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Production of Nitrobenzene
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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
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].
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].
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].
12
Figure 1-1 Reduction products of nitrobenzene [1, 2&14]
Na3AsO3 azoxybenzene
LiALH4 azoxybenzene
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]:
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].
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]:
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].
18
Main application areas or chemical Nitrobenzene consumption
manufacture (tones/year) in Western Europe
Aniline 380 000
m-Nitrobenzene sulfonic acid 5 000
Hydrazobenzene 1 000
Dinitrobenzene 4 000
Others (solvents, dyes) 4 000
Total 398 300
19
Chapter Two
Production Methods
of Nitrobenzene
20
Chapter Two
Production Methods of Nitrobenzene
2.1 General
21
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].
22
Nitrobenzene can be produced by either a batch or continuous
process [2].
Material Quantity, kg
Benzene 650
Sulfuric acid 720
23
Nitric acid 520
Water 110
Sodium carbonate 10
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].
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].
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].
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].
+ NO2+ + H+
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
Sulfuric acid
reconcentration
(Evaporator)
34
Chapter Three
Material Balance
35
Chapter Three
Material Balance
Main Reaction
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
5
3
Nitrator
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
38
Table 3-1 Material Balance on Nitrator
3 4 5
Component
[Kg/hr] [Kg/hr] [Kg/hr]
HNO3 7109.721139 - -
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
HNO3 - - -
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
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
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
44
Table 3-3 Material Balance on 1st Washing Unit
Component 7 8 9 10
HNO3 - - - -
H2SO4 170.6333073 - - -
Na2CO3 - 184.412016 - -
Na2SO4 - - 247.1294988 -
H2CO3 - - 107.91582408 -
14592.434959 14592.434959
45
3.4.2 2nd Washing process Material Balance
CaSO4
11
10 13
2nd Washing
12
CaSO4.2H2O
(Gypsum)
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
HNO3 - - - -
H2SO4 - - - -
H2O 62.9879325 - - -
CaSO4 - 237.9349925 - -
CaSO4.2H2O - - 300.922925 -
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
49
0.25 * 28438.88456
Stream 1 = = 11108.93928 Kg/hr
0.64
170.6333073
Stream 2 = = 174.11561969 Kg/hr
0.98
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
51
Table 3-5 Material Balance on Reconcentrator
6 16 17 18 2 1 3
52
3.6 Distillation Material Balance
14
13
Distillation
01
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
13 14 15
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.
HNO3 7109.721139 - - - - - - - - -
H2SO4 - - - - - - - - - -
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.
H2O 3999.21814 3.482312 4265.83268 - 6298.793251 6235.805319 62.9879325 - - 62.9879325 - - - - - 5972.67308 263.132234 266.614546
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
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
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
*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
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
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
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
12258726.6
n H2O = = 10354.265850 Kg.mol/hr
1183.930061
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
63
4086242.2
ncoil = = 3018.287115 Kg.mol/hr
1353.82819
6
mcoil = 54389.53381 Kg/hr flow rate of water in coil
7 6
Separator
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
6235.805319
QH2O = * 843.7765567 = 291988.1431 KJ/hr
18.02
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
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
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
Cooling
water
17 30oC 17
65.5 oC 100oC
50oC
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
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
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
3.482312
QH2O = * 168.3852983 = 32.539963 KJ/hr
18.02
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)]
72
ΔHdil. (mix.) = 11,864.53747 KJ/Kg.mol (5.104) [21].
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
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
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
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
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
300.922925
77
Q12 = * 186.149 ΔT
172.18
Q12 = 325.3368658 ΔT
Q13 = ΔHMixture * ni
𝑇
ΔHMixture = ∫𝑇𝑟𝑒𝑓 cpMixture dT
0.847861952
ΔHMixture =284.968122 ΔT - ΔT2
2
1.642023363 2.237621333
+ *10 ΔT +
-3 3
*10-9 ΔT4
3 4
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
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
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
145.2211532
Q14 = QBZ. = * 5,012.048424 = 9318.3389 KJ/hr
78.11
n
Q15 = ∑ i=1
* ΔHi * ni
𝑇
ΔHi =∫𝑇𝑟𝑒𝑓 cpi dT
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
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.
H2O 37370.11872 32.539963 199745.2613 - 294937.5183 291988.1431 2949.375183 - - 4505.2958 - - - - - - 14328058.92 631237.3210 19994.74738 20083.233
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
87
88
References
89
90
91