1)Mendapara Milan(190722012)

2)Panara Kishan(190722013)
Bechamp reduction:-
Bechamp reduction is a simple reduction system used for the large scale production of variety of
aromatic amines. This is a very commonly used method for reducing the aromatic nitro compound due
to its lower cost. This involves the reaction of Fe with a mineral acid e.g. HCl, commonly used in the
industry to produce nascent hydrogen which then reacts with an aromatic nitro compound to give the
corresponding amine As can be seen from, along with the formation of a hydrogen, several moles of
iron salts/ oxides are formed. Salts of iron produced from this reaction, which get converted in to iron
hydroxide sludge Atom economy for producing hydrogen by reagent based iron/acid route can be
calculated as follows.

56 + (2 × 36.2) → 127 + 2 = 0. 015% ………. 5.1

molecular weight of desired product 2

(atom economy = × 100 = × 100 = 0.015%)
molecular weight of all reactants 56+73

127 + (2 × 36.2) → 198 + 2 = 0. 01% ….. 5.2

Thus, atom economy for producing 1 mol of hydrogen by Bechamp route is 0.01- 0.015%, which is 10000
times lower than the catalytic hydrogenation (atom economy = 100%) method.

1
Overall atom economy for producing the p-aminophenol by Fe/HCl reduction method is 13.33%.

Atom economy

139 + (3 × 56) + 72 + 438 → 109 + 88 + 107 + 73 = 13. 33% …. 5.3

Scheme 5.6. Atom economy for PAP synthesis by metal/acid reduction route

This Bechamp reduction process suffers from several disadvantages:

 Quantity of formation of Fe-FeO sludge is very large (1.2 kg/kg of product) and
cannot be recycled, creating a serious effluent disposal problem.
 Fe-FeO sludge always contains the adsorbed reaction product and is difficult to
filter and having a serious dumping problem.
 Erosion of reactor takes place due to Fe particles.
 Formation of side products.
 Rate of reaction varies from batch to batch.
 Work up of reaction crude is cumbersome.
 Difficult to separate the final product from the reaction mass.

Sulfide Reduction:
Depending on pH, different sulfide reducing agents can be employed such as hydrogen
sulfide, NaHS, Na2S as shown below (Scheme 5.7) [13].
pH ~ 7: 3H2S + ArNO2  ArNH2 + 2H2O +3S0

pH < 7: 6NaHS + 4ArNO2 + H2O  4ArNH2 + 3Na2SO3

pH > 7: 6Na2S + ArNO2 + H2O  4ArNH2 + 6NaOH + 3Na2SO3

Scheme 5.7. Sulfide reduction at various pH

This sulfur reduction process also has major drawbacks:

 Use of stoichiometric quantities of reagents generating large amount of inorganic

wastes
 Toxicity and odor due to sulfur
 Formation of sulfur-containing organic side-products
 Formation of elemental sulfur

Catalytic Hydrogenation method:

Due to the serious problem of effluent disposal of the above reagent based reduction
processes, stringent regulatory laws have been implemented in various countries
including India to ban such processes. To overcome this problem, catalytic
hydrogenation is the best alternative for the preparation of p-aminophenol from
nitrobenzene. The catalytic route minimizes the effluent disposal problems to a great
extent and is also expected to improve overall economics as well as the product quality.
The catalytic route involves hydrogenation of nitrobenzene in a single step to p-
aminophenol using supported noble metal catalysts in the presence of acid like H 2SO4.
Initial reduction of nitrobenzene to give β-phenylhydroxylamine (PHA) as an
intermediate (Scheme 5.8) which then rearranges in situ to p-aminophenol in the presence
of an acid (Bamberger rearrangement). Formation of aniline (AN) is the main competing
side reaction in this process [15-20]. Atom economy for synthesizing p-aminophenol is
48.5/ 86 %, which is 3.6/6.5 times more than Bechamp reduction method.
 NO2 NH2 NH2
+
Pt/C, H
+

H2
OH
Nitrobenzene PAP Aniline

H2
Pt/C
NO NHOH H+ Pt/C

H2
+
 PHA

NB + (2H2) + sulfuric acid → PAP + AN

Atom economy based on sulfuric acid used for rearrangement of PHA,

123 + (2 × 2) + 98 → 109 + 93 = 48. 45% …..5.4

Atom economy based on only H+ which is the species responsible for rearrangement of
PHA.

123 + (2 × 2) → 109 + 93 = 85. 83% …..5.5

Scheme 5.8. Catalytic hydrogenation of nitrobenzene to p-aminophenol

Comparison of Catalytic, Bechamp and Sulfide reduction methods:

The photographs of the PAP pilot plant are shown below. Based on pilot plant trials, a
commercial plant of 30,000 tpa PAP is being planned by the client.
PAP pilot plant photo:
Thank You