AMMONIA

• The manufacture of ammonia is crucial for the world's agricultural industry for from

it all fertilizers that contain nitrogen are produced.

FIG. 1: USES OF AMMONIA

Annual production of ammonia:

• Ammonia ranks second, to sulfuric acid, as the chemical with the largest tonnage.

• It is being increasingly made in countries which have low cost sources of natural gas

and coal (China and Russia account for ca 40%).

LOCATION PRODUCTION (in millions of tonnes)

World 146
China 48
Russia 12
India 11
U.S.A 9
Indonesia 5
Trinidad and Tobago 5
Ukraine 4

FIG. 2: TABLE SHOWING AMMONIA PRODUCTION

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The manufacture of ammonia from nitrogen and hydrogen takes place in two main stages:

• the manufacture of hydrogen

• the synthesis of ammonia (the Haber Process)

a) THE MANUFACTURE OF HYDROGEN:

The manufacture of hydrogen involves several distinct processes. Figure 2 shows their

sequence and the location within an ammonia plant (steps 1-5). The converter used to make

ammonia from the hydrogen is also shown (step 6). What occurs in each of these steps is

described below the figure.

FIG.2: AMMONIA PLANT IN WESTERN AUSTRALIA

1) Desulfurisation units
2) Primary reformer
3) High temperature and low temperature shift reactors
4) Carbon dioxide absorber
5) Carbon dioxide stripper (recovery of the pure solvent, ethanolamine)
6) Ammonia converter
7) Ammonia storage as liquid
8) Pipeline to the ship for export

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Hydrogen is produced from a variety of feedstock, mostly from natural gas, coal or naphtha.

The ways in which hydrogen is obtained from this feedstock are dealt with separately.

Hydrogen from natural gas (methane) involves two stages:

i) the manufacture of synthesis gas (a mixture of carbon monoxide and hydrogen

(steam reforming))

ii) the removal of the carbon monoxide and production of a mixture of hydrogen and

nitrogen (the shift reaction)

i)MANUFACTURE OF SYNTHESIS GAS:

Whichever way the methane is obtained, it will contain some organic sulfur compounds and

hydrogen sulfide, both of which must be removed. Otherwise, they will poison the catalyst

needed in the manufacture of synthesis gas.

In the desulfurization unit, the organic sulfur compounds are often first converted into

hydrogen sulfide, prior to reaction with zinc oxide.

The feedstock is mixed with hydrogen and passed over a catalyst of mixed oxides of cobalt

and molybdenum on an inert support (a specially treated alumina) at ca 700 K.

Then the gases are passed over zinc oxide at ca 700 K and hydrogen sulfide is removed:

Primary steam reforming converts methane and steam to synthesis gas, a mixture of carbon

monoxide and hydrogen:

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Secondary steam reforming reacts oxygen from the air with some of the hydrogen present

and the resulting mixture is passed over a nickel catalyst. The steam and heat produced from

the combustion reforms most of the residual methane. Among the key reactions are:

The emerging gas from this net exothermic stage is at about 1200 K and is cooled in heat

exchangers. The steam formed from the water used in cooling the gases is used to operate

turbines and thus compressors and to preheat reactants.

Some recent designs use waste heat from the secondary reformer directly to provide heat for

the primary reformer.

At this stage the gas contains hydrogen, nitrogen, carbon monoxide and carbon dioxide and

about 0.25% methane. As air contains 1% argon, this also accumulates in the synthesis gas.

ii)THE SHIFT REACTION

This process converts carbon monoxide to carbon dioxide, while generating more hydrogen.

It takes place in two stages. In the first, the high temperature shift reaction, the gas is mixed

with steam and passed over an iron/chromium(III) oxide catalyst at ca700 K in a fixed bed

reactor. This decreases the carbon monoxide concentration from 11%:

In the second stage, the low temperature shift reaction, the mixture of gases is passed over a

copper-zinc catalyst at ca 500 K. The carbon monoxide concentration is further reduced to

0.2%.

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The gas mixture now contains about 18% carbon dioxide which is removed by scrubbing the

gas with a solution of a base, using one of several available methods.

The carbon dioxide is released on heating the solution in the carbon dioxide stripper). Much

of it is liquefied and sold, for example, for carbonated drinks, as a coolant for nuclear power

stations and for promoting the growth of plants in greenhouses.

The last traces of oxides of carbon are removed by passing the gases over a nickel catalyst at

600 K:

This process is known as methanation. A gas is obtained of typical composition: 74%

hydrogen, 25% nitrogen, 1% methane, together with some argon.

The heart of the process is the reaction between hydrogen and nitrogen in a fixed bed reactor.

The gases, in stoichiometric proportions, are heated and passed under pressure over a catalyst

(Fig. 3).

FIG. 3: FIXED BED REACTOR

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CONDITIONS FOR HABER PROCESS:

The proportion of ammonia in the equilibrium mixture increases with increasing pressure and

with falling temperature (Le Chatelier's Principle).

To obtain a reasonable yield and favourable rate, high pressures, moderate temperatures and a

catalyst are used.

A wide range of conditions are used, depending on the construction of the reactor.

Temperatures used vary between 600 and 700 K, and pressures between 100 and 200

atmospheres. Much work is being done to improve the effectiveness of the catalyst so that

pressures as low as 50 atmospheres can be used.

As the reaction is exothermic, cool reactants (nitrogen and hydrogen) are added to reduce the

temperature of the reactors (Figure 3).

The ammonia is usually stored on site (step 7) and pumped to another part of the plant where

it is converted into a fertilizer (urea or an ammonium salt). However, it is sometimes

transported by sea or by road, to be used in another plant.

The original catalyst that Haber used was Fe3O4, which was reduced by the reactant,

hydrogen, to iron. Much work was done to improve the catalyst and it was found that a small

amount of potassium hydroxide was effective as a promoter.

Recently research has been focused on finding even more effective catalysts to enable the

process to take place at lower pressures and temperatures. Ruthenium on a graphite surface is

a promising one.

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AMMONIA INDUSTRY IN TRINIDAD AND TOBAGO

• There are 11 ammonia plants that include 2 ammonia complexes on the Point Lisas

Industrial Estate with a total annual capacity of 5.2 million metric tonnes (MT).

• The first complex comprises the two Tringen plants which are joint ventures between

the Government and the Norwegian firm Norsk Hydro; and a third ammonia plant, the

oldest in the country, which was formerly owned by W.R. Grace and acquired by

Norsk Hydro in 1991; it was formally named Hydro-Agri but is now known as Yara

Trinidad Limited.

• The second fertilizer complex is one of the world’s largest ammonia complexes and is

owned by Potash Corporation of Saskatchewan (PCS) and comprises four ammonia

plants and one urea plant.

• One plant is owned by Pt Lisas Nitrogen Limited (formerly Farmland Misschem) with

an annual capacity of 650,000 MT. The Haber Process is used. The shareholders are

Terra Industries and KOCH Minerals Services LLC, being equal partners.

• Another plant is owned by Caribbean Nitrogen Company Ltd (CNC), with an annual

capacity of 650,000 MT. It is owned by a consortium comprising of subsidiary

companies of MAN Ferrostaal, PROMAN and KOCH Industries and local

company EOG Resources Trinidad Ltd.

• This consortium also owns another plant, the 650,000 MT per annum Nitrogen2000

plant, which commenced production in 2004.

• The ammonia plant of the Ammonia-Urea Ammonium Nitrate-Melamine (AUM)

complex is the newest addition to the ammonia manufacturing plants. Its production

capacity is approximately 650,000 MT per annum and started production in April

2009.

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FIG. 4: THE HABER PROCESS

FIG. 5: THE HABER PROCESS (FLOW CHART)

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USES OF AMMONIA:

 Used in the production of fertilizers

 Making other nitrogen-containing compounds, such as nitric acid, which is used to

make fertilizers, explosives and many organic nitrogen compounds in the

pharmaceutical and dye industries

 As components of household cleaners for shiny surfaces (such as glass and ovens. It

cleans without leaving ‘streaks’

 As a refrigerant (especially on large scales)

 To make dyes

IMPACT ON THE ENVIRONMENT:

FIG. 6: ENVIRONMENTAL IMPACT OF AMMONIA