Chlorobenzenes Plant Design Prize Thesis

A
TECHNICAL REPORT
ON
THE DESIGN FOR A PLANT THAT PRODUCES 20,000 TONNES PER YEAR
OF MONOCHLOROBENZENE AND WITH ABOUT 2,000 TONNES PER YEAR
OF DICHLOROBENZENE BY DIRECT CHLORINATION OF BENZENE.
PREPARED BY
POPOOLA,OLUWATOFUNMI
ADENIRAN, ABDULRAHIM BABATUNDE
TOMIWA
SUBMITTED TO
DR. O.J. ODEJOBI
DEPARTMENT OF CHEMICAL ENGINEERING,
OBAFEMI AWOLOWO UNIVERSITY, ILE-IFE, NIGERIA
IN PARTIAL FULFILMENT OF THE REQUIREMENT OF THE COURSE
PROCESS DESIGN I & II
(CHE 505/506)
FEBRUARY, 2020.
Department of Chemical Engineering,
Obafemi Awolowo University,
Ile-Ife, Osun State.
25th February, 2020.
The Course Supervisor, Process Design I&II (CHE 505 & 506),
Department of Chemical Engineering,
Obafemi Awolowo University,
Ile-Ife, Osun State,
Nigeria.
Dear Sir,
LETTER OF TRANSMITTAL
In partial fulfilment for the requirement of the course CHE 505/506 (Process Design).
POPOOLA, ABDULRAHIM
I, ADENIRAN, BABATUNDE
OLUWATOFUNMI TOMIWA hereby submit the report of the process
design project undertaken during the first and second semester of 500 level. We hereby
certify that all information contained therein are based on knowledge granted from
interactive discussion.
Yours faithfully,
POPOOLA, Abdulrahim
ADENIRAN Babatunde.
Oluwatofunmi T.
CHE/2014/069
CHE/2014/012
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ABSTRACT
Process design involves the selection of process equipment in such a way that the
interaction and integration between those equipment helps in translating raw materials
into final products and by-products. The design of a product can have different process
alternative routes but our desire is to pick the optimum or best production alternatives
for products. The best production alternative can be judged based on cost (capital and
operating cost), availability of raw materials, safety, environmental factors, conversion
obtained in the reactor.
Our main objectives in thus report is to design a plant that produces 20000 tonnes/year
of monochlorobenzene (which is the main product) and with about 2000tonnes/year of
dicghlorobenzene (by product) by direct chlorination of benzene. Benzene react with
chlorine in the presence of catalyst (FeCl3) and it replaces one of the hydrogen atom
on the ring by a chlorine atom.
The reaction takes place at moderate temperature at about 200C – 600C. the
chlorination of benzene in the liquid phase leads to the conversion of benzene to
chlorinated products (chlorobenzenes) in a single pass of the reactant (benzene and
chlorine) through the system. The ratio of monochlorobenzene to higher substitution
products such as dichlorobenzene varies but In this design, care is taken so as to avoid
the production of higher chlorinated benzene like trichlorobenzene etc. this is because
of the increase demand of monochlorobenzene as compared to other
polychlorobenzenes. It is a desirable product because of its great importance, it is used
as reagent for the preparation of phenol, aniline and other industrial chemicals.
Therefore, we want a process that is designed to produce a high percentage of
monochlorobenzene.
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The reaction is carried out in two continuous stirred tank operating operating in series
at 2.4 bars, liquid benzene is fed into this reactor system and gaseous chlorine is fed in
parallel to both tanks. Ferric oxide serves as a catalyst and its produced in-situ by the
action of hydrogenchloride on mld steam.
The reactor temperature is maintained and conversion of benzene per-pass is kept low
so as to suppress undesired reactions. Unreacted chlorine, hydrogen chloride and the
catalyst are removed from the reactor stream by passing them to an activated carbon
absorber where final traces of impurities are removed before leaving the plant.
The crude liquid chlorobenzene stream leaving the second reactor is washed with water
and caustic soda to remove any dissolved hydrochloride. The unreacted benzene is
recycled back into the process while monochlorobenzene and dichlorobenzene are
separated in a second distillation column. All three isomers of dichlorobenzene ( ortho-
meta- para-) are expected to be formed, but these species have similar boiling point, so
we treat all these three isomers of dichlorobenze as one specie.
Separation of unreacted benzene, monochlorobenzene and dichlorobenzene was
achieved using a series of distillation columns. The series of continuous stirred tanks
used aids in giving a better selectivity conversion profile.
The Purchased cost of equipment (PCE) was valued at ₦5,572,848,075. The physical
plant costs (PPC) or direct costs was obtained using the factorial costing method at 3.4
times the PCE and computed at ₦18,947,683,460. The Fixed Capital Investment (FCI)
was obtained by summing up the direct and indirect costs, and computed at
₦ 27,474,141,020. A working capital of 15% of the FCI was assumed and this brought
the Total Capital Investment to ₦ 31,595,262,170. The estimated net profit of the plant
was computed as ₦ 17,275,068,380.
iv
Aspen HYSYS, a computer program was used to carry out design of individual pieces
of equipment and to develop a full plant design and flowsheet for the process.
v
TABLE OF CONTENTS
COVER PAGE .................................................................................................................... I
LETTER OF TRANSMITTAL................................................................................................ II
ABSTRACT ...................................................................................................................... III
TABLE OF CONTENTS ..................................................................................................... VI
LIST OF TABLES............................................................................................................. XIV
LIST OF FIGURES........................................................................................................... XVI
CHAPTER ONE ............................................................................................................... 17
............................................................................................................................. INTRODUCTION
......................................................................................................................................................... 17
1.1 PROPERTIES OF CHLOROBENZENES ...................................................................................... 17
1.1.1 PROPERTIES OF MONOCHLOROBENZENE ............................................................................ 19
1.1.2 PROPERTIES OF DICHLOROBENZENES .................................................................................. 19
1.2 USES OF CHLOROBENZENES ................................................................................................. 20
1.3 BRIEF EVOLUTION OF CHLOROBENZENES PRODUCTION ..................................................... 23
1.4 PROBLEM DEFINITION .......................................................................................................... 25
1.5 INITIAL DESIGN CONSIDERATION.......................................................................................... 26
1.5.1 THE PROCESS INITIAL DESIGN CONSIDERATION ................................................................... 27
1.5.2 FEED SPECIFICATIONS ........................................................................................................... 28
1.5.3 Utilities ............................................................................................................................. 28
1.5.4 Expected product specification ........................................................................................ 28
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1.6 AIM AND OBJECTIVE OF THE DESIGN WORK ........................................................................ 28
1.7 SCOPE OF DESIGN WORK REQUIRED .................................................................................... 28
1.7.1 PROCESS DESIGN .................................................................................................................. 29
1.7.2 CHEMICAL ENGINEERING DESIGN ........................................................................................ 31
1.7.3 MECHANICAL DESIGN ........................................................................................................... 31
1.7.4 SAFETY .................................................................................................................................. 31
CHAPTER TWO .............................................................................................................. 32
....................................................................... RELEVANCE OF CHLOROBENEZENE TO LOCAL NEEDS
......................................................................................................................................................... 32
CHAPTER THREE ............................................................................................................ 35
...................................................................................................................... PROCESS SELECTION
......................................................................................................................................................... 35
3.1 PROCESS ROUTE ALTERNATIVE ............................................................................................. 35
3.2 PROCESS SELECTION ............................................................................................................. 36
3.3 PROCESS ROUTE JUSTIFICATION ........................................................................................... 39
3.4 DETAILED DESCRIPTION OF THE SELECTED PROCESS ........................................................... 40
CHAPTER FOUR ............................................................................................................. 44
................................................................................................ MATERIAL AND ENERGY BALANCES
......................................................................................................................................................... 44
4.1 THEORY ................................................................................................................................. 44
4.2 APPROACH TO MATERIAL AND ENERGY BALANCE ............................................................... 46
4.3 MATERIAL BALANCE .............................................................................................................. 47
4.3.1 THROUGHPUT ANALYSIS AS REQUIRED ................................................................................ 47
4.3.2 OVERALL MASS BALANCE ..................................................................................................... 51
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4.3.2.1 THE REACTORS IN SERIES (CSTRS) .................................................................................... 52
4.3.2.2 WASHER/NEUTRALIZER .................................................................................................... 58
4.3.2.3 DECANTER/SEPARATOR .................................................................................................... 59
4.3.2.4 THE FIRST DISTILLATION COLUMN (BZ-CLM).................................................................... 60
4.3.2.5 THE SECOND DISTILLATION COLUMN (CB-CLM) .............................................................. 62
4.3.2.6 DRYING COLUMN (DRYER)................................................................................................ 64
4.3.2.7 MIXER (M 101) .................................................................................................................. 65
4.4 ENERGY BALANCE ................................................................................................................. 68
4.4.1 ENTHALPIES CALCULATION ................................................................................................... 68
4.4.2 ENERGY BALANCE ABOUT UNIT OPERATIONS AND EQUIPMENT ......................................... 70
4.4.2.1 REACTOR SYSTEM TWO CSTRS IN SERIES ......................................................................... 70
4.4.2.2 NEUTRALIZER/WASHER .................................................................................................... 72
4.4.2.3 COMPRESSOR (COMP-1) .................................................................................................. 75
4.4.2.4 PUMP (BZ-PUMP) ............................................................................................................. 76
4.4.2.5 HEAT EXCHANGER (HX-1) ................................................................................................. 77
4.4.2.9 FIRST DISTILLATION COLUMN, BENZENE COLUMN (BZ-CLM) .......................................... 82
4.4.2.10 SECOND DISTILLATION COLUMN, BENZENE COLUMN (CB-CLM) ..................................... 82
4.4.2.11 BALANCE ABOUT DRYER, MIXER AND DECANTER ............................................................ 86
4.4.3 SUMMARY OF THE DUTIES AROUND EACH EQUIPMENT ..................................................... 86
CHAPTER FIVE ............................................................................................................... 88
....................................................................................................EQUIPMENT DESIGN AND SIZING
......................................................................................................................................................... 88
5.1 REACTORS ............................................................................................................................. 88
5.1.1 PRINCIPAL TYPES OF REACTOR ............................................................................................. 89
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5.1.1.1 STIRRED TANK REACTOR................................................................................................... 89
5.1.1.2 REACTOR SIZING AND DESIGN CONDITION ...................................................................... 90
5.2 BENZENE COLUMN SIZING AND DESIGN CONDITION ........................................................... 92
5.3 CHLOROBENZENE COLUMN SIZING AND DESIGN CONDITION ............................................. 95
5.4 DRYING COLUMN SIZING AND DESIGN CONDITION ............................................................. 97
5.5 SEPARATOR (WASHER/ NEUTRALIZER) ............................................................................... 100
5.6 COLUMN DESIGN ................................................................................................................ 104
5.6.1 TRAY TYPE USED ................................................................................................................. 105
5.7 MATERIAL OF CONSTRUCTION ........................................................................................... 106
CHAPTER SIX ............................................................................................................... 107
.................................................... CHEMICAL ENGINEERING DESIGN OF CHLOROBENZENE COLUMN
....................................................................................................................................................... 107
6.1 OVERVIEW OF CHEMICAL ENGINEERING DESIGN FOR THE CHLOROBENZENE COLUMN .. 108
6.2 NUMBER OF STAGES DETERMINATION .............................................................................. 108
6.3 DATA OBTAINED FROM HYSYS SIMULATION ...................................................................... 112
6.4 RECTIFYING OPERATING LINE ............................................................................................. 112
6.5 STRIPPING OPERATING LINE ............................................................................................... 113
6.6 ESTIMATING PHYSICAL PROPERTIES ................................................................................... 113
6.7 COLUMN DIAMETER AND FLOODING CHECK ..................................................................... 116
6.8 PROVISIONAL PLATE DESIGN .............................................................................................. 118
6.9 WEIR DESIGN ...................................................................................................................... 119
CHAPTER SEVEN.......................................................................................................... 120
................................................ MECHANICAL DESIGN OF CHLOROBENZENE DISTILLATION COLUMN
....................................................................................................................................................... 120
7.1 THEORY ............................................................................................................................... 120
7.2 SPECIFICATIONS .................................................................................................................. 121
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7.3 SHELL THICKNESS ................................................................................................................ 122
7.3.1 HEAD ................................................................................................................................... 123
7.4 AGITATOR DESIGN FOR THE CSTR ....................................................................................... 124
7.4.1 AGITATOR DIMENSION ....................................................................................................... 125
7.4.2 POWER REQUIREMENT ....................................................................................................... 127
CHAPTER EIGHT .......................................................................................................... 128
..................................................................................... PLANT CONTROL AND INSTRUMENTATION
....................................................................................................................................................... 128
8.1 INTRODUCTION ................................................................................................................... 128
8.2 GENERAL PRELIMINARY CONSIDERATIONS ........................................................................ 128
8.2.1 LEVEL CONTROLLERS ........................................................................................................... 128
8.2.2 MASS FLOW CONTROLLER .................................................................................................. 129
8.2.3 PRESSURE CONTROLLER/REGULATORS .............................................................................. 129
8.3 FEEDBACK CONTROLLER ..................................................................................................... 129
8.3.1 PUMPS ................................................................................................................................ 132
8.3.2 SENSORS ............................................................................................................................. 133
8.3.3 VALVES ................................................................................................................................ 134
8.4 PLANT WISE CONTROL SYSTEM .......................................................................................... 135
8.4.1 CONTROL SYSTEM OF DRYING COLUMN SYSTEM .............................................................. 136
8.4.2 CONTROL SYSTEM OF REACTOR SYSTEM (CSTR) SYSTEM .................................................. 139
8.4.3 CONTROL SYSTEM OF WASHER/NEUTRALIZER UNIT .......................................................... 141
CHAPTER NINE ............................................................................................................ 144
........................................................................................................ PLANT PROCESS/SITE LAYOUT
....................................................................................................................................................... 144
9.1 PLANT LOCATION AND SITE SELECTION .............................................................................. 144
9.2 PLANT SITE LAYOUT AND DESCRIPTION ............................................................................. 144
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9.2 PLANT PROCESS LAYOUT AND DESCRIPTION ...................................................................... 146
CHAPTER TEN.............................................................................................................. 153
..................................................................... PLANT COST ESTIMATION AND ECONOMIC ANALYSIS
....................................................................................................................................................... 153
10.1 BACKGROUND OF PLANT ECONOMICS ............................................................................... 153
10.2 PURCHASED COST OF EQUIPMENT ..................................................................................... 155
10.3 TOTAL PURCHASE COST OF EQUIPMENT ............................................................................ 161
10.4 TOTAL CAPITAL INVESTMENT ............................................................................................. 163
10.6 ESTIMATION OF TOTAL PRODUCTION COST ....................................................................... 163
10.7 PROFITABILITY ANALYSIS .................................................................................................... 167
CHAPTER ELEVEN ........................................................................................................ 169
............................................................................................................ SAFETY OF PROCESS PLANT
....................................................................................................................................................... 169
11.1 SAFETY AND LOSS PREVENTION IN PROCESS PLANT .......................................................... 169
11.1.1 THE NEEDS FOR SAFETY IN THE CHLOROBENZENE PLANT. ............................................ 170
11.2 HAZARDS ASSOCIATED WITH THE PRODUCTION OF CHLOROBENZENE ............................. 171
11.2.1 MATERIAL HAZARDS ....................................................................................................... 171
11.2.1.1 TOXICITY ......................................................................................................................... 171
11.2.1.2 FLAMMABILITY ............................................................................................................... 172
11.2.1.3 REACTIVITY ..................................................................................................................... 172
11.2.2 PROCESS HAZARDS ......................................................................................................... 172
11.2.2.1 PRESSURE HAZARDS ....................................................................................................... 173
11.2.2.2 TEMPERATURE DEVIATIONS ........................................................................................... 173
11.2.2.3 FIRE EXPLOSION .............................................................................................................. 173
11.2.2.4 HUMAN ERROR ............................................................................................................... 174
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11.3 INTERNATIONAL AND REGIONAL GUIDELINES ON SAFETY IN CHEMICAL PROCESS
INDUSTRIES ...................................................................................................................................... 174
11.3.1 IN THE UNITED STATES ................................................................................................... 174
11.3.2 SUB- REGIONAL LEGISLATION......................................................................................... 175
11.3.3 NATIONAL POLICY ON OCCUPATIONAL SAFETY AND HEALTH ....................................... 175
11.3.4 LAGOS STATE SAFETY COMMISSION .............................................................................. 176
11.4 KEY ACTIVITIES IN THE CHLOROBENZENE PLANT AND APPROPRIATE SAFETY MEASURES 177
11.4.1 SAFETY MEASURES IN PLANT DESIGN AND EQUIPMENT SIZING.................................... 177
11.4.2 SAFETY MEASURE IN PLANT CONTROL ........................................................................... 178
11.4.3 INSTALLATION OF CRITICAL ALARMS AND HUMAN INTERVENTION .............................. 178
11.4.4 OVERPRESSURE CONTROL AND PRESSURE RELIEF SYSTEM ........................................... 178
11.4.5 EMERGENCY RESPONSE .................................................................................................. 179
11.5 MATERIAL SAFETY DATA SHEET REACTIVITY ....................................................................... 179
11.5.1 PRODUCT AND COMPANY IDENTIFICATION ................................................................... 179
11.5.2 HAZARDS IDENTIFICATION ............................................................................................. 179
11.5.2 HAZARD IDENTIFICATION ............................................................................................... 180
11.5.3 CHRONIC EFFECTS: ......................................................................................................... 180
11.5.4 FIRST AID MEASURES ...................................................................................................... 181
11.5.5 HANDLING AND STORAGE .............................................................................................. 181
11.5.6 EXPOSURE CONTROLS/PERSONAL PROTECTION ............................................................ 181
11.5.7 PHYSICAL AND CHEMICAL PROPERTIES .......................................................................... 182
CHAPTER TWELVE ....................................................................................................... 184
.....................................................................................................................RECOMMENDATIONS
....................................................................................................................................................... 184
12.1 RECOMMENDATIONS FOR THE CHLOROBENZENE PLANT .................................................. 184
12.1.1 HANDLING AND STORAGE .............................................................................................. 184
12.1.2 ACCIDENTAL RELEASE MEASURE .................................................................................... 184
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12.1.3 PLANT OPERATION AND WORKER’S SAFETY .................................................................. 185
REFERENCES ............................................................................................................... 186
APPENDICES ................................................................................................................ 188
PROCESS BALANCES CALCULATIONS .............................................................................................. 188
MATERIAL BALANCE CALCULATIONS ............................................................................................... 188
ENERGY BALANCE CALCULATIONS ................................................................................................... 197
STEP RESPONSE PLOTS OF PLANT CONTROL SYSTEM ..................................................................... 205
DEVELOPED PIPING DIAGRAM OF THE PLANT ................................................................................ 222
3D PROCESS EQUIPMENT MODEL OF THE PLANT ........................................................................... 227
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LIST OF TABLES
TABLE 1:1 USE OF CHLOROBENZENES..................................................................................................... 21
TABLE 3:1 PROCESS COMPARISON ........................................................................................................... 38
TABLE 4:1 OVERALL MASS BALANCE ........................................................................................................ 52
TABLE 4:2 ANTOINE EQUATION PARAMETER ........................................................................................... 56
TABLE 4:3 RESULTS OF FLASH CALCULATION ........................................................................................... 56
TABLE 4:4 REACTORS SYSTEM MASS BALANCE SUMMARY ...................................................................... 57
TABLE 4:5 MASS BALANCE AROUND NEUTRALIZER.................................................................................. 59
TABLE 4:6 MASS BALANCE AROUND THE DECANTER ............................................................................... 60
TABLE 4:7 FIRST DISTILLATION COLUMN MASS BALANCE CALCULATIONS............................................... 61
TABLE 4:8 SECOND DISTILLATION COLUMN MASS BALANCE CALCULATIONS .......................................... 63
TABLE 4:9 MASS BALANCE AROUND DRYING COLUMN ........................................................................... 64
TABLE 4:10 MASS BALANCE AROUND M-101 ........................................................................................... 66
TABLE 4:11 MASS BALANCE CALCULATIONS FOR STREAMS ..................................................................... 67
TABLE 4:12 HEAT CAPACITY PARAMETERS ............................................................................................. 69
TABLE 4:13 HEAT CAPACITY PARAMETERS ............................................................................................... 69
TABLE 4:14 ENTHALPIES CALCULATIONS (ENTHALPIES (KJ/KMOL)) ......................................................... 71
TABLE 4:15 EXTENT OF REACTION AND HEAT OF FORMATION ................................................................ 72
TABLE 4:16 THE ENTHALPY VALUES FOR EACH STREAM IN KJ/H............................................................. 73
TABLE 4:17 REACTOR ENERGY BALANCE .................................................................................................. 73
TABLE 4:18 EXTENT OF REACTION AND HEAT OF FORMATION ................................................................ 74
TABLE 4:19 THE ENTHALPY VALUES FOR EACH STREAM IN KJ/H .............................................................. 74
TABLE 4:20 REACTOR ENERGY BALANCE .................................................................................................. 75
TABLE 4:22 DUTY OF COMPRESSOR ......................................................................................................... 76
TABLE 4:24 DUTY OF PUMP ...................................................................................................................... 77
xiv
TABLE 4:26 DUTY OF HEAT EXCHANGER................................................................................................... 78
TABLE 4:28 DUTY OF HEAT EXCHANGER.......................................................................................................... 79
TABLE 4:33 PARAMETERS FOR THE FIRST DISTILLATION COLUMN (BZ-CLM) ........................................... 84
TABLE 4:34 PARAMETERS FOR THE CALCULATIONS OF QC AND QR ......................................................... 84
TABLE 4:35 RESULTS FOR BZ-COLUMN ..................................................................................................... 84
TABLE 4:36 PARAMETERS FOR THE SECOND DISTILLATION COLUMN (CB-CLM) ...................................... 85
TABLE 4:37 PARAMETERS FOR THE CALCULATIONS OF QC AND QR ......................................................... 85
TABLE 4:38 RESULTS FOR CB-CLM ............................................................................................................ 85
TABLE 4:40 DUTIES OF VESSELS AND MIXTURE ........................................................................................ 86
TABLE 4:41 DUTIES SUMMARY OF THE EQUIPMENT ................................................................................ 87
TABLE 5:1 VOLUMETRIC FLOW RATE OF THE FEED INTO THE BENZENE COLUMN. .................................. 94
TABLE 5:2 VOLUMETRIC FLOW RATE OF THE FEED INTO THE CHLOROBENZENE COLUMN. ..................... 97
TABLE 5:3 VOLUMETRIC FLOW RATE OF THE FEED INTO THE DRYING COLUMN. ..................................... 99
TABLE 6:1 VAPOUR PRESSURE DATA (PRESSURE AT 482469.00 PA) ....................................................... 110
TABLE 6:2 VAPOUR-LIQUID EQUILIBRIUM DATA .................................................................................... 111
TABLE 10:1 TYPICAL FACTORS FOR ESTIMATION OF PROJECT FIXED CAPITAL COST ............................. 162
xv
LIST OF FIGURES
FIGURE 2:1 CONSUMPTION OF CHLOROBENZENE BY MAJOR REGIONS FOR THE YEAR 2016 (SOURCE IHS
MARKIT) ......................................................................................................................................... 34
FIGURE 2:2 GLOBAL CHLOROBENZENE MARKET SIZE AND FORECAST FROM 2015-2024 (US $MILLION)
(SOURCE: VARIANT MARKET RESEARCH) ....................................................................................... 34
FIGURE 4:1 PROPOSED BLOCK FLOW DIAGRAM FOR THE DESIGN ............................................................ 49
FIGURE 4:2 PROPOSED BLOCK FLOW DIAGRAM FOR THE DESIGN WITH LABELLED STREAMS ................. 50
FIGURE 4:3 REACTOR SYSTEM MADE UP OF TWO CSTRS IN SERIES .......................................................... 57
FIGURE 4:4 WASHER / NEUTRALIZER UNIT ............................................................................................... 58
FIGURE 4:5 DECANTING UNIT ................................................................................................................... 59
FIGURE 4:6 FIRST DISTILLATION COLUMN -BENZENE COLUMN ................................................................ 61
FIGURE 4:7 SECOND DISTILLATION COLUMN (CB-COLUMN) .................................................................... 62
FIGURE 4:8 BENZENE DRYING COLUMN ................................................................................................... 64
FIGURE 4:9 M-101..................................................................................................................................... 65
FIGURE 5:1 CHLOROBENZENES DISTILLATION COLUMN ........................................................................ 107
FIGURE 6:2 MCCABE THIELE PLOT SHOWING THE NUMBER OF STAGES................................................. 115
FIGURE 6:3 FLOODING VELOCITY CHECK ................................................................................................ 117
FIGURE 8:1 CONTROL DIAGRAM OF BENZENE COLUMN IN ASPEN HYSYS .............................................. 138
FIGURE 8:2 CONTROL DIAGRAM OF BENZENE COLUMN (INTERNAL FLOWSHEET) IN ASPEN HYSYS ...... 138
FIGURE 8:3 CONTROL DIAGRAM OF CSTR REACTOR SYSTEM IN ASPEN HYSYS ....................................... 140
FIGURE 8:4 CONTROL DIAGRAM OF WASHER/NEUTRALIZER IN ASPEN HYSYS ....................................... 142
FIGURE 9:1 CHLOROBENZENES PLANT SITE LAYOUT DIAGRAM .............................................................. 150
FIGURE 9:2 CHLOROBENZENES PLANT PROCESS LAYOUT DIAGRAM ...................................................... 151
FIGURE 10:1 CHEMICAL ENGINEERING PLANT COST INDEX .................................................................... 156
xvi
CHAPTER ONE
INTRODUCTION
Benzene is the simplest aromatic organic chemical compound with the chemical
formula of C6H6. Being a colorless liquid, it has a distinct smell and also the parent
compound to many aromatic compounds such as Chlorobenzenes.
Chlorobenzene is a colorless, flammable liquid with an aromatic, almond-like odor
which is manufactured by the reaction of benzene with chlorine with or without a
catalyst (Friedel-Craft reaction). The products of such a reaction would be
Monochlorobenzene, dichlorobenzene, trichlorobenzene and the higher chlorinated
benzenes. In actual practice, only Chlorobenzene and small amounts of
dichlorobenzene are usually formed.
The production of chlorobenzene was first described in 1851, and later in 1868, it was
observed as the formation by the chlorination of benzene (SRI-International, 1977).
Chlorobenzene is still often being manufactured by chlorination of benzene in the
presence of a catalytic amount of Lewis acids such as ferric chloride, sulphur
dichloride, and anhydrous aluminium chloride.
1.1 PROPERTIES OF CHLOROBENZENES
As a group, chlorobenzenes are much less reactive than the corresponding chlorinated
derivatives of alkyl compounds and are similar in reactivity to the vinyl halides. They
are very stable to nucleophilic attack due to resonance in the molecule resulting in a
shortening of the carbon-chlorine bond distance and an increase in bond strength (U.S.
Environmental Protection Agency, 1977).

At room temperature and pressure, chlorobenzenes are not attacked by air, moisture, or
light. They are not affected by steam, prolonged boiling with aqueous or alcoholic
ammonia, other alkalis, hydrochloric acid, or dilute sulfuric acid. Hydrolysis takes place
at elevated temperatures in the presence of a catalyst to form phenols (U.S.
Environmental Protection Agency, 1977).
Chlorobenzenes are subject to attack by hot concentrated sulfuric acid to form
chlorobenzene-p-sulfonic acid. Nitric acid will react with chlorobenzenes at the meta-
and para-positions on the ring to form chloronitrobenzenes at -30°C to 0°C (-22°C to
32°F). At higher temperatures, the nitration will either proceed further to form a
dinitrochloro-compound, chloronitrophenol, or a nitrophenol. Chlorobenzenes are
usually attacked by electrophilic agents. Substitution for monochlorobenzene is
predominantly para-; with some ortho-substitution. The higher chlorinated benzenes
tend to resist electrophilic substitution but can be substituted under extreme conditions
(U.S. Environmental Protection Agency, 1977).
Chlorobenzenes also undergo some free radical reactions. Formation of organometallic
compounds (grignards, aryl-lithium compounds) provides a useful route to many
organic intermediates. Photochemical transformations occur on irradiation of
chlorinated benzenes, which are much less stable to radiation than benzene. When
subjected to ultraviolet irradiation or pulse hydrolysis in solution, chlorobenzenes may
polymerize to biphenyls, chloronaphthalenes, or more complex products (U.S.
Environmental Protection Agency, 1977). The ability of chlorobenzenes to undergo
wide varieties of chemical reactions makes chlorinated benzenes useful as reactants in
numerous commercial processes to produce varied products. All chlorinated derivatives
of benzene are soluble in lipids. Partition coefficient data for chlorobenzenes show an
increase in partition coefficient with an increase in the degree of chlorination. In
18
general, a positive correlation exists between partition coefficient and degree of
bioaccumulation (U.S. Environmental Protection Agency, 1977).
1.1.1 PROPERTIES OF MONOCHLOROBENZENE
Monochlorobenzene has a high solubility in nonpolar solvents; however, it is almost
insoluble in water. If it accumulates in water systems, it tends to sink due to its density.
There may be a greater tendency for monochlorobenzene to accumulate in still lake
waters rather than fast-moving streams and rivers because of its comparatively high
volatility (U.S. Environmental Protection Agency, 1977). Monochlorobenzene is most
likely to enter the atmosphere from fugitive emission sources, including solvent
evaporation. Monochlorobenzene will exist in the atmosphere in the vapor phase and
will react with hydroxyl radicals, producing chlorophenol by-products of
decomposition.
The atmospheric half-life of monochlorobenzene is 17 days. Atmospheric half-life will
decrease in polluted air containing nitric oxide. Products of decomposition will include
chloronitrobenzene and chloronitrophenols. Photolysis in the atmosphere is expected
to be slower (30 days), resulting in monochlorobiphenyl production (Handbook of
Environmental Fate and Exposure Data for Organic Chemicals, 1990).
1.1.2 PROPERTIES OF DICHLOROBENZENES
Ortho- and meta-dichlorobenzene are neutral, mobile, colorless liquids with similar
characteristics and odors. Para-dichlorobenzene is a pleasant smelling white crystalline
solid. The crystals readily sublime at room temperature. Solubilities of the
dichlorobenzenes are similar to those of monochlorobenzene, and the dichlorobenzenes
also form several azeotropes (U.S. Environmental Protection Agency, 1977). Solvent
evaporation is the major source of o-dichlorobenzene in the atmosphere.
19
Approximately 25 percent of annual solvent production using o-dichlorobenzene is
expected to be lost to the atmosphere. It will exist in the atmosphere in the vapor phase
and will react with hydroxyl radicals for an estimated half-life of 24 days. Meta-
dichlorobenzene is most likely to enter the atmosphere from fumigation products
application, as well as a chemical intermediate and solvent use. It exists in the
atmosphere in the vapor phase and can react with hydroxyl radicals or an estimated
half-life of 14 days (Handbook of Environmental Fate and Exposure Data for Organic
Chemicals, 1990). Para-dichlorobenzene is most likely to enter the atmosphere from the
volatilization of household deodorant products and moth flakes.
Approximately 70 to 90 percent of p-dichlorobenzene’s annual production may
eventually be released to the atmosphere. It exists in the atmosphere in the vapor phase
and reacts with hydroxyl radicals for an estimated half-life of 31 days. By-products of
decomposition in the presence of smog include dichloronitriphenol,
dichloronitrobenzene, and dichlorophenol (Handbook of Environmental Fate and
Exposure Data for Organic Chemicals, 1990).
1.2 USES OF CHLOROBENZENES
Chlorobenzenes are widely used in dye and pharmaceutical industry to manufacture
some organic intermediates such as phenol, aniline, nitro phenol. Table 1.1 gives a
summary of the uses of Monochlorobenzenes and dichlorobenzene. Demand for
monochlorobenzene as a feedstock comes mostly from the synthetic organic chemical
manufacturing industries. Accordingly, the simple manufacturing process often allows
monochlorobenzene to be
20
TABLE 1:1 USE OF CHLOROBENZENES
Chlorobenzene Isomer and Use End Use
Monochlorobenzene
Nitrochlorobenzenes Used as intermediates in the manufacture
of rubber, chemicals, agricultural
chemicals, antioxidants, dyes and
pigments
Solvents Used as a solvent in processes to produce
rubber products, pesticides,
pharmaceuticals, and resins
Diphenol ether and phenylphenols Used as an intermediate for dyes,
optional bleaches, ultraviolet stabilizers
for plastics, pharmaceuticals, and
pesticides
Sulfone polymers Used in engineering plastics
Dichlorobenzenes
p-Dichlorobenzene
Deodorant Used as a space and sanitary deodorant
Moth repellent Used as moth repellent
21
Resins Used as an intermediate in
polyphenylene sulphide resins for high
performance plastics
o-Dichlorobenzene
Chemical manufacture Used as an intermediate for the
production of pesticides
Solvents Used in formulated paint strippers and
cleaners and as a heat transfer agent
22
manufactured in the same plant in which it is consumed. Historically, the two major
markets for monochlorobenzene have been in the manufacture of phenol and o and p-
nitrochlorobenzenes. However, the use of monochlorobenzene as a feedstock in phenol
manufacturing has been phased out and replaced by cumene (Chemical-Products-
Synopsis, 1990). Other feedstock uses for monochlorobenzene include use in the
manufacture of diphenyl oxide, dye and herbicide intermediates, and sulfone polymers.
Para-dichlorobenzene is used predominantly in the manufacture of polyphenylene
sulfide resins. In 1988, polyphenylene sulfide resin manufacturing consumed 22
percent of all the p-dichlorobenzene manufactured for that year. In addition to the
manufacture of polyphenylene sulfide, p-dichlorobenzene is used in the manufacture of
room deodorants, moth proofing products, and 1,2,4-trichlorobenzene. Para-
dichlorobenzene is also used as an intermediate in the dyes and insecticide industries
(Johnson, W. K., Leder, A. and Sakuma, Y., 1989).
1.3 BRIEF EVOLUTION OF CHLOROBENZENES PRODUCTION
The reaction of chlorine atoms with benzene has a long chemical history. It was first
described and prepared in 1851 by the reaction of phenol and phosphorus pentachloride
(SRI-International, 1977). Its formation by the chlorination of benzene was observed in
1868. In 1903 it was established that 1,2,3,4,5,6-hexachlorocyclohexane (HCH) was
the final product of the sequence of chlorination reactions initiated by photolysis of Cl2
in liquid benzene. The first quantitative studies of the gas phase reaction were
performed by Noyes and co-workers in the early 1930s using UV irradiation of
C6H6/Cl2 mixtures with the course of reaction monitored via changes in total pressure.
It was deduced that the reaction of chlorine atoms with benzene proceeds mainly via
addition, with chlorination occurring via a short-chain mechanism (chain length of 20-
50) giving HCH as the major product and chlorobenzene as a minor product. In the late
23
1950s Russell and co-workers (Russel, 1958) showed that the photochlorination of
organic compounds in benzene solvent proceeds via an unusual mechanism in which
the active chain carrier is not the free Cl atom but is instead a weakly bound C 6H5-Cl
adduct. The bonding in the C6H5-Cl adduct reduces its reactivity and increases its
selectivity when compared to free chlorine atoms (Sokolov, et al., 1998).
In the later years, Chlorobenzene is produced by the catalytic chlorination of benzene
at an elevated temperature in a batch or continuous process. Sublimed ferric chloride is
the most frequently used catalyst bit anhydrous chloride, stannic chloride, iron, and
aluminum are also used. The reaction sequence is as follows:
Following chlorination, the crude chlorobenzene (a mixture of chlorobenzene and
dichlorobenzene) is neutralized with dilute sodium hydroxide and separated into sludge
and supernatant. The sludge contains dichlorobenzenes which are separated by
distillation. The supernatant is fractionally distilled to separate benzene, chlorobenzene,
o-dichlorobenzene, and p-dichlorobenzene (TRW, 1977; Hydroscience, 1978).
The batch process, described above, is often a three-product process which produces o-
and p-dichorobenzene in addition to chlorobenzene. The quantities of dichlorobenzenes
produced were found to be controlled by various additives; fuller’s earth reduces
dichlorobenzene formation while aluminum chloride enhances their formation.
The continuous process on the other hand and for the production of chlorobenzene is
similar to the batch process but it minimizes the formation of dichlorobenzenes. In the
24
continuous process, the reaction occurs in a series of small vessels, there is a large
benzene to chlorine ratio, and once chlorinated, the chlorobenzene is rapidly removed
to prevent further chlorination. The yield for this process is 95% (Kirk-Othmer, 1964).
Dichlorobenzene (dCB) on the other hand is a further chlorination of chlorobenzene.
The process, essentially, two isomers result in the following percentages:
A very small amount of the meta isomer is formed (Morrison and Boyd, 1970)
O- and p- dichlorobenzene are produced primarily from the distillation residues from
the manufacture of chlorobenzene. Another method of obtaining dichlorobenzenes is
by chlorination of benzene or chlorobenzene. The products are usually being separated
by fractional distillation or by crystallization of the para isomer. If the crystals are
washed with methanol and heated to 100 oC under vacuum suction to remove the
alcohol, the ortho isomer separated from the crystalline para isomer (Snell and Ettre,
1970).
Now adays, to produce p-dicblorobenze, the products from chlorination of
chlorobenzene are further chlorinated. The ortho isomer chlorinated more rapidly than
the para isomer to form trichlorobenzene which is easily separated from the para isomer
by fractional distillation. Alternatively, the dichlorobenzene mixture is reacted with
chlorosulfonic acid; the ortho isomer forms o-dichlorobenzene sulfonic acid. Hereby
making the para isomer easily extracted by distillation (Snell and Ettre, 1970; Kirk-
Othmer, 1964).
1.4 PROBLEM DEFINITION
25
The chlorinated derivatives of benzene are a group of stable, colorless and pleasant-
smelling compounds. Only the mono-, di-, and trichlorobenzenes have important
industrial applications. Processes for the manufacture of chlorobenzenes include
various chemistry and product separation methods. The process currently used by
industry is direct chlorination of benzene in the presence of a FeCl3 catalyst to produce
monochlorobenzene. The monochlorobenzene reacts with the remaining chlorine to
form dichlorobenzenes. Hydrogen chloride is a byproduct in both reactions. In addition
to the two major isomers of dichlorobenzene, ortho- and para-, a very small amount of
the meta-isomer is formed. As chlorination is continued, tri-, tetra-, penta-, and
hexachlorobenzenes are formed. Usually, trichlorobenzene is the only highly
chlorinated product found in significant amounts. The degree of chlorination of benzene
can be controlled by the choice of the catalyst, temperature, and benzene: chlorine ratio
in the reactor feed. Hydrogen chloride, a byproduct of the reaction, is processed under
anhydrous conditions before it is absorbed in water. The reaction and the recovery
operations, in most cases, are continuous.
The initial design problem is to determine whether: “It is both economically and
technically feasible to establish a facility to produce chlorobenzenes in Nigeria”.
This is a diverse and complex undertaking that necessitates a full investigation into the
uses, properties, market, process technology, and production economics, associated
with this particular chemical.
Having considered these aspects and several others, an appropriate plant to fulfil the
assessed market requirements is to be sized and specified accordingly.
1.5 INITIAL DESIGN CONSIDERATION
The proposed process design is to design a plant to produce 20,000 metric tons/year of
monochlorobenzene together with not less than 2,000 metric tons/year of
26
dichlorobenzene, by the direct chlorination of benzene. The onstream time of the plant
would be 8000 hours per year (330 days per year).
The design economy can be visualized as a series of materials transformation processes.
From a technical and economical perspective, while considering the most important as
production, consumption and exchange, it is envisaged that this chlorobenzenes
production facility will be accommodated within a larger chemical complex and a free
trade zone to be located in the Lekki free trade zone of Lagos Nigeria. Other plants on
this site may include a chlorine recovery plant from hydrochloric acid gas or from
electrolysis of NaCl to support raw material. Nearness to Dangote Refineries would be
a major source of advantage as to getting benzene.
1.5.1 THE PROCESS INITIAL DESIGN CONSIDERATION
Liquid benzene (which must contain less than 30 ppm by weight of water) is fed into a
reactor system consisting of two continuous stirred tanks operating in series at 2.4 bar.
Gaseous chlorine is fed in parallel to both tanks. Ferric chloride acts as a catalyst and
is produced in situ by the action of hydrogen chloride on mild steel. Cooling is required
to maintain the operating temperature at 328oK. The hydrogen chloride gas leaving the
reactors is first cooled to condense most of the organic impurities. It then passes to an
activated carbon adsorber where the final traces of impurity are removed before it
leaves the plant for use elsewhere.
The crude liquid chlorobenzenes stream leaving the second reactor is washed with
water and caustic soda solution to remove all dissolved hydrogen chloride. The product
recovery system consists of two distillation columns in series. In the first column (the
‘‘benzene column’’) unreacted benzene is recovered as top product and recycled. In the
second column (the ‘‘chlorobenzene column’’) the mono- and dichlorobenzenes are
separated. The recovered benzene from the first column is mixed with the raw benzene
27
feed, and this combined stream is fed to a distillation column (the ‘‘drying column’’)
where water is removed as overhead. The benzene stream from the bottom of the drying
column is fed to the reaction system.
1.5.2 FEED SPECIFICATIONS
i. Chlorine: 293oK, atmospheric pressure, 100% purity.
ii. Benzene: 293oK, atmospheric pressure, 99.95 wt percent benzene, 0.05 wt
percent water.
1.5.3 Utilities
i. Stream: dry saturated at 8 bars and at 28 bars.
ii. Cooling water: 293 oK.
iii. Process water: 293 oK.
iv. Caustic soda solution: 5 wt percent NaOH, 293 oK
1.5.4 Expected product specification
i. Monochlorobenzene: 99.7 wt percent.
ii. Dichlorobenzene: 99.6 wt percent.
Hydrogen chloride gas: less than 250 ppm by weight benzene.
1.6 AIM AND OBJECTIVE OF THE DESIGN WORK
This design work aims at designing a production plant with a production capacity of
20,000 tonnes/year of Monochlorobenzene together with not less than 2,000
tonnes/year of dichlorobenzene, by the method of direct chlorination of benzene.
Production yields of 99.7 % pure Monochlorobenzene and 99.6% pure dichlorobenzene
are to be achieved at a minimal temperature possible. This was extracted from Towler,
G. P. and Sinnott, R. (2008).
1.7 SCOPE OF DESIGN WORK REQUIRED
28
1.7.1 PROCESS DESIGN
a. To prepare a material balance for the process, including an analysis of each
reactor stage (the kinetics of the chlorination reactions are given). On-stream
time is to be taken as 330days per year.
b. To prepare energy balances for the first reactor and for the chlorobenzene
column (taking the reflux ratio for this column as twice the minimum reflux
ratio).
c. Also, to prepare a process flow diagram for the plant, which should show the
major items of equipment with an indication of the materials of construction
and of the internal layout. Temperatures and pressures should also be indicated.
29
Benzene Chlorine Chlorobenzene Dichlorobenzene
Value ($/kmol) 15.00 15.00 45.00 0.00
Molecular weight
(g/mol) 78.11 70.91 112.56 147.00
Normal boiling
point (◦C) 80.1 −34.06 130 173-180
Mass density (g/cm3)
(at 20◦C) 0.877 – – 1.11 1.29
Molar volume (L/mol)
(at 20◦C) 0.089 – – 0.101 0.114
Enthalpy of formation
(kJ/mol) 49.0 0.0 11.0 −18
Heat capacity
(J/mol K) 136.3 – – 150.1 162.4
Relative volatility 13 – – 3.0 1
Enthalpy of vaporiz-
ation (kJ/mol) 30.72 – – 35.19 39
Notes: Normal boiling point is at 1 atm. Mass densities are in the liquid phase at 20◦C.
Enthalpies of formation are for the liquid phase at 298.15 K and 1 bar from the elements in their
standard states at 298.15 K and 1 bar.
Heat capacities are for the liquid phase at 298.15 K and 1 bar.
Relative volatilities are with reference to dichlorobenzene (the heaviest species) and are estimated from
data obtained from DISTIL6 using a phase equilibrium model with the NRTL activity coefficient model
for the liquid and ideal vapor phase. Physical property data are taken from CRC (1995).
30
1.7.2 CHEMICAL ENGINEERING DESIGN
A sieve-plate column design is to be prepared for the chlorobenzene distillation, with
dimensioned sketches showing details of the plate layout including the weir and the
down-comer.
1.7.3 MECHANICAL DESIGN
Preparation of a mechanical design of the chlorobenzene column, estimating the shell
thickness, the positions and sizes of all nozzles, and the method of support for the plates
and the column shell. Preparation of a dimensioned sketch suitable for submission to a
drawing office.
1.7.4 SAFETY
Indication of the safety measures required for this plant, bearing in mind the toxic and
flammable materials handled.
31
CHAPTER TWO
RELEVANCE OF CHLOROBENEZENE TO LOCAL
NEEDS
Chlorobenzene used mostly in the manufacture of pesticides, dyes and rubber
Nigeria is an industrious country with more the 180 million people. It has one of the
largest marketplaces in Africa for chemicals such as pesticides, dyes and rubber. In
Lagos alone, there are a few existing pesticides industries (Biostadt company, Alphayel
ventures, Environmental Fumigations Solution etc.), rubber industries (Poly Products
Nigeria Limited, Think and Thank Poly Products, Silla for Import and Export etc.),
dyes industries (Century Dyes and Chemical Limited, Abdul Dye and Chemical
Enterprises, Gem Dye Industries etc.). In Kaduna, there are some pesticide industries
(Harvest Field Industries, Alege Scientific limited (A.S.L) etc.), rubber industries
(Jafco Industries Limited, etc.) and few others in other industrial city of the nation.
chlorobenzene production plants are urgently needed to cater for raw materials needed
to produce these chemicals therefore resulting in less importation and economic self-
dependence of the nation.
In a long run, this will also serve as the stepping stone for the nation quest in
joining the global marketplace of these chemicals. Which will have a positive impact
on the economy of the country and also provide a means for its sustainable
development. In the analysis of global consumption of chlorobenzene shown in the
figure 2.3. Monochlorobenzene accounts for nearly 73% of total global chlorobenzene
consumption of which makeups are o-dichlorobenzene and p-dichlorobenzene. China
is the world’s largest manufacturer and consumer, accounting for nearly 82% of total
consumption in the four major regions of the world as shown in Figure 2.3.
Monochlorobenzene represents about 70% of chlorobenzene consumption in Western
Europe, and 52% of consumption in the United States, but only 10% in Japan, where
p- dichlorobenzene is a larger factor than in the other regions. According to the market
analysis and forecast study of Monochlorobenzene (2010-2033), released by sevas Edu
society, (2010), Nitrochlorobenzene manufacturer contribute to the highest market i.e.
Nitrochlorobenzene is the most significant end use for monochlorobenzene which are
heavily employed in the dyes and pigments industries, rubber processing and
pharmaceutical industries. Although this is estimated to grow over 12% in the next few
years. The gradual shift in global demand away from industrialized regions and further
into developing countries has resulted in a buildup of new chlorobenzene capacity in
Asia and Africa.
Chlorobenzenes can be shipped to those countries with consumption rate through our
major sea ports in Apapa in Lagos state and Onne in River State. Global Chlorobenzene
Market is estimated to reach $2,942 million by 2024; growing at a CAGR of 5.8% from
2016 to 2024. In terms of volume, the market was valued at 1,579 Kilo tons in 2016
and expected to reach 2,201-kilo tons by 2024, at a CAGR of 4.2% from 2016-2024.
Billions of revenue can be acquired from these to fund capital infrastructural project in
the country.
33
10%
3%
13%
China
Usa
74% Japan
Western europe
Figure 2:1 CONSUMPTION OF CHLOROBENZENE BY MAJOR REGIONS
FOR THE YEAR 2016 (SOURCE IHS MARKIT)
Figure 2:2 GLOBAL CHLOROBENZENE MARKET SIZE AND FORECAST
FROM 2015-2024 (US $MILLION) (SOURCE: VARIANT MARKET
RESEARCH)
34
CHAPTER THREE
PROCESS SELECTION
3.1 PROCESS ROUTE ALTERNATIVE
Over the years, several process routes on how optimal amount of cholorobenzene can
be produced from the direct chlorination of benzene has been discovered. There are
three different ways cholorobenzene can be manufactured through the direct
chlorination of benzene and they are:
a) Batch Process
This procedure is used when minimum formation of dichlorobenzenes is required. In
the batch process, benzene is contained in a deep, iron or steel vessel, fitted with lead
cooling coils. The chlorine feed-pipe enters at the bottom of the chlorinator and the
catalyst is ferric chloride. The temperature is maintained at less than 45°C. HCl
produced in the reaction can be recovered after separation from benzene by washing
with a refrigerated solvent. At temperatures below 40°C, the rate of formation of
dichlorobenzene is very low and this fact is used to suppress formation of
dichlorobenzene in the continuous process.
b) Continuous Process
A typical continuous process plant consists of a series of small, externally cooled steel
vessels containing the catalyst. The catalyst used is usually Ferric chloride. This can be
added as solution in benzene. Chlorine is supplied into each vessel through suitably
positioned inlets to maintain a large benzene-to-chorine reaction at all points along the
reaction stream. The temperature of the reaction is maintained between 20 - 40°C. As

the chlorobenzene is formed, it leaves the chlorination zone at a speed that allows no
further chlorination to take place.
Unreacted benzene and chlorobenzene are continuously separated by fractional
distillation, returning the benzene to the chlorination stage and the efficiency of this
process can be as high as 95%.
c) Raschig Process
In this process, benzene is chlorinated by chlorine that has been produced in situ in the
reactor by the catalytic oxidation of hydrogen chloride. A pre-heated mixture of
benzene vapour, air, steam, and HCl, at ordinary pressure, is brought into contact at
220°-260°C with a catalyst of copper oxide. 2% of the total benzene combusts, gives
rise to about one quarter of the total heat output of the process. The disadvantage of this
process is that the high temperature greatly favours high combustion rates of benzene
and the reaction may become uncontrollable. Moreover, the high costs of this vapour
phase chlorination process in comparison with other available processes, allows it to be
highly uneconomical for chlorobenzene manufacture and thus renders it obsolete. This
process also can only produce small amount of chlorobenzene since this once-through
conversion is limited.
3.2 PROCESS SELECTION
A comparison and determination of the comparative advantages and disadvantages of
physically available process routes for the formation of chlorobenzenes will be
necessary in order to select the best process route.
According to Sinnott (1993), the selection process can be considered to go through the
following stages:
 Possible designs (credible) within the external constraints.
 Plausible designs (feasible) within the internal constraints.
36
 Probable designs likely candidates.
 Best design (optimum) judged the best solution to the problem.
The selection process will become more detailed and more refined as the design
progresses from the area of possible to the area of probable solutions. In this early stage
a coarse screening based on common sense, engineering judgement, and rough costings
was used.
A comparison of the three methods is shown in Table 3.1. The best selection was made
comparison.
Based on the comparison made in Table 3.1, the most suitable process for the
production of the monochlorobenzene is observed to be continuous process. The
continuous process was selected because it is more beneficial compared to batch
process and Raschig process.
37
Table 3:1 PROCESS COMPARISON
Process/ Factors Continuous Batch Hooker/ Raschig
Process Process Process
Raw materials Liquid Benzene Benzene Liquid Benzene
Gaseous Chlorine Chlorine Hydrochloric acid
Oxygen (air)
Reaction Temperature range Temperature Temperature range
Conditions is between 200C – range is between is between 2200C –
400C and in liquid 400C – 600C and 2600C and in
phase. in liquid phase. gaseous phase.
Type of Reactor Continuous stirred Batch reactor Fixed bed Reactor
used tank Reactor
Catalyst used Ferric Chloride. Ferric Chloride. Copper and Iron
Chloride
Side Reactions Produces less by Produces higher Produces many by
products, it has high amount of by products such as
production of products such as dichlorobenzene,
monochlorobenzene dichlorobenzene trichlorobenzene,
and produces a and can produce tetrachlorobenzene
small amount of on only small and others
dichlorobenzene scale.
Conversion of High conversion of Lower conversion Benzene
reactant (benzene) benzene (95%) when compared to conversion is
limited (10-15%)
38
continuous
process (80%)
Operation and High cost of Low cost of High cost of
labour cost equipment, requires factory equipment vapour phase
special material of because of simple chlorination
construction for design of batch process and has
very low reactor, high large investments
temperature and has labour cost due to for corrosion
low operating equipment reactants.
labour. cleaning and
preparation, it
requires strict
scheduling and
control, it also
needs many
people to operate
the process
Operating Very simple Reaction is easy to Reaction is
Conditions operation because control due to low uncontrollable
reactant is its liquid temperature. because of high
phase temperature.
3.3 PROCESS ROUTE JUSTIFICATION
The continuous process does not produce as many chlorobenzene products at a
particular instant of time, which may be a disadvantage, but that is also one of the
39
features that make it a really desirable process for the production of
monochlorobenzene and dichlorobenzene, especially since the only products desired in
this plant are monochlorobenzene and dichlorobenzene. This limitation may be a
disadvantage, but the benefits of using the continuous process route overwhelms the
limitations
1. The low operating temperature range associated with this process reduces the
cost of utility and amount of energy consumed, and it also decreases the
possibility of side reactions that may yield undesirable products
2. For large production volumes, which in this case is 20,000 tons of MCB and
2,000 tons of DCB, the most appropriate production process is the continuous
process
3. It is an economical and efficient process
4. It decreases the chances of having undesirable side products, and it also makes
the recycle of unconverted reactants to be seamless.
3.4 DETAILED DESCRIPTION OF THE SELECTED PROCESS
The selected alternative starts with the chlorination of benzene in a continuous stirred
tank reactor from which the main product is monochlorobenzene. The reactor operates
at 328K and 2 atm. The reactor residence time is manageable and can be configured to
suit the best conversion. The feeds to the reactor are chlorine gas and a benzene feed in
a molar ratio of 2 to 1. The catalyst used is Ferric chloride produced in-situ by the action
of hydrogen chloride on mild steel. The catalyst promotes the action of chlorine as an
electrophile. The electronegativity of chlorine reduces possible electrophilic attack on
produced monochlorobenzene by other nearby electrophiles, hence reducing the
conversion of produced monochlorobenzene to other polysubstituted benzene
derivatives of chlorine. This is important as it allows the conversion to be controlled by
40
the use of factors such as multiple reactors and residence time in the production of
required products to required specifications if the need arises. Two reactors in series
are employed in this process to which the input chlorine is supplied to them in parallel.
The input chlorine gas stream requires a percentage purity of 100 % while the raw
benzene feed comes with a slight quantity of water. The water could be as a result of
the benzene recycle stream or the raw benzene stream. Complete removal of the water
is unnecessary since it has no detrimental effect on the chlorination of benzene. The
products from the chlorination stage depend on factors such as residence time, number
of reactors used and catalyst used. In this design, the process selection is made to
achieve a final product stream of not less than 2000 tonnes/year of dichlorobenzene and
20000 tonnes/year of monochlorobenzene. Some of the major operation stages are
highlighted below:
i. Ferric chloride generation.
Ferric chloride acts as a catalyst and is produced in-situ by the action of hydrogen
chloride on mild steel. Cooling is required to maintain the operating temperature at 328
K.
ii. Chlorinator (CSTR)
The next step is Chlorination reaction. The reactor operates isothermally. The feed to
the reactor comprises fluid benzene and chlorine. The Liquid benzene feed is comprised
of crude benzene and unreacted benzene that was recuperated as top item and reused
from the "benzene segment.” Ferric Chloride (produced in situ by the activity of
hydrogen chloride on mild steel) improves the electrophilicity of the chlorine and this
serves as a catalyst. Since chlorine is electronegative, monochlorobenzene displays
diminished powerlessness to assault by different electrophiles. Hence, the chlorination
procedure delivers just limited quantities of dichloro-and trichlorobenzenes. Chlorine
41
is almost used up in the reactor. The reactor effluent is in vapor and liquid phase. The
reactor effluent serves as a feed for the next reactor. The output from the second reactor
is cooled to condense most of the impurities. Since the reaction is exothermic cooling
is required to maintain the temperature at about 328K. Based on all the above
considerations, the continuous liquid phase chlorination of benzene at a temperature of
about 328K is best suited for production of large amounts of monochlorobenzene in the
industry. The reaction chemistry is shown below.
Reaction 1: 𝐶6𝐻6 + 𝐶𝑙2 𝐶6𝐻5𝐶𝑙 + 𝐻𝐶𝑙
Reaction 2: 𝐶6𝐻5𝐶𝑙 + 𝐶𝑙2 𝐶6𝐻4𝐶𝑙2 + 𝐻𝐶𝑙
iii. Neutralizer (Washer)
The crude chlorobenzene stream leaving the reactor is washed with NaOH solution (20
wt%; maintained slightly alkaline to protect downstream equipment from corrosion) in
a pre-neutralizer. The product stream is free of HCl. The product stream coming from
the reactor MCB, DCB, unreacted benzene and remaining HCl condensed out through
the carbon adsorber. Majority of the HCl gas had already been condensed of impurities
but the left out HCl still finds its way into the product and that is why passing the
product stream through the Neutralizer is very necessary. HCl reacts with Caustic soda
solution of 5 wt percent NaOH at 293 K, to precipitate Sodium Chloride salt and water.
iv. Benzene Column:
The benzene segment is a distillation column where the unreacted benzene and water
is isolated as the overhead item while the bottoms contain MCB and DCB. It is expected
that benzene is almost recovered at the top bottom. Likewise, larger moles of MCB and
DCB in the feed go out through the bottoms of the section. The unreacted benzene
containing water is routed to the drying section after which it is recycled to a mixer in
which it is combined with raw benzene feed going into the chlorinator.
42
v. Chlorobenzene Column:
In this column (the “chlorobenzene column”) the mono- and dichlorobenzenes are
separated. Monochlorobenzene is the overhead distillate product of a purity of 99.7%.
Dichlorobenzene is the bottom residue product of a purity of 99.6%. Lastly, some
equipment are fixed in between the resulting streams to allow the resulting stream
approach a desired operating condition in the next stage. These include mixers, valves,
compressors, coolers, recycles.
43
CHAPTER FOUR
MATERIAL AND ENERGY BALANCES
The starting point for mass and energy balances is from the law of conservation of mass
and first law of thermodynamic (the conservation laws) that is “Mass or energy can
neither be created nor destroyed but can be or are often changed from one form into
another”.
4.1 THEORY
Mass and energy balances can be developed to do calculations of mass flow, molar
flow, energy flow and compositions of streams.
Starting with general equation of mass balance which is as follows:
𝐼𝑛𝑝𝑢𝑡 – 𝑂𝑢𝑡𝑝𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 – 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
For a steady-state process the accumulation term will be zero. Except in nuclear
processes, mass is neither generated nor consumed; but if a chemical reaction takes
place a particular chemical species may be formed or consumed in the process. If there
is no chemical reaction the steady state balance reduces to:
𝑴𝒂𝒕𝒆𝒓𝒊𝒂𝒍 𝒐𝒖𝒕𝒑𝒖𝒕 = 𝑴𝒂𝒕𝒆𝒓𝒊𝒂𝒍 𝒊𝒏𝒑𝒖𝒕
The conservation of energy, however, differs from that of mass in that energy can be
generated (or consumed) in a chemical process. From the First law of
Thermodynamics, energy can neither be created nor destroyed but can be modified into
different forms. As with mass, energy can be considered to be separately conserved in
all but nuclear processes. Material can change form, new molecular species can be
formed by chemical reaction, but the total mass flow into a process unit must be equal
to the flow out at the steady state. The same is not true of energy. The total enthalpy of
the outlet streams will not equal that of the inlet streams if energy is generated or
consumed in the processes; such as that due to heat of reaction.
Energy can exist in several forms: heat, mechanical energy, electrical energy, and it is
the total energy that is conserved. In process design, energy balances are made to
determine the energy requirements of the process: the heating, cooling and power
required. In plant operation, an energy balance (energy audit) on the plant will show
the pattern of energy usage, and suggest areas for conservation and savings. Most
energy balances are carried out using process simulation software, but design engineers
occasionally have to incorporate energy balances into spreadsheet models or other
computer programs. It is therefore important for the design engineer to have a good
grasp of the basic principles of energy balances. For gases, the heats of mixing are
usually negligible, and the heat capacities and enthalpies can be taken as additive
without introducing any significant error into design calculations. For mixtures of
liquids and for solutions, the heat of mixing (heat of solution) may be significant, and
so must be included when calculating the enthalpy of the mixture. Heats of mixing and
heats of solution are determined experimentally and are available in the handbooks for
the more commonly used solutions. If no values are available, judgment must be used
to decide if the heat of mixing for the system is likely to be significant.
The general equation of energy balance is thus:
Energy Out = Energy In + Generation - Consumption – Accumulation
Can be specified based on the basic forms as:
𝐾𝐸 + 𝑃𝐸 + 𝑈 = 𝑄 + 𝑊
This is a statement of the First Law of Thermodynamics.
A chemical reaction will evolve energy (exothermic) or consume energy (endothermic)
and for steady state processes, the accumulation of both mass and energy will be zero.
45
4.2 APPROACH TO MATERIAL AND ENERGY BALANCE
However, the best way to tackle a problem will depend on the information given, the
information required from the balances (material and energy balances), and the
constraints that arise from the nature of the problem. The approach adopted in obtaining
the material and energy balances information was carried out as described by Towler
and Sinnott (2008).
According to Towler and Sinnott (2008), the following step-by-step procedure was
given as an aid to the efficient solution of material and energy balance problems. The
same general approach being usefully employed to organize the solutions in this design
problem.
Procedure
Step 1: Determine/decide the basis of the calculation.
Step 2: Draw a block diagram of the process, showing each significant step as a block,
linked by lines and arrows to show the stream connections and flow direction.
Step 3: List the available data, showing on the block diagram the known flows (or
quantities) and stream compositions.
Step 4: List all the information required from the balance.
Step 5: Decide the system boundaries.
Step 6: Write out the chemical reactions involved for the main products and by-
products.
Step 7: Note any other constraints, such as specified stream compositions, azeotropes,
phase or reaction equilibrium, tie substances.
Step 8: Note any stream compositions and flows that can be approximated.
46
Step 9: Check the number of conservation (and other) equations that can be written and
compare with the number of unknowns, deciding which variables are to be design
variables.
4.3 MATERIAL BALANCE
Material balances are the basis of process design. A material balance taken over the
complete process will determine the quantities of raw materials required and products
produced. Balances over individual process units set the process stream flows and
compositions; thereby providing the basic equations for sizing equipment. A good
understanding of material balance calculations is essential in process design (Towler
and Sinnott, 2008).
For this problem, the problem-solving technique adopted uses working from the known
to the unknown i.e. using established stoichiometric ratios in a reverse pattern to
determine the required feed inputs.
A simplified Block Flow Diagram (BFD) of the Process Flow Diagram (Figure 3.1) is
as presented in Figure 4.1 The material balance will be computed based on the BFD
in Figure 4.1
From the block flow diagram presented, we have shown that the output of mCB and
dCB from the CSTR remains fairly constant due to the fact the reactions at the
neutralizer do not involve mCB and dCB. Also, the processes occurring in the decanter
and the benzene column are simple separations processes and have assumed 99.9%
component recovery. This implies that the throughput of mCB and dCB obtained from
the chlorobenzene column would remain at equilibrium in the product stream from the
second CSTR i.e. the throughput remains unchanged as it passes through the
neutralizer, decanter and benzene column.
4.3.1 THROUGHPUT ANALYSIS AS REQUIRED
47
In this project it is required to design a plant to produce 20,000 metric tons/year of
monochlorobenzene, together with not less than 2,000 metric tons/year of
dichlorobenzene.
I. For Monochlorobenzene (mCB):
Expected Minimum Throughput: = 20,000 𝑡𝑜𝑛𝑛𝑒𝑠 𝑝𝑒𝑟 𝑎𝑛𝑛𝑢𝑚
Run time (that is, total number of operating hours of the plant per year):
24 ℎ𝑜𝑢𝑟𝑠
= 330 𝑑𝑎𝑦𝑠 × = 7,920 ℎ𝑜𝑢𝑟𝑠
1 𝑑𝑎𝑦
𝑘𝑖𝑙𝑜𝑔𝑟𝑎𝑚𝑠
Converting the throughput to (𝑘𝑔/ℎ)
ℎ𝑜𝑢𝑟
20000 𝑡𝑜𝑛𝑛𝑒𝑠 1 𝑦𝑟 1000 𝑘𝑔

Expected Minimum Throughput = × 7920 ℎ𝑜𝑢𝑟𝑠 × 1 𝑡𝑜𝑛𝑛𝑒 =
1 𝑦𝑟
2525.25 𝑘𝑔/ℎ
Converting to 𝑘𝑚𝑜𝑙/ℎ, with the molecular mass of monochlorobenzene(mCB) to be
112.5 𝑘𝑔/𝑘𝑚𝑜𝑙 (i.e. C6H5Cl = 12(6) + 5(1) + 35.5 = 72 + 5 + 35.5 = 112.5 kg/kmol)
2525.25 𝑘𝑔/ℎ
Expected Minimum Throughput: = 112.5 𝑘𝑔/𝑘𝑚𝑜𝑙 = 22.45 𝑘𝑚𝑜𝑙/ℎ𝑟
For Di-chlorobenzene (dCB):
Projected Minimum Throughput: = 2,000 𝑡𝑜𝑛𝑛𝑒𝑠 𝑝𝑒𝑟 𝑎𝑛𝑛𝑢𝑚
Run time (that is, total number of operating hours of the plant per year):
48
Figure 4:1 PROPOSED BLOCK FLOW DIAGRAM FOR THE DESIGN
Figure 4:2 PROPOSED BLOCK FLOW DIAGRAM FOR THE DESIGN WITH LABELLED STREAMS
50
24 ℎ𝑜𝑢𝑟𝑠
= 330 𝑑𝑎𝑦𝑠 × = 7,920 ℎ𝑜𝑢𝑟𝑠
1 𝑑𝑎𝑦
𝑘𝑖𝑙𝑜𝑔𝑟𝑎𝑚𝑠
Converting the throughput to (𝑘𝑔/ℎ)
ℎ𝑜𝑢𝑟
2000 𝑡𝑜𝑛𝑛𝑒𝑠 1 𝑦𝑟 1000 𝑘𝑔

Expected Minimum Throughput = × 7920 ℎ𝑜𝑢𝑟𝑠 × 1 𝑡𝑜𝑛𝑛𝑒 = 252.525 𝑘𝑔/
1 𝑦𝑟
Converting to 𝑘𝑚𝑜𝑙/ℎ, with the molecular mass of di-chlorobenzene (dCB) to be
147.01 𝑘𝑔/𝑘𝑚𝑜𝑙 (i.e. C6H4Cl2 = 12(6) + 4(1) + 35.5(2) = 72 + 5 + 71 = 147 kg/kmol):
252.525 𝑘𝑔/ℎ
Projected Throughput: = 147 = 1.718 𝑘𝑚𝑜𝑙/ℎ𝑟
𝑘𝑔/𝑘𝑚𝑜𝑙
Since the plant would run continuously, there would be some downtime needed for
maintenance, equipment test running, catalyst regeneration and other processes. We
therefore need to calculate the plant attainment i.e. the percentage of available hours in
a year that the plant operates.
ℎ𝑜𝑢𝑟𝑠 𝑜𝑝𝑒𝑟𝑎𝑡𝑒𝑑 100 7920 100

Plant attainment (%) = × = 8760 ×
8760 1 1
= 𝟗𝟎. 𝟒 % 𝒑𝒍𝒂𝒏𝒕 𝒂𝒕𝒕𝒂𝒊𝒏𝒎𝒆𝒏𝒕
The plant would run for 90.4 % of the available hours and there would be 9.6 %
downtime allocated to maintenance, equipment repairs, catalyst regeneration and other
processes.
4.3.2 OVERALL MASS BALANCE
Mass balance for this project was performed through connected cells for each
equipment in the production process with the help of Excel. This feature made us able
easily perform multiple calculations for the mass balance for the whole process
simultaneously until convergence.

However, a detail calculation of the process balances is shown in the appendices of this
report.
The streams label takes the order of the Block Flow Diagram
Table 4:1 OVERALL MASS BALANCE
IN OUT
2 1 14 19 22 23 16 S1 (Recycle) 25
Benzene 100.00 0.00 0.00 0.00 0.00 0.00 9.25 66.30 0.00
Chlorine 0.00 26.45 0.00 0.00 0.00 0.00 0.00 0.00 0.00
mCB 0.00 0.00 0.00 0.00 21.91 0.02 0.50 0.02 0.00
dCB 0.00 0.00 0.00 0.00 0.04 1.94 0.01 0.00 0.00
HCl 0.00 0.00 0.00 0.00 0.00 0.00 25.53 0.00 0.00
H2O 0.00 0.00 190.00 171.82 0.00 0.00 0.00 19.09 0.00
NaOH 0.00 0.00 10.00 9.08 0.00 0.00 0.00 0.00 0.00
NaCl 0.00 0.00 0.00 0.92 0.00 0.00 0.00 0.00 0.00
SUM 100.00 26.45 200.00 181.82 21.95 1.97 35.29 85.42 0.00
Total 326.45 326.45
4.3.2.1 THE REACTORS IN SERIES (CSTRS)
Being the heart of a chemical process, the reactor system for this design is such that
Two CSTRs are connected in series and would have the limiting reactant (Cl2 (g)) is
channeled to both reactors in parallel.
With this peculiarity, the conversion of the reactor system is none know and can only
be determined by experiment or otherwise by specification in the design. Nevertheless,
with the production rates of both the mCB and dCB known, a material balance can be
carried out base on selectivity and reaction extent, being an alternative approach, where
conversion of the reactants for the reacting system is not known.
With the design specifications given, which is to produce 20,000 tonnes/year of mCB,
and not less than 2,000 tonnes/year of dCB, which is equivalent to the calculated
through put already derived above as 22.45 kmol/hr of mCB and not less than 1.718
kmol/hr of dCB.
52
The reactions take place in two steps; the first step chlorine gas reacts with benzene to
produce mono-chlorobenzene and the later further reacts with chlorine to produce
dichlorobenzene. The operating conditions are fixed and already specified to obtain the
desired conversion and selectivity.
𝐶6 𝐻6 (𝑙) + 𝐶𝑙2 (𝑔) → 𝐶6 𝐻5 𝐶𝑙(𝑙) + 𝐻𝐶𝑙(𝑔)
𝐶6 𝐻5 𝐶𝑙(𝑙) + 𝐶𝑙2 (𝑔) → 𝐶6 𝐻4 𝐶𝑙2 (𝑙) + 𝐻𝐶𝑙(𝑔)
Also, with the composition of the feed without recycle stream, the expected design
selectivity can be calculated as adopted from (Douglas, 1985) which is a function of
conversion of the limiting reactant:
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑 𝐹(𝑚𝐶𝐵)

𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 = =
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐿𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑓𝑒𝑑 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝐹𝑖 𝐶𝑙2
Since, the design problem statement stated that the yield is calculated such that 𝐶𝑙2 (𝑔) is
to be the limiting reactant and should be negligible at the vapour stream outlet of the
reactor system, then:
𝐹(𝑑𝐶𝐵) = 𝐹𝑖 𝐶𝑙2 − 𝐹𝑖 𝐶𝑙2 ∙ 𝑥𝐶𝑙2
Where x is the fraction of fed chlorine that reacted via reaction one.
Where: 𝐹(𝑚𝐶𝐵) := Production rate of mCB
𝐹(𝑑𝐶𝐵) := Production rate of dCB
𝐹𝑖 𝐶𝑙2 := Feed rate of 𝐶𝑙2 (𝑔)
The mass balance performed around the reactor system:
Mass balance extent of reaction (ξ) method can be used. So mass balance around the
reactor using the extent of the reaction (ξ) will be:
𝐶6 𝐻6 (𝑙) + 𝐶𝑙2 (𝑔) → 𝐶6 𝐻5 𝐶𝑙(𝑙) + 𝐻𝐶𝑙(𝑔) ξ1
𝐶6 𝐻5 𝐶𝑙(𝑙) + 𝐶𝑙2 (𝑔) → 𝐶6 𝐻4 𝐶𝑙2 (𝑙) + 𝐻𝐶𝑙(𝑔) ξ2
53
𝐹 𝐵 = 𝐹𝑖 𝐵 − ξ1 (𝑖)
𝐹𝐶𝑙2 = 𝐹𝑖 𝐶𝑙2 − ξ1 − ξ2 (𝑖𝑖)
𝐹 𝐻𝐶𝑙 = 𝐹𝑖 𝐻𝐶𝑙 + ξ1 + ξ2 (𝑖𝑖𝑖)
𝐹𝑚𝐶𝐵 = 𝐹𝑖 𝑚𝐶𝐵 + ξ1 − ξ2 (𝑖𝑣)
𝐹𝑑𝐶𝐵 = 𝐹𝑖 𝑑𝐶𝐵 + ξ2 (𝑣)
𝑊ℎ𝑒𝑟𝑒:
𝐹(𝑚𝐶𝐵) 𝐹(𝑚𝐶𝐵)
ξ1 = and ξ2 = (1 − 𝑠)
𝑠 𝑠
The feed streams to the reactor system (two CSTRs) are stream 5 and stream 7 with
stream 5 being the feed rate of of 𝐶𝑙2 (𝑔) (i.e. 𝐹𝑖 𝐶𝑙2 ) and stream 7 being the feed rate of
𝐵𝑒𝑛𝑧𝑒𝑛𝑒. The outlet streams are stream 16 and 13 being the vapor and liquid reactors
effluent respectively. Streams 16 and 13 being effluents contain the products mono-
chlorobenzene(mCB), di-chlorobenzene(dCB), HCl and the unreacted benzene (B) and
chlorine (𝐶𝑙2 (𝑔) ).
Choosing a basis of 100 kmol/hr Benzene Feed rate and at first, 30 kmol/hr of 𝐶𝑙2 (𝑔) .
The chlorine feed was then recalculated to yield a negligible value in the vapour effluent
stream. 26.45 kmol/hr was found to be sufficient enough to get convergence of 𝐶𝑙2 (𝑔)
in the vapour effluent stream as 0.00 kmol/hr.
After a set of iterative solutions that were generated by Excel and scaling-up the fresh
feed to the process, the extents of reaction were found to be:
ξ1 = 22.45 kmol/hr and ξ2 = 2 kmol/hr.
Antoine equation was used to determine the fractions of the vapor and liquid content
leaving the reactor by using flash calculations, and these equations were used:
54
𝑩
log10 𝑃 𝑠𝑎𝑡 = 𝑨 +
𝑇(℃) + 𝑪
𝑃 𝑠𝑎𝑡
𝐾𝑖 =
𝑃
𝑧𝑖 𝑘𝑖
∑ =1
𝑉
1 + ( )(𝐾𝑖 − 1)
𝐹
𝑧𝑖 𝑘𝑖
𝑦𝑖 =
𝑉
1 + ( )(𝐾𝑖 − 1)
𝐹
𝑦𝑖
𝑥𝑖 =
𝐾𝑖
F= V+L
Where: F= Total Effluent; V = Vapour and L = Liquid Effluent
The Antoine equation parameters and the results of flash calculations are summarized
in Table 4.2 and Table 4 3
55
Table 4:2 ANTOINE EQUATION PARAMETER
A B C Psat (mm Hg) Psat (bar) Ki zi
Benzene 6.91 1211.03 220.79 326.97 0.436 0.182 0.597
Chlorine 4.06 861.34 246.33 - 16.01 6.670 0.000
mCB 6.98 1431.05 217.56 53.42 0.071 0.030 0.178
dCB 7.30 1782.40 230.01 11.22 0.015 0.006 0.016
HCl 4.57 868.36 1.75 - 87.20 36.335 0.209
Table 4:3 RESULTS OF FLASH CALCULATION
Feed zi yi xi Vapor Liquid
Benzene 75.55 0.597 0.141 0.774 4.963 70.587
Chlorine 0.00 0.000 0.000 0.000 0.000 0.000
mCB 22.45 0.178 0.007 0.243 0.255 22.195
dCB 2.00 0.016 0.000 0.022 0.005 1.995
HCl 26.45 0.209 0.700 0.019 24.694 1.756
Total 168.06 1.00 0.99 1.01 95.86 86.05
In addition, the following table summarizes flow rates of streams entering and leaving
the reactor.
56
Table 4:4 REACTORS SYSTEM MASS BALANCE SUMMARY
Component/ IN OUT
Stream 5 7 16 13
Benzene - 100.00 9.25 66.30
Chlorine 26.45 - 0.00 0.00
mCB - - 0.50 21.95
dCB - - 0.01 1.99
HCl - - 25.53 0.92
26.45 100.00 35.29 91.16
Total 126.45 126.45
A simple diagram of the reactor system is shown in Figure 4.1
Figure 4:3 REACTOR SYSTEM MADE UP OF TWO
CSTRS IN SERIES
57
4.3.2.2 WASHER/NEUTRALIZER
A simple diagram of the neutralizer is shown in Figure 4.2, where the flow rate of
stream 15 is zero. vk
Figure 4:4 WASHER /
NEUTRALIZER UNIT
The washer is a conversion reactor to remove hydrogen chloride. In this reactor solution
of sodium hydroxide at 25°C and 1 bar is introduced to react with hydrogen chloride
and produces sodium chloride. All the effluent goes with stream 17 which is sent to a
liquid decanter to remove diluted sodium chloride from the organic materials. The
overheads stream from the decanter is sent to a fractionation unit to separate unreacted
benzene and water from the products.
58
Table 4:5 MASS BALANCE AROUND NEUTRALIZER
Component/ IN OUT
Stream 13 14 17
Benzene 66.30 0.00 66.30
Chlorine 0.00 0.00 0.00
mCB 21.95 0.00 21.95
dCB 1.99 0.00 1.99
HCl 0.92 0.00 0.00
H2O 0.00 190.00 190.92
NaOH 0.00 10.00 9.08
NaCl 0.00 0.00 0.92
SUM 91.16 200.00 291.16
Total 291.16 291.16
4.3.2.3 DECANTER/SEPARATOR
A simple diagram of the Decanting Unit is shown in Figure 4.3
Figure 4:5 DECANTING UNIT
59
This unit separates the aqueous phase from the organic phase. The target of this process
is to separate NaCl solution from the product stream by using a liquid-liquid separator.
The following assumption were applied:
i. 0.90 fraction of water leaves with stream 19
ii. The pressure inside the vessel is 1 atm
iii. NaCl is completely removed from the product stream
The Stream results of inlet and outlet of the units are as presented on Table 4.6
4.3.2.4 THE FIRST DISTILLATION COLUMN (BZ-CLM)
The first distillation column in the flow process diagram of CB production is to separate
our product (mono-chlorobenzene & di-chlorobenzene) from other components
(unreacted benzene, chlorine, water & little amount of mCB and dCB). The following
assumptions were applied:
Table 4:6 MASS BALANCE AROUND THE DECANTER
Component/ IN OUT
Stream 17 18 19
Benzene 66.30 66.30 0.00
Chlorine 0.00 0.00 0.00
mCB 21.95 21.95 0.00
dCB 1.99 1.99 0.00
HCl 0.00 0.00 0.00
H2O 190.92 19.09 171.82
NaOH 9.08 0.00 9.08
NaCl 0.92 0.00 0.92
SUM 291.16 109.34 181.82
Total 291.16 291.16
i. Total condenser
ii. Partial reboilers
iii. Reflux ratio equal to 2
60
iv. Operating at 1.5 bar
The equations for overall and component mass balance are:
𝐹 = 𝐷 + 𝐵
𝐹𝑧 = 𝐷𝑥𝐷 + 𝐵𝑥𝐵
Overall mass balance:
Feed = 109.34 kmol/hr Distillate = 85.42 kmol/hr Bottom = 23.92 kmol/hr
Feed = Distillate + Bottom =109.34 kmol/hr
Figure 4:6 FIRST DISTILLATION COLUMN -BENZENE COLUMN
The overall and component mass balance are summarized in Table 4.7.
Table 4:7 FIRST DISTILLATION COLUMN MASS BALANCE
CALCULATIONS
Component/ IN OUT
Stream 18B 20 21
Benzene 66.30 66.30 0.00
Chlorine 0.00 0.00 0.00
mCB 21.95 0.02 21.93
dCB 1.99 0.00 1.99
HCl 0.00 0.00 0.00
H2O 19.09 19.09 0.00

NaOH 0.00 0.00 0.00
61
NaCl 0.00 0.00 0.00
SUM 109.34 85.42 23.92
Total 109.34 109.34

4.3.2.5 THE SECOND DISTILLATION COLUMN (CB-CLM)
A simple diagram of the second distillation column is shown below.
Figure 4:7 SECOND DISTILLATION COLUMN (CB-COLUMN)
The second distillation column in the flow process diagram is designed to separate the
desired product from the undesired product. The overhead stream which is the desired
product contains 99.7 wt% of mono-chlorobenzene. The bottoms stream contains
dichlorobenzene, which is the undesired product. The following assumptions were
applied when mass balance was performed around the second distillation column,
which are:
i. The feed contains 99.9 % mCB and dCB.
ii. Total condenser
iii. Partial reboiler
iv. Reflux ratio equal to 2
v. Operating at 1.5 bar
The equations for overall and component mass balance are:
𝐹 = 𝐷 + 𝐵
62
𝐹𝑧 = 𝐷𝑥𝐷 + 𝐵𝑥𝐵
Overall mass balance:
Feed = 23.92 kmol/hr Distillate = 21.95 kmol/hr Bottom = 1.97 kmol/hr
Feed = Distillate + Bottom = 23.92 kmol/hr
The overall and component mass balance are summarized in Table 4.8.
Table 4:8 SECOND DISTILLATION COLUMN MASS BALANCE
CALCULATIONS
Component/ IN OUT
Stream 21 22 23
Benzene 0.00 0.00 0.00
Chlorine 0.00 0.00 0.00
mCB 21.93 21.91 0.02
dCB 1.99 0.04 1.94
HCl 0.00 0.00 0.00
H2O 0.00 0.00 0.00
NaOH 0.00 0.00 0.00
NaCl 0.00 0.00 0.00
SUM 23.92 21.95 1.97
Total 23.92 23.92
63
4.3.2.6 DRYING COLUMN (DRYER)
A simple diagram of the vessel is shown below.
Figure 4:8 BENZENE DRYING COLUMN
The mass balance around the vessel is summarized in Table 4.9.
Table 4:9 MASS BALANCE AROUND DRYING COLUMN
Component/ IN OUT IN OUT
Stream Without Recycle With Recycle
26 25 26 26R 25R 6R
Benzene 100.00 0.00 100.00 166.30 0.00 166.30
Chlorine 0.00 0.00 0.00 0.00 0.00 0.00
mCB 0.00 0.00 0.00 0.02 0.02 0.00
dCB 0.00 0.00 0.00 0.00 0.00 0.00
HCl 0.00 0.00 0.00 0.00 0.00 0.00
H2O 0.00 0.00 0.00 19.09 19.09 0.00
NaOH 0.00 0.00 0.00 0.00 0.00 0.00
NaCl 0.00 0.00 0.00 0.00 0.00 0.00
SUM 100.00 0.00 100.00 185.42 19.12 166.30
Total 100.00 100.00 185.42 185.42
64
4.3.2.7 MIXER (M 101)
A simple diagram of the vessel is shown below.
Figure 4:9 M-101
A mixture is introduced to combine the recycled benzene with the fresh feed. The
equation for the mass balance is:
𝑅𝑒𝑐𝑦𝑐𝑙𝑒 + 𝐹𝑟𝑒𝑠ℎ 𝑓𝑒𝑒𝑑 = 𝑇𝑜𝑡𝑎𝑙 𝑓𝑒𝑒𝑑
The following table summarize the mass balance around the mixture:
N.B:
A summary of all Mass Balance Calculation for the Streams is as shown on Table 4.11
65
Table 4:10 MASS BALANCE AROUND M-101
Component/ IN OUT
Stream 2 S1(Recycle) 26
Benzene 100.00 66.30 166.30
Chlorine 0.00 0.00 0.00
mCB 0.00 0.00 0.02
dCB 0.00 0.00 0.00
HCl 0.00 0.00 0.00
H2O 0.00 19.09 19.09
NaOH 0.00 0.00 0.00
NaCl 0.00 0.00 0.00
SUM 100.00 85.42 185.42
Total 185.42 185.42
66
Table 4:11 MASS BALANCE CALCULATIONS FOR STREAMS
Streams 2 6 4 7 1 3 5 16 13 14 15 17 19 18 18B 20 21 22 23 S1 26 25 26R
T (°C) 20 19.85 19.89 55 20 85.31 55 55 55 20 55 55 55 55 80.5 93.64 144.2 144.5 185.8 24.85 19.85 19.85
Benzene 100.00 100.00 100.00 100.00 - - - 9.25 66.30 - - 66.30 - 66.30 66.30 66.30 - - - 66.30 100.00 - 166.30
Chlorine - - - - 26.45 26.45 26.45 - - - - - - - - - - - - - - - -
mCB - - - - - - - 0.50 21.95 - - 21.95 - 21.95 21.95 0.02 21.93 21.91 0.02 0.02 - - 0.02
dCB - - - - - - - 0.01 1.99 - - 1.99 - 1.99 1.99 - 1.99 0.04 1.94 0.00 - - -
HCl - - - - - - - 25.53 0.92 - - - - - - - - - - - - - -
H2O - - - - - - - - - 190.00 - 190.92 171.82 19.09 19.09 19.09 - - - 19.09 - 19.09 -
NaOH - - - - - - - - - 10.00 - 9.08 9.08 - - - - - - - - - -
NaCl - - - - - - - - - - - 0.92 0.92 - - - - - - - - - -
Total 100.00 100.00 100.00 100.00 26.45 26.45 26.45 35.29 91.16 200.00 - 291.16 181.82 109.34 109.34 85.42 23.92 21.95 1.97 85.42 100.00 19.09 166.32
Composition
Streams 2 6 4 7 1 3 5 16 13 14 15 17 19 18 18B 20 21 22 23 S1 26 25 26R
Benzene 1.000 1.000 1.000 1.000 0.000 0.000 0.000 0.262 0.727 0.000 - 0.228 0.000 0.606 0.606 0.776 0.000 0.000 0.000 0.776 1.000 0.000 0.897
Chlorine 0.000 0.000 0.000 0.000 1.000 1.000 1.000 0.000 0.000 0.000 - 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
mCB 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.014 0.241 0.000 - 0.075 0.000 0.201 0.201 0.000 0.917 0.998 0.011 0.000 0.000 0.000 0.000
dCB 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.022 0.000 - 0.007 0.000 0.018 0.018 0.000 0.083 0.002 0.989 0.000 0.000 0.000 0.000
HCl 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.724 0.010 0.000 - 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
H2O 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.950 - 0.656 0.945 0.175 0.175 0.224 0.000 0.000 0.000 0.224 0.000 1.000 0.103
NaOH 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.050 - 0.031 0.050 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
NaCl 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 - 0.003 0.005 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Total 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 - 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000
67
4.4 ENERGY BALANCE
In this section, energy balance was calculated around each equipment in this process,
which includes:
i. Two continuous stirred tank reactors
ii. A Neutralizer/Washer
iii. Two distillation columns
iv. Four heat exchangers
v. Two Vessels (Decanter and Dryer)
vi. A compressor
vii. A pump
4.4.1 ENTHALPIES CALCULATION
The enthalpy of each stream is required in order to complete the energy balance
calculation around each equipment. These enthalpies were calculated from the
integration of heat capacity equation, and the used heat capacity parameters are listed
on Table 4.12 and Table 4.13.
The enthalpy was calculated using:
𝐻 = ∫ 𝐶𝑝 𝑑𝑇
𝑇𝑅
Where, 𝑇𝑅 = 298 K
Enthalpies for each stream depending on its temperature were calculated.
68
TABLE 4:12 HEAT CAPACITY PARAMETERS
Product C1 C2 C3 C4 C5
Benzene 162940 -344.94 0.856 0.0000 0.00
Chlorine 63936 46.35 -0.162 0.0000 0.00
mCB -1307500 15338.00 -53.974 0.0635 0.00
dCB 133950 -24.84 0.482 0.0000 0.00
HCl 47300 90.00 0.000 0.0000 0.00
H2O 276370 -2090.10 8.125 -0.0141 9.37E-06
For these data, the following equation applies:
𝐶𝑝 = 𝐶1 + 𝐶2 𝑇 + 𝐶3 𝑇 2 + 𝐶4 𝑇 3 + 𝐶5 𝑇 4
Where, 𝑇 in kelvins (K) 𝐶𝑝 in J/(kmol.K)
Table 4:13 HEAT CAPACITY PARAMETERS
Product A B D
NaOH 0.121 0.01632 194800
NaCl 5.526 0.00196 0
For these data, the following equation applies:
𝐶𝑝 = 𝑅(𝐴 + 𝐵 𝑇 + 𝐷 𝑇 −2 )
Where,
𝑇 in kelvins (K)
𝑅 = 8.314 kJ/(kmol.K)
𝐶𝑝 in kJ/(kmol.K)
Also, the Energy of each stream is calculated as: ∑ 𝑭𝒊 𝑯𝒊
69
The resulting enthalpies and energies for the streams are as shown on Table 4.14.
4.4.2 ENERGY BALANCE ABOUT UNIT OPERATIONS AND EQUIPMENT
The energy balance for basic units and processes are as follows:
4.4.2.1 REACTOR SYSTEM TWO CSTRS IN SERIES
The CSTRs are operated at a temperature of 328 K (55℃) and a pressure of 2.4 bar.
The following assumptions are made:
i. Ideal CSTR
ii. Isothermal reactor
iii. No pressure drop
iv. Steady state
The duty of the reactor system is calculated from the following equation:
̂𝑟 + ∑ 𝐹𝑜𝑢𝑡 𝛥𝐻
𝑄 = ∑ 𝜉𝑗 𝛥𝐻 ̂𝑜𝑢𝑡 − ∑ 𝐹𝑖𝑛 𝛥𝐻𝑖𝑛
𝑗°
70
Table 4:14 ENTHALPIES CALCULATIONS (ENTHALPIES (KJ/KMOL))
Enthalpies (kJ/kmol)
Stream 2 6 4 7 1 3 5 16 13 14 15 17 19 18 18B 20 21 22 23 S1 26 25 26R V1 V2
T (°C) 20 19.85 19.89 55 20 85.31 55 55 55 20 55 55 55 55 80.5 93.64 144.2 144.5 185.8 24.85 19.85 19.85 0 80.94 148.2
T (K) 293 292.85 292.89 328 293 358.31 328 328 328 293 328 328 328 328 353.5 366.64 417.2 417.5 458.8 297.85 292.85 292.85 273 353.94 421.2
Benzene -679 -699 -694 4166 -679 8573 4166 4166 4166 -679 4166 4166 4166 4166 7858 9825 17882 17932 25209 -20 -699 -699 -3356 7923 18557
Chlorine -317 -327 -324 295 -317 3251 295 - - - - - - - - - - - - - - - - 3455 7319
mCB -750 -772 -766 4578 -750 9615 4578 4578 4578 -750 4578 4578 4578 4578 8766 11149 23249 23342 39662 -23 -772 -772 -3735 8843 24505
dCB -843 -869 -862 5203 -843 10726 5203 5203 5203 -843 5203 5203 5203 5203 9830 12294 22322 22384 31290 -25 -869 -869 -4154 9912 23155
HCl -369 -381 -378 2264 -369 4634 2264 2264 2264 -369 2264 2264 2264 2264 4252 5300 9474 9500 13082 -11 -381 -381 -1825 4287 9815
H2O -377 -388 -385 2258 -377 4545 2258 2258 2258 -377 2258 2258 2258 2258 4181 5176 9047 9070 12309 -11 -388 -388 -1893 4214 9357
NaOH -298 -307 -305 1801 -298 3660 1801 1801 1801 -298 1801 1801 1801 1801 3362 4181 7455 7475 10320 -9 -307 -307 -1491 3389 7723
NaCl -254 -261 -259 1532 -254 3094 1532 1532 1532 -254 1532 1532 1532 1532 2845 3526 6172 6188 8381 -8 -261 -261 -1265 2868 6383
TOTAL -3888 -4004 -3973 22096 -3888 48097 22096 21801 21801 -3570 21801 21801 21801 21801 41094 51450 95602 95891 140253 -107 -3677 -3677 -17719 44891 106814
FiHi (kJ/h)
Stream 2 6 4 7 1 3 5 16 13 14 15 17 19 18 18B 20 21 22 23 S1 26 25 26R
T (°C) 20 19.85 19.89 55 20 85.31 55 55 55 20 55 55 55 55 80.5 93.64 144.2 144.5 185.8 24.85 19.85 19.85 19.85
Benzene -67862 -69892 -69351 416587 - - - 38517 276214 - - 276214 - 276214 521026 651433 - - - -1354 -69892 - -558141
Chlorine - - - - -8393 85989 7803 - - - - - - - - - - - - - - - -
mCB - - - - - - - 2289 100486 - - 100486 - 100486 192420 245 509813 511324 870 - - - -82
dCB - - - - - - - 50 10356 - - 10356 - 10356 19567 24 44387 981 60849 - - - -8
HCl - - - - - - - 57813 2072 - - - - - - - - - - - - - -
H2O - - - - - - - - - -71660 - 431115 388003 43111 79823 98819 - - - -216 - -7416 -36134
NaOH - - - - - - - - - -2982 - 16362 16362 - - - - - - - - - -
NaCl - - - - - - - - - - - 1402 1402 - - - - - - - - - -
∑ FiHi -67862 -69892 -69351 416587 -8393 85989 7803 98669 389129 -74642 - 835935 405767 430168 812835 750522 554200 512305 61719 -1570 -69892 -7416 -594366
71
Where,
𝑄̇: =𝐷𝑢𝑡𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝜉: = 𝑒𝑥𝑡𝑒𝑛𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
̂𝑟 : = ℎ𝑒𝑎𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝛥𝐻 𝑗°
𝐹: = 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒
∆𝐻̂: = 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦
The extent of reaction and heat of reaction values are summarized in Table 4.15
Table 4:15 EXTENT OF REACTION AND HEAT OF FORMATION
𝝃 (kmol/h) 𝚫𝑯̂ °𝒓 (kJ/kmol)
1st reaction 22.45 -123467
2nd reaction 2.00 -118527
The molar flow rates multiplied by the enthalpies are shown below:
4.4.2.2 NEUTRALIZER/WASHER
The Neutralizer reactor is operated at a temperature of 328 K. The following
assumptions are made:
i. Ideal Reactor
ii. Isothermal reactor
iii. No pressure drop
iv. Steady state
The duty of the reactor is calculated from the following equation:

TABLE 4:16 THE ENTHALPY VALUES FOR EACH STREAM IN KJ/H
Stream 5 7 16 13
T (K) 328 328 328 328
Benzene - 416587 38517 276214
Chlorine 7803 - - -
mCB - - 2289 100486
dCB - - 50 10356
HCl - - 57813 2072
H2O - - - -
NaOH - - - -
NaCl - - - -
∑ FiHi 7803 416587 98669 389129
Table 4:17 REACTOR ENERGY BALANCE
REACTOR SYSTEM (CSTR-1 and CSTR-2)
T in (C) 55
T out (C) 55
P (bar) 2.4
Q (kJ/h) -3192414
73
̂𝑟 + ∑ 𝐹𝑜𝑢𝑡 𝛥𝐻
𝑄 = ∑ 𝜉𝑗 𝛥𝐻 ̂𝑜𝑢𝑡 − ∑ 𝐹𝑖𝑛 𝛥𝐻𝑖𝑛
𝑗°
The extent of reaction and heat of reaction values are summarized in Table 4.18
Table 4:18 EXTENT OF REACTION AND HEAT OF FORMATION
𝝃 (kmol/h) 𝚫𝑯̂ °𝒓 (kJ/kmol)
1st reaction 0.92 -133920
Table 4:19 THE ENTHALPY VALUES FOR EACH STREAM IN KJ/H
Stream 13 14 17
T (K) 328 328 328
Benzene 276214 - 276214
Chlorine - - -
mCB 100486 - 100486
dCB 10356 - 10356
HCl 2072 - -
H2O - -71660 431115
NaOH - -2982 16362
NaCl - - 1402
∑ FiHi 389129 -74642 835935
74
Table 4:20 REACTOR ENERGY BALANCE
WASHER/NEUTRALIZER
T in (C) 55
T out (C) 55
P (bar) 1.0
Q (kJ/h) 398863
4.4.2.3 COMPRESSOR (COMP-1)
A compressor is used to compress the chlorine gas coming from the storing cylinder to
be fed into the reactor. This compressor increased the pressure of the stream from 1 bar
to 2.4 bar, and due to this, the temperature is also increased. Using ASPEN Plus
simulation, the increase in temperature was found to be from 20°C to 85.31°C. The
high increase in temperature can be explained by knowing that chlorine is one of the
lightest gases. The energy balance was calculated using these equations:
̂𝑜𝑢𝑡 − ∑ 𝐹𝑖𝑛 𝛥𝐻𝑖𝑛

𝑄 = ∑ 𝐹𝑜𝑢𝑡 𝛥𝐻
𝑄
𝑊=
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦
75
Stream 1 3
T (°C) 20 85.31
Benzene - -
Chlorine -8393 85989
mCB - -
dCB - -
HCl - -
H2O - -
NaOH - -
NaCl - -
∑ FiHi -8393 85989
Table 4:22 DUTY OF COMPRESSOR
Duty of Compressor COMP-1

F (kmol/h) 26.45
Q (kJ/h) 94382
Q (kW) 26.2
efficiency (assumed) 0.75
W (kW) 34.93
4.4.2.4 PUMP (BZ-PUMP)
The pump is used to create a different in the pressure causing benzene to flow to the
reactor at a pressure of 2.4 bar. Energy balance around the pump was calculated using
these equations:

𝑄
𝑊=
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦
76
Stream 6 4
T (°C) 19.85 19.89
Benzene -69892 -69351
Chlorine - -
mCB - -
dCB - -
HCl - -
H2O - -
NaOH - -
NaCl - -
∑ FiHi -69892 -69351
Table 4:24 DUTY OF PUMP
Duty of BZ-PUMP
F (kmol/h) 100.00
Q (kJ/h) 541
Q (kW) 0
efficiency (assumed) 0.75
W (kW) 0
4.4.2.5 HEAT EXCHANGER (HX-1)
The duty of the heat exchanger HX-1 is to heat up the Benzene temperature from about
20oC to 55°C before entering the reactor system. Energy balance obtained using this
equation:

77
Stream 4 7
T (°C) 19.89 55
Benzene -69351 416587
Chlorine - -
mCB - -
dCB - -
HCl - -
H2O - -
NaOH - -
NaCl - -
∑ FiHi -69351 416587
Table 4:26 DUTY OF HEAT EXCHANGER
Duty of HX-1 1
F (kmol/h) 100.00
Q (kJ/h) 485938
Q (kW) 135
The duty of the heat exchanger HX-2 is to cool the Chlorine temperature from 85.31◦C
to 55◦C before entering the reactors (CSTRs). Energy balance obtained using the last
equation.
78
Stream 3 5
T (°C) 85.31 55
Benzene - -
Chlorine 85989 7803
mCB - -
dCB - -
HCl - -
H2O - -
NaOH - -
NaCl - -
∑ FiHi 85989 7803

Table 4:28 Duty of Heat Exchanger
Duty of HX-2 2
F (kmol/h) 26.45
Q (kJ/h) -78186
Q (kW) -21.7
The duty of the heat exchanger HX-4 is to cool the top products from distillation tower
BZ-CLM temperature from 93.64°C to 24.85°C before entering Drying Column,
DRYER.
79
Stream 20 S1
T (°C) 93.64 24.85
Benzene 651433 -1354
Chlorine - -
mCB 245 -
dCB 24 -
HCl - -
H2O 98819 -216
NaOH - -
NaCl - -
∑ FiHi 750522 -1570
Duty of HX-4 4
F (kmol/h) 85.42
Q (kJ/h) -752092
Q (kW) -209
The duty of the heat exchanger HX-3 is to heat up the top products from Decanter to
the saturation temperature, which is 80.5°C (the saturation Temp, Tsat is that of Benzene
at a pressure of 1 bar since the stream 18 has a pressure of about 1 atm). Energy balance
obtained using this equation:

80
Stream 18 18B
T (°C) 55 80.5
Benzene 276214 521026
Chlorine - -
mCB 100486 192420
dCB 10356 19567
HCl - -
H2O 43111 79823
NaOH - -
NaCl - -
∑ FiHi 430168 812835
Duty of HX-3 3
F (kmol/h) 109.34
Q (kJ/h) 382668
Q (kW) 106
81
4.4.2.9 FIRST DISTILLATION COLUMN, BENZENE COLUMN (BZ-CLM)
The first distillation column is used to separate unreacted materials (most especially
Benzene) and water from the products, mono- and dichlorobenzene, which will further
be separated in another distillation column. For BZ-CLM, these assumptions have been
made:
i. Operating at 1.5 bar.
ii. The reflux ratio is 2.
iii. The feed is a saturated liquid.
The equations used for the energy balance around the condenser and the distillation
column to find the duty of the condenser and reboiler are:
𝐿
𝑄𝐶 = (1 + ) ∙ 𝐷 ∙ (𝐻𝐷 − 𝐻𝑉 )
𝐷
𝑄𝑅 = 𝐷 ∙ 𝐻𝐷 + 𝐵 ∙ 𝐻𝐵 − 𝐹 ∙ 𝐻𝐹 − 𝑄𝐶 = 𝑄 − 𝑄𝐶
𝐿
Other equations used are: Reflux ratio = 𝐷
𝐿 + 𝐷 = 𝑉 (about the Condenser)
The calculations of the enthalpies around the first distillation column are summarized
in Table 4.33 and Table 4.34, while the results are shown in Table 4.35.
4.4.2.10 SECOND DISTILLATION COLUMN, BENZENE COLUMN
(CB-CLM)
The second distillation column is used to separate mono-chlorobenzene(mCB) from
dichlorobenzene (dCB). For CB-CLM, these assumptions have been made:
i. Operating at 1.5 bar.
ii. The reflux ratio is 2.
iii. The feed is a saturated liquid.
82
The calculations of the enthalpies around the second distillation column are
summarized in Table 4.36 and Table 4.37, while the results are shown in Table 4.38.
83
Table 4:33 PARAMETERS FOR THE FIRST DISTILLATION COLUMN (BZ-CLM)
V D B F
Flowrate Mole Enthalpy Flowrate Mole Enthalpy Flowrate Mole Enthalpy Flowrate Mole Enthalpy
(kmol/h) Frac. (kJ/kmol) (kmol/h) Frac. (kJ/kmol) (kmol/h) Frac. (kJ/kmol) (kmol/h) Frac. (kJ/kmol)
198.91 0.776 6042 66.30 0.776 7626 0.00 0.000 0 66.30 0.606 4765
Benzene
0.00 0.000 0 0.00 0.000 - 0.00 0.000 - 0.00 0.000 -

Chlorine
0.07 0.000 2 0.02 0.000 3 21.93 0.917 21316 21.95 0.201 1760
mCB
0.01 0.000 0 0.00 0.000 0 1.99 0.083 1856 1.99 0.018 179
dCB
0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0

HCl
57.27 0.224 926 19.09 0.224 1157 0.00 0.000 0 19.09 0.175 730
H2O
0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0

NaOH
0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0

NaCl
256.26 1.00 6971 85.42 1.000 8786 23.92 1.000 23172 109.34 1.000 7434
Total
Table 4:34 PARAMETERS FOR THE CALCULATIONS OF QC AND QR
V D B F
Flowrate (kmol/h) 256.26 85.42 23.92 109.34
Enthalpy (kJ/kmol) 6971 8786 23172 7434
Table 4:35 RESULTS FOR BZ-COLUMN
Value Unit
QC -7745698 kJ/h
QR 8237584 kJ/h
Table 4:36 PARAMETERS FOR THE SECOND DISTILLATION COLUMN (CB-CLM)
V D B F
Flowrate Mole Enthalpy Flowrate Mole Enthalpy Flowrate Mole Enthalpy Flowrate Mole Enthalpy
(kmol/h) Frac. (kJ/kmol) (kmol/h) Frac. (kJ/kmol) (kmol/h) Frac. (kJ/kmol) (kmol/h) Frac. (kJ/kmol)
Benzene 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0
Chlorine 0.00 0.000 0 0.00 0.000 - 0.00 0.000 - 0.00 0.000 -
mCB 65.78 0.917 22341 21.91 0.998 23295 0.02 0.011 442 21.93 0.917 21316
dCB 5.97 0.083 1918 0.04 0.002 45 1.94 0.989 30941 1.99 0.083 1856
HCl 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0
H2O 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0
NaOH 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0
NaCl 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0 0.00 0.000 0
Total 71.75 1.00 24259 21.95 1.00 23340 1.97 1.00 31384 23.92 1.00 23172
Table 4:37 PARAMETERS FOR THE CALCULATIONS OF QC AND QR
V D B F
Flowrate (kmol/h) 65.85 21.95 1.97 23.92
Enthalpy (kJ/kmol) 24259 23340 31384 23172
Table 4:38 RESULTS FOR CB-CLM
Value Unit
QC -2395165 kJ/h
QR 2414989 kJ/h
85
4.4.2.11 BALANCE ABOUT DRYER, MIXER AND DECANTER
In each one of the separation processes and the mixer used in this process, the energy balance
was calculated using the following equation:

Units M-101 DRYER DECANTER
OUT IN IN OUT IN OUT
Streams
26R S1(R) 2 26R 25 6 17 18 19
T(oC) 19.85 24.85 20 19.85 19.85 19.85 55 55 55
Benzene -558141 -1354 -67862 -558141 - -69892 276214 276214 -
Chlorine - - - - - - - - -
mCB -82 - - -82 - - 100486 100486 -
dCB -8 - - -8 - - 10356 10356 -
HCl - - - - - - - - -
H2O -36134 -216 - -36134 -7416 - 431115 43111 388003
NaOH - - - - - - 16362 - 16362
NaCl - - - - - - 1402 - 1402
PRESUM -594366 -1570 -67862 -594366 -7416 -69892 835935 430168 405767
TOTALS -594366 -69432 -594366 -77308 835935 835935
Table 4:40 DUTIES OF VESSELS AND MIXTURE
Equipment Q (kJ/h) Q (kW)

DRYER -531890 -148
DECANTER 0 0
MIXER 67862 19
4.4.3 SUMMARY OF THE DUTIES AROUND EACH EQUIPMENT
The duty of each equipment included in the process of chlorobenzene production is
summarized in Table 4.41
86
Table 4:41 DUTIES SUMMARY OF THE EQUIPMENT
Equipment Q (kJ/h) Q (kW)

CSTRS -3192414 -887
WASHER 398863 111
DECANTER 0 0
DRYER -75738 -21
DRYER-R -531890 -148
BZ-CLM 1133189 315
CB-CLM 315983 88
HX-1 485938 135
HX-2 -78186 -22
HX-3 382668 106
HX-4 -752092 -209
M-101 67862 19
BZ-PUMP 541 0
COMP-1 94382 26
It should be noted that these calculations were almost mainly based on the process flow diagram
as developed from the process statement that was provided with the problem statement
87
CHAPTER FIVE
EQUIPMENT DESIGN AND SIZING
The equipment used in the chemical industries can be generally divided into two classes which
are proprietary and nonproprietary. Proprietary equipment, such as pumps, compressors, filters,
centrifuges and dryers, is designed and manufactured by specialist firms. Nonproprietary
equipment is designed as special, one-off items for particular processes, for example, reactors,
distillation columns, and heat exchangers.
A chemical engineer is usually involved in the design of proprietary equipment because they
are usually designed as special items for projects.
For the chlorobenzene plant, focus will be placed on the design of the reactors, distillation
columns as well as other columns (drying and adsorption).
5.1 REACTORS
The reactor is the heart of a chemical process. It is the only place in the process where raw
materials are converted into products, and reactor design is a vital step in the overall design of
the process (Sinnot,2005).
The design of an industrial chemical reactor must satisfy the following requirements:
1. The chemical factors: The reaction kinetics and the design must have a sufficient residence
time for the desired reaction to proceed to the required degree of conversion.
2. The mass transfer factors: heterogeneous reactions rate may be controlled by the rates of
diffusion of the reacting species and not the chemical kinetics.
3. The heat transfer factors: The removal, or addition, of the heat of reaction.
4. The safety factors: The control of hazardous reactants and products, and the reaction and
lastly the process conditions.
88
However, one of the factors will be a major criterion to determine the choice of reactor type
and the design method.
5.1.1 PRINCIPAL TYPES OF REACTOR
The following characteristics are normally used to classify reactor designs:
1. Mode of operation: batch or continuous.
2. Phases present: homogeneous or heterogeneous.
3. Reactor geometry: flow pattern and manner of contacting the phases:
i. Stirred tank reactor;
ii. Tubular reactor;
iii. Packed bed, fixed and moving;
iv. Fluidized bed.
For this process, the stirred tank reactors (CSTR) is used.
5.1.1.1 STIRRED TANK REACTOR
In the plant, there is a reactor system that consists of two continuous stirred tanks operating in
series at a pressure of 2.4 bar and a temperature of 328 K (550c). Liquid benzene as well as
gaseous chlorine is fed into the tank. Continuous stirred tank reactors are used in order to ensure
proper mixing of the reagents while the reactor effluent is removed. The reactors are operated
in series so as to improve their conversion as well as their performance. Stirred tank reactors
are particularly suitable for reactions where good mass transfer or heat transfer is required.
Since it is operated in a continuous process, the composition in the reactor is constant and the
same as the product stream, and, except for very rapid reactions. Reactors depends on capital
investment of;
i. Volume of the reactor
ii. Operating condition
89
iii. Materials of construction
The catalyst used is ferric chloride and mild steel is used as material of construction.
5.1.1.2 REACTOR SIZING AND DESIGN CONDITION
To determine the total feed stream going into the reactor, we sum up the component feed flow:
100 + 66.3 + 26.45 = 192.75 kmols/hr
Assuming a Feed molar volume of 0.10m3/kmol,
The Feed stream volumetric flowrate = (0.1 × 192.75) m3/hr
= 19.275 m3/hr.
Assuming a maximum conversion of 99%, the volume (V) required to achieve this conversion
in the CSTR is;
𝐹 ∗𝑋
V = (−𝑟𝐴𝑂)𝑒𝑥𝑖𝑡
𝐵
Where FAO = Feed stream volumetric flowrate
X = conversion
-rB = rate of disappearance of reactant.
1∗19.275
V =1∗10−4 ∗3600m3
= 53.54 m3
Residence time;
The residence of the reactor can be calculated using the formula;
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
Residence time = 𝑓𝑒𝑒𝑑 𝑠𝑡𝑟𝑒𝑎𝑚 𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒
90
53.54
= 19.275hrs
= 2.7 hours
The reactors have equal residence time and can also be assumed to have the same volume
By design heuristics, design temperature and pressure of a reactor should be 10 % excess of
the operating temperature and pressure. Since the operating condition of the reactor is
550C and 2.4bar, then,
Design temperature = 1.1 x550C = 60.50C
Design pressure = 1.1x 2.4 bar = 2.64 bar
Dimension of the CSTRs
Based on an assumption that each reactor is half full of liquid (half-filled), the reactor volume
will be;
27.53
V= m3
0.5
=55.00 m3
Assuming that the reactor is Cylindrical Shaped and it’s in a vertical position;
The volume of the reactor can be calculated with the formula;
𝜋𝐷 2 𝐻
=
4
Where D= diameter of cylinder
L = length of the cylindrical part of the reactor
The height of a reactor can be said to be three times its radius.
Hence, the Volume of the reactor (V) is
91
3𝜋𝐷 3
55.0 m3 = 8
D = 3.60m
3∗3.6
The Height of the cylinder = 𝑚= 5.40m
2
5.2 BENZENE COLUMN SIZING AND DESIGN CONDITION
The total feed input the Benzene column is 109.34 kmol/hr. The feed specification is 66.30
kmol/hr Benzene, 21.95 kmol/hr monochlorobenzene, 19.09 kmol/hr water and 1.99 kmol/hr
dichlorobenzene at a temperature of 134.5 0C and 1.013 bar.
The separation is easy, so a fairly small column is required. A tray distillation column is used
in this case and it utilizes pressure and temperature differential to separate the products. A 10-
stage distillation column that utilizes sieve trays is used for the separation.
To Calculate the volume of the distillation column, the volumetric flow rate of each product
going into the column has to be determined using the formula;
𝑘𝑔
𝑚𝑎𝑠𝑠 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 ( )
ℎ𝑟
Volumetric flowrate = 𝑘𝑔
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 ( 3 )
𝑚
Calculations for the volumetric flowrate is shown below;
Molar mass of benzene = 78.11 kg/kmol
Mass flow rate of benzene = 78.11 kg/kmol x 66.30 kmol/hr = 5178.69 kg/hr
Density of benzene = 876 kg/m3, hence,
5178.69
Volumetric flowrate of benzene = m3/hr = 5.912 m3/hr
876
Molar mass of water = 18.015 kg/kmol
Mass flow rate of water = 18.015 kg/kmol x 19.09 kmol/hr = 343.91 kg/hr
Density of water = 1000 kg/m3, hence,
92
343.91
Volumetric flowrate of water = m3/hr = 0.344 m3/hr
1000
Molar mass of monochlorobenzene = 112.56 kg/kmol
Mass flow rate of monochlorobenzene = 112.56 kg/kmol x 21.95 kmol/hr = 2470.69 kg/hr
Density of monochlorobenzene = 1110 kg/m3, hence,
2470.69
Volumetric flowrate of monochlorobenzene = m3/hr = 2.226 m3/hr
1110
Molar mass of dichlorobenzene = 147.01 kg/kmol
Mass flow rate of dichlorobenzene = 147.01 kg/kmol x 1.99 kmol/hr = 292.55 kg/hr
Density of dichlorobenzene = 1300 kg/m3, hence,
292.55
Volumetric flowrate of dichlorobenzene = m3/hr = 0.225 m3/hr
1300
Total Volumetric flowrate = (5.912+2.226+0.344+0.225) m3/hr = 8.707 m3/hr
The residence time is taken to be 60 minutes
Total stream volume in the Benzene column = 8.707 x 1= 8.707 m3.
For distillation column sizing, the vessel volume is calculated when it is half full which is;
8.707
= = 17.41 m3
0.5
Assuming the Benzene column is a vertical cylindrical vessel.
𝜋𝐷 2 𝐻
Volume = 4
According to Walas (1990), the H/D ratio of a distillation and absorption column should be
less than 30. For this column, the H/D ratio is taken to 12.
Therefore, H = 4D
93
4𝜋𝐷 3
17.41 m3 = D = 1.77 m
4
The height of the cylinder (H) = 1.77 x4 = 7.08 m
Table 27 shows the volumetric flowrate of feed entering the Benzene column
Table 5:1 VOLUMETRIC FLOW RATE OF THE FEED INTO THE BENZENE
COLUMN.
COMPONENT MOLAR MOLECULA MASS DENSIT VOLUMETRI
FLOW R MASS FLOWRAT Y C FLOW RATE
RATE (kg/kmol) E (kg/hr)

(kg/m3) (m3/hr)
(kmol/hr
Benzene 66.30 78.110 5178.69 876.00 5.912
Water 19.09 18.015 343.91 1000.00 0.344
Monochlorobenzen 21.95 112.560 2470.692 1110.00 2.226
Dichlorobenzene 1.99 147.01 292.55 1300.00 0.225
Total 8.707
94
Design Temperature and Pressure: As earlier stated, the design temperature and pressure of
a benzene column would also be 10 % excess of the operating temperature and pressure.
Therefore,
Design temperature = 1.1 x134.50C = 147.950C
5.3 CHLOROBENZENE COLUMN SIZING AND DESIGN CONDITION
The total feed input the chlorobenzene column is 23.92 kmol/hr. The feed into the column
contains 21.93 kmol/hr monochlorobenzene and 1.99 kmol/hr dichlorobenzene at 134.5 0C and
1.013 bar.
A tray distillation column is also used as the chlorobenzenze column with 10 stages in this
case. The separation of these two components in the feed stream is relatively difficult because
they are organic solvents and soluble in each other, so a longer residence time will be needed
in the distillation column for good separation of monochlorobenzene and dichlorobenzene.
To determine the volume of the chlorobenzene column, the volumetric flow rate of each
product going into the column has to be determined using the formula;
𝑘𝑔
ℎ𝑟
𝑚
2468.44
Volumetric flowrate of monochlorobenzene = m3/hr = 2.224 m3/hr
1110
Molar mass of dichlorobenzene = 147.01 kg/kmol
Mass flow rate of dichlorobenzene = 147.01 kg/kmol x 1.99 kmol/hr = 292.55 kg/hr
95
Density of dichlorobenzene = 1300 kg/m3, hence,
292.55
Volumetric flowrate of dichlorobenzene = m3/hr = 0.225 m3/hr
1300
Total Volumetric flowrate = (2.224 + 0.225) m3/hr = 2.449 m3/hr.
All the calculated values are shown in Table 5.2
The residence time for the chlorobenzene column is taken to be 90 minutes
Total stream volume in the chlorobenzene column = 2.449 x 1.5= 3.67 m3.
3.67
= = 7.34 m3
0.5
Assuming the Benzene column is a vertical cylindrical vessel.
𝜋𝐷 2 𝐻
Volume = 4
For this column, the H/D ratio is also taken as 5.
Therefore, H = 5D
5𝜋𝐷 3
7.34 m3 = 4
D = 1.23 m
96
Table 5:2 VOLUMETRIC FLOW RATE OF THE FEED INTO THE
CHLOROBENZENE COLUMN.
RATE (kg/mol) E (kg/hr)

(kg/m3) (m3/hr)
(kmol/hr
Dichlorobenzene 1.99 147.01 292.55 1300.00 0.225
Total 2.449
Design Temperature and Pressure:
5.4 DRYING COLUMN SIZING AND DESIGN CONDITION
The total feed input the drying column is 185.42 kmol/hr. The feed into the column contains
166.30 kmol/hr benzene,0.02 kmol/hr of monochlorobenzene and 19.09 kmol/hr water at 134.5
0
C and 1.013 bar.
The recovered benzene from the benzene column and raw benzene feed goes into the drying
column. The drying column is responsible for separation of water from benzene. To determine
the volume of the column, the volumetric flow rate of each product going into the column has
to be determined using the formula;
97
𝑘𝑔
ℎ𝑟
𝑚
Molar mass of benzene = 78.11 kg/kmol
Mass flow rate of benzene = 78.11 kg/kmol x 166.30 kmol/hr = 12989.69 kg/hr
Density of benzene = 876 kg/m3, hence,
12989.69
Volumetric flowrate of benzene = m3/hr = 14.828 m3/hr
876
2.25
Volumetric flowrate of monochlorobenzene = 1110 m3/hr = 0.002 m3/hr
Molar mass of water = 18.015 kg/kmol
Mass flow rate of water = 18.015 kg/kmol x 19.09 kmol/hr = 343.91 kg/hr
Density of water = 1000 kg/m3, hence,
343.91
Volumetric flowrate of water = m3/hr = 0.344 m3/hr
1000
Total Volumetric flowrate = (14.828+0.344+0.002) m3/hr = 15.174 m3/hr.
All the calculated values are shown in Table 5.3
The residence time for the drying column is taken to be 60 minutes
Total stream volume in the drying column = 15.174 x 1 = 15.174 m3.
15.174
= = 30.35 m3
0.5
98
Assuming the drying column is a vertical cylindrical vessel.
𝜋𝐷 2 𝐻
Volume = 4
For this column, the H/D ratio is also taken as 4.
Therefore, H = 4D
4𝜋𝐷 3
30.35 m3 = D = 2.13 m
4
Table 5:3 VOLUMETRIC FLOW RATE OF THE FEED INTO THE DRYING
COLUMN.
RATE (kg/mol) E (kg/hr)

(kg/m3) (m3/hr)
(kmol/hr
Benzene 166.30 78.110 12989.69 876.00 14.828
Water 19.09 18.015 343.91 1000.00 0.344
Total 15.174
99
Design temperature = 1.1 x134.5 °C = 147.950C
5.5 SEPARATOR (WASHER/ NEUTRALIZER)
The crude chlorobenzene leaving the second reactor is washed with water and caustic soda
(NaOH) solution to remove all the dissolved hydrogen chloride. The washing was done in a
three-phase separator because it gives a cleaner separation of products and they can also handle
large throughput. The design of the separator requires very rigorous calculations so the
separator requires was sized using a separator sizing applications.
The feed inflow into the washer is 293.29 kmol/hr. The feed specifications are 165.00 kmol/hr
water, kmol/hr caustic soda, 82.95 kmol/hr benzene, 22.464 monochlorobenzene, 2.20
dichlorobenzene and 0.995 hydrogen chloride
𝑉𝑜𝑙. 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑝ℎ𝑎𝑠𝑒, 𝑉𝑜𝑟𝑔
𝐹𝐵𝑧 𝑜𝑟𝑔 × 𝑀𝑀𝐵𝑧 𝐹𝑀𝐶𝐵 𝑜𝑟𝑔 × 𝑀𝑀𝑀𝐶𝐵 𝐹𝐷𝐶𝐵 𝑜𝑟𝑔 × 𝑀𝑀𝐷𝐶𝐵

= + +
𝜌𝐵𝑧 𝜌𝑀𝐶𝐵 𝜌𝐷𝐶𝐵
𝐹𝐻2 0 𝑜𝑟𝑔 × 𝑀𝑀𝐻2 𝑂

+
𝜌𝐻2 𝑂
66.30 × 78.11 21.95 × 112.56 1.99 × 147 19.09 × 18.101528

= + + +
876 1107 1241 1000
𝑚3 𝑚3
= 8.724910121 = 0.002423586145
ℎ𝑟 𝑠
100
𝑉𝑜𝑙. 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒, 𝑉𝑎𝑞
𝐹𝑁𝑎𝐶𝑙 𝑎𝑞 × 𝑀𝑀𝑁𝑎𝐶𝑙 𝐹𝐻2 0 𝑎𝑞 × 𝑀𝑀𝐻2 𝑂 𝐹𝑁𝑎𝑂𝐻 𝑎𝑞 × 𝑀𝑀𝑁𝑎𝑂𝐻

= + +
𝜌𝑁𝑎𝐶𝑙 𝜌𝐻2 𝑂 𝜌𝑁𝑎𝑂𝐻
0.92 × 58.44 171.82 × 18.101528 9.08 × 39.997

= + +
2.16 × 103 1000 2130
𝑚3 𝑚3
= 3.305599295 = 0.0009182220265
ℎ𝑟 𝑠
Since aqueous phase is having lesser volumetric flow, it is the dispersed phase. While the
continuous phase is organic phase (Sinnott & Towler, 2013).
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑝ℎ𝑎𝑠𝑒, 𝜌𝑜𝑟𝑔 = 𝜌𝑐
= 𝑥𝐵𝑧 𝑜𝑟𝑔 × 𝜌𝐵𝑧 + 𝑥𝑀𝐶𝐵 𝑜𝑟𝑔 × 𝜌𝑀𝐶𝐵 + 𝑥𝐷𝐶𝐵 𝑜𝑟𝑔 × 𝜌𝐷𝐶𝐵 + 𝑥𝐻2 0 𝑜𝑟𝑔 × 𝜌𝐻2 𝑂 =
66.30 21.95 1.99 19.09

= × 876 + × 1107 + × 1241 + × 1000
291.16 291.16 291.16 291.16
𝑘𝑔
= 356.9756835
𝑚3
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒, 𝜌𝑎𝑞 = 𝜌𝑑
= 𝑥𝑁𝑎𝐶𝑙 𝑎𝑞 × 𝜌𝑁𝑎𝐶𝑙 + 𝑥𝐻2 0 𝑎𝑞 × 𝜌𝐻2 𝑂 + 𝑥𝑁𝑎𝑂𝐻 𝑎𝑞 × 𝜌𝑁𝑎𝑂𝐻 =
0.92 171.82 9.08

= × 2.16 × 103 + × 1000 + × 2130
181.82 181.82 181.82
𝑘𝑔
= 1062.301177
𝑚3
𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑛𝑡𝑖𝑛𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒, 𝜇𝑜𝑟𝑔 = 𝜇𝑐
= 𝑥𝐵𝑧 𝑜𝑟𝑔 × 𝜇𝐵𝑧 + 𝑥𝑀𝐶𝐵 𝑜𝑟𝑔 × 𝜇𝑀𝐶𝐵 + 𝑥𝐷𝐶𝐵 𝑜𝑟𝑔 × 𝜇𝐷𝐶𝐵 + 𝑥𝐻2 0 𝑜𝑟𝑔 × 𝜇𝐻2 𝑂
66.30 21.95 1.99

= × 0.000601 + × 0.00008 + × 0.000084
291.16 291.16 291.16
19.09 𝑁𝑠
+ × 0.0010042 = 0.0002092994848 2
291.16 𝑚
101
𝑇𝑎𝑘𝑒 𝑡ℎ𝑒 𝑑𝑖𝑠𝑝𝑒𝑟𝑠𝑒𝑑 𝑝ℎ𝑎𝑠𝑒 𝑑𝑟𝑜𝑝𝑙𝑒𝑡 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑑𝑑 = 150 𝜇𝑚
From Stokes’s law;
𝑑𝑑 2 𝑔(𝜌𝑑 − 𝜌𝑐 )
𝐷𝑖𝑠𝑝𝑒𝑟𝑠𝑒𝑑 𝑝ℎ𝑎𝑠𝑒 𝑑𝑟𝑜𝑝𝑙𝑒𝑡 𝑠𝑒𝑡𝑡𝑙𝑖𝑛𝑔 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦, 𝑢𝑑 =
18𝜇𝑐
(150 × 10−6 )2 × 9.81 × (1062.301177 − 356.9756835)

=
18 × 0.0002092994848
𝑚
= 0.004132381822 (𝑑𝑟𝑜𝑝𝑝𝑖𝑛𝑔)
𝑠
For small velocity, (Sinnott & Towler, 2013) suggest a vertical vessel.
𝑚3
𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑡𝑖𝑛𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒, 𝐿𝑐 = 𝑉𝑜𝑟𝑔 = 95.99070802
𝑠
𝐹𝑜𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑛𝑡𝑖𝑛𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒, 𝑢𝑐 < 𝑢𝑑
𝐿𝑐 𝐿𝑐 0.002423586145
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑖𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑒, 𝐴𝑖 = = = = 0.5864864984 𝑚2
𝑢𝑐 𝑢𝑑 0.004132381822
For vertical cylindrical shaped vessel with hemispherical ends;
𝐴𝑖 0.5864864984
𝐶𝑦𝑙𝑖𝑛𝑑𝑒𝑟 𝑟𝑎𝑑𝑖𝑢𝑠, 𝑟 = √ = √ = 0.4320699603 𝑚
𝜋 𝜋
𝑆𝑖𝑧𝑖𝑛𝑔 𝑡𝑜 110 𝑝𝑒𝑟𝑐𝑒𝑛𝑡, 1.1 × 0.4320699603 = 0.4752769563 𝑚
𝐶𝑦𝑙𝑖𝑛𝑑𝑒𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝐷 = 2 × 𝑟 = 0.9505539126 𝑚
𝐹𝑜𝑟 𝐻𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑣𝑒𝑠𝑠𝑒𝑙, 𝐻
𝑇𝑎𝑘𝑒 𝑡ℎ𝑒 𝑑𝑖𝑠𝑝𝑒𝑟𝑠𝑖𝑜𝑛 𝑏𝑎𝑛𝑑, 𝐻𝑑𝑏 = 0.1𝐻
102
𝐻𝑑𝑏 0.1𝐻
𝐷𝑟𝑜𝑝𝑙𝑒𝑡 𝑟𝑒𝑠𝑖𝑑𝑒𝑛𝑐𝑒 𝑡𝑖𝑚𝑒, 𝑡𝑑 = =
𝑢𝑑 𝑢𝑑
For feasible control purpose, the droplet residence time must be between 2 - 5 minutes. Also
the droplet residence time must less than the overall volumetric flow residence time in the
vessel.
4
0.1𝐻 𝜋 × 𝑟 2 (𝐻 − 2𝑟) + 3 𝜋𝑟 3
2 × 60 < < < 5 × 60
𝑢𝑑 𝑉𝑜𝑟𝑔 + 𝑉𝑎𝑞
120 < 24.19911913𝐻 < 67.28486283(3.156054549𝐻 − 1) < 300
𝐻𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑣𝑒𝑠𝑠𝑒𝑙, 𝐻 = 𝐻𝑚𝑖𝑛 = 4.958858186 𝑚
𝑉𝑜𝑟𝑔 0.002423586145 𝑚
𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑑𝑖𝑠𝑝𝑒𝑟𝑠𝑒𝑑 𝑝ℎ𝑎𝑠𝑒, 𝑣𝑑 = = = 0.004132381822
𝐴𝑖 0.5864864984 𝑠
𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑓𝑜𝑟 𝑟𝑎𝑖𝑠𝑖𝑛𝑔 𝑐𝑜𝑛𝑡𝑖𝑛𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒 , 𝑒𝑛𝑡𝑟𝑎𝑖𝑛𝑒𝑑 𝑑𝑟𝑜𝑝𝑙𝑒𝑡 𝑠𝑖𝑧𝑒 = 𝑑𝑑

1
𝑢𝑑 18𝜇𝑐 2
=( )
𝑔(𝜌𝑑 − 𝜌𝑐 )
1
0.004132381822 × 18 × 0.0002092994848 2
= ( )
9.81 × (1062.301177 − 356.9756835)
= 2.25 × 10−9 𝑚 < 150 𝜇𝑚 ( 𝑠𝑎𝑡𝑖𝑠𝑓𝑎𝑐𝑡𝑜𝑟𝑦)
𝑚3
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤, 𝑉𝑇 = 𝑉𝑜𝑟𝑔 + 𝑉𝑎𝑞 = 0.003341808172
𝑠
To keep the velocity at the feed nozzle (vn) below 1 m/s in other to reduce turbulence of entering
feed on the coalescing phase in the vessel.
𝑉𝑇 0.003341808172
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑓𝑒𝑒𝑑 𝑛𝑜𝑧𝑧𝑙𝑒, 𝐴𝑛 = = = 0.003341808172 𝑚2
𝑣𝑛 1
103
𝐴𝑟 0.003341808172
𝐹𝑒𝑒𝑑 𝑛𝑜𝑧𝑧𝑙𝑒 𝑟𝑎𝑑𝑖𝑢𝑠, 𝑛𝑟 = √ =√ = 0.03261488278 𝑚
𝜋 𝜋
𝐹𝑒𝑒𝑑 𝑛𝑜𝑧𝑧𝑙𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑛𝑑 = 2 × 𝑛𝑟 = 0.06522976556 𝑚
For a vertical decanter, the position of interface is usually at the halfway up the vessel and let
the aqueous phase be drawn at the top of cylindrical section of the vessel.
𝐴𝑞𝑢𝑒𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒 𝑛𝑜𝑧𝑧𝑙𝑒 ℎ𝑒𝑖𝑔ℎ𝑡, 𝑧1 = 𝐻 − 𝑟 = 4.958858186 − 0.4752769563
= 4.48358123 𝑚
𝐼𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑒 ℎ𝑒𝑖𝑔ℎ𝑡, 𝑧3 = 0.5 × 𝐻 = 2.479429093 𝑚
(𝑧1 − 𝑧3 )𝜌1 (𝑧1 − 𝑧3 )𝜌𝑎𝑞

𝐴𝑞𝑢𝑒𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒 𝑜𝑣𝑒𝑟𝑓𝑙𝑜𝑤 ℎ𝑒𝑖𝑔ℎ𝑡, 𝑧2 = + 𝑧3 = + 𝑧3
𝜌2 𝜌𝑜𝑟𝑔
(4.48358123 − 2.479429093 ) × 356.9756835

= + 2.479429093
1062.301177
= 3.15290437 𝑚
Dimension of Washer
Volume 3.5194 m3
Diameter 0.9506 m
Height 4.9589 m
5.6 COLUMN DESIGN
Distillation is the most economical method for the separation of liquid mixtures especially for
large scale production. The design optimization variables of a distillation column includes
pressure, total number of trays, feed tray location, and side stream tray location, height,
104
diameter and material of construction. The design of distillation columns requires good
knowledge and expertise in order for effective design.
5.6.1 TRAY TYPE USED
Sieve tray was selected to be used in the distillation column because they are the least expensive
tray option, they are simple to construct, have low fouling factor and low maintenance cost.
The cost of the trays depends on the column diameter and the type and material of the tray.
105
5.7 MATERIAL OF CONSTRUCTION
Many factors have to be considered when selecting engineering materials, but for the chemical
process plant, the overriding considerations are usually high temperature strength and the
ability to resist corrosion. The most important characteristics to be considered when selecting
a material of construction are mechanical properties (Strength, stiffness, hardness), the effect
of temperature, corrosion resistance, ease of fabrication, availability and cost.
For the chlorobenzene plant, the continuous stirred tank reactors are constructed from mild
steel and this because it’s efficiently malleable (it can be easily bent and cut, it is light and also
very affordable. The ferric chloride that acts as a catalyst in situ in reactor by the action of
hydrogen chloride on mild steel (material selected for construction).
The distillation columns are constructed with carbon steel because they are corrosion resistant,
easy to fabricate, fire and heat resistance and has a nice appearance.
106
CHAPTER SIX
CHEMICAL ENGINEERING DESIGN OF
CHLOROBENZENE COLUMN
Condenser
Distillate, D
Reflux L 22.3 kgmole/h

Rectifying section
Xᴅ = 0.997
Feed, F
24.23 kgmole/h
132.56 oC
Stripping section V’
Bottom, B
L’ 1.94 kgmole/h
Reboiler
Xᴃ = 0.9948
Figure 5:1 CHLOROBENZENES DISTILLATION COLUMN
6.1 OVERVIEW OF CHEMICAL ENGINEERING DESIGN FOR THE
CHLOROBENZENE COLUMN
In this design report, a sieve tray distillation column is to be designed for the separation of
chlorobenzene mixture stream containing monochlorobenzene and dichlorobenzene into
almost pure components. Monochlorobenzene is removed as the distillate while the
dichlorobenzene is removed as the bottom product.
6.2 NUMBER OF STAGES DETERMINATION
In determining the number of stages, the vapour-liquid equilibrium data have to be plotted with
the McCabe-Thiele method. The vapour-liquid data in Table 1 was obtained as Table 2 was
calculated from Table 1 using the Raoult’s equation given as:
𝛼𝑥
𝑦= (6.1)
1+(𝛼−1)𝑥
using the relativity volatility for the non-volatile component (monochlorobenzene) calculated
from below
𝑝
𝛼 = 𝑝𝐴 (6.2)
𝐵
Where PA = 775.17 mmHg (interpolated from Table 2 below) at entering temperature (133.9oC)
and PB = 203.67 mmHg (interpolated from Table 2 below) at entering temperature (133.9 oC)
775.17
𝛼 = 203.67 = 3.806 (6.3)
Assumptions
1. The stream coming from the benzene column serving as the feed entering the chlorobenzene
column is a binary mixture of mono-chlorobenzene and dichlorobenzene for simplicity of
calculation.
2. Feed, F is a saturated liquid at the boiling point hence, q is taken to be one (1).
108
From Perry’s Chemical Engineering Handbook, we obtain the vapour pressure data and the
vapour-liquid equilibrium data.
The feed F into the chlorobenzene column which is assumed to be a pure mixture of mono-
chlorobenzene and dichlorobenzene at a flowrate of 24.23 kmol/hr at saturated temperature.
From overall material balance and energy balance done around the chlorobenzene column, the
distillate D and bottoms B were obtained with their various exit temperature.
Feed, F (MCB and DCB) = 24.23kmols/hr
Distillate, D = 22.30kmols/hr
Bottoms, B = 1.94kmols/hr
XF = 0.917
XD = 0.997
XB = 0.515
109
Table 6:1 VAPOUR PRESSURE DATA (PRESSURE AT 482469.00 PA)
Temperature (K) Vapour Pressure of Vapour Pressure of

MCB (mmHg) DCB (mmHg)
405 700 190
408 810 210
411 900 240
415 1000 260
418 1050 300
422 1150 330
426 1300 370
429 1400 400
433 1500 450
437 1700 500
441 1800 575
444 2000 625
448 2200 680
453 2400 740
110
Table 6:2 VAPOUR-LIQUID EQUILIBRIUM DATA
Bubble Point Temperature, (K) X Y
419.637 0 0
416.329 0.05 0.135
413.256 0.1 0.251
410.394 0.15 0.351
407.722 0.2 0.436
405.22 0.25 0.511
402.873 0.3 0.575
400.665 0.35 0.632
398.584 0.4 0.683
396.617 0.45 0.727
394.755 0.5 0.766
392.989 0.55 0.803
391.311 0.6 0.833
389.714 0.65 0.862
388.19 0.7 0.888
386.735 0.75 0.911
385.344 0.8 0.932
384.011 0.85 0.951
382.733 0.9 0.969
381.506 0.95 0.985
380.32 1 1
111
Following the assumption that the feed mixture of MCB and DCB is a saturated liquid at boiling
point Bubble point temperature is interpolated from the above Table at x= 0.9263 (mole
fraction of the more volatile component).
Interpolating gives bubble point as 380.86 K =107.71oC
6.3 DATA OBTAINED FROM HYSYS SIMULATION
Entering Feed Temperature = 132.56 oC
Mean specific heat of feed = 177.4 kJ/kmol ᵒC
Latent Heat of Monochlorobenzene = 36,135 kJ/kmol
Latent Heat of Dichlorobenzene = 51,376.5 kJ/kmol
Latent Heat of the Feed = 0.9263(36,135) + 0.0789(51,376.5) = 37,525.46 kJ/kmol
𝐻𝑒𝑎𝑡 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡𝑜 𝑣𝑎𝑝𝑜𝑢𝑟𝑖𝑧𝑒 1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑖𝑣𝑒𝑛 𝑓𝑒𝑒𝑑

𝑞= (6.4)
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑓𝑒𝑒𝑑
where,
Heat required to vaporize 1 mole of the given feed = (107.71 – 132.56) ᵡ 177.4 + 37,525.46 =
33,117.07 kJ/kmol (6.5)
33,117.07
Therefore, 𝑞 = = 0.8825 (6.6)
37,525.46
𝑞 0.8825
The slope of the q-line = 𝑞−1 = = −7.51 (6.7)
0.8825−1
With the points (𝑥𝑓 , 𝑦𝑓 ) and the slope (-7.51), the equation for the q-line was gotten.
Also, the corresponding values of x and y were gotten to plot the q-line.
6.4 RECTIFYING OPERATING LINE
The equation is given as:
112
𝐿 𝐷
𝑦 = 𝑉𝑥 + 𝑥𝑑 (6.8)
𝑉
361.7 22.30
𝑦 = 385.8 𝑥 + (0.997) (6.9)
385.8
Which gives
𝑦 = 0.9375𝑥 + 0.057628 (6.10)
𝑥𝑑
The intercept, 0.0623 corresponds to the value 𝑅𝑚 +1
Therefore
𝐷 𝑥
𝑅𝑚 = 0.057628 −1 (6.11)
Minimum reflux ratio, Rm = 16 for xD = 0.997
Since reflux ratio, R = 2Rm
Now, reflux ratio, R = 32
6.5 STRIPPING OPERATING LINE

𝐿′ 𝐵
𝑦 = 𝑉′ 𝑥 − 𝑉′ 𝑥𝑏 (6.12)
339.1 1.94
𝑦 = 337.1 𝑥 − 337.1 (0.0052) (6.13)
𝑦 = 1.006𝑥 − 0.0000299 (6.14)
Figure 6.2 below shows the x-y plot with the Xb (monochlorobenzene concentration in
bottoms), Xd (monochlorobenzene concentration in distillate) and Xf (monochlorobenzene
concentration in feed) marked. The q-line is drawn from the point of intersection of Xf and the
45-degree line.
6.6 ESTIMATING PHYSICAL PROPERTIES
Number of stages = 8
113
Slope of the bottom operating line = 1.006
Slope of top operating line = 0.9375
Top composition = 99.7% MCB and 0.3% DCB
Bottom composition = 0.52% MCB and 99.485% DCB
Reﬂux ratio = 32
Assuming column efﬁciency of 60%, and taking the reboiler as equivalent to one stage,
8−1
Number of real stages = = 12
0.6
Top; 99.7% MCB, top temperature 118.80C (391.95 K)
Molecular weight = 112.5 g/mol
Surface tension, 𝜎 = 0.02713𝑁/𝑚
𝜌𝑙 = 10343.52𝑘𝑔/𝑚3
𝑃𝑀 70.93∗112.5
𝜌𝑣 = = = 2.449𝑘𝑔/𝑚3 (6.15)
𝑅𝑇 8.314∗391.95
Bottom; 99.485% DCB, bottom temperature 160.50C (433.65K)
Molecular weight = 147g/mol
Surface tension, 𝜎 = 0.02227𝑁/𝑚
114
Figure 6:2 MCCABE THIELE PLOT SHOWING THE NUMBER OF STAGES
115
𝜌𝑙 = 1122.89𝑘𝑔/𝑚3
𝑃𝑀 70.93∗112.5
𝜌𝑣 = = = 2.892 (6.16)
𝑅𝑇 8.314∗433.65
6.7 COLUMN DIAMETER AND FLOODING CHECK
The liquid-vapour flow factor is calculated as
𝐿𝑤 𝜌𝑣
𝐹𝐿𝑉 = √𝜌 (6.17)
𝑉𝑤 𝑙
Where 𝐿𝑤 𝑎𝑛𝑑 𝑉𝑤 are liquid and vapour mass flow rates respectively.
2.892
𝐹𝐿𝑉 𝑏𝑜𝑡𝑡𝑜𝑚 = 1.006 √1122.89 = 0.051 (6.18)
2.449
𝐹𝐿𝑉 𝑡𝑜𝑝 = 0.9375 √10343.52 = 0.0144 (6.19)
Assume a plate spacing of 0.5mm, from the flooding velocity graph.
Base 𝑘1 = 0.11
Top 𝑘1 = 0.12
Corrections for surface tensions:
0.02227 2
Base 𝑘1 = ( ) ∗ 0.11 = 0.13638 (6.20)
0.02
0.02713 2
Top 𝑘1 = ( ) ∗ 0.12 = 0.2208 (6.21)
0.02
1122.89−2.892
Base 𝑢𝑓 = 0.13638 √ = 2.684 m/s (6.22)
2.892
1034.52−2.446
Top 𝑢𝑓 = 0.2208 √ = 4.535 m/s (6.23)
2.446
Design for 80% flooding at maximum flowrate:
Base 𝑢𝑣 = 2.684 ∗ 0.80 = 2.147 m/s (6.24)
Top 𝑢𝑣 = 4.535 ∗ 0.80 = 3.628 m/s (6.25)
116
Figure 6:3 FLOODING VELOCITY CHECK
117
Maximum volumetric flowrate:
337.1 ∗ 147
Base = 2.892 ∗ 3600 = 4.759 𝑚3 /𝑠 (6.26)
385.8∗ 112.5
Top = 2.446 ∗ 3600 = 4.928 𝑚3 /𝑠 (6.27)
Net area required:
4.759
Base = 2.147 = 2.217 𝑚2 (6.28)
4.928
Top = 3.628 = 1.358 𝑚2 (6.29)
Taking down comer area as 12% of total. Column cross sectional area:
2.217
Base = = 2.519 𝑚2 (6.30)
0.88
1.358
Top = = 1.543 𝑚2 (6.31)
0.88
Therefore, the downcomer area gives;
Base = (2.519 - 2.217) = 0.302 𝑚2 (6.32)
Top = (1.543 – 1.358) = 0.185 𝑚2 (6.33)
Column Diameter:
2.519∗4
Base = √ = 1.791 m (6.34)
3.142
1.543∗4
Top = √ = 1.402 m (6.35)
3.142
Downcomer diameter:
0.302∗4
Base = √ = 0.6201 m (6.36)
3.142
0.1859∗4
Top = √ = 0.4853 m (6.37)
3.142
6.8 PROVISIONAL PLATE DESIGN
Column diameter, 𝐷𝑐 = 1.791 m (6.38)
Column area, 𝐴𝑐 =2.519 𝑚2 (6.39)
118
Downcomer area at 12%, 𝐴𝑑 = 0.12 ∗ 𝐴𝑐 = 0.30231 𝑚2 (6.40)
Net area, 𝐴𝑛 = 𝐴𝑐 − 𝐴𝑑 = 2.2167 𝑚2 (6.41)
0.785𝐷𝐶2 = 2.2167; 𝐷𝑐 = 1.680 m (6.42)
Active area, 𝐴𝑎 = 𝐴𝑐 − 2𝐴𝑑 = 0.06231 𝑚2 (6.43)
Hole area, 𝐴ℎ = 10%𝐴𝑎 = 0.006231 𝑚2 (6.44)
Weir length, 𝐼𝑑 = 0. 77 *1.791 = 1.3791 m (6.45)
6.9 WEIR DESIGN
Take weir height = 50.8 mm; Hole diameter (𝑑ℎ ) = 1.938 mm; Plate thickness = 1.163 mm.
119
CHAPTER SEVEN
MECHANICAL DESIGN OF CHLOROBENZENE
DISTILLATION COLUMN
7.1 THEORY
A process vessel is a tank or container designed and equipped with the controls and accessories to
complete a sub-process as part of an overall process. The material that the process vessel is made
of, as well as its accessories and controls, depend on its intended use. The sub-process involved in
the preparation of chlorobenzene are mixing, blending, separation by absorption and adsorption
mechanism, cooling, purification and changes of states of process materials.
A process vessel is a general term used to describe a variety of equipment which are designed to
handle pressure and temperature. These vessels are used in all types of industries.
These vessels are extremely useful whether your need is to agitate, hold, heat, store, or chemically
change the medium. Examples of process vessels are reactor pressure vessels, storage tanks,
centrifuges and heat exchanger tube sheets.
The various steps, stages or processes in the process industries usually have specific requirements
such as time, pressure, temperature and other operating conditions. The appropriate process vessels
allow the proper control of the required operating conditions in every step until the desired product
is attained. In the process industries, the design of chemical plants forms an integral part of the
overall design process. This specialized aspect is referred to as Mechanical design and is usually
overseen by specialist engineers.

Mechanical design of equipment addresses the stress and strain produced in different parts of the
equipment such as shell, head, support, etc. due to operating conditions of the process. The success
and failure of the process depends on how perfectly stress and strain are considered
while designing. According to Coulson, the chemical engineer will not usually be called on to
undertake the detailed mechanical design of a pressure vessel. Vessel design is a specialized
subject, and will be carried out by mechanical engineers who are conversant with the current design
codes and practices, and methods of stress analysis. However, the chemical engineer will be
responsible for developing and specifying the basic design information for a particular vessel, and
needs to have a general appreciation of pressure vessel design to work effectively with the
specialist designer.
The basic data needed by the specialist designer will be:
i. Vessel function.
ii. Process materials and services.
iii. Operating and design temperature and pressure.
iv. Materials of construction.
v. Vessel dimensions and orientation.
vi. Type of vessel heads to be used.
vii. Openings and connections required.
viii. Specification of heating and cooling jackets or coils.
ix. Type of agitator.
x. Specification of internal fittings
7.2 SPECIFICATIONS
Shell Specification
121
Inner diameter = 1.23m (Gotten from Equipment Design and Sizing)
Operating pressure = 1.1 bar = 1 x 105 Pa
Design pressure = 1.1143 x 105 Pa
Operating Temperature =134.5oC
Design Temperature =147.95oC
Shell material = Carbon steel (specific gravity =7.8)
Shell= double welded bolts joint stress relieved
Tray spacing =609.6mm
Tray thickness =2.75m
Permissible tensile stress =136.55 ×106N/m2
Insulation material = Asbestos
Tray types - Sieve type
Spacing =609.6mm
Materials for tray downcomers weirs - Carbon steel
Downcomer clearance = 38.1mm
7.3 SHELL THICKNESS
Assume it is an internally pressurized vessel
𝐷𝑖𝑎𝑚𝑒𝑡𝑒𝑟 = 1.245𝑚
Design Pressure = 1.1143bar
Operating Temperature = 134.50C
Maximum allowable stress = 88.94 X 106 N/m2
Weld Efficiency (E) = 1
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𝑃𝑖 𝑑𝑖
𝑆ℎ𝑒𝑙𝑙 𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 =
2𝑆𝐸 − 1.2𝑃𝑖
1.1143 × 105 × 1.23

=
2 × 88.94 × 106 × 1 − 1.2 × 1.1143 × 105
= 𝟖. 𝟒𝟒𝟑 × 𝟏𝟎−𝟒 𝒎
𝑆ℎ𝑒𝑙𝑙 𝑀𝑎𝑠𝑠 = 𝜋𝑑𝐿𝑊𝑇 𝜌
Density = 7800 kg/m3
𝑆ℎ𝑒𝑙𝑙 𝑀𝑎𝑠𝑠 = 𝜋 × 1.245 × 6.225 × 8.443 × 10−4 × 7800
= 𝟏𝟔𝟎. 𝟑𝟒𝑲𝒈
Taking corrosion allowance of 2mm
The selected thickness would be 0.844 + 2 = 2.844 mm
7.3.1 HEAD
Head – Hemispherical head
Material: Carbon Steel
Therefore,
𝑃𝑖𝐷𝑖
t = 4𝑆𝐸−0.4𝑃𝑖
1.1143×105 ×1.23
t = 4×88.94×106−0.4×1.1143×105
th = 0.39 mm
Since th < 2.844 mm (shell thickness), so a design thickness of 2.844 mm is sufficient for the head.
The design thickness chosen with a corrosion allowance: th= 2.844 mm
The approximate weight of the head is also calculated
Weight of head:
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Wh = Area × thickness × density of material
Area of head (Circular shape) = 0.25× 𝜋 × 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟
𝑂𝐷 2
Diameter = OD + 24 + 2St + 3 icr
Where OD= outside diameter of shell = Di + 2× 𝑡𝑤
Di= internal diameter = 1245mm
tw = thickness of shell = 2.844mm
OD = 1245 + 2 × 2.844 = 1250.688 mm
Assuming
St = self-flanges length = 1.5 inches =38.1mm
Icr= 0.75 inches = 19.05mm
Then, the outer diameter is calculated to be
1250.688 2
Outer Diameter = 1250.688 + + 2 × 38.1 + 3 ×19.05
24
Outer Diameter = 1391.7 mm
Area = 0.25 x π x 1391.7 = 1093.04 mm2
Density of head = 7.8 × 10−6 kg/mm3
Weight of head = 1093.04 x 7.8 × 10−6 x 2.844
Weight = 0.0242 kg
7.4 AGITATOR DESIGN FOR THE CSTR
An agitator is what makes it easy to stir a substance (mostly fluids) or a mixture of fluids, but,
even more, it helps to keep the fluid in that ‘mixed’ state required for the end product. There are
about six types of agitators including paddle agitators, anchor agitators, radial propeller agitators,
propeller agitators, turbine agitators, and helical agitators. They are used depending on the kind of
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substance(s) being mixed (solid, liquid, or gas) and the pattern of flow that is desired of the
substance(s) in the reactor.
For the production of monochlorobenzene and dichlorobenzene, the thorough mixing of benzene
and chlorine is very essential, and that’s what the agitator and baffles help to achieve. Hence, we
must determine the most appropriate agitator for the process and specify the dimension as well as
other parameters such as the impeller speed, number of impeller blades, distance between two
consecutive impellers, impeller length, impeller speed, and so on.
The most suitable agitator for a particular application mostly depends on the type of mixing
required for the process, the capacity of the reactant vessel, and the fluid properties such as its
viscosity Sinnott (2005). Since the reaction in the tank is between liquid benzene and gaseous
chlorine, the most appropriate agitator for the process is a turbine agitator.
7.4.1 AGITATOR DIMENSION
Impeller diameter, Di = 2/5 x Dt = 1.758m
Impeller height above vessel floor, E = 3/5 x CSTR Height = 3.955m
Length of impeller blade L = Di/4 = 0.659m
Width of impeller blade W = Di/5 = 0.527m
Width of baffle = Dt/10 = 0.440m
No of impellers = 3
No of impeller blades = 4
Distance between two consecutive impellers = 2.637m
Tip velocity = 5m/s
Speed of impeller = 142.5 rpm
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Chart from (pg. 489) Coulson Richardson’s Chemical engineering design, Volume 6, 4th edition.
126
7.4.2 POWER REQUIREMENT
Np = KRebFrc
Where,
Np = power number = P/ (Di x 5N3ρ)
Re = Reynolds number = D2Nρ/μ,
Fr = Froude number = DN2/g,
P = shaft power, W,
K = a constant, dependent on the agitator type, size, and the agitator-tank
Geometry,
ρ = fluid density = 876 kg/m3
μ = fluid viscosity = 562 Ns/m2
N = agitator speed, s-1 (revolutions per second),
D = agitator diameter, m = 0.40 x 4.395 = 1.758m
g = gravitational acceleration = 9.81 m/s2.
Given the equation above, the following estimations are made:
Np = 5
Shaft RPM, N = 142 rpm/60 = 2.375 rps
Power = (Np x N3 x Di x ρ)/gc) = 1.15 hp
Assuming the impeller is 99.8% efficient
Actual power required = 1.15 hp
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CHAPTER EIGHT
PLANT CONTROL AND INSTRUMENTATION
8.1 INTRODUCTION
Process control is an engineering mechanism that uses continuous monitoring of an industrial
process’ operational variable (e.g., temperature, pressure, flow rate, vessel level, etc.) and
algorithms and then uses that information to adjust variables to reach product output specifications
and objectives (Carvajal and Cullick, 2018). Sensors and various other types of instrumentation
are used to measures, monitor and maintain process control equipment for improved production,
product consistency and quality management, and workplace safety in manufacturing and
processing facilities. Process control instrumentation is also used in preventing fire outbreak in
facilities that store or process combustible substances. Various types of instrumentation are used
to measure variables such as temperature, fluid levels, flow rates, pressure, pH. These instruments
include many varied contrivances that can be as simple as valves and transmitters, and as complex
as analyzers.
8.2 GENERAL PRELIMINARY CONSIDERATIONS
Various types of instrumentation are used to measure variables such as temperature, fluid levels,
flow rates, pressure, pH and below are some of the major instrumentation to be used in the
chlorobenzene plant.
8.2.1 LEVEL CONTROLLERS
This measures the level of liquids and free-flowing solids in the reactor. Sensing liquid levels fall
into two categories; firstly, single-point sensing and secondly, continuous level monitoring. In the
case of single-point sensing, the actual level of the material is detected when it reaches a
predetermined level, so that the appropriate action can be taken to prevent overflowing or to refill
the container. Continuous level monitoring measures the level of the liquid on an uninterrupted
basis. In this case, the level of the material will be constantly monitored and hence, the volume
can be calculated if the cross-sectional area of the container is known. However, the latter is used
because the chlorobenzene plant has a continuous stirred tank reactor.
8.2.2 MASS FLOW CONTROLLER
This controls the flowrate of a gas according to a set flow rate sent as an electrical signal, without
being affected by use conditions or changes in gas pressure. It is used to regulate the flow rate of
chlorine gas feed.
8.2.3 PRESSURE CONTROLLER/REGULATORS
This is a control valve that reduces the input pressure of a fluid or gases to the desired value at its
output. Regulators are used for gases and liquids and can be an integral device with an output
pressure setting, a restrictor and a sensor all in one body, or consist of a separate pressure sensor,
controller and flow valve.
The restricting element is a valve that can provide a variable restriction to the flow, such as a globe
valve, butterfly valve etc. Pressure regulators are used in the separators to prevent unwanted
pressure build-up and to prevent the loss of materials through a relief valve.
8.3 FEEDBACK CONTROLLER
This determines the error between a set point and a measured variable. The error signal is then
used to produce an actuator control signal to operate a valve and reduce the error signal. This type
of control continuously monitors the measured variable and has three modes of operation which
are proportional, integral, and derivative. A combination of all three of the actions described above
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is more commonly referred to as PID action. PID is the most often used corrective action for
process control so the controller employed in the plant is a PID controller.
The feedback loop is the signal path from the output back to the input to correct for any variation
between the output level from the set level. In other words, the output of a process is being
continually monitored, the error between the setpoint and the output parameter is determined, and
a correction signal is then sent back to one of the process inputs to correct for changes in the
measured output parameter.
Controlled or measured variable is the monitored output variable from a process. The value of the
monitored output parameter is normally held within tight given limits. The controlled outputs are
dichlorobenzene and monochlorobenzene.
The manipulated variable is the input variable or parameter to a process that is varied by a control
signal from the processor to an actuator. By changing the input variable, the value of the measured
variable can be controlled. The manipulated variable is chlorine gas.
Setpoint is the desired value of the output parameter or variable being monitored by a sensor. Any
deviation from this value will generate an error signal.
Instrument is the name of any of the various device types for indicating or measuring physical
quantities or conditions, performance, position, direction, and the like.
Sensors are devices that can detect physical variables, such as temperature, light intensity, or
motion, and have the ability to give a measurable output that varies with the amplitude of the
physical variable.
Transducers are devices that can change one form of energy to another, e.g., a resistance
thermometer converts temperature into electrical resistance, or a thermocouple converts
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temperature into voltage. Both of these devices give an output that is proportional to the
temperature. Many transducers are grouped under the heading of sensors.
Converters are devices that are used to change the format of a signal without changing the energy
form, i.e., a change from a voltage to a current signal.
Actuators are devices that are used to control an input variable in response to a signal from a
controller. A typical actuator will be a flow-control valve that can control the rate of flow of a fluid
in proportion to the amplitude of an electrical signal from the controller. Other types of actuators
are magnetic relays that turn electrical power on and off. Examples are actuators that control power
to the fans and compressor in an air-conditioning system in response to signals from the room
temperature sensors.
Controllers are devices that monitor signals from transducers and take the necessary action to keep
the process within specified limits according to a predefined program by activating and controlling
the necessary actuators.
An error signal is a difference between the setpoint and the amplitude of the measured variable.
A correction signal is a signal used to control power to the actuator to set the level of the input
variable.
Transmitters are devices used to amplify and format signals so that they are suitable for
transmission over long distances with zero or minimal loss of information. The transmitted signal
can be in one of the several formats, that is, pneumatic, digital, analogue voltage, analogue current,
or as a radio frequency (RF) modulated signal. Digital transmission is preferred in newer systems
because the controller is a digital system, and as analogue signals can be accurately digitized,
digital signals can be transmitted without loss of information.
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8.3.1 PUMPS
It is almost impossible to talk about the control of a system without talking about the process pump
and other devices like the valves and sensors below are some of the general properties and
explanation of a pump. A pump is a device that moves fluids (liquids or gases), or sometimes
slurries, by mechanical action. Pumps can be classified into three major groups according to the
method they use to move the fluid: direct lift, displacement, and gravity pumps.
Pumps operate by some mechanism (typically reciprocating or rotary) and consume energy to
perform mechanical work moving the fluid. Pumps operate via many energy sources, including
manual operation, electricity, engines, or wind power, come in many sizes, from microscopic for
use in medical applications to large industrial pumps. Mechanical pumps serve in a wide range of
applications such as pumping water from wells, aquarium filtering, pond filtering and aeration, in
the car industry for water-cooling and fuel injection, in the energy industry for pumping oil and
natural gas or for operating cooling towers. In the medical industry, pumps are used for
biochemical processes in developing and manufacturing medicine, and as artificial replacements
for body parts, in particular the artificial heart and penile prosthesis.
When a casing contains only one revolving impeller, it is called a single-stage pump. When a
casing contains two or more revolving impellers, it is called a double- or multi-stage pump.
Pumps can be classified by their method of displacement into positive displacement pumps,
impulse pumps, velocity pumps, gravity pumps, steam pumps and valveless pumps. There are two
basic types of pumps: positive displacement and centrifugal. Although axial-flow pumps are
frequently classified as a separate type, they have essentially the same operating principles as
centrifugal pumps.
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8.3.2 SENSORS
The ability to detect a control signal is part of the major reasons why the entire control structure
requires a sensor input to the system as it transmits the required signal to make an action. A sensor
is a device, module, or subsystem whose purpose is to detect events or changes in its environment
and send the information to other electronics, frequently a computer processor. A sensor is always
used with other electronics. Sensors are used in everyday objects such as touch-sensitive elevator
buttons (tactile sensor) and lamps which dim or brighten by touching the base, besides innumerable
applications of which most people are never aware. With advances in micro machinery and easy-
to-use microcontroller platforms, the uses of sensors have expanded beyond the traditional fields
of temperature, pressure or flow measurement
A sensor's sensitivity indicates how much the sensor's output changes when the input quantity
being measured changes. For instance, if the mercury in a thermometer moves 1 cm when the
temperature changes by 1 °C, the sensitivity is 1 cm/°C (it is the slope Dy/Dx assuming a linear
characteristic). Some sensors can also affect what they measure; for instance, a room temperature
thermometer inserted into a hot cup of liquid cools the liquid while the liquid heats the
thermometer. Sensors are usually designed to have a small effect on what is measured; making the
sensor smaller often improves this and may introduce other advantages.
A chemical sensor is a self-contained analytical device that can provide information about the
chemical composition of its environment, that is, a liquid or a gas phase. [5] The information is
provided in the form of a measurable physical signal that is correlated with the concentration of a
certain chemical species (termed as analyte). Two main steps are involved in the functioning of a
chemical sensor, namely, recognition and transduction. In the recognition step, analyte molecules
interact selectively with receptor molecules or sites included in the structure of the recognition
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element of the sensor. Consequently, a characteristic physical parameter varies and this variation
is reported through an integrated transducer that generates the output signal.
8.3.3 VALVES
The valve importance to the control structure is explained generically below. A valve is a device
that regulates, directs or controls the flow of a fluid (gases, liquids, fluidized solids, or slurries) by
opening, closing, or partially obstructing various passageways. Valves are technically fittings but
are usually discussed as a separate category. In an open valve, fluid flows in a direction from higher
pressure to lower pressure. The word is derived from the Latin valve, the moving part of a door,
in turn from volvere, to turn, roll. The simplest and very ancient valve is simply a freely hinged
flap which drops to obstruct fluid (gas or liquid) flow in one direction but is pushed open by flow
in the opposite direction. This is called a check valve, as it prevents or "checks" the flow in one
direction. Modern control valves may regulate pressure or flow downstream and operate on
sophisticated automation systems. Valves have many uses, including controlling water for
irrigation, industrial uses for controlling processes, residential uses such as on/off and pressure
control to dish and clothes washers and taps in the home. Even aerosols have a tiny valve built-in.
Valves are also used in the military and transport sectors.
Valves vary widely in form and application. Sizes typically range from 0.1 mm to 60 cm. Special
valves can have a diameter exceeding 5 meters. Valve costs range from simple inexpensive
disposable valves to specialized valves which cost thousands of US dollars per inch of the diameter
of the valve. Disposable valves may be found in common household items including mini-pump
dispensers and aerosol cans. A common use of the term valve refers to the poppet valves found in
the vast majority of modern internal combustion engines such as those in most fossil fuel-powered
vehicles which are used to control the intake of the fuel-air mixture and allow exhaust gas venting.
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Valves are quite diverse and may be classified into several basic types. Valves may also be
classified by how they are actuated: Hydraulic, Pneumatic, Manual, Solenoid valve, Motor
Many valves are controlled manually with a handle attached to the stem. If the handle is turned
ninety degrees between operating positions, the valve is called a quarter-turn valve. Butterfly, ball
valves, and plug valves are often quarter-turn valves. If the handle is circular with the stem as the
axis of rotation in the centre of the circle, then the handle is called a handwheel. Valves can also
be controlled by actuators attached to the stem. They can be electromechanical actuators such as
an electric motor or solenoid, pneumatic actuators which are controlled by air pressure, or
hydraulic actuators which are controlled by the pressure of a liquid such as oil or water. Actuators
can be used for automatic control such as in washing machine cycles, remote control such as the
use of a centralised control room, or because manual control is too difficult such as when the valve
is very large. Pneumatic actuators and hydraulic actuators need pressurised air or liquid lines to
supply the actuator: an inlet line and an outlet line. Pilot valves are valves which are used to control
other valves. Pilot valves in the actuator lines control the supply of air or liquid going to the
actuators.
The fill valve in a toilet water tank is a liquid level-actuated valve. When a high water level is
reached, a mechanism shuts the valve which fills the tank.
In some valve designs, the pressure of the flowing fluid itself or pressure difference of the flowing
fluid between the ports automatically controls flow through the valve.
8.4 PLANT WISE CONTROL SYSTEM
The design of the control and instrumentation system for the chlorobenzene plant was done in
stages. Firstly, the whole process was divided into smaller sections. This is done to provide detailed
local dynamics information of each section to the control system. With these, the control system
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can have real-time influences and optimized ability to respond to disturbances to the plant process.
After each section of the whole plant, the process was defined, a model of the process dynamics
of these sections was set up with Aspen Hysys Dynamics code. These dynamics models were
studied and several sensitivity analyses were done with their operating parameters i.e valve
opening, to check these parameters influence on the process. Finally, control systems were
developed for each section based on the following criteria in order of precedence;
i. Safety
ii. Environmental Protection
iii. Equipment Protection
iv. Smooth Operation and Production Rate
v. Product Quality
vi. Profit
vii. Monitoring and Diagnosis
Each of these sections and their respective control system are explained below. Also, the transient
response of each control system when perturbed with a twenty per cent increase and decrease in
their respective feed stream can be found in appendices.
8.4.1 CONTROL SYSTEM OF DRYING COLUMN SYSTEM
In the preliminary process description of the drying distillation column, its operating conditions is
at temperature 351-358 K and close to ambient pressure. It also has an operating feed flow of
446395.3520 tons/year and product flow of 444025.8379 tons/year. To control and stabilize the
operation of this distillation column, several critical controllers must be installed. Luyben (2006)
suggested that at least five controller schemes should be used to control and stabilize the operation
of an industrial distillation column. These controllers are listed below;
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1. Pressure controller
2. Reflux drum-level controller
3. Base-level controller
4. Feed-flow controller
5. Tray temperature controller
To achieve regulation of pressure of the distillation column, the pressure of the topmost stage is
controlled with a PI controller. The manipulated variable is the duty supplied to the overhead
condenser. The controller is configured to be reverse acting such as an increase in the topmost
stage pressure will trigger the controller to increase the condenser duty.
Since the reflux drum is not included in the dynamics model developed for the drying column, its
level is controlled indirectly by controlling the condenser level. Therefore, a PI level controller
with a direct-acting effect is connected to the condenser. The manipulated variable for the process
is the desired valve opening of the distillate flow valve. With these configuration increase in liquid
level of the condenser will bring about an increase in distillate valve opening by the controller.
The control scheme is also simplified by fixing the reflux stream flow rate to a value. The base
level of the drying column is controlled and stabilized also by the action of a PI controller, a similar
configuration is applied for both controller schemes except that the output manipulated variable,
in this case, is the bottoms flow valve.
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Figure 8:1 CONTROL DIAGRAM OF BENZENE COLUMN IN ASPEN HYSYS
Figure 8:2 CONTROL DIAGRAM OF BENZENE COLUMN (INTERNAL
FLOWSHEET) IN ASPEN HYSYS
138
To control and stabilize the temperature profile of the distillation column, a temperature PI
controller is used. This controller is also configured to be reverse acting like the column pressure
controller. Before choosing the specific tray temperature to control, the column’s temperature
profile at steady state is studied and the tray with steepest temperature gradient is chosen. Also, to
model a realistic distillation column temperature control scheme, a time delay is added to the
control signal from the sensor to the controller. This is to compensate for the delay effect of most
temperature sensor in the real world. Finally, the adjusted output variable of the controller is the
column reboiler duty.
To fully stabilize the material balance of the column, the feed stream to the column must be
controlled. The controller employed for this is also a PI controller. The controller’s output variable
is the make-up benzene feed control valve’s desired valve opening. It has a reverse acting
configuration and a time filter of incorporated into its model to damped disturbance in flow
measurement. Also to improve the flexibility of the feed flow control scheme another similar flow
controller is employed to monitor and control the recycled benzene streamflow to the desired flow
rate.
8.4.2 CONTROL SYSTEM OF REACTOR SYSTEM (CSTR) SYSTEM
The rector system contains two CSTR in series. These CSTRs are operated at a pressure of 2.4
bars and isothermal temperature of 328 K respectively. There are two feed stream to the system,
benzene feed and chlorine gas feed stream. The benzene feed stream is fed in series, while the
chlorine stream is fed parallel to the two CSTRs. To minimize disturbance on the feed stream to
the reactor system, flow controllers are installed to each feed stream and a ratio controller is used
to control the chlorine feed ratio of reactor 1 to reactor 2. These controllers are configured to be
139
Figure 8:3 CONTROL DIAGRAM OF CSTR REACTOR SYSTEM IN ASPEN HYSYS
140
reverse acting and have their output manipulated variable to be the desired valve opening of their
respective controlled streams valve. The ratio controller is configured to control reactor 1 chlorine
feed stream because it is having the more flow. This will improve the throughput and the operating
range of the controller.
The reactors pressure is maintained and controlled by adjusting the vapour and liquid product flow
of each reactor. The vapour flow of each reactor is adjusted by a pressure controller, while the
liquid flow is adjusted by a level controller. These controllers are reverse acting so as, increase in
the reactors liquid level and pressure will bring about increase in the respective liquid and vapour
product valve’s desired valve openings. Finally, the reactor temperature has a significant effect on
the reaction rate. Therefore, the reactor temperature has to be kept at 328 K. This done by installing
a temperature controller for each reactor. These controllers measure the reactor temperature and
adjust the duty supply to the respective reactor to maintain its temperature. For more realistic
modelling of the temperature control, a time delay is connected between the sensor and the
controller. This is to represent the delay time effect of most thermocouple sensor used in process
industries.
8.4.3 CONTROL SYSTEM OF WASHER/NEUTRALIZER UNIT
The washer/neutralizer is phase separator use to neutralize and purge out aqueous HCl from the
crude chlorobenzene product from the reactor system. To control and stabilize the operation of this
system, aqueous NaOH and HCl must reduce to trace value in the system product stream. This is
because these components are the major impurities which reduce the purity of final MCBs and
DCBs produced in the plant. To ensure this, a feedback controller is installed on the
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Figure 8:4 CONTROL DIAGRAM OF WASHER/NEUTRALIZER IN ASPEN HYSYS
142
NaOH feed stream. This controller detects the NaOH in the system product stream and adjusts the
NaOH feed flow to keep the value to a minimum. The controller is designed to be reverse acting
which means an increase in NaOH impurities will make the controller reduce the NaOH feed flow.
The aqueous liquid level of the washer/neutralizer vessel is controlled by adjusting the purge
streamflow. This is done by a controller with reverse acting configuration. Finally, the temperature
of the vessel is controlled and stabilized by a reverse acting controller. The adjusted output variable
of the controller is the duty supply.
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CHAPTER NINE
PLANT PROCESS/SITE LAYOUT
9.1 PLANT LOCATION AND SITE SELECTION
The location of the plant can have a turning effect on the overall viability of the chlorobenzenes
plant and the scope of future expansion. Factors considered during the selection of a suitable plant
site are as follows; plant location with respect to marketing area, raw materials availability,
availability of suitable land, transport, availability of labours, availability of utilities, water,
electricity, environmental impact and effluent disposal, local community considerations, climate,
political and strategic, taxation and legal restrictions etc.
As discussed in chapter two and considering the above factors, the plant was decided to be built in
Oshodi Apapa Industrial Estate Lagos, Nigeria, that was estimated to cover about 10 hectares of
industrial lot ready land with price of #180,000.00 per square metre at Burma Road, Apapa, Apapa
Wharf, Apapa, Lagos. Apapa is a local government area in Lagos located to the west of Lagos
island. Also, the main objectives of doing this is to minimize the total distance of goods flow, the
material handling cost and the time spent in the manufacturing system.
9.2 PLANT SITE LAYOUT AND DESCRIPTION
Plant lay outing is the process of analyzing different physical configurations for a manufacturing
plant. Referring to the draft-out chlorobenzene plant site layout provided in FIG 9.1, administration
building is the main and most visited building for many purposes in a plant. It should be located
on the public and safe side of security point and as close as possible to main entrance.
Administration offices and laboratories, in which a relatively large number of people will be
working, are located well an away from potentially hazardous process which is the main processing
plant. Stores for maintenance and operating supplies was placed near to the administration
buildings so that the staff will have easy access to the service.
There is a bottom expansion just below the main process plant/tank farm and near to the waste
treatment plant. This free space is provided to be used for the placement of new equipment and
pipes in the future just in case the plant needs to be expanded. The waste treatment plant will
enable the direct transport of waste stream produced by the separation units. There is also a pond
that is placed next to the waste treatment plant and utilities plant were placed near to the main
process plant. The main process plant contains the processing unit and storage facilities.
This placement also reduces the distance and length of supply pipes used in the transporting
process of raw materials, waste, and utilities to or from the plant area, making it cost effective.
Beside it, it should be beside a road which will make it easier for loading and unloading of
materials.
Control room was placed near to the main processing plant so that easier for the operators to
monitor the operation of the plant because if the is malfunction in any of the operating process,
troops can be send to the site immediately.
Maintenance workshops and others that did not link to process materials should be located together
at the safe area and within easy access to process units. Direct access should be provided for traffic
purposes, which if possible should not pass through any process area. There is also a loading area
placed for transport of goods and raw materials where only the Lorries and other form of transport
to transfer these materials allowed entering the area. Canteen and prayer room are also provided
for the convenience of the staffs and were placed near to the administration and maintenance
workshop buildings because it is one of the most used workplace and it is a must have easy access
to these places. These buildings should be located in a safe area within a short distance of the main
145
concentration of workers. The surrounding should be attractive and relaxing for workers to release
some stress from hectic workloads.
For quality control of products, a plant needs a laboratory to inspect the products produced. Work
laboratories should be located at a safe area near the administration building, where most facilities
are completed. Clinic is placed next to the laboratory to handle any emergency case caused by
chemicals. Fire house to handle emergency cases for example fire or explosion of the plant is built
near to the main processing plant.
Sufficient car parks facilities also provided for the convenience of the staff and personnel or
visitors to park their vehicles. Car parks are placed near to the main entrance to prevent any
unwanted hazard to the properties.
9.2 PLANT PROCESS LAYOUT AND DESCRIPTION
Plant process layout refers to the arrangement of physical facilities such as equipment, tools,
machines, etc. in such a manner that so as to have quickest flow of materials at the lowest cost and
with the least amount of handling in processing the product from the receipt of raw materials to
the delivery of the final product. The economic construction and operation of a process unit will
depend on the how well the plant equipment specified on the process flow sheet are laid out. Plant
process layout designing and implementation is influenced by various factors. These factors are as
follows (Towler, G. P. and Sinnott, R., 2008); economic considerations (constructing and
operating costs), convenience of operations, convenience of maintenance, health and safety
considerations, future expansion, modular construction.
Developing a consistent layout for the chlorobenzene plant process is really a daunting task. Many
constraints such as those mention above has to be overcome. During the process of drafting out
the layout, the entire plant process was first divided into sub systems which includes the feed
146
storage section, reactor system section, product separation section, and product storage section.
For each of this sub systems, a plot plan is created. Since there are three distillation column in the
plant, a reasonable arrangement for the layout of the plant will be grade mounted horizontal inline.
In this arrangement, the process equipment units are aligned on either side of a pipe rack that runs
through the middle of the process unit. The purpose of the pipe rack is to carry piping for utilities,
product, and feed to and from the process unit. Equipment is located on either side of the pipe rack,
which allows for easy access. After each plot plan is screened, the entire plant process layout
divided of four areas i.e. Area 1-4 and 10 units. The areas and units whose operation have much
interactions with one another are sited closer. Information about the operation of the plant can be
found in the attached developed piping diagram of the plant process in the appendices. The drafted
process layout diagram of the plant is given in FIG 9.2. Also, the 3D model of process equipment
in the layout diagram is attached in the appendices section. Each areas and units in the layout are
explained below;
AREA 1
This area contains the feed and treated feed storage facilities and it has two units, which are;
1Unit 1: This unit contains the storage tanks for chlorine gas feed (TK-101) and raw benzene feed
(TK-102). It also contains the chlorine gas compressor (C-101A/C-101B), the benzene feed pump
(C-101A/C-101B) which are used to force the flow of feed into the processing areas.
1Unit 2: This unit contains the treated benzene storage tank (TK-104) which stores benzene
coming from drying column unit (2Unit 1). This benzene has been distilled to remove water
content to less than 30 ppm by weight. After storage, the treated benzene can then be send back to
processing units through the reactor system unit (2Unit 2). Where it is used as benzene feed for
chlorobenzene production. The unit also contains process water storage tank (TK-103) which is
147
used to store process water from drying column unit (2Unit 2) and water utility source. This
process water can then be pump to washer/neutralizer unit (3Unit 1) for utility uses.
AREA 2
This is the area where the main conversion of the feed benzene and chlorine takes place to produces
chlorobenzenes and HCl. It contains benzene drying column (T-201), the reactor system and HCl
purification system. It has three units which are;
2Unit 1: This unit contains the benzene drying column (T-201) used to reduce water content of
benzene stream feed to the reactor system to less than 30 ppm. All the components of the benzene
distillation column are sited in this unit. These component includes the column feed stabilizing
drum (V-201), the distillation tower(T-201), reboiler heat exchanger(E-201), condenser heat
exchanger (E-202), reflux drum (V-202) and pumps station. The area receives benzene and
recycled benzene from these units; 1Unit1, 3Unit2 and 4Unit 1. The benzene is processed and sent
to reactor system unit (1Unit 2) or to storage unit (1Unit 2). The process water removed is sent to
storage (1Unit2).
2Unit 2: This is the main unit where the reaction of benzene and chlorine to form chlorobenzenes
and HCl takes place. It houses the two series CSTR reactors (R-201/R-202) and all their component
equipment such as pumps. The unit receives processed benzene from storage (1Unit 2) and drying
column unit (2Unit 1) and chlorine gas feed from storage (1Unit1). The HCl gas product is sent to
HCl purification unit (2Unit 3) for purification and chlorobenzenes liquid is sent to
washer/neutralizer unit (3Unit 1) where all it remaining HCl content is washed out.
2Unit 3: This unit is serves as the HCl purification unit where benzene and impurities in the HCl
gas product from the reactor system unit (2Unit 2) are removed. It also contains a storage tank
(TK-201) for the purified HCl gas. Major equipment in the unit are the HCl air fin cooler (E-203),
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HCl adsorber column (T-202), HCl gas storage tank (TK-201) and pumps station. The benzene
removed from the process is recycled back through storage (4Unit1).
AREA 3
This area is where the separation of crude chlorobenzene produced in the reactor system unit
(2Unit 2) takes place. It contains the washer/neutralizer (V-302), the benzene distillation column
(T-301) and the chlorobenzenes distillation column (T-302). It has three units which are;
3Unit 1: In this unit, the liquid crude chlorobenzenes from reactor system unit (2Unit 2) is
washed/neutralized with NaOH solution to remove all its HCl content. This takes place in a three
phase separator called washer/neutralizer (V-302). Other process equipment in this unit include
mixing drum (V-301) for making a standard solution of NaOH and pumps station. The unit sends
HCl free chlorobenzenes to benzene distillation unit (3Unit 2) for removal of benzene.
3Unit 2: This unit contains the benzene distillation column (T-301) used to ensure chlorobenzenes
product specification. This is done by distilling out unreacted benzene in chlorobenzenes stream
from washer/neutralizer unit (3Unit 1). The benzene is either recycled back into the process
through drying column unit (2Unit 1) or sent to storage (4Unit 1). There is also provision for
returning stored benzene from storage unit (4Unit 1) for reprocessing. Finally, the benzene free
chlorobenzenes is pump to the chlorobenzenes distillation unit (3Unit 1) for separation into
monochlorobenzene and dichlorobenzene or to 4Unit 1 for storage. Major equipment in the unit
are the component of the distillation column which includes the column feed stabilizing drum (V-
303), the distillation tower (T-301), reboiler heat exchanger (E-301), condenser heat exchanger
(E-302), reflux drum (V-304) and pumps station.
3Unit 3: This unit houses the chlorobenzenes distillation column (T-302). The distillation column
is used to separate fed chlorobenzenes mixture into monochlorobenzene and
149
Figure 9:1 CHLOROBENZENES PLANT SITE LAYOUT DIAGRAM
150
Figure 9:2 CHLOROBENZENES PLANT PROCESS LAYOUT DIAGRAM
151
dichlorobenzene. This is done to meet the plant product specification for monochlorobenzene
product and dichlorobenzene product. After separation, both monochlorobenzene and
dichlorobenzene are sent to their storage unit (4Unit 2). The chlorobenzenes mixture feed to this
unit comes from benzene distillation unit (3Unit 2) and storage (4Unit 1). The unit contains all the
component of the chlorobenzenes distillation column which includes the column feed stabilizing
drum (V-305), the distillation tower (T-302), reboiler heat exchanger (E-303), condenser heat
exchanger (E-304), reflux drum (V-306) and pumps station.
AREA 4
This area contains the product and recycled product storage facilities. It stores chlorobenzenes,
benzene, monochlorobenzene and dichlorobenzene. It has two units, which are;
4Unit 1: This unit contains two storage tanks. One for recycled benzene from benzene distillation
unit (3Unit 2) and HCl purification unit (2Unit 3) (TK-402) and one for chlorobenzenes from
benzene distillation unit (3Unit 2) (TK-401). It also has pumps station used for moving fluid from
the unit to their destination unit. In the unit, benzene can be pump back to benzene distillation unit
(3Unit 2) or to drying column unit (2Unit 1). The chlorobenzenes from this unit is pump to
chlorobenzenes distillation unit (3Unit 3).
4Unit 2: This is the final product storage unit for the plant. It also has two storage tanks; one stores
the monochlorobenzene product (TK-404) while the other stores dichlorobenzene product (TK-
403). The unit receives monochlorobenzene and dichlorobenzene from chlorobenzenes distillation
unit (3Unit 3).
152
CHAPTER TEN
PLANT COST ESTIMATION AND ECONOMIC ANALYSIS
10.1 BACKGROUND OF PLANT ECONOMICS
Chemical plants are built to make a profit, and an estimate of the investment required and the cost
of production are needed before the profitability of a project can be assessed. An acceptable plant
design must present a process that is capable of operating under conditions which will yield a
profit. Since net profit equals total income minus all expenses, it is essential that the chemical
engineer be aware of the many different types of costs involved in manufacturing processes.
Capital must be allocated for direct plant expenses, such as those for raw materials, labour, and
equipment. Besides direct expenses, many other indirect expenses are incurred, and these must be
included if a complete analysis of the total cost is to be obtained. Some examples of these indirect
expenses are administrative salaries, product-distribution costs, and costs for interplant
communications.
A capital investment is required for any industrial process, and determination of the necessary
investment is an important part of a plant-design project. The total investment for any process
consists of fixed-capital investment for physical equipment and facilities in the plant plus working
capital which must be available to pay salaries, keep raw materials and products on hand, and
handle other special items requiring a direct cash outlay. Thus, in an analysis of costs in industrial
processes, capital-investment costs, manufacturing costs, and general expenses including income
taxes must be taken into consideration.

In the design of a project, just as optimal production is to be achieved, economic analysis is also required
to compare alternatives and make the right choice. The operating cost, equipment cost, the cost of producing
the product and all other costs put together are needed to judge the viability of a project.
There are various costs incurred in design and implementation of a process:
Capital costs
Capital cost is divided into two: Fixed capital (total cost of the plant ready for start-up) and Working capital
(additional investment needed to start the plant up and operate it to the point where income is earned). Fixed
capital includes the cost of design, equipment and their installation, piping, instrumentation and control
systems, buildings and structures, auxiliary facilities (utilities, land, civil engineering work); it is a once-
only cost that is not recovered at the end of the project life. Working capital includes the start-up costs,
initial catalyst charges (if any), raw materials and inventories; most of it is recovered at the end of the
project life.
Fixed operating costs
These types of costs do not vary with the production rate. They include: maintenance cost, operating labour,
laboratory costs, supervision, plant over heads, capital charged, rates and taxes, insurance, license fees and
royalty payments. The plant supervision has no control over the fixed-cost items.
Variable operating costs
Variable cost are dependent on the amount of products produced. They include items for which the plant
supervision can be held accountable, such as: raw materials, utilities, shipping and packaging and
miscellaneous operating materials.
In addition to this, general overheads costs, research and development, sales expense and reserves cost are
taken into consideration. The sum of all these costs is the total investment and production cost. ()
(fixed and working capitals-may 6, operating costs-may14; chemicalprojects.wordpress.com; May 6,
2014;Jan 6, 2020)
154
10.2 PURCHASED COST OF EQUIPMENT
Cost estimates are often not fixed. As a result of inflation over time, price values change and present costs
are estimated from past costs.
The method usually adopted in updating historical cost data makes use of published cost indices. These
indices relate present costs to past costs, and are based on data for labour, material and energy costs
published in government statistical digests. For different years, present costs can be estimated according to
the expression below:
Cost in present year = Cost in base year x (Cost index in present year/Cost index in base year)
In this report, 2004 is used as base year and Figure 10.1 gives a plot of cost indices for various years.
155
Figure 10:1 CHEMICAL ENGINEERING PLANT COST INDEX
156
Using the linear equation from the graph, cost index for 2004 is 444.2, the cost index for 2019 can be
obtained as:
y = 32.6x – 64411
y = 32.5(2019) – 64411 = 1206.5
Therefore, present costs can be obtained by the expression:
Present cost = base cost (2004) x (1206.5/444.2)
Present cost = base cost (2004) x 2.72
1. Reactors
(a) 2 CSTR Reactors
Type: Jacketed and Agitated
Material: Carbon steel
Capacity: 18,900Litres (Length 6m, Diameter 2m)
Internal pressure: 1atm to 25psi
Base cost (2004): $770328(material factor 1.0, pressure factor 1.1)
Present cost = $770328 x 2.72 x 1.0 x 1.1 x 2 = $4,609,646
(b) 2 Neutralization Reactors
Type: Mixer / Settler
Capacity: 22712Litres
Internal Pressure: 1atm to 25psi
Base cost (2004): $272200 (material factor = 1.0, pressure factor = 1.1)
Present Cost = $272200 x 2.72 x 1.0 x 1.1 x 2 = $1,628,845
2.Distillation Columns
(a) 2 Benzene Column
157
Weight: 32000kg
Type: No internals, large
Present Cost: $220100 x 2.72 x 2.0 x 1.1 x 2 = $2,634,157
(b) 2 Chlorobenzene Column
Weight: 32000kg
Type: Sphere ASME, large
Present Cost: $167000 x 2.72x 2.0 x 1.1 x 2 = $1,998,656
Cost of a plate = $650 (material factor = 1.7; Number of plates = 25)
Total cost of plates = $650 x 25 x 1.7 x 2.72 x 2 = $150280
Total cost of column = $1,998,656 + 150280
= $2,148,936
(c) 2 Drying columns
Weight: 32000kg; Material: Carbon Steel; Type: Column No Internals, large
Present Cost: $196400 x 2.72 x 2.0 x 1.1 x 2 = $2,350,515
3. Decanter Unit
Area: 18.58 m2
Material: Carbon Steel, 1atm pressure
Base Cost (2004): $103600 (type factor = 0.8, pressure factor = 1.1)
Present Cost: $103600 x 0.8 x 1.1 x 2.72 = $247,977
158
4. 2 Coolers
Type: Forced Draft
Cooling Load: 1 Million BTU/hr
Material: Carbon Steel; 1atm Pressure
Base cost(2004): $3600 (type factor = 0.85, pressure factor = 1.0)
Present Cost: $3600 x 0.85 x 1.0 x 2.72 x 2 = $16,646
5. Condenser
Type: Air Conditioner Package
Cooling Load: 1 Million BTU/hr
Material: Carbon Steel, 1atm pressure
Base cost (2004): $436,800 (type factor = 0.85, pressure factor = 1.0
Present Cost: $436,800 x 0.85 x 1.0 x 2.72 = $1,009,882
6. Mixer
Type: Propeller, Top Entering
Power: 10hp; 1atm to 25 psi Internal pressure
Base Cost (2004): $9000 (type factor = 0.85, pressure factor = 1.0)
Present Cost: $9000 x 2.72 x 0.85 x 1 = $20,808
7. 6 Pump
Type: Centrifugal Inline, API- 610 w/ Motor, 13.94 m2 head
Material: Cast Iron w/Rubber lining, Mechanical Seal
Base cost (2004): $13900 (type factor = 0.85, pressure factor = 1.0)
Present cost: $13900 x 2.72 x 0.85 x 1.0 X 6 = $192,821
159
8. 4 Compressor
Type: Air Rotary Screw
Material: Cast Iron, 125 psi pressure, I.R 200 HP
Base cost (2004): $5950(type factor = 0.85, pressure factor = 1.0)
Present Cost: $5950 x 2.72 x 0.85 x 1 x 4 = $55,025
9. 3 Reboilers
Type: Carbon Steel; 23.22 m2; 150 psi I.R
Base cost (2004): $17300 (type factor = 0.8, pressure factor = 1.0)
Present Cost: $17300 x 2.72 x 0.8 x 1.0 x 3 = $112,934
10. Storage Tanks
(a) Chlorine gas Tank: Horizontal, Fuel Storage; Capacity: 20000 gallons, Cast Iron
Base Cost (2004): $6, 900 (type factor = 0.85, pressure factor = 1.0)
Present Cost: $6,900 x 2.72 x 0.85 x 1.0 = $15,953
(b) Raw Benzene Feed Tank: API Floating Roof, Carbon Steel, 25000 gallons capacity
Base Cost: $9,200 (type factor = 0.85, pressure factor = 1.0)
Present Cost: $9,200 x 2.72 x 0.85 x 1.0 = $21,270
(c )Synthesis Gas Feed Horizontal Round Ends; 40000 gallons capacity; Carbon Steel & API
Base cost (2004): $7, 600 (type factor = 0.85, pressure factor = 1.0)
Present Cost: $7,600 x 2.72 x 0.85 x 1.0 = $17,571
(d)2 Chlorobenzene Storage Tank
Type: Vertical Cone, Floating Roof, Flat Bottom, 40000 gallons capacity, Carbon Steel & glass lined API
Present Cost: $8,400 x 2.72 x 0.85 x 1.0= $19,421
(e)8 Tanks for Intermediate Chemicals (Purge Streams, NaOH, Treated Water)
160
Type: 30000 gallons capacity, cast iron, Horizontal fuel storage
Present Cost: $4,300 x 2.72 x 0.85 x 1.0 x 8= $79,533
11. 2 Recycles
Base Cost (2004): $1,750 (type factor = 0.85, pressure factor = 1.0)
Present Cost: $1750 x 0.85 x 1 x 2.72 x 2 units = $8092
12. 10 Valves
Base Cost (2004): $1430
Present Cost: $1430 x 0.85 x 1 x 2.7233 x 10 pieces = $33,062
Purchase Cost of Equipment (PCE): $15,373,374
The equivalent of 1 US Dollar in naira, as at 14 January, 2020 was N362.5. Therefore, the purchase cost of
equipment in naira is N5,572,848,075.
10.3 TOTAL PURCHASE COST OF EQUIPMENT
The total purchase cost of equipment can then be obtained by making use of some factors, as detailed in
Table 10.1. These factors are summed up and multiplied with the purchase cost of equipment obtained in
section 10.2 to give the total physical plant cost (PPC).
161
TABLE 10:1 TYPICAL FACTORS FOR ESTIMATION OF PROJECT FIXED
CAPITAL COST
162
PPC = PCE (1 + f1+f2+………+f9)
= PCE (1+0.4+0.7+0.2+0.1+0.15+0.5+0.15+0.05+0.15)
= PCE (3.4)
PPC = N5,572,848,075 x 3.4 = N18,947,683,460
Including indirect cost factors to obtained the fixed capital for the purchase of equipment,
Fixed capital = PPC (1+f10+f11+f12)
=PPC (1+0.30+0.05+0.10)
=PPC (1.45)
Fixed capital = N18,947,683,460 x 1.45 = N27,474,141,020
10.4 TOTAL CAPITAL INVESTMENT
The total capital investment is obtained by adding the fixed capital to the working capital; the working
capital can vary from as low as 5% of the fixed capital for a simple, single product, process, with little or
no finished product storage; to as high as 30% for a process producing a diverse range of product grades
for a sophisticated market, such as synthetic fibers. But for petrochemical plant, atypical figure is 15%.
Working Capital = 15% of Fixed Capital
= 15% x N27,474,141,020 = N4,121,121,153
Total capital Investment = Fixed capital + Working capital
= N27,474,141,020 + N4,121,121,153
= N31,595,262,170
Start-up cost is usually 5-20% of TCI. Assume 10% of TCI
Start- Up Cost = 0.10 x N31,595,262,170
= N3,159,526,217
10.6 ESTIMATION OF TOTAL PRODUCTION COST
Manufacturing Cost = Direct production cost + Fixed charges + Plant overhead cost.
163
(a) Fixed Charges is10-20% total product cost
(i) Depreciation: Depends on life period, salvage value and method of calculation- about 10% of FCI for
machinery and equipment and 2-3% for Building Value.
Using Depreciation = 10% of FCI for machinery and equipment and 3% for Building Value for Buildings)
Depreciation =0.10 x N27,474,141,020 + 0.03 x N147,497,005 =N2,747,856,593
(ii) Local Taxes: 1-4% of Fixed Capital Investment
Using local taxes = 3% of fixed capital investment
Local Taxes = 0.03 x N27,474,141,020 = N824,224,231
(iii) Insurances (0.4-1% of Fixed Capital Investment)
Using Insurance = 1% of fixed capital investment
Insurance = 0.01 x N27,474,141,020 = N274,741,410
(iv) Rent: 8-12% of value of rented land and buildings
Using Rent = 8% of value of rented land and buildings
= 0.08 x 147,497,005 + 0.08 x 49,165,668
= N 15,733,014
Therefore, Fixed Charges = 2,747,856,593 + 824,224,231 + 274,741,410+ 15,733,014
= N3,848,395,248
(b) Direct Production Cost (about 60% of total product cost)
(i) Total Product Cost
Fixed charges = 10-20% of total product charges
Since the Fixed charges = 15% of total product cost
Total Product Cost (TPC) = (100/15) x N3,848,395,248= N25,655,968,320
(ii) Raw Materials (10-50% of total product cost)
Using Raw material cost = 30% of total product cost
164
Raw material cost = 0.30 x 25,633,968,320 = N7,696,790,496
(iii) Operating Labour (OL) is 10-20% of total product cost
Using Operating Labour = 12% of total product cost
Operating labour cost = 0.12 x 25,633,968,320 = N3,078,716,199
(iv) Direct Supervisory and Clerical Labour (DS & CL) is 10-25% of OL
Using Direct supervisory and Clerical labour = 15% of OL
Direct supervisory and Clerical labour cost = 0.15 x N3,078,716,199 = N461,807,430
(v) Utilities (10-20% of total product cost)
Using Utilities cost = 10% of total product cost
Utilities cost = 0.10 x 25,655,968,320 = N2,565,596,832
(vi) Maintenance and repairs (M & R) (2-10% of FCI)
Using Maintenance and Repair cost = 4% of fixed capital investment
Maintenance and Repair cost = 0.04 x N27,474,141,020 = N1,098,965,641
(vii) Operating Supplies: (10-20% of M & R or 0.5-1% of FCI)
Using Operating supplies cost = 15% of Maintenance & Repairs
Operating supplies cost = 0.15 x 136,877,220.70 = NGN 20,531,583.10
(viii) Laboratory Charges: (10-30% of OL)
Consider the Laboratory charges = 30% of OL
Laboratory charges = 0.30 x N3,078,716,199= N923,614,860
(ix) Patent and Royalties (0-6% of total product cost)
Using Patent and Royalties cost = 2% of total product cost
Patent and Royalties = 0.02 x 25,655,968,320 = N513,119,367
Thus, Direct Production Cost = N7696790496 + N3078716199 + N461807430 + N2565596832 +
N1098965641 + N20531583 + N923614860 + N513119367
165
=N16,359,142,410
(c) Plant overhead Costs: 50-70% of Operating labour, supervision, and maintenance or 5-15% of total
product cost; includes for the following: general plant upkeep and overhead, payroll overhead,
packaging, medical services, safety and protection, restaurants, recreation, salvage, laboratories, and
storage facilities.
Using Plant overhead cost = 60% of OL, DS & CL, and M & R
Plant overhead cost = 0.6 x (3078716199 + 461807430 + 1098965641)
= N2,783,693,562
Thus,
Manufacture cost = Direct production cost + Fixed charges + Plant overhead costs.
Manufacture cost = 16,359,142,410 + 3,848,395,248 + 273693562
= N22,991,231,220
General Expenses = Administrative costs + distribution and selling costs + research and development
costs
1. Administrative costs:
(About 15% of costs for operating labour, supervision, and maintenance or 2-6% of total product cost);
includes costs for executive salaries, clerical wages, legal fees, office supplies, and communications.
Using Administrative costs = 15% of OL, DS & CL, and M & R
Administrative costs = 0.15 x (3078716199 + 461807430 + 1098965641)
= N695,923,390
2. Distribution and Selling costs:
(2-20% of total product cost); includes costs for sales offices, salesmen, shipping, and advertising.
Using Distribution and Selling costs = 5% of total product cost
Distribution and selling costs = 0.05 x 25,655,968,320 = N1,282,798,416
166
3. Research and Development costs: (about 5% of total product cost)
Using Research and Development costs = 5% of total product cost
Research and development costs = 0.05 x 25,655,968,320 = N1,282,798,416
4. Financing (interest):(0-10% of TCI)
Using Interest = 5% of total capital investment
Interest = 0.05 × 31,595,262,170 = N1,579,763,109
General Expenses = N695,923,390 + N1,282,798,416 + N1,282,798,416 + N1,579,763,109
= N4,841,283,331
Total Product Cost = Manufacturing cost + General Expenses + Start- up cost
= N22,991,231,220 + N4,841,283,331+ N3,159,526,217
= N30,992,040,770
10.7 PROFITABILITY ANALYSIS
By market survey (http://alibaba.com/products/mono_chloro_benzene.html), the international selling price
of monochlorobenzene is between US $1-1.5/kg. Therefore, we can safely assume $1.3/kg of MCB.
By market survey (http://alibaba.com/products/dichlorobenzen.html), the international selling price of
dichlorobenzene is between US $2000-2160/metric tonne. Thus we can safely assume US$ 2050 /tonne of
DCB.
For 20,000 tonnes of MCB, total quantity in kg is 20,000,000
At 99.7 percent purity of monochlorobenzene = 20,000,000 x 0.997 = 1.994 x 107 kg
For 2,000 tonnes of DCB, total quantity in kg is 2,000,000 kg
At 99.6 percent purity of dichlorobenzene = 2,000,000 x 0.996 = 1.992 X 106 kg
Thus, income from MCB is calculated thus
= 1.3 x 1.994 x 107 x 362.5
= N9,396,725,000
167
Income from DCB is calculated thus
= 2050 x 362.5 x 1.992 x 106
= N1,480,305 x 106
Hence, Total Income = N9,396,725,000+ N1,480,305 x 106
= N9,398,205,305
Gross Income = Total Income - Total Product Cost
=N30,992,040,770 - N9,398,205,305
= N21,593,835,470
Assume Taxes (local, state, national) = 20% of Gross Income
Tax = 0.20 x N21,593,835,470
= N4,318,767,093
Net Profit = Gross Income – Tax
= N21,593,835,470- N4,318,767,093
= N17,275,068,380
Hence, a net profit of seventeen billion, two hundred and seventy-five million, sixty-eight thousand,
three hundred and eighty naira only is estimated on the 20,000 and 2,000 tonnes capacity per year
monochlorobenzene and dichlorobenzene plant.
168
CHAPTER ELEVEN
SAFETY OF PROCESS PLANT
11.1 SAFETY AND LOSS PREVENTION IN PROCESS PLANT
Process safety generally refers to the prevention of unintentional releases of chemicals, energy, or
other potentially dangerous materials (including steam) during the course of chemical processes
that can have a serious effect to the plant and environment. Process safety involves, for example,
the prevention of leaks, spills, equipment malfunction, over-pressures, over-
temperatures, corrosion, metal fatigue and other similar conditions.
Process safety programs focus on the design and engineering of facilities, maintenance of
equipment, effective alarms, effective control points, procedures and training. It is sometimes
useful to consider process safety as the outcome or result of a wide range of technical,
management and operational disciplines coming together in an organized way.
In the Petroleum industry, Process safety focuses on preventing fires, explosions and
accidental chemical releases in chemical process facilities or other facilities dealing
with hazardous materials such as refineries, and oil and gas (onshore and offshore) production
installations.
According to Lee, Loss prevention is a distinctive approach to hazards and failures that cause loss
of life and property in the process industry. This involves putting together much greater emphasis
on technological measures and to control hazards on trying to get things right first time.
Loss prevention is an insurance term, the loss being the financial loss caused by an accident. This
loss will be not only the cost of replacing the damaged plant, paying fines, and settling third-party
claims, but also the loss of earnings from lost production and lost sales opportunities. In the event
of a major incident, such costs can be large enough to overwhelm a company
According to Sinnot (2005), Processes can be divided into those that are intrinsically/inherently
safe and those for which the safety has to be engineered in. An intrinsically safe process is one in
which safe operation is inherent in the nature of the process, a process which causes no danger, or
negligible danger, under all foreseeable circumstances (all possible deviations from the design
operating conditions).
The term engineered safety is used to describe processes that depends on the design and provision
of engineered safety devices, and on good operating practices, to prevent a dangerous situation
developing, and to minimize the consequences of any incident that arises from the failure of these
safeguards.
Engineered safety covers the provision in the design of control systems, alarms, trips, pressure-
relief devices, automatic shutdown systems, duplication of key equipment services; and
firefighting equipment, sprinkler systems, and blast walls, to contain any fire or explosion.
According to Sinnot (2005), most chemical manufacturing processes are, to a greater or lesser
extent, inherently unsafe, and dangerous situations can develop if the process conditions deviate
from the design value.
11.1.1 THE NEEDS FOR SAFETY IN THE CHLOROBENZENE PLANT.
The chemical industry of which the Chlorobenzene plant is an important mention is a high-risk
industry where a fatal mistake can be catastrophic. Industrial Safety is thus employed to safeguard
lives, reduces risks to people, and processes Process control and safety systems are .usually
170
merged. Maintaining a safe and healthy working environment is not only an important human
resources issue, it's the law. Whether they're entry-level workers, seasoned veterans, supervisors,
or plant managers, the employees need to understand health and safety risks, the steps they need
to take to minimize those risks, and common safety standards and compliance procedures.
11.2 HAZARDS ASSOCIATED WITH THE PRODUCTION OF CHLOROBENZENE
The hazards associated with the production of chlorobenzene can be grouped into:
i. Material Hazards
ii. Process Hazards
11.2.1 MATERIAL HAZARDS
Material hazards are special hazards which are peculiar about the Chlorobenzene Plant. This
hazard results from the overall effect of all the chemicals that were used in the production process.
Material hazard caused by chlorobenzene is reviewed under the following headings:
i. Toxicity
ii. Flammability
iii. Reactivity
11.2.1.1 TOXICITY
Toxicological information available in MSDS for chlorobenzene shows that it is a carcinogenic
organic substance and thus poisonous in nature. The extent of poisoning depends on the degree
and duration of exposure.
Short term exposure to chlorobenzene may result in irritation of the eyes and skin. ingestion of
liquid chlorobenzene or its inhalation into the lungs may result in chemical pneumonitis. It may
also cause effects on the central nervous system which may result in lowering of consciousness.
171
Exposure to chlorobenzene over a long period of time defats the skin, which may cause dryness or
cracking. It may have effects on the liver and kidneys.
11.2.1.2 FLAMMABILITY
Information about the flashpoint, autoignition temperature, flammability limit and combustion
energy of chlorobenzene as obtained in the MSDS shows that chlorobenzene is a flammable liquid
having the potential of causing dangerous fire hazard when exposed to heat or flame.
11.2.1.3 REACTIVITY
Chlorobenzene is Stable under normal temperatures and pressure which has shown tested
incompatibility with strong oxidizing agents and bases. Hazardous Products of its decomposition
are Hydrogen chloride, phosgene, carbon monoxide, carbon dioxide with zero cases of hazardous
polymerization of the substance reported till date.
The details about the material hazard resulting from chlorobenzene is found in the Material, Safety
and Data Sheet (MSDS) which is discussed in the later part of this body of report.
11.2.2 PROCESS HAZARDS
In addition to the hazards caused by chemical or materials properties, hazards can arise from the
conditions under which processes are carried out and the equipment that is used.
Process hazards in chlorobenzene plant may arise as a result:
i. Pressure hazards
ii. Temperature Deviations
iii. Fire Explosion
iv. Human Error
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11.2.2.1 PRESSURE HAZARDS
Overpressure, a pressure exceeding the system designed pressure, is one of the most serious
hazards in chemical plant operation. If the pressure exceeds the maximum allowable working
pressure of the vessel by more than the safety margin allowed in the vessel design code, then failure
of the vessel can occur, usually at a joint or flange. Failure of a vessel, or the associated piping,
can precipitate a sequence of events that culminate in a disaster. Fire hazards, equipment rupturing,
structural damages and failures are about the most common form of pressure hazards.
11.2.2.2 TEMPERATURE DEVIATIONS
Excessively high temperature, over and above that for which the equipment was designed, can
cause structural failure and initiate a disaster. High temperatures can arise from loss of control of
reactors and heaters; and, externally, from open fires. In the design of chlorobenzene plant where
high temperature poses a threat, temperature deviation is prevented by provision of high-
temperature alarms, The selection of intrinsically safe heating systems and provision of quench
systems for emergency shutdown.
11.2.2.3 FIRE EXPLOSION
An explosion is the sudden, catastrophic release of energy, causing a pressure wave (blast wave).
An explosion can occur without fire, such as the failure through overpressure of a steam boiler or
an air receiver in the chlorobenzene plant.
In a chlorobenzene plant, explosion may arise as a result of Confined Vapor Cloud Explosion
(CVCE) where few kilogram of a flammable process material is released into the confined space,
or, Unconfined Vapor Cloud Explosions (UCVCE) resulting from the release of a considerable
quantity of flammable gas, or vapor, into the atmosphere, and its subsequent ignition. Such an
explosion can cause extensive damage
173
Boiling liquid expanding vapor explosions may also occur when there is a sudden release of vapor,
containing liquid droplets, due to the failure of a storage vessel.
11.2.2.4 HUMAN ERROR
Even with a capable, experienced, and well-trained staff, however, there is always a possibility of
human error. The likelihood of operator error is substantially increased if operating procedures are
not clearly documented and followed or if there are lapses in training and supervision. These errors
may lead to hazard the magnitude of which is dependent on the process material and operating
conditions
11.3 INTERNATIONAL AND REGIONAL GUIDELINES ON SAFETY IN CHEMICAL
PROCESS INDUSTRIES
Because of the particular hazards associated with processing large quantities of chemicals and
fuels, most governments have enacted legislation to ensure that best safety practices are followed.
These enactments serve as the basis for the formulation of safety regulation by organizations in a
country. These enactments will also serve as the framework for the formulation of safety rules,
regulations and legislations that will be applied in our chlorobenzene plant.
11.3.1 IN THE UNITED STATES
The major federal laws relating to chemical plant safety are:
1. The Occupational Safety and Health Act, 29 U.S.C. 651 et seq. (1970): Employers must
provide a place of employment free from recognized hazards to safety and health, such as
exposure to toxic chemicals, excessive noise, mechanical dangers, heat or cold stress, or
unsanitary conditions. Employers must provide personal protective equipment and
training, including communication of hazards. Facilities must undergo hazard analysis. The
174
Occupational Safety and Health Administration (OSHA) is established to promote best
practices, inspect facilities, set standards, and enforce the law.
2. The Toxic Substances Control Act (TSCA), 15 U.S.C. 2601 et seq. (1976): The
Environmental Protection Agency is required to regulate the 75,000 chemical substances
used in industry. Extensive review is required before a new chemical can be manufactured,
imported, or sold in the United States. The EPA can ban or restrict the import, manufacture,
and use of any chemical. Under TSCA, anyone has a right and an obligation to report
information about new or alleged health or environmental effects caused by a chemical.
Companies must submit a premanufacture notice (PMN) to EPA 90 days before
manufacturing or importing a new chemical.
3. The Emergency Planning and Community Right-to-Know Act (EPCRA), 42 U.S.C. 11011
et seq. (1986): Facilities must make plans for major incidents. Plans must be made public
to the local community.
11.3.2 SUB- REGIONAL LEGISLATION
According to OSH handbook, Nigeria belongs sub-regionally to the Economic Community of
West African States (ECOWAS) and the African Union, Regionally.
There are however no developed technical OSH policies and Codes of Practice by these Sub-
Regional and Regional bodies for adoption and adaptation by member countries.
11.3.3 NATIONAL POLICY ON OCCUPATIONAL SAFETY AND HEALTH
The competent national authority responsible for OSH regulation in Nigeria is the Federal Ministry
of Labor and Employment. The Ministry has the responsibility for safeguarding and promoting the
health, safety, and wellbeing of workers in their various workplaces, with a view of preventing the
occurrence of work-related illnesses, injuries and/or death and reduce damage to property, work
175
injury, treatment and rehabilitation of injured persons and compensation claims thereby improving
productivity.
This authority is held by the Occupational Safety and Health Department of the Ministry. The
Department was established as Factory Inspectorate Division in 1955, regulating the work
practices, work conditions, work materials/ substances used, as well as the work environment by
way of implementing and enforcing the National Policy on OSH, National Workplace Policy on
HIV and AIDS (Revised 2013) and its implementation Guideline and National Action Plan and
Factories Act 2004 and its subsidiary legislations. National Policy on occupational safety and
Health came into force in 2006.
The goals of the Policy are to:
a) Facilitate improvement of occupational safety and health performance by providing
the framework for participative occupational safety and health protection of workers
including the most vulnerable groups in all sectors of economic activities.
b) Ensure harmonization of workers‟ rights protection with regional and international
standards in a private sector-led economic growth thus, focusing the role of the competent
authority in facilitating an enabling environment and regulating various provisions for
securing safety, health and welfare of workers in Nigerian workplaces.
11.3.4 LAGOS STATE SAFETY COMMISSION
The Lagos State Safety Commission is an agency of government whose primary objective is to
ensure safety, health and welfare of all workers in all workplaces in Lagos State, South- West
Nigeria. The Commission derives its powers from the Lagos State Safety Commission (LSSC)
Law, 2011.
176
The LSSC Law empowers the Commission to enforce all safety laws, guidelines, policies,
standards and regulations in Lagos State
11.4 KEY ACTIVITIES IN THE CHLOROBENZENE PLANT AND APPROPRIATE
SAFETY MEASURES
The major activities, unit operations and processes that goes into the actual design of
chlorobenzene plant are:
1. Plant design and equipment sizing
2. Basic process control
3. Critical alarms and intervention
4. Pressure relief system
5. Emergency response
6. Material handling, storage and discharge
11.4.1 SAFETY MEASURES IN PLANT DESIGN AND EQUIPMENT SIZING.
The most basic area of plant safety is process selection and equipment design and the measure
taken in this regard includes:
1. The Selection of an inherently safe process which reduces the likelihood of an incident by
default.
2. Process equipment (reactor vessels, pressure and distillation columns) containing the
chemicals that are being processed are chosen in accordance with industry standard such
that they could withstand reaction temperature and pressure.
3. Vessel design codes and standards which incorporate safety margins for equipment to
reduce the risk of its failing in operation are selected.
177
11.4.2 SAFETY MEASURE IN PLANT CONTROL
The basic safety measure taken during the co-ordination of the process can be summarized as
follows:
1. The process control system is designed and selected to maintain the plant under safe
conditions of temperature, pressure, flow rates, levels, and compositions.
2. For continuous plants, the process control system will attempt to maintain the process
within reasonable bounds of a steady-state condition
3. The control valve is sized so that there is maximum and efficient controllability of the
process.
11.4.3 INSTALLATION OF CRITICAL ALARMS AND HUMAN INTERVENTION
1. Installation of warning alarms in the process for quick human intervention in the event that
the process variable deviates from safe operating range.
2. Alarms should be set so that they are not frequently triggered by normal process variability.
3. Use of automatic process controllers to reduce plant’s hazard that may arise as a result of
late human intervention and error
11.4.4 OVERPRESSURE CONTROL AND PRESSURE RELIEF SYSTEM
1. Use of Overpressure relief system to annul the effect of overpressure where shutdown of
system is not rapid.
2. vessel design codes such as the ASME Boiler and Pressure Vessel Code require relief
devices is fitted on all pressure vessels.
3. The pressure relief system should allow the plant to be relieved of any source of
overpressure before damage to process equipment (leaks, bursting, or explosion) can occur.
178
11.4.5 EMERGENCY RESPONSE
1. If a loss of containment does occur in a chemical plant, then an emergency response is
required
2. Plant personnel will be trained to respond to such emergencies.
3. Access to Local community emergency response providers in the event of a fatal accident
Other areas where safety measures are applied in the chlorobenzene plant are in the process
materials handling, material recycle and effluent discharge.
11.5 MATERIAL SAFETY DATA SHEET REACTIVITY
11.5.1 PRODUCT AND COMPANY IDENTIFICATION
Product Name: Chlorobenzene
Cat No. B254-4; B254-4LC; B254-20; B254RS-200; B255-1; B255-500
Synonyms: Monochlorobenzene; Benzene chloride (Laboratory/Certified)
Recommended Use: Laboratory chemicals. i
11.5.2 HAZARDS IDENTIFICATION
Target Organs: Eyes, Skin, Central nervous system (CNS), Liver, Kidney, Blood
Potential Health Effects:
1. Acute Effects
Principle Routes of Exposure
Eyes: Irritating to eyes.
Skin: Irritating to skin. May be harmful in contact with skin.
Inhalation: Harmful by inhalation. Inhalation may cause central nervous system effects.
May cause irritation of respiratory tract.
179
2. Ingestion:
Aspiration hazard. May be harmful if swallowed. May cause central nervous system effects.
Ingestion may cause gastrointestinal irritation, nausea, vomiting and diarrhoea
11.5.2 HAZARD IDENTIFICATION
i. Flammable liquid and vapor.
ii. Possible cancer hazard.
iii. May cause cancer based on animal data.
iv. Harmful by inhalation.
v. Irritating to eyes and skin.
vi. May cause central nervous system effects.
vii. May cause irritation of respiratory tract.
viii. Aspiration hazard if swallowed - can enter lungs and cause damage.
ix. Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic
environment.
11.5.3 CHRONIC EFFECTS:
i. Possible cancer hazard based on tests with laboratory animals.
ii. Tumorigenic effects have been reported in experimental animals.
iii. Experiments have shown reproductive toxicity effects on
laboratory animals.
iv. May cause adverse liver effects.
v. May cause adverse kidney effects.
180
11.5.4 FIRST AID MEASURES
Eye Contact: Rinse immediately with plenty of water, also under the eyelids, for at least 15
minutes. Obtain medical attention.
Skin Contact: Wash off immediately with plenty of water for at least 15 minutes. Obtain medical
attention.
Inhalation: Move to fresh air. If breathing is difficult, give oxygen. Do not use mouth-to-mouth
resuscitation if victim ingested or inhaled the substance; induce artificial respiration with a
respiratory medical device. Immediate medical attention is required.
Ingestion: Do not induce vomiting. Obtain medical attention.
Notes to Physician Treat symptomatically.
11.5.5 HANDLING AND STORAGE
Handling Use only under a chemical fume hood. Wear personal protective equipment. Do not get
in eyes, on skin, or on clothing. Do not breathe vapours or spray mist. Keep away from open
flames, hot surfaces and sources of ignition. Use only non-sparking tools. Use explosion-proof
equipment. Take precautionary measures against static discharges.
Storage Keep containers tightly closed in a dry, cool and well-ventilated place. Keep away from
heat and sources of ignition.
11.5.6 EXPOSURE CONTROLS/PERSONAL PROTECTION
Engineering Measures Use only under a chemical fume hood. Ensure that eyewash stations and
safety showers are close to the workstation location. Use explosion-proof
electrical/ventilating/lighting/equipment.
TWA: 10 ppm
NIOSH IDLH: Immediately Dangerous to Life or Health
181
Personal Protective Equipment
Eye/face Protection Wear appropriate protective eyeglasses or chemical safety goggles as
described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European
Standard EN166.
Skin and body protection Wear appropriate protective gloves and clothing to prevent skin
exposure.
Respiratory Protection Follow the OSHA respirator regulations found in 29 CFR 1910.134 or
European Standard EN149. Use a NIOSH/MSHA or European Standard EN 149 approved
respirators if exposure limits are exceeded or if irritation or other symptoms are experienced.
11.5.7 PHYSICAL AND CHEMICAL PROPERTIES
Physical State: Liquid
Appearance: Clear
odor: bitter almond
Odor Threshold: No information available.
pH: No information available.
Vapor Pressure: 12 mbar @ 20°C
Vapor Density: 3.9 (Air = 1.0)
Viscosity: 0.8 mPa.s @ 20°C
Melting Point/Range: -45°C / -49°F
Decomposition temperature °C: No information available.
Flash Point: 23°C / 73.4°F
Evaporation Rate: (Butyl Acetate = 1.0)
182
Specific Gravity 1.108
Solubility: Insoluble in water
log Pow: No data available
Molecular Weight: 112.56
Molecular Formula: C6H5Cl
183
CHAPTER TWELVE
RECOMMENDATIONS
12.1 RECOMMENDATIONS FOR THE CHLOROBENZENE PLANT
12.1.1 HANDLING AND STORAGE
The products (monochlorobenzene and dichlorobenzene) should be stored in cool/well-
ventilated place. Storage area should be clearly identified, clear of obstruction and accessible
only to trained and authorized personnel. Inspections should be done periodically for damage
or leaks. There should be no smoking in the chlorobenzene plant. High concentrations of the
chlorobenzene vapor are irritating to the upper respiratory system. Vapor exposure chamber
tests show that monochlorobenzene is capable of producing an anesthetic effect if excessive
amounts are inhaled. Overexposure causes depression of the central nervous system, the effects
varying with the amount of vapor inhaled and, of course the duration of such overexposure.
The necessary PPE must be worn before handling by any personnel. To be kept away from
flames and hot surfaces. A No smoking policy should be employed and enforce the Use of only
non-sparking tools. Take precautionary measures against static discharges. and ground all
equipment during handling. Also Use explosion-proof electrical and ventilating equipment.
12.1.2 ACCIDENTAL RELEASE MEASURE
Ventilate area of leak or spill. Remove all sources of ignition. Wear appropriate personal
protective equipment. Isolate hazard area. Keep unnecessary and unprotected personnel from
entering. Contain and recover liquid when possible. Use non-sparking tools and equipment.
Collect liquid in an appropriate container or absorb with an inert material (e. g., vermiculite,
dry sand, earth), and place in a chemical waste container. Do not use combustible materials,
such as saw dust. It is also not advisable to flush into sewer.If a leak or spill has not ignited,
water spray can be used to disperse the vapors, to protect personnel attempting to stop leak,
and to flush spills away from exposures.
12.1.3 PLANT OPERATION AND WORKER’S SAFETY
The optimum operation of a chlorobenzene plant should be priority, especially because the
methods of operation will determine the quality, quantity, and purity of the products
(monochlorobenzene and dichlorobenzene). Moreover, the methods of operation will also
determine the health and safety of workers, the plant, and the immediate environment.
Therefore, here are some recommendations that can make operations in the chlorobenzene
plant to yield the best possible returns in terms of production, while ensuring the safety of staff,
workers, and the environment:
1. Continuous production is more preferred as it turns out more of monochlorobenzene,
which is the most desired product, than dichlorobenzene.
2. Worker’s, especially the unskilled workers, should be taught regularly about safety
measures and precautions while working in the factory to prevent accident as well as to
create awareness of what to do in the event of an accident.
3. The research and development team should endeavour to stay updated with the latest
trends in the production of chlorobenzene, so that they can also incorporate such latest
developments in the plant too.
4. Machines which malfunction regularly should be replaced immediately to prevent
accident.
5. Staff should be educated regularly so that they can develop expertise in their fields and,
consequently, improve the method of operations in the chlorobenzene plant.
185
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Chemical Profile: Monochlorobenzene," Chemical Products Synopsis. (1990, July).
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Handbook of Environmental Fate and Exposure Data for Organic Chemicals (Vol. I). (1990).
Chelsea, Michigan: Lewis Publishers, Inc.
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Johnson, W. K., Leder, A. and Sakuma, Y. (1989, October). "CEH Review". Chlorobenzenes
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Chemical Society, 80, 4987.
Snell, F. D. and Ettre, L. S. (1970). Encyclopedia of Industrial Chemical Analysis. New York:
Wiley Interscience.
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Sokolov, O., Hurley, M. D., Wallington, T. J., and Kaiser E. W. . (1998). Kinetics and
Mechanism of the Gas-Phase Reaction of Cl Atoms with Benzene. J. Phys. Chem. A,
102, 10671-10681.
SRI International. (1977, August). A Study of Industrial Data on Candidate Chemicals for
Testing. EPA/OTS.
Towler, G. P. and Sinnott, R. (2008). Chemical Engineering Design: Principles, Practice and
Economics of Plant and Processes Design. Oxford, U.K. : Butterworth-Heinemann.
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Pesticides and Explosives Industry. EPA/OSW.
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Environmental Contaminants: Halogenated Benzenes. EPA-560/2-77-004,Office of
Toxic Substances, Washington DC, 6-43.
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ed.). Pearson Prentice Hall.
187
APPENDICES
PROCESS BALANCES CALCULATIONS
MATERIAL BALANCE CALCULATIONS
Stream Material Balance
S1 = 26.45Kmol/hr. Cl2 chosen so as to ensure limiting ability
S3 = S1 = 26.45 Kmol/hr. Cl2 S5 = S3 = 26.45Kmol/hr. Cl2
About the Reactors System (without Recycle)
Input Stream:
S7= 100Kmol/hr. Benzene
S5 = 26.45Kmol/hr. Cl2
Output Stream:
S13 = ? (Sum of all computed effluent in Liquid phase)
S16 = ? (Sum of all vapor/gases component effluent)
Overall Effluents (Gaseous + Liquid)
FBZ = Fi, BZ – Є1 ---------------------------------------(ii)
FCl2 = Fi, CL2 – Є1 – Є2 --------------------------------------- (iii)
FCl2 = Fi, Cl2 – Є1 – Є2 -------------------- ------------------- (iii)
FHCl2 = Fi, HCl2 – Є1 – Є2 --------------------------------------- (iv)
FMCB = Fi, MCB – Є1 – Є2 --------------------------------------- (v)
(1) Extent of Reaction
Є1 = Є2
Є1 = = F MCB
− − − − − −(1) and
FMCB
188
Є2 = (1 − 𝑆 − − − − − −(𝑖𝑖)
Selectivity, S
S= 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑢𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (𝑏𝑦 𝑝𝑟𝑜𝑑𝑢𝑐𝑡)
S = FMCB = = 0.9182 = 91.81%
Fi,Cl2−𝐹𝑑𝑐𝐵
Where Fi, CL2 - FdcB = Fi, CL2. x
Where x is the fraction of Cl2 that react to form dcB (Reaction 2)
Since FmcB = 22.45 Kmol/hr. and FdcB = 2kmol/hr.
From (1) Є1 = 22.45

( 1 − 0.9182) = 2.00 𝐾𝑚𝑜𝑙 .
0.9182 ℎ𝑟
FdcB = Fi, dcB + Є2 ----------------------(VI) Fi = initial flow of component with inlet stream
From S5; Fi, Cl2 - S5 = 26.45Kmol/hr.
From S7; Fi, BZ = S7 = 100Kmol/hr.
Fc, HCL = Fi, mcB = Fi, dcB = 0Kmol/hr. (Assuming no initial value in the reactor system)
S13 + S16 :
From (ii); F BZ = 100 – 24.45 = 75.55
(iii); FCl2 = 26.45 – 24.45 – 2kmol/hr. = 0
From (iv) FHCl = 0 + 24.45 + 2 = 26.45 From (v) FMCB = 0 + 24.45 – 2 = 22.45
From (vi); FdcB = 0 + 2 = 2Kmol/hr.
To determine the split behavior of the streams into gaseous S16 and liquid S13 stream flash calculation
was carried out as follow
Flash calculations
Log10 Psat = A + B + 𝐵 − − − − − −(7)
189
𝑇(0𝐶)+𝐶
Where A, B and C are Antione Parameters.
T(0C) = 550C (Operating condition)
P = Ptotal = 2.4bar (Operating Condition)
Component A B C Psat (mmHg) Psat (bar)
Benzene 6.91 1211.03 220.79 326.97 0.436
Chlorine 4.06 861.34 246.33 - 16.01
MCB 6.98 1431.95 217.56 53.42 0.071
dCB 7.30 1782.40 230.01 11.22 0.015
HCl 4.57 868.36 1.75 - 87.20
Psat as shown above were obtained from Equation (7)
Ki = 𝑃𝑠𝑎 𝑡 − − − −(8)
Benzene = 0 .
= 0.1817
Chlorine = = 6.6708
MCB = 0 .
= 0.00296
DCB = 0 .
= 0.0063
HCl = = 36.3335
Ƶi = FMCB − − − − − (9)
190
𝐹𝑡𝑜𝑡𝑎𝑙
(S13 + S16) Ƶi Component ki
(F)
75.55 0.597 Benzene 0.182
0.00 0.00 Cl2 6.670
22.45 0.178 MCB 0.030
2.00 0.016 dCB 0.006
26.45 0.209 HCl 36.335
Total = 1.00 1.00
V + L = 126.45 ----------------(a)
YBZ - 𝑍𝑏𝑧𝑉 . 𝐾𝑖 = 0 − − − −(𝑏) 1+( ) (𝐾𝑖−1)
126.45
YMCB - 𝑍𝑀𝐶𝐵𝑉 . 𝐾𝑖 = 0 − − − −(𝑐) 1+( ) (𝐾𝑖−1)
126.45
YdCB - 𝑍𝑑𝐶𝐵𝑉 . 𝐾𝑖 = 0 − − − −(𝑑) 1+( ) (𝐾𝑖−1)
126.45
YHCl - 𝑍𝐻𝐶𝑙𝑉 . 𝐾𝑖 = 0 − − − −(𝑒) 1+( ) (𝐾𝑖−1)
126.45
YMCB + YBZ – YCl + YdCB + YHCl = 1 ----(f) YCl - 𝑍𝐶𝑙𝑉 2 . 𝐾𝑖 = 0 − − − (𝑔)
1+( ) (𝐾𝑖−1)
126.45
Solving for YBZ, YMCB, YdCB, YHCl V, and L
(6 Equations 6 variables)
Xi = = 𝑌𝑖
𝐾𝑖
191
YCl = 0 and Ƶcl2 = 0 V = 28.03 L = 98.42
Component Yi Xi
BZ 0.133 0.730
Cl2 0.000 0.000
MCB 0.007 0.226
dCB 0.00013 0.020
HCl 0.861 0.0024
1.0 1.00
Results of Flash Calculations
Component (S13 + S16) Ƶi Yi Xi V (S16) L (S13)
Benzene 75.55 0.597 0.133 0.730 3.715 71.835
Cl2 0.000 0.000 0.000 0.000 0.000 0.000
MCB 22.45 0.178 0.007 0.226 0.188 22.262
dCB 2.00 0.016 0.00013 0.020 0.004 1.996
HCl 26.45 0.209 0.861 0.024 24.119 2.331
Total 126.45 1.000 1.000 1.000 28.03 98.42
Component Balance
Vi = Yi . V
Li = Xi . L
WASHER UNIT
IN = OUT
Inlet Streams;
S13 , S14
Outlet Streams = S19, S18
192
Overall Balance = S13 + S14 = S19 + S18
Assumptions;
0.90 fractions of water leaves with stream 19
Pressure at 1atm
NaCl is completely removed from the product stream
All HCl is converted
S14 = 200 Kmol/hr (H2O; 190Kmol/hr NaOH = 10Kmol/hr
Composition 95% water 5% NaOH
Reaction NaOH + HCl NaCl + H20
Stream 19 (S19)
Reaction Product ;
NaCl in S19 = 2.33Kmol/hr
Balance from inlet stream S14 ( H20; 190 Kmol/hr = 0.95 * 200 = 190
Total H20: 190 + 2.33 = 192.33Kmol
Since it is assumed that 90% of water leaves the stream S19
NaOH S19 = 10 – 2.33Kmol = 7.67Kmol
S19 = H2O S19 + NaOH S19 + NaCl S19
S19 = 173.10 + 7.67 + 2.33 = 183.10Kmol
Stream 18
Overall Balance = S18 = S14 + S13 – S19
= 200 + 98.43 – 183.10 = 115.32
Component Balance;
H2O : (0.10) * (192.33) = 19.23Kmol
BZ; S13BZ = 71.83Kmol /BZ MCB = S13, MCB = 22.26 Kmol/MCB dCB; = S13dCB = 2.00 Kmol/dCB
Total = 115.32kmol/hr
Summary
193
Component S13 S14 S18 S19
BZ 71.83 - 71.83 -
Cl2 0.00 - 0.00 -
MCB 22.26 - 22.26 -
dCB 2.00 - 2.00 -
HCl 2.33 6.00 - -
H20 0.00 190.00 19.23 173.10
NaOH 0.00 10.00 - 7.67
NaCl 0.00 0.00 - 2.33
Total 98.42 200.00 115.33 183.10
First Benzene Column
inlet = S18 outlet streams; S20, S21
S18 = S= + S21
D = S20
B = S21
Assumptions
Total separation of benzene and water is distilled out of chlorobenzene as Bottom Product
100% recovery in separation.
It is assumed that 99.9% of chlorobenzene into the tower is recovered at the bottom product
Stream 20
H2O = H2O S18 (19.23) = 19.33Kmol H2O
Benzene; 100% recovery
S18 Bz = S20BZ = 71.83Kmol
MCB: (1-0.999) MCB, S18 = (0.001) (22.26)
dCB: ((1-0.999) dCB S18) = 0.02kmol MCB
194
91.09Kmol
Stream 21;
MCB = (0.999) (MCB S18) = (0.999) (22.26) = 22.24Kmol MCB)
dCB = ( 0.999)( dCBS18) = (0.999)(2.0)
= 1.99Kmol dCB
Sum = 24.23kmol
Summary of Bz Column
Component S18 S20 S21
Bz 71.83 71.83 0.00
Cl2 - - -
MCB 22.26 0.02 22.24
dCB 2.00 0.01 1.99
HCl - - -
H20 19.23 19.23 -
NaOH - - -
NaCl 115.32 91.09 24.23
Chlorobenzene Column
Inlet ; S21 = F
ZMCB ?
F ZMCB = MCB S21
Equation F = D + B ----12a
F ZMCB = DXD + B(1-XB)
XB = 0.996 Purity of dCB given
XD = 0.997 Purity of MCB
195
D = S22 B = S23
D = = 𝑋𝐵𝐹𝑍𝑀𝐶𝐵−(1−𝑋𝐵)𝐹𝑍𝑑𝐶𝐵
𝑋𝐵𝑋𝐷−(1−𝑋𝐷)(1−𝑋𝐵)
S22 = D = 22.30 Kmol
B= F-D = 24.23 – 22.30
S23 = B = = 1.94Kmol
Component balance about the chlorobenzene column
FZ MCB = DXD + B(1-XB) - ---------(1) * XB
FZ dCB = D(1-XD) + BXB -----------------------(2) *(1- XB)
Eliminating B
XB FZ MCB = DXBXD + BXB(1-XB) ---------------------(I)
(1- XB) FZ dCB = D(1-XD) (1-XB) + BXB(1-XB) --------(II)
(I) - (II)
XB FZ MCB - (1-XB) FZ dCB = D ( XB XD – (1-XD) (1-XB))
D = = 𝑋𝐵𝐹𝑍𝑀𝐶𝐵−(1−𝑋𝐵)𝐹𝑍𝑑𝐶𝐵
𝑋𝐵𝑋𝐷−(1−𝑋𝐷)(1−𝑋𝐵)
FZ MCB A at top = D XD --------------------------------(A)
FZ dCB at top = D(1-XD)--------------------------(B)
From Bottom;
FMCB = FZ MCB - FMCB at top
Or
= B(1- XB) = FZ MCB - D XD
FdCB at Bottom = BXB
= FZ dCB - FdCB at top
196
= FZ dCB - D(1-XD)
S22 Stream
MCB = DXD 0.997 * 1
= 22.23
dCB = D(1-XD) = 0.003*1
= 0.07
= 22.30
Stream 23 MCB = B(1- XB) = 0.01 dCB = BX = 1.93 1.94
ENERGY BALANCE CALCULATIONS
Enthalpy Calculations
𝐶𝑃 = 𝐶1 + 𝐶2𝑇 + 𝐶3𝑇2 + 𝐶4𝑇3 + 𝐶5𝑇4
Where 𝐶1, 𝐶2, 𝐶3, 𝐶4 and 𝐶5 were obtained from Table X.Y.
For H2O at 328K, TR = 298
H = ∫𝑇𝑅𝑇 𝐶𝑝𝑑𝑇 𝑑𝑇
= 2258𝐾𝐽/𝐾𝑚𝑜𝑙
For Benzene at 328K1 TR = 298
For Chlorine
For Monochlorobenzene
197
For dichlorobenzene
For HCl
H = ∫𝑇𝑅𝑇 𝐶𝑝𝑑𝑇 𝑑𝑇 = 2264𝐾𝐽/𝐾𝑚𝑜𝑙
To get the enthalpy for NaOH and HCl,
𝐶𝑃 = 𝑅( 𝐴 + 𝐵𝑇 + 𝐷𝑇−2) ; Where R = 8.314KJ/Kmol.k T in Kelvin (K)
Where A, B and D were obtained from Table one for NaOH
H= 𝑇𝑅𝑇 𝐶𝑝𝑑𝑇 𝑑𝑇
= - 298𝐾𝐽/𝐾𝑚𝑜𝑙
For NaCl
For H2O at 293K
= −377𝐾𝐽/𝐾𝑚𝑜𝑙
To obtain the Duty of the reactor,
𝑄 𝐻𝑖𝑛
Where the outlet streams are stream 13 & 16
Flow rates are obtained from table X.X
𝑄 𝑜𝑢𝑡 𝐻𝑜𝑢𝑡
= [(3.72 × 4166) + (0.19 × 4578) + (24.12 × 2264) + (71.83 × 4166) + (22.26 ×
4578)
+ (2 × 5203) + (2.33 × 2264)]
198
𝐾𝐽⁄ℎ𝑟
= 487806.2
To get duty at inlet stream, i.e. stream 1 and 17
𝑄 𝐻𝑖𝑛
= [(26.45 × 295) + (100 × 4166)]
𝐾𝐽⁄ℎ𝑟
= 424402.75
Duty on heat of reaction
𝑄 𝐻𝑟𝑗
𝑤ℎ𝑒𝑟𝑒 𝜉1, 𝜉2 𝑎𝑛𝑑 Δ𝐻𝑟𝑗 𝑖𝑠 𝑡𝑎𝑘𝑒𝑛 𝑓𝑟𝑜𝑚 𝑇𝑎𝑏𝑙𝑒 4.15
𝑄 = [(22.45 × (−123465)) + (2.0 × (−118577))]
𝐾𝐽⁄ℎ𝑟
= −3008943.25
Applying eqn (iii),
𝑄 = −3008943.25 + 487806.2 − 424402.75
𝐾𝐽⁄ℎ𝑟 v
= −2945539.3
Obtaining Enthalpy Values around the Washer,
𝑄 𝐻𝑖𝑛
Stream inlet are Stream 13 and 14
Outlet streams are Streams 18 & 19
Obtaining the enthalpy of H2O and NaOH in stream 14
𝑄 = 𝐹𝐻2𝑂∆𝐻 = 190 × (−377) = −71630 𝐾𝐽⁄ℎ𝑟
𝑄 = 𝐹𝑁𝑎𝑂𝐻∆𝐻 = 10 × (−298) = −2980 𝐾𝐽⁄ℎ𝑟
In stream 13,
199
𝐾𝐽⁄ℎ𝑟
𝑄 = 𝐹𝐵𝑧∆𝐻 = 71.83 × 4166 = 299243.78
𝐾𝐽⁄ℎ𝑟
𝑄 = 𝐹𝑚𝐶𝐵∆𝐻 = 22.26 × 4578 = 101906.28
𝑄 𝑑𝐶𝐵 = 𝐹𝑑𝐶𝐵 𝑟
𝑄 𝐻𝐶𝑙 = 𝐹𝐻𝐶𝑙 𝑟
Stream 19;
Stream 19 contain H2O, NaOH and NaCl
𝑄𝐻 𝑟
𝑄 𝑁𝑎𝐶𝑙 = 𝐹𝑁𝑎𝐶𝑙 𝑟
𝑄 𝑁𝑎𝑂𝐻 = 𝐹𝑁𝑎𝑂𝐻 𝑟
Stream 18;
Stream 18 contain Benzene, MCB, DCB and H2O
𝑄𝐻 𝑟
𝑄 𝑀𝐶𝐵 = 𝐹𝑀𝐶𝐵 𝑟
𝑄 𝑑𝐶𝐵 = 𝐹𝑑𝐶𝐵 𝑟
𝑄 𝐵𝑧 𝑟
𝑄 19 = 408243.03𝐾𝐽/ℎ𝑟
𝑄 18 = 454977.4𝐽/ℎ𝑟
𝑄 14 = −74610𝐾𝐽/ℎ𝑟
Overall duty = 397792.85 𝐾𝐽/ℎ𝑟
At the Neutralizer
NaOH(aq) + HCl(aq) NaCl + H2O(L)
The enthalpy of the reactant and product are given to be
NaOH(aq) = –416.88 𝐾𝐽/ℎ𝑟
200
HCl(aq) = -166.106
H2O(L) = -285.83 𝐾𝐽/ℎ𝑟
NaCl = 411.12 𝐾𝐽/ℎ𝑟
Product – Reactant will yield -113960 𝐾𝐽/ℎ𝑟
Calculations around the two distillation column;
𝐿+𝐷=𝑉
𝐷 = 91.09𝐾𝑚𝑜𝑙/ℎ𝑟
𝐷( + 1) = 𝑉
273.27𝐾𝑚𝑜𝑙
𝑉 = 91.09 (2 + 1) =
ℎ𝑟
Enthalpy Balance for Benzene Column
The enthalpy of V at 800c
𝐻𝑉 𝑘𝐽/𝐾𝑚𝑜𝑙
𝐻𝐷 𝑘𝐽/𝐾𝑚𝑜𝑙
The specific latent heat of condensation (V)
𝐻𝐿 = (0.211)* (-41.58) + (0.789)*(30.77) = -33.05091 𝑘𝐽/𝑚𝑜𝑙
= - 33050.91𝑘𝐽/𝐾𝑚𝑜𝑙
𝑄 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 ) + 𝐻𝐿
−11135681.38𝑘𝐽/ℎ𝑟
201
𝑄𝑅 + 𝐵. 𝐻𝐵 − 𝐹. 𝐻𝐹 − 𝑄 𝐶 = 𝑄 − 𝑄 𝐶
For Bottom B
At 1200C
𝐻𝐵 = (0.91178)* (16718) + (0.0822)*(17409) = 16774.75155𝑘𝐽/𝐾𝑚𝑜𝑙
For Feed F at 550C
𝐻𝐹 = (0.6229)* (4166) + (0.1930)*(4578)+ (0.0173)*(5203) + (0.1668 *2258) =
3945.2017𝑘𝐽/𝐾𝑚𝑜𝑙
𝑄𝑅 = (91.09)*(-615.2238)+ (24.23) * (16774.75155)-(115.33)*
(3945.2017)-(-
11135681.38)= 11031092.76 𝑘𝐽/𝐾𝑚𝑜𝑙
The Enthalpy Balance for Chlorobenzene column is calculated below;
The enthalpy of V at 1320c
𝐻𝑉 𝑘𝐽/𝐾𝑚𝑜𝑙
𝐻𝐷 𝑘𝐽/𝐾𝑚𝑜𝑙
The specific latent heat of condensation (V)
𝐻𝐿 = (0.997)* (-35343.84) + (0.003)*(-39398.68) = -35356.00452 𝑘𝐽/𝐾𝑚𝑜𝑙
𝑄 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 )+
𝐻𝐿 𝐷
−3636078.783𝑘𝐽/ℎ𝑟
𝑄𝑅 + 𝐵. 𝐻𝐵 − 𝐹. 𝐻𝐹 − 𝑄 𝐶 = 𝑄 − 𝑄 𝐶
For Bottom B
At 1450C
𝐻𝐵 = (5*10-3)* (23496) + (1.19)*(22488) = 22493.1959𝑘𝐽/𝐾𝑚𝑜𝑙
202
For Feed F at 550C
𝐻𝐹 =16774.75155𝑘𝐽/𝐾𝑚𝑜𝑙
𝑄 𝑅 = (22.30)*(752.294)+ (1.94) * (22393.1959)-(24.23)* (16774.75155)-(-3636078.783)=
3290039509 𝑘𝐽/𝐾𝑚𝑜𝑙
Enthalpy Balance around the Heat Exchanger;
Heat exchanger 1
Flowrate in = flowrate out = 26.45
∆𝐻𝑂𝑢𝑡 = 295 at 550C
∆𝐻𝑖𝑛 = 32151 at 91.090C
𝑄 =∑Fout ∑Fin 𝐻𝑖𝑛
= 26.45(-3251+295) = -78186.2 𝑘𝐽
ℎ𝑟
Heat exchanger 2
Flowrate in (550C) = flowrate out (200C)
Flowrate: HCl = 24.12 2264 -369
MCB = 0.19 4578 -750
Benzene = 3.72 -679
= { (24.12*(-369) + (0.19 * (-750)) + (3.72 *(-679))} – {
(0.01*23496)+(1.93*22488)} 𝑄 = - 45,271.29 𝑘𝐽/ℎ𝑟
For Compressor
In stream 1 at 200C
Out stream 3 at 91.090C
Fin = Fout = 26.45
203
= 85989 – (-8393) = 94,382𝑘𝐽/ℎ𝑟
204
STEP RESPONSE PLOTS OF PLANT CONTROL SYSTEM
BENZENE COLUMN RECYCLE BENZENE FEED STREAM POSITIVE GAIN
STEP INPUT
205
BENZENE COLUMN’S TREATED BENZENE STREAM (BOTTOMS) TRANSIENT
RESPONSE
206
BENZENE COLUMN’S PROCESS WATER STREAM (DISTILLATE) TRANSIENT
RESPONSE
207
BENZENE COLUMN RECYCLE BENZENE FEED STREAM NEGATIVE GAIN
STEP INPUT
208
BENZENE COLUMN’S TREATED BENZENE STREAM (BOTTOMS) TRANSIENT
RESPONSE
209
BENZENE COLUMN’S PROCESS WATER STREAM (DISTILLATE) TRANSIENT
RESPONSE
210
CSTR REACTOR SYSTEM’S TREATED BENZENE FEED STREAM POSITIVE
GAIN STEP INPUT
211
CSTR REACTOR SYSTEM’S CRUDE CHLOROBENZENE STREAM (LIQUID
PRODUCT) TRANSIENT RESPONSE
212
CSTR REACTOR SYSTEM’S UNTREATED HCL STREAM (VAPOUR PRODUCT)
TRANSIENT RESPONSE
213
CSTR REACTOR SYSTEM’S TREATED BENZENE FEED STREAM NEGATIVE
GAIN STEP INPUT
214
CSTR REACTOR SYSTEM’S CRUDE CHLOROBENZENE STREAM (LIQUID
PRODUCT) TRANSIENT RESPONSE
215
CSTR REACTOR SYSTEM’S UNTREATED HCL STREAM (VAPOUR PRODUCT)
TRANSIENT RESPONSE
216
WASHER/NEUTRALIZER CRUDE CHLOROBENZENE FEED STREAM
POSITIVE GAIN STEP INPUT
217
WASHER/NEUTRALIZER TREATED CHLOROBENZENE STREAM TRANSIENT
RESPONSE
218
WASHER/NEUTRALIZER CRUDE CHLOROBENZENE FEED STREAM
NEGATIVE GAIN STEP INPUT
219
WASHER/NEUTRALIZER TREATED CHLOROBENZENE STREAM TRANSIENT
RESPONSE
220
WASHER/NEUTRALIZER NAOH REJECTION IN TREATED CHLOROBENZENE
STREAM TRANSIENT RESPONSE
221
DEVELOPED PIPING DIAGRAM OF THE PLANT
222
223
224
225
226
3D PROCESS EQUIPMENT MODEL OF THE PLANT
FRONT BIRD EYE VIEW
BACK BIRD EYE VIEW
227
228

Chlorobenzenes Plant Design Prize Thesis

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A

OF MONOCHLOROBENZENE AND WITH ABOUT 2,000 TONNES PER YEAR

OF DICHLOROBENZENE BY DIRECT CHLORINATION OF BENZENE.

DR. O.J. ODEJOBI

DEPARTMENT OF CHEMICAL ENGINEERING,

OBAFEMI AWOLOWO UNIVERSITY, ILE-IFE, NIGERIA

IN PARTIAL FULFILMENT OF THE REQUIREMENT OF THE COURSE

PROCESS DESIGN I & II

Obafemi Awolowo University,

Ile-Ife, Osun State.

25th February, 2020.

Department of Chemical Engineering,

Obafemi Awolowo University,

Ile-Ife, Osun State,

operating cost), availability of raw materials, safety, environmental factors, conversion

obtained in the reactor.

of monochlorobenzene (which is the main product) and with about 2000tonnes/year of

dicghlorobenzene (by product) by direct chlorination of benzene. Benzene react with

on the ring by a chlorine atom.

chlorination of benzene in the liquid phase leads to the conversion of benzene to

chlorinated products (chlorobenzenes) in a single pass of the reactant (benzene and

chlorine) through the system. The ratio of monochlorobenzene to higher substitution

of the increase demand of monochlorobenzene as compared to other

polychlorobenzenes. It is a desirable product because of its great importance, it is used

Therefore, we want a process that is designed to produce a high percentage of

action of hydrogenchloride on mld steam.

so as to suppress undesired reactions. Unreacted chlorine, hydrogen chloride and the

separated in a second distillation column. All three isomers of dichlorobenzene ( ortho-

we treat all these three isomers of dichlorobenze as one specie.

Separation of unreacted benzene, monochlorobenzene and dichlorobenzene was

used aids in giving a better selectivity conversion profile.

was computed as ₦ 17,275,068,380.

COVER PAGE .................................................................................................................... I

ABSTRACT ...................................................................................................................... III

TABLE OF CONTENTS ..................................................................................................... VI

LIST OF TABLES............................................................................................................. XIV

LIST OF FIGURES........................................................................................................... XVI

CHAPTER ONE ............................................................................................................... 17

1.1 PROPERTIES OF CHLOROBENZENES ...................................................................................... 17

1.1.1 PROPERTIES OF MONOCHLOROBENZENE ............................................................................ 19

1.1.2 PROPERTIES OF DICHLOROBENZENES .................................................................................. 19

1.2 USES OF CHLOROBENZENES ................................................................................................. 20

1.3 BRIEF EVOLUTION OF CHLOROBENZENES PRODUCTION ..................................................... 23

1.4 PROBLEM DEFINITION .......................................................................................................... 25

1.5 INITIAL DESIGN CONSIDERATION.......................................................................................... 26

1.5.1 THE PROCESS INITIAL DESIGN CONSIDERATION ................................................................... 27

1.5.2 FEED SPECIFICATIONS ........................................................................................................... 28

1.5.3 Utilities ............................................................................................................................. 28

1.5.4 Expected product specification ........................................................................................ 28

1.7 SCOPE OF DESIGN WORK REQUIRED .................................................................................... 28

1.7.1 PROCESS DESIGN .................................................................................................................. 29

1.7.2 CHEMICAL ENGINEERING DESIGN ........................................................................................ 31

1.7.3 MECHANICAL DESIGN ........................................................................................................... 31

1.7.4 SAFETY .................................................................................................................................. 31

CHAPTER TWO .............................................................................................................. 32

....................................................................... RELEVANCE OF CHLOROBENEZENE TO LOCAL NEEDS

CHAPTER THREE ............................................................................................................ 35

...................................................................................................................... PROCESS SELECTION

3.1 PROCESS ROUTE ALTERNATIVE ............................................................................................. 35

3.2 PROCESS SELECTION ............................................................................................................. 36

3.3 PROCESS ROUTE JUSTIFICATION ........................................................................................... 39

3.4 DETAILED DESCRIPTION OF THE SELECTED PROCESS ........................................................... 40

CHAPTER FOUR ............................................................................................................. 44