MANUFACTURE OF NITROBENZENE

(1 TON PER DAY)

A PROJECT REPORT
Submitted by

CHALUVADI ND PAVAN KUMAR 2011303038

In partial fulfillment for the award of the degree

of
BACHELOR OF TECHNOLOGY
In
CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

ALAGAPPA COLLEGE OF TECHNOLOGY

ANNA UNIVERSITY CHENNAI 600 025

MAY 2015
 ANNA UNIVERSITY : CHENNAI 600 025

BONAFIDE CERTIFICATE

Certified that this project report “MANUFACTURE OF NITROBENZENE (1

TON PER DAY)” is the bonafide work of CHALUVADI ND PAVAN KUMAR
(201130308) who carried out the project work under my supervision.

SIGNATURE SIGNATURE

Dr.N.BALASUBRAMANIAN Dr. K. MUTHUKUMAR

HEAD OF THE DEPARTMENT SUPERVISOR

Department of Chemical Engineering Associate Professor

Alagappa College of Technology, Department of Chemical Engineering

Anna University, Alagappa College of Technology,

Chennai – 600 025. Anna University,

Chennai – 600 025.

 ACKNOWLEDGEMENT

We sincerely thank our project guide, Dr.K.Muthukumar, Professor,

Department of Chemical Engineering for his kind motivation and guidance.

We would like to express our sincere thanks to Dr.S.Sivanesan, Dean and

Dr.N.Balasubramanian Professor and Head of Department of Chemical
Engineering, Alagappa College of Technology, Anna University as well as all the
Chemical Engineering Faculty members of Alagappa College of Technology, for
their support towards the completion of project.

It is our pleasure to specially thank our project coordinators Dr. N.Nagendragandhi,

Ms.A.Brindhalakshmi and Ms.D.Vidyalakshmi for help and motivation towards
the successful completion of the project on time.

We also would like to express our sincere thanks to Dr.N.Balasubramanian,

Professor& Head, Department of Chemical Engineering for his support and
motivation.

We also express our sincere thanks to all our classmates for their support.
INTRODUCTION
 CHAPTER 1

Nitrobenzene (oil of Mir bane) is a pale yellow liquid with an odour of bitter
almonds. Depending upon the compound impurity, its colour varies from pale
yellow to yellowish brown. Nitrobenzene is one of the important raw materials for
the dye manufacture and most nitrobenzene produced is used directly or indirectly
in dye manufacture. It is manufactured on large scale only by aniline manufactures.

1.1 HISTORY AND BACKGROUND

The earliest aromatic nitro compounds were obtained by MITSCHERLISH in 1834

by treating hydrocarbons derived from coal tar with fuming acid. 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 di -Nitrobenzenes by using a mixture of nitric and sulphuric acids .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”. 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 mould Streptomyces Venezuela’s and identified in
1949.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 .The choice of nitro compounds covered here is influenced
strongly by their commercial application of compounds in the 1981 European core
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.

1.2 PROPERTIES

PHYSICAL PROPERTIES

Nitrobenzene is a colourless to pale yellow oily liquid with an odour 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 vapour pressure is 20 Pa at 20°C, and its solubility in water is
1900 mg/litre 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.

SOME OTHER PHYSICAL PROPERTIES OF NITROBENZENE

Physical State : Liquid
Appearance : colourless to pale yellow
Odour: almond-like
pH : Not available.
Vapour Pressure: < 1 mm Hg at 20̊ C
Vapour Density: 4.25 (air=1)
Evaporation Rate: Not available.
Viscosity: Not available.
Boiling Point: 210-211̊C at 760 mm Hg
Freezing/Melting Point: 5 - 6 ̊ C
Decomposition Temperature: Not available.
Solubility: Insoluble.
Specific Gravity/Density: 1.2 g/cm3
 Molecular Formula: C6H5NO2
Molecular Weight: 123.11

CHEMICAL PROPERTIES

1. Nitrobenzene reactions involve substitution on the aromatic ring and reactions

involving the nitro group.

2. Under electrophilic conditions, the substitution occurs at a slower rate than for
benzene and the nitro group promotes met substitution.

3. Nitrobenzene can undergo halogenation, sulphonation and nitration, but it does not
undergo Friedel-crafts reactions.

4. Under nucleophilic conditions, the nitro group promotes ortho and para substitution.

5. The reaction of nitro group to yield aniline is the most commercially important
reaction of nitrobenzene.

6. Depending on the conditions, the reduction of nitrobenzene can lead to a variety of

products.
1.3 APPLICATIONS/USES

The largest end use of nitrobenzene is in the production of aniline. 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).

1.4 MANUFACTURERS IN INDIA

1. Sikko Industries ltd, Ahmedabad

2. A.B enterprises,Mumbai

3. Chaitanya Agro Chemicals,Ahmedabad.

4. Akshar Exim Company pvt ltd,Kolkata.

5. Adarsh Chemicals,Chennai.

6. Choice Organics pvt ltd,Thane.

7. Akash Agro Industries,Ahmedabad.

8. Indo-cell crop science,Rajkot.

9. Narmada chematur petrochemicals ltd,Gujarat.

MANUFACTURERS IN ABROAD

1. Richen satichem co.Ltd, china.

2. Wuhan Rison Trading co. Ltd, china.

3. RPE Russia.

4. Zaria, Ukraine.

5. Prince manufacturing, united states.

1.5 DIFFERENT METHODS OF PRODUCTION

Nitrobenzene is manufactured commercially by direct nitration of benzene using a

mixture of nitric and sulphuric acids which is commonly referred as mixed or
nitrating acid. Nitrobenzene is produced either by a batch or a continuous process.

BATCH PROCESS

The reactor vessel is charged with benzene and then the nitrating acid (56-
60wt%H2SO4, 27-30wt%HNO3 and 8-17wt%H2O) is added slowly below the
surface of the benzene. The temperature of the mixture is maintained at 50-55̊ C by
adjusting the feed rate of the mixed acid and the amount of cooling. The
temperature is raised to 90̊ C towards the end of the 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. The
batch reaction time is 2 to 4hrs and overall yields are 95-96wt% based on benzene
charged.
CONTINUOUS PROCESS

In a typical continuous process 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 in a cylindrical reactor with internal cooling coils and external heat
exchangers or a cascade of such reactors .The basic sequence of operations for a
continuous process is the same as that for a batch process, however for a given rate
of production the size of the nitrator is much smaller in the continuous process. The
nitration in continuous process can take place either adiabatic, or isothermal
condition.

Adiabatic Condition

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 sulphuric 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 ̊
C 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.
Crude nitrobenzene obtained from the separator is washed in several steps to
remove the impurities present. One observes that the nitrobenzene stream from the
separator is used to heat the benzene feed.
Isothermal condition

The isothermal process is different from the adiabatic process only in the nitration
section. 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- pre nitration. It is then 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.

Table 1- Comparison of process methods

Process Temperature No of Distillation Settler Evaporator Yield
reactors column
Batch 50-55̊C 1 No Yes Yes 95-
96%
Continuous
1.Isothermal 50-70 ̊C 1 Yes Yes Yes 98-
condition 99%
2.Adiabatic 120-160 ̊C 2-4 No Yes Yes 95-
condition 97%

1.6 PROCESS SELECTION

A continuous nitration process generally offers lower capital costs and more
efficient labour usage than a batch process. Thus most, if not all, of the nitrobenzene
producers use continuous processes. 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 .The
continuous nitration can take place with elimination of heat of reaction either in
isothermal or adiabatic condition. Since the nitration process in adiabatic condition
requires a special installation of corrosion resistant materials due to the high
temperature of the process and requires a more stringent safety measures when
compared to isothermal process we opt continuous process in isothermal condition
to produce nitrobenzene as it yields 98-99 wt % of nitrobenzene and number of
reactors used under isothermal condition is less when compared to adiabatic so it is
economical.

1.7 Raw Materials

Benzene
Concentrated nitric acid and sulphuric acid
Sodium carbonate
Calcium sulphate

1.8 DESCRIPTION OF THE SELECTED PROCESS

The concentrated sulphuric acid used for the production of nitrobenzene 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 nitro benzene. A charge of
benzene into a Nitrator (a slight excess of benzene is added to avoid nitric acid in
the spent acid then slowly feeding in a mixed nitrating acid ) 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 .The temperature in the nitrator is held at 50 ̊ C 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 c an be assured
by the use of jackets, coils, and good agitation in the nitration vessel.

Nitration vessels are usually made of stainless steel, although cast iron stands up
well against mixed acids. It then enters a separator tank from which a portion of
spent acid is removed from bottom, and the crude nitrobenzene is drawn off from
the top of the settler. The removed spent acid (sulphuric acid & water) enters into an
evaporator in order to concentrate the sulphuric acid and nitric acid out from the
acid mixture. The crude nitrobenzene (nitrobenzene, benzene,

sulphuric acid &water) is drawn from the top of the separator and is washed with
the sodium carbonate in order to remove sulphuric acid from crude nitrobenzene,
followed by final washing with calcium sulphate (anhydrite) to remove the water
and gypsum formed. The product is topped in still to remove benzene and give pure
nitrobenzene (98-99 wt. %).
MATERIAL BALANCE
 CHAPTER 2

Overall reaction is given by

C6H6 + HNO3 + H2SO4 → C6H5NO2 + H2O

In the above reaction sulphuric acid acts as an catalyst.

Basis:

Production rate = 1 ton/day

= 1000/24 kg/hr

= 0.338 kmol/hr

Conversion of benzene = 90%

Amount of benzene fed = 0.338/0.9

= 0.376 kmol/hr

2.1 Nitrator balance

benzene (1) Nitrobenzene + water+ HNO 3 +H2SO4 (3)

NITRATOR
Acid solution(HNO 3 ,H2SO 4),(2)
C6H6 + HNO3 + H2SO4 → C6H5NO2 + H2O

Where H2SO4 is an acid catalyst.

Input stream:

1 kmol of benzene ≡ 1 kmol of nitric acid

0.376 kmol of benzene ≡ 0.376 kmol of nitric acid

Therefore, 0.376 kmol of nitric acid is fed

1 kmol of nitric acid ≡ 1 kmol of sulphuric acid

0.376 kmol of nitric acid ≡ 0.376 kmol of sulphuric acid

Acid solution in = HNO3 + H2SO4

= 0.376 + 0.376= 0.752 kmol/hr

Product stream:

1 kmol of benzene ≡ 1 kmol of Nitrobenzene

Therefore, amount of benzene reacted = 0.338 kmol/hr

Thus, benzene in the product stream = 0.376 – 0.338 =0.038 kmol/hr

Similarly, Amount of nitric acid unreacted = 0.376- 0.338= 0.038 kmol/hr

1 kmol of benzene ≡ 1 kmol of H2O

0.338 kmol of benzene ≡ 0.338 kmol of H2O

Therefore, water in the product stream = 0.338 kmol/hr

Acid solution out = Sulphuric acid + water formed + Nitric acid unreacted
 = 0.376 + 0.338 + 0.038= 0.752 kmol/hr

Table 2- Nitrator Material balance

MOLES IN (kmol/hr) MOLES

OUT(kmol/hr)
1 2 3
C6H6 0.376 - 0.038
H2SO4 - 0.376 0.376
HNO3 - 0.376 0.038
C6H5NO2 - - 0.338
H2O - - 0.338

Moles in = 0.376 + 0.752 = 1.128 kmol/hr

Moles out = 1.128 kmol/hr

2.2 Acid Separator

Crude Nitrobenzene(5)
Acid
Output from Nitrator spent acid solution (4)
separator

5 mol % of sulphuric acid solution will go with the crude nitrobenzene. (reference-
John J.Mcketta, “Encyclopedia of chemical processing & design”,)

Sulphuric acid solution = 0.376 + 0.338 = 0.714 kmol/hr

Sulphuric Acid solution in crude nitrobenzene = 0.05 * 0.714 = 0.0357 kmol/hr

Crude nitrobenzene = excess benzene + C 6H5NO2 + 5 wt % of sulphuric acid

solution

Crude C6H5NO2 = 0.038+ 0.338 + 0.0357 = 0.4117 kmol/hr

Spent acid solution = 0.752 – 0.0357 = 0.7163 kmol/hr

Table 3 – Separator Material balance

MOLES MOLES OUT (kmol/hr)

IN (kmol/hr)
3 4 5
C6H6 0.038 - 0.038
C6H5NO2 0.338 - 0.338
H2SO4 0.376 0.3572 0.0188
HNO3 0.038 0.038 -
H2O 0.338 0.3211 0.0169

Moles in = 0.038+ 0.338 +0.376 + 0.038 + 0.338 = 1.128 kmol/hr

Moles out = 0.038 + 0.338 + 0.0188 + 0.0169 + 0.3572 + 0.038 + 0.3211

= 1.128 kmol/hr

Moles in = Moles out

2.3 Washing Tank 1:

Na2 CO3 (6)

Benzene+Nitrobenzene+H 2O

Benzene+Nitrobenzene+H 2O+H2SO 4 (5) Washing tank (7)

Sodium sulphate + carbonic acid (8)

Na2CO3 + H2SO4 → Na2SO4 + H2CO3

From stoichiometry,

Moles of Na2CO3 input in (6) ≡ moles of H2SO4 in (5)

Therefore, moles of Na2CO3 = 0.0188 kmol/hr

1 kmol of Na2CO3 ≡ 1 kmol of Na2SO4

0.0188 kmol of Na2CO3 = 0.0188 kmol of Na2SO4

Similarly, from stoichiometry 0.0188 kmol of H2CO3 is formed.

Table 4 – Washing tank 1 Material balance

MOLES IN (kmol/hr) MOLES OUT (kmol/hr)

5 6 7 8
C6H6 0.038 - 0.038 -
C6H5NO2 0.338 - 0.338 -
Na2CO3 - 0.0188 - -
Na2SO4 - - - 0.0188
H2CO3 - - - 0.0188
H2SO4 0.0188 - - -
H2O 0.0169 0.0169 -

Moles in = 0.038 + 0.338 +0.0188+0.0188 + 0.0169 = 0.4305 kmol/hr

Moles out = 0.038+ 0.338 + 0.0188 + 0.0188+ 0.0169 = 0.4305 kmol/hr

Moles in = Moles out

2.4 Washing Tank 2:

CaSO4 (9)
Benzene+Nitrobenzene+water (7) Washing Tank Nitrobenzene+ Benzene (11)

CaSO4 .2H2 O (10)

CaSO4 + 2H2O → CaSO4.2H2O

From stoichiometry,

2 kmol of H2O≡ 1 kmol of CaSO4

Therefore, 0.0169 kmoles of H2O ≡ 0.00845 kmol of CaSO 4 required.

Thus from stoichiometry 0.02535 kmoles of gypsum(CaSO 4.2H2O) will be formed.

Table 5- Washing tank 2 Material balance

MOLES IN (kmol/hr) MOLES OUT ( kmol/hr)

7 9 10 11
C6H6 0.038 - - 0.038
C6H5NO2 0.338 - - 0.338
H2O 0.0169 - - -
CaSO4 - 0.00845 - -
CaSO4.2H2O - - 0.02535 -

Moles in = 0.038 + 0.338 + 0.0169 + 0.00845 =0.40135 kmoles/hr

Moles out = 0.038 + 0.338 + 0.02535 = 0.40135 kmoles/hr

Moles in = Moles out

2.5 Distillation column

Benzene(12)

Feed (11)

Nitrobenzene(13)

Basis-

98 mole % nitrobenzene in bottom and 96 mole % benzene in top product.

F=D+W

F×xF = D×xD + W×xW

xD = 0.96

xW= 0.02

xF = 0.338/(0.038+ 0.338) = 0.89

0.89× (0.376) = W× (0.02) + 0.96× (0.376 – W)

Therefore, W = 0.34 kmol/hr

D = 0.036 kmol/hr
Nitrobenzene in distillate = 0.036- 0.0345 = 0.00144 kmol/hr

Benzene in residue = 0.34 -0.333 = 0.0068 kmol/hr

Table 6 – Distillation Column Material balance

MOLES MOLES OUT (kmol/hr)

IN(kmol/hr)
11 12 13
C6H6 0.038 0.035 0.0068
C6H5NO2 0.338 0.00144 0.333

Moles in = 0.038+ 0.338= 0.376 kmol/hr

Moles out = 0.035+ 0.00144 + 0.0068 + 0.333= 0.376kmol/hr

Moles in = Moles out

2.6 Evaporator:

Water (14)

HNO3 + H2 SO4 + H2 O (4) Evaporator HNO 3 + H2 SO4 (15)

Overall material balance around evaporator:

Weak liquor = water evaporated + thick liquor

amount of water that goes with crude nitrobenzene = 0.0169 kmol/hr

water in spent acid solution = 0.338 - 0.0169 = 0.3211 kmol/hr

spent acid solution out from separator = 0.3952 + 0.038 + 0.3211=0.7163 kmol/hr

water removed =0.3211 kmol/hr

acid solution out = 0.3952 kmol/hr

Table 7 – Evaporator Material balance

MOLES MOLES OUT (kmol/hr)

IN (kmol/hr)
4 14 15
Spent acid 0.7163 - -
solution
Mixed Acid - - 0.3933
Water - 0.3211 -

Moles in = 0.7163 kmol/hr

Moles out = 0.3933 + 0.3211 = 0.7163 kmol/hr

Moles in = Moles out

ENERGY BALANCE
 CHAPTER 3

Overall Reaction

C6H6 + HNO3 → C6H5NO2 + H2O

Acid catalyst : H2SO4

3.1 Nitrator energy balance

benzene (1) NITRATOR Nitrobenzene + water + HNO 3+ H2SO 4 + C6 H6 (3)

Acid solution (2) 50 ̊ C

30 ̊ C

Heat of formation of products = 15.9 + (-285.6) = -269.9 kJ/gmol

Heat of formation of reactants = 48.95 + (-173.2) = -124.25kJ/gmol

Heat of reaction ∆Hr = -269.9+124.25= -145.65 kJ/gmol= -14565 kJ/Kgmol

Qr = 0.338 × (-14565) = -49229.7 kJ/hr

Q= n∆Hi ( reference – Chemical engineering thermodynamics by J.M.Smith)

∆Hi = ∫ Cp idT

Cp =A + BT +CT 2 +DT3

Heat content of HNO3 = 131.250(303 -298) -0.129/2 ×(3032-2982) +

(0.1704*10- 3)/3 ×(3033-2983)

 =539.36 kJ/kgmol

Heat content ,Q(HNO3) = 0.376 × 539.36

= 202.79 kJ/hr

Heat content of sulphuric acid = 139.1(30-25) + 0.1559/2(302-252)

=716.936 kJ/kgmol

Heat content of H2SO4 , Q =0.376 ×3623.65 = 716.936 kJ/hr

Heat content of C 6H6 = -33.917 (303-298) + 4.743/2 ×10-3 (3032-2982) – (3.017×

10-4)/3 ×(3033-2983) + (7.130 ×10-8)/4×(3034 -2984)

=416.738 kJ/kgmol

Q of C6H6 = 0.376 × 416.738

=156.69 kJ/hr

Heat content of benzene in,Q 1 = 156.69 kJ/hr

Heat content in ,Q2 = QNitric acid + Qsulphuric acid =202.79+716.936 = 472.35 kJ/hr

Energy out:

Heat content of H2O= 32.243 (323-298) +( 1.923×10-3)/2×(3232-2982) + (1.055×10-

5)/3×(3233-2983) – (3.596×10-9)/4×(3234-2984)

= 843.75 kJ/kgmol

Q of H2O =0.338 × 843.75 = 285.19 kJ/hr

Heat content of nitric acid =131.250(323 -298) -0.129/2 ×(3232-2982) +(0.1704*10-

3)/3 ×(3233-2983)
 = 2690.81 kJ/kgmol

Q nitric acid = 0.038 × 2690.81 = 102.25 kJ/hr

Heat content of H2SO4 = 139.1(50-25) + 0.1559/2(502-252)=3623.65 kJ/kgmol

Q of H2SO4 =0.376 ×3623.65 = 1362.49 kJ/hr

Heat content of C 6H6 = -33.917 (323-298) + 4.743/2 ×10-3 (3232-2982) – (3.017× 10-
4)/3 × (3233-2983) + (7.130 ×10-8)/4×(3234 -2984)

= 2160.86 kJ/kgmol

Q of C6H6 = 0.038 ×2160.86 = 82.11 kJ/hr

Heat content of C6H5NO2 = 295.3 ( 323 -298) – ( 0.8907/2)(3232-2982) + (1.705 ×

10-3)/3(3233-2983)

= 4580.14 kJ/kgmol

Q of C6H5NO2 = 0.338 × 4580.14= 1548.09 kJ/hr

Heat out ,Q3 = Q of C6H5NO2 + Q of H2O + Q of unreacted C6H6 + Q of H2SO4 + Q

of HNO3

= 1548.09+82.11+1362.49+102.25+285.19

=3380.13 kJ/hr

Overall heat balance around Nitrator is given by,

Heat input + heat generated = heat out

Q1 +Q2 –Qr = Q3 +Qcooling

Qcooling = 156.69 +2454.96 +49229.7 -3380.13

= 46478.61kJ/hr
Table 8 – Nitrator Energy balance

HEAT IN HEAT OUT

(kJ/hr) kJ/hr
Heat content 156.69 -
of benzene,Q1
Heat content 472.35 -
of acid
mixture, Q2
Heat output, - 3380.13
Q3
Heat of 49229.7 -
reaction ,Qr
Qcooling - 46478.61
Total 49858.74 49858.74

3.2 Separator energy balance:

Crude Nitrobenzene (5)

Acid
Benzene,nitrobenzene, acid solution (3) spent acid solution(4)
separator

Acid separator is perfectly insulated so there is no energy loss from the system and
is maintained at 50 ̊ C. (reference- kirk othmer encylopedia).
Heat in,Q3 = 3380.13 kJ/hr

Energy out:

Heat content of C 6H5NO2 = 295.3 ( 323 -298) – ( 0.8907/2)(3232-2982) + (1.705 ×

10-3)/3(3233-2983)

= 4580.14 kJ/kgmol

Heat content ,Q of C 6H5NO2 = 0.338 ×4580.14 = 1548.09 kJ/hr

Heat content of C6H6 = -33.917 (323-298) + 4.743/2 ×10-3 (3232-2982) – (3.017× 10-
4)/3 × (3233-2983) + (7.130 ×10-8)/4×(3234 -2984)

= 2160.86 kJ/kgmol

Q of C6H6 = 0.038 × 2160.86 = 82.11 kJ/hr

Heat content of H2SO4 = 139.1(50-25) + 0.1559/2(502-252)=3623.65 kJ/kgmol

Q of H2SO4 =0.0188× 3623.65=68.12 kJ/hr

Heat content of water= 32.243 (323-298) +( 1.923×10-3)/2×(3232-2982) +

(1.055×10-5)/3×(3233-2983) – (3.596×10-9)/4×(3234-2984)

= 843.75 kJ/kgmol

Q of water = 0.0169 × 843.75= 14.25 kJ/hr

Heat out of crude nitrobenzene, Q 4 = 1548.09 + 82.11 + 68.12 + 14.25

= 1712.57 kJ/hr

Heat content of H2SO4 in spent acid solution= 3623.65 kJ/kgmol

Q of H2SO4 = 0.3672× 3623.65 =1294.36 kJ/hr

Heat content of HNO3 in spent acid = 2690.81 kJ/kgmol

Q of HNO3 = 0.038× 2690.81 = 102.25 kJ/hr

Heat content of water= 843.75 kJ/kgmol

Q of water = 0.3211 ×843.75

=270.84 kJ/hr

Heat out of spent acid solution, Q 5 =1294.36 + 102.25 + 270.84

= 1667.54 kJ/hr

Table 9 – Separator Energy balance

HEAT IN kJ/hr HEAT OUT kJ/hr

Heat content of 3380.13 -
nitrobenzene,benzene
and acid mixture,Q3
Heat content of crude - 1712.57
nitrobenzene ,Q5
Heat content of spent - 1667.54
acid solution, Q4
Total 3380.13 3380.13

3.3 Washing Tank 1:

Na2 CO3 (6)

Nitrobenzene, benzene, water(7)

Washing tank
Crude nitrobenzene (5)
55 ̊ C

Sodium sulphate, carbonic acid (8)

Na2CO3 + H2SO4 → Na2SO4 + H2CO3

Assuming temperature of the washer to be maintained at 55̊ C(reference- Kirk-

Othmer encylopedia)

∆Hr = (-1413.891 -699.65) - (-1130.77-811.3) (reference – Perry’s handbook)

= -171471 kJ/kgmol

Qr = -171471 ×0.0188 = -3223.65 kJ/hr

Heat content of Na2CO3 = 111.08 (30 – 25) = 555.4 kJ/Kgmol

Q of Na2CO3 = 0.0188 × 555.4 = 10.44 kJ/hr

Heat input of crude nitrobenzene , Q 5= 1712.57 kJ/hr

Heat input of sodium carbonate, Q 6 = 10.44 kJ/hr

Heat content of Na2SO4 = 128.229(55-25) = 3846.87 kJ/kgmol

Q of Na2SO4 = 0.0188 × 3846.87 = 72.32 kJ/hr

Heat content of H2CO3 = 126.112 × (55-25) = 3783.36 kJ/kgmol

Q of H2CO3 = 0.0188 × 3783.36 = 71.129 kJ/hr

Heat content of H2O = 32.243 (328-298) +( 1.923×10-3)/2×(3282-2982) + (1.055×10-

5)/3×(3283-2983) – (3.596×10-9)/4×(3284-2984)

= 1043.06 kJ/kgmol

Q of H2O = 0.0169 × 1043.06 =17.62 kJ/hr

Heat content of C 6H6 = -33.917 (328-298) + 4.743/2 ×10-3 (3282-2982) – (3.017×

10-4)/3 ×(3283-2983) + (7.130 ×10-8)/4×(3284 -2984)
 = 2614.512 kJ/kgmol

Q of C6H6 = 0.038 × 2614.512 = 99.351 kJ/hr

Heat content of C6H5NO2 = 295.3 ( 328 -298) – ( 0.8907/2)(3282-2982) + (1.705 ×

10-3)/3(3283-2983)

= 5510.27 kJ/kgmol

Q of C6H5NO2 = 0.338 × 5510.27 = 1862.47 kJ/hr

Heat output ,Q7 = 1862.47 + 99.351 + 17.62= 1979.44 kJ/hr

Heat output of sodium carbonate and carbonic acid mixture, Q 8 = 72.32 + 71.127
= 143.45 kJ/hr

Heat input + heat generated = heat output

Q5 + Q6 -Qr = Q7 + Q8 + Qcooling

Therefore, Qcooling = 2823.77 kJ/hr

Table 10- Washing tank 1 Energy balance

Heat input kJ/hr Heat output kJ/hr

Heat content of 1712.57 -

crude
nitrobenzene,Q5
Heat content 10.44
of sodium
carbonate, Q6
Heat content of - 1979.44
benzene,
nitrobenzene
and water , Q7
Heat content of - 143.45
sodium
sulphate and
carbonic acid,
Q8
Heat of -3223.65
reaction,Qr -
Qcooling -
2823.77
Total 4946.66 4946.66

3.4 Washing tank 2:

(9) CaSO4

Crude nitrobenzene,benzene,water(7)
Washing Tank Crudenitrobenzene, benzene(11)

57 ̊C

Gypsum (10)
CaSO4 + 2H2O → CaSO4.2H2O

Heat input ,Q7 = 1979.44 kJ/hr

The temperature of the second washing tank is maintained at 330 ̊ K.(reference

Kirk-Othmer encylopedia)

Heat of formation values are taken from Perry’s handbook.

∆Hr = -2024.021 – (- 2× 285.6 – 1435.097)

= -17.724 KJ/gmol = -17724 kJ/kgmol

Qr = 0.02535× -17724 = -449.30 kJ/hr

Heat content of C 6H6 = -33.917 (330-298) + 4.743/2 ×10-3 (3302-2982) – (3.017× 10-
4)/3 ×(3303-2983) + (7.130 ×10-8)/4×(3304 -2984)

= 2798.53 kJ/kgmol

Q of C6H6 = 0.038 × 2798.53 = 106.34 kJ/hr

Heat content of C6H5NO2 = 295.3 ( 330 -298) – ( 0.8907/2)(3302-2982) + (1.705 ×

10-3)/3(3303-2983)

= 5883.89 kJ/kgmol

Q of C6H5NO2 = 0.338 × 5883.89 = 1988.75 kJ/hr

Heat content of CaSO4 = 99.73 ( 30 -25 )= 498.65 kJ/kgmol

Heat content of CaSO4, Q9 = 0.00845 × 498.65 = 4.213 kJ/hr

Heat content of CaSO4.2H2O = 186.149 (330 -298) = 5956.768 kJ/kgmol

Heat content of CaSO4.2H2O,Q10 = 151.0 kJ/hr

 Q10 = 151.0 kJ/hr

Heat content of benzene and nitrobenzene ,Q 11 = 106.34 + 1988.75= 2095.09 kJ/hr

Qcooling = Q7 + Q9 +Qr –Q10 –Q11= 186.86 kJ/hr

Table 11 – Washing tank 2 Energy balance

Heat in Heat out

Heat generated Heat of cooling
Heat content 1979.44 -
of input
stream,Q7
Heat content 4.213 -
of calcium
sulphate,Q9
Qr 449.30 -

Q10 - 151.0

Heat content - 2095.09

nitrobenzene
and
benzene,Q11
Qcooling
- 186.86
Total 2432.95 2432.95

3.5 Distillation energy balance

 Benzene(12)

80 ̊ C

Feed(11)

57̊ C 192̊ C

Nitrobenzene(13)

210 ̊C

The feed from the washing tank 2 enters in the heat exchanger at 57 ̊ C and leaves
the heat exchanger at 192 ̊ C

Heat exchanger energy balance:

Steam is entering at 250 ̊ C and leaves at 210 ̊ C.

Q11 = 2095.09 kJ/hr

Q11 (out of H.E) = ∆Hini

Heat content of C6H6 = ∆HL + λ + ∆Hv

∆HL = -33.917 (353-298) + 4.743/2 ×10-3 (3532-2982) – (3.017× 10-4)/3 ×(3533-

2983) + (7.130 ×10-8)/4×(3534 -2984)

= 5012.48 kJ/kgmol

λ = 30781 kJ/kgmol
∆Hv = 8.314 ( -0.206(465-353)+(39.064×10-3)/2×( 4652-2982) – (13.301 × 10-
6)/2(4653-2983)

= 12607.37 kJ/kgmol

Heat content of C6H6 = 48388.02 kJ/kgmol

Q of C6H6 = 0.038 × 48388.02 = 1838.74 kJ/hr

Heat content of C6H5NO2 = 295.3 ( 465 -298) – ( 0.8907/2)(4652-2982) + (1.705 ×

10-3)/3(4653-2983)

= 34706.15 kJ/kgmol

Q of C6H5NO2 = 0.338 × 34706.15 = 11730.67 kJ/hr

Q11(out of HE) = 1838.74 + 11730.67 = 13569.41 kJ/hr

QinHE + Qheating = QoutHE

Qheating = 11474.32 kJ/hr

Distillation balance:

Q11(out of HE) + Qreboiler = Q12 + Q13 + Qcondenser

Q11 = 13569.41kJ/hr

Material balance on condenser :

Antoine Equation is given as

ln P = A - B/T (reference chemical engineering thermodynamics by J.M smith)

Table 12- Empirical values of constant

 A B
Benzene 83.107 -6486.2
Nitrobenzene -6528.59

For benzene;

ln P = 83.107 + 6486.2/T

At 80 ̊ C, P = 101.48 kpa

At 210 ̊ C,P= 96.535 kpa

For nitrobenzene;

lnP = 20.960 + 6528.59/T

At 80̊ C ,P = 39.155 kpa

At 210 ̊ C,P= 34.477 kpa

Relative volatility is found from the above vapour pressure values of benzene and
nitrobenzene calculated at top (80 ̊ C) and bottom (210 ̊ C) temperature of the
column

αT = 2.592

αB = 2.799

αavg = 2.694

Rm is found using Fenske Underwood equation.

Rm = 1/(α-1)×( XD/XF – α (1-XD)/(1-XF))

= 0.361

R = 1.2 Rm
 =0.433

R =L/D

L = 0.433× 0.036 = 0.0156 kgmol/hr

V = L +D=0.036 + 0.0156 = 0.0516 kgmol/hr

Qcondenser =0.0516 × 30781 = 1588.29 kJ/hr

Heat content of C 6H6 = -33.917 (353-298) + 4.743/2 ×10-3 (3532-2982) – (3.017× 10-
4)/3 ×(3533-2983) + (7.130 ×10-8)/4×(3534 -2984)

= 5012.048 kJ/kgmol

Q of C6H6 = 0.03528 × 5012.048 =176.82 kJ/hr

Heat content of C6H5NO2 = 295.3 ( 353 -298) – ( 0.8907/2)(4532-2982) + (1.705 ×

10-3)/3(3533-2983)

= 10254.86 kJ/kgmol

Q of C6H5NO2 = 0.00144 × 10254.86 =14.76 kJ/hr

Q12= 176.82 + 14.76= 191.203 kJ/hr

Q13 = ∆Hini

Heat content of C6H6 = ∆HL + λ + ∆Hv

∆HL = -33.917 (353-298) + 4.743/2 ×10-3 (3532-2982) – (3.017× 10-4)/3 ×(3533-

2983) + (7.130 ×10-8)/4×(3534 -2984)

=5012.048 kJ/kgmol

λ = 30781 kJ/kgmol

∆Hv = 8.314 ( -0.206(483-353)+(39.064×10-3)/2×( 4832-2982) – (13.301 × 10-

6)/2(4833-2983)
 = 1595.53 kJ/kgmol

Heat content of C6H6 =37388.578 kJ/kgmol

Q of C6H6 = 0.0068 × 37388.578 =254.24 kJ/hr

Heat content of C6H5NO2 = 295.3 ( 483 -298) – ( 0.8907/2)(4832-2982) + (1.705 ×

10-3)/3(4833-2983)

= 39282.96 kJ/kgmol

Q of C6H5NO2 = 0.333 × 39282.96 = 13081.22 kJ/hr

Q13= 254.24+13081.22=13335.46 kJ/hr

Q11 + Qreboiler = Q12 + Q13 + Qcondenser

Qreboiler = 191.203 +13335.46 +1588.29 – 13569.41 = 1545.54 KJ/hr

Q = mλ

Latent heat of vapourisation of steam, λ = 2260 kJ/kg

m, steam requirement = 1545.54/ 2260

= 0.683 kmol/hr

= 12.30 kg/hr

Table 13- Distillation Column Energy balance

 HEAT INPUT KJ/HR HEAT OUT KJ/HR

Heat content 13569.41 -

of
nitrobenzene,
benzene,Q11
Heat content
of - 191.203
distillate,Q12
Heat content - 13335.46
of residue,Q13
Qcondenser - 1588.29

Qreboiler 1545.54 -

Total 15114.95 15114.95

3.6 Evaporator energy balance

Water(14)

Sulphuric acid,nitric acid,water(4) (4)

Evaporator
Acid solution out(15)

Steam is used to remove the water from the spent acid solution, steam enters at
200̊C.
Q4= 1667.45 kJ/hr

λ water = 40683 kJ/kgmol

Energy in = 1667.45 kJ/hr

Energy out:

Heat content of nitric acid =131.250(333 -298) -0.129/2 ×(3332-2982) +(0.1704*10-

3)/3 ×(3233-2983)

= 3763.53 kJ/kgmol

Q nitric acid = 0.038 × 3763.53= 143.014 kJ/hr

Heat content of H2SO4 = 139.1(60-25) + 0.1559/2(602-252)=5100.4kJ/kgmol

Q of H2SO4 =0.376 × 5100.4 = 1917.75 kJ/hr

Q15= 143.014 + 1917.75 =2060.76 kJ/hr

Heat content of H2O = 32.243 (373-298) +( 1.923×10-3)/2×(3732-2982) + (1.055×10-

5)/3×(3733-2983) – (3.596×10-9)/4×(3734-2984) + 40683

= 44034.81 kJ/kgmol

Q of H2O = .3211 × 44034.81 =14139.57 kJ/hr

Q14 = 14139.57 kJ/hr

Heat in+ Qsteam = Heat out

Qsteam = 14139.57 + 2060.76 – 1667.45=14532.88 kJ/hr

Table 14- Evaporation Energy balance

Heat input kJ/hr Heat output kJ/hr

Q4 1667.45 -
Q14 - 14139.57
Q15 - 2060.76
Qsteam 14532.88 -
Total 16200.33 16200.33
DESIGN CALCULATIONS
 CHAPTER 4

4.1 REACTOR DESIGN

C6H6+HNO3→C6H5NO2+H2O

Rate equation,

-rA=KCACB

K=1.412lit/mol hr

Design Equation:

τ = V/V0=CA0XA/-rA

V0 – Initial volumetric flow rate of inputs

FA0=1.128kmol/hr

Table 15- Mass, Density and volume table of inputs of Nitrator

Components Mass(kg) Density(kg/m3) Volume(m3)

Benzene 29.32 867 0.03347
Nitric acid 23.68 1504 0.001575
Sulphuric acid 36.84 1834 0.0020

Vo=0.069312m3=69.312l/hr

CA0=FA0/V0=CB0=1128/69.312=16.27moles/L

V=0.90*69.312/1.412*16.27*(1-0.9)2

V,Volume of reactor=271.53 L

τ=V/V0=3.917 hr

H/D=1.5
V=ΠD2H/4= ΠD3*1.5/4

Theoretical Volume = 271.53 L

Actual Volume = 271.53*1.25=339.42 L

0.33942=ΠD3*1.5/4

D= 0.69m

H= 1.5*0.69=1.035m

AGITATOR DESIGN:

Anchor type paddle agitator is used.

We do not choose flat paddle because these are simple pushers and cause mass to
rotate in laminar swirling motion. Anchors are useful for preventing deposits on a
heat transferred surface as in reaction vessel and promote complete mixing.

Configuration of anchor agitator:

Da/Dt = 0.9

Da = 0.9 * Dt = 0.9*.69 = 0.621 m

W/Da = 0.2

Agitator blade width W= 0.2*0.621=0.1242 m

L/Da = 0.25

Length of turbine L = 0.155m

C/Dt = 0.33

Clearance between agitator and tank bottom, C= .2277 m

Ha/H = 0.9
Agitator height Ha = 0.9*1.035 = 0.9315 m

J/Dt = 0.083

Baffle diameter, J= 0.69*0.083 = 0.057 m

Baffle height Hb = H-C

= 1.035-0.2277=0.807 m

Commonly we use 4 baffles.

Necessity of baffles :

1. Prevention of vortex formation and swirling

2. Allows proper mixing

In unbaffled vessel there are strong tangential flow and vortex formation at
moderate speeds. In presence of baffles ,vortex flows are decreased and there is
more rapid mixing of the liquid.

MECHANICAL DESIGN:

Material of construction – haste alloy

Reasons and properties – Haste alloy is a nickel molybdenum chromium alloy with
the addition of tungsten and has excellent corrosion resistance in a wide range of
corrosive media and is especially resistant to pitting and crevice corrosion.

Requirement of material of construction should be corrosion resistance especially

since large amount of water is used.

Jacket Design:

Total surface area = ΠDH + 2*2/3 (ΠD2/4)

= Π*0.69*1.035 + Π/3(0.69)2
 = 3.36 m2

Jacket covers 70% reactor surface so,

0.7 * 3.36 = ΠDjL + 1/3ΠDj2

Dj = D + 2(thickness)

=0.69 + 2(50 mm)

= 0.79 m

2.352 = Π(0.79)L + 1/3 Π(0.79)2

Length of jacket Lj= 0.70 m

Result

Diameter of reactor= 0.69m

Height of reactor= 1.5*0.69=1.035m

Diameter of Anchor agitator = 0.621 m

Width of anchor agitator =0.124m

Length of turbine =.155m

Agitator height = 0.9315 m

Baffle diameter = 0.057m

Baffle height = 0.807 m

Diameter of jacket=0.68

Length of jacket = 0.7m

4.2 SEPARATOR
Table 16- Mass, Density and Volume values of separator inputs

Component Mass(kg) Density(Kg/m3) Volume(m3)

Nitrobenzene 41.574 1205 0.0345
Benzene 2.964 876 0.0034
Water 6.084 1834 0.021
H2SO4 36.848 1504 0.0016
HNO3 2.394 1000 0.0061

Volume of reactants=0.0666m3

Assuming 30% extra volume

Total volume = 0.3(0.0666)+0.0666

=0.0866m3

Πd2L/4 = 0.0866m3

Taking L as 1m

d2 = 0.0866*4/Π

d = 0.34m

= 34cm

L = 100cm

Separator is placed horizontal to increase the contact area for increased acid
separation.

Material of construction – Carbon steel

Thickness ts = P Ds/ (2fj - P)

 = 1.136x0.34/(2x(6727/25)-1.136)

=0.076m

GASKET:
Internal diameter of gasket = Internal diameter of vessel = 340mm
Material used = Soft steel
For soft steel m = 3, Y = 316Kg/cm3
Outer diameter of the gasket G 0 = Gi x ((Y-mP)/(Y-P(M+1)))0.5
= 340x[(316 – 3x1.136)/(316-1.136x4)]0.5
G0 = 340.61mm
Gasket width = G0 /2
=340.61 /2
= 170.30mm
Gasket seating width b 0= Gasket width /2
= 85.155mm

Effective gasket seating width b = 0.5(b 0)0.5

= 4.613mm
Diameter of gasket load location G = ID + 2x width – (2x effective gasket
seating width)
G = 0.501m
Gasket seating load Wm1 = ᴨ GbY
= 2294Kg
Gasket seating load at operating conditions W m2 = H +Hp
Where H = ᴨ x G2 x P/4
 = ᴨ x 0.5012 x 1.136/4
=2239Kg
Also Hp = 2ᴨGmPb
=2 xᴨx3x0.501x1.136x4.613
= 1522.39Kg
Wm2 = 2239+ 1522.39
= 3761.39Kg
Bolt area = Wm2 /fb
= 3761.39/((1250/25)x 46.29)
= 65.23 cm2
Diameter of bolt chosen = 1cm
Area = ᴨ x Db2 xN
N = 65.23/(ᴨ x 1)
N = 20 bolts
Bolt circle diameter = Outer diameter of the gasket + (12 x bolt diameter) +12
= 340.61+(12x 0.1) +12
=353.81 mm
Flange thickness T = G(P/fk)0.5
K = 1/(0.3+(1.5x Wm xhg/ HxG))
hg = (B-G)/2 = (50.1- 46.13)/2 = 1.985cm
H = 2239 Kg
Wm = 2294 Kg
K = 1/(0.3+(1.5x 2294x19.85/ 2239x 50.1))
= 1.1
 T = 50.1(1.136/(1250/25)x(1.1))0.5
=72.00mm
Corrosion allowance = 2mm
Flange thickness = 72.00 +2
= 74.0mm

Result

Diameter of separator = 0.34 m

Length of separator = 1m

Thickness of separator = 0.076m

4.3 HEAT EXCHANGER

Shell and tube heat exchanger is used.

Heat supplied=114743.2 KJ/hr

=31.87311 KW

=31873.1 W

Steam entering at 2500C

Steam leaving at 2100C

Temperature of entering stream = 570C

Temperature of leaving stream =1920C

Tube side - steam

Shell side – feed stream

Assuming counter current flow,

∆T1=153

∆T2=58

∆Tlm=∆T1-∆T2/ln(∆T1/∆T2)

=95/ln(2.637)=97.940C

U taken between (800-850W/m2K) standard value for condensing steam .

Average U=825W/m2K

A=Q/U∆Tlm = 3187.3/825*97.94

= 0.3944m2

Number of tubes = A/Π d oL

Do=33mm

L=1m

=0.3944/(Π(33*10-3)1)

N=8 tubes

For 2 pass and triangular pitch,

Tube bundle dia,Db=D0*(Nt /K)1/N

K=0.249, N=2.207

Db=33*10-3[8/0.249]1/2.207

=0.279m

Shell diameter, Ds = 10% excess than tube

=1.1*0.279

Ds = 0.3061 m

Shell thickness ts=PDf/2fj-P

Design pressure=1.1*operating pressure

=1.136kg/cm2

Material of construction is mild steel

Tensile strength of steel =3975kg/cm2

Safety factor=2.5

Working stress f=3975/2.5=1590 kg/cm2

Shell thickness ,ts=1.136*30.69/2(01590)(0.85)-1.136

 ts=0.0732mm

Baffle spacing=shell diameter/5

Lb=0.3069/5= 0.06122 mm

Number of baffle = length of tube/baffle spacing

= 1000/61.22= 17

Result

Diameter of shell = 0.306 m

Length of tube = 1 m

Diameter of tube = 33mm

Number of tubes = 8

Baffle spacing = 0.06122 mm

Number of baffles = 17

Shell thickness = 0.0732 mm

4.4 DISTILLATION COLUMN

Number of plates of the column is found using McCabe-thiele Modulus method

using the values given below,

xD = 0.96

xW = 0.02

xF = 0.85

αavg = 2.694

From α value x-y data is calculated,

Table 17- Vapour liquid equilibrium data

x 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

y 0 0.23 0.402 0.535 0.67 0.73 0.8 0.86 0.92 0.96 1

From graph we get

Number of stages = 10

Number of theoretical stages/ plates = 9 (leaving condenser which is considered as

another stage)

Considering efficiency to be 75 % actual number of plates eliminating reboiler stage

is given as,

Actual number of plates = 9/0.75 = 12

Sieve tray is used here which is of 2mm thickness having 5mm hole diameter.

Material of construction of tray – stainless steel

Height
Plate Spacing=500mm=0.5m

Ht = (actual plate-1)*0.5+2*0.5

= (12-1)*0.5 + 2*0.5 = 6.5m

Diameter

Vapour rate,v = D(R+1)

=0.028(0.433+1)

=0.1kmol/hr

Top Column

Volume rate = nRT/p

=.1*8.314*353/101.325

=2.896 m3/hr

=8.0457 * 10-2m3/s

Vapour velocity=1m/s

A= volumetric flow rate/vapour velocity

ΠD2t /4 = 8.0457*10-2

Dt = 0.32m

Bottom Column

Volume rate=nRT/P

=3.716m3/ hr

=10.32*10-2m3/s
Area= 10.32*10-2m2

ΠD2b/4 = 10.32*10-2

Therefore diameter of the column, D =0.36m

Larger diameter is chosen.

Average molecular weight of vapour, Mavg = 78 (.96) + 123 (.04)

= 79.8 g/mol

Average density of vapour = PMavg/ RT

= 101.325 x 79.8/(8.314 x 353)

= 2.755 Kg/m3

Average molecular weight of liquid Mavg= 78(0.02) + 123 (.98)

=122.1 g/mol

Average density of liquid = PMavg/ RT

= 101.325 x 122.1/(8.314 x 388)

= 3.08 Kg/m3

For tray spacing of 0.5m,

Kb = 0.8, Kd = 0.9

𝜌𝐿 −𝜌𝑉
Base flooding velocity, Ub = Kb √
𝜌𝐿

3.08−2.755
= 0.8 x √
2.755

= 0.274 m/s
 𝜌𝐿 −𝜌𝑉
Top flooding velocity, Ut = Kt √
𝜌𝐿

3.08−2.755
= 0.9 x √
2.755

= 0.309 m/s

85% of flooding velocity is chosen.

Mechanical Design

Design pressure = 1.1 x operating pressure

= 1.1 x 1.035

= 1.139Kg/cm2

Material of construction : Carbon steel

Shell thickness t = P xDi /(2fj –P)

= 1.139 x 360/(2x(6727.83/25) x 0.85 -1.139)

= 0.898m

Corrosion allowance of 2mm is used

Shell thickness = 0.898 + 0.002

= 0.9m

Result

Length of the column = 6.5 m

Diameter of the column = 0.32 m

Number of plates = 12
PLANT LAYOUT
 CHAPTER 5

Plant layout is the functional arrangement of machinery and equipment in a existing

plant. Plant layout may be defined as the floor plan for determining and arranging
the desired equipment of a plant, in the one best place, to permit the quickest flow
of materials at lowest cost and least amount of handling in processing the raw
material from the receipt of raw material to the shipment of finished products.

The material handling planned in the layout begins at the receiving point , where the
material arrives as raw material, then continuous progressively from storage through
process, moving the from of worked material from department to department , from
machine to machine, the material flows in and out of temporary storage is fed
through assembly lines for final assembly. Provision is made for inspection,
packaging and storing the material as finished product.

Fundamental concepts of plant layout

In apprising the advantages of good layout in the light of conditions prevailing in a

particular plant, it is well to bear in mind the following concepts of plant layout.

Major part of production works is not processed, as is initially suppose but

material handling.

Then speed of production in the plant is determined primarily by the

adequacies of its material handling facilities. A good plant layout is designed to
provide the proper facility for material handling.

The factory is altered or constructed around the prescribed plant layout. The
production efficiency of the plant is determined by the limitations of its layout.
TYPES OF DEPARTMENT

Processing Department- This Department performs machining assembly and

packaging.

Service Department- These constitutes the facilities provided keep the processing
department in operation without interruption.

Administrative Service department- This department administers sales, engineering,

accounting, production control departments,etc.

PLANNING THE PROCESSING

The plant layout engineer should obtain data on building elevation, column
spacing, door and conveyors. The conveyors should be placed at reasonable height
to mal functioning and waste.

The traffic in the plant may be greatly by location store rooms close to the
building entrances. In addition to the above vehicular traffic should be separated
from pedestrian traffic and the roads should be wider.

PLANNING THE PLANT SERVICE FACILITIES

• Material received at a plant arrives via the particular forms of transportation which
are generally prescribed.

• Liquids such as chemicals are transported in tank cars, drums or pipelines

• The receiving department must be well equipped to receive the material in all
modes.

• The design of a receiving involves the following considerations:

 1.Space, 2. climate conditions, 3. variety of vehicles

STORE ROOM

A store room is the reservoir for raw material. Worked materials, finished
products, maintenance supplies etc are kept.

The functional requirements of a store room are:

1.protection to materials

2.handling of the materials

3.control points
The above factors also help the layout engineer to design the store room as per
requirements.

INSPECTION ROOM

The inspection room or quality control room should be located near then production
unit, so that the samples from the production plant Can be checked for its quality
requirements. The labs should be well equipped and should be properly planned.

WATER STORAGE

Water is used in the plant for variety of purposes.A plant must have adequate water
supply to crater all these needs. By far the most reliable and effectives means of fire
protection is the automatic sprinkler system. The sprinkler system is fitted with a
sensitive transducer which lets water up to a height of 15 feet. So the water storage
system should be planned out with most more.

POWER AND LIGHTING SYSTEM:

• Power and lighting systems forms the main part of the plant.

• The significant features of the power plant operations are,

1.For supplying steam.

2.Providing heat for process operations.

3.supplying power to run motor.

4.providing light to plant.

5.power for surplus use.

PLANNING OF ADMINISTRATIVE BLOCK

Location of an administrative block depends upon the geographic location with

respect to the plant functions. The general administrative block should have
administrative rooms, conference room and vault room storage of documents and
records. The employee service facility consists of parking lots, Employment office
cafeteria, first aid stations and medical department etc.

STORE

ROOM
 WATER

STORAGE

INSPECTION

ROOM

PROCESSING AREA

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TRAINING CENTRE SECURITY

ADMIN
ROOM BLOCK
BLOCK
COST ESTIMATION

CHAPTER 6
COST ESTIMATION

Table 18-Process equipment cost

Sl.No Equipment Unit Rate Total cost

1 Mixed Reactor 1 10,00000 10,00000

2 Separating tank 1 85,000 85,000

3 Washing tank 1 1 70,000 70,000

4 Washing tank 2 1 70,000 70,000

5 Distillation column 1 20,00000 20,00000

6 Evaporator 1 2,50000 2,50000

7 Preheater 1 2,25000 2,25000

8 Condenser 1 2,25000 2,25000

9 Reboiler 1 2,25000 2,25000

Total 4150 000

Process Equipment Cost, PEC = Rs 4150000

TOTAL DIRECT COSTS DETAILS

Table 19- Total direct cost

Sl.no Type Amount Rs.
1. Purchase equipment cost 4150000

2 Instrumentation (5% 2,07500

PEC)

3 Electrical (15% PEC) 622500

4 Piping (25% PEC) 10,37500

5 Building (40% PEC) 16,60000

6 Service Facilities (10% 4,15000

PEC)

7 Yard Improvement (15% 6,22500

PEC)

8 Land Cost(10 acres) 10,000000

TOTAL DIRECT COSTS : 18,715,000

INDIRECT COSTS DETAILS

Table 20- Indirect cost

S:NO TYPE AMOUNT

Rs:

1. Engineering and 12,45000

supervision
(30% PEC)

2.
Construction expenses 12,45000
(30% PEC)

3. Construction fees(10 % of
DC) 18,71500

4. Contingency (5% of DC) 9,35750

TOTAL INDIRECT COSTS : Rs. 5,297250

TOTAL CAPITAL INVESTMENT

Fixed capital investment (FCI): = Total direct costs + Total indirect costs

= 18,715000 + 5,297250
 =Rs. 24,012,250

Start up capital = 10% FCI

= Rs.2,401225

Working capital = 25% FCI

= Rs. 6,003,0625

DIRECT PRODUCTION COSTS

No: of working days : 300 days / year.

RAW MATERIAL COST DETAILS

Table 21- Raw material cost

S.NO Raw Material Cost per kg Quantity Total cost

Kg
1 Benzene 55 211161 11613888
2 Nitric acid 15 170553 2558304
3 Sulphuric acid 12 265305 3183667.2
4 Sodium 18 14348 258266.88
carbonate
5 Calcium 12 16548 198581.76
sulphate

RAW MATERIAL COST : Rs .17812707.84

UTILITY COST DETAILS

Table 22- Utility cost

Sl.no Utility Total cost

1 Power 500 units/ton of 16560000
nitrobenzene
2 Water 1800000
3 Packing cost 800000

UTILITY COSTS : Rs. 19160000

OPERATING LABOUR COSTS

Table 23 – Operating labour cost

Sl.no Designation Number of Salary per Total salary

employees month per month
1 Plant 2 50000 100000
Manager
2 Shift manager 4 40000 160000
3 Engineers 5 30000 150000
4 Operators 12 14000 168000
5 Electricians 4 10000 40000
6 Lab 5 10000 50000
technician
7 Fire officer 2 8000 16000
8 Medical 1 24000 24000
officer
9 administrative 10 8000 80000
10 Security 3 4000 12000

TOTAL COST = Rs.8,00000

Operating labour cost per annum (OLC) = 800000 × 12 = 96,00000

MISCELLANEOUS FIXED COSTS DETAILS :

Stores maintenance and repair (10% FCI ) : Rs.24,01225

Depreciation (4% FCI) = Rs. 96, 0490

Total Miscellaneous Fixed Costs = Rs . 3,361715

TOTAL MANUFACTURING COST =Raw material cost + utilities +

Operating and maintenance cost +

miscellaneous cost

= Rs . 49934422.84

SALES REVENUE

Selling price of nitrobenzene = Rs. 35/kg

Amount produced = 300000 kg

Sales Revenue (SR) =10500000

PROFIT

PROFIT = Sales revenue - Total manufacturing cost

= 10500000– 4993442284
 = 39.43 crores per annum

Tax rate = 40 %

tax = 15.772 crores

Net Profit = 23.66 crores

Pay back period = ( fixed capital cost + O &M)/(depreciation + Profit 40% tax)

= 3.2 years
SAFETY AND HEALTH ASPECTS
 CHAPTER 7

Safety is an important aspect followed in any industry. Safety handling practices

must begin with an assessment of its use from the laboratory to full manufacturing
processes, by the establishment of an appropriate safety program.
A safety committee is responsible for personnel protection and should establish
safety programs. The following are safety procedures to be followed while handling
the substance.

MATERIAL SAFETY DATA SHEET

NITROBENZENE

Hazards identification
Appearance: colourless to pale yellow liquid.
Physical state : Liquid
Odour: Almond like
Routes of entry : skin contact and inhalation
Medical conditions aggravated by exposure : May be fatal if swallowed. Causes
eye, skin, and respiratory tract irritation. Possible risk of impaired fertility.

First Aid Measures

Eyes: Immediately flush eyes with plenty of water for at least 15 minutes,
occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin: Get medical aid immediately. Flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and shoes.
Ingestion: Call a poison control centre. If swallowed, do not induce vomiting unless
directed to do so by medical personnel. Never give anything by mouth to an
unconscious person. Get medical aid.
Inhalation: Get medical aid immediately. Remove from exposure and move to
fresh air immediately. If not breathing, give artificial respiration. If breathing is
difficult, give oxygen.
Notes to Physician: Absorption of this product into the body may cause
cyanosis(bluish discoloration of skin due to deficient oxygenation of the blood).
Moderate degrees of cyanosis need to be treated only by supportive measures: bed
rest and oxygen inhalation. For methemoglobinemia, administer oxygen alone or
with Methylene Blue depending on the methemoglobin concentration in the blood.
Cleansing of the entire contaminated area of the body is of utmost importance.

Fire Fighting Measures

Extinguishing Media: Use water spray, dry chemical, carbon dioxide, or
appropriate Foam.

Accidental Release Measures:

Spills/Leaks: Absorb spill with inert material (e.g. vermiculite, sand or earth), then
place in suitable container. Wear a self contained breathing apparatus and
appropriate personal protection. (See Exposure Controls, Personal Protection
section). Remove all sources of ignition. A vapor suppressing foam may be used to
reduce vapours.

Handling and Storage:

Handling: Wash thoroughly after handling. Remove contaminated clothing and
wash before reuse. Ground and bond containers when transferring material. Use
spark-proof tools and explosion proof equipment. Do not get in eyes, on skin, or son
clothing. Empty containers retain product residue, (liquid and/or vapour), and can
be dangerous. Keep container tightly closed. Do not ingest or inhale. Do not
pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat,
sparks or open flames. Use only with adequate ventilation. Keep away from heat
and flame.

Storage: Keep away from sources of ignition. Do not store in direct sunlight. Store
in a cool, dry, well-ventilated area away from incompatible substances.

Exposure Controls/Personal Protection:

Engineering Controls: Use adequate general or local exhaust ventilation to keep
airborne concentrations below the permissible exposure limits

Personal Protective Equipment

Eyes: Wear chemical splash goggles.
Skin: Wear appropriate gloves to prevent skin exposure.
Clothing: Wear appropriate protective clothing to prevent skin exposure.
Respirators: Follow the OSHA respirator regulations found in 29 CFR 1910.134 or
European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149
approved respirator if exposure limits are exceeded or if irritation or other
symptoms are experienced.

Stability and Reactivity

Chemical Stability: Stable at room temperature in closed containers under normal
storage and handling conditions.
Conditions to Avoid: High temperatures, incompatible materials, ignition sources.
Incompatibilities with Other Materials: Substance can dangerously react with
nitric acid, phenol, aluminium chloride, aniline, glycerine, silver perchlorate, di
nitrogen tetroxide, caustics, tin, and zinc.
Hazardous Decomposition Products: Nitrogen oxides, carbon monoxide, carbon
dioxide.
Hazardous Polymerization: Has not been reported.

BENZENE
Potential health effects
Inhalation
Short Term Exposure: irritation, ringing in the ears, nausea, vomiting, chest pain,
difficult in breathing, irregular heartbeat, headache, drowsiness, symptoms of
drunkenness, disorientation,blurred vision, lung congestion, blood disorders,
paralysis, convulsions, coma
Long Term Exposure: hearing loss, visual disturbances, reproductive effects, brain
damage,cancer
Skin contact
Short Term Exposure: irritation, blisters
Long Term Exposure: tingling sensation
Eye contact
Short Term Exposure: irritation
Long Term Exposure: no information on significant adverse effects
Ingestion
Short Term Exposure: nausea, vomiting, chest pain, headache, drowsiness,
symptoms of drunkenness, disorientation, visual disturbances, lung congestion,
paralysis, convulsions, coma
Long Term Exposure: impotence, cancer
First Aid Measures
Inhalation
When safe to enter area, remove from exposure. Use a bag valve mask or similar
device to perform artificial respiration (rescue breathing) if needed. Keep warm and
at rest. Get medical attention immediately.
Skin contact
Remove contaminated clothing, jewelry, and shoes immediately. Wash with soap or
mild detergent and large amounts of water until no evidence of chemical remains (at
least 15-20minutes). Get medical attention, if needed.
Eye contact
Wash eyes immediately with large amounts of water or normal saline, occasionally
lifting upper and lower lids, until no evidence of chemical remains. Get medical
attention immediately.
Ingestion
Contact local poison control centre or physician immediately. Never make an
unconscious person vomit or drink fluids. When vomiting occurs, keep head lower
than hips to help prevent aspiration. If person is unconscious, turn head to side. Get
medical attention immediately.

Fire Fighting Measures

Extinguishing media:
regular dry chemical, carbon dioxide, water, regular foam
Large fires: Use regular foam or flood with fine water spray.
Fire fighting:
Move container from fire area if it can be done without risk. Cool containers with
water spray until well after the fire is out. Stay away from the ends of tanks.
For fires in cargo or storage area: Cool containers with water from unmanned hose
holder or monitor nozzles until well after fire is out. If this is impossible then take
the following precautions: Keep unnecessary people away, isolate hazard area and
deny entry. Let the fire burn. Withdraw immediately in case of rising sound from
venting safety device or any discoloration of tanks due to fire. For tank, rail car or
tank truck, Evacuation radius: 800 meters (1/2 mile). Water may be ineffective.
 CALCIUM SULPHATE

First-Aid Measures
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting
the upper and lower eyelids. Get medical aid immediately.
Skin: Get medical aid. Flush skin with plenty of water for at least 15 minutes while
removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion: If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never
give anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation: Remove from exposure and move to fresh air immediately. If not
breathing, give artificial respiration. If breathing is difficult, give oxygen. Get
medical aid.
Fire Fighting Measures
Extinguishing Media: Use water spray, dry chemical, carbon dioxide, or
Appropriate foam.

SODIUM CARBONATE

First-Aid Measures
Eye Contact
Check for and remove any contact lenses. In case of contact, immediately flush eyes
with plenty of water for at least 15 minutes. Cold water may be used. Get medical
attention.
Skin Contact
In case of contact, immediately flush skin with plenty of water. Cover the irritated
skin with an emollient. Remove contaminated clothing and shoes. Cold water may
be used. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get
medical attention.
Serious Skin Contact
Wash with a disinfectant soap and cover the contaminated skin with an anti-
bacterial cream. Seek immediate medical attention.
Inhalation
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If
breathing is difficult, give oxygen. Get medical attention.

CONCLUSION
In this project the manufacture of 1 ton of nitrobenzene per day has been dealt.
Nitrobenzene is used for the production of aniline. The process used for
manufacturing nitrobenzene is continuous isothermal process. A detailed process
flowsheet, material and energy balances have been done. The detailed design of
some equipments, cost estimation, safety aspects have been discussed. In India till
date there are many companies manufacturing Nitrobenzene. This project has short
pay back period and so it is found to be economically feasible.

REFERENCE
1. Kirk and Othmer, Encyclopedia of chemical technology vol.15.
2. Robert H.Perry, Perry’s chemical engineers hand book 5th and 6th edition.
3. John J.Mcketta, Encyclopedia of chemical processing & design,vol.31.
4. George T.Austin, Shreve’s Chemical Process industries 5th edition.
5. K.A. Gavhane,Process calculations.
6. M v Joshi, Process Equipment Design.
7. Treybal R.E, Mass Transfer Operations.
8. K.A. Gavhane, Chemical Reaction Engineering, 9th edition.
9. McCabe and Smith, Unit Operations of Chemical Engineering.
10. K.A.Gavhane, Mass Transfer, revised edition.