Professional Documents
Culture Documents
College of Engineering
Chemical Engineering Department
NITROBENZENE PRODUCTION
by
SARAH RASHEED Ghayeb
Jumada II
1430
June
2009
Abstract
List of Contents
Content
Page
Abstract
List of Content
II
List of Figures
VI
List of Tables
VII
Nomenclature
VIII
History
1.2
Specification of Nitrobenzene
1.3
Identity
1.4
Physical Properties
1.5
Chemical Properties
1.6
Uses
11
1.7
Nitrobenzene Derivative
12
General
14
2.2
Batch Process
16
2.3
17
2.4
Continuous Process
18
2.4.1
19
2.4.2
21
II
2.5
Non-Industrial Sources
21
2.6
Process Selection
23
2.7
23
General Information
27
3.2
28
3.3
30
3.4
30
3.4.1
32
3.4.2
32
3.5
35
3.6
38
42
4.2
46
4.3
48
4.4
52
4.4.1
52
4.4.2
54
4.5
57
III
Nitrator Design
64
5.2
Settler Design
77
5.3
82
5.4
Distillation Design
90
Introduction
104
6.2
Control of Nitrator
105
6.3
Settler Control
107
6.4
Vaporizer Control
108
6-5
109
6.6
110
Site Considerations
113
7.2
Site Layout
116
7.3
Plant Layout
118
7.4
Utilities
119
7.5
Environmental Consideration
120
7.6
Waste Management
120
7.8
122
IV
General
123
8.2
Effects on humans
124
125
8.4
126
8.5
Industrial safety
128
129
References
Appendixes
Appendix A: Physical Properties
A-1
B-1
List of Figures
Figure No.
Title
1-1
1-2
13
2-1
19
2-2
20
2-3
22
2-4
4-1
63
5-1
91
6-1
Nitrator Control
106
6-2
Settler control
107
6-3
Settler control
107
6-4
vaporizer control
108
6-5
109
6-6
111
6-7
Composition control
111
6-8
Composition control
112
7-1
118
VI
page
26
List of Tables
Table NO.
Title
1-1
1-2
1-3
1-4
1-5
11
3-1
29
3-2
31
3-3
33
3-4
35
3-5
38
3-6
39
3-7
40
3-8
41
4-1
62
2-1
VII
Page
15
Nomenclature
Symbol
Definition
Aa
Active Area
m2
Aap
m2
Ac
m2
Ad
Downcomer Area
m2
Ah
Hole Area
m2
Ai
m2
Am
m2
An
Net Area
m2
Ao
m2
Ap
m2
As
m2
Blade Width
Baffle Width
Corrosion Allowance
Co
Orifice Coefficient
cp
Specific heat
Diameter
DA
Agitator Diameter
Db
Bundle Diameter
Deff
mm
KJ/Kg.mol.K
VIII
Unit
de
Equivalent Diameter
dh
Diameter of Hole
di
dm
Diameter of Manholes
mm
do
dp
Droplet Diameter
FC
Flow Controller
FLV
Ft
FW
Wind Load
mm
N/m
N/mm2
Gt
Kg/m2.s
Gs
Kg/m2.s
HA
Height of agitator
HL
hap
mm
hb
Downcomer back-up
mm
hbc
mm
hd
mm Liquid
hdc
mm Liquid
hi
W/m2.oC
hid
W/m2.oC
ho
W/m2.oC
IX
how
hr
Residence Head
hT
ht
mm
hv
W/m2.oC
hw
Weir Height
Joined Efficiency
jf
Friction Factor
Kf
Thermal Conductivity
LC
Level Control
Lc
m3/s
Lm
Kg/s
Ln
Kg/s
LW
Weir Length
lB
Baffle spacing
mm
lp
Hole Pitch
mm
Ms
N.m
Mass flowrate
Kg/s
Agitator Speed
rps
Np
Power Number
Np
Number of passes
Nt
Number of Tubes
Pressure Design
N/mm2
mm Liquid
mm
W/m.oC
-
W/m2.oC
hod
PA
Shaft Power
Pch
Sugdens Parachor
Pt
Pitch
mm
Pw
N/m2
Blade Length
TC
Temperature Controller
TM
Measuring Element
tr
Residence time
Uo
uc
m/s
ud
m/s
uf
Flooding Velocity
m/s
uh
m/s
m/s
ut
m/s
uv
m/s
Volume of Nitrator
m3
Vm
Kg/s
Vn
Kg/s
umin
XI
W/m2.oC
Greek Notation
Viscosity
Pa.s
Pa.s
Pa.s
Pa.s
Residence Time
min
m3/hr
Surface Tension
mJ/m2
Density
Kg/ m3
Kg/ m3
Kg/ m3
Latent Heat
KJ/Kg.mol
TLm
Tm
Pt
pa
Ps
pa
XII
Dimensionless Groups
Nu = h d /K
Nusselt Number
Pr = cp / K
Prandtle Number
Re = u d /
Reynolds Number
XIII
Chapter One
Introduction
Chapter One
Introduction
1.1 History
The earliest aromatic nitro compounds were obtained by MITSCHERLISH
in 1834 by treating hydrocarbons derived from coal tar with fuming acid [1, 2,
&3]. By 1835 LAURENT was working on the nitration of naphthalene, the most
readily available pure aromatic hydrocarbon at that time. DALE reported on
mixed nitro compounds derived from crude benzene at the 1838 annual meeting
of the British Association for the Advancement of Science. Not until 1845,
however, did HOFMANN and MUSPRATT report their systematic work on the
nitration of benzene to give mono- and dinitrobenzenes by using a mixture of
nitric and sulfuric acids [1].
The first small-scale production of nitrobenzene was carefully distilled to
give a yellow liquid with a smell of bitter almonds for sale to soap and perfume
manufacturers as essence of mirbane.[1]
The number of naturally occurring nitro aromatic compounds is small; the
first to be recognized was chloramphenicol, an important compound extracted
from cultures of a soil mold Steptomyces venezuelas and identified in 1949 [1].
This discovery stimulated investigations into the role of nitro group in
pharmacological activity, following the earlier (1943) discvery of the
antibacterial activity of nitrofuran derivatives. Many synthetic pharmaceuticals
and agrochemicals contain nitro aromatic groups, although the function of the
nitro group is often obscure [1].
The choice of nitro compounds covered here is influenced strongly by
their commercial application of compounds in the 1981 European core
1
specifications
have
been
developed
for
technical-grade
Appearance
Water content
Specific gravity (15.5/15.5oC)
Dinitrobenzene content
Low-boiling impurities (benzene + aliphatic
hydrocarbons)
Sulfur- containing impurities (CS2 +
nitrothiophene +elementary sulfur)
0.25% (maximum)
2.5 ppm (maximum, as sulfur)
0.5oC (maximum)
Crystallization point
5.5oC (minimum)
1.208 1.211
Aniline content
0.0075% (maximum)
1.3Identity [5]
Common name:
nitrobenzene
Chemical formula:
C6H5NO2
Chemical structure:
123.11
CAS name:
nitrobenzene
IUPAC name:
nitrobenzene
98-95-3
NIOSH RTECS
DA6475000
Synonyms:
5.58
210.9
1.900599219*10-3
0.14473
43.35
1.473
1.418
94.1
331
3.074
88
482
1.8
20
38
47
1900
2090
Freely soluble in ethanol, acetone, ether
1198.484586
The reduction of the nitro group to yield aniline is the most commercially
important reaction of the nitrobenzene. Usually the reaction is carried out by the
catalytic hydrogenation of nitrobenzene, either in the gas phase or in solution, or by
using iron borings and dilute hydrochloric acid (the Bechamp process). Depending on
the conditions, the reduction of nitrobenzene can lead to variety of products. The
series of reduction products is shown in figure 1-1 Nitrosobenzen, Nphenylhydroxylamine, and aniline are primary reduction products. Azoxybenzene is
formed by the condensation of nitrosobenzene and N-phenylhdroxylamine in alkaline
solutions,
and
azoxybenzene
can
be
reduced
to
form
azobenzene
and
Product
Fe, Zn or Sn + HCL
aniline
aniline
Zn + NaOH
hydrazobenzene, azobenzene
Zn + H2O
N-phenylhydroxylamine
Na3AsO3
azoxybenzene
LiALH4
azoxybenzene
Na2S2O3 + Na3PO4
The process used most commonly for the manufacture of aniline is the catalytic
hydrogenation of nitrobenzene which has largely replaced the older Bechamp
process. In this latter process nitrobenzene reacts with iron and water in the presence
of small amounts of hydrochloric acid to form aniline, iron oxide, and hydrogen. The
chemistry of the two nitrobenzene-based aniline processes is described through the
following stoichiometric equations [4]:
C6H5NO2 + 3H2
CU/SiO2
C6H5NO2 +3 Fe + 4 H2O
C6H5NH2 + 2H2O
HCL/Fecl
1.1
1.2
Nitration, which is introduction of nitro group or the NO2 group into the
molecule, is achieved by bringing mixed acid and the compound to be nitrated into
intimate contact under vigorous agitation. Care must be taken to remove the heat of
nitrating. The acid left on completion of the nitration reaction is called spent acid. In
benzene nitration of the reaction is heterogeneous; benzene and nitrobenzene have
7
very low solubility in the mixed and spent acids. The overall stoichiometry for the
reaction of benzene and nitric acid to form nitrobenzene and water is
NO2
+ HNO3
+ H2O
Ho = -34.825 Kcal/g.mol
1.3
H2SO4
Sulfuric acid is a catalyst in the nitration reaction and does not enter directly into the
stoichiometry of Equation 1.3. The role of sulfuric acid is two fold: it acts as a
dehydrating agent by absorbing the water formed in the nitration reaction and it is
responsible for the dissociation of nitric acid and through which the reactive species,
the nitronium ion, is formed. The positively charged nitronium ion, NO2, reacts with
the aromatic compound by electrophilic attack to form a positively charged complex.
This complex breaks down fast through reaction of the proton with an anion such as
HSO4. The reaction mechanism is described through the following stoichiometric
equations[4]:
Equations 1.4 to 1.7 add up to Equation 1.3. The rate-controlling reaction is that
of Equation 1.5. The rate of nitration reaction is a function of many variables, but
most importantly it is a function of sulfuric acid strength, which is capable of
changing the rate by several orders of magnitude. The steep increase of the nitration
rate with the sulfuric acid strength is generally though to be due to the parallel
increase in the concentration of the nitronium ion in the mixed acid. It is the
nitronium ion which is the reactive species in the rate-controlling Equation 1.5 [4].
The nitronium ion is also present in strong nitric acid, and benzene can be nitrated
using nitric acid alone. The incentive for this process is that it would eliminate the
sometimes costly disposal or reconcentration of the spent sulfuric acid. No
commercial plant appears to be operating using a nitric acid only process. Of concern
would be the fact that mixtures of nitric acid and benzene or nitrobenzene can be
detonated [4].
The main by-products formed in commercial nitrobenzene plants are
dinitrobenzene (C6H4 (NO2)2), dinitrophenol (C6H3OH (NO2)2), and picric acid
(C6H2OH (NO2)2). The fraction of dinitrobenzene obtained is usually well below 100
ppm, but can reach a few hundred ppm if the nitration is accidentally operated with
excess nitric acid. The introduction of nitro groups into the benzene ring lowers the
electron density, thereby impeding electrophilic attack. Substantial rates of
conversion to dinitrobenzene are possible only at high spent acid strengths.
Furthermore, commercial nitrobenzene plants usually operate with excess benzene
which will consume most of the nitric acid well before significant quantities of
dinitrobenzene can be formed [4].
A possible but not proven mechanism is the one where the nitronium ion becomes
attached to the benzene ring through one of its oxygen atoms instead of the nitrogen
9
atom, the product being phenol and the nitrosyl ion, NO+. The phenol then reacts with
nitric acid, possibly through a complex between the nitrosyl ion and the phenol, to
form nitrophenol and nitrous acid, HNO2. The one-to-one molar ratio between
nitrophenol and nitrous acid is confirmed through experiment. Nitrophenol is further
nitrated to dinitrophenol and picric acid. The rates for this di- and trinitration are
relatively fast; there is usually only a trace of mononitrophenol found in the crude
nitrobenzene. The stoichiometry of the reactions is shown in the following equations
[2]:
Other by-products are formed from trace impurities in the benzene feedstock or in
the recycle sulfuric acid. There is also the possibility that very small amounts of
10
benzene and nitrobenzene undergo other reactions. Most of these by-products are
removed in the washing stage of the process together with the nitrophenols. The yield
loss caused by these side reactions is negligible. Of more concern is the fast that
some of these trace impurities from surface-active compounds which can
oceasionally lead to the formation of stable emulsions in the washing section [4].
1.6 Uses
Nitrobenzene is used primarily in the production of aniline, but it is also used as
a solvent and as an ingredient in metal polishes and soaps. In the USA, around 98%
of nitrobenzene produced is converted into aniline; the major use of aniline is in the
manufacture of polyurethanes. Nitrobenzene is also used as a solvent in petroleum
refining, as a solvent in the manufacture of cellulose ethers and cellulose acetate
(around 1.5%), in Friedel-Crafts reactions to hold the catalyst in solution (it dissolves
anhydrous aluminium chloride as a result of the formation of a complex) and in the
manufacture of dinitrobenzenes and dichloroanilines (around 0.5%). It is also used in
the synthesis of other organic compounds, including acetaminophen [3].
According to the BUA (1994), nitrobenzene is used in Western Europe for the
purposes shown in Table 5-1 [5].
Nitrobenzene
consumption
(tones/year) in Western Europe
380 000
5 000
4 300
1 000
11
Dinitrobenzene
Others (solvents, dyes)
Total
4 000
4 000
398 300
Dunlap (1981) reported that most of the production of aniline and other
substituted nitrobenzenes from nitrobenzene go into the manufacture of various
plastic monomers and polymers (50%) and rubber chemicals (27%), with a
smaller proportion into the synthesis of hydroquinones (5%), dyes and
intermediates (6%), drugs (3%), pesticides and other specialty items (9%) [5].
Past minor uses of nitrobenzene included use as a flavouring agent, as a
solvent in marking inks and in metal, furniture, floor and shoe polishes, as a
perfume, including in perfumed soaps, as a dye intermediate, as a deodorant and
disinfectant, in leather dressing, for refining lubricating oils and as a flavouring
agent. It is not known whether it may still be used in some countries as a solvent
in some consumer products (e.g., shoe polish) [5].
The 22,680 metric ton of nitrobenzene left was used to produce a variety
of other products, such as para-aminophenole [123-30-8] (PAP) and nigrosine
dyes. The U.S. producers of PAP are Mallinckrodt, Inc., Rho^ne-Poulene, and
Hoechst Celanese, with combined production capacities > 35,000 metric tons (as
of may 1995). Mallinckrodt is the largest producer, with over 50% of capacity.
PAP primarily is used as an intermediate for acetaminophen [103-90-2] [2].
2,5-dichloronitobenzene
2,5-dimethoxynitrobenzene
Dinitrobenzene
O-nitrobenzene
12
13
Chapter Two
Production Methods of
Nitrobenzene
Chapter Two
Production Methods of Nitrobenzene
2.1General
World production of nitrobenzene in 1994 was estimated at 2 133 800
tones; about one-third was produced in the USA [5].
In the USA, there has been a gradual increase in nitrobenzene production,
with the following production/demand amounts, in thousands of tones, reported:
73 (1960), 249 (1970), 277 (1980), 435 (1986), 533 (1990) and 740 (1994).
Based on increased production capacity and increased production of aniline (the
major end-product of nitrobenzene), it is likely that nitrobenzene production
volume will continue to increase [5].
Production of nitrobenzene in Japan was thought to be around 70 000
tones in 1980 and 135 000 tones in 1990. Patil & Shinde (1989) reported that
production of nitrobenzene in India was around 22 000 tones per year [5].
Nitrobenzene is produced at two sites in the United Kingdom with a total
capacity of 167 000 tones per year. It has been estimated that a maximum of
115 400 tones of aniline was produced in the United Kingdom in 1990. If it is
assumed that 98% of the nitrobenzene in the United Kingdom is used to make
aniline, then the total amount of nitrobenzene used in the United Kingdom would
be around 155 600 tones per year [5].
14
Capacity (tones)
200 000
240 000
18 000
70 000
5 000
145 000
434 000
97 000
2.2Batch process
With a typical batch process, the reactor is charged with benzene, then the
nitrating acid (56-60 wt % H2SO4, 27-32 wt% HNO3, and 8-17 wt % H2O) is
added slowly below the surface of benzene. The temperature can be raised to
about 90oC toward the end of reaction to promote completion of reaction. The
reaction mixture is fed into a separator where the spent acid settles to the bottom
and is drawn off to be refortified. The crude nitrobenzene is drawn from the top
of the separator and washed in several steps with a dilute base, such as sodium
carbonate, sodium hydroxide, magnesium hydroxide, etc, and then water.
Depending upon the desired purity of the nitrobenzene, the product can be
distilled. Usually a slight excess of benzene is used to ensure that little or no
nitric acid remains in the spent acid. The batch reaction time generally is 2-4
hours, and typical yields are 95-98 wt % based on benzene charged [2].
Based on yield of 1000 kg of nitrobenzene, material requirements for the process
are as follows [3]
Material
Quantity, kg
Benzene
650
Sulfuric acid
720
Nitric acid
520
Water
110
Sodium carbonate
10
The separation of the nitrobenzene is accomplished in large conicalbottomed lead tanks, each capable of holding one or more charges. The nitrator
charges are permitted to settle here for 4-12 hr, when the spent acid is drawn off
from the bottom of the lead tanks and delivered to the spent-acid tanks for
additional settling or for treatment with benzene next to be nitrated, in order to
16
17
18
20
measured in the five hazardous waste landfills were 0.05, 0.65, 2.7, 1.0 and 6.6
g/m3. The maximum level recorded was 51.8 g/m3. At the sanitary landfill,
nitrobenzene was below the detection limit (0.25 g/m3) at all locations [5].
Nitrobenzene has been shown to be formed from the atmospheric reactions
of benzene in the presence of nitrogen oxides. The reaction is thought to be
initiated by hydroxyl radicals. Nitrobenzene, once formed, reacts quite slowly in
the atmosphere; this could therefore provide a major source of atmospheric
nitrobenzene, although it has not been possible to quantify this source. Atkinson
et al. (1987) reported that aniline is slowly oxidized to nitrobenzene by ozone.
These reactions are summarized in Figure 2-3 [5].
two functions: it reacts with nitric acid to form the nitronium ion, and it absorbs
the water formed during the reaction, which shifts the equilibrium to the
formation of nitrobenzene [4, 8, 13, &14]
24
nitration vessel [16]. Nitration vessels are usually made of stainless steel,
although cast iron stands up well against mixed acids [16&18].
It then enters a separator tank from which a portion of spent acid is
removed from bottom, and the crude nitrobenzene is drawn off the top of the
separator [18].
The removed of spent acid (sulfuric acid & water) is enter to evaporator in
order to concentrating the sulfuric acid with fresh sulfuric acid (98 wt. % [4])
and then with fresh nitric acid (64 wt. % [4]) to the nitrator [12].
The crude nitrobenzene (nitrobenzene, benzene, sulfuric acid &water) is
drawn from the top of the separator and is wash with the sodium carbonate in
order to remove sulfuric acid from crude nitrobenzene, fellowing by final
washing with calcium sulfate (anhydrite) to remove the water from react the
calcium sulfate with water to formed calcium sulfate (Gypsum) [2,12,&14]. The
product is topped in still to remove benzene and give pure product (96-99 wt. %)
[1,2 & 3].
25
Benzene
Nitrating acid
Nitric
acid
64wt. %
nitrator
Na2CO3
CaSO4
Crude
nitrobenzene
Acid separation
1st washing
2nd washing
Distillation
NaSO4
H2CO3
Gypsum
Nitrobenzene
H2O
Spent acid
26
Benzene
Chapter Three
Material Balance
Chapter Three
Material Balance
Note: Data necessary in appendix A.
= 9722.222222 Kg/day
= 78.9718188 Kg.mol/hr
27
5
Nitrator
= 19907.21938 Kg/hr
= 2986.082907 Kg/hr
Component
[Kg/hr]
[Kg/hr]
5
[Kg/hr]
C6H6
6368.348857
199.8590691
HNO3
4976.804845
H2SO4
11944.33163
11944.33163
H2O
2986.082907
4409.155317
C6H5NO2
9722.222222
19907.21938
6368.348857
26275.56824
Total
26275.56824
29
7
5
Aid Separation
1 wt % of total acid solution (sulfuric acid + water) will goes with crude
nitrobenzene [16].
Stream 5 Acid solution input to separator = 4409.155317 + 11944.33163
= 16353.48695 kg/hr
Stream 7 (Crude Nitrobenzene) = excess BZ.+ N.B. + 1 wt. % of acid solution
Excess BZ. = 199.8590691 Kg/hr
N.B. = 9722.222222 kg/hr
Wt. of acid solution in stream 7 = 0.01 * 16353.48695 = 163.5348695 Kg/hr
* 100 = 73.03843924 %
30
[Kg/hr]
[Kg/hr]
C6H6
199.8590691
199.8590691
HNO3
H2SO4
11944.33163
11824.88831
119.4433163
H2O
4409.155317
4365.063767
44.0915532
C6H5NO2
9722.222222
9722.222222
16189.95208
Total
26275.56824
[Kg/hr]
10085.61616
26275.56824
31
10
1st Washing
Na2CO3 + H2SO4
Na2SO4 + H2CO3
From stoichiometry
Mole of Na2CO3 input in stream 8 = mole of sulfuric acid in stream 7
Mole of sulfuric acid in stream 7 =
= 1.217815215 Kg.mol/hr
32
10
7
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
C6H6
199.8590691
199.8590691
HNO3
H2SO4
119.4433163
H2O
44.0915532
44.0915532
C6H5NO2
9722.222222
9722.222222
Na2CO3
129.0884128
Na2SO4
172.9906513
H2CO3
75.4510778
10085.61616
129.0884128
248.5317291
9966.172836
Total
10214.70457
10214.70457
33
CaSO4
11
10
13
2nd Washing
12
CaSO4.2H2O
(Gypsum)
CaSO4 + 2H2O
CaSO4.2H2O
From stoichiometry
Mole of CaSO4 = 1.223406027 Kg.mol/hr
Wt. of CaSO4 = 1.223406027 * 136.14 = 166.5544965 Kg/hr = stream 11
Mole of CaSO4.2H2O = 1.223406027 Kg.mol/hr
Wt. of CaSO4.2H2O = 1.223406027 * 172.18
Wt. of CaSO4.2H2O = 210.6460497 Kg/hr = stream 12
34
10
12
13
Component
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
C6H6
199.8590691
199.8590691
HNO3
H2SO4
H2O
44.0915532
C6H5NO2
9722.222222
9722.222222
CaSO4
166.5544965
CaSO4.2H2O
210.6460497
Total
10132.72733
9922.0812
10132.72734
1
2 mixing point
nd
18
1st mixing point
H2O
6
16
2
Sulfuric acid
reconcentration
1
35
= 7776.25757 Kg/hr
= 121.880935 Kg/hr
37
16
17
18
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
HNO3
H2SO4
11824.88831
3
[Kg/hr]
4976.804845 4976.804845
-
11944.33159
H2O
4365.063767 4180.871204
186.6301817
2.4376187
2799.452725 2986.082907
Total
121.880935
7776.25757
184.192563
14
13
Distillation
15
19907.21934
Stream 15 (bottom) =
Component
C6H6
C6H5NO2
Total
13
14
15
[Kg/hr]
[Kg/hr]
[Kg/hr]
101.6548042
98.20426486
9722.222222
101.6548042
9820.426987
199.8590691
9722.222222
9922.081291
9922.081291
39
Comp.
No.
[Kg/hr]
[Kg/hr]
[Kg/hr]
Out (Kg/hr)
8
[Kg/hr]
11
[Kg/hr]
[Kg/hr]
12
[Kg/hr]
16
14
15
[Kg/hr]
[Kg/hr]
[Kg/hr]
6368.348857
101.6548042 98.20426486
C6H6
4976.804845
HNO3
119.4433163
4180.871204
H2SO4
2799.452725
2.376187
H 2O
C6H5NO2
9722.222222
129.0884128
Na2CO3
75.4510778
H2CO3
172.9906513
Na2SO4
166.5544965
CaSO4
210.6460497
CaSO4.2H2O
7776.25757
Total
121.880935
6368.348857
129.0884128
166.5544965
14562.13027
210.6460497
4180.871204
14562.13027
40
248.5317291
101.6548042
9820.426987
Stream
NO.
COMP.
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
14
13
12
11
[Kg/hr]
15
17
16
[Kg/hr]
[Kg/hr]
[Kg/hr]
[Kg/hr]
18
[Kg/hr]
[Kg/hr]
C6H6
6368.348857
199.8590691
199.8590691
199.8590691
199.8590691
101.6548042
98.20426486
HNO3
4976.804845
4976.804845
H2SO4
11944.33163
11944.33163
11824.88831
119.4433163
11824.88831
11944.33163
H2O
2799.452725
119.4433163
2986.082907
4409.155317
4365.063767
44.0915532
44.0915532
4180.871204
184.192563
186.6301817
C6H5NO2
2.4376187
9722.222222
9722.222222
9722.222222
9722.222222
9722.222222
Na2CO3
129.0884128
H2CO3
75.4510778
Na2SO4
172.9906513
CaSO4
166.5544965
CaSO4.2H2O
210.6460497
Total
7776.25757
121.880935
16189.95208
10085.61616
129.0884128
248.5317291
9966.172836
166.5544965
210.6460497
9722.0812
101.6548042
9820.426987
4180.871204
12009.08088
12130.96181
19907.21938
6368.348857
26275.56824
41
10
Chapter Four
Energy Balance
Chapter Four
Energy Balance
H.W
C.w
70oC
30oC
H.W
60oC
C.W
30oC
H2SO4
C6H5NO2 + H2O
Hr = -146948.0527 KJ/Kg.mol
Qr =
Q3 =
* Hi * ni
Hi =
cpi dT
(323.152 298.152) +
QHNO3 =
*10-3(323.152-298.152) +
*10-5
*10-9(323.154-298.154)
QH2O =
HH2SO4 = 139.1(50-25) +
QH2SO4 =
*10-1(303.152-298.152)
* Hi * ni
Hi =
cpi dT
*10-1(323.152-298.152)
*10-8(323.154-298.154)
43
-4
Q5 =
*10
HH2SO4 = 139.1(50-25) +
QH2SO4 =
*10-5
*10-9(323.154-298.154)
*10-3
*10-5
*10-9 (338.154-303.154)
= 7,209.391374 Kg.mol/hr
*10-3 (343.152-303.152) +
*10-9 (343.154-303.154)
= 2,109.142088 Kg.mol/hr
45
*10-5
Separator
5
* Hi * ni
Hi =
cpi dT
* (502-252) = 3623.65625 KJ/Kg.mol
HH2SO4 = 139.1(50-25) +
QH2SO4 =
*10-9(323.154-298.154)
46
*10-5
QH2O =
* Hi * ni
Hi =
cpi dT
*10-1(323.152-298.152)
*10-4
*10-8(323.154-298.154)
HH2SO4 = 139.1(50-25) +
QH2SO4 =
*10-5
*10-9(323.154-298.154)
(323.152-298.152) +
*10-3
*
16
3
1
HNO3
64wt. %
18
H2SO4
98 wt.%
250oC
17 Out
Steam 250oC
3973000 pa
17 In
Q6 = 641273.13 KJ/hr
H16 = 32.243 (373.15 298.15) +
(373.153-298.153)
*10-3(323.152-298.152) +
*10-9(373.154-298.154) + 40683
Q17 =
* Hi * ni
Hi =
cpi dT
48
*10-5
HH2SO4 = 139.1(100-25) +
QH2SO4 =
*10-9(373.154-298.154) + 40683
mSteam =
= 6,512.131986 Kg/hr
17
Cooling water
30oC
17
100oC
65.5 oC
50oC
49
*10-5
HH2SO4 = 139.1(65.5-25) +
QH2SO4 =
(338.653-298.153)
*10-9(338.654-298.154)
*10-9(323.154-303.154)
= 1,569.621871 KJ/hr
*10-
Q2 =
* Hi * ni
Hi =
cpi dT
* (302-252) = 716.93625 KJ/Kg.mol
HH2SO4 = 139.1(30-25) +
* 716.93625
QH2SO4 =
= 873.0958735 KJ/hr
*10-3(303.152-298.152) +
(303.153-298.153)
*10-
*10-9(303.154-298.154)
* 168.3852983
= 22.77797736 KJ/hr
*139.1(T-25) +
Q18 =[
32.243 (T 298.15) +
* (T2-252)] +[
*10-3(T2-298.152) +
*10-9(T4-298.154) ]
Find T18 by trial & error
T18 = 65.15oC
Note
Heat of mixing of HNO3 not takes under consideration.
Hdil.(mix.) = 11,864.53747 KJ/Kg.mol (5.104) [21].
51
*10-5 (T3-298.153)
Na2SO4 + H2CO3
HH2CO3 = 126.1128611 T
HNa2SO4 = 128.229 T
HProduct - HReactant = 126.1128611 T + 128.229 T - 3,623.65625 - 555.4
HProduct - HReactant = 254.3418611 T 4,179.05625
Hr = -170,485 + 254.3418611 T 4,179.05625
Hr = -174,664.0563 + 254.3418611 T
Qr =
[-174,664.0563 + 254.3418611 T]
Q9 =
* Hi * ni
Hi =
cpi dT
HNa2SO4 = 128.229 T
HH2CO3 = 126.1128611 T
Q9 = [
* 128.229 T] + [
* 126.1128611 T]
Q9 = 156.1592272 T + 153.5821611T
Q9 = 309.7413883 T
Q10 = HMixture * ni
HMixture =
cpMixture dT
*10-3
*10-9T4
CaSO4 + 2H2O
CaSO4.2H2O
*10-5(336.03295023-298.153) -
*10-9 (336.03295024-298.154)
HH2O = 1,280.433889 KJ/Kg.mol
HCaSO4 = 99.73 (30 25)
HCaSO4 = 498.65 KJ/Kg.mol
HCaSO4.2H2O = 186.149 T
HProduct - HReactant = 186.149 T - 498.65 (2* 1,280.433889)
HProduct - HReactant = 186.149 T - 3,059.517779
Hr = -16,874 + 186.149 T - 3,059.517779
Hr = -19,933.51778 + 186.149 T
Qr =
[-19,933.51778 + 186.149 T]
Qr = -24,386.78579 + 227.7358085T
Q10 = 563,676.1122 KJ/hr
H11 = 99.73 (30 25)
H11 = 498.65 KJ/Kg.mol
Q11 =
* 186.149 T
Q12 = 227.7358085 T
55
Q13 = HMixture * ni
HMixture =
cpMixture dT
HMixture =284.968122 T -
*10-3 T3 +
*10-9 T4
HMixture = H13 =284.968122 T - 0.423930976 T2 + 5.47341121*10-4
T3 + 5.594053333 *10-10 T4
Q13 = 81.53051923 [284.968122 T - 0.423930976 T2 + 5.47341121*10-4
T3 + 5.594053333 *10-10 T4]
Q13 = 23,233.59895 - 34.56331259T2 + 0.044625005 T3 + 4.560860728 *10-8
T4
Heat input + Heat generation = Heat out + Heat accumulation
0.0 S.S
Q10 + Q11- Qr = Q12 + Q13
563,676.1122 + 610.0514153 (-24,386.78579 + 227.7358085T) =
227.7358085 T + 23,233.59895 - 34.56331259T2 + 0.044625005 T3 +
4.560860728 *10-8 T4
588,672.9494 = 23,789.07057 T- 34.56331259T2 + 0.044625005 T3 +
4.560860728 *10-8 T4
This equation above is solved by trial and error until the right hand equals the
left hand.
T= 63.33466274 oC
Qr -15,656.61038 KJ/hr
Q12 = 10,646.90855 KJ/hr
56
14
R
13 IN
63.335oC
80.1oC
13 Out
192.1oC
15
200.87oC
From calculation of bubble point at feed finds T13 (OUT H.EX.) = 192.1oC, & find T=
200.87oC at bottom section.
13 In
63.334 oC
Steam
250oC
Steam
210oC
57
13 Out
192.1oC
* Hi * ni
cpi dT
cpi dT
*10-1(353.252-298.152)
*10-8(353.254-298.154)
cpi dT
* 10-3 * (465.252
(465.252-298.152) +
*10-3
m=
= 765,756.968 Kg/hr
= poBZ./ PoN.B
=
= 19.54121672
Rm =
19.54121672 *
Rm = 1.1718560223
Ractual = 1.2 Rm
Ractual = 2.062272268
V=L+D
L = Ractual * D
59
L = 2.062272268 * 101.6548042
L = 209.6398836 Kg/hr
L = 2.68390582 Kg.mol/hr
V = 209.6398836 + 101.6548042
V = 311.2946878 Kg/hr
V = 3.985337189 Kg.mol/hr
QCondencer = V BZ.
QCondencer = 3.985337189 * 30,781
QCondencer = 122,672.664 KJ/hr
Q14 = HBZ. * ni
HBZ. = -33.917 (353.25-298.15) +
*10-4(353.253-298.153) +
*10-1(353.252-298.152)
*10-8(353.254-298.154)
Q15 =
* Hi * ni
Hi =
cpi dT
cpi dT
*10-1(353.252-298.152)
60
*10-4(353.253-298.153) +
*10-8(353.254-298.154)
cpi dT
* 10-3 * (474.022
(474.022-298.152) +
*10-3
61
Stream
NO.
10
12
11
13
IN
17
out
14
15
17
IN
16
17
OUT
18
COMP.
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr] [KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[Kg/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
[KJ/hr]
C6H6
33976.886
5528.96818
8567.670381
8676.50917
123841.5502
6522.83704
62245.68484
HNO3
43435.94798
216846.4298
H2SO4
873.0958735
441294.3716
441294.3716
436881.4277
4412.943716
713647.4704
714329.4225
H2O
26159.21003
22.77797736
139821.6844
206456.2648
204391.7023
2064.562649
3132.981073
10029641.36
441866.1228
13996.32311
14055.2733
C6H5NO2
361752.5534
361752.5534
551975.5477
558702.6315
2740808.486
2916071.298
Na2CO3
676.3745704
H2CO3
5915.772227
Na2SO4
5818.145361
CaSO4
610.0514153
CaSO4.2H2O
10646.90855
Total
69595.15801
895.8738509
797962.4858
33976.886
1015032.158
641273.13
373759.0279
676.3745704
11733.91759
563676.1992
610.0514153
10646.90855
567379.1321
2864650.036
6522.83704
2978316.983
10029641.36
1787752.684
727643.7935
728384.6957
Pressure atm
Temperature
o
C
30
30
50
30
50
50
50
30
62.88295021
62.88295021
30
63.33466274
63.33466274
192.1
80.1
200.87
100
100
65.5
65.15
62
14
Feed
Benzene
8
4
7
3
Washing Tank
nd
1
13
13
10
Heater
9
1
18
15
Settler
Product N.B
10
Nitrator
Distillation Column
11
2
Washing Tank
st
2
13
12
17
17
Vaporizer
Cooling
Production of Nitrobenzene
63
Figure
4-1 Process Flow Diagram
Chapter Five
Equipment Design
Chapter Five
Equipment Design
Note: Data necessary in appendix A.
o = stream 3 + stream 4
o = [
o = 20.37924292 m3/hr
V = * o
V = 0.166666666 * 20.37924292
64
0.218
2.181
0.7
0.73
2.181
66
Assume the agitator rotation per minute (N) = 100 rpm =1.67 rps.
Re =
Re = 8.074454885 * 104 [is very suitable]
NP = 5
PA = 5 * 1173.870615 * (1.67)3 * (0.727023659)5
PA = 5,519.239048 watt = 5.519239048 Kwatt
= 8.72428391
de =
= 133.333mm
length of channel = 9 *
* 2.181070978 = 61.66832905 m
= 47.5oC as fellows
[32]:
Cp= 4.174 KJ/Kg.oC, = 989.25 Kg/m3, = 5.755 * 10-4, pr = 3.74 &
K = 0.64225.
u=
u = 1.823958001m/s
Nu = 0.023 Re0.8 Pro.33 [
]0.14
Re =
= 62,867.15905
68
Re = 4.180355498 * 105
Nu = 0.023 * (418,035.5498)0.8 * (3.74)0.33
Nu = 1,116.21033
Nu =
= 5,376.659075 W/m2.oC
hj =
p = 8 jf (
)(
]*
= 0.072702365 m
Not found pipe diameter 72.7mm in standerd, so take outside diameter standard
steel pipe as 76.1mm, wall thickness as 3.65mm [34]
Inside diameter = di = do + 2Lw
69
]a [
]b [
]c
C,a,b,c are constants according to type of agitator and surface type (coil or
jacket)
C = 1.1, a = 0.62, b = 0.33, c = 0.14 [23]
Neglect the viscosity correction term.
= 1.1
] 0.62
[
]
[
hv = 4,269.214368 W /m2.oC
Tube side
hi = 4200 (1.35 + 0.02 t) ut0.8 / di0.2
t=
= 50oC
70
A=
d i2
A=
* (68.8)2
A = 3717.635083 mm2
u=
u = 2.869804254 m / s
hi = 4200 (1.35 + 0.02 (50)) (2.869804254)0.8 / (68.8)0.2
hi = 9,841.95296 W / m2. oC
=
= 7.705482183 * 10-4
Uo = 1,297.777318 W/m2.oC
Q = Uo Ao T
From Energy Balance:
Qcoil = 2,855,416.028 KJ /hr = 793,171.1189 J/s
71
= 15.27941481 m2
Ao =
Length of tube =
Length of tube =
= 63. 910491481m
Diameter of turn=
1m
+C
t = 1.817438078mm
+1
2mm
72
t = 0.694606292mm
Calculations of the Height of cover
The height of cover (distance from the head of reactor to the tangent line)
can be calculated by knowing the major &minor axis.
Rs = a2/b , Rs = Di = 2.181070978 m
2a = major axis = Do
Do = Di + 2(thickness)
Do = 2.181070978 + 2(1.817438078*10-3)
Do = 2.184706233 m
2b = minor axis = 2h
h = height of head from tangent line
a = 2.184706233/2 = 1.092353117m
b = a2/Rs
73
b = 1.0923531172/2.184706233 = 0.546176558 m
h = 0.546176558 m height of cover
Calculation of the volume of Nitrator
V = 0.05Di3 + 1.65 t D2
V = 0.05* 2.1810709783 + 1.65 * 0.694606292*10-3 * 2.1810709782
V = 0.524227513 m3
Over all volume of Nitrator = volume of cylindrical part + volume of covers
VTotal = 3.73619452 + 2(0.524227513)
VTotal = 4.784649546 m3
Overall length of reactor = length of cylindrical part + 2*length of cover
LTotal = 2.181070978 + 2* 0.546176558
LTotal = 3.273424094 m
Calculation of the weight of Nitrator
Wv = 240 Cv Dm (Hv + 0.8 Dm) t
Cv = 1.08, factor to account weight of nozzles
Dm = Di + t
Dm = 2.181070978 + 1.817438078*10-3 = 2.182888416 m
Hv = Di = 2.181070978 m
Wv = 240 * 1.08 * 2.182888416 (2.181070978 + 0.8 * 2.182888416)
74
Wv = 2222.130942 Kg
Design the supporting of Nitrator
The reactor supporting legs depend mainly on the weight of Nitrator and
material inside.
Wv = 2222.130942 Kg
Weight of material inside = 26,275.56824 Kg
Total weight of Nitrator = 2222.130942 + 26,275.56824 = 28,497.69918 Kg
Density of stainless steel (18% Cr, 8% Ni) = 7,817 Kg/m3 [32].
Each support bear weight of =
= 7,124.424796 Kg
= 0.911401405 m3
D 2L
V=
D2 (8D) =2
D=
D3
= 0.525424043m
75
L = 8* 0.525424043 = 4.203392345m
Wind load
The effect of the wind on tall vessels (over 50m) although the calculation
about this small effect is made.
Wind load = Fw = Pw * Deff
Pw = 1280 N/m2
Deff = Do = 2.184706233 m
Fw = 1280 * 2.184706233 = 2,796.423978 N/m
Bending moment at any plane = Ms = Fw / 2 *S2
S = Di = 2.181070978m
Ms =
* (2.181070978)2 = 6,645.304084N.m
The Nitrator does not consider tall vessel so the effect of wind is not high.
76
ud =
ud = -1.779029395 * 10-3 m/s (rising)
As the flow rate is small, use a vertical cylindrical vessel.
LC =
77
ud > uc ( the decanter vessel is sized on the basis that the velocity of the
continuous phase must be less than settling velocity of the droplets of the
dispersed phace) [23].
Ai = Lc/uc
Ai =
= 1.597184548 m2
Ai =
r=
= 0.71302148 m
dd =
dd =
Pipe diameter =
= 5.22803863 * 10-3 m2
Z2 =
+ 1.426042961
Z2 = 2.272174706 m
Proposed Design
Liquid- light
D = 1.4 m
Heavy liquid
take off
take off
Crude N.B
Z1 = 2.6 m
Z3 = 1.4 m
Z2 =2 m
Spent Acid
80
Mechanical Design
The material of construction used is stainless steel [4], select stainless steel
(18 Cr / 8 Ni) (304) which is corrosion resistance.
Calculation of the Thickness of Decanter
Thickness of the decanter can be calculated directly from equation bellow:
t=
+C
t = 1.645072183 mm
+1
2mm less than 7mm so that take the thickness 6mm [23]
t=
t = 0.644838821mm
0.645mm
81
Spent Acid
T2=65.5oC
Cooling water
hot water
t2=30oC
t1 =30 C
Spent Acid
T1=100oC
The heat exchanger which is used as cooller to cool the spent acid from
vaporizer from 100oC to 65.5 by using cold water.
water is corrosive more than Spent acid, so assign to tube side.
Operating Condition
Temperature of a hot spent acid inputT1 = 100oC
Temperature of a cold spent acid outputT1 = 65.5oC
Temperature of a cold water input t1 = 30oC
Temperature of a hot water input t2 = 50oC
T1=100oC
T1
{
T2=65.5oC
T2=50 C
}T
t1=30oC
82
The hot spent acid & cold water passed counter currently ( more efficient
than co-current).
From energy balance:
QCooling = 1,060,108.891 KJ/hr = 294.4746919 KWatt
Tlm =
(T
t 2 ) ( T2 t1
( T1 t 2 )
ln
( T2 t1 )
= 42.33696435 o C
Tm = Ft Tlm
Use one shell and two tube passes.
T2 = 65.5 C
R = ( T1 T2 ) / ( t2 t1 )
t1 = 30 C
S = ( t2 t1 ) / ( T1 t1)
t2 = 50 C
T1 =100 C
S = ( 50 30 ) / (100 30 ) = 0.285714285
From figure (12.19) [23] at R = 1.725 & S = 0.285714285 Ft = 0.95
Provisional area
Q = U A Tm
A=
= 9.151971708 m2
Pipe Dimension
Choose 20mm o.d, 16mm i.d, 4.88m long tube table (12.3) [23]
Allowing for tube sheet thicness, take L = 4.83m, material of construction
Cupro-Nickel.
Area of one tube = do L
Area of one tube = * 20*10-3 * 4.83 * 10-3= 0.30347785 m2
Number of tubes = Nt = A / At
Number of tubes = 9.151971708 / 0.30347785 = 30.15696763
30 tube
Use 1.25 Triangular pitch, this type of pitch is more efficient than rectangular
pitch.
Db = bundle diameter = do (Nt / k1 ) 1/n1
Pt
Flow
Triangular Pitch
84
)0.14
43 oC
]0.14 =
]0.14 = 1.007864243
needed]
Shell Side Coefficient
Choose baffle spacing = lB = 0.2Ds [23]
lB = 0.2 * 205.3490987 = 41.06981914mm
tube pitch = 1.25 do = 1.25 (20) = 25mm
As =
= 1.686730069*10-3m2
As =
= 1977.705776 Kgde =
86
( pt2 0.917 do )
de =
= 5.223851997 * 103
Choose 25 percent baffle cut, from figure ( 12.29) [23], jh = 2.4 * 10-2
hs =
jh Re pr1/3 [
]0.14
hs = 4,559.6671 W /m2.oC
Calculation of the Shell Temperature
hS (TTw) = U (T t)
4,559.6671 (tw 40) = 800 (82.75 40)
tw = 75.24945243oC
75.25 oC
87
]0.14 =
]0.14 = 0.982977327
needed]
Checking for over all Heat Transfer Coefficient
The value of over heat transfer coefficient must be checked and the new
value of U must be greater than assumed value (800 W/ m2.oC).
1
=
Uo
d ln(d o / d i )
d 1
d 1
1
1
+
+ o
+ o
+ o
2 kw
ho hod
d i hid
d i hi
= 7.28006325 * 10-4
Uo = 1,373.614614 W/ m2.oC (Above the assumed value of 800 W/ m2.oC)
Calculation of Pressure Drop
Tube Side
Pressure drop in the tube side can be calculated from equation below, the
pressure drop calculated must be smaller than 10 psi.
Pt = Np [ 8jf
+ 2.5]
Pt = 2[ 8 * 3 * 10-3 *
+ 2.5]
89
Top
Comp.
Wt.%
Mol.%
C6H6
2.014285745
3.31381848
Bottom
C6H5NO2
97.98571425 96.86168152
TemperatureoC
192.1
Mol.%
100
100
1.567082484
99
98.43291752
80.1
200.87
Y
0
0.451
0.759
0.923
0.957
0.969
0.975
0.981
0.985
0.988
0.989
0.99
0.992
0.994
0.995
0.996
0.996
0.997
0.999
0.999
1
90
BenzeneVaporMoleFraction
0.8
0.6
0.4
0.2
0
0
0.2
0.4
0.6
0.8
= 0.326554895
0.33
Ln
Vn
V
L
V =
V =
P Mwt.
RT
= 2.694828052 Kg/m3
FLV =
= 0.038722801
Take plate spacing 0.45 [ The plate spacing is reduced to avoid the problem of
supporting a tall, slender column] [30].
From figure (11.29) [23] at FLV = 0.038722801 and plate spacing = 0.45,
K1 = 7.5 * 10-2
Correction for surface tension
4
* 10-12
* 10-12
93
uf = 0.013081
= 0.227120984 m/s
for design a value of 80-85 percent of the flooding velocity should be used.
uv = 0.85 * uf
uv = 0.85 * 0.227120984 = 0.193052836 m/s
maximum volumetric flow-rate =
= 0.032087667 m3/s
= 0.16621184 m2
An =
= 0.188877091 m2
Dc =
= 0.490393497 m
Lm
Vm
V
L
0.5 m
Lm = Vm + stream 15
Vm = Vn = 0.086470746 Kg/s
Stream 15 = 9,820.426487 Kg/ hr = 2.727896246 Kg/s
Lm = 0.086470746 + 2.727896246 = 2.814366992 Kg/s
L(mix.) = 1002.856487 Kg/m3 at 200.87 oC [28]
V(mix.) =
Mwt. av. = 122.4048129 Kg/Kg.mol
= 3.229930538 Kg/m3
V(mix.) =
FLV =
= 1.847096398
From figure (11.29) [23] at FLV =1.847096398 and plate spacing = 0.45,
K1 = 1.8 * 10-2
Correction for surface tension
=
* 10-12
= 0.032994305 Kg/m3
95
* 10-12
BZ. =
V BZ. =
L N.B = 1,008.377286 Kg/m3
N.B =
* 10-12
uf = 0.013081
= 0.219920976m/s
for design a value of 80-85 percent of the flooding velocity should be used.
uv = 0.85 * uf
96
= 0.026207778 m3/s
An =
= 0.140198909 m2
= 0.159316942 m2
Dc =
= 0.450387201 m
0.5 m
]2/3
uh min. =
= 6.810578219 m/s
= 5.21179869 m/s
uh =
hd = 51 [
= 8.737700255 m/s
]2 [
Ah / Aa =0.03,
Co = 0.81
]2 [
hd = 51 [
hr =
] = 19.30499388 mm Liquid
= 12.46439562 mm Liquid
hdc = 166 * [
]2
]2 = 5.65854496 mm
100
hb = ( hw + how ) + ht + hdc
hb = (50 + 28.4424389) + 110.2118279 + 5.65854496
hb = 194.3128113 mm = 0.1943128112 m
hb < (tray spacing + wier hight)
0.1943128112 m < (0.45 + 0.05)
0.2632 m < 0.25 m
So tray spacing acceptable.
Check Residence Time
tr =
tr =
tr = 1.631438149s < 3 sec ( not satifactory)
Check Entrainment
uv =
= 0.15167627 m/s
percentage flooding =
percentage flooding =
* 100 = 68.96853282%
Perforated Area
From figure (11.32) [23],
At lw / Dc = 0.76
lw= 0.38
o = 99o
D = 0.5 m
50 mm
= 219 holes
103
Chapter Six
Control System
Chapter Six
Control System
6.1 Introduction
Instruments are provided to monitor the key process variables during plant
operation. They may be incorporated in automatic control loops, or used for the
manual monitoring of the process operation. They may also be part of an
automatic computer data lagging system. Instruments monitoring critical process
variables will be fitted with automatic alarms to alert the operators to critical and
hazardous situations.
The primary objectives of the designer when specifying instrumentation
and control schemes are:
1. Safe plant operation:
a) To keep the process variables within known safe operation limits.
b) To detect dangerous situations as they develop and to provide alarms
and automatic shut-down systems.
c) To provide interlocks and alarms to prevent dangerous operating
procedures.
2. Production rate:
To achieve the design product out put.
3. Product quality:
To maintain the product composition within specified quality standards.
4. Cost:
104
strength produced, must be integrated with the nitration section [4], figure 6-1
illustrated the control of isothermal nitrator [23].
FC
Feed
FC
TC
TC
FC
LC
FC
106
Liquid- light
take off
Heavy liquid
take off
Crude N.B
Feed
Spent Acid
Liquid- light
Feed
LC
Heavy liquid
TC
LC
Feed
Steam
Trap
108
TC
With this arrangement interaction can occur between the top and bottom
temperature controllers, figure 6-5 [23].
111
112
Chapter Seven
Plant Layout
Chapter Seven
Plant Layout
113
3) Transport
The transport of materials and products to and from the plant will be an
overriding consideration in site selection. If practicable, a site should be selected
that is close to at least two major forms of transport: road, rail, waterway (canal
or river), or a sea port. Road transport is being increasingly used, and is suitable
for local distribution from a central warehouse. Rail transport will be cheaper for
the long-distance transport of bulk chemicals. Air transport is convenient and
efficient for the movement of personnel and essential equipment and supplies,
and the proximity of the site to a major airport should be considered.
4) Availability of labor
Labor will be needed for construction of the plant and its operation.
Skilled construction workers will usually be brought in from outside the site
area, but there should be an adequate pool of unskilled labor available locally;
and labor suitable for training to operate the plant. Skilled tradesmen will be
needed for plant maintenance. Local trade union customs and restrictive
practices will have to be considered when assessing the availability and
suitability of the local labor for recruitment and training.
5) Utilities (services)
Chemical processes invariably require large quantities of water for cooling
and general process use, and the plant must be located near a source of water of
suitable quality. Process water may be drawn from a river, from wells, or
purchased from a local authority.
can be taken from a river or lake, or from the sea; at other locations cooling
towers will be needed. Electrical power will be needed at all sites.
Electrochemical processes that require large quantities of power; for example,
114
115
9) Climate
Adverse climatic conditions at a site will increase costs. Abnormally low
temperatures will require the provision of additional insulation and special
heating for equipment and pipe runs. Stronger structures will be needed at
locations subject to high winds (cyclone/hurricane areas) or earthquakes.
10) Political and strategic considerations
Capital grants, tax concessions, and other inducements are often given by
governments to direct new investment to preferred locations; such as areas of
high unemployment. The availability of such grants can be the overriding
consideration in site selection.
Cooling towers should be sited so that under the prevailing winds the
plume of condensate spray drifts away from the plant area and adjacent
properties. The main storage areas should be placed between the loading and
unloading facilities and the process units they serve. Storage tanks containing
hazardous materials should be sited at least 70m (200ft) from the site boundary.
A typical plot plant is shown in figure 7-1.
119
121
122
Chapter Eight
Toxicity and Effects of
Nitrobenzene
Chapter Eight
Toxicity and Effects of Nitrobenzene
8.1 General
Nitrobenzene is very toxic substance; the maximum allowable
concentration for nitrobenzene is 1 ppm or 5 mg/m3. It was exposed for eight
hours to 1 ppm nitrobenzene in the working atmosphere, about 25 mg of
nitrobenzene would be absorbed, of which about one-third would be by skin
absorption and the remainder by inhalation. The primary effect of nitrobenzene
is the conversion of hemoglobin to methemoglobin; thus the conversion
eliminates hemoglobin from the oxygen-transport cycle. Exposure to
nitrobenzene may irritate the skin and eyes. Nitrobenzene affects the central
nervous system and produces fatigue, headache, vertigo, vomiting, general
weakness and in some cases unconsciousness and coma. There generally is a
latent period of 1-4 hours before signs or symptoms appear. Nitrobenzene is a
powerful methemoglobin former, and cyanosis appears when the methemoglobin
level reaches 15%. Chronic exposure can lead to spleen and liver damage,
jaundice, and anemia. Alcohol ingestion tends to increase the toxic effects of
nitrobenzene; thus alcohol in any form should not be ingested by the victim of
nitrobenzene poisoning for several days after the nitrobenzene poisoning or
exposure. Impervious protective clothing should be worn in areas where risk of
splash exists. Ordinary work clothes that have been splashed should be removed
immediately, and the skin washed thoroughly with soap and worm water. In
areas of high vapor concentration (>1 ppm), full face mask with organic-vapor
123
124
orally exposed persons have also included those symptoms, as well as apnoea
and coma [5].
Nitrobenzene
appears
to
and
an
8-day
lowest-observed-effect
concentration of 1.9 mg/litre for the blue-green be toxic to bacteria and may
adversely affect sewage treatment facilities if present in high concentrations in
influent. The lowest toxic concentration reported for microorganisms is for the
bacterium Nitrosomonas, with an EC50 of 0.92 mg/litre based upon the inhibition
of ammonia consumption. Other reported values are a 72-h no-observed-effect
concentration of 1.9 mg/litre for the protozoan Entosiphon sulcatum alga
Microcystis aeruginosa [5].
For freshwater invertebrates, acute toxicity (24- to 48-h LC50 values)
ranged from 24 mg/litre for the water flea (Daphnia magna) to 140 mg/litre for
the snail (Lymnaea stagnalis). For marine invertebrates, the lowest acute toxicity
value reported was a 96-h LC50 of 6.7 mg/litre for the mysid shrimp (Mysidopsis
bahia). The lowest chronic test value reported was a 20-day NOEC of 1.9
mg/litre for Daphnia magna, with an EC50, based on reproduction, of 10 mg/litre
[5].
Freshwater fish showed similar low sensitivity to nitrobenzene. The 96-h
LC50 values ranged from 24 mg/litre for the medaka (Oryzias latipes) to142
mg/litre for the guppy (Poecilia reticulata). There was no effect on mortality or
behaviour of medaka at 7.6 mg/litre over an 18-day exposure [5].
125
of
the
exposureresponse
relationship.
In
rodents,
126
risk for non-neoplastic effects. If exposure values are low enough to avoid nonneoplastic effects, it is expected that carcinogenic effects will not occur [5].
Acute poisonings by nitrobenzene in consumer products have occurred
frequently in the past. Significant human exposure is possible, due to the
moderate vapour pressure of nitrobenzene and extensive skin absorption.
Furthermore, the relatively pleasant almond smell of nitrobenzene may not
discourage people from consuming food or water contaminated with it. Infants
are especially susceptible to the effects of nitrobenzene [5].
There is limited information on exposure in the workplace. In one
workplace study, exposure concentrations were of the same order of magnitude
as the lowest-observed-adverse-effect levels in a long-term inhalation study.
Therefore, there is significant concern for the health of workers exposed to
nitrobenzene [5].
Nitrobenzene shows little tendency to bioaccumulate and appears to
undergo both aerobic and anaerobic biotransformation. For terrestrial systems,
the levels of concern reported in laboratory tests are unlikely to occur in the
natural environment, except possibly in areas close to nitrobenzene production
and use and areas contaminated by spillage [5].
Using the available acute toxicity data and a statistical distribution
method, together with an acute: chronic toxicity ratio derived from data on
crustaceans, the concentration limit for nitrobenzene to protect 95% of
freshwater species with 50% confidence may be estimated to be 200 g/litre.
Nitrobenzene is thus unlikely to pose an environmental hazard to aquatic species
at levels typically reported in surface waters, around 0.11 g/litre. Even at
127
airway is
128
References
1- Ullmanns Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH Verlag
GmbH & Co. KGaA.
2- Krik and Othmer, Encyclopedia of Chemical Technology, Vol.17, 4th Ed.,
p (133-152).
3- Krik and Other, Encyclopedia of Chemical Technology, Vol.15, 3rd Ed., p
(917-932).
4- John J.Mcketta, Encyclopedia of Chemical Processing & Design, Vol. 31,
p. (165-188).
5- http:// Whqlibdoc.Who.int / ech / who.EH.C.230.
6- www. Technology bank.dupont.com.
7- Hydrocarbon Processing, Vol.58,1979, NO.11
8- Hydrocarbon Processing, 1978.
9- P.H.Grogins, Unit Process Organic Synthesis, fifth edition.
10- H.Scott Fogler, Elements of Chemical Reaction Engineering.
11- U.S.pat. 7,326,816 B2 (Feb. 5, 2008).
12- U.S.pat. 4,772,757 (Sep.20, 1988).
13- Sami Matter & Lewis Hatch, From Hydrocarbon to Petrochemicals.
14- Sami Matter & Lewis F. Hatch, (2000), Chemistry of petrochemicals
Processes, 2nd.
15- U.S.pat. 2,773,911 (Dec.11, 1956).
16- James G. Speight, Chemical & Process Design Handbook.
17- Austin, G.T., (1984), Shreves Chemical Process Industries, 5th Ed., p.
(772).
18- SEP Handbook, Petrochemical & Downstream Projects.
19- Robert H. Perry (1997), Perrys Chemical Engineers Handbook, 7th Ed.
129
131
Appendixes
Appendix A
Physical Properties
1- General Properties [19,20,21,22,23,24,25,26,27&28]
Comp.
Hof
Mwt.
[Kg /Kg.mol]
B.P
[oC]
C6H6 (L)
HNO3 (L)
H2SO4 (L)
H2O (L)
C6H5NO2 (L)
Na2CO3 (c)
78.11
63.02
98.08
18.02
123.11
106
80.1
100
210.9
-
49.1
-173.230
-811.32
-285.840
12.500
-1131.546
30781
40683
-
H2CO3 (aq)
Na2SO4 (c)
CaSO4 (c)
CaSO4.2H2O(c)
62.03
142.05
136.14
172.18
-699.65
-1413.891
-1432.7
-2024.021
(298.15K)
[KJ /g.mol]
[KJ / Kg.mol]
(Soda Ash)
(Gypsum)
A
-33.917
131.250
32.243
295.3
B
4.743 * 10-1
-0.1219
1.923 * 10-3
-0.8907
A-1
C
-3.017 * 10-4
0.1704 *10-3
1.055 * 10-5
1.705 * 10-3
D
7.130 * 10-9
-3.596 *10-9
-
A
139.1
B
0.1559
Comp.
Na2CO3 (c) (Soda Ash)
Na2SO4 (c)
CaSO4 (c)
CaSO4.2H2O(c) (Gypsum)
C6H6 (V)
-0.206
39.064*10-3
-13.301*10-6
H2O (V)
3.470
1.450*10-3
0.121*10+5
A-2
=
Comp.
C6H6 (L)
HNO3 (L)
H2SO4 (L)
H2O (L)
C6H5NO2 (L)
1.0259
1.5943
0.8322
5.4590
0.69123
0.26666
0.2311
0.19356
3.0542*10-1
0.24124
562.05
520
925
6.4713*102
719
0.28394
0.1917
0.2857
8.1*10-2
0.28135
Range
Temperature
K
279-562
232-373
284-364
273-333
279-719
C6H6 (L)
HNO3 (L)
96wt.%
H2SO4 (L)
98wt.%
H2O (L)
C6H5NO2 (L)
7.5117
-28.886
294.68
1940
-2.794
2.678
Range
Temperature
K
279-545
240-356
-179.84
10694
24.611
284- 367
-51.964
-34.557
3.6706*103
2611.3
5.7331
3.4283
-5.349*10-29
-
10
-
273-643
273-481
A-3
C6H6 (L)
HNO3 (L)
96wt.%
H2SO4 (L)
98wt.%
H2O (L)
C6H5NO2 (L)
0.23444
0.12107
-0.00030572
0.0005383
Range
Temperature
K
279-413
233-433
0.014247
0.0010763
283-371
-0.4267
0.1869
0.00569
-0.0001305
-8.0065*10-6
-
1.815*10-9
-
273-633
283-371
[23]
T = Temperature in K
Comp.
C6H6 (L)
15.9008
Log po = A -
2788.51
-52.36
Range
Temperature
o
C
7-104
[25]
T = Temperature in oC
Comp.
C6H6 (L)
C6H5NO2 (L)
7.1156
6.90565
1746.6
1211.033
201.8
220.79
A-4
Range
Temperature
o
C
134-211
8-103
Appendix B
Equilibrium Data
Bij
659.89
T Deg C
210.635
151.914
126.933
112.693
103.357
96.798
92.010
88.401
85.524
82.944
80.129
Bji
-263.35
P atm
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
Alpha
0.311
X1
0.00000
0.10000
0.20000
0.30000
0.40000
0.50000
0.60000
0.70000
0.80000
0.90000
1.00000
Aij
0.00
Aji
0.00
Mole Fractions
Y1
Gamma1
0.00000
1.416
0.82031
1.376
0.93286
1.340
0.96616
1.303
0.98015
1.261
0.98727
1.214
0.99139
1.162
0.99406
1.108
0.99603
1.057
0.99781
1.017
1.00000
1.000
B-1
Cij
0.00
Cji
0.00
Gamma2
1.000
1.001
1.005
1.013
1.031
1.063
1.123
1.228
1.418
1.778
2.529
Dij
0.00
Phi1
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
Dji
0.00
Phi2
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
B-2
:
.
.
.
1430
2009