Process Background

HISTORY
Ammonia was first discovered in 1774 by an English chemist Joseph Priestley.
He obtains the ammonia from ammonium salt which can be found near volcano and
mountain area. The ammonium salt also called sal ammoniac (ammonium chloride)
heated with slack lime (calcium hydroxide) producing ammonia purely. The reaction
equation is 2NH4Cl + Ca(OH)2 NH3 + CaCl2 and still used in laboratories if required a
small quantities of this gas. At first ammonia being called "alkaline air" because water
solution of ammonia had all attributes of alkalis. Years later in 1784, a French chemist
Claude Louis Berthollet decomposed ammonia into elements with the help of electric
discharge thus identified the composition of this gas.
Backbone of Haber Process is Hydrogen and nitrogen to produce Ammonia. One
of problem is choosing source of oxygen while nitrogen can be found in air about 78%
percent from its composition. Hydrogen can be used from many source such reforming
from methane, steam electrolyser or naphtha. Ammonia consist of 3 hydrogen atom and
1 atom of nitrogen. In this era, hydrogen more easily to synthesis from natural gas
because of natural gas can be easily get. Natural gas used are methane from petroleum
based.
First step to produce Hydrogen is by the reaction of methane and water(steam) .
Before the process to begin, all sulfurous compounds from the natural gas containing
methane need to be eliminated. Most of natural gas, it contain sulfurous compound. The
aim of elimination of sulfurous compounds from the natural gas is to prevent catalyst
from poisoning. The natural gas will be heated to 400C and the addition of zinc oxide:
ZnO + H2S ZnS + H2O
The gas will be sent to the primary reformer to be prepared for steam reforming.
The methane will be react with the superheated steam in the reactor. The gas mixture
heated with natural gas and purge gas to 770c in the presence of nickel that act as
catalyst. The gaseous mixture is known as synthesis gas .
CH4 + H20 3H2 + CO
CH4 + 2H20 4H2 + CO2
CO + H20 H2 + CO2

The next step is air addition to the air reformer. The synthesis gas will be cooled
slightly to 735C . The compositon of air is consist of 78% of nitrogen gas, so this
process also be known as nitrogen addition. We dont need oxygen in Haber process so
after the gas has been cooled, it will be flows to the secondary reformer and it will be
mixed with calculated amount of air to occur the reaction of oxygen and methane
produce more hydrogen and and it is highly exothermic reaction.
2CH4 + O2 = 2CO + 4H2 H298 = -71 kJ
CH4 + O2 = CO2 + 2H2 H298 =
CO + H2O = CO2 + H2 H298 =

In further process, carbon monoxide can oxidize the iron catalyst in ammonia
synthesis reactor. Carbon monoxide still unstable in it nature form so it can be react with
other active element. To avoid catalyst oxidation, the necessary of convert carbon
monoxide to carbon monoxide are crucial. The carbon monoxide contaminated stream
are pass to fixed bed reactor which pass two catalysts bed first at 360 oC with catalyst of
FeO3/Cr. Then it is pass at second catalyst Cu bed at 225 oC. The conversion of carbon
monoxide is 99.7% in dry basis.
After most of Carbon monoxide eliminated, the raw substance still not highly
pure. It still has carbon dioxide to be removed and it is passes through CO 2 scrubber.
CO2 scrubber is gas adsorption unit separating carbon dioxide from the stream and also
water. The gas adsorption unit use amine as solvent to remove the carbon dioxide gas.
The CO2 completely removed.
The highly pure nitrogen and hydrogen gas are now ready to pass into further
process which backbone of the ammonia plant, Haber process. Haber process is
process of hydrogenation of nitrogen at high temperature and high pressure with
presence of iron catalyst. This process are originate by principle of Le Chatelier. If a
dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium
moves to counteract the change. According to Le Chatelier's Principle, if you increase
the pressure the system will respond by favouring the reaction which produces fewer
molecules. That will cause the pressure to fall again. To get as much ammonia as
possible in the equilibrium mixture, you need as high a pressure as possible. 330 bar is
a high pressure, but not amazingly high. This is why high pressure require to fasten up
process and higher the conversion. The purity can be up to 99.7 percent.

In ammonia industry, it is surely such a high demand for agriculture because of

properties of nitrogen for selection of fertilizer. Ammonia ranks are now in second,
down to sulfuric acid, as the chemical with the largest tonnage produced. The largest
plants produce about 3000 tonnes a day and there are plans to build plants that
produce 4000-5000 tonnes a day, which would mean that the total world output could be
managed with 100 such units. Current production is:
World

140 million tonnes

Europe

16 million tonnes

North America

15 million tonnes

US

8 million tonnes

Asia

74 million tonnes

Russia
Middle East

12.5 million tonnes1

13 million tonnes

Data from:
1. Federal State Statistics Service: Russian Federation 2011

The world population is increasing by about 1.4% a year, This plant can produce
up to 1000-2000 tonnes per day which not leading producing ammonia.