Production of Aniline by Hydrogenation of Nitrobenzene: Anusha Halageri Glen Pauls Ananya Srivastava
Production of Aniline by Hydrogenation of Nitrobenzene: Anusha Halageri Glen Pauls Ananya Srivastava
Production of Aniline by Hydrogenation of Nitrobenzene: Anusha Halageri Glen Pauls Ananya Srivastava
nitrobenzene
Anusha Halageri Glen Pauls Ananya Srivastava
Department of Chemical Engineering Department of Chemical Engineering Department of Chemical Engineering
Ramaiah Institute of Technology Ramaiah Institute of Technology Ramaiah Institute of Technology
Bangalore, India Bangalore, India Bangalore, India
[email protected] [email protected] [email protected]
Abstract—Aniline, an important compound in organic chem- be done under relatively mild conditions. [4] However, in
istry, is mainly used to synthesize polyurethane and its precur- this paper, the side reactions and formation of intermediates
sors. Being one of the most important industrial chemicals, it have been neglected. Hence, simulation has been performed
is used to produce other industrial chemicals like methylene
diphenyl diisocyanate (MDI), cyclohexylamine, benzoquinone, accordingly. These assumptions were made due to lack of
alkyl anilines, methylene dianiline etc. In this study, production literature or existing papers available for the simulation of the
of aniline at 10 tons/h was done by reducing nitrobenzene using process. Basic knowledge from scientific papers was taken into
hydrogen and this process was simulated using DWSIM open consideration to create the DWSIM flowsheet and simulation.
source software. The operating conditions of the different unit The non-random two-liquid model (NRTL) is an activity
operations for this simulation were selected to achieve 75 percent
conversion of nitrobenzene to aniline. Heat integrations were coefficient model used to calculate phase equilibria and mainly
done by heating the reactants with the heat liberated from applied for processes involving polar compounds. In this pro-
reactor. The property packages used were Lee-Kesler-Plocker cess, there are 3 polar chemicals, namely, nitrobenzene, aniline
and NRTL models. Sensitivity analysis was performed on three and water. Hence, the NRTL property package was selected.
of the main units used in the process i.e. on the cooler, heat Lee-Kesler-Plocker (LKP) model is applied for systems with
exchanger and distillation column.
high Hydrogen content. Since the production of aniline is done
Keywords—Nitrobenzene, Aniline, Hydrogenation, Sensitivity by hydrogenation of nitrobenzene it was necessary to apply
Analysis, Rigorous Distillation this property package.
II. P ROCESS DESCRIPTION
I. I NTRODUCTION The main process for aniline production is hydrogenation
Aniline is an organic compound consisting of a phenyl of nitrobenzene, given by the reaction equation:
group attached to an amino group, where aniline is the proto-
typical aromatic amine. The amino group provides unique re- C6 H5 N O2 (g) + 3H2 (g) → C2 H5 N H2 (g) + 2H2 O(g)
activity which makes it an industrially important intermeditate.
[1] It is a flammable liquid chemical and is slightly soluble in The process flowsheet designed for the production of aniline
water. It is also known as phenylamine or aminobenzene. from nitrobenzene and hydrogen is shown in Fig.1.
Its main applications are in the production of herbicides, Nitrobenzene (MSTR-NB) at room temperature of 24◦ C
dyes, explosives, pigments, pesticides, plastics (polyurethanes) is sent to a heat exchanger (HE-1) where it is heated to
where aniline acts as an important intermediate. In the field of 214.93◦ C. The heated nitrobenzene (MSTR-NB1) is then sent
pharmaceuticals, paracetamol (acetaminophen), a widely used to the heater (HEAT-1) and further heated to 450◦ C. Gaseous
antipyretic is also prepared from aniline. [2,3] Polyaniline, an nitrobenzene (MSTR-NB2) gets mixed with gaseous hydrogen
intrinsically conducting polymer is also produced from aniline. (MSTR-H2) in a mixer (MIX-1). This reactants mixture stream
Aniline is formed by the reduction of nitrobenzene using (MSTR-1) is sent to the conversion reactor (RCTR) where the
hydrogen. This process was proposed by Haber and his reaction takes place at 330◦ C. [5]
initial scheme was published in 1898. The scheme proposed Standard Gibbs free energy was calculated using enthalpy
that the transformation of nitrobenzene to aniline is a three- and entropy data from the literature for every compound.
step process in which the intermediates nitrosobenzene and Further, the reaction’s equilibrium constant was found and
phenylhydroxylamine are formed. In addition to this, it was equilibrium conversion was calculated. For this process, an
suggested that the by-products azobenzene, azoxybenzene, approximate of 75 percent conversion with respect to nitroben-
and hydrazobenzene could be formed via a side reaction zene was obtained. This value was entered in the conversion
of the above intermediate species. Hydrogenation can also reactor (RCTR) to obtain the desired yield of aniline.
be done using a catalyst to enhance the rate of reaction The heat of reaction from the reactor is used to heat the
but the transformation is extremely superficial and needs to feed nitrobenzene in the heat exchanger (HE-1). After heat
Fig. 1. DWSIM flow sheet
exchange the mixture is at 163◦ C and is now sent to a Since aniline is more volatile than nitrobenzene, it was
cooler (COOL-1) to further reduce its temperature to 50◦ C. obtained as distillate product from distillation column 1 (refer
The cooled mixture (MSTR-5) contains only hydrogen in the first half of table 2). The less volatile component, nitrobenzene,
vapor phase which is removed using a phase separator (PS- was observed in residue with a mole fraction of about 0.843
1).The liquid stream (MSTR-7) from the phase separator is (refer second half of table 2) which is further purified in
sent to a compound separator (CS-1) (which has been assumed distillation column 2. Again in the other distillation column,
to be a decanter) where water is completely separated from the nitrobenzene was obtained as residue product which could be
organic mixture. reused again by recycling. To avoid accumulation of reactants,
This organic mixture of nitrobenzene and aniline (MSTR- a part of the recycled stream was removed as purge.
8) is sent to a distillation column (DSTL) to separate aniline
and nitrobenzene based on their boiling points. Rigorous TABLE I
distillation column model of DWSIM has been used to sim-
ulate the distialltion column. The preliminary data required Products from reactor
for the rigorous distillation column (DSTL-1) was generated
using a short cut distillation column assuming the top product Species Mass Flows (kg/h) Mole Fraction
composition (MSTR-AP) to be 98.1 percent aniline. Aniline 11482 0.246
Nitrobenzene coming in the residue (MSTR-NBR) consists Water 4411.99 0.488
of traces of aniline which is further purified using another Nitrobenzene 4936.18 0.08
distillation column (DSTL-2). The recovered nitrobenzene Hydrogen 187.11 0.185
stream (MSTR-NBR1) is recycled and a part of the recycle
stream is purged.
TABLE II
III. R ESULTS AND D ISCUSSION Products from distillation column 1 (Distillate and Residue)
A. Sensitivity Analysis for Cooler was cooled to 50◦ C to separate the unreacted hydrogen. The
Hydrogenation of nitrobenzene to aniline is an exothermic water present along with the aniline and nitrobenzene forms
reaction occurring at 330◦ C. The reactor product stream a two phase liquid mixture which could be separated using a
contains aniline, water and unreacted reactants nitrobenzene, decanter.
hydrogen. After being sent to the heat exchanger, the products B. Effect of reflux ratio
attain a temperature of 163.69◦ C. They were further cooled by
For the Distillation Column (DSTL-1), where a mixture of
the cooler to facilitate the formation of two phases. The vapor
aniline and nitrobenzene (MSTR-8) is separated, sensitivity
phase after cooling mainly consisted of unreacted hydrogen
analysis was done by varying the reflux ratio from 1 to 6 and
which was separated using a gas-liquid separator. In order to
its effect on condenser duty, distillate molar flow, reboiler duty
determine the temperature at which maximum phase separa-
and number of stages was analyzed. However, no effect on any
tion occurs, a sensitivity analysis was performed on the coolers
of the above parameters was observed by the software (refer
output stream (MSTR-5). Change in mass flow of each of the
Fig.4). Hence, a manual analysis was performed by changing
species, in vapor phase, was studied for a temperature range
the number of stages and noting the effect on the distillate
of 50◦ C to 150◦ C. The tabulated and graphical results are
and residue compositions. These results have been mentioned
shown in Fig. 2 and Fig. 3 respectively. At 50◦ C, aniline was
below in Table 3.
TABLE III
IV. C ONCLUSION
Process simulation for the production of aniline by reduc-
tion of nitrobenzene was done using DWSIM. The various
thermodynamic data were entered for each unit operation
after thorough research and calculation for its feasibility.
The simulation 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, the team felt that the sensi-
tivity analysis parameters could be improved i.e. more number
of dependent and independent variable combinations could be