NITROGEN INDUSTRIES (AMMONIA)

Why study ammonia?

Raw materials to ammonia and its derivations

Why is ammonia used in fertilisers?

it provides nitrogen for plants to make plant proteins necessary for growth and repair of plant cells nitrogen fertilisers promote plant growth and increase crop yields

Nitrogenous Fertilisers
most plants are unable to make use of atmospheric nitrogen (79%) directly plants get nitrogen supply by absorbing soluble nitrogen compounds from the soil Examples: ammonium nitrate, ammonium sulfate, urea CO(NH2)2

History
Haber and Nernst: study of the equilibrium between N2 and H2 under pressure to form ammonia Haber and Bosch (1913): commercial high pressure synthesis of ammonia Ammonia is the base form which virtually all nitrogen-containing products are derived

Reversible Reaction

reactions that can go either direction forward and backward reactions take place at the same time

Reversible Reaction
do not go into completion reactions achieve equilibrium [equilibrium is achieved when amounts of reactants and products no longer change] a mixture of reactants and products at the end of the reaction amounts of reactants and products at equilibrium can be changed by altering conditions [e.g. temperature and pressure]

The Haber Process

invented in 1908 by Fritz Haber originally used to make explosives soon became the main source of ammonia to make nitrogen fertilisers

The Haber Process

Effect of conditions on the yield of ammonia

temperature A lower temperature increases the yield of ammonia. However, a lower temperature also results in a slower reaction.

Effect of conditions on the yield of ammonia

pressure A greater pressure increases the yield of ammonia, as well as the rate of reaction. However, maintaining higher pressure is costly and involves a safety risk.

Conditions for Haber Process

temperature of 450 C pressure of 250 atm presence of iron catalyst for maximum yield of ammonia

Methane based ammonia process

0.5N2 + 1.5H2 NH3 H=-46 kJ Catalyst: Ni 1st reformer: conversion of methane with steam 2nd reformer: partial oxidation of the gas from 1st reformer; molar ratio H2/N2=2.5-3 CO shift converter: conversion of CO with steam to CO2 and H2 Removal of CO2 using an absorption solution

%amonia at equilibrium from an initial mixture of 3:1 H2/N2 gas

The Kellogg ammonia process

Ammonia-synthesis converter

shift converter

pemurnian gas

reformasi kukus

metanator absorbsi CO2 ammonia converter

21

Ammonium nitrate (AN)

Made from nitric acid and ammonia:
NH3 + HNO3 NH4NO3 H=-86.2 kJ

Very important N-fertilizer (33% N), cheapness of its manufacture, and ts valuable combination of quick-acting nitrate and slower-ammoniacal nitrogen Amatol: military explosive, a mixture of TNT and AN Explosive decomposition:
NH4NO3 2N2 + 4H2O + O2

At 200-260oC : safely decomposed

NH4NO3 N2O + 2H2O

Stengel process for ammonium nitrate manufacture

Urea
Highest nitrogen content (46%) Two reactions: Ammonium carbamate formation (14MPa, 180oC):
CO2 + 2NH3 NH2COONH4 H=-155MJ/kgmol

Endothermic decomposition of NH4-carbamate:

NH2COONH4 NH2CONH2 + H2O H=42MJ/kgmol

Stamicarbon urea process

Equilibrium constant for HNO3

Reactions

The manufacture of 60% HNO3 from ammonia