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University of Technology

Chemical Engineering Department


Branch of Chemical processes

Production of Nitrobenzene

A project report submitted to the Department of Chemical


Engineering / University of Technology in partial fulfillment
of the requirements for the degree of B.Sc. in Chemical
Engineering.

By

Abdulkhaliq jassim Mohammed


&
Hamza Khalid

Supervised by

Lec. Fadel Hashim Kazem

Academic Year 2018-2019


Dedication
‫ـــــــــــــــــــــــــــــــــــــــــ‬

We dedicate our harvest to those who were


interested, cares and participate to the
achievement of this project, first of them Lec.
Fadel Hashim Kazem …
Certification of Supervisor
For First Part of Project
I certify that this project report
entitled................................................
…………………………………………………………………………
.
Was prepared by ………………………… and
………………………. under my supervision at the Chemical
Engineering Department/ University of Technology in partial
fulfillment of the requirement for the degree of B.SC. In Chemical
Engineering.

Supervisor:
Signature:
Name:
Date:
Certificate of Examiners
For First Part of Project
We certify, as an examining committee, that we have read this
project report entitled
…………………………………………………… examined the
students ……………………………………………... and
…………………………….. , In its contents and found the project
meet the standard for degree of B.SC. in Chemical Engineering.

Chairman
Signature:
Name:
Date:

Member Member
Signature: Signature:
Name: Name:
Date: Date:
‫أستمارة تصحيحات مشروع التخرج للفصل األول‬
‫‪ -‬الفرع‪-:‬‬
‫‪ -‬أسم المشروع‪-:‬‬
‫‪( ...........................................‬رئيس اللجنة)‪.‬‬
‫‪ -‬اللجنة الممتحنة‪-:‬‬
‫‪ ( ..........................................‬العضو)‪.‬‬
‫‪( ..........................................‬المشرف)‪.‬‬
‫‪ -‬الفقرات المطلوب تصحيحها في المشروع‪-:‬‬
‫‪-1‬‬
‫‪-2‬‬
‫‪.‬‬
‫‪.‬‬
‫‪.‬‬
Abstract
Nitrobenzene is a chemical material use in the manufacture of various
plastic monomers and polymers, rubber chemicals, drugs, pesticides, soaps,
and as a solvent in petroleum refining and manufacture of cellulose ethers and
cellulose acetate…etc.
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.
This report is so limited to academic use .most of data are available from
internet, so the authenticity of data has to been checked by the reader himself.
.

1
‫خالصة المشروع‬
‫نتروبنزين هو مادة كيميائية تستخدم في تصنيع مونومرات وبوليمرات بالستيكية مختلفة ‪،‬‬
‫ومواد كيميائية مطاطية ‪ ،‬ومخدرات ‪ ،‬ومبيدات ‪ ،‬وصابون ‪ ،‬وكمذيب في تكرير النفط وتصنيع إثير‬
‫السيليلوز وخالت السليولوز ‪ ...‬الخ‪.‬‬
‫يتم تصنيع النتروبنز تجاريا بواسطة النيترة المباشرة للبنزين باستخدام خليط من حامض النيتريك‬
‫وحامض الكبريتيك ‪ ،‬والعديد من العمليات لهذا التصنيع ولكن كلما زادت تكلفة السالمة واالقتصاد‬
‫وانخفاض التكلفة الرأسمالية هي عملية نتروية متساوية الحرارة‪.‬‬
‫يقتصر هذا التقرير على االستخدام األكاديمي ‪ ،‬حيث تتوفر معظم البيانات من اإلنترنت‪.‬‬

‫‪2‬‬
List of contents

Content Page

Abstract 1
Chapter One: Introduction

1.1 History 7
1.2 Specifications of Nitrobenzene 8
Identity 1.3 10
1.4 Physical properties 11
1.5 Chemical properties 12
1.6 Uses 20
1.7 Nitrobenzene Derivatives 24
Chapter Two: Production Methods.
2.1 General 23
2.2 Batch process 25
2.3 Tubular Reactor process 27
2.4 Continuous process 28
2.4.1 Adiabatic Continuous Process 29
2.4.2 Isothermal Continuous Process 31
3
2.5 Non-Industrial Sources 31
2.6 Process Selection 33
2.7 Description of the Selected Process 34

Chapter Three: Material Balance

3.1 General Information 38


3.2 Material Balance on Nitrator 39
3.3 Separator Material Balance 42
3.4 Washing Process Material Balance 45
3.4.1 1st Washing process Material Balance 45
3.4.2 2nd Washing process Material Balance 48
3.5 Reconcentrator Material Balance 51
3.6 Distillation Material Balance 55

Chapter four: Energy Balance


4.1 Energy Balance on Nitrator 60
4.2 Separator Energy Balance 66
4.3 Energy Balance on Evaporator 69
4.4 Washing Process Energy Balance 75
4
4.4.1 1st Washing process Energy Balance 75
4.4.2 2nd Washing process Energy Balance 78
4.5 Distillation Energy Balance 82

References 90

5
Chapter One

Introduction

6
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]. 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 dinitrobenzene 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 Step to my case Venezuela’s and identified in
1949 [1].This discovery stimulated investigations into the role of nitro group
in pharmacological activity, following the earlier (1943) discovery of the
antibacterial activity of nitro furan 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

7
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), C6H5 NO2, is colorless to
pale yellow oily liquid with on odor resembling that of bitter almonds or "shoe
polish." Depending on the purity, its color varies from pale yellow to
yellowish brown [2].
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 captivity 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 be champ
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. Nitro phenols are 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

8
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]


Appearance Pale yellow oil with a characteristic
order. It may be slightly hazy owing
to the presence of small globules of
free water
Water content 0.5% (maximum)
Specific gravity (15.5/15.5oC) 1.206-1.209
Dinitrobenzene content 0.1% (maximum)
Low-boiling impurities (benzene + 0.25% (maximum)
aliphatic hydrocarbons)
Sulfur- containing impurities 2.5 ppm (maximum, as sulfur)
(CS2+nitrothiophene +elementary
sulfur)

9
1.3 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 211°C. Its vapor pressure is 20 Pa at 20°C, and its
solubility in water is 1900 mg/liter at 20°C. It represents a fire hazard, with a
flash point (closed cup method) of 88°C and an explosive limit (lower) of
1.8% by volume in air [3].

Table 1-3 Some Physical Properties of Nitrobenzene [1]


Mp.oC 5.58
Bp.oC 210.9
Viscosity pa.sec 1.900599219*10-3
Thermal conductivity W/moC 0.14473
Surface tension (20oC) mN/m 43.35
Specific heat J/goC
At 25oC 1.473
At 30oC 1.418
Latent heat of fusion J/g 94.1
Latent heat of vaporization J/g 331
Heat of combustion 3.074
(at constant volume)MJ/mol
Flash point (closed cup)oC 88
Auto ignition temperature oC 482

10
Explosive limit in air (93oC)vol% 1.8
Vapor pressure pa
At 20oC 20
At 25oC 38
At 30oC 47
Solubility in water mg/liter
At 20oC 1900
At 25oC 2090
Solubility in organic solvent freely soluble in ethanol,
Acetone, ether
Density (25oC)Kg/m3 1198.484586

11
1.4 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].
The reduction of the nitro group to yield aniline is the most
commercially important reaction of the nitrobenzene. Usually the reaction is
carried out by the catalytic hydrogenation of nitrobenzene, either in the gas
phase or in solution, or by using iron borings and dilute hydrochloric acid (the
Bechamp process). Depending on the conditions, the reduction of
nitrobenzene can lead to variety of products. The series of reduction products
is shown in figure 1-1 Nitrosobenzen, N- phenyl hydroxylamine, and aniline
are primary reduction products. Azoxybenzene is formed by the condensation
of nitrosobenzene and N-phenyl hydroxyl amine 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].

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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 aniline
or solution)

SnCL2+ acetic acid aniline

Zn + NaOH hydrazobenzene, azobenzen


Zn + H2O N- phenyl hydroxyl amine

Na3AsO3 azoxybenzene

LiALH4 azoxybenzene

Na2S2O3+ Na3PO4 Sodium phenylsulfamate,


C6H5NHSO3Na

13
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 C6H5NH2+ 2H2O ….. 1.1

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

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 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 H2SO4 + H2O

∆Ho= -34.825 Kcal/g.mol …. 1.3


14
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]:

15
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 atom, the product being phenol and the nitrosyl ion,

16
NO+. The phenol then reacts with nitric acid, possibly through a complex
between the nitrosyl ion and the phenol, to form nitro phenol and nitrous acid,
HNO2. The one-to-one molar ratio between nitro phenol and nitrous acid is
confirmed through experiment. Nitro phenol is further nitrated to
dinitrophenol and picric acid. The rates for this di- and Trinitarian 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 benzene and nitrobenzene undergo other reactions. Most of
these by-products are removed in the washing stage of the process together

17
with the nitro phenols. 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 occasionally 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 aluminum
chloride as a result of the formation of a complex) and in the manufacture of
dinitrobenzene’s 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

18
Main application areas or chemical Nitrobenzene consumption
manufacture (tones/year) in Western Europe
Aniline 380 000
m-Nitrobenzene sulfonic acid 5 000

m-Chloro nitrobenzene 4 300

Hydrazobenzene 1 000
Dinitrobenzene 4 000
Others (solvents, dyes) 4 000
Total 398 300

Dunlap (1981) reported that most of the production of aniline and


other substituted nitrobenzene’s 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 hydroquinone’s (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].

19
Chapter Two
Production Methods
of Nitrobenzene

20
Chapter Two
Production Methods of Nitrobenzene

2.1 General

World production of nitrobenzene in 1994 was estimated at 2 133


800tones; 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 000tones in 1980 and 135 000 tones in 1990. Patil & Shinde (1989)
reported that production of nitrobenzene in India was around 22 000 tons per
year [5].

Nitrobenzene is produced at two sites in the United Kingdom with a


total capacity of 167 000 tons per year. It has been estimated that a maximum
of 115 400 tons 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 tons per year [5].

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

Table 2-1 nitrobenzene production capacities in European countries in


1985
Country Capacity (tones)
Belgium 200 000
Germany 240 000
Italy 18 000
Portugal 70 000
Switzerland 5 000
United Kingdom 145 000
USA 434 000
Japan 97 000

Nitrobenzene is manufactured commercially by the direct nitration


of benzene using a mixture of nitric acid and sulfuric acid [2].

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].

22
Nitrobenzene can be produced by either a batch or continuous
process [2].

2.2 Batch 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 817 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 2-4hours, 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
23
Nitric acid 520
Water 110
Sodium carbonate 10

The separation of the nitrobenzene is accomplished in large conical-


bottomed lead tanks, each capable of holding one or more charges. The
nitrator charges are permitted to settle here for 4-12 hr., when the spent acid is
drawn off from the bottom of the lead tanks and delivered to the spent-acid
tanks for additional settling or for treatment with benzene next to be nitrated,
in order to extract the residual nitrobenzene. The nitrobenzene is then
delivered to the neutralizing house [9].

The neutralizing tub may be either a large lead conical-shaped tub


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

24
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 a portion of the mixture is withdrawn and fed into the
separator. A slight excess of benzene usually is fed into the nitrator to ensure
that the nitric acid in the nitrating acid is consumed to the maximum possible
extent and to minimize the formation of dinitrobenzene. The temperature of
nitrator is maintained at 50-100 oC 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].

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].

25
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 fora 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].

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

26
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 120-160 oC.
Because excess benzene is used, the higher temperature allows water to be
removed as a water-benzene azeotrope. The water is separated and the
benzene phase, 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 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 190 oC, 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 190 oC, thereby allowing a boil-off of
water and benzene, which would drop the reactor temperature [10].

27
Figure 2-2 Flow sheet for the production of nitrobenzene adiabatically
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 stripping or through
benzene extraction-prenitration. It is then either reconcentrated or 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].

28
2.5 Non-Industrial Sources
Nitrobenzene has been shown to be emitted from a multiple-hearth
sewage sludge incineration unit in the USA. The unit consisted of 12 hearths
and operated at a rate of 13–15 tones per hour, with a maximum temperature
of 770°C at the sixth hearth. Nitrobenzene was monitored at the scrubber inlet
and outlet. The concentrations measured were 60 µg/m3 at the scrubber inlet
(corresponding to an emission of 3.2 g/h) and 16 µg/m3 at the scrubber outlet
(corresponding to an emission of 0.9 g/h). The scrubber reduced
the nitrobenzene concentration by 71% [5].
The levels of nitrobenzene in air have been measured at five
hazardous waste landfills and one sanitary landfill in New Jersey, USA.
Samples were collected over a 24-h period at five locations within each
landfill. Mean levels measured in the five hazardous waste landfills were 0.05,
0.65, 2.7, 1.0 and 6.6µg/m3. The maximum level recorded was 51.8 µg/m3.
At the sanitary landfill, nitrobenzene was below the detection limit (0.25
µg/m3) at all locations [5].
Nitrobenzene has been shown to be formed from the atmospheric
reactions of benzene in the presence of nitrogen oxides. The reaction is
thought to be initiated by hydroxyl radicals. Nitrobenzene, once formed,
reacts quite slowly in the atmosphere; this could therefore provide a major
source of atmospheric nitrobenzene, although it has not been possible to
quantify this source. Atkins net al. (1987) reported that aniline is slowly
oxidized to nitrobenzene by ozone. These reactions are summarized in Figure
2-3 [5].

29
Figure 2-3 atmospheric reactions generating and removing nitrobenzene

30
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 24 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,]

HNO3 + 2H2SO4 2 HSO4 + H3O+ NO2+


31
NO2

+ NO2+ + H+

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], 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 25 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].

32
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, following by final
washing with calcium sulfate (anhydrite) to remove the water from react the
calcium sulfate with water to formed calcium sulfate (Gypsum) [2]. The
product is topped in still to remove benzene and give pure product (96-99 wt.
%) [1].

33
Benzene

Nitrating acid Na2CO3 Benzene


CaSO4
Nitric
acid Crude
64wt. % Nitrobenzene

Acid 1st 2nd


nitrator separation Distillation
washing washing
Fresh
sulfuric
acid
98 wt. % H2O

Spent acid NaSO4


Gypsum Nitrobenzene
H2CO3

Sulfuric acid
reconcentration
(Evaporator)

Fig. 2-4 typical continuous nitrobenzene process

34
Chapter Three
Material Balance

35
Chapter Three
Material Balance

Note: Data necessary in appendix A.

3.1 General Information

Main Reaction

C6H6 + HNO3 C6H5NO2 +H2O … (3.1)


H2SO4

Capacity = 100000 ton / year [5]


Year = 300 working day

100000
= 333.33333 ton / day
300

333.33333*0111
= 18111.11175 kg / hr
42

08111811175
= 112.8169016 kg.mol / hr
123.11

36
No nitric acid remains in the spent acid [2&14]
Conversion = 100 % [2&14, 1&4]
From stoichiometry:
Benzene required = 112.8169016 Kg.mol/hr
Water formed = 112.8169016 Kg.mol/hr
Required nitric acid = 112.8169016 Kg.mol/hr

3.2 Material Balance on Nitrator

5
3

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].

37
Wt. of benzene = 112.8169016 * 78.11 = 8812.128184 Kg/hr
Wt. of benzene excess = 8812.128184 * 0.0324 = 285.5129532 Kg/hr
Total wt. of benzene input = 8812.128184 + 285.5129532
Total wt. of benzene input = 9097.641137 Kg/hr
Total nitric acid input = 112.8169016 * 63.02= 7109.721139 Kg/hr
Nitrating acid composition H2SO4 60 wt %, HNO3 25 wt %,
& H2O 15 wt % [2&21].
7109.721139
Total weight of nitrating acid = = 28438.88456 Kg/hr
0.25

Wt. of sulfuric acid input = 28438.88456 * 0.6


Wt. of sulfuric acid input = 17063.33073 Kg/h
Wt. of water input = 28438.88456 * 0.15 = 4265.832684 Kg/hr
Wt. of water formed = 112.8169016 * 18.02 = 2032.960567 Kg/hr
Water output in Stream 5 = 4265.832684 + 2032.960567
Water output in Stream 5 = 6298.793251 Kg/hr

38
Table 3-1 Material Balance on Nitrator

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

C6H6 - 9097.641137 285.5129532

HNO3 7109.721139 - -

H2SO4 17063.33073 - 17063.33073

H2O 4265.832684 - 6298.793251

C6H5NO2 - - 18111.11175

28438.884553 9097.641137
Total 37536.5256842
37536.5256842

39
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 =
6298.793251 + 17063.33073 = 23362.123981 kg/hr
Stream 7 (Crude Nitrobenzene) = excess BZ. + N.B. + 1 wt. % of acid
solution
Excess BZ. = 285.5129532 Kg/hr
N.B. = 18111.11175 kg/hr

40
Wt. of acid solution in stream 7 =
0.01 * 23362.123981 = 233.62123981 Kg/hr

17063.33073
Wt. % sulfuric acid in acid solution= * 100
23362.123981
= 73.03843924 %
Wt. % water in acid solution = 26.96156075 %
This above acid wt% is the same for stream 6 & stream 7.
Wt. of sulfuric acid in stream 7= 233.62123981 * 0.7303843924412568

Wt. of sulfuric acid in stream 7 =170.6333073 Kg/h


Wt. water in stream 7 = 233.62123981 * 0.2696156075587432
= 62.9879325 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 = 23362.123981 * 0.99 = 23128.5027411 Kg/hr = stream 6
Wt. of sulfuric acid in spent acid = 23128.5027411 * 0.7303843924
Wt. of sulfuric acid in spent acid = 16892.69742168 Kg/hr
Wt. of water in spent acid = 23128.5027411 * 0.269615607587
Wt. of water in spent acid = 6235.805319 Kg/hr

Table 3-2 Material balance on separator


41
5 6 7
Component
[Kg/hr] [Kg/hr] [Kg/hr]

C6H6 285.5129532 - 285.5129532

HNO3 - - -

H2SO4 17063.33073 16892.6974216 170.6333073

H2O 6298.793251 6235.805319 62.9879325

C6H5NO2 18111.11175 - 18111.11175

23128.5027406 14408.022943
Total
37536.52568
37536.52568

42
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

170.6333073
Mole of sulfuric acid in stream 7 =
98.08

Mole of sulfuric acid in stream 7 = 1.739736 Kg.mol/hr

43
Wt. of Na2CO4 input = 1.739736 * 106.00
Wt. of Na2CO4 input = 184.412016 Kg.mol/hr = stream 8
Mole of Na2SO4 = 1.739736 Kg.mol/hr
Wt. of Na2SO4 = 1.739736 * 142.05
Wt. of Na2SO4 = 247.1294988 Kg/hr
Mole of H2CO3 = 1.739736 Kg.mol/hr
Wt. of H2CO3 = 1.739736 * 62.03

Wt. of H2CO3 = 107.91582408 Kg/hr


Wt. of water input in stream 7 = wt. of water output in stream 9

Wt. of water input in stream 7 = 62.9879325 Kg/hr

44
Table 3-3 Material Balance on 1st Washing Unit

Component 7 8 9 10

[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]


C6H6 285.5129532 - - 285.5129532

HNO3 - - - -

H2SO4 170.6333073 - - -

H2O 62.9879325 - - 62.9879325

C6H5NO2 18111.11175 - - 18111.11175

Na2CO3 - 184.412016 - -

Na2SO4 - - 247.1294988 -

H2CO3 - - 107.91582408 -

14408.022943 184.412016 355.04532288 14237.3896357


Total

14592.434959 14592.434959

45
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 = 62.9879325 Kg/hr

62.9879325
Mole of water input in 10 = = 3.495445755 Kg
18.02

46
From stoichiometry
Mole of CaSO4 = 1.7477228775 Kg.mol/hr
Wt. of CaSO4 = 1.7477228775 * 136.14 = 237.9349925 Kg/hr
= stream 11
Mole of CaSO4.2H2O = 1.7477228775 Kg.mol/hr
Wt. of CaSO4.2H2O = 1.7477228775 * 172.18
Wt. of CaSO4.2H2O = 300.922925 Kg/hr = stream 12

47
Table 3-4 Material Balance on 2nd Washing Unit

Component 10 11 12 13

[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]


C6H6 285.5129532 - - 285.5129532

HNO3 - - - -

H2SO4 - - - -

H2O 62.9879325 - - -

C6H5NO2 18111.11175 - - 18111.11175

CaSO4 - 237.9349925 - -

CaSO4.2H2O - - 300.922925 -

14237.3896357 237.9349925 300.922925 14174.4017032


Total

14475.3246282 14475.3246282

48
3.5 Reconcentrator Material Balance

1
3
2nd mixing
point

H2O
18
1st mixing point 6
16

2
Sulfuric acid
Reconcentration

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

49
0.25 * 28438.88456
Stream 1 = = 11108.93928 Kg/hr
0.64

Wt. of nitric acid input in stream 1 = 0.64 * 11108.93928


= 7109.721139 Kg/hr
Wt. of water in stream1 = 0.36 * 11108.93928 = 3999.2181408 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 = 170.6333073 Kg/hr

170.6333073
Stream 2 = = 174.11561969 Kg/hr
0.98

Wt. of water in input in stream 2 = 174.11561969 * 0.02 = 3.48231239 Kg/hr

Material balance on water that must be removed


Total wt. of water input = 3999.2181408 + 3.48231239
= 4002.70045 Kg/hr
Wt. of water in stream 17 (after reconcentrator)
= wt. of water in nitrating acid – total wt. of water input
= 4265.832684 - 4002.70045 = 263.132234 Kg/hr

50
Wt. of water must be removed in stream17
= wt. of water in spent acid (stream 6) – water after reconcentrator in
stream17
= 6235.805319 - 263.132234
= 5972.673085 Kg/hr = stream 16

Material balance on reconcentrator


Stream 6 = stream 16 + stream 17
Stream 17 = 23128.5027411 - 5972.673085= 17155.829656 Kg/hr
Wt. of water in stream 17 = 263.132234 Kg/hr
Wt. of sulfuric acid in stream 17 = 17155.829656- 263.132234
Wt. of sulfuric acid in stream 17 = 16892.697422 Kg/hr

Material balance on 1st mixing point


Stream 17 + stream 2 = stream 18
Stream 18 = 17155.829656 + 174.11561969= 17329.94527 Kg/hr
Wt. of water in stream 18 = 263.132234+ 3.48231239
Wt. of water in stream 18 =266.614546 Kg/hr
Wt. of sulfuric acid in stream 18 = 17329.94527 + 266.614546
Wt. of sulfuric acid in stream 18 = 17596.55981 Kg/hr

51
Table 3-5 Material Balance on Reconcentrator

6 16 17 18 2 1 3

Component [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]

HNO3 - - - - - 7109.72113 7109.72113

H2SO4 16892.69742 - 16892.69742 17596.55981 170.6333 - 17596.5598

H2O 6235.805319 5972.67308 263.132234 266.614546 3.482312 3999.21814 4265.83268

total 23128.50273 5972.67308 17155.82965 17863.17435 174.1156 11108.9392 28972.1136

52
3.6 Distillation Material Balance

14

13

Distillation

01

Stream 13 = 9922.081291 Kg/hr


Benzene in stream 13 = 285.5129532 Kg/hr
Nitrobenzene in stream 13 = 18111.11175 Kg/hr
Purity between 96 – 99 wt. % [2 & 14]
Select purity = 99 wt. %

08111811175
Stream 15 (bottom) = = 14029.18055 Kg/hr
0.99

53
Benzene in stream 15 = 14029.18055 - 18111.11175
Benzene in stream 15 = 140.2918 Kg/hr
Benzene in stream 14 (top) = 285.5129532 – 140.2918
= 145.2211532 Kg /hr

Table 3-6 Material Balance on Distillation

13 14 15

Component [Kg/hr] [Kg/hr] [Kg/hr]

C6H6 285.5129532 145.2211532 140.2918

C6H5NO2 18111.11175 - 18111.11175

145.2211532 14029.18055

Total 14174.4017032
14174.4017032

54
3.7 Overall Material Balance
Table 3-7 Overall Material Balance
In ( Kg/hr) Out(Kg/hr)
Stream

1 2 4 8 11 9 12 16 14 15

N0.
[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]

Comp.

C6H6 - - 9097.641137 - - - - - 145.2211532 140.2918

HNO3 7109.721139 - - - - - - - - -

H2SO4 - - - - - - - - - -

H2O 3999.21814 170.6333 - - - - - 5972.67308 - -

C6H5NO2 - 3.482312- - - - - - - - 88111811175

Na2CO3 - - - 184.412016 - - - - - -

H2CO3 - - - - - 107.91582408 - - - -

Na2SO4 - - - - - 247.1294988 - - - -

CaSO4 - - - - 237.9349925 - - - - -

CaSO4.2H2O - - - - - - 300.922925 - - -

11108.939279 174.115612 9097.641137 184.412016 237.9349925 355.04532288 300.922925 5972.67308 145.2211532 14029.18055

total

20803.04303 20803.04303

55
Table 3-8 all Streams of Material Balances

Stream

6 10 12 14 15 16 17 18
1 2 3 4 5 7 8 9 11 13

N0.
[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]
Comp.

C6H6 - - 9097.641137 9097.641137 285.5129532 - 285.5129532 - - 285.5129532 - - 285.5129532 145.2211532 140.2918 - - -

HNO3 7109.721139 - 7109.72113 - - - - - - - - - - - - - - -

H2SO4 - 170.6333 17596.5598 - 17063.33073 16892.69742 170.6333073 - - - - - - - - - 16892.69742 17596.55981

H2O 3999.21814 3.482312 4265.83268 - 6298.793251 6235.805319 62.9879325 - - 62.9879325 - - - - - 5972.67308 263.132234 266.614546

C6H5NO2 - - - - 88111811175 - 88111811175 - - 88111811175 - - 88111811175 88111811175

Na2CO3 - - - - - - - 184.412016 - - - - - - - - - -

H2CO3 - - - - - - - - 107.91582408 - - - - - - - - -

Na2SO4 - - - - - - - - 247.1294988 - - - - - - - - -

CaSO4 - - - - - - - - - - 237.9349925 - - - - - - -

CaSO4.2H2O - - - - - - - - - - - 300.922925 - - - - - -

total 11108.939279 174.115612 28972.1136 9097.641137 37536.52568 23128.50273 14408.022943 184.412016 355.04532288 14237.389635 237.9349925 300.922925 14174.4017032 145.2211532 14029.18055 5972.67308 17155.82965 17863.17435
7

56
Chapter four
Energy Balance

57
Chapter four
Energy Balance

H.W C.w
4 3 70oC 30oC

H.W
60oC

C.W
30oC

4.1 Energy Balance on Nitrator

C6H6 + HNO3 C6H5NO2 + H2O


H2SO4

ΔHr = -146948.0527 KJ/Kg.mol

13888.88875
Qr = * -146948.0527 = -16593050.048 KJ/hr
123
58
n
Q3 = ∑ * ΔHi * ni
i=1

𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT

0.129
Qr = ΔHHNO3 = 131.250 (323.15 – 298.15) –
2
0.1704
* (323.152 – 298.152) + * 10-3 (323.153 – 298.153)
3

= 2690.7302 KJ/Kg.mol

7109.7211
QHNO3 = 3 *2690.7302 = 303559.8425 KJ/hr
63.02
1.923
ΔHH2O = 32.243 (323.15 – 298.15) +
2
1.055
*10-3(323.152-298.152) + *10-5 (323.153-298.153)
3
3.596
– *10-9(323.154-298.154)
4

ΔHH2O = 843.7765567 KJ/Kg.mol

4265.83268
QH2O = * 843.7765567 = 199745.2613 KJ/hr
2
59
0.1559
ΔHH2SO4 = 139.1(50-25) + 9 * (502-252)
= 3623.65625 KJ/Kg.mol 2

17596.5598
QH2SO4 = * 3623.65625 = 650121.1653KJ/hr
98.08

Q3 = 303559.8425 + 199745.2613 + 650121.1653


= 1153426.2691 KJ/hr
Q4 = ΔH4 * nBZ.
4.743
ΔH4 = -33.917 (303.15-298.15) + *10-1(303.152-298.152)
2
3.017 7.130
– *10-4(303.153-298.153) +
3 4

*10-8(303.154-298.154) = 416.7382512

9097.641137
Q4 = * 416.7382512 = 48538.408 KJ/hr
78.11

n
Q5 = ∑ i=1
* ΔHi * ni
𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT

60
4.743
ΔHBZ. = -33.917 (323.15-298.15) +
2
3.017
*10 (323.15 -298.15 ) –
-1 2 2
*10-4(323.153-298.153)
3
7.130
+ *10-8(323.154-298.154)
4

ΔHBZ. = 2160.861183 KJ/Kg.mol

285.5129532
QBZ. = * 2160.861183 = 7898.52589 KJ/hr
78.11
0.1559
ΔHH2SO4 = 139.1(50-25) + * (502-252)
2
= 3623.65625 KJ/Kg.mol

17063.33073
QH2SO4 = * 3623.65625 = 630420.5245 KJ/hr
98.08
1.923
ΔHH2O = 32.243 (323.15 – 298.15) +
2
1.055
-3 2 2
*10 (323.15 -298.15 ) + *10-5(323.153-298.153)
3
3.596
– *10-9(323.154-298.154)
4

ΔHH2O = 843.7765567 KJ/Kg.mol

61
6298.793251
QH2O = * 843.7765567 = 294937.5183 KJ/hr
18.02
0.8907
ΔHN.B. = 295.3 (323.15-298.15) – (323.152-298.152)
2
1.705
+ *10-3(323.153-298.153) = 4580.779561 KJ/Kg.mol
3
08111811175
QN.B. = * 4580.779561 =516789.3567 KJ/hr
123.11

Q5 = 7898.52589 + 630420.5245+ 294937.5183 + 516789.3567


Q5 = 1450045.925 KJ/hr

The overall heat balance around nitrator


Heat input + Heat generation = Heat out + Heat accumulation
Q3+ Q4- Qr = Q5 + Qcooling 0.0 s.s
Qcooling = 1153426.2691 + 48538.408 + 16593050.048 – 1450045.925
Qcooling = 16344968.80 KJ/hr
Qcooling = QJacketed + QCoil
QJacketed = 0.75 Qcooling & QCoil = 0.25 Qcooling [explanatory note in chapter five]

QJacketed = 0.75*16344968.80 = +12258726.6 KJ/hr


QCoil = 0.25*16344968.80 = 4086242.2 KJ/hr

62
Water inter jacket at T=30oC and leaves at T=65oC.
QJacketed = ΔHH2O * n H2O
1.923
ΔHJacketed =32.243 (338.15 -303.15) +
2
1.055
-3 2 2
*10 (338.15 -303.15 ) + *10-5(338.153-303.153)
3
3.5936
– *10-9 (338.154-303.154)
4

ΔHJacketed = 1183.930061 KJ/Kg.mol

12258726.6
n H2O = = 10354.265850 Kg.mol/hr
1183.930061

mjacket = 186583.8706 Kg/hr flow rate of water in jacket


Water inter coil at T=30oC and leaves at T=70oC.

1.923
ΔHcoil = 32.243 (34315 -303.15) +
2
1.055
-3 2 2
*10 (343.15 -303.15 ) + *10-5(343.153-303.153)
3
3.5936
– *10-9 (343.154-303.154)
4

ΔHcoil = 1353.828196 KJ/Kg.mol

63
4086242.2
ncoil = = 3018.287115 Kg.mol/hr
1353.82819
6
mcoil = 54389.53381 Kg/hr flow rate of water in coil

4.2 Separator Energy Balance

7 6

Separator

Assume perfect insulated system, so there is no energy loose


Through system.
Q5 = 1450045.925 KJ/hr
n
Q6 = ∑ i=1
* ΔHi * ni
𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT

0.1559

64
ΔHH2SO4 = 139.1(50-25) + * (502-252)
2
= 3623.65625 KJ/Kg.mol

16892.69742
QH2SO4 = * 3623.65625 = 624116.3191 KJ/hr
98.08
1.923
ΔHH2O = 32.243 (323.15 – 298.15) +
2
1.055
-3 2 2
*10 (323.15 -298.15 ) + *10-5(323.153-298.153)
3
3.596
– *10-9(323.154-298.154)
4

ΔHH2O = 843.7765567 KJ/Kg.mol

6235.805319
QH2O = * 843.7765567 = 291988.1431 KJ/hr
18.02

Q6 = 624116.3191 + 291988.1431 = 916104.46 KJ/hr


n
Q7 = ∑ i=1 * ΔHi * ni
𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT
4.743
ΔHBZ. = -33.917 (323.15-298.15) +
2
*10-1(323.152-298.152)

3.017 7.130
– -4 3
*10 (323.15 -298.15 ) + 3
*10-8(323.154-298.154)
3 4

65
ΔHBZ. = 2160.861183 KJ/Kg.mol

285.5129532
QBZ. = * 2160.861183 = 7898.52589 KJ/hr
78.11
0.1559
ΔHH2SO4 = 139.1(50-25) + * (502-252)
2
= 3623.65625 KJ/Kg.mol

170.633307
QH2SO4 = 3 * 3623.65625 = 6304.205245 KJ/hr
98.08
1.923
ΔHH2O = 32.243 (323.15 – 298.15) +
2
*10-3(323.152-298.152)

1.055
+ *10-5(323.153-298.153)
3
3.596
– *10-9(323.154-298.154)
4

ΔHH2O = 843.7765567 KJ/Kg.mol

62.987932
QH2O = 5 * 843.7765567 = 2949.375183 KJ/hr
18.02

0.8907
ΔHN.B. = 295.3 (323.15-298.15) – (323.152-298.152)
2
1.705
66
+ *10-3(323.153-298.153) = 4580.779561 KJ/Kg.mol
3
13888.88875
QN.B. = *4580.779561 =516789.3567 KJ/hr
123.11

Q7 = 7898.52589 + 6304.205245 +2949.375183 + 516789.3567


Q7 = 533941.4630 KJ/hr

4.3 Energy Balance on Evaporator

16

1
3 6

HNO3
64wt. %
18
Steam
H2SO4 250oC
98 wt.% 3973000 pa
250oC

17out 17in
Q6 = 916104.46 KJ/hr
1.923
ΔH16 = 32.243 (373.15 – 298.15) +
2
*10-3 (323.152-298.152)

67
1.055 3.596
+ *10-5(373.153-298.153) –
3 4

*10-9(373.154-298.154) + 40683
ΔH16 = 2545.822066 + 40683 = 43228.82207 KJ/Kg.mol

5972.67308
Q16 = * 43228.82207 = 14328058.92 KJ/hr
18.02

n
Q17 =∑ i=1
* ΔHi * ni
𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT
0.1559
ΔHH2SO4 = 139.1(100-25) + * (1002-252)
2
= 11163.28125 KJ/Kg.mol

16892.69742
QH2SO4 = * 11163.28125 = 1922695.069 KJ/hr
98.08
1.923
ΔHH2O = 32.243 (373.15 – 298.15) +
2
1.055
-3 2 2
*10 (323.15 -298.15 ) + *10-5(373.153-298.153)
3
3.596
– *10-9(373.154-298.154) + 40683
4
ΔHH2O = 43228.82207 KJ/Kg.mol

263.132234
QH2O = * 43228.82207 = 631237.3210 KJ/hr
18.02
68
Q17 = 1922695.069 + 631237.3210 = 2553932.39 KJ/hr
Q6 + QSteam = Q16 + Q17
QSteam = Q16 + Q17 - Q6
QSteam = 14328058.92 + 2553932.39 - 916104.46
= 15965886.85 KJ/hr

15965886.85
mSteam = = 9303.045594 Kg/hr
1716.2

nsteam = 516.262241 Kg.mol/hr

Heat Exchanger Energy Balance

Cooling
water
17 30oC 17

65.5 oC 100oC

50oC

Q17 (In H.Ex.) = 2553932.39 KJ/hr


0.1559
ΔHH2SO4 = 139.1(65.5-25) + * (65.52-252)
2
= 5,919.256238 KJ/Kg.mol
69
16892.69742
QH2SO4 = * 5,919.256238 = 1019496.3501 KJ/hr
98.08
1.923
ΔHH2O = 32.243 (338.65 – 298.15) +
2
*10-3(338.652-298.152)

1.055 3.596
+ *10 (338.65 -298.15 ) –
-5 3 3

3 4

*10-9(338.654-298.154)
ΔHH2O = 1,369.293843 KJ/Kg.mol

263.132234
QH2O = * 1,369.293843 = 19994.74738 KJ/hr
18.02

Q17 (Out H.Ex.) = 1019496.3501 + 19994.74738 = 1039491.0974 KJ/hr


Q17 (In H.Ex.) = Q17 (Out H.Ex.) + Qcooling
Qcooling = Q17 (In H.Ex.) - Q17 (Out..Ex.)
Qcooling = 2553932.39 - 1039491.09748 = 1514441.292 KJ/hr

1.923
ΔHCooling = 32.243 (323.15 – 303.15) +
2
*10-3(323.152-303.152)

11.055 3.596
+ *10-5(323.153-303.153) –
3 4

70
*10-9(323.154-303.154)
ΔHCooling = 675.3912584 KJ/Kg.mol

1514441.292
nCooling = = 2242.316987 Kg.mol /hr
675.3912584

mCooling = 40406.5521 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].

n
Q2 =∑ *
i=1
ΔHi * ni

𝑇
ΔHi =∫𝑇𝑟𝑒𝑓 cpi dT
0.1559
ΔHH2SO4 = 139.1(30-25) + * (302-252) = 716.93625 KJ/Kg.mol
2
170.6333
QH2SO4 = * 716.93625 = 1247.279753 KJ/hr
98.08

1.923
ΔHH2O = 32.243 (303.15 – 298.15) +
2
*10-3(303.152-298.152)

1.055 3.596
71
+ *10-5(303.153-298.153) – *10-9(303.154-298.154)
3 4

ΔHH2O = 168.3852983 KJ/Kg.mol

3.482312
QH2O = * 168.3852983 = 32.539963 KJ/hr
18.02

Q2 = 1247.279753 + 32.539963 = 1279.819716 KJ/hr

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


Q18 = 1039491.0974 + 1279.819716 = 1040770.9171 KJ/hr

17596.55981 0.1559
Q18 = [ [ ] * 139.1(T-25) + * (T2-252)]
98.08 2
266.614546 1.923
+[[ ] * 32.243 (T – 298.15) +
18.02 2
1.055 3.596
-3 2
* 10 (T -298.15 ) + 2
* 10 (T -298.15 ) –
-5 3 3

3 4
*10-9(T4-298.154)]

Find T18 by trial & error


T18 = 64.15oC
Note
Heat of mixing of HNO3 not takes under consideration.

72
ΔHdil. (mix.) = 11,864.53747 KJ/Kg.mol (5.104) [21].

4.4 Washing Process Energy Balance


4.4.1 1st Washing process Energy Balance

Na2CO3 + H2SO4 Na2SO4 + H2CO3


ΔHro = -699.65 – 1413.891 + 1131.546
ΔHro = -170.485 KJ/g.mol
ΔHro = -170,485 KJ/Kg.mol
ΔHr = ΔHro + ΔHProduct - ΔHReactant
ΔHNa2CO3 = 111.08 ΔT
ΔHNa2CO3 = 111.08 * (30 – 25) = 555.4 KJ/Kg.mol

0.1559
ΔHH2SO4 = 139.1(50-25) + * (502-252)
2
= 3,623.65625 KJ/Kg.mol
ΔHH2CO3 = 126.1128611 ΔT
ΔHNa2SO4 = 128.229 ΔT
ΔHProduct - ΔHReactant = 126.1128611 ΔT + 128.229 ΔT - 3,623.65625
- 555.4
ΔHProduct - ΔHReactant = 254.3418611 ΔT – 4,179.05625
ΔHr = -170,485 + 254.3418611 ΔT – 4,179.05625
ΔHr = -174,664.0563 + 254.3418611 ΔT

184.412016
73
Qr = [-174,664.0563 + 254.3418611 ΔT]
106

Qr = 1.739736 [-174,664.0563 + 254.3418611 ΔT]


Qr = -303869.3466 + 442.487692 ΔT
Q7 = 533941.463 KJ/hr
ΔH8 = 111.08 * (30 – 25) = 555.4 KJ/Kg.mol

184.412016
Q8 = * 555.4 = 966.249374 KJ/hr
106
n
Q9 = ∑ i=1
* ΔHi * ni
𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT

ΔHNa2SO4 = 128.229 ΔT
ΔHH2CO3 = 126.1128611 ΔT

247.1294988
Q9 = [ * 128.229 ΔT]
142.05
107.91582408
+[ * 126.1128611 ΔT]
62.03

Q9 = 223.0846075 ΔT + 219.4030845ΔT
Q9 = 442.4876915 ΔT
Q10 = ΔHMixture * ni
𝑇
ΔHMixture = ∫𝑇𝑟𝑒𝑓 cpMixture dT

74
cp10 = cpMixture = 277.604511 - 0.823102128 ΔT
+ 1.594487804*10-3ΔT2 +2.067652194*10-9ΔT3

0.823102128
ΔH10 = ΔHMixture = 277.604511 ΔT - ΔT2
2
1.594487804 2.067652194 -9 4
+ *10-3ΔT3 + *10 ΔT
3 4

ΔHMixture = ΔH10 = 277.604511 ΔT - 0.411551064 ΔT2


+ 5.314959347*10-4ΔT3 + 5.169130485 *10-10 ΔT4
Q10 = 83.97733129 [277.604511 ΔT - 0.411551064 ΔT2 +5.314959347*10-
4
ΔT3 + 5.169130485 *10-10 ΔT4
Q10 = 23,312.48936 ΔT – 34.56096004 ΔT2 + 0.04463361 ΔT3 +
4.340897832 *10-8 ΔT4
Heat input + Heat generation = Heat out + Heat accumulation
0.0 S.S
Q7 + Q8 - Qr = Q9 + Q10
533941.4630 + 966.249374 – (-303869.3466 + 442.487692 ΔT)
= 442.4876915 ΔT + 23,312.48936 ΔT – 34.56096004 ΔT2
+ 0.04463361 ΔT3 +4.340897832 * 10-8 ΔT4

838777.0589 = 23,931.97214 ΔT - 34.56096004 ΔT2


+ 0.04463361 ΔT3 +4.340897832 * 10-8 ΔT4

This equation above is solved by trial and error until the right hand equals the
75
left hand.
T = 83.88295021 oC
Q7 = 533941.4630 KJ/hr
Q8 = 966.249374 KJ/hr
Q9 = 16320.251494 KJ/hr
Q10 = 115011.1491 KJ/hr
Qr = -287549.09508 KJ/hr

4.4.2 2nd Washing process Energy Balance

CaSO4 + 2H2O CaSO4.2H2O

ΔHro = -2,024.021 + (2* 286.025) + 1,435.097


ΔHro = -16.874 KJ/g.mol
ΔHro = -16,874 KJ/Kg.mol
ΔHr = ΔHro + ΔHProduct - ΔHReactant

1.923
ΔHH2O =32.243 (336.0329502 – 298.15) +
2
1.055
-3
*10 (336.0395022-298.152) +
3
*10-5(336.03295023-298.153)

3.596
76
- *10-9 (336.03295024-298.154)
4

ΔHH2O = 1,280.433889 KJ/Kg.mol


ΔHCaSO4 = 99.73 (30 – 25)
ΔHCaSO4 = 498.65 KJ/Kg.mol
ΔHCaSO4.2H2O = 186.149 ΔT
ΔHProduct - ΔHReactant = 186.149 ΔT - 498.65 – (2* 1,280.433889)
ΔHProduct - ΔHReactant = 186.149 ΔT - 3,059.517779
ΔHr = -16,874 + 186.149 ΔT - 3,059.517779
ΔHr = -19,933.51778 + 186.149 ΔT

300.922925
Qr = [-19,933.51778 + 186.149 ΔT]
172.18

Qr = -34838.26504+ 325.3368658ΔT
Q10 = 115011.1491 KJ/hr
ΔH11 = 99.73 (30 – 25)
ΔH11 = 498.65 KJ/Kg.mol

237.9349925
Q11 = * 498.65 = 871.5020127 KJ/hr
136.14

ΔH12 = ΔHGypsum = 186.149ΔT

300.922925
77
Q12 = * 186.149 ΔT
172.18

Q12 = 325.3368658 ΔT
Q13 = ΔHMixture * ni
𝑇
ΔHMixture = ∫𝑇𝑟𝑒𝑓 cpMixture dT

Cp13=cpMixture = 284.968122 – 0.847861952 ΔT+ 1.642023363


*10-3ΔT2 +2.237621333 *10-9ΔT3

0.847861952
ΔHMixture =284.968122 ΔT - ΔT2
2
1.642023363 2.237621333
+ *10 ΔT +
-3 3
*10-9 ΔT4
3 4

ΔHMixture = ΔH13 =284.968122 ΔT - 0.423930976 ΔT2


+ 5.47341121*10-4ΔT3 + 5.594053333 *10-10 ΔT4
Q13 = 81.53051923 [284.968122 ΔT - 0.423930976 ΔT2
+ 5.47341121*10-4 ΔT3 + 5.594053333 *10-10 ΔT4]
Q13 = 23,233.59895 ΔT - 34.56331259 ΔT2 + 0.044625005 ΔT3
+ 4.560860728 *10-8 ΔT4
Heat input + Heat generation = Heat out + Heat accumulation
0.0 S.S
Q10 + Q11- Qr = Q12 + Q13

563,676.1122 + 871.5020127 – (-34838.26504+ 325.3368658ΔT) =


78
325.3368658 ΔT + 23,233.59895 - 34.56331259 ΔT2
+ 0.044625005 ΔT3 +4.560860728 *10-8 ΔT4
576152.2803 = 23,789.07057 ΔT- 34.56331259 ΔT2
+ 0.044625005 ΔT3 +4.560860728 *10-8 ΔT4
This equation above is solved by trial and error until the right hand equals the
left hand.
T= 20.33466274 oC
Qr = -26595.96526 KJ/hr
Q12 = 8242.29977 KJ/hr
Q13 = 565705.45546 KJ/hr

5. Distillation Energy Balance


14

13 13
IN Out 80.1oC

79
63.335oC 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 Steam 13
IN 250oC Out

63.334 oC 192.1oC

Steam
210oC

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


n
Q13 (OUT H.EX.) = ∑ i=1 * ΔHi * ni
𝑇
ΔHi = ∫𝑇𝑟𝑒𝑓 cpi dT

ΔHBZ. = ΔHLiquid + λ + ΔHVapoure


𝑇𝐵.𝑃
ΔHLquid = ∫𝑇𝑟𝑒𝑓 cpi dT
4.743
80
ΔHLiquid = -33.917 (353.25-298.15) +
2
3.017
*10 (353.25 -298.15 ) –
-1 2 2
*10-4(353.253-298.153)
3
7.130
+ *10-8(353.254-298.154)
4

ΔHLiquid = 5,012.048424 KJ/Kg.mol


λ = 30,781 KJ/Kg.mol
𝑇
ΔHVapour = ∫𝑇𝐵.𝑃 cpi dT
39.064
ΔHVapoure = 8.314 [ -0.206 (465.25 – 353.25) +
2
13.301
* 10 * (465.25 –353.25 ) –
-3 2 2
* 10-6 (465.253 – 353.253)
3

ΔHVapoure = 12,607.37459 KJ/Kg.mol


ΔHBZ = 5,012.048424 + 30,781+ 12,607.37459 = 48400.423 KJ/Kg.mol

285.5129532
QBZ. = * 48400.423 = 176916.4986 KJ/hr
78.11
0.8907
ΔHN.B. = 295.3 (465.25-298.15) – (465.252-298.152)
2
1.705
+ *10-3(465.253-298.153) = 34,706.15308 KJ/Kg.mol
3
13888.88875
QN.B. = * 34,706.15308 = 3915440.655 KJ/hr
123.11
81
Q13 (OUT H.EX.) = 176916.4986 + 3915440.655 = 4092357.153 KJ/hr
Q13 (IN H.EX.) + QHeating = Q13 (OUT H.EX.)
QHeating = Q13 (OUT H.EX.) - Q13(IN H.EX.)
QHeating = 4092357.153 - 567,379.1321= 3524978.02 KJ/hr
QHeating = m. * ( hg2 – hg1)

3524978.02
.
m = = 1174992.673 Kg/hr
2801.5 – 2798.5

Distillation Energy Balance


Q13 (OUT H.EX.) + QReboiler = Q14 + Q15 + QCondencer
Material Balance on Condenser
L
R = Reflux ratio =
D

Assume:-
Ractual = 2.06
V=L+D
L = Ractual * D
L = 2.06 * 101.6548042
L = 209.4088966 Kg/hr

82
L = 2.68390582 Kg.mol/hr
V = 209.4088966 + 101.6548042
V = 311.0637008 Kg/hr
V = 3.985337189 Kg.mol/hr
QCondencer = V λBZ.
QCondencer = 3.985337189 * 30,781
QCondencer = 122,672.664 KJ/hr
Q14 = ΔHBZ. * ni
4.743
ΔHBZ. = -33.917 (353.25-298.15) +
2
3.017
*10 (353.25 -298.15 ) –
-1 2 2
*10-4(353.253-298.153)
3
7.130
+ *10-8(353.254-298.154)
4

ΔHBZ. = 5,012.048424 KJ/Kg.mol

145.2211532
Q14 = QBZ. = * 5,012.048424 = 9318.3389 KJ/hr
78.11
n
Q15 = ∑ i=1
* ΔHi * ni
𝑇
ΔHi =∫𝑇𝑟𝑒𝑓 cpi dT

ΔHBZ. = ΔHLiquid + λ + ΔHVapoure


𝑇𝐵.𝑃
ΔHLquid = ∫𝑇𝑟𝑒𝑓 cpi dT
4.743

83
ΔHLiquid = -33.917 (353.25-298.15) + *10-1(353.252-298.152)
2
3.017 7.130 -8
– *10-4(353.253-298.153) + *10 (353.254-298.154)
3 4

ΔHLiquid = 5,012.048424 KJ/Kg.mol


λ = 30,781 KJ/Kg.mol
𝑇
ΔHVapour = ∫𝑇𝐵.𝑃 cpi dT
39.064
ΔHVapoure = 8.314 [ -0.206 (474.02 – 353.25) +
2
13.301
* 10 (474.02 –353.25 ) –
-3 2 2
* 10-6 (474.023– 353.253)
3

ΔHVapoure = 13,716.10935 KJ/Kg.mol


ΔHBZ. = 5,012.048424 + 30,781+ 13,716.10935
= 49,509.15778 KJ/Kg.mol

285.5129532
QBZ. = * 49,509.15778 = 180969.22094 KJ/hr
78.11

0.8907
ΔHN.B. = 295.3 (474.02-298.15) – (474.022-298.152)
2
1.705
+ *10-3(474.023-298.153) = 36,925.461 KJ/Kg.mol
3
13888.88875
QN.B. = * 36,925.461 = 4165816.098 KJ/hr
123.11
84
Q15 = 180969.22094 + 4165816.098 = 4346785.318 KJ/hr
Q13 (OUT H.EX.) + QReboiler = Q14 + Q15 + QCondencer
QReboiler = Q14 + Q15 + QCondencer - Q13 (OUT H.EX.)
QReboiler = 9318.3389 + 4346785.318 +122,672.664 - 4092357.153
QReboiler = 386419.1679 KJ/hr

85
Table 4-1 all Streams of Energy Balances

Stream

13 13 14 17 17 18
1 2 3 4 5 6 7 8 9 10 11 12 out 15 16 ou
in in
t
N0.
[Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr] [Kg/hr]
Comp.

C6H6 - - - 48538.408 7898.52589 - 7898.52589 - - 12320.49879 - - 8676.50917 176916.4986 9318.3389 180969.22094 - - - -

HNO3 60848.01192 - 303559.8425 - - - - - - - - - - - - - - - - -

H2SO4 - 1247.279753 650121.1653 - 630420.5245 624116.3191 6304.205245 - - - - - - - - - - 1922695.069 1019496.3501 1020687.684

H2O 37370.11872 32.539963 199745.2613 - 294937.5183 291988.1431 2949.375183 - - 4505.2958 - - - - - - 14328058.92 631237.3210 19994.74738 20083.233

C6H5NO2 - - - - 516789.3567 - 516789.3567 - - 358398.00002 - - 991355.63149 3915440.655 - 4165816.098

Na2CO3 - - - - - - - 966.249374 - - - - - - - - - - - -

H2CO3 - - - - - - - - 8092.23304 - - - - - - - - - - -

Na2SO4 - - - - - - - - 8228.01847 - - - - - - - - - - -

CaSO4 - - - - - - - - - - 871.5020127 - - - - - - - - -

CaSO4.2H2O - - - - - - - - - - - 8242.29977 - - - - - - - -

total 98218.13064 1279.819716 1153426.2691 48538.408 1450045.925 916104.46 533941.4630 966.249374 16320.25151 185931.3593 871.5020127 8242.29977 567379.1321 4092357.153 9318.3389 4346785.318 14328058.92 2553932.39 17863.17435 1040770.911

Pressure atm 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

TemperatureoC 30 30 50 30 50 50 50 30 83.88295021 83.88295021 30 59.3346627 59.3346627 192.1 80.1 200.87 100 100 65.5 65.15

86
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References

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