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Lecture 22

Lecture

Nitrogen Industries

Nitrogen Industries

•• Ammonia

Ammonia

•• Nitric Acid

Nitric Acid

•• Urea

Urea

•• Ammonium Nitrate

Ammonium Nitrate

Ammonia

Ammonia

All processes for synthetic ammonia are based on the pressure catalytic reaction of nitrogen and hydrogen

Industry

Use

Fertilizer

Production of Ammonium sulfate Ammonium Phosphate Ammonium Nitrate Urea

Chemicals

Synthesis of Nitric acid Sodium hydrogen carbonate (sodium bicarbonate), NaHCO 3 Sodium carbonate, Na 2 CO 3 Hodrogen cyanide, HCN Hydrazine, N 2 H 4 (used in rocket propulsion systems)

Explosives

Ammonium Nitrate

Fibers and Plastics

Nylon and other polyamides

Refrigeration

Used for making ice, large scale refrigeration plants, air conditioning units in buildings and plants

Pharmaceuticals

Manufacture of drugs

Pulp and paper

Ammonium hydrogen sulfite, NH4HSO3, enables some hardwoods to be used

Production of Ammonia

Production of Ammonia

All processes for synthetic ammonia are based on the pressure catalytic reaction of nitrogen and hydrogen

In 1909 Fritz Haber established the conditions under which nitrogen, N 2 (g), and hydrogen, H 2 (g), would combine using medium temperature ( around 500 o C), very high pressure (around 250 atmospheres, i.e. 25,500kPa) with a catalyst (a porous iron catalyst prepared by reducing magnetite, Fe 3 O 4 )

Osmium (Os) is a much better catalyst for the reaction but is very expensive.

This process produces an ammonia, NH 3 (g), yield of approximately 10 - 20%. The Haber synthesis was developed into an industrial process by Carl Bosch.

The reaction between nitrogen gas and hydrogen gas to produce ammonia gas is an exothermic equilibrium reaction, releasing 92.4kJ/mol of energy at 298K (25 o C).

2N

2

+ 3H

2

Fe, 500 C, High pressure

o

2NH

3

O

H = - 22.0 Kcal/92.4 kJ/mol

Flowsheet of production of

Flowsheet of production

of Ammonia

Ammonia

Flowsheet of production of Flowsheet of production of Ammonia Ammonia

Nitric Acid

Nitric Acid

Industry

Use

Fertilizer

Production of Ammonium Nitrate

Chemicals

Synthesis of Sodium, Potassium and Calcium Nitrate

Explosives

Ammonium Nitrate and other nitro copmpounds

Fibers and Plastics

Nylon precurser, Adipic acid production

Solvents

Such as dinitrotoluene, nitrobenzene

Ammonia Oxidation Process for the production of Nitric

Ammonia Oxidation Process for the production of Nit

ric Acid

Acid

Fundamental steps

  • 1. Oxidation of NH 3 to NO

  • 2. Oxidation of NO to NO 2

  • 3. Absorption of NO 2 in water

  • 4. Concentration of HNO 3

Ammonia Oxidation Process for the production of Nitric Ammonia Oxidation Process for the production of Nit

Flowsheet of

Flowsheet

of for

for the

the production

production of

of Nitric Acid

Nitric Acid

Flowsheet of Flowsheet of for for the the production production of of Nitric Acid Nitric Acid

Urea -- CO(NH

Urea

CO(NH 22 )) 22

Urea

 

Mol wt.

60.05

M.P.

132.7

o C

B.P.

 

Decomposes

Solubility

Fairly solubility in water (110gm per 100 gm at 20 o C)

Uses

Used in solid fertilizer (51%), liquid fertilizer (31%), and other applications such as animal food, formaldehyde resins and adhesives

Production of Urea

Production of Urea

Raw Materials: Carbon dioxide from synthesis gas

manufacturing unit and ammonia

Process: Carbon dioxide and ammonia are compressed and

reacted at 100-200 atm, and 170 o C – 190 o C in an

autoclave to form ammonium carbamate. Urea is

f

d b

orme

y

d

e

h

y

d

l

ration in a ow pressure stripping

operation

Chemical Reactions:

CO

2

+ 2NH

3

NH

4

i

CO NH

i

2

O

H = - 37.4 Kcal

Ammonium carbamate

NH

4

i

CO NH

i

2

(

CO NH

2

)

2

+ H O

2

O

H = 6.3 Kcal

Undesirable side reaction:

(

2CO NH

2

)

2

H NCONHCONH + NH

2

2

3

Biuret

Flowsheet of for the

Flowsheet of for

the production

production of

of Urea

Urea

Flowsheet of for the Flowsheet of for the production production of of Urea Urea Process description

Process description

Process description

Ammonium Nitrate

Ammonium Nitrate

Urea

 

Mol. Wt.

60.05

M.P.

170.0

o C

B.P.

Decomposes at 200 o C or higher

Solubility

Soluble in water (900gm/ 1 liter at 20 o C)

Uses

Agricultural fertilizer due to high nitrogen content and explosives manufacturing

Production of Ammonium Nitrate

Production of Ammonium Nitrate

Raw Materials:

60% nitric acid

Liquid ammonia

Clay e.g. kieselguhr, diatomaceous earth for coating end

product to prevent explosion

Chemical Reactions:

HNO

3

+ NH

3

NH NO

4

3

O

H = - 20.6 Kcal

Flowsheet of

Flowsheet

of for

for the

the production

production of

of Ammonium

Ammonium Nitrate

Nitrate

Flowsheet of Flowsheet of for for the the production production of of Ammonium Ammonium Nitrate Nitrate

Process description

Process description