MANUFACTURE OF AMMONIA FROM SYNTHESIS GAS

BY AMUTHAN.M UNDER THEGUIDANCE OF Dr.N.STALIN M.Tech PhD ANNA UNIVERSITY TIRUCHIRAPPALLI

INTRODUCTION
Synthetic ammonia (NH3) refers to ammonia that has been synthesized from natural gas. Natural gas molecules are reduced to carbon and hydrogen. The hydrogen is then purified and reacted with nitrogen to produce ammonia. Approximately 82 percent of the ammonia produced is used as fertilizer.

 It is either directly as ammonia or indirectly after synthesis as urea, ammonium nitrate, and monoammonium or diammonium phosphates. The remainder is used as raw material in the manufacture of polymeric resins, explosives, nitric acid, and other products.

USES
It is the starting material for the production of a various number of nitrogenous fertilizers like ammonium phosphates, ammonium sulfate, ammonium nitrate etc. It is used directly or indirectly as the source for the production of hexamethylene diamine for the manufacture of nylon 6,6. As a corrosion inhibitor in petroleum refineries

PROPERTIES
Molecular Formula Molar mass Appearance Density Melting point Boiling point Solubility in water NH3 17.031 g/mol Colourless gas with strong pungent odour 0.73 kg/m3 @ 1.013 bar at 15 C 195 K 240 K 42.8% @ 0 C 34% @ 25 C 18% @ 50 C

Acidity (pKa)
Basicity (pKb)

32.5 @ 33 C

4.75

GENERAL PROPERTIES
STABILITY Anhydrous ammonia is stable at normal temperatures and pressures Decomposes at temperatures above 450C. It is stored in steel containers with pressure relief valves and with welded (not braised) joints since Ammonia will corrode copper, brass and bronze materials

CONTD.

TOXICITY For humans, inhalation of ammonia vapour causes irritation and corrosive damage to skin, eyes and respiratory tracts. At very high levels, inhalation of ammonia vapour can be fatal. When dissolved in water, elevated levels of ammonia are also toxic to a wide range of aquatic organisms

VARIOUS MANUFACTURING PROCESSES

Braun Purifier process

Foster Wheeler AM2 process

ICI process

Braun Purifier process

In the secondary reformer 1.5 times the stoichiometric quantity of air is used. This increases the heat load and reduces the radiant duty of the primary reformer to less than two thirds its usual duty. Excess nitrogen is removed by a cryogenic purification unit after methanation occurs. Owing to the high purity of synthesis gases, lower recycle gas flow, lower refrigeration duty and lower purge duty will suffice

Foster Wheeler AM2 process

Instead of treating the whole feed in primary reformer, some bypass is fed to the secondary reformer. Excess air used is much higher than in the case of Braun purifier process. Absorption system provides refrigeration for ammonia recovery.

ICI Process
Hydrocarbon feed is subjected to steam reforming in two stages to form oxides of Carbon, methane and hydrogen. In the secondary reformer air is mixed with the gases to get a N2 : H2 ratio of 1:3. Carbon monoxide is removed by shift conversion. Carbon dioxide is removed by absorption into MEA or K2CO3

SELECTION OF PROCESS

ICI process

Because. Waste heat can be recovered steam generated can be used to other process plants. Less dependency on electricity. Capital cost is less.

FLOW SHEET

SEQUENCE OF OPERATION
Feedstock desulphurization Primary reforming Secondary reforming Shift conversion CO2 removal Methanation ammonia synthesis

DESULFURIZATION
Desulfurization is carried out to remove the sulfur content in the feed. Sulfur is poisonous to catalyst and it corrodes the pipes. The sulfur in the naphtha feed stock is converted to hydrogen sulfide Cobalt Molybdenum catalyst used at a temperature of about 673 K Reaction: R-SH+H2 RH+H2 S

Primary Reforming
Desulfurized naphtha is mixed with steam in a tubular reforming furnace. Steam to carbon ratio must be maintained between 3.5 and 4.5 to ensure that carbon deposition does not occur. Reaction: Heat + CH4 + H2O 3H2 + CO

Secondary Reforming
The gases from the primary reformer are mixed with air and steam in the secondary reformer. The remaining hydrocarbon are further sent to reformation and the overall yield of hydrogen is increased. Reaction: O2 + 2H2 2H2O + heat heat + CH4 + H2O 3H2 + CO

Shift Conversion
HIGH TEMP SHIFT CONVERSION

CO concentration is reduced to about 3% by volume by means of water gas shift reaction at a temperature of 593 to 693 K. The reaction being exothermic the exit gases are at a higher temperature. Reactions: CO + H2O CO2 + H2 + heat

LOW TEMP SHIFT CONVERSION

The unconverted CO is converted to CO2 in the low temp shift conversion

REACTION

CO + H2O CO2 + H2 + heat

CO2 removal
The converted CO2 by shift conversion is absorbed in Absorber. Common absorbing medium Monoethanolamine Diethanolamine The solvents are regenerated using a stripper column

Methanation
Carbon monoxide and Carbon dioxide will act as catalyst poisons in the synthesis loop. So the unconverted CO & CO2 are converted as methane The methane is removed as an inert gas Reactions: CO + 3H2 CH4 + H2O CO2 + 4H2 CH4 + 2H2O

Ammonia Synthesis
The H2 and N2 are mixed in the reactor to produce ammonia The yield is about 17-19%

To increase the yield the ammonia is recycled. The system is called Ammonia Synthesis Loop.

Ammonia Synthesis

The reaction is a reversible one The high pressure favours product formation High temperature reduces the yield as it favours the decomposition reaction

Ammonia Separation
The product ammonia is removed by using mechanical Refrigeration (or) Distillation.

Typically Refrigeration is most economical.