University of Engineering & Technology Lahore, KSK Campus

Unit Processes

Mr. Ahmed Hassam Khan

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AMINATION BY REDUCTION
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Topics to be covered
• Introduction
• Types of Amines
• Preparation of Amines
• Methods of Reduction
• Iron and Acid Reduction
– Reaction Mechanism
– Chemical and Physical Factors
– Equipment
• Manufacture of Aniline
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Introduction
• Amination by reduction involves the synthesis of amines
by reductive methods.
• Amines may be defined as derivatives of ammonia, where
one or more of the hydrogen are replaced by alkyl, aryl,
hydroaryl (cycloalkyl), or heterocyclic groups.
• Amines can be produced by reducing nitro, hydroxyl
amino, azoxy, azo, and hydrazo compounds, as well as
amides, nitriles, and azides.
• Amines may also be formed by reacting compounds
containing certain groups (e.g., halogens, hydroxyl and
sulfonic) with ammonia.

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Types of Amines
• Amines are divided into three classes-primary,
secondary, and tertiary-depending upon the number
of replaced hydrogen in the parent substance
ammonia.
• Primary amines contain two remaining hydrogen
atoms attached to the ammonia nitrogen, secondary
amines contain one, and tertiary amines have none
remaining.

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Amides & Imides

• Amides are derivatives of ammonia, where one of the
hydrogen atoms has been replaced by an organic acid-
derived group, such as acyl, aroyl, heteroyl, sulfonyl, etc.

• An imide is one in which two hydrogen of the parent

ammonia have been so replaced.
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Preparation of Amines
• The methods generally used for the preparation of primary
amines are the following:
1. The reduction of nitro, hydroxyl amino, azoxy, azo, and
hydrazo compounds.
2. The reduction of nitriles, amides, and azides.
3. The replacement of certain groups, such as nitro, halogen,
hydroxyl, and sulfonic acid by reaction with ammonia or urea.
4. Intramolecular rearrangement of (a) hydrazobenzenes and
hydroxylamines, (b) amides, and (c) secondary and tertiary
amines.
5. The hydrolysis of N-substituted amides.
6. Direct amination by means of hydroxylamine and sulfuric acid.

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Amines: Occurrence and Importance

• Amines occur as gases (methyl amine: Boiling point, -

6.7°C), liquids (aniline: Boiling point, 184°C), and
solids (1-naphthyl amine: Melting point, 50°C).

• They are used in the production of dyes, rubber

chemicals, nylon, pharmaceuticals, gasoline additives,
surfactants, textile auxiliaries, agricultural chemicals,
polyurethanes, inks, plastics, etc.

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Methods of Reduction
• A great variety of reductive methods have been used for the
preparation of amines. Among these are:
1. Metal and acid. Iron and acid (Bechamp method) is the major
example in this category, but other metals (tin, zinc) have also
been employed. Generally, hydrochloric acid is preferred, but
sulfuric, acetic, and formic acids have also been used.
2. Catalytic. This method involves the use of hydrogen (or
hydrogen containing gases) and a catalyst such as nickel,
copper, platinum, palladium, or molybdenum sulfide.
3. Sulfide. This is used mainly for the partial reduction of
polynitroaromatic compounds to nitroamines and for the
reduction of nitroanthraquinones to aminoanthraquinones.
4. Electrolytic.
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Methods of Reduction
5. Metal and alkali. This method is used mainly for the
production of azoxy, azo, and hydrazo compounds. The
latter are important in the manufacture of the benzidine
series.
6. Sodium hydrosulfite (hyposulfite).
7. Sulfite (Piria method). The reaction of sodium sulfite and
bisulfite on an aromatic nitro compound leads to a
mixture of amine and amino-aryl sulfonic acid.
8. Metal hydrides.
9. Sodium and sodium alcoholate.
10. Strong caustic oxidation reduction.
11. Hydrogenated quinolines and naphthalenes.
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Methods of Reduction
• By selection of reducing agent and careful regulation of
the process, reductions may often be stopped at
intermediate stages and valuable products other than
amines obtained.
• Metal and acid reductions are most vigorous and usually
yield amines as end products.
• When nitrobenzene is treated with zinc and a mineral
acid, the resultant product is aniline. When an alkaline
solution is employed, hydrazo-benzene is generally
obtained, but very vigorous conditions sometimes result
in the formation of aniline. When zinc dust and water are
used, the reaction product is phenyl-hydroxyl amine.

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Iron and Acid Reduction

Reaction Mechanism
• Chemical Mechanism. The arylamines, in contrast to the
alkylamines, dissociate on solvation only to a slight extent,
forming weak bases. In the case of aniline, this can be
represented as:
(1)

• The salts of aromatic amines (e.g., aniline hydrochloride)

are thus quite acidic and easily hydrolyzed. It is this
hydrolysis of the amine salt that gives the acidic medium
in which the reduction takes place. The degree to which
this hydrolysis occurs determines the treatment given the
final reducer charge prior to isolation of the amine.

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Chemical Mechanism
• Hydrogen is evolved when iron powder and water are
well mixed. This reaction is greatly accelerated by
heating in the presence of salts derived from strong
acids.
(2)

• When a nitro compound is introduced into such a

system, the hydrogen (possibly as hydrogen ions) and
ferrous hydroxide participate in the reduction
process.

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Chemical Mechanism
• The basic reactions may be represented as follows:
(3)
(4)

• When the reduction of nitrobenzene is carried out in a

glass vessel, the early formation of a greenish precipitate,
characteristic of ferrous hydroxide [Eq. (1)], is observed.
This turns to a brown [Eq. (2)] and finally to a black color,
which suggests that the formation of the known end
product, magnetic iron oxide Fe3O4 , is a secondary effect
resulting from the interaction of ferrous and ferric
hydroxides.
(5)

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Chemical Mechanism
• The amine hydrochloride produced in Eq. 1 may be presumed to react
further with iron and nitrobenzene:
(6)
• The step which is hidden in Eq. 1 and which permits the replacement
of acids by acidic salts is shown as:

(7)

• The reactions indicated by Eqs. (1) and (7) show that weak bases such
as aniline behave similarly to ammonia. They unite with water to form
weakly dissociated bases.
• These, like ammonium hydroxide, precipitate the hydroxides of the
heavy metals from solutions of their salts. The last step [Eq. (6)]
shows the completion of the "catalytic" cycle and emphasizes the role
of iron in the regeneration of the "catalyst," ferrous chloride, and the
amine.
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Chemical Mechanism
• This reaction is in accord with practical observations that
aqueous solutions of aniline hydrochloride, or other salts-
that are hydrolyzed in the presence of metals with the
formation of hydrogen ions, are useful "catalysts." The
over-all reaction can be represented as:

• This is an idealized equation, since in practice it has been

found that the iron oxide sludge (after dehydration) often
contains some FeO. The FeCl2 is not a true catalyst in that
it is continually consumed and new FeCl2 formed from
fresh iron.

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Electronic Mechanism (Nitrobenzene to aniline)

• According to the electronic theory, the nitro group is electrophilic and
accepts electrons from the iron.
• The nitrogen atom is bound to be electrophilic because of the pull on
its electrons by the phenyl group and the two oxygen atoms.

• In the presence of iron and H+, the first step in the reduction is an
almost simultaneous addition of two electrons and two protons to the
nitro group:

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Electronic Mechanism (Nitrobenzene to aniline)

• The second step is the formation of phenylhydroxylamine
by the same process as assumed in the first step:

• The third step is essentially the same but is shown in

two parts to explain it in detail:

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Chemical and Physical Factors

Amount of Iron Used

• In plant practice, it is customary to use slightly over 2
moles Fe per mole of nitro compound to carry out the
reduction process.
• Under such circumstances, not all the iron is
converted to the ferrosoferric oxide, some reducto-
active ferrous hydroxide also being present.
• The iron oxide sludge analysis show that slight
fluctuations in the ratio of iron to nitrobenzene will
produce magnified differences in the composition of
the final sludge.
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Chemical and Physical Factors

Physical Condition of Iron
• From a study of the equations outlining the reduction
process, it is obvious that the iron enters into the
reactions by providing the iron for the regeneration of the
ferrous chloride upon the hydrolysis of the phenyl
ammonium chloride (aniline hydrochloride) and also acts
as an oxygen carrier.
• Analysis of the residual sludge reveals that the bulk of the
iron is converted to iron oxides, the degree of oxidation
depending on the quantity of iron employed.
• Since the reaction velocity for nitro compound reduction
is a function of the rate of iron oxidation, it is clear that
the use of finely divided iron shortens the time of
reaction.
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Chemical and Physical Factors

Amount of Water Used
• Theoretical considerations involving the progressive
oxidation of the iron indicate the desirability of using
4-5 moles of water per mole of nitro compound
treated.
• This approximation is based, on the assumption that
the iron employed is converted to ferrous and ferric
hydroxide as intermediate products during its
oxidation to the oxide.

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Chemical and Physical Factors

Amount of Acid Used
• This reaction requires the presence of small amounts of
ferrous ion to act as a catalyst.
• Generally about 0.05-0.2 of an equivalent of acid is used.
• The acids usually employed in the reduction process are
hydrochloric and sulfuric acids.
• Hydrochloric acid sometimes causes the formation of
small amounts of chlorinated amines whereas sulfuric acid
may rearrange the intermediate arylhydroxylamines to
hydroxyarylamines and cause the formation of darker
amines and lower yields, particularly in the case of solid
amines.
• Where the danger of hydrolysis or contamination by such
products exists, acetic or formic acid is employed instead.
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Chemical and Physical Factors

Effect of Agitation
• Since the reduction process is a multi-phase reaction,
it is clear that the best results are obtainable only
when the nitro compound, iron and catalyst are in
intimate contact.
• A stirrer that merely pushes the iron around the
bottom of the vessel and permits the charge to
separate out into layers does not function efficiently.
• It is apparent, therefore, that a sturdy sleeve-and-
propeller or double-impeller type of stirrer will in
some cases be superior to the slow moving plow
type.
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Chemical and Physical Factors

Reaction Temperature
• It has been found that the use of a high catalyst
concentration (3 per cent or more compared to
nitrobenzene taken) during reduction results in a finely
divided iron sludge which is of possible commercial value.
• This result can be obtained by limiting the quantity of
water introduced into the jacketed reducer and utilizing
the heat of reaction to carry on the reaction.
• A study of reduction of nitrobenzene shows that the
reaction is exothermic. It is necessary, therefore, to
remove the surplus heat generated while maintaining the
reduction at optimum reaction temperature.
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Chemical and Physical Factors

Additions of Solvents
• Where a very insoluble and difficultly reducible nitro
compound is to be reduced, the addition of a solvent
miscible with water, such as ethyl alcohol, methanol,
or pyridine, is often of considerable help.
• This makes for a smoother and more rapid reduction.

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Chemical and Physical Factors

Testing for Completion
• Reduction will not take place in the absence of
ferrous ions, which can be demonstrated by the lack
of a black precipitate on spot testing with sodium
sulfide solution.
• The reaction is considered complete when an aliquot
no longer increases its take-up of sodium nitrite on
further reduction with a stronger reducing agent,
such as zinc and hydrochloric acid.

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Chemical and Physical Factors

Work-Up of Reaction Mixture
• Soluble iron is generally precipitated with alkali, using
caustic soda, soda ash, lime, or magnesia.
• Where the amine is volatile, it may be isolated by steam
distillation or by vacuum distillation from the iron oxide
cake after distilling off the water.
• In the latter case, an efficient agitator must be used to
keep the iron oxide from lumping and occluding the
product.
• Where the final amine is soluble in alkaline solution, as is
the case with sulfonic acids, carboxylic acids, or
sulfonamides, the iron oxide cake is filtered off and the
amine isolated from the filtrate.

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Chemical and Physical Factors

Work-Up of Reaction Mixture
• Where neither of these two methods may be applied,
a third and technically undesirable process is
sometimes used.
• This involves solvent extraction of the iron oxide cake,
which brings with it filtration problems and costly
solvent recovery.
• Where a cheap solvent, such as naphtha, can be used,
these difficulties are somewhat mitigated.
• Where a water-miscible solvent can be used, it is
usually added to the reduction mixture initially.
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Chemical and Physical Factors

Continuous Processing
• Although the Bechamp reduction is generally carried
out on a batch basis, it has been run continuously.
• This involves passing an acidified solution or emulsion
of the nitro compound through a suitable tower
packed with iron or scrap iron and kept at the
required temperature.

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Chemical and Physical Factors

Yields of Amine
• In plant practice, yields in the range of 85-98 percent
of theory are obtained with the Bechamp reduction.
• Depending upon the solubility and stability of the
starting nitro and final amine, many variations of this
process can be used to obtain the highest yield in the
most economical fashion.
• Method and rate of addition of the nitro compound,
temperature, agitation, addition of a solvent or an
emulsifying agent may all influence the yield.
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Equipment
Materials of Construction
• Bechamp reductions are usually carried out in cast-iron vessels
and alkali reductions in carbon-steel vessels of desired sizes.
• The larger ones are favored by plant engineers because of the
possibilities of more economical operation.
• Each manufacturer has, however, introduced one or more
accessories or refinements calculated to appeal to the
experienced chemical engineer.
• The reducers for iron and acid reductions are sometimes
equipped with side and bottom cast-iron lining plates, which
may be replaced, in order to protect the vessel against the
continuous erosive action of the iron.
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Equipment
Agitation
• In some reducers. a vertical shaft carries a set of cast-iron
plows which can be removed through the side door to the
reactor.
• These plows travel at the rate of 30-50 rpm and serve to
keep the iron particles in suspension in the lower part of
the vessel.
• Agitator needs to be made of material that will resist both
the corrosion and erosion.

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Equipment
Jacketing of Reducers
• Practically all the iron reducers employed for the Bechamp
reduction of liquid nitro compounds are equipped with
jackets.
• Although the reduction process is exothermic, the
reaction proceeds best at slightly elevated temperatures.
• It is customary, therefore, to warm the reactants at the
start.

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Equipment
Reducer Accessories
• The reducer is equipped with a suitable feeding device, which
will deliver the iron as required.
• The bin is frequently attached to a scale so that the charge
entering the reducer is being weighed continuously and
accurately.
• Suitable screwed openings are provided for the introduction of
the liquid nitro compound and catalyst solution.
• Steam connections are made in accordance with specific
requirements, depending on whether or not the vessel is
jacketed and whether or not the resulting amine is to be
distilled with steam.
• A sight box is located over the reducer to enable the operator
to watch the progress of the reduction.
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Manufacture of Aniline
• It is entirely feasible to add all the water, iron, and
soluble catalyst at the start. This mass is then
thoroughly heated and agitated.
• The aromatic nitro compounds can thereupon be
introduced at definite time intervals, the precaution
being taken that each portion is completely reduced
before continuing with further addition.
• This technique gives satisfactory results in the
reduction of many nitro compounds.

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Recovery of Aniline
• The most important problem in the preparation of aniline
concerns its separation from the reducer charge.
• The engineer's goal is to provide for the continual
mechanical separation of the aniline and water from the
iron oxide sludge and to recover the latter as a finely
divided dry powder of commercial value, where a market
exists.
• The aniline should then be separated from the water in a
reasonably pure state while the aqueous solution
containing catalyst and some amine is returned to the
reducer.
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Selection of Equipment
• The following criteria were suggested as a guide in the selection
of equipment:
1. Simplicity. Minimum handling of material.
2. Yields. Reduction to a minimum of the known sources of loss.
3. Productivity. Discharging the batch immediately after
reduction is complete.
4. Water balance. Elimination of methods that cause an
accumulation of water, as this involves a great loss in yield and
an increase in power costs.
5. Power load. The consumption of steam, water, and electricity
is an important factor in determining the cost.
6. By-product sludge. In some localities, a market can be
obtained for a dry, clean, finely divided aniline-free iron oxide.
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