Liquid-phase Nitartion

• Less importance than vapor phase nitration because of low yields, lower
conversion and occurance of unwanted side reactons.
• Principal of Liquid-phase Nitartion: Replacement of hydrogen atom by nitro
groups.
• Ease of formation of product for paraffins as:
tertiary > secondary > primary nitroparaffins.
• Reaction is comparatevily slow because of low solubility of paraffins and
the nitration medium.
• Higher hydrocarbon can be nitarted at higher temperature due to their higher
boiling points.
Liquid-phase Nitartion

• Mononitroparaffins easliy and more soluble in nitric acid than

polynitroparraffin.
• Due to the the much reduction of nitric acid to elementry nitrogen,
prevents recovery of reoxidation, which is economic barrier to the
industrialization.
• Example: Nitrocyclohexane, 2-nitropropane,Olefins, Acetylene etc.
Process Equipments for Nitration
• Batch operation: Stoneware vessles.
• Continous opertaion: Gleaming stainless-steel vessles.

• High heat of reaction and dilution involved, absorbed by Stoneware

vessles in water bath, or coil or jackets.
• No control in reaction for automatic system, preffered remote
locations, beacuse of their hazardous, explosive compounds.
Advantages of batch process
compared to continuous process
1. Flexibility: Easier to introduce process variation in to batch process
than continuous one.
2. Labor usage: For high rate of production, large batches are used the
labor efficiency.
Advantages of continuous process compared to batch process

1. Lower capital costs

2. Safety
3. Labor usage
Assignment
• Batch and Continuous Nitration, in detail
Mixed Acid Preparation
• Preparation
• Adjustment to the needs of nitration
• Handling as spent acid

Manufacturing of glyceryl trinitrate

Mixed Acid Preparation

• Processing:
• Raw material
65% oleum
50-60 % nitric acid
Spent acid
• Products:
Nitroglycerine mixed acid
Conc. nitric acid
93% Sulfuric acid
Mixed Acid Preparation

• Freezing point of oleum is 5 degree C.

• To avoide this, oleum is diluted.(40%)
• Mixed with 97% nitric acid and make necessary adjustment.
• Then, ready for nitration.
• To make 97% nitric acid:
need:
93% sulfuric acid
spent acid
weak nitric acid,
to prepare:
35% sulfuric acid
23% nitric acid
Mixed-acid Composition
• Nitric acid and sulfuric acid, there are two primary conditions, that
must be met.
These are:
1)The amount of 100% nitric acid present in nitration must be enough
to satisfy the stoichiometric requirements of nitration. It is usually
present in excess in order to maintain reasonably fast over-all reaction
rates.
2)The amount of 100% sufuric acid with, if necessary, its associate
dissolved SO3(oleum) must be sufficient to promote the desired
reaction.
Mixed-acid Composition
• Two values which are calculated form the reaction stochiometry.
• These values are D.V.S. (dehydrating values of sufuric acid) and the
nitric ratio.
• D.V.S. is the ratio of H2SO4 to H2O present at the end of their
reaction.
• Nitric ratio (R) is the ratio of the weights of 100% HNO3 to weight of
material being nitrated.
• D.V.S.= S/[(EN/R) +W]
s=% actual h2so4, N=%actual HNO3, W=%water, E=water equivalent of
material to be nitrated, R=nitric ratio