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National Conference on Chemical Process


Production of aniline by hydrogenation of nitrobenzene


Aniline is an organic compound consisting of a phenyl group attached to an amino group, where
aniline is the prototypical aromatic amine.
The amino group provides unique reactivity which makes it an industrially important
Properties: It is a flammable liquid chemical and has pungent unpleasant odor. It is slightly
soluble in water. Its color ranges from colorless to brown and is oily to touch.
1. Herbicides, dyes, explosives, pesticides, plastics(polyurethanes) and other pigments.
2. Paracetamol (acetaminophen)
3. Intrinsically conducting polymer, polyaniline.
Mechanism used: Haber’s process was taken as the basis i.e. hydrogenation of nitrobenzene.
Global demand and production of aniline

As the global consumption of aniline is

increasing by the year, new novel methods
for production of aniline are going to be a
necessity in order to meet its global
consumption demand.

Global consumption graph

DWSIM flowsheet
1) Conversion Reactor
𝐶6 𝐻5 𝑁𝐻2 + (products)
𝐻2 𝑂
𝐶6 𝐻5 𝑁𝑂2 + 𝐻2 Reactor
𝐶6 𝐻5 𝑁𝑂2 + (unreacted reactants)

Compound Mole fraction Mass flow (kg/h)

Aniline 0.24 11482.442
Water 0.48 4411.468
Nitrobenzene 0.08 4935.59
Hydrogen 0.18 187.19
2) Heat Exchanger
Feed Nitrobenzene

Reactor output Reactor output

stream stream
(311°C) (163°C)

Feed Nitrobenzene

• Nitrobenzene at room temperature of 24°C is sent to a heat exchanger to be heated to a temperature of

• The heat of reaction from the reactor is used to heat the feed nitrobenzene in this heat exchanger.
• After this heat exchange the output stream from the reactor, containing the products and unreacted
reactants, is cooled to a temperature of 163°C.

(Manual analysis done on cold

and hot fluid temperatures)
3) Cooler

Reactor Reactor
Output Cooler Output
(163 °C) (50°C)

• The cooler is used to bring down the temperature of reactor output, to bring down aniline
concentration in vapour phase.
• Also at a temperature below 100°C, aniline, nitrobenzene and water will be in liquid state while
hydrogen would be in vapor. This helps in easier separation.
• Using the software, a sensitivity analysis was performed on the cooler’s output stream. This stream
contains aniline, water, nitrobenzene, hydrogen at a temperature of 50◦C and 1.4 bar.
• Change in mass flow of each of the species, in vapour phase, was studied for a temperature range of
50◦C to 150◦C. The tabulated and graphical results are shown in the next slide.
Sensitivity Analysis table and chart
4) Phase Separator

Hydrogen (vapor)
Reactor Phase
output Separator
Aniline +
stream (liquid)
Nitrobenzene +

The phase separator is essentially a gas-liquid separator. The reactor mixture exiting the cooler consists
of 92% hydrogen in vapor phase which is separated here.
5) Decanter (component separator)

Aniline + Water (Inorganic)

(liquid) Nitrobenzene + Decanter
Water Nitrobenzene + Aniline (Organic Mixture)

• The compound separator used , is assumed to be a decanter since decanter is not available in the
• The material stream entering the decanter consists of aniline, nitrobenzene and water. Aniline and
nitrobenzene forms an organic mixture which is partially miscible with water (negligible). Therefore
water is separated from the organic mixture using the decanter.
6) Distillation column

Aniline (98% pure)

Aniline + Nitrobenzene Distillation
Nitrobenzene (84% pure)

• Since aniline and nitrobenzene are organic solvents, distillation is the best applicable separation
• Aniline has a boiling point of 184.1°C while nitrobenzene has a boiling point of 210.9°C. Therefore, these
compounds can be easily separated using the distillation column.
• The no. of stages required and optimum feed entry stage is first found out using shortcut distillation
column data, this data is then inputted into the rigorous distillation column.
• It is observed that aniline (distillate) has a purity of 98% which is as desired, however, nitrobenzene
(residue) is only 84% pure.
• To increase the efficiency and optimize the simulation we send the residual product to a 2nd rigorous
distillation column which gives us a 91% pure nitrobenzene.
• For the 1st Distillation Column, where a mixture of aniline and nitrobenzene is separated, sensitivity
analysis was performed by varying the reflux ratio from 1 to 6 and its effect on condenser duty, distillate
molar flow, reboiler duty and number of stages was analyzed.
• However, no effect on any of the above parameters was given by the software, as shown in figure. Hence,
a manual analysis was performed by changing the number of stages and noting the effect on the distillate
and residue compositions. These results have been mentioned below in table.


( Manual analysis on upstream and

downstream aniline composition)
It was observed that at a temperature and pressure of 311.17◦C and 1.4 bar, the product stream
from reactor contained aniline in large quantity i.e. around 11 tons/h.
Even though large amount of aniline was produced, it was a diluted stream with mole fraction of
about 0.246. Therefore, its purity was improved using two distillation columns, a phase separator
and a decanter.
From the sensitivity analysis studies done by the software and manual analysis performed by the
user, the following observations can be concurred:
Greater the heat exchanged between the hot and cold fluid in the heat exchanger, greater is the
process optimization and efficiency, since the electrical load on the cooler and heater will be lower.
Lower the temperature of cooler output, greater is yield of aniline.
As the number of stages increases, greater separation and hence greater purity of aniline is
•Simulation using DWSIM yielded good results providing with better knowledge relating the
thermodynamics and kinetics of the reaction.
•Number of separation units were included based on the different separation principles to obtain
considerable purity of the final aniline product.
•Sensitivity analysis was performed on the cooler and it showed that as the outlet temperature of
the cooler increases, mass flow of aniline in vapor phase also increases. Hence, lower temperature
condition is preferred in order to get higher mass flow of liquid aniline which is the desired product.
•While working with DWSIM, it was felt that the sensitivity analysis parameters could be improved
i.e. more number of dependent and independent variable combinations could be added in the
software, because, even after trying to perform different types of analysis on the process, the
desired results were not obtained from the software. It was possible only after manually changing
the specifications of the unit. Also, the software could include other objects like decanter,
crystallizer, extractor, dryer etc. to improve the simulation and flowsheet design