2.0.

LITERATURE

Aniline if manufactured by various processes. Hydrogenation of nitrobenzene is currently being

used to produce on a commercial scale. In United States, manufacturing is aniline is predominantly on the
continuous, vapour phase, catalytic reduction of nitrobenzene. In previous years, 97% of nitrobenzene
production is captive to aniline manufacture. [1]

Manufacturing of aniline from hydrogenation of nitrobenzene requires the materials and suitable
processing conditions which is displayed in Table 2.1.

REACTION CONDITIONS

The stochiometric equations describing Table 2.1: Materials required

the reaction of nitrobenzene to yield aniline, are
Substrate Nitrobenzene <10ppm thiophene
too often regarded as sufficient description of
the industrial synthesis of Gas Hydrogen gas of 99.5% purity at
350 kN/m3
nitrobenzene/aniline.The gas phase Catalyst Cu on silica gel
heterogeneous catalytic reduction of
Stream 1400 kN/m2, 197 C & 280
nitrobenzene using a copper catalyst which is kN/m2, 1650C
Cooling water 240C
shown below. The below equation does not
account for observed reaction by-products such as diphenyl hydrazine. [1]

FEEDSTOCK COMPOSITION

Accurate prediction of the formation of reaction by-products from nitrobenzene/aniline

manufacture necessarily requires identification of significant (in terms of chemical reactivity, potential
toxicity, and quantity present) impurities in all starting materials (benzene, nitric acid, and sulpuric acid).
Unfortunately, a truly representative analysis of nitrobenzene is difficult to obtain because of varying
sources (thus leading to potentially different impurities). For the purpose of this study (and consistent
with the accuracy of the above data), it is assumed that the sum of these impurities is less than one tenth
of 1 %. [1]

Feedstock of aniline production is nitrobenzene and hydrogen. By-products of nitrobenzene

manufacture (and thus, possible contaminants of nitrobenzene) will be extensively considered in
following sections of this report and will not be discussed further at this point. Hydrogen, required for the
industrial manufacture of aniline, in tonnage quantities is obtained from a variety of sources which
include natural gas via steam reforming, petroleum via partial oxidation, refinery tail gas and coke oven
gas. The impurities present in hydrogen will be at least somewhat dependent on its source but may be
divided contaminants are nitrogen, carbon monoxide, argon and methane. Impurities belonging to the
high boiling group include acetylene, carbon dioxide, paraffinic and olefinic hydrocarbons, hydrogen
sulfide, carbonyl sulfide, mercaptans and water. Of these two groups, generally only the low boiling
contaminates percent purification problems. Table TV illustrates typical compositions of several feed and
product streams. [1]

From the information presented above, the principal impurities most likely to occur in feedstock
hydrogen, regardless of its source, are methane, carbon monoxide, and nitrogen. There are no
specifications stated in the patent literature regarding hydrogen other than a purity of greater than 90% et
al., 1959; Sperber and Poehler, 1964); however, considering the low sulphur specification for
nitrobenzene (Karkalits, 1959), it is not unlikely that a similar requirement exists for hydrogen. Other
impurities, for example methane and carbon monoxide, though not necessarily inhibitory, may also be
detrimental to the yield of aniline and should probably be kept to a minimum. [1]

REACTION MECHANISMS

An understanding of the reaction mechanism, specifically identification of those reactive

intermediate which describe the reaction pathway, results in a complete, although qualitative, description
of by-products. Only a limited number of by-products have been explicitly associated or identified from
nitrobenzene/aniline manufacture in the chemical literature, though a large number of species have been
found in the wastewater at such facilitates. Known by-products of nitrobenzene, azobenzene, phenylene-
diamine, nitrates and sulfates. A detailed examination of the reaction mechanism will provide an
indication of which minor side reactions may generate other hazardous or toxic compounds. [1]

.
HYDROGENATION OF NITROBENZENE

The major processes used for the aniline manufacturing is the continuous vapour phase processes.
Typically, nitrobenzene (containing less than 10ppm thiophene) is vaporized in a stress of hydrogen and
introduced into the fluidized bed reactor. The catalyst, 10 to 20 % copper by weight on silica, is made by
spray-drying a silicic acid matrix (20 to 150m) with a cuprammonium compound and activated in situ
with hydrogen at 2500C. the nitrobenzene vapour-hydrogen mixture (300% excess hydrogen) is fed
through a porous distribution plate at the bottom of the fluidized bed reactor. Actual reaction conditions
have not been publicized but the basic patent (Karkalits, 1959) claims operation at catalyst and reaction
mixture. The reaction is highly exothermic and heat is removed by circulating a cool fluid (most probably
nitrobenzene) through tubes suspended in the fluidized bed. Catalyst fines are removed from the product
gas with porous stainless steel filters in the top of the reactor. [1]

The crude product mixture (aniline, hydrogen and water) leaving the reactor is condensed and
separated from the gas stream (3.5% water, 0.5% aniline, balance hydrogen); most of this gas stream is
compressed and recycled to the reactor, but a small portion is vented to prevent buildup of gaseous
impurities introduced with the hydrogen feed. [1]

The aqueous and organic phases are separated in a decanter. The organic phase (lower layer),
containing principally of aniline, up to 0.5% nitrobenzene, and 5% water is purified by two stage
distillation. In the crude still bottoms. The overheat product from the first column, is purified in a
finishing still; water is withdraw from the top of the column while aniline is withdraw in a side-stream
near the bottom of the column. The bottom product is recycled to the crude aniline still. Obviously other
separation processes are possible: water may first be removed distillation from the organic material; this
may then be distilled to produce aniline as an overhead product. The waste streams from this separation
process are similar to those described previously. [1]

Sulphur compounds (e.g. thiophenes) irreversibly poison the catalyst by forming copper sulphide;
in addition, dinitrobenzene is also reported to decreases catalyst activity. Since commercial production of
aniline is reported to be 1500 grams of aniline per gram of catalyst, deactivation via these mechanisms
which deposits during normal operation, the catalyst may be reactivated to near initial activity.
Presuming, this reaeration is done in situ, and probably not more than several times a year. [1]

Recovery of aniline from the aqueous phase (approx. 3% by weight) of the decanter, if not
economically justified, is required to meet current water quality standards. Aniline may be recovered from
this phase by countercurrent extraction with nitrobenzene, for which an extraction efficiency of 98% is
claimed. An alternative technique is to concentrate aniline from this stream using a stream using a stream
stripper and to then incinerate the enriched aniline water mixture. [1]

To facilitate
the discussion of Fig 2.1: Aniline production process: hydrogenation of nitrobenzene. Stream (1) nitrobenzene, (2)

the hydrogenation hydrogen feed, (3) reactor product gases, (4) condensed materials, (5) non- condensed materials,

of (6) crude aniline, (7) aqueous phase, (8) overheads, (9) bottom streams, (10) overheads

nitrobenzene, it is containing aniline product and (11) bottoms containing tars

useful to first
consider the general
relationships
existing in

heterogeneous processes in the gas or vapour phase over solid catalyst. Whereas simple gas phase
reactions are characterized by radical rather than ionic mechanisms, heterogeneous reactions, such as
those which take place partly in the gas phase and partly on a solid surface, are considerably more
complex. A reaction occurring on a surface may usually be regarded as involving the following five
consecutive steps:

1. Diffusion of the reacting molecules on the catalyst surface;

2. Adsorption of the gases on the catalyst surface;
3. Reaction on the catalyst surface;
4. Desorption of the products;
5. Diffusion of the desorbed products into the main body of the gas.

For reactions such as the gas phase hydrogenation of nitrobenzene which occur over porous
catalysts, the diffusion process, 1, may be the slowest process and, thus, the rate determining step.
Separation of steps 3 and 4 is difficult since product desorption rates are not generally known; therefore,
the reaction on the surface, giving the gaseous products, is most often regarded as a single step. [1]

The adsorption of nitrobenzene on Cu surface; however, it is not unreasonable to assume that, upon
adsorption, a molecule of nitrobenzene bonds to two atoms of Cu through oxygen. Taking into account
that molecular hydrogen is not effectively adsorbed below 300 0C, together with empirical evidence,
Pogorelov (1976) suggests a variation of an impact mechanism similar to that proposed by Twigg (1950).
This mechanism may be expressed by the following reactions given below and shown in figure 2.1. [1]
 NO 2 + M M NO 2 (1)

M NO2 + H 2 M NOOH +mH (2)

M NOOH + mH M NO + H 2 O (3)

M NO+ H 2 M NOH + mH (4)

M NOH +mH M N + H 2 O (5)

M N + H 2 M NH + mH (6)

M NH + mH M + NH 2 (7)

[where M equals 2m denotes an adsorption, center consisting of two surface atoms of Cu, denoted as m]

If the rate limiting step is reaction (2) and nitrobenzene adsorption (1) is at equilibrium, then the rate
equation may be expressed as:

k 2 K 1 P NO P H
v= 2 2

1+ K 1 P NO 2

where k2 is the rate constant for reaction (2) and K1 the adsorption coefficient for nitrobenzene. It is
pertinent to note that where K1PNO2 is large (i.e., where PNO2 is large) this equation reduces to

v =k 2 P H 2

In summary, the mechanism of catalytic hydrogenation of nitrobenzene to aniline is assumed to be

applicable to both the vapour and liquid phase hydrogenation processes over copper catalysts. [1]
 Fig 2.2: Reaction mechanism for the hydrogenation of nitrobenzene over copper catalysts
BY-
PRODUCTS
FORMATION

Two possible pathways leading to by-product formation, either by alternative reaction route or by
feedstock impurities. It is important to realize that, even though a feedstock impurity may be inert under a
given set of reaction conditions, the direct discharge of such an impurity to the environment may still
represent a significant effluent. [1] As there is obvious overlap between the two sections, the following
differentiations are made:

1. No formal distinction is made between by-products arising from nitrobenzene production and
aniline production; that is to say, that while relevant reactive intermediate is considered
sequentially, there is but one overall process;
2. By-products which result from alternate reaction pathways are considered from the viewpoint of
reactive intermediated identified as defined in the previous subsection;
3. Regardless of the source of compound (i.e., whether a feedstock impurity or reaction product),
once introduced, the entire reaction course of that compound is considered in that subsection;
4. Only those impurities identified and defined in the previous subsection, feedstock composition,
will be considered initially.

SIDE REACTION
Examination of intermediate species (NOOH, N, etc.) together with consideration of the subsequent
reactions of these initial products, provides a logical basis for prediction of additional by-products [1].
Some of the side reactions occurring during the process is shown here

REFERENCE

1. W. Lowenbach, J. Schlesinger, J. King; Toxic Pollutant Identification: Nitrobenzene/aniline

Manufacturing; U.S. Environmental Protection Agency.