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AL-

Nahrain
Universi
ty
College
of
Enginee
ring
Chemical Engineering Department

NITROBENZENE PRODUCTION

A Final Year Project Submitted to the


Department of Chemical
Engineering in the Engineering of
Nahrain University in Partial Fulfillment
of the Requirements for the Degree
Bachelors in Scienece of Chemical
Engineering

by
SARAH RASHEED Ghayeb

Jumada II 1430
June 2009
Abstract

Nitrobenzene or caswell No. 600


chemical material use in the manufacture of
various plastic monomers and polymers, rubber
chemicals, drugs, pesticides, soaps, and as a
solvent in petroleum refining and
manufacture of cellulose ethers and cellulose
acetate…ect

The production capacity of nitrobenzene


70000 ton/year, this capacity was take as rough
estimation for the requirements of our country.

Nitrobenzene is manufacture
commercially by the direct nitration of benzene
using a mixture of nitric acid and sulfuric acid,
many processes for this manufacture but the
more safety, economic and lower capital cost is
the continuous isothermal nitration process.

In this project material balance, energy


balance, design of the nitrator, settler, heat
exchanger and distillation column, process
control, plant location & Toxicity and Effect of
Nitrobenzene.

I
List of Contents

Content

Page
Abstract

I
List of Content

II
List of Figures

VI
List of Tables

VII
Nomenclature

VIII
Chapter One: Introduction
1.1 History
1

1.2 Specification of Nitrobenzene


2

1.3 Identity
4
1.4 Physical Properties
4

1.5 Chemical Properties


5

1.6 Uses
11

1.7 Nitrobenzene Derivative


12

Chapter Two: Production Methods of Nitrobenzene


2.1 General
14

2.2 Batch Process


16

2.3 Tubular Reactor Process


17

2.4 Continuous Process


18

2.4.1 Adiabatic continuous process


19

2.4.2 Isothermal continuous process


21

II
2.5 Non-Industrial Sources
21

2.6 Process Selection


23

2.7 Description of the Selected Process


23

Chapter Three: Material Balance


3.1 General Information
27

3.2 Material Balance on Nitrator


28

3.3 Separator Material Balance


30

3.4 Washing Process Material Balance


30

3.4.1 1st Washing Process Material Balance


32

3.4.2 2nd Washing Process Material Balance


32

3.5 Reconcentrator Material Balance


35

3.6 Distillation Material Balance


38

Chapter four: Energy Balance


4.1 Energy Balance on Nitrator
42

4.2 Separator Energy Balance


46

4.3 Energy Balance on Evaporator


48

4.4 Washing Process Energy Balance


52

4.4.1 1st Washing process Energy Balance


52

4.4.2 2nd Washing process Energy Balance


54

4.5 Distillation Energy Balance


57

III
Chapter Five: Equipment Design
5.1 Nitrator Design
64

5.2 Settler Design


77

5.3 Heat Exchanger Design


82

5.4 Distillation Design


90

Chapter Six: Control System


6.1 Introduction
104

6.2 Control of Nitrator


105

6.3 Settler Control


107

6.4 Vaporizer Control


108

6-5 Heat Exchanger Control

109

6.6 Distillation column control


110

Chapter Seven: Plant Layout


7.1 Site Considerations
113

7.2 Site Layout


116
7.3 Plant Layout
118

7.4 Utilities
119

7.5 Environmental Consideration


120

7.6 Waste Management


120

7.8 Nitrobenzene Plant Location


122

IV
Chapter Eight: Toxicity and Effects of
Nitrobenzene

8.1 General

123

8.2 Effects on humans

124

8-3 Effects on organisms in the environment

125
8.4 Hazard and risk evaluation

126
8.5 Industrial safety

128
References

129
Appendixes
Appendix A: Physical Properties

A-1
Appendix B: Equilibrium Data

B-1
V
List of Figures

Figure No. Title


page

1-1 Reduction products of nitrobenzene


6
1-2 Key intermediates derived from nitrobenzene
13
2-1 production of Nitrobenzene- continuous process
19
2-2 Flow sheet for the production of nitrobenzene
20
adiabatically
2-3 Atmospheric reactions generating and removing
22
nitrobenzene
2-4 Typical continuous Nitrobenzene Process
26
4-1 Process Flow Diagram
63

5-1 Vapor-Liquid Equilibrium diagram (Isothermal)


at 91
70oC
6-1 Nitrator Control
106
6-2 Settler control
107
6-3 Settler control
107
6-4 vaporizer control
108
6-5 Heat Exchanger control
109
6-6 Temperature pattern control
111
6-7 Composition control
111
6-8 Composition control
112
7-1 A typical site plant
118

VI
List of Tables

Table NO. Title


Page

1-1 Specification for technical-Grade Nitrobenzene


3
1-2 Specifications for Distilled-grade Nitrobenzene
3
(mirbane oil)
1-3 Some Physical Properties of Nitrobenzene
5
1-4 Reduction products of nitrobenzene
7
1-5 Type and estimated consumption of nitrobenzene
in 11
Western Europe in 1994
2-1 nitrobenzene production capacities in European
15
countries in 1985

3-1 Material Balance on Nitrator


29
3-2 Material balance on separator
31
3-3 Material Balance on 1st Washing Unit
33
3-4 Material Balance on 2nd Washing Unit
35
3-5 Material Balance on Reconcentrator
38
3-6 Material Balance on Distillation
39
3-7 Overall Material Balance
40
3-8 all Streams of Material Balances
41
4-1 all Streams of Energy Balances
62

VII
Nomenclature

Symbol Definition
Unit

Aa Active Area
m2

Aap Area under Apron


m2
Ac Distillation Column Area
m2
Ad Downcomer Area
m2
Ah Hole Area
m2
Ai Area or the Interface
m2
Am Clearance Area under Downcomer
m2
An Net Area
m2
Ao Heat Transfer Area
m2
Ap Total Area available for perforation
m2
As Cross flow Area
m2
a Blade Width
m
b Baffle Width
m
C Corrosion Allowance
mm
Co Orifice Coefficient
-
cp Specific heat
KJ/Kg.mol.K
D Diameter
m
DA Agitator Diameter
m
Db Bundle Diameter
m
Deff Effective Column Diameter
m

VIII
de Equivalent Diameter
m
dh Diameter of Hole
mm
di Inside Tube Diameter
m
dm Diameter of Manholes
mm
do Outside Tube Diameter
m
dp Droplet Diameter
µm
FC Flow Controller
-
FLV Liquid Vapor Factor
-
Ft Correction factor for ∆TLm
-
FW Wind Load
N/m
f Material Tensile Strength
N/mm2
Gt Mass Velocity of the Fluid Tube Side
Kg/m2.s
Gs Mass Velocity of the Fluid Shell Side
Kg/m2.s
HA Height of agitator
m
HL Height of the nitrator content
m
hap Height of bottom edge of the apron above the
mm
plate
hb Downcomer back-up
mm
hbc Clear liquid back-up
mm
hd Pressure drop through the tray plate
mm Liquid
hdc Head loss in downcomer
mm Liquid
hi Inside (tube) Heat Transfer coefficient
W/m2.oC
hid Inside tube foaling coefficient
W/m2.oC
ho outside (shell) Heat Transfer coefficient
W/m2.oC

IX
hod Outside tube foaling coefficient
W/m2.oC
how Weir Crest (height of the liquid over weir)
mm Liquid
hr Residence Head
s
hT Total Height of Distillation Column
m
ht Total plate drop head
mm
hv Heat transfer to vessel
W/m2.oC
hw Weir Height
mm
J Joined Efficiency
-
jf Friction Factor
-
Kf Thermal Conductivity
W/m.oC
LC Level Control
-
Lc Continuous phase Volumetric flowrate
m3/s
Lm Liquid mass flowrate
Kg/s
Ln Liquid mass flowrate
Kg/s
LW Weir Length
m
lB Baffle spacing
mm
lp Hole Pitch
mm
Ms Bending moment at any plane
N.m
m Mass flowrate
Kg/s
N Agitator Speed
rps
Np Power Number
-
Np Number of passes
-
Nt Number of Tubes
-
P Pressure Design
N/mm2

X
PA Shaft Power
W
Pch Sugden’s Parachor
-
Pt Pitch
mm
Pw Wind Pressure (Load per unit area)
N/m2
r Blade Length
m
S Distance measured from the free end
m
T Temperature of the fluid in shell side
o
C
TC Temperature Controller
-
TM Measuring Element
-
t Temperature of the fluid in tube side
o
C
tr Residence time
s
Uo Overall Heat Transfer coefficient
W/m2.oC
uc Velocity of Continuous phase
m/s
ud Settling velocity through hole
m/s
uf Flooding Velocity
m/s
uh Vapor Velocity through Hole
m/s
umin Actual minimum Velocity of the Vapor
m/s
ut Linear Velocity of the Fluid flow in Tube
m/s
uv Corrected Flooding Vapor Velocity
m/s

V Volume of Nitrator
m3
Vm Vapor mass flowrate
Kg/s
Vn Vapor mass flowrate
Kg/s

XI
Greek Notation

µ Viscosity
Pa.s

µc Viscosity of the Continuous phase


Pa.s

µd Viscosity of the dispersed phase


Pa.s

µw Viscosity at the wall Temperature


Pa.s

τ Residence Time
min

νo Initial Volumetric flowrate


m3/hr

σ Surface Tension
mJ/m2

ρ Density
Kg/ m3

ρc Density of the Continuous phase


Kg/ m3

ρd Density of the dispersed phase


Kg/ m3
λ Latent Heat
KJ/Kg.mol
∆TLm Mean Logarithm Temperature
o
C
∆Tm Mean Temperature Difference
o
C
∆Pt Pressure Drop in Tube Side
pa
∆Ps Pressure Drop in Shell Side
pa

XII
Dimensionless Groups

Nu = h d /K Nusselt Number
Pr = cp µ / K Prandtle Number
Re = ρ u d / µ Reynolds Number
XIII
Cha
pter
One
Intro
ducti
on
C
h
a
p
t
e
r

O
n
e

I
n
t
r
o
d
u
c
t
i
o
n
1.1 History

The earliest aromatic nitro compounds were


obtained by MITSCHERLISH

in 1834 by treating hydrocarbons derived from coal


tar with fuming acid [1, 2,
&3]. By 1835 LAURENT was working on the
nitration of naphthalene, the most
readily available pure aromatic hydrocarbon at
that time. DALE reported on
mixed nitro compounds derived from crude benzene
at the 1838 annual meeting
of the British Association for the Advancement of
Science. Not until 1845,
however, did HOFMANN and MUSPRATT report
their systematic work on the
nitration of benzene to give mono- and
dinitrobenzenes by using a mixture of
nitric and sulfuric acids [1].

The first small-scale production of


nitrobenzene was carefully distilled to give a yellow
liquid with a smell of bitter almonds for sale to soap
and perfume manufacturers as “essence of
mirbane.”[1]
The number of naturally occurring nitro
aromatic compounds is small; the
first to be recognized was chloramphenicol, an
important compound extracted
from cultures of a soil mold Steptomyces
venezuelas and identified in 1949 [1].
This discovery stimulated investigations
into the role of nitro group in pharmacological
activity, following the earlier (1943) discvery
of the antibacterial activity of nitrofuran
derivatives. Many synthetic pharmaceuticals and
agrochemicals contain nitro aromatic groups,
although the function of the nitro group is often
obscure [1].
The choice of nitro compounds covered here
is influenced strongly by
their commercial application of compounds in
the 1981 European core
1
Inventory. Most nitro compounds, or their
derivatives, are intermediates for colorants,
agrochemicals, pharmaceuticals, or other fine
chemicals with a few major volume outlets for
synthetic materials and explosives [1].

1.2 Specifications of Nitrobenzene

Nitrobenzene [98-95-3](oil of
mirbane),C6H5NO2, is colourless to pale
yellow oily liquid with on odour resembling that
of bitter almonds or "shoe
polish." Depending on the purity, its color varies
from pale yellow to yellowish
brown [2 & 3].

Product specifications have been


developed for technical-grade
nitrobenzene and for distilled-grade nitrobenzene,
also called mirbane oil. An
example of a typical set of specification used by
a major manufacturer of
nitrobenzene is given in Tables 1-1 and 1-2.
Equivalent specifications are usually
negotiated between manufactures and major
customers. Specification on
technical-grade nitrobenzene often is drawn up as
an internal quality standard
since most nitrobenzene is converted captively to
aniline. The type of aniline
process used and certain design details of the plant
can result in small changes in
the specifications deemed necessary for
technical-grade nitrobenzene. The
presence of small amounts of water is little
consequence in the operation of
aniline plants; water is formed in process in the
catalytic hydrogenation of
nitrobenzene and is a required reactant in the
Bechamp process. However, sulfur
is known to be catalyst poison in the catalytic
hydrogenation of nitrobenzene,
and dinitrobenzene and dinitrophenol are thought to
form tarlike deposits on the
catalysts. The level of sulfur in technical-grade
nitrobenzene is controlled
through specifications on its level in the feedstock
benzene. Nitrophenols are
2
easily removed to a level of below 10 ppm
through an alkaline wash. The fraction of
dinitrobenzene found in commercial nitrobenzene
plants is usually well below 100 ppm, and at this
low level dinitrobenzene can be tolerated as a minor
impurity of the nitrobenzene fed to an aniline plant
[4].

Mirbane oil is produced by purification of


technical-grade nitrobenzene through distillation.
Trace contamination by aniline plant to the
nitrobenzene plant. Again, specifications for
distilled-grade nitrobenzene are usually
negotiated between the manufacturer and major
customers. Through distillation it is possible to
further reduce the fraction of low and high boiling
impurities in technical-grade nitrobenzene [4].

Table 1-1 Specification for technical-Grade


Nitrobenzene [4]

Pale yellow oil with a characteristic order. I


Appearance may be slightly hazy owing to the presence
small globules of free water
Water content 0.5% (maximum)
Specific gravity (15.5/15.5 oC) 1.206-1.209
Dinitrobenzene content 0.1% (maximum)
Low-boiling impurities (benzene + aliphatic
0.25% (maximum)
hydrocarbons)
Sulfur- containing impurities (CS 2 +
2.5 ppm (maximum, as sulfur)
nitrothiophene +elementary sulfur)

Table 1-2 Specifications for Distilled-grade


Nitrobenzene (mirbane oil) [4]
Appearance Clear yellow oil free from visible water and boiling at
approximately 211oC at 760 mmHg pressure

Distillation range (5-95Ml) 0.5oC (maximum)

Crystallization point 5.5oC (minimum)

Specific gravity (15.5/15.5 oC) 1.208 - 1.211

Aniline content 0.0075% (maximum)

3
1.3 Identity [5]
Com NIOSH
mon RTECS
name: Synonyms:

Chem
ical
1.4 Physical
formu
properties
la:
Chemical structure:

Relative
molecular
mass: CAS
name:
IUPAC name:
CAS
registry
number:
nitrobenzene
r
C6H5NO2
o
b
e
n
123.11
z
n
e
i
n
t
e
r
o
9
b
8
e
-
n
9
z
5
e
-
n
3
e
DA6475000
nitrobenzol, mononitrobenzol,
n MNB, C.I. solvent black 6,
essence of mirbane, essence of
i myrbane, mirbane oil, oil of
t mirbane, oil of myrbane,
nigrosine spirit soluble B

Nitrobenzene is a colorless to pale yellow


oily liquid with an odor
resembling that of bitter almonds or "shoe polish."
It has a melting point of 5.7
°C and a boiling point of 211°C. Its vapor
pressure is 20 Pa at 20°C, and its
solubility in water is 1900 mg/liter at 20°C. It
represents a fire hazard, with a
flash point (closed cup method) of 88°C and an
explosive limit (lower) of 1.8%
by volume in air [3].

4
Table 1-3 Some Physical Properties of
Nitrobenzene [1,2,3&5]
Solu
Mp. Co bility
Bp. C
o in
Viscosity pa.sec wate
Thermal r
conductivity mg/li
W/m C o ter
Surface At
tension (20 C)o 20 oC
mN/m Specific At 25 oC
heat J/goC Solubi
At 25 C o lity in
At 30 C o organi
Latent heat of c
fusion J/g solven
Latent heat of t
vaporization J/g Densit
Heat of y
combustion (at (25oC)
constant Kg/m3
volume)MJ/mol
Flash point (closed cup) 1.5 Chemical
o
C
properties
Auto ignition
temperature oC
Explosive limit in
air (93 oC)vol%
Vapor pressure pa
At 20 oC
At 25 oC
At 30 oC
5.58 88
210.9
1.900599219 482
*10-3 1.8
0.14473
43.35 20
38
1.473 47
1.418
94.1 1900
331 2090
3.074 Freely soluble in ethanol,
acetone, ether
1198.484586

Nitrobenzene reactions involve substitutions on the


aromatic ring and reactions involving the nitro group.
Under electrophilic conditions, the substitution occurs at
a slower rate than for benzene, and the nitro group
promotes meta substitution. Nitrobenzene can undergo
halogenations, sulfonation, and nitration, but it does not
undergo Friedel-Crafts reactions. Under nucleophilic
conditions, the nitro group promotes ortho and para
substitution [2].

5
The reduction of the nitro group to yield aniline
is the most commercially
important reaction of the nitrobenzene. Usually the
reaction is carried out by the
catalytic hydrogenation of nitrobenzene, either in the gas
phase or in solution, or by
using iron borings and dilute hydrochloric acid (the
Bechamp process). Depending on
the conditions, the reduction of nitrobenzene can lead
to variety of products. The
series of reduction products is shown in figure
1-1 Nitrosobenzen, N-
phenylhydroxylamine, and aniline are primary reduction
products. Azoxybenzene is
formed by the condensation of nitrosobenzene and N-
phenylhdroxylamine in alkaline
solutions, and azoxybenzene can be reduced to
form azobenzene and
hydrazobenzene. The reduction products of nitrobenzene
under various conditions are
given in Table 1-4 [2].
Figure 1-1 Reduction products of
nitrobenzene [1, 2&14]

6
Table 1-4 Reduction products of
nitrobenzene [2]

Reagent Product
Fe, Zn or Sn + HCL aniline
H2 + metal catalyst + heat (gas phase or aniline
solution)
SnCL2 + acetic acid aniline
Zn + NaOH hydrazobenzene, azobenzene
Zn + H2O N-phenylhydroxylamine
Na3AsO3 azoxybenzene
LiALH4 azoxybenzene
Na2S2O3 + Na3PO4 Sodium phenylsulfamate, C 6H5NHSO3Na

The process used most commonly for the


manufacture of aniline is the catalytic hydrogenation of
nitrobenzene which has largely replaced the older
Bechamp process. In this latter process nitrobenzene
reacts with iron and water in the presence of small
amounts of hydrochloric acid to form aniline, iron oxide,
and hydrogen. The chemistry of the two nitrobenzene-
based aniline processes is described through the
following stoichiometric equations [4]:

C6H5NO2 + 3H2 C6H5NH2 + 2H2O


1.1
CU/SiO2
C6H5NO2 +3 Fe + 4 H2O C6H5NH2 +Fe(OH)2 + FeO + Fe
(OH)3 + 0.5H2 1.2
HCL/Fecl

Nitration, which is introduction of nitro group


or the NO2 group into the
molecule, is achieved by bringing mixed acid and the
compound to be nitrated into
intimate contact under vigorous agitation. Care must be
taken to remove the heat of
nitrating. The acid left on completion of the nitration
reaction is called spent acid. In
benzene nitration of the reaction is heterogeneous;
benzene and nitrobenzene have

7
very low solubility in the mixed and spent acids. The
overall stoichiometry for the reaction of benzene and
nitric acid to form nitrobenzene and water is
NO2

+ HNO3 + H2O ∆Ho =


-34.825 Kcal/g.mol 1.3
H2SO4
Sulfuric acid is a catalyst in the nitration reaction and
does not enter directly into the
stoichiometry of Equation 1.3. The role of sulfuric
acid is two fold: it acts as a
dehydrating agent by absorbing the water formed in the
nitration reaction and it is
responsible for the dissociation of nitric acid and through
which the reactive species,
the nitronium ion, is formed. The positively charged
nitronium ion, NO2, reacts with
the aromatic compound by electrophilic attack to form a
positively charged complex.
This complex breaks down fast through reaction of the proton
with an anion such as
-
HSO4. The reaction mechanism is described through the
following stoichiometric equations[4]:
8
Equations 1.4 to 1.7 add up to Equation 1.3. The
rate-controlling reaction is that
of Equation 1.5. The rate of nitration reaction is a
function of many variables, but
most importantly it is a function of sulfuric acid
strength, which is capable of
changing the rate by several orders of magnitude. The
steep increase of the nitration
rate with the sulfuric acid strength is generally
though to be due to the parallel
increase in the concentration of the nitronium ion in
the mixed acid. It is the
nitronium ion which is the reactive species in the rate-
controlling Equation 1.5 [4].

The nitronium ion is also present in strong nitric acid,


and benzene can be nitrated
using nitric acid alone. The incentive for this process is
that it would eliminate the
sometimes costly disposal or reconcentration of the
spent sulfuric acid. No
commercial plant appears to be operating using a nitric
acid only process. Of concern
would be the fact that mixtures of nitric acid and
benzene or nitrobenzene can be
detonated [4].

The main by-products formed in commercial


nitrobenzene plants are
dinitrobenzene (C6H4 (NO2)2), dinitrophenol (C6H3OH
(NO2)2), and picric acid
(C6H2OH (NO2)2). The fraction of dinitrobenzene
obtained is usually well below 100
ppm, but can reach a few hundred ppm if the nitration is
accidentally operated with
excess nitric acid. The introduction of nitro groups into
the benzene ring lowers the
electron density, thereby impeding electrophilic
attack. Substantial rates of
conversion to dinitrobenzene are possible only at
high spent acid strengths.
Furthermore, commercial nitrobenzene plants usually
operate with excess benzene
which will consume most of the nitric acid well
before significant quantities of
dinitrobenzene can be formed [4].

A possible but not proven mechanism is the one


where the nitronium ion becomes
attached to the benzene ring through one of its oxygen
atoms instead of the nitrogen

9
atom, the product being phenol and the nitrosyl ion, NO +.
The phenol then reacts with
nitric acid, possibly through a complex between the
nitrosyl ion and the phenol, to
form nitrophenol and nitrous acid, HNO 2. The one-
to-one molar ratio between
nitrophenol and nitrous acid is confirmed through
experiment. Nitrophenol is further
nitrated to dinitrophenol and picric acid. The rates for
this di- and trinitration are
relatively fast; there is usually only a trace of
mononitrophenol found in the crude
nitrobenzene. The stoichiometry of the reactions is
shown in the following equations
[2]:
Other by-products are formed from trace impurities in
the benzene feedstock or in
the recycle sulfuric acid. There is also the possibility that
very small amounts of

10
benzene and nitrobenzene undergo other reactions.
Most of these by-products are
removed in the washing stage of the process together
with the nitrophenols. The yield
loss caused by these side reactions is negligible. Of
more concern is the fast that
some of these trace impurities from surface-active
compounds which can
oceasionally lead to the formation of stable emulsions in
the washing section [4].

1.6 Uses

Nitrobenzene is used primarily in the production of


aniline, but it is also used as
a solvent and as an ingredient in metal polishes and
soaps. In the USA, around 98%
of nitrobenzene produced is converted into aniline; the
major use of aniline is in the
manufacture of polyurethanes. Nitrobenzene is also used
as a solvent in petroleum
refining, as a solvent in the manufacture of cellulose
ethers and cellulose acetate
(around 1.5%), in Friedel-Crafts reactions to hold the
catalyst in solution (it dissolves
anhydrous aluminium chloride as a result of the
formation of a complex) and in the
manufacture of dinitrobenzenes and dichloroanilines
(around 0.5%). It is also used in
the synthesis of other organic compounds, including
acetaminophen [3].

According to the BUA (1994), nitrobenzene is used


in Western Europe for the purposes shown in Table 5-1
[5].

Table 5-1 Type and estimated


consumption of nitrobenzene in Western
Europe in 1994

Main application areas or chemical Nitrobenzene consumption


manufacture (tones/year) in Western Europe
Aniline 380 000
m-Nitrobenzenesulfonic acid 5 000
m-Chloronitrobenzene 4 300
Hydrazobenzene 1 000

11
Dinitrobenzene 4 000
Others (solvents, dyes) 4 000
Total 398 300

Dunlap (1981) reported that most of the


production of aniline and other
substituted nitrobenzenes from nitrobenzene go into
the manufacture of various
plastic monomers and polymers (50%) and rubber
chemicals (27%), with a
smaller proportion into the synthesis of
hydroquinones (5%), dyes and
intermediates (6%), drugs (3%), pesticides and other
specialty items (9%) [5].

Past minor uses of nitrobenzene included use


as a flavouring agent, as a solvent in marking inks
and in metal, furniture, floor and shoe polishes, as
a perfume, including in perfumed soaps, as a dye
intermediate, as a deodorant and disinfectant, in
leather dressing, for refining lubricating oils and as a
flavouring agent. It is not known whether it may still
be used in some countries as a solvent in some
consumer products (e.g., shoe polish) [5].
The 22,680 metric ton of nitrobenzene left
was used to produce a variety
of other products, such as para-aminophenole
[123-30-8] (PAP) and nigrosine
dyes. The U.S. producers of PAP are Mallinckrodt,
Inc., Rho^ne-Poulene, and
Hoechst Celanese, with combined production
capacities > 35,000 metric tons (as
of may 1995). Mallinckrodt is the largest producer,
with over 50% of capacity.
PAP primarily is used as an intermediate for
acetaminophen [103-90-2] [2].

1.7 Nitrobenzene Derivatives

• 2,5-dichloronitobenzene
• 2,5-dimethoxynitrobenzene
• Dinitrobenzene
• O-nitrobenzene
12
• M-nitrobenzenesulfonic acid, sodium salt
• O-nitrochlorobenzene
• P-nitrochlorobenzene
• M-nitrochlorobenzene [15].
• 1,3,5-Trinitrobenzene
• 1, 3-Dinitrobenzene [1].

Figure 1-2 Key intermediates derived from


nitrobenzene
13
Chapter
Two
Production
Methods of
Nitrobenzen
e
Chapter Two
Production Methods of
Nitrobenzene

2.1General

World production of nitrobenzene in 1994


was estimated at 2 133 800 tones; about one-
third was produced in the USA [5].

In the USA, there has been a gradual increase


in nitrobenzene production,
with the following production/demand amounts, in
thousands of tones, reported:
73 (1960), 249 (1970), 277 (1980), 435 (1986),
533 (1990) and 740 (1994). Based on increased
production capacity and increased production of
aniline (the major end-product of nitrobenzene), it
is likely that nitrobenzene production volume will
continue to increase [5].

Production of nitrobenzene in Japan was


thought to be around 70 000 tones in 1980 and 135
000 tones in 1990. Patil & Shinde (1989) reported
that production of nitrobenzene in India was around
22 000 tones per year [5].

Nitrobenzene is produced at two sites in the


United Kingdom with a total capacity of 167 000
tones per year. It has been estimated that a
maximum of 115 400 tones of aniline was
produced in the United Kingdom in 1990. If it is
assumed that 98% of the nitrobenzene in the United
Kingdom is used to make aniline, then the total
amount of nitrobenzene used in the United Kingdom
would be around 155 600 tones per year [5].

14
Capacities for nitrobenzene production are
available for several Western European countries
and are shown in Table 3-1 Production for Western
Europe was reported as 670 000 tones in 1990 [5].

Table 2-1 nitrobenzene production capacities in


European countries in 1985

Country Capacity (tones)


Belgium 200 000
Germany 240 000
Italy 18 000
Portugal 70 000
Switzerland 5 000
United Kingdom 145 000
USA 434 000
Japan 97 000
Nitrobenzene is manufactured commercially
by the direct nitration of benzene using a mixture of
nitric acid and sulfuric acid [2, 4, 7, &8].

This commonly is referred to as mixed acid or


nitrating acid. Because two
phases are formed in the reaction mixture and the
reactants are distributed
between them, the rate of nitration is controlled by
mass transfer between the
phases as well as by chemical kinetics. The reaction
vessels are acid-resistant,
glass-lined steel vessels equipped with efficient
agitators. By vigorous agitation,
the interfacial area of the heterogeneous reaction
mixture is maintained as high
as possible, thereby enhancing the mass transfer
of reactants. The reactors
contain internal cooling coils which control the
temperature of the highly
exothermic reaction [2&3].

Nitrobenzene can be produced by either a


batch or continuous process
[2&3].

15
2.2Batch process

With a typical batch process, the reactor is


charged with benzene, then the
nitrating acid (56-60 wt % H 2SO4, 27-32 wt%
HNO3, and 8-17 wt % H2O) is
added slowly below the surface of benzene. The
temperature can be raised to
about 90oC toward the end of reaction to promote
completion of reaction. The
reaction mixture is fed into a separator where the
spent acid settles to the bottom
and is drawn off to be refortified. The crude
nitrobenzene is drawn from the top
of the separator and washed in several steps with a
dilute base, such as sodium
carbonate, sodium hydroxide, magnesium
hydroxide, etc, and then water.
Depending upon the desired purity of the
nitrobenzene, the product can be
distilled. Usually a slight excess of benzene is
used to ensure that little or no
nitric acid remains in the spent acid. The batch
reaction time generally is 2-4
hours, and typical yields are 95-98 wt % based on
benzene charged [2].

Based on yield of 1000 kg of nitrobenzene, material


requirements for the process are as follows [3]

Material

Quantity, kg
Benzene 650
Sulfuric acid 720
Nitric acid 520
Water 110
Sodium carbonate 10
The separation of the nitrobenzene is accomplished in
large conical-
bottomed lead tanks, each capable of holding one or
more charges. The nitrator
charges are permitted to settle here for 4-12 hr, when
the spent acid is drawn off
from the bottom of the lead tanks and delivered
to the spent-acid tanks for
additional settling or for treatment with benzene
next to be nitrated, in order to

16
extract the residual nitrobenzene. The
nitrobenzene is then delivered to the neutralizing
house [9].

The neutralizing tub may be either a


large lead conical-shaped tub containing an air-
spider, which is used for agitating the charge of
nitrobenzene during the washing process, or a
standard cast-iron kettle similar to the nitrator with
sleeve-and -propeller agitation. The neutralizing
vessel is prepared with a "heel" of warm water,
which is delivered from an adjacent vat, and
the nitrobenzene is blown into it. The charge is
thoroughly agitated and warmed with live stream for
30 min, or until neutral to congo, and then allowed
to settle for a similar period. The supernatant acid
water is then run off through side outlets into a
labyrinth where practically all the enmeshed
nitrobenzene will settle out. The charge is now
given a neutralizing wash at 40-50 oC with a warm
sodium carbonate solution, until alkaline to
phenolphthalein [9].

2.3 Tubular Reactor process


Most homogeneous gas-phase flow reactor is
tubular [19]. The nitrator
also can be designed as a tubular reactor, e.g., a
tube-and-shell heat exchanger
with appropriate cooling, involving turbulent flow.
Generally, with a tubular
reactor, the reaction mixture is pumped through the
reactor in a recycle loop and
aportion of the mixture is withdrawn and fed into the
separator. A slight excess
of benzene usually is fed into the nitrator to ensure
that the nitric acid in the
nitrating acid is consumed to the maximum possible
extent and to minimize the
formation of dinitrobenzene. The temperature of
nitrator is maintained at 50-
100oC by varying the amount of cooling. The
reaction mixture flows from the
nitrator into a separator or centrifuge where it is
separated into two phases [2].

17
The tubular reactor [i.e., plug-flow reactor
(PFR)] is relatively easy to maintain (no moving
parts), and it usually produces the highest
conversion per reactor volume of any of the flow
reactors. The disadvantage of the reactor and hot
spots can occur when the reaction is exothermic.
The tubular reactor is commonly found either in
the form of one long tube or as one of a number of
shorter reactors arranged in a tube bank [10].

2.4 Continuous process

A typical continuous process for the


production of the nitrobenzene is given in Figure 2.
Benzene and the nitrating acid (56-65 wt % H 2SO4,
20-26 wt % HNO3, and 15-18 wt % water) are fed
into the nitrator, which can be a stirred cylindrical
reactor with internal cooling coils and external heat
exchangers or a cascade of such reactors [2].

The basic sequence of operations for a continuous


process is the same as that for a batch process;
however for a given rate of production, however,
for a given rate of production, the size of the
naitrators is much smaller in the continuous
process. A 0.114-m3 (30-gal) continuous nitrator
has roughly the same production capacity as a
5.68-m3 (1500-gal) batch reactor [3].

The nitration in continuous process can take


place with elimination of heat of reaction, e.g.
adiabatically, or isothermally [11].

18
Figure 2-1 production of Nitrobenzene-
continuous process [1]

2.4.1 Adiabatic Continuous Process

The processes where the heat of nitration is


used to directly boil off water,
benzene and nitrobenzene from the nitrator [4]. An
adiabatic nitration process
was developed for the production of nitrobenzene.
This method eliminated the
need to remove the heat of reaction by excessive
cooling. The excess heat can be
used in the sulfuric acid reconcentration step. An
additional advantage of this
method is the reduction in reaction times to 0.5-7.5
minutes. The nitration step is
carried out at higher than usual temperatures 120-
160oC. because excess benzene
is used, the higher temperature allows water to be
removed as a water-benzene
azeotrope. The water is separated and the
benzenephase, containing
approximately 8 %nitrobenzene, is recycled back
into the reactor. The dry
sulfuric acid is then reused continuously [2].

The adiabatic process integrates nitration with


sulfuric acid concentration,
thus using the heat of nitration to reconcentrate the
spent sulfuric acid. This is

19
achieved by circulating a large volume of sulfuric
acid through the nitrators, absorbing the heat of
nitration without undue temperature rise. the spent
acid is then flash concentrated under vacuum [4].

One observes that the nitrobenzene stream


from the separator is used to heat the benzene feed.
However, care must be taken so that the
temperature never exceeds 190oC, where secondary
reactions could result in an explosion. One of the
safety precaution is the installation of relief valves
that will rupture before the temperature approaches
190oC, thereby allowing a boil-off of water and
benzene, which would drop the reactor temperature
[10].
Figure 2-2 Flow sheet for the production of
nitrobenzene adiabatically

20
2.4.2 Isothermal Continuous Process

The isothermal process is different from the


adiabatic process only in the
nitration section. In the isothermal process, typically
a minimum of 2 nitrators in
series is used with up to 4 nitrators in large
plants. Spent acid and crude
nitrobenzene are usually separated through gravity
settlers, but in some designs
centrifugal separation is used. The spent acid is
stripped free of dissolved
nitrobenzene and nitric acid either by steam
srripping or through benzene
extraction-prenitration. It is then either
reconcentrated and recycled or
discharged, often for use in phosphate rock
digestion. Spent acid stripping is
sometimes omitted in small plants; yield losses and
emissions of nitrobenzene
and nitrogen oxide must then be tolerated [4].
2.5 Non-Industrial Sources

Nitrobenzene has been shown to be emitted


from a multiple-hearth sewage
sludge incineration unit in the USA. The unit
consisted of 12 hearths and
operated at a rate of 13-15 tones per hour, with a
maximum temperature of 770
°C at the sixth hearth. Nitrobenzene was
monitored at the scrubber inlet and
outlet. The concentrations measured were 60
µg/m3 at the scrubber inlet
(corresponding to an emission of 3.2 g/h) and 16
µg/m3 at the scrubber outlet
(corresponding to an emission of 0.9 g/h). The
scrubber reduced the nitrobenzene
concentration by 71% [5].

The levels of nitrobenzene in air have been


measured at five hazardous
waste landfills and one sanitary landfill in New
Jersey, USA. Samples were
collected over a 24-h period at five locations within
each landfill. Mean levels

21
measured in the five hazardous waste landfills were
0.05, 0.65, 2.7, 1.0 and 6.6
µg/m3. The maximum level recorded was 51.8
µg/m3. At the sanitary landfill,
nitrobenzene was below the detection limit (0.25
µg/m3) at all locations [5].

Nitrobenzene has been shown to be formed


from the atmospheric reactions of benzene in the
presence of nitrogen oxides. The reaction is
thought to be initiated by hydroxyl radicals.
Nitrobenzene, once formed, reacts quite slowly in
the atmosphere; this could therefore provide a
major source of atmospheric nitrobenzene,
although it has not been possible to quantify this
source. Atkinson et al. (1987) reported that aniline is
slowly oxidized to nitrobenzene by ozone. These
reactions are summarized in Figure 2-3 [5].
Figure 2-3 Atmospheric reactions generating and
removing nitrobenzene

22
2.6 Process Selection

A continuous nitration process generally


offers lower capital costs and more efficient labor
usage than a batch process; thus, most, if not all,
of the nitrobenzene producers use continuous
processes [2&3].

In contrast to the batch process, a continuous


process typically utilizes a lower nitric acid
concentration and, because of the rapid and efficient
mixing in the smaller reactors, higher reaction rates
are observed [3].

The continuous nitration can take place


with elimination of heat of reaction, e.g.
isothermally, or adiabatically [11].

In adiabatic process, the heat of reaction is


not dissipated by cooling
during the process, but instead is subsequently used
for evaporating the water of
reaction, so that a sulfuric acid suitable for
recirculation obtained. One factor
common to all the processes which have been
proposed for this purpose is that
they require new installations of special
corrosion-resistant materials to
accommodate the high process temperatures (up to
145oC.) and they also require
considerably more stringent safety measures.
This offsets the potential
advantages of these processes [12].

The isothermal processes such that


considerable economic and ecological advantages
are obtained over the state-of-the-art [12].

2.7 Description of the Selected Process

The production of nitrobenzene by subjecting


benzene to isothermal nitration
with a mixture of nitric acid and sulfuric acid [9],
concentrated sulfuric acid has

23
two functions: it reacts with nitric acid to form the
nitronium ion, and it absorbs the water formed
during the reaction, which shifts the equilibrium
to the formation of nitrobenzene [4, 8, 13, &14]

A charge of benzene into a nitrator (a slight


excess of benzene is added to
avoid nitric acid in the spent acid [1, 2, &3]), then
slowly feeding in a mixed
nitrating acid (60 wt. % H 2SO4, 25 wt. % HNO3, 15
wt. % H 2O [2&14]), and
thereafter digesting the reaction mixture in the same
vessel. Since the addition of
the mixed acids requires several hours in order to
avoid uncontrollable rises in
temperature, and the digestion period requires
several more hours, the apparatus
used, particularly the nitrator, has to be large in
order to provide a high
production rate, and constant operator
surveillance must be maintained. In
addition, an explosion hazard is present at the start
of any run due to the large
unreacted charge in the nitrator [15].

The temperature in the nitrator is held at 50 oC


[2, 3, 16&17], governed by
the rate of feed of benzene. Reaction is rapid in
well-stirred and continuous
nitration vessels. The reaction must be cooled to
keep it under control. Good heat
transfer can be assured by the use of jackets, coils,
and good agitation in the

24
nitration vessel [16]. Nitration vessels are
usually made of stainless steel, although cast iron
stands up well against mixed acids [16&18].

It then enters a separator tank from which


a portion of spent acid is removed from bottom,
and the crude nitrobenzene is drawn off the top of
the separator [18].

The removed of spent acid (sulfuric acid &


water) is enter to evaporator in order to
concentrating the sulfuric acid with fresh sulfuric
acid (98 wt. % [4]) and then with fresh nitric acid
(64 wt. % [4]) to the nitrator [12].

The crude nitrobenzene (nitrobenzene,


benzene, sulfuric acid &water) is
drawn from the top of the separator and is wash
with the sodium carbonate in
order to remove sulfuric acid from crude
nitrobenzene, fellowing by final
washing with calcium sulfate (anhydrite) to
remove the water from react the
calcium sulfate with water to formed calcium sulfate
(Gypsum) [2,12,&14]. The
product is topped in still to remove benzene and give
pure product (96-99 wt. %)
[1,2 & 3].

25
Benzene

Na2CO3
it
r CaSO4
a
ti Benzene
n
g
a Crude
c nitrobenzene
i Acid separation 1st washing
d 2nd washing
N Distillation
it
r
i
c
H 2O
ac Spent acid NaSO4
id Gypsum
6 Nitrobenzene
4
H2CO3
w
t
S
.

%
u

l
nitrator
f

u
Fresh
sulfuric
acid r
98
i
wt.
%
c
a

c
(
i
E
d
v

a
r
p
e
o
c
r
o
a
n
t
c
o
e
r
n
)
t

t
Fig. 2-4 Typical continuous
i
nitrobenzene process
o

26
Chapte
r Three
Material
Balance
C

e
M

n
c

Note: Data necessary in appendix A.

3.1 General Information

Main Reaction
C6H5NO2 +H2O … (3.1)
C6H6 H 2 SO
4
+
HNO3

Ca

pa

cit

70

00

to

n/
ye

ar

[5]

Ye

ar

30

or

ki

ng

da

= 233.333333 ton/day

= 9722.222222 Kg/day

= 78.9718188 Kg.mol/hr
No nitric acid

remains in the spent

acid [2&14]

Conversion = 100 %

[2&14,1&4]

From stoichiometry:

Benzene required = 78.97183188 Kmol/hr

Water formed = 78.97183188 Kg.mol/hr

Required nitric acid = 78.97183188 Kg.mol/hr

27
3.2 Material Balance on Nitrator
4

3 5

Nitrator

Usually a slight excess of benzene (3.24 wt %) is


used to ensure that little or no nitric acid remains
in the spent acid [2, 4, 16&21].

Wt. of benzene = 78097183188 * 78.11 = 6168.489788 Kg/hr

Wt. of benzene excess = 6168.489788 *

0.0324 = 199.8590691 Kg/hr Total wt. of

benzene input = 6168.489788 +

199.8590691

Total wt. of benzene input = 6368.348857

Kg/hr
Total nitric acid input = 78.97183188 * 63.02= 4976.804845
Kg/hr
Nitrating acid composition H2SO4 60 wt %,
HNO3 25 wt %, & H 2O 15 wt %
[2&21].

Total weight of nitrating acid = =


19907.21938 Kg/hr

Wt. of sulfuric acid input =

Wt. of sulfuric acid input = 11944.33163 Kg/h

Wt. of water input = = 2986.082907


Kg/hr

Wt. of water formed = 78.97183188 *

18.02 = 1423.07241 Kg/hr

28
Water output in Stream 5 =

2986.082907 + 1423.07241

Water output in Stream 5 =

4409.155317 Kg/hr

Table 3-1 Material Balance on


Nitrator

3 4 5
Component [Kg/hr] [Kg/hr] [Kg/hr]

C6H6 - 6368.348857 199.8590691

HNO3 4976.804845 - -

H2SO4 11944.33163 - 11944.33163

H2O 2986.082907 - 4409.155317

C6H5NO2 - - 9722.222222

19907.21938 6368.348857
Total 26275.56824
26275.56824
29
3.3 Separator Material Balance

7
5

Aid Separation

1 wt % of total acid solution (sulfuric acid +


water) will goes with crude nitrobenzene
[16].

Stream 5 Acid solution input to separator =

4409.155317 + 11944.33163

16353.48695 kg/hr

Stream 7 (Crude Nitrobenzene) = excess BZ.+

N.B. + 1 wt. % of acid solution Excess BZ. =

199.8590691 Kg/hr
N.B. = 9722.222222 kg/hr

Wt. of acid solution in stream 7 = 0.01 * 16353.48695 =


163.5348695 Kg/hr

Wt. % sulfuric acid in acid solution = * 100 =


73.03843924 %

Wt. % water in acid solution = 26.96156076 %


this above acid wt% is the same for stream 6 & stream 7.

Wt. of sulfuric acid in stream 7= 163.5348695 * 0.73038439

30
Wt. of sulfuric acid in stream 7 =119.4433163 Kg/h
Wt. water in stream 7 = 163.5348695 * 0.2696156076 =
44.09515532 Kg/hr

Stream 6 (spent acid) = water + sulfuric acid

99 Wt % of total acid solution will goes in


stream 6(spent acid).Wt. of spent acid =
16353.48695 * 0.99 = 16189.95208 Kg/hr =
stream 6

Wt. of sulfuric acid in spent acid =

16189.95208 * 0.7303843924 Wt. of

sulfuric acid in spent acid =

11824.88831 Kg/hr

Wt. of water in spent acid =

16189.9520 * 0.2696156076

Wt. of water in spent acid =

4365.063767 Kg/hr

Table 3-2 Material balance on


separator
Component
5 6 7
[Kg/hr] [Kg/hr] [Kg/hr]

C6H6 199.8590691 - 199.8590691

HNO3 - - -

H2SO4 11944.33163 11824.88831 119.4433163

H2O 4409.155317 4365.063767 44.0915532

C6H5NO2 9722.222222 - 9722.222222

16189.95208 10085.61616
Total
26275.56824 26275.56824

31
3.4 Washing Process Material Balance

3.4.1 1st Washing process Material Balance

Na2CO3

8
7 10

1st
Was
hing

Na2CO3 + H2SO4 Na2SO4 + H2CO3

From stoichiometry

Mole of Na2CO3 input in stream 8 = mole

of sulfuric acid in stream 7 Mole of

sulfuric acid in stream 7 =


Mole of sulfuric acid in
stream 7
= 1.217815215 Kg.mol/hr

Wt. of Na2SO4 input = 1.217815215 * 106.00

Wt. of Na2SO4 input =

129.0884128 Kg.mol/hr = stream

8 Mole of Na2SO4 =

1.217815215 Kg.mol/hr

Wt. of

Na2SO4 =

1.217815215

* 142.05

Wt. of

Na2SO4 =

172.9906513

Kg/hr

32
Mole of H2CO3 = 1.217815215 Kg.mol/hr

Wt. of

H2CO3 =

1.21781521

5 * 62.03

Wt. of

H2CO3 =

75.4510778

Kg/hr

Wt. of water input in stream 7 = wt.

of water output in stream 9 Wt. of

water input in stream 7 =

44.0915532 Kg/hr

Table 3-3Material Balance on 1st


Washing Unit
Component
7 8 9 10
[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]

C6H6 199.8590691 - - 199.8590691

HNO3 - - - -

H2SO4 119.4433163 - - -

H2O 44.0915532 - - 44.0915532

C6H5NO2 9722.222222 - - 9722.222222

Na2CO3 - 129.0884128 - -

Na2SO4 - - 172.9906513 -

H2CO3 - - 75.4510778 -

10085.61616 129.0884128 248.5317291 9966.172836

Total
10214.70457 10214.70457

33
3.4.2 2nd Washing process Material Balance

CaSO4

11

10 13
2nd Washing

12

C
a
S
O
4

.
2
H
2

(
G
y
p
s
u
m
)

CaSO4 + 2H2O CaSO4.2H2O

Wt. of water input in stream 10 = 44.0915532 Kg/hr

Mole of water input in 10 = = 2.446812053 Kg

From stoichiometry

Mole of CaSO4 = 1.223406027 Kg.mol/hr

Wt. of CaSO4 = 1.223406027 * 136.14 =

166.5544965 Kg/hr = stream 11 Mole of

CaSO4.2H2O = 1.223406027 Kg.mol/hr

Wt. of CaSO4.2H2O = 1.223406027 * 172.18

Wt. of CaSO4.2H2O = 210.6460497 Kg/hr = stream 12

34
Table 3-4 Material Balance on 2nd
Washing Unit

10 11 12 13
Component [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]

C6H6 199.8590691 - - 199.8590691

HNO3 - - - -

H2SO4 - - - -

H2O 44.0915532 - - -

C6H5NO2 9722.222222 - - 9722.222222

CaSO4 - 166.5544965 - -

CaSO4.2H2O - - 210.6460497 -

9966.172836 166.5544965 210.6460497 9922.0812


Total
10132.72733 10132.72734

3.5 Reconcentrator Material Balance

18
1
1st mixing point
3
2 mixing point
nd
2
1

H2O
6
16

d
t

r r

e a

c t

o i

n o

c n

e
35
n
The concentrated of nitric acid added in
stream 1 is 64wt. %, and the
concentrated of sulfuric acid added in
stream 2 is 98 wt. % [4].

Material balance on nitric acid

Stream of fresh nitric acid = stream 1

0.64 stream 1 = 0.25 stream 3

Stream 1 = = 7776.25757 Kg/hr

Wt. of nitric acid input in

stream 1 = 0.64 * 7776.25757

= 4976.804845 Kg/hr

Wt. of water in stream1 = 0.36 *

7776.25757 = 2799.452725 Kg/hr

Material balance on sulfuric acid

Stream of fresh sulfuric acid = stream 2


Amount of sulfuric acid input in stream 2 equal
to amount that consumed in 1st washing process =
119.4433163 Kg/hr

Stream 2 = = 121.880935 Kg/hr

Wt. of water in input in stream 2 =

121.880935 * 0.02 = 2.4376187 Kg/hr

Material balance on water that must be

removed

Total wt. of water input =

2799.452725 +

2.4376187

= 2801.890344 Kg/hr

Wt of water in stream 17 (after reconcentrator)

= wt. of water in nitrating

acid - total wt. of water

input

36
= 2986.082907 -

2801.890344 = 184.1925633

Kg/hr Wt. of water must be

removed in stream17

= wt. of water in spent acid (stream 6) - water


after reconcentrator

in stream17

= 4365.063767 - 184.1925633

4180.8

71204

Kg/hr

stream

16

Materia

l
balance

on

reconce

ntrator

Stream

6 =

stream

16 +

stream

17

Stream 17 = 16189.95208 -

4180.871204= 12009.08088 Kg/hr

Wt. of water in stream 17 =

184.1925633 Kg/hr

Wt of sulfuric acid in stream 17 =

12009.08088 - 184.1925633 Wt of

sulfuric acid in stream 17 =

11824.88831 Kg/hr
Material balance on 1st mixing

point

Stream 17 + stream 2 = stream 18

Stream 18 = 12009.08088 +

121.880935= 12130.96182 Kg/hr

Wt. of water in stream 18 =

184.1925633 + 2.4376187

Wt. of water in stream 18

=186.630182 Kg/hr

Wt. of sulfuric acid in stream 18 =

12130.96182 + 186.630182 Wt. of

sulfuric acid in stream 18 =

11944.33163 Kg/hr

37
Table 3-5 Material Balance on
Reconcentrator

6 16 17 18 2 1 3
component [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [K

HNO3 - - - - - 4976.804845 4976

H2SO4 11824.88831 - 11824.88831 11944.33163 119.4433163 - 1194

H2O 4365.063767 4180.871204 184.192563 186.6301817 2.4376187 2799.452725 2986

Total 16189.95208 4180.871204 12009.08088 12130.96181 121.880935 7776.25757 1990

3.6 Distillation Material Balance

14

13
Distillation

Stream 13 =
97722.081291 Kg/hr
15

Benzene in stream 13 = 199.8590691 Kg/hr


Nitrobenzene in

stream 13 =

9722.222222 Kg/hr

Purity between 96 -

99 wt. % [2 & 14]

38
Select purity = 99 wt. %

Stream 15 (bottom) = = 9820.426487 Kg/hr

Benzene in stream 15 =

9820.426487 -

9722.222222 Benzene in

stream 15 =

98.20426486 Kg/hr

Benzene in stream 14 (top) =

199.8590691 - 98.20426486

101.6548042 Kg /hr

Table 3-6 Material Balance on


Distillation

13 14 15
Component [Kg/hr] [Kg/hr] [Kg/hr]

C6H6 199.8590691 101.6548042 98.20426486

C6H5NO2 9722.222222 - 9722.222222


101.6548042 9820.426987

Total 9922.081291

9922.081291

39
3.7 Overall Material Balance

Table 3-7
Overall Material
Balance

In ( Kg/hr)
Stream
1 2 4 8 11 9
Comp. No.
[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]
C 6H 6 - - 6368.348857 - - -
HNO3 4976.804845 - - - - -
H2SO4 - 119.4433163 - - - -
H2 O 2799.452725 2.376187 - - - -
C6H5NO2 - - - - - -
Na2CO3 - - - 129.0884128 - -
H2CO3 - - - - - 75.4510778
Na2SO4 - - - - - 172.9906513
CaSO4 - - - - 166.5544965 -
CaSO4.2H2O - - - - - -
7776.25757 121.880935 6368.348857 129.0884128 166.5544965 248.5317291
Total 14562.13027

40
T
a
b
l
e

3
-
8

a
l
l

S
t
r
e
a
m
s

o
f

M
a
t
e
r
i
a
l

B
a
l
a
n
c
e
s

Stream 1 2 3
4 5 6 7
NO.

COMP. [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]


C6H6 - - - 6368.348857 199.8590691 - 199.8590691

HNO3 4976.804845 4976.804845 - - - -

H2SO4 - - 11944.33163 - 11944.33163 11824.88831 119.4433163

H2O 2799.452725 119.4433163 2986.082907 - 4409.155317 4365.063767 44.0915532


C6H5NO2 - 2.4376187 - - 9722.222222 - 9722.222222

Na2CO3 - - -
- -

H2CO3 - - - - - -

Na2SO4 - - - - - -

CaSO4 - - - - - -

CaSO4.2H2O - - - - - -

Total 7776.25757 121.880935 19907.21938 6368.348857 16189.95208 10085.61616


26275.56824

41
Chapt
er Four

Energy
Balanc
e
C
h
a
p
t
e
r

F
o
u
r

E
n
e
r
g
y

B
a
l
a
n
c
e
30oC

C.W
H.W C.w
o
70 C 30oC

H.W
60 5

Note: Data necessary in appendix A.

4.1 Energy Balance on Nitrator


C6H6 + HNO3 C6H5NO2 + H2O
H2SO4
∆Hr = -146948.0527 KJ/Kg.mol

Qr = * -146948.0527 = -11604756.91 KJ/hr

Q3 = * ∆Hi * ni

∆Hi = cpi dT

Qr = ∆HHNO3 = 131.250 (325.15 - 298.15) - (323.152 -


298.152) +

*10-3 (325.153 -

298.153) = 2745.87058

KJ/Kg.mol

42
QHNO3 = *2745.87058 = 216846.4298 KJ/hr

∆HH2O = 32.243 (323.15 - 298.15) + *10-3(323.152-


298.152) + *10-5

(323.153-298.153) - *10-9(323.154-298.154)

∆HH2O = 843.7765567 KJ/Kg.mol

QH2O = * 843.7765567 = 139,821.6844 KJ/hr

∆HH2SO4 = 139.1(50-25) + * (502-252) = 3623.65625


KJ/Kg.mol

QH2SO4 = * 3623.65625 = 441294.3716 KJ/hr

Q3 = 216846.4298 + 139,821.6844 +

441294.3716 = 797962.4858 KJ/hr Q 4 =

∆H4 * nBZ.

∆H4 = -33.917 (303.15-298.15) + *10-1(303.152-298.152)


- *10-4

(303.153-298.153) + *10-8(303.154-298.154) =
416.7382512 KJ/Kg.mol
Q4 = * 416.7382512 = 33976.886 KJ/hr

Q5 = * ∆Hi * ni

∆Hi = cpi dT

∆HBZ. = -33.917 (323.15-298.15) + *10-1(323.152-


298.152) -

*10-4(323.153-298.153) + *10-8(323.154-298.154)

43
∆HBZ. = 2160.861183 KJ/Kg.mol

QBZ. = * 2160.861183 = 5528.96818 KJ/hr

∆HH2SO4 = 139.1(50-25) + * (502-252) = 3623.65625


KJ/Kg.mol

QH2SO4 = * 3623.65625 = 441294.3716 KJ/hr

∆HH2O = 32.243 (323.15 - 298.15) + *10-3(323.152-


298.152) + *10-5

(323.153-298.153) - *10-9(323.154-298.154)

∆HH2O = 843.7765567 KJ/Kg.mol

QH2O = * 843.7765567 = 206456.2648 KJ/hr

∆HN.B. = 295.3 (323.15-298.15) - (323.152-298.152) +


*10-3
(323.153-298.153) = 4580.779561 KJ/Kg.mol

QN.B. = * 4580.779561 =361752.5534 KJ/hr

Q5 = 5528.96818 + 441294.3716 +

206456.2648 + 361752.5534 Q 5 =

1015032.158 KJ/hr
The over all heat balance around nitrator

Heat input + Heat generation = Heat out + Heat accumulation


0.0 S.S
Q3+ Q4- Qr = Q5 + Qcooling
Qcooling = 797962.4858 + 33976.886 + 11604765.9 -
1015032.158

44
Qcooling = 11,421,664.11 KJ/hr

Qcooling = QJacketed + QCoil

QJacketed = 0.75 Qcooling & QCoil = 0.25 Qcooling

[explanatory note in chapter five] Q Jacketed =

0.75*11,421,664.11 = +8,566,248.085 KJ/hr

QCoil =

0.25*11,421,664.11 =

2,855,416.028 KJ/hr

Water inter jacket at

T=30oC and leaves at

T=65oC.

QJacketed = ∆HH2O * n H2O

∆HJacketed =32.243 (338.15 -303.15) + *10-3 (338.152-


303.152) + *10-5

(338.153-303.153) - *10-9 (338.154-303.154)

∆HJacketed = 188.206832 KJ/Kg.mol

n H2O = = 7,209.391374 Kg.mol/hr

mjacket = 129,913.2326
Kg/hr flow rate of water in
jacket Water inter coil at
T=30oC and leaves at
T=70oC.

∆Hcoil = 32.243 (34315 -303.15) + *10-3 (343.152-303.152)


+ *10-5

(343.153-303.153) - *10-9 (343.154-303.154)

∆Hcoil = 1353.828196 KJ/Kg.mol

ncoil = = 2,109.142088 Kg.mol/hr

mcoil = 38,006.74043 Kg/hr flow rate of water in coil

45
4.2 Separator Energy Balance

7 6

r
5

Assume perfect insulated system, so


there is no energy loose through system.
Q5 = 1015032.158 KJ/hr

Q6 = * ∆Hi * ni

∆Hi = cpi dT

∆HH2SO4 = 139.1(50-25) + * (502-252) = 3623.65625


KJ/Kg.mol

QH2SO4 = * 3623.65625 = 436881.4277 KJ/hr

∆HH2O = 32.243 (323.15 - 298.15) + *10-3(323.152-


298.152) + *10-5

(323.153-298.153) - *10-9(323.154-298.154)

∆HH2O = 843.7765567 KJ/Kg.mol

46
QH2O = * 843.7765567 = 204391.7023 KJ/hr

Q6 = 436881.4277 + 204391.7023 = 641273.13 KJ/hr

Q7 = * ∆Hi * ni

∆Hi = cpi dT

∆HBZ. = -33.917 (323.15-298.15) + *10-1(323.152-


298.152) - *10-4

(323.153-298.153) + *10-8(323.154-298.154)

∆HBZ. = 2160.861183 KJ/Kg.mol

QBZ. = * 2160.861183 = 5528.96818 KJ/hr

∆HH2SO4 = 139.1(50-25) + * (502-252) = 3623.65625


KJ/Kg.mol

QH2SO4 = * 3623.65625 = 4412.943716 KJ/hr

∆HH2O = 32.243 (323.15 - 298.15) + *10-3(323.152-


298.152) + *10-5

(323.153-298.153) - *10-9(323.154-298.154)

∆HH2O = 843.7765567 KJ/Kg.mol


QH2O = * 843.7765567 = 2064.562649 KJ/hr

∆HN.B. = 295.3 (323.15-298.15) - (323.152-298.152) +


*10-3

(323.153-298.153) = 4580.779561 KJ/Kg.molQN.B. =

*
4580.779561 =361752.5534 KJ/hr

47
Q7 = 5528.96818 + 4412.943716

+2064.562649 + 361752.5534 Q 7 =

373759.0279 KJ/hr

4.3 Energy Balance on Evaporator

16
13
HNO
6
3

64wt.
%
18
Steam
H2SO4 250oC
98 wt. 250oC
%
2 3973000 pa

17 Out 17 In

Q6 =
641273.13
KJ/hr

∆H16 = 32.243 (373.15 - 298.15) + *10-3(323.152-


298.152) + *10-5
(373.153-298.153) - *10-9(373.154-298.154) + 40683

∆H16 = 2545.822066 + 40683 = 43228.82207 KJ/Kg.mol

Q16 = * 43228.82207 = 10029641.36 KJ/hr

Q17 = * ∆Hi * ni

∆Hi = cpi dT

48
∆HH2SO4 = 139.1(100-25) + * (1002-252) = 11163.28125
KJ/Kg.mol

QH2SO4 = * 11163.28125 = 1345886.562 KJ/hr

∆HH2O = 32.243 (373.15 - 298.15) + *10-3(323.152-


298.152) + *10-5

(373.153-298.153) - *10-9(373.154-298.154) + 40683

∆HH2O = 43228.82207 KJ/Kg.mol

QH2O = * 43228.82207 = 441866.1228 KJ/hr

Q17 = 1345886.562 + 441866.1228 = 1,787,752.684 KJ/hr


Q6 + QSteam = Q16 + Q17
QSteam = Q16 + Q17 - Q6
QSteam = 10029641.36 + 1,787,752.684 + 641273.13 =
11,176,120.91 KJ/hr

mSteam = = 6,512.131986 Kg/hr

nsteam = 361.383573 Kg.mol/hr

Heat Exchanger Energy Balance

Cooling water
30oC
17 17

65.5 oC 100oC

50oC

49
Q17(In H.Ex.) = 1,787,752.684 KJ/hr

∆HH2SO4 = 139.1(65.5-25) + * (65.52-252) =


5,919.256238 KJ/Kg.mol

QH2SO4 = * 5,919.256238 = 713,674.4704 KJ/hr

∆HH2O = 32.243 (338.65 - 298.15) + *10-3(338.652-


298.152) + *10-
5

(338.653-298.153) - *10-9(338.654-298.154)

∆HH2O = 1,369.293843 KJ/Kg.mol

QH2O = * 1,369.293843 = 13,996.32311 KJ/hr

Q17(Out..Ex.) = 713,674.4704 + 13,996.32311 = 727,643.7935


KJ/hr

Q17(In H.Ex.) = Q17(Out..Ex.) + Qcooling

Qcooling = Q17(In H.Ex.) - Q17(Out..Ex.)

Qcooling = 1,787,752.684 - 727,643.7935 = 1,060,108.891 KJ/hr

∆HCooling = 32.243 (323.15 - 303.15) + *10-3(323.152-


303.152) +

*10-5(323.153-303.153) - *10-9(323.154-303.154)

∆HCooling = 675.3912584 KJ/Kg.mol


nCooling = = 1,569.621871 KJ/hr

mCooling = 28,284.58611 Kg/hr


Energy Balance on 1st. mixing point

Because high concentration of H 2SO4 added


(98wt.%) the heat of mixing is Zero p.433,
figure (12.17) [26].

50
Q2 = * ∆Hi * ni

∆Hi = cpi dT

∆HH2SO4 = 139.1(30-25) + * (302-252) = 716.93625


KJ/Kg.mol

QH2SO4 = * 716.93625 = 873.0958735 KJ/hr

∆HH2O = 32.243 (303.15 - 298.15) + *10-3(303.152-


298.152) + *10-
5

(303.153-298.153) - *10-9(303.154-298.154)

∆HH2O = 168.3852983 KJ/Kg.mol

QH2O = * 168.3852983 = 22.77797736 KJ/hr

Q2 = 873.0958735 + 22.77797736 = 895.8738509 KJ/hr

Q18= Q17(Out..Ex.) + Q2

Q18 = 727,643.7935 + 895.8738509 = 728,539.6673 KJ/hr

Q18 =[ *139.1(T-25) + * (T2-252)] +[


*
*10 .154)
32.243 (T -
-
]
298.15) +
9
(T
-
298
Find T18 by *10-3(T2-298.152) *10-5 (T3-298.153) -
+
trial & error
T18 = 65.15oC
Note

Heat of mixing of HNO3


not takes under
consideration.
∆Hdil.(mix.) = 11,864.53747
KJ/Kg.mol (5.104) [21].

51
4.4 Washing Process Energy Balance
4.4.1 1st Washing process Energy Balance

Na2CO3 + H2SO4 Na2SO4 + H2CO3


∆Hro =

-699.65 -

1413.891

1131.546

∆Hro =

-170.485

KJ/g.mol

∆Hro = -170,485 KJ/Kg.mol

∆Hr

∆Hro

∆HPr

oduct -

∆HRe
actant

∆HNa

2CO3 =

111.

08

∆T

∆HNa2CO3 = 111.08 * (30 - 25) = 555.4 KJ/Kg.mol

∆HH2SO4 = 139.1(50-25) + * (502-252) = 3,623.65625


KJ/Kg.mol

.
1

2
8

∆HProduct - ∆HReactant = 126.1128611 ∆T +

128.229 ∆T - 3,623.65625 - 555.4 ∆H Product -

∆HReactant = 254.3418611 ∆T - 4,179.05625

∆Hr = -170,485 +

254.3418611 ∆T -

4,179.05625 ∆Hr =

-174,664.0563 +

254.3418611 ∆T

Qr = [-174,664.0563 + 254.3418611 ∆T]

Qr = 1.217815215 [-
174,664.0563 +

254.3418611 ∆T] Qr =

-212,708.5452 +

309.7413883 ∆T
Q7 = 373759.0279 KJ/hr

52
∆H8 = 111.08 * (30 - 25) = 555.4 KJ/Kg.mol

Q8 = * 555.4 = 676.374704 KJ/hr

Q9 = * ∆Hi * ni

∆Hi = cpi dT

∆HNa2SO4 = 128.229 ∆T

∆HH2CO3 = 126.1128611 ∆T
* 126.1128611 ∆T]
Q9 = [ * 128.229
∆T] + [

Q9 = 156.1592272 ∆T +

153.5821611∆T Q9 =

309.7413883 ∆T

Q10 = ∆HMixture * ni

∆HMixture = cpMixture dT

cp10 = cpMixture = 277.604511 - 0.823102128 ∆T +


1.594487804*10-3∆T2 +
2.067652194*10-9∆T3

∆H10 = ∆HMixture = 277.604511 ∆T - ∆T2 +


*10-3
∆T3 + *10-9∆T4

∆HMixture = ∆H10 = 277.604511 ∆T -

0.411551064 ∆T2 + 5.314959347*10-4 ∆T3 +

5.169130485 *10-10 ∆T4

Q10 = 83.97733129 [277.604511 ∆T -

0.411551064 ∆T2 +5.314959347*10-4 ∆T3 +

5.169130485 *10-10 ∆T4

53
Q10 = 23,312.48936 ∆T - 34.56096004 ∆T 2 +
0.04463361 ∆T3 + 4.340897832 *
10 ∆T
-8 4

Heat input + Heat generation = Heat out + Heat accumulation

Q7 + Q8 - Qr = Q9 + Q10 0.0 S.S

373759.0279 + 676.374704 - (-212,708.5452 + 309.7413883


∆T)

= 309.7413883 ∆T + 23,312.48936 ∆T - 34.56096004 ∆T 2 +


0.04463361 ∆T3 +
4.340897832 * 10-8 ∆T4

587,143.9477 = 23,931.97214 ∆T - 34.56096004 ∆T 2 +


0.04463361 ∆T3 +
4.340897832 * 10-8 ∆T4

This equation above is solved by trial and error


until the right hand equals the left hand.

T = 62.88295021 oC

3
7

=
6

=
1

1
0

r
Q

J
/

4.4.2 2nd Washing process Energy Balance

CaSO4 + 2H2O CaSO4.2H2O

∆Hro = -2,024.021

+ (2* 286.025) +

1,435.097 ∆Hro =

-16.874 KJ/g.mol

∆Hro = -16,874 KJ/Kg.mol

54
∆Hr = ∆Hro + ∆HProduct - ∆HReactant∆HH2O = 32.243 (336.0329502 -
298.15) +
*10-3 (336.0395022-
298.152) + *10-5(336.03295023-298.153) -

*10-9
(336.03295024-
298.154)

∆HH2O =

1,280.433889

KJ/Kg.mol ∆HCaSO4

= 99.73 (30 - 25)

∆HCaSO4 =

498.65

KJ/Kg.mol

∆HCaSO4.2H2O =

186.149 ∆T

∆HProduct - ∆HReactant = 186.149 ∆T -

498.65 - (2* 1,280.433889)

∆HProduct - ∆HReactant = 186.149 ∆T -

3,059.517779

∆Hr = -16,874 + 186.149 ∆T -


3,059.517779

∆Hr = -19,933.51778 + 186.149 ∆T

Qr = [-19,933.51778 + 186.149 ∆T]

Qr =

-24,386.7

8579 +

227.7358

085∆T

Q10 =

563,676.1

122 KJ/hr

∆H11 = 99.73 (30 - 25)

∆H11 = 498.65 KJ/Kg.mol

Q11 = * 498.65 = 610.0514153 KJ/hr

∆H12 = ∆HGypsum = 186.149∆T

Q12 = * 186.149 ∆T

Q12 = 227.7358085 ∆T

55
Q13 = ∆HMixture * ni

∆HMixture = cpMixture dT

Cp13=cpMixture = 284.968122 - 0.847861952 ∆T+ 1.642023363


*10-3∆T2 +
2.237621333 *10-9∆T3

∆HMixture =284.968122 ∆T - ∆T2 +


*10-3 ∆T3 +

*10-9 ∆T4

∆HMixture = ∆H13 =284.968122 ∆T -

0.423930976 ∆T2 + 5.47341121*10-4 ∆T3 +

5.594053333 *10-10 ∆T4

Q13 = 81.53051923 [284.968122 ∆T -

0.423930976 ∆T2 + 5.47341121*10-4 ∆T3 +

5.594053333 *10-10 ∆T4]

Q13 = 23,233.59895 - 34.56331259∆T 2 +


0.044625005 ∆T3 + 4.560860728 *10-8
∆T4

Heat input + Heat generation = Heat out + Heat accumulation

Q10 + Q11- Qr = Q12 + Q13 0.0 S.S

563,676.1122 + 610.0514153 - (-24,386.78579 +


227.7358085∆T) =
227.7358085 ∆T + 23,233.59895 - 34.56331259∆T 2 +
0.044625005 ∆T3 +
4.560860728 *10-8 ∆T4

588,672.9494 = 23,789.07057 ∆T- 34.56331259∆T 2 +


0.044625005 ∆T3 +
4.560860728 *10-8 ∆T4

This equation above is solved by trial and error


until the right hand equals the left hand.

T= 63.33466274 oC

Qr -15,656.61038 KJ/hr

Q12 = 10,646.90855 KJ/hr


56
Q13 = 567,379.1321 KJ/hr

4.5 Distillation Energy Balance

14

R 80.1oC D
13 IN 13 Out

63.335oC 192.1oC

15

200.87oC

From calculation of bubble point at feed finds T 13 (OUT


H.EX.) = 192.1 C, & find T= 200.87 C at bottom
o o

section.

Heat Exchanger Energy Balance

Steam
13 63.334
In
Q13(IN H.EX.) = 250oC 13 Out
567,379.1321 KJ/hr

192.1oC
Steam
210oC

57
Q13 (OUT H.EX.) = * ∆Hi * ni

∆Hi = cpi dT

∆HBZ. = ∆HLiquid + λ + ∆HVapoure

∆HLquid = cpi dT
*10-1(353.252-298.152) -
∆HLiquid = -33.917
(353.25-298.15) +
*10-8(353.254-298.154)

*10-4(353.253-
298.153) +

∆HLiquid =

5,012.048424

KJ/Kg.mol λ = 30,781

KJ/Kg.mol

∆HVapour = cpi
dT

∆HVapoure = 8.314 [ -0.206 (465.25 - 353.25) + * 10-3 *


(465.252 -

353.252) - * 10-6 (465.253 - 353.253)

∆HVapoure = 12,607.37459 KJ/Kg.mol


∆HBZ = 5,012.048424 + 30,781+ 12,607.37459 = 48.42302
KJ/Kg.mol

QBZ. = * 48.42302 = 123,841.5502 KJ/hr

∆HN.B. = 295.3 (465.25-298.15) - (465.252-298.152) +


*10-3
(465.253-298.153) = 34,706.15308 KJ/Kg.mol

QN.B. = * 34,706.15308 = 2,740,808.486 KJ/hr

Q13 (OUT H.EX.) = 123,841.5502 +

2,740,808.486 = 2,864,650.036 KJ/hr

58
Q13(IN

H.EX.) +

QHeating

= Q13

(OUT

H.EX.)

QHeating

= Q13

(OUT

H.EX.) -

Q13(IN

H.EX.)

QHeating = 2,864,650.036 -

567,379.1321= 2,279,270.904

KJ/hr QHeating = m * ( hg2 - hg1)

m= = 765,756.968 Kg/hr

Distillation Energy Balance


Q13 (OUT H.EX.) +

QReboiler = Q14 +

Q15 + QCondencer

Material Balance

on Condenser

R = Reflux ratio =

Rm = [ -α ]

α = poBZ./ PoN.B

α= = 19.54121672

Rm = [ -19.54121672 *

1
8

2
R

8
V

L = Ractual * D

59
L =

2.06

2272

268

101.

6548

042

L =

209.

6398

836

Kg/h
r

L = 2.68390582 Kg.mol/hr

V =

209.

6398

836

+
101.

6548

042

V =

311.

2946

878

Kg/h

8
9

=
V

QConde

ncer =

3.985

3371

89 *

30,78

QConde

ncer =

122,6

72.66

KJ/hr

Q14 =

∆HBZ.

* ni
∆HBZ. = -33.917 (353.25-298.15) + *10-1(353.252-
298.152) -

*10-4(353.253-298.153) + *10-8(353.254-298.154)

∆HBZ. = 5,012.048424 KJ/Kg.mol

Q14 = QBZ. = * 5,012.048424 = 6,522.83704


KJ/hr

Q15 = * ∆Hi * ni

∆Hi = cpi dT

∆HBZ. = ∆HLiquid + λ + ∆HVapoure

∆HLquid = cpi dT

∆HLiquid = -33.917 (353.25-298.15) + *10-1(353.252-


298.152) -

60
*10-4(353.253-298.153) + *10-8(353.254-298.154)

∆HLiquid = 5,012.048424 KJ/Kg.mol

λ = 30,781 KJ/Kg.mol

∆HVapour = cpi dT

∆HVapoure = 8.314 [ -0.206 (474.02 - 353.25) + * 10-3 *


(474.022 -

353.252) - * 10-6 (474.02- 353.253)

∆HVapoure = 13,716.10935 KJ/Kg.mol

∆HBZ = 5,012.048424 + 30,781+ 13,716.10935 = 49,509.15778


KJ/Kg.mol

QBZ. = * 49,509.15778 = 62,245.68482 KJ/hr

∆HN.B. = 295.3 (474.02-298.15) - (474.022-298.152) +


*10-3
(474.023-298.153) = 36,925.461 KJ/Kg.mol

QN.B. = * 36,925.461 = 2,916,071.298 KJ/hr

Q15 = 62,245.68482 + 2,916,071.298 = 2,978,316.983 KJ/hr


Q13 (OUT H.EX.) +

QReboiler = Q14 +

Q15 + QCondencer

QReboiler = Q14 +

Q15 + QCondencer -

Q13 (OUT H.EX.)

QReboiler = 6,522.83704 + 2,978,316.983

+122,672.664 - 2,864,650.036 Q Reboiler =

242,862.4479 KJ/hr

61
T
a
b
l
e

4
-
1

a
l
l
S
t
r
e
a
m
s

o
f
E
n
e
r
g
y

B
a
l
a
n
c
e
s

Stream 1 2 3 4 5 6 7 8
NO.

COMP.
[KJ/hr] [KJ/hr] [KJ/hr] [KJ/hr] [KJ/hr] [KJ/hr] [KJ/hr] [KJ/hr
C6H6 - - - 33976.886 5528.96818 - - -

HNO3 43435.94798 - 216846.4298 - - - - -

H2SO4 - 873.0958735 441294.3716 - 441294.3716 436881.4277 4412.943716 -

H 2O 26159.21003 22.77797736 139821.6844 - 206456.2648 204391.7023 2064.562649 -

C6H5NO2 - - - - 361752.5534 - 361752.5534 -

Na2CO3 - - - - - - - 676.3745

H2CO3 - - - - - - - -

Na2SO4 - - - - - - - -

CaSO4 - - - - - - - -

CaSO4.2H2O - - - - - - - -

Total 69595.15801 895.8738509 797962.4858 33976.886 1015032.158 641273.13 373759.0279 676.3745


Pressure atm 1 1 1 1 1 1 1 1

Temperature 30 30 50 30 50 50 50 30
o
C

62
Feed
Benzene 8
4
7
Washing Tank
1nd 13
3 7
10

9
1

Settler
18 5
10
Nitrator 6
11
2

Washing Tank 13
2st

12
17 17
Vaporizer

Cooling

63
Chapter
Five
Equipment
Design
Chapter Five

Equipment Design

Note: Data necessary in appendix A.

5.1 Nitrator Design

A simple stirred tank reactor is used, sized


to give sufficient residence
time, and provided with sufficient agitation to
promote dispersion of the organic
phase [4].

Good heat transfer can be assumed by use


external jacket & internal coil. Nitration vessel
made of stainless steel (18Cr/8 Ni) (316) [4&16].

Calculation of Nitrator volume

Resi

denc

time

=τ=
10

min

[29]

τ =

0.16

6666

666

hr

τ =

νo = stream 3 + stream 4

νo = [ + + +
]

=
2

r
V

V = 0.166666666 * 20.37924292

64
V = 3.396540473 m3 = 897.1088536 gal

This volume is very satisfied and very close to reference [16].

Added 10% to the volume of nitrator for


safety and increase the efficiency of mixing.

0
4

7
3

=
2

i
t

According to figure (9-16) [30] illustrated the


relationship between vessel
volume and viscosity, so selected turbine impeller
(disk mounted flat blade
turbine).

DA = D/3

DA =

2.1810709
78/3 =

0.7270236

59 m HA =

D/3

HA =

2.1810709

78/3 =

0.7270236

59 m

r = D/4

r =

2.18107

0978/4 =

0.54526

7744 m

a =

2.18107

0978/5 =
0.43621

4195 m

HL = D = 2.181070978 m
65
Als

use

fou

sy

mm

etri

baff

les

b =

wid

th

of

baff
le =

D/1

b = 2.181070978/10 = 0.2181070978 m

0.218

2.181

0.73
0.7

2.181

Calculation the shaft power required to drive the an agitator

The shaft power required to operate the


stirrer can be calculated by the following equation
[31]:

PA = NP* ρ * N3 *D5A

NP = Power Number, determined from figure (9.7)[31].


Re =

66
Assume the agitator rotation per minute (N) = 100 rpm =1.67 rps.

Re =

Re =

8.074454885

* 104 [is very

suitable]

NP = 5

PA = 5 *

1173.870615 *

(1.67)3 *

(0.727023659)5

PA = 5,519.239048

watt = 5.519239048

Kwatt

Design the Jacket around Nitrator


The jacket is used to cool the nitrator
content and keep temperature at
50oC. Select dimple jacket, assume the spacing
between jacket and vessel wall is
100mm and the jacket is fitted with a spiral baffle,
the pitch between the spirals
is 200mm.

The jacket is fitted to the nitrator section and extend


to a height of 80% from the height of the nitrator.

HJacket = 0.80 * 2.181070978 = 1.744856782 m

The baffle forms continuous spiral

chanel section 100mm * 200mm.

Number of spirals = height of jacket /

pitch

Number of spirals = = 8.72428391 9

Cross- sectional area of channel


= 100 * 200 * 10-6 = 0.02m2

67
de = = 133.333mm

length of channel = 9 * * 2.181070978 = 61.66832905 m

From Energy Balance:

mJacket = 129,913.2326 Kg/hr

Physical properties of water at mean temperature =


47.5oC as fellows

[32]:

Cp= 4.174 KJ/Kg.oC, ρ = 989.25 Kg/m3,

µ = 5.755 * 10-4, pr = 3.74 & K =

0.64225.

u= *

u = 1.823958001m/s

Nu = 0.023 Re0.8 Pro.33 [ ]0.14


Water is not viscose so

neglect viscosity correction

term. Nu = 0.023 Re0.8 Pro.33

Re =

Re = = 62,867.15905

68
Re = 4.180355498 * 105

Nu = 0.023 *

(418,035.5498

)0.8 * (3.74)0.33

Nu =

1,116.21033

Nu =

hj = = 5,376.659075 W/m2.oC

∆p = 8 jf ( )( )

jf = 2* 10-3 from figure (12.24) [23].

∆p = 8 * (2 * 10-3) ]* ]

∆p = 12,177.17195 pa =

1.767PSI < 10 PSI


(acceptable) Design the

Coil inside the Nitrator

Diameter of pipe of coil = D/30

Diameter of pipe of coil = = 0.072702365 m

Not found pipe diameter 72.7mm in standerd, so


take outside diameter standard steel pipe as 76.1mm,
wall thickness as 3.65mm [34]

Inside diameter = di = do + 2Lw

69
di = 76.1- 3.65 = 68.8mm

Physical proprieties of vessel content at 50 oC as fellows [22, 23,


28&33]:

Kav. = 0.326087319, ρav. = 1,425.7889 Kg/m3, µav. =


2.228013388 *10-3 pa.s & cpav. = 1.947772473
KJ/Kg.k

The heat transfer coefficient of vessel can be calculated from


equation below:

=C [ ]a [ ]b [ ]c

C,a,b,c are constants according to type of agitator


and surface type (coil or
jacket)

C = 1.1, a =

0.62, b =

0.33, c =

0.14 [23]

Neglect the
viscosity

correction

term.

= 1.1 [ ] 0.62

[ ]

2
1

e
s

hi = 4200 (1.35 + 0.02 t) ut0.8 / di0.2

t= = 50oC

70
2

A
=
d
i

A= * (68.8)2

A = 3717.635083 mm2

u= * *

u = 2.869804254 m / s

hi = 4200 (1.35 + 0.02

(50)) (2.869804254)0.8 /

(68.8)0.2 hi = 9,841.95296

W / m 2. oC

= + + + *

Kw = 16.3 for stainless steel [32].

= + + + *
= 7.705482183 * 10-4

8
W

o

From Energy Balance:

Qcoil = 2,855,416.028 KJ /hr = 793,171.1189 J/s

71
Ao = = 15.27941481 m2

Length of tube =

Length of tube = = 63. 910491481m

Assume Number of turns = 19 turns

Diameter of turn= = 1.090535489m 1m

Mec

han

ical

Des

ign

[23&

30]

Calcu
lation

of the

cylin

drical

part

Thickness of cylindrical part of Nitrator can


be calculated directly from equation bellow:

t= +C

J = 0.85, f = 175N/mm2, C = 1mm

P= 1.1*1 =1.1atm = 0.1114575N/mm 2

t= +1

t = 1.817438078mm 2mm

72
Calculations of the Reactor cover thickness

Thickness of the cover can be calculated from:

t=

J = 1[The cover consist of one piece]

t=

t = 0.694606292mm

Calculations of the Height of cover

The height of cover (distance from the head


of reactor to the tangent line) can be calculated by
knowing the major &minor axis.

Rs = a2/b , Rs = Di = 2.181070978 m

2a = major axis = Do

Do = Di + 2(thickness)

Do =

2.181070978
+

2(1.81743807

8*10-3) Do =

2.184706233

2b = minor axis = 2h

h =

height

of head

from

tangent

line

a =

2.18470

6233/2

1.09235

3117m

b = a2/Rs
73
b =

1.0923531172/2.1847

06233 = 0.546176558

m h = 0.546176558

m height of cover

Calculati

on of the

volume

of

Nitrator

V =

0.05Di3 +

1.65 t D2

V = 0.05* 2.1810709783 + 1.65 *

0.694606292*10-3 * 2.1810709782 V =

0.524227513 m3
Over all volume of Nitrator = volume of

cylindrical part + volume of covers V Total =

3.73619452 + 2(0.524227513)

VTotal = 4.784649546 m3

Overall length of reactor = length of

cylindrical part + 2*length of cover L Total =

2.181070978 + 2* 0.546176558

LTotal = 3.273424094 m

Calculat

ion of

the

weight

of

Nitrator

Wv =

240 Cv

Dm (Hv
+ 0.8

Dm ) t

Cv = 1.08, factor

to account weight

of nozzles Dm =

Di + t

Dm = 2.181070978 +

1.817438078*10-3 =

2.182888416 m Hv = Di =

2.181070978 m

Wv = 240 * 1.08 * 2.182888416

(2.181070978 + 0.8 * 2.182888416)

74
Wv = 2222.130942 Kg

Design the supporting of Nitrator

The reactor supporting legs depend mainly on


the weight of Nitrator and material inside.

Wv = 2222.130942 Kg

Weight of material inside = 26,275.56824 Kg

Total weight of Nitrator = 2222.130942 +

26,275.56824 = 28,497.69918 Kg Density of

stainless steel (18% Cr, 8% Ni) = 7,817 Kg/m 3

[32].

Each support bear weight of =


For supporting leg L/D = 8

Each support bear V = D2L


weight of =

V = D2 (8D) =2 D3
The volume of one leg
support =

D= =
0.525424043m
= 7,124.424796 Kg

= 0.911401405 m3

75
L = 8*

0.525424

043 =

4.203392

345m

Wind

load

The effect of the wind on tall vessels (over


50m) although the calculation about this small effect
is made.

o
a

f
P

Deff = Do = 2.184706233 m

Fw = 1280 *

2.184706233 =

2,796.423978 N/m
Bending moment at

any plane = Ms =

Fw / 2 *S2 S = Di =

2.181070978m

Ms = * (2.181070978)2 = 6,645.304084N.m

The Nitrator does not consider tall vessel so the effect of wind is
not high.

76
5.2 Settler Design [23]

Design of Settler (Decanter) to separate a crude


nitrobenzene from a spent acid (heavy phase).

Crude nitrobenzene flow rate

(stream 7) = 10,085.61616 Kg/hr

Spent acid flow rate (stream 6) =

16,189.95208 Kg/hr

ρd(Croude Nitrobenzene) =

1,173.870615 Kg/m3

[22,28&33]. ρC(Spent Acid)

= 1,582.722727 Kg/m3

[22,28&33].

µd(Croude Nitrobenzene) =

1.280716063 * 10-3 pa.s

µc (Spent Acid) = 2.81813726

* 10-3 pa.s
Take dd = 150µm

(droplet diameter)

ud =

ud =

ud = -1.779029395 * 10-3 m/s (rising)

As the flow rate is small, use a vertical cylindrical vessel.

LC = * = 2.84143826 * 10-3 m3/s

77
ud > uc ( the decanter vessel is sized on the
basis that the velocity of the continuous phase
must be less than settling velocity of the droplets
of the dispersed phace) [23].

Ai = Lc/uc

Ai = = 1.597184548 m2

Ai =

r= = 0.71302148 m

Diameter of vertical cylinder = 1.426048961 m

Take the height as twice the diameter, a

reasonable value for a cylinder. Height =

2.852085922 m

Take the dispersion as 10 percent of

the height =0.285208592 m


Check the residence time of the

droplets in the dispersion band

= = 160.3169644 s = 2.671949407 min

This is satisfactory , atime of 2-5 min is normally recommended.

Check the size of the spent acid (continuous,


heavy phase) droplets that
could be entrained with the crude Nitrobenzene
(light phase).Velocity of the

Velocity crude Nitrobenze phase = * *

78
Velocity crude Nitrobenze phase = 1.494254608 * 10 -3 m/s

dd = (stock’s law)

dd =

dd = 9.267388216 * 10-5 m = 92.67388216 µm


( which is very satifactory; below
150µm).

Piping Arrangement

To minimize entrainment by the jet of the


liquid entering the vessel, the inlet velocity for a
decanter should keep below 1m/s.

Flow-rate = *

Flow-rate = 5.22803863 * 10-3 m3/s

Area of pipe = = 5.22803863 * 10-3 m2


Pipe diameter = = 0.081587655 m =
81.587655 mm say

88.9 diameter of the standerd steel pipe [34].

Take the position of the interface as half-way


up the vessel and the light liquid off-take as at 90
percent of the vessel height.

79
Z1 = 0.9 *

2.85208592

2 =

2.56687733

Z3 = 0.5 *

2.85208592

2 =

1.42604296

Z2 =

Z2 = 2.272174706 m Proposed

Z2 = Design

Liquid- light take off


Z1 = 2.6 m

+ 1.426042961

D = 1.4 m

Heavy liquid
take off
Crude N.B

Spent Acid Z2 =2
m
Z3 = 1.4 m

80
Mechanical Design

The material of construction used is stainless


steel [4], select stainless steel (18 Cr / 8 Ni) (304)
which is corrosion resistance.

Calculation of the Thickness of Decanter

Thickness of the decanter can be calculated directly from equation


bellow:

t= +C

J = 0.85, f = 145N/mm2, C

= 1mm, D = 1.426 *

103mm P= 1.1*1 =1.1atm

= 0.1114575N/mm2

t= +1

t = 1.645072183 mm 2mm less than 7mm so that take the


thickness 6mm [23]
Calculation

the thicness

of domed

ends:

Select the

ellipsodial

heads

t=

t=

t = 0.644838821mm 0.645mm

81
5.3 Heat Exchanger Design [23]

Spent Acid
T2=65.5oC

Cooling water hot water


t1 =30oC t2=30oC

S
p
e
n
t

A
c
i
d

T
1

=
1
0
0
o

The heat exchanger which is used as cooller


to cool the spent acid from vaporizer from 100oC to
65.5 by using cold water.
water is corrosive more than

Spent acid, so assign to tube side.

Operating Condition

Temperature of a hot

spent acid inputT1 =

100oC

Temperature of a cold

spent acid outputT1 =

65.5oC

Temperature of a cold

water input t1 = 30oC

Temperature of a hot

water input t2 = 50oC

T1=100oC

∆T1 {
T2=65.5oC
o
T2=50 C
82
}∆T 2

t1=30oC
The hot spent acid & cold water passed
counter currently ( more efficient than co-current).

From energy balance:

QCooling = 1,060,108.891

KJ/hr = 294.4746919

KWatt mH2O =

28,284.58611 Kg/hr =

7.856829475 Kg / s

Mean Temperature

Difference (∆Tm)

(T −t )− (T −t )
1 2 2 1

Tlm (T1 − 2 )
=
ln t
(T − t)
2 1

(100−50)− ( = 
∆ 42.336964 C
T 65.5−30) 35
l ( 100−3
m 0)

ln( 65.5−30 )

∆Tm = Ft ∆Tlm

Use one shell and two tube passes.


T2 = 65.5 °C

R = ( T 1 - T 2 ) / ( t 2 - t1 )
t1 = 30 °C

S = ( t 2 - t1 ) / ( T 1 - t1 ) t2 = 50 °C

R = (100 - 65.5) / ( 50
T1 =100 °C

-30)= 1.725

S = ( 50 - 30 ) / (100 - 30 )

= 0.285714285

From figure (12.19) [23] at R = 1.725 & S

= 0.285714285 → Ft = 0.95 ∆Tm = 0.95 *

42.33696435 = 40.22011613oC

From table (12-1) [23] choose U = 800 W/m 2.oC.

83
P

Q
=

A= = 9.151971708 m2

Pipe Dimension

Choose 20mm o.d, 16mm i.d, 4.88m long tube table (12.3) [23]

Allowing for tube sheet thicness, take L =


4.83m, material of construction Cupro-
Nickel.

Area of one tube = π do L

Area of one tube = π* 20*10-3 *

4.83 * 10-3= 0.30347785 m2

Number of tubes = Nt = A / At

Number of tubes = 9.151971708 / 0.30347785 = 30.15696763

30 tube
Use 1.25 Triangular pitch, this type of pitch is more
efficient than rectangular
pitch.

Db = bundle diameter = Pt
Flow
do (Nt / k1 ) 1/n1 From table

(12-4) [23], k1 = 0.24, n1=

2.207 Db = 20 * (30 / Triangular Pitch

0.249)1/2.207

Db = 175.3490987 mm

Use a split-ring floating head

type, assume clearance = 30mm

Shell diameter; Ds =

175.3490987+ 30 = 205.3490987

mm

84
Tube - Side Coefficient

Mean temperature = (30 + 50) /2 =40°C

Physical properties of water at mean temperature [32]:

Cp = 4.174kJ/kg.°C, ρ = 992.04 kg/m 3, µ = 6.556


* 10-4 pa.s, Kf =0.6328 W/m °C , Pr = 4.334.

tube cross-sectional area = π di2 /4 =

π (16)2 /4 = 201.0619296 m2 tube per

pass = 30 / 2 = 15

total flow area = At = 15 * 201.0619296 *

10-6 = 3.015928947 * 10-3 m2 Mass velocity

(G) = mH2O/At

Mass velocity (G) =

7.856829475/

3.015928947*10-3 Mass

velocity (G) =

2,605.110934kg/m2.s

Water linear velocity =

2,605.110934 / 992.04 = 2.626014005

m/s Re = ρ ut d /µ
Re = 992.04 * 2.626014005 * 16 * 10 -3 / 6.556

* 10-4 = 6.357805817 * 104 hi = 4200 (1.35 +

0.02 t) ut0.8 / di0.2

hi = 4200 ( 1.35 + 0.02

(40)) (2.626014005)0.8 /

(16)0.2 hi = 11,227.97364

W/m2.oC

or

h d 0.14
i
=h . ( µ / w)
0

J 3µ
3
i
k Re Pr
f

Negiect (µ/µw) 0.14

From Figure (12.23)[23], jh = 3.1×10-3

85
hi = (0.6328/16 * 10-3) ( 3.1 * 10-3) (6.357805817 * 104) (4.334)
0.33

h
= 12,647.03674W/m2 °C
take the lower value

hi = 11,227.97364

W/m2.oC calculation

of tube teperature

hi (tw - t) = U (T - t)

11,227.97364 (t w - 40) = 800 (82.75 - 40)

tw = 43.03245965oC 43 oC

µw = 6.199243243 * 10-4 pa.s at 43 oC

[ ] =[
0.14
]0.14 = 1.007864243 1[no
correction factor

needed]

Shell - Side Coefficient

Choose baffle spacing = lB = 0.2Ds [23]

lB = 0.2 *

205.3490987
=

41.06981914

mm

tube pitch =

1.25 do = 1.25

(20) = 25mm

As =

As = =
1.686730069*10-3m2

mspent acid = 12,009.08088 Kg/hr = 3.3358558 Kg/s

Gs = = 1977.705776 Kgde = ( pt2 - 0.917


do )

86
de = (252 - 0.917 * 202 ) = 14.201 mm

all physical properties at

82.75oC of spent acid [24,

28&32]: Cp = 1.590330869

kJ/kg.°C

ρ = 1,748.959499 kg/m3

7
7

0
-

0
.

=
2

Re = = = 5.223851997 * 103

Choose 25 percent baffle cut, from figure ( 12.29) [23], j h = 2.4 *


10-2

hs = jh Re pr1/3 [ ]0.14

Negiect (µ/µw) 0.14

hs = * 2.4 * 10-2 * ( 5223.851997) *


( 2.130055474)1/3

hs = 4,559.6671 W /m2.oC
Calculati

on of the

Shell

Tempera

ture hS

(T-Tw) =

U (T - t)

4,559.6671 (tw - 40) = 800 (82.75 - 40)

tw = 75.24945243oC 75.25 oC

87
µw = 6.077856682* 10-3 pa.s at 75.25 oC

[ ] =[
0.14
]0.14 = 0.982977327 1[no
correction factor

needed]

Checking for over all Heat Transfer Coefficient

The value of over heat transfer coefficient


must be checked and the new value of U must be
greater than assumed value (800 W/ m 2.oC).

1 1 do ln(do / do do 1
= + + + +
1 h h di )
i d hi
U o od 2 kw 1
di

h id

Kw = 50 W / m .oC (for curpo-Nikel) [32].

Take the foaling coefficient as 6000 W/ m 2.oC [23].

= + + + * + *

= 7.28006325 * 10-4
Uo = 1,373.614614 W/ m 2.oC (Above the

assumed value of 800 W/ m 2.oC) Calculation

of Pressure Drop

Tube Side

Pressure drop in the tube side can be


calculated from equation below, the pressure drop
calculated must be smaller than 10 psi.

∆Pt = Np [ 8jf + 2.5]

jf = 3 * 10-3 from figure (12.24) [23].


88
∆Pt = 2[ 8 * 3 * 10-3 * + 2.5]

∆Pt = 66,666.10822 pa =

9.671766996 psi < 10 psi

( acceptable). Shell Side

∆Ps = 8jf

us = GS /ρ = 1977.705776 / 1748.959499 = 1.130789922 m/s

from figure (12.30) [23], at Re =

5.223851997 * 103 → jf = 5.7 * 10-3 ∆Ps

= 8* 5.7 * 10-3 *

∆Ps = 75,096.10397 pa = 10.89477156 psi considered suitable not


mor large than
10 psi .

Input and Output Manholes

Diameter of manholes is given in equation below:


. ρ
dm = 282 m 0.52 -0.37

Manhol for Input Hot Spent Acid


dm = 282 *

( 3.3358558)0.52 *

( 1,748.959499)-0.37

dm = 33.30338513

mm

Manhol for Input Cold Water


dm = 282 *

( 7.856829475)
0.52
* (992.04)-
0.37
dm =

64.13010051

mm

89
5.4 Distillation Design [23,30&35]

Feed Top Bottom

Comp. Wt.% Mol.% Wt.% Mol.% Wt.% Mol.%

C 6H 6 2.014285745 3.31381848 100 100 1 1.567082484

C6H5NO2 97.98571425 96.86168152 - - 99 98.43291752

TemperatureoC 192.1 80.1 200.87

Vapor-liquid equilibrium data for Benzene-Nitrobenzene [36]:


(see appendex B)

X Y
0 0
0.05 0.451
0.1 0.759
0.15 0.923
0.2 0.957
0.25 0.969
0.3 0.975
0.35 0.981
0.4 0.985
0.45 0.988
0.5 0.989
0.55 0.99
0.6 0.992
0.65 0.994
0.7 0.995
0.75 0.996
0.8 0.996
0.85 0.997
0.9 0.999
0.95 0.999
1 1

90
1

0.8

0.6

0.4

0.2

0 0.2 0.4 0.6 0.8


1

Benzene Liquid Mole Fraction

Figure 5-1 Vapor-Liquid Equilibrium

diagram (Isothermal) at 70 oC R =

2.062272268
Intercept = = = 0.326554895 0.33

From equilibrium curve by Mc cabe-Tiele method


find the number of stages
equal 3.
Benzene Vapor Mole Fraction

Number of theoretical plate = 3 + 1 = 4

91
assume column efficiency of 60 percent. Take
reboiler as equivalent to one
stage.

No. of real stages = =5

Estimate base pressure

Assume 100mm water, pressure drop per plate.

column pressure drop = 100 * 10 -3

* 1000 * 9.81 * 5 = 4905 pa top

pressure, 1 atm = 101.325 * 103 pa

bottom pressure drop = 101.325 * 10 3 + 4905

= 106,230 pa = 106.230 Kpa Column

Diameter

At Top of the Column

Top

temperatu

re = 80.1
o
C =

353.25 K

Top

pressure =
101.325 *

103 pa

L ρ
F n V
V ρL
=
L
V
n

From material Balance:

Ln = 209.6398836

Kg/hr =

0.058233301Kg/s

Vn =

311.2946878

Kg/hr =

0.086470746

Kg/s

P Mwt
ρV =
RT

ρV = = 2.694828052 Kg/m3

ρL = 815.0831896 Kg/m3 at 80.1 oC [28].

92
FLV = = 0.038722801

Take plate spacing 0.45 [ The plate spacing is


reduced to avoid the problem of supporting a tall,
slender column] [30].

From figure (11.29) [23] at F LV =

0.038722801 and plate spacing = 0.45, K 1 =

7.5 * 10-2

Correction for surface tension


4
σ= * 10-12

pch for Benzene = ( 4.8 * 6) + ( 17.1 * 6) = 131.4


4
σ= * 10-12

σ = 3.488266696 mJ/m2 = 3.488266696 * 10-3 J/m2


(K1)correct
(K
1)cor
(K1)correct
rect
= [σ / 20 *
[3.488266696
10-3 ]0.2 * K1
* 10-3]0.2 * 7.5
=
* 10-2 =

0.013081

uf = (K1)correct

93
uf = 0.013081 = 0.227120984
m/s

for design a value of 80-85 percent of the

flooding velocity should be used. u v = 0.85 * uf

uv = 0.85 *

0.227120984 =

0.193052836

m/s maximum

volumetric

flow-rate =

maximum volumetric flow-rate = = 0.032087667


m3/s

An = = 0.16621184 m2

At first trial take downcomer area as 12 percent of total.

Ac = = = 0.188877091 m2
Dc = = 0.490393497 m 0.5 m

At Bottom of the Column

Top temperature = 200.87 oC = 474.02 K

Top pressure = 106.230 Kpa

L ρ
F m V
V ρ
=
L
V
m L

From material Balance:

94
Lm = Vm + stream 15

Vm = Vn = 0.086470746 Kg/s

Stream 15 = 9,820.426487

Kg/ hr = 2.727896246

Kg/s Lm = 0.086470746 +

2.727896246 =

2.814366992 Kg/s ρL(mix.) =

1002.856487 Kg/m3 at

200.87 oC [28]

ρV(mix.) =

Mwt. av. = 122.4048129 Kg/Kg.mol

ρV(mix.) = = 3.229930538 Kg/m3

FLV = = 1.847096398

From figure (11.29) [23] at F LV

=1.847096398 and plate spacing = 0.45, K 1

= 1.8 * 10-2
Correction for surface tension
4
σ= * 10-12

pch for Benzene = ( 4.8 * 6) + ( 17.1 * 6) = 131.4

ρV BZ. = = 0.032994305 Kg/m3

ρL BZ. = 656.0793695 Kg/m3

95
4
σBZ. = * 10-12

σ BZ. = 1.483518856mJ/m2 = 1.483518856 * 10-3 J/m2

pch for Nitrobenzene = (4.8*6) + ( 17.1*5) + (12.1*1) + (20*2) =


166.8

ρV BZ. = = 3.266436233Kg/m3

ρL N.B = 1,008.377286 Kg/m3

4
σN.B = * 10-12

σN.B = 3.49273426 mJ/m2 = 3.439273426*10-3 J/m2

σmix. = (1.483518856 * 10-3 *


0.01567082484)
0.9843291752) = 3.408625139 * 10-
3
J/m2

(K1)correct = [σ / 20 * 10-3 ]0.2 * K1

(K1)correct = [3.408625139*10-3]0.2 *
7.5 * 10-2

(K1)correct = 0.012635206

uf = (K1)correct
+ (3.439273426*10-3 *

uf = 0.013081 =
0.219920976m/s

for design a value of 80-85 percent of the

flooding velocity should be used. u v = 0.85 * uf

96
uv = 0.85

*0.219920976

= 0.186932829

m/s maximum

volumetric

flow-rate =

maximum volumetric flow-rate = = 0.026207778


m3/s

An = = 0.140198909 m2

At first trial take downcomer area as 12 percent of total.

Ac = = = 0.159316942 m2

Dc = = 0.450387201 m

So we will take column diameter D c = 0.490393497 m 0.5 m

Provisional Plate Design


Column diameter Dc = 0.5 m

Column area Ac = 0.19634954 m 2

Downcomer area Ad = 0.12 Ac = 0.12*0.19634954 = 0.03561944


m2

Net area An =Ac - Ad = 0.19634954 - 0.03561944 = 0.172787595


m2

Active area Aa = Ac- 2Ad = 0.19634954 - 2*

0.03561944 = 0.14922565 m 2 Holes area Ah =

take 10 percent Aa as first trial

Ah = 0.1 * Aa

Ah = 0.1 * 0.14922565

Ah = 0.014922565 m2
97
Weir length from figure (11.31) [23], at

Ad/ Ac = 12 → lw = 0.76 Dc lw = 0.76 *

0.5 =0.38 m
Take: weir height hw = 50mm
Hole diameter dh = 5 mm
Plate thickness = 5 mm Check weeping

how = 750
[ ]2/3

maximum liquid rate = 2.814366992 Kg/s

maximum how = 750 [ ]2/3 = 28.44243839


mm Liquid

minimum liquid rate, at 70 percent turn down.

minimum liquid rate = 2.81436699 * 0.7 = 1.970056894 Kg/s

minimum how = 750 [ ]2/3 = 22.42326516


mm Liquid

At minimum rate hw + how = 50 +

22.42326516 = 72.42326518 mm From

fig (11.30) [23], K2 = 30.6


uh min. =

uh min. = = 6.810578219 m/s

actual minimum vapour velocity = minimum vapour rate / A h

98
actual minimum vapour velocity = 0.7 * 0.02607778 /
0.014922562

actual minimum vapour velocity =

1.22937613m/s < 6.810578219 m/s

So minimum operating rate below weep

point, so reduced the hole area.

Second Trial

Take: dh = 4.167 mm

Ah = 0.02 Aa = 0.02 * 0.14922565 =2.984513 * 10-3m2

uh min. = = 5.21179869 m/s

actual minimum vapour velocity = 0.7 *

0.02607778 / 2.984513 * 10-3 actual

minimum vapour velocity =

6.116390178m/s > 5.21179869 m/s So

minimum operating rate will be well

above weep point.

Plate Pressure Drop

Dry plate drop


Maximum

vapor

velocity

through

holes

uh =

uh = = 8.737700255 m/s

hd = 51 [ ]2 [ ]

from figure (11.39)

[23], at Ah / AP Ah / Aa

=0.03,

plate thicness / hole

diameter = 5 / 4.167 =

1.2

99
Co = 0.81

hd = 51 [ ]2 [ ] = 19.30499388 mm
Liquid

hr = = = 12.46439562 mm Liquid

P
r

d
+

r
ht = 19.30499388 + (50 +

28.4424389) +

12.46439562 ht =

110.2118279 mm liquid

100mm was assumed to calculate the base


pressure. The calculation could
be repeated with a revised estimate but the small
change in physical properties
will have little effect on the plate design. 110.219279
mm per plate is considered
acceptable.

L
i

o
m

Take hap =

hw - 10 =

50 - 10 =

40 mm Aap
= hap lw =

Am

Aap = 40 * 10-3 * 0.38 = 0.0152 m2

hdc = 166 [ ]2

hdc = 166 * [ ]2 = 5.65854496 mm

100
hb = ( hw + how ) + ht + hdc
hb = (50 + 28.4424389) +

110.2118279 +

5.65854496 hb =

194.3128113 mm =

0.1943128112 m

hb < ½ (tray spacing +

wier hight)

0.1943128112 m < ½ (0.45 + 0.05)

0.2632 m < 0.25 m

y
s

.
C

tr =
tr =

tr =

1.631438149s

< 3 sec ( not

satifactory)

Check

Entrainment

uv = = 0.15167627 m/s

percentage flooding =

percentage flooding = * 100 = 68.96853282%

from figure ( 11-29) [23], ψ =0.03

well bellow 0.1, satifactory plate

Layout

use sieve plate. Allow 50mm


unperforated strip round plate edge;

101
50mm wide callming zones.

Perforated Area 50 mm

From

figure
θ D = 0.5 m
(11.32) lw= 0.38

α
[23],

At lw / Dc
50 mm

= 0.76

θo = 99o

α = 180 o - 99o =81o

mean length of

unperforated edge strip

= (0.5 -0.01)( π / 180 * 81) = 0.636172512 m

Area of unperforated edge strips = 0.636172512 * 50 * 10 -3

Area of unperforated edge strips = 0.031808625 m 2

Area of calming zones = 2 (0.05) * (

0.38 - 2 * 0.05) = 0.028 m 2

Ap = active area - unperforated edge


strip area - calming area

Ap = 0.14922565 - (0.031808625 +

0.028 ) = 0.089416724 m2

At (Ah/ Ap) = 2.984513*10-3/

0.089416724 = 0.03337757

From fig. (11.33) [23]

lp/dh = 4

lp = 4 *

4.167

16.668

mm

(pitch).

Numbe

r of

holes

Area of one hole = (π/4) dh2

= (π/4) (0.004167) 2

= 1.363756653*10-5 m2

102
Number of holes = hole area / area of one hole

Number of holes = 2.984513*10-3/ 1.363756653*10-5

Number of holes = 219 holes

Total Height of Distillation Column

hT = (Tray Spacing *

No. plate) + thicness

of plate hT = (0.45 *

5) + 0.005 = 2.255m
103
Chap
ter Six

Contro
l
Syste
m
C
h
a
p
t
e
r

S
i
x

C
o
n
t
r
o
l

S
y
s
t
e
m

6.1 Introduction

Instruments are provided to monitor the key


process variables during plant
operation. They may be incorporated in automatic
control loops, or used for the
manual monitoring of the process operation.
They may also be part of an
automatic computer data lagging system.
Instruments monitoring critical process
variables will be fitted with automatic alarms to alert
the operators to critical and
hazardous situations.

The primary objectives of the designer when


specifying instrumentation and control schemes are:

1. Safe plant operation:


a) To keep the process variables within known safe
operation limits.
b) To detect dangerous situations as they
develop and to provide alarms
and automatic shut-down systems.
c) To provide interlocks and alarms to
prevent dangerous operating
procedures.
2. Production rate:

To achieve the design product out put.

3. Product quality:

To maintain the product composition within specified


quality standards.

4. Cost:
104
To operate at the lowest production cost,
commensurate with the other objectives.

6.2 Control of Nitrator

Nitration reactions must be considered


potentially hazardous. This is because of heat of
nitration is substantial but also because further
heat release is possible through nitric acid
oxidation if the reaction gets out of hand. An
incident is reported where a batch nitrobenzene
plant caught fire after the belt drive of an
agitator slipped, and unreacted benzene and
nitric acid were allowed to accumulate without
adequate cooling. Great care has to be taken to
properly design the control system for a nitration
plant and to properly size the pressure relief
system, which serves as last resort [4].

In the isothermal process, nitric acid and


benzene are fed in a fixed molar
ratio of C6H6 / HNO3, usually about 1.05. The
sulfuric acid rate is matched in
proportion to give a spent acid strength of about
70% H2SO4. Temperature in
the nitrator is controlled by throttling the
cooling water flow rate to the
nitratar. High temperature switches will shut
off the feeds and open the
cooling water valve wide. A low speed or
power switch on the nitrator
agitator will also shut off all feeds. The level in
the nitrator is set by gravity
overflow [4].

Control of the adiabatic process also requires


control of the benzene and
nitric acid feed in affixed molar ratio. No direct
temperature is required since
sulfuric acid is the heat sink of the process. The
temperature is controlled by
controlling the sulfuric acid circulation rate.
Safty interlocks must be
provided to shut the process safely in the case
of failure of sulfuric acid
circulation. Control of the acid concentrator, in
particular of the sulfuric acid

105
strength produced, must be integrated with the
nitration section [4], figure 6-1 illustrated the
control of isothermal nitrator [23].

FC

Feed
FC

TC
TC

FC

LC
FC

Figure 6-1 Nitrator Control


106
6.3 Settler Control
Decanter are normally designed for continuous
operation, the position of the interface can be
controlled, with or without the use of the
instruments, by use of the siphon take-off for the
heavy liquid [23].

Liquid- light
tak Heavy liquid
e Crude N.B take off
off
Feed

Spent Acid

Figure 6-2 Settler control

Liquid- light

Feed
LC

Heavy liquid

Figure 6-3 Settler control

107
6.4 Vaporizer Control
Level control is often used for vaporizers; the
controller controlling the
steam supply to the heating surface, with the liquid
feed to the vaporizer on flow
control, as shown in figure 6-4. An increased the
feed results in an automatic
increase in steam to the vaporizer to vaporize the
increased flow and maintain
the level constant [23].

TC

LC
Feed

Steam

Trap

Figure 6-4 vaporizer control


108
6-5 Heat Exchanger Control

Exchangers do not always require special


temperature control. Since their purpose in a
process is to provide the maximum recovery of heat,
there is reason to restrict their performance by the
use of controls [22].

When a fluid is cooled in an exchanger, it usually


passes through a cooler and its temperature is
controlled by a flow adjustment of the water. It is
not possible to control both the flow quantities and
the outlet temperatures of both streams passing
through an exchanger at the exchanger itself, since
one adjustable quality must always be present. Thus,
if the outlet temperatures of both streams are to be
controlled and the flow or temperature of one stream
may vary, the flow or outlet temperature of the other
stream must also vary [22].

Most of the problems of exchanger


instrumentation are encountered when the
two streams are of unequal size, the one being very
much larger than other [22].
If the heat exchanger is between two process
streams whose flows are fixed, by-pass control
will have to be used, figure 6-5 shows the
control of heat exchanger [23].

TC

Figure 6-5 Heat Exchanger


control

109
6.6 Distillation column control

The primary objective of distillation column


control is to maintain the specified composition
of the top and bottom products, and any side
streams; correcting for the effects of Disturbances
in:

1. Feed flow-rate, composition and temperature.

2. Steam supply pressure.

3. Cooling water pressure and header temperature.

4. Ambient conditions, which cause changes in internal reflux

The compositions are controlled by regulating


reflux flow and boil-up. The column overall material
balance must also be controlled; distillation
columns have little surge capacity (hold-up) and the
flow of distillate and bottom product (and side-
streams) must match the feed flows. Column
pressure is normally controlled at a constant value
[23].

The use of variable pressure control to


conserve energy, Feed temperature is not normally
controlled, unless a feed preheater is used.
Temperature is often used as an indication of
composition. The temperature sensor should be
located at the position in the column where the
rate of change of temperature with change in
composition of the key component is a maximum
[23].

Near the top and bottom of the column the


change is usually small. Top temperatures are
usually controlled by varying the reflux ratio and
bottom temperatures by varying the boil-up rate.
If reliable on-line analyzers are available they can
be incorporated in the control loop, but more
complex control equipment will be needed [23].

110
Figure 6-6 Temperature pattern
control

With this arrangement interaction can occur


between the top and bottom temperature
controllers, figure 6-5 [23].
Figure 6-7 Composition
control.
Reflux ratio controlled by a ratio controller, or
splitter box, and the bottom product as a fixed ratio
of the feed flow, figure 6-6 [23].

111
Figure 6-8 Composition
control

Top product take-off and boil-up controlled by feed;


figure 6-7 [23].
112
Chapt
er
Seven
Plant
Layou
t
C
h
a
p
t
e
r

S
e
v
e
n

P
l
a
n
t

L
a
y
o
u
t

7.1 Site Considerations [23]


The location of the plant can have a crucial
effect on the profitability of a
project, and the scope for future expansion. Many
factors must be considered
when selecting a suitable site, and only a brief
review of the principal factors will
be given in this chapter. The principle factors to consider are:

1) Marketing area
For materials that are produced in bulk
quantities; such as cement, mineral
acids, and fertilisers, where the cost of the product
per tonne is relatively low and
the cost of transport a significant fraction of the
sales price, the plant should be
located close to the primary market. This
consideration will be less important for
low volume production, high-priced products; such
as pharmaceuticals.

In an international market, there may be an


advantage to be gained by locating the plant within
an area with preferential tariff agreements; such as
the European Community (EC).

2) Raw materials

The availability and price of suitable raw


materials will often determine
the site location. Plants producing bulk chemicals
are best located close to the
source of the major raw material; where this is also
close to the marketing area.

113
3) Transport

The transport of materials and products to


and from the plant will be an
overriding consideration in site selection. If
practicable, a site should be selected
that is close to at least two major forms of transport:
road, rail, waterway (canal
or river), or a sea port. Road transport is being
increasingly used, and is suitable
for local distribution from a central warehouse. Rail
transport will be cheaper for
the long-distance transport of bulk chemicals. Air
transport is convenient and
efficient for the movement of personnel and
essential equipment and supplies, and the proximity
of the site to a major airport should be considered.

4) Availability of labor

Labor will be needed for construction of


the plant and its operation. Skilled construction
workers will usually be brought in from outside
the site area, but there should be an adequate pool
of unskilled labor available locally; and labor
suitable for training to operate the plant. Skilled
tradesmen will be needed for plant maintenance.
Local trade union customs and restrictive
practices will have to be considered when
assessing the availability and suitability of the
local labor for recruitment and training.

5) Utilities (services)

Chemical processes invariably require large


quantities of water for cooling
and general process use, and the plant must be
located near a source of water of
suitable quality. Process water may be drawn
from a river, from wells, or
purchased from a local authority. At some sites, the
cooling water required
can be taken from a river or lake, or from the sea;
at other locations cooling
towers will be needed. Electrical power will
be needed at all sites.
Electrochemical processes that require large
quantities of power; for example,
114
aluminium smelters, need to be located close to a
cheap source of power. A
competitively priced fuel must be available on
site for steam and power
generation.

6) Environmental impact, and effluent disposal

All industrial processes produce waste


products, and full consideration
must be given to the difficulties and cost of their
disposal. The disposal of toxic
and harmful effluents will be covered by local
regulations, and the appropriate
authorities must be consulted during the initial
site survey to determine the
standards that must be met. An environmental
impact assessment should be
made for each new project, or major medication
or addition to an existing
process.

7) Local community considerations


The proposed plant must fit in with and
be acceptable to the local
community. Full consideration must be given to the
safe location of the plant so
that it does not impose a significant additional risk
to the community. On a new
site, the local community must be able to provide
adequate facilities for the plant
personnel: schools, banks, housing, and recreational
and cultural facilities.

8) Land (site considerations)

Sufficient suitable land must be available for


the proposed plant and for future expansion. The
land should ideally be flat, well drained and have
suitable load-bearing characteristics. A full site
evaluation should be made to determine the need for
piling or other special foundations.

115
9) Climate

Adverse climatic conditions at a site will


increase costs. Abnormally low
temperatures will require the provision of
additional insulation and special
heating for equipment and pipe runs. Stronger
structures will be needed at
locations subject to high winds (cyclone/hurricane
areas) or earthquakes.

10) Political and strategic considerations

Capital grants, tax concessions, and other


inducements are often given by governments to
direct new investment to preferred locations; such
as areas of high unemployment. The availability of
such grants can be the overriding
consideration in site selection.

7.2 Site Layout [23]

The process units and ancillary buildings


should be laid out to give the
most economical flow of materials and personnel
around the site. Hazardous
processes must be located at a safe distance from
other buildings. Consideration
must also be given to the future expansion of the
site. The ancillary buildings
and services required on a site, in addition to
the main processing units
(buildings), will include:

1. Storages for raw materials and products: tank farms and


warehouses.

2. Maintenance workshops.

3. Stores, for maintenance and operating supplies.

4. Laboratories for process control.

5. Fire stations and other emergency services.

116
6. Utilities: steam boilers, compressed air, power
generation, refrigeration, transformer stations.

7. Effluent disposal plant.

8. Offices for general administration.

9. Canteens and other amenity buildings, such as medical


centres.

10. Car parks.

When roughing out the preliminary site


layout, the process units will
normally be sited first and arranged to give a smooth
flow of materials through
the various processing steps, from raw material to
final product storage. Process
units are normally spaced at least 30 m apart; greater
spacing may be needed for
hazardous processes.

The location of the principal ancillary


buildings should then be decided. They should be
arranged so as to minimize the time spent by
personnel in travelling between buildings.
Administration offices and laboratories, in which a
relatively large number of people will be working,
should be located well away from potentially
hazardous processes. Control rooms will normally
be located adjacent to the processing units, but with
potentially hazardous processes may have to be
sited at a safer distance.

The sitting of the main process units will


determine the layout of the plant roads, pipe alleys
and drains. Access roads will be needed to each
building for construction, and for operation and
maintenance.

Utility buildings should be sited to give the


most economical run of pipes to and from the
process units.

117
Cooling towers should be sited so that under
the prevailing winds the plume of condensate
spray drifts away from the plant area and
adjacent properties. The main storage areas should
be placed between the loading and unloading
facilities and the process units they serve. Storage
tanks containing hazardous materials should be
sited at least 70m (200ft) from the site boundary. A
typical plot plant is shown in figure 7-1.

Figure 7-1 A typical site plan


7.3 Plant Layout

The economic construction and efficient


operation of a process unit will
depend on how well the plant and equipment
specified on the process flow-sheet
is laid out.

The principal factors to be considered are:

1. Economic considerations:

construction and operating costs.

118
2. The process requirements.

3. Convenience of operation.

4. Convenience of maintenance.

5. Safety.

6. Future expansion.

7. Modular construction.

7.4 Utilities [23]

The word “Utilities” is now generally used for the


ancillary services
needed in the Operation of any production process.
These services will normally be supplied from
Central site facility; and will include:

1. Electricity.

2. Steam, for process heating.

3. Cooling water.

4. Water for general use.

5. Demineralised water.

6. Compressed air.
7. Inert-gas supplies.

8. Refrigeration.

9. Effluent disposal facilities.

119
7.5 Environmental Consideration [23]

All individuals and companies have a duty of


care to their neighbors, and
to the environment in general. In the United
Kingdom this is embodied in the
Common Law. In addition to this moral duty,
stringent controls over the
environment are being introduced in the United
Kingdom, the European Union,
the United States, and in other industrialized
countries and developing countries.

Vigilance is required in both the design and


operation of process plant to
ensure that legal standards are met and that no harm
is done to the environment.

Consideration must be given to:

1. All emissions to land, air, water.

2. Waste management.

3. Smells.

4. Noise.
5. The visual impact.

6. Any other nuisances.

7. The environmental friendliness of the products.

7.6 Waste Management [23]

Waste arises mainly as byproducts or unused


reactants from the process,
or as off- specification product produced through
mis-operation. There will also
be fugitive emissions from leaking seals and flanges,
and inadvertent spills and
discharges through mis-operation. In emergency
situations, material may be

120
discharged to the atmosphere through vents
normally protected by bursting discs and relief
values.

The designer must consider all possible


sources of pollution and, where
practicable, select processes that will eliminate or
reduce (minimize) waste
generation.

Unused reactants can be recycled and


off-specification product
reprocessed. Integrated processes can be selected:
the waste from one process
becoming the raw material for another. For
example, the otherwise waste
hydrogen chloride produced in a chlorination
process can be used for
chlorination using a different reaction; as in
the balanced, chlorination-
oxyhydrochlorination process for vinyl chloride
production. It may be possible to
sell waste to another company, for use as raw
material in their manufacturing
processes. For example, the use of off-specification
and recycled plastics in the
production of lower grade products, such as the
ubiquitous black plastics bucket.

Processes and equipment should be designed


to reduce the chances of mis-
operation; by drains, and pumps should be sited so
that any leaks flow into the
plant effluent collection system, not directly to
sewers. Hold-up systems, tanks
and ponds, should be provided to retain spills for
treatment. Flanged joints
should be kept to the minimum needed for the
assembly and maintenance of
equipment.

When waste is produced, processes must be


incorporated in the design for its treatment and safe
disposal. The following techniques can be
considered:

1. Dilution and dispersion.

121
2. Discharge to foul water sewer (with the
agreement of the appropriate authority).

3. Physical treatments: scrubbing, settling, absorption and


adsorption.

4. Chemical treatment: precipitation (for


example, of heavy metals), neutralization.

5. Biological treatment: activated sludge and other processes.

6. Incineration on land, or at sea.

7.8 Nitrobenzene Plant Location

Based on these previous factors which are


required in nitrobenzene manufacturing plant, I
select AL- Basrah as plant location in a place at
which the wind pass through the plant must not hit
the cities and inter to the goverarate because
nitrobenzene plant causing ambient air pollutant
which may effected on people negatively this
location will provide to the plant utilities which need
since it near the river and Shatt AL-Arab which also
contain a large harbor which we can use it for
export purposes. The foundation of the refinery in
Basrah “AL Rumela Refinery” which provide low
cost of transport requirement, also labors and local
community which satisfied the labor requirement.

122
Chapter
Eight
Toxicity and
Effects of
Nitrobenzen
e
Chapter Eight
Toxicity and Effects of
Nitrobenzene

8.1 General
Nitrobenzene is very toxic substance;
the maximum allowable
concentration for nitrobenzene is 1 ppm or 5
mg/m3. It was exposed for eight
hours to 1 ppm nitrobenzene in the working
atmosphere, about 25 mg of
nitrobenzene would be absorbed, of which about
one-third would be by skin
absorption and the remainder by inhalation. The
primary effect of nitrobenzene
is the conversion of hemoglobin to
methemoglobin; thus the conversion
eliminates hemoglobin from the oxygen-
transport cycle. Exposure to
nitrobenzene may irritate the skin and eyes.
Nitrobenzene affects the central
nervous system and produces fatigue, headache,
vertigo, vomiting, general
weakness and in some cases unconsciousness and
coma. There generally is a
latent period of 1-4 hours before signs or symptoms
appear. Nitrobenzene is a
powerful methemoglobin former, and cyanosis
appears when the methemoglobin
level reaches 15%. Chronic exposure can lead to
spleen and liver damage,
jaundice, and anemia. Alcohol ingestion tends to
increase the toxic effects of
nitrobenzene; thus alcohol in any form should not
be ingested by the victim of
nitrobenzene poisoning for several days after the
nitrobenzene poisoning or
exposure. Impervious protective clothing should be
worn in areas where risk of
splash exists. Ordinary work clothes that have been
splashed should be removed
immediately, and the skin washed thoroughly with
soap and worm water. In
areas of high vapor concentration (>1 ppm), full face
mask with organic-vapor

123
consters or air-supplied respirators should be used.
Clean work clothing should be worn daily, and
showering after each shift should be mandatory
[2&3].

With respect to the hazards of fire and


explosion, nitrobenzene is classified as modrate
hazard when exposed to heat or flame.
Nitrobenzene is classified by the ICC as a class-B
poisonous liquid [2&3].

8.2 Effects on Humans

Nitrobenzene is toxic to humans by


inhalational, dermal and oral exposure. The
main systemic effect associated with human
exposure to nitrobenzene is methaemoglobinaemia
[5].

Numerous accidental poisonings and deaths in


humans from ingestion of nitrobenzene have been
reported. In cases of oral ingestion or in which
the patients were apparently near death due to
severe methaemoglobinaemia, termination of
exposure and prompt medical intervention resulted
in gradual improvement and recovery. Although
human exposure to sufficiently high quantities of
nitrobenzene can be lethal via any route of
exposure, it is considered unlikely that levels of
exposure high enough to cause death would occur
except in cases of industrial accidents or suicides [5].

The spleen is likely to be a target organ


during human exposure to nitrobenzene; in a
woman occupationally exposed to nitrobenzene
in paint (mainly by inhalation), the spleen was
tender and enlarged [5].

Neurotoxic symptoms reported in humans


after inhalation exposure to
nitrobenzene have included headache, confusion,
vertigo and nausea. Effects in

124
orally exposed persons have also included those
symptoms, as well as apnoea and coma [5].

8-3 Effects on Organisms in the Environment

Nitrobenzene appears to and an 8-


day lowest-observed-effect
concentration of 1.9 mg/litre for the blue-green be
toxic to bacteria and may
adversely affect sewage treatment facilities if
present in high concentrations in
influent. The lowest toxic concentration reported for
microorganisms is for the
bacterium Nitrosomonas, with an EC50 of 0.92
mg/litre based upon the inhibition
of ammonia consumption. Other reported values are
a 72-h no-observed-effect
concentration of 1.9 mg/litre for the protozoan
Entosiphon sulcatum alga
Microcystis aeruginosa [5].

For freshwater invertebrates, acute toxicity

(24- to
48-h LC50 values)
ranged from 24 mg/litre for the water flea
(Daphnia magna) to 140 mg/litre for
the snail (Lymnaea stagnalis). For marine
invertebrates, the lowest acute toxicity
value reported was a 96-h LC 50 of 6.7 mg/litre for
the mysid shrimp (Mysidopsis
bahia). The lowest chronic test value reported
was a 20-day NOEC of 1.9
mg/litre for Daphnia magna, with an EC50, based
on reproduction, of 10 mg/litre
[5].

Freshwater fish showed similar low sensitivity


to nitrobenzene. The 96-h LC50 values ranged from
24 mg/litre for the medaka (Oryzias latipes)
to142 mg/litre for the guppy (Poecilia
reticulata). There was no effect on mortality or
behaviour of medaka at 7.6 mg/litre over an 18-day
exposure [5].

125
8.4 Hazard and Risk Evaluation

Methaemoglobinaemia and subsequent


haematological and splenic
changes have been observed in exposed humans,
but the data do not allow
quantification of the exposure-response
relationship. In rodents,
methaemoglobinaemia, haematological effects,
testicular effects and, in the
inhalation studies, effects on the respiratory system
were found at the lowest
doses tested. Methaemoglobinaemia, bilateral
epididymal hypospermia and
bilateral testicular atrophy were observed at the
lowest exposure level studied, 5
mg/m3 (1 ppm), in rats. In mice, there was a
dose-related increase in the
incidence of bronchiolization of alveolar
walls and alveolar/bronchial
hyperplasia at the lowest dose tested of 26
mg/m3 (5 ppm). Carcinogenic
response was observed after exposure to
nitrobenzene in rats and mice:
mammary adenocarcinomas were observed in
female B6C3F1 mice, and liver
carcinomas and thyroid follicular cell
adenocarcinomas were seen in male
Fischer-344 rats. Benign tumours were observed
in five organs. Studies on
genotoxicity have usually given negative results [5].

Although several metabolic products of


nitrobenzene are candidates for
cancer causality, the mechanism of carcinogenic
action is not known. Because of
the likely commonality of redox mechanisms in test
animals and humans, it is
hypothesized that nitrobenzene may cause cancer
in humans by any route of
exposure [5].

Exposure of the general population to


nitrobenzene from air or drinking-
water is likely to be very low. Although no no-
observed-adverse-effect level
could be derived from any of the toxicological
studies, there is a seemingly low

126
risk for non-neoplastic effects. If exposure values
are low enough to avoid non-
neoplastic effects, it is expected that carcinogenic
effects will not occur [5].

Acute poisonings by nitrobenzene in


consumer products have occurred frequently in the
past. Significant human exposure is possible,
due to the moderate vapour pressure of
nitrobenzene and extensive skin absorption.
Furthermore, the relatively pleasant almond smell
of nitrobenzene may not discourage people from
consuming food or water contaminated with it.
Infants are especially susceptible to the effects of
nitrobenzene [5].

There is limited information on exposure


in the workplace. In one
workplace study, exposure concentrations were of
the same order of magnitude
as the lowest-observed-adverse-effect levels in a
long-term inhalation study.
Therefore, there is significant concern for the
health of workers exposed to
nitrobenzene [5].

Nitrobenzene shows little tendency to


bioaccumulate and appears to undergo both
aerobic and anaerobic biotransformation. For
terrestrial systems, the levels of concern reported
in laboratory tests are unlikely to occur in the
natural environment, except possibly in areas close
to nitrobenzene production and use and areas
contaminated by spillage [5].

Using the available acute toxicity data


and a statistical distribution
method, together with an acute: chronic toxicity
ratio derived from data on
crustaceans, the concentration limit for
nitrobenzene to protect 95% of
freshwater species with 50% confidence may be
estimated to be 200 µg/litre.
Nitrobenzene is thus unlikely to pose an
environmental hazard to aquatic species
at levels typically reported in surface waters, around
0.1-1 µg/litre. Even at

127
highest reported concentrations (67 µg/litre),
nitrobenzene is unlikely to be of concern to
freshwater species [5].

There is not enough information to derive a


guideline value for marine organisms [5].

8.5 Industrial Safety

• Storage precaution: store in a refrigerator or in a


cool, dry place [37].
• Skin contact: Flood all areas of body that have
contacted the substance
with water. Don’t wait to remove
contaminated clothing; do it under the water
stream. Use soap to help assure removal.
Isolate contaminated clothing when removed
to prevent contact by others [37].
• Inhalation: leave contaminated area immediately;
breathe fresh air.
Proper respiratory protection must be
supplied to any rescuers. If
coughing, difficult breathing or any other
symptoms develop, seek
medical attention at once, even if symptoms
develop many hours after
exposure [37].
• Eye contact: remove any contact lenses at once.
Flush eyes well with
copious quantities of water or normal saline for at least
20-30 minutes.
• Ingestion: if convulsions are not present, give a glass
or two of water or
milk to dilute the substance. Assure that
the person’s airway is unobstructed and
contact a hosnital or poison center
immediately for advice on wiether or not to
induce vomiting [37].

128
References

1- Ullmann’s Encyclopedia of Industrial


Chemistry, 2005 Wiley-VCH Verlag
GmbH & Co. KGaA.
2- Krik and Othmer, “Encyclopedia of Chemical
Technology”, Vol.17, 4th Ed.,
p (133-152).
3- Krik and Other, “Encyclopedia of Chemical
Technology”, Vol.15, 3rd Ed., p
(917-932).
4- John J.Mcketta, “Encyclopedia of Chemical Processing &
Design”, Vol. 31,
p. (165-188).
5- http://
Whqlibdoc.Who.int /
ech / who.EH.C.230.
6- www. Technology
bank.dupont.com.
7- “ Hydrocarbon
Processing”,
Vol.58,1979, NO.11 8-
“Hydrocarbon
Processing”, 1978.
9- P.H.Grogins, “Unit Process
Organic Synthesis”, fifth edition. 10-
H.Scott Fogler, “Elements of Chemical
Reaction Engineering”. 11- U.S.pat.
7,326,816 B2 (Feb. 5, 2008).
12- U.S.pat. 4,772,757 (Sep.20, 1988).
13- Sami Matter & Lewis Hatch, “From
Hydrocarbon to Petrochemicals”. 14- Sami
Matter & Lewis F. Hatch, (2000), “Chemistry
of petrochemicals
Processes”, 2nd.
15- U.S.pat. 2,773,911 (Dec.11, 1956).
16- James G. Speight, “Chemical & Process Design Handbook”.
17- Austin, G.T., (1984), “Shreve’s Chemical
Process Industries”, 5th Ed., p.
(772).
18- SEP Handbook, “Petrochemical & Downstream Projects”.
19- Robert H. Perry (1997), “Perry’s Chemical Engineer’s
Handbook”, 7th Ed.

129
20- John A. Dean, (1999), “Lange’s Handbook of
Chemistry”, Fifteenth Edition,
McGraw-Hill, INC.
21- David R. Lide, (2000-2001), “CRC
Handbook of Chemistry & Physics”,
editor-in-chief.
22- Donald Q. Kern, (2005), “Process Heat
Transfer”, Twelfth reprint 2005.
Tata McGraw-Hill Edition.
23- Coulson & Richardson’s, (2005), “Chemical
Engineering Design”, Vol.6,
Fourth Edition.
24- David M. Himmelblau, (1989), “Basic Principles
& Calculation in Chemical
Enginnring”, Fifth Edition.
25- Jack Winnick, (1997), “Chemical
Engineering Thermodynamics”, John
Wily & Sons, Inc.
26- J M Smith & H C Van Ness, (2003), “Introduction to Chemical
Engineering
Thermodynamics”, Sixth Edition, Tata McGraw-Hill Publishing Company
Limited.
27- Reid & Prausintz, (1987), “The Properties
of Gases & Liquids”, Fourth
Edition.
28- Chemicad 6.0.1 Program.
29- Stanley M. Walas, (1990), “Chemical Process Equipment Selection &
Design”, Butterworth-Heinemann Series in Chemical Engineering.
30- H. R. Backhurts & J. H. Harker, (1973) “Process Design”, Heinemamm
Education Books.

31- Brodkey & Hershey, (1988), “Transport


Phenomena”, McGraw-Hill Book
Company.
32- Holman, (1981), “Heat Transfer”, 5 th edition, McGraw Hill.
33- Coulson & Richardson’s, (1999),
“Chemical Engineering”, Vol.1, Sixth
Edition.
130
34- Alan S. Foust, (1980), “Principles of Unit
Operation”, Second Edition.
35- Coulson & Richardson’s, (2002),
“Chemical Engineering”, Vol.2, Fifth
Edition.
36- Shuzo Ohe, (1989), “Vapor-Liquid Equilibrium Data”.
37- Lawrence H. Keith & Douglas B. Walters,
“Compendium of Safety Data
Sheets for Research & Industrial Chemicals”,
Part III.
131
Appendix
es
Appendix A
Physical Properties
1- General Properties [19,20,21,22,23,24,25,26,27&28]
Comp. Mwt. B.P ∆Hof λ
[Kg /Kg.mol] [oC] (298.15K) [KJ / Kg.mol]
[KJ /g.mol]
C6H6 (L) 78.11 80.1 49.1 30781
HNO3 (L) 63.02 - -173.230 -
H2SO4 (L) 98.08 - -811.32 -
H2O (L) 18.02 100 -285.840 40683
C6H5NO2 (L) 123.11 210.9 12.500 -
Na2CO3 (c) 106 - -1131.546 -
(Soda Ash)
H2CO3 (aq) 62.03 - -699.65 -
Na2SO4 (c) 142.05 - -1413.891 -
CaSO4 (c) 136.14 - -1432.7 -
CaSO4.2H2O(c) 172.18 - -2024.021 -
(Gypsum)

2- Specific Heat Capacity

A- Specific Heat Capacity of

Liquid [KJ / Kg.mol.K] [23&28]

Cp = A + BT + CT2 + DT3

Comp. A B C D
C6H6 (L) -33.917 4.743 * 10-1 -3.017 * 10-4 7.130 * 10-9
HNO3 (L) 131.250 -0.1219 0.1704 *10-3 -
H2O (L) 32.243 1.923 * 10-3 1.055 * 10-5 -3.596 *10-9
C6H5NO2 (L) 295.3 -0.8907 1.705 * 10-3 -

A-1
Specific Heat Capacity of

Sulfuric acid [KJ / Kg.mol. oC]

[24] Cp = A + BT

Comp. A B
H2SO4 (L) 139.1 0.1559

B- Specific Heat Capacity of Crystals [19,20,21,24&25]

Comp. Cp [KJ / Kg.mol.oC]


Na2CO3 (c) (Soda Ash) 111.08
Na2SO4 (c) 128.229
CaSO4 (c) 99.73
CaSO4.2H2O(c) (Gypsum) 186.149

C- Specific Heat Capacity of Carbonic acid (predicted) [24]

Cp = K (Mwt.) a

For

Aci

ds:

K=

0.9

1, a

=
-0.1

52

Cp

=0.

91*

(63.

03)-
0.152

Cp = 0.485921283 cal /g.oC = 126.1128611 KJ /Kg.mol.oC

D- Specific Heat Capacity of

Vapor [KJ / Kg.mol.K] [26]

Cpig / R = A + BT + CT 2 +

DT-2

Comp. A B C

C6H6 (V) -0.206 39.064*10-3 -13.301*10-6

H2O (V) 3.470 1.450*10-3 0.121*10+5

A-2
4- Density of

Liquids ,

[Kg.mol / m3]

[28]

ρ=

Comp. A B C D Range
Tempera
K
C6H6 (L) 1.0259 0.26666 562.05 0.28394 279-56
HNO3 (L) 1.5943 0.2311 520 0.1917 232-37
H2SO4 (L) 0.8322 0.19356 925 0.2857 284-36
H2O (L) 5.4590 3.0542*10-1 6.4713*102 8.1*10-2 273-33
C6H5NO2 (L) 0.69123 0.24124 719 0.28135 279-71

5- Viscosity of Liquids, [pa.s][28]

µ = exp. [A + B/T + C LnT + DTE] [28]


Comp. A B C D E Range
Temperatu
K
C6H6 (L) 7.5117 294.68 -2.794 - - 279-545
HNO3 (L) -28.886 1940 2.678 - - 240-356
96wt.%
H2SO4 (L) -179.84 10694 24.611 - - 284- 367
98wt.%
H2O (L) -51.964 3.6706*103 5.7331 -5.349*10-29 10 273-643
C6H5NO2 (L) -34.557 2611.3 3.4283 - - 273-481

µ H2SO4 (60wt.%) = 3.65*10-3

pa.s at 50 oC figure (14) [22]

µ HNO3 (60wt.%) = 1.47*10-3

pa.s at 50 oC figure (14) [22].

A-3
6- Thermal Conductivity of Liquids, [W / m.oC]
K = A + BT + CT2 + DT3

Comp. A B C D Range
Temperature
K
C6H6 (L) 0.23444 -0.00030572 - - 279-413
HNO3 (L) 0.12107 0.0005383 - - 233-433
96wt.%
H2SO4 (L) 0.014247 0.0010763 - - 283-371
98wt.%
H2O (L) -0.4267 0.00569 -8.0065*10-6 1.815*10-9 273-633
C6H5NO2 (L) 0.1869 -0.0001305 - - 283-371

6-Vapor Pressure of liquids using Antoine’s Equation,


[mmHg]

Ln po = A - [23]

T = Temperature in K

Comp. A B C Range
Temperatur
o
C
C6H6 (L) 15.9008 2788.51 -52.36 7-104

Log po = A - [25]

T = Temperature in oC

Comp. A B C Range
Temperature
o
C
C6H6 (L) 7.1156 1746.6 201.8 134-211
C6H5NO2 (L) 6.90565 1211.033 220.79 8-103

A-4
Appendix B
Equilibrium Data

XY data for Benzene / Nitrobenzene


NRTL Bij Bji Alpha Aij Aji Cij Cji Dij
Dji
659.89 -263.35 0.311 0.00 0.00 0.00 0.00 0.00
0.00

Mole Fractions
T Deg C P atm X1 Y1 Gamma1 Gamma2 Phi1
Phi2
210.635 1.000 0.00000 0.00000 1.416 1.000
1.000 1.000
151.914 1.000 0.10000 0.82031 1.376 1.001
1.000 1.000
126.933 1.000 0.20000 0.93286 1.340 1.005
1.000 1.000
112.693 1.000 0.30000 0.96616 1.303 1.013
1.000 1.000
103.357 1.000 0.40000 0.98015 1.261 1.031
1.000 1.000
96.798 1.000 0.50000 0.98727 1.214 1.063
1.000 1.000
92.010 1.000 0.60000 0.99139 1.162 1.123
1.000 1.000
88.401 1.000 0.70000 0.99406 1.108 1.228
1.000 1.000
85.524 1.000 0.80000 0.99603 1.057 1.418
1.000 1.000
82.944 1.000 0.90000 0.99781 1.017 1.778
1.000 1.000
80.129 1.000 1.00000 1.00000 1.000 2.529
1.000 1.000
B-1
B-2
‫ﺮﻳﺪﻘﺘﻟا و ﺮﻜﺷ‬

‫و ﻦﻴﻤﻻﻌﻠﻟ ﺔﻤﺣر ثﻮﻌﺒﻤﻟا ﻦﻴﻣﻻا ﻪﻟﻮﺳر ﻰﻠﻋ ﻪﻣﻼﺳ و‬


‫ﻪﺗﻼﺻ و ‪،‬ﻢﻌﻧا ﺎﻣ ﻰﻠﻋ ﷲ ﺪﻤﺤﻟا‬

‫ﺪﻌﺑ‪:‬‬

‫سﺎﻧا ﻰﻟا يﺮﻳﺪﻘﺗ و يﺮﻜﺷ مﺪﻗا ﺔﻴﻣﻼﺳﻻا ةرﺎﻀﺤﻟا ﺔﻤﺻﺎﻋ ﺔﺒﻴﺒﺤﻟا‬


‫داﺪﻐﺑ ﻦﻣ‬
‫ﻦﻳﺮﻬﻨﻟا ﺔﻌﻣﺎﺟ ةﺬﺗﺎﺳا ﺮآﺬﻻﺑ ﺺﺧا تﺎﻌﻣﺎﺠﻟا ةﺬﺗﺎﺳا‬
‫داﺪﻐﺑ زﻮﻨآ ﻰﻟا ﻢهءﺎﻄﻌﺑ ءﺎﻤﻈﻋ‬
‫ﻢﺳﺎﻗ رﻮﺘآﺪﻟا مﺮﺘﺤﻤﻟا ﻢﺴﻘﻟا ﺲﻴﺋر ﻰﻟا صﺎﺧ ﺮﻳﺪﻘﺗ و‬
‫ﻢﺴﻗ‬ ‫ﺔﺳﺪﻨﻬﻟااااا‬ ‫ﺔﻳوﺎﻴﻤﻴﻜﻟااااا‬ ‫‪،‬اااا‬ ‫ﺮﻜﺷاااا‬
‫ﺪﻴﺣﻮﻟا ﻢﻬﻤه نﺎآ ﻦﻳﺬﻟا ﻦﻳﺪﻌﻣ و ةﺬﺗﺎﺳا ﻦﻣ ﻲﺴﻳرﺪﺘﻟا‬
‫ردﺎﻜﻟا ﻊﻴﻤﺟ و نﺎﻤﻴﻠﺴﻟا ﺮﺑﺎﺟ‬
‫ﻖﻳﺮﻔﺗ وا ﺰﻴﻤﺗ ﻳﺎ ﻧﻮد ﺎﻨﻟ ةﺪﻴﻔﻤﻟا ‪.‬‬
‫ﺔﻣﻮﻠﻌﻤﻟا لﺎﺼﻳا‬

‫ﻞﻤﻌﻟا اﺬه زﺎﺠﻧا ﻲﻓ ﻞﻀﻔﻟا ﻪﻟ ﻊﺟﺮﻳ يﺬﻟا ﺪﻣﺮﺳ ‪.‬د‬


‫ﻳﺬﺎﺘﺳا ﻰﻟا يﺮﻳﺪﻘﺗ و يﺮﻜﺷ مﺪﻗا يﺬﻟا ﺮﻤﺘﺴﻤﻟا‬
‫يﻮﻨﻌﻤﻟا ﻢﻋﺪﻟا ﻚﻠﻟﺬآ و ‪ ،‬ﻪﻴﻓ ﺔﻴﺳارﺪﻟا داﻮﻤﻟا ﻊﻴﻤﺟ‬
‫ﻖﻴﺒﻄﺗ ﺔﻟوﺎﺤﻣ و‬
‫ﻞﻤﻌﻟا اﺬه مﺎﻤﺗا ﻰﻠﻋ ‪.‬‬
‫ﻲﺗدارا ﺔﻳﻮﻘﺗ ﻲﻓ ﺮﻴﺒآ ﻞﻜﺸﺑ ﻲﻧﺪﻋﺎﺳ‬

‫ﻦﻣ ﺮﺜآﻻا ﻢﻬﻠﻣﺎﻌﺗ ﻰﻠﻋ ﻦﻳﺮﻬﻨﻟا ﺔﻌﻣﺎﺟ ﺔﻳﺰآﺮﻤﻟا‬


‫ﺔﺒﺘﻜﻤﻟا ﻲﻔﻇﻮﻣ ﻰﻟا ﺮﻳﺪﻘﺗ و ﺮﻜﺷ‬
‫ﻞﻠﻣ ‪.‬‬
‫وا ﻞﻠآ ﻳﺎ ﻧﻮد ﺔﺒﻠﻄﻟا ﻊﻣ ﻊﺋاﺮﻟا‬
‫ﻦﻳﺮﻬﻨﻟا‬
‫ﺔﻌﻣﺎﺟ‬
‫ﺔﺳﺪﻨﻬﻟا‬
‫ﺔﻴﻠآ‬
‫ﺔ‬
‫ﻳ‬
‫و‬
‫ﺎ‬
‫ﻴ‬
‫ﻤ‬
‫ﻴ‬
‫ﻜ‬
‫ﻟ‬
‫ا‬

‫ﺔ‬
‫ﺳ‬
‫ﺪ‬
‫ﻨ‬
‫ﻬ‬
‫ﻟ‬
‫ا‬

‫ﻢ‬
‫ﺴ‬
‫ﻗ‬
‫ﻦﻳﺰﻨﺑوﺮﺘﻳﺎﻨﻟا جﺎﺘﻧا‬

‫جﺮﺨﺗ ﻋﻮﺮﺸﻣ‬

‫ﻦﻳﺮﻬﻨﻟا ﺔﻌﻣﺎﺟ ﺔﺳﺪﻨﻬﻟا ﺔﻴﻠآ ﻲﻓ‬

‫ﺔﻳوﺎﻴﻤﻴﻜﻟا ﺔﺳﺪﻨﻬﻟا ﻢﺴﻗ ﻰﻟا مﺪﻘﻣ‬

‫ﺔﻳوﺎﻴﻤﻴﻜﻟا ﺔﺳﺪﻨﻬﻟا ﻲﻓ سﻮﻳرﻮﻠﻜﺒﻟا‬

‫ةدﺎﻬﺷ ﻞﻴﻧ تﺎﺒﻠﻄﺘﻣ ﻦﻣ ءﺰﺟ ﻲهﻮ‬

‫ﻞﺒﻗ ﻦﻣ‬

‫ﺐﻳﺎﻏ ﺪﻴﺷر ةرﺎﺳ‬

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