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AL- Nahrain University

College of Engineering
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 acetateect
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.

List of Contents
Content

Page

Abstract

List of Content

II

List of Figures

VI

List of Tables

VII

Nomenclature

VIII

Chapter One: Introduction


1.1

History

1.2

Specification of Nitrobenzene

1.3

Identity

1.4

Physical Properties

1.5

Chemical Properties

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

57

Distillation Energy Balance

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
129

References
Appendixes
Appendix A: Physical Properties

A-1

Appendix B: Equilibrium Data

B-1

List of Figures
Figure No.

Title

1-1

Reduction products of nitrobenzene

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


adiabatically

20

2-3

22

2-4

Atmospheric reactions generating and removing


nitrobenzene
Typical continuous Nitrobenzene Process

4-1

Process Flow Diagram

63

5-1

Vapor-Liquid Equilibrium diagram (Isothermal) at


70oC

91

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

page

26

List of Tables
Table NO.

Title

1-1

Specification for technical-Grade Nitrobenzene

1-2

Specifications for Distilled-grade Nitrobenzene


(mirbane oil)

1-3

Some Physical Properties of Nitrobenzene

1-4

Reduction products of nitrobenzene

1-5

Type and estimated consumption of nitrobenzene in


Western Europe in 1994
nitrobenzene production capacities in European
countries in 1985

11

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

2-1

VII

Page

15

Nomenclature
Symbol

Definition

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

Blade Width

Baffle Width

Corrosion Allowance

Co

Orifice Coefficient

cp

Specific heat

Diameter

DA

Agitator Diameter

Db

Bundle Diameter

Deff

Effective Column Diameter

mm
KJ/Kg.mol.K

VIII

Unit

de

Equivalent Diameter

dh

Diameter of Hole

di

Inside Tube Diameter

dm

Diameter of Manholes

mm

do

Outside Tube Diameter

dp

Droplet Diameter

FC

Flow Controller

FLV

Liquid Vapor Factor

Ft

Correction factor for TLm

FW

Wind Load

mm

N/m

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

HL

Height of the nitrator content

hap

Height of bottom edge of the apron above the


plate

mm

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

Outside tube foaling coefficient

how

Weir Crest (height of the liquid over weir)

hr

Residence Head

hT

Total Height of Distillation Column

ht

Total plate drop head

mm

hv

Heat transfer to vessel

W/m2.oC

hw

Weir Height

Joined Efficiency

jf

Friction Factor

Kf

Thermal Conductivity

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

lB

Baffle spacing

mm

lp

Hole Pitch

mm

Ms

Bending moment at any plane

N.m

Mass flowrate

Kg/s

Agitator Speed

rps

Np

Power Number

Np

Number of passes

Nt

Number of Tubes

Pressure Design

N/mm2

mm Liquid

mm

W/m.oC
-

W/m2.oC

hod

PA

Shaft Power

Pch

Sugdens Parachor

Pt

Pitch

mm

Pw

Wind Pressure (Load per unit area)

N/m2

Blade Length

Distance measured from the free end

Temperature of the fluid in shell side

TC

Temperature Controller

TM

Measuring Element

Temperature of the fluid in tube side

tr

Residence time

Uo

Overall Heat Transfer coefficient

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

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

Volume of Nitrator

m3

Vm

Vapor mass flowrate

Kg/s

Vn

Vapor mass flowrate

Kg/s

umin

XI

W/m2.oC

Greek Notation

Viscosity

Pa.s

Viscosity of the Continuous phase

Pa.s

Viscosity of the dispersed phase

Pa.s

Viscosity at the wall Temperature

Pa.s

Residence Time

min

Initial Volumetric flowrate

m3/hr

Surface Tension

mJ/m2

Density

Kg/ m3

Density of the Continuous phase

Kg/ m3

Density of the dispersed phase

Kg/ m3

Latent Heat

KJ/Kg.mol

TLm

Mean Logarithm Temperature

Tm

Mean Temperature Difference

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 / K

Prandtle Number

Re = u d /

Reynolds Number

XIII

Chapter One
Introduction

Chapter One
Introduction
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. It
may be slightly hazy owing to the presence of
small globules of free water
0.5% (maximum)
1.206-1.209
0.1% (maximum)

Appearance
Water content
Specific gravity (15.5/15.5oC)
Dinitrobenzene content
Low-boiling impurities (benzene + aliphatic
hydrocarbons)
Sulfur- containing impurities (CS2 +
nitrothiophene +elementary sulfur)

0.25% (maximum)
2.5 ppm (maximum, as 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 (15.5/15.5oC)

1.208 1.211

Aniline content

0.0075% (maximum)

1.3Identity [5]

Common name:

nitrobenzene

Chemical formula:

C6H5NO2

Chemical structure:

Relative molecular mass:

123.11

CAS name:

nitrobenzene

IUPAC name:

nitrobenzene

CAS registry number:

98-95-3

NIOSH RTECS

DA6475000

Synonyms:

nitrobenzol, mononitrobenzol, MNB, C.I.


solvent black 6, essence of mirbane, essence of
myrbane, mirbane oil, oil of mirbane, oil of
myrbane, nigrosine spirit soluble B

1.4 Physical properties


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 211C. Its vapor pressure is 20 Pa at 20C, and its
solubility in water is 1900 mg/liter at 20C. It represents a fire hazard, with a
flash point (closed cup method) of 88C and an explosive limit (lower) of 1.8%
by volume in air [3].

Table 1-3 Some Physical Properties of Nitrobenzene [1,2,3&5]


Mp.oC
Bp.oC
Viscosity pa.sec
Thermal conductivity W/moC
Surface tension (20oC) mN/m
Specific heat J/goC
At 25 oC
At 30 oC
Latent heat of fusion J/g
Latent heat of vaporization J/g
Heat of combustion (at constant
volume)MJ/mol
Flash point (closed cup) oC

5.58
210.9
1.900599219*10-3
0.14473
43.35
1.473
1.418
94.1
331
3.074
88

Auto ignition temperature oC


Explosive limit in air (93 oC)vol%
Vapor pressure pa
At 20 oC
At 25 oC
At 30 oC
Solubility in water mg/liter
At 20 oC
At 25 oC
Solubility in organic solvent
Density (25oC)Kg/m3

482
1.8
20
38
47
1900
2090
Freely soluble in ethanol, acetone, ether
1198.484586

1.5 Chemical properties


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, Nphenylhydroxylamine, 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]

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, C6H5NHSO3Na

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

CU/SiO2

C6H5NO2 +3 Fe + 4 H2O

C6H5NH2 + 2H2O

HCL/Fecl

C6H5NH2 +Fe(OH)2 + FeO + Fe (OH)3 + 0.5H2

1.1
1.2

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]:

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, HNO2. 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
manufacture
Aniline
m-Nitrobenzenesulfonic acid
m-Chloronitrobenzene
Hydrazobenzene

Nitrobenzene
consumption
(tones/year) in Western Europe
380 000
5 000
4 300
1 000
11

Dinitrobenzene
Others (solvents, dyes)
Total

4 000
4 000
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
Nitrobenzene

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
Belgium
Germany
Italy
Portugal
Switzerland
United Kingdom
USA
Japan

Capacity (tones)
200 000
240 000
18 000
70 000
5 000
145 000
434 000
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 % H2SO4, 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 conicalbottomed 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 40-50oC 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 50100oC 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 % H2SO4, 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 1315 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 g/m3 at the scrubber inlet
(corresponding to an emission of 3.2 g/h) and 16 g/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
g/m3. The maximum level recorded was 51.8 g/m3. At the sanitary landfill,
nitrobenzene was below the detection limit (0.25 g/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. % H2SO4, 25 wt. % HNO3, 15 wt. % H2O [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 50oC [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

Nitrating acid
Nitric
acid
64wt. %

nitrator

Fresh sulfuric acid


98 wt. %

Na2CO3

CaSO4

Crude
nitrobenzene

Acid separation

1st washing

2nd washing

Distillation

NaSO4
H2CO3

Gypsum

Nitrobenzene

H2O
Spent acid

Sulfuric acid reconcentration


(Evaporator)

Fig. 2-4 Typical continuous nitrobenzene process

26

Benzene

Chapter Three
Material Balance

Chapter Three
Material Balance
Note: Data necessary in appendix A.

3.1 General Information


Main Reaction
C6H6 + HNO3 H SO
2
4

C6H5NO2 +H2O (3.1)

Capacity = 70000 ton/year [5]


Year = 300 working day
= 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

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 %, & H2O 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

Component

[Kg/hr]

[Kg/hr]

5
[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
26275.56824

Total
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
* 100 = 73.03843924 %

Wt. % sulfuric acid in acid solution =

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

[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

Total
26275.56824

[Kg/hr]

10085.61616

26275.56824

31

3.4 Washing Process Material Balance


3.4.1 1st Washing process Material Balance
Na2CO3
8
7

10
1st Washing

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 = 1.217815215 * 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

10

7
[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
CaSO4.2H2O
(Gypsum)

CaSO4 + 2H2O

CaSO4.2H2O

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


= 2.446812053 Kg

Mole of water input in 10 =

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


11

10

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

Total

10132.72733

9922.0812

10132.72734

3.5 Reconcentrator Material Balance

1
2 mixing point
nd

18
1st mixing point

H2O
6
16

2
Sulfuric acid
reconcentration
1
35

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
= 4180.871204 Kg/hr = stream 16
Material balance on reconcentrator
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
component [Kg/hr]

16

17

18

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

HNO3

H2SO4

11824.88831

11824.88831 11944.33163 119.4433163

3
[Kg/hr]

4976.804845 4976.804845
-

11944.33159

H2O

4365.063767 4180.871204

186.6301817

2.4376187

2799.452725 2986.082907

Total

16189.95208 4180.871204 12009.08088 12130.96181

121.880935

7776.25757

184.192563

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

19907.21934

Select purity = 99 wt. %


= 9820.426487 Kg/hr

Stream 15 (bottom) =

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

Component

C6H6
C6H5NO2

Total

13

14

15

[Kg/hr]

[Kg/hr]

[Kg/hr]

101.6548042

98.20426486

9722.222222

101.6548042

9820.426987

199.8590691
9722.222222

9922.081291
9922.081291

39

3.7 Overall Material Balance

Table 3-7 Overall Material Balance


In ( Kg/hr)
Stream

Comp.

No.

[Kg/hr]

[Kg/hr]

[Kg/hr]

Out (Kg/hr)
8

[Kg/hr]

11

[Kg/hr]

[Kg/hr]

12

[Kg/hr]

16

14

15

[Kg/hr]

[Kg/hr]

[Kg/hr]

6368.348857
101.6548042 98.20426486
C6H6
4976.804845
HNO3
119.4433163
4180.871204
H2SO4
2799.452725
2.376187
H 2O
C6H5NO2
9722.222222
129.0884128
Na2CO3
75.4510778
H2CO3
172.9906513
Na2SO4
166.5544965
CaSO4
210.6460497
CaSO4.2H2O
7776.25757

Total

121.880935

6368.348857

129.0884128

166.5544965

14562.13027

210.6460497

4180.871204

14562.13027

40

248.5317291

101.6548042

9820.426987

Table 3-8 all Streams of Material Balances

Stream
NO.
COMP.

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

14

13

12

11

[Kg/hr]

15

17

16

[Kg/hr]

[Kg/hr]

[Kg/hr]

[Kg/hr]

18

[Kg/hr]

[Kg/hr]

C6H6

6368.348857

199.8590691

199.8590691

199.8590691

199.8590691

101.6548042

98.20426486

HNO3

4976.804845

4976.804845

H2SO4

11944.33163

11944.33163

11824.88831

119.4433163

11824.88831

11944.33163

H2O

2799.452725

119.4433163

2986.082907

4409.155317

4365.063767

44.0915532

44.0915532

4180.871204

184.192563

186.6301817

C6H5NO2

2.4376187

9722.222222

9722.222222

9722.222222

9722.222222

9722.222222

Na2CO3

129.0884128

H2CO3

75.4510778

Na2SO4

172.9906513

CaSO4

166.5544965

CaSO4.2H2O

210.6460497

Total

7776.25757

121.880935

16189.95208

10085.61616

129.0884128

248.5317291

9966.172836

166.5544965

210.6460497

9722.0812

101.6548042

9820.426987

4180.871204

12009.08088

12130.96181

19907.21938

6368.348857

26275.56824

41

10

Chapter Four
Energy Balance

Chapter Four
Energy Balance
H.W

C.w

70oC

30oC

H.W

60oC

C.W

30oC

Note: Data necessary in appendix A.

4.1 Energy Balance on Nitrator


C6H6 + HNO3

H2SO4

C6H5NO2 + H2O

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

*2745.87058 = 216846.4298 KJ/hr

QHNO3 =

*10-3(323.152-298.152) +

HH2O = 32.243 (323.15 298.15) +


(323.153-298.153)

*10-5

*10-9(323.154-298.154)

HH2O = 843.7765567 KJ/Kg.mol

* 843.7765567 = 139,821.6844 KJ/hr

QH2O =

* (502-252) = 3623.65625 KJ/Kg.mol

HH2SO4 = 139.1(50-25) +

* 3623.65625 = 441294.3716 KJ/hr

QH2SO4 =

Q3 = 216846.4298 + 139,821.6844 + 441294.3716 = 797962.4858 KJ/hr


Q4 = H4 * nBZ.
H4 = -33.917 (303.15-298.15) +
(303.153-298.153) +
Q4 =

*10-1(303.152-298.152)

* Hi * ni

Hi =

cpi dT

HBZ. = -33.917 (323.15-298.15) +


*10-4(323.153-298.153) +

*10-1(323.152-298.152)
*10-8(323.154-298.154)
43

-4

*10-8(303.154-298.154) = 416.7382512 KJ/Kg.mol

* 416.7382512 = 33976.886 KJ/hr

Q5 =

*10

HBZ. = 2160.861183 KJ/Kg.mol


QBZ. =

* 2160.861183 = 5528.96818 KJ/hr


* (502-252) = 3623.65625 KJ/Kg.mol

HH2SO4 = 139.1(50-25) +
QH2SO4 =

* 3623.65625 = 441294.3716 KJ/hr


*10-3(323.152-298.152) +

HH2O = 32.243 (323.15 298.15) +


(323.153-298.153)

*10-5

*10-9(323.154-298.154)

HH2O = 843.7765567 KJ/Kg.mol


QH2O =

* 843.7765567 = 206456.2648 KJ/hr


(323.152-298.152) +

HN.B. = 295.3 (323.15-298.15)

(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


Q5 = 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

*10-3

Qcooling = 11,421,664.11 KJ/hr


Qcooling = QJacketed + QCoil
QJacketed = 0.75 Qcooling & QCoil = 0.25 Qcooling [explanatory note in chapter five]
QJacketed = 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
*10-3 (338.152-303.152) +

HJacketed =32.243 (338.15 -303.15) +


(338.153-303.153)

*10-5

*10-9 (338.154-303.154)

HJacketed = 188.206832 KJ/Kg.mol


n H2O =

= 7,209.391374 Kg.mol/hr

m.jacket = 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) +
(343.153-303.153)

*10-3 (343.152-303.152) +

*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

*10-5

4.2 Separator Energy Balance

Separator
5

Assume perfect insulated system, so there is no energy loose


through system.
Q5 = 1015032.158 KJ/hr
Q6 =

* Hi * ni

Hi =

cpi dT
* (502-252) = 3623.65625 KJ/Kg.mol

HH2SO4 = 139.1(50-25) +
QH2SO4 =

* 3623.65625 = 436881.4277 KJ/hr


*10-3(323.152-298.152) +

HH2O = 32.243 (323.15 298.15) +


(323.153-298.153)

*10-9(323.154-298.154)

HH2O = 843.7765567 KJ/Kg.mol

46

*10-5

* 843.7765567 = 204391.7023 KJ/hr

QH2O =

Q6 = 436881.4277 + 204391.7023 = 641273.13 KJ/hr


Q7 =

* Hi * ni

Hi =

cpi dT

HBZ. = -33.917 (323.15-298.15) +


(323.153-298.153) +

*10-1(323.152-298.152)

*10-4

*10-8(323.154-298.154)

HBZ. = 2160.861183 KJ/Kg.mol


QBZ. =

* 2160.861183 = 5528.96818 KJ/hr


* (502-252) = 3623.65625 KJ/Kg.mol

HH2SO4 = 139.1(50-25) +
QH2SO4 =

* 3623.65625 = 4412.943716 KJ/hr


*10-3(323.152-298.152) +

HH2O = 32.243 (323.15 298.15) +


(323.153-298.153)

*10-5

*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) +

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


4580.779561 =361752.5534 KJ/hr
47

*10-3
*

Q7 = 5528.96818 + 4412.943716 +2064.562649 + 361752.5534


Q7 = 373759.0279 KJ/hr

4.3 Energy Balance on Evaporator

16
3

1
HNO3
64wt. %

18

H2SO4
98 wt.%

250oC

17 Out

Steam 250oC
3973000 pa

17 In

Q6 = 641273.13 KJ/hr
H16 = 32.243 (373.15 298.15) +
(373.153-298.153)

*10-3(323.152-298.152) +

*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

*10-5

HH2SO4 = 139.1(100-25) +
QH2SO4 =

* (1002-252) = 11163.28125 KJ/Kg.mol

* 11163.28125 = 1345886.562 KJ/hr


*10-3(323.152-298.152) +

HH2O = 32.243 (373.15 298.15) +


(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

17

Cooling water
30oC

17

100oC

65.5 oC
50oC

49

*10-5

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


* (65.52-252) = 5,919.256238 KJ/Kg.mol

HH2SO4 = 139.1(65.5-25) +
QH2SO4 =

* 5,919.256238 = 713,674.4704 KJ/hr


*10-3(338.652-298.152) +

HH2O = 32.243 (338.65 298.15) +


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
*10-3(323.152-303.152) +

HCooling = 32.243 (323.15 303.15) +


*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 H2SO4 added (98wt.%) the heat of mixing is
Zero p.433, figure (12.17) [26].
50

*10-

Q2 =

* Hi * ni

Hi =

cpi dT
* (302-252) = 716.93625 KJ/Kg.mol

HH2SO4 = 139.1(30-25) +

* 716.93625

QH2SO4 =

= 873.0958735 KJ/hr
*10-3(303.152-298.152) +

HH2O = 32.243 (303.15 298.15) +


5

(303.153-298.153)

*10-

*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

*139.1(T-25) +

Q18 =[

32.243 (T 298.15) +

* (T2-252)] +[

*10-3(T2-298.152) +

*10-9(T4-298.154) ]
Find T18 by 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

*10-5 (T3-298.153)

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 + HProduct - HReactant
HNa2CO3 = 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

HH2CO3 = 126.1128611 T
HNa2SO4 = 128.229 T
HProduct - HReactant = 126.1128611 T + 128.229 T - 3,623.65625 - 555.4
HProduct - 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
Q9 = [

* 128.229 T] + [

* 126.1128611 T]

Q9 = 156.1592272 T + 153.5821611T
Q9 = 309.7413883 T
Q10 = HMixture * ni
HMixture =

cpMixture dT

cp10 = cpMixture = 277.604511 - 0.823102128 T + 1.594487804*10-3T2 +


2.067652194*10-9T3
T2 +

H10 = HMixture = 277.604511 T T3 +

*10-3

*10-9T4

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 T2 + 0.04463361 T3 + 4.340897832 *


10-8 T4
Heat input + Heat generation = Heat out + Heat accumulation
0.0 S.S
Q7 + Q8 - Qr = Q9 + Q10
373759.0279 + 676.374704 (-212,708.5452 + 309.7413883 T)
= 309.7413883 T + 23,312.48936 T 34.56096004 T2 + 0.04463361 T3 +
4.340897832 * 10-8 T4
587,143.9477 = 23,931.97214 T - 34.56096004 T2 + 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
Q7 = 373759.0279 KJ/hr
Q8 = 676.3475704 KJ/hr
Q9 = 11,733.91759 KJ/hr
Q10 = 563,676.1122 KJ/hr
Qr = - 200,974.6276 KJ/hr

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 - HReactantHH2O = 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 = -24,386.78579 + 227.7358085T
Q10 = 563,676.1122 KJ/hr
H11 = 99.73 (30 25)
H11 = 498.65 KJ/Kg.mol
Q11 =

* 498.65 = 610.0514153 KJ/hr

H12 = HGypsum = 186.149T


Q12 =

* 186.149 T

Q12 = 227.7358085 T
55

Q13 = HMixture * ni
HMixture =

cpMixture dT

Cp13=cpMixture = 284.968122 0.847861952 T+ 1.642023363 *10-3T2 +


2.237621333 *10-9T3
T2 +

HMixture =284.968122 T -

*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 - 34.56331259T2 + 0.044625005 T3 + 4.560860728 *10-8
T4
Heat input + Heat generation = Heat out + Heat accumulation
0.0 S.S
Q10 + Q11- Qr = Q12 + Q13
563,676.1122 + 610.0514153 (-24,386.78579 + 227.7358085T) =
227.7358085 T + 23,233.59895 - 34.56331259T2 + 0.044625005 T3 +
4.560860728 *10-8 T4
588,672.9494 = 23,789.07057 T- 34.56331259T2 + 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
13 IN

63.335oC

80.1oC

13 Out

192.1oC
15
200.87oC

From calculation of bubble point at feed finds T13 (OUT H.EX.) = 192.1oC, & find T=
200.87oC at bottom section.

Heat Exchanger Energy Balance

13 In

63.334 oC

Steam
250oC

Steam
210oC

Q13(IN H.EX.) = 567,379.1321 KJ/hr

57

13 Out

192.1oC

Q13 (OUT H.EX.) =


Hi =

* Hi * ni

cpi dT

HBZ. = HLiquid + + HVapoure


HLquid =

cpi dT
*10-1(353.252-298.152)

HLiquid = -33.917 (353.25-298.15) +


*10-4(353.253-298.153) +

*10-8(353.254-298.154)

HLiquid = 5,012.048424 KJ/Kg.mol


= 30,781 KJ/Kg.mol
HVapour =

cpi dT

HVapoure = 8.314 [ -0.206 (465.25 353.25) +


353.252)

* 10-3 * (465.252

* 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) +

(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

*10-3

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 =

= poBZ./ PoN.B
=

= 19.54121672

Rm =

19.54121672 *

Rm = 1.1718560223
Ractual = 1.2 Rm
Ractual = 2.062272268
V=L+D
L = Ractual * D
59

L = 2.062272268 * 101.6548042
L = 209.6398836 Kg/hr
L = 2.68390582 Kg.mol/hr
V = 209.6398836 + 101.6548042
V = 311.2946878 Kg/hr
V = 3.985337189 Kg.mol/hr
QCondencer = V BZ.
QCondencer = 3.985337189 * 30,781
QCondencer = 122,672.664 KJ/hr
Q14 = HBZ. * ni
HBZ. = -33.917 (353.25-298.15) +
*10-4(353.253-298.153) +

*10-1(353.252-298.152)
*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 + + HVapoure


HLquid =

cpi dT
*10-1(353.252-298.152)

HLiquid = -33.917 (353.25-298.15) +

60

*10-4(353.253-298.153) +

*10-8(353.254-298.154)

HLiquid = 5,012.048424 KJ/Kg.mol


= 30,781 KJ/Kg.mol
HVapour =

cpi dT

HVapoure = 8.314 [ -0.206 (474.02 353.25) +


353.252)

* 10-3 * (474.022

* 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
QReboiler = 242,862.4479 KJ/hr

61

Table 4-1 all Streams of Energy Balances

Stream
NO.

10

12

11

13
IN

17
out

14

15

17
IN

16

17
OUT

18

COMP.

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr] [KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[Kg/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

[KJ/hr]

C6H6

33976.886

5528.96818

8567.670381

8676.50917

123841.5502

6522.83704

62245.68484

HNO3

43435.94798

216846.4298

H2SO4

873.0958735

441294.3716

441294.3716

436881.4277

4412.943716

713647.4704

714329.4225

H2O

26159.21003

22.77797736

139821.6844

206456.2648

204391.7023

2064.562649

3132.981073

10029641.36

441866.1228

13996.32311

14055.2733

C6H5NO2

361752.5534

361752.5534

551975.5477

558702.6315

2740808.486

2916071.298

Na2CO3

676.3745704

H2CO3

5915.772227

Na2SO4

5818.145361

CaSO4

610.0514153

CaSO4.2H2O

10646.90855

Total

69595.15801

895.8738509

797962.4858

33976.886

1015032.158

641273.13

373759.0279

676.3745704

11733.91759

563676.1992

610.0514153

10646.90855

567379.1321

2864650.036

6522.83704

2978316.983

10029641.36

1787752.684

727643.7935

728384.6957

Pressure atm

Temperature
o
C

30

30

50

30

50

50

50

30

62.88295021

62.88295021

30

63.33466274

63.33466274

192.1

80.1

200.87

100

100

65.5

65.15

62

14

Feed
Benzene

8
4
7
3

Washing Tank
nd
1

13

13
10
Heater

9
1

18

15

Settler

Product N.B

10

Nitrator

Distillation Column

11

2
Washing Tank
st
2

13

12
17

17
Vaporizer
Cooling

Production of Nitrobenzene

63

Figure
4-1 Process Flow Diagram

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
Residence time = = 10 min [29]
= 0.166666666 hr

o = stream 3 + stream 4
o = [

o = 20.37924292 m3/hr
V = * o
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.
V = 3.396540473 * 1.1
V = 3.73619452 m3
D=
D = 2.181070978 m
Agitator Design
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 = 2.181070978/3 = 0.727023659 m
HA = D/3
HA = 2.181070978/3 = 0.727023659 m
r = D/4
r = 2.181070978/4 = 0.545267744 m
a = 2.181070978/5 = 0.436214195 m
HL = D = 2.181070978 m
65

Also use four symmetric baffles


b = width of baffle = D/10
b = 2.181070978/10 = 0.2181070978 m

0.218

2.181
0.7

0.73

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* * 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

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, = 989.25 Kg/m3, = 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 =

= 5,376.659075 W/m2.oC

hj =

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 50oC as fellows [22, 23, 28&33]:
Kav. = 0.326087319, av. = 1,425.7889 Kg/m3, av. = 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

[
]

[
hv = 4,269.214368 W /m2.oC
Tube side
hi = 4200 (1.35 + 0.02 t) ut0.8 / di0.2
t=

= 50oC

70

A=

d i2

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 / m2. oC
=

Kw = 16.3 for stainless steel [32].


=

= 7.705482183 * 10-4

Uo = 1,297.777318 W/m2.oC
Q = Uo Ao T
From Energy Balance:
Qcoil = 2,855,416.028 KJ /hr = 793,171.1189 J/s
71

= 15.27941481 m2

Ao =

Length of tube =

Length of tube =

= 63. 910491481m

Assume Number of turns = 19 turns


= 1.090535489m

Diameter of turn=

1m

Mechanical Design [23&30]


Calculation of the cylindrical 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/mm2
t=

t = 1.817438078mm

+1

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(1.817438078*10-3)
Do = 2.184706233 m
2b = minor axis = 2h
h = height of head from tangent line
a = 2.184706233/2 = 1.092353117m
b = a2/Rs
73

b = 1.0923531172/2.184706233 = 0.546176558 m
h = 0.546176558 m height of cover
Calculation 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
VTotal = 3.73619452 + 2(0.524227513)
VTotal = 4.784649546 m3
Overall length of reactor = length of cylindrical part + 2*length of cover
LTotal = 2.181070978 + 2* 0.546176558
LTotal = 3.273424094 m
Calculation 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/m3 [32].
Each support bear weight of =

Each support bear weight of =

= 7,124.424796 Kg

= 0.911401405 m3

The volume of one leg support =

For supporting leg L/D = 8


V=

D 2L

V=

D2 (8D) =2

D=

D3

= 0.525424043m
75

L = 8* 0.525424043 = 4.203392345m
Wind load
The effect of the wind on tall vessels (over 50m) although the calculation
about this small effect is made.
Wind load = Fw = Pw * Deff
Pw = 1280 N/m2
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
d(Croude Nitrobenzene) = 1,173.870615 Kg/m3 [22,28&33].
C(Spent Acid) = 1,582.722727 Kg/m3 [22,28&33].
d(Croude Nitrobenzene) = 1.280716063 * 10-3 pa.s
c (Spent Acid) = 2.81813726 * 10-3 pa.s
Take dd = 150m (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


(stocks law)

dd =

dd =

dd = 9.267388216 * 10-5 m = 92.67388216 m ( which is very satifactory; below


150m).
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 =

Pipe diameter =

= 5.22803863 * 10-3 m2

= 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 * 2.852085922 = 2.56687733 m


Z3 = 0.5 * 2.852085922 = 1.42604296 m
Z2 =

Z2 =

+ 1.426042961

Z2 = 2.272174706 m
Proposed Design

Liquid- light

D = 1.4 m
Heavy liquid

take off

take off

Crude N.B

Z1 = 2.6 m

Z3 = 1.4 m

Z2 =2 m

Spent Acid

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=

t = 1.645072183 mm

+1

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

t2=30oC

t1 =30 C

Spent Acid
T1=100oC

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

T2=50 C

}T
t1=30oC

82

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)
Tlm =

Tlm =

(T

t 2 ) ( T2 t1
( T1 t 2 )
ln
( T2 t1 )

(100 50) (65.5 30)


(100 30)
ln
(65.5 30)

= 42.33696435 o C

Tm = Ft Tlm
Use one shell and two tube passes.

T2 = 65.5 C

R = ( T1 T2 ) / ( t2 t1 )

t1 = 30 C

S = ( t2 t1 ) / ( T1 t1)

t2 = 50 C

R = (100 65.5) / ( 50 30)= 1.725

T1 =100 C

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/m2.oC.
83

Provisional area
Q = U A Tm
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 = do L
Area of one tube = * 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 = do (Nt / k1 ) 1/n1

Pt
Flow

From table (12-4) [23], k1 = 0.24, n1= 2.207


Db = 20 * (30 / 0.249)1/2.207
Db = 175.3490987 mm

Triangular Pitch

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 =40C
Physical properties of water at mean temperature [32]:
Cp = 4.174kJ/kg.C, = 992.04 kg/m3, = 6.556 * 10-4 pa.s, Kf =0.6328 W/m
C , Pr = 4.334.
tube cross-sectional area = di2 /4 = (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 = ut d /
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
hi d i
= J h Re Pr 0.33 ( / w
kf

)0.14

Negiect (/w) 0.14


From Figure (12.23)[23], jh = 3.110-3
85

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


hi = 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 (tw 40) = 800 (82.75 40)
tw = 43.03245965oC

43 oC

w = 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 = 41.06981914mm
tube pitch = 1.25 do = 1.25 (20) = 25mm
As =

= 1.686730069*10-3m2

As =

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


Gs =

= 1977.705776 Kgde =
86

( pt2 0.917 do )

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
= 1,748.959499 kg/m3
= 5.376377382 * 10-3 pa.s
Kf =0.401408274 W/m C
Pr = 2.130055474
Re =

= 5.223851997 * 103

Choose 25 percent baffle cut, from figure ( 12.29) [23], jh = 2.4 * 10-2
hs =

jh Re pr1/3 [

]0.14

Negiect (/w) 0.14


hs =

* 2.4 * 10-2 * ( 5223.851997) * ( 2.130055474)1/3

hs = 4,559.6671 W /m2.oC
Calculation of the Shell Temperature
hS (TTw) = U (T t)
4,559.6671 (tw 40) = 800 (82.75 40)
tw = 75.24945243oC

75.25 oC

87

w = 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/ m2.oC).

1
=
Uo

d ln(d o / d i )
d 1
d 1
1
1
+
+ o
+ o
+ o
2 kw
ho hod
d i hid
d i hi

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


Take the foaling coefficient as 6000 W/ m2.oC [23].
=

= 7.28006325 * 10-4
Uo = 1,373.614614 W/ m2.oC (Above the assumed value of 800 W/ m2.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 / = 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:
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

Comp.

Wt.%

Mol.%

C6H6

2.014285745

3.31381848

Bottom

Wt.% Mol.% Wt.%

C6H5NO2

97.98571425 96.86168152

TemperatureoC

192.1

Mol.%

100

100

1.567082484

99

98.43291752

80.1

200.87

Vapor-liquid equilibrium data for Benzene-Nitrobenzene [36]: (see appendex B)


X
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1

Y
0
0.451
0.759
0.923
0.957
0.969
0.975
0.981
0.985
0.988
0.989
0.99
0.992
0.994
0.995
0.996
0.996
0.997
0.999
0.999
1

90

BenzeneVaporMoleFraction

0.8

0.6

0.4

0.2

0
0

0.2

0.4

0.6

0.8

Benzene Liquid Mole Fraction

Figure 5-1 Vapor-Liquid Equilibrium diagram (Isothermal) at 70oC


R = 2.062272268
Intercept =

= 0.326554895

0.33

From equilibrium curve by Mc cabe-Tiele method find the number of stages


equal 3.
Number of theoretical plate = 3 + 1 = 4
91

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


stage.
=5

No. of real stages =


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 * 103 + 4905 = 106,230 pa = 106.230 Kpa
Column Diameter
At Top of the Column
Top temperature = 80.1 oC = 353.25 K
Top pressure = 101.325 * 103 pa
FLV =

Ln
Vn

V
L

From material Balance:


Ln = 209.6398836 Kg/hr = 0.058233301Kg/s
Vn = 311.2946878 Kg/hr = 0.086470746 Kg/s

V =
V =

P Mwt.
RT
= 2.694828052 Kg/m3

L = 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 FLV = 0.038722801 and plate spacing = 0.45,
K1 = 7.5 * 10-2
Correction for surface tension
4

* 10-12

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


4

* 10-12

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


(K1)correct = [ / 20 * 10-3 ]0.2 * K1
(K1)correct = [3.488266696 * 10-3]0.2 * 7.5 * 10-2
(K1)correct = 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.
uv = 0.85 * uf
uv = 0.85 * 0.227120984 = 0.193052836 m/s
maximum volumetric flow-rate =

= 0.032087667 m3/s

maximum volumetric flow-rate =

= 0.16621184 m2

An =

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


Ac =

= 0.188877091 m2

Dc =

= 0.490393497 m

At Bottom of the Column


Top temperature = 200.87 oC = 474.02 K
Top pressure = 106.230 Kpa
FLV =

Lm
Vm

V
L

From material Balance:


94

0.5 m

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
L(mix.) = 1002.856487 Kg/m3 at 200.87 oC [28]
V(mix.) =
Mwt. av. = 122.4048129 Kg/Kg.mol
= 3.229930538 Kg/m3

V(mix.) =

FLV =

= 1.847096398

From figure (11.29) [23] at FLV =1.847096398 and plate spacing = 0.45,
K1 = 1.8 * 10-2
Correction for surface tension
=

* 10-12

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


V BZ. =

= 0.032994305 Kg/m3

L BZ. = 656.0793695 Kg/m3

95

* 10-12

BZ. =

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
= 3.266436233Kg/m3

V BZ. =
L N.B = 1,008.377286 Kg/m3

N.B =

* 10-12

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


mix. = (1.483518856 * 10-3 * 0.01567082484) + (3.439273426*10-3 *
0.9843291752) = 3.408625139 * 10-3 J/m2
(K1)correct = [ / 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

uf = 0.013081

= 0.219920976m/s

for design a value of 80-85 percent of the flooding velocity should be used.
uv = 0.85 * uf
96

uv = 0.85 *0.219920976 = 0.186932829 m/s


maximum volumetric flow-rate =

= 0.026207778 m3/s

maximum volumetric flow-rate =

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 Dc = 0.490393497 m

0.5 m

Provisional Plate Design


Column diameter Dc = 0.5 m
Column area Ac = 0.19634954 m2
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 m2
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

]2/3 = 28.44243839 mm Liquid

maximum how = 750 [

minimum liquid rate, at 70 percent turn down.


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

]2/3 = 22.42326516 mm Liquid

minimum how = 750 [

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 / Ah


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 =

hd = 51 [

= 8.737700255 m/s

]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
]2 [

hd = 51 [

hr =

] = 19.30499388 mm Liquid

= 12.46439562 mm Liquid

Total Plate Pressure Drop


ht = hd + ( hw + how ) + hr
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.
Downcomer Liquid back-up
Downcomer pressure loss
Take hap = hw - 10 = 50 10 = 40 mm
Aap = hap lw = Am
Aap = 40 * 10-3 * 0.38 = 0.0152 m2
hdc = 166 [

hdc = 166 * [

]2
]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 < (tray spacing + wier hight)
0.1943128112 m < (0.45 + 0.05)
0.2632 m < 0.25 m
So tray spacing acceptable.
Check Residence Time
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], =0.03 well bellow 0.1, satifactory


plate Layout
use sieve plate. Allow 50mm unperforated strip round plate edge;
101

50mm wide callming zones.


50 mm

Perforated Area
From figure (11.32) [23],
At lw / Dc = 0.76
lw= 0.38

o = 99o

D = 0.5 m

= 180 o 99o =81o


mean length of unperforated edge strip
= (0.5 0.01)( / 180 * 81) = 0.636172512 m
Area of unperforated edge strips = 0.636172512 * 50 * 10-3
Area of unperforated edge strips = 0.031808625 m2

Area of calming zones = 2 (0.05) * ( 0.38 2 * 0.05) = 0.028 m2


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).
Number of holes
Area of one hole = (/4) dh2
= (/4) (0.004167) 2
= 1.363756653*10-5 m2
102

50 mm

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

Chapter Six
Control System

Chapter Six
Control System

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
take off

Heavy liquid
take off

Crude N.B
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

Chapter Seven
Plant Layout

Chapter Seven
Plant Layout

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 7-1A 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, chlorinationoxyhydrochlorination process for vinyl chloride production. It may bepossible 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 misoperation; 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
Nitrobenzene

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 LC50 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

exposureresponse

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 drinkingwater 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 nonneoplastic 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 g/litre.
Nitrobenzene is thus unlikely to pose an environmental hazard to aquatic species
at levels typically reported in surface waters, around 0.11 g/litre. Even at
127

highest reported concentrations (67 g/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. Dont 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 persons

airway is

unobstructed and contact a hosnital or poison center immediately for


advice on wiether or not to induce vomiting [37].

128

References
1- Ullmanns 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.
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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), Shreves Chemical Process Industries, 5th Ed., p.
(772).
18- SEP Handbook, Petrochemical & Downstream Projects.
19- Robert H. Perry (1997), Perrys Chemical Engineers Handbook, 7th Ed.
129

20- John A. Dean, (1999), Langes 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 & Richardsons, (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, 5th edition, McGraw Hill.
33- Coulson & Richardsons, (1999), Chemical Engineering, Vol.1, Sixth
Edition.
130

34- Alan S. Foust, (1980), Principles of Unit Operation, Second Edition.


35- Coulson & Richardsons, (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

Appendixes

Appendix A
Physical Properties
1- General Properties [19,20,21,22,23,24,25,26,27&28]
Comp.

Hof

Mwt.
[Kg /Kg.mol]

B.P
[oC]

C6H6 (L)
HNO3 (L)
H2SO4 (L)
H2O (L)
C6H5NO2 (L)
Na2CO3 (c)

78.11
63.02
98.08
18.02
123.11
106

80.1
100
210.9
-

49.1
-173.230
-811.32
-285.840
12.500
-1131.546

30781
40683
-

H2CO3 (aq)
Na2SO4 (c)
CaSO4 (c)
CaSO4.2H2O(c)

62.03
142.05
136.14
172.18

-699.65
-1413.891
-1432.7
-2024.021

(298.15K)

[KJ /g.mol]

[KJ / Kg.mol]

(Soda Ash)

(Gypsum)

2- Specific Heat Capacity


A- Specific Heat Capacity of Liquid [KJ / Kg.mol.K] [23&28]
Cp = A + BT + CT2 + DT3
Comp.
C6H6 (L)
HNO3 (L)
H2O (L)
C6H5NO2 (L)

A
-33.917
131.250
32.243
295.3

B
4.743 * 10-1
-0.1219
1.923 * 10-3
-0.8907

A-1

C
-3.017 * 10-4
0.1704 *10-3
1.055 * 10-5
1.705 * 10-3

D
7.130 * 10-9
-3.596 *10-9
-

Specific Heat Capacity of Sulfuric acid [KJ / Kg.mol.oC] [24]


Cp = A + BT
Comp.
H2SO4 (L)

A
139.1

B
0.1559

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


Cp [KJ / Kg.mol.oC]
111.08
128.229
99.73
186.149

Comp.
Na2CO3 (c) (Soda Ash)
Na2SO4 (c)
CaSO4 (c)
CaSO4.2H2O(c) (Gypsum)

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


Cp = K (Mwt.) a
For Acids: K = 0.91, a = -0.152
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 + CT2 + DT-2
Comp.

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]

=
Comp.

C6H6 (L)
HNO3 (L)
H2SO4 (L)
H2O (L)
C6H5NO2 (L)

1.0259
1.5943
0.8322
5.4590
0.69123

0.26666
0.2311
0.19356
3.0542*10-1
0.24124

562.05
520
925
6.4713*102
719

0.28394
0.1917
0.2857
8.1*10-2
0.28135

Range
Temperature
K
279-562
232-373
284-364
273-333
279-719

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

= exp. [A + B/T + C LnT + DTE] [28]


Comp.

C6H6 (L)
HNO3 (L)
96wt.%
H2SO4 (L)
98wt.%
H2O (L)
C6H5NO2 (L)

7.5117
-28.886

294.68
1940

-2.794
2.678

Range
Temperature
K
279-545
240-356

-179.84

10694

24.611

284- 367

-51.964
-34.557

3.6706*103
2611.3

5.7331
3.4283

-5.349*10-29
-

10
-

273-643
273-481

H2SO4 (60wt.%) = 3.65*10-3 pa.s at 50 oC figure (14) [22]


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.

C6H6 (L)
HNO3 (L)
96wt.%
H2SO4 (L)
98wt.%
H2O (L)
C6H5NO2 (L)

0.23444
0.12107

-0.00030572
0.0005383

Range
Temperature
K
279-413
233-433

0.014247

0.0010763

283-371

-0.4267
0.1869

0.00569
-0.0001305

-8.0065*10-6
-

1.815*10-9
-

273-633
283-371

6-Vapor Pressure of liquids using Antoines Equation, [mmHg]


Ln po = A -

[23]

T = Temperature in K
Comp.
C6H6 (L)

15.9008

Log po = A -

2788.51

-52.36

Range
Temperature
o
C
7-104

[25]

T = Temperature in oC
Comp.

C6H6 (L)
C6H5NO2 (L)

7.1156
6.90565

1746.6
1211.033

201.8
220.79

A-4

Range
Temperature
o
C
134-211
8-103

Appendix B
Equilibrium Data

XY data for Benzene / Nitrobenzene


NRTL

Bij
659.89

T Deg C
210.635
151.914
126.933
112.693
103.357
96.798
92.010
88.401
85.524
82.944
80.129

Bji
-263.35

P atm
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

Alpha
0.311

X1
0.00000
0.10000
0.20000
0.30000
0.40000
0.50000
0.60000
0.70000
0.80000
0.90000
1.00000

Aij
0.00

Aji
0.00

Mole Fractions
Y1
Gamma1
0.00000
1.416
0.82031
1.376
0.93286
1.340
0.96616
1.303
0.98015
1.261
0.98727
1.214
0.99139
1.162
0.99406
1.108
0.99603
1.057
0.99781
1.017
1.00000
1.000

B-1

Cij
0.00

Cji
0.00

Gamma2
1.000
1.001
1.005
1.013
1.031
1.063
1.123
1.228
1.418
1.778
2.529

Dij
0.00

Phi1
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

Dji
0.00

Phi2
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

B-2



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