthalpy, heat flow, and and
temperature. Table 3.11 show the energy balance results.

Table 3.11: Result of energy balance for column T-100

Name F1 F2 D1 B1
Temperature [C] 25.00 72.01 82.25 148.00
Pressure [kPa] 132 111.50 101.30 111.50
Molar Enthalpy [kJ/kgmole] -3.02E+05 -1.97E+05 -3.07E+05 -2.15E+05
Molar Entropy [kJ/kgmole-C] 74.68 133.60 169.90 163.8
Heat Flow [kJ/h] -3.02E+07 -1.97E+07 -1.53E+07 -3.22E+07
Condenser (QC1) Reboiler (QR1)
Column duty (kJ/h)
4.95E+06 7.19E+06

Distillation column T-101

Mass balance around the distillation column T-101 is

performed so that the water is separated as a top product with
a purity of 99.57%, while the DMSO is separated as a bottom
product with 100% purity. The results of mass balance are
shown in table 3.12.

Table 3.12: Result of mass balance for column T-101

B1 D2 B2
Molar flowrate (kgmole/h) 150 50.1 99.9
Mass flowrate (kg/h) 8710.7 904.6 7806.1
Composition (mass fraction)
Propylene 0 0 0
H2O 0.103 0.996 0
2-propanol 0 0 0
DIPE 0 0 0
DMSO 0.897 0 1

35
CHAPTER THREE PROCESS CALCULATION

The energy balance around the column T-101 is performed to estimate the condenser
and reboiler duties, and streams properties such as enthalpy, heat flow, and and
temperature. Table 3.13 show the energy balance results.

Table 3.13: Result of energy balance for column T-101

Name B1 D2 B2
Temperature [C] 148 100 190.8
Pressure [kPa] 111.5 101.3 101.3
Molar Enthalpy [kJ/kgmole] -2.15E+05 -279100 -17740
Molar Entropy [kJ/kgmole-C] 163.8 74.46 217.60
Heat Flow [kJ/h] -3.22E+07 -1.40E+07 -1.77E+07
Condenser (QC2) Reboiler (QR2)
Column duty (kJ/h)
3.83E+06 4.37E+06

Auxiliary equipment

The auxiliary equipment including pump P-100 and cooler E-100. Since the process is
steady state, so the mass enter is equal to mass exit the pump and cooler.

Energy balance around the cooler E-100 is performed to estimate the energy required
to cool down the DMSO comes out of column T-101 before recycled. Result is shown
in table 3.14.

Table 3.13: Result of energy balance for cooler E-100

Name 3 1
Temperature [C] 72.00 72.01
Pressure [kPa] 101 111.50
Molar Enthalpy [kJ/kgmole] -196800.00 -196800.00
Molar Entropy [kJ/kgmole-C] 134.30 133.60
Heat Flow [kJ/h] -1.97E+07 -1.97E+07
Energy required
100.2 kJ/h 2.78E-02 KW

Energy balance around pump P-100 is performed to estimate the power required to
pump the recycled DMSO out of the cooler to the column T-100, where the result is
shown in table 3.15

36
CHAPTER THREE PROCESS CALCULATION

Table 3.13: Result of energy balance for pump P-100

Name B2 3
Vapour 0 0
Temperature [C] 191.01 72.00
Pressure [kPa] 102 102
Molar Enthalpy [kJ/kgmole] -177404.61 -196791.90
Molar Entropy [kJ/kgmole-C] 217.69 134.27
Heat Flow [kJ/h] -1.77E+07 -1.97E+07
Energy required (kJ/h)
Q-101 1.94E+06

37
CHAPTER FOUR
PROJECT EVALUATION
CHAPTER FOUR PROJECT EVALUATION

4.1 Project Evaluation

4.1.1 Evaluation Methodology
Methodology of project evaluation is shown in figure (4.5), and to eliminate or at least
reduce the human and random error that can be occur due to hand calculation and
manual design, all the evaluation steps including the flow sheet conversion, equipment
mapping, design and sizing, as well as the economic evaluation are performing
automatically using a package of software and features that are available commercially.

Flow sheet Equipment Auto sizing of Project

converged mapping the equipment evaluation

Figure 4.1: Describe the project evaluation methodology

First step is the flow sheet conversion (material and energy balance) which is already
performed and discussed in the preceding section, second step is the equipment
mapping which means the choose of the design criteria and the assumptions that can be
implemented to simplify the design and sizing procedure, where the mapping options
and assumptions applied are shown in the table 4.2.

Table 4.2 Shown the assumptions of the equipments

Equipment Mapping option and assumption
Cooler, heater, heat
exchanger, reboiler, Shell & Tube heat exchanger, with TEMA type BEM
condenser
Distillation column Sieve tray column
Pump Centrifugal, adiabatic efficiency 75%
Reactors Agitated tank
Vessel, Separator, Pressurized vessel

Once we have the results of material and energy balance along with a mapping criterion,
an auto-design and equipment sizing is performed as a following

 Exchanger design and rating software (EDR) is used for a design of all heat
transfer equipment, including coolers, heaters, heat exchangers, reboiler and
condenser
 Vessel sizing tool is used for a design of pressurize vessels, separators and
reactors
 Tray sizing tool is used for a design of the tray section and column internals for
the absorber and regeneration columns

38
CHAPTER FOUR PROJECT EVALUATION

Based on the results of equipment design and sizing, economic analysis and cost
estimation are performed using Aspen process economic analyser software (APEA)
where the capital, installation, and operating costs are calculated, moreover, for more
precise and reliability, the NPC is evaluated based on the assumptions shown in table

Table 4.3: Shown the assumptions to estimate the NPC

Option Assumption
Operation life of te plant (year) 20
Length of plant startup (year) 0
Operational time per year (hours) 8766
ROR Interest factor 1.2
Cost index 1 Q 2021

4.2 Result of Cost Estimation

Using information from Table 4.3, the economic results of individual equipment in the
process are shown in Table 4.4.

Table 4.4: Result of cost estimation for each equipment

Installed Equipment Installed

Equipment Utility Cost
Name Cost Weight Weight
Cost [USD] [USD/HR]
[USD] [LBS] [LBS]
E-100 1.12E+04 7.28E+04 1200 8835 1.3
CRV-100 1.06E+05 2.57E+05 41300 66174 0.0
T-101 1.08E+05 5.31E+05 17320 65231 51.6
P-100 1.05E+06 1.11E+06 57900 62667 4.3
V-100 2.42E+04 1.36E+05 4100 15359 0.0
P-102 4.90E+03 3.58E+04 170 3399 0.0
P-101 2.63E+05 3.25E+05 14700 22610 8.7
T-100 2.72E+05 7.86E+05 54070 122936 22.1

The overall result of cost estimation for the entire plant is shown in table 4.5, where it
found that the total installed cost of the project is about 3.25E+06 with total operating cost
of 88.03 USD/HR.

Table 4.5: Economic results of entire process

Description Amount
Total Equipment Cost [USD] 1.84E+06
Total Installed Cost [USD] 3.25E+06
Utility Cost [USD/HR] 88.03

39
 CHAPTER FIVE
CONCLUSION & RECOMMENDATION
CHAPTER FIVE CONCLUSION & RECOMMENDATION

5.1 Conclusion
The research was aimed for study the production of IPA through the direct hydration
of propylene, where the study was divided into two sections. in the first section,
thermodynamic analysis was performed manually using principles that have been
learned and application of MS excel, to estimate the equilibrium conversion, extent of
reaction, and conversion under different operating conditions such as, temperature,
pressure, water to propylene ratio, where the result show that the reaction is favored at
low temperature due to the exothermic nature of the reaction, and high pressure until
around 20 bar where further increase will have no significant effect on the conversion,
moreover, the increase in the water to propylene ratio will have a positive effect on the
equilibrium conversion.

The second part of the study was to investigate the best option for IPA purification,
where it forms an azeotropic mixture with water, which make the purification process
extremely complicated, for this reason the extractive distillation using DMSO as an
entrainment was recommended.

40
CHAPTER FIVE CONCLUSION & RECOMMENDATION

5.2 Recommendation
By the end of this research, one can propose some recommendation to be taken as a
starting point for future work as following:

 Perform a hydraulic analysis to ensure a smooth operation without problems of

flooding, weeping and entrainment.
 Study the ability of using other production methods and compare the results.
 Study and simulation the methods for IPA/Water separation process.
 Perform a dynamic simulation of the process and propos the best control
strategy to control the process variables.

41
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