UNIVERSITI KEBANGSAAN

MALAYSIA

DEPARTMENT OF CHEMICAL AND PROCESS ENGINEERING
FACULTY OF ENGINEERING & BUILT ENVIRONMENT
2013/2014

PRODUCTION OF TOLUENE

KKKR 3554: PROF. IR. DR. ZAHIRA BINTI YAAKOB
KKKR3634: PROF. MADYA DR. SITI MASRINDA BINTI TASIRIN
KKKR3544: PROF. MADYA IR. DR. MASTURAH BINTI MARKOM
KKKR3544: DR. MUHAMMAD SHUKRI BIN ABD. RAHAMAN
KKKR3524: PROF. MADYA. DR. MEOR ZAINAL BIN MEOR TALIB
KKKR3524: DR. MASLI IRWAN BIN ROSLI

GROUP KK4
NOR ZURAINI BINTI CHE HASHIM A136485
NURUN NADIYATU IZZATI BINTI AHMAD AFIFI A136730
NOOR SHAZLEEN BINTI SHARFADEEN A136900
NASIBAH BINTI MAT HUSSAIN A136386
MUHAMAD FADZLI BIN MAJID A136736
ii

DECLARATION

We hereby declare that the work in this report is our own except for quotations and
summaries which have been duly acknowledged.

6
th
DECEMBER 2013




MUHAMAD FADZLI BIN MAJID
(A136736)




NOR ZURAINI BINTI CHE HASHIM
(A136485)




NASIBAH BINTI MAT HUSSAIN
(A136386)




NOOR SHAZLEEN BINTI SHARFADEEN
(A136900)




NURUN NADIYATU IZZATI BINTI AHMAD AFIFI
(A136730)




iii

ACKNOWLEDGEMENT

We would like to express our sincere gratitude to all those who lent us a
helping hand in completing and making this Integrated Project a success. Firstly, we
appreciate the advice and time spent by Prof Ir. Dr. Zahira Yaakob, Assoc. Prof. Dr
Siti Masrinda Bt Tasirin, Assoc. Prof. Ir Dr. Masturah Markom, Dr Muhammad
Syukri Bin Abd Rahaman, Assoc. Prof. Dr. Meor Zainal Meor Talib, and Dr. Masli
Irwan Bin Rosli as their assistance and feedback has helped us to compile this project.

Secondly, we truly appreciate the cooperative nature of each person in this
group. We are grateful with the information, suggestions and encouragements shared
between us members. We also appreciate the members precious time and energy
contributed throughout this project.

Furthermore, we would like to thank our course mates for providing
information and data regarding this project, as their help enabled us to complete this
report successfully at the stipulated time.

Hence, we would like to acknowledge everyone once again for their kind help
and contribution towards this project.

Thank you.
iv

ABSTRACT

This report is about the production of Toluene. Toluene is a clear colorless liquid,
sweet, pungent and benzene like odor. Toluene are mainly used in fuel industry,
solvent industry and coolant industry. This plant aims to produce 10% from the Asia
market shortage of toluene which is 84240 tons per year with a mass flowrate of
11700kg/hr. For the production of toluene in our project, there are three raw materials
that involved which are benzene, bromine gas and methane. The chosen reactors for
the reactions process in R-101, R-102 and R-103 is packed-bed reactor (PBR). The
process in reactors R-101 and R-102 are exothermic meanwhile R-103 is endothermic
and the catalyst used is isotope sodium-22. According to the reactor mass balance
calculated manually, the total input mass flow rate for reactor R-103 is similar to
the total output mass flow rate which is also similar to the iCON

result where the
error is only 0.0016%. While at distillation column the condenser heat duty is
10183.33kW. As for separator mass balance, the total input mass flow rate also
similar to the total output mass flow rate 13433.33 kghr
-1
and the result by iCON

is
13433.10 kghr
-1
,

gives the error of 0.0017%. Sieve plate-trays column with 11.35
theoretical stages, and total height of 7.49 m, diameter of 2.5 m is being used.
MATLAB software was used to perform part of the tasks in the project.
v

CONTENT PAGE
Page
DECLARATION ii
ACKNOWLEDGEMENT iii
ABSTRACT iv
CONTENT PAGE v
LIST OF TABLES ix
LIST OF FIGURES x

CHAPTER I INTRODUCTION TO TOLUENE
1.1 INTRODUCTION 1
1.2 PHYSICAL STRUCTURE OF TOLUENE 2
1.3 CHEMICAL PROPERTIES 3
1.4 USAGES OF TOLUENE 4
1.5 RAW MATERIALS
1.5.1 Benzene
1.5.2 Bromine Gas
1.5.3 Methane

5
6
6

CHAPTER II ECONOMIC ASPECT
2.1 INTRODUCTION 8
2.2 DEMAND OF TOLUENE 8
2.3 SUPPLY OF TOLUENE 10
2.4 GLOBAL TOLUENE PRODUCER 10
2.5 FUTURE MARKET POTENTIAL 11
2.6 PROPOSED CAPACITY 11

CHAPTER III ENVIRONMENTAL AND SAFETY ISSUES
PRODUCTION OF TOLUENE

3.1 INTRODUCTION 12
3.2 WASTE GENERATION AND SAFETY
PRECAUTIONS
12

vi

3.2.1 Toluene
3.2.2 Hydrogen Gas
3.2.3 Bromobenzene
3.2.4 Benzene
3.2.5 Bromine Gas
3.2.6 Methane
3.2.7 Hydrogen Bromide
3.2.8 Bromomethane
12
14
15
16
17
18
19
20
3.3 ENVIRONMENTAL ACT 21

CHAPTER IV PROCESS FLOW DIAGRAM
4.1 BLOCK DIAGRAM 23
4.2 PFD DESCRIPTIONS 24

CHAPTER V MASS BALANCE AND ENERGY
BALANCE

5.1 MASS BALANCE 26
5.2 ENERGY BALANCE 32
5.3 iCON COMPARISON FOR MASS AND
ENERGY BALANCE
5.3.1 Mass Balance Comparison
5.3.2 Energy Balance Comparison


37
37

CHAPTER VI REACTOR
6.1 REACTOR DETERMINATION 38
6.2 TYPE OF PROCESS 39
6.3 TYPE OF REACTION 39
6.4 CATALYST 40
6.5 STEPS IN A HETEROGENOUS CATALYTIC
REACTION
40
6.6 GENERAL MASS BALANCE EQUATIONS
AND KINETIC RATE EXPRESSION
41
6.7 KINETIC RATE EXPRESSION 44
vii

CHAPTER VII PARTICLE TECHNOLOGY
7.1 INTRODUCTION 46
7.2 CATALYST SPECIFICATION
7.2.1 Type Of Catalyst
7.2.2 Catalyst Half-Life
7.2.3 Properties Of Catalyst
7.2.4 Catalyst Pore Property
7.2.5 Catalyst Classification
7.2.6 Fluid Flow Through Packed Bed With
Catalyst
7.2.7 Catalyst Contact With Reactants

47
48
49
50
50
52

56

CHAPTER VIII SEPARATION PROCESS
8.1 INTRODUCTION OF SEPARATION
PROCESS
58
8.2 GAS PERMEATION MEMBRANE (G101)
8.2.1 Membrane Selection
8.2.2 Mechanism Of Gas Transport
Mechanism
8.2.3 Type Of Equipment For Gas
Permeation Membrane Process
8.2.4 Type Of Flow In Gas Permeation
Membrane
8.2.5 Membrane Design
8.2.6 Advantages Of Gas Permeation
Membrane
59
60
61

62

63

64
66
8.3 DISTILLATION COLUMN
8.3.1 Mass Balance
8.3.2 Process Design
8.3.3 Heat Duty
8.3.4 Comparison With iCON
8.3.5 Structural Design

66
68
69
70
72
72

viii

8.3.6 Calculation for the Minimum Number
of Stages
8.3.7 Diameter of Distillation Column
8.3.8 Height of Distillation Column
74

75
77

CHAPTER IX CHEMICAL ENGINEERING
COMPUTATION (MATLAB)

9.1 MATLAB SOFTWARE 78
9.2 MASS BALANCE IN R-103
9.2.1 Algorithm And Flowchart
9.2.2 5 Steps Of Problem Solving

78
79
9.3 ENERGY BALANCE IN REACTOR R-103
9.3.1 Algorithm And Flowchart
9.3.2 5 Steps Of Problem Solving

82
83
9.4 SUPPLY AND DEMAND
9.4.1 Algorithm And Flowchart
9.4.2 5 Steps Of Problem Solving

86
87

CONCLUSION 90

REFERENCES 92

APPENDIX 96




ix

LIST OF TABLES
No Table Page
1.1 Material Safety and Data Sheet of Toluene 2
3.1 Hazard ratings production of toluene 13
3.2 Methane Exposure Levels and Effects 18
3.3 Parameters and standard value of waste water discharge limits 22
5.1 Stoichiometric Coefficient 27
5.2 Molar Flow Rate R-103 (kmol/h) 32
5.3 Mass Flow Rate R-103 (kg/h) 32
5.4 Enthalpy of formation of the components 33
5.5 Coefficients of molar heat capacities of the components 33
5.6 Error of mass flowrate (kg/h) at stream 15 and iCON 37
6.1 Stoichiometric table for a flow system 45
7.1 Characteristic of sodium-22 48
7.2 Characteristics of Group C powder 52
8.1 Separation units in process flow diagram 58
8.2 Characteristics of non-porous dense polymeric membrane 60
8.3 Specifications of hollow-fiber membrane 63
8.4 Degree of Freedom Analysis 67
8.5 Molar Flow Rate and Composition 70
8.6 Streams Temperature and Pressure 70
8.7 Molar flow rate, and vapour heat capacity, 71
8.8 Comparison with iCON 72
8.9 K-Values of Components at Distillate and Bottom 74








x


LIST OF FIGURES
No Figure Page
1.1 Molecular diagram of toluene 2
1.2 World consumptions of benzene 6
2.1 Global demand and supply in year 2002 to 2012 9
2.2 Asian demand and supply in year 2002 to 2012 9
2.3 World Consumption of Toluene-2012 10
5.1 Mass Balance for R103 27
5.2 Schematic diagram of Packed bed reactor (R103) 34
6.1 Packed bed reactor 39
6.2 The basis and application of heterogeneous catalysis 41
6.3 Schematic diagram of fixed bed reactor 42
7.1 Hydrodynamic volume of the catalyst 47
7.2 Graph of half-life of isotope sodium-22 49
7.3 Geldarts Classification 51
7.4 Expanded view of a catalyst in a packed bed reactor 53
7.5 Cross sectional area of the packed bed reactor 56
7.6 Pressure drop versus fluid velocity for packed bed and fluidized bed 57
8.1 Membrane Classification 59
8.2 Schematic representation of major gas-transport mechanism 61
8.3 Structure of a hollow-fiber membrane 63
8.4 Ideal flow patterns in a membrane separator for gases 64
8.5 Distillation Column, D102 67
8.6 The Structural of Sieve Tray 73
8.7 Sieve Tray Fractional Distillation Column 73
9.1 Flow chart of the MATLAB code for mass balance 79
9.2 Script MATLAB code for mass balance 81
9.3 Result in Command Window MATLAB 82
9.4 Flow chart of the MATLAB code for energy balance 83
9.5 Script MATLAB code for energy balance 85
9.6 Output MATLAB command window for energy balance 85
xi

9.7 Flow chart of the MATLAB code for supply and demand 87
9.8 Demand and Supply Script MATLAB 88
9.9 Graph of Demand Worldwide 88
9.10 Graph of Supply Worldwide 89





1

CHAPTER I


INTRODUCTION TO TOLUENE


1.1 INTRODUCTION
Toluene is a chemical that was derived from a natural resin namely Tolu balsam, from
Columbia, South America. It was discovered when the resin was burnt and toluene
was obtained as one of the degradation product. The chemical formula of toluene
C
7
H
8
whereby it is a mono-substitued benzene derivative. A methyl atom, CH
3

replaces a single hydrogen atom from a group of six hydrogen atoms from a benzene
molecule. The International Union of Pure and Applied Chemistry (IUPAC) name for
toluene is methylbenzene. Among the other names for toluene are phenylmethane,
toluol and anisen. Toluene undergoes electrophilic aromatic substitution when reacted
with aromatic hydrocarbon compounds. It usually undergoes oxidation when reacting
with other reagents such as potassium permanganate, sulphuric acid, halogens and
many more due to the existence of the methyl side chain. There are several methods to
produce toluene such as the Friedel-Crafts reaction, Wurtz-Fittig reaction and
decarboxylation reaction. Toluene is majorly used as a solvent for cleaning and
thinning. It is also used for the production of organic compounds. Below shows the
structure of toluene whereby the methyl group is the substituent for the benzene
group.
2




Figure 1.1 Molecular diagram of toluene
Source : Nguyen K. D., 2011

1.2 PHYSICAL STRUCTURE OF TOLUENE
Toluene is a clear colourless liquid. It exhibits a sweet, pungent and benzene like
odor. It is insoluble in water, however soluble in diethyl ether, acetone, ethanol,
benzene, chloroform, and glacial acetic. Generally, toluene is a stable chemical but
can become unstable if exposed to heat, ignition sources incompatible materials such
as oxidising agents. Below shows a table on the physical properties of toluene.
Table 1.1 Material Safety and Data Sheet of Toluene
Properties Data
Apperance Clear, colourless liquid
Physical state
Chemical Formula
Liquid
C
7
H
8

Odor Sweet, pungent
Molecular Weight 92.14 g/mol
Boiling Point 110.6
o
C
Melting Point -95.0
o
C
Critical Temperature 318.6
o
C
Specific Gravity 0.8636
Vapour Pressure 3.8 kPa @ 25
o
C
Flash Point 4
o
C
Solubility in water (weight %) 0.074% @ 20
o
C
Vapour Density 3.1
Odor Threshold 1.62 ppm
Source : Sciencelab, 2013.
3

1.3 CHEMICAL PROPERTIES
Due to the high electron density in the aromatic ring, toluene acts as a base both in the
formation of charge transfer complexes and in the formation complexes with super
acids. Chemical derivatives of toluene can be obtained through substitution of the
hydrogen atoms of the methyl group, by substitution of the hydrogen atoms of the
ring, and by addition to the double bonds of the ring. Besides that, toluene can also
undergo a disproportionation reaction whereby two molecules react to produce one
molecule of benzene and one molecule of xylene. Below shows some reactions of
toluene (Helmenstein. A.M., 2003).

Substitution of methyl group
Due to the presence of methyl, toluene is approximately 25 times more reactive than
benzene in a substitution reaction. Usually a free-radical and high temperature
reaction gives substitution on the methyl group. Therefore, in the presence of
ultraviolet light or other free-radical initiator at 100
o
C can yield benzyl chloride,
benzal chloride. Ortho and para isomers are formed in a substitution reaction.

(1.1)

(1.2)

The methyl side chain in toluene may react with other reagent through
oxidation process. If oxygen in the liquid phase and a catalyst is present such as
potassium permanganate with concentrated sulphuric acid, very good yields of
benzoic acid can be obtained.

4



(1.3)

Addition to the ring
Addition reaction can occur to the double bond in the aromatic ring of toluene through
free-radical reaction and catalytic reaction. Chlorination using free-radical initiators at
temperatures <0
o
C saturates the aromatic ring. This reaction is not entirely selective,
as it may affect substitution process on the methyl group. Hydrogenation with typical
hydrogenation catalysts can form methylcyclohexane. However, rates for
hydrogenation of toluene are only 60-70 % of that for benzene.

Substitution on the ring
The substitution reaction of the hydrogen atoms in the aromatic ring may occur by
electrophilic substitution. This process will increase the reactivity of toluene its
selectivity to the ortho and para positions because the electron density in the ring is
increased, and the methyl group will thus stabilizing the reaction intermediates.
Besides the three above main said reactions, toluene can also undergo thermal
hydrogenolysis to produce methane, biphenyl and benzene. It can also undergo
catalytic hydrogenation to yield methylcyclohexane however a high pressure of
hydrogen is need for completion of the reaction (Sevas Educational Society, 2007).

1.4 USAGES OF TOLUENE
Toluene is a versatile chemical as it can be used for many purposes. It is the primary
substance for the manufacture of benzene derivatives. The hydrodealkylation process
is as shown below:
C
6
H
5
CH
3
+ H
2
C
6
H
6
+ CH
4
(1.4)
5

Below shown are some of the uses of toluene in various types of industries.
Fuel Industry
Toluene can be utilised as an octane booster in gasoline fuels used in internal
combustion engines. In the 1980, toluene was used as the fuel for all the turbo
Formula 1 teams by 86% in volume. Besides used in land vehicles, toluene can also be
used as a component for jet fuel surrogate blends due to its content of aromatic
compounds.
Solvent Industry
Toluene is also commonly used as a solvent. It has the ability to dissolve paint,
lacquer, silicone sealants, and disinfectant. Toluene is used as a solvent for carbon
nanotubes. Besides that, it is used as a cement for fine polystyrene kits. In addition,
toluene is used as a solvent to break open red blood cell in order to extract
haemoglobin. Toluene can be used as a fullerene indicator. It also is a raw material for
toluene diisocyanate and trinitrotoluene (TNT) which is an explosive substance.
Coolant Industry
Since toluene has good heat transfer capabilities in sodium cold traps, it is used as a
coolant in a nuclear reactor system. Moreover, toluene is used in the process of
removing cocaine from coca leaves in the production in Coca Cola syrup (Hudson. R.,
2012).

1.5 RAW MATERIALS
1.5.1 Benzene
Benzene is an organic chemical compound with the molecular formula C
6
H
6
and it is
classed as a hydrocarbon. Benzene is one of the alkene hydrocarbon. It is a colourless
liquid and one of the aromatic liquid. The molecular weight for benzene is
78.11kg/kmol. Benzene is soluble in alcohol, chloroform, CCl
4
, diethyl either and
acetone. Its density and boiling point is between 0.8765 g/cm
3
and 80.1 C
respectively.
6

Figure 1.2 below is the pie chart world consumptions of benzene in 2008.


Figure 1.2: World consumptions of benzene.
Source: HIS Chemical

1.5.2 Bromine Gas
Bromine is a dense, mobile, slightly transparent reddish-brown liquid. It will
evaporate easily at standard temperature and pressures to become an orange vapor that
is bromine gas. Bromine is the only liquid nonmetallic element. The orange vapor has
a strong unpleasant odor. Bromine is soluble in organic solvents and in water.
Bromine gas can get commercially in various industries. The industrial production of
bromine involves the direct reaction of chlorine with brine rich in bromine ions and
steam into the reaction tower.

1.5.3 Methane
Methane is a tetrahedral molecule with four equivalent C-H bonds. It is a colorless
and odorless gas at room temperature and standard pressure. The boiling point of
methane is -161C at a pressure of one atmosphere. Because of methane is in gas
phase, it wills flammable only over a narrow range concentration of 5-15% in air. But
when methane in liquid phase, it wills not burn unless under high pressure that
7

normally in between 4-5 atmospheres. In industrial routes, methane is produced by
hydrogenating carbon dioxide through the Sabatier process. Other than that, it is also
produced from a side product of the hydrogenation of carbon monoxide in the Fischer-
Tropsch process.

8

CHAPTER II


ECONOMIC ASPECT


2.1 INTRODUCTION
Toluene is an aromatic compound used in the manufacture of benzene, p-xylene for
polyethylene terephthalate (PET) solid-state resins, and toluene diisocyanates (TDI)
for polyurethane applications, and it is widely used as a solvent.
Toluene into the solvents market was basically flat in 2012 with little
economic stimulus in many regions. There is an inherent value in toluene's use in the
gasoline pool both to build octane and to reduce the vapor pressure. This is especially
true when ethanol, which although high in octane has a high vapor pressure, is being
blended into gasoline. Nonetheless, demand for toluene blending into the gasoline
pool is a function of supply, as the reformers need to operate at reasonable rates.

2.2 DEMAND OF TOLUENE
From the source, global demand toluene in 2002 came 18.9 million tons (2.1%
increase on year). In term of average annual growth rates for demand during 2002-
2008 period, demand for toluene is expected to increase 5.6% (Forecast of Global
Supply and Demand Trends for Petrochemical Products, 2004).

9

Estimates suggest that global toluene demand grew by 5.3% in 2012, with
Northeast Asia being the largest market at just over 46% of world demand. The world
toluene petrochemical market slightly exceeded the previously highest level, attained
in 2007 (IHS Chemical Report 2013).

Figure 2.1 Global demand and supply in year 2002 to 2012
Source: Forecast of Global Supply and Demand Trends for Petrochemical Products,
2004

Figure 2.2 Asian demand and supply in year 2002 to 2012
0
5
10
15
20
25
30
2000 2002 2004 2006 2008 2010 2012 2014
M
i
l
l
i
o
n

t
o
n
s

Year
Demand
Supply
0
1
2
3
4
5
6
7
8
9
2000 2002 2004 2006 2008 2010 2012 2014
M
i
l
l
i
o
n

t
o
n
s

Year
Supply
Demand
10

Source: Forecast of Global Supply and Demand Trends for Petrochemical Products ,
2004
2.3 SUPPLY OF TOLUENE
Throughout the world, consumption in virtually every region was negatively impacted
by the economic recession in 2008 and/or 2009. The developed regions (North
America and Western Europe) declined 8% and 17%, respectively. However, three
regions increased their production of toluene over the same time framethe Middle
East, Northeast Asia and Southeast Asia. Since 2010, most regions have experienced
growth. The fastest growing regions are Africa, the Indian Subcontinent and Northeast
Asia.
However, demand in developing regions such as China, Thailand and the
Middle East saw continued growth during this period. As global economies begin to
slowly recover, toluene markets are anticipated to improve.
The following pie chart shows world consumption of toluene:

Figure 2.3 World Consumption of Toluene-2012
Source: http://www.ihs.com/products/chemical/planning/ceh/toluene.aspx, 2013

2.4 GLOBAL TOLUENE PRODUCER
There are 20 toluene-producing companies in the United States with the capacity to
isolate at least 15 million gallons per year: Amerada Hess, American Petrofina,
11

Amoco Oil, Ashland Oil, BP Chemicals, Champlin, Chevron Chemical, Coastal
Corp., Dow Chemical, Exxon Chemical, Koch Industries, Lyondell Petrochemical,
Marathon Oil, Mobil Oil, Oxy Petrochemicals, Phillips Petroleum, Shell Chemical,
Sun Company, Texaco, and Triangle Refining. These companies represent over 90
percent of US capacity. Annual production capacity for toluene is estimated at 1.5 to
1.7 billion gallons. In 1991, just over 800 million gallons of toluene were isolated in
the US. In the same year, 62 million gallons were imported and 52 million gallons
were exported (Mannsville 1992).

2.5 FUTURE MARKET POTENTIAL
From the Figure 2.2, the ASEAN demand on toluene in year 2002 is 0.4 million tons
and in year 2008 is 0.7 million tons. This show the increase trend in demand on
toluene. Although, the supply on toluene always higher than demand, the toluene still
widely used in industry. Hence, it can be seen that toluene is marketable for current
and future market and has a very good marketing potential as its demand will continue
to increase.

2.6 PROPOSED CAPACITY

From the market research statements above, it has been concluded that the marketing
potential for toluene is good in Asia.
From Figure 2.2, it can be seen that the Asian demand of toluene in 2012 is
7.6869 million tons per year. Thus, the proposed capacity of our plant is 84240 tons
per year with a mass flowrate of 11700 kg/hr. This proposed capacity is calculated
based on Figure 2.2. From Figure 2.2, the Asian demand of toluene in the year 2012
was 7.6869 million tons per year while its production is 6.8445 million tons per year.
The gap between the demand and supply of toluene is 842400 tons per year. Then, our
plant is planned to provide 10% of the shortage of toluene in Asian market, which is
84240 tons per year.

12

CHAPTER III


ENVIRONMENTAL AND SAFETY ISSUES
PRODUCTION OF TOLUENE


3.1 INTRODUCTION
Environmental issues are one of the important considering during the production of
toluene. Any single inappropriate way of handling the chemical will cause huge
impact to the environment especially pollutions. Exposure of chemical to environment
will disturb the balance of the nature. Therefore, it is necessary to pay more attention
to the environmental issues to ensure that the production of toluene does not cause any
pollution.

3.2 WASTE GENERATION AND SAFETY PRECAUTIONS
During a production of a chemical substance, many products will be produced, either
it is a desired product or the undesired products. Any chemical products generated
which are not handle properly, it will become waste and can cause pollution. Different
chemical products are produced and used during the production such as toluene,
hydrogen gas, bromobenzene, benzene, bromine gas, methane, hydrogen bromide and
bromomethane.
3.2.1 Toluene
The appearance of toluene is colourless and the physical state is liquid. It has an
aromatic odor, flammable liquid and vapor. It causes eye, skin, and respiratory tract
irritation. Vapors may cause drowsiness and dizziness. Aspiration hazard if
swallowed, can enter lungs and cause damage. Possible risk of harm to the unborn
13

child. May cause adverse kidney effects and adverse liver effects. Danger of serious
damage to health by prolonged exposure.

Table 3.1: Hazard ratings production of toluene
Hazard Rating NFPA (National Fire Protection Association)
Health 2
Flammability 3
Reactivity 0
Hazard Rating Key: 0=no hazard; 1=slight hazard; 2=moderate hazard; 3=serious
hazard; 4=severe hazard
Source: Toluene MSDS Reliance Industries Ltd, 2011

Precautions: Use personal protective equipment. Remove all sources of ignition.
Take precautionary measures against static discharges. Environmental precautions
should not be released into the environment. Methods for containment and clean up
soak up with inert absorbent material. Keep in suitable and closed containers for
disposal. Remove all sources of ignition. Use spark-proof tools and explosion-proof
equipment.
First Aid Measures and Responses: For inhalation, take precautions to prevent a
fire, for an example remove sources of ignition. Move victim to fresh air. Call a
Poison Centre or doctor if the victim feels unwell. While, for skin contact, avoid direct
contact. Wear chemical protective clothing if necessary. Quickly take off
contaminated clothing, shoes and leather goods such as watchbands and belts. Quickly
and gently blot or brush away excess chemical. Immediately wash gently and
thoroughly with lukewarm, gently flowing water and non-abrasive soap for 15-20
minutes. If irritation or pain persists, see a doctor. Thoroughly clean clothing, shoes
and leather goods before reuse or dispose of safely. Avoid direct eye contact. Wear
chemical protective gloves if necessary. Quickly and gently blot or brush chemical off
the face. Immediately flush the contaminated eye(s) with lukewarm, gently flowing
water for 5 minutes, while holding the eyelid(s) open. If irritation or pain persists, see
a doctor.
14

Handling and Storage: In the event of a spill or leak, exit the area immediately.
Eliminate heat and ignition sources such as sparks, open flames, hot surfaces and
static discharge. Post "No Smoking" signs. Avoid generating vapours or mists.
Electrically bond and ground equipment. Ground clips must contact bare metal. Avoid
repeated or prolonged skin contact with product or with contaminated equipment or
surfaces. Store in an area that is cool, well-ventilated, out of direct sunlight and away
from heat and ignition sources, clear of combustible and flammable materials such as
old rags and cardboard, separate from incompatible materials. Keep amount in storage
to a minimum. Electrically bond and ground containers. Ground clips must contact
bare metal. Avoid bulk storage indoors.
3.2.2 Hydrogen Gas

Hydrogen is the most plentiful gas in the universe. It has high energy content by
weight, but a low energy content by volume. Hydrogen, H
2
is a colorless, odorless,
tasteless, and highly flammable gaseous substance which is flammability range from
4% to 74% in air will ignite, while mixtures of between 18% and 59% in air may
explode. It creates a pale blue flame when ignited, but is virtually invisible in a well
lighted area or bright day light.

The substance can be absorbed into the body by inhalation. High
concentrations of this gas can cause an oxygen-deficient environment. Individuals
breathing such an atmosphere may experience symptoms which include headaches,
ringing in ears, dizziness, drowsiness, unconsciousness, nausea, vomiting and
depression of all the senses. The skin of a victim may have a blue color. Under some
circumstances, death may occur. Hydrogen is not expected to cause mutagenicity,
embryotoxicity, teratogenicity or reproductive toxicity. Pre-existing respiratory
conditions may be aggravated by overexposure to hydrogen. Inhalation risk, on loss of
containment, a harmful concentration of this gas in the air will be reached very
quickly.

Precautions: Follow all proper safety procedures for returning the system or systems
back to the owner after repairs or maintenance. After repairs or maintenance, gaseous
15

and liquid hydrogen systems must be purged of all air and oxygen with an inert gas
and tested with the proper metering analyzer to ensure no oxygen remains in the
system prior to re-introducing hydrogen to the lines, vessels and equipment.

First Aid Measures and Responses: In fire, shut off supply, if not possible and no
risk to surroundings, let the fire burn itself out, in other cases extinguish with water
spray, powder, carbon dioxide. Explosion, in case of fire, keep cylinder cool by
spraying with water. Combat fire from a sheltered position. Inhalation, fresh air and
rest. Artificial respiration may be needed and refer to medical attention. For skin may
refer to medical attention.

Handling and Storage: Know and understand the properties, proper uses and safety
precautions of hydrogen before using the gas and associated equipment. Consult the
Air Products Material Safety Data Sheet (MSDS) for safety information. Never crack
open a hydrogen cylinder to clear the valve of dust as the escaping hydrogen may
ignite. Never drop, drag, roll or slide cylinders. Use a specifically designed hand-truck
for cylinder movement. If a cylinder or valve is defective or leaking, remove the
cylinder to a remote outdoor location away from possible sources of ignition and post
the as to the hazard involved. Notify the gas supplier. For storage, cylinders should be
stored upright in a well ventilated, dry, cool, secure area that is protected from the
weather and preferable fire-resistant. No part of a cylinder should ever be allowed to
exceed 125F (52C) and areas should be free of combustible materials. Never
deliberately over heat a cylinder to increase the pressure or discharge rate. Cylinders
should be stored away from heavily traveled areas and emergency exits. Avoid areas
where salt and other corrosive materials are present.

3.2.3 Bromobenzene

Bromobenzene also known as phenyl bromide is a clear, colorless liquid with a
pleasant odor. It is used as a solvent and motor oil additive and in making other
chemicals. It is flammable and irritating to skin. Toxic to aquatic organisms, may
cause long-term adverse effects in the aquatic environment.

16

Precautions: For ventilation, supply mechanical or local exhaust. Wear chemical-
resistant clothing. Wear safety glasses with splash shields or safety goggles or shield.
To prevent skin contact, wear rubber or neoprene gloves and use rubber safety boots.

First Aid Measures and Responses: Immediately flush eyes with plenty of water for
at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
For skin, flush skin with plenty of soap and water for at least 15 minutes while
removing contaminated clothing and shoes. Get medical aid. If victim is conscious
and alert, give 2-4 cup fulls of milk or water. Never give anything by mouth to an
unconscious person. Get medical aid immediately. Inhalation, remove from exposure
to fresh air immediately. If not breathing, give artificial respiration. If breathing is
difficult, give oxygen. Get medical aid.

Handling and Storage: Protect against physical damage. Store in a cool, dry well-
ventilated location, away from any area where the fire hazard may be acute. Outside
or detached storage is preferred. Separate from incompatibles. Containers should be
bonded and grounded for transfers to avoid static sparks. Storage and use areas should
be No Smoking areas. Use non-sparking type tools and equipment, including
explosion proof ventilation

3.2.4 Benzene
Benzene is a clear, sweet-smelling, highly flammable liquid. It is also known as
benzol, benzole, coal naphtha, cyclohexatriene, phene, phenyl hydride, and
pyrobenzol. Benzene is harmful if it is inhaled, absorbed through the skin or
swallowed. Although benzene is carcinogenic, it can be used with little risk to health
if used properly
Precautions: Benzene is explosive in nature and it can affect skin. Safety glasses or
goggles are recommended where there is a possibility of splashing or spraying. For
skin protection, gloves constructed of nitrile or neoprene are recommended. Chemical
protective clothing such as of E.I.DuPont Tyvek-Saranex 23, Tychem, Barricade
or equivalent recommended based on degree of exposure.

17

First Aid Measures and Responses: Splashed in eyes, wash out immediately with
large amounts of water and if eyes remain irritated or vision becomes blurry, see a
doctor as soon as possible. Spilled on body, take off the contaminated clothing,
thoroughly wash the contacted skin with soap and water immediately. Inhaled large
amounts, quickly get the exposed person to fresh air. Apply artificial respiration if
the person has stopped breathing and call for medical assistance

Handling and Storage: Store in tightly closed containers in a cool, well-ventilated
area away from sparks or flames. Transfer of benzene from one container to another
must be done in well ventilated area. Transfer only with grounded, non-sparking
equipment. Benzene vapors are heavier than air so vapors may travel along the ground
and ignite somewhere away from where it is being handled. Fire extinguishers must be
readily available.
3.2.5 Bromine Gas
Bromine is a volatile liquid that possesses a very strong, suffocating odor. It is
reddish-brown in appearance and highly corrosive, capable of dissolving both metals
and nonmetals. Because it is an oxidizer, it can also react with inorganic material such
as sawdust, creating extreme heat and possibly fire. When exposed to sunlight and
humid air or hot water, bromine can react to form hydrobromic acid, which is not as
toxic as bromine but retains its irritant properties.
Precautions: Gloves and lab coats are required when handling hazardous chemicals.
Closed shoes are required in the lab for safety protections while handling hazardous
chemicals.
First Aid Measures and Responses: For eyes get medical aid immediately. Do not
allow victim to rub or keep eyes closed. Extensive irrigation with water is required at
least 30 minutes. While for skin, immediately flush skin with plenty of soap and water
for at least 15 minutes while removing contaminated clothing and shoes. Wash
clothing before reuse. Destroy contaminated shoes. Inhalation, remove from exposure
to fresh air immediately. If not breathing, give artificial respiration. If breathing is
difficult, give oxygen.
18

Handling and Storage: Avoid contact with skin and eyes and avoid formation of
vapors, dusts, mists and aerosols. Use appropriate exhaust ventilation and keep
flammable, pyrophoric, potentially explosive and water reactive chemicals away from
sources of ignition. The conditions for safe storage is keep in proper storage away
from heat, sparks and flame. Segregate incompatible chemicals and keep away from
reducing agents.
3.2.6 Methane
Methane is an odourless gas and is lighter than air. Because methane is lighter than
air, it tends to rise and accumulate near the higher, stagnant parts of enclosed
buildings and tightly closed manure storage pits. It is most likely to accumulate during
hot, humid weather. National Institute for Occupational Safety and Health's (NIOSH)
maximum recommended safe methane concentration for workers during an 8-hour
period is 1,000 ppm (0.1 percent). Methane is considered an asphyxiation at extremely
high concentrations and can displace oxygen in the blood according Table 3.2 below.
Table 3.2 Methane Exposure Levels and Effects
Exposure Level (ppm) Effect or Symptom
1 000 NIOSH 8-hours Threshold Limit Value
50 000 to 150 000 Potentially Explosive
500 000 Asphyxiation
Source : Atta Atia, 2004
Precautions: Safety eyewear complying with an approved standard should be used
when a risk assessment indicates this is necessary to avoid exposure to liquid splashes,
mists or dusts. Personal protective equipment for the body should be selected based on
the task being performed and the risks involved and should be approved by a specialist
before handling this product Insulated gloves suitable for low temperatures.
First Aid Measures and Responses: Eye contact safety. Immediately flush eyes with
plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids
and get medical attention immediately. In case of contact, immediately flush skin with
plenty of water for at least 15 minutes while removing contaminated clothing and
shoes. To avoid the risk of static discharges and gas ignition, soak contaminated
19

clothing thoroughly with water before removing it. Wash clothing before reuse. For
inhalation problem, move exposed person to fresh air and provide artificial respiration
or oxygen by trained personnel.
Handling and Storage: Use only with adequate ventilation. Use explosion-proof
electrical ventilating, lighting and material handling equipment. Do not puncture or
incinerate container. Keep container closed. Keep away from heat, sparks and flame.
Keep container in a cool, well-ventilated area. Keep container tightly closed and
sealed until ready for use. Avoid all possible sources of ignition either spark or flame.
Segregate from oxidizing materials. Cylinders should be stored upright, with valve
protection cap in place, and firmly secured to prevent falling or being knocked over.
3.2.7 Hydrogen Bromide
Hydrogen Bromide is a colorless gas with a sharp, suffocating pungent odor. Shipped
as liquefied compressed gas and often used in an aqueous solution. Excessive
inhalation may cause burning sensations, coughing, shortness of breath, headache,
nausea and vomiting. May produce bronchitis, chemical pneumonitis and pulmonary
edema. Contact with liquid HBr may cause skin burns. Eye contact may result in
destruction of eye tissue. Excessive exposure can be fatal.
Precautions: Engineering controls, provide adequate general and local exhaust
ventilation to maintain concentration below exposure limits. For eye or face
protection, wear safety glasses and for skin protection,impervious gloves, coveralls,
boots, or other resistant protective clothing. Safety shoes when handling cylinders.
First Aid Measures and Responses: Inhalation, immediately remove victim to fresh
air. If breathing has stopped, give artificial respiration. If breathing is difficult, give
oxygen. For eye contact, immediately flush eyes, including under the eyelids, gently
but thoroughly with plenty of running water for at least 15 minutes. Meanwhile, for
skin contact, immediately flush with copious amounts of water for at least 15 minutes
while removing contaminated clothing.
Handling and Storage: Secure cylinder when using to protect from falling. Use
suitable hand truck to move cylinders. Precautions to be taken in storage is keep in a
20

cool, well ventilated place. Keep valve protection cap on cylinders when not in use.
Store away from heat, flame, and sparks.
3.2.8 Bromomethane
Bromomethane, commonly known as methyl bromide, is an organobromine
compound with formula CH
3
Br. This odorless, colorless nonflammable gas is
produced both industrially and particularly biologically. It has a tetrahedral shape and
it is a recognized ozone-depleting chemical. It was used extensively as a pesticide
until being phased out by most countries in the early 2000s.
Precautions: Provide local exhaust or process enclosure ventilation system. Ensure
compliance with applicable exposure limits. Wear splash resistant safety goggles with
a face shield. Provide an emergency eye wash fountain and quick drench shower in
the immediate work area. Protective clothing is not required. Wear appropriate
chemical resistant gloves.
First Aid Measures and Responses: Inhalation aid if adverse effects occur, remove
to uncontaminated area. Give artificial respiration if not breathing, get immediate
medical attention. Skin contact, wash skin with soap and water for at least 15 minutes
while removing contaminated clothing and shoes. For eye contact, flush eyes with
plenty of water for at least 15 minutes. Then get immediate medical attention. If
swallowed, drink plenty of water, do not induce vomiting. get immediate medical
attention.
Handling and Storage: Avoid bodily contact. Use an appropriate monitoring
instrument for bromomethane in any area where it is being stored or handled. Store
cylinders and cans upright, in a secure manner, either outdoors under ambient
conditions, or indoors in a well ventilated area, away from seeds, foods or feed-stuffs
and human and animal habitation.





21

3.3 ENVIRONMENTAL ACT
The purpose of environmental act is to ensure that the plant will not discharge any
particular material that is hazardous and toxic to the environment. Next, it is to make
sure that the plant is safe to human kind and the ecosystem from any critical
environment disturbance. The environmental act that is related to the production of
toluene plant is the Environmental Quality Act 1974 quote by Law of Malaysia, Act
127, and Environmental Quality Act 1974.
These are the list of Environmental Quality Act regulation that is followed by the
toluene plant:
- Section 21:
Power to specify conditions of emission and discharge.
- Section 22:
Restriction on pollution to the atmosphere.
- Section 25:
Restriction on pollution of inland waters.
- Section 29 and section 29 (a):
Prohibition discharge waste into Malaysia Water.
- Section 31 (a):
Prohibition order to the owner or occupier of any industrial plant or process to
prevent its continued operation and release of environmentally hazardous
substances, pollutants or wastes either absolutely or conditionally, or for such
period as he may direct, or until requirements to make remedy as directed by
him have been complied with.
Table 3.3 below shown the waste water discharge limit, according to the Malaysias
Environmental Law, Environmental Quality Act, 1974, the Malaysia Environmental
Quality (Sewage and Industrial Effluent) regulation, 1979, 1999, 2000:



22

Table 3.3: Parameters and standard value of waste water discharge limits
Parameters Standards
Temperature 40
o
C
pH Value 6.0-9.0
BOD at 20
o
C 50 mg/l
COD 100 mg/l
Oil and Grease 10 mg/l
Suspended solids 100 mg/l
Source : Malaysia Department of Environment, 2008
23

CHAPTER IV


PROCESS FLOW DIAGRAM


4.1 BLOCK DIAGRAM

Where:
CH
4
= Methane G101 = Gas Permeation Membrane 1
Br
2
= Bromine gas R103 = Reactor 3
C
6
H
6
= Benzene P101 = Phase Separator 1
H
2
= Hydrogen gas D102 = Distillation Column 2
C
7
H
8
= Toluene
C
6
H
5
Br = Bromobenzene
R101 = Reactor 1
D101 = Distillation Column 1
R102 = Reactor 2
24

4.2 PFD DESCRIPTIONS
From the process flow diagram for production of toluene, the process is being start by
feed benzene,C
6
H
6
to the H101 at stream 3. The temperature of the benzene will be
increase from 25C to 98C until it is suitable to be react and mix in the R101.
Benzene is then feed into the R101 at stream 4 and will be react with bromine gas that
being feed at stream 2. This reaction will produce bromobenzene,C
6
H
5
Br and
hydrogen bromide,HBr. The product, byproduct byproduct and unreacted reactant will
be cooled from 310C to 45C and then it being purge into the D101 through stream
6. Hydrogen bromide will distilled into the upper stream 7 and feed into R102 to react
with methane that feed at stream 1. This reaction will then produce
bromomethane,CH
3
Br and hydrogen gas,H
2
. From R102, the product will feed into
G101 through stream 11. Hydrogen gas will be purge into the storage tank through
stream 13 while hydrogen bromide and another unreacted reactant will continue being
purge into R103 through stream 14 for the next reactor. At C101, bromobenzene,
byproduct and unreacted reactant will be feed into R103 through stream 12. In R103,
bromobenzene and bromobenzene will be react to form toluene and bromine gas with
the present of Sodium-22 metal as the catalyst. All the product and byproduct will be
feed into P101 and through H103 the product will be heat up from 250C to 260C.
The gas product will be purge from P101 through stream 16 into the waste storage
tank while the liquid product, bromobenzene and toluene,C
7
H
8
will be purge into
another distillation column,D102 through stream 18. Based on the molecular weight,
toluene is more lighter than bromobenzene, so toluene will be purge into upper stream
through stream 19 to the storage tank and bromobenzene will be purge down stream
through stream 22 into the storage tank.





25


26

CHAPTER V


MASS BALANCE AND ENERGY BALANCE


5.1 MASS BALANCE
Based on the demand and supply for toluene in Asia in year 2012, the supply of
toluene does not meet the demand thus causing a shortage of toluene. Below shown is
the data for the toluene in the Asia region.
Asia demand for toluene in 2012 = 7.6869 million tonnes
Asia supply for toluene in 2012 = 6.8445 million tonnes
Shortage of toluene in 2012 = 0.8424 million tonnes
This project proposes to produce a plant that produces 10% of the Asia region
shortage.
10% of 0.8424 million tonnes = 84 240 000 kg.
The process design is expected to work for 300 days per year.
300 days x 24 hours/day = 7200 hours/year
Mass flowrate =

= 11 700 kg/hr
Molar flowrate =

= 126.98 kmol/hr
27

There are three reactors in our design process. The main reaction occurs in Reactor 3
whereby the reaction equation is shown below.
C
6
H
5
Br (g) + CH
3
Br(g) + Na(s) C
7
H
8
(l) + Br
2
(g) (5.1)



R103
X = 0.92


Figure 5.1 Mass Balance for R103
Note : C
6
H
5
Br = Bromobenzene
HBr = Hydrogen Bromide
C
6
H
8
= Benzene
Br
2
= Bromine gas
CH
3
Br = Bromomethane
C
7
H
8 =
Toluene

Table 5.1: Stoichiometric Coefficient
Ethanolamine Ammonia Ethylenediamine Water
-1 -1 1 1

Estimated conversion, X = 0.92
F
8, C6H5Br

F
8,HBr

F
8,C6H6
F
8,Br

F
12, C6H5Br

F
12, HBr

F
12, C6H6

F
12,Br
F
12, CH3Br
F
12,

C7H8



F
10,CH3Br
28

Estimated equilibrium constant, K
e
= 5
Mole balance for components:
(a) Toluene,
Given No= 126.98 kmole/h
No=Ni+r
126.98 = 0+(1)r
r = 126.98 kmole/h

(b) Bromine gas,
No=Ni+r
No= 0+(1)(126.98)
= 126.98 kmole/h

(c) Bromobenzene,
No=Ni+r
Conversion, X=

XNi= Ni-No
XNi= -r
(0.92)Ni= -(-1)(126.98)
Ni= 138.02 kmole/h
No=Ni+r
= 138.02 + (-1)(126.98)
= 11.04 kmole/h
29

From equilibrium constant:
Ke = (N
ik
+
k
r)
k



=

5.0 =

5.0 =

N
iCH3Br
= 419.08 kmole/h

(d) Bromomethane,
No=Ni+r
No= 419.08 + (-1) (126.98)
= 292.10 kmole/h

To determine the limiting reactant,
For bromobenzene (C
6
H
5
Br) =

= 138.02 kmole/h
For bromomethane (CH
3
Br) =

=



= 419.08 kmole/h
Hence, the limiting reactant is bromobenzene (C
6
H
5
Br) .

30

Total input molar flow rate, N
iT
= Ni
C6H5Br
+ Ni
CH3Br
+ Ni
C7H8
+ Ni
Br2

= (138.02 + 419.08 + 0 + 0) kmole/h
= 557.10 kmole/h
Total output molar flow rate, N
oT
= No
C6H5Br
+ No
CH3Br
+ No
C7H8
+ No
Br2

= (11.04 + 292.10 + 126.98 + 126.98) kmole/h
= 557.10 kmole/h

Composition of input components:
Bromobenzene, x
iC6H5Br
=

= 0.2477
Bromomethane, x
iCH3Br
=

= 0.7523
Composition of output components:
Bromobenzene, x
oC6H5Br
=

= 0.0198
Bromomethane, x
oCH3Br
=

= 0.5243
31

Toluene, x
oC7H8
=

= 0.2279
Bromine gas, x
oBr2
=

= 0.2279

Mass flow rate for input components :
Bromobenzene (C
6
H
5
Br), F
iC6H5Br
= N
iC6H5Br
x M
C6H5Br

= 138.02 x 157.01 = 21670.52 kg/h
Bromomethane (CH
3
Br), F
iCH3Br
= N
iCH3Br
M
CH3Br
= 419.08 x 94.94 = 39787.46 kg/h
Total input mass flow rate = F
iC6H5Br
+ F
iCH3Br
= 61457.98 kg/h

Mass flow rate for output components :
Bromobenzene (C
6
H
5
Br), F
oC6H5Br
= N
oC6H5Br
x M
C6H5Br

= 11.04 x 157.01 = 1733.39 kg/h
Bromomethane (CH
3
Br), F
oCH3Br
= N
oCH3Br
M
CH3Br
= 292.10 x 94.94 = 27731.97 kg/h
Toluene (C
7
H
8
), F
oC7H8
= N
oC7H8
M
C7H8

= 126.98 x 92.14 = 11699.94 kg/h
Bromine gas (Br
2
), F
oBr2
= N
oBr2
M
Br2

32

= 126.98 x 159.80
= 20291.40 kg/h
Total output mass flow rate = F
oC6H5Br
+ F
oCH3Br
+ F
oC7H8
+ F
oBr2
= 61456.70 kg/h
Table 5.2: Molar Flow Rate R-103 (kmol/h)
Components N
in
(kmol/h) N
out
(kmol/h)
Bromobenzene,C
6
H
5
Br 138.02 11.04
Bromomethane,CH
3
Br 419.08 292.10
Toluene,C
7
H
8
0 126.98
Bromine gas,Br
2
0 126.98
Total 557.10 557.10

Table 5.3: Mass Flow Rate R-103 (kg/h)
Components N
in
(kmol/h) N
out
(kmol/h)
Bromobenzene,C
6
H
5
Br 21670.52 1733.39
Bromomethane,CH
3
Br 39787.46 27731.97
Toluene,C
7
H
8
0 11699.94
Bromine gas,Br
2
0 20291.40
Total 61457.98 61457.70

F
in
=

F
out
61457.00 kg/h
Hence, reaction inside reactor R-103 is balanced.

5.2 ENERGY BALANCE
To calculate the energy balance for reactor unit operation in the plant design, the data
for the enthalpy of formation of the components is needed as shown in Table 5.4
below.

33


Table 5.4: Enthalpy of formation of the components
Components Enthalpy of formation,H
o
f
(kJ/mol)
Bromobenzene, C
6
H
5
Br
Bromomethane, CH
3
Br

Toluene, C
7
H
8

Bromine, Br
2

58.60
-33.50
12.00
30.91
Source: Perry Handsbook, 2008

Moreover, to find the molar enthalpy change of a component that flow in and out at
every unit operation, have to get the information for the coefficients of molar heat
capacities of the components where T
1
in standard condition, 25
o
C or 298 K .
Assumptions:
1. There are no kinetic energy, potential energy and work done by the system.
2. The references temperature is 25
o
C

Table 5.5 Coefficients of molar heat capacities of the components
Cp = a + bT + cT
2
+ dT
3
, unit in kJ/kmol.K
Components a b c d
Bromobenzene,
C
6
H
5
Br
0.721x10
-5
2.064x10
-5
1.650x10
-3
1.687x10
-5

Bromomethane,
CH
3
Br

0.3377x10
-5
0.715x10
-5
1.578x10
-3
0.418x10
-5

Toluene, C
7
H
8
0.5814x10
-5
2.863x10
-5
1.441x10
-3
1.898x10
-5

Bromine, Br 0.301x10
-5
0.081x10
-5
0.751x10
-3
0.108x10
-5

Source: Property Tables Booklet, 2011

34


Energy Balance Calculation for Packed Bed Reactor (R-103)

Figure 5.2 Schematic diagram of Packed bed reactor (R103)

Chemical reaction in the reactor is as below,
C
6
H
5
Br (g) + CH
3
Br(g) + Na(s) C
7
H
8
(l) + Br
2
(g) (5.2)
Rate of reaction = r
N
o,C7H8
= N
i,C7H8
+ (

x r)
126.98 = 0 + (1)r
r = 126.98 kmol/hr

reaction =

o
-
i

= (
formation ,C7H8
+
formation,Br2
) (
formation,C6H5Br
+
formation,CH3Br
)
= [12.0 + 30.91] [58.6+(-33.5)]
= 17.81 kJ/mol
H
reaction
= r x
reaction
= 126.98 kmol/hr x 17.81 kJ/mol

T= 423K
N
i,CH3Br
= 419.08 kmol/hr
T= 303K
N
i,C6H5Br
= 138.02 kmol/hr

T= 523K
N
o,C7H8
= 126.98 kmol/hr
N
o,C6H5Br
=11.04 kmol/hr
N
o,Br2
=126.98 kmol/hr
N
o,CH3Br
=292.10 kmol/hr

35

= 22615.51 kJ/hr
Inlet components :
Stream 10,
Bromomethane, CH
3
Br

CH3Br
=

0.3377x10
-5
+0.715x10
-5
T+1.578x10
-3
T
2
+0.418x10
-5
T
3
dT
= 51076.92 J/kmol
Stream 8,
Bromobenzene, C
6
H
5
Br

C6H5Br
=

0.721x10
-5
+2.064x10
-5
T+1.650x10
-3
T
2
+1.687x10
-5
T
3
dT
= 3034.22 J/kmol
Thus, N
i

i
=
CH3Br2
x N
i
,
CH3Br
+
C6H5Br
x N
i,C6H5Br
=(51076.92x419.08) + (3034.22x138.02)
=21.824x10
6
kJ/hr

Outlet components: Stream 12
Toluene, C
7
H
8

C7H8
=

0.5814x10
-5
+2.863x10
-5
T+1.441x10
-3
T
2
+1.898x10
-5
T
3
dT
=373582.33 J/kmol
Bromobenzene, C
6
H
5
Br

C6H5Br
=

0.721x10
-5
+2.064x10
-5
T+1.650x10
-3
T
2
+1.687x10
-5
T
3
dT
36

=346428.65 J/kmol
Bromine, Br
2

Br2
=

0.301x10
-5
+0.081x10
-5
T+0.751x10
-3
T
2
+0.108x10
-5
T
3
dT
=47240.67 J/kmol
Bromomethane, CH
3
Br

CH3Br
=

0.3377x10
-5
+0.715x10
-5
T+1.578x10
-3
T
2
+0.418x10
-5
T
3
dT
= 131188.33 J/kmol
Thus, N
o

o
=
C7H8
x N
o
,
C7H8
+
C6H5Br
x N
o
,
C6H5Br
+
Br2
x N
o
,
Br2
+
CH3Br2
x
N
o
,
CH3Br

=(373582.33x126.98)+( 346428.65x11.04)+(47240.67x126.98)+(131188.33x292.10)
= 95.581 x 10
6
kJ/hr
So, the heat of energy, Q
Q = N
o

o
N
i

i
+ H
reaction
= (95.581 x 10
6
) (21.824x10
6
) + (22615.51) = 73.780 x 10
6
kJ/hr

The reaction in packed bed reactor is endothermic process. The heat energy absorbed
by the reactor is 73.780 x 10
6
kJ/hr.

37

5.3 iCON COMPARISON FOR MASS AND ENERGY BALANCE
5.3.1 Mass Balance Comparison
Table 5.6: Error of mass flowrate (kg/h) at stream 15 and iCON
Components Stream 15 iCON Error(%)
Bromobenzene,C
6
H
5
Br 1733.39 1733.64 0.0144
Bromomethane,CH
3
Br

27731.97 27732.16 0.0007
Toluene,C
7
H
8
11699.94 11699.75 -0.0016
Bromine gas,Br
2
20291.40 20292.44 0.0052
Total 61456.70 60897.99 -0.9175

5.3.2 Energy Balance Comparison
Q
calc
= 73.780 x 10
6
kJ/hr.
Q
iCON
= 4058312.4894 W
= 14.6099x10
6
kJ/hr.
Error =

x 100%
= 80.20%


38

CHAPTER VI


REACTOR


6.1 REACTOR DETERMINATION
A reactor is designed to contain chemical reactions. It is the place where the
conversion of raw materials occur into desired products thus it known to be the heart
of a chemical process. The design of a reactor in a commercial scale would be affected
by several aspects of chemical engineering. Since it is an important step in the overall
design process, one should ensure that the reaction proceeds with the highest yield of
product in the most cost efficient way and also the highest efficiency towards the
desired output.
There are three reactors in this process, however the most important reactor
namely R103, is used to synthesis the main product that is toluene. A packed bed
reactor is chosen as the suitable reactor to ensure an optimum reaction process in the
reactor. A packed bed reactor is a hollow tube that is filled with packing material such
as raschig rings. It is made up of ceramic or metal and it provides large surface area
within the volume of the column for interaction between the reactant.
39






Figure 6.1 Packed bed reactor
Source : Hindawi Publication Corp. 2013

6.2 TYPE OF PROCESS
The chemical reaction in the packed bed reactor undergoes a continuous process. This
process occurs when the reactants are fed into the reactor and the products are
withdrawn while the reaction is still in progress. A continuous packed bed reactor is
chosen as it has much more advantages compared to a batch packed bed reactor.
Firstly, it has an easy and automatic control operation. Secondly, a continuous packed
bed reactor can reduce labour costs. Thirdly, the operating conditions can be stabilized
certainly with the use of a packed bed reactor. Finally, it will be easier to control the
quality of the products formed from a packed bed reactor. Hence continuous reactors
are preferred for large scale production (Rensselaer, 2004).

6.3 TYPE OF REACTION
For the synthesis of toluene, gaseous methyl bromide and liquid bromobenzene are
fed into the continuous packed bed reactor. Since there is a mixture of gas and liquid
in the feed stream, a heterogeneous reaction occurs in the reactor. In a heterogeneous
reaction, two or more phases exists and the usual problem that may arise in the reactor
design is to promote mass transfer between the phases (Nanda. S. et al. 2008).

Packing material
40

6.4 CATALYST
A catalyst is a substance that alters a rate of reaction without itself undergoing any
permanent chemical change. It also provides an alternative pathway or lowers the
activation energy for e specific reaction. For the production of toluene, solid isotopes
Sodium-22 catalyst is needed to speed up the reaction. The usage of the catalyst can
further be optimized with the presence of sodium metal in the presence of dry ether.

6.5 STEPS IN A HETEROGENOUS CATALYTIC REACTION
There are several steps in a heterogeneous catalytic reaction. Firstly, there is mass
transfer via diffusion of the reactants namely bromobenzene and bromomethane from
the bulk fluid to the external surface of the catalyst pellet, isotope Sodium-22 metal.
Then the diffusion of the reactants from the pore mouth through the catalyst pores to
the immediate vicinity of the internal catalytic surface occurs. The reactors are
adsorbed onto the catalyst surface and a reaction takes place on the surface of the
catalyt. After the reaction has taken place, desorption of the product namely toluene
and bromine from the catalyst surface occurs. Then, the products formed are diffused
from the interior of the catalyst pellet to the pore mouth at the external surface. Lastly,
mass transfer of the products from the external pellet surface to the bulk fluid takes
place.
41


Figure 6.2 The basis and application of heterogeneous catalysis
Source : Bowker. M. 1998.

6. 6 GENERAL MASS BALANCE EQUATIONS AND KINETIC RATE
EXPRESSION
The production of toluene shown by the following reaction:
Na(s)
C
6
H
5
Br (l) + CH
3
Br (g) C
7
H
8
(l) + Br
2
(g) (6.0)
(Bromobenzene) (Methyl bromide) (Toluene) (Bromine gas)
Adsorption process. Catalytic reaction for the catatlyst:
Let A = C
6
H
5
Br
B = CH
3
Br
C = C
7
H
8

42

D = Br
2

N = Na
Assume this reaction is reversible process:
Adsorption on Surface: A + N A . S
B + N B . S
Surface Reaction: A . S + B . S C . S + D . S
Dual Site: A . S + B . S C . S + D . S
Eley-Rideal: A . S + B (g) C . S + D(g)
Desorption from surface: C . S C + S

The general mole equation is

(6.1)


Figure 6.3 Schematic diagram of fixed bed reactor.
43


In - Out + Generation = Accumulation
F
A0
- F
A1
+ r
A
W = dN
A
/ dt (6.2)
Assume that FBR is operated at steady state,

F
A0
- F
A1
+ r
A
W = 0 (6.3)
Dividing by W and rearranging,
(F
A0
- F
A1
) / W = r
A
(6.4)

Taking the limit as W approaches zero, we obtain the differential from of steady
state mole balance on a Fixed Bed Reactor (FBR):
dF
A
/ dW = r
A
(6.5)
For a flow system,
F
A
= F
A0
- F
A0
X (6.6)
Differentiating,
dF
A
= -F
A0
dX (6.7)
Subsitute (6.7) into (6.5) gives the differential form of mole balance on a Fixed Bed
Reactor (FBR) based on the conversion:
F
A0
(dX/dW) = -r
A
(6.8)
Use the above differential form of the mole balance on FBR when there is pressure
drop or catalyst decay.




44

6. 7 KINETIC RATE EXPRESSION
Main reaction:
Na(s)
C
6
H
5
Br (l) + CH
3
Br (g) C
7
H
8
(l) + Br
2
(g) (6.9)
(Bromobenzene) (Methyl bromide) (Toluene) (Bromine gas)
Let A = C
6
H
5
Br
B = CH
3
Br
C = C
7
H
8

D = Br
2

Reaction Stoichiometry
-r
A
= -r
B
= r
C
= r
D
(6.10)
Rate Law:
-

= kC
A
C
B
(6.11)
Because we are taking bromobenzene as our basis, we divide through by the
stoichiometric coefficient of toluene to put the reaction expression in the for
A + B C + D (6.12)
Where,
O
B
= F
B0
/ F
A0
= C
B0v0
/ C
A0v0
= C
B0
/ C
A0
= y
B0
/ y
A0
(6.13)
O
C
and O
D
are defined similarly.
For gases, volume change with reaction is :
(6.14)
as P
0
= P and T
0
= T
45

So,

(6.15)

We may then perform the calculation shown below:
Table 6.1: Stoichiometric table for a flow system
Species Symbol Feed rate to
reactor
(mol/time)
Change
within
reactor
(mol/time)
Effluent rate
from reactor
(mol.time)
Concentration
(mol/liter)
C
6
H
5
Br

A

CH
3
Br

B

O
B

O
B

C
7
H
8
C

O
C

O
C

Br
2
D

O
D

O
D

Thus, subtitute the value of concentration C
A
and C
B
into the rate law equation,
-

= k

(6.16)



46

CHAPTER VII


PARTICLE TECHNOLOGY


7.1 INTRODUCTION
The handling and processing of particles and powders is referred by the term of
particle technology. It is also often described as powder technology and powder
science. Among the industries that utilize this technology includes petrochemical,
chemical, pharmaceuticals, mineral processing and many more. In the production of
toluene, no solid formation is involved, however the only solid phase that is present is
in the third reactor, R103 when bromobenzene and bromomethane comes in contact
with the catalyst, isotope sodium-22 metal. The catalyst remains in and does not exit
the reactor. Hence, in the particle technology section, we will elaborate further about
the catalyst specifications and how the catalyst gets in contact with the reactants
(Rhodes. M. 2007).
47

7.2 CATALYST SPECIFICATION
7.2.1 Type Of Catalyst
Isotope sodium-22 is used as a catalyst in this toluene production plant. Below shows
the characteristics of the catalyst that we are using, isotope sodium-22. There are
several steps to consider during a catalytic reaction. Firstly, the transport of reactants
and energy from the bulk fluid to the exterior surface of the catalyst surface. Then the
transfer of the reactant and energy from the external surface into the porous catalyst
pellets occur. Further on, adsorption, chemical reaction and desorption of products
take place at the catalytic sites. The products from the catalyst interior is transported
to the external surface of the pellet. Finally the products are transferred into the bulk
fluid. The coupling of transport process and chemical reaction may lead to
temperature and concentration gradient within the catalyst pellet, between the surface
and the bulk or maybe even both. Below shows the hydrodynamic volume of the
catalyst characteristics of sodium-22 catalyst.

Figure 7.1 Hydrodynamic volume of the catalyst
Source : Rhodes. M., 2007.




Pores
Hydrodynamic
volume
Solid catalyst
48

Table 7.1 below shown is the characteristic of the catalyst used.
Table 7.1 Characteristic of sodium-22
Characteristic Description
Nuclide symbol
22
Na
Proton number 11
Nucleon number 11
Isotopic mass 21.9944364
Half life 2.6027 years
Decay mode
+

Daughter isotope
22
Ne
Source : Sciencelab. 2003.
7.2.2 Catalyst Half-Life
It is vital to know the half-life of a catalyst. Half-life is defined as the amount of time
requirement for a quantity to fall to half its value as measured at the beginning of the
time period. Thus it is important to know how long it takes for the catalyst to decay
and to be replaced. Below shows the calculation for the half-life of isotope sodium-22
catalyst. This catalyst has a remarkable long half-life of 2.602 years. Based on our
plant which operates 300 days a year, this catalyst can be used up to 650 days. Below
shows the calculation for the half-life of the catalyst.
The initial weight of the catalyst 22.6 kg
The final weight of catalyst is hereby assumed to degrade 90% in weight.
Thus, the remaining catalyst weight 10% x 22.6 kg = 2.26 kg
Based on literature review, half-life of isotope sodium-22 catalyst is 2.602 years
equivalent to 950days
49

Elapsed time =

= 5390 days
Figure 7.2 below shows the graph of half-life of sodium-22 catalyst

Figure 7.2 Graph of half-life of isotope sodium-22

7.2.3 Properties Of Catalyst
In order to ensure that a catalytic process is commercially feasible, the number of sites
per unit reactor volume should be in a way that the rate of product formation is in the
order of 1 mol/L.hour. (P.B. Weisz.1973). Since a metal catalyst, isotope sodium-22 is
used, the metal is dispersed onto a high area oxide such as alumina. This can further
increase the surface area from 0.05 m
2
/g to greater than 100 m
2
/g. The diameter of the
pellet ranges from 0.3-0.7 cm (Nob Hill Publishing, 2011).



0
5
10
15
20
25
0 1000 2000 3000 4000 5000 6000
A
m
o
u
n
t

(
k
g
)

Time(Days)
Graph of half-life of isotope Sodium-22
50

7.2.4 Catalyst Pore Property
The solid density is denoted by
s
. Since the pellet volume consists of both solid and
void regions, the pellet void fraction or also known as porosity is denoted by the sign
. Such that to calculate , we use the formula stated below.
=
s
V
g

whereby
s
: pellet density

V
g
: pore volume
Thus, based on the catalyst isotope sodium-22, the porosity of the catalyst is
=

] x

= 0.485
Since the pore structure is a crucial function of the preparation method, based on
literature review, the pore volume of a catalyst is said to range between 0.1-1 cm
3
/g
pellet. The pore size may be the same size or can be a bimodal distribution with pores
of two different sizes, a large size to help transport and a small size to contain the
active catalyst site. Besides that, pore size can also be as small as molecular
dimensions namely several angstroms or as large as several millimeters. The method
to determine the total catalyst area is by using a physically adsorbed species like
nitrogen gas, N
2
. This procedure was developed by Brunauer, Emmet and Teller and is
known as the BET theorem (S. Brunauer et al. 1938).


7.2.5 Catalyst Classification
Before choosing the type of group to classify the catalyst, several considerations must
be made to obtain the best choice. Firstly, since its a packed bed reactor, we first
calculate the superficial fluid velocity, since its a packed bed catalyst, then U
mf
= U.
Thus,
51

U =

= 6755.01m/s
Then we calculate superficial fluid velocity at minimum bubbling, U
mb

U
mb
= 2.07exp(0.716F)

U
mb
= 2.07exp(0.716x (45 x 10
-6
)

= 18130

m/s
We now see that U > U
mb
. Thus we can decide that the catalyst is classifies under
group C. Below shows the simplified diagram showing Geldarts classification of
powders according to their fluidization behavior in air under ambient conditions.

Figure 7.3 Geldarts Classification
Source : Kobayashi. T. et al. 2002.




52

Attached Table 7.2 below is the characteristics of group C powder.
Table 7.2 Characteristics of Group C powder
Characteristic Description
Obvious feature Cohesive and difficult to fluidize
Property bed expansion Low because of channeling
De-aeration rate Initially fast then exponential
Bubble properties No bubbles, only channels
Solid mixing Very low
Gas backmixing Very low
Spouting
Example
No
Flour, cement
Source : Rhodes. M., 2007.
It is said that group C powders are very fine powders and are cohesive in
nature. It is difficult for normal fluidization to occur for these solids due to strong
interparticle forces that are greater than those resulting from the action of the fluid.
Since group C particles are difficult to fluidize, they usually rise as plug of solids
where in larger diameter beds channel form from distributor to bed surface without
any fluidization of solids.

7.2.6 Fluid Flow Through Packed Bed With Catalyst
Since a packed bed reactor is used to host the main reaction, the catalyst pellets are
held in place and do not move with respect to a fixed reference time. The species
production rates in the bulk fluid is zero at first, therefore we use a catalyst to
complete the reaction. Essentially, all the reaction occurs inside the catalyst pellets.
The below diagram shows expanded view of catalysts in a packed bed reactor.
53


Figure 7.4 Expanded view of a catalyst in a packed bed reactor
Source : Nob Hill Publishing, 2011.
The symbols are denoted as
c
j
: Concentration on species j
c
js
: Concentration of species j at the catalyst surface
T : Temperature
R : Gas constant

The flow of fluid through a packed bed of catalyst is governed by the relationship :
[pressure gradient] [liquid velocity] or

whereby is the pressure drop
H is the bed depth
U is the fluid volumetric flow rate

54

Hence, below shows the calculation to know the type of fluid flow through a packed
bed with catalyst isotope sodium-22.
R
e
=

Where:
R
e
= Reynolds number
D = diameter of the reactor(m)
= velocity of the reactant flow(m
3
/s)
= density of the reactant(kg/m
3
)
= viscosity of the reactant(kg/ms)

R
e
=

= 43233963.5
Since Re > 4000, thus we can conclude the fluid flow through packed bed with
catalyst is turbulent flow.
The flow of fluid through a packed bed of solid catalyst particles can be
analyzed in terms of the fluid flow through tubes. The starting point is the Hagen-
Poiseuille equation for turbulent flow through the tube is as shown below:

Where

: fluid density
: fluid velocity
x : diameter of packed bed catalys
: void fraction of packed bed

55

To find H, rearrange the equation:
H =

= (101.3-200)kPa = -98.7 kPa

f
= 1.495x10
3
kg/m
3
U = 21.67 m
3
/s
x = 0.2434
= 0.9649
So, H =

H = 0.5 m
Hence the depth of the packed bed is 0.5m.

The area of the packed bed is
2r
2
+ 2rh = 2[ x 0.75
2
m] + 2[ x 0.75 x 0.5]
= 5.89 m
2

The area of one catalyst pellet is
r
2
= [0.005m]
2
= 7.85 x 10
-5
m
2
Thus, the amount if catalyst needed in the packed bed is

= 75031.85
Mass of catalyst needed
75031.85 x 23kg/kmol = 1725732.48 kg
56

Since the fluid flow is through tube with proposed cross sectional area of 1m
2
, we use
1725732.48 kg of isotope-22 catalyst with a bed depth of 0.5 m, the bed density is

= 3,451,464.97 kg/m
3


7.2.7 Catalyst Contact With Reactants
The packed bed reactor that we are using will have a top sprayer to disperse the
bromomethane gas onto bromobenzene liquid that will be flowed into the reactor via a
pipeline. Then both reactants come in contact with a packed bed catalyst spreaded
over alumina to increase surface area of contact.
The sprayer is used to ensure that the bromomethane is evenly distributed
throughout the reactor to get maximum coverage in contact with the bromobenzene
and catalyst. After contact with the catalyst, the desired product namely toluene is
formed and collected at the end of the reactor before being flowed to the next unit
operation. Below shows the cross sectional area of the packed bed reactor.

Figure 7.5 Cross sectional area of the packed bed reactor

57

Below shows the plot of fluid pressure loss across the bed versus superficial fluid
velocity through the bed.

Figure 7.6 Pressure drop versus fluid velocity for packed bed and fluidized bed
Source : Rhodes. M., 2007
Since in this process we are using a packed bed reactor, we only consider the region
OA. The solid catalysts do not move relative to another and their separation is
constant (Rhodes. M., 2007).


58

CHAPTER VIII


SEPARATION PROCESS


8.1 INTRODUCTION OF SEPARATION PROCESS
Based on the process flow diagram, it is seen that the process design has four main
unit operations that are used to separate various components thus obtaining the desired
product which is toluene. Table 8.1 below shows a short description of the separation
units used to separate the components.
Table 8.1 Separation units in process flow diagram
Unit Separation Description Phases of components
D101 Distillation Column Separates Bromobenzene
and Hydrogen Bromide
Bromobenzene (l)
Hydrogen bromide (g)

G101 Gas Permeation
Membrane
Separates Bromomethane
and Hydrogen
Bromomethane (g)
Hydrogen (g)

59

P101 Phase Separator Separates Toluene from
Bromine, Bromomethane
and Bromobenzene
Bromine (g)
Bromobenzene (l)
Bromomethane(g)
Bromine (g)
Toluene (l)
D102 Distillation Column Further separates Toluene
from Bromobenzene
Toluene (l)
Bromobenzene (l)

8.2 GAS PERMEATION MEMBRANE (G101)
Bromomethane and hydrogen are in gaseous phase and needs to be separated because
bromomethane has to be supplied to the third reactor R103 to produce the desired
product, toluene. Gas permeation membrane is chosen as the most suitable gas
separation unit because a high purity of bromomethane can be obtained.
A membrane can be defined as a selective barrier between two fluid phases.
Gas separation process needs a membrane with high permeability and selectivity.
Membranes can be classified into two categories namely symmetrical and
asymmetrical. Figure 8.1 below shows the membrane classification.

Figure 8.1 Membrane Classification
Source : Abedini R. 2010.
Membrane
Classification


Symmetrical
- Homogenous (dense)
- Porous
- Cylindrical Porous


Assymetrical
- Porous
-Porous with dense top layer
- Composite
60

8.2.1 Membrane Selection
For our system design we choose to use an asymmetrical porous with dense top layer
polymeric membrane. This type of membrane has a high selectivity property towards
the type of gases that needs to be separated. Hydrogen is one of the smallest molecule
with a bond length of 0.74. Bromomethane is a larger molecule compared to
hydrogen bromide with a bond length of 1.930+0.003. An important property of a
porous dense membrane is that even permeates of similar sizes may be separated
easily. These membranes are elastomers from cross linked copolymers of high
molecular weights. They are then prepared as thin films by extrusion or casting. It
demonstrates a high unique permeability property with high selectivity towards H
2
.
Hence, our desired product, bromomethane can be obtained since the membrane has a
high selectivity towards hydrogen gas. Table 8.2 below shows the characteristics of
the non-porous dense polymeric membrane.
Table 8.2 Characteristics of non-porous dense polymeric membrane
Characteristics Description
Type of material
Additives

Length
Polyetherimide (PEI)
Polybenzimidazole (PBI) and
Poly(ethylene glycol) (PEG600)
5-10m
Thickness of dense skin
Porous support thickness
Method of preparation
Operating temperature
1000
25-100m
Extrusion, solvent casting or
impregnation
30C
Thermal Stability 250C
Biodegradability Biodegradable
61

Source : Abedini. R. 2010.

8.2.2 Mechanism Of Gas Transport Mechanism
Among the established gas transport mechanisms include the Poiseuille flow,
Knudsen diffusion, molecular diffusion, capillary diffusion, surface diffusion and
solution diffusion. Figure 8.2 below shows the schematic representation of major gas-
transport mechanisms in membranes.

Figure 8.2 Schematic representation of major gas-transport mechanism
Source : Shao. L. et al. 2008

Usually in porous membranes, Poiseuille flow or Knudsen diffusion dominates mostly
the overall gas transport. However, Knudsen diffusion is majorly used if the pore size
of the membrane is smaller that 50nm, however in our case, the proposed membrane
has a size 25-100 m. The propertiy of Knudsen flow is governed by the ratio of the
pore radius (r) to the mean free path () of the gas molecule. If the /r <<1, Poiseuille
flow predominates the gas flux. In the Poiseuille flow, there are more collision
between the gas molecules than the collision with the pore walls.
62

8.2.3 Type Of Equipment For Gas Permeation Membrane Process
A structure of hollow fiber membrane is chosen to separate bromomethane and
hydrogen. Their modular structure proves to separate gas efficiently. (Jay.M.S. 1981).
The membranes have the shape of very small diameter hollow fibers. The hollow
fibers looks like a shell-and-tube heat exchanger. Thousands of fine tubes are bounded
together in a tube sheet. The tube sheet is surrounded by a metal shell. A high pressure
feed is fed into the shell inlet and leaves at the other end. The hollow tubes remain
enclosed at one end of the tube bundles. The permeate gas inside the fiber flows to the
shell-tube and is collected in a chamber where the open ends of the fibers terminate.
Hence, the permeate exits the membrane. Figure 8.3 below shows the structure of a
hollow-fiber membrane (Geankoplis C.J. 2003).


Figure 8.3 Structure of a hollow-fiber membrane
Source : KOCH membrane system. 2013.
A hollow fiber membrane have several specification and caters for molecules that
suits the specification. Thus Table 8.3 below shown the specifications of the hollow-
fiber membrane.


63

Table 8.3 Specifications of hollow-fiber membrane
Specification Description
Inside diameter 200 m
Outside diameter 400 m
Metal shell diameter 6 m
Metal shell length 3 m
Source : Geankoplis C.J. 2003.

8.2.4 Type Of Flow In Gas Permeation Membrane
There are several types of flow in a gas permeation membrane. For example complete
mixing, cross flow, countercurrent flow and concurrent flow. Based on this design, we
propose a complete mixing flow. Since high pressure is fed at the inlet of the
membrane, the permeate leaves in a direction normal to the membrane, thus
accumulating on the lower pressure side of the membrane. Due to high diffusion
coefficient in gases, concentration gradient in the gas phase in the direction normal to
the surface of the membrane is quite small. Thus gas film resistance compared to
membrane resistance is neglected. Hence, a complete mixing flow is assumed for the
feed and permeate chamber. Figure 8.4 below shows the ideal flow pattern in a
membrane separator, the highlighted region depicts a complete mixing flow pattern
that is chosen for our membrane.
64


Figure 8.4 Ideal flow patterns in a membrane separator for gases : (a) complete
mixing, (b) cross-flow, (c) countercurrent flow, (d) concurrent flow.
Source : Geankoplis C.J. 2003.

8.2.5 Membrane Design
A membrane is to be used to separate a gaseous mixture of bromomethane(A) and
hydrogen gas(B). The details and calculation is as follow.
Feed flow rate,L
f
= 40.626 x10
6
cm
3
(STP)/s
Feed composition for bromomethane, x
f
= 0.92
Desired composition of the reject, x
o
= 0.90
Membrane thickness, t = 50x10
-3
cm
Pressure on the feed side, p
h
= 71.256 cm Hg
Pressure on the permeate side, p
l
= 19.502 cm Hg
Permeabilities of bromomethane, P
A
= 54x10
-10
cm
3
(STP).cm/(s.cm
2
.cm Hg)
Permeabilities of hydrogen gas, P
B
= 12x10
-10
cm
3
(STP).cm/(s.cm
2
.cm Hg)

*
= P
A
/ P
B
=

= 4.5
65

r = p
l /
p
h
=

= 0.2737
a = 1 -
*

= 1 4.5 = -3.5
b = -1 +
*
+

= -1 + 4.5 +

= 18.9183
c = -
*
x
o
/ r =

= 15.1261
Therefore, permeate composition, y
p
y
p
=

= 0.9757
Using material balance equation: to find fraction permeate,
x
o
=

0.92 =

= 0.35
Membrane area, A
m
A
m
=

A
m
=

A
m
= 2.7609x10
12
cm
2
= 2.7609x10
8
m
2
.


66

8.2.6 Advantages Of Gas Permeation Membrane
Membranes separation offers great potential. A high degree of permeability coupled
with a large selectivity of a specific gaseous species guarantees higher performances
in the gas processing industry.
In terms of economics, the advantage of membrane separation technology is
vast. Among the advantages which membrane technology benefits from, includes low
capital investment, low weight, space requirement and high process flexibility.
Although pressure swing adsorption techniques to separate gaseous mixture may seem
to be a more common technique for gas separation, however ongoing research has
been conducted thus membrane separation process is seen to be one of the emerging
technology which has undergone a fast growth during the past decades. Temperature
swing adsorption which is a type of variation on pressure swing adsorption, but it is
not widely used because of the relatively long time it takes to heat and cool sorbents.
Therefore, it is clearly seen that membrane gas separation technology has
progressed greatly thus can be considered as a competitive industrial gas separation
method. Hence a high recovery of the desired gaseous effluent, bromomethane can be
reused for multiple purposes hence can be supplied to the third reactor, R103
(Abedini. R. et.al. 2010).

8.3 DISTILLATION COLUMN
A fractional distillation column is used during the separation of toluene from the
byproducts bromobenzene. The chemical compounds are separated based on their
boiling points whereby they are heated to certain temperature. The columns are
designed to separate two or more components effectively. The significant traits of our
Fractional Distillation Column are durable, corrosion resistant, dimensionally
accurate, high performance and low maintenance. For the D102 distillation column as
shown in Figure 8.5 below, the purity of toluene that is produced is 96%
(Encyclopedia 2011).
67


Figure 8.5 Distillation Column, D102
In distillation column, the vapour feed that enters generally falls down the
column and the temperature increase gradually down the column. Toluene is light
key component (LK) will vaporizing toward the distillate part while bromobenzene is
a heavy key component (HK) which will go to the bottom. Reflux is widely used in
industrial distillation tower to achieve higher purity of the top and bottom product.
Table 8.4 Degree of Freedom Analysis
Variables Specification Number of Specifications
Feed flow rate 1
Feed mole fractions C-1
Feed temperature 1
Feed pressure 1
Adiabatic stages (excluding reboiler) N-1
Stage pressures (including reboiler) N
Split of light key component 1
Feed (Stream 18)

T=280.1C
P=2414 kPa

N
18
= 138.02 kmol hr
-1
N
18,C7H8
=126.98 kmol hr
-1
N
14,C6H5Br
=

11.04 kmol hr
-1


Distillate (Stream 23)

T=270.75C
P=2155 kPa

N
23

X
23,C7H8
= 0.96
X
23,C6H5Br


Bottom (Stream 24)

T=341.26C
P=2932 kPa

N
24

X
24,C7H8

X
24,C6H5Br
= 0.8

68

Split of heavy key component 1
Feed stage location 1
Reflux ratio (as multiple of minimum
reflux)
1
Reflux temperature 1
Adiabatic reflux divider 1
Pressure at total condenser 1
Pressure at reflux divider 1
Degrees of Freedom 2N + C + 9

8.3.1 Mass Balance
From Table 8.4, degree of freedom analysis:
4 Unknown variables: N
23,C7H8
, N
23,C6H5Br,
N
24,C7H8
, N
24,C6H5Br

2 Mass balance equations since there are 2 components involve in this reaction (C
7
H
8

and C
6
H
5
Br)
2 Composition: X
23,C7H8
=0.96, X
22,C6H5Br
= 0.8
Degree of freedom= 4-2-2=0
Overall Mass Balance: N
18
=N
23
+ N
24

Component Balance on toluene: N
18,C7H8
= N
23,C7H8
+ N
24,C7H8
Component Balance on bromobenzene: N
18,C6H5Br
=N
23,C6H5Br
+ N
24,C6H5Br


By solving the above equations,
N
23,C7H8
= 119.3835 kmol hr
-1

69

N
23,C7H8
=4.4583 kmol hr
-1

N
24,C6H5Br
=2.5288 kmol hr
-1

N
24,C6H5Br
=9.5535 kmol hr
-1


Total mass input:
126.98(92.14) + 11.04(157.01) = 13433.33 kghr
-1

Total mass output:
119.3835(92.14) + 4.4583(157.01) +2.5288(92.14) + 9.5535(157.01) = 13432.99
kghr
-1

Percentage Error =

x 100% = 0.003%

Since the error is small, so it can be considered that the law of conservation of mass is
obeyed for the system.

8.3.2 Process Design
Based on the overall component balance calculations, Table 8.5 shows the molar flow
rates and compositions of feed, distillate and bottom products. Meanwhile, Table 8.6
shows the conditions for the separation process.




70


Table 8.5 Molar Flow Rate and Composition
Component
Feed Distillate Bottom
kmol hr
-
1

Z
i,F
kmol hr
-1
X
i,D

kmol hr
-
1

X
i,B

Toluene, C
7
H
8
126.98 0.92 119.3835 0.96 2.5288 0.20
Bromobenzene, C
6
H
5
Br 11.04 0.08 4.4593 0.04 9.5535 0.80
Total 138.02 1.00 123.8418 1.00 12.0823 1.00

Table 8.6 Streams Temperature and Pressure
Feed Distillate Bottom
Temperature (
o
C) 280.10 270.75 341.26
Pressure (kPa) 2027 1931 2069

8.3.3 Heat Duty
There are the assumptions used in the calculation:
1. The flow in unit process is at steady state.
2. The reference temperature is 25 oC.
3. There is no potential energy, kinetic energy and work done by the system.
Based on the thermodynamic path, the overhead is cooled from
because of the temperature change is small. Then, the vapor
specific heats at the two temperatures are calculated and the arithmetic average is
obtained.
The vapour heat capacity is in
71

For toluene,

= 0.581x10
-5
+2.863x10
-5
T + 1.441x10
-3
T
2
+1.898x10
-5
T
3

For bromobenzene,

= 0.721x10
-5
+ 2.064x10
-5
T + 1.65x10
-3
T
2
+ 1.687x10
-5
T
3

Table 8.7 Molar flow rate, and vapour heat capacity,
Component
Molar flow rate
(k
Vapour heat capacity,
Average
Toluene 119.3835 4942.718 3477.431 4210.07
Bromobenzene 4.4583 4532.538 3200.002 3866.27

The sensible vapour enthalpy charge

from is,

= 36.655 x 10
6
kJ/hr

For the latent heat of condensation, to estimate the molar heats of vaporization of at
for the two components using the vapour pressure constants from Perrys 2008.

38.06

= 44.13

72

The latent heat of condensation,

is

Thus the total condenser duty

= (36.655x10
6
+ 4740.48) kJ/hr
= 36.66x10
6
kJ/hr
= 10 183.33k W

8.3.4 Comparison With iCON
Table 8.8 Comparison with iCON
Condenser
Duty(kW)
Mass Balance In
(kg/hr)
Mass Balance
Out (kg/hr)
iCON 86885.40 13433.10 13432.77
Calculated 10183.33 13433.33 13432.99
% error 14.0 1.7x10
-3
1.6x10-3

8.3.5 Structural Design
Sieve trays distillation column is used for the separation process. Sieve trays are flat
perforated plate in which vapour rises through small holes in tray floor and bubbles
through liquid in fairly uniform manner. They have comparable capacity as valve
trays. Sieve trays have lowest pressure drop and relative cost compared with baffle
trays, valve trays and bubble cap trays. Besides, they are lighter in weight, can be
installed easily and hence ease of maintenance. The trays can also handle wide
73

variations in flow rates. Figure 8.6 shows the structural of sieve tray. Meanwhile
Figure 8.7 shows the sieve tray fractional distillation column (Tham.M.T 1997).


Figure 8.6 The Structural of Sieve Tray
Source : Tham M.T 1997

Figure 8.7 Sieve Tray Fractional Distillation Column
Source: James W. 2012



74

8.3.6 Calculation for the Minimum Number of Stages
Table 8.9 K-Values of Components at Distillate and Bottom
Component X
i,D
K
i,D
X
i,B
K
i,B

Toluene,C
7
H
8
0.96 1.0067 0.20 1.6373
Bromobenzene, C
6
H
5
Br 0.04 0.4272 0.80 0.7701

By using Fenske equation,
Let i=LK, j=HK
Relative volatility,
(i,)N
=
KD,C7H8
KD,C6H5Br
= 1.0067/0.4272 = 2.3566

(i,)1
=
KB,C7H8
KB,C6H5Br
= 1.6373/0.7701= 2.1261
Mean relative volatility,
m
= (2.3566 x 2.1261)
0.5
= 2.2384
( ) | | ( ) | |
m
N j j i N i
x x x x
N
o log
/ / , log
1 , 1 , 1 , 1
min
+ +
=

N
min
= log[(0.96/0.20)(0.80/0.04)] / log 2.2384 = 5.665 stages

The relative volatility with respect to the heavy key as follow:
(C
7
H
8
,C
6
H
5
Br)
m
= 2.2384, (C
6
H
5
Br,C
6
H
5
Br)
m
=1.00
R
min
is determined through the Underwood equations.
From First Underwood equation, q=1
( )
( )

u o
o
r i
f i
r i z
q
,
,
,
1

75

= 1.0463

From the Second Underwood equation,

1+(R

)
min

Therefore, R
min
= 1.00
Assuming R=1.5R
min
= 1.5
By using Gilliland correlation equation,



Substituting R and R
min
, X = 0.20; knowing that N
min
= 5.665, solving for,
Y = 0.4605
N = 11.35
Therefore, there is 12 stages including a partial reboiler.
Efficiency = N
min
/N= 5.665/11.35 x 100% = 50%
Hence, the tray efficiency is 50%.
N
actual
= N
theory
/E
o
= 11.35/ 0.5 = 22.7 stages.

8.3.7 Diameter of Distillation Column
To determine the height and diameter of the distillation column,
76

Knowing:
Tray spacing = 18inch = 0.475m
= liquid surface tension = 20dynes/cm
w = liquid flow rate = 1733 kg/hr
W= vapour flow rate =11700 kg/hr

L
= liquid density =827.19 kg/m
3

v
= vapour density =590.69 kg/m
3
V= 123.50 kmole/hr
M
v
= 97.328 kmol/kg
f = 0.8

Thus, F
LV
= 0.125
From Separation Process Principle (Seader, J.D et. al., 2011), Figure 6.24
C
F
= 0.65 ft/s
U
f
=
|
|
.
|

\
|
v
v L
C

F HA F ST
C F F F C =


0 . 1 =
F
F
(non-foaming system)

1 . 0 / , 0 . 1 > =
a h HA
A A F

F
ST
= (/20)
0.2
= (20/20)
0.2
=1.0
77


|
|
.
|

\
|
=
v
v L
C F F F U
F HA F ST f

U
f
= 0.1554 ms
-1

A
d
/A = 0.10

D
T
= 2.50m

Therefore, the diameter of the column is 2.5 m or 8.20 ft. Consider the calculated
column diameter, using a plate tower for this distillation process is reasonable, as for
industrial plate towers,the diameter are normally in between 1.5m to 4.6m or (5ft to
15ft).

8.3.8 Height of Distillation Column
Height of the trays, H
o
= Tray spacing x Number of Stages
= 0.6 x 11.35 = 6.81m
Therefore, height of the column = Ho + (Ho x 0.1)
= 6.81+ (6.81 x 0.1)
= 7.49m
Ratio of the height and diameter is, H
o
/D
T
= 3.0. In industrial practice, the H
o
/D
T
ratio
is always less than 20-30. Thus, the D102 column structure is reasonable.

78

CHAPTER IX


CHEMICAL ENGINEERING COMPUTATION (MATLAB)


9.1 MATLAB SOFTWARE
MATLAB

is a high-level language and interactive environment for numerical

computation, visualization, and programming. Using MATLAB, we can analyse data,
develop algorithms, and create models and applications. From this software, we have
done the mass balance energy balance calculation on the R-103 (Packed Bed Reactor).

9.2 MASS BALANCE IN R-103
9.2.1 Algorithm And Flowchart
Algorithm of the code:
1. Start
2. Input inlet molar flow rate of component.
3. Compute r by equation r=X*N1A // where X is conversion rate, Nia is inlet molar
flow of A.
4. Compute outlet molar flow rate by equation (outlet)=(inlet)+(stoichiometric
coefficient)*r.
5. Convert all molar flow rates to mass flow rate by multiply it with molecular weight.
79

6. Display table of input and output mass flowrate data.
7. End

Flow diagram of the code:












Figure 9.1 Flow chart of the MATLAB code for mass balance

9.2.2 5 Steps Of Problem Solving
1. State the problem:
Write a program that prompts users for input of the inlet molar flow rate of the
component that into the reactor unit in kmol/h. Then the outlet molar flow rate will be
calculated using the code created in MATLAB. The entire molar flow rate is
converted to mass flow rate. By using suitable equation, display also the table for
mass balance data to prove that the calculated inlet and outlet mass flow rate in reactor
is balanced.
Start
End
Input inlet molar flow rate
Compute r=X*N1A
Compute (outlet)=(inlet)+(stoichiometric coefficient)*r
Compute

*(molecular weight of component i)

Display the mass flowrate in table
80

2. Describe the input and output:
a. Input:
i. Inlet molar flow rate of the component that into the reactor unit in kmol/h.
b. Output:
I. Outlet mass flow rate of the component that into the reactor unit in kg/h.
ii. A mass flow rate table to prove that mass flow rate are balance.
iii. Bar chart about mass flow rate is drawn.

3. Work the problem manually:
The manual calculation of this part is calculated and shown in chapter V (mass and
energy balance) of this integrated project.

4. Develop the MATLAB solution:
a. Create a script file

81


Figure 9.2 Script MATLAB code for mass balance








82

5. Results

Figure 9.3 Result in Command Window MATLAB

9.3 ENERGY BALANCE IN REACTOR R-103
9.3.1 Algorithm And Flowchart
Algorithm of the code:
1.Start
2.Input inlet and outlet temperature, T in unit Kelvin (K) of each stream.
3.Input inlet and outlet molar flowrate, N
i
in unit kmol/hr of each component.
4.Insert the reaction rate, r in unit kmol/hr.
5.Compute enthalphy change of each component, H
i
in unit kJ/kmol in each stream
6.Compute enthalphy, H in unit kJ/kmol in each stream.
7.Compute standard heat reaction, H
rxn
in unit kJ/kmol.
83

8.Compute energy balance, Q of R-103 in unit kJ/hr.
9.End
Flow diagram of the code:














Figure 9.4 Flow chart of the MATLAB code for energy balance

9.3.2 5 Steps Of Problem Solving
1. State the problem:
Write a program that show users calculation of energy balance that show a step-by-
step towards getting the heat inlet and outlet value, and Q value
Start
End
Input inlet and outlet temperature each stream
Compute enthalphy change of component
Input inlet and outlet molar flowrate each component each stream
Compute enthalphy and standard heat of reaction
Input reaction
rate
Compute energy balance, Q of reactor
84


2. Describe the input and output:
a. Input:
i.A set of vector value of temperature inlet, outlet and reference.
b. Output:
i.Heat outlet, heat inlet and Q .

3. Work the problem manually:
The manual calculation of this part is calculated and shown in chapter 2 (mass and
energy balance) of this integrated project.

4. Develop the Matlab solution:
a. Create a script file


85


Figure 9.5 Script MATLAB code for energy balance


Figure 9.6 Output MATLAB command window for energy balance



86

9.4 SUPPLY AND DEMAND
9.4.1 Algorithm And Flowchart
Algorithm of the code:
1. Start
2. Input data of world demand and supply in vector set.
3. Set the x-axis parameter label.
4. Label each type of axis and set the title.
5. Plot a bar graph of world demand and supply vs year
6. Repeat for Asian demand and supply
7. End












87

Flow diagram of the code:













Figure 9.7 Flow chart of the MATLAB code for supply and demand

9.4.2 5 Steps Of Problem Solving
1. State the problem:
Write a program that prompts users to view a graphic demonstrate related to demand
and supply vs year.

2. Describe the input and output:
a. Input:
i. Set of vector data of demand.
Start
Input data demand & supply in vector
set
Display a graph
End
Set the x-axis parameter
label
Set the x-axis parameter
label
Label each type of axis and set the
title

88

b. Output:
i. A graph of Demand and Supply vs Year.

3. Develop the Matlab solution:
a. Create a script file

Figure 9.8 Demand and Supply Script MATLAB
b. Output of script file

Figure 9.9 Graph of Demand Worldwide
89


Figure 9.10 Graph of Supply Worldwide

90

CONCLUSION

Toluene, C
7
H
8
also known as methylbenzene, toluol or phenylmethane is an aromatic
hydrocarbon commonly used as an industrial solvent for the manufacturing of paints,
chemicals, pharmaceuticals, and rubber. Toluene is also found in gasoline, acrylic
paints, varnishes, adhesives, glues, rubber cement, airplane glue, and shoe polish. At
room temperature, toluene is a colorless, sweet smelling, and volatile liquid. Toluene
undergoes electrophilic aromatic substitution when reacted with aromatic hydrocarbon
compounds. Statistics shows that the demand of toluene is growing every year and is
predicted to continue for several more years. The toluene production of our plant is
estimated to be 84240 tons per year with a mass flowrate of 11700 kg/hr. Toluene is
produced by the heterogeneous of benzene reaction, in which the raw material of
benzene. Continuous Packed Bed Reactor (PBR), R103 is used in this production
process since there is a mixture of gas and liquid in the feed with the presence of
catalyst solid isotopes Sodium-22. In the Packed Bed Reactor, it is proven that the
reactor obeyed the law of conversion of mass where the mass flow rate at inlet
61457.98 kg/hr is approximately the same to the total mass flow rate at outlet
61456.70 kg/hr. In addition, from the calculation of energy balance, this reaction is
identified as an endothermic reaction where the energy absorbed is 73.78x10
6
kJ/hr or
20494.44 kW. As for the mass balance inside the distillation column, D102, the flow
rate of the feed stream is 13433.33 kg/hr while the output flow rate for both top and
bottom stream is 13432.99 kg/hr. Meanwhile, the condenser heat duty is 10183.33
kW. By comparing these results to iCON software, the error percentage is 14%.
There are 3 types of separation units used in the production of toluene which is
distillation column, gas permeation membrane and phase separator. Gas permeation
membrane is chosen because to separate gaseous phase which are bromomethane and
hydrogen gas and then supplied the high purity of bromomethane to the third reactor
R103 to produce the desired product, toluene. We choose to use an asymmetrical
porous with dense top layer polymeric membrane that has a high selectivity property
towards the type of gases that needs to be separated. We proposed a complete mixing
flow since high pressure is fed at the inlet of the membrane, the permeate leaves in a
direction normal to the membrane, thus accumulating on the lower pressure side of the
91

membrane. For the membrane design, we calculated the membrane area which is
2.7609x10
8
m
2
. For the other separation unit, we used sieve tray fractional distillation
column D102. The light key chosen for this process is toluene because its lower
boiling point and volatility while bromobenzene is the heavy key component. The
theoretical number of stages is approximately 12 stages with the height of the column
is 7.49m and the diameter 2.5m, where the ratio of the height and the diameter is
H
o
/D
T
=3.0. Isotope sodium-22 is used as a catalyst in this toluene production plant.
There are several steps to consider during a catalytic reaction and this catalyst has a
remarkable long half-life of 2.602 years. Based on our plant which operates 300days a
year, this catalyst can be used up to 650days. From the calculation, the porosity of the
catalyst is 0.485, the superficial fluid velocity is U
mf
= 6755.01m/s and the superficial
fluid velocity at minimum bubbling, U
mb
=18130 m/s. Thus we decide the catalyst is
classifies under Group C which this powders are very fine and are cohesive in nature.
Besides, the mass of catalyst needed in the packed bed reactor is 1725732.48 kg of
isotope-22 catalyst with a bed depth of 0.5m. Computer codes were successfully being
prepared in MATLAB in order to calculate the mass balance and energy balance for
packed bed reactor R103, as well as make an economic analysis.

92

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https://www.spectrumchemical.com/MSDS/TCI-B0439.pdf [4 Disember
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Wikipedia. 2013. Toluene.
http://en.wikipedia.org/wiki/Toluene [22 October 2013]
96


APPENDIX

iCON for Packed Bed Reactor, R103



97

iCON for Distillation Column, D102


98


99