Ammonia production

Contents
Ammonia
History
Modern ammonia-producing plants
Sustainable ammonia production
Ammonia Made from coal
Frank-Caro Process
Perdaman Plant
Byproducts & Shortages due to shutdowns
See also
References
External links

Ammonia
Ammonia is one of the most highly produced inorganic chemicals. There are numerous large-scale
ammonia production plants worldwide, producing a total of 144 million tonnes of nitrogen (equivalent to
175 million tonnes of ammonia) in 2016.[1] China produced 31.9% of the worldwide production, followed
by Russia with 8.7%, India with 7.5%, and the United States with 7.1%. 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.

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
tonnes per day. In this process, N2 and H2 gases are allowed to react at pressures of 200 bar. Ammonia is
also processed by coal.

The American Oil Co in the mid-1960s positioned a single-converter ammonia plant engineered by M.W.
Kellogg at Texas City, TX, with a capacity of 544 m.t./day. The single-train design concept was so
thoroughgoing that it received the “Kirkpatrick Chemical Engineering Achievement Award” in 1967. The
plant used a four-case centrifugal compressor to compress the syngas to a pressure of 152 bar, and final
compression to an operating pressure of 324 bar
occurred in a reciprocating compressor. Centrifugal
compressors for the synthesis loop and refrigeration
services were also implemented, which provided
significant cost, penny pinching it by a lot.

Almost every plant built between 1964 and 1992

had large single-train designs with synthesis gas
manufacturing at 25–35 bar and ammonia synthesis
at 150–200 bar. Another variation by Braun ((now
KBR)) offered slight tempering to the plain design.
The Braun Purifier process plants utilized a primary
or tubular reformer with a low outlet temperature
and high methane leakage to reduce the size and cost Block flow diagram of the ammonia synthesis
of the reformer. Excess air was added to the process.
secondary reformer to reduce the methane content of
the primary reformer exit stream to 1–2%. Excess
nitrogen and other impurities were erased downstream of the methanator. Because the synthesis gas was
essentially free of impurities, two axial-flow ammonia converters were used to attain a high ammonia
conversion.

Modern ammonia-producing plants

A typical modern ammonia-producing plant first converts natural gas, liquified petroleum gas, or petroleum
naphtha into gaseous hydrogen. The method for producing hydrogen from hydrocarbons is known as steam
reforming.[2] The hydrogen is then combined with nitrogen to produce ammonia via the Haber-Bosch
process.

Starting with a natural gas (CH4 ) feedstock, the different steps used in the process of producing hydrogen
are the following:

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 + 3 H2

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 + 3 H2 → CH4 + Illustrating inputs and outputs of steam reforming of natural gas, a

H2O process to produce hydrogen.

CO2 + 4 H2 → CH4 + 2
H2O

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):

3 H2 + N2 → 2 NH3

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 H2 O) 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.

Because of 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, Thyssenkrupp Industrial Solutions GmbH of Germany, Casale SA of Switzerland and Kellogg
Brown & Root of the United States are among the most experienced companies in that field.

Sustainable ammonia production

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 non-polluting methane pyrolysis or
generating hydrogen by electrolysis of water (or Illustrating inputs and outputs of methane
steam) utilizing zero carbon electricity from renewable pyrolysis, a process to produce hydrogen.
energy sources or nuclear power.
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
Illustrating inputs and outputs of simple
generate renewable nitric acid from 1911 to 1971,[4]
electrolysis of water, for production of hydrogen.
requiring 15 MWh/Ton of nitric acid. The same
reaction is carried out by lightning, providing a natural
source for converting atmospheric nitrogen to soluble nitrates.[5] In practice, natural gas will remain the
major source of hydrogen for ammonia production as long as it is the cheapest.

Waste water is often high in ammonia. Because discharging ammonia laden water into the environment,
even in wastewater treatment plants, can cause problems, nitrification is often necessary to remove the
ammonia.[6] 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.[7] Alternatively, ammonia from waste water
is sent into an ammonia electrolyzer (ammonia electrolysis) operating with renewable energy sources (Solar
PV and Wind turbine) to produce hydrogen and clean treated water.[8] Ammonia electrolysis may require
much less thermodynamic energy than water electrolysis (only 0.06 V in alkaline media).[9]

Another option for recovering ammonia from waste water is to use the mechanics of the ammonia-water
thermal absorption cycle.[10][11] Using this option, ammonia can be recovered either as a liquid or as
ammonium hydroxide. The advantage of the former is that it is much easier to handle and transport,
whereas the latter also has a commercial value when a concentration of 30 percent ammonium hydroxide in
solution is produced.

Ammonia Made from coal

Ammonia made from coal is a process mainly practiced by China.
China produced about 32.6% of the global production in 2014,
while Russia, India, and the U.S. produced 8.1%, 7.6%, and
6.4%.[12] Most of their ammonia came from coal. The basic
processing in a coal-based ammonia plant consists of an air
separation module for the separation of O2 and N2 from air, the
gasifier, the sour gas shift module, the acid gas removal module,
and the ammonia synthesis module. Oxygen from the air The Process to make ammonia from
coal.
separation module is fed to the gasifier to convert coal into
synthesis gas (H2, CO, CO2) and CH4. There are many gasifier
designs, but most gasifiers are based on fluidized beds that operate
above atmospheric pressure and have the ability to utilize different coal feeds.

Frank-Caro Process
Adolph Frank and Nikodem Caro found that N² could be fixed by calcium carbide to form calcium-
cyanamide, which could then be divide with water to form ammonia.
 [13]

Perdaman Plant
The world's largest plant Perdaman is located in Western Australia. It produces 3,500 metric tons per day
and 1,277,500 metric tons per year. [14] Perdaman Chemicals and Fertilizers (Perdaman) has signed a
licensing and engineering contract for Haldor Topsoe's SynCOR Ammonia solution for its A$ 4 billion
ammonia/urea plant in Karratha, Western Australia. Stamicarbon has been chosen as urea licensor, and gas
supply has been secured. The next milestone project was expected toward the end of March 2020.
Perdaman Chemicals and Fertilisers has signed a binding Heads of Agreement with SNC-Lavalin for the
EPC work for its Urea Project in Western Australia.

Byproducts & Shortages due to shutdowns

One of the main industrial byproducts of ammonia production is CO2 . In 2018, high oil prices resulted in
an extended summer shutdown of European ammonia factories causing a commercial CO2 shortage, thus
limiting production of carbonated drinks such as beer and fizzy soft drinks.[15] This situation repeated in
September 2021 due to a 250-400% increase in the wholesale price of natural gas over the course of the
year.[16][17]

See also
Amine gas treating
Haber process
Hydrogen economy
Methane pyrolysis

References
1. United States Geological Survey publication (https://minerals.usgs.gov/minerals/pubs/comm
odity/nitrogen/mcs-2018-nitro.pdf)
2. Twygg, Martyn V. (1989). Catalyst Handbook (2nd ed.). Oxford University Press. ISBN 978-
1-874545-36-1.
3. "Iceland launches energy revolution" (https://web.archive.org/web/20080407034506/http://n
ews.bbc.co.uk/2/hi/science/nature/1727312.stm). BBC News. 2001-12-24. Archived from the
original (http://news.bbc.co.uk/2/hi/science/nature/1727312.stm) 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" (https://web.archive.org/web/20081029051004/http://greengold.org/wind/do
cuments/107.pdf) (PDF). Archived from the original (http://greengold.org/wind/documents/10
7.pdf) (PDF) on 29 October 2008. Retrieved 2008-10-04.
5. Karl Fisher; William E. Newton (2002). G. J. Leigh (ed.). Nitrogen fixation at the millennium
(https://archive.org/details/nitrogenfixation00cuon). Elsevier. pp. 2 (https://archive.org/details/
nitrogenfixation00cuon/page/n16)–3. ISBN 978-0-444-50965-9.
6. "StackPath" (http://www.waterworld.com/articles/print/volume-26/issue-3/editorial-features/a
ddressing-the-challenge.html).
 7. Huang, Jianyin; Kankanamge, Nadeeka Rathnayake; Chow, Christopher; Welsh, David T.;
Li, Tianling; Teasdale, Peter R. (January 2018). "Removing ammonium from water and
wastewater using cost-effective adsorbents: A review". Journal of Environmental Sciences.
63: 174–197. doi:10.1016/j.jes.2017.09.009 (https://doi.org/10.1016%2Fj.jes.2017.09.009).
PMID 29406102 (https://pubmed.ncbi.nlm.nih.gov/29406102).
8. Muthuvel, Madhivanan; Botte, Gerardine G (2009). "Trends in Ammonia Electrolysis".
Modern Aspects of Electrochemistry, No. 45. Modern Aspects of Electrochemistry. 45.
pp. 207–245. doi:10.1007/978-1-4419-0655-7_4 (https://doi.org/10.1007%2F978-1-4419-06
55-7_4). ISBN 978-1-4419-0654-0.
9. Gwak, Jieun; Choun, Myounghoon; Lee, Jaeyoung (February 2016). "Alkaline Ammonia
Electrolysis on Electrodeposited Platinum for Controllable Hydrogen Production".
ChemSusChem. 9 (4): 403–408. doi:10.1002/cssc.201501046 (https://doi.org/10.1002%2Fc
ssc.201501046). PMID 26530809 (https://pubmed.ncbi.nlm.nih.gov/26530809).
10. Lin, P.; Wang, R.Z.; Xia, Z.Z.; Ma, Q. (June 2011). "Ammonia–water absorption cycle: a
prospective way to transport low-grade heat energy over long distance" (https://doi.org/10.10
93%2Fijlct%2Fctq053). International Journal of Low-Carbon Technologies. 6 (2): 125–133.
doi:10.1093/ijlct/ctq053 (https://doi.org/10.1093%2Fijlct%2Fctq053).
11. Shokati, Naser; Khanahmadzadeh, Salah (August 2018). "The effect of different
combinations of ammonia-water Rankine and absorption refrigeration cycles on the
exergoeconomic performance of the cogeneration cycle". Applied Thermal Engineering.
141: 1141–1160. doi:10.1016/j.applthermaleng.2018.06.052 (https://doi.org/10.1016%2Fj.ap
plthermaleng.2018.06.052).
12. "Introduction to Ammonia Production" (https://www.aiche.org/resources/publications/cep/201
6/september/introduction-ammonia-production). www.aiche.org. 2016-09-08. Retrieved
2021-08-19.
13. "Introduction to Ammonia Production" (https://www.aiche.org/resources/publications/cep/201
6/september/introduction-ammonia-production). www.aiche.org. 2016-09-08. Retrieved
2021-08-19.
14. "Home" (https://perdaman.com.au/). Welcome to Perdaman. Retrieved 2021-08-20.
15. "This is exactly why we're running out of CO2 for beer and meat production" (https://inews.c
o.uk/news/consumer/why-were-running-out-of-co2-beer-meat-production/). iNews. 2018-06-
28.
16. "Why is there a CO2 shortage and how will it hit food supplies?" (https://www.bbc.com/news/
explainers-58626935). BBC News. 2021-09-20. Retrieved 2021-09-21.
17. "Gas crisis: No chance lights will go out, says government" (https://www.bbc.com/news/busi
ness-58620167). BBC News. 2021-09-20. Retrieved 2021-09-21.

External links
Today's Hydrogen Production Industry (http://www.fossil.energy.gov/programs/fuels/hydroge
n/currenttechnology.html)
Energy Use and Energy Intensity of the U.S. Chemical Industry (https://www.energystar.gov/i
a/business/industry/industrial_LBNL-44314.pdf), Report LBNL-44314, Lawrence Berkeley
National Laboratory (Scroll down to page 39 of 40 PDF pages for a list of the ammonia
plants in the United States)
Ammonia: The Next Step (http://www.cheresources.com/ammonia.shtml) includes a detailed
process flow diagram.
Ammonia production process plant flow sheet (https://web.archive.org/web/2013102111430
1/http://www.inclusive-science-engineering.com/design-parameters-for-automation-control-s
ystem-for-ammonia-process-plant-front-end/ammonia-plant-process-flow-diagram-of-single-t
rain-section-front-end/) in brief with three controls.
 Ammonia For quick access

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