MEMO # 2

TO:

J. C. WATTERS

FROM:
SUBJECT:

NITROBENZENE PROCESS INDUSTRIES: REACTION PATH ANALYSIS

DATE:

SEPTEMBER 9, 2013

DUE DATE:

SEPTEMBER 13, 2013

Commercial production of nitrobenzene is achieved by the nitration of benzene; there are no

other reaction pathways that are utilized on the industrial scale. Nitration is achieved by
application of mixed acid, a solution of water, sulfuric acid, and nitric acid. The mechanism
proceeds via electrophilic aromatic substitution, with a positively-charged nitronium ion
intermediate. The sulfuric acid acts as a catalyst, facilitating nitronium formation but
regenerating upon removal of a hydrogen atom from the benzene ring. The reaction can be
illustrated as follows:

Nitronium Formation
Aromatic Substitution
Catalyst Regeneration
Total

HNO3 + H2SO4 NO2+ + HSO4- + H2O

C6H6 + NO2+ + H2O C6H5NO2 + H3O+
H3O+ + HSO4- H2SO4 + H2O
HNO3 + C6H6 C6H5NO2 + H2O

All three reactive steps can occur simultaneously and concurrently in situ; separate reactors for
each step are not required. Net energy of 117 kJ/mol is released as the reaction proceeds.
Added value of this pathway is calculated below, using precursor spot prices, and estimated
precursor contract prices at a 10% discount.
Nitric Acid
Benzene
Nitrobenzene
Total VA

63.01 g / mol
78.11 g / mol
123.06 g / mol

$0.20 / lb
$0.58 / lb
$0.65 / lb

1 eq
1 eq
1 eq

$0.05 / lb
$0.06 / lb

(spot)
(contract)

There are a few different ways of achieving this reaction on an industrial scale. Batch processes
were used in the past but have since been overshadowed by the sheer throughput of continuous
processes. Liquid-phase and vapor-phase continuous nitration plants both exist, but nowadays
production facilities producing 100,000 tons per year or more are dominated by the liquid-phase
design. Further subdivisions include the historically standard isothermal liquid process, and the
newer adiabatic liquid process. These two will beare compared in the remainder of this
document.
The adiabatic and isothermal processes differ solely in the process conditions of the reactor(s),
and how the enthalpy of reaction is handled. Both processes can use one to four stirred tank or
plug flow reactors, at or near atmospheric pressure. Both processes also utilize one or more
separation steps (centrifuge, extractor, etcetc.) to purify the final product. An acid
reconcentration and recycling stream is often included, with similar designs for both setups.
Main differences between the two schemes are outlined in the following table:

Acid Makeup
Temperature
Reaction Time
Theoretical Yield

Isothermal

Adiabatic

20-26% HNO3, 56-65% H2SO4

50 - 100*C
10 - 30 mins
96 99%

4-8% HNO3, 62-64% H2SO4

80 - 140*C
5 - 25 mins
99.3 99.8%

The adiabatic scheme offers quite a few advantages over the isothermal scheme. The lower acid
concentration allows cheaper, less dangerous azeotropic nitric acid (68% concentration) to be fed
into the system, rather than the 98% acid required by the isothermal process. Reaction times are
lower and theoretical yield with one reactor is higher in the adiabatic setup as well. The most
significant difference is in reactor temperature. In the isothermal process, the reactor is often
fitted with a cooling jacket or coils and a cooling water system in order to remove excess heat
from the reaction. Acid distillation is then facilitated with steam heating. This requires a
significant utilities expense. The adiabatic process allows the reactive mixture to heat up, and
with a heat exchanger downstream from the reactor, uses this heat to fuel the subsequent acid
reconcentration. This allows the process to be run almost autothermally, with very little heat
energy input required.
Process hazards are essentially identical between the two schemes. The exothermic nature of the
process leads to high-temperature conditions. Care would have to be taken to properly insulate
lines and equipment, both for energy conservation and personnel safety. Nitric and sulfuric acid
present corrosion and operator exposure hazards. Benzene and nitrobenzene are flammable and
carcinogenic. High heat in very acidic conditions may call for higher-strength alloys or glass
linings to be used on piping or vessels. In both cases, pressure fluctuations can affect separation,
distillation, and mixing efficiency, but engineering controls will be put in place to maximize
production.
After analyzing documentation for each of the process schemes, it is advised to proceed with
design of an adiabatic nitrobenzene production system.

Bibliography
Booth, Gerald. "Aromatic Nitro Compounds." Ullman's Encyclopedia of Industrial Chemistry.
Weinheim: Wiley-VCH, 2002. Wiley Online Library. Web.
Dugal, Markus. "Nitrobenzene and Nitrotoluenes." Kirk-Othermer Encyclopedia of Chemical
Technology. John Wiley & Sons, 2000. Wiley Online Library. 14 Oct. 2005. Web. 10
Sept. 2013.
Dugal, Markus. "Aniline and its Derivatives." Kirk-Othermer Encyclopedia of Chemical
Technology. John Wiley & Sons, 2000. Wiley Online Library. 14 Oct. 2005. Web. 10
Sept. 2013.
Kirschner, Mark. "Chemical Profile: Nitrobenzene." ICIS.com. Reed Business Information
Limited, 25 Apr. 2005. Web. 2 Sept. 2013.