Process Flow Diagram

Water, H20
i) Primary Stream
Reforming
Methane, CH4

Air ii) Secondary Stream

Reforming

iii) Carbon Monoxide

Conversion and Carbon
Dioxide Removal

iv) Ammonia Synthesis and

Product Separation (Unreacted
Nitrogen Gas, N2
synthesis gas)

Ammonia, NH3
 i) Primary Steam Reforming
The methane from the desulphurisation unit is mixed with steam, heated to 500 - 600ºC before
entering the primary reformer, where the mixed gases pass over a catalyst in a furnace at 780 - 830ºC
and at about 30 atmospheres pressure.
The catalyst used is nickel oxide catalyst on a calcium aluminate support, packed into nickel/
chromium alloy tubes.
The overall reaction is endothermic, consisting of the following equilibria:

The conditions in the primary reformer mean that only 30 - 40 % of the methane is converted
to hydrogen, so the resulting mixture contains methane, water (as steam), carbon monoxide, carbon
dioxide and hydrogen.

ii) Secondary Steam Reforming

The temperature must be raised to move the equilibrium position towards the right, producing
more process gases, carbon monoxide and hydrogen.
This is done by introducing air into the secondary reformer, where it has two functions:
The methane and hydrogen gases combust in the air, raising the temperature:

The resulting increase in temperature, and the increased steam concentration, forces the further
steam reforming of residual methane, as the process gases are passed through a nickel catalyst:

The overall reaction is exothermic, and the emerging gases have to be cooled in heat exchangers
from 1200ºC to 350 - 400ºC. The resulting steam can be used to generate electricity to drive compressors
and to pre-heat gases entering both primary and secondary reformers.
After the secondary steam reforming, the process gas contains hydrogen, nitrogen, carbon
monoxide, carbon dioxide and residual methane
 iii) Carbon Monoxide Conversion and Carbon Dioxide Removal
The proportion of carbon monoxide is reduced from 12%-15% to about 3% by passing it with
steam through a bed of iron oxide/ chromium oxide catalyst at about 400 ºC

Further reduction of carbon monoxide, to around 0.2%, is produced by passing the resulting
gases over a copper oxide/ zinc oxide based catalyst at lower temperatures of about 230ºC.

The carbon dioxide is removed by two methods:

 Physical absorption in solvents such as poly(ethylene glycol) dimethylether
 Chemical absorption in basic solvents such as methyl diethanolamine (MDEA) or hot aqueous
potassium carbonate solutions:

Heating then reverses this equilibrium allowing the carbon dioxide to be recovered.
Final CO2 levels can be as low as 50 - 1000 ppm.

iv) Ammonia Synthesis and Product Separation.

The synthesis gas is compressed to 100 - 250 atmospheres, heated to 350 - 550ºC and passed
over an iron oxide catalyst with potassium hydroxide and alumina promoters.

Under the reactor conditions, the iron oxide (Fe3O4) is reduced to give iron particles with many
small pores. The alumina prevents the pores in the iron collapsing, which would reduce the surface area.
Potassium hydroxide increases the activity of the iron catalyst by donating its outer electron to the iron,
increasing its electron density and its ability to bond to the nitrogen.

The synthesis reactor normally contains 2 - 4 catalyst beds, with heat exchangers or injections
of cold process gas to remove heat between catalyst beds. This helps to ensure maximum conversion to
ammonia. The ammonia produced is cooled and condensed, with un-reacted gases added back into the
synthesis gas and recycled. By continuous recycling of un-reacted gas, yields of up to 98% ammonia
are produced.
Introduction

Ammonia is the chief raw ingredient in the production of urea and is used in the manufacture
of other fertilizer products. When applied directly to soil, it provides high nitrogen for increased crop
yields. In addition to agricultural uses, ammonia is used widely in industrial and pharmaceutical
applications
Azane or ammonia is a compound of nitrogen and hydrogen with the formula NH3. The
simplest pnictogen hydride, ammonia is a colourless gas with a characteristic pungent smell. It is a
common nitrogenous waste, particularly among aquatic organisms, and it contributes significantly to
the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia,
either directly or indirectly, is also a building block for the synthesis of many pharmaceutical products
or is used in many commercial cleaning products. It is mainly collected by downward displacement of
both air and water.
Although common in nature and in wide use, ammonia is both caustic and hazardous in its
concentrated form. It is classified as an extremely hazardous substance, and is subject to strict reporting
requirements by facilities which produce, store, or use it in significant quantities.
It is a very important industrial chemical, and is used widely in both its pure form and as a
feedstock for a wide variety of other chemicals. Ammonia ranks second behind sulfuric acid in the
quantity produced worldwide per year. Ammonia itself is used as a fertiliser. In many alkaline cleansers,
such as window and floor cleaners. As a refrigerant gas, ammonia is used in the manufacture of
fertilisers, such as ammonium sulfate, ammonium nitrate, ammonium hydrogen phosphate, and urea.