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Ammonia production
From Wikipedia, the free encyclopedia
Because of its many uses, ammonia is one of the most highly produced inorganic
chemicals. There are numerous large-scale ammonia production plants worldwide,
producing a total of 131 million tonnes of nitrogen (equivalent to 159 million tonnes of
ammonia) in 2010.[1] China produced 32.1% of the worldwide production, followed by
India with 8.9%, Russia with 7.9%, and the United States with 6.3%. 80% or more of the
ammonia produced is used for fertilizing agricultural crops. Ammonia is also used for the
production of plastics, fibers, explosives, nitric acid (via the Ostwald process) and
intermediates for dyes and pharmaceuticals.

Contents

1 History

2 Modern ammonia-producing plants

3 Sustainable ammonia production

4 See also

5 References

6 External links

History
Before the start of World War I, most ammonia was obtained by the dry distillation of
nitrogenous vegetable and animal products; by the reduction of nitrous acid and nitrites
with hydrogen; and also by the decomposition of ammonium salts by alkaline hydroxides
or by quicklime, the salt most generally used being the chloride (sal-ammoniac).
Today, most ammonia is produced on a large scale by the Haber process with capacities of
up to 3,300 metric tons per day. 1) Ammonia is manufactured on a large scale by Haber's
process. 2) In this process,N2 and H2 gases are allowed to react at high pressure of 200 bar
(a).

Modern ammonia-producing plants

Block flow diagram of the ammonia synthesis process

A typical modern ammonia-producing plant first converts natural gas (i.e., methane) or
LPG (liquefied petroleum gases such as propane and butane) or petroleum naphtha into
gaseous hydrogen. The method for producing hydrogen from hydrocarbons is referred to as
"Steam Reforming".[2] The hydrogen is then combined with nitrogen to produce ammonia
via the Haber-Bosch process.
Starting with a natural gas feedstock, the processes used in producing the hydrogen are:

The first step in the process is to remove sulfur compounds from the feedstock
because sulfur deactivates the catalysts used in subsequent steps. Sulfur removal
requires catalytic hydrogenation to convert sulfur compounds in the feedstocks to
gaseous hydrogen sulfide:
H2 + RSH RH + H2S(gas)

The gaseous hydrogen sulfide is then adsorbed and removed by passing it through
beds of zinc oxide where it is converted to solid zinc sulfide:
H2S + ZnO ZnS + H2O

Catalytic steam reforming of the sulfur-free feedstock is then used to form hydrogen
plus carbon monoxide:
CH4 + H2O CO + 3H2

The next step then uses catalytic shift conversion to convert the carbon monoxide to
carbon dioxide and more hydrogen:
CO + H2O CO2 + H2

The carbon dioxide is then removed either by absorption in aqueous ethanolamine

solutions or by adsorption in pressure swing adsorbers (PSA) using proprietary solid
adsorption media.

The final step in producing the hydrogen is to use catalytic methanation to remove
any small residual amounts of carbon monoxide or carbon dioxide from the
hydrogen:
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 +2H2O

To produce the desired end-product ammonia, the hydrogen is then catalytically reacted
with nitrogen (derived from process air) to form anhydrous liquid ammonia. This step is
known as the ammonia synthesis loop (also referred to as the Haber-Bosch process):
3H2 + N2 2NH3
Due to the nature of the (typically multi-promoted magnetite) catalyst used in the ammonia
synthesis reaction, only very low levels of oxygen-containing (especially CO, CO2 and
H2O) compounds can be tolerated in the synthesis (hydrogen and nitrogen mixture) gas.
Relatively pure nitrogen can be obtained by Air separation, but additional oxygen removal
may be required.
Since relatively low single pass conversion rates (typically less than 20%), a large recycle
stream is required. This can lead to the accumulation of inerts in the loop gas.
The steam reforming, shift conversion, carbon dioxide removal and methanation steps each
operate at absolute pressures of about 25 to 35 bar, and the ammonia synthesis loop
operates at absolute pressures ranging from 60 to 180 bar depending upon which
proprietary design is used. There are many engineering and construction companies that
offer proprietary designs for ammonia synthesis plants. Haldor Topsoe of Denmark, Uhde
GmbH of Germany, Ammonia Casale of Switzerland and Kellogg Brown & Root of the
United States are among the most experienced companies in that field.

Sustainable ammonia production

Further information: Haber process#Economic and environmental aspects
Ammonia production depends on plentiful supplies of energy, predominantly natural gas.
Due to ammonia's critical role in intensive agriculture and other processes, sustainable
production is desirable. This is possible by using renewable energy to generate hydrogen by
electrolysis of water. This would be straightforward in a hydrogen economy by diverting
some hydrogen production from fuel to feedstock use. For example, in 2002, Iceland
produced 2,000 tons of hydrogen gas by electrolysis, using excess electricity production
from its hydroelectric plants, primarily for the production of ammonia for fertilizer.[3] The
Vemork hydroelectric plant in Norway used its surplus electricity output to generate

renewable ammonia from 1911 to 1971.[4] In practice, natural gas will remain the major
source of hydrogen for ammonia production as long as it is cheapest.
As an alternative to the relatively inefficient electrolysis, hydrogen can be generated from
organic wastes (such as biomass or food-industry waste), using catalytic (thermal)
reforming. This releases hydrogen from carbonaceous substances at only 10-20% of energy
used by electrolysis and may lead to hydrogen being produced from municipal wastes at
below zero cost (allowing for the tipping fees and efficient catalytic reforming, such as
cold-plasma). Catalytic reforming is possible in small, distributed (even mobile) plants, to
take advantage of stranded biomass/biowastes or natural gas deposits. Conversion of such
wastes into ammonia solves the problem of hydrogen storage, as hydrogen can be released
economically from ammonia on-demand, without the need for high-pressure or cryogenic
storage.
It is also easier to store ammonia on-board of vehicles than to store hydrogen, as ammonia
is less flammable than gasoline or LPG.
Waste water is often high in ammonia. Because discharging ammonia laden water into the
environment can cause problems, nitrification is often necessary to remove the ammonia.
This may be a potentially sustainable source of ammonia in the future because of its
abundance and the need to remove it from the water anyway.

See also

Ammonia

Amine gas treating

Haber process

References
1.

United States Geological Survey publication

2.

Twygg, Martyn V. (1989). Catalyst Handbook (2nd Edition ed.). Oxford

University Press. ISBN 1-874545-36-7.

3.

"Iceland launches energy revolution". BBC News. 2001-12-24. Archived

from the original on 7 April 2008. Retrieved 2008-03-23.

4.

Bradley, David (2004-02-06). "A Great Potential: The Great Lakes as a

Regional Renewable Energy Source" (PDF). Archived from the original (PDF) on 29
October 2008. Retrieved 2008-10-04.

External links

Today's Hydrogen Production Industry

Energy Use and Energy Intensity of the U.S. Chemical Industry, Report LBNL44314, Lawrence Berkeley National Laboratory (Scroll down to page 39 of 40 PDF
pages for a list of the ammonia plants in the USA)

Ammonia: The Next Step includes a detailed process flow diagram.

Ammonia production process plant flow sheet in brief with three controls.